A photosensitive composition, a preparation method and application thereof

Abstract

The application provides a photosensitive composition, a preparation method and application thereof. The photosensitive composition is a PI, PAE and polyamide acid photosensitive system containing fillers. In the 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 better processability of the photosensitive composition and a photosensitive layer prepared from the photosensitive composition, and the patterned film prepared from the photosensitive composition also has good physical and chemical properties and mechanical properties. The photosensitive composition can be used in the manufacture of semiconductor devices, and improves the integrity and reliability of the semiconductor devices.

Description

Technical Field

[0001] This application relates to the field of photosensitive materials technology, and in particular to a photosensitive composition, preparation method and application thereof. Background Technology

[0002] Photosensitive compositions can typically form high-precision patterned films after patterning processes such as exposure. In the application of polyimide (PI) or polyamide ester (PAE) photosensitive compositions, they can be first made into photosensitive films, and then the photosensitive films can be patterned and micro-processed to obtain high-precision patterned films. This allows for further expansion of applications for photosensitive films, such as their use as packaging materials for high-performance electronic components. To meet the requirements of these applications, the photosensitive films often need to possess superior photosensitivity, high photocurability, and good processability, while the cured products need to have high mechanical properties and good physicochemical properties. Essentially, obtaining photosensitive films with these properties requires a photosensitive composition with superior overall performance. Summary of the Invention

[0003] In view of this, embodiments of this application provide a photosensitive composition, a preparation method, and its application. The photosensitive composition is a PI, PAE, and polyamic acid photosensitive system containing fillers. Further selection of a photoinitiator with a specific structure within the aforementioned photosensitive system containing fillers can effectively improve the patterning resolution, analytical properties, deep curing performance, and processability of the photosensitive composition and the resulting photosensitive layer. Furthermore, the patterned film obtained also possesses excellent physicochemical and mechanical properties.

[0004] The first aspect of this application provides a photosensitive composition, including a soluble resin, a photoinitiator, a crosslinkable monomer, and a filler;

[0005] The soluble resin includes one or more of the following: polymers with repeating imide rings in the main chain, polymers with repeating amide bonds and ester bonds in the main chain, and polymers with repeating amide bonds in the main chain; and / or, the soluble resin includes a polymer with a repeating first structure in the main chain, the first structure including a structure composed of amide bonds and ester bonds, an imide ring, and a variety of amide bonds.

[0006] The photoinitiator includes a first photoinitiator, wherein the first photoinitiator is a photoinitiator having... Compounds;

[0007] in, The term "linking site" indicates the connection site. R1, R2, and R3 are independently selected from one or more of the following: hydrogen atom, hydroxyl group, carboxyl group, nitro group, cyano group, -NR4R5, substituted or unsubstituted C1-C10 hydrocarbon group, substituted or unsubstituted C1-C10 hydrocarbon group with a second structure in the main chain, substituted or unsubstituted C1-C10 acyl group, substituted or unsubstituted C1-C10 alkoxy group with a second structure in the main chain, substituted or unsubstituted C1-C10 alkoxy group, and substituted or unsubstituted C1-C10 alkoxy group with a second structure in the main chain. The second structure includes one or more of the following: ether oxygen bond, thioether bond, ester bond, thioester bond, amide bond, or carbamate bond. R4 and R5 are independently selected from one or more of the following: hydrogen atom, oxygen atom, substituted or unsubstituted C1-C10 alkoxy group, or substituted or unsubstituted C1-C10 alkyl group. R4 and R5 may be linked to an N atom to form a ring.

[0008] Based on the mass of the soluble resin, the mass content of the filler is >80%.

[0009] This application embodiment improves the deep curing ability, pattern resolution, and patterning resolution of the PI, PAE, and polyamic acid photosensitive composition system with a high filler ratio by controlling the photoinitiator in the system. Furthermore, the photosensitive layer prepared by this composition can achieve good exposure morphology patterns at lower post-exposure baking temperatures and shorter post-exposure baking times, with low risk of residue after development, lower process requirements, and higher energy efficiency. In addition, the photosensitive composition provided in this application embodiment maintains excellent adhesion even with high filler content, effectively reducing the risk of bubbles or delamination at the interface between the photosensitive layer and the substrate during application.

[0010] In some embodiments of this application, in R1, R2, and R3, the substituents in 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, and the substituted or unsubstituted C1-C10 alkoxy group with a second structure in the main chain are independently selected from one or more of halogen atoms, hydroxyl groups, carboxyl groups, nitro groups, cyano groups, or -NR4R5.

[0011] In some embodiments of this application, the first photoinitiator has a molar absorptivity ≥200 L / (mol·cm) under at least one light source with a wavelength ≤450 nm. This effectively improves the surface photocuring effect of the photosensitive composition, reduces the risk of device failure due to the high absorbance of polyimide resins causing obvious indentation at the bottom of the pattern after exposure and easy delamination at the openings after development, and avoids negatively impacting the morphology, resolution, and resolving power of the patterned photosensitive film. In some specific embodiments, the first photoinitiator has a molar absorptivity ≥200 L / (mol·cm) under light with a wavelength of 365 nm.

[0012] In some embodiments of this application, the first photoinitiator further includes chemically bonded to the... The indicated linking site contains a substituted or unsubstituted oxime ester group or a substituted or unsubstituted main chain group containing an oxime ester group; and / or, the photoinitiator further includes a second photoinitiator, the second photoinitiator including an oxime ester photoinitiator. This is more conducive to optimizing the subsequent surface curing and deep curing effects of the photosensitive layer, especially beneficial for the deep and surface curing of photosensitive layers with a certain thickness.

[0013] In some embodiments of this application, the soluble resin comprises a polymer with a main chain containing repeating amide and ester bonds, or a polymer with a main chain containing repeating imide rings. This is more conducive to improving the stability of the composition and subsequent photosensitive layer, and more conducive to optimizing the performance of the final semiconductor device.

[0014] In some embodiments of this application, the soluble resin comprises a polymer with a main chain containing repeating amide and ester bonds, and a polymer with a main chain containing repeating imide rings; and / or, the first structure in the soluble resin comprises the structure containing amide and ester bonds and the imide rings. In the high-filler system photosensitive composition of this application, the simultaneous introduction of PI and PAE can further enhance the photosensitivity and transparency of the system, improve the patterning resolution of the photosensitive composition and photosensitive layer, and also improve the storage stability of the photosensitive composition and photosensitive film.

[0015] In some embodiments of this application, the mass percentage of PAE in the soluble resin is ≥50%. In other words, the mass ratio of PAE to PI is ≥1:1. This is more conducive to optimizing the resolution and pattern resolution of the photosensitive composition and photosensitive layer, and also more conducive to improving the elastic modulus of the photosensitive composition and photosensitive layer after curing.

[0016] In some embodiments of this application, the soluble resin has carboxyl and / or hydroxyl groups. This promotes the dissolution of the soluble resin, thereby improving the resolution and patterning of the composition and the photosensitive layer after development.

[0017] In some embodiments of this application, the weight-average molecular weight of the soluble resin is 5 kDa-50 kDa. This facilitates controlling the viscosity of the photosensitive composition within a suitable range, which is beneficial for film formation and for the photosensitivity, patterning effect, and resolution of the composition.

[0018] In some embodiments of this application, the first photoinitiator comprises one or more of formulas (1-1) to (1-15):

[0019] Equation (1-1), Equation (1-2), Equation (1-3), Equation (1-4),

[0020] Equation (1-5), Equation (1-6), Equation (1-7), Equation (1-8), Equation (1-9), Equation (1-10), Equation (1-11), Equation (1-12), Equation (1-13),

[0021] Equation (1-14), Equation (1-15).

[0022] In some embodiments of this application, the crosslinkable monomer has carboxyl and / or hydroxyl groups. This improves the pattern resolution of the photosensitive layer.

[0023] In some embodiments of this application, the average free radical functionality of the crosslinkable monomer is a positive integer from 2 to 8. This does not negatively affect the photosensitivity of the composition.

[0024] In some embodiments of this application, the free radical equivalent of the crosslinkable monomer is 90-250. This effectively improves the resolution of the photosensitive composition after exposure and development, thereby enhancing pattern quality.

[0025] In some embodiments of this application, the crosslinkable monomer accounts for 1%-10% of the mass of the soluble resin. This helps to ensure that the cured composition and photosensitive layer have superior photosensitivity and mechanical properties, and helps to improve the film retention rate of the composition after development.

[0026] In some embodiments of this application, the photoinitiator accounts for 0.05%-5% of the mass of the soluble resin. This is more conducive to improving the deep and surface curing effect of the composition and the photosensitive layer, and optimizing the pattern performance of the photosensitive layer after exposure and development.

[0027] In some embodiments of this application, the filler accounts for 81%-500% of the mass of the soluble resin. Thus, the photosensitive composition not only possesses superior film-forming properties but also benefits the subsequent photosensitive film by exhibiting high mechanical properties. This effectively reduces the risk of collapse when the photosensitive film is attached to the top wall of the hollow structure or after lamination, exposure, development, and curing, thereby effectively improving the yield of the encapsulated device.

[0028] In some embodiments of this application, the filler comprises an inorganic filler. This is more conducive to improving the mechanical properties and chemical resistance of the composition and the cured photosensitive layer. In some specific embodiments, the filler is a crystalline inorganic filler; this is more conducive to improving the mechanical properties and chemical resistance of the composition and the cured photosensitive layer.

[0029] In some embodiments of this application, the inorganic filler includes, but is not limited to, one or more of the following: silicon dioxide, aluminum oxide, glass powder, titanium dioxide, calcium oxide, magnesium oxide, zinc oxide, boron oxide, yttrium oxide, zirconium oxide, mica powder, and talc powder.

[0030] In some embodiments of this application, the D50 particle size of the filler is 0.5 μm-5 μm. This facilitates its dispersion in the composition, optimizes the mechanical and chemical resistance of the subsequent photosensitive layer and its cured product, and further improves the surface and cross-sectional flatness of the photosensitive layer after exposure, development, and curing, thereby reducing the packaging process difficulty of the encapsulated device.

[0031] In some embodiments of this application, the surface of the filler is modified with a coupling agent. Modifying the filler surface with a coupling agent can increase the dispersibility of the filler, thereby improving the stability of the photosensitive composition during mixing, storage, and coating processes. This helps optimize the uniformity of the photosensitive composition to improve the uniformity of the final photosensitive layer, improves the transparency of the final photosensitive layer to light sources with a wavelength ≤450 nm, improves the surface and deep curing effects, reduces the baking dependence after exposure and development, and further improves the mechanical properties of the photosensitive layer and its cured product.

[0032] In some embodiments of this application, the room temperature viscosity of the photosensitive composition is 1000 cps-5000 cps. This is beneficial to the film-forming properties of the composition and reduces the risk of gelation.

[0033] In some embodiments of this application, the solid content of the photosensitive composition is 30 wt.%-80 wt.%. This facilitates control over the content of soluble resin, which is beneficial to the solubility, dispersibility, and film-forming properties of the photosensitive composition.

[0034] In some embodiments of this application, the surface roughness of the cured photosensitive composition is ≤0.25 μm.

[0035] In some embodiments of this application, the cured form of the photosensitive composition has an elastic modulus ≥6 GPa at 180 °C.

[0036] In some embodiments of this application, the patterning resolution of the photosensitive composition is ≤40 μm.

[0037] In some embodiments of this application, the pattern formed by the exposure and development of the photosensitive composition has no bottom indentation.

[0038] A second aspect of this application provides a method for preparing a photosensitive composition, comprising: mixing a soluble resin, a photoinitiator, a crosslinkable monomer, and a filler; wherein the soluble resin comprises one or more of a polymer having a repeating imide ring in its main chain, a polymer having repeating amide bonds and ester bonds in its main chain, and a polymer having repeating amide bonds in its main chain; and / or, the soluble resin comprises a polymer having a repeating first structure in its main chain, the first structure comprising a structure composed of amide bonds and ester bonds, an imide ring, and a plurality of amide bonds;

[0039] The photoinitiator includes a first photoinitiator, wherein the first photoinitiator is a photoinitiator having... Compounds;

[0040] in, The linkage sites are indicated by R1, R2, and R3, which are independently selected from one or more of the following: hydrogen atom, hydroxyl group, carboxyl group, nitro group, cyano group, -NR4R5, substituted or unsubstituted C1-C10 hydrocarbon group, substituted or unsubstituted C1-C10 hydrocarbon group with a second structure in the main chain, substituted or unsubstituted C1-C10 acyl group, substituted or unsubstituted C1-C10 alkoxy group with a second structure in the main chain, substituted or unsubstituted C1-C10 alkoxy group, and substituted or unsubstituted C1-C10 alkoxy group with a second structure in the main chain; the second structure includes one or more of the following: ether oxygen bond, thioether bond, ester bond, thioester bond, amide bond, or urethane bond; R4 and R5 are independently selected from one or more of the following: hydrogen atom, oxygen atom, substituted or unsubstituted C1-C10 alkoxy group, or substituted or unsubstituted C1-C10 alkyl group, wherein R4 and R5 can be linked to an N atom to form a ring; based on the mass of the soluble resin, the mass content of the filler is >80%.

[0041] The above preparation method has high process reliability, high production yield, and is suitable for large-scale industrial production.

[0042] A third aspect of this application provides a photosensitive film, including a support film, a protective film, and a photosensitive layer disposed between the support film and the protective film. The photosensitive layer is made of a photosensitive composition provided in the first aspect of this application, or the photosensitive layer is made of a photosensitive composition prepared by the method of preparing the photosensitive composition provided in the second aspect of this application.

[0043] Since the photosensitive layer of the photosensitive film is prepared using the aforementioned photosensitive composition or the photosensitive composition prepared by the method described in the embodiments of this application, the photosensitive layer of this photosensitive film has high adhesion, high interfacial bonding with the substrate, and low risk of defects such as collapse and delamination. Furthermore, the photosensitive film has high transmittance, low haze, and is easy to detect film defects, facilitating the discovery of problems in the post-filming process. It also has strong surface and deep curing capabilities, low risk of surface powdering and roughness, and superior surface and cross-sectional flatness. In addition, the photosensitive layer can obtain good exposure morphology patterns at lower baking temperatures and shorter baking times, with low risk of residue after development, high pattern resolution and patterning resolution, lower process requirements, and higher production efficiency.

[0044] In some embodiments of this application, the photosensitive layer with a thickness of 40 μm has a transmittance of ≥50% for at least one wavelength of light source in the wavelength range ≤450 nm. This ensures superior deep curing effect of the photosensitive layer. In some specific embodiments, the photosensitive layer with a thickness of 40 μm has a transmittance of ≥50% for a wavelength of 405 nm.

[0045] In some embodiments of this application, the haze of the photosensitive layer is ≤10%.

[0046] In some embodiments of this application, the melt viscosity of the photosensitive layer at 80°C is 20000 Pa·s-70000 Pa·s.

[0047] In some embodiments of this application, the surface roughness of the cured photosensitive layer is ≤0.25μm.

[0048] In some embodiments of this application, the cured photosensitive layer has an elastic modulus ≥ 6 GPa at 180 °C.

[0049] In some embodiments of this application, the patterning resolution of the photosensitive layer is ≤40 μm.

[0050] In some embodiments of this application, the pattern formed after the photosensitive layer is exposed, developed, and cured has no bottom indentation.

[0051] A fourth aspect of this application provides a method for preparing a photosensitive film, comprising:

[0052] The photosensitive composition prepared by the method of the first aspect of the present application or the second aspect of the present application is coated on a support film to form a photosensitive layer, and then a protective film is disposed on the surface of the photosensitive layer opposite to the support film to obtain a photosensitive film.

[0053] The above preparation method has high process reliability, high production yield, and allows for flexible and precise control of the thickness and uniformity of the photosensitive layer, making it suitable for large-scale industrial production.

[0054] A fifth aspect of this application provides a semiconductor device, including a hollow structure with a cavity, electronic components, and a cured or patterned photosensitive layer of a photosensitive film provided in a second aspect of this application; the electronic circuit is disposed on the hollow structure; and the cured or patterned photosensitive layer is disposed at the top of the cavity.

[0055] Because the semiconductor device uses the photosensitive layer provided in the embodiments of this application, the integrity and reliability of the semiconductor device can be improved.

[0056] In some embodiments of this application, the cavity of the hollow structure contains electronic circuits and / or functional structures.

[0057] In some embodiments of this application, the semiconductor device includes, but is not limited to, a packaging device. In some specific embodiments, the packaging device includes, but is not limited to, a radio frequency (RF) device; the RF device includes, but is not limited to, elastic wave filters, sensors, and surface acoustic wave (SAW) filters.

[0058] The sixth aspect of this application provides a method for fabricating a semiconductor device, comprising:

[0059] A support layer is formed on the surface of a substrate containing electronic circuitry;

[0060] A photosensitive layer is disposed on the surface of the support layer, and the photosensitive layer is prepared by the photosensitive composition provided in the first aspect of the present application or by the photosensitive composition prepared by the method of the photosensitive composition provided in the second aspect of the present application.

[0061] After the photosensitive layer is cured, it forms a protective film. The substrate, the support layer, and the protective film are arranged to form a hollow structure with a cavity structure to obtain a semiconductor device.

[0062] The preparation method provided in this application is suitable for large-scale industrial production and has high process reliability.

[0063] A sixth aspect of this application provides an electronic device, including a semiconductor device and a circuit board provided in the fifth aspect of this application, wherein the circuit board is electrically connected to the semiconductor device; and / or, the electronic device includes a cured or patterned photosensitive layer of a photosensitive film provided in the third aspect of this application.

[0064] In some embodiments of this application, the electronic device includes, but is not limited to, terminal devices such as mobile phones, tablet computers, laptop computers, in-vehicle devices, and smart wearable devices. Attached Figure Description

[0065] Figure 1 This is a simplified schematic diagram of the structure of a photosensitive film provided in one embodiment of this application;

[0066] Figure 2A This is a schematic diagram illustrating the collapse of the photosensitive layer.

[0067] Figure 2B A scanning electron microscope (SEM) image of a photosensitive layer adhering to the top of a cavity in a hollow structure, provided in an embodiment of this application.

[0068] Figure 3A An optical microscope image of the patterned photosensitive layer obtained after exposure, development and curing of the photosensitive layer provided in Embodiment 6 of this application;

[0069] Figure 3B This is an optical microscope photograph of the patterned photosensitive layer obtained after exposure, development and curing of the photosensitive layer of Comparative Example 1.

[0070] Explanation of the reference numerals: 1-Photosensitive film; 10-Supporting film; 20-Photosensitive layer; 30-Protective film; 40-Hollow structure. Detailed Implementation

[0071] Photosensitive compositions can typically form high-precision patterned films after patterning processes such as exposure. Depending on the application scenario, photosensitive compositions have different application forms. For example, photosensitive compositions can be made into photosensitive film layers and then used as packaging materials for semiconductor devices. Specifically, to ensure the normal operation of semiconductor devices such as filters, it is usually necessary to construct dimensionally stable hollow structural cavities, and photosensitive film layers are often used as the top wall material of these cavities. These application scenarios place high performance requirements on the packaging materials: they must be able to open vias through exposure and development, and the cured product, after lamination, exposure, post-exposure baking, development, and thermal curing, must be resistant to high temperatures and high molding pressure, and have a high modulus to reduce the risk of top wall material collapse or other defects. PI-based or PAE-based photosensitive layers are ideal materials for achieving these properties. During sale or storage, they are often sandwiched between a support layer and a protective layer to form a three-layer structure. During application, the photosensitive layer is peeled off from the protective layer and support layer, and the photosensitive film is laminated to the hollow structure, followed by exposure, baking, development, and high-temperature curing processes to form the top wall of the cavity. In related technologies, some polyimide photosensitive layers can achieve certain technical effects. However, with the continuous improvement of parameters such as the integration level of semiconductor devices, the industry's requirements for the patterning accuracy, modulus, photosensitivity, and deep curing of photosensitive layers are also increasing. Furthermore, in order to ensure molding resistance and protect the device structure, the thickness of the photosensitive layer in related technologies is usually high (≥20 μm). This makes it difficult to fully cure during application, easily leading to problems such as surface oxidation, rough surface powder shedding, insufficient bottom curing, weak adhesion, and abnormal pattern morphology. Related technologies often use a large exposure dose and rely on high baking temperatures (e.g., above 120 °C) and baking times to optimize pattern morphology for full curing, but this places stringent process requirements and affects production capacity.

[0072] To address the aforementioned technical problems, embodiments of this application provide a photosensitive composition comprising a soluble resin, a photoinitiator, a crosslinkable monomer, and a filler;

[0073] In this application embodiment, the soluble resin includes a resin that is soluble in the developer, which may include a main chain and photosensitive groups attached to the main chain. In this application embodiment, the light of a specific wavelength may be, for example, but is not limited to, ultraviolet light or various types of radiation. The photosensitive group refers to a functional group that can undergo a chemical reaction under the irradiation of the aforementioned specific wavelength, enabling the soluble resin to crosslink under the irradiation of the light source. In some embodiments of this application, the photosensitive group includes one or more of the following: carbon-carbon double bond, unsaturated bond, epoxy group, isocyanate group or blocked isocyanate group, disulfide bond, etc.

[0074] In this application embodiment, the soluble resin includes one or more of the following: polymers with repeating imide rings in the main chain, polymers with repeating amide bonds and ester bonds in the main chain, and polymers with repeating amide bonds in the main chain; and / or, the soluble resin includes a polymer with a repeating first structure in the main chain, the first structure including a structure composed of amide bonds and ester bonds, imide rings, and amide bonds. In this application embodiment, "multiple" refers to two or more; that is, the soluble resin includes at least one of polyimide, polyamide ester, and polyamic acid; and / or, the soluble resin includes copolymers of two or more of the following: a first monomer for obtaining polyimide, a second monomer for obtaining polyamide ester, and a third monomer for obtaining polyamic acid; specifically, "two or more monomers" refers to two or more of the first monomer, second monomer, and third monomer. The first monomer, second monomer, and third monomer can be materials well known to those skilled in the art, and each of the first monomer, second monomer, and third monomer can independently include multiple monomers, which is not limited in this application.

[0075] The photoinitiator includes a first initiator, wherein the first initiator contains... Compounds of formula (1);

[0076] in, The term "linking site" indicates the connection site. R1, R2, and R3 are independently selected from one or more of the following: hydrogen atom, hydroxyl group, carboxyl group, nitro group, cyano group, -NR4R5, substituted or unsubstituted C1-C10 hydrocarbon group, substituted or unsubstituted C1-C10 hydrocarbon group with a second structure in the main chain, substituted or unsubstituted C1-C10 acyl group, substituted or unsubstituted C1-C10 alkoxy group with a second structure in the main chain, substituted or unsubstituted C1-C10 alkoxy group, and substituted or unsubstituted C1-C10 alkoxy group with a second structure in the main chain. The second structure includes one or more of the following: ether oxygen bond, thioether bond, ester bond, thioester bond, amide bond, and carbamate bond. R4 and R5 are independently selected from one or more of the following: hydrogen atom, oxygen atom, substituted or unsubstituted C1-C10 alkoxy group, or substituted or unsubstituted C1-C10 alkyl group. R4 and R5 may be linked to an N atom to form a ring.

[0077] Based on the mass of soluble resin, the filler content is >80%.

[0078] In this application embodiment, the polymer mentioned in the soluble resin includes polymer precursors. Specifically, polyimide includes polyimide precursors, polyamide ester includes polyamide ester precursors, and polyamic acid includes polyamic acid precursors. In this application embodiment, the polymer precursor includes materials that are processable before final processing (such as light exposure, heating, chemical reaction, etc.) and that yield the target polymer after processing, including but not limited to low molecular weight compounds or oligomers of polymers. The aforementioned chemical reactions include but are not limited to polymerization, chemical bond breaking of side chains or groups, and functional group transformation.

[0079] In the embodiments of this application, the second structures in the aforementioned hydrocarbon groups, acyl groups, and alkoxy groups containing a second structure in the substituted or unsubstituted main chain can be the same or different. Each of the above structures can independently contain one or more second structures. In some specific embodiments, the aforementioned hydrocarbon groups, acyl groups, and alkoxy groups containing a second structure in the substituted or unsubstituted main chain independently contain 1 to 5 second structures. Specifically, the number of second structures in the aforementioned hydrocarbon groups, acyl groups, and alkoxy groups containing a second structure in the substituted or unsubstituted main chain is independently 1, 2, 3, 4, or 5.

[0080] For photosensitive compositions based on PI, PAE, and polyamic acid systems, fillers can be introduced to enhance the mechanical properties of the cured photosensitive composition. However, there is usually a difference in refractive index between the filler and the soluble resin and other components. Simply introducing fillers into the existing system often reduces the deep curing capability of the photosensitive composition and the photosensitive layer, reduces pattern resolution, and leads to problems such as post-development residue. This application embodiment improves the deep curing capability, pattern resolution, and patterning resolution of photosensitive compositions containing PI, PAE, and polyamic acid or mixtures thereof with a high filler ratio, by controlling the photoinitiator in the system. Furthermore, the photosensitive layer prepared by this composition can obtain good exposure morphology patterns at lower post-exposure baking temperatures and shorter post-exposure baking times, with low post-development residue risk, lower process requirements, and higher production capacity. In addition, the photosensitive composition provided in this application embodiment maintains excellent adhesion even with high filler content, effectively reducing the risk of bubbles or delamination at the interface between the photosensitive layer and the substrate during application.

[0081] In the embodiments of this application, crosslinkable monomers refer to compound monomers having groups that can undergo crosslinking reactions. These groups that can undergo crosslinking reactions include, but are not limited to, carbon-carbon unsaturated bonds, epoxy groups, hydroxyl groups, carboxyl groups, isocyanate groups, mercapto groups, and amino groups.

[0082] In the embodiments of this application, the photosensitive composition may include one or more first initiators. These first initiators may have distinct groups among R1, R2, and R3, and / or... The groups attached to the marked sites are different. A single molecule of the first initiator may contain one or more structures as shown in formula (1).

[0083] In the embodiments of this application, R1, R2, and R3 are independently selected from one or more of the following: hydrogen atom, hydroxyl group (-OH), carboxyl group (-COOH), nitro group (-NO2), cyano group (-CN), -NR4R5, substituted or unsubstituted C1-C10 hydrocarbon group, substituted or unsubstituted C1-10 acyl group, substituted or unsubstituted C1-C10 alkoxy group, substituted or unsubstituted C1-C10 hydrocarbon group with a second structure in the main chain, substituted or unsubstituted C1-10 acyl group, substituted or unsubstituted C1-C10 alkoxy group, etc. The main chain contains one or more of C1-C10 alkoxy groups, substituted or unsubstituted, with a second structure; the second structure includes one or more of ether oxygen bond (-O-), thioether bond (-S-), ester bond (-COO-), thioester bond (-S-CO-, -O-CS-), amide bond (-CONH-), and urethane bond (-CO-N-CO-, -N-CO-); R4 and R5 are independently selected from one or more of hydrogen atom, oxygen atom, substituted or unsubstituted C1-C10 alkoxy groups or substituted or unsubstituted C1-C10 alkyl groups, wherein R4 and R5 may be linked to N atom to form a ring. Specifically, the hydrocarbon groups in R1, R2, R3, R4, and R5 can be either chain hydrocarbon groups or cyclic hydrocarbon groups. Examples include substituted or unsubstituted C1-C10 straight-chain hydrocarbon groups, substituted or unsubstituted C1-C10 branched hydrocarbon groups, and substituted or unsubstituted C3-C10 cyclic hydrocarbon groups. Chain hydrocarbon groups can be chain alkyl, chain alkenyl, or chain alkynyl groups. Cyclic hydrocarbon groups can be, for example, cycloalkyl, cycloalkyl, or cycloalkynyl groups. The number of carbon atoms in the substituted or unsubstituted hydrocarbon groups can be 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10. The acyl groups can be, for example, -CO-R. x R x -S(=O)2-,R x This is an organic group. Unsubstituted acyl groups can be, for example, formyl, acetyl, sulfonyl, etc. The number of carbon atoms in the substituted or unsubstituted acyl groups can be, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10. The unsubstituted alkoxy group is -OR. y R yThe alkyl group can be alkyl, such as methoxy, ethoxy, propoxy, etc., and the number of carbon atoms in the substituted or unsubstituted alkoxy group can be 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10. The substituted hydrocarbon group, substituted alkoxy group, and substituted acyl group may independently contain one or more substituents. In some specific embodiments, the substituted groups independently contain 1 to 5 substituents. Specifically, the number of substituents in the substituted groups can independently be 1, 2, 3, 4, or 5.

[0084] In this embodiment, the substituted or unsubstituted C1-C10 hydrocarbon group containing a second structure in the main chain is a group with a second structure embedded in the main chain. Specifically, it can be a group with a second structure embedded in the carbon chain. For example, it can be a group obtained by interrupting the hydrocarbon group in the substituted or unsubstituted C2-C10 hydrocarbon group with a second structure, or a group composed of a methyl group and a second structure and connected to a benzene ring through the second structure, as long as it conforms to the principle of chemical bonding. The substituent group can replace any substituted hydrogen atom on the C1-C10 hydrocarbon group containing the second structure in the main chain, as long as substitution can be achieved. The above-mentioned group can contain one or more substituents. In some specific embodiments, the substituted group independently contains 1-5 substituents. Specifically, the number of substituents in the substituted group can be independently 1, 2, 3, 4, or 5.

[0085] In this embodiment, the substituted or unsubstituted C1-C10 acyl group containing a second structure in the main chain is a group with a second structure embedded in the main chain. Specifically, it can be a group with a second structure embedded in the carbon chain. For example, it can be a group obtained by interrupting the hydrocarbon group in the substituted or unsubstituted C2-C10 acyl group with a second structure, or a C1-C10 acyl group connected to a benzene ring through a second structure, as long as it conforms to the principle of chemical bonding. The substituent group can replace any substituted hydrogen atom on the C1-C10 acyl group containing the second structure in the main chain, as long as substitution can be achieved. The above-mentioned group can contain one or more substituents. In some specific embodiments, the substituted group independently contains 1-5 substituents. Specifically, the number of substituents in the substituted group can be independently 1, 2, 3, 4, or 5.

[0086] In this embodiment, the substituted or unsubstituted C1-C10 alkoxy group containing a second structure in the main chain is a group with a second structure embedded in the main chain. Specifically, it can be a group with a second structure embedded in the carbon chain. For example, it can be a group obtained by interrupting the hydrocarbon group in the aforementioned substituted or unsubstituted C2-C10 alkoxy group with a second structure, or a C1-C10 alkoxy group connected to a benzene ring through a second structure, as long as it conforms to the principle of chemical bonding. The substituent group can replace any substituted hydrogen atom on the C1-C10 alkoxy group containing the second structure in the main chain, as long as substitution can be achieved. The aforementioned group can contain one or more substituents. In some specific embodiments, the substituted group independently contains 1-5 substituents. Specifically, the number of substituents in the substituted group can be independently 1, 2, 3, 4, or 5.

[0087] In some embodiments of this application, the substituents in R1, R2, and R3 above, including substituted or unsubstituted C1-C10 hydrocarbon groups, substituted or unsubstituted C1-C10 hydrocarbon groups with a second structure in the main chain, substituted or unsubstituted C1-C10 acyl groups, substituted or unsubstituted C1-C10 acyl groups with a second structure in the main chain, substituted or unsubstituted C1-C10 alkoxy groups, and substituted or unsubstituted alkoxy groups with a second structure in the main chain, are independently selected from one or more of halogen atoms, hydroxyl (-OH), carboxyl (-COOH), nitro (-NO2), cyano (-CN), or -NR4R5.

[0088] In this embodiment of the application, R3 can be connected to... The groups at the marked positions form rings.

[0089] In some embodiments of this application, in R4 and R5 above, the substituents in the substituted or unsubstituted C1-C10 alkoxy groups or the substituted or unsubstituted C1-C10 hydrocarbon groups are independently selected from one or more of halogen atoms, hydroxyl groups, carboxyl groups, nitro groups, and cyano groups.

[0090] In the embodiments of this application, nuclear magnetic resonance hydrogen spectroscopy (NMR) may be used, but is not limited to, 1 H Nuclear Magnetic Resonance, 1 The presence of soluble resins, photoinitiators, and crosslinkable monomers in the photosensitive composition was determined by 1H NMR and high performance liquid chromatography-mass spectrometry (HLPC-MS).

[0091] In some embodiments of this application, the molar absorptivity of the first photoinitiator is ≥200 L / (mol·cm) under a light source of at least one wavelength ≤450 nm. In the embodiments of this application, the light with a wavelength ≤450 nm can be, for example, any light source within the wavelength range of 248 nm to 450 nm. In some specific embodiments, the molar absorptivity of the first photoinitiator is ≥200 L / mol·cm under a 365 nm light source. This can effectively improve the surface photocuring effect of the photosensitive composition, reduce the risk of significant undercut at the bottom of the pattern after exposure due to the high absorbance of polyimide resins, and the risk of device failure due to delamination at the openings after development, without negatively affecting the morphology, resolution, and resolving power of the patterned photosensitive film. Specifically, the molar absorptivity of the first photoinitiator at 365 nm can be, for example, 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.

[0092] In the embodiments of this application, the specific reagent of the first photoinitiator can be characterized by HPLC-MS, and its molar absorptivity to a light source of at least one wavelength with a wavelength ≤450 nm (e.g., a light source with a wavelength of 365 nm) can be obtained by testing the corresponding standard sample using ultraviolet-visible spectroscopy (UV-vis), or by consulting the literature.

[0093] In some embodiments of this application, the photoinitiator further includes substituted or unsubstituted oxime ester groups ( , 1 #、 2 #、 3 # The positions marked indicate connection sites. In the photosensitive composition of this application embodiment, the oxime ester group and Synergistic group formation is more conducive to optimizing the surface curing and deep curing effects of the subsequent photosensitive layer, especially for the deep and surface curing of photosensitive layers with a certain thickness; specifically, the aforementioned 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, or ≥45 μm; in some embodiments, the thickness of the photosensitive layer is 20 μm-50 μm.

[0094] 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.

[0095] In some embodiments of this application, the second photoinitiator includes .

[0096] 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 used as a linking site, the oxime ester group can share a carbonyl group with the structure shown in formula (1), that is, the oxime ester group... 3 #The location of the marker is bonded to The location of the marker, and the oxime ester group and Shared 1 The labeled carbonyl group. In other specific embodiments, the substituted or unsubstituted main-chain oxime ester group is chemically bonded to formula (1). The location of the marker, that is, the oxime ester group, is associated with the oxime ester group in formula (1) through other divalent groups. The marked position is connected; wherein, the substituted group can be any position in the oxime ester group of the main chain that can be replaced by a hydrogen atom, for example, its end or middle. In some embodiments of this application, the above-mentioned divalent group can be, for example, an alkylene group, an arylene group, etc. wait.

[0097] In some embodiments of this application, the connection sites to formula (1) or the benzene ring structure are removed. The remaining two connection sites can be connected to organic groups, such as hydrocarbon groups.

[0098] In some specific embodiments, at least a portion of the first photoinitiator contains an oxime ester group, and the photoinitiator also includes the aforementioned second photoinitiator.

[0099] In some embodiments of this application, the photoinitiator contains... The molar ratio of the structure shown in formula (1) to the oxime ester group is 0.01:1 to 99:1. It is understood that, as mentioned above, when the structure of formula (1) is stoichiometric with the oxime ester group, the two can share the carbonyl group. Specifically, the molar ratio of the structure shown in 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, or 95:1. In some specific embodiments, with the structure of formula (1) and the oxime ester group, the photosensitive layer with a thickness of 40 μm prepared by the photosensitive composition has a transmittance of ≥50% for light with a wavelength of 405 nm.

[0100] In some embodiments of this application, the first photoinitiator comprises one or more of formulas (1-1) to (1-15):

[0101] Equation (1-1), Equation (1-2), Equation (1-3), Equation (1-4),

[0102] Equation (1-5), Equation (1-6), Equation (1-7), Equation (1-8), Equation (1-9), Equation (1-10), Equation (1-11), Equation (1-12), Equation (1-13),

[0103] Equation (1-14), Equation (1-15). The first photoinitiator described above has a molar absorptivity ≥200 L ( / mol·cm) at at least one wavelength in the wavelength range ≤450 nm (e.g., wavelength 365 nm), and has good compatibility with the system.

[0104] In some embodiments of this application, the mass percentage of the photoinitiator is 0.05%-5% based on the mass of the soluble resin. Controlling the amount of photoinitiator within this range is more conducive to improving the deep and surface curing effects of the composition and the photosensitive layer, and optimizing the pattern representation after exposure and development of the photosensitive layer. Specifically, based on the mass of the soluble resin, the mass percentage of the photoinitiator can be, for example, 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 this application, the mass content of the photoinitiator can be tested using HPLC-MS, the mass content of the soluble resin can be tested using HPLC-MS, and then the mass ratio of the photoinitiator to the soluble resin can be calculated.

[0105] In this embodiment, the filler content is >80% based on the mass of the soluble resin. Specifically, if the filler content is too low, the mechanical properties of the cured composition will be insufficient to meet the process requirements, resulting in defects such as low modulus, poor molding resistance, excessively high coefficient of thermal expansion, and insufficient heat resistance. In some embodiments of this application, the filler content is 81%-500% of the soluble resin mass. Thus, the photosensitive composition not only has superior film-forming properties but also benefits the subsequent photosensitive film, which has high mechanical properties. This effectively reduces the risk of collapse when the photosensitive film is attached to the top wall of the hollow structure cavity and after lamination, exposure, development, and curing, thereby effectively improving the yield of encapsulated devices. Furthermore, with the aforementioned high filler ratio, the photosensitive composition in this embodiment still has high exposure light source transparency, enabling the simultaneous achievement of superior surface and deep curing effects. Specifically, the mass of the filler can account for 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%, etc. of the soluble resin.

[0106] In the embodiments of this application, TGA or sedimentation, centrifugation, drying and weighing of the photosensitive composition can be used to test the mass content of the filler, HPLC-MS can be used to test the mass content of the soluble resin, and then the mass ratio of the filler to the soluble resin can be calculated.

[0107] In some embodiments of this application, the filler includes inorganic fillers. 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 silica, alumina, glass powder, titanium dioxide, 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; this is more conducive to improving the mechanical properties and chemical resistance of the composition and the cured photosensitive layer. In the embodiments of this application, the shape of the filler can be, for example, spherical, angular, needle-shaped, irregular, etc.

[0108] In some embodiments of this application, the D50 particle size of the filler is 0.5 μm-5 μm. Controlling the D50 particle size of the filler within this range is beneficial for its dispersion in the composition, for optimizing the mechanical and chemical resistance properties of the subsequent photosensitive layer and its cured product, and for improving the surface and cross-sectional flatness of the photosensitive layer after exposure, development, and curing, thereby reducing the packaging process difficulty of the encapsulated device. Specifically, the D50 particle size of the filler can be, for example, 0.5 μm, 0.8 μm, 1 μm, 1.1 μm, 1.2 μm, 1.3 μm, 1.4 μm, 1.5 μm, 1.8 μm, 2 μm, 2.2 μm, 2.5 μm, 2.8 μm, 3 μm, 3.2 μm, 3.5 μm, 3.8 μm, 4 μm, 4.2 μm, 4.5 μm, 4.8 μm, 5 μm, etc. In the embodiments of this application, the D50 particle size of the filler can be tested using, but is not limited to, scanning electron microscopy (SEM) or dynamic light scattering (DLS).

[0109] In some embodiments of this application, the photosensitive composition further includes a coupling agent. In some embodiments, the coupling agent includes 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 this application, modifying 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 in the wavelength range ≤450 nm (e.g., a light source with a wavelength of 405 nm), improve the surface and deep curing effects, reduce the baking dependence after exposure and development, and further improve 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, a chemical force, such as a chemical bond, is formed between the silane coupling agent and the filler; the silicon-oxygen bond end of the silane coupling agent may form a chemical force with the filler.

[0110] In some embodiments of this application, the silane coupling agent includes an active group, which includes, but is not limited to, one or more of epoxy, styrene, vinyl, amino, isocyanate, urea, propenyl, and mercapto groups. Specifically, the aforementioned silane coupling agents include, but are not limited to, triethoxysilylpropylmaleic acid, methacryloxypropyltriethoxysilane, 3-ureapropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-propyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptomethyltrimethoxysilane, 3-mercaptomethyldimethoxysilane, 3-mercaptopropylethoxydimethoxysilane, 3-mercaptopropyltripropoxysilane, 3-thiopropyltributoxysilane, 2-(3,4-epoxycyclohexane)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexane)ethyltriethoxysilane, epoxybutyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, and p-aminophenyltrimethoxysilane. The silane coupling agent comprises one or more of the following: aminophenyltrimethoxysilane, 3-(m-aminophenyl)trimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-propenoxypropyltrimethoxysilane, 3-ethoxypropyltrimethoxysilane, vinyltrimethoxysilane, methacryloxydimethoxysilane, 3-aminopropyltrimethoxysilane, trimethoxysilylbenzoic acid, 3-methacryloyloxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, vinyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, vinyltriacetoxysilane, and γ-glycidoxypropyltrimethoxysilane. The above-mentioned silane coupling agents have a higher compatibility with the system of the embodiments in this application, which is more conducive to improving the transparency of the final photosensitive layer and increasing the adhesion between the cured film and the substrate.

[0111] In some embodiments of this application, the soluble resin comprises a polymer with repeating imide rings in its main chain or a polymer with repeating amide and ester bonds in its main chain. That is, preferably, the soluble resin comprises polyimide or polyamide ester. This is more conducive to improving the stability of the composition and subsequent photosensitive layer, and more conducive to improving the performance of the final semiconductor device.

[0112] In some embodiments of this application, the soluble resin includes polyimide, polyamide ester, and / or a copolymer comprising a first monomer for forming the polyimide and a second monomer for forming the polyamide ester. In some specific embodiments, the soluble resin includes a mixture of polyimide and polyamide ester. In the high-filler system photosensitive composition of this application, the simultaneous introduction of PI and PAE can further improve the photosensitivity and transparency of the system, and can also improve the patterning resolution of the photosensitive composition and photosensitive layer, and is also beneficial to improving the storage stability of the photosensitive composition and photosensitive film.

[0113] In other embodiments of this application, the first structure in the soluble resin includes a structure composed of amide bonds and ester bonds, as well as an imide ring. That is, the soluble resin comprises a copolymer of a first monomer for forming a polyimide and a second monomer raw material for forming a polyamide ester. Similarly, the above-described copolymeric soluble resin can improve the patterning resolution of the photosensitive composition and the photosensitive layer, as well as their storage stability. In some specific embodiments, the soluble resin simultaneously comprises blends and copolymers of the above-described PI and PAE.

[0114] In some embodiments of this application, the mass percentage of PAE in the soluble resin is ≥50%. In other words, the mass ratio of PAE to PI is ≥1:1. 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, or 1.4:1. Understandably, for cases containing copolymers, the mass ratio of the sum of the mass of repeating units belonging to PAE to the mass of repeating units belonging to PI is calculated accordingly. This is more conducive to optimizing the resolution and pattern resolution of the photosensitive composition and photosensitive layer, and also more conducive to improving the elastic modulus of the photosensitive composition and photosensitive layer after curing.

[0115] In some embodiments of this application, the soluble resin has carboxyl and / or hydroxyl groups. Carboxyl and hydroxyl groups can promote the dissolution of the soluble resin, specifically by increasing its solubility in an alkaline developer (e.g., tetramethylammonium hydroxide TMAH), thereby improving the resolution and patterning of the composition and the photosensitive layer after development. In the embodiments of this application, the carboxyl and hydroxyl groups can be located on the side chain of the soluble resin or on the main chain of the soluble resin, for example, as end-capping groups of the main chain.

[0116] In some embodiments of this 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 this range facilitates controlling the viscosity of the photosensitive composition within a suitable range, which is beneficial for film formation and improves the photosensitivity, patterning, and 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 this application, the weight-average molecular weight of the soluble resin can be tested using gel chromatography, but is not limited to this method.

[0117] In some embodiments of this application, the photosensitive composition further includes a solvent. The solvent can be any solvent well-known to those skilled in the art suitable for polyimide-based photosensitive compositions. 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, γ-butyrolactone (GBL), ethyl acetate, methyl lactate, ethyl lactate (EL), acetone, methyl ethyl ketone (MEK), methyl n-pentyl 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), etc.

[0118] In some embodiments of this application, the solid content of the photosensitive composition is 30 wt.%-80 wt.%. The solid content of the photosensitive composition refers to the proportion of the total mass of the components other than the solvent to the total mass of the photosensitive composition. Controlling the solid content of the photosensitive composition within the above range is beneficial for controlling the content of soluble resin, and for improving 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.%.

[0119] In some embodiments of this application, the room temperature viscosity of the photosensitive composition is 1000 cps-5000 cps. Controlling the room temperature viscosity of the photosensitive composition within this range also ensures that the Mw and mass content of the soluble resin are within a suitable range, which is beneficial to the film-forming properties of the composition and reduces the risk of gelation. In the embodiments of this application, the room temperature viscosity of the photosensitive composition can be tested using a rotational rheometer, with a rotational speed of 50 rpm-100 rpm and a shear rate of 50 / s-100 / s.

[0120] In some embodiments of this application, the crosslinkable monomer includes a free radical polymerizable crosslinkable monomer; the average free radical functionality of the free radical polymerizable crosslinkable monomer is a positive integer from 2 to 8. Average free radical functionality refers to the number of functional groups in the molecule of the crosslinkable monomer that can participate in free radical polymerization. Controlling the average free radical functionality of the crosslinkable monomer within the above range will not negatively affect the photosensitivity of the composition and is beneficial to the performance of the photosensitive composition and the photosensitive layer. Specifically, the average free radical functionality of the crosslinkable monomer can be, for example, 2, 3, 4, 5, 6, 7, or 8. The aforementioned free radical functional groups include, but are not limited to, carbon-carbon unsaturated bonds, epoxy groups, hydroxyl groups, carboxyl groups, isocyanate groups, mercapto groups, and amino groups. In the embodiments of this application, the type of crosslinkable monomer can be determined by NMR spectroscopy, and its average free radical functionality can be further obtained.

[0121] In some embodiments of this application, the average free radical equivalent of the crosslinkable monomer is 90-250, where free radical equivalent = molecular weight / functionality, which can be determined by HPLC-MS and... 1 The mean free radical equivalent of a crosslinkable monomer is calculated after analyzing the monomer structure using methods such as ¹H NMR. It refers to the average molecular weight of the functional groups in the crosslinkable monomer that can participate in free radical polymerization. This effectively improves the resolution of the photosensitive composition after exposure and development, thus enhancing pattern quality. Specifically, the mean free radical equivalent of the crosslinkable monomer can be, for example, 90, 100, 120, 150, 180, 200, 220, 250, etc.

[0122] In some embodiments of this application, the crosslinkable monomer further includes carboxyl and / or hydroxyl groups. Introducing hydroxyl and / or carboxyl groups into the crosslinkable monomer can improve the pattern resolution of the photosensitive layer, that is, improve the resolution of the pattern obtained after exposure and development of the photosensitive layer, especially beneficial for improving the pattern resolution after development with an alkaline developer (e.g., TMAH).

[0123] In some embodiments of this application, the crosslinkable monomers include, but are not limited to, one or more of the following: 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, ethylene oxide modified bisphenol A diacrylate, ethylene oxide modified diacrylate of isocyanurate, and N,N-methylenebisacrylamide.

[0124] In some embodiments of this application, the mass percentage of crosslinkable monomers is 1%-10% based on the mass of the soluble resin. Controlling the content of crosslinkable monomers relative to the soluble resin within this range helps ensure superior photosensitivity and mechanical properties of the composition and the cured photosensitive layer, and improves the film retention rate of the composition after development. Specifically, the mass content of crosslinkable monomers relative to the soluble resin can be, for example, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, or 10%. In the embodiments of this application, the mass content of crosslinkable monomers can be tested using HLPC-MS, and then the mass content of the soluble resin can be tested to calculate the mass ratio between the two.

[0125] In some embodiments of this application, to improve the overall performance of the photosensitive composition, other additives may be included in the photosensitive composition. These 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. The content of other additives in the photosensitive composition can be adjusted according to actual needs.

[0126] In some embodiments of this application, the surface roughness Ra of the cured photosensitive composition is ≤0.25 μm. In the embodiments of this application, the surface roughness of the cured composition can be tested using, but is not limited to, an atomic force microscope (AFM) and a roughness tester.

[0127] In some embodiments of this application, the cured photosensitive composition has an elastic modulus ≥6 GPa at 180 °C; for example, ≥6.5 GPa, ≥7.0 GPa, further ≥7.3 GPa. In some embodiments, the cured photosensitive composition has an elastic modulus ≥7.5 GPa at 180 °C, for example 7.9 GPa. The elastic modulus of the cured composition at 180 °C can be tested using, but is not limited to, dynamic mechanical analysis (DMA).

[0128] In the embodiments of this application, the cured products of the above-mentioned photosensitive compositions refer to the cured products obtained after curing at 270 °C for 2 h under a protective atmosphere (e.g., nitrogen). During the above curing process, the soluble resin and / or crosslinkable monomers after exposure will react with each other under the action of a thermal field, such as the crosslinking reaction between the soluble resins after exposure, and the reaction between the soluble resin and the crosslinkable monomers after exposure, but not limited to these.

[0129] In some embodiments of this application, the patterning resolution of the photosensitive composition is ≤40 μm. Patterning resolution refers to the resolution of the pattern obtained after exposure and development using a mask. In some embodiments of this application, the pattern obtained after exposure and development of the photosensitive composition has no bottom incut.

[0130] In some embodiments of this application, the photosensitive composition is a negative photosensitive composition.

[0131] This application also provides a method for preparing a photosensitive composition, which can be used to prepare the aforementioned photosensitive composition provided in this application. Specifically, the preparation method includes:

[0132] The aforementioned soluble resin, the aforementioned photoinitiator, the aforementioned crosslinkable monomer, and the aforementioned filler are mixed together;

[0133] Soluble resins include one or more of the following: polymers with repeating imide rings in the main chain, polymers with repeating amide bonds and ester bonds in the main chain, and polymers with repeating amide bonds in the main chain; and / or, soluble resins include polymers with repeating first structures in the main chain, the first structure including a structure composed of amide bonds and ester bonds, imide rings, and multiple types of amide bonds.

[0134] Photoinitiators include a first photoinitiator, which is a photoinitiator having... Compounds;

[0135] in, Indicates the linking site; R1, R2, and R3 are independently selected from one or more of the following: hydrogen atom, hydroxyl group, carboxyl group, nitro group, cyano group, -NR4R5, substituted or unsubstituted C1-C10 hydrocarbon group, substituted or unsubstituted C1-C10 hydrocarbon group with a second structure in the main chain, substituted or unsubstituted C1-C10 acyl group, substituted or unsubstituted C1-C10 acyl group with a second structure in the main chain, substituted or unsubstituted C1-C10 alkoxy group, and substituted or unsubstituted C1-C10 alkoxy group with a second structure in the main chain; the second structure includes one or more of the following: ether oxygen bond, thioether bond, ester bond, thioester bond, amide bond, or carbamate bond; R4 and R5 are independently selected from one or more of the following: hydrogen atom, oxygen atom, substituted or unsubstituted C1-C10 alkoxy group, or substituted or unsubstituted C1-C10 alkyl group, and R4 and R5 may be linked to an N atom to form a ring;

[0136] Based on the mass of soluble resin, the filler content is >80%.

[0137] In some embodiments of this application, the preparation of the photosensitive composition includes:

[0138] S1. Mix the above-mentioned soluble resin, photoinitiator, crosslinkable monomer and filler to obtain a photosensitive composition.

[0139] In some embodiments, step S1 specifically includes: adding the soluble resin, photoinitiator, crosslinkable monomer and filler into a solvent, sealing, and stirring under sealed conditions to obtain a photosensitive composition.

[0140] This application also provides a photosensitive film, such as... Figure 1 As shown, the photosensitive film 1 includes a support film 10, a protective film 30, and a photosensitive layer 20 disposed between the support film 10 and the protective film 30. The photosensitive layer 20 is made of the aforementioned photosensitive composition provided in the embodiments of this application.

[0141] Since the photosensitive layer of the photosensitive film is made using the aforementioned photosensitive composition provided in the embodiments of this application, the photosensitive layer of the photosensitive film has high adhesion, high interfacial bonding strength with the adhered substrate, and low risk of defects such as collapse and delamination. Furthermore, the photosensitive film has high light transmittance, low haze, and is easy to detect film defects, facilitating the discovery of problems in the post-filming process. It also has strong surface and deep curing capabilities, low risk of surface powdering and roughness, and superior surface and cross-sectional flatness. In addition, the photosensitive layer can obtain good exposure morphology patterns at lower baking temperatures and shorter baking times, with low risk of residue after development, high pattern resolution and patterning resolution, lower process requirements, and higher production efficiency.

[0142] In some embodiments of this application, the photosensitive layer is obtained by drying a photosensitive composition. In some embodiments of this application, the solvent may not be completely removed during drying.

[0143] In the embodiments of this application, the materials of the support film and the protective film can be those well known to those skilled in the art, such as PET (polyethylene terephthalate), and this application does not limit them.

[0144] In some embodiments of this 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 °C is 20000 Pa·s-70000 Pa·s. In the embodiments of this application, a rheometer can be used to test the melt viscosity of the photosensitive layer at 25 °C. o C-100 o Melt viscosity at C.

[0145] In some embodiments of this 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.

[0146] 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.

[0147] 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.

[0148] 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.

[0149] 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.

[0150] 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.

[0151] 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 .

[0152] In some embodiments of this application, any developer known in the art can be used to treat the exposed photosensitive layer, such as TMAH with a mass concentration of 2.38%.

[0153] In some embodiments of this application, the surface roughness Ra of the cured photosensitive layer is ≤0.25 μm.

[0154] In some embodiments of this application, the cured photosensitive layer has an elastic modulus ≥6 GPa at 180 °C; for example, ≥6.5 GPa, ≥7.0 GPa, further ≥7.3 GPa. In some embodiments, the cured photosensitive composition has an elastic modulus ≥7.5 GPa at 180 °C, for example 7.9 GPa.

[0155] In the embodiments of this application, the cured product of the aforementioned photosensitive layer refers to the cured product obtained after curing at 270°C for 2 hours under a protective atmosphere (e.g., nitrogen). During the curing process, the soluble resin and / or crosslinkable monomers in the photosensitive layer react with each other under the action of a thermal field, such as the crosslinking reaction between the soluble resins after exposure, or the reaction between the soluble resin and the crosslinkable monomers after exposure, but not limited to these.

[0156] This application also provides a method for preparing a photosensitive film, which can be used to prepare the aforementioned photosensitive film provided in this application, comprising:

[0157] The photosensitive composition provided in the embodiments of this application or the photosensitive composition prepared by the method provided in the embodiments of this application is coated on a support film to form a photosensitive layer, and then a protective film is disposed on the surface of the photosensitive layer opposite to the support film to obtain a photosensitive film.

[0158] In some embodiments of this application, the preparation of the above-mentioned photosensitive film includes: coating a photosensitive composition onto a support film, baking it at 60 ℃-90 ℃ for 5 min-8 min to obtain a photosensitive layer; and then setting a protective film on the surface of the photosensitive layer opposite to the support film to obtain a photosensitive film.

[0159] This application also provides a semiconductor device, including a hollow structure 40 with a cavity, electronic circuitry, and a cured or patterned version of the aforementioned photosensitive layer 20; the electronic circuitry is disposed on the hollow structure 40; the cured or patterned photosensitive layer 20 is disposed at the top of the cavity. It is understood that the cured or patterned photosensitive layer 20 constitutes the top wall of the cavity. By employing the photosensitive layer 20 provided in this application, the integrity and reliability of the semiconductor device can be improved.

[0160] In some embodiments of this application, the cavity of the hollow structure 40 contains electronic circuits and / or functional structures.

[0161] In some embodiments of this application, the semiconductor devices include, but are not limited to, packaging devices. In some specific embodiments, the packaging devices include, but are not limited to, radio frequency (RF) devices; RF devices include, but are not limited to, elastic wave filters, sensors, and surface acoustic wave (SAW) filters.

[0162] This application also provides a method for fabricating a semiconductor device, comprising:

[0163] A support layer is formed on the surface of a substrate containing electronic circuitry;

[0164] A photosensitive layer is disposed on the surface of the support layer, and the photosensitive layer is prepared by the photosensitive composition provided in the embodiments of this application or by the photosensitive composition prepared by the method provided in the embodiments of this application;

[0165] After the photosensitive layer is cured, it forms a protective film. The substrate, the support layer, and the protective film are arranged to form a hollow structure with a cavity structure to obtain a semiconductor device.

[0166] The preparation method provided in this application is suitable for large-scale industrial production and has high process reliability.

[0167] The fabrication method provided in this application can be used to manufacture semiconductor devices such as integrated circuits. This fabrication method can produce semiconductor devices suitable for etching machines.

[0168] This application also provides an electronic device, including a semiconductor device and a circuit board provided in this application, wherein the circuit board is electrically connected to the semiconductor device; and / or, the electronic device includes a cured or patterned photosensitive layer provided in this application.

[0169] In some embodiments of this application, the electronic device includes, but is not limited to, terminal devices such as mobile phones, tablet computers, laptop computers, in-vehicle devices, and smart wearable devices.

[0170] The technical solution of this application is further illustrated below with reference to several specific embodiments.

[0171] Synthesis example 1

[0172] PAE Synthesis

[0173] Under ice bath conditions, 0.56 g of hydroquinone, 132.7 g of hydroxyethyl methacrylate (HEMA), 158.2 g of 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride (ODPA), and 450 mL of N-methylpyrrolidone (NMP) were added to a three-necked flask and stirred at 100 rpm to dissolve, yielding a mixture. 5.16 g of triethylamine (TEA) was dissolved in 60 mL of NMP and then slowly added dropwise to the mixture using a separatory funnel to obtain a second mixture. The mixture was stirred at room temperature under a nitrogen atmosphere for 18 h. The temperature of the second mixture was then lowered to below 0 °C, and 123.78 g of thionyl chloride was slowly added dropwise to the second mixture using a constant-pressure dropping funnel. The reaction was carried out under ice bath conditions for 1 h, followed by a 1 h reaction at room temperature. After the reaction was complete, the system temperature was lowered to below 0 °C. 177.4 g of 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6FAP) and 0.4 g of hydroquinone were dissolved in 350 mL of NMP and added to the second mixture obtained from the above reaction. After stirring overnight at room temperature, 134.1 g of triethylamine was slowly added, and the reaction was continued for 3 h to obtain the third mixture. After the reaction was completed, 40 g of anhydrous ethanol was added to the third mixture, and after reacting for 30 min, the mixture was filtered through a Buchner funnel. The filtrate was slowly added dropwise to deionized water to precipitate a light-colored solid. After repeated sedimentation three times, the solid was dried under vacuum to obtain PAE resin powder with Mw = 8 kDa and a molecular weight distribution index (PDI) of 2.32.

[0174] Synthesis example 2

[0175] Synthesis of PI

[0176] Under a dry nitrogen stream, 46.7 g of 6FAP, 1.86 g of 1,1',3,3'-tetramethyl-1,3-bis(3-aminopropyl)disiloxane (SiDA), and 150 g of NMP were added to a 1 L four-necked flask. The mixture was stirred at room temperature until completely dissolved. 46.5 g of ODPA was added, and the mixture was washed with 45 mL of NMP. The temperature was raised to 80 °C and maintained for 1 h until completely dissolved, yielding a polymerization solution. 3.27 g of m-aminophenol was added to the polymerization solution, and the mixture was kept at 80 °C for another 1 h. 45 mL of xylene was added, and the mixture was heated to 185 °C and stirred for 4 h. The heating was turned off, and the temperature was lowered to 100 °C. 150 g of NMP was added and stirred until homogeneous. The solution was slowly added to deionized water under high-speed stirring, resulting in the precipitation of a white fibrous precipitate. The precipitate was collected by filtration, washed with water, and dried under vacuum at 80 °C for 12 h to obtain PI resin with a molecular weight of Mw = 9 kDa and PDI = 2.58.

[0177] Example 1

[0178] 25g of silica, 0.3g of γ-glycidyl etheroxypropyltrimethoxysilane, 10g of PAE resin, 4.5g of PETA, 0.2g of the first photoinitiator shown in formula (1-7), 0.1g of the first photoinitiator shown in formula (1-14), and 25g of solvent (EL:GBL in a mass ratio of 8:2) were weighed into a clean, straight bottle. After sealing, the bottle was stirred to dissolve and disperse the contents, thus obtaining a photosensitive composition. The photosensitive composition was then coated onto a PET support film and baked at 80°C for 6.5 min. A PET (polyethylene terephthalate) protective film was then laminated onto the surface of the film to obtain a photosensitive film with a thickness of 40 μm.

[0179] Example 2

[0180] 30g of silica, 0.35g of γ-glycidyl etheroxypropyltrimethoxysilane, 6g of PAE resin, 4g of PI resin, 5g of PETA, 0.1g of the first photoinitiator shown in formula (1-7), 0.2g of the first photoinitiator shown in formula (1-14), and 20g of GBL were weighed into a clean, straight bottle. After sealing, the bottle was stirred to dissolve and disperse the contents, thus obtaining a photosensitive composition. The photosensitive composition was then coated onto a PET support film and baked at 80°C for 6 minutes. A PET protective film was then laminated onto the surface of the film to obtain a photosensitive film with a thickness of 40 μm.

[0181] Example 3

[0182] 30g of silica, 0.4g of γ-glycidyl etheroxypropyltrimethoxysilane, 4g of PAE resin, 6g of PI resin, 4g of PETA, 0.1g of the first photoinitiator shown in formula (1-14), 0.2g of the first photoinitiator shown in formula (1-2), and 30g of NMP were weighed into a clean, straight bottle. After sealing, the bottle was stirred to dissolve and disperse the contents, thus obtaining a photosensitive composition. The photosensitive composition was then coated onto a PET support film and baked at 80°C for 7 minutes. A PET protective film was then laminated onto the surface of the film to obtain a photosensitive film with a thickness of 40 μm.

[0183] Example 4

[0184] 35g of silica, 0.25g of γ-glycidyl etheroxypropyltrimethoxysilane, 10g of PI resin, 4.5g of ETPTA, 0.15g of the first photoinitiator shown in formula (1-7), 0.15g of the first photoinitiator shown in formula (1-14), and 25g of EL were weighed into a clean, straight bottle. After sealing, the bottle was stirred to dissolve and disperse the contents, thus obtaining a photosensitive composition. The photosensitive composition was then coated onto a PET support film and baked at 80°C for 6.5 min. A PET protective film was then laminated onto the surface of the film to obtain a photosensitive film with a thickness of 40 μm.

[0185] Example 5

[0186] 25g of silica, 0.2g of γ-glycidyl etheroxypropyltrimethoxysilane, 10g of PAE resin, 3g of PETA, 3g of ETPTA, 0.05g of the first photoinitiator shown in formula (1-14), 0.1g of the first photoinitiator shown in formula (1-2), and 25g of GBL were weighed into a clean, straight bottle. After sealing, the bottle was stirred to dissolve and disperse the contents, thus obtaining a photosensitive composition. The photosensitive composition was then coated onto a PET support film and baked at 80°C for 6.5 min. A PET protective film was then laminated onto the surface of the film to obtain a photosensitive film with a thickness of 40 μm.

[0187] Example 6

[0188] 30g of silica, 0.4g of γ-glycidyl etheroxypropyltrimethoxysilane, 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), and 20g of solvent (EL:GBL in a mass ratio of 8:2) were weighed into a clean straight bottle, sealed, and stirred to dissolve and disperse, thus obtaining a polyimide photosensitive composition. The photosensitive composition was then coated onto a PET release film, baked and dried at 80°C for 6 minutes, and then a PET protective film was laminated onto its surface to obtain a photosensitive dry film with a thickness of 40 μm.

[0189] Example 7

[0190] Weigh out 35g of silica, 0.4g of γ-glycidyl etheroxypropyltrimethoxysilane, 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), and 30g of NMP into a clean, straight bottle. Seal the bottle and stir to dissolve and disperse the contents to obtain a polyimide photosensitive composition. Then, coat the photosensitive composition onto a PET release film and heat at 80°C. oThe film is baked and dried at C for 7 minutes, and then a PET protective film is laminated onto its surface to obtain a photosensitive dry film with a thickness of 40 μm.

[0191] Example 8

[0192] Weigh out 8.5g of silica, 0.2g of γ-glycidyl etheroxypropyltrimethoxysilane, 5g of PAE resin, 5g of PI resin, 2g of PETA, 1g of ETPTA, 4.5g of BPA2EODMA, 0.1g of the first photoinitiator shown in formula (1-2), 0.15g of the initiator of formula (1-8), 0.15g of the initiator of formula (1-14), and 30g of NMP into a clean, straight bottle. Seal the bottle and stir to dissolve and disperse the NMP to obtain a polyimide photosensitive composition. Then, coat the photosensitive composition onto a PET release film and heat at 80°C. o The film is baked and dried at C for 7 minutes, and then a PET protective film is laminated onto its surface to obtain a photosensitive dry film with a thickness of 40 μm.

[0193] Comparative Example 1

[0194] 30 g of silica, 0.3 g of γ-glycidyl etheroxypropyltrimethoxysilane, 10 g of PAE resin, 4.5 g of BPA2EODMA, 0.2 g of hexaaryl diimidazole (HABI), and 25 g of solvent (EL:GBL in a mass ratio of 8:2) were weighed into a clean, straight-sided bottle. After sealing, the bottle was stirred to dissolve and disperse the contents, thus obtaining a photosensitive composition. The photosensitive composition was then coated onto a PET support film and baked at 80°C for 6.5 min. Finally, a PET protective film was laminated onto the surface of the film to obtain a photosensitive film with a thickness of 40 μm.

[0195] Performance testing

[0196] (1) Cut the photosensitive layer into strips with a width of 25 mm using a cutter, then place them in an oxygen-free nitrogen oven and cure them at 270℃ for 2 hours. Then use DMA to measure the modulus of the cured film in the temperature range of 40-350℃ and record the elastic modulus of the cured film at 180℃.

[0197] (2) Cut a 2cm×2cm photosensitive layer and test its light transmittance using ultraviolet-visible spectroscopy (UV-vis) under a 405 nm light source.

[0198] (3) Cut a photosensitive film to the size of an A4 sheet of paper, peel off the release film, and attach it to the surface of the structural sheet (pattern height 8-12μm). Verify the film application process using a semi-automatic wafer laminator, where the lamination table temperature is 65 ℃, the roller pressure is 0.35MPa, the lamination speed is 5.5 mm / s, and the table height is -50mm. After lamination, observe the bonding condition using an optical microscope. It is required to achieve 100% bonding without collapse or bubbles.

[0199] (4) Cut a photosensitive layer to the appropriate size and attach it to the surface of the silicon wafer. Then expose it using a mixed light source with wavelengths of 365nm and 405nm, with an exposure dose of 150 mW / cm². 2 After post-baking at 110℃ for 5 min, the unexposed portions were removed by dissolving with 2.38 wt.% TMAH to obtain a negative pattern. The surface and cross-sectional morphology of the pattern were observed using an optical microscope, and the minimum size of the pattern opening was determined to be its resolution accuracy, as recorded in Table 1. Figure 3A An optical microscope image of the patterned photosensitive layer obtained after exposure, development and curing of the photosensitive layer provided in Embodiment 6 of this application; Figure 3B This is an optical microscope photograph of the patterned photosensitive layer obtained after exposure, development and curing of the photosensitive layer of Comparative Example 1.

[0200] For ease of reading, the specific parameters of the photosensitive compositions of the above embodiments and comparative examples, as well as the test results of the photosensitive layers, are summarized in Table 1.

[0201] Table 1

[0202]

[0203] As can be seen from the data in Table 1, the embodiments of this application provide a photosensitive composition with a high filler content. Based on the high filler content, the photosensitive layer prepared by the photosensitive composition has good uniformity and still has high transparency. There is no risk of collapse during application, and the deep and surface curing effects are good. After exposure, curing and other processes, the pattern resolution is good and the mechanical properties are good.

[0204] It should be understood that the use of the terms "first," "second," and various numerical designations in this document is merely for descriptive convenience and is not intended to limit the scope of this application.

[0205] In this application, "and / or" describes the relationship between related objects, indicating that three relationships can exist. For example, A and / or B can represent: A existing alone, A and B existing simultaneously, or B existing alone, where A and B can be singular or plural. The character " / " generally indicates that the related objects before and after it are in an "or" relationship.

[0206] In this application, "at least one" means one or more, and "more than one" means two or more. "At least one of the following" or similar expressions refer to any combination of these items, including any combination of single or multiple items. For example, "at least one of a, b, or c", or "at least one of a, b, and c", can both mean: a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, and c can be single or multiple.

[0207] In this application, "-" indicates a range value, including the endpoint values ​​at both ends. For example, the value of a can be 0.5-15, meaning that the value of a can be between 0.5 and 15, and includes the endpoint values ​​of 0.5 and 15.

Claims

1. A photosensitive composition, characterized in that, This includes soluble resins, photoinitiators, crosslinkable monomers, and fillers; The soluble resin includes polyimide and polyamide ester; and / or, the soluble resin includes a copolymer of a first monomer for obtaining polyimide and a second monomer for obtaining polyamide ester; The photoinitiator includes a first photoinitiator, wherein the first photoinitiator is a photoinitiator having... Compounds; in, The term "linking site" indicates the connection site. R1, R2, and R3 are independently selected from one or more of the following: hydrogen atom, hydroxyl group, carboxyl group, nitro group, cyano group, -NR4R5, substituted or unsubstituted C1-C10 hydrocarbon group, substituted or unsubstituted C1-C10 hydrocarbon group with a second structure in the main chain, substituted or unsubstituted C1-C10 acyl group, substituted or unsubstituted C1-C10 alkoxy group with a second structure in the main chain, substituted or unsubstituted C1-C10 alkoxy group, and substituted or unsubstituted C1-C10 alkoxy group with a second structure in the main chain. The second structure includes one or more of the following: ether oxygen bond, thioether bond, ester bond, thioester bond, amide bond, or carbamate bond. R4 and R5 are independently selected from one or more of the following: hydrogen atom, oxygen atom, substituted or unsubstituted C1-C10 alkoxy group, or substituted or unsubstituted C1-C10 alkyl group. R4 and R5 may be linked to an N atom to form a ring. Based on the mass of the soluble resin, the mass content of the filler is 250%-500%.

2. The photosensitive composition according to claim 1, characterized in that, In R1, R2, and R3, the substituents in 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, and the substituted or unsubstituted C1-C10 alkoxy group with a second structure in the main chain are independently selected from one or more of halogen atoms, hydroxyl groups, carboxyl groups, nitro groups, cyano groups, or -NR4R5.

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

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

5. The photosensitive composition according to any one of claims 1-3, characterized in that, The soluble resin has carboxyl and / or hydroxyl groups; 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 1-3, characterized in that, The first photoinitiator comprises one or more of formulas (1-1) to (1-15): Equation (1-1), Equation (1-2), Equation (1-3), Equation (1-4), Equation (1-5), Equation (1-6), Equation (1-7), Equation (1-8), Equation (1-9), Equation (1-10), Equation (1-11), Equation (1-12), Equation (1-13), Equation (1-14), Equation (1-15).

7. The photosensitive composition according to any one of claims 1-3, characterized in that, The crosslinkable monomer has a carboxyl group and / or a hydroxyl group; and / or, the average free radical functionality of the crosslinkable monomer is a positive integer from 2 to 8; and / or, The free radical equivalent of the crosslinkable monomer is 90-250; and / or, The crosslinkable monomer accounts for 1%-10% of the mass of the soluble resin; and / or, The photoinitiator comprises 0.05%-5% of the mass of the soluble resin; and / or, The filler constitutes 81%-500% of the mass of the soluble resin; and / or, The packing material includes inorganic packing; 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 1-3, characterized in that, The photosensitive composition has a room temperature viscosity of 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 cured product of the photosensitive composition has an elastic modulus ≥6 GPa at 180 °C; and / or, The patterning resolution of the photosensitive composition is ≤40 μm; and / or, The pattern formed by the exposure and development of the photosensitive composition has no bottom indentation.

9. A method for preparing a photosensitive composition, characterized in that, include: A mixture of soluble resin, photoinitiator, crosslinkable monomer, and filler; The soluble resin includes polyimide and polyamide ester; And / or, the soluble resin comprises a copolymer of a first monomer for producing a polyimide and a second monomer for producing a polyamide ester; The photoinitiator includes a first photoinitiator, wherein the first photoinitiator is a photoinitiator having... Compounds; in, The term "linking site" indicates the connection site. R1, R2, and R3 are independently selected from one or more of the following: hydrogen atom, hydroxyl group, carboxyl group, nitro group, cyano group, -NR4R5, substituted or unsubstituted C1-C10 hydrocarbon group, substituted or unsubstituted C1-C10 hydrocarbon group with a second structure in the main chain, substituted or unsubstituted C1-C10 acyl group, substituted or unsubstituted C1-C10 alkoxy group with a second structure in the main chain, substituted or unsubstituted C1-C10 alkoxy group, and substituted or unsubstituted C1-C10 alkoxy group with a second structure in the main chain. The second structure includes one or more of the following: ether oxygen bond, thioether bond, ester bond, thioester bond, amide bond, or carbamate bond. R4 and R5 are independently selected from one or more of the following: hydrogen atom, oxygen atom, substituted or unsubstituted C1-C10 alkoxy group, or substituted or unsubstituted C1-C10 alkyl group. R4 and R5 may be linked to an N atom to form a ring. Based on the mass of the soluble resin, the mass content of the filler is 250%-500%.

10. A photosensitive film, characterized in that, It includes a support film, a protective film, and a photosensitive layer disposed between the support film and the protective film, wherein the photosensitive layer is made of a photosensitive composition as described in any one of claims 1-8, or the photosensitive layer is made of a photosensitive composition prepared by the method of preparing the photosensitive composition as described in claim 9.

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

12. A method for preparing a photosensitive film, characterized in that, include: A photosensitive composition prepared by any one of the photosensitive compositions described in claims 1-8 or by the method of preparing the photosensitive composition described in claim 9 is coated onto a support film to form a photosensitive layer, and then a protective film is disposed on the surface of the photosensitive layer opposite to the support film to obtain a photosensitive film.

13. A semiconductor device, characterized in that, The semiconductor device includes a hollow structure with a cavity, electronic circuitry, and a cured or patterned photosensitive layer of the photosensitive layer in the photosensitive film as described in claim 10 or 11; or, the semiconductor device includes a hollow structure with a cavity, electronic circuitry, and a cured or patterned photosensitive layer of the photosensitive layer prepared by the method of preparing the photosensitive film as described in claim 12; the electronic circuitry is disposed on the hollow structure. The cured or patterned photosensitive layer is disposed at the top of the cavity.

14. A method for fabricating a semiconductor device, characterized in that, include: A support layer is formed on the surface of a substrate containing electronic circuitry; A photosensitive layer is disposed on the surface of the support layer, and the photosensitive layer is prepared by the photosensitive composition according to any one of claims 1-8 or the photosensitive composition prepared by the preparation method according to claim 9; After the photosensitive layer is cured, it forms a protective film. The substrate, the support layer, and the protective film are arranged to form a hollow structure with a cavity structure to obtain a semiconductor device.

15. An electronic device, characterized in that, The electronic device includes the semiconductor device as described in claim 14 and a circuit board, the circuit board being electrically connected to the semiconductor device; and / or, the electronic device includes a cured or patterned photosensitive layer as described in claim 10 or 11.

Images