Photosensitive composition, preparation method and application thereof

Abstract

The embodiment of the invention provides a photosensitive composition, a preparation method and application thereof. The photosensitive composition is a filler-containing PI, PAE and polyamide acid photosensitive system, and a photoinitiator with a specific structure is further selected from the filler-containing photosensitive system, so that the patterning resolution, resolution, deep curing performance and better machinability of the photosensitive composition and a photosensitive layer prepared from the photosensitive composition can be effectively improved; the prepared patterned film also has good physical and chemical properties and mechanical properties; the photosensitive composition can be used in the manufacturing of semiconductor devices, and improves the integrity and reliability of the semiconductor devices.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of photosensitive materials, in particular to a photosensitive composition, a preparation method and application thereof. BACKGROUND

[0002] The photosensitive composition can form a high-precision patterned film after a patterning process such as exposure. In the application of a polyimide (abbreviated as PI) or polyamide ester (abbreviated as PAE) photosensitive composition, the photosensitive film can be first prepared, and then the photosensitive film is subjected to patterned microprocessing to obtain a high-precision patterned film. As the photosensitive film is applied to the application scenarios, it can be used for packaging materials of high-performance electronic components. In order to meet the use requirements of the above-mentioned application scenarios, the photosensitive film often needs to have relatively optimal photosensitive performance, relatively high photocuring ability, good processability, and the cured product thereof needs to have relatively high mechanical properties and good physicochemical properties. In order to obtain the photosensitive film with the above-mentioned properties, it is essentially necessary to provide a photosensitive composition with relatively optimal comprehensive performance. SUMMARY

[0003] In view of this, the present application provides a photosensitive composition, a preparation method and application thereof. The photosensitive composition is a PI, PAE or polyamide acid photosensitive system containing fillers. In the above-mentioned photosensitive system containing fillers, a specific structure of a photoinitiator is further selected, which can effectively improve the patterning resolution, resolution, deep curing performance and relatively optimal processability of the photosensitive composition and the photosensitive layer prepared therefrom, and the patterned film prepared therefrom also has good physicochemical properties and mechanical properties.

[0004] The first aspect of the present application provides a photosensitive composition, which comprises a soluble resin, a photoinitiator, a cross-linkable monomer and a filler. 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 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 amide bond and ester bond structures, imide ring and amide bond. The photoinitiator comprises a first photoinitiator, and the first photoinitiator is a compound having the structure of ; 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 C1-C10 hydrocarbon group with a second structure in the main chain, a substituted or unsubstituted C1-C10 acyl group, a substituted or unsubstituted C1-C10 acyl group with a second structure in the main chain, a substituted or unsubstituted C1-C10 alkoxy group, a substituted or unsubstituted C1-C10 alkoxy group with a second structure in the main chain; the second structure comprises one or more of an ether oxygen bond, a thioether bond, an ester bond, a thioester bond, an amide bond or a urethane bond; 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, and R4, R5may be connected to the N atom to form a ring; The mass content of the filler is > 80% based on the mass of the soluble resin.

[0005] The embodiments of the present application can improve the deep curing ability of the PI, PAE and polyamide acid photosensitive composition system with high filler ratio, the resolution of the pattern and the patterning resolution by regulating the photoinitiator in the system; and the photosensitive layer 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 requirement for the process and has a higher energy efficiency. In addition, the photosensitive composition provided in the embodiments of the present application still has a better adhesion of the photosensitive layer prepared therefrom, and can effectively reduce the risk of bubbles or delamination at the interface between the photosensitive layer and the adhered substrate in the application process.

[0006] In some embodiments of the present application, the substituents in the R1, R2, R3, the substituted or unsubstituted C1-C10 hydrocarbon group, the substituted or unsubstituted C1-C10 hydrocarbon 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, the substituted or unsubstituted C1-C10 alkoxy group with a second structure in the main chain are independently selected from one or more of a halogen atom, a hydroxyl group, a carboxyl group, a nitro group, a cyano group or the -NR4R5.

[0007] In some embodiments of the present application, the first photoinitiator has a molar absorption coefficient ≥ 200 L / (mol·cm) under light source at at least one wavelength ≤ 450 nm. In this way, the surface photocuring effect of the photosensitive composition can be effectively improved, the risk of device failure caused by the obvious inner cutting of the pattern bottom of the photosensitive layer after exposure and the easy delamination of the opening after development due to the large absorbance of the polyimide-based resin can be reduced, and the negative impact on the morphology, resolution and resolvability of the patterned photosensitive film can be avoided. In some specific embodiments, the first photoinitiator has a molar absorption coefficient ≥ 200 L / (mol·cm) under light at a wavelength of 365 nm.

[0008] In some embodiments of the present application, the first photoinitiator further comprises a substituted or unsubstituted oxime ester group or a substituted or unsubstituted main chain oxime ester-containing group chemically bonded to the In some embodiments of the present application, the first photoinitiator further comprises a substituted or unsubstituted oxime ester group or a substituted or unsubstituted main chain oxime ester-containing group chemically bonded to the

[0009] In some embodiments of the present application, the soluble resin comprises a polymer having a main chain containing a structure composed of repeating amide bonds and ester bonds, or a polymer having a main chain containing repeating imide rings. In this way, the stability of the composition and the subsequent photosensitive layer can be further improved, and the performance of the final semiconductor device can be further optimized.

[0010] In some embodiments of the present application, the soluble resin comprises a polymer having a main chain containing a structure composed of 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 amide bonds and ester bonds and the imide ring. In the high filler system photosensitive composition of the present application, the simultaneous introduction of 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 layer, and also facilitate the improvement of the storage stability of the photosensitive composition and the photosensitive film.

[0011] In some embodiments of the present application, the mass fraction of PAE in the soluble resin is ≥ 50%. In other words, the mass ratio of PAE to PI is ≥ 1:1. In this way, the resolvability and pattern resolution of the photosensitive composition and the photosensitive layer can be further optimized, and the elastic modulus of the photosensitive composition and the photosensitive layer after curing can be further improved.

[0012] In some embodiments of the present application, the soluble resin has carboxyl and / or hydroxyl groups. In this way, the solubility of the soluble resin can be promoted to improve the resolvability and patterning of the composition and the photosensitive layer after development.

[0013] In some embodiments of the present application, the weight average molecular weight of the soluble resin is 5 kDa-50 kDa. In this way, the viscosity of the photosensitive composition can be controlled in a suitable range, which is conducive to film formation and the photosensitivity and patterning effect and resolution of the composition.

[0014] In some embodiments of the present application, the first photoinitiator comprises one or more of formula (1-1) to formula (1-15): 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), Formula (1-11), Formula (1-12), Formula (1-13), Formula (1-14), Formula (1-15).

[0015] In some embodiments of the present application, the cross-linkable monomer has a carboxyl group and / or a hydroxyl group. In this way, the pattern resolution of the photosensitive layer can be improved.

[0016] In some embodiments of the present application, the average radical functionality of the cross-linkable monomer is a positive integer of 2-8. In this way, the photosensitivity of the composition is not negatively affected.

[0017] In some embodiments of the present application, the radical equivalent weight of the cross-linkable monomer is 90-250. In this way, the resolution of the photosensitive composition after exposure and development can be effectively improved, and the pattern quality can be improved.

[0018] In some embodiments of the present application, the cross-linkable monomer accounts for 1%-10% of the mass of the soluble resin. In this way, the photosensitivity and mechanical properties of the composition and the cured product of the photosensitive layer can be ensured to be relatively good, and the post-development film retention rate of the composition can be improved.

[0019] In some embodiments of the present application, the photoinitiator accounts for 0.05%-5% of the mass of the soluble resin. In this way, the deep and surface curing effects of the composition and the photosensitive layer can be further improved, and the pattern performance of the photosensitive layer after exposure and development can be optimized.

[0020] 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 performance, and the photosensitive film prepared subsequently has higher mechanical properties, which can effectively reduce the risk of collapse of the photosensitive film when attached to the cavity top wall of the hollow structure, and after the film is attached, exposed, developed and cured, and can effectively improve the yield of the packaged device.

[0021] In some embodiments of the present application, the filler includes inorganic fillers. In this way, the mechanical properties and chemical resistance of the composition and the cured product of the photosensitive layer are more improved. In some specific embodiments, the filler is a crystalline inorganic filler; in this way, the mechanical properties and chemical resistance of the composition and the cured product of the photosensitive layer are more improved.

[0022] In some embodiments of the present application, the inorganic filler includes, but is not limited to, one or more of silicon dioxide, aluminum oxide, glass powder, titanium oxide, calcium oxide, magnesium oxide, zinc oxide, boron oxide, yttrium oxide, zirconium oxide, mica powder, and talc powder.

[0023] In some embodiments of the present application, the D50 particle size of the filler is 0.5-5 μm. In this way, it is beneficial to its dispersion in the composition, and it is also beneficial to optimize the mechanical properties and chemical resistance of the subsequent photosensitive layer and its cured product, and it is also more beneficial to improve the surface and cross-sectional flatness of the photosensitive layer after exposure, development and curing, and to reduce the packaging process difficulty of the packaged device.

[0024] In some embodiments of the present application, the surface of the filler is modified with a coupling agent. The modification of the filler surface with a coupling agent can increase the dispersibility of the filler, improve the stability of the photosensitive composition during mixing, storage and coating, optimize the uniformity of the photosensitive composition to improve the uniformity of the final photosensitive layer, improve the transparency of the final photosensitive layer to at least one wavelength of light source with a wavelength of ≤450 nm, improve the surface and deep curing effect, reduce the dependence on baking after exposure and development, and more improve the mechanical properties of the photosensitive layer and its cured product.

[0025] In some embodiments of the present application, the room temperature viscosity of the photosensitive composition is 1000-5000 cps. In this way, it is beneficial to the film-forming performance of the composition and reduces the risk of gelation.

[0026] In some embodiments of the present application, the solid content of the photosensitive composition is 30-80 wt.%. In this way, it is beneficial to control the content of the soluble resin more appropriately, and it is beneficial to the solubility, dispersibility and film-forming performance of the photosensitive composition.

[0027] In some embodiments of the present application, the surface roughness of the cured product of the photosensitive composition is ≤0.25 μm.

[0028] In some embodiments of the present application, the cured product of the photosensitive composition has an elastic modulus ≥ 6 GPa at 180 ℃.

[0029] In some embodiments of the present application, the photosensitive composition has a patterning resolution ≤ 40 μm.

[0030] In some embodiments of the present application, the pattern formed by exposing and developing the photosensitive composition has no bottomless interior.

[0031] The second aspect of the embodiments of the present application provides a preparation method of a photosensitive composition, comprising: mixing a soluble resin, a photoinitiator, a cross-linkable monomer, and a filler; the soluble resin comprises one or more of a polymer having a main chain containing a repeating imide ring, a polymer having a main chain containing a repeating amide bond and ester bond, and a polymer having a main chain containing a repeating amide bond; and / or, the soluble resin comprises a polymer having a main chain containing a repeating first structure, the first structure comprising a plurality of structures formed by an amide bond and an ester bond, an imide ring, and an amide bond; The photoinitiator comprises a first photoinitiator, the first photoinitiator being a compound having ; wherein, represents a connection site; R1, R2, R3 are 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 C1-C10 hydrocarbon group having a main chain containing a second structure, a substituted or unsubstituted C1-10 acyl group, a substituted or unsubstituted C1-C10 acyl group having a main chain containing a second structure, a substituted or unsubstituted C1-C10 alkoxy group, and a substituted or unsubstituted C1-C10 alkoxy group having a main chain containing a second structure; the second structure comprises one or more of an ether oxygen bond, a thioether bond, an ester bond, a thioester bond, an amide bond, or a urethane bond; R4, R5 are 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, and R4 and R5 can be connected to form a ring with the N atom; the mass content of the filler is > 80% based on the mass of the soluble resin.

[0032] The above preparation method has strong process reliability, high production yield, and is suitable for large-scale industrial production.

[0033] The third aspect of the embodiments of the present application provides a photosensitive film, comprising a support film, a protective film, and a photosensitive layer arranged between the support film and the protective film, the photosensitive layer is made of the photosensitive composition provided by the first aspect of the embodiments of the present application, or the photosensitive layer is made of the photosensitive composition prepared by the preparation method of the photosensitive composition provided by the second aspect of the embodiments of the present application.

[0034] The photosensitive layer of the photosensitive film has high adhesion, high interfacial bonding force with the adhered substrate, and low risk of collapse and delamination defects. The photosensitive film has high light transmittance, low haze, low difficulty in film defect detection, and is conducive to the discovery of problems in the post-film pasting process. The surface and deep curing ability of the photosensitive film are both strong, the risk of powder falling and roughness on the surface is low, and the surface and cross-sectional flatness are good. In addition, the photosensitive layer can obtain a good exposure pattern under a low baking temperature and a short baking time, has a low risk of residue after development, high pattern resolution and patterning resolution, low process requirements, and high production efficiency.

[0035] In some embodiments of the present application, the photosensitive layer with a thickness of 40 μm has a transmittance of ≥50% to at least one wavelength of light source in the range of ≤450 nm. In this way, the deep curing effect of the photosensitive layer can be ensured to be good. In some specific embodiments, the photosensitive layer with a thickness of 40 μm has a transmittance of ≥50% to a light source with a wavelength of 405 nm.

[0036] In some embodiments of the present application, the haze of the photosensitive layer is ≤10%.

[0037] In some embodiments of the present application, the melt viscosity of the photosensitive layer at 80℃ is 20000 Pa·s-70000 Pa·s.

[0038] In some embodiments of the present application, the surface roughness of the cured product of the photosensitive layer is ≤0.25 μm.

[0039] In some embodiments of the present application, the elastic modulus of the cured product of the photosensitive layer at 180℃ is ≥6 GPa.

[0040] In some embodiments of the present application, the patterning resolution of the photosensitive layer is ≤40 μm.

[0041] In some embodiments of the present application, the pattern formed after the photosensitive layer is exposed, developed, and cured has no bottom incision.

[0042] The fourth aspect of the present application provides a preparation method of a photosensitive film, comprising: The photosensitive layer is formed by coating the photosensitive composition provided in the first aspect of the present application or the photosensitive composition prepared by the preparation method of the photosensitive composition provided in the second aspect of the present application on a support film, and then arranging a protective film on the surface of the photosensitive layer away from the support film to obtain a photosensitive film.

[0043] The preparation method has strong process reliability, high production yield, and can flexibly and accurately control the thickness and uniformity of the photosensitive layer, and is suitable for large-scale industrial production.

[0044] The fifth aspect of the embodiments of the present application provides a semiconductor device, which comprises a hollow structure with a cavity, an electronic component, and a cured product of a photosensitive layer of the photosensitive film or a patterned photosensitive layer provided in the second aspect of the embodiments of the present application; the electronic circuit is arranged on the hollow structure; and the cured product of the photosensitive layer or the patterned photosensitive layer is arranged at the top end of the cavity.

[0045] The semiconductor device provided by the embodiments of the present application can improve the integrity and reliability of the semiconductor device.

[0046] In some embodiments of the present application, the cavity of the hollow structure contains an electronic circuit and / or a functional structure.

[0047] 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.

[0048] The sixth aspect of the embodiments of the present application 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; disposing a photosensitive layer on the surface of the support layer, wherein the photosensitive layer is prepared by the photosensitive composition provided in the first aspect of the embodiments of the present application or the photosensitive composition prepared by the preparation method of the photosensitive composition provided in the second aspect of the embodiments of the present application; forming a protective film after curing the photosensitive layer, and surrounding the substrate, the support layer, and the protective film to form a hollow structure with a cavity to obtain a semiconductor device.

[0049] The preparation method provided by the embodiments of the present application is suitable for large-scale industrial production and has strong process reliability.

[0050] The sixth aspect of the embodiments of the present application provides an electronic device, which comprises the semiconductor device provided in the fifth aspect of the embodiments of the present application and a circuit board electrically connected to the semiconductor device; and / or, the electronic device comprises the cured product of the photosensitive layer of the photosensitive film or the patterned photosensitive layer provided in the third aspect of the embodiments of the present application.

[0051] In some embodiments of the present application, the electronic device includes but is not limited to a mobile phone, a tablet computer, a notebook computer, a vehicle-mounted device, a smart wearable device, and other terminal devices. BRIEF DESCRIPTION OF DRAWINGS

[0052] Figure 1A schematic diagram of the structure of the photosensitive film provided in an embodiment of the present application; Figure 2A A schematic diagram of the collapse of the photosensitive layer; Figure 2B A Scanning Electron Microscope (SEM) photo of the photosensitive layer adhering to the top of the cavity of the hollow structure provided in an embodiment of the present application; Figure 3A An optical microscope photo of the patterned photosensitive layer obtained after the photosensitive layer provided in Embodiment 6 of the present application is exposed, developed and cured; Figure 3B An optical microscope photo of the patterned photosensitive layer obtained after the photosensitive layer of Comparative Example 1 is exposed, developed and cured.

[0053] BRIEF DESCRIPTION OF DRAWINGS 1 - photosensitive film; 10 - support film; 20 - photosensitive layer; 30 - protective film; 40 - hollow structure. DETAILED DESCRIPTION

[0054] 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 and then applied as a packaging material for semiconductor devices. Specifically, in order to ensure the normal operation of semiconductor devices such as filters, a hollow structure with stable size is usually needed to build a cavity, and the photosensitive film layer is often used as a top wall material of the cavity. The above application scenario has high performance requirements for the packaging material: it can be opened by exposure and development, and the cured product after lamination, exposure, post-exposure baking, development and thermal curing can withstand high temperature and high mold pressure, and has high modulus to reduce the risk of top wall material collapse or other defects. PI-based or PAE-based photosensitive layer is an ideal material to achieve the above performance. When sold or stored, it is usually sandwiched between a support layer and a protective layer to form a three-layer structure. In the application process, the photosensitive layer is peeled off from the protective layer and the support layer, and the photosensitive film is laminated with the hollow structure, and then subjected to processes such as exposure, baking, development and high-temperature curing to form the top wall of the cavity. In the related art, the polyimide photosensitive layer of some 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 patterning precision, modulus, photosensitivity and deep curing of the photosensitive layer are also increasing. Furthermore, in order to ensure the mold pressure resistance performance to protect the device structure, the thickness of the photosensitive layer in the related art is usually high (≥20 μm), which is not easy to be fully cured in the application process, and is prone to problems such as surface oxidation, surface powdering and roughness, insufficient bottom curing, weak adhesion and abnormal pattern morphology. In order to fully cure, the related art often uses a large exposure dose, and relies on a high baking temperature (for example, higher than 120 ℃) and a long time to optimize the pattern morphology, but the process requirements are strict and affect the production capacity.

[0055] To solve the above technical problems, the embodiments of the present application provide a photosensitive composition, which comprises a soluble resin, a photoinitiator, a cross-linkable monomer and a filler. In the embodiments of the present application, the soluble resin includes a resin that can be dissolved in a developer, 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 may, for example, but is not limited to, ultraviolet light, various types of radiation. 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 cross-linked under irradiation of a 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, etc.

[0056] In the embodiments of the present application, 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 one or more of a structure composed of an amide bond and an ester bond, an imide ring, and an amide bond. In the embodiments of the present application, multiple refers to two or more; that is, the soluble resin includes at least one of a polyimide, a polyamide ester, and a polyamide acid; and / or, the soluble resin includes a copolymer of two or more of a first monomer used to prepare the polyimide, a second monomer used to prepare the polyamide ester, and a third monomer used to prepare the polyamide acid; specifically, the two or more monomers refer to two or more of the first monomer, the second monomer, and the third monomer. 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 multiple monomers, which are not limited in the present application.

[0057] The photoinitiator includes a first initiator, the first initiator being a compound containing a compound of formula (1); wherein, represents a connection site; R1, R2, R3 are 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 C1-C10 hydrocarbon group having a main chain containing a second structure, a substituted or unsubstituted C1-C10 acyl group, a substituted or unsubstituted C1-C10 acyl group having a main chain containing a second structure, a substituted or unsubstituted C1-C10 alkoxy group, and a substituted or unsubstituted C1-C10 alkoxy group having a main chain containing a second structure; the second structure includes one or more of an ether oxygen bond, a thioether bond, an ester bond, a thioester bond, an amide bond, and a carbamate bond; R4, R5 are 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, and R4 and R5 can be connected to form a ring with the N atom; The mass content of the filler is >80% based on the mass of the soluble resin.

[0058] 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 polyamide acid includes a precursor of the polyamide acid. In the embodiments of the present application, the precursor of the polymer includes a material that has processability before final treatment (such as light irradiation, heating, chemical reaction, etc.) and that, after processing, obtains the 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 breaking of side chains or groups, functional group conversion, etc.

[0059] In the embodiments of the present application, the second structure in the aforementioned hydrocarbon group, acyl group, and alkoxy group with a main chain containing a second structure can be the same or different. Each of the aforementioned structures can independently contain one or more second structures. In some specific embodiments, the aforementioned hydrocarbon group, acyl group, and alkoxy group with a main chain containing a second structure independently contain 1-5 second structures. Specifically, the number of second structures in the aforementioned hydrocarbon group, acyl group, and alkoxy group with a main chain containing a second structure is independently 1, 2, 3, 4, or 5.

[0060] For the photosensitive composition of PI, PAE, and polyamic acid system, fillers can be introduced to enhance the mechanical properties of the cured product of the photosensitive composition, but there is usually a difference in refractive index between the fillers and the soluble resin and other components. Simply introducing fillers into the existing system tends to reduce the deep layer photocuring ability of the photosensitive composition and the photosensitive layer, reduce the resolution of the pattern, and cause the occurrence of problems such as post-development residue. The embodiments of the present application can improve the deep layer curing ability of the photosensitive composition system and the photosensitive layer of the photosensitive composition containing PI, PAE, and polyamic acid or a mixed system with a high filler ratio, the resolution of the pattern, and the patterning resolution by regulating the photoinitiator in the system. Moreover, the photosensitive layer prepared from the photosensitive composition can obtain a good exposure topography pattern at a lower post-exposure baking temperature and a shorter post-exposure baking time, has a small risk of post-development residue, has a lower requirement for the process, and has a higher productivity. In addition, the photosensitive composition provided in the embodiments of the present application still has a relatively good adhesion of the photosensitive layer prepared therefrom, which can effectively reduce the risk of bubbles or delamination at the interface between the photosensitive layer and the adhered substrate during application.

[0061] In the embodiments of the present application, the crosslinkable monomer refers to a compound monomer having a group capable of undergoing a crosslinking reaction, wherein the group capable of undergoing a crosslinking reaction 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, and the like.

[0062] In the embodiments of the present application, the photosensitive composition can include one or more first initiators, and the plurality of first initiators can be different in one or more groups of R1, R2, and R3, and / or, The groups connected at the marked sites are different. A single molecule of the first initiator can contain one or more structures as shown in formula (1).

[0063] In the embodiments of the present application, R1, R2, R3are independently selected from one or more of a hydrogen atom, a hydroxyl group (-OH), a carboxyl group (-COOH), a nitro group (-NO2), a cyano group (-CN), -NR4R5, a substituted or unsubstituted C1-C10 hydrocarbon group, a substituted or unsubstituted C1-10 acyl group, one or more of a substituted or unsubstituted C1-C10 alkoxy group, a substituted or unsubstituted C1-C10 hydrocarbon group with a second structure in the main chain, a substituted or unsubstituted C1-10 acyl group, a substituted or unsubstituted C1-C10 acyl group with a second structure in the main chain, a substituted or unsubstituted C1-C10 alkoxy group, a substituted or unsubstituted C1-C10 alkoxy group with a second structure in the main chain; 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, and the R4, R5may be connected to the N atom to form a ring. Specifically, the above-mentioned hydrocarbon groups in R1, R2, R3and R4, R5may be chain hydrocarbon groups or cyclic hydrocarbon groups, for example, a substituted or unsubstituted C1-C10 straight-chain hydrocarbon group, a substituted or unsubstituted C1-C10 branched-chain hydrocarbon group, a substituted or unsubstituted C3-C10 cyclic hydrocarbon group, the chain hydrocarbon group may be a chain alkyl group, a chain alkenyl group, a chain alkinyl group, the cyclic hydrocarbon group may be a cyclic alkyl group, a cyclic alkenyl group, a cyclic alkinyl group, the number of carbon atoms of the substituted or unsubstituted hydrocarbon group may be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10. The above-mentioned acyl group may be, for example, -CO-R x , R x -S(=O)2-, 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 1, 2, 3, 4, 5, 6, 7, 8, 9, 10. The unsubstituted alkoxy group is -OR y , R y is an alkyl group, for example, a methoxy group, an ethoxy group, a propoxy group, etc., the number of carbon atoms of the substituted or unsubstituted alkoxy group may be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10. The above-mentioned substituted hydrocarbon group, substituted alkoxy group, substituted acyl group may independently contain one or more substituents. In some specific embodiments, the substituted above-mentioned group independently contains 1-5 substituents. Specifically, the number of substituents in the substituted above-mentioned group may be independently 1, 2, 3, 4, 5.

[0064] In the embodiments of the present application, the substituted or unsubstituted C1-C10 alkyl group with a second structure in the main chain is a group with a second structure embedded in the main chain, which can be a group with a second structure embedded in the carbon chain, for example, a group obtained by interrupting the hydrocarbon group in the above-mentioned substituted or unsubstituted C2-C10 alkyl group with a second structure, or a group of a methyl group and a second structure connected to the benzene ring through the second structure, which conforms to the principle of chemical bonding. The substituent group can substitute any substitutable hydrogen atom on the C1-C10 alkyl group with a second structure in the main chain, which can achieve substitution. The above-mentioned group can contain one or more substituents. In some specific embodiments, the substituted above-mentioned group independently contains 1-5 substituents. Specifically, the number of substituents in the substituted above-mentioned group can be independently 1, 2, 3, 4, 5.

[0065] In the embodiments of the present application, the substituted or unsubstituted C1-C10 acyl group with a second structure in the main chain is a group with a second structure embedded in the main chain, which can be a group with a second structure embedded in the carbon chain, for example, a group obtained by interrupting the hydrocarbon group in the above-mentioned substituted or unsubstituted C2-C10 acyl group with a second structure, or a C1-C10 acyl group connected to the benzene ring through the second structure, which conforms to the principle of chemical bonding. The substituent group can substitute any substitutable hydrogen atom on the C1-C10 acyl group with a second structure in the main chain, which can achieve substitution. The above-mentioned group can contain one or more substituents. In some specific embodiments, the substituted above-mentioned group independently contains 1-5 substituents. Specifically, the number of substituents in the substituted above-mentioned group can be independently 1, 2, 3, 4, 5.

[0066] In the embodiments of the present application, the substituted or unsubstituted C1-C10 acyl group with a second structure in the main chain is a group with a second structure embedded in the main chain, which can be a group with a second structure embedded in the carbon chain, for example, a group obtained by interrupting the hydrocarbon group in the above-mentioned substituted or unsubstituted C2-C10 acyl group with a second structure, or a C1-C10 acyl group connected to the benzene ring through the second structure, which conforms to the principle of chemical bonding. The substituent group can substitute any substitutable hydrogen atom on the C1-C10 acyl group with a second structure in the main chain, which can achieve substitution. The above-mentioned group can contain one or more substituents. In some specific embodiments, the substituted above-mentioned group independently contains 1-5 substituents. Specifically, the number of substituents in the substituted above-mentioned group can be independently 1, 2, 3, 4, 5.

[0067] In some embodiments of the present application, in the above R1, R2, R3, the substituents in the substituted or unsubstituted C1-C10 hydrocarbon group, the substituted or unsubstituted main chain containing a second structure C1-C10 hydrocarbon group, the substituted or unsubstituted C1-10 acyl group, the substituted or unsubstituted main chain containing a second structure C1-C10 acyl group, the substituted or unsubstituted C1-C10 alkoxy group, and the substituted or unsubstituted main chain containing a second structure C1-C10 alkoxy group are independently selected from one or more of a halogen atom, a hydroxyl group (-OH), a carboxyl group (-COOH), a nitro group (-NO2), a cyano group (-CN), or -NR4R5.

[0068] In some embodiments of the present application, R3may form a ring with the group at the position marked by .

[0069] In some embodiments of the present application, in the above R4, R5, the substituents in the substituted or unsubstituted C1-C10 alkoxy group and the substituted or unsubstituted C1-C10 hydrocarbon group are independently selected from one or more of a halogen atom, a hydroxyl group, a carboxyl group, a nitro group, and a cyano group.

[0070] In some embodiments of the present application, the presence of the soluble resin, the photoinitiator, and the crosslinkable monomer in the photosensitive composition can be tested by, but not limited to,1H nuclear magnetic resonance (1H Nuclear Magnetic Resonance,1H NMR) and high performance liquid chromatography-mass spectrometry (High Performance Liquid Chromatography-Mass Spectrometry, HLPC-MS). 1 H Nuclear Magnetic Resonance, 1 H NMR) and high performance liquid chromatography-mass spectrometry (High Performance Liquid Chromatography-Mass Spectrometry, HLPC-MS).

[0071] In some embodiments of the present application, the first photoinitiator has a molar absorption coefficient ≥ 200 L / (mol·cm) under light source of at least one wavelength ≤ 450 nm. In the embodiments of the present application, the light of wavelength ≤ 450 nm may, for example, be light source of any wavelength in the range of 248 nm-450 nm. In some specific embodiments, the first photoinitiator has a molar absorption coefficient ≥ 200 L / (mol·cm) under light source of 365 nm, which can effectively improve the surface photocuring effect of the photosensitive composition, reduce the risk of obvious undercut at the bottom of the pattern after exposure of the photosensitive layer due to the large absorbance of the polyimide resin, and cause the device to fail due to easy delamination at the opening after development, and also will not have a negative impact on the morphology, resolution and resolution of the patterned photosensitive film. Specifically, the molar absorption coefficient of the first photoinitiator under 365 nm may, for example, be 200 L / (mol·cm), 300 L / (mol·cm), 500 L / (mol·cm), 800 L / (mol·cm), 1000 L / (mol·cm), 2000 L / (mol·cm), 3000 L / (mol·cm), 4000 L / (mol·cm), 5000 L / (mol·cm), 6000 L / (mol·cm) or higher.

[0072] In the embodiments of the present application, the specific reagent of the first photoinitiator can be characterized by HPLC-MS, and the corresponding standard sample is tested by UV-vis to obtain its molar absorption coefficient to light source of at least one wavelength ≤ 450 nm (for example, light source of 365 nm), or it can be obtained by consulting literature.

[0073] In some embodiments of the present application, the photoinitiator further comprises a substituted or unsubstituted oxime ester group ( , 1 #, 2 #, 3 The positions marked indicate the connection sites. In the photosensitive composition of the embodiments of the present application, the oxime ester group cooperates with the group to more favorably optimize the surface curing and deep curing effects of the subsequent photosensitive layer, especially for the deep and surface curing of the photosensitive layer with a certain thickness. Specifically, the photosensitive layer with a certain thickness refers to a photosensitive film with a thickness ≥ 20 μm, which can be ≥ 25 μm, ≥ 30 μm, ≥ 35 μm, ≥ 40 μm, ≥ 45 μm. In some embodiments, the thickness of the photosensitive layer is 20 μm-50 μm.

[0074] In some embodiments, the photoinitiator includes a second photoinitiator, which includes an oxime ester photoinitiator. Specifically, an oxime ester photoinitiator refers to an initiator containing an oxime ester group and having photoinitiating ability under irradiation by a light source of at least one wavelength ≤ 450 nm, and the second photoinitiator does not contain the structure of formula (1). In this case, the first photoinitiator may not contain an oxime ester group, for example, the first photoinitiator has the structure shown in formula (1). The groups attached to the marked positions include, but are not limited to, substituted or unsubstituted hydrocarbon groups. 4 #-R f -NR4R5, the above R f For example, it can be a single bond or a carbazole group, specifically, it can be... , , , , , , , , , In the above formula 5 #、 6 #、 7 #、 8 #、 9 #、 10 #、 11 #、 12 #、 13 #、 14 The position of the # mark is connected to the position of the mark in formula (1), and R3 is the R3 in the aforementioned formula (1). R3 forms a ring with the carbon atoms at the positions of the 13# and 14# marks.

[0075] In some embodiments of this application, the second photoinitiator includes .

[0076] In other embodiments, the first initiator comprises a substituted or unsubstituted oxime ester group. 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 may 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 position marked, and the oxime ester group is chemically bonded to the position marked, and the oxime ester group is chemically bonded to 1 the position marked, and the oxime ester group is chemically bonded to the position marked, and the oxime ester group is chemically bonded to the position marked, and the oxime ester group is chemically bonded to the position marked, and the oxime ester group is chemically bonded to

[0077] In some embodiments of the present application, in addition to the linking site to the structure of formula (1) or the benzene ring structure, the remaining two linking sites can be connected with organic groups, which can be hydrocarbon groups, etc.

[0078] In some embodiments, at least part of the first photoinitiator contains an oxime ester group, and the photoinitiator further comprises the second photoinitiator described above.

[0079] In some embodiments of the present application, the photoinitiator contains The molar ratio of the structure represented by formula (1) to the oxime ester group is 0.01:1 to 99:1. It can be understood that, as described above, when the structure of formula (1) and the oxime ester group are counted, they can share a carbonyl group. Specifically, the molar ratio of the structure represented by formula (1) to the oxime ester group can be, for example, 0.01:1, 0.02:1, 0.05:1, 0.08:1, 0.1:1, 0.2:1, 0.3:1, 0.4:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1:1, 2:1, 5:1, 8:1, 10:1, 12:1, 15:1, 20:1, 25:1, 30:1, 35:1, 40:1, 45:1, 50:1, 55:1, 60:1, 65:1, 70:1, 75:1, 80:1, 85:1, 90:1, 95:1. In some embodiments, the photosensitive composition prepared by the coordination of the structure of formula (1) and the oxime ester group has a photosensitive layer with a thickness of 40 μm, and the transmittance of light with a wavelength of 405 nm is ≥50%.

[0080] In some embodiments of the present application, the first photoinitiator comprises one or more of formula (1-1) to formula (1-15): 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), Formula (1-11), Formula (1-12), Formula (1-13), Formula (1-14), Formula (1-15). The first photoinitiator has a molar absorption coefficient ≥ 200 L / (mol-cm) at at least one wavelength (e.g., a wavelength of 365 nm) in the range of wavelengths ≤ 450 nm, and has good adaptability to the system.

[0081] In some embodiments of the present application, the mass ratio of the photoinitiator to the soluble resin is 0.05%-5%. Controlling the amount of photoinitiator within the above range is more conducive to improving the deep layer and surface layer curing effect of the composition and the photosensitive layer, and optimizing the pattern performance of the photosensitive layer after exposure and development. Specifically, the mass ratio of the photoinitiator to 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 can be used to test the mass content of the photoinitiator, HPLC-MS can be used to test the mass content of the soluble resin, and then the mass ratio of the photoinitiator to the soluble resin can be calculated.

[0082] In the embodiments of the present application, the mass percentage of the filler in the soluble resin is greater than 80%. Specifically, if the mass percentage of the filler is too small, the mechanical properties of the cured composition will be insufficient to meet the process requirements, and there will be defects such as low modulus, poor resistance to mold pressing, high thermal expansion coefficient, insufficient heat resistance, and the like. In some embodiments of the present application, the mass percentage of the filler in the soluble resin is 81% to 500%. In this way, the photosensitive composition has good film-forming properties, and the photosensitive film prepared therefrom has high mechanical properties, which can effectively reduce the risk of collapse of the photosensitive film when attached to the top wall of the cavity of the hollow structure, and after the film is attached, exposed, and developed, and cured. The yield of the packaged device can be effectively improved. Moreover, under the above high filler ratio, the photosensitive composition of the embodiments of the present application still has high transparency to the exposure light source, and can achieve good surface and deep curing effects at the same time. Specifically, the mass percentage of the filler in the soluble resin can be 80.1%, 80.5%, 81%, 85%, 90%, 95%, 100%, 120%, 150%, 180%, 200%, 220%, 250%, 280%, 300%, 320%, 350%, 380%, 400%, 420%, 450%, 480%, 500%, and the like.

[0083] In the embodiments of the present application, the mass content of the filler can be tested by TGA or by performing sedimentation precipitation centrifugal drying and weighing of the photosensitive composition, and 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 filler includes an inorganic filler. In some specific embodiments, the filler is an inorganic filler. In some specific embodiments, the inorganic filler includes, but is not limited to, one or more of silicon dioxide, aluminum oxide, glass powder, titanium oxide, calcium oxide, magnesium oxide, zinc oxide, boron oxide, yttrium oxide, zirconium oxide, mica powder, and 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 composition and the photosensitive layer are improved. In the embodiments of the present application, the shape of the filler can be, for example, spherical, angular, needle-shaped, irregular, and the like.

[0085] In some embodiments of the present application, the D50 particle size of the filler is 0.5-5 μm. Controlling the D50 particle size of the filler within the above range is conducive to its dispersion in the composition, and is conducive to optimizing the mechanical properties and chemical resistance of the subsequent photosensitive layer and its cured product, and is more conducive to improving the surface and cross-sectional flatness of the photosensitive layer after exposure, development and curing, and reducing the packaging process difficulty of the packaged device. Specifically, the D50 particle size of the filler may, for example, be 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 the embodiments of the present application, the D50 particle size of the filler can be tested by a scanning electron microscope (SEM) or dynamic light scattering (DLS), but is not limited thereto.

[0086] In some embodiments of the present application, the photosensitive composition further comprises a coupling agent. In some embodiments, the coupling agent comprises a silane coupling agent. In some specific embodiments, the coupling agent is modified on the surface of the filler. In the photosensitive composition system of the embodiments of the present application, modifying the coupling agent on the surface of the filler can increase the dispersibility of the filler, improve the stability of the photosensitive composition during compounding, storage and coating, and is conducive to optimizing the uniformity of the photosensitive composition to improve the uniformity of the final photosensitive layer, improving the transparency of the final photosensitive layer to at least one wavelength of light source in the wavelength range of ≤450 nm (for example, a light source with a wavelength of 405 nm), improving the surface and deep curing effect, reducing the baking dependence after exposure and development, and more conducive to improving the mechanical properties of the photosensitive layer and its cured product. In some specific embodiments, the surface of the filler is modified with a silane coupling agent; that is, the silane coupling agent forms a chemical force, such as a chemical bond, with the filler; and the silicon-oxygen bond end of the silane coupling agent can form a chemical force with the filler.

[0087] In some embodiments of the present application, the silane coupling agent includes active groups, which include, but are not limited to, one or more of epoxy, styryl, vinyl, amino, isocyanate, ureido, acryl, mercapto. Specifically, the silane coupling agent includes, but is not limited to, one or more of triethoxysilylpropyl maleate, methacryloxypropyl triethoxysilane, 3-ureidopropyl triethoxysilane, 3-mercaptopropyl trimethoxysilane, 3-mercaptopropyl triethoxysilane, 3-mercaptopropyl methyl dimethoxysilane, 3-mercapto methyl trimethoxysilane, 3-mercapto methyl dimethoxysilane, 3-mercaptopropyl ethoxy dimethoxysilane, 3-mercaptopropyl tripropoxysilane, 3-thiopropyl tributoxysilane, 2-(3,4-epoxycyclohexane) ethyl trimethoxysilane, 2-(3,4-epoxycyclohexane) ethyl triethoxysilane, epoxy butyl trimethoxysilane, N-phenyl-3- aminopropyl trimethoxysilane, p-aminophenyl trimethoxysilane, aminophenyl trimethoxysilane, 3-(m-aminophenyl) trimethylsilane, 3-methacryloxypropyl trimethoxysilane, 3-acryloxypropyl trimethoxysilane, 3-ethoxypropyl trimethoxysilane, vinyl trimethoxysilane, methacryloxydimethoxysilane, 3- aminopropyl trimethoxysilane, trimethoxysilylbenzoic acid, 3-methacryloxypropyl trimethoxysilane, N-2-(aminoethyl)-3-aminopropyl trimethoxysilane, N-phenyl-3- aminopropyl trimethoxysilane, vinyl trimethoxysilane, gamma- glycidoxypropyl trimethoxysilane, vinyl triacetoxysilane, gamma-glycidoxypropyl trimethoxysilane. The above-mentioned silane coupling agent is more suitable for the system of the present application, and is more conducive to improving the transparency of the final photosensitive layer and the adhesion of the cured film to the substrate.

[0088] In some embodiments of the present application, the soluble resin includes a polymer with repeating imide rings in the main chain or a polymer with 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, it is more conducive to improving the stability of the composition and the subsequent photosensitive layer, and more conducive to improving the performance of the final semiconductor device.

[0089] In some embodiments of the present application, the soluble resin includes a polyimide, a polyamide ester, and / or a copolymer including a first monomer for forming a polyimide and a second monomer for forming a polyamide ester. In some specific embodiments, the soluble resin includes a mixture of a polyimide and a polyamide ester. In the high filler system photosensitive composition of the present application, the simultaneous introduction of 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 layer, and is also conducive to improving 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 includes structures formed by amide bonds and ester bonds, and imide rings. That is, the soluble resin includes a copolymer of a first monomer for forming polyimide and a second monomer for forming polyamide ester. Similarly, the above-mentioned copolymerized soluble resin can improve the resolution of the pattern of the photosensitive composition and the photosensitive layer, and the storage stability of the above-mentioned two. In some specific embodiments, the soluble resin includes a blend and a copolymer of the above-mentioned PI and PAE.

[0091] In some embodiments of the present application, the mass ratio of PAE in the soluble resin is ≥ 50%. In other words, the mass ratio of PAE to PI is ≥ 1:1, and specifically, the mass ratio of PAE to PI can be, for example, 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 sum 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 layer, and it is more beneficial to improve the elastic modulus of the photosensitive composition and the photosensitive layer 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 the solubility of the soluble resin in an alkaline developing solution (for example, tetramethylammonium hydroxide TMAH), to improve the resolution and patterning of the composition and the photosensitive layer after development. 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 kDa-50 kDa. Controlling the molecular weight of the soluble resin within the above-mentioned range is beneficial to controlling the viscosity of the photosensitive composition within a suitable range, and is beneficial to film formation and the photosensitivity and pattern resolution of the composition. Specifically, the Mw of the soluble resin can be, for example, 5 kDa, 8 kDa, 10 kDa, 12 kDa, 15 kDa, 18 kDa, 20 kDa, 22 kDa, 25 kDa, 28 kDa, 30 kDa, 32 kDa, 35 kDa, 38 kDa, 40 kDa, 42 kDa, 45 kDa, 48 kDa, 50 kDa, etc. In the embodiments of the present application, gel chromatography can be used to test the weight average molecular weight of the soluble resin, but is not limited thereto.

[0094] In some embodiments of the present application, the photosensitive composition further comprises a solvent. The solvent can be any solvent suitable for a polyimide-based photosensitive composition as 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), and the like.

[0095] 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 removal of the solvent to the total mass of the photosensitive composition. Controlling the solid content of the photosensitive composition within the above range is conducive to controlling the content of the soluble resin therein to be more appropriate, and is conducive to the solubility, dispersibility, and film-forming properties of the photosensitive composition; for example, the uniformity of the photosensitive layer 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.%, or 80 wt.%.

[0096] In some embodiments of the present application, the photosensitive composition has a room temperature viscosity of 1000 cps to 5000 cps. Controlling the room temperature viscosity of the photosensitive composition within the above range is also to control the Mw and mass content of the soluble resin within an appropriate range, which is conducive to the film-forming properties of the composition and reduces the risk of gelation. In the embodiments of the present application, the room temperature viscosity of the photosensitive composition can be tested using, but is not limited to, a rotational rheometer, at a rotational speed of 50 rpm to 100 rpm and a shear rate of 50 / s to 100 / s.

[0097] In some embodiments of the present application, the cross-linkable monomer includes a radical polymerization type cross-linkable monomer; the average radical functionality of the radical polymerization type cross-linkable monomer is a positive integer of 2-8. The average radical functionality refers to the number of functional groups in the molecule of the cross-linkable monomer that can participate in the radical polymerization reaction. Controlling the average radical functionality of the cross-linkable monomer within the above range does not negatively affect the photosensitivity of the composition, and is conducive to the performance of the photosensitive composition and the photosensitive layer. Specifically, the average radical functionality of the cross-linkable monomer may, for example, be 2, 3, 4, 5, 6, 7, or 8. The above radical functional groups include, but are not limited to, carbon-carbon unsaturated bonds, epoxy groups, hydroxyl groups, carboxyl groups, isocyanate groups, mercapto groups, amino groups, and the like. In the embodiments of the present application, the type of cross-linkable monomer can be determined by nuclear magnetic resonance testing, and the average radical functionality thereof can be further obtained.

[0098] In some embodiments of the present application, the average radical equivalent of the cross-linkable monomer is 90-250, wherein the radical equivalent = molecular weight / functional group, which can be calculated after testing and analyzing the structure of the monomer by HPLC-MS and 1 The average radical equivalent of the cross-linkable monomer refers to the average molecular weight of the functional groups of the cross-linkable monomer that can participate in the radical polymerization reaction in the radical polymerization reaction. In this way, the resolution of the photosensitive composition after exposure and development can be effectively improved, and the pattern quality can be improved. Specifically, the average radical equivalent of the cross-linkable monomer may, for example, be 90, 100, 120, 150, 180, 200, 220, or 250.

[0099] In some embodiments of the present application, the cross-linkable monomer further includes a carboxyl group and / or a hydroxyl group. The introduction of a hydroxyl group and / or a carboxyl group in the cross-linkable monomer can improve the pattern resolution of the photosensitive layer, i.e., improve the resolution of the pattern obtained after the photosensitive layer is exposed and developed, and is particularly conducive to improving the pattern resolution after development in an alkaline developer (e.g., TMAH).

[0100] In some embodiments of the present application, the cross-linkable monomer includes one or more of ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, pentaerythritol triacrylate (PETA), pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, dipentaerythritol hexaacrylate, ethoxylated trimethylolpropane triacrylate (ETPTA), ethoxylated bisphenol A dimethacrylate (BPA2EODMA), propylene oxide modified bisphenol A diacrylate, propoxylated ethoxylated bisphenol A diacrylate, propoxylated ethoxylated bisphenol A dimethacrylate, oxirane modified bisphenol A diacrylate, isocyanuric acid oxirane modified diacrylate, N,N-methylene bisacrylamide, and the like.

[0101] In some embodiments of the present application, the mass percentage of the cross-linkable monomer in the soluble resin is 1% to 10%. Controlling the content of the cross-linkable monomer in the soluble resin within the above range is conducive to ensuring the photosensitivity and mechanical properties of the cured product of the composition and the photosensitive layer, and is conducive to improving the film retention rate of the composition after development. Specifically, the mass content of the cross-linkable monomer in the soluble resin may, for example, be 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, or 10%. In the embodiments of the present application, the mass content of the cross-linkable monomer may, but is not limited to, be tested by HPLC-MS, and the mass content of the soluble resin is then tested, and the mass ratio of the two is calculated.

[0102] In some embodiments of the present application, in order to improve the comprehensive performance of the photosensitive composition, other additives may also be included in the photosensitive composition. The other additives may be one or more of leveling agents, surfactants, and polymerization inhibitors. The addition of leveling agents and surfactants can improve the uniformity of the coated film layer. The content of the other additives in the photosensitive composition can be adjusted according to actual needs.

[0103] In some embodiments of the present application, the surface roughness Ra of the cured product of the photosensitive composition is ≤0.25 μm. In the embodiments of the present application, the surface roughness of the cured product may, but is not limited to, be tested by an atomic force microscope (AFM) or a roughness tester.

[0104] In some embodiments of the present application, the elastic modulus of the cured product of the photosensitive composition at 180 ℃ is ≥6 GPa; for example, ≥6.5 GPa, ≥7.0 GPa, and further ≥7.3 GPa. In some embodiments, the elastic modulus of the cured product of the photosensitive composition at 180 ℃ is ≥7.5 GPa, for example, 7.9 GPa. The elastic modulus of the cured product at 180 ℃ may, but is not limited to, be tested by dynamic mechanical analysis (DMA).

[0105] 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). During the curing process, the soluble resin and / or the cross-linkable monomer after exposure may, for example, but not limited to, react with each other under the action of heat, such as cross-linking reaction between the soluble resin after exposure, and reaction between the soluble resin after exposure and the cross-linkable monomer.

[0106] In some embodiments of the present application, the patterning resolution of the photosensitive composition is ≤ 40 μm. The patterning resolution refers to the resolution of the pattern obtained after the photosensitive composition is exposed and developed using a mask. In some embodiments of the present application, the pattern obtained after the photosensitive composition is exposed and developed has no bottom cut.

[0107] In some embodiments of the present application, the photosensitive composition is a negative photosensitive composition.

[0108] The present application also provides a preparation method of the photosensitive composition, which can be used to prepare the aforementioned photosensitive composition provided by the present application. Specifically, the preparation method comprises the following steps: mixing the aforementioned soluble resin, the aforementioned photoinitiator, the aforementioned cross-linkable monomer and the aforementioned filler; 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 photoinitiator comprises a first photoinitiator, the first photoinitiator being a compound having ; wherein, represents a linking site; 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 C1-C10 hydrocarbon group having a main chain containing a second structure, a substituted or unsubstituted C1-C10 acyl group, a substituted or unsubstituted C1-C10 acyl group having a main chain containing a second structure, a substituted or unsubstituted C1-C10 alkoxy group, and a substituted or unsubstituted C1-C10 alkoxy group having a main chain containing a second structure; the second structure comprises one or more of an ether oxygen bond, a thioether bond, an ester bond, a thioester bond, an amide bond, or a urethane bond; 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, and R4, R5may be connected to form a ring with the N atom; The mass content of the filler is > 80% based on the mass of the soluble resin.

[0109] In some embodiments of the present application, the preparation of the photosensitive composition comprises the following steps: S1, mixing the aforementioned soluble resin, the photoinitiator, the cross-linkable monomer and the filler to obtain the photosensitive composition.

[0110] In some embodiments, the aforementioned step S1 specifically comprises the following steps: adding the aforementioned soluble resin, the photoinitiator, the cross-linkable monomer and the filler into a solvent, sealing, stirring under the sealed condition, and obtaining the photosensitive composition.

[0111] The application also provides a photosensitive film, which comprises a support film, a protective film, and a photosensitive layer between the support film and the protective film. Figure 1 As shown in the figure, the photosensitive film 1 comprises a support film 10, a protective film 30, and a photosensitive layer 20 between the support film 10 and the protective film 30, wherein the photosensitive layer 20 is made of the photosensitive composition provided by the application.

[0112] Since the photosensitive layer of the photosensitive film is made of the photosensitive composition provided by the application, the photosensitive layer has high adhesion, high interfacial bonding force with the adhered substrate, and low risk of collapse and delamination; the photosensitive film has high light transmittance, low haze, low difficulty in film defect detection, and is conducive to the discovery of problems in the post-film process; the surface and deep curing capacity of the photosensitive film are both strong, the risk of powder falling and roughness on the surface is low, and the surface and cross-section flatness are both excellent. In addition, the photosensitive layer can obtain a good exposure pattern under a low baking temperature and a short baking time, has a low risk of residue after development, high pattern resolution and patterning resolution, low process requirements, and high production efficiency.

[0113] In some embodiments of the application, the photosensitive layer is obtained by drying the photosensitive composition. In some embodiments, the drying can not completely remove the solvent.

[0114] In the embodiments of the application, the materials of the support film and the protective film can be well known to those skilled in the art, for example, PET (polyethylene terephthalate), which is not limited in the application.

[0115] In some embodiments of the application, the solid content of the photosensitive layer is 90-99.5 wt.%. In some specific embodiments, the melt viscosity of the photosensitive layer at 80 ℃ is 20000 Pa·s-70000 Pa·s. In the embodiments of the application, the melt viscosity of the photosensitive layer at 25 o C-100 o C can be tested by a rheometer.

[0116] In some embodiments of the application, the thickness of the photosensitive layer is 20 μm-50 μm. Specifically, the thickness of the photosensitive layer can be, for example, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, etc.

[0117] In some embodiments of this application, the transmittance of a 40 μm thick photosensitive layer to a light source with a wavelength ≤450 nm is ≥50%. In some specific embodiments, the transmittance of a 40 μm thick photosensitive layer to a light source with a wavelength of 405 nm is ≥50%. This ensures a better deep curing effect of the photosensitive layer. Specifically, the transmittance of a 40 μm thick photosensitive layer to a light source with a wavelength ≤450 nm can be, for example, ≥55%, ≥60%, ≥65%, ≥70%, etc.

[0118] In some embodiments of this application, the haze of the photosensitive layer is ≤10%. In the embodiments of this application, a haze meter may be used, but is not limited to, to measure the haze of the photosensitive layer.

[0119] In some embodiments of this application, the patterning resolution of the photosensitive layer is ≤40 μm. In the embodiments of this application, the patterning resolution can be obtained by observation using an optical microscope or SEM, and the minimum aperture size of the patterned photosensitive layer is its patterning resolution.

[0120] In some embodiments of this application, the photosensitive layer adheres to the top of the cavity of the hollow structure without collapsing, and there are no air bubbles at the interface between the photosensitive layer and the material of the hollow structure to which it is adhered. Specifically, Figure 2A The diagram illustrates the collapse of the photosensitive layer, which refers to the photosensitive layer contacting the bottom of the cavity. In some specific embodiments, the photosensitive layer adhered to the top of the cavity of the hollow structure does not collapse after exposure, development, and curing (see [link to documentation]). Figure 2B After exposure, development and curing, the photosensitive layer has no defects such as bubbles or delamination at the interface with the material of the hollow structure to which it is adhered.

[0121] In some embodiments of this application, when the baking temperature after exposure is below 120°C and the baking time is ≤8 min, the photosensitive layer can obtain a good pattern morphology. A good pattern morphology includes no undercut, that is, the sidewalls of the patterned photosensitive layer have high verticality. Specifically, the photosensitive layer provided in the embodiments of this application can obtain the above-mentioned good pattern morphology when the baking temperature is below 110°C and the baking time is less than or equal to 8 min. In some embodiments, the photosensitive layer provided in the embodiments of this application can obtain the above-mentioned good pattern morphology when the baking temperature is below 110°C and the baking time is less than or equal to 5 min, for example, 5 min, 4 min, 3 min, 2 min, etc.

[0122] In this embodiment, the exposure light source suitable for the photosensitive layer includes, but is not limited to, ultraviolet light, the violet band of visible light, and various types of radiation; the exposure dose can be, for example, 50 mW / cm². 2 -300 mW / cm2 .

[0123] In some embodiments of the present application, any developer known in the art can be used to treat the exposed photosensitive layer, for example, TMAH with a mass concentration of 2.38%.

[0124] In some embodiments of the present application, the surface roughness Ra of the cured product of the photosensitive layer is ≤0.25 μm.

[0125] In some embodiments of the present application, the elastic modulus of the cured product of the photosensitive layer at 180 ℃ is ≥6 GPa; for example, ≥6.5 GPa, ≥7.0 GPa, further ≥7.3 GPa, in some embodiments, the elastic modulus of the cured product of the photosensitive composition at 180 ℃ is ≥7.5 GPa, for example, 7.9 GPa.

[0126] In the embodiments of the present application, the cured product of the photosensitive layer mentioned above refers to the cured product obtained after curing at 270 ℃ for 2 h under a protective atmosphere (for example, nitrogen). In the above curing process, the exposed soluble resin and / or cross-linkable monomer in the photosensitive layer will react with each other under the action of heat field, for example, cross-linking reaction between the exposed soluble resins, reaction between the exposed soluble resins and the cross-linkable monomers, but not limited thereto.

[0127] The embodiments of the present application also provide a preparation method of a photosensitive film, which can be used to prepare the aforementioned photosensitive film provided by the embodiments of the present application, comprising: The aforementioned photosensitive composition provided by the embodiments of the present application or the photosensitive composition prepared by the aforementioned preparation method of the photosensitive composition provided by the embodiments of the present application is coated on a support film to form a photosensitive layer, and a protective film is arranged on the surface of the photosensitive layer away from the support film to obtain a photosensitive film.

[0128] In some embodiments of the present application, the preparation of the aforementioned photosensitive film comprises: coating the photosensitive composition on a support film, baking at 60 ℃-90 ℃ for 5 min-8 min to obtain a photosensitive layer; and then arranging a protective film on the surface of the photosensitive layer away from the support film to obtain a photosensitive film.

[0129] The embodiments of the present application also provide a semiconductor device comprising a hollow structure 40 with a cavity, an electronic circuit, and a cured product of the aforementioned photosensitive layer 20 or the aforementioned patterned photosensitive layer 20; the electronic circuit is arranged on the hollow structure 40; the cured product of the photosensitive layer 20 or the patterned photosensitive layer 20 is arranged at the top end of the cavity. It can be understood that the cured product of the photosensitive layer 20 or the patterned photosensitive layer 20 constitutes the top wall of the cavity. Since the photosensitive layer 20 provided by the embodiments of the present application is used, the integrity and reliability of the semiconductor device can be improved.

[0130] In some embodiments of the present application, the hollow structure 40 has a cavity containing electronic circuits and / or functional structures.

[0131] 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, an acoustic surface wave filter.

[0132] The present application also provides a method for preparing a semiconductor device, comprising: forming a support layer on the surface of the substrate provided with electronic circuits; forming a photosensitive layer on the surface of the support layer, the photosensitive layer being prepared by the photosensitive composition provided by the present application or the method for preparing the photosensitive composition provided by the present application; the photosensitive layer forms a protective film after curing, and the substrate, the support layer and the protective film form a hollow structure with a cavity to prepare a semiconductor device.

[0133] The preparation method provided by the present application is suitable for large-scale industrial production and has strong process reliability.

[0134] The preparation method provided by the present application can be used for the manufacture of semiconductor devices such as integrated circuits. The preparation method can be used to prepare semiconductor devices suitable for etching machines.

[0135] The present application also provides an electronic device comprising the semiconductor device provided by the present application and a circuit board, the circuit board being electrically connected to the semiconductor device; and / or, the electronic device comprises the cured product or the patterned photosensitive layer of the photosensitive layer provided by the present application.

[0136] In some embodiments of the present application, the electronic device includes but is not limited to a mobile phone, a tablet computer, a notebook computer, a vehicle-mounted device, a smart wearable device and other terminal devices.

[0137] The technical solutions of the present application will be further described below in combination with a plurality of specific embodiments.

[0138] Synthesis Example 1 Synthesis of PAE Into a three-necked flask, 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-methyl pyrrolidone (NMP) were added under ice bath condition, and stirred at 100 rpm to dissolve, to obtain a mixture. 5.16 g of triethylamine (TEA) was dissolved in 60 mL of NMP, and then slowly dripped into the above mixture using a separatory funnel to obtain a second mixture. After stirring the reaction at room temperature under nitrogen atmosphere for 18 h, the temperature of the second mixture was reduced to below 0°C, and 123.78 g of thionyl chloride was slowly added to the second mixture using a constant pressure dropping funnel, reacted for 1 h under ice bath condition, and then returned to room temperature for 1 h. After the reaction was completed, the temperature of the system was reduced 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 then added to the above second mixture after reaction. After stirring at room temperature overnight, 134.1 g of triethylamine was slowly added, and the stirring reaction was continued for 3 h to obtain a third mixture. After the reaction was completed, 40 g of anhydrous ethanol was added to the third mixture, and after 30 min of reaction, filtration was performed using a Buchner funnel. The filtrate was slowly dripped into deionized water to precipitate a light-colored solid, which was repeatedly settled three times, and then dried under vacuum to obtain a PAE resin powder, with a molecular weight Mw=8 kDa and a polymer dispersity index (PDI)=2.32.

[0139] 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 (SiDA) and 150 g of NMP were added, and stirred at room temperature until completely dissolved. 46.5 g of ODPA was added, and washed with 45 mL of NMP. The temperature was increased to 80°C and kept for 1 h until completely dissolved to obtain a polymerization solution. 3.27 g of m-aminophenol was added, and the temperature was kept at 80°C for 1 h. 45 mL of dimethylbenzene was added, and the temperature was increased to 185°C and stirred for 4 h. After the heating was turned off and the temperature was decreased to 100°C, 150 g of NMP was added and stirred uniformly. The solution was slowly added to deionized water stirred at high speed to precipitate a white fibrous precipitate. After filtration and washing with water, the precipitate was dried under vacuum at 80°C for 12 h to obtain a PI resin, with a molecular weight Mw=9 kDa and a PDI=2.58.

[0140] Example 1 Into a clean straight bottle, 30 g of silica, 0.35 g of γ-glycidoxypropyltrimethoxysilane, 6 g of PAE resin, 4 g of PI resin, 5 g of PETA, 0.1 g of the first photoinitiator represented by formula (1-7), 0.2 g of the first photoinitiator represented by formula (1-14), and 20 g of GBL were weighed out respectively, and after sealing, a photosensitive composition was obtained by stirring, dissolving and dispersing. The photosensitive composition was then coated on a PET support film, baked and dried at 80°C for 6 min, and then a PET protective film was laminated on the surface to obtain a photosensitive film; wherein the thickness of the photosensitive layer was 40 μm.

[0141] Example 2 Into a clean straight bottle, 30 g of silica, 0.35 g of γ-glycidoxypropyltrimethoxysilane, 6 g of PAE resin, 4 g of PI resin, 5 g of PETA, 0.1 g of the first photoinitiator represented by formula (1-7), 0.2 g of the first photoinitiator represented by formula (1-14), and 20 g of GBL were weighed out respectively, and after sealing, a photosensitive composition was obtained by stirring, dissolving and dispersing. The photosensitive composition was then coated on a PET support film, baked and dried at 80°C for 6 min, and then a PET protective film was laminated on the surface to obtain a photosensitive film; wherein the thickness of the photosensitive layer was 40 μm.

[0142] Example 3 Into a clean straight bottle, 30 g of silica, 0.35 g of γ-glycidoxypropyltrimethoxysilane, 6 g of PAE resin, 4 g of PI resin, 5 g of PETA, 0.1 g of the first photoinitiator represented by formula (1-7), 0.2 g of the first photoinitiator represented by formula (1-14), and 20 g of GBL were weighed out respectively, and after sealing, a photosensitive composition was obtained by stirring, dissolving and dispersing. The photosensitive composition was then coated on a PET support film, baked and dried at 80°C for 6 min, and then a PET protective film was laminated on the surface to obtain a photosensitive film; wherein the thickness of the photosensitive layer was 40 μm.

[0143] Example 4 Into a clean straight bottle, 30 g of silica, 0.35 g of γ-glycidoxypropyltrimethoxysilane, 6 g of PAE resin, 4 g of PI resin, 5 g of PETA, 0.1 g of the first photoinitiator represented by formula (1-7), 0.2 g of the first photoinitiator represented by formula (1-14), and 20 g of GBL were weighed out respectively, and after sealing, a photosensitive composition was obtained by stirring, dissolving and dispersing. The photosensitive composition was then coated on a PET support film, baked and dried at 80°C for 6 min, and then a PET protective film was laminated on the surface to obtain a photosensitive film; wherein the thickness of the photosensitive layer was 40 μm.

[0144] Example 5 Respectively, 25g of silica, 0.2g of γ-glycidoxypropyltrimethoxysilane, 10g of PAE resin, 3g of PETA, 3g of ETPTA, 0.05g of the first photoinitiator as shown in formula (1-14), 0.1g of the first photoinitiator as shown in formula (1-2), 25g of GBL were weighed into a clean straight bottle, and after sealing, stirring, dissolving and dispersing 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 its surface to obtain a photosensitive film; wherein the thickness of the photosensitive layer was 40 μm.

[0145] Example 6 Respectively, 30g of silica, 0.4g of γ-glycidoxypropyltrimethoxysilane, 10g of PI resin, 1g of ETPTA, 4g of BPA2EODMA, 0.1g of the first photoinitiator as shown in formula (1-7), 0.1g of formula (1-8), 20g of solvent (mass ratio of EL:GBL is 8:2) were weighed into a clean straight bottle, and after sealing, stirring, dissolving and dispersing to obtain a polyimide photosensitive composition. Then the photosensitive composition was coated on a PET release film, baked and dried at 80°C for 6 min, and then a PET protective film was laminated on its surface to obtain a photosensitive dry film, the thickness was 40 μm.

[0146] Example 7 Respectively, 35g of silica, 0.4g of γ-glycidoxypropyltrimethoxysilane, 5g of PAE resin, 5g of PI resin, 1g of PETA, 4g of BPA2EODMA, 0.05g of the first photoinitiator as shown in formula (1-2), 0.2g of formula (1-8), 30g of NMP were weighed into a clean straight bottle, and after sealing, stirring, dissolving and dispersing to obtain a polyimide photosensitive composition. Then the photosensitive composition was coated on a PET release film, baked and dried at 80 o C for 7 min, and then a PET protective film was laminated on its surface to obtain a photosensitive dry film, the thickness was 40 μm.

[0147] Example 8 Respectively, 8.5g of silica, 0.2g of γ-glycidoxypropyltrimethoxysilane, 5g of PAE resin, 5g of PI resin, 2g of PETA, 1g of ETPTA, 4.5g of BPA2EODMA, 0.1g of the first photoinitiator as shown in formula (1-2), 0.15g of formula (1-8) initiator, 0.15g of formula (1-14) initiator, 30g of NMP were weighed into a clean straight bottle, and after sealing, stirring, dissolving and dispersing to obtain a polyimide photosensitive composition. Then the photosensitive composition was coated on a PET release film, baked and dried at 80o C The photosensitive dry film was obtained by laminating a PET protective film on the surface of the photosensitive layer after baking and drying for 7 min.

[0148] Comparative Example 1 The photosensitive composition was obtained by stirring and dissolving and dispersing 30 g of silica, 0.3 g of γ-glycidoxypropyltrimethoxysilane, 10 g of PAE resin, 4.5 g of BPA2EODMA, 0.2 g of hexaarylbiimidazole (HABI), and 25 g of solvent (mass ratio of EL:GBL = 8:2) in a clean straight bottle, and then sealing and stirring to dissolve and disperse. The photosensitive composition was then 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 layer was 40 μm.

[0149] Performance Test (1) The photosensitive layer was cut into a strip with a width of 25 mm using a cutting tool, and then placed in an oxygen-free nitrogen oven for high-temperature curing at 270°C for 2 h. Then the modulus of the cured film was measured in the temperature range of 40-350°C using DMA, and the elastic modulus of the cured film at 180°C was recorded.

[0150] (2) The photosensitive layer was cut into a size of 2 cm x 2 cm, and its light transmittance was tested using UV-vis under a light source of 405 nm.

[0151] (3) The photosensitive film was cut to the size of A4 paper, and after the release film was torn off, it was attached to the surface of the structure sheet (pattern height 8-12 μm). The film attachment process was verified using a semi-automatic wafer film attachment machine, with a film attachment table temperature of 65°C, a roller pressure of 0.35 MPa, a film attachment speed of 5.5 mm / s, and a table height of -50 mm. After attachment, the attachment was observed using an optical microscope, and it was required to meet 100% attachment without collapse and bubbles.

[0152] (4) The photosensitive layer was cut to an appropriate size and attached to the surface of a silicon wafer, and then exposed using a mixed light source with wavelengths of 365 nm and 405 nm, with an exposure dose of 150 mW / cm 2 After post-baking at 110°C for 5 min, the unexposed part was removed using 2.38 wt.% TMAH solution to obtain a negative pattern. The pattern surface and cross-sectional morphology were observed using an optical microscope, and the minimum size of the pattern opening was the resolution accuracy, which was recorded in Table 1. Figure 3A The optical microscope photo of the patterned photosensitive layer obtained after exposure, development, and curing of the photosensitive layer provided in Example 6 of the present application; Figure 3B The optical microscope photo of the patterned photosensitive layer obtained after exposure, development, and curing of the photosensitive layer of Comparative Example 1.

[0153] For the convenience of reading, the specific parameters of the photosensitive composition and the test results of the photosensitive layer of each embodiment and the comparative example are summarized in Table 1.

[0154] Table 1

[0155] It can be seen from the data in Table 1 that the photosensitive composition provided by the embodiments has a high filler ratio, and the photosensitive layer prepared from the photosensitive composition has good uniformity, still has high transparency, no risk of collapse during application, and good curing effect in the deep layer and the surface layer. After the process of exposure, curing and other processes, the pattern has good resolution and good mechanical properties.

[0156] It should be understood that the first, second, and various numerical numbers referred to herein are only for the convenience of description and do not limit the scope of the application.

[0157] In the present application, "and / or" describes the association relationship of the associated objects, which means that there can be three kinds of relationships, for example, A and / or B, which can represent the following cases: A exists alone, A and B exist together, and B exists alone, where A and B can be singular or plural. The character " / " generally represents an "or" relationship between the associated objects before and after it.

[0158] In the present application, "at least one" means one or more, and "multiple" means two or more. "At least one of the following" or the like means 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, where a, b, and c can be single or multiple.

[0159] 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 photosensitive composition, characterized by comprising: The soluble resin includes one or more of a polymer having a main chain containing a repeating imide ring, a polymer having a main chain containing a repeating amide bond and an ester bond, and a polymer having a main chain containing a repeating amide bond; and / or, the soluble resin includes a polymer having a main chain containing a repeating first structure, the first structure including one or more of a structure composed of an amide bond and an ester bond, an imide ring, and an amide bond. The soluble resin includes one or more of a polymer having a main chain containing a repeating imide ring, a polymer having a main chain containing a repeating amide bond and an ester bond, and a polymer having a main chain containing a repeating amide bond; and / or, the soluble resin includes a polymer having a main chain containing a repeating first structure, the first structure including one or more of a structure composed of an amide bond and an ester bond, an imide ring, and an amide bond. The photoinitiator comprises a first photoinitiator which is a compound having ​ wherein, represents a connection site; 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 hydrocarbyl group, a substituted or unsubstituted main-chain second-structure-containing C1-C10 hydrocarbyl group, a substituted or unsubstituted C1-C10 acyl group, a substituted or unsubstituted main-chain second-structure-containing C1-C10 acyl group, a substituted or unsubstituted C1-C10 alkoxy group, a substituted or unsubstituted main-chain second-structure-containing C1-C10 alkoxy group; the second structure includes one or more of an ether oxygen bond, a thioether bond, an ester bond, a thioester bond, an amide bond, or a urethane bond; 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, and R4, R5may be connected to the N atom to form a ring; The mass content of the filler is >80% based on the mass of the soluble resin.

2. The photosensitive composition according to claim 1, characterized by In the R1, R2, and R3, the substituent in the substituted or unsubstituted C1-C10 hydrocarbon group, the substituted or unsubstituted C1-C10 hydrocarbon group having a main chain containing a second structure, the substituted or unsubstituted C1-10 acyl group, the substituted or unsubstituted C1-C10 acyl group having a main chain containing a second structure, the substituted or unsubstituted C1-C10 alkoxy group, and the substituted or unsubstituted C1-C10 alkoxy group having a main chain containing a second structure is independently selected from one or more of a halogen atom, a hydroxyl group, a carboxyl group, a nitro group, a cyano group, and the -NR4R5.

3. The photosensitive composition according to claim 1, characterized by The first photoinitiator has a molar absorption coefficient ≥200 L / (mol·cm) under a light source at at least one wavelength ≤450 nm.

4. The photosensitive composition according to any one of claims 1 to 3, characterized in that, The first photoinitiator also includes a substituted or unsubstituted oxime ester group or a substituted or unsubstituted main chain oxime ester-containing group chemically bonded to the a substituted or unsubstituted oxime ester group or a substituted or unsubstituted main chain oxime ester-containing group at the linking site represented by ; and / or, the photoinitiator also includes a second photoinitiator, the second photoinitiator including an oxime ester photoinitiator.

5. The photosensitive composition according to any one of claims 1 to 3, characterized in that, The soluble resin includes one or more of a polymer having a main chain containing a repeating imide ring, a polymer having a main chain containing a repeating amide bond and an ester bond, and a polymer having a main chain containing a repeating amide bond; and / or, the soluble resin includes a polymer having a main chain containing a repeating first structure, the first structure including one or more of a structure composed of an amide bond and an ester bond, an imide ring, and an amide bond. The first structure in the soluble resin includes the structure composed of an amide bond and an ester bond and the imide ring; and / or, The soluble resin has a carboxyl group and / or a hydroxyl group; and / or, The weight average molecular weight of the soluble resin is 5 kDa-50 kDa.

6. The photosensitive composition according to any one of claims 1 to 3, characterized in that, The first photoinitiator includes one or more of formula (1-1) to formula (1-15): 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), Formula (1-11), Formula (1-12), Formula (1-13), Formula (1-14), Formula (1-15).

7. The photosensitive composition according to any one of claims 1 to 3, wherein The cross-linkable monomer has a carboxyl group and / or a hydroxyl group; and / or, the average radical functionality of the cross-linkable monomer is a positive integer of 2-8; and / or, The radical equivalent of the cross-linkable monomer is 90-250; and / or, The cross-linkable monomer accounts for 1%-10% of the mass of the soluble resin; and / or, The photoinitiator accounts for 0.05%-5% of the mass of the soluble resin; and / or, The filler accounts for 81%-500% of the mass of the soluble resin; and / or, The filler includes an inorganic filler; and / or, The D50 particle size of the filler is 0.5 μm-5 μm; and / or, The surface of the filler is modified with a coupling agent.

8. The photosensitive composition according to any one of claims 1 to 3, characterized by, The room temperature viscosity of the photosensitive composition is 1000 cps-5000 cps; and / or, The solid content of the photosensitive composition is 30 wt.%-80 wt.%; and / or, The surface roughness of the cured product of the photosensitive composition is ≤0.25 μm; and / or, The elastic modulus of the cured product of the photosensitive composition at 180 ℃ is ≥6 GPa; and / or, The patterning resolution of the photosensitive composition is ≤40 μm; and / or, The pattern formed by the photosensitive composition after exposure and development has no bottom incision.

9. A method for producing a photosensitive composition, characterized by, The photosensitive composition includes: The mixed soluble resin, the photoinitiator, the cross-linkable monomer and the filler are mixed; 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 photoinitiator comprises a first photoinitiator which is a compound having ​ wherein, represents a connection site; 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 hydrocarbyl group, a substituted or unsubstituted main-chain second-structure-containing C1-C10 hydrocarbyl group, a substituted or unsubstituted C1-C10 acyl group, a substituted or unsubstituted main-chain second-structure-containing C1-C10 acyl group, a substituted or unsubstituted C1-C10 alkoxy group, a substituted or unsubstituted main-chain second-structure-containing C1-C10 alkoxy group; the second structure includes one or more of an ether oxygen bond, a thioether bond, an ester bond, a thioester bond, an amide bond, or a urethane bond; 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, and R4, R5may be connected to the N atom to form a ring; The mass content of the filler is > 80% based on the mass of the soluble resin.

10. A photosensitive film characterized by comprising: The photosensitive layer is prepared from the photosensitive composition according to any one of claims 1-8, or the photosensitive layer is prepared from the photosensitive composition prepared by the preparation method according to claim 9.

11. The photosensitive film according to claim 10, characterized by The photosensitive layer has a transmittance of > 50% for a light source at at least one wavelength of ≤ 450 nm with a thickness of 40 μm; and / or, The photosensitive layer has a haze of ≤ 10%; and / or, The photosensitive layer has a melt viscosity of 20000 Pa·s-70000 Pa·s at 80 ℃; and / or, The photosensitive layer has a surface roughness of the cured product of ≤ 0.25 μm; and / or, The photosensitive layer has an elastic modulus of the cured product of ≥ 6 GPa at 180 ℃; and / or, The photosensitive layer has a patterning resolution of ≤ 40 μm; and / or, The pattern formed after the photosensitive layer is exposed, developed and cured has no bottom incision.

12. A method for producing a photosensitive film, characterized by comprising the steps of: The photosensitive layer is prepared from the photosensitive composition according to any one of claims 1-8, or the photosensitive layer is prepared from the photosensitive composition prepared by the preparation method according to claim 9. The photosensitive layer is prepared from the photosensitive composition according to any one of claims 1-8, or the photosensitive layer is prepared from the photosensitive composition prepared by the preparation method according to claim 9.

13. A semiconductor device, characterized by comprising: The photosensitive layer is prepared from the photosensitive composition according to any one of claims 1-8, or the photosensitive layer is prepared from the photosensitive composition prepared by the preparation method according to claim 9. The photosensitive layer is prepared from the photosensitive composition according to any one of claims 1-8, or the photosensitive layer is prepared from the photosensitive composition prepared by the preparation method according to claim 9.

14. A method of manufacturing a semiconductor device, characterized by, The photosensitive layer is prepared from the photosensitive composition according to any one of claims 1-8, or the photosensitive layer is prepared from the photosensitive composition prepared by the preparation method according to claim 9. The photosensitive layer is prepared from the photosensitive composition according to any one of claims 1-8, or the photosensitive layer is prepared from the photosensitive composition prepared by the preparation method according to claim 9. The photosensitive layer is prepared from the photosensitive composition according to any one of claims 1-8, or the photosensitive layer is prepared from the photosensitive composition prepared by the preparation method according to claim 9. The photosensitive layer is prepared from the photosensitive composition according to any one of claims 1-8, or the photosensitive layer is prepared from the photosensitive composition prepared by the preparation method according to claim 9.

15. An electronic device, comprising: ​

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