A semiconductor protective film and coating process thereof

Abstract

The present invention provides a semiconductor protective film and a coating process thereof, wherein the semiconductor protective film comprises a base layer, a functional layer, a stress buffer layer and an anti-corrosion layer. The base layer is composed of raw materials such as vinyl chloride resin, polyimide resin, and phenoxy resin; the functional layer contains a heat dissipation medium, a stabilizer, a plasticizer, and the like. The stress buffer layer is composed of styrene-butadiene-styrene block copolymer, α-silicon dioxide, and α-aluminum oxide in a specific mass ratio, and the anti-corrosion layer is silicon nitride or silicon oxide. Raw materials such as the heat dissipation medium and the stabilizer have specific compositions and proportions. The coating process comprises the steps of ultrasonic cleaning, spin coating the base layer, spraying the functional layer, vacuum sputtering the stress buffer layer, and chemical vapor deposition of the anti-corrosion layer. The protective film improves the heat dissipation performance and thermal shrinkage performance of semiconductor devices by optimizing the material ratio and coating process.

Description

Technical Field

[0001] The present invention relates to the field of manufacturing semiconductor devices, and in particular to a semiconductor protective film and a coating process thereof. Background Art

[0002] With the rapid development of semiconductor technology, the integration of semiconductor devices continues to increase, and power density has also increased. This has placed higher demands on the heat dissipation performance and thermal stability of semiconductor protective films. Although traditional semiconductor protective films can protect semiconductor devices from external environmental corrosion to a certain extent, they still have significant shortcomings in heat dissipation performance and thermal shrinkage performance.

[0003] In terms of heat dissipation performance, traditional semiconductor protective films are often unable to effectively and quickly dissipate the heat generated by semiconductor devices, causing heat accumulation inside the device, which in turn leads to temperature increases, performance degradation, and even failure. This problem is particularly prominent in high-power, high-density semiconductor devices. In terms of thermal shrinkage performance, because semiconductor devices experience temperature changes during operation, the materials of traditional protective films often do not match the thermal expansion coefficient of the semiconductor substrate, resulting in the protective film being prone to thermal shrinkage or deformation when the temperature changes, which in turn causes mechanical stress to the semiconductor device, affecting its stability and reliability. At the same time, after a period of use, the protective film will shrink at both ends, seriously affecting the service life and protective effect of the protective film. Summary of the Invention

[0004] In view of this, the present invention proposes a semiconductor protection film and a coating process thereof to solve the above problems.

[0005] The technical solution of the present invention is achieved as follows: a semiconductor protective film: comprising a base layer, a functional layer, a stress buffer layer and an anti-corrosion layer; the base layer comprises the following raw materials in parts by weight: 30-50 parts of vinyl chloride resin, 25-35 parts of polyimide resin, 15-33 parts of phenoxy resin, 12-22 parts of polyethylene terephthalate, 10-20 parts of soybean oil, and 12-22 parts of calcium carbonate; the functional layer comprises the following raw materials in parts by weight: 5-10 parts of heat dissipation medium, 12-33 parts of stabilizer, and 20-40 parts of plasticizer; the stress buffer layer comprises styrene-butadiene-styrene block copolymer, α-silicon dioxide and α-alumina in a mass ratio of (14-25):(6-10):(2-5); the anti-corrosion layer includes but is not limited to silicon nitride or silicon oxide.

[0006] Furthermore, the base layer includes the following raw materials in parts by weight: 40 parts of vinyl chloride resin, 30 parts of polyimide resin, 25 parts of phenoxy resin, 17 parts of polyethylene terephthalate, 15 parts of soybean oil, and 17 parts of calcium carbonate; the functional layer includes the following raw materials in parts by weight: 8 parts of heat dissipation medium, 25 parts of stabilizer, and 30 parts of plasticizer; the stress buffer layer includes styrene-butadiene-styrene block copolymer, α-silicon dioxide, and α-alumina in a mass ratio of 20:8:3, and the anti-corrosion layer includes but is not limited to silicon nitride or silicon oxide.

[0007] Furthermore, the α-silicon dioxide and α-alumina are prepared by dispersing silicon dioxide or alumina in water, respectively, with a mass-to-volume ratio of g / mL of 10-18:30, and ultrasonically dispersing the dispersed solution with an ultrasonic power of 500-1000 W, a frequency of 15-25 kHz, and ultrasonication for 20-60 min. The dispersed solution is mixed with a chromate solution with a mass concentration of 50-70% and stirred at a temperature of 12-22° C. for 4-6 h, with a volume ratio of the dispersed solution to the chromate solution of 1-3:1, and dried to obtain α-silicon dioxide or α-alumina with a particle size of less than 0.5 μm.

[0008] Furthermore, the heat dissipation medium is silicone grease, carbon fiber, and metal particles in a mass ratio of (6-12):(5-10):(3-8), the particle size of the heat dissipation medium is less than 10 μm, and the metal particles are selected from any one of copper, aluminum, nickel, chromium, and tungsten.

[0009] Furthermore, the stabilizer is dibutyltin dilaurate, calcium isooctanoate and boron nitride nanoparticles in a mass ratio of (4-9):(1-3):(8-12).

[0010] Furthermore, the plasticizer includes but is not limited to dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, dioctyl adipate, and epoxy fatty acid methyl ester.

[0011] Furthermore, a coating process for a semiconductor protective film comprises the following steps:

[0012] Step A: Using ultrasonic waves to clean the semiconductor surface to remove contaminants and impurities on the surface of the semiconductor substrate;

[0013] Step B: mixing the base layer raw materials, spin-coating on the surface of the semiconductor substrate at a rotation speed of 5000-8000 rpm, and drying at 80-120° C. to form a base layer with a thickness of 10-50 μm;

[0014] Step C: spraying the functional layer raw material on the upper surface of the base layer to form a functional layer with a thickness of 5-20 μm;

[0015] Step D: sputtering a stress buffer layer material on the functional layer by a vacuum sputtering process to form a stress buffer layer with a thickness of 5-10 μm;

[0016] Step E: placing the semiconductor substrate with the stress buffer layer formed thereon into a chemical vapor deposition reaction chamber, introducing silane and ammonia or oxygen for deposition, and obtaining an anti-corrosion layer with a thickness of 3-10 μm.

[0017] Step F: drying and curing at a temperature of 100-200° C. for 30-60 minutes to obtain a semiconductor protective film.

[0018] Furthermore, the spraying gun pressure in step C is 0.2-0.4 MPa, the spraying distance is 15-25 cm, the coating flow rate is 50-100 mL / min, the spray gun speed is 0.1-1 m / s, and the spraying temperature is 15-30°C.

[0019] Furthermore, the parameters of the sputtering process in step D are: sputtering power of 300-500 W, sputtering pressure of 0.1-0.5 Pa, and sputtering time of 25-45 min.

[0020] Furthermore, in the chemical vapor deposition reaction chamber of step E, the radio frequency power is 100-300 W, the temperature is 300-1200° C., the reaction gas pressure is 10-100 Pa, the silane flow rate is 50-100 sccm, and the ammonia or oxygen flow rate is 50-300 sccm.

[0021] Compared with the prior art, the present invention has the following beneficial effects:

[0022] The present invention optimizes the material ratio and coating process of the semiconductor protective film, particularly by introducing a heat dissipation medium and a stress buffer layer with a specific ratio. The rationally proportioned heat dissipation medium effectively improves the thermal conductivity of the semiconductor protective film, enhances the thermal radiation capability of the film, dissipates heat in the form of thermal radiation, reduces the device operating temperature, and ensures stable device performance. The optimized combination of the stress buffer layer and the materials of each layer absorbs and disperses the stress generated by the mismatch of thermal expansion coefficients, effectively reducing the thermal shrinkage rate of the semiconductor protective film at different temperatures, allowing it to maintain dimensional stability over a wide temperature range, and avoiding problems such as deformation, cracking, or separation of the protective film from the semiconductor device due to thermal shrinkage, thereby improving the long-term protective effect of the protective film on the semiconductor device. The anti-corrosion layer, made of materials such as silicon nitride or silicon oxide, can effectively block the erosion of the semiconductor device by external corrosive substances, providing reliable protection for the semiconductor device and enabling it to operate stably in harsh environments.

[0023] The base layer, functional layer, stress buffer layer and anti-corrosion layer work together to give full play to their respective functional advantages, so that the semiconductor protective film has comprehensive high performance and can meet the protection needs of semiconductor devices under complex working conditions.

[0024] The coating process in the scheme of the present invention adopts multiple technical means such as ultrasonic cleaning, spin coating, spraying, vacuum sputtering and chemical vapor deposition to optimize the coating process, thereby achieving precise control and efficient preparation of each layer of the semiconductor protective film, and reducing local shrinkage caused by uneven coating, poor adhesion and poor edge coverage.

[0025] The protective film and coating process thereof of the present invention are intended to significantly improve the heat dissipation performance of semiconductor devices and reduce the thermal shrinkage problem caused by temperature changes, providing strong support for the further development of semiconductor technology. DETAILED DESCRIPTION

[0026] In order to better understand the technical content of the present invention, specific examples are provided below to further illustrate the present invention.

[0027] Unless otherwise specified, the experimental methods used in the examples of the present invention are all conventional methods.

[0028] Unless otherwise specified, the materials, reagents, etc. used in the examples of the present invention can be obtained from commercial sources.

[0029] Example 1

[0030] A semiconductor protective film: comprising a base layer, a functional layer, a stress buffer layer and an anti-corrosion layer;

[0031] The base layer comprises the following raw materials in parts by weight: 30 parts of vinyl chloride resin, 25 parts of polyimide resin, 15 parts of phenoxy resin, 12 parts of polyethylene terephthalate, 10 parts of soybean oil, and 12 parts of calcium carbonate;

[0032] The functional layer comprises the following raw materials in parts by weight: 5 parts of a heat dissipation medium, 12 parts of a stabilizer, and 20 parts of a plasticizer; the heat dissipation medium comprises silicone grease, carbon fibers, and copper metal particles in a mass ratio of 6:5:3, and the particle size of the heat dissipation medium is less than 10 μm; the stabilizer comprises dibutyltin dilaurate, calcium isooctanoate, and boron nitride nanoparticles in a mass ratio of 4:1:8; and the plasticizer comprises dibutyl phthalate.

[0033] The stress buffer layer comprises a styrene-butadiene-styrene block copolymer, α-silicon dioxide, and α-alumina in a mass ratio of 14:6:2; the α-silicon dioxide and α-alumina are prepared by dispersing silicon dioxide or aluminum oxide in water at a mass-to-volume ratio of 10:30 g / mL, ultrasonically dispersing the obtained dispersion at an ultrasonic power of 500 W, a frequency of 15 kHz, and ultrasonication for 20 minutes. The obtained dispersion is mixed with a 50% mass concentration chromate solution at a temperature of 12° C. and stirred for 4 hours. The volume ratio of the dispersion to the chromate solution is 1:1, and the mixture is dried to obtain α-silicon dioxide or α-alumina having a particle size of less than 0.5 μm.

[0034] The anti-corrosion layer is silicon nitride.

[0035] Example 2

[0036] A semiconductor protective film: comprising a base layer, a functional layer, a stress buffer layer and an anti-corrosion layer;

[0037] The base layer comprises the following raw materials in parts by weight: 50 parts of vinyl chloride resin, 35 parts of polyimide resin, 33 parts of phenoxy resin, 22 parts of polyethylene terephthalate, 20 parts of soybean oil, and 22 parts of calcium carbonate;

[0038] The functional layer comprises the following raw materials in parts by weight: 10 parts of a heat dissipation medium, 33 parts of a stabilizer, and 40 parts of a plasticizer; the heat dissipation medium comprises silicone grease, carbon fibers, and aluminum metal particles in a mass ratio of 12:10:8, and the particle size of the heat dissipation medium is less than 10 μm; the stabilizer comprises dibutyltin dilaurate, calcium isooctanoate, and boron nitride nanoparticles in a mass ratio of 9:3:12; and the plasticizer comprises dioctyl phthalate.

[0039] The stress buffer layer comprises a styrene-butadiene-styrene block copolymer, α-silicon dioxide, and α-alumina in a mass ratio of 25:10:5; the α-silicon dioxide and α-alumina are prepared by dispersing silicon dioxide or aluminum oxide in water at a mass-to-volume ratio of 18:30 g / mL, ultrasonically dispersing the obtained dispersion at an ultrasonic power of 1000 W, a frequency of 25 kHz, and ultrasonication for 60 minutes. The obtained dispersion is mixed with a 70% mass concentration chromate solution at a temperature of 22° C. and stirred for 6 hours. The volume ratio of the dispersion to the chromate solution is 3:1, and the mixture is dried to obtain α-silicon dioxide or α-alumina having a particle size of less than 0.5 μm.

[0040] The anti-corrosion layer is silicon nitride.

[0041] Example 3

[0042] A semiconductor protective film comprising a base layer, a functional layer, a stress buffer layer, and an anti-corrosion layer; the base layer comprises the following raw materials in parts by weight: 40 parts of vinyl chloride resin, 30 parts of polyimide resin, 25 parts of phenoxy resin, 17 parts of polyethylene terephthalate, 15 parts of soybean oil, and 17 parts of calcium carbonate;

[0043] The functional layer comprises the following raw materials in parts by weight: 8 parts of a heat dissipation medium, 25 parts of a stabilizer, and 30 parts of a plasticizer; the heat dissipation medium comprises silicone grease, carbon fibers, and metal particles in a mass ratio of 9:8:5, the particle size of the heat dissipation medium being less than 10 μm, and the metal particles being selected from copper metal particles; the stabilizer comprises dibutyltin dilaurate, calcium isooctanoate, and boron nitride nanoparticles in a mass ratio of 7:2:10; and the plasticizer is selected from tricresyl phosphate;

[0044] The stress buffer layer includes a styrene-butadiene-styrene block copolymer, α-silicon dioxide, and α-alumina in a mass ratio of 20:8:3. The α-silicon dioxide and α-alumina are prepared by dispersing silicon dioxide or aluminum oxide in water at a mass-to-volume ratio of 15:30 g / mL, respectively. Ultrasonic dispersion is performed with an ultrasonic power of 800 W, a frequency of 20 kHz, and ultrasonication for 40 minutes. The resulting dispersion is mixed with a chromate solution with a mass concentration of 60%, stirred at a temperature of 17° C. for 5 hours, and the dispersion and chromate solution are stirred at a volume ratio of 2:1. The mixture is dried to obtain α-silicon dioxide or α-alumina with a particle size of less than 0.5 μm.

[0045] The anti-corrosion layer is silicon nitride;

[0046] The above examples 1-3 adopt the following coating process:

[0047] Step A: Using ultrasonic waves to clean the semiconductor surface to remove contaminants and impurities on the surface of the semiconductor substrate;

[0048] Step B: mixing the base layer raw materials, spin-coating on the surface of the semiconductor substrate at a rotation speed of 7000 rpm, and drying at 100° C. to form a base layer with a thickness of 30 μm;

[0049] Step C: spraying the functional layer raw material on the upper surface of the base layer to form a functional layer with a thickness of 15 μm; the spraying gun pressure is 0.3 MPa, the spraying distance is 20 cm, the coating flow rate is 80 mL / min, the spray gun speed is 0.5 m / s, and the spraying temperature is 22°C;

[0050] Step D: sputtering a stress buffer layer material on the functional layer by a vacuum sputtering process to form a stress buffer layer with a thickness of 8 μm; the sputtering power is 400 W, the sputtering pressure is 0.3 Pa, and the sputtering time is 35 min;

[0051] Step E: Place the semiconductor substrate with the stress buffer layer formed thereon into a chemical vapor deposition reaction chamber, introduce silane and ammonia, and perform deposition at an RF power of 200 W, a temperature of 700°C, a reaction gas pressure of 50 Pa, a silane flow rate of 80 sccm, and an ammonia flow rate of 200 sccm to obtain a silicon nitride anti-corrosion layer with a thickness of 8 μm.

[0052] Step F: Drying and curing at a temperature of 150° C. for 50 minutes to obtain a semiconductor protection film.

[0053] Example 4

[0054] A semiconductor protective film comprising a base layer, a functional layer, a stress buffer layer, and an anti-corrosion layer; the base layer comprises the following raw materials in parts by weight: 40 parts of vinyl chloride resin, 30 parts of polyimide resin, 25 parts of phenoxy resin, 17 parts of polyethylene terephthalate, 15 parts of soybean oil, and 17 parts of calcium carbonate;

[0055] The functional layer comprises the following raw materials in parts by weight: 8 parts of a heat dissipation medium, 25 parts of a stabilizer, and 30 parts of a plasticizer; the heat dissipation medium comprises silicone grease, carbon fibers, and metal particles in a mass ratio of 9:8:5, the particle size of the heat dissipation medium being less than 10 μm, and the metal particles being selected from copper metal particles; the stabilizer comprises dibutyltin dilaurate, calcium isooctanoate, and boron nitride nanoparticles in a mass ratio of 7:2:10; and the plasticizer is selected from tricresyl phosphate;

[0056] The stress buffer layer includes a styrene-butadiene-styrene block copolymer, α-silicon dioxide, and α-alumina in a mass ratio of 20:8:3. The α-silicon dioxide and α-alumina are prepared by dispersing silicon dioxide or aluminum oxide in water at a mass-to-volume ratio of 15:30 g / mL, respectively. Ultrasonic dispersion is performed with an ultrasonic power of 800 W, a frequency of 20 kHz, and ultrasonication for 40 minutes. The resulting dispersion is mixed with a chromate solution with a mass concentration of 60%, stirred at a temperature of 17° C. for 5 hours, and the dispersion and chromate solution are stirred at a volume ratio of 2:1. The mixture is dried to obtain α-silicon dioxide or α-alumina with a particle size of less than 0.5 μm.

[0057] The anti-corrosion layer is silicon oxide;

[0058] The above embodiment 4 adopts the following coating process:

[0059] Step A: Using ultrasonic waves to clean the semiconductor surface to remove contaminants and impurities on the surface of the semiconductor substrate;

[0060] Step B: mixing the base layer raw materials, spin-coating on the surface of the semiconductor substrate at a rotation speed of 5000 rpm, and drying at 80° C. to form a base layer with a thickness of 10 μm;

[0061] Step C: spraying the functional layer raw material on the upper surface of the base layer to form a functional layer with a thickness of 5 μm. The spraying pressure of the spray gun is 0.2 MPa, the spraying distance is 15 cm, the coating flow rate is 50 mL / min, the spray gun speed is 0.1 m / s, and the spraying temperature is 15°C.

[0062] Step D: sputtering a stress buffer layer material on the functional layer by a vacuum sputtering process with a sputtering power of 300 W, a sputtering pressure of 0.1 Pa, and a sputtering time of 25 min to form a stress buffer layer with a thickness of 5 μm;

[0063] Step E: Place the semiconductor substrate with the stress buffer layer formed thereon into a chemical vapor deposition reaction chamber, introduce silane and oxygen, and perform deposition at an RF power of 100 W, a temperature of 300°C, a reaction gas pressure of 10 Pa, a silane flow rate of 50 sccm, and an oxygen flow rate of 50 sccm to obtain a silicon oxide anti-corrosion layer with a thickness of 3 μm.

[0064] Step F: Drying and curing at a temperature of 100° C. for 30 minutes to obtain a semiconductor protection film.

[0065] Example 5

[0066] A semiconductor protective film comprising a base layer, a functional layer, a stress buffer layer, and an anti-corrosion layer; the base layer comprises the following raw materials in parts by weight: 40 parts of vinyl chloride resin, 30 parts of polyimide resin, 25 parts of phenoxy resin, 17 parts of polyethylene terephthalate, 15 parts of soybean oil, and 17 parts of calcium carbonate;

[0067] The functional layer comprises the following raw materials in parts by weight: 8 parts of a heat dissipation medium, 25 parts of a stabilizer, and 30 parts of a plasticizer; the heat dissipation medium comprises silicone grease, carbon fibers, and metal particles in a mass ratio of 9:8:5, the particle size of the heat dissipation medium being less than 10 μm, and the metal particles being selected from copper metal particles; the stabilizer comprises dibutyltin dilaurate, calcium isooctanoate, and boron nitride nanoparticles in a mass ratio of 7:2:10; and the plasticizer is selected from tricresyl phosphate;

[0068] The stress buffer layer includes a styrene-butadiene-styrene block copolymer, α-silicon dioxide, and α-alumina in a mass ratio of 20:8:3. The α-silicon dioxide and α-alumina are prepared by dispersing silicon dioxide or aluminum oxide in water at a mass-to-volume ratio of 15:30 g / mL, respectively. Ultrasonic dispersion is performed with an ultrasonic power of 800 W, a frequency of 20 kHz, and ultrasonication for 40 minutes. The resulting dispersion is mixed with a chromate solution with a mass concentration of 60%, stirred at a temperature of 17° C. for 5 hours, and the dispersion and chromate solution are stirred at a volume ratio of 2:1. The mixture is dried to obtain α-silicon dioxide or α-alumina with a particle size of less than 0.5 μm.

[0069] The anti-corrosion layer is silicon oxide;

[0070] The above embodiment 5 adopts the following coating process:

[0071] Step A: Using ultrasonic waves to clean the semiconductor surface to remove contaminants and impurities on the surface of the semiconductor substrate;

[0072] Step B: mixing the base layer raw materials, spin-coating on the surface of the semiconductor substrate at a rotation speed of 8000 rpm, and drying at 120° C. to form a base layer with a thickness of 50 μm;

[0073] Step C: spraying the functional layer raw material on the upper surface of the base layer to form a functional layer with a thickness of 20 μm; the spray gun pressure is 0.4 MPa, the spraying distance is 25 cm, the coating flow rate is 100 mL / min, the spray gun speed is 1 m / s, and the spraying temperature is 30°C;

[0074] Step D: sputtering a stress buffer layer material on the functional layer by a vacuum sputtering process to form a stress buffer layer with a thickness of 10 μm; the sputtering power is 500 W, the sputtering pressure is 0.5 Pa, and the sputtering time is 45 min;

[0075] Step E: Place the semiconductor substrate with the stress buffer layer formed thereon into a chemical vapor deposition reaction chamber, introduce silane and oxygen, and perform deposition at an RF power of 300 W, a temperature of 1200° C., a reaction gas pressure of 100 Pa, a silane flow rate of 100 sccm, and an oxygen flow rate of 300 sccm to obtain a silicon oxide anti-corrosion layer with a thickness of 10 μm.

[0076] Step F: Drying and curing at a temperature of 200° C. for 60 minutes to obtain a semiconductor protection film.

[0077] Comparative Example 1

[0078] The difference between this comparative example and Example 3 is that a semiconductor protective film includes a base layer, a functional layer, a stress buffer layer and an anti-corrosion layer; the base layer includes the following raw materials in parts by weight: 10 parts of vinyl chloride resin, 40 parts of polyimide resin, 45 parts of phenoxy resin, 10 parts of polyethylene terephthalate, 5 parts of soybean oil, and 8 parts of calcium carbonate; the functional layer includes the following raw materials in parts by weight: 2 parts of heat dissipation medium, 10 parts of stabilizer, and 12 parts of plasticizer.

[0079] Comparative Example 2

[0080] The difference between this comparative example and Example 3 is that no heat dissipation medium is added to the functional layer.

[0081] Comparative Example 3

[0082] The difference between this comparative example and Example 3 is that no stabilizer is added to the functional layer.

[0083] Comparative Example 4

[0084] The difference between this comparative example and Example 3 is that the semiconductor protection film is not coated with a stress buffer layer.

[0085] Comparative Example 5

[0086] The difference between this comparative example and Example 3 is that in the coating process of the semiconductor protection film, the functional layer and the stress buffer layer are both coated by spraying, specifically:

[0087] Step A: Using ultrasonic waves to clean the semiconductor surface to remove contaminants and impurities on the surface of the semiconductor substrate;

[0088] Step B: mixing the base layer raw materials, spin-coating on the surface of the semiconductor substrate at a rotation speed of 7000 rpm, and drying at 100° C. to form a base layer with a thickness of 30 μm;

[0089] Step C: spraying the functional layer material on the upper surface of the base layer to form a functional layer with a thickness of 15 μm, and spraying the stress buffer layer material to form a stress buffer layer with a thickness of 8 μm; the spraying gun pressure is 0.3 MPa, the spraying distance is 20 cm, the coating flow rate is 80 mL / min, the spray gun speed is 0.5 m / s, and the spraying temperature is 22°C;

[0090] Step E: Place the semiconductor substrate with the stress buffer layer formed thereon into a chemical vapor deposition reaction chamber, introduce silane and ammonia, and perform deposition at an RF power of 200 W, a temperature of 700°C, a reaction gas pressure of 50 Pa, a silane flow rate of 80 sccm, and an ammonia flow rate of 200 sccm to obtain a silicon nitride anti-corrosion layer with a thickness of 8 μm.

[0091] Step F: Drying and curing at a temperature of 150° C. for 50 minutes to obtain a semiconductor protection film.

[0092] Test Example 1-Heat Dissipation Performance

[0093] The heat dissipation performance of the semiconductor protection films coated in the above-mentioned Examples 1-5 and Comparative Examples 1-5 was measured, including thermal resistance, thermal diffusion coefficient, thermal conductivity and maximum surface temperature.

[0094] 1. Thermal resistance test

[0095] (1) Experimental steps: Place the sample coated with a semiconductor protective film between a heating stage and a heat sink. Install a heat flux meter and thermocouples on the upper and lower surfaces of the sample to measure heat flux and temperature. Turn on the heating stage and set the heating power to 1200W. After the system reaches thermal stability (temperature and heat flux no longer change with time), record the heat flux Q measured by the heat flux meter and the temperature difference ΔT measured by the thermocouples on the upper and lower surfaces through the data acquisition system.

[0096] (2) Thermal resistance calculation formula: (Where R is the thermal resistance, ΔT is the temperature difference, and Q is the heat flow) Calculate the thermal resistance.

[0097] 2. Thermal diffusivity test

[0098] (1) Experimental steps: Prepare the sample into a thin sheet and ensure that the surface is flat and smooth. Place the sample in the sample chamber of the laser flash thermal diffusivity tester with its front surface facing the laser beam. Start the laser to illuminate the front surface of the sample, while using an infrared detector to monitor the temperature change of the back surface of the sample. The instrument records the change of surface temperature over time and calculates the thermal diffusivity using data processing software based on relevant models and formulas.

[0099] 3. Thermal conductivity test

[0100] (1) Experimental steps:

[0101] Place the sample between a hot plate and a cold plate and secure it with a clamp. Install temperature sensors and heat flow meters on the hot and cold plates, as well as inside the sample. Turn on the temperature control systems for the hot and cold plates to create a stable temperature difference between them. Once the system reaches steady state, record the heat flux Q measured by the heat flow meter, the temperature difference ΔT across the sample, and the sample's thickness d and area A.

[0102] (2) Thermal conductivity calculation formula: (where k is thermal conductivity, Q is heat flow, d is sample thickness, A is sample area, and ΔT is temperature difference)

[0103] Calculate the thermal conductivity according to the above formula.

[0104] 4. Maximum surface temperature (°C) test: Use an infrared thermal imager to photograph the sample surface, analyze the thermal imaging image, and obtain the maximum temperature value of the sample surface.

[0105] 5. Test results:

[0106] Table 1:

[0107]

[0108]

[0109] From the above results, it can be seen that the thermal resistance value of the embodiment group is between 0.15 and 0.26 K / W, which is relatively low, indicating that the materials in these embodiments have good heat transfer capabilities, which may be because their internal structure is conducive to rapid heat conduction; the thermal diffusion coefficient is between 0.34 and 0.38, which is relatively high, indicating that heat can diffuse rapidly in these materials, which is conducive to uniform heat distribution; the thermal conductivity is between 1.30 and 1.40, showing good thermal conductivity, indicating that the protective film can effectively conduct heat, and the maximum surface temperature is between 35 and 38°C, which is relatively low and stable, indicating that these materials can effectively control the temperature rise under the test conditions.

[0110] Test Example 2-Heat Shrinkage Test

[0111] 1. Sample preparation: Cut rectangular samples of 100 mm × 100 mm from the substrates coated with the semiconductor protective film of Example 3 and Comparative Examples 2-5, measure the initial length (L0) and width (W0) at three different locations on the sample, and record the measured values.

[0112] 2. Heat shrinkage treatment: Place the sample flat on a clean metal mesh or ceramic tray, and then place it in a precision oven preheated to the set temperature of 50℃, 100℃, 150℃, or 200℃ for 1-2 hours.

[0113] 3. Cooling and measurement: Take out the sample and cool it to room temperature (about 25℃) for 30-60 minutes. After the sample cools down, measure the length (L1) and width (W1) of the sample again.

[0114] 4. The thermal shrinkage rate is calculated according to the following formula:

[0115]

[0116] 5. Test results

[0117] Table 2: Longitudinal heat shrinkage

[0118]

[0119] Table 3: Transverse thermal shrinkage

[0120]

[0121] According to the above results and the test data of the longitudinal thermal shrinkage rate and the transverse thermal shrinkage rate, the thermal shrinkage rate of the semiconductor protective film of Example 3 under different temperature conditions is significantly lower than that of Comparative Examples 2-5, indicating that the semiconductor protective film of Example 3 has better performance in terms of stability, can better adapt to the working requirements under different temperature environments, and reduce the performance changes and potential failure risks caused by thermal shrinkage.

[0122] The material of Example 3 showed better performance than the comparative example in terms of heat dissipation performance and thermal shrinkage rate.

[0123] Compared with comparative example 1, embodiment 3 shows that the raw materials of the protective film of the present invention can achieve better heat dissipation performance under specific proportions.

[0124] Compared with Comparative Example 2, Example 3 of the present invention selects silicone grease, carbon fiber, and metal particles in a reasonable ratio as heat dissipation media, which can synergistically improve heat dissipation efficiency, improve thermal cycle stability, and reduce thermal resistance. Silicone grease provides efficient thermal conductivity and electrical isolation functions; carbon fiber provides excellent thermal conductivity and mechanical strength; and metal particles improve electrical conductivity, thermal conductivity, and the hardness and wear resistance of the protective film.

[0125] Compared with Comparative Example 3, the stabilizer made of dibutyltin dilaurate, calcium isooctanoate and boron nitride nanoparticles, dibutyltin dilaurate, can absorb and neutralize harmful substances such as hydrogen chloride generated by thermal decomposition during the processing and use of the semiconductor protective film, inhibit the dehydrochlorination reaction, thereby improving the thermal stability of the semiconductor protective film, and can also coordinate with the active sites in the polymer molecular chain to form a stable complex, thereby limiting the movement and thermal vibration of the molecular chain and reducing the conformational change and thermal shrinkage behavior of the molecular chain when heated; calcium isooctanoate can react with hydrogen chloride to form a stable compound, reducing the effect of hydrogen chloride on the polymer chain. The catalytic degradation of the semiconductor protective film can delay the decomposition and aging process of the semiconductor protective film when heated, improve its long-term thermal stability, and reduce the thermal shrinkage of the semiconductor protective film; Boron nitride nanoparticles have excellent thermal stability and high temperature tolerance. When evenly dispersed in the semiconductor protective film, they can form a physical barrier to hinder the transfer of heat and the movement of molecular chains, reduce the degradation and cross-linking reaction of molecular chains under thermal action, thereby improving the overall thermal stability of the semiconductor protective film and reducing the thermal expansion and thermal contraction of molecular chains caused by heat accumulation; the three together can significantly improve the thermal stability of the semiconductor protective film and prevent thermal degradation and performance degradation at high temperatures.

[0126] Compared with Comparative Example 4, Example 3 shows that adding a stress buffer layer between the functional layer and the anti-corrosion layer can reduce the internal stress generated in the functional layer and the anti-corrosion layer, which has a destructive effect on the two-layer structure, improve the bonding strength and adhesion between the two layers, prevent the occurrence of interlayer separation or peeling, and improve the overall stability of the semiconductor protective film; at the same time, the stress buffer layer can coordinate the thermal expansion difference between the two layers to a certain extent through its lower elastic modulus and higher thermal expansion coefficient, reduce the generation of thermal stress, and improve thermal stability.

[0127] Among them, the combined action of styrene-butadiene-styrene block copolymer, α-silica and α-alumina can more effectively disperse and buffer the stress generated by the semiconductor during coating. The modified α-silica and α-alumina have better thermal stability and can effectively absorb and disperse the stress generated by semiconductor devices under temperature changes or mechanical stress, preventing the impact of thermal damage on semiconductor devices.

[0128] Compared with Comparative Example 5, Example 3 shows that the use of chemical vapor deposition to coat the stress buffer layer in the preparation of the semiconductor protective film can achieve uniform deposition on a complex three-dimensional surface, ensuring uniform coverage of the stress buffer layer to form a coating with good conformality; it can form tight chemical bonding and physical adsorption with the functional layer and the anti-corrosion layer, thereby establishing a good interface bond between the layers. This strong interface bond helps to improve the adhesion and synergy between the layers, reduce the risk of interlayer separation, peeling or interface failure, and ensure the structural integrity and performance stability of the semiconductor protective film during long-term use; chemical vapor deposition coating can accurately control the deposition thickness of the stress buffer layer. By adjusting the deposition parameters (such as reaction gas flow, deposition time, temperature and pressure, etc.), a stress buffer layer with a specific thickness can be prepared, reducing the problem of local shrinkage caused by uneven coating.

[0129] 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 in the scope of protection of the present invention.

Claims

1. A semiconductor protective film, characterized in that: The invention comprises a base layer, a functional layer, a stress buffer layer and an anti-corrosion layer; the base layer comprises the following raw materials in parts by weight: 30-50 parts of vinyl chloride resin, 25-35 parts of polyimide resin, 15-33 parts of phenoxy resin, 12-22 parts of polyethylene terephthalate, 10-20 parts of soybean oil and 12-22 parts of calcium carbonate; the functional layer comprises the following raw materials in parts by weight: 5-10 parts of heat dissipation medium, 12-33 parts of stabilizer and 20-40 parts of plasticizer; the stress buffer layer comprises styrene-butadiene-styrene block copolymer, α-silicon dioxide and α-alumina in a mass ratio of (14-25):(6-10):(2-5); the anti-corrosion layer comprises but is not limited to silicon nitride or silicon oxide; the stabilizer is dibutyltin dilaurate, calcium isooctanoate and boron nitride nanoparticles in a mass ratio of (4-9):(1-3):(8-12).

2. A semiconductor protection film according to claim 1, characterized in that: The base layer includes the following raw materials in parts by weight: 40 parts of vinyl chloride resin, 30 parts of polyimide resin, 25 parts of phenoxy resin, 17 parts of polyethylene terephthalate, 15 parts of soybean oil, and 17 parts of calcium carbonate; the functional layer includes the following raw materials in parts by weight: 8 parts of heat dissipation medium, 25 parts of stabilizer, and 30 parts of plasticizer; the stress buffer layer includes styrene-butadiene-styrene block copolymer, α-silicon dioxide, and α-alumina in a mass ratio of 20:8:3; the anti-corrosion layer includes but is not limited to silicon nitride or silicon oxide.

3. A semiconductor protection film according to claim 1 or 2, characterized in that: The α-silicon dioxide and α-alumina are prepared by dispersing silicon dioxide or aluminum oxide in water, respectively, with a mass-to-volume ratio of g / mL of 10-18:30, and performing ultrasonic dispersion with an ultrasonic power of 500-1000W, a frequency of 15-25kHz, and an ultrasonication time of 20-60min. The obtained dispersion is mixed with a chromate solution with a mass concentration of 50-70%, and the mixture is stirred for 4-6h at a temperature of 12-22°C, with a volume ratio of the dispersion to the chromate solution of 1-3:

1. The mixture is then dried to obtain α-silicon dioxide or α-alumina with a particle size of less than 0.5μm.

4. The semiconductor protection film according to claim 1, wherein: The heat dissipation medium is silicone grease, carbon fiber, and metal particles in a mass ratio of (6-12): (5-10): (3-8). The particle size of the heat dissipation medium is less than 10 μm, and the metal particles are selected from any one of copper, aluminum, nickel, chromium, and tungsten.

5. The semiconductor protection film according to claim 1, wherein: The plasticizer includes but is not limited to dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, dioctyl adipate, and epoxy fatty acid methyl ester.

6. A semiconductor protection film coating process according to claim 1, characterized in that: The following steps are included Step A: Using ultrasonic waves to clean the semiconductor surface to remove contaminants and impurities on the surface of the semiconductor substrate; Step B: mixing the base layer raw materials, spin-coating on the surface of the semiconductor substrate at a rotation speed of 5000-8000 rpm, and drying at 80-120° C. to form a base layer with a thickness of 10-50 μm; Step C: spraying the functional layer raw material on the upper surface of the base layer to form a functional layer with a thickness of 5-20 μm; Step D: sputtering a stress buffer layer material on the functional layer by a vacuum sputtering process to form a stress buffer layer with a thickness of 5-10 μm; Step E: placing the semiconductor substrate with the stress buffer layer formed thereon into a chemical vapor deposition reaction chamber, introducing silane and ammonia or oxygen for deposition to obtain an anti-corrosion layer with a thickness of 3-10 μm; Step F: drying and curing at a temperature of 100-200° C. for 30-60 minutes to obtain a semiconductor protective film.

7. A semiconductor protection film coating process according to claim 6, characterized in that: The spraying gun pressure in step C is 0.2-0.4 MPa, the spraying distance is 15-25 cm, the coating flow rate is 50-100 mL / min, the spray gun speed is 0.1-1 m / s, and the spraying temperature is 15-30°C.

8. The semiconductor protection film coating process according to claim 6, wherein: The parameters of the sputtering process in step D are: sputtering power of 300-500 W, sputtering pressure of 0.1-0.5 Pa, and sputtering time of 25-45 min.

9. The semiconductor protection film coating process according to claim 6, wherein: In the chemical vapor deposition reaction chamber of step E, the radio frequency power is 100-300 W, the temperature is 300-1200° C., the reaction gas pressure is 10-100 Pa, the silane flow rate is 50-100 sccm, and the ammonia or oxygen flow rate is 50-300 sccm.

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