Photosensitive composition containing PFAS-free polycyclic olefin polymer and semiconductor device

Abstract

The present invention relates to a photosensitive composition containing copolymers and terpolymers of PFAS-free polynorbornene, i.e., PNB, in combination with specific additives, which can be used to form microelectronic and / or optoelectronic devices and components thereof, and more particularly, to a composition which can be used to form microelectronic and / or optoelectronic devices and components thereof. The present invention relates to a composition containing PNB that does not contain PFAS, a specific polyfunctional cross-linking agent, and two or more phenolic compounds that are resistant to thermal oxidation chain degradation and exhibit improved mechanical properties.

Description

[0001] Cross-references to related applications This application claims the benefit of U.S. Provisional Application No. 63 / 564,344, filed March 12, 2024, and Japanese Patent Application No. JP2023-170440, filed September 29, 2023, the entire contents of which are incorporated herein by reference. Technical Field

[0002] The embodiments of the present invention generally relate to a PFAS-free composition that can be used to form microelectronic and / or optoelectronic devices and components thereof, the composition containing a copolymer or a terpolymer derived from various functionalized norbornene monomers and some additives, and more specifically, to a composition containing a copolymer or terpolymer containing a functionalized norbornene repeating unit, wherein the first repeating unit comprises a polyether functionalized end group, the second repeating unit comprises a phenolic group, and the third repeating unit comprises a carboxylic acid group. Such compositions exhibit improved solubility and improved thermal, mechanical and optoelectronic properties. Background Technology

[0003] Organic polymer materials are finding increasingly widespread applications in the microelectronics and optoelectronics industries. For example, these materials are used as interlayer dielectric layers, redistribution layers, stress-buffered layers, leveling or planarization layers, alpha particle blocking layers, and passivation layers in microelectronic and optoelectronic devices. Because these organic polymer materials are photosensitive and capable of self-imaging, they offer the added advantage of reducing the number of processing steps required for the application of such layers and the structures they form. Furthermore, these organic polymer materials enable direct bonding of devices to device components, resulting in a wide variety of structures. Such devices include microelectromechanical systems (MEMS) and micro-opto-electromechanical systems (MOEMS).

[0004] While polyimide (PI), polybenzoxazole (PBO), and benzocyclobutene (BCB) compositions are generally preferred for these applications due to their good thermal stability and mechanical strength, each of these materials undergoes precursor reactions during curing, altering the polymer backbone (PI and PBO) or forming the backbone (BCB). Therefore, specific processing conditions are typically required during curing to remove byproducts and / or eliminate oxygen or water vapor that may hinder curing. Furthermore, curing these materials often requires processing temperatures exceeding 250°C (up to 400°C for some materials), resulting in excessive or undesirable processing costs. Consequently, these materials may be unsuitable for some applications, such as redistribution and interlayer dielectric layers, and direct bonding of transparent covers over image sensor arrays.

[0005] Therefore, it is advantageous to provide a material for forming the structure that exhibits thermal stability and mechanical strength comparable to known PI, PBO, and BCB compositions, wherein such a material has a fully formed polymer backbone capable of curing at temperatures below 200°C. Furthermore, such an advantageous material should be tunable in properties to provide suitable levels or values ​​of stress, modulus, dielectric constant, elongation at break, and water vapor permeability as desired in the application. Moreover, the material's self-imaging capability would be even more advantageous. Additionally, several currently available compositions may be unsuitable for some applications because they lack the required solubility (DR) characteristics, including the resolution and photosensitivity described in further detail below.

[0006] Polynorbornene, as described in U.S. Patent No. 11,537,045 and some of the techniques cited therein, is a photosensitive composition that has effectively overcome some of the aforementioned problems. However, most polynorbornene used therein contains at least one norbornene repeating unit comprising a perfluoroalkyl group. In recent years, most perfluoroalkyl or polyfluoroalkyl substances (PFAS) have been found to be environmentally persistent (i.e., they are not easily degraded in the environment) and may be associated with harmful health effects on humans and animals. Therefore, the development of PFAS-free compositions for electronic applications is receiving increasing attention, especially as a flexible material that provides the adhesive strength and mechanical strength (especially chip shear strength) urgently needed in the manufacture of various micro-optoelectronic devices such as display devices.

[0007] Therefore, there is still a need to develop a PFAS-free composition capable of optical imaging, characterized by desired thermal properties, solubility, adhesion, and most importantly, integration of all relevant process steps associated with the microelectronics industry. Attached Figure Description

[0008] Hereinafter, embodiments of the present invention will be described with reference to the illustrations and / or images. When illustrations are provided, they are simplified portions of various embodiments of the present invention and are for illustrative purposes only.

[0009] Figure 1 This is a cross-sectional view showing one embodiment of the semiconductor device of the present invention. Detailed Implementation

[0010] Embodiments of the present invention relate to a self-imaging composition comprising a PFAS-free polymer derived from norbornene monomer as described in this specification, and films, layers, structures, devices, or components that can be formed using such compositions. Some embodiments include self-imaging compositions that can be developed using an alkaline developing aqueous solution after image exposure of a film formed from the composition to provide a positive-tone image.

[0011] Furthermore, the embodiments described in this specification generally provide a film with a required thickness in the range of about 2 to 5 micrometers (µm) or more, in which images exhibit a separated line / groove resolution with an aspect ratio greater than 1:2. Films, layers, and structures formed from polymers according to embodiments of the present invention are particularly suitable for use as interlayer dielectric layers, redistribution layers, stress buffer layers, leveling or planarization layers, alpha particle blocking layers, and for bonding chip stacks and fixing transparent covers onto image sensing arrays in microelectronic and optoelectronic devices and components thereof.

[0012] The terms used in this specification have the following meanings: Unless otherwise stated, all figures, values, and / or expressions relating to the amounts of components, reaction conditions, polymer compositions, and formulations used in this specification are in any instance modified by the term "about," because these figures are, by their very nature, approximations reflecting the various measurement uncertainties encountered in obtaining these values. Furthermore, unless otherwise stated, when numerical ranges are disclosed in this specification, these ranges are continuous and include every value from the minimum to the maximum of the range. Furthermore, unless otherwise stated, these ranges refer to integers, including every integer from the minimum to the maximum. Moreover, when multiple ranges are provided to describe a feature or property, these ranges may be combined to describe that feature or property.

[0013] Unless otherwise specified, the articles “a / an” and “the” used in this specification include multiple objects.

[0014] It should be understood that the term "microelectronic device" as used in this specification includes "micro-optoelectronic device" and "optoelectronic device". Therefore, references to microelectronic devices or microelectronic device assemblies include optoelectronic devices and micro-optoelectronic devices and their assemblies. Similarly, microelectromechanical systems (MEMS) include micro-opto-electromechanical systems (MOEMS).

[0015] It should be understood that the term "redistribution layer (RDL)" refers to an electrical signal routing insulating material with the required reliable properties. The term RDL can also be used interchangeably to describe a buffer coating, such as a stress-relieving layer or buffer layer between solder balls and a fragile low-k structure.

[0016] The term "polymer" as used in this specification should be understood as a molecule comprising a backbone of one or more repeating units of different types (the smallest constituent units of a polymer), and includes residues derived from initiators, catalysts, and other elements involved in the formation of the polymer, in addition to the polymer itself. These residues are not typically considered covalently bonded to the polymer backbone, but in some catalyst-initiated polymerization reactions, they may be covalently bonded to the front or end of the polymer chain. Furthermore, although these residues and other elements are usually removed during post-polymerization purification, they are often mixed or blended with the polymer, and therefore, a small amount usually remains in the polymer during transfer between containers or between solvents or dispersion media.

[0017] As used in this specification, the term "polymer composition" refers to a composition comprising at least one synthetic polymer and materials added after polymerization to provide or modify specific properties. Exemplary materials that can be added include, but are not limited to, solvents, photoactive compounds (PACs), solubility inhibitors, solubility enhancers, solubility accelerators, crosslinking components, reactive diluents, antioxidants, adhesion promoters, and plasticizers.

[0018] The term "modulus" as used in this specification should be understood as the ratio of stress to strain, and unless otherwise stated, refers to the Young's modulus or tensile modulus measured in the linear elastic region of the stress-strain curve. Modulus values ​​are typically measured according to ASTM method DI708-95. A membrane with a low modulus should be understood to also have low internal stress.

[0019] The term "photolithographically definable" refers to a material or material composition (e.g., a polymer or polymer composition according to embodiments of the invention) that inherently possesses the property of forming a patterned layer or structure. In other words, a "photolithographically definable layer" can form the patterned layer or structure without the need to form another material layer (e.g., a photoresist layer) thereon. It can be further understood that polymer compositions possessing such properties are commonly used in patterning schemes to form patterned films / layers or structures. Notably, this scheme includes "image exposure" of the photolithographically definable material or the layer formed therefrom. Such image exposure refers to exposing selected portions of the layer to photochemical radiation, while unselected portions are protected from such photochemical radiation exposure.

[0020] The term “self-imaging composition” as used in this specification should be understood as a photolithographically defined material, so that after direct image exposure of a film formed therefrom, the image in the film can be developed using a suitable developer to provide a patterned layer and / or structure.

[0021] As used in this specification, "hydrocarbyl" refers to a free radical or group containing only carbon and hydrogen atoms, with non-limiting examples including alkyl, cycloalkyl, aryl, aralkyl, alkylaryl, and alkenyl. The term "halohydrocarbyl" refers to a hydrocarbon group in which at least one hydrogen atom is replaced by a halogen atom. The term "perhalocarbyl" refers to a hydrocarbon group in which all hydrogen atoms are replaced by a halogen. The term "heterohydrocarbyl" refers to any of the aforementioned hydrocarbon groups, halohydrocarbyl groups, and perhalohydrocarbyl groups, wherein at least one carbon atom of the carbon chain is replaced by an N, O, S, Si, or P atom.

[0022] The symbol “ “ used in this instruction manual "Based on the structure of the shown base, indicate the position where it bonds to another repeating unit, another atom, molecule, base, or part."

[0023] As used in this specification, the term "alkyl" refers to a saturated straight-chain or branched hydrocarbon substituent having a specified number of carbon atoms. Specific examples of alkyl include methyl, ethyl, n-propyl, isopropyl, tert-butyl, etc. Derivative terms such as "alkoxy," "thioalkyl," "alkoxyalkyl," "hydroxyalkyl," "alkylcarbonyl," "alkoxycarbonylalkyl," "alkoxycarbonyl," "diphenylalkyl," "phenylalkyl," "phenylcarboxyalkyl," and "phenoxyalkyl" shall also be interpreted accordingly.

[0024] The term "cycloalkyl" as used in this specification includes all known cyclic aliphatic free radicals. Representative examples of "cycloalkyl" include, without limitation, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, etc. Derivative terms such as "cycloalkoxy," "cycloalkylalkyl," "cycloalkylaryl," and "cycloalkylcarbonyl" should also be interpreted accordingly.

[0025] As used in this specification, the term "alkenyl" refers to a non-cyclic, straight-chain or branched hydrocarbon chain having a specified number of carbon atoms and at least one carbon-carbon double bond, including vinyl and straight-chain or branched propenyl, butenyl, pentenyl, and hexenyl. Similarly, the term "alkynyl" refers to a non-cyclic, straight-chain or branched hydrocarbon chain having a specified number of carbon atoms and at least one carbon-carbon triple bond, including ethynyl and straight-chain or branched butynyl, pentynyl, and hexynyl.

[0026] The term "acyl" as used in this specification shall have the same meaning as "alkanoyl" and can also be represented structurally as "R-CO-", where R is an "alkyl" having the specified number of carbon atoms as described in this specification. Furthermore, "alkylcarbonyl" shall have the same meaning as "acyl" as used in this specification. Specifically, "(C1-C4)acyl" refers to acyl, acetyl / ethanoyl, propionyl, n-butyryl, etc. Derivative terms such as "acyloxy" and "acyloxyalkyl" shall also be interpreted accordingly.

[0027] The term "perfluoroalkyl" as used in this specification means that all hydrogen atoms in the alkyl group are replaced by fluorine atoms. Exemplary examples include trifluoromethyl and pentafluoroethyl, straight-chain or branched heptafluoropropyl, nonafluorobutyl, undecafluoropentyl, and tridecafluorohexyl. The derived term "perfluoroalkoxy" should also be interpreted accordingly.

[0028] As used in this specification, the term "aryl" refers to a substituted or unsubstituted phenyl or naphthyl group. Specific examples of substituted phenyl or substituted naphthyl groups include o-tolyl, p-tolyl, m-tolyl, 1,2-xylyl, 1,3-xylyl, 1,4-xylyl, 1-methylnaphthyl, 2-methylnaphthyl, etc. "Substituted phenyl" or "substituted naphthyl" also includes any substituents further defined in this specification or known in the art. The derived term "arylsulfonyl" should also be interpreted accordingly.

[0029] The terms "arylalkyl" or "arylalkyl" are used interchangeably in this specification; specifically, "(C6-C)" refers to the arylalkyl group. 10 aryl (C1-C4) alkyl or (C7-C4) alkyl 14 "Aryl" indicates that the (C6-C) group described in this specification is an aryl group. 10 The aryl group is further bonded to the (C1-C4) alkyl group described in this specification. Representative examples include benzyl, phenylethyl, 2-phenylpropyl, 1-naphthylmethyl, 2-naphthylmethyl, etc.

[0030] "Halogen" or "halogenated" refers to chlorine, fluorine, bromine, and iodine.

[0031] In a broad sense, the term "substituted" can be considered to include all permissible substituents of an organic compound. In some specific embodiments disclosed in this specification, the term "substituted" means substituted by one or more substituents independently selected from the group consisting of (C1-C6)alkyl, (C2-C6)alkenyl, (C1-C6)perfluoroalkyl, phenyl, hydroxyl, -CO2H, ester, amide, (C1-C6)alkoxy, (C1-C6)thioalkyl, (C1-C6)perfluoroalkoxy, -NH2, Cl, Br, I, F, -NH-lower alkyl, and -N (lower alkyl)2. However, any other suitable substituents known to those skilled in the art can also be applied to these embodiments.

[0032] In this specification, the terms "dielectric" and "insulating" should be understood to be used interchangeably. Therefore, references to insulating materials or insulating layers include dielectric materials or dielectric layers, and vice versa.

[0033] The terms “polycyclic olefin,” “poly(cyclic) olefin,” and “polynorbornene type” used herein are used interchangeably to refer to polymers formed from addition polymerizable monomers, repeating units in the resulting polymers, or compositions comprising such polymers, wherein the repeating units of such resulting polymers include at least one norbornene type moiety. The simplest norbornene type polymerizable monomer included in embodiments of the invention is norbornene itself, as shown below in the bicyclic [2.2.1]hept-2-ene: It is understood that when some of the polymers shown in this specification are combined with various additives in the compositions of the present invention, the performance of the compositions in forming thick films or thin films that can be used in a variety of applications including but not limited to mechanical, electronic or electromechanical devices, including chip stacking applications, as redistribution layers (RDLs) and dam structures for complementary metal-oxide-semiconductor (CMOS) image sensors and various other devices containing MEMS and MOEMS is significantly improved.

[0034] Therefore, according to an embodiment of the present invention, a photosensitizing composition is provided, comprising: a) A polymer having a first repeating unit of formula (IA) derived from a monomer of formula (I): (IA) (I); and The second repeating unit of formula (IIA) derived from the monomer of formula (II): (IIA) (II) in: Indicates the location where it is bonded to another repeating unit; a is an integer from 0 to 3; b is an integer from 1 to 4; c is an integer from 1 to 4; R1 is selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, isopropyl, and n-butyl, wherein one or more methylene groups, i.e., CH2 groups, may be selectively and independently substituted by groups selected from the group consisting of (C1-C4) alkyl, phenyl, and phenyl (C1-C4) alkyl. R 18 For -(CH2) v -CO2R 19 , where v is an integer from 0 to 4, and R 19 It is hydrogen or C1-C4 alkyl; b) Photoactive compounds, including the diazonoquinone moiety of formula (A): (A); c) Multifunctional crosslinking agents, selected from the group consisting of the following: Compounds of formula (IV): (IV); and Compounds of formula (V): (V) in: n is an integer from 3 to 8; A is the correct answer; C is the correct answer; CH-(CR2) d The group consisting of -CH and substituted or unsubstituted aryl groups, wherein d is an integer from 0 to 4 and R is selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, isopropyl and n-butyl; Option B is selected from the group consisting of substituted or unsubstituted (C1-C6) alkyl groups, (C2-C6) alkylene groups, and substituted or unsubstituted aryl groups; The substituents are selected from halogens, methyl, ethyl, straight-chain or branched (C3-C6) alkyl, (C3-C8) cycloalkyl, (C6-C6) alkyl, and cycloalkyl. 10 )Aryl, (C7-C 12 Aryl alkyl, methoxy, ethoxy, straight-chain or branched (C3-C6) alkoxy, (C3-C8) cycloalkoxy, (C6-C6) alkyl alkyl, methoxy alkyl, ethoxy alkyl ... 10 ) aryloxy groups and (C7-C 12 The group consisting of arylalkoxy groups; d) Phenolic compounds, selected from the group consisting of the following: a-1; a-2; a-3; a-4; a-5; and a-6.

[0035] The compositions of the present invention may further comprise a polymer containing a third repeating unit of formula (IIIA) of a monomer derived from formula (III): (IIIA) (III) in, d is an integer from 1 to 4; Y represents a bond or CH2; Each R 20 The group consisting of hydroxyl, methoxy, and acetoxy groups is selected independently.

[0036] Furthermore, the compositions of the present invention may further comprise one or more phenolic compounds. Generally, one or more compounds of formula (VIA) or compounds of formula (VIB), or combinations thereof, are known to be able to be used to form the compositions of the present invention, which provide additional benefits.

[0037] (VIA); (VIB); Where d and e are integers from 1 to 4; f and g are integers from 0 to 4; X is selected from the group consisting of free bonds, -O-, -OCH2O-, -OCH2CH2O-, -S-, -SS-, -SO2-, and the group of -CR2R3-; wherein R2 and R3 are the same or different and are each independently selected from hydrogen, methyl, ethyl, straight-chain or branched C3-C6 alkyl, C3-C8 cycloalkyl, C6-C 10 Aryl and C7-C 12 Aryl alkyl; or R2 and R3 together with the carbon atoms they are bonded to form 5 to 8 substituted or unsubstituted carbon rings, wherein the substituents are selected from C1-C8 alkyl groups; R4 and R5 may be the same or different and are each independently selected from hydrogen, methyl, ethyl, straight-chain or branched (C3-C6) alkyl, (C3-C8) cycloalkyl, (C6-C5) alkyl, and (C6-C6) alkyl. 10 ) aryl and (C7-C 12 Aryl alkyl group.

[0038] In some embodiments, the polymer of the present invention includes repeating units of formula (IIIA), wherein R 18 Typically, it is hydroxyl or methoxy. However, some embodiments comprise polymers comprising a mixture of repeating units of formula (IIA), wherein a portion of the repeating unit of formula (IIA) has R. 18As a hydroxyl group, and having R in another part of the repeating unit of formula (IIA) 18 As an acetoxy group, it should be readily understood by those skilled in the art that such variations are all part of this invention.

[0039] Similarly, in some embodiments, the polymer of the present invention includes repeating units of formula (IIIA), wherein R 20 Typically, it is hydrogen. However, in some embodiments, the polymer comprises a mixture of repeating units of formula (IIIA), wherein a portion of the repeating units of formula (IIIA) has R. 20 As hydrogen, and having R in another part of the repeating unit of formula (IIIA) 20 As (C1-C4) alkyl groups. Therefore, those skilled in the art will readily understand that such variations are all part of this invention.

[0040] Non-limiting examples of monomers that can be used to form the first repeating unit of the polymer of the present invention include the following: 5-((2-(2-methoxyethoxy)ethoxy)methyl)bicyclo[2.2.1]hept-2-ene, also known as trioxanenonyl norbornene (NBTON); 1-(bicyclo[2.2.1]hept-5-en-2-yl)-2,5,8,11-tetraoxadodecyl, also known as tetraoxadodecylnorbornene (NBTODD); 5-(3-methoxybutoxy)methyl-2-norbornene (NB-3-MBM); 5-(3-methoxypropoxy)methyl-2-norbornene (NB-3-MPM); 5-(2-(2-ethoxyethoxy)ethyl)bicyclo[2.2.1]hept-2-ene; and 5-(2-(2-(2-propoxyethoxy)ethoxy)ethoxy)bicyclo[2.2.1]hept-2-ene; Non-limiting examples of monomers that can be used to form the second repeating unit of the polymer of the present invention include the following: Ethyl 3-(bicyclo[2.2.1]hept-2-en-2-yl)propionate (EPEsNB); 3-(bicyclo[2.2.1]hept-5-en-2-yl)acetic acid (NBMeCOOH); Norborneol alkenylpropionic acid (NBEtCOOH); and Bicyclic [2.2.1]hept-5-en-2-carboxylic acid (Acid NB); Non-limiting examples of monomers that can be used to form the third repeating unit (when present) of the polymer of the present invention include the following: 4-(bicyclo[2.2.1]hept-5-en-2-yl)-phenylacetate (PhOAcNB); 4-(bicyclo[2.2.1]hept-5-en-2-yl)phenol (PhOHNB); 4-Norbornenylmethyl-2-methoxyphenol acetate (EugOAcNB); and 4-(bicyclo[2.2.1]hept-4-en-2-ylmethyl)-2-methoxyphenol (EugOHNB).

[0041] It should be noted that the photosensitive compositions of the present invention can be prepared using polymers derived from any two or three monomers within the range of monomers listed above in formulas (I) to (II) and (III). Furthermore, copolymers or terpolymers that yield the desired benefits can be formed using any amount of monomers from formulas (I) to (III), the desired benefits of which are described in detail below. Therefore, all possible monomer ratios are part of the present invention.

[0042] In some embodiments of the present invention, the photosensitive composition of the present invention is prepared by using a copolymer or terpolymer comprising any two or three monomers described in this specification.

[0043] Typically, polymers according to embodiments of the present invention comprise one or more of the first, second, and third repeating units of different types described above. If necessary, as shown below, other repeating units included in such polymer embodiments may be selected to impart properties suitable for the intended use of such polymer embodiments and required to such polymer embodiments. Thus, such polymer embodiments can be used for a variety of specific applications.

[0044] For example, polymeric implementations typically require at least one repeating unit designed to provide imageability. Therefore, different types of repeating units represented by structural formula (IIA) include a carboxylic acid R with side groups. 18 However, any other functional group that provides an acidic side group can also be used instead. Carboxylic acid side groups are generally used to react with appropriately selected additives or other repeating units that can fix positive-tone images by post-development thermal crosslinking. Therefore, similar side groups (including but not limited to phenolic, sulfonic acid, and other functional groups) can also play a role in this embodiment of the invention. It should also be noted that those skilled in the art will readily understand that such polymer compositions containing acidic side groups can be prepared by post-polymerization using appropriate monomers. For example, polymers containing NBEtCOOH monomer repeating units can generally be prepared by first forming a polymer with EPEsNB, and then hydrolyzing the ester functional groups in the resulting polymer using any method known in the art. Therefore, a certain balance of ester monomer repeating units may always be present in the polymers used in this specification. That is, when using polymers containing repeating units such as NBEtCOOH, such polymers may still contain some monomer repeating units derived from EPEsNB, i.e., starting monomers.

[0045] It should also be noted that one or more monomers of different types from formulas (I) to (III) can be used in any molar ratio to form the polymer of the present invention. That is, one or more monomers of formula (I) can be used simultaneously with one or more monomers of formula (II) and one or more monomers of formula (III) as needed to form the polymer of the present invention. Therefore, the polymer of the present invention typically contains about 1 mol% to about 98 mol% of the repeating unit of formula (IA). The remaining repeating units are derived from combinations of one or more repeating units of formulas (IIA) and (IIIA). Therefore, in some embodiments, in copolymers comprising any combination of repeating units of monomers of formula (IA) and (IIA), the molar ratio of repeating units can be 99:1 to 1:99, more specifically 5:95, 10:90, 15:85, 20:80, 25:75, 30:70, 35:65, 40:60, 45:55, 50:50, 55:45, 60:60, 65:35, 70:30, 75:25, 80:20, 85:95, 90:10, 95:5, etc. Similarly, in other embodiments, the terpolymer comprises any combination of repeating monomer units of formulas (IA), (IIA), and (IIIA), wherein the molar ratio of the repeating units can be 40:30:30, 40:40:20, 50:20:30, 50:25:25, 50:30:20, 50:40:10, 50:45:5, 60:20:20, etc. In other embodiments, examples of monomer molar ratios (I):(II):(III) used to form the polymer are in the range of 1:1:98 to 99:1:0 to 1:98:1, wherein the molar ratios of repeating units of formula (IA):(IIA):(IIIA) are substantially of the same order of magnitude. In other implementations, such ratios include 30:40:30, 40:30:30, 40:40:20, 40:45:15, 40:50:10, 45:40:15, 45:35:20, 50:35:15, 50:40:10, or any such combination.

[0046] It is known that polymers generally containing repeating monomer units with acidic side groups (typically of formula (IIA)) advantageously provide specific beneficial effects to the photosensitive compositions of the present invention. Therefore, in some embodiments of the invention, the polymer used in the compositions of the present invention contains about 10 to 80 mol% of repeating monomer units containing acidic side groups, and in other embodiments, it contains 20 to 70 mol%. In still other embodiments, the mol% of repeating monomer units of formula (IA) in the polymer can be about 0 to 80 mol%, 10 to 80 mol%, and in still other embodiments, about 20 to 70 mol%. In still other embodiments, the mol% of repeating monomer units of formula (IIIA) in the polymer can be about 5 to 80 mol%, about 10 to 80 mol%, and in still other embodiments, about 20 to 70 mol%.

[0047] The weight-average molecular weight (M) of the polymer used in the photosensitizing composition according to the present invention w Typically, it is at least about 30,000. In other embodiments, the M of the polymer used in this invention is... w At least approximately 40,000. In yet other embodiments, the polymer's M... w At least approximately 50,000. Furthermore, in one embodiment of the invention, the weight-average molecular weight of the polymer used in this specification is 30,000–100,000, 40,000–80,000, or 50,000–75,000. Weight-average molecular weight (M) is typically defined using gel permeation chromatography (GPC) with a polystyrene correction standard. w ) and number-average molecular weight (M n However, any well-known method can also be used to define M. w and M n This also allows us to define the polydispersity index (PDI) of polymers (M). w / M n ).

[0048] In another aspect of the invention, the photosensitive composition of the invention comprises a photoactive compound that typically has a photoactive diazonoquinone moiety. Such photoactive compounds (PACs) are known to undergo photorearrangement upon exposure to photochemical (or electromagnetic) radiation at suitable wavelengths, such as 254, 365, 405, or 436 nm. Depending on the nature of the PAC used, the radiation wavelength can be varied by using a suitable light source. For example, in some embodiments of the invention, the PAC used comprises one or more diazonoquinone moieties, respectively represented by formulas (C), (D), or (E): (C) (D) (E).

[0049] Typically, the structures shown in formulas (C), (D), and / or (E) are introduced into the photosensitive composition as esterification products of their respective sulfonyl chlorides (or other reactive groups) and phenolic compounds (e.g., any one of structures b-1 to b-6 shown below), which are generally referred to as photoactive compounds or PACs, as specifically as described above. Thus, any mixture of one or more such PACs is combined with a polymer to form the positive-tone composition of embodiments of the invention. In formulas (b-1) to (b-6), Q represents any structure of formula (C), (D), or (E). Advantageously, when a portion of the film or layer of the photosensitive composition is exposed to appropriate photochemical or electromagnetic radiation, these esterification products generate a carboxylic acid, which enhances the solubility of the exposed portion in an alkaline aqueous solution compared to any unexposed portion of the film. Typically, such photosensitive materials are incorporated into the composition in an amount of 5 to 50 pphr of polymer, wherein the specific ratio of the photosensitive material to the polymer is a function of the solubility of the exposed portion relative to the unexposed portion and the amount of radiation required to achieve the desired solubility difference. Advantageous photosensitive materials that can be used in embodiments of the invention are shown in the following formulas b-1 to b-6; other useful photosensitive materials are exemplified in patents 14–20 of U.S. Patent No. 7,524,594 B2, the relevant portions of which are incorporated herein by reference.

[0050] b-1; b-2; b-3; b-4; b-5; and b-6; At least one of the Qs is a group of formula (C) or (D), and the remaining Qs are hydrogen. Commercially available examples of such photoactive compounds include TrisP-3M6C-2(4)-201 manufactured by Toyo Gosei Co., Ltd.

[0051] In the photosensitive composition of the present invention, any amount of photoactive compound that produces the desired results described herein can be used. Typically, this amount is in the range of 1 to 50 parts by weight per 100 parts by weight (pphr) of the polymer (i.e., resin) described herein. In other embodiments, this amount is in the range of 5 to 30 pphr.

[0052] Advantageously, it is known that the use of at least one suitable multifunctional crosslinking agent of formula (IV) or (V) as described in this specification in the photosensitive compositions of the present invention can bring beneficial effects to the compositions of the present invention. These benefits include, but are not limited to, improvements in mechanical and thermal properties.

[0053] Any amount of crosslinking agent of formula (IV) or (V) that brings the expected benefits can be used in the compositions of the present invention. In some embodiments, the amount of one or more compounds of formula (IV) or (V) used in the compositions of the present invention is in the range of 8 to 30 parts by weight per 100 parts by weight (pphr) of the resin (i.e., the polymer used in the composition). In other embodiments, the amount is in the range of about 10 to 25 pphr; in still other embodiments, the amount is in the range of about 12 to 20 pphr; and in yet another embodiment, the amount is in the range of 14 to 18 pphr. However, it should be noted that, especially when using one or more compounds of formula (IV) or (V), compounds of formula (IV) or (V) with a content higher than 30 pphr can also be used. Non-limiting examples of multifunctional crosslinking agents of formula (IV) or (V) that can be used in this invention include the following: 2,2'-(((2-ethyl-2-((ethylene oxide-2-ylmethoxy)methyl)propane-1,3-diyl)bis(oxy))bis(methylene))bis(ethylene oxide); also known as trimethylolpropane triglycidyl ether (manufactured by Nagase Chemtex, EX-321L); 2,2'-(((2,2-bis((ethylene oxide-2-ylmethoxy)methyl)propane-1,3-diyl)bis(oxy))bis(methylene))bis(ethylene oxide); also known as pentaerythritol tetraglycidyl ether (PETG, manufactured by Showa Denko); 2,2'-(((2-(1,3-bis(ethylene oxide-2-ylmethoxy)prop-2-yl)propane-1,3-diyl)bis(oxy))bis(methylene))bis(ethylene oxide); 1,1,2,2-Tetra(4-((ethylene oxide-2-ylmethoxy)methyl)phenyl)ethane; 1,2,4,5-Tetratetra((ethylene oxide-2-ylmethoxy)methyl)benzene; and 2,2'-(((2-(1,3-bis(ethylene oxide-2-ylmethoxy)prop-2-yl)-2-((ethylene oxide-2-ylmethoxy)methyl)propane-1,3-diyl)bis(oxy))bis(methylene))bis(ethylene oxide).

[0054] Other suitable crosslinking agents include the following: Where n = 1 to 3 (OXBP), for example, when n = 1, 4,4'-bis(((3-ethyloxetane-3-yl)methoxy)methyl)-1,1'-biphenyl; bis(4-(ethylene oxide-2-ylmethoxy)phenyl)methane; Phenolic-formaldehyde polymer glycidyl ether, wherein n=1~10 (EPON 862); Triglycidyl ether of glycerol polyoxypropylene epoxy ether, commercially available under the trade names Heloxy 84 or GE-36, is manufactured by Momentive Specialty Chemicals Inc. ;and Heloxy 107.

[0055] It is understood that using one or more phenolic compounds of formulas a-1 to a-6 further provides advantageous benefits to the compositions of the present invention. These phenolic compounds are, for example, the commercially available TrisP-3M6C-2Ballast from Toyo Gosei Co., Ltd. Furthermore, in the photosensitive compositions of the present invention, any amount of one or more phenolic compounds of formulas a-1 to a-6 that produce the desired results described herein can be used. Typically, this amount is in the range of 1 to 25 parts by weight (pphr) per 100 parts by weight of the polymer (i.e., resin) described herein. In some other embodiments, this amount is in the range of 3 to 20 pphr, and in still other embodiments, this amount is in the range of 5 to 15 pphr.

[0056] As described above, one or more compounds of formula (VIA) and / or formula (VIB) are also used in the compositions of the present invention. Non-limiting examples of compounds of formula (VIA) or formula (VIB) are listed below: 4-Ethylresorcinol; 4-Propylresorcinol; 4-Butylresorcinol; 4-Hexylresorcinol; 2-Hydroxybenzoic acid; 3-Hydroxybenzoic acid; 4-Hydroxybenzoic acid; 4,4'-Dihydroxydiphenyl sulfide; 3,3'-Dihydroxydiphenyl disulfide; 4,4'-Dihydroxydiphenyl disulfide; 4,4'-Dihydroxydiphenyl sulfone; 2,2'-Dihydroxydiphenyl ether; 4,4'-Dihydroxydiphenyl ether; Biphenyl; 2,2'-Methylenediphenol (2,2'-dihydroxydiphenylmethane or o,o'-BPF); 4,4'-Methylenediol; 2,2'-(ethane-1,1-diyl)diol; 4,4'-(ethane-1,1-diyl)diol; 2,2'-(propane-1,1-diyl)diol; 4,4'-(propane-1,1-diyl)diol; 2,2'-(propane-2,2-diyl)diol; 4,4'-(propane-2,2-diyl)diol; 4,4'-(1,3-dimethylbutylene)diol; 2,2'-(4-methylpentane-2,2-diyl)diol; 4,4'-(4-methylpentane-2,2-diyl)diol; 4,4'-(2-ethylhexylene)diol; 2,2'-(5-methylheptane-3,3-diyl)diol; 4,4'-(5-methylheptane-3,3-diyl)diol; 4,4'-Ethylenebisphenol; 2,2'-Ethylenedioxydiphenol; 4,4'-(propane-2,2-diyl)bis(2-cyclohexylphenol); 4,4'-(2-methylpropane-1,1-diyl)bis(2-cyclohexyl-5-cresol); 5,5''-(cyclohexane-1,1-diyl)bis(([1,1'-biphenyl]-2-ol)); 4,4'-(cyclohexane-1,1-diyl)bis(2-cyclohexylphenol); 4,4'-(4-methylcyclohexane-1,1-diyl)diol; 2-Cyclohexyl-4-(2-(4-hydroxyphenyl)propyl-2-yl)-5-cresol; 6,6'-Methylenebis(2-(tert-butyl)-4-cresol); 6,6'-(2-methylpropane-1,1-diyl)bis(2,4-xylenol); 4,4'-(2-methylpropane-1,1-diyl)bis(2-(tert-butyl)-5-cresol); and mixtures of any combination thereof.

[0057] Furthermore, as described in this specification, any amount of one or more compounds of formula (VI) that produce the desired results can be used in the photosensitive composition of the present invention. Typically, this amount is in the range of 5 to 30 parts by weight per 100 parts by weight (pphr) of the polymer (i.e., resin) described in this specification. In some other embodiments, this amount is in the range of 7 to 20 pphr, and in still other embodiments, this amount is in the range of 9 to 15 pphr.

[0058] Advantageously, among other benefits, it has been surprisingly found that by using appropriate amounts of one or more phenolic compounds described in this specification, particularly when etching a coated wafer or bonding semiconductor chips together via an adhesive layer, air bubbles between the adhesive layer and the semiconductor chip in a semiconductor device using the photosensitive composition of the present invention can be reduced. Furthermore, even if air bubbles are generated between the adhesive layer and the semiconductor chip, these bubbles are removed due to the enhanced adhesive force of the adhesive layer on the semiconductor chip, thus preventing air bubbles from remaining at the interface between the adhesive layer and the semiconductor chip, thereby enabling the semiconductor chips to be firmly bonded together. Therefore, a highly reliable chip laminate can ultimately be obtained.

[0059] Furthermore, since the photosensitive composition of the present invention contains phenolic compounds, a bonding layer with relatively high solubility in organic solvents can be obtained in semiconductor devices using the photosensitive composition of the present invention. Therefore, even when it is necessary to remove a coating obtained, for example, by applying the photosensitive composition onto a wafer, the coating can be effectively dissolved and removed while suppressing the formation of any residue. As a result, the wafer can be reused (reprocessed) in the bonding process without being wasted. Therefore, the process yield of semiconductor devices can be improved.

[0060] In some embodiments of the present invention, the phenolic compounds used have two or more phenolic groups as described in this specification. However, it has been found that phenolic compounds containing 2 to 6 phenolic functional groups provide more advantageous effects. Furthermore, in some embodiments, the compositions of the present invention comprise two phenolic compounds; one having two phenolic groups and the other having three or more phenolic groups. Therefore, the above-mentioned effects can be achieved more significantly.

[0061] The phenolic compounds contained in the compositions of the present invention can be condensed polycyclic structures listed in this specification, such as polycyclic phenolic compounds of formulas a-1 to a-6, or any similar compounds known in the art, and any phenolic compound represented by formula (VIA) or (VIB). Therefore, in semiconductor devices using the photosensitive compositions of the present invention, an adhesive layer with extremely high adhesion to the semiconductor chip and better solubility in organic solvents can be obtained.

[0062] The photosensitive composition of the present invention also includes additives capable of bonding to the acidic side groups of a polymer resin. Such materials include additives incorporating one or more epoxy groups such as glycidyl, epoxycyclohexyl, or oxacyclobutyl; oxazolinyl groups such as 2-oxazolin-2-yl; hydroxymethyl groups such as N-hydroxymethylaminocarbonyl; or alkoxymethyl groups such as N-methoxymethylaminocarbonyl, but are not limited thereto. Typically, the bonding to the acidic side groups of the polymer is a crosslinking reaction initiated by heating to a suitable temperature, typically at a temperature above 110°C for a suitable time. Therefore, in some embodiments of the present invention, the photosensitive composition of the present invention comprises one or more epoxy compounds selected from the following, but is not limited thereto: (2R,3R,4R,5S)-1,3,5,6-tetratetra(ethylene oxide-2-ylmethoxy)hexane-2,4-diol (also known as tetra-O-(ethylene oxide methyl)-D-glucanol) (Denacol EX-614, manufactured by Nagase); and 1,2-bis(ethylene oxide-2-ylmethoxy)ethane.

[0063] Other exemplary crosslinkable or crosslinkable materials that can be used as additives to form the photosensitive compositions of the present invention include bisphenol A epoxy resin, bisphenol F epoxy resin, silicone-containing epoxy resin, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycidyloxypropyltrimethoxysilane, polymethyl(glycidyloxypropyl)cyclohexane, etc.; polymers containing an oxazoline ring, such as 2-methyl-2-oxazoline, 2-ethyl-2-oxazoline, 1,3-bis(2-oxazoline-2-yl)benzene, 1,4-bis(2-oxazoline-2-yl)benzene, 2,2′-bis(2-oxazoline) ), 2,6-bis(4-isopropyl-2-oxazoline-2-yl)pyridine, 2,6-bis(4-phenyl-2-oxazoline-2-yl)pyridine, 2,2'-isopropylidene bis(4-phenyl-2-oxazoline), (S,S)-(-)-2,2'-isopropylidene bis(4-tert-butyl-2-oxazoline), poly(2-propenyl-2-oxazoline), etc.; N-hydroxymethylacrylamide, N-hydroxymethylmethacrylamide, furfuryl alcohol, benzyl alcohol, succinate, 1,2-benzenedimethanol, 1,3-benzenedimethanol, 1,4-benzenedimethanol and Resole-type phenolic resins or mixtures thereof, etc. It is known that such materials are generally effective when using polymers of 5 pphr to 40 pphr. However, it should be understood that more or less additions have also proven effective, as their effectiveness depends at least in part on the nature of the polymer used and the mol% of repeating units containing crosslinking side groups.

[0064] In another aspect of the invention, the photosensitive composition comprises a compound or mixture of compounds that enhances the properties of the composition, including, but not limited to, photosensitivity, solubility, and various other uses. Advantageously, it is understood that, according to embodiments of the invention, the compound of formula (VII) can be used as an additive.

[0065] (VII) Where x and y are integers from 0 to 4. R 21 and R 22 The same or different and each independently selected from hydrogen, halogen, methyl, ethyl, straight-chain or branched C3-C 18 Alkyl, C1-C 18 Perfluoroalkyl, methoxy, ethoxy, straight-chain or branched C3-C 18 Alkoxy, C3-C 16 cycloalkyl, C6-C 16 Bicycloalkyl, C8-C 16 Tricycloalkyl, C6-C 10 Aryl, C7-C 18 Aryl group, -(CH2) w CO2R 23 -(CH2) z OR24 Ar1 and Ar2 may be the same or different and are each independently selected from C6-C. 10 Aryl, C7-C 18 Aryl group, wherein the aryl or aryl group can be further substituted by substituents known to those skilled in the art. Z is selected from alkyl groups, O, S, P, -NR-, -C(=O)-, -C(=O)-O-, -C(=O)-NR-, -SO-, -SO2-, -SO2NH- alkyl groups, or any carbocyclic crosslinking group including cycloalkyl, heterocycloalkyl, aryl, aryl, etc. Wherein, any cycloalkyl, bicycloalkyl, or tricycloalkyl group may contain one or more heteroatoms selected from O, S, N, P, and Si. Wherein, w is an integer from 0 to 8, R 23 It is hydrogen, methyl, ethyl, straight-chain or branched C3-C 18 Alkyl group. Where z is an integer from 0 to 8, R 24 It is hydrogen, methyl, ethyl, straight-chain or branched C3-C 18 Alkyl group. Wherein, R is hydrogen, methyl, ethyl, straight-chain or branched C3-C. 18 Alkyl, C1-C 18 Perfluoroalkyl, C3-C 16 cycloalkyl, C6-C 16 Bicycloalkyl, C8-C 16 Tricycloalkyl.

[0066] Generally, the various compounds and additives listed in this specification enhance the overall performance of the photosensitive compositions of the present invention, thus providing clear optical patterning structures for a variety of applications, including chip stacking applications, redistribution layers, and damming structures for forming CMOS image sensors. Advantageously, it is understood that some additives described in this specification may have more than one function. For example, some of the additives listed above not only exhibit specific solubility-enhancing activities after exposure but can also act as crosslinking agents as described above. Therefore, the additives used in this specification do not limit the activity of such compounds to one of these properties and can also promote other functions of the photosensitive compositions of the present invention.

[0067] It should also be noted that any of the additives described above can be used alone, i.e., as a single compound and / or in any combination of one or more compounds. Furthermore, the amount of additive that can be used depends on the desired results of the photosensitive composition of the present invention. Therefore, any amount that yields the desired results can be used in the present invention. Typically, the amount of additive that can be used is in the range of 0.5 to 20 pphr, and in some embodiments, this amount is in the range of 1 to 12 pphr.

[0068] The photosensitive compositions of the present invention further comprise compounds that can be used, in particular, as adhesion promoters, antioxidants, crosslinking agents, coupling agents, or curing agents. Representative examples of adhesion promoters or adhesion aids include: vinylsilanes, such as vinyltrimethoxysilane or vinyltriethoxysilane; epoxysilanes, such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane; styrylsilanes, such as p-styryltrimethoxysilane; and methacryloxysilanes, such as 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropyltriethoxysilane. 3-Methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane; acrylate silanes, such as 3-acryloxypropyltrimethoxysilane; alkyl silanes as detailed below; ureosilanes, such as 3-ureopropyltrialkoxysilane; mercaptosilanes, such as 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane; isocyanate silanes, such as 3-isocyanatepropyltriethoxysilane; titanium is a compound; aluminum chelates; representative examples including aluminum / zirconium are compounds, etc. Other non-limiting examples of such compounds are selected from the group consisting of the following, and commercially available materials are specified by such trade names. Triethoxy (3-(ethylene oxide-2-ylmethoxy)propyl)silane, also commonly known as 3-glycidoxypropyltriethoxysilane (3-GTS or (KBE-403, manufactured by Shin-Etsu Chemical Co., Ltd.)). Trimethoxy(3-(ethylene oxide-2-ylmethoxy)propyl)silane, also commonly known as 3-glycidoxypropyltrimethoxysilane (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.); C6H5(CH3O)3Si Phenylacetyltrimethoxysilane C6H5(C2H5O)3Si Phenylacetoxysilane (KBE-103, commercially available from Gelest, Inc. or Shin-Etsu Chemical Co., Ltd.) 3,3,10,10-Tetramethoxy-2,11-dioxa-3,10-disildodecane (SIB-1832, manufactured by Gelest, Inc.); Undecyl-1-en-1-ylsilane (SIU9048.0); 3-(dimethoxy(methyl)silyl)propane-1-thiol (SIM6474.0); 2,2'-((3-(triethoxysilyl)propyl)aminoidene)bis(ethane-1-ol) (SIB1140.0); N,N'-bis[(3-triethoxysilylpropyl)aminocarbonyl]polyethylene oxide (SIB-1824.84, manufactured by Gelest, Inc.); 4,4,13,13-Tetraethoxy-3,14-dioxa-8,9-dithia-4,13-disilhexadecane; Triethoxy(3-thiocyanopropyl)silane (SIT7908.0) 3,3,12,12-Tetramethoxy-2,13-dioxa-7,8-dithia-3,12-disilazane (Si-75 or Si-266, manufactured by Evonik Industries AG); 2,2'-((2-hydroxy-5-methyl-1,3-phenylene)bis(methylene))bis(4-cresol) (antioxidant AO-80, manufactured by TCI Japan); 4,4'-((2-hydroxy-5-methyl-1,3-phenylene)bis(methylene))bis(2,6-xylenol) (Bis26X-PC) 6,6'-Methylenebis(2-(2-hydroxy-5-methylbenzyl)-4-cresol)(4-PC); Pentaerythritol tetra(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) (Irganox 1010, manufactured by BASF); 3,5-Bis(1,1-dimethylethyl)-4-hydroxy-octadecyl phenylpropionic acid (Irganox 1076, manufactured by BASF). Bis(4-(2-phenylprop-2-yl)phenyl)amine (Naugard 445 (NG445), commercially available from Chemtura Corporation); Bis(4-(tert-butyl)phenyl)amine (Stearer Star, manufactured by Seiko Chemical Products); Bis(4-methoxyphenyl)amine (Thermoflex); bis(4-ethylphenyl)amine; bis(4-isopropylphenyl)amine Bis(4-(2,4,4-trimethylpentan-2-yl)phenyl)amine (Irganox 5057, manufactured by BASF); Bis(4-(1-phenylethyl)phenyl)amine (Wingstay 29); Bis(4-(2,4,4-trimethylpentyl)phenyl)amine (Irganox L 57, manufactured by BASF); 1-Benzyloctahydropyrrolo[1,2-a]pyrimidine (CGI-90, manufactured by BASF); Tetra(2,3,4,5,6-pentafluorophenyl)borate (1-)[4-(1-methylethyl)phenyl] (4-Methylphenyl)-Molybdenum (Rhodorsil PI 2074, manufactured by Blue Star Silicones) 1-Chloro-4-propoxy-9H-thioxanthro-9-one (CPTX, Lambson PLC). 10H-Phenothiazine (Phenothiazine, manufactured by Kanto Corporation) 1,4-Bis[(ethoxy)methyl]cyclohexane (cyclohexane divinyl ether (CHDVE)) Wherein, R and R' are independently (C1-C4) alkyl groups, and GE = glycidyl ether (BY-16-115). Silicone-modified epoxy compound, commercially available from Toray-Dow Corning Silicone Co., Ltd., BY16-115. (HP-7200); and Lowinox CPL.

[0069] Other exemplary epoxy resins or crosslinking additives include Araldite MTO163 and Araldite CY179 (manufactured by Ciba Geigy); and EHPE-3150 and Epolite GT300 (manufactured by Daicel Chemical).

[0070] It must be emphasized again that any of these compounds can be used alone or in any combination, and should only be used when necessary, according to the intended use and to obtain the desired effect. Furthermore, any amount of the above compounds can be used to obtain the desired results. It is understood that this amount is typically in the range of 0.5 to 30 parts by mass per 100 parts by mass (pphr) of the polymer (resin). In some embodiments, this amount is in the range of 1 to 10 pphr.

[0071] The photosensitive composition according to the invention may also contain other components that can be used to improve the properties of the composition and the resulting film or polymer layer. For example, as described below, the sensitivity of the composition to the desired exposure wavelength can lead to improved desired properties. Examples of such optional components include, but are not limited to, more than one compound / various additives, such as surfactants, silane coupling agents, leveling agents, phenolic resins, antioxidants, flame retardants, plasticizers, and curing accelerators.

[0072] The photosensitive compositions according to embodiments of the present invention are generally dissolved in a solvent to form a homogeneous solution. Any solvent for dissolving copolymers or terpolymers, or mixtures thereof, and all additives described herein can be used. Non-limiting examples of such solvents include methyl ethyl ketone (MEK), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), γ-butyrolactone (GBL), and tetrahydrofuran (THF), and mixtures thereof. In some embodiments, the compositions of the present invention are dissolved in one or more solvents selected from the group consisting of propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME), and mixtures thereof.

[0073] Any amount of solvent required to dissolve all components of the photosensitive composition of the present invention can be used. Typically, such solvent can be 50 parts by weight or more, 100 parts by weight or more, or 200 parts by weight or more. In some embodiments, the amount of solvent used is 300 parts by weight or more, but can be 400 parts by weight or less, 1000 parts by weight or less, 2000 parts by weight or less, or 3000 parts by weight or less. In some embodiments, the amount of solvent used is 800 parts by weight or less or 1000 parts by weight or less relative to 100 parts by weight of the polymer.

[0074] First, the photosensitive composition according to embodiments of the present invention is coated onto a desired substrate to form a film. Such substrates include any suitable substrate itself, or, for example, semiconductor substrates, ceramic substrates, glass substrates, etc., used in electrical, electronic, or optoelectronic devices. In the above applications, any suitable coating method can be used, such as spin coating, spray coating, blade coating, meniscus coating, inkjet coating, and slot coating. For example, the photosensitive composition of the present invention is coated onto the entire surface of a silicon substrate with dimensions of 10 × 10 mm.

[0075] Next, the coated substrate is heated to facilitate the removal of residual casting solvent, for example, at a temperature of 70°C to 130°C for approximately 1 to 40 minutes, although other suitable temperatures and times may also be used. After heating, the film image is typically exposed to a suitable photochemical radiation wavelength, usually selected based on the photoactive compound and / or photosensitizer incorporated into the polymer composition described in this specification. However, such a suitable wavelength is typically 200 to 700 nm. It should be understood that the term "image exposure" refers to exposure through a mask to obtain a pattern of the exposed and unexposed portions of the film.

[0076] After the image of the film formed by the photosensitive composition or formulation according to an embodiment of the present invention is exposed, a development process is performed. In the case of the positive-tone polymer formulation of the present invention, this development process removes only the exposed portion of the film, thus leaving a positive image of the mask layer on the film. In the case of the negative-tone polymer formulation of the present invention, this development process removes only the unexposed portion of the film, thus leaving a negative image of the mask layer on the film. In some embodiments, post-exposure baking can be performed before the above-described development process.

[0077] Developers particularly suitable for positive-tone formulations such as the photosensitive compositions of the present invention may include aqueous solutions of inorganic alkaline solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, and ammonia, as well as aqueous solutions of organic alkaline solutions such as 0.26N tetramethylammonium hydroxide (TMAH), ethylamine, triethylamine, and triethanolamine. Therefore, as described above, in some embodiments of the present invention, the photosensitive compositions are soluble in alkaline developers.

[0078] When using organic bases, organic solvents that are substantially miscible with water are typically used to provide the solubility of the organic base. Aqueous TMAH solutions are known developing solutions in the semiconductor industry. Suitable developing agents can also include organic solvents such as propylene glycol methyl ether acetate (PGMEA), 2-heptanone, cyclohexanone, toluene, xylene, ethylbenzene, mesitylene, and butyl acetate.

[0079] Therefore, some embodiments of the present invention provide a self-imaging film that, after image exposure, develops the obtained image using an alkaline aqueous solution, while other embodiments develop the obtained image using an organic solvent. Regardless of the type of developer used, after image development, the substrate is cleaned to remove excess developer solution; typical cleaning agents are water or suitable alcohols and mixtures thereof.

[0080] After the above cleaning, the substrate is dried, and the imaging film is finally cured. In other words, the image is fixed. If the remaining layer was not exposed during the image exposure process, fixing is usually accomplished by initiating a reaction in the remaining portion of the film. Such a reaction is usually a crosslinking reaction that can be initiated by heating and / or non-image exposure or blanket exposure of the remaining material. The exposure and heating can be performed separately or in appropriate combination depending on the specific application of the imaging film. Blanket exposure is usually performed using the same energy as that used in image exposure, but any suitable energy can be used. Heating is usually performed at the desired temperature, for example, at a temperature above 110°C for 40 minutes to 1 hour or more. If the remaining layer was exposed during the image exposure process, it is usually accomplished by adjusting the heating step to end any reaction initiated by the exposure. However, as mentioned above, additional blanket exposure and heating can also be performed. However, it should be understood that the final curing process is also selected according to the type of device formed, so when the remaining layer is used as an adhesive layer or structure, final fixing may not be final curing.

[0081] Using the embodiments of the alkali-soluble photosensitive resin composition of the present invention, a layer with properties such as high heat resistance, excellent water absorption, high transparency, and low dielectric constant is formed, thereby manufacturing a device. Furthermore, such layers typically exhibit excellent elastic modulus after curing, typically 0.1 kg / mm². 2 ~200kg / mm 2 .

[0082] As described above, exemplary applications of the photosensitive compositions according to the present invention include chip bonding adhesives, wafer bonding adhesives, insulating films (interlayer dielectric layers), protective films (passivation layers), mechanical buffer films (stress buffer layers), or planarization films for various semiconductor devices and printed circuit boards. Specific applications of such embodiments include chip bonding adhesives for forming single-layer or multi-layer semiconductor devices; dielectric films formed on semiconductor devices; buffer films formed on passivation films; and interlayer insulating films formed on circuits formed on semiconductor devices.

[0083] Therefore, according to embodiments of the present invention, a positive-tone photosensitive polymer composition is provided, which exhibits enhanced characteristics in more than one mechanical property (e.g., maintaining low-stress elongation at break after aging) and has chemical resistance at least comparable to that of alternative materials. Furthermore, such embodiments generally provide excellent electrical insulation, adhesion to substrates, etc. Therefore, semiconductor devices, device packages, and display devices incorporating embodiments of the present invention are provided.

[0084] Advantageously, the photosensitive composition of the present invention can be used in chip stacking applications to form adhesive layers that bond semiconductor chips together. For example, the bonding layer for this purpose is formed from the cured product of the photosensitive adhesive composition of the present invention. Surprisingly, although the adhesive layer is a single-layer structure, it not only has sufficient adhesion to the substrate, but no significant stress caused by the curing step has been found. Therefore, unnecessary thick layers of films containing chips as laminates can be avoided. Laminates formed according to the present invention have been found to be reliable in mitigating stress concentration caused by differences in thermal expansion, etc. As a result, semiconductors with low aspect ratios and high reliability can be obtained. That is, devices with low aspect ratios and thin thicknesses can be obtained. Such semiconductor devices are particularly advantageous for electronic devices with very small internal volumes, such as those carried as mobile devices. More advantageously, by implementing the present invention, various electronic devices characterized by miniaturization, thinning, and lightweighting that have not been achieved until now can be formed, and the function of the semiconductor devices is not easily damaged even when subjected to harsh operations such as shaking or dropping.

[0085] The cured products of the photosensitive adhesive compositions of the present invention, i.e., adhesive layers or films, typically exhibit excellent adhesion to suitable substrates such as semiconductor chips and adhesive strengths, such as chip shear strength, that can be measured by any known method. Therefore, in some embodiments, the photosensitive compositions of the present invention exhibit chip shear strengths greater than 3.0 MPa, greater than 4.0 MPa, greater than 5.0 MPa, greater than 6.0 MPa, greater than 6.5 MPa, greater than 7.0 MPa, greater than 8.0 MPa, greater than 9.0 MPa, greater than 10.0 MPa, etc. In some embodiments, the photosensitive compositions of the present invention exhibit chip shear strengths in the range of about 5.0 MPa to 10.0 MPa. However, it should be understood that there is no particular upper limit to the grain shear strength of the photosensitive resin composition, and it can be, for example, less than 30.0 MPa, less than 20.0 MPa, less than 15.0 MPa, and less than 12.0 MPa.

[0086] Chip shear strength can be determined by any method known in the art. For example, a photosensitive resin composition is coated onto the entire surface of a 10×10 mm silicon substrate and heat-treated at 120°C for 30–60 minutes to produce a cured product with a thickness of 1 μm. A suitable test substrate, such as a 5×5 mm silicon substrate, is placed on the surface of the cured product, and a hot press is used to press the silicon substrate and the cured product together at 150°C with a force of approximately 25 N for 10 seconds, from the top of the silicon substrate toward the cured product, to obtain a sample. The sample is then heat-treated at 230°C for 60 minutes in a nitrogen atmosphere. The chip shear strength between the silicon substrate and the cured material in the sample is then measured at 180°C, a test distance of 5 μm from the surface of the cured material, and a test speed of 300 μm / s.

[0087] Furthermore, as described above, in some embodiments of the present invention, the electronic and / or semiconductor device according to the present invention includes a stacked semiconductor element, wherein the stack comprises a photosensitive composition according to the present invention.

[0088] In some embodiments of the invention, the semiconductor device includes a redistribution layer (RDL) structure further comprising a photosensitive composition according to the invention.

[0089] Furthermore, as described above, in some embodiments of the present invention, the semiconductor device includes a chip stack structure that further includes the photosensitive composition according to the present invention.

[0090] As described above, in some other embodiments of the present invention, the semiconductor device includes a damming structure of a complementary metal-oxide-semiconductor (CMOS) image sensor that further includes the photosensitive composition according to the present invention. In other embodiments of the present invention, the semiconductor device including the photosensitive composition of the present invention includes, for example, various semiconductor packages that stack and seal transistors, diodes, solid-state imaging devices, semiconductor chips, etc.; wafer-level packages (WLP); display devices, such as LCD displays, OLED displays, touch panels, electronic paper, color filters, mini-LED displays, and micro-LED displays; and light-receiving devices, such as solar cells, etc., are all considered.

[0091] Furthermore, as described above, in some embodiments of the present invention, a film is formed from the photosensitive composition according to the present invention. As mentioned above, such films generally exhibit excellent chemical, mechanical, and elastic properties, making them widely applicable in electronic, optoelectronic, and microelectromechanical applications with excellent dielectric properties.

[0092] Therefore, in some embodiments of the present invention, a microelectronic or optoelectronic device is provided that includes one or more of a redistribution layer (RDL) structure, a chip stack structure, and a dam structure of a CMOS image sensor, wherein the structure further includes a photosensitive composition according to the present invention.

[0093] Furthermore, in some embodiments of the present invention, a method for forming a film for manufacturing microelectronic or optoelectronic devices is provided, the method comprising the following steps: A film is formed by coating the composition according to the invention onto a suitable substrate; The film is patterned using a mask by exposing it to appropriate radiation; After exposure, the film is developed to form a light pattern; and The film is cured by heating it to a suitable temperature.

[0094] The photosensitive composition of the present invention can be coated onto a substrate using any coating method described in this specification and / or coating methods such as spin coating known to those skilled in the art.

[0095] Furthermore, the development according to the method of the present invention can be performed using any known development technique, such as an aqueous developer.

[0096] In some embodiments of the present invention, the developer used in the method according to the present invention is an aqueous solution of tetramethylammonium hydroxide (TMAH).

[0097] Furthermore, in some embodiments of the present invention, before the curing step, the substrate is first hard-baked at a temperature of 130°C to 160°C for 20 to 60 minutes.

[0098] Finally, in some other embodiments of the present invention, the product is cured at a temperature of 170°C to 200°C with an incremental heating slope of 5°C for 1 to 5 hours.

[0099] Figure 1 A cross-sectional view showing one embodiment of the semiconductor device of the present invention is shown.

[0100] In one embodiment of the invention, a semiconductor device comprising stacked semiconductor elements is further provided, wherein the stacked semiconductor elements include a plurality of semiconductor elements and a cured product of the composition embodiment of the invention between the semiconductor elements. Because the photosensitive composition of the invention improves adhesion, the semiconductor elements adhere well to each other. Refer to the cross-sectional view schematically illustrating a structural example of the semiconductor device of the invention. Figure 1 The semiconductor device of the present invention will be described below. Figure 1The semiconductor device 10 shown is an example of a ball grid array (BGA) semiconductor package. The semiconductor device 10 includes a plurality of semiconductor chips (semiconductor elements) 20 stacked on top of each other, an adhesive layer 601 for bonding the semiconductor chips 20 together, a package substrate 30 supporting the semiconductor chips 20, an adhesive layer 101 for bonding the semiconductor chips 20 to the package substrate 30, a mold portion 50 sealing the semiconductor chips 20, and solder balls 80 located on the underside of the package substrate 30. Each component will be described in detail below.

[0101] Semiconductor chip 20 can use any type of component, such as storage components like NAND (not AND) flash memory and DRAM, as well as integrated circuit components like IC (Integrated Circuit) and LSI (Large Scale Integration).

[0102] The semiconductor chip 20 is made of materials such as single-crystal materials, polycrystalline materials, or amorphous materials such as silicon or silicon carbide, but is not limited to these.

[0103] Multiple semiconductor chips 20 are stacked in a planar direction with slight offsets from each other, thereby forming a chip stack 200 (stacked semiconductor elements). The gaps between the semiconductor chips 20 are bonded by an adhesive layer 601. The adhesive layer 601 is also provided on the upper surface of the chip stack 200, and it is also composed of a cured product of the photosensitive composition of the embodiments of the present invention (cured photosensitive composition).

[0104] Figure 1 The packaging substrate 30 shown is an add-on substrate having a core substrate 31, an insulating layer 32, a solder resist layer 33, wiring 34 and conductive holes 35.

[0105] The core substrate 31 is a substrate that supports the semiconductor device 10, and is made of, for example, composite material or glass fiber filled with resin material.

[0106] The insulating layer 32 is an interlayer insulating layer that insulates the wirings 34 from each other and from the wirings 34 to the conductive vias 35, and is formed, for example, from a resin material. The solder mask layer 33 is a surface protective layer that protects the wirings formed on the outermost surface of the package substrate 30, and is formed, for example, from a resin material.

[0107] Wiring 34 and conductive hole 35 are electrical signal transmission paths, and are made of elemental or alloy metal materials such as Au, Ag, Cu, Al or Ni, respectively.

[0108] Solder ball 80 is electrically connected to wiring 34 and functions as an electrode connecting wiring 34 to another circuit by melting with an external circuit.

[0109] A chip stack 200, formed by stacking multiple semiconductor chips 20, is disposed on the upper surface of the packaging substrate 30. The gap between the chip stack 200 and the packaging substrate 30 is bonded by an adhesive layer 101.

[0110] A portion of the wiring 34 of the packaging substrate 30 is exposed on the upper surface of the packaging substrate 30, and this exposed portion is connected to the electrode portion of each semiconductor chip 20 via wiring 70.

[0111] Figure 1 The mold portion 50 shown covers the sides and top surface of the chip stack 200 and is formed to cover the entire upper surface of the packaging substrate 30. Therefore, it can protect the chip stack 200 from the influence of the external environment. For example, such a mold portion 50 is made of any resin material such as epoxy resin or phenolic resin.

[0112] The semiconductor device according to this embodiment can be a semiconductor device comprising a semiconductor element, a bonded component, and a curable material according to this embodiment between the semiconductor element and the bonded component. Because the photosensitive composition according to this embodiment has improved adhesion, the semiconductor element and the bonded component are well bonded.

[0113] The present invention has been described above, but it is not limited thereto. For example, any component can be added to the photosensitive resin composition. Furthermore, any structure can be added to the semiconductor device.

[0114] Example The following abbreviations, used throughout this specification, are used to describe certain compounds, instruments, and / or methods used in specific embodiments of the present invention: EPEsNB: ethyl 3-(bicyclo[2.2.1]hept-2-en-2-yl)propionate; NBTON: trioxane-nonyl norbornene; PhOAcNB: 4-(bicyclo[2.2.1]hept-5-en-2-yl)phenyl acetate; PhOHNB: 4-(bicyclo[2.2.1]hept-5-en-2-yl)phenol; EugOAcNB: 4-norbornenylmethyl-2-methoxyphenol acetate; EugOHNB: 4-(bicyclo[2.2.1]hept-4-en-2-ylmethyl)-2-methoxyphenol; HexNB: 4-(bicyclo[2.2.1]hept-5-en-2-yl)hexane; MeOAcNB: bicyclo[2.2]... .1] Hept-5-en-2-ylmethyl acetate; HFANB: norbornen-2-trifluoromethyl-3,3,3-trifluoroprop-2-ol; PGMEA: propylene glycol monomethyl ether acetate; PGME: propylene glycol monomethyl ether; PAC: TrisP-3M6C-2(4)-201, as described in this specification, having structure b-1; Epoxy compound 1: trimethylolpropane triglycidyl ether; Epoxy compound 2: pentaerythritol tetraglycidyl ether; Phenolic compound 1: (4,4'-[(2-hydroxyphenyl)methylene]bis[2-cyclohexyl-5-methylphenol]), also represented in this specification as formula a-1 (TrisP-3M6C-2, Honshu Phenolic compound 2: 2,2'-dihydroxydiphenylmethane (o,o'-BPF, manufactured by Honshu Chemical Co., Ltd.); KBE-103: phenyltriethoxysilane; TMAH: tetramethylammonium hydroxide.

[0115] The polymers described throughout this specification and used in the compositions of the present invention can be prepared using methods commonly found in known literature for the preparation of similar vinyl addition polymers. For example, reference is made to U.S. Patent Nos. 8,753,790 B2 and 9,696,623 B2, the relevant portions of which are incorporated herein by reference.

[0116] Examples 1-15 Generally, any copolymer or terpolymer described in this specification can be used. For example, the copolymer or terpolymer of the polynorbornene derivatives shown in Table 1 can be dissolved in a suitable solvent such as PGMEA or PGME. Then, a specific amount of additive, expressed as parts per hundred parts of resin (pphr), is added to the polymer in an appropriately sized amber HDPE bottle. The mixture is stirred for 18 hours to prepare a homogeneous solution. Particulate impurities are removed by filtering the polymer solution through a polytetrafluoroethylene (PTFE) disc filter with 0.45 µm pores at 35 psi. The filtered polymer solution is collected in a low-particle HDPE amber bottle and stored at 5°C.

[0117] Table 1 M w Weight-average molecular weight Table 2 The resulting composition was placed at room temperature and then spin-coated onto multiple 125mm diameter silicon wafers (thickness: 625µm) at 200 rpm for 10 seconds, followed by 500 rpm for 30 seconds. The resulting substrate was then placed on a hot plate at 120°C for 5 minutes, resulting in a polymer film approximately 1 micrometer (µm) thick. Each polymer film was then imaged through a 100µm wide line and spatial pattern mask. The image was obtained by irradiation with light at a wavelength of 365nm and an intensity of 5mW / cm². 2 The films were exposed to light. Then, they were developed by immersion in a 2.38% TMAH aqueous solution at 23°C for 40 seconds using a spin-dip development method. After development, the wafers were cleaned by spraying deionized water for 20 seconds, followed by spin drying at 3000 rpm for 15 seconds.

[0118] The developed coating (adhesive layer) was then observed using an optical microscope, and the pattern formation properties were evaluated according to the following evaluation criteria. The results are shown in Table 2. In Examples 1-7, openings with a width of 100 μm were formed.

[0119] Example 2 Chip shear strength measurement The compositions described in Examples 1-15 were spin-coated onto a 10mm × 10mm silicon wafer and heat-treated at 120ºC for 40 minutes to form a cured film with a thickness of approximately 1µm. The film was then hard-baked at 150°C for 40 minutes. The wafer was then monolithized into 5mm × 5mm chips. Next, the chips were placed on a hot plate at 150°C, and simultaneously, using a hot press, a force of 25N was applied from the top of the Si test wafer towards the cured product, pressing the individual 5mm × 5mm silicon chips onto the coated monolithized chips over 10 seconds, thereby bonding the test wafer and the cured product to obtain a sample. The test wafer was then heat-treated at 230°C for 60 minutes under a nitrogen atmosphere. The chip shear strength between the Si test wafer and the cured wafer within the test wafer was then measured at 180°C, a test distance of 5μm from the surface of the cured material, and a test speed of 300μm / s. The results are shown in Table 2.

[0120] As clearly shown in Tables 1 and 2, the photosensitive compositions of the present invention specifically exemplified in Examples 1-15 demonstrate excellent photopatterning properties, as evidenced by openings with a width of 100 μm in all pattern-forming evaluations shown in Table 2. Furthermore, the chip shear strength is 4 MPa or higher, and as most of the examples summarized in Table 2 show, it can be easily adjusted to exhibit even higher chip shear strengths up to 10 MPa. Most advantageously, the fluorine content in all compositions of Examples 1-15 is 0.0% by mass, thus enabling the environmental benefits that have not been achieved to date.

[0121] Therefore, it can be seen that the balance of pattern-forming properties, adhesion and environmental compatibility of the photosensitive resin compositions of Examples 1 to 15 has been improved.

[0122] While the present invention has been described through some of the above embodiments, it should not be construed as being limited thereto, but rather should be understood as encompassing the general scope described above. Various modifications and implementations can be made without departing from the spirit and scope of the invention.

Claims

1. A photosensitizing composition comprising: a) A polymer having a first repeating unit of formula (IA) derived from a monomer of formula (I): (I.A.) (I); The second repeating unit of formula (IIA) derived from the monomer of formula (II): (IIA) (II) in: Indicates the location where it is bonded to another repeating unit; a is an integer from 0 to 3; b is an integer from 1 to 4; c is an integer from 1 to 4; R1 is selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, isopropyl, and n-butyl. R 18 For -(CH2) v -CO2R 19 , where v is an integer from 0 to 4, and R 19 It is hydrogen or (C1-C4) alkyl; b) Photoactive compounds, including the diazonoquinone moiety of formula (A): （A）； c) Multifunctional crosslinking agents, selected from the group consisting of the following: Compounds of formula (IV): (IV); and Compounds of formula (V): （V） in: n is an integer from 3 to 8; A is the correct answer; C is the correct answer; CH-(CR2) d The group consisting of -CH and substituted or unsubstituted aryl groups, wherein d is an integer from 0 to 4 and R is selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, isopropyl and n-butyl; Option B is selected from the group consisting of substituted or unsubstituted (C1-C6) alkyl groups, (C2-C6) alkylene groups, and substituted or unsubstituted aryl groups; The substituents are selected from halogens, methyl, ethyl, straight-chain or branched (C3-C6) alkyl, (C3-C8) cycloalkyl, (C6-C6) alkyl, and cycloalkyl. 10 )Aryl, (C7-C 12 Aryl alkyl, methoxy, ethoxy, straight-chain or branched (C3-C6) alkoxy, (C3-C8) cycloalkoxy, (C6-C6) alkyl alkyl, methoxy alkyl, ethoxy alkyl ... 10 ) aryloxy groups and (C7-C 12 The group consisting of arylalkoxy groups; d) Phenolic compounds, selected from the group consisting of the following: a-1; a-2; a-3; a-4; a-5; and a-6.

2. The photosensitizing composition according to claim 1, wherein, The first repeating unit of the polymer is derived from monomers selected from the group consisting of: Trioxane-nonyl norbornene (NBTON). Tetraoxadodecylnorbornene (NBTODD). 5-(3-methoxybutoxy)methyl-2-norbornene (NB-3-MBM); and 5-(3-methoxypropoxy)methyl-2-norbornene (NB-3-MPM).

3. The photosensitizing composition according to claim 1, wherein, The second repeating unit of the polymer is derived from monomers selected from the group consisting of: 3-(bicyclo[2.2.1]hept-5-en-2-yl)acetic acid (NBMeCOOH); Ethyl 3-(bicyclo[2.2.1]hept-2-en-2-yl)propionate (EPEsNB); Bicyclic [2.2.1]hept-5-en-2-carboxylic acid (Acid NB); and Norborneol-alkenylpropionic acid (NBEtCOOH).

4. The photosensitizing composition according to claim 1, wherein, The polymer further comprises a third repeating unit of formula (IIIA) derived from a monomer of formula (III): (IIIA) (III); in, d is an integer from 1 to 4; Y represents a bond or CH2; Each R 20 The group consisting of hydroxyl, methoxy, and acetoxy groups is selected independently.

5. The photosensitizing composition according to claim 4, wherein, The third repeating unit of the polymer is derived from monomers selected from the group consisting of: 4-(bicyclo[2.2.1]hept-5-en-2-yl)-phenylacetate (PhOAcNB); 4-(bicyclo[2.2.1]hept-5-en-2-yl)phenol (PhOHNB); 4-Norbornenylmethyl-2-methoxyphenol acetate (EugOAcNB); and 4-(bicyclo[2.2.1]hept-4-en-2-ylmethyl)-2-methoxyphenol (EugOHNB).

6. The photosensitizing composition according to claim 1, wherein, The diazonoquinone moiety is represented by formula (C), (D), or (E): (C) (D) (E)。 7. The photosensitizing composition according to claim 1, wherein, The photoactive compound is selected from one or more of the following: b-1; b-2; b-3; b-4; b-5; and b-6; Where at least one Q is a basis of equation (C) or (D): (C) (D); and The remaining Q is hydrogen.

8. The photosensitizing composition according to claim 1, wherein, The multifunctional crosslinking agent is selected from the group consisting of: 2,2'-(((2-ethyl-2-((ethylene oxide-2-ylmethoxy)methyl)propane-1,3-diyl)bis(oxy))bis(methylene))bis(ethylene oxide); also known as trimethylolpropane triglycidyl ether (manufactured by Nagase Chemtex, EX-321L); 2,2'-(((2,2-bis((ethylene oxide-2-ylmethoxy)methyl)propane-1,3-diyl)bis(oxy))bis(methylene))bis(ethylene oxide); also known as pentaerythritol tetraglycidyl ether (PETG, manufactured by Showa Denko); 2,2'-(((2-(1,3-bis(ethylene oxide-2-ylmethoxy)prop-2-yl)propane-1,3-diyl)bis(oxy))bis(methylene))bis(ethylene oxide); 1,2,4,5-Tetratetra((ethylene oxide-2-ylmethoxy)methyl)benzene; and 2,2'-(((2-(1,3-bis(ethylene oxide-2-ylmethoxy)prop-2-yl)-2-((ethylene oxide-2-ylmethoxy)methyl)propane-1,3-diyl)bis(oxy))bis(methylene))bis(ethylene oxide).

9. The photosensitizing composition according to claim 1, further comprising the group consisting of compounds selected from formula (VIA) and formula (VIB): (GO); (VIB); Where d and e are integers from 1 to 4; f and g are integers from 0 to 4; X is a group consisting of free bonds, -O-, -OCH2O-, -OCH2CH2O-, -S-, -SS-, -SO2-, and the base of the formula -CR2R3-; among which, R2 and R3 may be the same or different and are each independently selected from hydrogen, methyl, ethyl, straight-chain or branched C3-C6 alkyl, C3-C8 cycloalkyl, C6-C 10 Aryl and C7-C 12 Aryl alkyl; or R2 and R3 together with the carbon atoms they are bonded to form 5 to 8 substituted or unsubstituted carbon rings, wherein the substituents are selected from C1-C8 alkyl groups; R4 and R5 may be the same or different and are independently selected from hydrogen, -CO2H, methyl, ethyl, straight-chain or branched (C3-C6) alkyl, (C3-C8) cycloalkyl, (C6-C5) alkyl, and (C6-C6) alkyl. 10 ) aryl and (C7-C 12 Aryl alkyl group.

10. The photosensitizing composition according to claim 1, wherein, The phenolic compounds are selected from the group consisting of the following: a-1; a-4; a-5; and a-6.

11. The photosensitizing composition according to claim 9, wherein, The compounds of formula (VIA) or formula (VIB) are selected from the group consisting of: 4-Ethylresorcinol; 4-Propylresorcinol; 4-Butylresorcinol; 4-Hexylresorcinol; 2-Hydroxybenzoic acid; 3-Hydroxybenzoic acid; 4-Hydroxybenzoic acid; 4,4'-Dihydroxydiphenyl sulfide; 3,3'-Dihydroxydiphenyl disulfide; 4,4'-Dihydroxydiphenyl disulfide; 4,4'-Dihydroxydiphenyl sulfone; 2,2'-Dihydroxydiphenyl ether; 4,4'-Dihydroxydiphenyl ether; Biphenyl; 2,2'-Methylenediphenol (2,2'-dihydroxydiphenylmethane or o,o'-BPF); 4,4'-Methylenediol; 2,2'-(ethane-1,1-diyl)diol; 4,4'-(ethane-1,1-diyl)diol; 2,2'-(propane-1,1-diyl)diol; 4,4'-(propane-1,1-diyl)diol; 2,2'-(propane-2,2-diyl)diol; 4,4'-(propane-2,2-diyl)diol; 4,4'-(1,3-dimethylbutylene)diol; 2,2'-(4-methylpentane-2,2-diyl)diol; 4,4'-(4-methylpentane-2,2-diyl)diol; 4,4'-(2-ethylhexylene)diol; 2,2'-(5-methylheptane-3,3-diyl)diol; 4,4'-(5-methylheptane-3,3-diyl)diol; 4,4'-Ethylenebisphenol; 2,2'-Ethylenedioxydiphenol; 4,4'-(propane-2,2-diyl)bis(2-cyclohexylphenol); 4,4'-(2-methylpropane-1,1-diyl)bis(2-cyclohexyl-5-cresol); 5,5''-(cyclohexane-1,1-diyl)bis(([1,1'-biphenyl]-2-ol)); 4,4'-(cyclohexane-1,1-diyl)bis(2-cyclohexylphenol); 4,4'-(4-methylcyclohexane-1,1-diyl)diol; 2-Cyclohexyl-4-(2-(4-hydroxyphenyl)propyl-2-yl)-5-cresol; 6,6'-Methylenebis(2-(tert-butyl)-4-cresol); 6,6'-(2-methylpropane-1,1-diyl)bis(2,4-xylenol); 4,4'-(2-methylpropane-1,1-diyl)bis(2-(tert-butyl)-5-cresol); and mixtures of any combination thereof.

12. The photosensitizing composition according to claim 1, further comprising one or more compounds selected from the group consisting of: Triethoxy(3-(ethylene oxide-2-ylmethoxy)propyl)silane; 3,3,10,10-Tetramethoxy-2,11-dioxa-3,10-disiladodecane; 4,4,13,13-Tetraethoxy-3,14-dioxa-8,9-dithia-4,13-disilhexadecane; 2,2'-((2-hydroxy-5-methyl-1,3-phenylene)bis(methylene))bis(4-cresol); 6,6'-Methylenebis(2-(2-hydroxy-5-methylbenzyl)-4-cresol); Bis(4-(2-phenylprop-2-yl)phenyl)amine; bis(4-(tert-butyl)phenyl)amine; bis(4-methoxyphenyl)amine; bis(4-ethylphenyl)amine; and mixtures of any combination thereof.

13. A semiconductor or optoelectronic device comprising stacked semiconductor elements or bonding elements, wherein, The element comprises the photosensitive composition of claim 1.

14. A semiconductor device comprising a chip stack structure, wherein, The chip stack structure further comprises the photosensitive composition of claim 1.

15. A membrane comprising the composition of claim 1.

16. A microelectronic or optoelectronic device comprising one or more of a redistribution layer (RDL) structure, a chip stacking structure, and a damming structure for a CMOS image sensor, wherein, The structure further comprises the composition of claim 1.

17. A method for forming a film for manufacturing microelectronic or optoelectronic devices, the method comprising the following steps: The composition of claim 1 is coated onto a suitable substrate to form a film; The film is patterned using a mask by exposing it to appropriate radiation; After exposure, the film is developed to form a light pattern; and The film is cured by heating it to a suitable temperature.

18. The method according to claim 17, wherein, The development is performed using an aqueous developer.

19. The method of claim 17, wherein, Before curing, the substrate is first hard-baked at a temperature of 120°C to 160°C for 20 to 60 minutes.

20. The method of claim 17, wherein, The curing process involves heating at a temperature of 150°C to 200°C for 1 to 5 hours with an incremental heating slope of 5°C.

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