Coating based on nano material, preparation method thereof and semiconductor application

Abstract

The invention discloses a coating based on a nano material, a preparation method of the coating and semiconductor application, and relates to the technical field of coatings. The coating is prepared by taking a water-borne epoxy resin-acrylic emulsion as a composite resin matrix, compounding a quaternary synergistic filler consisting of nano SiC, nano carbon black, nano silicon nitride and nano calcium carbonate, and supplementing a composite modification aid through low-temperature dispersion, in-situ modification and mild curing processes. The low-dielectric-loss high-temperature-resistant anti-ionic-migration coating has the comprehensive performance of low dielectric loss, high temperature resistance, high adhesive force and ionic migration resistance, and can be widely applied to the scenes of semiconductor chip packaging, device shell protection, substrate surface modification and the like. The problems that a traditional semiconductor coating is single in function and poor in environmental adaptability are solved, and the preparation process is green, efficient and high in practicability and has remarkable industrial application value.

Description

Technical Field

[0001] This invention relates to the interdisciplinary field of polymer coatings and nanocomposite materials, specifically to the field of non-stick coating preparation and application technology, and particularly to a high thermal conductivity casting coating based on nanomaterials, its preparation method, and its semiconductor application. Background Technology

[0002] The rapid development of semiconductor technology has driven the evolution of chips, power devices, and other products towards higher integration and higher power density. However, issues such as insulation protection, thermal stability, and signal transmission loss during operation have become key factors restricting product performance improvement. Core components such as semiconductor chip packaging and device casings place stringent requirements on the performance of protective coatings. These coatings must not only possess excellent insulation properties to avoid short-circuit risks but also exhibit low dielectric loss, high temperature resistance, high adhesion, and resistance to environmental corrosion to ensure long-term stable operation of devices under complex conditions.

[0003] Existing semiconductor coatings have several shortcomings: some coatings use a single resin matrix or functional filler, making it difficult to achieve synergistic optimization of properties such as insulation, low dielectric constant, and high temperature resistance. For example, while traditional epoxy resin coatings have good insulation properties, they have high dielectric loss and are prone to brittleness at high temperatures. Some coatings suffer from single-function defects, only meeting basic insulation requirements and lacking key properties such as resistance to ion migration and resistance to damp heat aging. During long-term operation of semiconductor devices, problems such as coating peeling and performance degradation are likely to occur, affecting device reliability. In addition, some coatings have complex preparation processes, requiring high-temperature curing or specialized equipment, which not only increases production costs but may also damage the semiconductor substrate due to the high-temperature process. Furthermore, the use of solvent-based coatings does not conform to the current trend of green and environmentally friendly industrial development.

[0004] Although existing technologies have led to the development of coatings for semiconductor-related applications—such as some coatings using composite fillers to improve insulation performance or employing water-based systems to reduce environmental impact—a comprehensive solution combining low dielectric loss, high temperature resistance, high adhesion, and environmental friendliness has yet to be established. This makes it difficult to fully meet the precise needs of scenarios such as semiconductor chip packaging protection and device casing protection. Therefore, developing a nanomaterial-based coating with synergistic performance optimization, simple preparation process, environmental friendliness, and suitability for core semiconductor applications has become a pressing technical challenge in the field of semiconductor protective materials. Summary of the Invention

[0005] The primary objective of this invention is to provide a coating based on nanomaterials that can precisely meet the core requirements of semiconductor chip packaging protection and semiconductor device casing protection, and has comprehensive properties such as low dielectric loss, high temperature resistance, high adhesion and anti-ion migration, thus solving the technical defects of existing semiconductor coatings, such as single function, poor environmental adaptability and difficulty in meeting multi-dimensional performance requirements.

[0006] The nanomaterial-based coating provided by this invention comprises, by weight, 28-36 parts of a composite resin matrix, 20-31 parts of a quaternary synergistic nanofiller, and 6-10 parts of a composite modifying agent; the composite resin matrix is ​​an aqueous epoxy resin-acrylic emulsion compound system with a weight ratio of 1.5-2.5:1; the quaternary synergistic nanofiller includes 5-8 parts of nano-SiC, 2-4 parts of nano-carbon black, 6-9 parts of nano-silicon nitride, and 7-10 parts of nano-calcium carbonate; the composite modifying agent includes 3-5 parts of a silane coupling agent, 1-2 parts of triethanolamine, 1-2 parts of naphthate, and 1-1.5 parts of emulsified silicone oil.

[0007] Preferably, the particle size gradient of the quaternary synergistic nanofiller is: nano SiC 40-60nm, nano carbon black 15-30nm, nano silicon nitride 25-45nm, and nano calcium carbonate 30-50nm.

[0008] Preferably, the silane coupling agent is one or a combination of two of silane coupling agents KH550 or KH560.

[0009] Preferably, the coating has a dielectric constant of 3.5-5.0, a dielectric loss factor ≤0.02, and an insulation strength ≥15kV / mm.

[0010] The second objective of this invention is to provide a method for preparing the above-mentioned nanomaterial-based coating. This method is simple, green, and efficient, does not require harsh conditions such as high temperature and high pressure, is easy to scale up, and can avoid the problems of nanofiller agglomeration and damage to semiconductor substrates during the preparation process.

[0011] Specifically, the method includes the following steps: S1. Weigh each raw material according to the weight parts, mix the waterborne epoxy resin and acrylic emulsion, add triethanolamine and emulsified silicone oil, stir for 15-20 minutes, and obtain the composite resin matrix premix. S2. Add the quaternary synergistic nanofiller to the composite resin matrix premix and treat it with a combination of ultrasonic dispersion and mechanical stirring for 20-30 min, with an ultrasonic power of 300-500 W and a stirring speed of 800-1200 r / min; S3. Add silane coupling agent and naphthalate to the mixture system of step S2, continue stirring for 10-15 min, and then let it stand at 20-30℃ for 5-8 h to obtain the coating based on nanomaterials.

[0012] Preferably, step S3 is followed by a mild curing step: first, pre-curing at room temperature for 12-24 hours, and then post-curing at a medium temperature of 80-100℃ for 1-2 hours.

[0013] The third objective of this invention is to provide the application of the above-mentioned nanomaterial-based coatings in the semiconductor field, enabling them to be stably applied in semiconductor chip packaging protection and semiconductor device casing protection scenarios, thereby improving the operational stability and service life of semiconductor devices.

[0014] Specifically, the aforementioned nanomaterial-based coatings can be applied to semiconductor devices or equipment.

[0015] More specifically, the coating can be used for semiconductor chip packaging protection, and its coating thickness is preferably 100-200μm when applied.

[0016] Preferably, the coating is used for the protection of semiconductor device housings, and is applied by spraying or dipping, forming a coating with a temperature resistance range of -50°C to 200°C.

[0017] Preferably, in the application according to claim 7, the coating is used for surface modification of a semiconductor substrate, and the contact angle of the substrate surface after coating is ≥110°.

[0018] A fourth objective of the present invention is to provide a semiconductor device wherein the chip pins, housing, or substrate surface of the semiconductor device are provided with an insulating coating formed by the above-mentioned nanomaterial-based coating.

[0019] Compared with the prior art, the beneficial effects of the present invention are as follows: 1. Breaking the functional limitations of single fillers or resins, the coating achieves synergistic optimization of low dielectric loss, high insulation, high temperature resistance, and high adhesion through the compounding of "waterborne epoxy-acrylic" resin and the gradation design of "carbide / nitride / oxide / carbon" quaternary nanofillers. 2. An aqueous system is used, and the system compatibility is increased through component optimization. No organic solvents are used, which reduces VOC emissions. The "ultrasonic + mechanical" dual dispersion process effectively solves the industry problem of easy agglomeration of nanofillers. The medium-temperature (≤100℃) post-curing process significantly reduces energy consumption and avoids the potential thermal damage to semiconductor chips and substrates caused by traditional high-temperature curing. 3. In addition to providing basic protection, the coating is endowed with anti-ion migration, resistance to damp heat aging and high hydrophobicity (self-cleaning) properties through the compounding and particle size distribution of different nano-functional fillers, which can significantly improve its long-term reliability under complex working conditions when applied to semiconductor devices. Detailed Implementation

[0020] To solve the above-mentioned technical problems, the present invention provides the following technical solution: A coating based on nanomaterials, by weight, comprises 28-36 parts of a composite resin matrix, 20-31 parts of a quaternary synergistic nanofiller, and 6-10 parts of a composite modifying agent; the composite resin matrix is ​​an aqueous epoxy resin-acrylic emulsion blend system with a weight ratio of 1.5-2.5:1; the quaternary synergistic nanofiller includes nano-SiC. The composite modifier comprises 5-8 parts of nano-carbon black, 2-4 parts of nano-silicon nitride, 6-9 parts of nano-silicon nitride, and 7-10 parts of nano-calcium carbonate, with the particle size gradient of each nanofiller being: nano-SiC 40-60nm, nano-carbon black 15-30nm, nano-silicon nitride 25-45nm, and nano-calcium carbonate 30-50nm; the composite modifier comprises 3-5 parts of silane coupling agent, 1-2 parts of triethanolamine, 1-2 parts of naphthate, and 1-1.5 parts of emulsified silicone oil; the silane coupling agent is one or a combination of two of silane coupling agents KH550 or KH560.

[0021] Preferably, the coating has a dielectric constant of 3.5-5.0 (50Hz), a dielectric loss factor ≤0.02, an insulation strength ≥15kV / mm, and a temperature resistance range of -50℃ to 200℃.

[0022] A method for preparing the above-mentioned nanomaterial-based coating includes the following steps: S1: Weigh each raw material according to the weight proportions, mix the waterborne epoxy resin and acrylic emulsion, add triethanolamine and emulsified silicone oil, and stir for 15-20 minutes at a speed of 800-1200 r / min to obtain a composite resin matrix premix. S2: Add the quaternary synergistic nanofiller to the composite resin matrix premix and treat it with a combination of ultrasonic dispersion and mechanical stirring for 20-30 minutes, where the ultrasonic power is 300-500W and the stirring speed is 800-1200r / min to ensure uniform dispersion of the nanofiller. S3: Add silane coupling agent and naphthalate to the mixture in step S2, continue stirring for 10-15 min, and then let it stand at 20-30℃ for 5-8 h to obtain the coating based on nanomaterials. S4: Optionally, the coating obtained in step S3 is subjected to curing treatment: first, pre-curing at room temperature for 12-24 hours, and then post-curing at a medium temperature of 80-100℃ for 1-2 hours to form a coating with stable performance.

[0023] A semiconductor application of the above-mentioned nanomaterial-based coating, wherein the coating is used for semiconductor chip packaging protection, with a coating thickness of 100-200 μm; or for semiconductor device housing protection, applied by spraying or dipping.

[0024] A semiconductor device, wherein the chip pins or the surface of the housing of the semiconductor device are provided with an insulating coating formed by the above-mentioned nanomaterial-based coating.

[0025] Raw material preparation The raw materials used in this embodiment are as follows: waterborne epoxy resin (industrial grade, solid content 50%), acrylic emulsion (industrial grade, solid content 45%), nano SiC (particle size 40-60nm, purity ≥99.5%), nano carbon black (particle size 15-30nm, purity ≥99%), nano silicon nitride (particle size 25-45nm, purity ≥99.5%), nano calcium carbonate (particle size 30-50nm, purity ≥98%), silane coupling agent KH550 (industrial grade), silane coupling agent KH560 (industrial grade), triethanolamine (analytical grade), naphthalate (industrial grade, metal content 8%), and emulsified silicone oil (industrial grade, viscosity 100mPa·s).

[0026] Example 1 Coatings based on nanomaterials and their preparation: S1. Weigh the raw materials according to the following parts by weight: 18 parts of water-based epoxy resin, 9 parts of acrylic emulsion (weight ratio of the two is 2:1), 6 parts of nano SiC, 3 parts of nano carbon black, 7 parts of nano silicon nitride, 8 parts of nano calcium carbonate, 4 parts of silane coupling agent KH550, 1.5 parts of triethanolamine, 1.5 parts of naphthate, and 1.2 parts of emulsified silicone oil; S2. Preparation of composite resin matrix premix: Weigh the waterborne epoxy resin and acrylic emulsion into a stirring tank, then add triethanolamine and emulsified silicone oil, set the stirring speed to 1000 r / min, and stir for 18 min to obtain a uniform composite resin matrix premix. S3. Nanofiller dispersion: Nano SiC, nano carbon black, nano silicon nitride, and nano calcium carbonate are added sequentially to the composite resin matrix premix and treated with a combination of ultrasonic dispersion and mechanical stirring for 25 min, wherein the ultrasonic power is 400W and the stirring speed is 1000 r / min to ensure that the nanofiller is uniformly dispersed in the premix. S4. Modification and Curing: Add silane coupling agent KH550 and naphthalate to the above mixture, and continue to rotate at 1000 r / min. Stir for 12 minutes, then let stand at 25°C for 6 hours to obtain a coating based on nanomaterials; S5. Curing treatment: The above coating is applied to the surface of the semiconductor chip pin by spraying, with a coating thickness of 150μm. It is first pre-cured at room temperature for 18h, and then cured at medium temperature at 90℃ for 1.5h to form an insulating coating.

[0027] Example 2 Coatings based on nanomaterials and their preparation: S1. Weigh the raw materials according to the following parts by weight: 15 parts of waterborne epoxy resin, 10 parts of acrylic emulsion (weight ratio of the two is 1.5:1), 5 parts of nano SiC, 2 parts of nano carbon black, 6 parts of nano silicon nitride, 7 parts of nano calcium carbonate, 3 parts of silane coupling agent KH560, 1 part of triethanolamine, 1 part of naphthate, and 1 part of emulsified silicone oil. S2. Preparation of composite resin matrix premix: Weigh the waterborne epoxy resin and acrylic emulsion into a stirring tank, then add triethanolamine and emulsified silicone oil, set the stirring speed to 800 r / min, and stir for 20 min to obtain a uniform composite resin matrix premix. S3. Nanofiller dispersion: Nano SiC, nano carbon black, nano silicon nitride, and nano calcium carbonate are added sequentially to the composite resin matrix premix and treated with a combination of ultrasonic dispersion and mechanical stirring for 30 min, wherein the ultrasonic power is 300W and the stirring speed is 800 r / min to ensure that the nanofiller is uniformly dispersed in the premix. S4. Modification and curing: Add silane coupling agent KH560 and naphthalate to the above mixture, continue stirring at 800 r / min for 15 min, and then let stand at 20℃ for 8 h to obtain a coating based on nanomaterials; S5. Curing treatment: The above coating is applied to the surface of the semiconductor device housing by dip coating, with a coating thickness of 100μm. It is first pre-cured at room temperature for 24h, and then cured at medium temperature at 80℃ for 2h to form an insulating coating.

[0028] Example 3 Coatings based on nanomaterials and their preparation: S1. Weigh the raw materials according to the following parts by weight: 20 parts of waterborne epoxy resin, 8 parts of acrylic emulsion (weight ratio of the two is 2.5:1), 8 parts of nano SiC, 4 parts of nano carbon black, 9 parts of nano silicon nitride, 10 parts of nano calcium carbonate, 5 parts of silane coupling agent KH550 and KH560 compound (weight ratio of the two is 1:1), 2 parts of triethanolamine, 2 parts of naphthate, and 1.5 parts of emulsified silicone oil; S2. Preparation of composite resin matrix premix: Weigh the waterborne epoxy resin and acrylic emulsion into a stirring tank, then add triethanolamine and emulsified silicone oil, set the stirring speed to 1200 r / min, and stir for 15 min to obtain a uniform composite resin matrix premix. S3. Nanofiller dispersion: Nano SiC, nano carbon black, nano silicon nitride, and nano calcium carbonate are added sequentially to the composite resin matrix premix and treated with a combination of ultrasonic dispersion and mechanical stirring for 20 min, wherein the ultrasonic power is 500W and the stirring speed is 1200 r / min to ensure that the nanofiller is uniformly dispersed in the premix. S4. Modification and curing: Add silane coupling agent complex and naphthalate to the above mixture, continue stirring at 1200 r / min for 10 min, and then let stand at 30℃ for 5 h to obtain a coating based on nanomaterials; S5. Curing treatment: The above coating is applied to the semiconductor chip packaging area by roller coating, with a coating thickness of 200μm. It is first pre-cured at room temperature for 12h, and then cured at medium temperature at 100℃ for 1h to form an insulating coating.

[0029] Comparative Example 1 This comparative paint contains the following components in parts by weight: Epoxy phenolic resin: 45 parts; Talc (micron-sized, 5μm): 25 parts; Solvent (xylene / butanol = 7:3): 30 parts; Curing agent (dicyandiamide): 4 parts; Leveling agent (BYK-358N): 0.5 parts; Defoamer (BYK-066N): 0.3 parts; The preparation process is the same as in Example 1.

[0030] Comparative Example 2 Without the addition of acrylic emulsion, other characteristics are the same as in Example 1.

[0031] Comparative Example 3 Without adding nano carbon black and nano calcium carbonate, 10 parts of nano SiC and 11 parts of nano silicon nitride were added, and other characteristics were the same as in Example 1.

[0032] Performance Testing and Result Analysis The performance of the insulating coatings prepared in Examples 1-3 was tested using the following methods: Adhesion test: Refer to GB / T 1720-1979 "Determination of Adhesion of Paint Films"; Dielectric performance testing: The dielectric constant (50Hz) and dielectric loss factor (50Hz) were tested in accordance with GB / T 1692-2008 "Determination of Insulation Resistivity of Vulcanized Rubber". Insulation strength test: Refer to GB / T 1408.1-2016 "Test Methods for Electrical Strength of Insulating Materials"; High temperature resistance test: The coating was placed in a 200℃ constant temperature chamber for 1000h, and the appearance was observed and the dielectric properties were tested. Moisture and heat resistance test: Refer to GB / T 1740-2007 "Determination of Moisture and Heat Resistance of Coating Film", place it at 85℃ and 85%RH for 1500h, and test the change in adhesion.

[0033] The test results are shown in the table below:

[0034] The test results of Examples 1-3 show that the coating adhesion reaches Grade 1, the dielectric constant is controlled between 3.5 and 5.0, the dielectric loss factor is ≤0.02, the insulation strength is ≥15kV / mm, and it can work stably in the range of -50℃ to 200℃. It has excellent resistance to damp heat and fully meets the usage requirements for semiconductor chip packaging protection and device shell protection. Moreover, the preparation process is simple, the construction method is flexible, no special equipment is required, and it can realize large-scale production and on-site construction, making it highly practical.

[0035] Comparative Example 1: Adhesion / Humidity / Heat Difference: High-temperature curing results in high shrinkage stress, preventing the rigid resin from relaxing due to the easy hydrolysis of ester bonds. High Dielectric Loss: Numerous interfacial voids in the micron-filler interface lead to severe interfacial polarization due to the high density of polar hydroxyl groups.

[0036] Comparative Example 2: Decreased adhesion at high temperatures: The lack of acrylic flexible chains prevents the release of post-crosslinking shrinkage stress, ultimately leading to interfacial microcracks. Deterioration of dielectric properties: Due to residual hydrophilic emulsifiers and undiluted polar groups, filler wetting is poor.

[0037] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A coating based on nanomaterials, characterized in that, The product, by weight, comprises 28-36 parts of a composite resin matrix, 20-31 parts of a quaternary synergistic nanofiller, and 6-10 parts of a composite modifying agent; the composite resin matrix is ​​an aqueous epoxy resin-acrylic emulsion compound system with a weight ratio of 1.5-2.5:1; the quaternary synergistic nanofiller includes 5-8 parts of nano-SiC, 2-4 parts of nano-carbon black, 6-9 parts of nano-silicon nitride, and 7-10 parts of nano-calcium carbonate; the composite modifying agent includes 3-5 parts of a silane coupling agent, 1-2 parts of triethanolamine, 1-2 parts of naphthate, and 1-1.5 parts of emulsified silicone oil.

2. The coating based on nanomaterials according to claim 1, characterized in that, The particle size gradient of the quaternary synergistic nanofiller is as follows: nano SiC 40-60nm, nano carbon black 15-30nm, nano silicon nitride 25-45nm, and nano calcium carbonate 30-50nm.

3. The coating based on nanomaterials according to claim 1, characterized in that, The silane coupling agent is one or a combination of two of silane coupling agents KH550 or KH560.

4. The coating based on nanomaterials according to claim 1, characterized in that, The coating has a dielectric constant of 3.5-5.0, a dielectric loss factor ≤0.02, and an insulation strength ≥15kV / mm.

5. A method for preparing a coating based on nanomaterials as described in any one of claims 1-4, characterized in that, Includes the following steps: S1. Weigh each raw material according to the weight parts, mix the waterborne epoxy resin and acrylic emulsion, add triethanolamine and emulsified silicone oil, stir for 15-20 minutes, and obtain the composite resin matrix premix. S2. Add the quaternary synergistic nanofiller to the composite resin matrix premix and treat it with a combination of ultrasonic dispersion and mechanical stirring for 20-30 min, with an ultrasonic power of 300-500 W and a stirring speed of 800-1200 r / min; S3. Add silane coupling agent and naphthalate to the mixture system of step S2, continue stirring for 10-15 min, and then let it stand at 20-30℃ for 5-8 h to obtain the coating based on nanomaterials.

6. The preparation method according to claim 5, characterized in that, Step S3 is followed by a mild curing step: first, pre-curing at room temperature for 12-24 hours, and then post-curing at a medium temperature of 80-100℃ for 1-2 hours.

7. A semiconductor application of a nanomaterial-based coating as described in any one of claims 1-4, characterized in that, The coating is used for semiconductor chip packaging protection, and the coating thickness is 100-200μm.

8. The application according to claim 7, characterized in that, The coating is used for the protection of semiconductor device casings. It is applied by spraying or dipping, and the resulting coating has a temperature resistance range of -50℃ to 200℃.

9. The application according to claim 7, characterized in that, The coating is used to modify the surface of a semiconductor substrate, and the contact angle of the substrate surface after coating is ≥110°.

10. A semiconductor device, characterized in that, The semiconductor device has an insulating coating formed by the coating material based on nanomaterials as described in any one of claims 1-4 on its chip pins, housing, or substrate surface.

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