Ink for semiconductor passive element packaging, method for preparing the same, and use thereof

Abstract

The application provides an ink for semiconductor passive element packaging and a preparation method and application thereof, the ink for semiconductor passive element packaging comprises, in parts by weight, 20-35 parts of a first epoxy resin, 5-10 parts of a second epoxy resin, 5-10 parts of a curing agent, 0.1-5 parts of a curing accelerator and 25-50 parts of a filler. The ink for semiconductor passive element packaging provided by the application has good weather resistance, good water resistance, high substrate adhesion and excellent technical effects.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of semiconductor packaging, and particularly relates to an ink for packaging semiconductor passive elements and a preparation method and application thereof. BACKGROUND

[0002] To improve the electrical characteristics of a semiconductor packaging structure, a passive element such as a capacitor, a resistor or an inductor is arranged in the semiconductor packaging structure. Among them, the resistor is generally used for voltage division, current division, filtering and impedance matching, and the main type of resistor used is chip resistor, also known as SMD resistor. Chip resistor is a kind of metal glass enamel resistor, which is made by screen printing metal silver paste and glass enamel powder on a substrate, and an insulating protective ink coating is printed on the outermost layer. Chip resistors can generally be divided into conventional series thick film chip resistors and high-precision high-stability chip resistors. Among them, the conventional series thick film chip resistor is mainly used for general consumer products; the high-precision stability chip resistor is mainly used for medical equipment, precision measuring instruments, electronic communication, vehicle-mounted equipment, etc.

[0003] The rapid development of the integrated circuit industry has higher and higher requirements for the performance of passive elements, especially for the structure density and weather resistance of the protective coating of high-precision stability chip resistors. Poor structure density will result in poor coating sealing during use; poor weather resistance will cause the packaging ink to be invaded by sulfur and water molecules under the condition of sulfur and sulfide, thereby causing the resistor to be damaged; poor water resistance will cause the protective layer to separate from the substrate during use, resulting in a shorter service life of the passive element.

[0004] CN109913034A discloses an insulating ink for packaging semiconductor passive elements, which comprises 10-50wt% of linear phenolic resin, 1-30wt% of organic silicone rubber, 1-10wt% of impact-resistant polystyrene, 5-35wt% of low-alpha radiation inorganic filler, 0.1-20wt% of curing accelerator, 1-10wt% of pigment, 0.1-8wt% of additive, and the balance of organic solvent. The insulating ink provided by the application has good weather resistance, thermal stability and insulation reliability, and meets the requirements of advanced packaging for low-alpha radiation level.

[0005] CN115124880B discloses an insulating ink for semiconductor passive element packaging, a preparation method and application, which comprises 15-35 parts by weight of polyurethane resin, 20-40 parts by weight of phenolic resin, 10-35 parts by weight of epoxy resin, 1-10 parts by weight of auxiliary agent, 1-10 parts by weight of solvent and 15-20 parts by weight of carbon material composite, the 15-20 parts by weight of carbon material composite comprising 1-3 parts of zero-dimensional fullerene carbon material, 2-5 parts of one-dimensional carbon nanotube carbon material, 3-6 parts of two-dimensional graphene carbon material and 6-9 parts of three-dimensional graphite carbon material. The present application has good hardness, thermal conductivity, anti-bending particle cracking resistance and high temperature resistance.

[0006] The above-mentioned ink solution solves some problems, but as a whole, it still cannot meet the current requirements for the weather resistance, water resistance and sealing performance of the packaging ink. Therefore, how to provide an insulating ink for semiconductor element packaging with good weather resistance, good waterproof performance and good sealing performance has become a problem to be solved. SUMMARY

[0007] In view of the deficiencies of the prior art, the purpose of the present application is to provide an ink for semiconductor passive element packaging and a preparation method and application thereof. The ink for semiconductor passive element packaging provided by the present application has good weather resistance and water resistance, high substrate adhesion and excellent technical effects.

[0008] To achieve the purpose of the present application, the following technical solutions are adopted:

[0009] In a first aspect, the present application provides an ink for semiconductor passive element packaging, which comprises 20-35 parts by weight of a first epoxy resin, 5-10 parts by weight of a second epoxy resin, 5-10 parts by weight of a curing agent, 0.1-5 parts by weight of a curing accelerator and 25-50 parts by weight of a filler.

[0010] The first epoxy resin can be 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, 26 parts, 27 parts, 28 parts, 29 parts, 30 parts, 31 parts, 32 parts, 33 parts, 34 parts or 35 parts, etc., the second epoxy resin can be 5 parts, 6 parts, 7 parts, 8 parts, 9 parts or 10 parts, etc., the curing agent can be 5 parts, 6 parts, 7 parts, 8 parts, 9 parts or 10 parts, etc., the curing accelerator can be 0.1 parts, 0.5 parts, 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts or 5 parts, etc., and the filler can be 25 parts, 30 parts, 35 parts, 40 parts, 45 parts or 50 parts, etc., but is not limited to the above-mentioned values, and other values within the above-mentioned value range are also applicable.

[0011] Preferably, the first epoxy resin comprises dicyclopentadiene type phenol novolac epoxy resin and phenol novolac epoxy resin.

[0012] Preferably, the second epoxy resin comprises alicyclic epoxy resin and / or aliphatic epoxy resin, the total chlorine of the alicyclic epoxy resin is ≤ 50 ppm.

[0013] The specific epoxy resin described above can effectively prevent resin crystallization, improve resin flowability, facilitate material dispersion during processing, and impart excellent weather resistance, water resistance, and substrate adhesion to the ink by compounding dicyclopentadiene type phenol novolac epoxy resin and phenol novolac epoxy resin.

[0014] The semiconductor passive component packaging ink described above can effectively improve the weather resistance, water resistance, and substrate adhesion of the product by using a specific epoxy resin and combining a curing agent with a curing accelerator.

[0015] Preferably, the mass ratio of the dicyclopentadiene type phenol novolac epoxy resin and the phenol novolac epoxy resin is (1-5):10, such as 1:5, 1:6, 1:7, 1:8, 1:9, or 1:10, but is not limited to the values listed above, and other values not listed within the above value range are also applicable.

[0016] Preferably, the alicyclic epoxy resin has a molar mass of 240-255 g / mol and an epoxy equivalent of 126-132 g / Eq.

[0017] Preferably, the curing agent is a solid latent amine curing agent.

[0018] The solid latent amine curing agent comprises any one or a combination of at least two of solid dicyandiamide, diamino diphenyl sulfone, or sebacic acid dihydrazide containing active hydrogen;

[0019] Preferably, the solid dicyandiamide has an amine value ≥ 50, a melting point of 180-190°C, and an active hydrogen equivalent of 140-150.

[0020] Preferably, the curing accelerator comprises any one or a combination of at least two of urea-based curing accelerator, phenol-based curing accelerator, imidazole-based curing accelerator, or hydrazide-based curing accelerator, preferably urea-based curing accelerator (melting point of 150-155°C).

[0021] The specific curing agent and curing accelerator described above are matched with each other, effectively improving the corrosion resistance, chemical resistance, weather resistance, water resistance, and substrate adhesion of the product.

[0022] Preferably, the filler comprises any one or a combination of at least two of barium sulfate, talc powder, mica powder, calcium carbonate, silicon dioxide, or aluminum oxide.

[0023] Preferably, the semiconductor passive element packaging ink further comprises an additive 1-10 parts by weight, such as 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, or 10 parts, etc., but is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned value range are also applicable.

[0024] Preferably, the additive comprises any one or a combination of at least two of a defoaming agent, a leveling agent, a film-forming aid, a thickening agent, or a wet dispersing agent.

[0025] Preferably, the semiconductor passive element packaging ink further comprises a pigment 5-10 parts by weight, such as 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, or 10 parts, etc., but is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned value range are also applicable.

[0026] Preferably, the semiconductor passive element packaging ink further comprises a diluent, and the diluent comprises any one or a combination of at least two of an ether solvent, an ester solvent, an alcohol solvent, or a ketone solvent.

[0027] In a second aspect, the present application provides a preparation method of the semiconductor passive element packaging ink as described above, and the preparation method comprises the following steps:

[0028] Grinding and mixing the first epoxy resin, the second epoxy resin, the curing agent, the curing accelerator, and the filler to obtain the semiconductor passive element packaging ink.

[0029] Preferably, the mixing further comprises mixing with the additive, the pigment, and the diluent.

[0030] In a third aspect, the present application provides a semiconductor device comprising the semiconductor passive element packaging ink as described above.

[0031] In a fourth aspect, the present application further provides a semiconductor device comprising the semiconductor device as described above.

[0032] Compared with the prior art, the present application has the following beneficial effects:

[0033] The present application provides a semiconductor passive element packaging ink, which can effectively improve the weather resistance, water resistance, and substrate adhesion of the product by using specific epoxy resins and combining a curing agent with a curing accelerator. DETAILED DESCRIPTION

[0034] In order to further illustrate the technical means adopted by the present application and its effects, the technical solutions of the present application will be further described below in combination with preferred embodiments of the present application, but the present application is not limited in the scope of the embodiments.

[0035] In the following example, epoxy resin A2 is phenolic epoxy resin, purchased from Shandong Shengquan, model SQPN-051;

[0036] Epoxy resin A3 is a dicyclopentadiene type phenolic epoxy resin, purchased from Anhui Xinyuan, model XY646;

[0037] Epoxy resin B is an alicyclic epoxy resin, purchased from Dassard Road, model number 2021P;

[0038] The curing agent C1 is solid dicyandiamide, purchased from Idico, model EH-3636AS;

[0039] Curing agent C2 is diaminodiphenylmethyl sulfone, purchased from Guangdong Wengjiang Chemical, model PA04296;

[0040] The curing agent C3 is sebacic acid dihydrazide, purchased from Weifang Firmenich Chemical Co., Ltd., model ADH;

[0041] Curing accelerator I1 is a urea-based accelerator, purchased from Taicang Canghe New Materials, model GLOC-300;

[0042] Curing accelerator I2 is a phenolic curing accelerator, purchased from Shandong Xuguang Chemical Co., Ltd., model number DMP-30;

[0043] Curing accelerator I3 is an imidazole curing accelerator, purchased from Ajinomoto, model number AH154;

[0044] The first filler D is spherical silica, purchased from Lianrui New Materials, model QB002;

[0045] The second filler E is talc powder, purchased from Jiangyin Chemical, model E-52D;

[0046] Pigment H was purchased from Zhengzhou Tairui Carbon Black Chemical Co., Ltd., model TR600R;

[0047] Additive G was purchased from BYK Chemicals as a leveling agent, model BYK-346.

[0048] Example 1

[0049] This embodiment provides an ink for packaging semiconductor passive components, and the specific preparation method is as follows:

[0050] (1) Epoxy resin A2 is heated and mixed with diethylene glycol monobutyl ether (mass ratio 15:100) to obtain a phenolic epoxy resin solution; epoxy resin A3 is heated and mixed with diethylene glycol monobutyl ether (mass ratio 25:100) to obtain a dicyclopentadiene-type phenolic epoxy resin solution; then the dicyclopentadiene-type phenolic epoxy resin solution is mixed with the phenolic epoxy resin solution to obtain epoxy resin blend A1;

[0051] (2) Epoxy resin blend A1 is mixed with epoxy resin B, curing agent C, curing accelerator I, first filler D, second filler E, pigment H, and additive G. The mixture is dispersed at 500 rpm for 20 minutes in a disperser, then ground three times in a three-roll mill, and finally filtered at 60°C in a filter to obtain the ink for packaging semiconductor passive components.

[0052] The raw material ratios for each comparative example are shown below (in parts by weight), and the preparation method is the same as in Example 1.

[0053]

[0054]

[0055] Effect test:

[0056] The semiconductor passive component packaging inks provided in the above embodiments and comparative examples were tested. During testing, a 325-mesh screen was used to screen print the insulating ink for passive component packaging. The ink was then heated in a hot air circulating drying oven at 200°C for 30 minutes to form an insulating ink coating with a thickness of 15 μm (error ±3 μm). The following tests were then performed:

[0057] (1) Viscosity test

[0058] The viscosity of ink at 25°C was measured using a DV2THBTJ0 viscometer with a 14# rotor at a speed of 100 r / min.

[0059] The viscosity evaluation criteria are as follows:

[0060] ○: Viscosity in the range of 35,000-45,000 cP;

[0061] ×: The viscosity is not within the range of 35000-45000 cP.

[0062] (2) Film thickness uniformity test

[0063] A 0.85×60mm graphic was printed on a 70×60mm grooved blank ceramic substrate using a 325-mesh stainless steel mesh. After curing at 200℃ for 30 minutes, 12 sample points (top, bottom, left, right, and center) that could cover the entire substrate were tested.

[0064] The evaluation criteria for film thickness uniformity testing are as follows:

[0065] ○: The film thickness range of 12 sample points is ≤2μm;

[0066] ×: The film thickness range of 12 sample points is >2μm.

[0067] (3) Acid resistance test

[0068] Using a screen with a graphic design of 2×2mm×100pcs, a graphic with a thickness of 15±3 was printed on a blank substrate without grooves. Two samples of the graphic were taken and cured, and then immersed in 5 parts of 5% hydrochloric acid and 5 parts of 5% sulfuric acid solution for 1 hour respectively. The surface was cleaned with deionized water, dried and observed. Then, 3M tape was used to vertically tear the sample.

[0069] The acid resistance test evaluation criteria are as follows:

[0070] ○: The graphic appearance showed no corrosion after acid immersion, and the 3M tape did not peel off when torn vertically;

[0071] ×: The graphic appearance is corroded after acid immersion, and the 3M tape peels off when torn vertically.

[0072] (4) Solvent resistance test

[0073] Using a 2×2mm×100pcs screen, a pattern with a thickness of 15±3 was printed on a blank substrate without grooves. Two samples of the pattern were cured and then immersed in a solution with a volume ratio of isopropanol:butanone = 1:1 for 1 hour. The surface was cleaned with deionized water, dried, and the appearance was observed. Then, 3M tape was used to vertically tear the sample.

[0074] The solvent resistance test evaluation criteria are as follows:

[0075] ○: The graphic appearance showed no erosion after solvent immersion, and the 3M tape did not peel off when torn vertically;

[0076] ×: The graphic appearance is eroded after being soaked in solvent, and the 3M tape peels off when torn vertically.

[0077] (5) Resistance to breakage of grain:

[0078] A 0.85×60mm graphic was printed on a 70×60mm grooved blank ceramic substrate using a 325-mesh stainless steel mesh. After curing at 200℃ for 30 minutes, the substrate was folded into pellets using a 0201 type pelletizing machine.

[0079] The evaluation criteria for particle breakage resistance are as follows:

[0080] ○: Ink coating breakage rate < 5 parts;

[0081] ×: Ink coating damage rate ≥ 5 parts.

[0082] (6) Adhesion test:

[0083] Using a screen with a design of 2×2mm×100pcs, a pattern with a thickness of 15±3μm was printed on a blank substrate without grooves. After curing, one sample of the pattern was boiled in water at normal pressure for 16 hours (the time can be accumulated) and then dried. Finally, it was vertically torn using 3M tape.

[0084] The adhesion test evaluation criteria are as follows:

[0085] ○: The 3M tape did not peel off when torn vertically;

[0086] ×: 3M tape peels off when torn vertically.

[0087] (7) Heat resistance test:

[0088] A 50mm×50mm pattern with a thickness of 15μm (error ±3μm) was printed on a blank ceramic substrate. After curing at 200℃ for 30min, it was immersed in a tin bath at 288℃ for 10s / 3 times.

[0089] The evaluation criteria for heat resistance testing are as follows:

[0090] ○: The ink coating is intact and free of cracks;

[0091] ×: The ink coating has peeled off or cracked.

[0092] The results are as follows:

[0093]

[0094]

[0095] The above results show that the semiconductor passive component packaging ink provided by the present invention has excellent weather resistance, water resistance, and substrate adhesion. Comparing Examples 1-3 with Comparative Examples 1-3, it can be seen that the addition of epoxy resin blends within the specified range resulted in all test results passing. However, Comparative Example 1, which did not add epoxy resin blends, failed in acid resistance, solvent resistance, particle breakage, adhesion, and heat resistance. In Comparative Example 2, the addition of epoxy resin blends within the specified range resulted in the ink coating failing in acid resistance, solvent resistance, particle breakage, and adhesion. In Comparative Example 3, the addition of epoxy resin blends exceeding the specified range resulted in the ink coating passing in acid resistance, solvent resistance, and heat resistance, but its viscosity was too high, and it failed the particle breakage test. In Comparative Examples 4 and 5, the use of dicyclopentadiene phenolic epoxy resin or phenolic epoxy resin alone resulted in test failures, fully demonstrating the synergistic effect of dicyclopentadiene phenolic epoxy resin and phenolic epoxy resin in the present invention. In Examples 8-11, different curing agents and curing accelerators were replaced, and the effect was significantly reduced. Combined with Comparative Examples 6-7, it can be found that the present invention effectively improves the chemical resistance, weather resistance, water resistance and substrate adhesion of the product by using specific curing agents and curing accelerators in combination.

[0096] The applicant declares that this invention illustrates the semiconductor passive component packaging ink, its preparation method, and its application through the above embodiments. However, this invention is not limited to the above embodiments, meaning that this invention does not necessarily rely on the above embodiments for implementation. Those skilled in the art should understand that any improvements to this invention, equivalent substitutions of raw materials, additions of auxiliary components, and selection of specific methods, etc., all fall within the protection and disclosure scope of this invention.

[0097] The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited to the specific details in the above embodiments. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solution of the present invention, and these simple modifications all fall within the protection scope of the present invention.

[0098] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, the present invention will not describe the various possible combinations separately.

Claims

1. An ink for packaging semiconductor passive components, characterized in that, The semiconductor passive component packaging ink comprises, by weight, 20-35 parts of first epoxy resin, 5-10 parts of second epoxy resin, 5-10 parts of curing agent, 0.1-5 parts of curing accelerator, and 25-50 parts of filler. The first epoxy resin includes dicyclopentadiene-type phenolic epoxy resin and phenolic epoxy resin; The second epoxy resin includes alicyclic epoxy resin and / or aliphatic epoxy resin, wherein the total chlorine content of the alicyclic epoxy resin is ≤50ppm; The mass ratio of the dicyclopentadiene-type phenolic epoxy resin to the phenolic epoxy resin is (1-5):10; The curing agent is a solid latent amine curing agent, which includes solid dicyandiamide containing active hydrogen. The curing accelerator includes urea-based curing accelerators.

2. The ink for packaging semiconductor passive components according to claim 1, characterized in that, The alicyclic epoxy resin has a molar mass of 240-255 g / mol and an epoxy equivalent of 126-132 g / Eq.

3. The ink for packaging semiconductor passive components according to claim 1, characterized in that, The solid latent amine curing agent also includes any one or a combination of at least two of diaminodiphenylmethyl sulfone or sebacate dihydrazide.

4. The ink for packaging semiconductor passive components according to claim 1, characterized in that, The solid dicyandiamide has an amine value ≥50, a melting point of 180-190℃, and an active hydrogen equivalent of 140-150.

5. The ink for packaging semiconductor passive components according to claim 1, characterized in that, The curing accelerator also includes any one or a combination of at least two of the following: phenolic curing accelerators, imidazole curing accelerators, or hydrazide curing accelerators.

6. The ink for packaging semiconductor passive components according to claim 1, characterized in that, The filler includes any one or a combination of at least two of barium sulfate, talc, mica powder, calcium carbonate, silicon dioxide, or alumina.

7. The ink for packaging semiconductor passive components according to claim 1, characterized in that, The ink for packaging semiconductor passive components also includes 1-10 parts by weight of additives.

8. The ink for packaging semiconductor passive components according to claim 7, characterized in that, The additives include any one or a combination of at least two of the following: defoamers, leveling agents, film-forming aids, thickeners, or wetting and dispersing agents.

9. The ink for packaging semiconductor passive components according to claim 1, characterized in that, The ink for packaging semiconductor passive components also includes 5-10 parts of pigment by weight.

10. The ink for packaging semiconductor passive components according to claim 1, characterized in that, The ink for packaging semiconductor passive components also includes a diluent, which includes any one or a combination of at least two of the following: ether solvents, ester solvents, alcohol solvents, or ketone solvents.

11. A method for preparing an ink for packaging semiconductor passive components according to any one of claims 1-10, characterized in that, The preparation method includes the following steps: The first epoxy resin, the second epoxy resin, the curing agent, the curing accelerator and the filler are mixed and ground to obtain the ink for packaging semiconductor passive components.

12. The preparation method according to claim 11, characterized in that, The mixing also includes mixing with auxiliaries, pigments, and diluents.

13. A semiconductor device, characterized in that, The semiconductor device includes the ink for packaging semiconductor passive components according to any one of claims 1-10.

14. A semiconductor device, characterized in that, The semiconductor device includes the semiconductor device of claim 13.

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