Ink for semiconductor passive component packaging and preparation method, device and equipment thereof

Abstract

The present invention discloses an ink for encapsulating semiconductor passive components, a preparation method, a device, and an apparatus. The ink comprises, by mass percentage, 20-35 parts of a phenolic resin, 5-15 parts of a polyurethane resin, 5-25 parts of an epoxy resin, 10-20 parts of a silica-grafted carbon fiber filler, 5-10 parts of a first filler, 1-10 parts of an additive, and 8-11 parts of a pigment. By optimizing the composition and process of the encapsulated ink, the present invention effectively improves the stability and tolerance of the ink product, thereby meeting its adaptability in production environments and applications, and ensuring the product's service life.

Description

Technical Field

[0001] The present invention relates to semiconductor packaging technology, and in particular to an ink for semiconductor passive component packaging and a preparation method, device and equipment thereof. Background Art

[0002] To improve the electrical properties of semiconductor packaging structures, passive components such as capacitors, resistors, or inductors are installed in the semiconductor packaging structure. Among them, resistors are generally used for voltage division, current shunting, filtering, and impedance matching. The main type of resistor used is chip resistor (Chip Resistor), also known as chip resistor (SMD Resistor). Chip resistors are a type of metal glass glaze resistor. The resistor is made by printing metal silver paste and glass glaze powder on a substrate using the silk screen printing method, and then a layer of insulating ink protective coating is printed on the outermost layer. Chip resistors can generally be divided into conventional series thick film chip resistors and high-precision and high-stability chip resistors. Among them, conventional series thick film chip resistors are mainly used in general consumer products; high-precision and high-stability chip resistors are mainly used in medical equipment, precision measuring instruments, electronic communications, automotive equipment, etc.

[0003] The rapid development of the integrated circuit industry is driving increasingly higher performance demands on passive components, particularly the flexibility and acid resistance of the protective coatings used in high-precision and stable chip resistors. Poor flexibility can lead to chip breakage and cracking during production. Poor acid resistance can corrode the encapsulating ink in the acidic conditions of the electroplating solution, ultimately destroying the resistor. Poor solvent resistance can cause the ink to fall off during use.

[0004] The information disclosed in this background technology section is only intended to enhance understanding of the overall background of the invention and should not be regarded as an admission or any form of suggestion that the information constitutes the prior art already known to a person skilled in the art. Summary of the Invention

[0005] The purpose of the present invention is to provide an ink for semiconductor passive component packaging and its preparation method, device and equipment. By optimizing the composition and process of the packaging ink, the stability and tolerance of the ink product are effectively improved, thereby meeting the adaptability in the production environment and application, and ensuring the service life of the product.

[0006] To achieve the above objectives, embodiments of the present invention provide an ink for semiconductor passive component encapsulation, comprising, by mass percentage: 20-35 parts of phenolic resin, 5-15 parts of polyurethane resin, 5-25 parts of epoxy resin, 10-20 parts of silica-grafted carbon fiber filler, 5-10 parts of a first filler, 1-10 parts of an additive, and 8-11 parts of a pigment. Preferably, an ink for semiconductor passive component encapsulation comprises, by mass percentage: 25-34 parts of phenolic resin, 8-13 parts of polyurethane resin, 10-22 parts of epoxy resin, 15-20 parts of silica-grafted carbon fiber filler, 8-10 parts of a first filler, 5-10 parts of an additive, and 8-11 parts of a pigment.

[0007] The phenolic resin may be present in an amount of 25, 26, 27, 28, 29, 30, 31, 32, 33, or 34 parts, the polyurethane resin may be present in an amount of 8, 9, 10, 11, 12, or 13 parts, the epoxy resin may be present in an amount of 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22 parts, the silica-grafted carbon fiber filler may be present in an amount of 15, 16, 17, 18, 19, or 20 parts, the first filler may be present in an amount of 8, 9, or 10 parts, the additive may be present in an amount of 5, 6, 7, 8, 9, or 10 parts, and the pigment may be present in an amount of 8, 9, 10, or 11 parts. However, the present invention is not limited to the values ​​listed above, and other values ​​not listed within the above numerical range are also applicable.

[0008] In one or more embodiments of the present invention, the silica-grafted carbon fiber filler is obtained by grafting modified silica onto activated carbon fibers. Preferably, the silica is crystalline silica or amorphous silica with a particle size of 20-200 nm.

[0009] In one or more embodiments of the present invention, the polyurethane resin is an aliphatic polyurethane resin or an aromatic polyurethane resin, and satisfies the following requirements: an elastic modulus of 100-900 MPa and a tensile strength of 10-550 psi.

[0010] In one or more embodiments of the present invention, the phenolic resin is a thermosetting phenolic resin, wherein the free phenol content is ≤20%. Preferably, the phenolic resin is a thermosetting phenolic resin, wherein the free phenol content is ≤15%.

[0011] In one or more embodiments of the present invention, the epoxy resin is a bisphenol A epoxy resin or a novolac epoxy resin, wherein the epoxy equivalent weight is 0.45-0.60. Preferably, the epoxy resin is a bisphenol A epoxy resin, wherein the epoxy equivalent weight is 0.50-0.55.

[0012] In one or more embodiments of the present invention, the first filler is selected from barium sulfate, talc, mica powder, and calcium carbonate.

[0013] In one or more embodiments of the present invention, the additive is selected from defoamers (233A, LP2700, BYK-346), leveling agents (organic silicone leveling agents, non-organic silicone leveling agent 361S), film-forming agents (BDG, divalent acid esters), thickeners (talc, fumed silica), and wetting and dispersing agents (P-193, 680U). The additive can be a combination of a leveling agent and a defoamer, a combination of a defoamer and a film-forming agent, or a combination of a leveling agent and a film-forming agent.

[0014] In one or more embodiments of the present invention, a method for preparing ink for semiconductor passive component packaging comprises the following steps: mixing and dispersing the constituent raw materials evenly, grinding with three rollers, filtering and filling. During the operation, the silica grafted carbon fiber filler, polyurethane resin, phenolic resin, epoxy resin, first filler, pigment and additives can be mixed, stirred and dispersed evenly, ground with three rollers, filtered and filled, and the final viscosity of the ink is 35000-45000 cP. Preferably, the stirring rate is 300-500 rpm, and the time is 1-1.5h. The rate can be 300rpm, 400rpm, 500rpm and any other value in the range of 300-500rpm, and the time can be 1h, 1.5h and any other value in the range of 1-1.5h, but is not limited to the values ​​listed above. Other values ​​not listed within the above numerical range are also applicable.

[0015] In one or more embodiments of the present invention, a semiconductor device includes a stack formed by the ink for semiconductor passive component packaging as described above. The stack is a structure formed after the ink is fixed.

[0016] In one or more embodiments of the present invention, the device includes the aforementioned semiconductor device. That is, the device may be at least a packaged semiconductor device connected to a circuit or cable, etc., and can achieve a basic function.

[0017] The surface of silica has many hydroxyl groups and a large specific surface area. The smaller the particles, the easier it is to agglomerate. Carbon fiber materials have excellent impact resistance, excellent toughness, acid resistance, and solvent resistance. After silica is modified with a silane coupling agent and compounded with isocyanate, in addition to being able to be grafted into one with the carbon fiber after oxidation activation, some unreacted isocyanate groups can also participate in the curing of epoxy phenolic resin, enhancing the connectivity between the filler and the resin and improving the solvent resistance of the ink. By grafting modified silica onto carbon fiber, the agglomeration of silica particles can be effectively prevented, making it easy to disperse in the organic resin system. The composite of carbon fiber also gives the ink excellent acid resistance and resistance to folding and cracking (toughness).

[0018] Compared with the prior art, the present invention has the following beneficial effects:

[0019] The ink for semiconductor passive component packaging of the present invention significantly improves the acid resistance, solvent resistance and resistance to folding and cracking of the ink by optimizing the composition and ratio, including mixing silica-grafted carbon fiber filler, polyurethane resin, phenolic resin, epoxy resin, first filler, pigment and additives, thereby achieving more excellent application performance. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 4 is a flow chart of a silica-grafted carbon fiber filler according to one embodiment of the present invention. DETAILED DESCRIPTION

[0021] The specific embodiments of the present invention are described in detail below, but it should be understood that the protection scope of the present invention is not limited by the specific embodiments.

[0022] Unless expressly stated otherwise, throughout the specification and claims, the term "comprise" or variations such as "include" or "comprising", etc., will be understood to include the stated elements or components but not to exclude other elements or other components.

[0023] like Figure 1 As shown, the preparation process of silica grafted carbon fiber filler may include: modification of silica, activation of carbon fiber and silica grafting of carbon fiber.

[0024] A. Modification of silica:

[0025] Step 1: Modify silica using a silane coupling agent. First, mix silica and toluene in a weight ratio of 1:50-350 silica:toluene. Ultrasonic dispersion is performed for 1-2 hours to obtain a silica suspension. The silane coupling agent is pre-hydrolyzed in a weight ratio of 1:0.5-1.2 deionized water. The pH is adjusted to 2-5 with an organic acid. Mixing and stirring are performed for 1-1.5 hours to obtain a pre-hydrolyzed silane coupling agent solution. The silica suspension is poured into a three-necked flask and heated to 65-90°C. The pre-hydrolyzed silane coupling agent solution is then slowly poured into a three-necked flask and mixed uniformly with the silica suspension. The pre-hydrolyzed silane coupling agent solution and silica suspension are mixed uniformly in a ratio of 1:150-300 silica:toluene. Maintain the temperature at 65-90°C, reflux for 10 hours, and then centrifuge dry to obtain the modified silica powder.

[0026] Preferably, the ratio of silica to toluene is 1:250-300, the ratio of silane coupling agent to deionized water is 1:0.8-1.0, and the ratio of silane coupling agent pre-hydrolyzed solution to silica suspension is 1:220-250.

[0027] The silicon dioxide used can be nanocrystalline or amorphous silicon dioxide with a particle size of 20-200 nm. Preferably, the silicon dioxide is spherical silicon dioxide with a particle size of 20-50 nm.

[0028] The structural formula of the silane coupling agent is (YR-Si(OX)3). X can be a halogen or a C1-C6 alkoxy group, R can be a C1-C12 alkyl group, and Y can be a substituted or unsubstituted amino group, a hydroxyl group, a substituted or unsubstituted epoxy group, or the like. The silane coupling agent can be selected from any one of KH550, KH560, KH570, Z-6040, and Z-6020, or a combination of at least two. More preferably, the silane coupling agent is KH550 or KH560.

[0029] Step 2: Compound the modified nano-silica with isocyanate groups. The isocyanate groups can react with the Y groups of the silane coupling agent, thereby attaching the isocyanate groups to the surface of the silica. The production process is as follows:

[0030] Modified silica: toluene = 1:20-50, mixed evenly to form a suspension, to which isocyanate is slowly added dropwise at room temperature in a ratio of 1:23-102. The reaction is stirred at room temperature for 5-8 hours, refluxed at 30-75°C in a nitrogen atmosphere for 6 hours, and then centrifugally dried to obtain a composite of isocyanate and modified silica. Preferably, the ratio of modified silica: toluene is 1:35-42, and the ratio of suspension: isocyanate is 1:65-78.

[0031] Isocyanate-modified silica, wherein the isocyanate includes any one of monoisocyanate, diisocyanate, polyisocyanate, etc., or a combination of at least two thereof.

[0032] Preferred are diisocyanates having the structural formula (O=C=NRN=C=O), where R can be a substituted or unsubstituted C1 to C12 alkyl, alkenyl, or substituted or unsubstituted C1 to C12 aryl or heteroaryl group. The diisocyanates include any one or a combination of at least two of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, and dicyclohexylmethane diisocyanate. More preferably, the isocyanate is toluene diisocyanate or diphenylmethane diisocyanate.

[0033] B. Activation of carbon fiber: Use strong oxidants to activate carbon fiber to produce a large number of hydroxyl and carboxyl functional groups.

[0034] The carbon fiber activation method is as follows:

[0035] The strong oxidant is composed of concentrated H2SO4 and K2Cr2O7 in a ratio of 1:(1-1.5), with a mass concentration of 85-98% for concentrated H2SO4 and 15-30% for K2Cr2O7. The ratio of carbon fiber material to strong oxidant is 1:15-25. The strong oxidant is slowly added to the carbon fiber material according to the ratio, heated to 50-65°C, reacted for 1-1.5 hours, and then rinsed and dried with deionized water to obtain the activated carbon fiber material. Preferably, the mass concentration of concentrated H2SO4 is 90-98%, the mass concentration of K2Cr2O7 is 25-30%, and the ratio of carbon fiber material to strong oxidant is 1:20-24.

[0036] The carbon fiber can be a combination of one or more of polyacrylonitrile-based carbon fiber, cellulose-based carbon fiber, pitch-based carbon fiber, viscose-based carbon fiber, and the like.

[0037] C. Silica grafted carbon fiber: The composited silica is grafted onto the carbon fiber material to react, ultimately generating silica grafted carbon fiber filler.

[0038] The modified silica: activated carbon fiber: toluene: catalyst ratio is 1: (1-2.5): (50-200): (0.05-0.1). The catalyst is a mixture of triethylamine: dibutyltin dilaurate (1: (1-1.5). The modified silica, activated carbon fiber, and toluene are added to a three-necked flask in the aforementioned ratio, stirred and ultrasonicated at 45-65°C for 1 hour, and then the catalyst is slowly added dropwise. Stirring and ultrasonicating are continued for 4-5 hours. The mixture is then rotary evaporated at 55°C for 3 hours under a nitrogen atmosphere and centrifuged to obtain the silica-grafted carbon fiber filler. Preferably, the isocyanate-modified silica: activated carbon fiber: toluene: catalyst ratio is 1: (1.6-2.1): (75-130): (0.08-0.1). The triethylamine: dibutyltin dilaurate ratio is 1: (1.2-1.4).

[0039] The infrared absorption peak of silicon dioxide is at 1101.13 cm -1 and 801.55cm -1 There are the original Si-O bond asymmetric stretching vibration absorption peak and symmetric stretching vibration absorption peak at 3441.90cm -1 There is a broad absorption peak at 1660.37cm, which corresponds to the antisymmetric stretching vibration and symmetric stretching vibration of -OH. After being treated with silane coupling agent and reacting with isocyanate, it still has a peak at 1660.37cm -1 and 1550.83cm -1 The absorption peak of carbamate appeared on the surface. The grafted carbon fiber structure was analyzed by infrared spectroscopy at 1481.20 cm -1The bending vibration absorption peak of -CH2- appears at 1110.45cm. The silica grafted carbon fiber is equivalent to introducing a large number of Si-O-Si bonds, and the absorption is further enhanced, which is manifested as a peak at 1110.45cm -1 The absorption peak near 806 cm becomes larger again, and the -1 The symmetrical stretching vibration peak of Si—O—Si bond appears at

[0040] Specifically, the silica-grafted carbon fiber A1 can be obtained by the following process, including but not limited to the following examples:

[0041] A. Modification of silica:

[0042] Step 1: Modify silica using a silane coupling agent. First, mix silica (spherical silica, 20 nm particle size) and toluene at a weight ratio of 1:50. Ultrasonic dispersion is performed for 1 hour to obtain a silica suspension. Silane coupling agent KH550 is pre-hydrolyzed at a weight ratio of 1:0.5. The pH is adjusted to 5 with an organic acid, and the mixture is stirred for 1 hour to obtain a silane coupling agent pre-hydrolyzed solution. The silica suspension is poured into a three-necked flask and heated to 65°C. The pre-hydrolyzed silane coupling agent solution is then slowly poured into a three-necked flask and mixed uniformly with the silica suspension. The ratio of 1:150 is achieved. Maintain the temperature at 65°C and reflux for 10 hours before centrifugal drying to obtain modified silica powder.

[0043] Step 2: Compound the modified nano-silica with isocyanate groups:

[0044] Modified silica and toluene were mixed in a ratio of 1:35 to obtain a suspension. Isocyanate (toluene diisocyanate) was slowly added dropwise at room temperature at a ratio of 1:65. The mixture was stirred at room temperature for 5 hours. After refluxing at 30°C in a nitrogen atmosphere for 6 hours, the mixture was centrifugally dried to obtain a composite of isocyanate and modified silica.

[0045] B. Activation of carbon fiber:

[0046] The carbon fiber activation method is as follows:

[0047] The strong oxidant is composed of concentrated H2SO4 and K2Cr2O7 in a ratio of 1:1, with a mass concentration of 98% H2SO4 and 25% K2Cr2O7. The carbon fiber material: strong oxidant ratio is 1:20. The strong oxidant is slowly added to the carbon fiber material (polyacrylonitrile-based carbon fiber) according to the ratio. The mixture is heated to 50°C, reacted for 1 hour, and then rinsed with deionized water and dried to obtain the activated carbon fiber material.

[0048] C. Silica grafted carbon fiber:

[0049] The modified silica: activated carbon fiber: toluene: catalyst ratio is 1:1.6:75:0.08. The catalyst is a mixture of triethylamine: dibutyltin dilaurate (dibutyltin dilaurate) in a ratio of 1:1.2. The modified silica, activated carbon fiber, and toluene are added to a three-necked flask in the aforementioned ratio, stirred and ultrasonicated at 45-65°C for 1 hour, and then the catalyst is slowly added dropwise. Stirring and ultrasonicating are continued for 4 hours. The mixture is then rotary evaporated at 55°C for 3 hours under a nitrogen atmosphere and centrifuged to obtain the silica-grafted carbon fiber filler.

[0050] Silica grafted carbon fiber filler A1, prepared by the above scheme;

[0051] Silica powder A2 was purchased from Lianrui New Materials, model number XFI03;

[0052] Carbon fiber powder A3 was purchased from Jiaxing Naco New Materials, model PWGX-22 (1000);

[0053] Thermosetting phenolic resin B was purchased from Wuxi Xinyehao Chemical, model number 2124;

[0054] Polyurethane resin C was purchased from Sartomer, model number CN966H90 NS;

[0055] Epoxy resin D was purchased from Nantong Xingchen, model E-52D;

[0056] The first filler E was purchased from Anmi Micro-Nano, model FD-61;

[0057] Additive F is a leveling agent purchased from BYK Chemical, model number BYK-346;

[0058] Pigment G was purchased from Anhui Xuyang New Materials Co., Ltd., model number XY1000.

[0059] Examples 1-6 and Comparative Examples 1-4 respectively provide an ink for semiconductor passive component encapsulation, and the compositions and proportions thereof are as follows (in parts by weight):

[0060]

[0061]

[0062] The preparation method of the ink for semiconductor passive component packaging provided in Example 1 is as follows:

[0063] The preparation method of silica grafted carbon fiber filler is as follows: first, silica is dried in an oven at 100°C for 6 hours to dry out the moisture. Then, it is mixed with a toluene solution in a ratio of 1:1.5, and toluene diisocyanate and diphenylmethane diisocyanate are added. Finally, it is filtered and washed, and repeated 2 to 3 times. Then, it is dried in a 150°C oven for 8 hours, placed in a rotary evaporator, and rotary evaporated at 70°C for 6 hours. The product is then placed in an oven for 8 hours to obtain modified SiO2. The modified SiO2 and carbon fiber powder are mixed in a ratio of 1:2 and added to toluene. An ethanol solution containing 5 parts of silane coupling agents KH550 and KH560 is added, and the reaction is rotary evaporated for 10 hours to obtain silica grafted carbon fiber filler.

[0064] The prepared silica grafted carbon fiber filler, polyurethane resin, phenolic resin, epoxy resin, filler, pigment and additives are mixed, dispersed at 500 rpm in a disperser for 20 minutes, then ground two to three times in a three-roll grinder, and then filtered at 60° C. using a filter to obtain an ink for semiconductor passive component packaging.

[0065] The preparation method of the ink for semiconductor passive component packaging provided in Examples 2-10 and Comparative Examples 1-11 refers to Example 1.

[0066] Performance testing:

[0067] During testing, the ink is applied to the substrate surface by screen printing, inkjet printing, gravure printing, spin coating, spray coating, roller coating, doctor blade coating, etc. Finally, the ink is cured at a temperature range of 120°C to 250°C for 30 minutes to obtain a dense and smooth ink coating with a thickness of 10 to 30 μm, with a curing temperature range of 150°C to 230°C being preferred.

[0068] Here, a 325-mesh screen was used to screen-print insulating ink for passive component packaging. The ink was then heated in a hot air circulation drying oven at 200°C for 30 minutes to form a 15μm thick insulating ink coating (with an error of ±3μm). The following tests were then performed:

[0069] (1) Viscosity test

[0070] The viscosity of the ink at 25°C was measured using a DV2THBTJ0 viscometer with a 14# rotor and a rotation speed of 100 r / min.

[0071] The viscosity evaluation criteria are as follows:

[0072] ○: viscosity is in the range of 35000-45000 cP;

[0073] ×: The viscosity is not within the range of 35000-45000 cP.

[0074] (2) Film thickness uniformity test

[0075] A 0.85 × 60 mm pattern was printed on a 70 × 60 mm blank ceramic substrate with grooves using a 325 mesh stainless steel screen. After curing at 200°C for 30 min, 12 sample points covering the entire substrate were tested, including the top, bottom, left, right, and center.

[0076] The evaluation criteria for film thickness uniformity test are as follows:

[0077] ○: The extreme difference of film thickness at 12 sample points is ≤ 2 μm;

[0078] ×: The extreme difference in film thickness at 12 sample points is greater than 2 μm.

[0079] (3) Acid resistance test

[0080] A 2×2mm×100-piece silk screen was used to print a pattern with a thickness of 15±3 on a blank substrate without grooves. Two samples were sampled and cured. The samples were immersed in 5 parts hydrochloric acid and 5 parts sulfuric acid solutions for 1 hour respectively. The surface was cleaned with deionized water, dried, and the appearance was observed. The samples were then torn vertically with 3M tape.

[0081] The acid resistance test evaluation criteria are as follows:

[0082] ○: There is no corrosion on the surface of the pattern after acid immersion, and the 3M tape does not fall off when torn vertically;

[0083] ×: The pattern is corroded after acid immersion, and the 3M tape falls off when torn vertically.

[0084] (4) Solvent resistance test

[0085] A 2×2mm×100-piece silk screen was used to print a pattern with a thickness of 15±3 on a blank substrate without grooves. Two samples were sampled and cured. The samples were immersed in a solution of isopropyl alcohol and butanone (1:1) for 1 hour. The surface was cleaned with deionized water, dried, and observed for appearance. The samples were then torn vertically with 3M tape.

[0086] The evaluation criteria for solvent resistance testing are as follows:

[0087] ○: There is no corrosion on the graphic appearance after solvent immersion, and the 3M tape does not fall off when torn vertically;

[0088] ×: The graphics are corroded after being soaked in solvent, and the 3M tape falls off when torn vertically.

[0089] (5) Anti-fragmentation and cracking test:

[0090] A 0.85×60mm pattern was printed on a 70×60mm blank ceramic substrate with a 325-mesh stainless steel screen. After curing at 200°C for 30 minutes, the pattern was folded using a 0201 folding machine.

[0091] The evaluation criteria for folding and breaking properties are as follows:

[0092] ○: ink coating damage rate <5 parts;

[0093] ×: The ink coating damage rate is ≥5 copies.

[0094] (6) Adhesion test:

[0095] A 2×2mm×100-piece silk screen was used to print a pattern with a thickness of 15±3μm on a blank substrate without grooves. After one piece of the pattern was cured, the sample was boiled in water at normal pressure for 16 hours (the time can be accumulated) and then dried. It was then torn vertically using 3M tape.

[0096] The adhesion test evaluation criteria are as follows:

[0097] ○: 3M tape does not fall off when torn vertically;

[0098] ×: The 3M tape falls off when torn vertically.

[0099] (7) Heat resistance test:

[0100] A 50mm×50mm pattern with a thickness of 15μm (error ±3μm) was printed on a blank ceramic substrate. After curing at 200℃ for 30min, the pattern was immersed in a tin furnace at 288℃ for 10s / 3 times.

[0101] The heat resistance test evaluation criteria are as follows:

[0102] ○: The ink coating is intact and has no cracks;

[0103] ×: The ink coating is peeled or cracked.

[0104] Here are the results:

[0105] Table 1: Performance evaluation results of ink and coating The test results are as follows:

[0106]

[0107] Table 2: Performance evaluation results of ink and coating The test results are as follows:

[0108]

[0109]

[0110] The above results show that the ink for semiconductor passive component encapsulation provided by the present invention has excellent acid resistance, solvent resistance, and resistance to grain breakage. Comparing Examples 1-3 with Comparative Examples 1-3, it can be seen that the addition of silica-grafted carbon fiber filler and the addition amount within the stated range all passed the test results. However, Comparative Example 1, which did not add silica-grafted carbon fiber filler, failed the acid resistance, solvent resistance, and grain breakage test. In Comparative Example 2, insufficient silica-grafted carbon fiber filler was added, resulting in the ink coating failing the acid resistance, solvent resistance, and grain breakage test. In Comparative Example 3, excessive silica-grafted carbon fiber filler was added. Although the ink coating passed the acid resistance, solvent resistance, and grain breakage test, it failed due to excessive viscosity. Comparative Examples 4 and 5 used silica and carbon fiber materials alone, and both failed the test results. Comparing Examples 4-7 with Comparative Examples 6-11, it is shown that the addition of the phenolic resin and the addition amount within the stated range can improve the heat resistance of the ink coating, while too little or too much will be detrimental to the heat resistance of the ink coating. The addition of the polyurethane resin within the range can improve the adhesion resistance of the ink coating, while too little or too much will be detrimental to the adhesion of the ink coating. The addition of the epoxy resin within the range can improve the uniformity of the film thickness of the ink coating, while too little or too much will be detrimental to the uniformity of the ink coating.

[0111] Example 8

[0112] The ink for semiconductor passive component packaging in this embodiment comprises, in percentage by mass: 20 parts of phenolic resin (thermosetting phenolic resin, wherein the free phenol content is ≤20%), 5 parts of polyurethane resin (aliphatic polyurethane resin or aromatic polyurethane resin, and meeting: elastic modulus of 100 MPa, tensile strength of 10 psi), 5 parts of epoxy resin (bisphenol A type epoxy resin, wherein the epoxy equivalent is 0.45), 10 parts of silica grafted carbon fiber filler, 5 parts of mica powder, 1 part of additives (defoaming agent 233A, non-silicone leveling agent 361S, film-forming aid BDG, wetting and dispersing agent P-193, the mass ratio of the four is 1:1:1:1), and 8 parts of pigment.

[0113] The silica grafted carbon fiber filler of this embodiment is:

[0114] A. Modification of silica:

[0115] Step 1: Modify silica using a silane coupling agent. First, mix 50 nm amorphous silica and toluene at a weight ratio of 1:150 silica:toluene. Ultrasonic dispersion is performed for 1 hour to obtain a silica suspension. The silane coupling agent is pre-hydrolyzed at a weight ratio of 1:0.8 deionized water. The pH is adjusted to 3 with an organic acid. Mixing and stirring are performed for 1.2 hours to obtain a pre-hydrolyzed silane coupling agent solution. The silica suspension is poured into a three-necked flask and heated to 70°C. The pre-hydrolyzed silane coupling agent Z-6020 is then slowly poured into the three-necked flask and mixed uniformly with the silica suspension. The pre-hydrolyzed silane coupling agent solution and silica suspension are mixed uniformly at a weight ratio of 1:220. Maintain the temperature at 70°C and reflux for 10 hours before centrifugal drying to obtain modified silica powder.

[0116] Step 2: Compound the modified nano-silica with isocyanate groups:

[0117] A suspension was obtained by mixing modified silica and toluene in a ratio of 1:35. A 1:1 mixture of diphenylmethane diisocyanate and dicyclohexylmethane diisocyanate (methylene diisocyanate) was slowly added dropwise at room temperature, with a suspension:isocyanate ratio of 1:65. The reaction was stirred at room temperature for 6 hours. After refluxing at 45°C under nitrogen for 6 hours, the mixture was centrifugally dried to obtain a composite of isocyanate and modified silica.

[0118] B. Activation of carbon fiber:

[0119] The carbon fiber activation method is as follows:

[0120] The strong oxidant is composed of concentrated H2SO4 and K2Cr2O7 in a ratio of 1:1.2, with a H2SO4 mass concentration of 85% and a K2Cr2O7 mass concentration of 30%. The viscose-based carbon fiber: strong oxidant ratio is 1:17. The strong oxidant is slowly added to the carbon fiber material according to this ratio, heated to 55°C, reacted for 1.1 hours, and then rinsed with deionized water and dried to obtain the activated carbon fiber material.

[0121] The carbon fiber may be one or more combinations thereof.

[0122] C. Silica grafted carbon fiber: The composited silica is grafted onto the carbon fiber material to react, ultimately generating silica grafted carbon fiber filler.

[0123] The modified silica: activated carbon fiber: toluene: catalyst ratio is 1:1:50:0.09. The catalyst is a mixture of triethylamine: dibutyltin dilaurate (dibutyltin dilaurate) in a ratio of 1:1.2. The modified silica, activated carbon fiber, and toluene were added to a three-necked flask in the aforementioned ratio and stirred at 55°C under ultrasonication for 1 hour. The catalyst was then slowly added dropwise. Stirring and ultrasonication were continued for 4 hours. The mixture was then rotary evaporated at 55°C under a nitrogen atmosphere for 3 hours and centrifuged to obtain the silica-grafted carbon fiber filler.

[0124] Example 9

[0125] The ink for semiconductor passive component packaging in this embodiment comprises, by mass percentage: 25 parts of phenolic resin (thermosetting phenolic resin, wherein the free phenol content is ≤20%), 10 parts of polyurethane resin (aliphatic polyurethane resin or aromatic polyurethane resin, and meeting: elastic modulus of 500 MPa, tensile strength of 350 psi), 15 parts of epoxy resin (phenolic epoxy resin, wherein the epoxy equivalent is 0.50), 15 parts of silica grafted carbon fiber filler, 7 parts of calcium carbonate, 6 parts of additives (defoaming agent LP2700, leveling agent silicone leveling agent, wetting and dispersing agent 680U, the mass ratio of the three is 1:2:3), and 10 parts of pigment.

[0126] The silica grafted carbon fiber filler of this embodiment is:

[0127] A. Modification of silica:

[0128] Step 1: Modify silica using a silane coupling agent. First, mix 200 nm amorphous silica and toluene at a weight ratio of 1:250 silica:toluene. Ultrasonic dispersion is performed for 2 hours to obtain a silica suspension. The silane coupling agent is pre-hydrolyzed at a weight ratio of 1:1 deionized water. The pH is adjusted to 4 with an organic acid, and the mixture is stirred for 1.3 hours to obtain a pre-hydrolyzed silane coupling agent solution. The silica suspension is poured into a three-necked flask and heated to 80°C. The pre-hydrolyzed silane coupling agent KH560 is then slowly poured into the flask and mixed uniformly with the silica suspension. The pre-hydrolyzed silane coupling agent solution and silica suspension are mixed uniformly at a weight ratio of 1:250. The mixture is maintained at 80°C and refluxed for 10 hours before centrifugal drying to obtain modified silica powder.

[0129] Step 2: Compound the modified nano-silica with isocyanate groups:

[0130] Modified silica and toluene were mixed in a ratio of 1:42 to obtain a suspension. Isophorone diisocyanate was slowly added dropwise at room temperature in a ratio of 1:78. The reaction was stirred at room temperature for 7 hours. After refluxing at 55°C in a nitrogen atmosphere for 6 hours, the mixture was centrifugally dried to obtain a composite of isocyanate and modified silica.

[0131] B. Activation of carbon fiber:

[0132] The carbon fiber activation method is as follows:

[0133] The strong oxidant is composed of concentrated H2SO4 and K2Cr2O7 in a ratio of 1:1.3, with a mass concentration of 90% H2SO4 and 20% K2Cr2O7. The cellulose-based carbon fiber: strong oxidant ratio is 1:20. The strong oxidant is slowly added to the carbon fiber material according to this ratio. The material is heated to 60°C, reacted for 1.3 hours, and then rinsed with deionized water and dried to obtain the activated carbon fiber material.

[0134] The carbon fiber may be one or more combinations thereof.

[0135] C. Silica grafted carbon fiber: The composited silica is grafted onto the carbon fiber material to react, ultimately generating silica grafted carbon fiber filler.

[0136] The modified silica: activated carbon fiber: toluene: catalyst ratio is 1:2.1:130:0.08. The catalyst is a mixture of triethylamine: dibutyltin dilaurate (dibutyltin dilaurate) in a ratio of 1:1.4. The modified silica, activated carbon fiber, and toluene were added to a three-necked flask in the aforementioned ratios. Stirring and ultrasonicating at 60°C for 1 hour was followed by slowly adding the catalyst dropwise. Stirring and ultrasonicating were continued for 4.5 hours. The mixture was then rotary evaporated at 55°C for 3 hours under a nitrogen atmosphere and centrifuged to obtain the silica-grafted carbon fiber filler.

[0137] Example 10

[0138] The ink for semiconductor passive component packaging in this embodiment comprises, by mass percentage: 35 parts of phenolic resin (thermosetting phenolic resin, wherein the free phenol content is ≤20%), 15 parts of polyurethane resin (aliphatic polyurethane resin or aromatic polyurethane resin, and meeting: elastic modulus of 900 MPa, tensile strength of 550 psi), 25 parts of epoxy resin (bisphenol A type epoxy resin, wherein the epoxy equivalent is 0.60), 20 parts of silica grafted carbon fiber filler, 10 parts of a mixture of barium sulfate, talc powder, mica powder, and calcium carbonate in a mass ratio of 1:1:1:1, 10 parts of additives (non-silicone leveling agent 361S, thickener fumed silica, wetting and dispersing agent P-193, the three in a mass ratio of 1:1:3), and 11 parts of pigment carbon black.

[0139] The silica grafted carbon fiber filler of this embodiment is:

[0140] A. Modification of silica:

[0141] Step 1: Modify silica using a silane coupling agent. First, mix 150 nm amorphous silica and toluene at a weight ratio of 1:350 silica:toluene. Ultrasonic dispersion is performed for 1.5 hours to obtain a silica suspension. The silane coupling agent is pre-hydrolyzed at a weight ratio of 1:1.2 deionized water. The pH is adjusted to 5 with an organic acid. Mixing and stirring are performed for 1.5 hours to obtain a pre-hydrolyzed silane coupling agent solution. The silica suspension is poured into a three-necked flask and heated to 90°C. The pre-hydrolyzed silane coupling agent KH570 is then slowly poured into the flask and mixed evenly with the silica suspension. The pre-hydrolyzed silane coupling agent solution and silica suspension are mixed at a ratio of 1:300. Maintain the temperature at 90°C and reflux for 10 hours before centrifugal drying to obtain modified silica powder.

[0142] Step 2: Compound the modified nano-silica with isocyanate groups:

[0143] Modified silica and toluene were mixed in a ratio of 1:50 to obtain a suspension. Dicyclohexylmethane diisocyanate was slowly added dropwise at room temperature in a ratio of 1:102. The reaction was stirred at room temperature for 8 hours. After refluxing at 75°C in a nitrogen atmosphere for 6 hours, the mixture was centrifugally dried to obtain a composite of isocyanate and modified silica.

[0144] B. Activation of carbon fiber:

[0145] The carbon fiber activation method is as follows:

[0146] The strong oxidant composition is concentrated H2SO4 and K2Cr2O7 in a ratio of 1:1.5, with a H2SO4 mass concentration of 95% and a K2Cr2O7 mass concentration of 15%. A mixture of cellulose-based carbon fibers, pitch-based carbon fibers, and viscose-based carbon fibers in a 1:1:1 mass ratio is added to the strong oxidant in a ratio of 1:24. The strong oxidant is slowly added to the carbon fiber material according to the ratio, heated to 65°C, reacted for 1.5 hours, and then rinsed with deionized water and dried to obtain the activated carbon fiber material.

[0147] The carbon fiber may be one or more combinations thereof.

[0148] C. Silica grafted carbon fiber: The composited silica is grafted onto the carbon fiber material to react, ultimately generating silica grafted carbon fiber filler.

[0149] The modified silica: activated carbon fiber: toluene: catalyst ratio is 1:2.5:200:0.05. The catalyst is a mixture of triethylamine: dibutyltin dilaurate (dibutyltin dilaurate) in a ratio of 1:1.5. The modified silica, activated carbon fiber, and toluene were added to a three-necked flask in the aforementioned ratios. Stirring and ultrasonicating at 65°C for 1 hour was followed by slowly adding the catalyst dropwise. Stirring and ultrasonicating were continued for 5 hours. The mixture was then rotary evaporated at 55°C for 3 hours under a nitrogen atmosphere and centrifuged to obtain the silica-grafted carbon fiber filler.

[0150] The foregoing descriptions of specific exemplary embodiments of the present invention are for purposes of illustration and description. These descriptions are not intended to limit the invention to the precise forms disclosed, and it is apparent that many variations and modifications are possible in light of the foregoing teachings. The exemplary embodiments have been selected and described for the purpose of explaining the specific principles of the invention and their practical application, thereby enabling those skilled in the art to realize and utilize a variety of exemplary embodiments of the invention and various options and modifications. The scope of the invention is intended to be defined by the claims and their equivalents.

Claims

1. An ink for semiconductor passive component encapsulation, comprising, by mass percentage, 20-35 parts of a phenolic resin, 5-15 parts of a polyurethane resin, 5-25 parts of an epoxy resin, 10-20 parts of a silica-grafted carbon fiber filler, 5-10 parts of a first filler, 1-10 parts of an auxiliary agent, and 8-11 parts of a pigment, wherein the silica-grafted carbon fiber filler is obtained by grafting modified silica onto activated carbon fiber, wherein the activation is to activate the carbon fiber with a strong oxidant to generate a large number of hydroxyl and carboxyl functional groups, and the modification is to modify the silica with a silane coupling agent.

2. The semiconductor passive component encapsulation ink according to claim 1, wherein: The polyurethane resin is an aliphatic polyurethane resin or an aromatic polyurethane resin and meets the following requirements: elastic modulus of 100-900 MPa and tensile strength of 10-550 psi.

3. The semiconductor passive component encapsulation ink according to claim 1, wherein: The phenolic resin is a thermosetting phenolic resin, wherein the free phenol content is ≤20%.

4. The semiconductor passive component encapsulation ink according to claim 1, wherein: The epoxy resin is bisphenol A epoxy resin or novolac epoxy resin, wherein the epoxy equivalent is 0.45-0.

60.

5. The semiconductor passive component encapsulation ink according to claim 1, wherein: The first filler is selected from barium sulfate, talc powder, mica powder, and calcium carbonate.

6. The semiconductor passive component encapsulation ink according to claim 1, wherein: The auxiliary agent is selected from defoaming agents, leveling agents, film-forming agents, thickeners, and wetting and dispersing agents.

7. The method for preparing the ink for semiconductor passive component packaging according to any one of claims 1 to 6, comprising the following steps: The raw materials are mixed and dispersed evenly, ground with three rollers, filtered and filled.

8. A semiconductor device comprising a stack formed by the ink for semiconductor passive component packaging according to any one of claims 1 to 6.

9. An apparatus comprising the semiconductor device according to claim 8.

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