Photosensitive resin composition, photoresist cured film and application thereof

Abstract

The invention provides a photosensitive resin composition, a photoresist cured film and application thereof. The photosensitive resin composition comprises a combination of alkali-soluble resin, a photosensitive compound and a cross-linking agent, the cross-linking agent has a structure as shown in a formula I. Through design of a specific cross-linking agent structure and compounding with other components, the photosensitive resin composition has relatively high cross-linking density in the early stage of curing, forms a rich cross-linked network in curing and reduces the hydroxyl content in the system, so that the water absorption / moisture absorption rate is reduced; according to the invention, gas overflow in the subsequent process of the product is effectively improved, so that the photoresist cured film has better barrier property, higher adhesive force and adherence, high strength and excellent chemical corrosion resistance, and the yield of the device and the reliability in the subsequent use process are effectively improved.

Description

Technical Field

[0001] The present invention belongs to the field of lithography technology, and particularly relates to a photosensitive resin composition, a photoresist cured film and their applications. Background Art

[0002] Since devices such as semiconductors and display panels are developing towards miniaturization, thinning and flexibility, improving the reliability of products is one of the important issues faced by the current industrial community. In terms of the field of materials science, improving the performance of packaging materials and interlayer dielectric materials is an effective means to improve the reliability of devices. Typical examples of packaging and interlayer dielectric materials include the redistribution layer (RDL layer), bump layer (Bump layer) in microelectronic devices (IC devices), anti-radiation protection of devices, insulating layers, the pixel definition layer (PDL), planarization layer (PL) in organic light-emitting diode (OLED) devices, etc. The expected properties of the aforementioned hierarchical materials include better mechanical strength, barrier properties, adhesion to the substrate, lower moisture absorption rate, etc., which are also the long-term pursuits in the current fields of packaging and interlayer dielectric materials.

[0003] Photosensitive resin compositions prepared by compounding alkali-soluble resins such as polyamic acid, polyamic acid ester, polyimide, polyhydroxyamide, polybenzoxazole, etc. with photosensitive compounds and the like have characteristics such as high resolution, good heat resistance, and good chemical resistance, and are widely used in the fields of semiconductor device packaging, interlayer dielectrics, etc. However, in the existing technology, due to the residual hydrophilic groups with a relatively high content in the photosensitive resin cured film, such as hydroxyl groups, carboxyl groups, etc., there are problems of high moisture absorption rate and poor barrier properties of the cured film. An excessively high moisture absorption rate is likely to cause a large change in the thermal expansion coefficient of the material and generate a relatively large amount of outgassing in the subsequent process, resulting in phenomena such as rupture of the additional film layer in the subsequent process, reducing the yield of the device, and may also lead to a reduction in the reliability of the device during long-term use.

[0004] In addition, during the thermal curing process of resins such as polyamic acid, polyamic acid ester, and polyhydroxyamide, due to the relatively low degree of crosslinking and imidization in the early stage of curing, they have a certain fluidity at high temperatures, which is likely to cause phenomena such as closed holes, line width reduction, and adhesion between lines, resulting in a reduction in the yield of device production.

[0005] Therefore, there is an urgent need in this field to develop a new type of photosensitive resin material to effectively improve the phenomenon of graphic deformation or even closed holes after curing, while ensuring that the cured film has excellent barrier properties, adhesion, low moisture absorption and water absorption rates. Summary of the Invention

[0006] In view of the deficiencies of the prior art, the purpose of the present invention is to provide a photosensitive resin composition, a photoresist cured film and its application. By designing a crosslinking agent with a specific structure and compounding it with other components, the photosensitive resin composition has low fluidity during the curing process, which can prevent adverse phenomena such as pattern deformation and closed pores. Moreover, the formed photoresist cured film has high barrier properties and excellent adhesion, while the water absorption and moisture absorption rate are effectively reduced, thereby reducing the gas overflow of the cured film in the device manufacturing process, improving the yield of the device and the reliability during subsequent use.

[0007] To achieve this purpose, the present invention adopts the following technical solutions:

[0008] In the first aspect, the present invention provides a photosensitive resin composition, which includes a combination of an alkali-soluble resin, a photosensitive compound and a crosslinking agent; the crosslinking agent has the structure shown in Formula I:

[0009]

[0010] In Formula I, X represents an aromatic group, preferably an aromatic group of C6-C60 (such as C6, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28, C30, C32, C35, C36, C38, C40, C42, C45, C48, C50, C52, C55 or C58, etc.).

[0011] In Formula I, R1 represents an ester bond-containing group of C2-C20 (such as C3, C4, C5, C6, C9, C10, C12, C14, C16, C18, etc.).

[0012] In Formula I, R2 represents *-CH2-OR A R A selected from any one of H, C1-C8 (such as C1, C2, C3, C4, C5, C6, C7, C8) straight-chain or branched-chain alkyls; -* represents the connection site of the group.

[0013] In Formula I, m represents the number of -OH, which is an integer of ≥1, that is, from 1 to the maximum substitution number, for example, it can be 1, 2, 3, 4, 5, 6, 7, 8 or 9, etc. n represents the number of R2, which is an integer of ≥1, that is, from 1 to the maximum substitution number, for example, it can be 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10, etc.; when n≥2, multiple R2 are the same or different groups. p represents the number of R1, which is an integer of ≥1, that is, from 1 to the maximum substitution number, for example, it can be 1, 2, 3, 4, 5, 6, 7, 8 or 9, etc.; when p≥2, multiple R1 are the same or different groups.

[0014] In Formula I, -OH is directly connected to the aromatic ring by a single bond, that is, -OH is a phenolic hydroxyl group.

[0015] The photosensitive resin composition provided by the present invention contains a crosslinking agent having the structure shown in Formula I. The crosslinking agent contains three specific functional groups: phenolic hydroxyl group, ester bond-containing group R1, and benzyl ether / benzyl alcohol group R2, and has excellent reactivity. During the curing process of the photosensitive resin composition, the ester bond-containing group can undergo a crosslinking reaction through transesterification and other reactions in the initial stage of curing, improving the crosslinking density and increasing the yield and reliability of the photoresist cured film and product devices. At the same time, the crosslinking agent contains three functional groups, significantly increasing the density of the crosslinking groups in the photosensitive resin composition. Through the crosslinking reaction, the hydroxyl groups are consumed and the hydroxyl group content in the system is reduced, reducing the hydrophilic group content in the photoresist cured film, thereby reducing the water absorption rate / moisture absorption rate, effectively improving the gas overflow in the subsequent process of the product, making the photoresist cured film have better barrier properties, higher adhesion, high strength and excellent chemical corrosion resistance, and improving the reliability of device use.

[0016] The following are the preferred technical solutions of the present invention, but do not limit the technical solutions provided by the present invention. Through the following preferred technical solutions, the purpose and beneficial effects of the present invention can be better achieved and realized.

[0017] In the present invention, for the expression of chemical elements, unless otherwise specified, the concept of isotopes with the same chemical properties is included. For example, hydrogen (H) includes 1 H (protium), 2 H (deuterium, D), 3 H (tritium, T), etc.; carbon (C) includes 12 C, 13 C, etc.

[0018] In the present invention, the expression of "Ca-Cb" represents that the group has a carbon atom number of a-b; generally, the carbon atom number does not include the carbon atom number of the substituent unless otherwise specified.

[0019] In the present invention, "independently of each other" means that when its subject has multiple, they can be the same or different from each other.

[0020] In the present invention, the expression of a ring structure with a "-" drawn across it indicates that the connection site is at any position on the ring structure capable of forming a bond.

[0021] In the present invention, both "-*" and "*" represent the connection site of the group.

[0022] In the present invention, the "C6-C60 aromatic group" may be an aromatic group such as C6, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28, C30, C32, C34, C36, C38, C40, C42, C44, C46, C48, C50, C52, C54, C56 or C58, etc., including aryl groups (such as phenyl, naphthyl, biphenyl, terphenyl, fluorenyl, anthracenyl, phenanthryl, triphenylene, tetraphenyl, etc.) or aryl groups connected by a bridging bond (O, S, sulfinyl, sulfonyl, substituted or unsubstituted alkylene, etc.).

[0023] The "C2-C20 ester bond-containing group" may be a monovalent organic group containing such as C2, C3, C4, C5, C6, C9, C10, C12, C14, C16, C18, etc.

[0024] In formula I, X may be a small molecule structure or a polymer chain structure, preferably a C6-C60 small molecule aromatic group, and more preferably a C6-C50 small molecule aromatic group.

[0025] Preferably, the number average molecular weight of the polymer chain structure is 1000-50000, for example, it may be 1500, 2000, 3000, 4000, 5000, 6000, 7000, 8000, 9000, 10000, 15000, 20000, 25000, 30000, 35000, 40000, 45000, etc., more preferably 2000-20000, and even more preferably 2000-5000.

[0026] Preferably, X is selected from any one of the following groups:

[0027]

[0028]

[0029] Among them, X1, X2, X4, X6, X7 are each independently selected from any one of a single bond, -O-, -S-, -CO-, and unsubstituted or halogen-substituted C1-C10 (such as C2, C3, C4, C5, C6, C7, C8, C9, etc.) linear or branched alkylene groups.

[0030] X3, X5 are each independently selected from any one of unsubstituted or halogen-substituted C1-C10 (such as C2, C3, C4, C5, C6, C7, C8, C9, etc.) linear or branched sub-alkylene groups.

[0031] n1, n2, n3, and n4 are each independently selected from integers from 0 to 2, such as 0, 1, or 2; when n1 is 2, the two X1s are the same or different; when n2 is 2, the two X2s are the same or different; when n3 is 2, the two X4s are the same or different; when n4 is 2, the two X6s are the same or different.

[0032] R1, R2, and -OH are substituted at any substitutable position of the benzene ring in the above structure; taking the first structure as an example, at any substitutable position of each benzene ring (the number of benzene rings in the first structure is 2 - 4), R1, R2, and -OH are substituted, and the number of R1, R2, and -OH on X is each independently ≥1; taking the second structure as an example, at any substitutable position of each benzene ring (the number of benzene rings in the second structure is 3 - 7), R1, R2, and -OH are substituted, and the number of R1, R2, and -OH on X is each independently ≥1; taking the third structure as an example, at any substitutable position of each benzene ring (the number of benzene rings in the third structure is 5 - 11), R1, R2, and -OH are substituted, and the number of R1, R2, and -OH on X is each independently ≥1; taking the fourth and fifth structures as examples, at any substitutable position of each benzene ring (the number of benzene rings in the fourth and fifth structures is 4 - 12), R1, R2, and -OH are substituted, and the number of R1, R2, and -OH on X is each independently ≥1.

[0033] In the present invention, the halogen includes fluorine, chlorine, bromine, or iodine; the "halogen substitution" means that at least 1 hydrogen in the group is substituted by a halogen (fluorine, chlorine, bromine, or iodine), preferably fluorine substitution.

[0034] Preferably, X1, X2, X4, X6, and X7 are each independently selected from any one of a single bond, -O-, an unsubstituted or halogen-substituted C1-C6 straight-chain or branched-chain alkylene group, preferably a single bond, -O-, -CH2-, -* represents the connection site of the group.

[0035] Preferably, X3 and X5 are each independently selected from any one of an unsubstituted or halogen-substituted C1-C6 straight-chain or branched-chain sub-alkylene group, more preferably

[0036] Preferably, n1, n2, n3, and n4 are each independently 0 or 1.

[0037] Preferably, X is selected from any one of the following groups:

[0038]

[0039]

[0040]

[0041] R1, R2, and -OH are substituted at any substitutable position of the benzene ring in the above structure.

[0042] Preferably, 0.1 ≤ m / (n + m + p) ≤ 0.3, and m / (n + m + p) can be 0.12, 0.15, 0.18, 0.2, 0.22, 0.25, 0.28, etc.

[0043] Preferably, 0.4 ≤ n / (n + m + p) < 0.7, and n / (n + m + p) can be 0.42, 0.45, 0.48, 0.5, 0.52, 0.55, 0.58, 0.6, 0.62, 0.65, 0.68, etc.

[0044] Preferably, the R1 is selected from any one of them; - * represents the connection site of the group to the aromatic ring.

[0045] R B is selected from any one of straight-chain or branched-chain alkyl groups having 1 to 10 carbon atoms (such as C2, C3, C4, C5, C6, C7, C8, C9, etc.) or aryl groups having 6 to 20 carbon atoms (such as C6, C9, C10, C12, C14, C16, C18, etc.).

[0046] L is selected from any one of straight-chain or branched-chain alkylene groups having 1 to 10 carbon atoms (such as C2, C3, C4, C5, C6, C7, C8, C9, etc.).

[0047] Preferably, the ester bond in the R1 is directly connected to the aromatic ring (benzene ring) through a single bond.

[0048] Preferably, the R1 is selected from

[0049] Preferably, the R B is selected from any one of straight-chain or branched-chain alkyl groups having 1 to 10 carbon atoms, and more preferably any one of straight-chain or branched-chain alkyl groups having 1 to 3 carbon atoms.

[0050] Preferably, the crosslinking agent is selected from any one or a combination of at least two of the following compounds:

[0051]

[0052]

[0053] Preferably, the alkali-soluble resin includes any one or a combination of at least two of polyimide, polyimide precursor resin, polyamide acid-polyimide copolymer, polyamide acid ester-polyimide copolymer, polyisoimide-polyamide acid copolymer, and polyisoimide.

[0054] Preferably, the polyimide precursor resin includes polyamide acid ester and / or polyamide acid.

[0055] Preferably, the alkali-soluble resin contains at least one of the structural units represented by Formula II, Formula III, or Formula IV:

[0056]

[0057]

[0058]

[0059] Among them, R3, R6, R8, R 11 each independently represents a tetravalent organic group of C4-C60 (such as C5, C6, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28, C30, C32, C35, C36, C38, C40, C42, C45, C48, C50, C52, C55, or C58, etc.).

[0060] R4, R7, R9, R 12 each independently represents a divalent organic group of C3-C60 (such as C4, C5, C6, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28, C30, C32, C35, C36, C38, C40, C42, C45, C48, C50, C52, C55, or C58, etc.).

[0061] R5, R 10 each independently represents any one of straight-chain or branched-chain alkyl groups of C1-C10 (such as C2, C3, C4, C5, C6, C7, C8, or C9, etc.).

[0062] As a preferred technical solution of the present invention, the alkali-soluble resin includes any one or a combination of at least two of polyimide precursor resin (polyamide acid and / or polyamide acid ester, preferably containing the structural unit represented by Formula II), polyamide acid-polyimide copolymer, and / or polyamide acid ester-polyimide copolymer (preferably containing the structural unit represented by Formula III), and polyimide (preferably containing the structural unit represented by Formula IV).

[0063] Preferably, the number of structural units represented by Formula II in the alkali-soluble resin is f, and the number of structural units represented by Formula IV is g. Each of f and g is independently an integer from 2 to 200, such as 3, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 60, 70, 80, 90, 100, 110, 130, 150, 170, or 190, etc.

[0064] Preferably, the structural unit represented by Formula III in the alkali-soluble resin includes a polyimide fragment and a polyamic acid (polyamic acid ester) fragment The two fragments are connected by chemical bonds, and their numbers are each independently an integer from 2 to 200, such as 3, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 60, 70, 80, 90, 100, 110, 130, 150, 170, or 190, etc.

[0065] Preferably, R3, R6, R8, R 11 are each independently selected from a substituted or unsubstituted tetravalent aromatic group having 6 to 30 carbon atoms (such as C6, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26, or C28, etc.), and a substituted or unsubstituted tetravalent alicyclic group having 4 to 20 carbon atoms (such as C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, etc.).

[0066] R3, R6, R8, R 11 The substituents in are each independently selected from at least one of halogen, hydroxyl, a linear or branched alkyl group having 1 to 20 carbon atoms (such as C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, or C18, etc.) that is unsubstituted or substituted with halogen, and an alkoxy group having 1 to 20 carbon atoms (such as C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, or C18, etc.) that is unsubstituted or substituted with halogen.

[0067] In the present invention, the "substituted or unsubstituted" group may be substituted with one substituent or multiple substituents. When there are multiple substituents (at least 2), they may be the same or different substituents; when the same expression is involved hereinafter, it shall have the same meaning. The selection range of substituents involved in the alkali-soluble resin is as shown above, and will not be elaborated one by one.

[0068] In the alkali-soluble resin of the present invention, the C6-C30 (such as C6, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26 or C28, etc.) tetravalent aromatic group includes C6-C30 aryl groups (such as phenyl, naphthyl, biphenyl, terphenyl, fluorenyl, anthracenyl, phenanthryl, triphenylene, tetraphenyl, etc.), and also includes aryl groups connected by a bridging bond (O, S, sulfinyl, sulfonyl, substituted or unsubstituted alkylene, etc.). The following description of the "C6-C30 divalent aromatic group" has similar examples.

[0069] The C4-C20 (such as C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, etc.) tetravalent alicyclic group, "alicyclic group" means a non-aromatic saturated or unsaturated cyclic structure, including monocyclic, bridged cyclic, spirocyclic or fused cyclic, etc. Exemplarily, it includes but is not limited to: cyclobutyl, cyclopentyl, cyclohexyl, bicyclooctyl, etc. The following description of the "C4-C20 divalent alicyclic group" has similar examples.

[0070] The C1-C20 straight-chain or branched-chain alkyl group can be a straight-chain or branched-chain alkyl group such as C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17 or C18, etc.; Exemplarily, it includes but is not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, n-octyl, n-heptyl, n-nonyl or n-decyl, etc.

[0071] Specific examples of the C1-C20 (such as C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17 or C18, etc.) alkoxy group can be a monovalent group obtained by connecting the examples of the above straight-chain or branched-chain alkyl groups with O.

[0072] In the present invention, the halogen includes fluorine, chlorine, bromine or iodine; the "halogen substitution" means that at least 1 hydrogen in the group is substituted by a halogen (fluorine, chlorine, bromine or iodine), preferably fluorine substitution.

[0073] Preferably, the R3, R6, R8, R 11 are each independently selected from any one of the following groups:

[0074] -* represents the connection site of the group.

[0075] R 21 、R 22 、R 23 、R24 , R 25 , R 26 Each independently selected from hydrogen, halogen, hydroxy, unsubstituted or halogen-substituted C1-C20 (such as C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17 or C18, etc.) linear or branched alkyl, unsubstituted or halogen-substituted C1-C20 (such as C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17 or C18, etc.) alkoxy, and more preferably hydrogen, fluorine, methyl, methoxy, perfluoromethyl or perfluoromethoxy.

[0076] L 21 Selected from a single bond, -O-, -S-, carbonyl sulfonyl sulfinyl unsubstituted or R'-substituted (such as C2, C3, C4, C5, C6, C7, C8 or C9, etc.) linear or branched alkylene, unsubstituted or R'-substituted C6-C20 (such as C6, C9, C10, C12, C14, C16 or C18, etc.) arylene, *-L 22 -Ar 21 -L 23 -* of any one.

[0077] L 22 , L 23 Each independently selected from -O-, -S-, carbonyl, sulfonyl, sulfinyl, unsubstituted or R'-substituted C1-C10 (such as C2, C3, C4, C5, C6, C7, C8 or C9, etc.) linear or branched alkylene of any one.

[0078] Ar 21 Selected from unsubstituted or R'-substituted C6-C20 (such as C6, C9, C10, C12, C14, C16 or C18, etc.) arylene of any one.

[0079] R' is selected from at least one of halogen, hydroxy, unsubstituted or halogen-substituted C1-C20 (such as C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17 or C18, etc.) linear or branched alkyl, unsubstituted or halogen-substituted C1-C20 (such as C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17 or C18, etc.) alkoxy.

[0080] Preferably, the L 21Selected from a single bond, -O-, -CH2-, any one of them.

[0081] Preferably, the R3, R6, R8, R 11 each independently selected from any one of the following groups:

[0082]

[0083] wherein, -* represents the connection site of the group.

[0084] Preferably, the R4, R7, R9, R 12 each independently selected from the group represented by formula V, a substituted or unsubstituted C6-C30 (such as C6, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26 or C28, etc.) divalent aromatic group, a substituted or unsubstituted C4-C20 (such as C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, etc.) divalent alicyclic group.

[0085] R4, R7, R9, R 12 The substituents in the above-mentioned substitution are each independently selected from at least one of halogen, hydroxyl, an unsubstituted or halogen-substituted C1-C20 (such as C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17 or C18, etc.) straight-chain or branched-chain alkyl group, an unsubstituted or halogen-substituted C1-C20 (such as C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17 or C18, etc.) alkoxy group.

[0086]

[0087] In formula V, -* represents the connection site of the group.

[0088] In Formula V, A is selected from any one of a single bond, -O-, -S-, a carbonyl group, a sulfone group, a substituted or unsubstituted C1-C10 (such as C2, C3, C4, C5, C6, C7, C8 or C9, etc.) divalent aliphatic hydrocarbon group, a substituted or unsubstituted C3-C20 (such as C4, C5, C6, C7, C8, C9, C10, C12, C14, C15, C17 or C18, etc.) divalent alicyclic group, and a substituted or unsubstituted C6-C30 (such as C6, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26 or C28, etc.) divalent aromatic group.

[0089] The substituents of the substituted A are each independently selected from at least one of a halogen, an unsubstituted or halogen-substituted C1-C10 (such as C2, C3, C4, C5, C6, C7, C8 or C9, etc.) straight-chain or branched-chain alkyl group, an unsubstituted or halogen-substituted C6-C30 (such as C6, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26 or C28, etc.) aryl group, and an unsubstituted or halogen-substituted C6-C30 (such as C6, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26 or C28, etc.) phenol group.

[0090] In Formula V, R 31 , R 32 are each independently selected from any one of a halogen, a nitro group, a cyano group, a carboxyl group, an unsubstituted or halogen-substituted C1-C10 (such as C2, C3, C4, C5, C6, C7, C8 or C9, etc.) straight-chain or branched-chain alkyl group, an unsubstituted or halogen-substituted C1-C10 (such as C2, C3, C4, C5, C6, C7, C8 or C9, etc.) alkoxy group, an unsubstituted or halogen-substituted C6-C30 (such as C6, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26 or C28, etc.) aryl group, an amide group, a benzyloxy group or a benzyl alcohol group.

[0091] R 33 , R 34 are each independently selected from any one of a C1-C10 (such as C2, C3, C4, C5, C6, C7, C8 or C9, etc.) straight-chain or branched-chain alkylene group, a C1-C10 (such as C2, C3, C4, C5, C6, C7, C8 or C9, etc.) alkyleneoxy group, and a C1-C10 (such as C2, C3, C4, C5, C6, C7, C8 or C9, etc.) Si-containing divalent group.

[0092] In Formula V, R 35 , R 36 are each independently selected from *-CH2-OR 51 , R51 Any one selected from H, C1-C8 (such as C2, C3, C4, C5, C6, C7, etc.) straight-chain or branched-chain alkyl groups.

[0093] In formula V, R 37 , R 38 Each independently selected from halogen, hydroxyl, nitro, cyano, carboxyl, unsubstituted or halogen-substituted C1-C10 (such as C2, C3, C4, C5, C6, C7, C8 or C9, etc.) straight-chain or branched-chain alkyl groups, unsubstituted or halogen-substituted C1-C10 (such as C2, C3, C4, C5, C6, C7, C8 or C9, etc.) alkoxy groups, unsubstituted or halogen-substituted C6-C30 (such as C6, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26 or C28, etc.) aryl groups, C1-C10 (such as C2, C3, C4, C5, C6, C7, C8 or C9, etc.) ester groups or amide groups.

[0094] In formula V, a1, a2, b1, b2, c1, c2, d1, d2 respectively represent the number of groups, each independently selected from integers of 0-4, for example, can be 0, 1, 2, 3, 4.

[0095] In formula V, t1, t2 are each independently 0 or 1; when t1, t2 are 0, it means that the benzene ring is directly connected to -CO- through a single bond.

[0096] Preferably, in formula V, A is selected from any one of a sulfone group, a substituted or unsubstituted C1-C6 (such as C1, C2, C3, C4, C5 or C6) straight-chain or branched-chain alkylene group; the substituents of the substituted A are each independently selected from at least one of halogen, phenol group, unsubstituted or halogen-substituted C1-C6 (such as C1, C2, C3, C4, C5 or C6) straight-chain or branched-chain alkyl groups, unsubstituted or halogen-substituted C1-C6 (such as C1, C2, C3, C4, C5 or C6) alkoxy groups.

[0097] Further preferably, in formula V, A is selected from a sulfone group,

[0098] Preferably, in formula V, the R 33 , R 34 Each independently selected from any one of C1-C6 (such as C1, C2, C3, C4, C5 or C6) straight-chain or branched-chain alkylene groups, C1-C6 (such as C1, C2, C3, C4, C5 or C6) alkylene oxides, and further preferably *-CH2-*, *-CH2-O-* or *-O-CH2-*.

[0099] Preferably, in formula V, the R 35, R 36 Each independently is *-CH2-OH or *-CH2-O-CH3.

[0100] Preferably, in formula V, a1, a2, b1, and b2 each independently are selected from integers of 1-3, more preferably 1 or 2.

[0101] Preferably, the group represented by formula V has any one of the following structures:

[0102]

[0103]

[0104]

[0105] Wherein, -* represents the connection site of the group.

[0106] Preferably, R4, R7, R9, R 12 Each independently is selected from any one of the groups represented by formula V, ; -* represents the connection site of the group.

[0107] R 41 、R 42 Each independently is selected from any one of halogen, hydroxyl, unsubstituted or halogen-substituted C1-C20 (such as C2, C3, C4, C5, C6, C7, C8, C9, C10, C12, C15 or C18, etc.) straight-chain or branched-chain alkyl, unsubstituted or halogen-substituted C1-C20 (such as C2, C3, C4, C5, C6, C7, C8, C9, C10, C12, C15 or C18, etc.) alkoxy, more preferably hydroxyl, fluorine, methyl, methoxy, perfluoromethyl or perfluoromethoxy.

[0108] L 41 Is selected from single bond, -O-, -S-, carbonyl, sulfone group, sulfoxide group, unsubstituted or halogen-substituted C1-C10 (such as C2, C3, C4, C5, C6, C7, C8 or C9, etc.) straight-chain or branched-chain alkylene, unsubstituted or halogen-substituted C6-C20 (such as C6, C9, C10, C12, C14, C16 or C18, etc.) arylene, *-L 42 -Ar 41 -L 43 -* any one of them.

[0109] L 42 、L 43Each independently selected from -O-, -S-, carbonyl, sulfone, sulfoxide, and any one of unsubstituted or halogen-substituted C1-C10 (such as C2, C3, C4, C5, C6, C7, C8, or C9, etc.) linear or branched alkylene groups.

[0110] Ar 41 Selected from any one of unsubstituted or R”-substituted C6-C20 (such as C6, C9, C10, C12, C14, C16, or C18, etc.) arylene groups.

[0111] R” is selected from any one of halogen, hydroxyl, unsubstituted or halogen-substituted C1-C10 (such as C2, C3, C4, C5, C6, C7, C8, or C9, etc.) linear or branched alkyl groups, and unsubstituted or halogen-substituted C1-C10 (such as C2, C3, C4, C5, C6, C7, C8, or C9, etc.) alkoxy groups.

[0112] u1 and u2 each independently selected from integers from 0 to 4, for example, can be 0, 1, 2, 3, or 4.

[0113] Preferably, the L 41 Selected from a single bond, -O-, -CH2-,

[0114] Any one of them.

[0115] Preferably, the R4, R7, R9, R 12 Each independently selected from the groups shown in Formula V,

[0116]

[0117] Any one of them.

[0118] Preferably, the weight-average molecular weight of the alkali-soluble resin is 2000 - 100000, for example, can be 3000, 5000, 8000, 10000, 15000, 20000, 25000, 30000, 35000, 40000, 45000, 50000, 55000, 60000, 70000, 80000, or 90000, etc., and more preferably 5000 - 50000.

[0119] Preferably, the alkali-soluble resin includes a polyimide precursor resin (polyamic acid and / or polyamic acid ester, preferably containing the structural unit shown in Formula II), which can be prepared by a method well-known in the art. Exemplarily, any of the following routes can be used: Route (1) directly polymerize diamine with dianhydride to obtain polyamic acid, and then generate polyamic acid ester through an esterification reaction; Route (2) react dianhydride with alcohol to form dicarboxylic acid diester, then react with thionyl chloride to generate diacyl chloride diester, and then polymerize with diamine compound to obtain polyamic acid ester; Route (3) react dianhydride with alcohol to form dicarboxylic acid diester, and then react and polymerize with diamine compound in the presence of a dehydrating agent such as cyclohexylcarbodiimide to obtain polyamic acid ester.

[0120] Preferably, the method for preparing the polyimide precursor resin includes: First, polymerize a diamine monomer (NH2-R4-NH2) with a dianhydride monomer to obtain polyamic acid; the polyamic acid undergoes an esterification reaction to obtain the polyimide precursor resin.

[0121] Preferably, the reagents for the esterification reaction include N,N-dimethylformamide dimethyl acetal and / or N,N-dimethylformamide diethyl acetal.

[0122] Preferably, the photosensitive compound is a compound containing a diazonaphthoquinone group.

[0123] Preferably, the structure of the diazonaphthoquinone group is -* represents the connection site of the group.

[0124] Preferably, the photosensitive resin composition further includes additives and / or solvents.

[0125] Preferably, the additives include any one or a combination of at least two of silane coupling agents, surfactants, and curing accelerators.

[0126] In order to improve the processing performance and application performance of the photosensitive resin composition, additives such as surfactants (leveling agents), silane coupling agents, and curing accelerators (catalysts) can be added to improve the film thickness uniformity during the coating process of the photosensitive resin composition, the adhesion to the substrate, and increase the rate and conversion rate of the curing reaction, etc., thereby improving the flatness of the film, increasing the adhesion between the photoresist cured film and the substrate, and reducing the residual film after development.

[0127] Preferably, in addition to containing an alkoxysilyl group, the silane coupling agent further contains at least one reactive functional group.

[0128] Preferably, the silane coupling agent contains at least one of vinyl, allyl, oxacyclic group, styryl, acyloxy group, acryloyloxy group, ureido group, amino group, imidazolyl group, tertiary amine group, secondary amine group, mercapto group, and isocyanate group.

[0129] Preferably, the surfactant includes any one or a combination of at least two of fluorosurfactants, poly(ethylene glycol)-containing surfactants, and siloxane structure-containing surfactants.

[0130] Preferably, the curing accelerator includes any one or a combination of at least two of photoacid generators, thermal acid generators, photobase generators, and thermal base generators. Further preferably, thermal acid generators and / or thermal base generators, which can promote transesterification, esterification reaction, crosslinking reaction, and / or ring-closing reaction of the alkali-soluble resin and the crosslinking agent during the curing process.

[0131] Preferably, the thermal acid generator includes compounds that generate strong acids, such as p-toluenesulfonic acid, methyl p-toluenesulfonate, ethyl methanesulfonate, trifluoromethanesulfonic acid, methyl mercaptotetrazole, disulfone compounds, etc. Particularly preferably, acid generators with a thermal decomposition temperature between 90 - 250 °C, which can be used in the form of salts (such as ammonium salts, sulfonium salts, iodonium salts), or in the form of chemical bonds such as imide sulfonates.

[0132] Preferably, the thermal base generator includes substances that generate organic nitrogen-containing compounds as bases, specifically, primary aliphatic amines, tertiary aliphatic amines, primary aromatic amines, tertiary aromatic amines, imidazole, pyridine, amidinium salts, guanidinium salts, phosphazenes, etc. From the perspective of improving device stability, compounds without halogens are preferred. Specific examples include: guanidine p-toluenesulfonylacetate, guanidine phenylpropiolate, 1-(tert-butoxycarbonyl)imidazole, 1-(methoxycarbonyl)imidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, 1-(anthraquinon-2-yl)ethylimidazole-1-carboxylic acid, 1-(ethoxycarbonyl)imidazole, 2-(3-benzoylphenyl)propanoic acid 1,6-diazabicyclo[4.3.0]non-5-enium, (E)-N-cyclohexyl-3-(2-hydroxyphenyl)acrylamide, (E)-1-piperidinyl-3-(2-hydroxyphenyl)-2-propen-1-one, 9-anthrylmethyl N-cyclohexylcarbamate, 2-(3-benzoylphenyl)propanoic acid 1,5,7-triaza-7-methyl-bicyclo[4.4.0]dec-5-enium, guanidino 2-(3-benzoylphenyl)propanoic acid, (2-nitrophenyl)methyl tert-butyl 4-hydroxypiperidine-1-carboxylate, cyclohex-2-(3-benzoylphenyl)propanoic acid, 9-anthrylmethyl N,N-dicyclohexylcarbamate, etc.

[0133] Preferably, the solvent is a commonly used solvent in the art, including but not limited to: any one or a combination of at least two of γ-butyrolactone, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether formate, propylene glycol monoethyl ether formate, ethyl lactate, butyl lactate, N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide.

[0134] Preferably, the photosensitive resin composition comprises the following components in mass percentage:

[0135]

[0136] Preferably, the mass percentage of the alkali-soluble resin in the photosensitive resin composition is 4-30 wt.%, for example, it can be 5 wt.%, 6 wt.%, 8 wt.%, 10 wt.%, 12 wt.%, 15 wt.%, 18 wt.%, 20 wt.%, 22 wt.%, 25 wt.% or 28 wt.% etc., and more preferably 5-20 wt.%.

[0137] Preferably, the mass percentage of the photosensitive compound in the photosensitive resin composition is 0.4-20 wt.%, for example, it can be 0.5 wt.%, 0.8 wt.%, 1 wt.%, 2 wt.%, 3 wt.%, 4 wt.%, 5 wt.%, 6 wt.%, 7 wt.%, 8 wt.%, 9 wt.%, 10 wt.%, 12 wt.%, 15 wt.% or 18 wt.% etc., and more preferably 1-10 wt.%.

[0138] Preferably, the mass percentage of the crosslinking agent having the structure shown in Formula I in the photosensitive resin composition is 0.1-20 wt.%, for example, it can be 0.2 wt.%, 0.3 wt.%, 0.4 wt.%, 0.5 wt.%, 0.8 wt.%, 1 wt.%, 2 wt.%, 3 wt.%, 4 wt.%, 5 wt.%, 6 wt.%, 7 wt.%, 8 wt.%, 9 wt.%, 10 wt.%, 12 wt.%, 15 wt.% or 18 wt.% etc., and more preferably 1-10 wt.%.

[0139] Preferably, the mass percentage of the auxiliary agent in the photosensitive resin composition is 0.001-2 wt.%, for example, it can be 0.003 wt.%, 0.005 wt.%, 0.008 wt.%, 0.01 wt.%, 0.03 wt.%, 0.05 wt.%, 0.08 wt.%, 0.1 wt.%, 0.3 wt.%, 0.5 wt.%, 0.8 wt.%, 1 wt.%, 1.2 wt.%, 1.5 wt.% or 1.8 wt.%, and more preferably 0.002-1 wt.%.

[0140] Preferably, the mass percentage of the solvent in the photosensitive resin composition is 55-95 wt.%, and can be, for example, 58 wt.%, 60 wt.%, 62 wt.%, 65 wt.%, 68 wt.%, 70 wt.%, 72 wt.%, 75 wt.%, 78 wt.%, 80 wt.%, 82 wt.%, 85 wt.%, 88 wt.%, 90 wt.% or 92 wt.%, etc.

[0141] Preferably, a solvent is added to the photosensitive resin composition so that the solid content is 5-45 wt.%, more preferably 8-30 wt%. An excessively low solid content is not conducive to forming a continuous film with a certain thickness, while an excessively high solid content may lead to too high viscosity, and then cause problems such as air bubbles and poor flatness during the film coating process.

[0142] In a second aspect, the present invention provides a photoresist cured film, which is prepared from the photosensitive resin composition as described in the first aspect.

[0143] In a third aspect, the present invention provides an application of the photosensitive resin composition as described in the first aspect and the photoresist cured film as described in the second aspect in semiconductor devices or flat panel display devices.

[0144] Preferably, the photosensitive resin composition and the photoresist cured film are used as stress buffer materials, passivation layers, pixel definition layers, planarization layers, etc. in semiconductor devices.

[0145] Preferably, after the photosensitive resin composition is coated, pre-baked, lithographed, developed, and cured, a photoresist cured film can be formed and permanently retained in semiconductor devices or flat panel display devices (display panels). The photoresist cured film has excellent substrate adhesion and can be used in the encapsulation process of flexible semiconductors, flat panel displays and other devices.

[0146] In a fourth aspect, the present invention provides a semiconductor device, which contains at least one of the photosensitive resin composition as described in the first aspect and the photoresist cured film as described in the second aspect.

[0147] Preferably, the semiconductor device includes a stress buffer layer and / or a passivation layer, and the stress buffer layer and / or the passivation layer contains at least one of the photosensitive resin composition as described in the first aspect and the photoresist cured film as described in the second aspect.

[0148] In a fifth aspect, the present invention provides a flat panel display device, which contains at least one of the photosensitive resin composition as described in the first aspect and the photoresist cured film as described in the second aspect.

[0149] Preferably, the flat panel display device includes a pixel defining layer and / or a planarization layer, and the pixel defining layer and / or the planarization layer contains at least one of the photosensitive resin composition as described in the first aspect and the photoresist cured film as described in the second aspect.

[0150] Compared with the prior art, the present invention has the following beneficial effects:

[0151] In the photosensitive resin composition provided by the present invention, through the design of a specific crosslinker structure and compounding with other components, the photosensitive resin composition has a relatively high crosslinking density in the early stage of curing, forming a rich crosslinking network during curing, increasing the crosslinking density, reducing the hydroxyl content in the system, thereby reducing the water absorption rate / moisture absorption rate, with the water absorption rate < 1%, effectively improving the gas overflow in the subsequent manufacturing process of the product, enabling the photoresist cured film to have better barrier properties, higher adhesion and close adhesion, high strength and excellent chemical corrosion resistance, effectively improving the yield of the device and the reliability during subsequent use. Specific Embodiments

[0152] The technical solutions of the present invention will be further described below through specific embodiments. Those skilled in the art should understand that the embodiments are only for helping to understand the present invention and should not be regarded as specific limitations on the present invention.

[0153] In the present invention, the crosslinker can be obtained through market channels or can be self-made by organic synthesis methods well-known in the art.

[0154] In a specific embodiment, the crosslinker can be prepared through the following synthetic route A:

[0155]

[0156] Among them, R1, R2, m, n, p have the same definitions as in formula I; Hal1 is selected from halogens, and further preferably Cl or Br;

[0157]

[0158] represents X in formula I.

[0159] In another specific embodiment, the crosslinker can be prepared through the following synthetic route B:

[0160]

[0161] Among them, X, R2, m, n have the same definitions as in formula I; Hal2 is selected from halogens, and further preferably Cl or Br; L is selected from C1-C10 linear or branched alkylene groups, and Y is selected from R BAny one selected from C1-C10 linear or branched alkyl groups and C6-C20 aryl groups.

[0162] The following will take synthesis examples as an illustration to elaborate on the specific preparation method of the crosslinking agent described in the present invention, but the preparation method of the crosslinking agent is not limited to these synthesis examples.

[0163] In the following synthesis examples of the present invention, the mass spectrometry data (m / z) of the target product was obtained by testing with an Agilent Qtof G6530 mass spectrometer.

[0164] Synthesis Example 1: Preparation of compound The synthesis route is as follows:

[0165]

[0166] Under nitrogen protection, 40 g of compound S1 and 22.8 g of methyl p-bromobenzoate were dissolved in anhydrous N,N-dimethylformamide, 45.1 g of potassium phosphate, 2.02 g of copper(I) iodide, and 4.2 g of N1,N2(bis(1,1'-biphenyl)-2-yl)oxalamide were added, and the mixture was stirred at 100 °C for 36 h. The crude product was purified by washing with water and column chromatography to obtain the target compound A1; the mass spectrometry test result: m / z value (M+Na): 533.24.

[0167] Synthesis Example 2: Preparation of compound The synthesis route is as follows:

[0168] Under nitrogen protection, 40 g of compound S1 and 16.2 g of methyl bromoacetate were dissolved in acetonitrile, 14.7 g of potassium carbonate was added, the mixture was heated to reflux and stirred for 16 h, and after cooling to room temperature, it was washed with water and purified by column chromatography to obtain the target compound A2; the mass spectrometry test result: m / z value (M-H): 447.20.

[0169] Synthesis Example 3: Preparation of compound The synthesis route is as follows:

[0170]

[0171] Under nitrogen protection, 60 g of compound S3 and 22.6 g of methyl p-bromobenzoate were dissolved in anhydrous N,N-dimethylformamide, 67 g of potassium phosphate, 2.0 g of copper(I) iodide, and 4.7 g of N1,N2(bis(1,1'-biphenyl)-2-yl)oxalamide were added, and the mixture was stirred at 120 °C for 40 h. The crude product was purified by washing with water and column chromatography to obtain the required target compound A3; the mass spectrometry test result: m / z value (M+Na): 727.33.

[0172] Synthesis Example 4: Preparation of compound Preparation, the synthetic route is as follows:

[0173]

[0174] Under nitrogen protection, 60 g of compound S4 and 15.1 g of methyl 4-bromobenzoate were dissolved in anhydrous N,N-dimethylformamide, 76 g of potassium phosphate, 4.3 g of copper(I) iodide, and 5.9 g of N1,N2-bis(1,1'-biphenyl-2-yl)oxalamide were added, and the mixture was stirred at 120 °C for 48 h. The crude product was purified by washing with water and column chromatography to obtain the desired target compound A4; the mass spectrometry test result: m / z value (M+Na): 1145.50.

[0175] Synthesis Example 5: Compound Preparation, the synthetic route is as follows:

[0176]

[0177] Under nitrogen protection, 60 g of compound S5 and 20.1 g of methyl 4-bromobenzoate were dissolved in anhydrous N,N-dimethylformamide, 79 g of potassium phosphate, 4.6 g of copper(I) iodide, and 5.9 g of N1,N2-bis(1,1'-biphenyl-2-yl)oxalamide were added, and the mixture was stirred at 100 °C for 40 h. The crude product was purified by washing with water and column chromatography to obtain the desired target compound A5; the mass spectrometry test result: m / z value (M+Na): 961.44.

[0178] Synthesis Example 6: Compound Preparation, the synthetic route is as follows:

[0179]

[0180] Under nitrogen protection, 60 g of compound S6 and 41.7 g of methyl 4-bromobenzoate were dissolved in anhydrous N,N-dimethylformamide, 102.7 g of potassium phosphate, 6.0 g of copper(I) iodide, and 7.7 g of N1,N2-bis(1,1'-biphenyl-2-yl)oxalamide were added, and the mixture was stirred at 120 °C for 40 h. The crude product was purified by washing with water and column chromatography to obtain the desired target compound A6; the mass spectrometry test result: m / z value (M+Na): 1219.61.

[0181] In the following specific embodiments of the present invention, the weight-average molecular weight of the alkali-soluble resin was measured by gel permeation chromatography (GPC). The test instrument was a Viscotek gel permeation chromatograph from Malvern Instruments, with a D6000M chromatographic column.

[0182] Preparation Example 1

[0183] Alkali-soluble resin B1, which is a polyimide precursor resin, is prepared as follows: Under nitrogen protection, 6.04 g of diamine compound 1 is dissolved in 20 mL of N-methylpyrrolidone (NMP), the temperature is lowered to 0 °C, and a mixture of 3.87 g of 3,3,4,4-diphenylether tetracarboxylic dianhydride and 12 g of anhydrous NMP is quickly added to the reaction system, and the reaction is carried out at 0 °C for 5 h. The temperature is raised to 60 °C, 2.68 g of N,N-dimethylformamide dimethyl acetal is slowly added dropwise to the reaction system, and the reaction is carried out at 60 °C for 2 h. The temperature is lowered to room temperature, the reaction solution is poured into 300 mL of deionized water, the precipitate is collected by filtration, and the precipitate is vacuum dried at 50 °C for 24 h to obtain alkali-soluble resin B1, with a weight average molecular weight of 8500.

[0184]

[0185] Preparation Example 2

[0186] Alkali-soluble resin B2, which is a polyimide precursor resin, the difference in the preparation method from Preparation Example 1 is only that diamine compound 1 is replaced with an equimolar amount of diamine compound 2, and other raw materials and process parameters are the same as those in Preparation Example 1, to obtain the said alkali-soluble resin B2, with a weight average molecular weight of 8300.

[0187]

[0188] Preparation Example 3

[0189] Alkali-soluble resin B3, which is a polyimide precursor resin, is prepared as follows: Under nitrogen protection, 0.692 g of diamine compound 3 and 5.44 g of diamine compound 2 are dissolved in 20 mL of NMP, the temperature is lowered to 0 °C, and a mixture of 3.87 g of 3,3,4,4-diphenylether tetracarboxylic dianhydride and 12 g of NMP is quickly added to the reaction system, and the reaction is carried out at 0 °C for 5 h. The temperature is raised to 60 °C, 2.68 g of N,N-dimethylformamide dimethyl acetal is slowly added dropwise to the reaction system, and the reaction is carried out at 60 °C for 2 h. The temperature is lowered to room temperature, the reaction solution is poured into 300 mL of deionized water, the precipitate is collected by filtration, and the precipitate is vacuum dried at 50 °C for 24 h to obtain the said alkali-soluble resin B3, with a weight average molecular weight of 8500.

[0190]

[0191] Preparation Example 4

[0192] Alkali-soluble resin B4, specifically a polyimide precursor resin, is prepared as follows: Under nitrogen protection, 1.10 g of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 1.00 g of 4,4-diaminodiphenyl ether are dissolved in 15 mL of NMP. The temperature is lowered to 0 °C, and a mixture of 2.92 g of 3,3,4,4-diphenylethertetracarboxylic dianhydride and 8 g of NMP is quickly added to the reaction system. The reaction is carried out at 0 °C for 5 h. The temperature is raised to 60 °C, and 2.68 g of N,N-dimethylformamide dimethyl acetal is slowly added dropwise to the reaction system. The reaction is carried out at 60 °C for 2 h. The temperature is lowered to room temperature, and the reaction solution is poured into 300 mL of deionized water. The precipitate is collected by filtration, and the precipitate is dried in vacuo at 50 °C for 24 h to obtain the alkali-soluble resin B4 with a weight-average molecular weight of 8400.

[0193] Preparation Example 5

[0194] Alkali-soluble resin B5, specifically a polyamic acid-polyimide copolymer resin, is prepared as follows: Under nitrogen protection, 1.10 g of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 1.00 g of 4,4-diaminodiphenyl ether are dissolved in 15 mL of NMP. The temperature is lowered to 0 °C, and a mixture of 2.92 g of 3,3,4,4-diphenylethertetracarboxylic dianhydride and 8 g of NMP is quickly added to the reaction system. The reaction is carried out at 0 °C for 5 h. While maintaining 0 °C, 0.7 g of N,N'-diisopropylcarbodiimide and 0.01 g of 4-dimethylaminopyridine are added to the reaction system. After reacting for 10 h, the reaction solution is poured into 300 mL of deionized water. The precipitate is collected by filtration, and the precipitate is dried in vacuo at 50 °C for 24 h to obtain the alkali-soluble resin B5 with a weight-average molecular weight of 8300.

[0195] Example 1

[0196] A photosensitive resin composition comprises the following components in parts by mass: 10 g of alkali-soluble resin B1 (Preparation Example 1), 2 g of a photosensitive compound, 1.5 g of crosslinking agent A1 (Synthesis Example 1), 0.1 g of a thermal acid generator 4-nitrobenzyl 3-(trifluoromethyl)benzenesulfonate, 0.1 g of a fluorine-containing surfactant, 0.1 g of a silane coupling agent (Shin-Etsu Chemical KBM403), and 85 g of γ-butyrolactone;

[0197] Among them, the photosensitive compound is Q is -* represents the connection site of the group.

[0198] The preparation method of the photosensitive resin composition is as follows: All components are mixed according to the formula amount and dissolved uniformly to obtain the photosensitive resin composition.

[0199] Examples 2-5

[0200] A photosensitive resin composition, which is different from Example 1 only in that the alkali-soluble resin is replaced with an equal mass of alkali-soluble resins B2 - B5, and other components and dosages (items not listed in Table 1) are the same as those in Example 1.

[0201] Examples 6 - 10

[0202] A photosensitive resin composition, which is different from Example 1 only in that the crosslinking agent is replaced with an equal mass of crosslinking agents A2 - A5, and other components and dosages (items not listed in Table 1) are the same as those in Example 1.

[0203] Comparative Examples 1 - 2

[0204] A photosensitive resin composition, which is different from Example 1 only in that the crosslinking agent is replaced with an equal mass of crosslinking agents B1 - B2, and other components and dosages (items not listed in Table 1) are the same as those in Example 1.

[0205] Table 1

[0206]

[0207]

[0208] In Table 1, "--" represents that the component is not added; the crosslinking agents A1, A2, A3, A4, A5, and A6 with the structure shown in Formula I are respectively from Synthesis Examples 1 - 6; the other crosslinking agent D1 is D2 is

[0209] Performance tests were carried out on the aforementioned photosensitive resin compositions, and the specific contents are as follows:

[0210] (1) Water absorption test

[0211] The photosensitive resin composition to be tested was coated on a 4-inch square glass substrate by spin coating, pre-baked at 120 °C for 180 s to remove most of the solvent, and a film of about 10 μm was formed. It was exposed without a mask under an ultraviolet exposure machine to promote the decomposition of the photosensitive compound, and then the coated glass substrate was placed in a clean oven at 250 °C under nitrogen protection (oxygen concentration < 20 ppm) and cured for 60 min. The coated glass substrate was soaked in a 5% HF aqueous solution and the film was peeled off from the glass substrate. After the film was washed with deionized water, it was placed in a clean oven at 200 °C under nitrogen protection (oxygen concentration < 20 ppm) and cured for 30 min. After the cured film was treated in a constant temperature and humidity chamber at 80 °C and 80% relative humidity for 24 h, about 10 mg of the sample was accurately weighed. Using a thermogravimetric analyzer (TGA), it was kept at 50 °C for 40 min under a nitrogen flow, and the reduction amount relative to the initial weight divided by the initial weight was measured as the water absorption rate. If the water absorption rate was less than 0.5%, it was judged as excellent; between 0.5% and 1%, it was judged as good; between 1% and 2%, it was judged as qualified.

[0212] (2) Chemical resistance test

[0213] The photosensitive resin composition to be tested was coated on a 4-inch square glass substrate by spin coating (250 rpm), pre-baked at 120 °C for 180 s to remove most of the solvent, and the film thickness t was measured. Then the coated glass substrate was placed in a clean oven at 250 °C under nitrogen protection (oxygen concentration < 20 ppm) and cured for 60 min, and the film thickness (t1) was measured by an ellipsometer. The coated glass substrate was soaked in a stripping solution (GES-T01, Glinda Electronic Materials) at 40 °C for 130 s, or soaked in NMP at room temperature for 15 min. After taking it out, it was quickly rinsed with deionized water, and then dried in a clean oven at 100 °C under nitrogen protection (oxygen concentration < 20 ppm) for 20 min. The film thickness t2 was measured by an ellipsometer, and the change in film thickness before and after etching was calculated as Δt = ∣(t2 - t1) / t1∣ × 100%. If Δt was less than 1%, it was judged as excellent; between 1% and 2%, it was judged as good; between 2% and 5%, it was judged as qualified.

[0214] The test results are shown in Table 2:

[0215] Table 2

[0216] Water absorption rate (%) Δt (%, stripping liquid) Δt (%, NMP) Example 1 Excellent Excellent Excellent Example 2 Excellent Excellent Excellent Example 3 Excellent Excellent Excellent Example 4 Good Good Excellent Example 5 Excellent Excellent Excellent Example 6 Good Good Good Example 7 Excellent Excellent Excellent Example 8 Excellent Excellent Excellent Example 9 Excellent Excellent Excellent Example 10 Excellent Excellent Excellent Comparative Example 1 Qualified Qualified Qualified Comparative Example 2 Qualified Qualified Qualified

[0217] According to the performance test results in Table 2, in the photosensitive resin composition provided by the present invention, by introducing a crosslinking agent with a specific structure, the crosslinking density in the early stage of curing can be increased. After etching in the stripping solution for 130 s, the cured film formed all reaches Δt < 2%, and the minimum value of Δt can reach < 1%. After soaking in NMP for 15 min, Δt < 1%. It has high strength, adhesion, chemical resistance and other properties, and has the technical advantage of significantly improving the reliability of the device. At the same time, the moisture absorption rate of the cured film is effectively reduced, the water absorption rate < 1%, and can reach below 0.5%, thereby reducing the gas overflow of the cured film in the device manufacturing process, improving the yield of the device and the reliability in the subsequent use process. The photosensitive resin compositions of Comparative Examples 1-2 do not contain the crosslinking agent defined in the present invention, resulting in high water absorption rate and insufficient chemical resistance of the cured film.

[0218] The applicant declares that the present invention illustrates the photosensitive resin composition, photoresist cured film and their applications of the present invention through the above embodiments, but the present invention is not limited to the above embodiments, that is, it does not mean that the present invention must rely on the above embodiments to be implemented. Those skilled in the art should understand that any improvement to the present invention, the equivalent substitution of each raw material of the product of the present invention, the addition of auxiliary components, the selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A photosensitive resin composition, characterized in that, The photosensitive resin composition comprises a combination of an alkali-soluble resin, a photosensitive compound, and a crosslinking agent; The crosslinking agent has a structure shown in Formula I: Wherein, X represents an aromatic group; R1 represents a C2-C20 ester bond-containing group; R2 represents *-CH2-OR A , R A is selected from any one of H, C1-C8 straight-chain or branched-chain alkyl; -* represents the connection site of the group; m, n, and p are each independently an integer of ≥1; -OH is directly connected to the aromatic ring through a single bond.

2. The photosensitive resin composition according to claim 1, wherein The X is selected from any one of the following groups: ； Wherein, X1, X2, X4, X6, and X7 are each independently selected from any one of a single bond, -O-, -S-, -CO-, an unsubstituted or halogen-substituted C1-C10 straight-chain or branched-chain alkylene; X3 and X5 are each independently selected from any one of an unsubstituted or halogen-substituted C1-C10 straight-chain or branched-chain sub-alkylene; n1, n2, n3, and n4 are each independently selected from an integer of 0-2; R1, R2, and -OH are substituted at any substitutable position of the benzene ring in the above structure.

3. The photosensitive resin composition according to claim 2, wherein Each of X1, X2, X4, X6, and X7 is independently selected from any one of a single bond, -O-, and an unsubstituted or halogen-substituted C1-C6 straight-chain or branched-chain alkylene group, preferably a single bond, -O-, -CH2-, -* represents the connection site of the group; Preferably, each of X3 and X5 is independently selected from any one of unsubstituted or halogen-substituted C1-C6 linear or branched alkylene groups, more preferably Preferably, the n1, n2, n3, and n4 are each independently 0 or 1.

4. The photosensitive resin composition according to claim 2, wherein The X is selected from any one of the following groups: R1, R2, and -OH are substituted at any substitutable position of the benzene ring in the above structure.

5. The photosensitive resin composition according to any one of claims 1 to 4, characterized in that, 0.1 ≤ m / (n + m + p) ≤ 0.3; Preferably, 0.4 ≤ n / (n + m + p) < 0.

7.

6. The photosensitive resin composition according to any one of claims 1-4, characterized in that, The R1 is selected from any one of them; -* represents the connection site of the group to the aromatic ring; R B selected from any one of C1-C10 linear or branched alkyl groups and C6-C20 aryl groups; L is selected from any one of a C1-C10 straight-chain or branched-chain alkylene; Preferably, the R1 is selected from Preferably, the R B is selected from any one of C1-C10 linear or branched alkyl groups, and more preferably any one of C1-C3 linear or branched alkyl groups.

7. The photosensitive resin composition according to claim 1, wherein The crosslinking agent is selected from any one or a combination of at least two of the following compounds:

8. The photosensitive resin composition according to claim 1, wherein The alkali-soluble resin includes any one or a combination of at least two of polyimide, polyimide precursor resin, polyamic acid-polyimide copolymer, polyamic acid ester-polyimide copolymer, polyisoimide-polyamic acid copolymer, and polyisoimide; Preferably, the alkali-soluble resin contains at least one of the structural units shown in Formula II, Formula III, or Formula IV: Among them, R3, R6, R8, R 11 each independently represents a tetravalent organic group having 4 to 60 carbon atoms; R4, R7, R9, R 12 each independently represents a divalent organic group having 3 to 60 carbon atoms; R5, R 10 Each independently selected from any one of C1-C10 linear or branched alkyl groups.

9. The photosensitive resin composition according to claim 8, wherein The R3, R6, R8, R 11 are each independently selected from any one of a substituted or unsubstituted C6-C30 tetravalent aromatic group and a substituted or unsubstituted C4-C20 tetravalent alicyclic group; R3, R6, R8, R 11 each of the substituents described in 11 is independently selected from at least one of halogen, hydroxy, unsubstituted or halogen-substituted C1-C20 straight-chain or branched alkyl, and unsubstituted or halogen-substituted C1-C20 alkoxy; Preferably, the R3, R6, R8, R 11 are each independently selected from any one of the following groups: - * represents the connection site of the group; R 21 、R 22 、R 23 、R 24 、R 25 、R 26 each independently selected from any one of hydrogen, halogen, hydroxy, unsubstituted or halogen-substituted C1-C20 straight or branched chain alkyl, and unsubstituted or halogen-substituted C1-C20 alkoxy; L 21 Selected from a single bond, -O-, -S-, a carbonyl group, a sulfone group, a sulfoxide group, an unsubstituted or R'-substituted C1-C10 straight-chain or branched alkylene group, an unsubstituted or R'-substituted C6-C20 arylene group, *-L 22 -Ar 21 -L 23 -*; L 22 and L 23 each independently selected from any one of -O-, -S-, carbonyl, sulfone, sulfoxide, unsubstituted or R'-substituted C1-C10 straight-chain or branched alkylene; Ar 21 Any one selected from unsubstituted or R'-substituted C6-C20 arylene groups; R' is selected from at least one of a halogen, a hydroxyl group, an unsubstituted or halogen-substituted C1-C20 straight-chain or branched-chain alkyl, and an unsubstituted or halogen-substituted C1-C20 alkoxy group; Preferably, the R3, R6, R8, R 11 are each independently selected from any one of the following groups: Wherein, -* represents the connection site of the group.

10. The photosensitive resin composition according to claim 8, characterized in that, The R4, R7, R9, R 12 are each independently selected from any one of the groups represented by Formula V, a substituted or unsubstituted C6-C30 divalent aromatic group, and a substituted or unsubstituted C4-C20 divalent alicyclic group; R4, R7, R9, R 12 each of the substituents described in 12 is independently selected from at least one of halogen, hydroxy, unsubstituted or halogen-substituted C1-C20 straight or branched chain alkyl, and unsubstituted or halogen-substituted C1-C20 alkoxy; -* represents the connection site of the group; A is selected from any one of a single bond, -O-, -S-, a carbonyl group, a sulfone group, a substituted or unsubstituted C1-C10 divalent aliphatic hydrocarbon group, a substituted or unsubstituted C3-C20 divalent alicyclic group, and a substituted or unsubstituted C6-C30 divalent aromatic group; The substituents in A are each independently selected from at least one of a halogen, an unsubstituted or halogen-substituted C1-C10 straight-chain or branched-chain alkyl, an unsubstituted or halogen-substituted C6-C30 aryl, and an unsubstituted or halogen-substituted C6-C30 phenol group; R 31 and R 32 each independently selected from any one of halogen, nitro, cyano, carboxyl, unsubstituted or halogen-substituted C1-C10 straight-chain or branched alkyl, unsubstituted or halogen-substituted C1-C10 alkoxy, unsubstituted or halogen-substituted C6-C30 aryl, amide group, benzyloxy group or benzyl alcohol group; R 33 and R 34 each independently selected from any one of C1-C10 linear or branched alkylene groups, C1-C10 alkoxy groups, and C1-C10 divalent Si-containing groups; R 35 and R 36 are each independently selected from *-CH2-OR 51 wherein R 51 is selected from any one of H, C1-C8 linear or branched alkyl; R 37 、R 38 each independently selected from any one of halogen, hydroxyl, nitro, cyano, carboxyl, unsubstituted or halogen-substituted C1-C10 straight-chain or branched alkyl, unsubstituted or halogen-substituted C1-C10 alkoxy, unsubstituted or halogen-substituted C6-C30 aryl, C1-C10 ester group or amide group; a1, a2, b1, b2, c1, c2, d1, and d2 are each independently selected from an integer of 0-4; t1 and t2 are each independently 0 or 1; Preferably, the group shown in Formula V has any one of the following structures: Wherein, -* represents the connection site of the group.

11. The photosensitive resin composition according to claim 10, wherein The R4, R7, R9, R 12 are each independently selected from the groups represented by Formula V, any one of them; -* represents the connection site of the group; R 41 、R 42 each independently selected from any one of halogen, hydroxy, unsubstituted or halogen-substituted C1-C20 straight-chain or branched alkyl, and unsubstituted or halogen-substituted C1-C20 alkoxy; L 41 selected from a single bond, -O-, -S-, a carbonyl group, a sulfone group, a sulfoxide group, an unsubstituted or halogen-substituted C1-C10 straight-chain or branched alkylene group, an unsubstituted or halogen-substituted C6-C20 arylene group, *-L 42 -Ar 41 -L 43 -*, any one of them; L 42 and L 43 each independently selected from any one of -O-, -S-, carbonyl, sulfone, sulfoxide, and unsubstituted or halogen-substituted C1-C10 straight-chain or branched alkylenes; Ar 41 Any one selected from unsubstituted or R”-substituted C6-C20 arylene groups; R” is selected from any one of a halogen, a hydroxyl group, an unsubstituted or halogen-substituted C1-C10 straight-chain or branched-chain alkyl, and an unsubstituted or halogen-substituted C1-C10 alkoxy group; u1 and u2 are each independently selected from an integer of 0-4; Preferably, the R4, R7, R9, R 12 each independently selected from the group represented by formula V, Any one of them.

12. The photosensitive resin composition according to claim 1, wherein The weight-average molecular weight of the alkali-soluble resin is 2,000-100,000, preferably 5,000-50,000; Preferably, the photosensitive compound is a compound containing a diazonaphthoquinone group; Preferably, the photosensitive resin composition further comprises an auxiliary agent and / or a solvent; Preferably, the auxiliary agent comprises any one or a combination of at least two of a silane coupling agent, a surfactant, and a curing accelerator.

13. The photosensitive resin composition according to claim 1, wherein The photosensitive resin composition comprises the following components by mass percentage:

14. A photoresist cured film, characterized in that, The photoresist cured film is prepared from the photosensitive resin composition according to any one of claims 1-13.

15. Use of the photosensitive resin composition according to any one of claims 1-13 and the photoresist cured film according to claim 14 in a semiconductor device or a flat panel display device.

16. A semiconductor device, characterized in that, The semiconductor device comprises at least one of the photosensitive resin composition according to any one of claims 1-13 and the photoresist cured film according to claim 14; Preferably, the semiconductor device comprises a stress buffer layer and / or a passivation layer, and the stress buffer layer and / or the passivation layer comprise at least one of the photosensitive resin composition according to any one of claims 1-13 and the photoresist cured film according to claim 14.

17. A flat panel display device, characterized in that, The flat panel display device comprises at least one of the photosensitive resin composition according to any one of claims 1-13 and the photoresist cured film according to claim 14; Preferably, the flat panel display device comprises a pixel defining layer and / or a planarization layer, and the pixel defining layer and / or the planarization layer comprise at least one of the photosensitive resin composition according to any one of claims 1-13 and the photoresist cured film according to claim 14.

Images