Photosensitive composition and application thereof

Abstract

The embodiment of the invention provides a light-sensitive composition and application thereof. The photoinitiator, the crosslinkable monomer thermal crosslinking agent, the silane coupling agent and the filler are simultaneously introduced into the light-sensitive composition, and the relationship of the amount of active functional groups of specific substances is controlled within a certain range, so that the light-sensitive composition can realize higher and more appropriate crosslinking density after light crosslinking and thermal crosslinking; the reinforcing effect of the filler is excellent, so that the light-sensitive composition or a cured product of a light-sensitive film prepared from the light-sensitive composition can have relatively high film retention rate, relatively excellent mechanical property and good chemical resistance; the photosensitive composition can be used for manufacturing semiconductor devices, and the production reliability and the product yield of the semiconductor devices are improved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of light-sensing materials, in particular to a light-sensing composition and application thereof. BACKGROUND

[0002] The light-sensing composition and the light-sensing film prepared therefrom are prone to problems such as insufficient pressure resistance, low resolution, insufficient chemical resistance, and poor processability. For the light-sensing composition exhibiting low elastic modulus and low pressure resistance after curing, simply increasing the proportion of fillers can easily lead to problems such as poor resolution and insufficient curing of the composition, resulting in defects such as powder falling off after curing, affecting the subsequent application of the composition in devices and the reliability of the devices. Although the selection of resin structures can affect the resolution and physical and chemical properties of the light-sensing composition, the composition still has disadvantages such as low elastic modulus after curing, low film retention rate after development, and poor chemical resistance. SUMMARY

[0003] In view of this, the present application provides a light-sensing composition and application thereof. The light-sensing composition can achieve a relatively high and appropriate crosslinking density after photo-crosslinking and thermal-crosslinking, and the reinforcing effect of the fillers is relatively good. The cured product of the light-sensing composition or the light-sensing film prepared therefrom can have relatively high film retention rate, relatively good mechanical properties, and good chemical resistance.

[0004] The first aspect of the present application provides a light-sensing composition, comprising a soluble resin, a crosslinkable monomer, a filler, a silane coupling agent, a photoinitiator, and a thermal crosslinking agent. The soluble resin comprises one or more of a polymer having a repeating imide ring in the main chain, a polymer having a repeating amide bond and an ester bond in the main chain, and a polymer having a repeating amide bond in the main chain; and / or, the soluble resin comprises a polymer having a repeating first structure in the main chain, the first structure comprising a plurality of structures consisting of an amide bond and an ester bond, an imide ring, and an amide bond; the crosslinkable monomer comprises a first active functional group, the silane coupling agent comprises a second active functional group, and the thermal crosslinking agent comprises a third active functional group; the first active functional group, the second active functional group, and the third active functional group can chemically react with each other, and at least one of the first active functional group, the second active functional group, and the third active functional group can chemically react with the soluble resin; in the light-sensing composition, the molar amount of the first active functional group is A mol, the molar amount of the second active functional group is B mol, and the molar amount of the third active functional group is C mol. The light-sensing composition satisfies 0.05≤C / (A+B)≤5.

[0005] The light-sensitive composition provided by the embodiments of the present application has good dispersibility of the filler in combination with the silane coupling agent, can improve the transparency of the light-sensitive film, effectively reduce the loss of photosensitivity of the composition caused by the difference in refractive index between the filler and other components in the system, is conducive to the photocuring of the composition and the light-sensitive film, and can maintain a high film-forming level of the light-sensitive composition. Meanwhile, the introduction of the photoinitiator, the cross-linkable monomer and the thermal cross-linking agent can enable the composition and the light-sensitive film to be fully photocured and thermally cured, and more importantly, the active functional groups of the cross-linkable monomer, the thermal cross-linking agent and the silane coupling agent can be controlled to undergo specific reactions in the system, and the molar amounts of the first active functional group, the second active functional group and the third active functional group in the composition satisfy 0.05≤C / (A+B)≤5, which can effectively improve the cross-linking degree of the composition and the light-sensitive film after curing, thereby improving the elastic modulus and chemical resistance of the cured product, maintaining a high patterning resolution of the composition, a high retention rate of the cured product, and better chemical resistance and film retention rate, and a low linear expansion coefficient; and can also avoid the decrease in the elastic modulus caused by insufficient cross-linking due to excessive third active functional groups, and can avoid the decrease in the patterning resolution of the composition and the light-sensitive film, the increase in the loss rate of the cured product, the decrease in the film retention rate of the cured product, and the decrease in the chemical resistance of the cured product.

[0006] In some embodiments of the present application, the first active functional group includes one or more of a carbon-carbon unsaturated bond, an epoxy group, a hydroxyl group, a carboxyl group, an isocyanate group, a mercapto group or an amino group. The above first active functional group has high radical reaction activity, and can react with additives such as a soluble resin, a coupling agent and a thermal cross-linking agent during the curing process to form a cross-linked network, which is more conducive to improving the modulus and chemical resistance of the cured product.

[0007] In some embodiments of the present application, the second active functional group includes one or more of an epoxy group, an amino group, a mercapto group, a carbon-carbon unsaturated bond or a cyano group. The above second active functional group can react with the active groups of the soluble resin and the first active functional group in the composition system to improve the mechanical properties of the cured product, and can also react with the third active functional group in the system to more effectively improve the mechanical properties of the composition and the light-sensitive film after curing.

[0008] In some embodiments of the present application, the third active functional group includes one or more of a multi-functional alkoxy methyl group, a hydroxymethyl group or an epoxy group. In this way, the thermal curing of the light-sensitive composition and the light-sensitive film can be promoted.

[0009] In some embodiments of the present application, the photosensitive composition satisfies: 0.1≤C / (A+B)≤3. In this way, the elastic modulus of the cured product of the photosensitive composition and the photosensitive film is improved, the height retention rate after 6 MPa molding is still high, the chemical resistance is better, and the patterning resolution of the photosensitive film is high and the film retention rate after development is high.

[0010] In some embodiments of the present application, the number of the third active functional groups in a single molecule of the thermal crosslinking agent is ≥2. In this way, the formation of a crosslinked network is facilitated, and the chemical resistance of the cured product of the composition and the photosensitive film is improved.

[0011] In some embodiments of the present application, the thermal crosslinking agent accounts for 0.1%-20% of the mass of the soluble resin. In this way, the crosslinking degree of the system after curing is facilitated to be within a suitable range, and a cured product with higher elastic modulus is obtained; and the patterning resolution of the photosensitive film is improved.

[0012] In some embodiments of the present application, the silane coupling agent accounts for 0.1%-5% of the mass of the soluble resin. In this way, the uniform dispersion of the filler in the composition is facilitated, and the C / (A+B) value is controlled to improve the mechanical properties of the composition and the cured product of the photosensitive film.

[0013] In some embodiments of the present application, the crosslinkable monomer accounts for 0.1%-10% of the mass of the soluble resin. In this way, the C / (A+B) value is controlled, the flowability, dispersibility and curability of the photosensitive composition are improved, and the mechanical properties and chemical resistance of the cured product of the composition and the photosensitive film are ensured to be better.

[0014] In some embodiments of the present application, the mass of the filler accounts for >80% of the mass of the soluble resin. In some embodiments of the present application, the filler accounts for 81%-500% of the mass of the soluble resin. In this way, the photosensitive composition has better film-forming properties, and the mechanical properties of the photosensitive film and its cured product can be effectively enhanced, the risk of collapse of the photosensitive film when attached to the cavity top wall of a hollow structure and after exposure, development and curing can be effectively reduced, the height retention rate after molding is improved, and the yield of packaged devices can be effectively improved.

[0015] In some embodiments of the present application, the filler includes an inorganic filler. In some specific embodiments, the filler is a crystalline inorganic filler; in this way, the mechanical properties and chemical resistance of the cured product of the composition and the photosensitive film are improved.

[0016] In some embodiments of the present application, the filler includes an inorganic filler. In some embodiments of the present application, the inorganic filler includes, but is not limited to, one or more of silica, alumina, glass powder, titanium oxide, calcium oxide, magnesium oxide, zinc oxide, boron oxide, yttrium oxide, zirconium oxide, mica powder, talc powder.

[0017] In some embodiments of the present application, the D50 particle size distribution of the filler is in the range of 0.5 μm-5 μm. In this way, it is beneficial for the dispersion of the filler in the composition, and it is also beneficial for optimizing the mechanical properties and chemical resistance of the photosensitive film and its cured product, and it is further beneficial for improving the surface and cross-sectional flatness of the photosensitive film after exposure, development and curing, and reducing the packaging process difficulty of the packaged device.

[0018] In some embodiments of the present application, the mass ratio of the filler to the silane coupling agent is 1:0.001 to 1:0.1. In this way, it is more beneficial for optimizing the dispersion of the filler in the photosensitive composition, thereby benefiting the uniformity of the photosensitive film and further benefiting the mechanical properties of the photosensitive composition and the photosensitive film after curing.

[0019] In some embodiments of the present application, the silane coupling agent is modified on the surface of the filler. In this way, it is more beneficial for the dispersion of the filler in the photosensitive composition, improving the uniformity of the photosensitive film, and further improving the overall performance of subsequent patterning and thermal curing.

[0020] In some embodiments of the present application, the soluble resin includes a polymer with repeating amide bonds and ester bonds in the main chain, or a polymer with repeating imide rings in the main chain. In this way, it is more beneficial for improving the stability of the composition and the subsequent photosensitive film, and it is more beneficial for improving the performance of the final semiconductor device.

[0021] In some embodiments of the present application, the soluble resin includes a polymer with repeating amide bonds and ester bonds in the main chain, and a polymer with repeating imide rings in the main chain. In this way, it is possible to improve the patterning resolution of the photosensitive composition and the photosensitive film, and the storage stability of the above two.

[0022] In some embodiments of the present application, the first structure in the soluble resin includes a structure composed of the amide bond and the ester bond, and the imide ring. In this way, it is possible to improve the patterning resolution of the photosensitive composition and the photosensitive film, and the storage stability of the above two.

[0023] In some embodiments of the present application, the weight average molecular weight of the soluble resin is 5 kDa-60 kDa. In this way, it is beneficial for film formation and for the photosensitivity and patterning and resolution of the composition.

[0024] In some embodiments of the present application, the mass ratio of the photoinitiator to the mass of the soluble resin is 0.05%-5%. Controlling the amount of the photoinitiator within the above range is more conducive to improving the curing effect of the composition and the photosensitive film, and optimizing the pattern performance of the photosensitive film after exposure and development.

[0025] In some embodiments of the present application, the silane coupling agent includes one or more of γ-glycidoxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, bis-[3-(triethoxysilyl)propyl]tetrasulfide, or 11-mercaptoundecyltrimethoxysilane. In this way, in the system of the photosensitive composition of the present application, the photosensitive composition cooperates with other substances to improve the overall performance of the final cured product.

[0026] In some embodiments of the present application, the cross-linkable monomer includes one or more of an acrylate cross-linkable monomer, a cyclic ether compound, an olefinically unsaturated compound, an epoxy compound, or a vinyl ether.

[0027] In some embodiments of the present application, the thermal cross-linking agent includes one or more of a compound represented by formula (1-1) to formula (1-10): Formula (1-1), Formula (1-2), Formula (1-3), Formula (1-4), Formula (1-5), Formula (1-6), Formula (1-7), Formula (1-8), Formula (1-9), Formula (1-10).

[0028] In some embodiments of the present application, the photoinitiator is a compound containing a compound of formula (1); wherein, R1, R2, R3are independently selected from one or more of a hydrogen atom, a hydroxyl group, a carboxyl group, a nitro group, a cyano group, -NR4R5, a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted main chain containing second structure C1-C10 alkyl group, a substituted or unsubstituted C1-C10 acyl group, a substituted or unsubstituted main chain containing second structure C1-C10 acyl group, a substituted or unsubstituted C1-C10 alkoxy group, a substituted or unsubstituted main chain containing second structure C1-C10 alkoxy group; the second structure comprises one or more of an ether oxygen bond (-O-), a sulfide bond (-S-), an ester bond (-COO-), a thioester bond (-S-CO-, -O-CS-), an amide bond (-CONH-), a carbamate bond (-CO-N-CO-, -N-CO-); R4, R5are independently selected from one or more of a hydrogen atom, an oxygen atom, a substituted or unsubstituted C1-C10 alkoxy group, or a substituted or unsubstituted C1-C10 alkyl group, R4, R5may be connected with the N atom to form a ring. In this way, it is more conducive to improving the deep curing ability, pattern resolution and patterning resolution of the PI and / or PAE photosensitive composition system with a high filler ratio and the photosensitive film; and the photosensitive film prepared from the photosensitive composition can obtain a good exposure topography pattern under a lower post-exposure baking temperature and a shorter post-exposure baking time, has a small risk of residue after development, has a lower process requirement, and has a higher productivity.

[0029] In some embodiments of the present application, the photosensitive composition has a room temperature viscosity of 1000 cps-5000 cps. In this way, it is conducive to the film forming performance of the composition and reduces the risk of gelation.

[0030] In some embodiments of the present application, the photosensitive composition has a solid content of 30 wt.%-80 wt.%. In this way, it is conducive to controlling the content of the soluble resin therein to be more appropriate, and conducive to the film forming performance of the photosensitive composition.

[0031] In some embodiments of the present application, the cured product of the photosensitive composition has an elastic modulus ≥6 GPa at 180 ℃.

[0032] In some embodiments of the present application, the cured product of the photosensitive composition has a glass transition temperature ≥280 ℃.

[0033] In some embodiments of the present application, the cured product of the photosensitive composition has a linear expansion coefficient <40 ppm / K.

[0034] The second aspect of the present application provides a preparation method of a photosensitive composition, comprising: mixing the soluble resin, the crosslinkable monomer, the filler, the silane coupling agent, the photoinitiator, and the thermal crosslinking agent; The soluble resin comprises one or more of a polymer having a main chain comprising repeating imide rings, a polymer having a main chain comprising repeating amide bonds and ester bonds, and a polymer having a main chain comprising repeating amide bonds; and / or, the soluble resin comprises a polymer having a main chain comprising repeating first structures, the first structures comprising a plurality of structures consisting of amide bonds and ester bonds, imide rings, and amide bonds; the cross-linkable monomer comprises a first active functional group, the silane coupling agent comprises a second active functional group, and the thermal cross-linking agent comprises a third active functional group; the first active functional group, the second active functional group, and the third active functional group can chemically react with each other, and at least one of the first active functional group, the second active functional group, and the third active functional group can chemically react with the soluble resin; In the photosensitive composition, the first active functional group has a molar amount of A mol, the second active functional group has a molar amount of B mol, and the third active functional group has a molar amount of C mol; the photosensitive composition satisfies: 0.05≤C / (A+B)≤5.

[0035] The preparation method has high process reliability and high production yield, and is suitable for large-scale industrial production.

[0036] The third aspect of the embodiments of the present application provides a photosensitive film, comprising a support film, a protective film, and a photosensitive film arranged between the support film and the protective film, wherein the photosensitive film is made of the photosensitive composition provided in the first aspect of the embodiments of the present application, or the photosensitive film is made of the photosensitive composition prepared by the preparation method provided in the second aspect of the embodiments of the present application.

[0037] Since the photosensitive film of the photosensitive film is made of the aforementioned photosensitive composition provided in the embodiments of the present application, the photosensitive film has high patterning resolution and film retention rate, and the cured product after curing has high elastic modulus, high glass transition temperature, low linear thermal expansion coefficient, and high chemical resistance.

[0038] In some embodiments of the present application, the photosensitive film has a melt viscosity of 20000 Pa·s-70000 Pa·s at 80℃.

[0039] In some embodiments of the present application, the photosensitive film has a film retention rate of ≥90% after exposure, baking, and development.

[0040] In some embodiments of the present application, the cured film of the photosensitive film after exposure, baking, development, and heat curing treatment has a dimensional change rate of ≤1% after being immersed in at least one of a 2.38 wt% tetramethylammonium hydroxide solution, acetone, propylene glycol monomethyl ether acetate, N-methyl pyrrolidone, 1 wt% HF, 30 wt% HNO3, 30 wt% H2O2, and 15 wt% KOH for 1 h.

[0041] In some embodiments of the present application, the height retention rate of the cured film of the light-sensitive film after exposure, baking, development and heat curing treatment is ≥ 90% under 6 MPa mold pressing.

[0042] In some embodiments of the present application, the glass transition temperature of the cured product of the light-sensitive film is ≥ 280 ℃.

[0043] In some embodiments of the present application, the linear expansion coefficient of the cured product of the light-sensitive film is < 40 ppm / K.

[0044] The fourth aspect of the present application provides a preparation method of a light-sensitive film, comprising: The light-sensitive composition provided in the first aspect of the present application or the light-sensitive composition prepared by the preparation method of the light-sensitive composition provided in the second aspect of the present application is coated on a support film to form a light-sensitive film, and a protective film is arranged on the surface of the light-sensitive film away from the support film to obtain a light-sensitive film.

[0045] The above preparation method has strong process reliability, high production yield, and can flexibly and accurately adjust the thickness of the light-sensitive film, and is suitable for large-scale industrial production.

[0046] The fifth aspect of the present application provides a semiconductor device, comprising a hollow structure with a cavity, an electronic circuit, and a cured product of a light-sensitive film provided in the third aspect of the present application or a patterned light-sensitive film; or, comprising a hollow structure with a cavity, an electronic circuit, and a cured product of a light-sensitive film prepared by the preparation method of the light-sensitive film provided in the fourth aspect of the present application or a patterned light-sensitive film; the electronic circuit is arranged on the hollow structure; the cured product of the light-sensitive film or the patterned light-sensitive film is arranged at the top end of the cavity.

[0047] Since the light-sensitive film provided in the present application is used, the integrity and reliability of the semiconductor device can be improved.

[0048] In some embodiments of the present application, the cavity of the hollow structure contains an electronic circuit and / or a functional structure.

[0049] In some embodiments of the present application, the semiconductor device includes but is not limited to a packaged device. In some specific embodiments, the packaged device includes but is not limited to a radio frequency device; the radio frequency device includes but is not limited to an elastic wave filter, a sensor, and a surface acoustic wave filter.

[0050] The sixth aspect of the present application provides a preparation method of a semiconductor device, comprising: forming a support layer on the surface of a substrate provided with an electronic circuit; The light-sensitive film is prepared by the light-sensitive composition provided in the first aspect of the present application or the light-sensitive composition prepared by the preparation method provided in the second aspect of the present application; the light-sensitive film forms a cured film after curing; and the substrate, the support layer and the cured film form a hollow structure with a cavity structure to obtain a semiconductor device.

[0051] The above preparation method is suitable for large-scale industrial production, has strong production reliability and high product yield.

[0052] The seventh aspect of the present application provides an electronic device comprising the semiconductor device provided in the sixth aspect of the present application and the circuit board, and the circuit board is electrically connected with the semiconductor device; and / or, the electronic device comprises the cured product or the patterned light-sensitive film of the light-sensitive film provided in the fourth aspect of the present application.

[0053] In some embodiments of the present application, the electronic device includes, but is not limited to, a mobile phone, a tablet computer, a vehicle-mounted device, a notebook computer, a smart wearable device and other terminal devices. BRIEF DESCRIPTION OF DRAWINGS

[0054] Figure 1 A structural schematic diagram of the light-sensitive film provided in an embodiment of the present application; Figure 2A A surface microscope photograph of the light-sensitive composition provided in an embodiment of the present application after exposure, baking and development; Figure 2B A surface microscope photograph of the light-sensitive composition provided in an embodiment of the present application after exposure, baking and development; Figure 3A A surface optical microscope photograph of the light-sensitive composition of Example 1 after exposure, baking, development and heat curing and after the evaluation of the surface resistance; Figure 3B A surface optical microscope photograph of the light-sensitive composition of Example 1 after exposure, baking, development and heat curing and after the evaluation of the surface resistance; Figure 3A A surface optical microscope photograph of the light-sensitive composition of Example 1 after exposure, baking, development and heat curing and after the evaluation of the surface resistance; Figure 4A A surface optical microscope photograph of the light-sensitive composition of Example 1 after exposure, baking, development and heat curing and after the evaluation of the surface resistance; Figure 4B A surface optical microscope photograph of the light-sensitive composition of Example 1 after exposure, baking, development and heat curing and after the evaluation of the surface resistance; Figure 3A A surface optical microscope photograph of the light-sensitive composition of Example 1 after exposure, baking, development and heat curing and after the evaluation of the surface resistance.

[0055] Explanation of reference numerals: 1, light-sensitive film; 10, support film; 20, light-sensitive film; 30, protective film. DETAILED DESCRIPTION

[0056] The photosensitive composition can generally form a high-precision patterned film after a patterning process such as exposure. Depending on the application scenario, the photosensitive composition has different application forms. For example, the photosensitive composition is made into a photosensitive film layer with no or low solvent content and is then applied as a packaging material for semiconductor devices. Specifically, in order to ensure the normal operation of semiconductor devices such as filters, a size-stable hollow structure cavity usually needs to be constructed, and the photosensitive film layer is often used as a top wall material for the cavity. The above application scenarios have high performance requirements for the packaging material: the packaging material can be opened by exposure and development, and the cured product after exposure, development and curing can withstand high temperature, resist high-temperature molding, and has a high modulus to reduce the risk of collapse or other defects of the top wall material. Polyimide (PI) or polyamide ester (PAE) photosensitive film is an ideal material to achieve the above performance. When sold or stored, it is usually clamped between a support film and a protective film to form a three-layer structure. In the application process, the photosensitive film is peeled off from the protective film and the support film, and the photosensitive film is attached to the hollow structure, and then the processes of exposure, baking, development, and high-temperature curing are performed to form the top wall of the cavity. In related technologies, some PI or PAE films with certain formulations can achieve certain technical effects, but as the integration and other parameters of semiconductor devices continue to improve, the industry's requirements for the mechanical properties, film retention rate, patterning performance, and chemical resistance of the photosensitive film are also increasing. That is, it is necessary to provide a photosensitive composition with an optimized formulation design.

[0057] To solve the above technical problems, the embodiments of the present application provide a photosensitive composition, which comprises a soluble resin, a cross-linkable monomer, a silane coupling agent, a filler, a photoinitiator, and a thermal cross-linking agent. The soluble resin comprises one or more of a polymer with a main chain containing repeating imide rings, a polymer with a main chain containing repeating amide bonds and ester bonds, and a polymer with a main chain containing repeating amide bonds; and / or, the soluble resin comprises a polymer with a main chain containing a first structure, the first structure comprising multiple ones of an amide bond and an ester bond structure, an imide ring, and an amide bond. In the embodiments of the present application, multiple means two or more.

[0058] The cross-linkable monomer comprises a first active functional group, the silane coupling agent comprises a second active functional group, and the thermal cross-linking agent comprises a third active functional group; the first active functional group and the second active functional group can chemically react with the third active functional group, and at least one of the first active functional group, the second active functional group, and the third active functional group can chemically react with the soluble resin. It should be further noted that in some embodiments of the present application, the cross-linkable monomer contains multiple first active functional groups, and the multiple first active functional groups can chemically react with each other; the silane coupling agent contains multiple second active functional groups, and the multiple second active functional groups can chemically react with each other. In the photosensitive composition, the first active functional group has a molar amount of A mol, the second active functional group has a molar amount of B mol, and the third active functional group has a molar amount of C mol. The photosensitive composition satisfies: 0.05≤C / (A+B)≤5.

[0059] In the embodiments of the present application, the soluble resin includes a resin that is soluble in the developing solution, which can include a main chain and a photosensitive group connected to the main chain. In the embodiments of the present application, the specific wavelength of light can be, for example, but is not limited to, ultraviolet light, various types of rays. The photosensitive group refers to a functional group that can undergo a chemical reaction under irradiation of the above-mentioned specific wavelength, so that the soluble resin can be crosslinked under irradiation of the light source. In some embodiments of the present application, the photosensitive group includes one or more of a carbon-carbon double bond, an unsaturated bond, an epoxy group, an isocyanate group or a blocked isocyanate group, a disulfide bond, and the like.

[0060] In the embodiments of the present application, the soluble resin includes one or more of a polymer having a main chain containing a repeating imide ring (-CO-NH-CO-), a polymer having a main chain containing a structure composed of a repeating amide bond (-CO-NH-) and an ester bond (-COO-), and a polymer having a main chain containing a repeating amide bond (-CONH-); and / or, the soluble resin includes a polymer having a main chain containing a first structure, the first structure including two or more of a structure composed of an amide bond and an ester bond, an imide ring, and an amide bond. That is, the soluble resin includes at least one of a polyimide, a polyamide ester, and a polyamic acid; and / or, the soluble resin includes a copolymer of two or more of a first monomer for preparing a polyimide, a second monomer for preparing a polyamide ester, and a third monomer for preparing a polyamic acid, specifically, two or more of the first monomer, the second monomer, and the third monomer. Specifically, the first monomer, the second monomer, and the third monomer can be materials well known to those skilled in the art, and each of the first monomer, the second monomer, and the third monomer can independently include a plurality of monomers, which are not limited by the present application. In the embodiments of the present application, the polymers mentioned in the soluble resin include precursors of the polymers. Specifically, the polyimide includes a precursor of the polyimide, the polyamide ester includes a precursor of the polyamide ester, and the polyamic acid includes a precursor of the polyamic acid. In the embodiments of the present application, the precursor of the polymer includes a material that has processability before a final treatment (such as light irradiation, heating, chemical reaction, etc.) and that, after processing, obtains a target polymer, including but not limited to a low-molecular-weight compound or an oligomer of the polymer, and the above-mentioned chemical reaction includes but is not limited to polymerization, chemical bond cleavage of a side chain or a group, conversion of a functional group, and the like.

[0061] In the embodiments of the present application, the cross-linkable monomer refers to a compound monomer having a group capable of undergoing a cross-linking reaction. In some embodiments of the present application, the cross-linkable monomer includes a photo-cross-linkable monomer, specifically, a monomer capable of undergoing a cross-linking reaction after being photo-initiated.

[0062] In the embodiments of the present application, the thermal cross-linking agent refers to a chemical substance capable of forming covalent bonds or ionic bonds between the polymer chains of the soluble resin after exposure to light, thereby constructing a three-dimensional network structure.

[0063] In the embodiments of the present application, the presence of the soluble resin, the photo-initiator, the cross-linkable monomer, the thermal cross-linking agent, and the silane coupling agent in the photosensitive composition can be tested by, but not limited to, High Performance Liquid Chromatography-Mass Spectrometry (HPLC-MS), and the molar amounts of the first active functional group, the second active functional group, and the third active functional group in the photosensitive composition can be characterized. In the embodiments of the present application, the presence of the filler can be characterized by Scanning Electron Microscope (SEM).

[0064] The photosensitive composition provided in the embodiments of the present application has good dispersibility of the filler with the silane coupling agent in the system, which can improve the transparency of the photosensitive film, effectively reduce the loss of photosensitivity of the composition caused by the difference in refractive index between the filler and other components in the system, facilitate the photocuring of the composition and the photosensitive film, and enable the photosensitive composition to maintain a high film-forming level. Meanwhile, the introduction of the photo-initiator, the cross-linkable monomer, and the thermal cross-linking agent enables the composition and the photosensitive film to be fully photocured and thermally cured. More importantly, the active functional groups of the cross-linkable monomer, the thermal cross-linking agent, and the silane coupling agent in the system can undergo specific reactions, and the molar amounts of the first active functional group, the second active functional group, and the third active functional group in the composition satisfy 0.05≤C / (A+B)≤5, which can effectively improve the cross-linking degree of the composition and the photosensitive film after curing, thereby improving the elastic modulus and the chemical resistance of the cured product, maintaining a high patterning resolution of the composition, a high retention rate of the mold height after curing, and relatively good chemical resistance and film retention rate, and a low linear expansion coefficient; and can avoid the decrease in the elastic modulus caused by excessive third active functional groups, and can avoid the decrease in the patterning resolution of the composition and the photosensitive film, the increase in the loss rate of the mold height after curing, and the decrease in the film retention rate and the chemical resistance of the cured product.

[0065] In the embodiments of the present application, the value of C / (A+B) can be, for example, 0.05, 0.09, 0.1, 0.15, 0.2, 0.5, 0.8, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, or 5.

[0066] In some embodiments of the present application, the photosensitive composition satisfies: 0.1≤C / (A+B)≤3. Controlling the value of C / (A+B) within the above range is more conducive to improving the modulus of elasticity of the cured product of the composition and the photosensitive film, the height retention rate after 6 MPa embossing is still high, the chemical resistance is better, and the patterning resolution of the photosensitive film is high, the film retention rate after development is high. In addition, controlling the photosensitive composition to satisfy the above condition is more conducive to the final patterning effect, pattern resolution, and chemical resistance of the high filler ratio (for example, the mass of the filler relative to the soluble resin >80%) system. Specifically, the value of C / (A+B) can be, for example, 0.1, 0.2, 0.5, 0.8, 1, 1.2, 1.5, 1.8, 2, 2.2, 2.5, 2.8, 3, etc.

[0067] In some embodiments of the present application, the soluble resin includes a fourth active group, which can chemically react with one or more of the first active group, the second active group, and the third active group. The fourth active group includes, but is not limited to, a hydroxyl group, a carboxyl group, an amino group, an unsaturated bond, etc.

[0068] In some embodiments of the present application, the first active functional group includes, but is not limited to, a carbon-carbon unsaturated bond, an epoxy group, a hydroxyl group, a carboxyl group, an isocyanate group, a mercapto group, an amino group, etc. The above first active functional group has high radical reactivity, and can react with additives such as soluble resin, coupling agent, and thermal crosslinking agent during the curing process to form a crosslinked network, which is more conducive to improving the modulus and chemical resistance of the cured product. It can be understood that when there are multiple different crosslinkable monomers in the system, crosslinking reactions can also occur between the crosslinkable monomers.

[0069] In some embodiments of the present application, the crosslinkable monomer also includes a carboxyl group and / or a hydroxyl group. The introduction of a hydroxyl group and / or a carboxyl group in the crosslinkable monomer can improve the pattern resolution and resolution of the photosensitive film, that is, improve the resolution of the pattern obtained after the photosensitive film is exposed and developed, especially the pattern resolution after development in tetramethylammonium hydroxide (TMAH) developer.

[0070] In some embodiments of the present application, the cross-linkable monomer includes acrylate cross-linkable monomers, cyclic ether compounds, olefinically unsaturated compounds, epoxy compounds, vinyl ethers, etc.; the acrylate cross-linkable monomers include, but are not limited to, one or more of ethylene glycol diacrylate, 1,9-nonanediol dimethacrylate, isobornyl acrylate, isobornyl methacrylate, pentaerythritol triacrylate (PETA), pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, ethoxylated trimethylolpropane triacrylate (ETPTA), ethylene oxide-modified bisphenol A diacrylate, ethoxylated bisphenol A dimethacrylate (BPA2EODMA), propylene oxide-modified bisphenol A diacrylate, propylene oxide-modified bisphenol A methacrylate, oxirane-modified bisphenol A diacrylate, oxirane-modified bisphenol A dimethacrylate, 2-isocyanatoethyl acrylate, 2-isocyanatoethyl methacrylate, isocyanurate oxirane-modified diacrylate, methylene bisacrylamide, N,N-dimethylacrylamide, N-hydroxymethyl acrylamide, N,N-methylene bisacrylamide, etc. The cyclic ether compounds include, but are not limited to, epoxy compounds and oxetane compounds, etc.; the olefinically unsaturated compounds include, but are not limited to, vinyl ethers and styrenes, etc.; the epoxy compounds include, but are not limited to, aromatic epoxy compounds, alicyclic epoxy compounds and aliphatic epoxy compounds; the vinyl ethers include, but are not limited to, methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether and cyclohexyl vinyl ether, 2-phenoxyethyl vinyl ether, phenyl vinyl ether and p-methoxyphenyl vinyl ether, butanediol-1,4-di vinyl ether, etc.

[0071] In some embodiments of the present application, the cross-linkable monomer accounts for 0.1%-10% of the mass of the soluble resin. Controlling the content of the cross-linkable monomer relative to the soluble resin within the above range is conducive to the regulation of the C / (A+B) value, the improvement of the curability, flowability and dispersibility of the photosensitive composition, and the guarantee of the mechanical properties and chemical resistance of the cured product of the composition and the photosensitive film. Specifically, the content of the cross-linkable monomer relative to the mass of the soluble resin may, for example, be 0.1%, 0.5%, 0.8%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%. In some specific embodiments, the cross-linkable monomer accounts for 0.5%-5% of the mass of the soluble resin. In the embodiments of the present application, the mass content of the cross-linkable monomer can be tested by HPLC-MS, and then the mass content of the soluble resin is tested to calculate the mass ratio of the two.

[0072] It can be understood that the surface of the filler (e.g., inorganic filler) generally contains silanol groups, which can form chemical bonds with the silicon-oxygen bonds of the silane coupling agent, so that the silane coupling agent can be modified on the surface of the filler.

[0073] In some embodiments of this application, the second active functional group includes, but is not limited to, one or more of epoxy groups, hydroxyl groups, carboxyl groups, amino groups, mercapto groups, carbon-carbon unsaturated bonds, or cyano groups. It is understood that at least one end of the silane coupling agent includes a group capable of forming a chemical interaction with the filler, such as a siloxane bond; at least one end of the silane coupling agent is the aforementioned second active functional group, which can react with the fourth active group (e.g., carbon-carbon unsaturated bonds, hydroxyl groups, etc.) and the first active functional group (e.g., carbon-carbon unsaturated bonds, etc.) of the soluble resin in the composition system to improve the mechanical properties of the cured product, and can also react with the third active functional group (e.g., alkoxy groups, etc.) in the system to further improve the mechanical properties of the cured composition and photosensitive film. In some specific embodiments, the second active functional group includes a mercapto group. This further improves the mechanical properties of the cured photosensitive composition and photosensitive film.

[0074] In some embodiments of this application, the silane coupling agent includes, but is not limited to, γ-glycidoxypropyltrimethoxysilane, triethoxysilylpropylmaleic acid, methacryloxypropyltriethoxysilane, 3-ureapropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-propyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptomethyltrimethoxysilane, 3-mercaptomethyldimethoxysilane, 3-mercaptopropylethoxydimethoxysilane, 3-mercaptopropyltripropoxysilane, 3-thiopropyltributoxysilane, 2-(3,4-epoxycyclohexane)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexane)ethyltriethoxysilane, epoxybutyltrimethoxysilane, and N-phenyl-3-aminopropyltrimethoxysilane. The following are some of the following: trimethoxysilane, p-aminophenyltrimethoxysilane, aminophenyltrimethoxysilane, 3-(m-aminophenyl)trimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-propenyloxypropyltrimethoxysilane, 3-ethoxypropyltrimethoxysilane, vinyltrimethoxysilane, methacryloyloxydimethoxysilane, 3-aminopropyltrimethoxysilane, trimethoxysilylbenzoic acid, 3-methacryloyloxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, vinyltrimethoxysilane, γ-epoxypropoxypropyltrimethoxysilane, and vinyltriacetoxysilane. In some embodiments of this application, the silane coupling agent includes one or more of γ-glycidoxypropyltrimethoxysilane and silane coupling agents whose second active functional group includes a thiol group, such as, but not limited to, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, bis-[3-(triethoxysilane)propyl]tetrasulfide, 11-mercaptoundecyltrimethoxysilane, etc.

[0075] In some embodiments of the present application, the silane coupling agent accounts for 0.1%-5% of the mass of the soluble resin. In this way, it is beneficial for the uniform dispersion of the filler in the composition and the adjustment of the C / (A+B) value, thereby improving the mechanical properties of the cured product of the composition and the photosensitive film. Specifically, the mass content of the silane coupling agent relative to the soluble resin may, for example, be 0.1%, 0.15%, 0.2%, 0.3%, 0.4%, 0.5%, 0.8%, 1%, 2%, 3%, 4%, or 5%. In the embodiments of the present application, the mass content of the silane coupling agent can be tested by HPLC-MS, and the mass content of the soluble resin can be tested, and the mass ratio of the two can be calculated.

[0076] In some embodiments of the present application, the third active functional group includes one or more of a multifunctional alkoxy methyl group, a hydroxymethyl group, or an epoxy group. The above-mentioned groups have relatively high reactivity, which can promote the thermal curing of the photosensitive composition and the photosensitive film.

[0077] In some embodiments of the present application, the number of third active functional groups in a single molecule of the thermal crosslinking agent is ≥2. In this way, it is beneficial for the formation of a crosslinking network and the improvement of the chemical resistance of the cured product of the composition and the photosensitive film. Specifically, the number of third active functional groups in a single molecule of the thermal crosslinking agent may, for example, be 2, 3, 4, 5, 6, 7, 8, etc.

[0078] In some embodiments of the present application, the thermal crosslinking agent includes one or more of the compounds represented by formula (1-1) to formula (1-10).

[0079] Formula (1-1), Formula (1-2), Formula (1-3), Formula (1-4), Formula (1-5), Formula (1-6), Formula (1-7), Formula (1-8), Formula (1-9), Formula (1-10).

[0080] In some embodiments of the present application, the thermal crosslinking agent includes the structure represented by formula (1-1); in this way, the modulus and chemical resistance of the photosensitive composition after thermal curing are more optimal.

[0081] In some embodiments of the present application, the thermal crosslinking agent accounts for 0.1%-20% of the mass of the soluble resin. The thermal crosslinking agent plays a major role in the thermal curing process. Controlling the thermal crosslinking agent within the above range is more conducive to helping the crosslinking degree of the system after curing to be within a suitable range, obtaining a cured product with a higher elastic modulus; and is more conducive to improving the patterning resolution of the photosensitive film. Specifically, the mass ratio of the thermal crosslinking agent to the soluble resin may, for example, be 0.1%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, etc.

[0082] In some embodiments of the present application, the mass ratio of the filler to the soluble resin is >80%. In some specific embodiments, the mass of the filler accounts for 81%-500% of the mass of the soluble resin. In this way, the photosensitive composition not only has better film-forming performance, but also can effectively enhance the mechanical properties of the photosensitive film and its cured product, effectively reduce the risk of collapse of the photosensitive film when attached to the cavity top wall of the hollow structure and after exposure, development and curing, and is more conducive to improving the height retention rate after molding, which can effectively improve the yield of packaged devices. Specifically, the mass of the filler may, for example, account for 80.5%, 81%, 85%, 90%, 95%, 100%, 120%, 150%, 180%, 200%, 220%, 250%, 280%, 300%, 320%, 350%, 380%, 400%, 420%, 450%, 480%, 500%, etc. of the mass of the soluble resin.

[0083] In the embodiments of the present application, the mass content of the filler can be tested by a thermal gravimetric analyzer (TGA), or the filler can be separated by sedimentation, centrifugation and drying to measure the mass content of the filler, the mass content of the soluble resin can be tested by HPLC-MS, and then the mass ratio of the filler to the soluble resin is calculated.

[0084] In some embodiments of the present application, the mass ratio of the filler to the silane coupling agent is 1:0.001 to 1:0.1. In this way, it is more conducive to optimizing the dispersion of the filler in the photosensitive composition, thereby facilitating the uniformity of the photosensitive film and more conducive to improving the mechanical properties of the photosensitive composition and the photosensitive film after curing. Specifically, the mass ratio of the filler to the silane coupling agent may, for example, be 1:0.001, 1:0.002, 1:0.005, 1:0.008, 1:0.01, 1:0.02, 1:0.05, 1:0.08, 1:0.1.

[0085] In some embodiments of the present application, the silane coupling agent is modified on the surface of the filler. In this way, the dispersion of the filler in the photosensitive composition is more favorable, the uniformity of the photosensitive film is improved, and the subsequent patterning and thermal curing are further improved. Specifically, the silane coupling agent forms a covalent bond with the filler, which can be characterized by infrared spectrum (IR). In some embodiments of the present application, for example, the surface of the filler has a silicon hydroxyl group, which forms a covalent bond with the silane coupling agent.

[0086] In some embodiments of the present application, the filler is an inorganic filler. In some specific embodiments, the inorganic filler includes, but is not limited to, one or more of silica, alumina, glass powder, titanium oxide, calcium oxide, magnesium oxide, zinc oxide, boron oxide, yttrium oxide, zirconium oxide, mica powder, talc powder. In some specific embodiments, the filler is a crystalline inorganic filler; in this way, the mechanical properties and chemical resistance of the cured product of the composition and the photosensitive film are improved. In some embodiments of the present application, the shape of the filler can be spherical, angular, needle-shaped, irregular, etc.

[0087] In some embodiments of the present application, the D50 particle size of the filler is 0.5 μm-5 μm. Controlling the particle size of the filler in the above range is beneficial for its dispersion in the composition, optimization of the mechanical properties and chemical resistance of the photosensitive film and its cured product, and further improvement of the surface and cross-sectional flatness of the photosensitive film after exposure, development and curing, and reduction of the packaging process difficulty of the packaged device. Specifically, the D50 particle size of the filler can be, for example, 0.5 μm, 0.8 μm, 1 μm, 1.1 μm, 1.2 μm, 1.3 μm, 1.4 μm, 1.5 μm, 1.8 μm, 2 μm, 2.2 μm, 2.5 μm, 2.8 μm, 3 μm, 3.2 μm, 3.5 μm, 3.8 μm, 4 μm, 4.2 μm, 4.5 μm, 4.8 μm, 5 μm, etc. In some embodiments of the present application, the D50 particle size of the filler can be measured by scanning electron microscopy (SEM) or dynamic light scattering (DLS).

[0088] In some embodiments of the present application, the soluble resin includes a polymer having repeating imide rings in the main chain or a polymer having repeating amide bonds and ester bonds in the main chain. That is, preferably, the soluble resin includes a polyimide or a polyamide ester. In this way, the stability of the composition and the subsequent photosensitive film is improved, and the performance of the final semiconductor device is improved.

[0089] In some embodiments of the present application, the soluble resin comprises a polyimide, a polyamide ester, and / or a copolymer comprising a first monomer for forming a polyimide and a second monomer for forming a polyamide ester. In some specific embodiments, the soluble resin comprises a mixture of a polyimide and a polyamide ester. In the high-filler system photosensitive composition of the present application, the introduction of both PI and PAE can further improve the photosensitivity and transparency of the system, and can improve the patterning resolution of the photosensitive composition and the photosensitive film, and also facilitate the improvement of the storage stability of the photosensitive composition and the photosensitive film.

[0090] In some embodiments of the present application, the first structure in the soluble resin comprises an amide bond and an ester bond structure and an imide ring. That is, the soluble resin comprises a copolymer of a first monomer for forming a polyimide and a second monomer for forming a polyamide ester. The copolymer soluble resin described above can improve the patterning resolution of the photosensitive composition and the photosensitive film, and the storage stability of both. In some specific embodiments, the soluble resin comprises both the blend and the copolymer described above.

[0091] In some embodiments of the present application, the mass ratio of PAE to PI in the soluble resin is ≥ 50%. In other words, the mass ratio of PAE to PI is ≥ 1:1, and specifically, for example, it can be 1:1, 1.1:1, 1.15:1, 1.2:1, 1.25:1, 1.3:1, 1.35:1, 1.4:1. It can be understood that for the case of containing a copolymer, the mass ratio of the repeating units belonging to PAE to the repeating units belonging to PI is calculated accordingly. In this way, it is more beneficial to optimize the resolution and pattern resolution of the photosensitive composition and the photosensitive film, and it is more beneficial to improve the elastic modulus of the photosensitive composition and the photosensitive film after curing.

[0092] In some embodiments of the present application, the soluble resin has carboxyl and / or hydroxyl groups. The carboxyl and / or hydroxyl groups can promote the dissolution of the soluble resin, and specifically improve its solubility in an alkaline developer, so as to improve the patterning effect and resolution of the composition and the photosensitive film. In the embodiments of the present application, the carboxyl and / or hydroxyl groups can be located in the side chain of the soluble resin, or can be located in the main chain of the soluble resin, for example, as an end-capping group of the main chain.

[0093] In some embodiments of the present application, the weight average molecular weight (Mw) of the soluble resin is 5-60 kDa. Controlling the molecular weight of the soluble resin within the above range is conducive to film formation and the photosensitivity and patterning effect and resolution of the composition. Specifically, the Mw of the soluble resin may, for example, be 5, 8, 10, 12, 15, 18, 20, 22, 25, 28, 30, 32, 35, 38, 40, 42, 45, 48, 50, 55, 60 kDa, etc. In the embodiments of the present application, gel chromatography may, but not limited to, be used to test the weight average molecular weight of the soluble resin.

[0094] In some embodiments of the present application, the mass percentage of the photoinitiator in the soluble resin is 0.05-5%. Controlling the amount of the photoinitiator within the above range is more conducive to improving the curing effect of the composition and the photosensitive film and optimizing the pattern performance of the photosensitive film after exposure and development. Specifically, the mass percentage of the photoinitiator in the soluble resin may, for example, be 0.05, 0.1, 0.15, 0.2, 0.5, 0.8, 1, 1.2, 1.5, 1.8, 2, 2.2, 2.5, 2.8, 3, 3.2, 3.5, 3.8, 4, 4.2, 4.5, 4.8, 5%, etc. In the embodiments of the present application, HPLC-MS may, but not limited to, be used to test the mass content of the photoinitiator, HPLC-MS is used to test the mass content of the soluble resin, and then the mass ratio of the photoinitiator to the soluble resin is calculated.

[0095] In some embodiments of the present application, the photoinitiator is a compound containing a compound of formula (1); wherein, R1, R2, R3are independently selected from one or more of a hydrogen atom, a hydroxyl group, a carboxyl group, a nitro group, a cyano group, -NR4R5, a substituted or unsubstituted C1-C10 hydrocarbon group, a substituted or unsubstituted main chain containing a second structure C1-C10 hydrocarbon group, a substituted or unsubstituted C1-C10 acyl group, a substituted or unsubstituted main chain containing a second structure C1-C10 acyl group, a substituted or unsubstituted C1-C10 alkoxy group, a substituted or unsubstituted main chain containing a second structure C1-C10 alkoxy group; the second structure includes one or more of an ether oxygen bond (-O-), a sulfide bond (-S-), an ester bond (-COO-), a thioester bond (-S-CO-, -O-CS-), an amide bond (-CONH-), a carbamate bond (-CO-N-CO-, -N-CO-); R4, R5are independently selected from one or more of a hydrogen atom, an oxygen atom, a substituted or unsubstituted C1-C10 alkoxy group, or a substituted or unsubstituted C1-C10 alkyl group, R4, R5may be connected to the N atom to form a ring. In this way, it is more conducive to improving the deep curing ability of the PI and / or PAE photosensitive composition system with a high filler ratio, the pattern resolution and the patterning resolution; and the photosensitive film prepared from the photosensitive composition can obtain a good exposure topography pattern under a lower post-exposure baking temperature and a shorter post-exposure baking time, has a small risk of residue after development, has a lower process requirement, and has a higher productivity.

[0096] In the embodiments of the present application, the above-mentioned hydrocarbon groups in R1, R2, R3and R4, R5may be chain hydrocarbon groups or cyclic hydrocarbon groups, for example, substituted or unsubstituted C1-C10 straight chain hydrocarbon groups, substituted or unsubstituted C1-C10 branched chain hydrocarbon groups, substituted or unsubstituted C3-C10 cyclic hydrocarbon groups, the chain hydrocarbon groups may be chain alkyl groups, chain alkenyl groups, chain alkynyl groups, the cyclic hydrocarbon groups may be, for example, cyclic alkyl groups, cyclic alkenyl groups, cyclic alkynyl groups, the number of carbon atoms of the substituted or unsubstituted hydrocarbon groups may be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10. The above-mentioned acyl groups may be, for example, -CO-R x , R x -S(=O)2- and R x is an organic group, the unsubstituted acyl group may be, for example, a formyl group, an acetyl group, a sulfonyl group, etc., the number of carbon atoms of the substituted or unsubstituted acyl group may be, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10. The unsubstituted alkoxy group is -OR y , R yR is a substituted or unsubstituted C1-C10alkyl group, which can be a substituted or unsubstituted C1-C10alkyl group, for example, the number of carbon atoms of the substituted or unsubstituted alkyl group can be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10. The substituted alkyl group can independently contain one or more substituents. In some specific embodiments, the substituted alkyl group independently contains 1-5 substituents. Specifically, the number of substituents in the substituted alkyl group can independently be 1, 2, 3, 4, 5.

[0097] In the embodiments of the present application, the substituted or unsubstituted C1-C10alkyl group containing a second structure in the main chain is a group in which a second structure is embedded in the main chain, specifically, it can be a group in which a second structure is embedded in the carbon chain, for example, it can be a group obtained by interrupting the hydrocarbon group in the above-mentioned substituted or unsubstituted C2-C10alkyl group with a second structure, or a group in which a methyl group and a second structure are connected to a benzene ring through a second structure, which conforms to the principle of chemical bonding. The substituent group can substitute any substitutable hydrogen atom on the C1-C10alkyl group containing a second structure in the main chain, as long as substitution can be achieved. The above-mentioned group can contain one or more substituents. In some specific embodiments, the substituted alkyl group independently contains 1-5 substituents. Specifically, the number of substituents in the substituted alkyl group can independently be 1, 2, 3, 4, 5.

[0098] In the embodiments of the present application, the substituted or unsubstituted C1-C10acyl group containing a second structure in the main chain is a group in which a second structure is embedded in the main chain, specifically, it can be a group in which a second structure is embedded in the carbon chain, for example, it can be a group obtained by interrupting the hydrocarbon group in the above-mentioned substituted or unsubstituted C2-C10acyl group with a second structure, or a C1-C10acyl group connected to a benzene ring through a second structure, which conforms to the principle of chemical bonding. The substituent group can substitute any substitutable hydrogen atom on the C1-C10acyl group containing a second structure in the main chain, as long as substitution can be achieved. The above-mentioned group can contain one or more substituents. In some specific embodiments, the substituted alkyl group independently contains 1-5 substituents. Specifically, the number of substituents in the substituted alkyl group can independently be 1, 2, 3, 4, 5.

[0099] In some embodiments of the present application, the substituted or unsubstituted C1-C10 alkyl group in R1, R2, and R3 is selected from one or more of a hydrogen atom, a halogen atom, a hydroxyl group, a carboxyl group, a nitro group, and a cyano group.

[0100] In some embodiments of the present application, the substituents in the substituted or unsubstituted C1-C10 alkyl group, the substituted or unsubstituted C1-C10 alkyl group with a second structure in the main chain, the substituted or unsubstituted C1-C10 acyl group, the substituted or unsubstituted C1-C10 acyl group with a second structure in the main chain, the substituted or unsubstituted C1-C10 alkoxy group, and the substituted or unsubstituted C1-C10 alkoxy group with a second structure in the main chain in R1, R2, and R3 are independently selected from one or more of a hydrogen atom, a halogen atom, a hydroxyl group, a carboxyl group, a nitro group, and a cyano group.

[0101] In some embodiments of the present application, R3 can form a ring with the group at the marked position.

[0102] In some embodiments of the present application, the substituents in the substituted or unsubstituted C1-C10 alkyl group, the substituted or unsubstituted C1-C10 alkyl group with a second structure in the main chain, the substituted or unsubstituted C1-C10 acyl group, the substituted or unsubstituted C1-C10 acyl group with a second structure in the main chain, the substituted or unsubstituted C1-C10 alkoxy group, and the substituted or unsubstituted C1-C10 alkoxy group with a second structure in the main chain in R1, R2, and R3 are independently selected from one or more of a hydrogen atom, a halogen atom, a hydroxyl group, a carboxyl group, a nitro group, and a cyano group.

[0103] In some embodiments of the present application, the photoinitiator further comprises a substituted or unsubstituted oxime ester group 1 2 3 The marked positions all represent the connection sites. The oxime ester group is connected to the group at the marked position. ​​​​Synergistic group formation is more conducive to optimizing the surface and deep curing effects of the subsequent photosensitive film, especially for the deep and surface curing of photosensitive films with a certain thickness. In some embodiments, the thickness of the photosensitive film is 5 μm-100 μm, and the thickness of the photosensitive film can be, for example, 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm, etc.

[0104] In some embodiments of this application, the substituents of the substituted oxime ester group include, but are not limited to, hydrocarbon groups, aryl groups, hydrocarbon groups containing heteroatoms in the main chain, and aryl groups. The heteroatoms can be, for example, sulfur atoms, nitrogen atoms, etc. In some specific embodiments, the substituted or unsubstituted oxime ester group is chemically bonded to formula (1). The marked site can be 1 #、 2 #or 3 #The position of the marker and in equation (1) The marker site is chemically bonded; understandably, based on the principle of chemical bonding. 3 When # is used as a linking site, the oxime ester group can share a carbonyl group with the structure shown in formula (1), that is, the oxime ester group... 3 #The location of the marker is bonded to The location of the marker, and the oxime ester group and Shared 1 The carbonyl group is labeled. In other specific embodiments, the substituted or unsubstituted main-chain oxime ester group is chemically bonded to formula (1). The location of the marker, that is, the oxime ester group, is connected to the oxime ester group in formula (1) via other divalent groups. The marked position is connected; wherein, the substituted group can be any position in the oxime ester group of the main chain that can be replaced by a hydrogen atom, for example, its end or middle. In some embodiments of this application, the above-mentioned divalent group can be, for example, an alkylene group, an arylene group, etc. wait.

[0105] In some embodiments of this application, the connection sites to formula (1) or the benzene ring structure are removed. The remaining two connection sites can be connected to organic groups, such as hydrocarbon groups.

[0106] In some embodiments of this application, the photoinitiator includes one or more of formulas (2-1) to (2-15): Equation (2-1), Equation (2-2), Equation (2-3), Formula (2-4), Formula (2-5), Formula (2-6), Formula (2-7), Formula (2-8), Formula (2-9), Formula (2-10), Formula (2-11), Formula (2-12), Formula (2-13), Formula (2-14), Formula (2-15).

[0107] In some embodiments, the photoinitiator can also include an oxime ester photoinitiator. Specifically, the oxime ester photoinitiator refers to an initiator containing an oxime ester group and having a photoinitiating ability under irradiation of a light source at at least one wavelength of ≤450 nm, and the initiator does not contain the structure of Formula (1). Specifically, for example, the oxime ester photoinitiator includes but is not limited to .

[0108] In some embodiments of the present application, the photosensitive composition further includes a solvent. The solvent can be any solvent suitable for the polyimide-based photosensitive composition well known to those skilled in the art. In some embodiments, the solvent includes but is not limited to one or more of N-methylpyrrolidone (NMP), N,N-dimethylacetamide, N,N-dimethylformamide, tetrahydrofuran, cyclohexanone, gamma-butyrolactone (abbreviated as GBL), ethyl acetate, methyl lactate, ethyl lactate (EL), acetone, methyl ethyl ketone (MEK), methyl n-amyl ketone, ethylene glycol, propylene glycol, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether (PGME), anisole, diphenyl ether, toluene, dimethyl sulfoxide (DMSO).

[0109] In some embodiments of the present application, the photosensitive composition has a solid content of 30 wt% to 80 wt%. The solid content of the photosensitive composition refers to the proportion of the sum of the mass of the other components after removing the solvent to the total mass of the photosensitive composition. Controlling the solid content of the photosensitive composition within the above range is beneficial to controlling the content of the soluble resin therein to be more appropriate, which is beneficial to the film forming performance of the photosensitive composition; for example, the uniformity of the photosensitive film is higher, and the surface roughness is lower. Specifically, the solid content of the photosensitive composition can be, for example, 30 wt.%, 40 wt.%, 50 wt.%, 60 wt.%, 70 wt.%, 80 wt.%.

[0110] In some embodiments of the present application, the light-sensitive composition has a room temperature viscosity of 1000 cps to 5000 cps. Controlling the room temperature viscosity of the light-sensitive composition within the above range, as well as controlling the Mw and mass content of the soluble resin within a suitable range, is conducive to the film-forming performance of the composition and reduces the risk of gelation. In embodiments of the present application, the room temperature viscosity of the light-sensitive composition can be tested using a rotational rheometer, for example, at a rotational speed of 50 rpm to 100 rpm and a shear rate of 50 / s to 100 / s. Specifically, the light-sensitive composition can have a room temperature viscosity of, for example, 1000 cps, 1500 cps, 2000 cps, 2500 cps, 3000 cps, 3500 cps, 4000 cps, 4500 cps, 5000 cps, etc.

[0111] In some embodiments of the present application, other additives can be included in the light-sensitive composition to improve the overall performance of the light-sensitive composition. The other additives can include one or more of a leveling agent, a surfactant, and a polymerization inhibitor. The addition of the leveling agent and the surfactant can improve the uniformity of the coated film layer. The content of the other additives in the light-sensitive composition can be adjusted as needed.

[0112] In some embodiments of the present application, the cured product of the light-sensitive composition has an elastic modulus at 180 °C of ≥ 6 GPa; for example, ≥ 7.0 GPa, further ≥ 8.0 GPa, ≥ 8.3 GPa, ≥ 8.5 GPa, ≥ 8.8 GPa, ≥ 9.0 GPa, ≥ 9.2 GPa. In some embodiments, the cured product of the light-sensitive composition has an elastic modulus at 180 °C of ≥ 8.5 GPa, for example, 8.5 GPa to 9.2 GPa. The elastic modulus of the cured product at 180 °C can be tested using dynamic mechanical analysis (DMA), for example, but not necessarily so.

[0113] In some embodiments of the present application, the cured product of the light-sensitive composition has a glass transition temperature Tg of ≥ 280 °C; for example, 280 °C to 310 °C. The glass transition temperature of the cured product can be tested using dynamic mechanical analysis (DMA), for example, but not necessarily so.

[0114] In some embodiments of the present application, the cured product of the light-sensitive composition has a linear expansion coefficient CET of < 40 ppm / K; for example, 20 ppm / K, 25 ppm / K, 30 ppm / K, 35 ppm / K, 38 ppm / K, etc. The linear thermal expansion coefficient of the cured product can be tested using thermal mechanical analysis (TMA), for example, but not necessarily so.

[0115] In the embodiments of the present application, the cured product of the photosensitive composition described above refers to a cured product obtained after curing at 270 ℃ for 2 h under a protective atmosphere (for example, nitrogen). In the curing process described above, the soluble resin after exposure, the cross-linkable monomer, and the thermal cross-linking monomer may, for example, but not limited to, react with each other under the action of heat, such as the cross-linking reaction between the soluble resin after exposure, the cross-linking reaction between the soluble resin after exposure and the thermal cross-linking monomer, the reaction between the soluble resin after exposure and the cross-linkable monomer, and the reaction between the thermal cross-linking monomer and the cross-linkable monomer.

[0116] Figure 2A The surface microscope photograph of the photosensitive composition provided by an embodiment of the present application after exposure, baking, and development; Figure 2B The cross-section microscope photograph of the photosensitive composition provided by an embodiment of the present application after exposure, baking, and development.

[0117] In some embodiments of the present application, the patterning resolution of the photosensitive composition is ≤ 40 μm. In some specific embodiments, the opening resolution of the photosensitive composition is ≤ 40 μm. The opening resolution refers to the minimum size of the opening obtained after exposure and development of the photosensitive composition using a mask.

[0118] In some embodiments of the present application, the photosensitive composition is a negative photosensitive composition.

[0119] The present application also provides a preparation method of a photosensitive composition, which can be used to prepare the aforementioned photosensitive composition provided by the embodiments of the present application. The preparation method comprises the following steps: mixing the soluble resin, the cross-linkable monomer, the filler, the silane coupling agent, the photoinitiator, and the thermal cross-linking agent; The soluble resin comprises one or more of a polymer having a main chain containing repeating imide rings, a polymer having a main chain containing repeating amide bonds and ester bonds, and a polymer having a main chain containing repeating amide bonds; and / or, the soluble resin comprises a polymer having a main chain containing repeating first structures, the first structures comprising one or more of a structure composed of an amide bond and an ester bond, an imide ring, and an amide bond; the cross-linkable monomer comprises a first active functional group, the silane coupling agent comprises a second active functional group, and the thermal cross-linking agent comprises a third active functional group; the first active functional group and the second active functional group can chemically react with the third active functional group, and at least one of the first active functional group, the second active functional group, and the third active functional group can chemically react with the soluble resin; In the photosensitive composition, the molar amount of the first active functional group is A mol, the molar amount of the second active functional group is B mol, and the molar amount of the third active functional group is C mol; the photosensitive composition satisfies 0.05 ≤ C / (A+B) ≤ 5.

[0120] That is, the preparation of the photosensitive composition comprises: S01, mixing the soluble resin, the photoinitiator, the crosslinkable monomer, the thermal crosslinking agent, the silane coupling agent and the filler to obtain the photosensitive composition.

[0121] In some embodiments, the step S01 specifically comprises: S011, modification of the filler; the modification of the filler comprises: mixing the filler with the silane coupling agent at a mass ratio of 1:0.005 to 1:0.5; S012, pre-dissolution of the soluble resin: dissolving the soluble resin in the solvent for 1 min-5 h to obtain a soluble resin solution; S013, mixing the filler modified by the silane coupling agent, the soluble resin solution, the photoinitiator, the crosslinkable monomer and the thermal crosslinking agent to obtain the photosensitive composition.

[0122] The present application also provides a photosensitive film, which comprises: Figure 1 As shown in the figure, the photosensitive film 1 comprises a support film 10, a protective film 30 and a photosensitive film 20 arranged between the support film 10 and the protective film 30, and the photosensitive film 20 is made of the aforementioned photosensitive composition provided by the present application.

[0123] Since the photosensitive film of the photosensitive film is made of the aforementioned photosensitive composition provided by the present application, the photosensitive film has high patterning resolution and film retention rate, and the cured product after curing has high elastic modulus, high glass transition temperature, low linear thermal expansion coefficient and excellent chemical resistance.

[0124] In the present application, the materials of the support film and the protective film can be well known to those skilled in the art, for example, they can be PET (polyethylene terephthalate), which is not limited in the present application.

[0125] In some embodiments of the present application, the aforementioned photosensitive film is obtained by drying the photosensitive composition. In some embodiments of the present application, the aforementioned solvent can not be completely removed during drying. In some specific embodiments, the preparation of the photosensitive film comprises: coating the photosensitive composition on the support film, baking at 30 ℃-150 ℃ for 3 min-15 min to obtain the photosensitive film; and then arranging the protective film on the surface of the photosensitive film away from the support film to obtain the photosensitive film.

[0126] In some embodiments of the present application, the photosensitive film has a solid content of 90-99.5wt.%. In some specific embodiments, the photosensitive film has a melt viscosity of 20000 Pa·s-70000 Pa·s at 80 ℃. In the present application, the rheometer can be used to test the melt viscosity of the photosensitive film at 25 o C-100 o C.

[0127] In some embodiments of the present application, the photosensitive film has a thickness of 5 μm to 100 μm.

[0128] In some embodiments of the present application, the photosensitive film has a patterning resolution of ≤ 40 μm. In some embodiments of the present application, the patterning resolution can be observed by optical microscope or SEM, and the minimum opening size of the patterned photosensitive film is the patterning resolution.

[0129] In some embodiments of the present application, the exposure light source suitable for the photosensitive film includes, but is not limited to, ultraviolet light, visible light, violet light, and various types of rays. The exposure dose can be, for example, 50 mW / cm 2 - 300 mW / cm 2 .

[0130] In some embodiments of the present application, any developer known in the art can be used to treat the exposed photosensitive film, for example, TMAH with a mass concentration of 2.38%.

[0131] In some embodiments of the present application, the cured product of the photosensitive film has an elastic modulus of ≥ 6 GPa at 180 °C, for example, ≥ 7.0 GPa, further ≥ 8.0 GPa, ≥ 8.3 GPa, ≥ 8.5 GPa, ≥ 8.8 GPa, ≥ 9.0 GPa, ≥ 9.2 GPa. In some embodiments, the cured product of the photosensitive composition has an elastic modulus of ≥ 8.5 GPa at 180 °C, for example, 8.5 GPa to 9.2 GPa.

[0132] In some embodiments of the present application, the photosensitive film has a patterning resolution of ≤ 40 μm. The patterning resolution refers to the resolution of the pattern obtained after the photosensitive film is exposed and developed using a mask.

[0133] In some embodiments of the present application, the cured product of the photosensitive film has a linear thermal expansion coefficient CTE of < 40 ppm / K.

[0134] In some embodiments of the present application, the photosensitive film has a film retention rate of ≥ 90% after exposure, baking, and development. In some embodiments of the present application, the initial thickness of the photosensitive film is X1, the thickness of the patterned photosensitive film obtained after the photosensitive film is exposed and developed is X2, and the film retention rate = X2 / X1 x 100%. Specifically, after exposure, the photosensitive film is subjected to baking treatment before development. Specifically, the film retention rate of the photosensitive film can be, for example, 90%, 91%, 92%, 93%, 94%, 95%, 96%, etc. The thickness of the photosensitive film before and after development can be tested by optical microscope or step profiler, but is not limited thereto.

[0135] In some embodiments of the present application, the cured film of the photosensitive film after exposure, baking, development and heat curing treatment has a dimensional change rate of ≤10% after being immersed in at least one of 2.38 wt% tetramethylammonium hydroxide solution, acetone, PGMEA, NMP, 1 wt% HF, 30 wt% HNO3, 30 wt% H2O2, and 15 wt% KOH for 1 h. In some specific embodiments, the cured film of the photosensitive film after exposure, baking, development and heat curing treatment has a dimensional change rate of ≤1% after being immersed in at least one of 2.38 wt% tetramethylammonium hydroxide solution, acetone, PGMEA, NMP, 1 wt% HF, 30 wt% HNO3, 30 wt% H2O2, and 15 wt% KOH for 1 h. Specifically, the thickness change rate of the photosensitive film before and after the above treatment can represent the dimensional change rate thereof, the thickness of the photosensitive film after the above exposure, baking, development and heat curing is X3, the thickness of the photosensitive film after being immersed in at least one of the above liquids for 1 h is X4, and |X3-X4| / X3x100%≤1%. In some embodiments of the present application, the dimensional change rates of the cured film after being immersed in 2.38 wt% tetramethylammonium hydroxide solution, acetone, PGMEA, NMP, 1 wt% HF, 30 wt% HNO3, 30 wt% H2O2, and 15 wt% KOH respectively for 1 h are all ≤1%.

[0136] In the embodiments of the present application, the cured product of the photosensitive film refers to a cured product obtained after being cured at 270°C for 2 h under a protective atmosphere (for example, nitrogen). During the above curing process, the soluble resin after exposure, the cross-linkable monomer and the thermal cross-linking monomer can react with each other under the action of heat, for example, cross-linking reaction between the soluble resins after exposure, cross-linking reaction between the soluble resins after exposure and the thermal cross-linking monomer, reaction between the soluble resins after exposure and the cross-linkable monomer, reaction between the thermal cross-linking monomer and the cross-linkable monomer, but not limited thereto.

[0137] In some embodiments of the present application, the height retention rate of the cured film of the photosensitive film after exposure, baking, development and heat curing treatment is ≥90% under 6 MPa molding. Specifically, the photosensitive film is attached to the top of a cavity with a height of 10 μm of a structural member, after mask exposure, baking, development and curing at 270°C under nitrogen for 2 h, an epoxy cross-linking agent is cast on the surface of the cured photosensitive film away from the cavity, the cross-linking agent is cured, and then a molding test is performed thereon under 6 MPa, and then the above structure is subjected to slicing treatment, the morphology of the cavity is observed by SEM, and the distance y μm from the side of the cured photosensitive film layer close to the cavity to the bottom of the cavity is measured, and the height retention rate thereof is calculated as (10-y) / 10≥90%.

[0138] The application further provides a preparation method of the photosensitive film, which can be used to prepare the photosensitive film. The photosensitive film is obtained by coating the photosensitive composition provided by the application or the photosensitive composition prepared by the preparation method of the photosensitive composition provided by the application on a support film to form a photosensitive film, and then arranging a protective film on the surface of the photosensitive film away from the support film.

[0139] The application further provides a semiconductor device, which comprises a hollow structure with a cavity, an electronic circuit, and a cured product of the photosensitive film 20 or a patterned photosensitive film 20; the electronic circuit is arranged on the hollow structure; and the cured product of the photosensitive film 20 or the patterned photosensitive film 20 is arranged at the top end of the cavity. It can be understood that the cured product of the photosensitive film or the patterned photosensitive film 20 constitutes the top wall of the cavity. Since the photosensitive film 20 provided by the application is used, the integrity and reliability of the semiconductor device can be improved.

[0140] In some embodiments of the application, the cavity of the hollow structure contains an electronic circuit and / or a functional structure.

[0141] In some embodiments of the application, the semiconductor device includes but is not limited to a packaged device. In some specific embodiments, the packaged device includes but is not limited to a radio frequency device; the radio frequency device includes but is not limited to an elastic wave filter, a sensor, and a surface acoustic wave filter.

[0142] The application further provides a preparation method of a semiconductor device, which comprises: forming a support layer on the surface of a substrate provided with an electronic circuit; arranging a photosensitive film on the surface of the support layer, wherein the photosensitive film is prepared by the photosensitive composition provided by the application or the photosensitive composition prepared by the preparation method of the photosensitive composition provided by the application; the photosensitive film forms a cured film after curing; and the substrate, the support layer, and the cured film form a hollow structure with a cavity to obtain a semiconductor device.

[0143] The above preparation method is suitable for large-scale industrial production, has strong production reliability, and has high product yield.

[0144] The preparation method provided by the application can be used to manufacture semiconductor devices such as integrated circuits. The preparation method can be used to prepare semiconductor devices suitable for etching machines.

[0145] The application further provides an electronic device, which comprises the semiconductor device provided by the application and a circuit board, and the circuit board is electrically connected to the semiconductor device; and / or the electronic device comprises a cured product of the photosensitive film or a patterned photosensitive film provided by the application.

[0146] In some embodiments of this application, the electronic device includes, but is not limited to, terminal devices such as mobile phones, tablet computers, laptop computers, vehicle-mounted devices, and smart wearable devices.

[0147] The technical solution of this application is further illustrated below with reference to several specific embodiments.

[0148] Synthesis example 1 PAE Synthesis Under ice bath conditions, 0.56 g of hydroquinone, 132.7 g of hydroxyethyl methacrylate (HEMA), 158.2 g of 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride (ODPA), and 450 mL of N-methylpyrrolidone (NMP) were added to a three-necked flask and stirred at 100 rpm to dissolve, yielding a mixture. 5.16 g of triethylamine (TEA) was dissolved in 60 mL of NMP and then slowly added dropwise to the mixture using a separatory funnel to obtain a second mixture. The mixture was stirred at room temperature under a nitrogen atmosphere for 20 h. The temperature of the second mixture was then lowered to below 0 °C, and 123.78 g of thionyl chloride was slowly added dropwise to the second mixture using a constant-pressure dropping funnel. The reaction was carried out under ice bath conditions for 1 h, followed by a 1 h reaction at room temperature. After the reaction was complete, the system temperature was lowered to below 0 °C. 177.4 g of 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6FAP) and 0.4 g of hydroquinone were dissolved in 350 mL of NMP and added to the second mixture obtained from the above reaction. After stirring overnight at room temperature, 134.1 g of triethylamine was slowly added, and the reaction was continued for 4 h to obtain the third mixture. After the reaction was completed, 40 g of anhydrous ethanol was added to the third mixture, and after reacting for 30 min, the mixture was filtered through a Buchner funnel. The filtrate was slowly added dropwise to deionized water to precipitate a light-colored solid. After repeated sedimentation three times, the solid was dried under vacuum to obtain PAE resin powder with Mw = 12 kDa and a molecular weight distribution index (PDI) of 2.45.

[0149] Synthesis example 2 Synthesis of PI Into a 1 L four-necked flask, 46.7 g of 6FAP and 1.86 g of 1,1',3,3'-tetramethyl-1,3-bis(3-aminopropyl)disiloxane and 150 g of NMP were added under a stream of dry nitrogen, stirred at room temperature until completely dissolved, 46.5 g of ODPA was added, and washed with 45 mL of NMP, warmed to 80 °C and kept for 1 h until completely dissolved, to obtain a polymerization solution. 3.27 g of m-aminophenol was added to the polymerization solution, and continued to keep at 80 °C for 1 h; 45 mL of xylene was added, and warmed to 185 °C and stirred for 5 h, after cooling to 100 °C, 150 g of NMP was added and stirred uniformly, the solution was slowly added to deionized water under high speed stirring, a white fibrous precipitate was separated out, filtered and collected, washed with water and dried at 80 °C under vacuum for 12 h to obtain a PI resin, the molecular weight Mw=15 kDa, PDI=2.56.

[0150] Example 1 Into a clean straight bottle, 25 g of silica, 0.4 g of γ-glycidoxypropyltrimethoxysilane, 10 g of PAE resin, 4.5 g of PETA, 0.25 g of No. 1 photoinitiator, 0.5 g of thermal crosslinking agent as shown in formula (1-1), and 25 g of solvent (mass ratio of EL:GBL is 8:2) were weighed respectively, sealed and stirred to dissolve and disperse to obtain a photosensitive composition. Then the photosensitive composition was coated on a PET support film, baked and dried at 80 °C for 6.5 min, and then a PET protective film was laminated on the surface to obtain a photosensitive film; wherein the thickness of the photosensitive film was 40 μm.

[0151] Example 2 Into a clean straight bottle, 30 g of silica, 0.3 g of γ-glycidoxypropyltrimethoxysilane, 10 g of PI resin, 4.5 g of ETPTA, 0.3 g of No. 1 photoinitiator, 1 g of thermal crosslinking agent as shown in formula (1-1), and 25 g of solvent (mass ratio of EL:GBL is 8:2) were weighed respectively, sealed and stirred to dissolve and disperse to obtain a photosensitive composition. Then the photosensitive composition was coated on a PET support film, baked and dried at 80 °C for 6.5 min, and then a PET protective film was laminated on the surface to obtain a photosensitive film; wherein the thickness of the photosensitive film was 40 μm.

[0152] Example 3 Take 30 g of silica, 0.2 g of γ-glycidoxypropyltrimethoxysilane, 5 g of PAE resin, 5 g of PI resin, 4.5 g of BPA2EODMA, 0.25 g of No. 2 photoinitiator, 1.5 g of thermal crosslinking agent as shown in formula (1-2), 20 g of solvent (mass ratio of EL:GBL is 8:2) into a clean straight bottle, after sealing, stirring, dissolving and dispersing to obtain a photosensitive composition. Then the photosensitive composition is coated on the PET support film, baked and dried at 80°C for 6 min, and then a PET protective film is laminated on its surface to obtain a photosensitive film; wherein the thickness of the photosensitive film is 40 μm.

[0153] Example 4 Take 35 g of silica, 0.3 g of γ-glycidoxypropyltrimethoxysilane, 8 g of PAE resin, 2 g of PI resin, 1 g of PETA, 4.5 g of ETPTA, 0.2 g of No. 2 photoinitiator, 2 g of thermal crosslinking agent as shown in formula (1-2), 20 g of solvent (mass ratio of EL:GBL is 8:2) into a clean straight bottle, after sealing, stirring, dissolving and dispersing to obtain a photosensitive composition. Then the photosensitive composition is coated on the PET support film, baked and dried at 80°C for 6 min, and then a PET protective film is laminated on its surface to obtain a photosensitive film; wherein the thickness of the photosensitive film is 40 μm.

[0154] Example 5 Take 35 g of silica, 0.3 g of γ-glycidoxypropyltrimethoxysilane, 2 g of PAE resin, 8 g of PI resin, 1.5 g of PETA, 3.5 g of BPA2EODMA, 0.3 g of No. 2 initiator, 3 g of thermal crosslinking agent as shown in formula (1-1), 30 g of solvent (mass ratio of EL:GBL is 8:2) into a clean straight bottle, after sealing, stirring, dissolving and dispersing to obtain a photosensitive composition. Then the photosensitive composition is coated on the PET support film, baked and dried at 80°C for 7 min, and then a PET protective film is laminated on its surface to obtain a photosensitive film; wherein the thickness of the photosensitive film is 40 μm.

[0155] Example 6 Respectively, 30 g of silica, 0.4 g of γ-glycidoxypropyltrimethoxysilane, 5 g of PAE resin, 5 g of PI resin, 5 g of PETA, 0.1 g of No. 1 photoinitiator, 0.15 g of No. 2 photoinitiator, 0.25 g of thermal crosslinking agent as shown in formula (1-2), 25 g of solvent (mass ratio of 8:2 of EL:GBL) into a clean straight bottle, after sealing, stirring, dissolving and dispersing to get a photosensitive composition. Then the photosensitive composition is coated on the PET support film, baked and dried at 80℃ for 7 min, and then a PET protective film is laminated on its surface to obtain a photosensitive film; wherein the thickness of the photosensitive film is 40 μm.

[0156] Example 7 Respectively, 30 g of silica, 0.4 g of γ-glycidoxypropyltrimethoxysilane, 5 g of PAE resin, 5 g of PI resin, 5 g of PETA, 0.1 g of No. 1 photoinitiator, 0.15 g of No. 2 photoinitiator, 0.25 g of thermal crosslinking agent as shown in formula (1-2), 25 g of solvent (mass ratio of 8:2 of EL:GBL) into a clean straight bottle, after sealing, stirring, dissolving and dispersing to get a photosensitive composition. Then the photosensitive composition is coated on the PET support film, baked and dried at 80℃ for 7 min, and then a PET protective film is laminated on its surface to obtain a photosensitive film; wherein the thickness of the photosensitive film is 40 μm.

[0157] Example 8 Respectively, 30 g of silica, 0.4 g of γ-glycidoxypropyltrimethoxysilane, 5 g of PAE resin, 5 g of PI resin, 5 g of PETA, 0.1 g of No. 1 photoinitiator, 0.15 g of No. 2 photoinitiator, 0.25 g of thermal crosslinking agent as shown in formula (1-2), 25 g of solvent (mass ratio of 8:2 of EL:GBL) into a clean straight bottle, after sealing, stirring, dissolving and dispersing to get a photosensitive composition. Then the photosensitive composition is coated on the PET support film, baked and dried at 80℃ for 7 min, and then a PET protective film is laminated on its surface to obtain a photosensitive film; wherein the thickness of the photosensitive film is 40 μm.

[0158] Example 9 Take 30 g of silica, 0.45 g of 3-mercaptopropyltrimethoxysilane, 8 g of PAE resin, 2 g of PI resin, 3 g of PETA, 2 g of BPA2EODMA, 0.1 g of No. 1 photoinitiator, 0.1 g of No. 2 photoinitiator, 0.5 g of a thermal crosslinking agent represented by formula (1-1), 0.5 g of a thermal crosslinking agent represented by formula (1-2), and 25 g of a solvent (mass ratio of EL:GBL = 8:2) into a clean straight bottle, and after sealing, stir to dissolve and disperse to obtain a photosensitive composition. Then, the photosensitive composition is coated on a PET support film, baked and dried at 80°C for 7 min, and then a PET protective film is laminated on the surface to obtain a photosensitive film; wherein the thickness of the photosensitive film is 40 μm.

[0159] Comparative Example 1 Take 30 g of silica, 0.2 g of γ-glycidoxypropyltrimethoxysilane, 10 g of PAE resin, 3 g of PETA, 3 g of ETPTA, 0.3 g of No. 1 photoinitiator, 0.05 g of a thermal crosslinking agent represented by formula (1-1), and 25 g of a solvent (mass ratio of EL:GBL = 8:2) into a clean straight bottle, and after sealing, stir to dissolve and disperse to obtain a photosensitive composition. Then, the photosensitive composition is coated on a PET support film, baked and dried at 80°C for 6.5 min, and then a high-transmittance PET protective film is laminated on the surface to obtain a photosensitive film; wherein the thickness of the photosensitive film is 40 μm.

[0160] Comparative Example 2 Take 30 g of silica, 0.3 g of γ-glycidoxypropyltrimethoxysilane, 10 g of PI resin, 2 g of PETA, 2 g of BPA2EODMA, 0.3 g of No. 2 photoinitiator, and 20 g of a solvent (mass ratio of EL:GBL = 8:2) into a clean straight bottle, and after sealing, stir to dissolve and disperse to obtain a photosensitive composition. Then, the photosensitive composition is coated on a PET support film, baked and dried at 80°C for 6.5 min, and then a PET protective film is laminated on the surface to obtain a photosensitive film; wherein the thickness of the photosensitive film is 40 μm. Comparative Example 3 Take 30 g of silica, 0.3 g of γ-glycidoxypropyltrimethoxysilane, 5 g of PAE resin, 5 g of PI resin, 0.5 g of ETPTA, 0.5 g of BPA2EODMA, 0.1 g of No. 1 photoinitiator, 0.15 g of No. 2 photoinitiator, 1 g of a thermal crosslinking agent represented by formula (1-1), 3 g of a thermal crosslinking agent represented by formula (1-2), and 30 g of a solvent (EL:GBL at a mass ratio of 8:2) into a clean straight bottle, stir, dissolve and disperse to obtain a photosensitive composition after sealing. Then, the photosensitive composition is coated on a PET support film, baked and dried at 80°C for 7 min, and then a PET protective film is laminated on the surface to obtain a photosensitive film; wherein the thickness of the photosensitive film is 40 μm.

[0161] Comparative Example 4 Take 0.3 g of γ-glycidoxypropyltrimethoxysilane, 5 g of PAE resin, 5 g of PI resin, 2 g of PETA, 2 g of ETPTA, 0.1 g of No. 1 photoinitiator, 0.15 g of No. 2 photoinitiator, 1 g of a thermal crosslinking agent represented by formula (1-1), 1 g of a thermal crosslinking agent represented by formula (1-2), and 30 g of a solvent (EL:GBL at a mass ratio of 8:2) into a clean straight bottle, stir, dissolve and disperse to obtain a photosensitive composition after sealing. Then, the photosensitive composition is coated on a PET support film, baked and dried at 80°C for 7 min, and then a PET protective film is laminated on the surface to obtain a photosensitive film; wherein the thickness of the photosensitive film is 40 μm.

[0162] Performance Test (1) The photosensitive film is cut into a strip with a width of 25 mm using a cutter, and then placed in an oxygen-free nitrogen oven for high-temperature curing at 270°C for 2 h, and then the modulus and Tg of the cured film in the temperature range of 40-350°C are measured using DMA, the elastic modulus of the cured film at 180°C is recorded, and the linear thermal expansion coefficient is tested.

[0163] (2) The photosensitive film is cut to an appropriate size and attached to the surface of a silicon wafer, and then exposed to a mixed light source of 405 nm and 365 nm, with an exposure dose of 150 mW / cm 2 After post-baking at 110°C for 8 min, the unexposed part is removed by dissolution with 2.38 wt.% TMAH to obtain a negative pattern. The surface and cross-sectional morphology of the pattern is observed using an optical microscope, the minimum size of the pattern opening is the resolution accuracy, resolution ≤40 μm is A, greater than 40 μm and less than 60 μm is B, and ≥60 μm is C; and the film retention rate is calculated and recorded in Table 1.

[0164] (3) The photosensitive film is attached to the top of the cavity with a height of 10 μm of the structural component. After mask exposure, baking, development and heat curing at 270 ℃ in nitrogen for 2 h, a crosslinking agent is cast on the surface of the cured photosensitive film away from the cavity. After the crosslinking agent is cured, it is subjected to a molding test at 6 MPa. Then the above structure is sliced, the morphology of the cavity is observed by SEM and the distance y μm from the side of the cured photosensitive film layer near the cavity to the bottom of the cavity is measured. The height retention rate (10-y) / 10 is calculated.

[0165] (4) The photosensitive film was exposed, baked, developed and heat-cured in sequence, and the dimensional change rate of the cured film after being immersed in 2.38 wt% tetramethylammonium hydroxide solution for 1 h was tested.

[0166] Figure 3A An optical microscope photograph of the surface of the photosensitive composition of Example 1 after chemical resistance evaluation following exposure, baking, development and thermal curing; Figure 3B for Figure 3A Optical microscope images of the cross-section of the above-mentioned structure; Figure 4A An optical microscope photograph of the surface of the photosensitive composition of Comparative Example 1 after chemical resistance evaluation following exposure, baking, development and thermal curing. Figure 4B for Figure 3A Optical microscope images of the cross-section of the above-mentioned structure.

[0167] Photoinitiator No. 1: ; Photoinitiator No. 2: .

[0168] For ease of reading, the specific parameters of the photosensitive compositions of the above embodiments and the test results of the photosensitive layers are summarized in Table 1-1; the specific parameters of the photosensitive compositions of the above comparative examples and the test results of the photosensitive layers are summarized in Table 1-2.

[0169] Table 1-1

[0170] Table 1-2

[0171] It can be found from the data in Table 1-1 to Table 1-2 that the photosensitive composition provided by the embodiment of the present application containing the silane coupling agent and the filler system, while introducing the photoinitiator, the crosslinkable monomer and the thermal crosslinking agent, and controlling the molar amount of the first active functional group, the second active functional group and the third active functional group in the composition to satisfy 0.05≤C / (A+B)≤5, can make the photosensitive composition and the photosensitive film have better mechanical properties and chemical resistance, and maintain higher patterning resolution, mold height retention rate after curing, and better chemical resistance and film retention rate, and lower linear expansion coefficient.

[0172] It should be understood that the first, second and various numerical numbers involved herein are only for the convenience of differentiation in description, and do not limit the scope of the present application.

[0173] In the present application, the association relationship of the associated objects described by "and / or" indicates that there can be three kinds of relationships, for example, A and / or B can represent the following three cases: A exists alone, A and B exist together, and B exists alone, wherein A and B can be singular or plural. The character " / " generally represents an "or" relationship between the associated objects before and after it.

[0174] In the present application, "at least one" means one or more, and "a plurality of" means two or more. "At least one of the following" or the like refers to any combination of these items, including any combination of single item or multiple items. For example, "at least one of a, b, or c", or "at least one of a, b, and c" can represent a, b, c, a-b (i.e. a and b), a-c, b-c, or a-b-c, wherein a, b, and c can be single or multiple.

[0175] In the present application, "-" represents a range value, including the end point values at both ends. For example, the value of a can be 0.5-15, which means that the value of a can be between 0.5 and 15, and includes the end point values 0.5 and 15.

Claims

1. A photosensitizing composition, characterized by comprising: The light-sensitive composition comprises a soluble resin, a cross-linkable monomer, a filler, a silane coupling agent, a photoinitiator, and a thermal cross-linking agent. The soluble resin comprises one or more of a polymer having a main chain containing repeating imide rings, a polymer having a main chain containing repeating amide bonds and ester bonds, and a polymer having a main chain containing repeating amide bonds; and / or, the soluble resin comprises a polymer having a main chain containing repeating first structures, the first structures comprising one or more of a structure composed of an amide bond and an ester bond, an imide ring, and an amide bond. The cross-linkable monomer comprises a first active functional group, the silane coupling agent comprises a second active functional group, and the thermal cross-linking agent comprises a third active functional group; the first active functional group and the second active functional group are chemically reactive with the third active functional group, and at least one of the first active functional group, the second active functional group, and the third active functional group is chemically reactive with the soluble resin. In the light-sensitive composition, the first active functional group has a molar amount of A mol, the second active functional group has a molar amount of B mol, and the third active functional group has a molar amount of C mol. The light-sensitive composition satisfies 0.05≤C / (A+B)≤5.

2. The photosensory composition according to claim 1, characterized in that, The light-sensitive composition satisfies 0.1≤C / (A+B)≤3.

3. The photosensory composition according to claim 1 or 2, characterized in that, The mass fraction of the filler in the soluble resin is greater than 80%.

4. The photosensing composition according to claim 1 or 2, wherein The number of the third active functional groups in a single molecule of the thermal cross-linking agent is greater than or equal to 2; and / or, The mass fraction of the thermal cross-linking agent in the soluble resin is 0.1%-20%; and / or, The mass fraction of the silane coupling agent in the soluble resin is 0.1%-5%; and / or, The mass fraction of the cross-linkable monomer in the soluble resin is 0.1%-10%; and / or, The mass fraction of the filler in the soluble resin is 81%-500%; and / or, The filler comprises an inorganic filler; and / or, The D50 particle size distribution of the filler is in the range of 0.5 μm-5 μm; and / or, The mass ratio of the filler to the silane coupling agent is 1:0.001 to 1:0.1; and / or, The silane coupling agent is modified on the surface of the filler.

5. The photosensory composition according to claim 1 or 2, wherein The first active functional group comprises one or more of a carbon-carbon unsaturated bond, an epoxy group, a hydroxyl group, a carboxyl group, an isocyanate group, a mercapto group, or an amino group; and / or, the second active functional group comprises one or more of an epoxy group, an amino group, a mercapto group, a carbon-carbon unsaturated bond, or a cyano group; and / or, the third active functional group comprises one or more of a multifunctional alkoxymethyl group, a hydroxymethyl group, or an epoxy group.

6. The light-sensitive composition according to claim 1 or 2, wherein The soluble resin comprises one or both of a polymer having a main chain containing repeating amide bonds and ester bonds and a polymer having a main chain containing repeating imide rings; and / or, The first structure in the soluble resin comprises the structure composed of the amide bond and the ester bond and the imide ring; and / or, The weight average molecular weight of the soluble resin is 5 kDa-60 kDa.

7. The photosensory composition according to claim 1 or 2, wherein the silane coupling agent includes one or more of γ-glycidoxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, bis-[3-(triethoxysilyl)propyl]tetrasulfide, or 11-mercaptoundecyltrimethoxysilane; and / or, the cross-linkable monomer includes one or more of an acrylate cross-linkable monomer, a cyclic ether compound, an olefinically unsaturated compound, an epoxy compound, or a vinyl ether; and / or, the thermal cross-linking agent includes one or more of compounds as shown in formula (1-1) to formula (1-10): formula (1-1), formula (1-2), formula (1-3), formula (1-4), formula (1-5), formula (1-6), formula (1-7), , formula (1-8), Formula (1-9), Formula (1-10).

8. The photosensory composition according to claim 1 or 2, characterized by the light-sensitive composition has a room temperature viscosity of 1000 cps to 5000 cps; and / or, the light-sensitive composition has a solid content of 30 wt.% to 80 wt.%; and / or, the cured product of the light-sensitive composition has an elastic modulus ≥ 6 GPa at 180 ℃; and / or, the cured product of the light-sensitive composition has a glass transition temperature ≥ 280 ℃; and / or, the cured product of the light-sensitive composition has a linear expansion coefficient < 40 ppm / K.

9. A method for preparing a photosensitive composition, characterized by, comprising: mixing a soluble resin, a cross-linkable monomer, a filler, a silane coupling agent, a photoinitiator, and a thermal cross-linking agent; the soluble resin includes one or more of a polymer having a main chain containing repeating imide rings, a polymer having a main chain containing repeating amide bonds and ester bonds, and a polymer having a main chain containing repeating amide bonds; and / or, the soluble resin includes a polymer having a main chain containing repeating first structures, the first structures including multiple ones of amide bonds and ester bonds, imide rings, and amide bonds; the cross-linkable monomer includes a first active functional group, the silane coupling agent includes a second active functional group, and the thermal cross-linking agent includes a third active functional group; the first active functional group and the second active functional group are chemically reactive with the third active functional group, and at least one of the first active functional group, the second active functional group, and the third active functional group is chemically reactive with the soluble resin; in the light-sensitive composition, the first active functional group has a molar amount of A mol, the second active functional group has a molar amount of B mol, and the third active functional group has a molar amount of C mol; the light-sensitive composition satisfies: 0.05 ≤ C / (A+B) ≤ 5.

10. A photosensitive film characterized by comprising: comprising a support film, a protective film, and a light-sensitive film disposed between the support film and the protective film, the light-sensitive film being made of the light-sensitive composition according to any one of claims 1 to 8, or the light-sensitive film being made of the light-sensitive composition prepared according to the method of claim 9.

11. The photosensitive film according to claim 10, wherein the light-sensitive film has a melt viscosity at 80 ℃ of 20000 Pa·s to 70000 Pa·s; and / or, the light-sensitive film has a post-exposure bake (PEB) of 30 s to 120 s; and / or, the light-sensitive film has a post-exposure bake (PEB) of 30 s to 120 s; and / or, The cured film of the photosensitive film after exposure, baking, development and heat curing treatment has a dimensional change rate ≤1% after immersion in at least one of 2.38 wt% tetramethylammonium hydroxide solution, acetone, propylene glycol monomethyl ether acetate, N-methyl pyrrolidone, 1 wt% HF, 30 wt% HNO3, 30 wt% H2O2, 15 wt% KOH for 1 h; and / or, The cured film of the photosensitive film after exposure, baking, development and heat curing treatment has a height retention rate ≥90% under 6 MPa molding; and / or, The glass transition temperature of the cured product of the photosensitive film is ≥280 ℃; and / or, The linear expansion coefficient of the cured product of the photosensitive film is <40 ppm / K.

12. A method for producing a photosensitive film, characterized by comprising the steps of: Comprising: The photosensitive film is prepared by coating the photosensitive composition according to any one of claims 1-8 or the photosensitive composition prepared by the preparation method according to claim 9 on a support film, and then arranging a protective film on the surface of the photosensitive film away from the support film to obtain a photosensitive film.

13. A semiconductor device, characterized by comprising: The semiconductor device comprises a hollow structure with a cavity, an electronic circuit, and a cured product of the photosensitive film according to claim 10 or 11 or a patterned photosensitive film; or, the semiconductor device comprises a hollow structure with a cavity, an electronic circuit, and a cured product of the photosensitive film prepared by the preparation method according to claim 12 or a patterned photosensitive film; The electronic circuit is arranged on the hollow structure; The cured product of the photosensitive film or the patterned photosensitive film is arranged at the top end of the cavity.

14. A method of manufacturing a semiconductor device, characterized by, Comprising: Forming a support layer on the surface of a substrate provided with an electronic circuit; Arranging a photosensitive film on the surface of the support layer, wherein the photosensitive film is prepared by the photosensitive composition according to any one of claims 1-8 or the photosensitive composition prepared by the preparation method according to claim 9; The photosensitive film forms a cured film after curing, and the substrate, the support layer and the cured film form a hollow structure with a cavity to prepare a semiconductor device.

15. An electronic device, comprising: The semiconductor device and a circuit board are electrically connected, wherein the semiconductor device is prepared according to claim 13 or the preparation method according to claim 14, and / or the electronic device comprises a cured product of the photosensitive film according to claim 10 or 11.

Images