Semiconductor device, epoxy resin and preparation method thereof, packaging material and terminal

Abstract

The present application provides a semiconductor device, which includes a chip and a packaging layer covering the chip, wherein the packaging layer is formed by curing a packaging material; the packaging material includes a fluorine-containing epoxy resin; the chemical structure of the fluorine-containing epoxy resin has the following characteristics: 4 F elements are directly connected to a single benzene ring; two epoxy groups are also connected to the single benzene ring, and one or more CH2 functional groups are also connected between each epoxy group and the benzene ring; the two epoxy groups are located at the ortho, meta or para position of the benzene ring. The present application also provides the fluorine-containing epoxy resin and a preparation method thereof, a packaging material containing the fluorine-containing epoxy resin and a terminal using the semiconductor device. The packaging material has a low dielectric constant and dielectric loss, and has excellent heat resistance, thermomechanical properties, mechanical properties and hydrophobic properties, so that the semiconductor device has excellent performance.

Description

Technical Field

[0001] The present application relates to the semiconductor field, and in particular to a semiconductor device, a fluorine-containing epoxy resin used in the semiconductor device, a preparation method thereof, a packaging material and a terminal. Background Art

[0002] In recent years, with the development of information and communication technology, new technologies such as the Internet of Things (IoT), 5G, and Artificial Intelligence (AI) have brought high-speed, low-latency, large-capacity, and humanized technical elements. The realization of these technical elements requires high-speed and large-capacity signal transmission, so high-frequency bands need to be used, and the transmission of high-frequency signals requires materials to have low dielectric loss characteristics. In information technologies such as IoT, 5G, and Automatic Data Acquisition System (ADAS), a large number of chips, modules, and devices are involved. These modules and devices require packaging materials, antenna materials, bottom fill materials, substrate materials, and transmission materials. These materials all need to have low dielectric and low dielectric loss characteristics. Among them, low dielectric properties are more important for packaging materials and substrate materials.

[0003] After curing, epoxy resin has excellent mechanical strength, bonding performance, dimensional stability, corrosion resistance and heat resistance, so it is widely used in advanced composite matrix, electronic packaging and aerospace fields. The dielectric constant of traditional epoxy resin is about 3.6-4.5, and the water contact angle is less than 90°, which can no longer meet people's demand for low dielectric constant and low water absorption materials. Therefore, the development of high-performance epoxy resin materials to meet the performance requirements in the field of electronic packaging has become a current research hotspot. Reducing the dielectric loss of packaging materials mainly includes the following technical solutions: 1. Reducing the density of polar groups; 2. Reducing the number of polar groups involved in the reaction; 3. Adding Dk and Df polymers; 4. Increasing the content of non-polar inorganic fillers. Among the above solutions, the best technical solution is to use polymers with low dielectric constant and low dielectric loss. For existing packaging materials, such as epoxy molding compounds and epoxy-based resins, the filler content is relatively high, and the curing agent used is mainly relatively mature. Therefore, the use of epoxy resin with low dielectric constant is one of the key technical solutions to reduce the overall dielectric constant of the material. In the formulation design of epoxy molding compound (EMC), substrate (Substrate) and liquid epoxy molding compound (LMC), the use of low-viscosity epoxy resin helps to improve the fluidity of material processing, which is also one of the requirements of packaging materials for epoxy resin properties.

[0004] At present, the main methods for reducing the dielectric constant of epoxy resin compounds mainly include: 1. Blending or co-curing with other low dielectric resins: such as blending or co-curing with polyimide resins and cyanate resins; 2. Studying amine curing agents with low dielectric properties and epoxy curing to reduce the dielectric constant of epoxy resin curing; 3. Reducing the dielectric constant by compounding with inorganic materials with micropores or mesopores, such as cage-shaped silsesquioxanes, mesoporous silica, montmorillonite, hollow glass microspheres, etc. The above-mentioned technical routes for reducing the dielectric constant have their own advantages and disadvantages, which are different dimensions and can also be a symbiotic relationship. Among them, epoxy resins with low viscosity, low dielectric, high hydrophobicity and certain flexibility have comprehensive performance advantages in formula design for underfill, EMC, substrate and LMC. Summary of the invention

[0005] The embodiment of the present application provides a semiconductor device, in which the packaging layer covering the chip has a low dielectric constant; is hydrophobic and has a low water absorption rate; has low internal stress and a flexible chain segment molecular structure; is high strength, and the main molecule has a certain rigidity, thereby improving the performance of the semiconductor device.

[0006] A first aspect of an embodiment of the present application provides a semiconductor device, comprising:

[0007] Chips; and

[0008] A packaging layer covering the chip, wherein the packaging layer is formed by curing a packaging material;

[0009] The packaging material includes a fluorine-containing epoxy resin; the chemical structure of the fluorine-containing epoxy resin has the following characteristics: four F elements are directly connected to a single benzene ring; two epoxy groups are also connected to the single benzene ring, and one or more CH 2 Functional group; the two epoxy groups are located at the ortho, meta or para position of the benzene ring.

[0010] The packaging material of the packaging layer has low dielectric constant, hydrophobicity, low water absorption, low internal stress, flexible segment molecular structure, high strength, and main molecule has certain rigidity due to the introduction of the fluorine-containing epoxy resin.

[0011] In the embodiment of the present application, the chemical structural formula of the fluorine-containing epoxy resin is at least one of the following (1), (2), and (3):

[0012]

[0013] Wherein, 5≥n≥1, and the substituent R is a F atom.

[0014] In the embodiment of the present application, the viscosity of the fluorine-containing epoxy resin is less than or equal to 500 mPa·S.

[0015] In the implementation manner of the present application, the packaging material further includes:

[0016] anhydride curing agent; and

[0017] Accelerators;

[0018] Wherein, the weight ratio of the fluorine-containing epoxy resin, the acid anhydride curing agent, and the accelerator is 1:(0.1-1.4):(0.02-0.2), and the above range value includes the end value.

[0019] In the embodiment of the present application, the acid anhydride curing agent is at least one of methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, alkylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, succinic anhydride, methylnadic anhydride, 5-norbornene-2,3-dianhydride, and trialkyltetrahydrophthalic anhydride.

[0020] In the embodiment of the present application, the accelerator is at least one of an imidazole series accelerator, an amine series accelerator and a microcapsule latent accelerator.

[0021] In the embodiment of the present application, an inorganic filler is further added to the packaging material, and the inorganic filler is at least one of silicon dioxide and aluminum oxide.

[0022] In the embodiment of the present application, at least one of a fluorine-free epoxy resin, a toughening agent, carbon black, and an auxiliary agent is further added to the packaging material; in the packaging material, the weight ratio of the fluorine-containing epoxy resin, the acid anhydride curing agent, the accelerator, the inorganic filler, the fluorine-free epoxy resin, the toughening agent, the carbon black, and the auxiliary agent is 1: (0.1-1.4): (0.02-0.2): (0-1.5): (0-1): (0-0.5): (0-0.3): (0-0.08), wherein the above range values ​​can all be end values.

[0023] In the embodiment of the present application, the fluorine-free epoxy resin is a bisphenol epoxy resin.

[0024] In the embodiment of the present application, the auxiliary agent includes at least one of a silane coupling agent, a defoaming agent, a leveling agent, a wetting and dispersing agent, and an ion capture agent.

[0025] In the embodiment of the present application, the toughening agent is rubber particles.

[0026] In the embodiment of the present application, the dielectric constant of the packaging material is less than or equal to 3.3, the water contact angle is above 100°, and the glass transition temperature is 100-140°C.

[0027] The second aspect of the embodiment of the present application provides a fluorine-containing epoxy resin, wherein the chemical structure of the fluorine-containing epoxy resin has the following characteristics: four F elements are directly connected to a single benzene ring; two epoxy groups are also connected to the single benzene ring, and one or more CH 2 Functional group; the two epoxy groups are located at the ortho, meta or para position of the benzene ring.

[0028] The fluorinated epoxy resin has low viscosity and low dielectric constant.

[0029] In the embodiment of the present application, the chemical structural formula of the fluorine-containing epoxy resin is at least one of the following (1), (2), and (3):

[0030]

[0031] Wherein, 5≥n≥1, and the substituent R is a F atom.

[0032] In the embodiment of the present application, the viscosity of the fluorine-containing epoxy resin is less than or equal to 500 mPa·S.

[0033] The third aspect of the embodiment of the present application provides a method for preparing a fluorine-containing epoxy resin, which comprises: using a tetrafluorobenzene substance containing an alcoholic hydroxyl group and epichlorohydrin as reactants, adding a solid base and a quaternary ammonium salt as catalysts, and reacting at 40 to 80° C. for 0.5 to 5 hours; wherein the weight ratio of the tetrafluorobenzene substance containing an alcoholic hydroxyl group, epichlorohydrin, the quaternary ammonium salt and the solid base is 1: (1 to 10): (0.001 to 0.05): (0.5 to 3).

[0034] The preparation method of the fluorine-containing epoxy resin has few reaction steps and only requires one chemical reaction. It does not require complex equipment and has a simple process. At the same time, the reaction efficiency is high. By grafting epoxy functional groups with alcohol hydroxyl groups, the epoxy value can reach 90-95%, which is 70% higher than the existing yield of alcohol hydroxyl synthesized epoxy in the industry.

[0035] In the embodiment of the present application, the quaternary ammonium salt is at least one of tetramethylammonium bromide, tetrabutylammonium bromide, tetramethylammonium chloride, tetrabutylammonium chloride, hexadecylammonium bromide and hexadecyltrimethylammonium chloride.

[0036] In an embodiment of the present application, the solid base is at least one of sodium hydroxide and potassium hydroxide.

[0037] A fourth aspect of the embodiments of the present application provides a packaging material, which includes:

[0038] Fluorinated epoxy resin;

[0039] anhydride curing agent; and

[0040] Accelerators;

[0041] Wherein, the weight ratio of the fluorine-containing epoxy resin, the acid anhydride curing agent, and the accelerator is 1: (0.1-1.4): (0.02-0.2), and the above range value includes the end value;

[0042] The chemical structure of the fluorine-containing epoxy resin has the following characteristics: four F elements are directly connected to a single benzene ring; two epoxy groups are also connected to the single benzene ring, and one or more CH 2 Functional group; the two epoxy groups are located at the ortho, meta or para position of the benzene ring.

[0043] The fluorinated epoxy resin added to the packaging material has the following advantages: the dielectric constant of the fluorinated epoxy resin is low, which can improve and reduce the dielectric constant of the entire packaging material; the viscosity of the fluorinated epoxy resin is low, which can improve the processing fluidity of the packaging material; there are one or more CH 2 The functional group is connected to the hydroxyl group, which has better flexibility, thereby improving the flexibility of the packaging material, lowering the glass transition temperature and modulus, and reducing internal stress; the introduction of the fluorine-containing group of the above-mentioned fluorine-containing epoxy resin will improve the hydrophobic properties of the packaging material and reduce the water absorption rate of the packaging material.

[0044] In the embodiment of the present application, the chemical structural formula of the fluorine-containing epoxy resin is at least one of the following (1), (2), and (3):

[0045]

[0046]

[0047] Wherein, 5≥n≥1, and the substituent R is a F atom.

[0048] In the embodiment of the present application, the acid anhydride curing agent is at least one of methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, alkylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, succinic anhydride, methylnadic anhydride, 5-norbornene-2,3-dianhydride, and trialkyltetrahydrophthalic anhydride.

[0049] In the embodiment of the present application, the accelerator is at least one of an imidazole series accelerator, an amine series accelerator and a microcapsule latent accelerator.

[0050] In the embodiment of the present application, an inorganic filler is further added to the packaging material, and the inorganic filler is at least one of silicon dioxide and aluminum oxide.

[0051] In the embodiment of the present application, at least one of a fluorine-free epoxy resin, a toughening agent, carbon black, and an auxiliary agent is further added to the packaging material; in the packaging material, the weight ratio of the fluorine-containing epoxy resin, the acid anhydride curing agent, the accelerator, the inorganic filler, the fluorine-free epoxy resin, the toughening agent, the carbon black, and the auxiliary agent is 1: (0.1-1.4): (0.02-0.2): (0-1.5): (0-1): (0-0.5): (0-0.3): (0-0.08), wherein the above range values ​​can all be end values.

[0052] In the embodiment of the present application, the fluorine-free epoxy resin is a bisphenol epoxy resin.

[0053] In the embodiment of the present application, the auxiliary agent includes at least one of a silane coupling agent, a defoaming agent, a leveling agent, a wetting and dispersing agent, and an ion capture agent.

[0054] In the embodiment of the present application, the toughening agent is rubber particles.

[0055] In the embodiment of the present application, the dielectric constant of the packaging material is less than or equal to 3.3, the water contact angle is above 100°, and the glass transition temperature is 100-140°C.

[0056] A fifth aspect of an embodiment of the present application provides a terminal, which includes a shell and a semiconductor device accommodated in the shell, and the semiconductor device includes the semiconductor device described in the first aspect of the present application.

[0057] The above-mentioned packaging material has low dielectric constant and dielectric loss, and has excellent heat resistance, thermomechanical properties, mechanical properties and hydrophobic properties, so that the semiconductor device has excellent performance.

[0058] Adding the special fluorine-containing epoxy resin to the packaging material of the semiconductor device provided in the embodiment of the present application can improve and reduce the overall dielectric constant of the packaging material, improve the processing fluidity of the packaging material, improve the flexibility of the packaging material, reduce the glass transition temperature and modulus, reduce internal stress; improve the hydrophobic properties, and reduce the water absorption rate of the packaging material; thereby improving the performance of the semiconductor device. BRIEF DESCRIPTION OF THE DRAWINGS

[0059] Figure 1 It is a schematic diagram of the cross-sectional structure of the semiconductor device according to an embodiment of the present application.

[0060] Figure 2 It is the infrared spectrum of the epoxy resin FEP of the embodiment of the present application.

[0061] Figure 3 (a) and (b) are the NMR spectra of the epoxy resin FEP of the examples of the present application.

[0062] Figure 4 This is a diagram of the thermal mechanical properties of the epoxy resin FEP after curing according to an embodiment of the present application.

[0063] Figure 5 This is a diagram of the dielectric properties of the epoxy resin FEP after curing according to an embodiment of the present application.

[0064] Main component symbols

[0065] Semiconductor device 100

[0066] Chip 10

[0067] Encapsulation layer 30

[0068] DETAILED DESCRIPTION OF THE EMBODIMENTS The present invention will be further described in conjunction with the above-mentioned drawings. DETAILED DESCRIPTION

[0069] The embodiments of the present application are described below in conjunction with the drawings in the embodiments of the present application.

[0070] The semiconductor device 100 involved in the embodiment of the present application is as follows: Figure 1 As shown, in this embodiment, the semiconductor device 100 is a chip packaging structure, and the semiconductor device 100 includes a chip 10 and a packaging layer 30 covering / encapsulating the chip 10. The chip 10 may be a silicon-based chip. The packaging layer 30 covering / encapsulating the chip 10 is generally required to have electrical, mechanical, and thermal performance requirements. For example, it is required to have a low dielectric constant; be hydrophobic and have low water absorption; have low internal stress and a flexible segment molecular structure; have high strength, and the main molecule has a certain rigidity. The packaging layer 30 is formed by curing the packaging material, that is, it is the product after the packaging material is cured. The packaging material is generally cured by thermal curing (above 90 degrees Celsius).

[0071] In order to achieve the above requirements of the encapsulation layer 30, an embodiment of the present application provides an encapsulation material, which includes a fluorine-containing epoxy resin. The chemical structure of the fluorine-containing epoxy resin has the following characteristics: four F elements are directly connected to a single benzene ring; two epoxy groups are also connected to the single benzene ring, and one or more CH 2 Functional groups, so that the fluorine-containing epoxy resin has better flexibility; the two epoxy groups are located at the ortho position, meta position or para position of the benzene ring.

[0072] The packaging material also includes an anhydride curing agent and an accelerator. The weight ratio of the fluorine-containing epoxy resin, the anhydride curing agent, and the accelerator is 1: (0.1-1.4): (0.02-0.2), and the above range value includes the end value.

[0073] In the embodiment of the present application, the chemical structural formula of the fluorine-containing epoxy resin is at least one of the following (1), (2), and (3):

[0074]

[0075]

[0076] Among them, 5≥n≥1, and the substituent R is F.

[0077] The fluorine-containing epoxy resin itself has a low viscosity, less than or equal to 500mPa·s, while the viscosity of other fluorine-containing resins is usually above 2000mPa·s. Compared with fluorine-free epoxy resins, the dielectric constant of the fluorine-containing epoxy resin can be reduced by 20% to 30% compared with the dielectric constant of fluorine-free epoxy resins.

[0078] The preparation of the packaging material is to mix the above components, grind, stir and vacuum centrifuge to degas. When the packaging material is actually used, for example, when encapsulating a chip, it is necessary to heat and cure the packaging material (for example, above 90°C); during the heating and curing process, the accelerator promotes the curing reaction between the acid anhydride curing agent and the fluorine-containing epoxy resin, and the accelerator will react with the fluorine-containing epoxy resin, and the acid anhydride curing agent will also react with the fluorine-containing epoxy resin. If the accelerator is not added, it is difficult for the acid anhydride curing agent to react with the fluorine-containing epoxy resin, or the reaction requires an extremely high temperature.

[0079] The packaging material can be used in the field of semiconductor packaging, such as chip packaging. The packaging material can be used as chip-level bottom filling glue (Capillary Underfill Material, CUF), chip-level molded underfill material (Molded Underfill Material, MUF), epoxy molding compound (Epoxy Molding Compound, EMC), liquid epoxy molding compound (Liquid Molding Underfill, LMC), epoxy thermal curing film (Die Attach Film, DAF), etc.

[0080] The anhydride curing agent can be at least one of methylhexahydrophthalic anhydride (MeHHPA), hexahydrophthalic anhydride, alkylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, succinic anhydride, methylnadic anhydride, 5-norbornene-2,3-dianhydride, and trialkyltetrahydrophthalic anhydride.

[0081] The accelerator is at least one of an imidazole series accelerator, an amine series accelerator and a microcapsule latent accelerator; for example, DMP-30.

[0082] Imidazole curing agents are five-membered rings containing two nitrogen atoms, one nitrogen atom constituting a secondary amine and the other nitrogen atom constituting a tertiary amine. They can utilize the active hydrogen of the secondary amine group to undergo an addition reaction on epoxy resins, and can also use the tertiary nitrogen atom to cure epoxy resins as an anionic polymerization curing agent, just like tertiary amines.

[0083] Amine accelerators are nucleophilic accelerators. For amine-cured epoxy resins, they only catalyze the curing agent and react anion etherification through the hydroxyl groups in the system. For anhydride-cured epoxy resins, they have a dual catalytic effect, catalyzing both anhydride and epoxy resin. Active hydrogen-containing compounds such as phenol, acid, alcohol, and water can accelerate the reaction, and finally form two cross-linked networks of polyether and polyester. Amine accelerators have strong catalytic activity for epoxy resins. The stronger the alkalinity, the smaller the substituent, and the greater the dialogue activity. Commonly used amine accelerators: DMP-30, HDG-A / B epoxy resin curing accelerator, tertiary amine accelerators (triethylamine, triethanolamine, BMDA, DBU, DMP-10, pyridine), quaternary ammonium salt accelerators, fatty amine accelerators (only have a promoting effect on low molecular weight polyamides).

[0084] Adding the above-mentioned fluorine-containing epoxy resin to the packaging material has the following advantages:

[0085] The above-mentioned fluorine-containing epoxy resin has a low dielectric constant, which can improve and reduce the overall dielectric constant of the packaging material;

[0086] The above-mentioned fluorine-containing epoxy resin has low viscosity, which can improve the processing fluidity of the packaging material;

[0087] There is one or more CH between the epoxy group and the benzene ring of the above-mentioned fluorinated epoxy resin. 2 The functional group is connected to the hydroxyl group, which has good flexibility, thus improving the flexibility of the packaging material, reducing the glass transition temperature and modulus, and improving the modulus of EMC or LCM type packaging, reducing internal stress;

[0088] The introduction of the fluorine-containing groups in the fluorine-containing epoxy resin mentioned above will improve the hydrophobic properties of the packaging material and reduce the water absorption rate of the packaging material.

[0089] The packaging material may also selectively add at least one of inorganic fillers, fluorine-free epoxy resin, toughening agent, carbon black, and auxiliary agents as needed. Among them, selectively adding at least one of fluorine-free epoxy resin, toughening agent, carbon black, and auxiliary agents can further improve the overall performance of the packaging material.

[0090] In the packaging material, the weight ratio of the fluorine-containing epoxy resin, anhydride curing agent, accelerator, inorganic filler, fluorine-free epoxy resin, toughening agent, carbon black and auxiliary agent is 1: (0.1-1.4): (0.02-0.2): (0-1.5): (0-1): (0-0.5): (0-0.3): (0-0.08), and the above range values ​​can all be end values.

[0091] In some embodiments, the weight ratio of the fluorine-containing epoxy resin, anhydride curing agent, accelerator, inorganic filler, fluorine-free epoxy resin, toughening agent, carbon black, and additives is 1: (1-1.2): (0.05-0.06): (1-1.3): 0.8: (0.2-0.3): (0.2-0.3): (0.03-0.04), and the above range values ​​can all be end values.

[0092] The inorganic filler can be at least one of silicon dioxide and aluminum oxide, for example, fused spherical silicon dioxide with a sphericity of 98% and a particle size distribution between 200nm and 2μm. The addition of the inorganic filler can improve the mechanical properties of the packaging material and reduce the cost of the packaging material.

[0093] The fluorine-free epoxy resin may be a bisphenol epoxy resin, such as bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol AD ​​epoxy resin, bisphenol S epoxy resin, or bisphenol fluorene epoxy resin.

[0094] The toughening agent can improve the toughness of the packaging material. The toughening agent is a rubber particle, such as styrene-butadiene rubber (SBR), nitrile-butadiene rubber (NBR), butadiene (BR), urethane rubber (UR), acrylic rubber (AR), core-shell particles, silicone rubber, etc., or a mixture of several thereof.

[0095] The auxiliary agent includes at least one of a silane coupling agent, a defoaming agent, a leveling agent, a wetting and dispersing agent, and an ion capture agent.

[0096] The dielectric constant of the packaging material is less than or equal to 3.3, has hydrophobic properties (water contact angle is above 100°), and the glass transition temperature (Tg) is 100-140°C. The glass transition temperature (Tg) refers to the temperature corresponding to the transition from the glass state to the highly elastic state. The glass transition temperature (Tg) is the lowest temperature at which the molecular chain segments can move, and its level is directly related to the flexibility of the molecular chain. The greater the flexibility of the molecular chain, the lower the glass transition temperature; the greater the rigidity of the molecular chain, the higher the glass transition temperature.

[0097] In some embodiments, the formula design of the low dielectric packaging material LCM is as follows: the fluorinated aromatic epoxy resin (FEP) containing para-tetrafluorophenyl prepared according to the above steps, the acid anhydride curing agent, the tertiary amine accelerator, and the inorganic filler are uniformly mixed in a weight ratio of 1: (0.95-1.05): (0.05-0.1): (1-1.2). The acid anhydride curing agent is methyl hexahydrophthalic anhydride (MeHHPA), the tertiary amine accelerator is DMP-30, and the inorganic filler is silica powder.

[0098] Since FEP has extremely low room temperature viscosity, the mixture can be directly applied to the surface of various metal or ceramic substrates to be bonded, and a pressure of 0.5-2MPa is applied to make the bonding position fully contact, and the excess colloid is removed for thermal curing. The thermal curing process is pre-curing at 90-130°C for 1-4h, post-curing at 120-150°C for 2-4h, and the final bonding device can be obtained by naturally cooling after the curing is completed. The mixture can also be applied to various metal / ceramic substrates as a coating, and can also be directly cured into various forms of composite materials.

[0099] In the embodiment of the present application, the preparation method of the fluorine-containing epoxy resin is as follows: a tetrafluorobenzene substance containing an alcoholic hydroxyl group and epichlorohydrin (organic solvent) are used as reaction products, a solid base and a quaternary ammonium salt are added as catalysts, and the reaction is carried out at 40 to 80° C. for 0.5 to 5 hours to obtain the desired fluorine-containing epoxy resin, wherein the weight ratio of the tetrafluorobenzene substance containing an alcoholic hydroxyl group, epichlorohydrin, quaternary ammonium salt, and solid base is 1: (1 to 10): (0.001 to 0.05): (0.5 to 3).

[0100] The quaternary ammonium salt may be at least one of tetramethylammonium bromide, tetrabutylammonium bromide, tetramethylammonium chloride, tetrabutylammonium chloride, hexadecylammonium bromide and hexadecyltrimethylammonium chloride. The solid base may be at least one of sodium hydroxide and potassium hydroxide.

[0101] The preparation method of the fluorine-containing epoxy resin adopts quaternary ammonium salt and solid base as catalysts, has few reaction steps, only needs one chemical reaction, does not require complex equipment, has a simple process, and has high reaction efficiency. By grafting epoxy functional groups with alcohol hydroxyl groups, the epoxy value can reach 90-95%, which is higher than the 70% yield of epoxy synthesized by alcohol hydroxyl groups in the industry.

[0102] In some embodiments, the tetrafluorobenzene substance containing alcoholic hydroxyl group is 2,3,5,6-tetrafluorophenylene glycol, the solid base is sodium hydroxide, and the quaternary ammonium salt is tetramethylammonium bromide. The raw materials are prepared by a one-step method according to the weight ratio of 2,3,5,6-tetrafluorophenylene glycol, epichlorohydrin, tetramethylammonium bromide, and sodium hydroxide of 1:(4-5):(0.02-0.03):(0.5-0.7). The reaction temperature is maintained at 60-70°C. After the reaction is carried out under the protection of high-purity nitrogen for 2.5 hours, the lower clear liquid is filtered out, washed with deionized water to a neutral pH, and vacuum dried to obtain a high-purity fluorinated aromatic epoxy resin (FEP), and the epoxidation rate of FEP is 90-95%.

[0103] The chemical reaction formula for synthesizing FEP is as follows:

[0104]

[0105] The technical solution of the embodiment of the present application is further illustrated by means of specific examples below.

[0106] (1) Preparation of fluorinated epoxy resin (FEP): Add raw materials into a 500 ml three-necked flask, wherein the raw materials are 22 g of 2,3,5,6-tetrafluorophenylenediol, 100 g of epichlorohydrin, 0.5 g of tetramethylammonium bromide, and 15 g of sodium hydroxide. The reaction temperature is maintained at 60-70° C. The reaction is carried out under the protection of high-purity nitrogen for 2.5 hours, and the lower clear liquid is filtered out. The liquid is washed with deionized water until the pH is neutral, and vacuum dried to obtain a high-purity fluorinated aromatic epoxy resin FEP.

[0107] (2) Preparation of packaging materials: 10 g of fluorinated aromatic epoxy resin monomer (FEP), 9.2 g of curing agent methylhexahydrophthalic anhydride (MeHHPA) and 0.05 g of accelerator DMP-30 were mixed and stirred at room temperature; poured into a mold placed in a blast oven preheated to 70-90°C, pre-cured for 1-4 h, post-cured at 120-150°C for 2-4 h, and naturally cooled after curing to obtain the final packaging material.

[0108] The packaging material can also be applied on various metal or ceramic substrates as a coating, or can be directly cured into various forms of composite materials.

[0109] See also Figure 2 , the infrared spectrum of the epoxy resin FEP in the embodiment of the present application, the wave number is 903cm -1 Department Figure 2 The characteristic peak (indicated by the dotted line) is the characteristic peak of the epoxy group, indicating that the prepared FEP contains epoxy groups.

[0110] See also Figure 3 , the NMR spectrum of the embodiment of the present application, wherein Figure 3 (a) is the hydrogen spectrum, Figure 3 (b) is the carbon spectrum. Chemical shift: The absorption peaks of the same nucleus at different resonant magnetic induction intensities due to different chemical environments in the molecule. Figure 3 The characteristic peaks shown in correspond to the annotated molecular structures; for example Figure 3 The absorption peaks marked as 1, 2, 3, and 4 in (a) correspond to Figure 3 (a) The 1, 2, 3, and 4 cases of hydrogen (H) in the chemical structure in the upper left corner; Figure 3 The absorption peaks marked as 1, 2, 3, 4, 5, 6, and 7 in (b) correspond to Figure 3 (b) The chemical structure in the upper left corner shows the number of carbon atoms (C) 1, 2, 3, 4, 5, 6, and 7.

[0111] Figure 4 This is the thermomechanical performance diagram of the epoxy resin FEP after curing in the embodiment of the present application. The storage modulus is also called the elastic modulus, which refers to the amount of energy stored in the material due to elastic (reversible) deformation when the material is deformed, reflecting the elasticity of the material; the loss modulus is also called the viscous modulus, which refers to the amount of energy lost due to viscous deformation (irreversible) when the material is deformed, reflecting the viscosity of the material; the loss angle, the ratio of the loss modulus to the storage modulus, reflects the vibration absorption, also known as the vibration absorption factor. It can be seen that the glass transition temperature of the epoxy resin FEP is 117.5°C.

[0112] Figure 5 This is a graph of the dielectric properties of the epoxy resin FEP after curing according to an embodiment of the present application. At 1 MHz, the dielectric constant is 3.14 and the dielectric loss is 0.019.

[0113] The specific performance parameters of the epoxy resin FEP in the embodiment of the present application are shown in Table 1.

[0114] Table 1

[0115]

[0116] The epoxy resin FEP of the embodiment of the present application and several existing epoxy resins with different structures were cured with the same curing agent MeHHPA, and the glass transition temperature Tg, dielectric constant, dielectric loss, contact angle, and mechanical properties of the cured material were tested. The specific test results are shown in Table 2.

[0117] Table 2

[0118]

[0119] It can be seen from Table 2 that the product after curing of epoxy resin FEP and curing agent has a lower glass transition temperature, indicating that its molecular chain is highly flexible, has a lower dielectric constant and dielectric loss, is hydrophobic, and has good mechanical properties.

[0120] The packaging material prepared with low-viscosity FEP as the base resin in the embodiment of the present application has good fluidity, low dielectric, mechanical properties, durability and hydrophobic properties; the fluorinated aromatic epoxy resin / anhydride cured product can break through the bottleneck and has a lower dielectric constant and dielectric loss, and stronger mechanical properties and hydrophobicity, thereby reducing heat generation and loss, and has the potential to be applied in electronic packaging and other fields; the fluidity of the epoxy resin is improved, the intrinsic mechanical properties are 70 to 75 MPa, and the dielectric properties are a dielectric constant of 3.14 at 1 MHz.

[0121] The preparation process of FEP in the embodiment of the present application is simple, requiring only a one-step method, without the need for complex equipment, and having a simple process and an epoxy yield of more than 90%, which is green and environmentally friendly; FEP crystallizes at low temperatures, has low viscosity after melting at 33°C, and has a room temperature viscosity as low as 143 mPa·s, having good storage stability and processing usability; the room temperature refers to 25±5°C.

[0122] The embodiment of the present application also provides a terminal (not shown), which may be a mobile phone, or a tablet computer, a laptop computer, a portable device, a smart wearable product, or other electronic product, including a housing (not shown) and the semiconductor device 100 contained in the housing.

[0123] It should be noted that the above are only specific implementations of the present application, but the protection scope of the present application is not limited thereto. Any technician familiar with the technical field can easily think of changes or substitutions within the technical scope disclosed in the present application, which should be included in the protection scope of the present application; the implementation methods of the present application and the features in the implementation methods can be combined with each other without conflict. Therefore, the protection scope of the present application shall be based on the protection scope of the claims.

Claims

1. A semiconductor device, comprising: chip; as well as A packaging layer covering the chip, wherein the packaging layer is formed by curing a packaging material; Characterized in that the packaging material includes fluorine-containing epoxy resin; The chemical structure of the fluorine-containing epoxy resin has the following characteristics: four F elements are directly connected to a single benzene ring; two epoxy groups are also connected to the single benzene ring, and one or more CH2 functional groups are connected between each epoxy group and the benzene ring; the two epoxy groups are located at the ortho, meta or para position of the benzene ring.

2. The semiconductor device according to claim 1, wherein The chemical structural formula of the fluorine-containing epoxy resin is at least one of the following (1), (2), and (3): （1） （2） （3） Wherein, 5≥n≥1, and the substituent R is a F atom.

3. The semiconductor device according to claim 2, characterized in that The viscosity of the fluorine-containing epoxy resin is less than or equal to 500 mPa·S.

4. The semiconductor device according to claim 1, wherein The packaging material also includes: anhydride curing agent; and Accelerators; Wherein, the weight ratio of the fluorine-containing epoxy resin, the acid anhydride curing agent, and the accelerator is 1: (0.1-1.4): (0.02-0.2), and the above range value includes the end value.

5. The semiconductor device according to claim 4, characterized in that The acid anhydride curing agent is at least one of methyl hexahydrophthalic anhydride, hexahydrophthalic anhydride, alkyl hexahydrophthalic anhydride, tetrahydrophthalic anhydride, succinic anhydride, methyl nadic anhydride, 5-norbornene-2,3-dianhydride and trialkyltetrahydrophthalic anhydride.

6. The semiconductor device according to claim 4, characterized in that The accelerator is at least one of an imidazole series accelerator, an amine series accelerator and a microcapsule latent accelerator.

7. The semiconductor device according to claim 4, characterized in that Inorganic filler is also added into the packaging material, and the inorganic filler is at least one of silicon dioxide and aluminum oxide.

8. The semiconductor device according to claim 7, characterized in that The packaging material also contains at least one of a fluorine-free epoxy resin, a toughening agent, carbon black, and an auxiliary agent; in the packaging material, the weight ratio of the fluorine-containing epoxy resin, the acid anhydride curing agent, the accelerator, the inorganic filler, the fluorine-free epoxy resin, the toughening agent, the carbon black, and the auxiliary agent is 1: (0.1-1.4): (0.02-0.2): (0-1.5): (0-1): (0-0.5): (0-0.3): (0-0.08), wherein the above range values ​​can all be end values.

9. The semiconductor device according to claim 8, characterized in that The fluorine-free epoxy resin is a bisphenol epoxy resin.

10. The semiconductor device according to claim 8, characterized in that The auxiliary agent includes at least one of a silane coupling agent, a defoaming agent, a leveling agent, a wetting and dispersing agent, and an ion capture agent.

11. The semiconductor device according to claim 8, characterized in that The toughening agent is rubber particles.

12. The semiconductor device according to claim 1, wherein: The dielectric constant of the packaging material is less than or equal to 3.3, the water contact angle is above 100°, and the glass transition temperature is 100-140°C.

13. A packaging material, characterized in that: The packaging materials include: Fluorinated epoxy resin; anhydride curing agent; and Accelerators; Wherein, the weight ratio of the fluorine-containing epoxy resin, the acid anhydride curing agent, and the accelerator is 1: (0.1-1.4): (0.02-0.2), and the above range value includes the end value; The chemical structure of the fluorine-containing epoxy resin has the following characteristics: four F elements are directly connected to a single benzene ring; two epoxy groups are also connected to the single benzene ring, and one or more CH2 functional groups are connected between each epoxy group and the benzene ring; the two epoxy groups are located at the ortho, meta or para position of the benzene ring.

14. The packaging material according to claim 13, characterized in that The chemical structural formula of the fluorine-containing epoxy resin is at least one of the following (1), (2), and (3): （1） （2） （3） Wherein, 5≥n≥1, and the substituent R is a F atom.

15. The packaging material according to claim 13, characterized in that: The acid anhydride curing agent is at least one of methyl hexahydrophthalic anhydride, hexahydrophthalic anhydride, alkyl hexahydrophthalic anhydride, tetrahydrophthalic anhydride, succinic anhydride, methyl nadic anhydride, 5-norbornene-2,3-dianhydride and trialkyltetrahydrophthalic anhydride.

16. The packaging material according to claim 13, characterized in that: The accelerator is at least one of an imidazole series accelerator, an amine series accelerator and a microcapsule latent accelerator.

17. The packaging material according to claim 13, characterized in that: Inorganic filler is also added into the packaging material, and the inorganic filler is at least one of silicon dioxide and aluminum oxide.

18. The packaging material according to claim 17, characterized in that The packaging material also contains at least one of a fluorine-free epoxy resin, a toughening agent, carbon black, and an auxiliary agent; in the packaging material, the weight ratio of the fluorine-containing epoxy resin, the acid anhydride curing agent, the accelerator, the inorganic filler, the fluorine-free epoxy resin, the toughening agent, the carbon black, and the auxiliary agent is 1: (0.1-1.4): (0.02-0.2): (0-1.5): (0-1): (0-0.5): (0-0.3): (0-0.08), wherein the above range values ​​can all be end values.

19. The packaging material according to claim 18, characterized in that The fluorine-free epoxy resin is a bisphenol epoxy resin.

20. The packaging material according to claim 18, characterized in that The auxiliary agent includes at least one of a silane coupling agent, a defoaming agent, a leveling agent, a wetting and dispersing agent, and an ion capture agent.

21. The packaging material according to claim 18, characterized in that The toughening agent is rubber particles.

22. The packaging material according to claim 13, characterized in that The dielectric constant of the packaging material is less than or equal to 3.3, the water contact angle is above 100°, and the glass transition temperature is 100-140°C.

23. A terminal, characterized in that: It comprises a shell and a semiconductor device accommodated in the shell, wherein the semiconductor device comprises the semiconductor device according to any one of claims 1 to 12.

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