Dielectric film-forming compositions containing acylgermanium compounds

Abstract

The present disclosure relates to dielectric film-forming compositions comprising at least one resin and at least one acylgermanium compound, as well as related methods, films, dry film structures, and articles.

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to U.S. Provisional Patent Application No. 63 / 437,151, filed January 5, 2023, the entire contents of which are incorporated herein by reference.

[0002] FIELD OF THE DISCLOSURE The present disclosure relates to dielectric film-forming compositions containing acylgermanium compounds, as well as related methods, films, dry film structures, and articles. [Background technology]

[0003] The requirements for dielectric materials in semiconductor packaging applications continue to evolve. Trends in electronic packaging continue to move toward faster processing speeds, increased complexity, and increased packaging density while maintaining high levels of reliability. As electronic packaging technology advances and chips become increasingly smaller, the demand for innovative, high-performance resin compositions is increasing. Various proposals have been made for photosensitive dielectric compositions aimed at supporting high resolution. In some cases, photoinitiators with high sensitivity at longer wavelengths can be beneficial when used in photosensitive compositions using laser direct imaging (LDI) technology. Summary of the Invention [Problem to be solved by the invention]

[0004] The present disclosure is based on the unexpected discovery that certain acylgermanium compounds can be used as photoinitiators or photosensitizers in photosensitive dielectric film-forming compositions, thereby enabling the compositions to be developed at relatively long UV wavelengths (e.g., about 405 nm) to form dielectric films. The acylgermanium compounds can be non-toxic and can significantly improve the resolution of the dielectric films thus formed. As a result, the dielectric films thus formed can have excellent pattern shape and film hardness. [Means for solving the problem]

[0005] In one aspect, the disclosure features a dielectric film-forming composition that includes at least one resin (eg, a polymer) and at least one acylgermanium compound.

[0006] In some embodiments, the dielectric film-forming compositions described herein may further comprise at least one ethylenically unsaturated polymerizable compound, at least one thiol compound, at least one siloxane compound, or a mixture thereof.

[0007] In some embodiments, the dielectric film-forming compositions described herein may further include a radical initiator (e.g., a photoinitiator) different from the acylgermanium compound. In some embodiments, the radical initiator does not generate free radicals when exposed to a wavelength of UV light (e.g., because the radical initiator itself does not substantially absorb UV light at that wavelength). In such cases, it is believed that the acylgermanium compounds described herein may act as a sensitizer, synergistically promoting the generation of free radicals from the radical initiator.

[0008] In some embodiments, the dielectric film-forming compositions described herein may further include a photosensitizer different from the acylgermanium compound, wherein the photosensitizer is capable of absorbing light within a wavelength range of about 150 nm to about 600 nm (e.g., about 405 nm).

[0009] In some embodiments, the resins described herein may include fully imidized polyimides, cyclized rubbers, cyclic olefin polymers, polyphenylene ethers, acrylic compounds, cyanate ester compounds, polybenzoxazole precursor polymers, novolac polymers, epoxy phenol novolac polymers, or alkali-soluble polyimides. In some embodiments, the resins are selected from the group consisting of incompletely imidized polyimide resins (sometimes referred to in this disclosure as precursor polyimides) that may contain functional groups.

[0010] In some embodiments, the dielectric film-forming compositions described herein may optionally include one or more of the following components: a) one or more adhesion promoters; b) one or more corrosion inhibitors; c) one or more surfactants; d) one or more fillers or particles; e) one or more additives including a dye, a mixture of dyes, a pigment, or a mixture of pigments; and f) one or more metal-containing (meth)acrylate compounds.

[0011] In another aspect, the disclosure features a method of preparing a patterned dielectric film, the method including: a) depositing a dielectric film-forming composition described herein on a substrate to form a dielectric film; b) exposing the dielectric film to radiation or heat or a combination of radiation or heat; and c) patterning the dielectric film to form a patterned dielectric film having openings.

[0012] In another aspect, the disclosure features a method of forming a three-dimensional object, the method includes: a) providing a substrate containing a metal wire structure (which can include copper) forming a network of lines and interconnects on the substrate; b) depositing a dielectric film-forming composition described herein on the substrate to form a dielectric film; and c) exposing the dielectric film to radiation or heat or a combination of radiation and heat.

[0013] In another aspect, the disclosure features a method of preparing a three-dimensional object (e.g., an object containing a metal layer), the method includes: a) depositing a dielectric film-forming composition described herein on a substrate to form a dielectric film; b) exposing the dielectric film to radiation or heat or a combination of radiation and heat; c) patterning the dielectric film to form a patterned dielectric film having an opening; d) optionally depositing a seed layer on the patterned dielectric film; and e) depositing a metal layer in at least one opening in the patterned dielectric film.

[0014] In another aspect, the disclosure features a dry film construction that includes a carrier substrate and a dielectric film supported on the carrier substrate, the dielectric film prepared from a dielectric film-forming composition described herein.

[0015] In another aspect, the disclosure features a method of preparing a dry film structure, the method includes: (a) coating a carrier substrate with a dielectric film-forming composition described herein to form a coated composition; (b) drying the coated composition to form a dielectric layer; and (c) optionally applying a protective layer to the dielectric layer to form the dry film structure.

[0016] In another aspect, the disclosure features a method for producing a dielectric film on a substrate having a copper pattern, the method including depositing a dielectric film-forming composition described herein on a substrate having a copper pattern to form a dielectric film, wherein the difference in height between the highest point and the lowest point on a surface of the dielectric film is about 2 microns or less.

[0017] In yet another aspect, the present disclosure describes a method of producing a cured film, the method comprising exposing a photosensitive dielectric film described herein to electromagnetic radiation in the range of about 150 to about 600 nm, an electron beam, or X-rays; after said exposure, developing the dielectric film with a developer to obtain a pattern; and heating the patterned film to produce the cured film.

[0018] In yet another aspect, the disclosure features a three-dimensional object prepared by a method described herein. In some embodiments, the object includes at least two or three stacks of dielectric films. DETAILED DESCRIPTION OF THE INVENTION

[0019] Generally, the present disclosure relates to dielectric film-forming compositions. In some embodiments, the dielectric film-forming compositions described herein can be photosensitive. For example, the dielectric film-forming compositions described herein can be photosensitive to electromagnetic or actinic radiation in a wavelength range of about 150 nm to 600 nm (e.g., 405 nm), electron beam, or X-ray, thereby resulting in a solubility change (e.g., increased or decreased solubility) in an appropriate developer (e.g., TMAH solution).

[0020] In some embodiments, the present disclosure provides a dielectric film-forming composition that includes at least one (e.g., two, three, or four) resins (e.g., polymers such as dielectric polymers) and at least one (e.g., two, three, or four) acylgermanium compounds according to structure (I): [ka] In the formula, R 1 is C1~C 12 Alkyl, C2-C 12 Alkenyl, C4-C 18 Cycloalkyl, C6-C 22 Aryl or C6-C 22 Heteroaryl; R 2 , R 3 , R 4 Each of C1 to C 12 Alkyl, C2-C 12 Alkenyl, C4-C 18 Cycloalkyl, C6-C 22 Aryl, C6-C 22 heteroaryl, or —C(O)R, where R is C1-C4 alkyl, C5-C 12 Cycloalkyl, C6-C 18 Aryl or C6-C 18 and heteroaryl; and each of the alkyl, alkenyl, cycloalkyl, aryl, or heteroaryl independently is selected from at least one (e.g., two or three) of C1-C4 alkyl, halogen, C1-C4 haloalkyl, -OR 5 , -OC(O)R 5 , or -COOR 5 and optionally substituted by, wherein R 5 is H, C1-C4 alkyl, C5-C 12 Cycloalkyl, C6-C 18 Aryl or C6-C 18 In some embodiments, the acylgermanium compounds described herein may contain one acyl group (i.e., a monoacylgermanium compound), two acyl groups (i.e., a diacylgermanium compound), three acyl groups (i.e., a triacylgermanium compound), or four acyl groups (i.e., a tetraacylgermanium compound).

[0021] Examples of alkyl groups described herein include methyl, ethyl, propyl, isopropyl, and butyl. Examples of alkenyl groups described herein include vinyl and allyl. Examples of cycloalkyl groups described herein include cyclopentyl and cyclohexyl. Examples of aryl groups described herein include phenyl, naphthyl, pyrenyl, anthryl, and phenanthryl. Examples of heteroaryl groups described herein include furyl, furylene, fluorenyl, pyrrolyl, thienyl, oxazolyl, imidazolyl, thiazolyl, pyridinyl, pyrimidinyl, quinazolinyl, quinolyl, isoquinolyl, and indolyl.

[0022] Suitable examples of compounds of structure (I) include, but are not limited to, (2,4,6-trimethylbenzoyl)triethylgermanium, (2,4,6-trimethylbenzoyl)tripropylgermanium, (2,4,6-trimethylbenzoyl)tributylgermanium, (2,6-dimethoxybenzoyl)triethylgermanium, (2,6-dimethoxybenzoyl)tripropylgermanium, (2,6-dimethoxybenzoyl)tributylgermanium, bisbenzoyldiethylgermanium, bisbenzoyldipropylgermanium, bis(4-methoxybenzoyl)diethylgermanium, bis(2,4,6-trimethylbenzoyl)diethylgermanium, trisbenzoylethylgermanium, tris(2,4,6-trimethylbenzoyl)ethylgermanium, etc. A commercially available example of an acylgermanium compound is Ivocerin (i.e., bis(4-methoxybenzoyl)diethylgermanium). Other examples of such acylgermanium compounds are disclosed, for example, in US Pat. Nos. 7,605,190 and 9,532,930, the entire contents of which are incorporated herein by reference.

[0023] In some embodiments, the acylgermanium compound is present in an amount of about 0.05 wt% or more (e.g., about 0.1 wt% or more, about 0.2 wt% or more, about 0.4 wt% or more, about 0.5 wt% or more, about 0.6 wt% or more, about 0.8 wt% or more, about 1 wt% or more, about 1.5 wt% or more, or about 2 wt% or more) to about 20 wt% or less (e.g., about 18 wt% or less, about 16 wt% or less, about 15 wt% or less, about 14 wt% or less, about 12 wt% or less, about 10 wt% or less, about 8 wt% or less, about 6 wt% or less, about 5 wt% or less, about 4 wt% or less, about 2 wt% or less, or about 1 wt% or less), based on the weight of the solids of the dielectric film-forming composition described herein. As used herein, the weight of the solids of a dielectric film-forming composition refers to the total weight of solids in such composition (i.e., not including solvent).

[0024] Without being bound by theory, it is believed that dielectric film-forming compositions containing the acylgermanium compounds described herein (alone or in combination with an initiator different from the acylgermanium compound) can be developed at relatively long UV wavelengths (e.g., about 405 nm) to form dielectric films. Surprisingly, the dielectric films thus formed have significantly improved resolution and exceptional pattern shape while being environmentally benign.

[0025] The dielectric film-forming compositions described herein may optionally contain at least one (e.g., two, three, or four) radical initiators different from the acylgermaniums described herein. As used herein, radical initiator refers to a compound capable of generating free radicals that can initiate radical polymerization or crosslinking upon heating or irradiation with light in a certain wavelength range (e.g., about 150 nm (e.g., about 157 nm) or about 600 nm). In some embodiments, the wavelength range is selected such that the radical initiator absorbs but the radically polymerizable monomer does not substantially absorb. Examples of radical initiators are photoradical initiators (also referred to herein as photoinitiators) and thermal radical initiators (also referred to herein as thermal initiators). In some embodiments, photoradical initiators are preferred.

[0026] In some embodiments, the amount of the radical initiator (e.g., photoinitiator) is about 0.1 wt % or more (e.g., about 0.2 wt % or more, about 0.5 wt % or more, about 0.8 wt % or more, about 1 wt % or more, about 1.5 wt % or more, about 2 wt % or more, about 3 wt % or more, about 4 wt % or more, or about 5 wt % or more) to about 10 wt % or less (e.g., about 9 wt % or less, about 8 wt % or less, about 7 wt % or less, about 6 wt % or less, about 5 wt % or less, about 4 wt % or less, about 3 wt % or less, about 2 wt % or less, or about 1 wt % or less) based on the solids weight of the dielectric film-forming composition described herein.

[0027] In some embodiments, the photoinitiator is sensitive to radiation ranging from the ultraviolet radiation range to the visible range, hi some embodiments, the photoinitiator can be an activator that generates free radicals by some interaction with a photoexcited sensitizer.

[0028] An example of a photoinitiator is an oxime ester of structure (II): [ka] In the formula, R 11 and R 12each independently represents a substituted or unsubstituted C1-C 12 Alkyl, substituted or unsubstituted C4-C 18 Cycloalkyl, substituted or unsubstituted C6-C 22 Aryl or substituted or unsubstituted C6-C 22 Heteroaryl; R 13 is a UV-absorbing functional group (e.g., substituted or unsubstituted C6-C 22 Aryl or substituted or unsubstituted C6-C 22 In some embodiments, the alkyl, cycloalkyl, aryl, or heteroaryl is optionally substituted with at least one (e.g., two or three) C1-C4 alkyl, halogen, C1-C4 haloalkyl, -OR', -OC(O)R', or -COOR', where R' is H, C1-C4 alkyl, C5-C 12 Cycloalkyl, C6-C 18 Aryl or C6-C 18 It is heteroaryl.

[0029] Examples of oxime esters of formula (II) include, but are not limited to: [ka]

[0030] Another example of a photoinitiator is an organic compound of structure (III): [ka] wherein M is selected from the group consisting of titanium atoms, zirconium atoms, and hafnium atoms; R 14 and R 15 each independently represents a substituted or unsubstituted C1-C 12 Alkyl, substituted or unsubstituted C4-C 18 Cycloalkyl, substituted or unsubstituted C6-C 22 Aryl, substituted or unsubstituted C6-C 22 Heteroaryl, substituted or unsubstituted C6-C 22Heteroaryl and substituted or unsubstituted alkylsulfonyloxy (e.g., substituted or unsubstituted C1-C 12 In some embodiments, the alkyl, cycloalkyl, aryl, or heteroaryl is optionally substituted with at least one (e.g., two or three) C1-C4 alkyl, halogen, C1-C4 haloalkyl, -OR', -OC(O)R', or -COOR', where R' is H, C1-C4 alkyl, C5-C6 alkyl, C5-C6 haloalkyl, -OR', -OC(O)R', or -COOR'. 12 Cycloalkyl, C6-C 18 Aryl or C6-C 18 It is heteroaryl.

[0031] Commercially available examples of photoinitiators include, but are not limited to, IRGACURE-784, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04, and IRGACURE OXE 05, available from BASF; ADEKA OPTOMER N-1919, ADEKA ARKLS NCI-831, and ADEKA ARKLS NCI-930, available from ADEKA Corporation. Other examples of photoinitiators are disclosed, for example, in EP 3,492,982, the entire contents of which are incorporated herein by reference.

[0032] Examples of thermal initiators include, but are not limited to, benzoyl peroxide, cyclohexanone peroxide, lauroyl peroxide, tert-amyl peroxybenzoate, tert-butyl hydroperoxide, di(tert-butyl)peroxide, dicumyl peroxide, cumene hydroperoxide, succinic acid peroxide, di(n-propyl)peroxydicarbonate, 2,2-azobis(isobutyronitrile), 2,2-azobis(2,4-dimethylvaleronitrile), dimethyl-2,2-azobisisobutyrate, 4,4-azobis(4-cyanopentanoic acid), azobiscyclohexanecarbonitrile, 2,2-azobis(2-methylbutyronitrile), and the like.

[0033] Other examples of radical photopolymerization initiators include benzophenone derivatives such as benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, and fluorenone; acetophenone derivatives such as 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, and 1-hydroxycyclohexylphenyl ketone; thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, and diethylthioxanthone; benzil derivatives such as benzil, benzil dimethyl ketal, and benzyl β-methoxyethyl acetal; benzoin derivatives such as benzoin and benzoin methyl ether; benzoin, Benzoin derivatives such as benzoin methyl ether; oximes such as 1-phenyl-1,2-butanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-benzoyl)oxime, 3-diphenylpropanetrione-2-(o-ethoxycarbonyl)oxime, and 1-phenyl-3-ethoxypropanetrione-2-(o-benzoyl)oxime; N-arylglycines such as N-phenylglycine, peroxides such as benzoyl peroxide, and aromatic biimidazoles. These may be used alone or in a mixture of two or more.

[0034] In some embodiments, the dielectric film-forming compositions described herein may include at least one (e.g., two, three, or four) photosensitizers different from the acylgermanium compound, wherein the photosensitizer absorbs light within a wavelength range of about 150 nm to about 600 nm (e.g., about 405 nm). Examples of suitable photosensitizers that can be used in the dielectric film-forming compositions include benzophenone compounds, thioxanthone compounds, anthraquinone compounds, anthracene compounds, coumarin compounds, and mixtures thereof. Specific examples of photosensitizers include, but are not limited to, 9-methylanthracene, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, anthracenemethanol, acenaphthylene, thioxanthone, methyl-2-naphthyl ketone, 4-acetylbiphenyl, and 1,2-benzofluorene. Other examples of photosensitizers are disclosed, for example, in U.S. Patent Application Publication No. 2022 / 0171285, the entire contents of which are incorporated herein by reference. In some embodiments, the acylgermanium compounds described herein can function as photosensitizers.

[0035] In some embodiments, the amount of photosensitizer other than an acylgermanium compound is from about 0.01 wt % or more (e.g., about 0.05 wt % or more, about 0.1 wt % or more, or about 0.5 wt % or more) to about 1 wt % or less (e.g., about 0.8 wt % or less, about 0.6 wt % or less, about 0.5 wt % or less, about 0.4 wt % or less, about 0.2 wt % or less, or about 0.1 wt % or less) based on the solids weight of the dielectric film-forming composition described herein.

[0036] In some embodiments, the dielectric film-forming compositions described herein may optionally include at least one (e.g., two, three, or four) crosslinking agent, which may include an ethylenically unsaturated polymerizable compound (e.g., an ethylenically unsaturated photopolymerizable compound), a thiol compound, a siloxane compound, a metal-containing (meth)acrylate compound, or a mixture thereof.

[0037] In some embodiments, the crosslinking agent described herein may comprise a multifunctional thiol compound containing at least two thiol groups. Examples of such thiol compounds include, but are not limited to, trimethylolpropane tris(mercaptoacetate), pentaerythritol tetrakis(mercaptoacetate), trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), dipentaerythritol hexakis(3-mercaptopropionate), tris[2-(3-mercaptopropionyloxy)ethyl]isocyanurate, ethoxylated trimethylolpropane tri-3-mercaptopropionate, propylene glycol-3-mercaptopropionate 800, trimethylolpropane tris(4-sulfanylcyclohexanecarboxylate), pentaerythritol tetrakis(4-sulfanylcyclohexanecarboxylate), etc. Other examples of such thiol compounds are disclosed, for example, in US Pat. No. 9,695,284, the entire contents of which are incorporated herein by reference.

[0038] In some embodiments, the crosslinker described herein may comprise an ethylenically unsaturated polymerizable compound containing at least two (meth)acrylate groups. In some embodiments, the crosslinker may be 1,6-hexanediol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propoxylated (3) glycerol tri(meth)acrylate, ethoxylated bisphenol-A di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate. The ester compound is selected from the group consisting of methyl acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta- / hexa-(meth)acrylate, isocyanurate tri(meth)acrylate, bis(2-hydroxyethyl)-isocyanurate di(meth)acrylate, 1,3-butanediol tri(meth)acrylate, 1,4-butanediol tri(meth)acrylate, neopentyl glycol di(meth)acrylate, (meth)acrylate-modified urea-formaldehyde resin, (meth)acrylate-modified melamine-formaldehyde resin, and (meth)acrylate-modified cellulose. Other examples of such compounds are disclosed, for example, in U.S. Pat. Nos. 10,036,952 and 10,563,014, as well as U.S. Patent Application Publication No. 2015 / 0219990 and European Patent No. 3,492,982, the entire contents of which are incorporated herein by reference.

[0039] In some embodiments, the crosslinking agents described herein may include polyfunctional siloxane compounds containing at least two siloxane groups, such as disiloxane. Examples of such disiloxane compounds include, but are not limited to, 1,1,3,3-tetramethyldisiloxane, 1,1,3,3,5,5-hexamethyltrisiloxane, 1,2-bis(tetramethyldisiloxanyl)ethane, and the like. In some embodiments, the polyfunctional siloxane may be a cyclic compound of structure (IVa), where each R 22 are independently hydrogen or a C1-C4 alkyl group, and i is an integer from 0 to 3; or a silsesquioxane compound of structure (IVb), where each R 23 are independently -O-Si(R 24 )H group, and each R 24 are independently a C1 to C4 alkyl group. [ka]

[0040] In some embodiments, the crosslinking agent described herein can be a metal-containing (meth)acrylate (MCA) compound. As used herein, the term "(meth)acrylate" refers to both acrylate and methacrylate compounds. Examples of suitable MCAs include, but are not limited to, titanium tetra(meth)acrylate, zirconium tetra(meth)acrylate, hafnium tetra(meth)acrylate, titanium butoxide tri(meth)acrylate, titanium (meth)acryloxyethyl acetoacetate triisopropoxide, titanium tris(2-ethylhexanoate)(carboxyethyl(meth)acrylate), titanium dibutoxide di(meth)acrylate, titanium tributoxide (meth)acrylate, and titanium tetra(meth)acrylate. Acrylate, titanium oxide di(meth)acrylate, zirconium butoxide tri(meth)acrylate, zirconium dibutoxide di(meth)acrylate, zirconium tributoxide (meth)acrylate, zirconium oxide di(meth)acrylate, hafnium butoxide tri(meth)acrylate, hafnium dibutoxide di(meth)acrylate, hafnium tributoxide (meth)acrylate, hafnium oxide di(meth)acrylate, titanium (2,4 -pentanedionate)tri(carboxyethyl(meth)acrylate), titanium tetra(carboxyethyl(meth)acrylate), zirconium tetra(carboxyethyl(meth)acrylate), hafnium tetra(carboxyethyl(meth)acrylate), titanium butoxide tri(carboxyethyl(meth)acrylate), titanium dibutoxide di(carboxyethyl(meth)acrylate), titanium tributoxide(carboxyethyl(meth)acrylate), titanium oxide di(carboxyethyl(meth)acrylate), zirconium butoxide tri(carboxyethyl(meth)acrylate), zirconium dibutoxide di(carboxyethyl(meth)acrylate), zirconium tributoxide(carboxyethyl(meth)acrylate), zirconium oxide di(carboxyethyl(meth)acrylate), zirconium bis(2-ethylhexanoate)di(carboxyethyl(meth)acrylate), zirconium bis(2,4-pentanedionate)di(carboxyethyl(meth)acrylate), hafnium butoxide tri(carboxyethyl(meth)acrylate), hafnium dibutoxide di(carboxyethyl(meth)acrylate), hafnium tributoxide(carboxyethyl(meth)acrylate), and hafnium oxide di(carboxyethyl(meth)acrylate).

[0041] In some embodiments, the crosslinking agent described herein can be present in an amount of about 0.5% by weight or more (e.g., about 1% by weight or more, about 2% by weight or more, about 3% by weight or more, about 4% by weight or more, about 5% by weight or more, about 6% by weight or more, about 7% by weight or more, about 8% by weight or more, about 9% by weight or more, about 10% by weight or more) to about 25% by weight or less (e.g., about 24% by weight or less, about 22% by weight or less, about 20% by weight or less, about 18% by weight or less, about 16% by weight or less, about 15% by weight or less, about 14% by weight or less, about 12% by weight or less, about 10% by weight or less, about 8% by weight or less, about 6% by weight or less, or about 5% by weight or less), based on the solids weight of the dielectric film-forming composition described herein.

[0042] In some embodiments, the dielectric film-forming compositions described herein include at least one (e.g., two, three, or four) resins (e.g., polymer resins). In some embodiments, the resins may include fully imidized polyimides, optionally containing functional groups; cyclized rubbers; cyclic olefin polymers, optionally containing functional groups; polyphenylene ethers; acrylic compounds; cyanate ester compounds; polybenzoxazole precursor polymers; novolac polymers; epoxy phenol novolac polymers; or alkali-soluble polyimides. In some embodiments, the functional groups on the polymer may be acidic groups, such as carboxylic acid groups, hydroxyl groups, or sulfonic acid groups.

[0043] In some embodiments, the fully imidized polyimides described herein may be polymers of structure (V): [ka] In the formula, R 31 is an end group (e.g., a functional or non-functional end group), n is an integer greater than 5 (e.g., 5 to 100), B1 is the core of the precursor diamine, and A1 is the core of the precursor dianhydride. As used herein, "core" when referring to a precursor diamine refers to the portion between the two amine functional groups. When referring to a precursor dianhydride, "core" refers to the portion between the two anhydride functional groups. Examples of such diamines and dianhydrides are disclosed, for example, in U.S. Pat. No. 9,695,284, the entire contents of which are incorporated herein by reference. Functional or non-functional acid anhydrides or acid chlorides can be used to end-capping unreacted amine functional groups on amino-terminated polyamic acids.

[0044] Examples of suitable diamines that can be used to prepare polymers of structure (V) include, but are not limited to, 1-(4-aminophenyl)-1,3,3-trimethylindan-5-amine (also known as 4,4'-[1,4-phenylene-bis(1-methylethylidene)]bisaniline, 1-(4-aminophenyl)-1,3,3-trimethyl-2H-inden-5-amine, 1-(4-aminophenyl)-1,3,3-trimethyl-indan-5-amine, and [1-(4-aminophenyl)-1,3,3-trimethyl-inden-5-iamine]. amine), 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-inden-5-amine, 5-amino-6-methyl-1-(3'-amino-4'-methylphenyl)-1,3,3-trimethylindan, 4-amino-6-methyl-1-(3'-amino-4'-methylphenyl)-1,3,3-trimethylindan, 5,7-diamino-1,1-dimethylindan, 4,7-diamino-1,1-dimethylindan, 5,7-diamino-1,1,4-trimethylindan, 5,7-diamino-1,1,6-trimethylindan, Chilindan, 5,7-diamino-1,1-dimethyl-4-ethylindan, p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 3-methyl-1,2-benzene-diamine, 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,2-diaminocyclohexane, 1,4-diaminocyclohexane, 1,3-cyclohexane Bis(methylamine), 5-amino-1,3,3-trimethylcyclohexanemethanamine, 2,5-diaminobenzotrifluoride, 3,5-diaminobenzotrifluoride, 1,3-diamino-2,4,5,6-tetrafluorobenzene, 4,4'-oxydianiline, 3,4'-oxydianiline, 3,3'-oxydianiline, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 4,4'-isopropylidenedianiline, 4,4'-diaminodiphenylmethane, 2,2-bis(4-aminophenyl)propane, 4,4'-Diaminodiphenylpropane, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 4-aminophenyl-3-aminobenzoate, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)benzidine, 3,3'-bis(trifluoromethyl)benzidine, 2,2-bis[4-(4-aminophenoxyphenyl)]hexafluoropropane, 2,2-bis( 3-amino-4-methylphenyl)-hexafluoropropane, 2,2-bis(3-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 1,3-bis-(4-aminophenoxy)benzene, 1,3-bis-(3-aminophenoxy)benzene, 1,4-bis-(4-aminophenoxy)benzene, 1,4-bis-(3-aminophenoxy)benzene, 1-(4-aminophenoxy)-3-(3-aminophenoxy)benzene, 2,2'-bis-(4-phenoxyaniline) isopropylidene, bis(p-β-amino-t-butylphenyl) ether, p-bis-2-(2-methyl-4-aminopentyl)benzene, p-bis(1,1-dimethyl-5-aminopentyl)benzene, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diaminobenzophenone, 3'-dichlorobenzidine, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 4,4'-[1,3-phenylenebis(1-methyl-ethylidene)]bisaniline, 4,4' 1,4-phenylenebis(1-methyl-ethylidene)]bisaniline, 2,2-bis[4-(4-aminophenoxy)phenyl]sulfone, 2,2-bis[4-(3-aminophenoxy)benzene], 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3'-bis(3-aminophenoxy)benzene, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, and 9H-fluorene-2,6-diamine. Any of these diamines may be used individually or in any suitable ratio in combination to form the polyimides described herein.

[0045] Examples of suitable dianhydrides that can be used to prepare polymers of structure (V) include, but are not limited to, 1-(3',4'-dicarboxyphenyl)-1,3,3-trimethylindane-5,6-dicarboxylic dianhydride, 1-(3',4'-dicarboxyphenyl)-1,3,3-trimethylindane-6,7-dicarboxylic dianhydride, 1-(3',4'-dicarboxyphenyl)-3-methylindane-5,6-dicarboxylic dianhydride, 1-( 3',4'-Dicarboxyphenyl)-3-methylindan-6,7-dicarboxylic dianhydride, pyromellitic dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, 2,3,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene- 1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, phenanthrene-8,9,10-tetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride, thiophene-2,3,4,5-tetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, butane-1,2,3,4-tetracarboxylic dianhydride tetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, cyclobutane-1,2,3,4-tetracarboxylic dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride, norbornane-2,3,5,6-tetracarboxylic dianhydride, bicyclo[2.2.2]oct-7-ene-3,4,8,9-tetracarboxylic dianhydride, tetracyclo[4.4.1.0]oct-1-ene-3,4,8,9-tetracarboxylic dianhydride 2,5 .0 7,10]undecane-1,2,3,4-tetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 2,3,3',4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 2,2',3,3'-diphenylsulfonetetracarboxylic dianhydride, 2,3,3',4'-diphenylsulfonetetracarboxylic dianhydride, 3, Examples of suitable tetracarboxylic dianhydrides include 3',4,4'-diphenylethertetracarboxylic dianhydride, 2,2',3,3'-diphenylethertetracarboxylic dianhydride, 2,3,3',4'-diphenylethertetracarboxylic dianhydride, 2,2-[bis(3,4-dicarboxyphenyl)]hexafluoropropane dianhydride, ethylene glycol bis(anhydrotrimellitate), and 5-(2,5-dioxotetrahydro)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride. Any of these tetracarboxylic dianhydrides may be used alone or in any suitable ratio in combination to form the polyimides described herein.

[0046] In some embodiments, the fully imidized polyimides described herein are at least about 90% imidized (e.g., at least about 95%, at least about 98%, at least about 99%, or about 100%).

[0047] In some embodiments, the weight average molecular weight of the fully imidized polyimide is about 20,000 daltons or more (e.g., about 25,000 daltons or more, about 30,000 daltons or more, about 35,000 daltons or more, about 40,000 daltons or more, about 45,000 daltons or more, about 50,000 daltons or more, or about 55,000 daltons or more) and / or about 100,000 daltons or less (e.g., about 95,000 daltons or less, about 90,000 daltons or less, about 85,000 daltons or less, about 80,000 daltons or less, about 75,000 daltons or less, about 70,000 daltons or less, about 65,000 daltons or less, or about 60,000 daltons or less).

[0048] In some embodiments, the fully imidized polyimide is prepared by reacting at least one diamine with at least one tetracarboxylic dianhydride. In some embodiments, the resulting polymer is soluble in the organic solvents of the present disclosure to facilitate the formation of a dielectric film, such as a dielectric film having a planarized surface (e.g., the difference between the highest and lowest points on the top surface of the dielectric film is less than about 2 microns). Examples of fully imidized polyimides are known in the art and are described, for example, in U.S. Patent Application Publication No. 2019 / 0077913, the entire contents of which are incorporated herein by reference.

[0049] Methods for synthesizing end-capped and non-end-capped PI precursor polymers are known to those skilled in the art, and examples of such methods and PI precursor polymers are described, for example, in U.S. Pat. Nos. 2,731,447, 3,435,002, 3,856,752, 3,983,092, 4,026,876, 4,040,831, 4,579,809, 4,629,777, 4,656,116, 4,960,860, and 4,985, the entire contents of which are incorporated herein by reference. ,529, U.S. Patent No. 5,006,611, U.S. Patent No. 5,122,436, U.S. Patent No. 5,252,534, U.S. Patent No. 5,4789,15, U.S. Patent No. 5,773,559, U.S. Patent No. 5,783,656, U.S. Patent No. 5,969,055, U.S. Patent No. 9,617,386, and U.S. Patent Application Publication Nos. 2004 / 0265731, 2004 / 0235992, and 2007 / 0083016.

[0050] In some embodiments, the fully imidized polyimides described herein may be alkali-soluble polyimides having at least one (e.g., two or three) functional groups (e.g., at one or both ends of the polymer backbone or on a side chain) such as a carboxylic acid group, a hydroxyl group (e.g., a phenolic hydroxyl group), a sulfonic acid group, or a thiol group. As used herein, the term "alkali-soluble" means that the solubility in a 2.38 weight percent aqueous tetramethylammonium hydroxide solution at 25°C is about 0.1 g / 100 mL or greater.

[0051] In some embodiments, the polymeric resin suitable for the dielectric film-forming compositions described herein may include at least one (e.g., two, three, or four) dielectric polymers, such as a dielectric polymer containing an epoxy resin, a novolac resin, or a mixture of an epoxy resin and a novolac resin, a polybenzoxazole (PBO) precursor polymer, or a mixture thereof.

[0052] Examples of suitable epoxy resins that can be used as dielectric film materials are known to those skilled in the art and include, for example, those disclosed in U.S. Pat. No. 4,882,245 and U.S. Patent Application Publication No. 2006 / 0257785, the entire contents of which are incorporated herein by reference.

[0053] Suitable examples of novolac polymers described herein include those containing at least one photoactive o-quinone diazide compound, and are known to those skilled in the art.Examples of such novolac polymers are disclosed in U.S. Patent Nos. 5,413,894, 5,306,594, 4,959,292, 8,334,092 and 8,492,067, and U.S. Patent Application Publication Nos. 2012 / 0296053 and 2012 / 0052438, the entire contents of which are incorporated herein by reference.

[0054] In some embodiments, the resin in the dielectric film-forming composition described herein can include a polyamic ester. The polyamic ester of the present disclosure has a number average degree of polymerization of 5 to 100 and is synthesized by polycondensation of monomers A and B as follows: (1) [ka] Monomer A can be obtained by the reaction of a dianhydride compound with an alcohol R'OH to give a diester-diacid, followed by conversion of the diacid-diester to a diester-diacid chloride with a suitable reagent (Equation 2). [ka] The R group represents a tetravalent aromatic group containing at least one six-membered carbon ring, and four carbonyl groups are directly bonded to different carbon atoms of R, and each of two pairs of four carbonyl groups is bonded to adjacent carbon atoms. The dianhydride compound may be the same as that shown above. The tetracarboxylic dianhydrides may be used alone or in combination, and the selection of the dianhydride compound is not limited to the compounds listed above. The R' group contains at least one unsaturated group, which may be a vinyl group, an allyl group, an acrylyl group, a methacryl group, an acetylene group, a cyano group, or other suitable radiation-crosslinkable group.

[0055] Monomer B is a divalent diamine. Suitable diamines are the same as those discussed above.

[0056] In some embodiments, the resin in the dielectric film-forming composition described herein may include a curable PBO (polybenzoxazole) precursor, such as a chemically amplified PBO precursor. The aqueous base solubility of the PBO precursor is reduced by protecting the aromatic hydroxyl groups in the PBO precursor with acid-labile groups. Restoration of the polymer's alkaline solubility is achieved by the action of an acid generated by photolysis of a photoacid generator (PAG). The protecting group may be any suitable acid-labile group, such as an acetal, ketal, carbonate, ether, silyl ether, t-butyl ester-containing moiety, or a combination thereof. Using this concept, a positive-acting photosensitive resin composition containing a PBO precursor with acid-labile functional groups, a photoacid generator, and a solvent may be prepared and used to form a dielectric film. In some embodiments, after photolithography processing, the patterned layer may be converted into a heat-resistant polybenzoxazole coating by applying additional heat.

[0057] In some embodiments, the PBO precursors described herein may include an acid-labile functional group and have the following structure (VI): [ka] In the formula, k1 is an integer of 0, 1, or 2, k2 is an integer of 0 or 1, and the sum of k1 and k2 is 0 or 2; Ar1 ​​is a tetravalent aromatic group, aliphatic group, or heterocyclic group, or a mixture of a tetravalent aromatic group, aliphatic group, or heterocyclic group and a divalent aromatic group, aliphatic group, or heterocyclic group, the proportion of divalent groups in Ar1 is 0 to 60 mol %, and the sum of the tetravalent groups in Ar1 and the divalent groups in Ar1 is 100 mol %; Ar2 is a divalent aromatic group, aliphatic group, or heterocyclic group, or a siloxane group; D is a monovalent acid labile group that, in combination with the oxygen atom to which it is bonded, is selected from the group consisting of acetal, ketal, carbonate, ether, t-butyl ester group-containing moiety, and combinations thereof; and n is an integer of 20 to 200.

[0058] In some embodiments, Ar1 is selected from the following moieties: [ka] wherein X1 is -O-, -S-, -C(CF3)2-, -C(CH3)2-, -CH2-, -SO2-, -NHCO-, -C(O)-, -C(O)-C(O)-, -C(O)O-, or -(CH2) m -Si(Z)2-O-Si(Z)2-(CH2) m -, Z is H or C1-C6 alkyl, and m is an integer of 1-6.

[0059] In some embodiments, Ar2 is the following moiety: [ka] wherein X2 is -C(O)-C(O)-, -C(O)O-, or -(CH2) p -Si(Z)2-O-Si(Z)2-(CH2) p -, Z is H or C1-C6 alkyl, and p is an integer from 1 to 6. In some embodiments, the PBO precursor can contain one or more different Ar1 and Ar2 groups.

[0060] In some embodiments, D is any suitable monovalent acid-labile group, such as an acetal, ketal, carbonate, ether, silyl ether, t-butyl ester-containing moiety, and combinations thereof. For example, D can be, but is not limited to, a moiety of the following formula: [ka] In some embodiments, D can be a monovalent quinone diazide ester compound formed between a PBO precursor having one or more phenolic hydroxyl groups and 1,2-naphthoquinone diazide-4-sulfonic acid, 1,2-naphthoquinone diazide-5-sulfonic acid, or a mixture thereof.

[0061] In some embodiments, when the dielectric film-forming composition described herein includes a protected PBO precursor having an acid-labile functional group, the composition can also include a photoacid generator and a solvent. Optionally, the composition may contain a photosensitizer, adhesion promoter, leveling agent, or other additives. After exposure to light, the photogenerated acid catalyzes the deprotection of the protected PBO precursor, converting it to an aqueous base-soluble PBO precursor, as shown in Reaction (1). [ka]

[0062] Generally, any suitable photoacid generator compound may be used to remove the acid-labile functional group. For example, suitable photoacid generator compounds include triazine compounds, sulfonates, disulfones, onium salts, and mixtures thereof. Examples of suitable onium salts include iodonium, sulfonium, phosphonium, diazonium, sulfoxonium, and mixtures thereof.

[0063] The PBO precursor having an acid labile functional group represented by formula (VI) can be prepared by reacting the PBO precursor with a compound represented by formula R 1 =CH-OR 2 and a vinyl ether having the formula: 1 is (a) a linear, branched, or cyclic alkylene group having 1 to 10 carbon atoms, (b) a linear, branched, or cyclic haloalkylene group having 1 to 10 carbon atoms, or (c) an aralkylene group; R 2 is a linear, branched, or cyclic alkyl group, an aralkyl group, or a linear or branched alkyl group having 1 to 10 carbon atoms, including a cycloalkyl group, a substituted cycloalkyl group, an aryl group, and a substituted aryl group. Another suitable method for preparing the PBO precursor having the acid labile functional group is by reacting the PBO precursor with di-t-butyl dicarbonate in the presence of a base. The PBO precursor having the acid labile functional group can also be synthesized by reacting the PBO precursor, an alcohol, and t-butyl vinyl ether in the presence of an acid.

[0064] In some embodiments, the PBO precursors described herein may be free of acid-labile functional groups and may have structure (VII) shown below: [ka] In the formula, Ar1, Ar 2 , and n are defined above.

[0065] Acetal-protected PBO precursors can be prepared by the acid-catalyzed addition reaction of a vinyl ether with a PBO precursor. Any suitable acid catalyst may be used in the reaction. Examples of suitable acid catalysts include hydrochloric acid, p-toluenesulfonic acid, and pyridinium p-toluenesulfonate. The acid catalyst may be added in an amount ranging from about 0.001% by weight to about 3.0% by weight. Several vinyl ethers with various activation energies for acid-induced deprotection may be used in this reaction. In some embodiments, acetal-protected PBO precursors can be prepared using a process comprising the acid-catalyzed reaction of a PBO precursor, t-butyl vinyl ether, and an alkyl alcohol, alkylene alcohol, cycloalkyl alcohol, or arylalkyl alcohol.

[0066] Methods for synthesizing polybenzoxazole precursor polymers are known to those skilled in the art, and examples of such methods and PBO precursor polymers are disclosed, for example, in U.S. Patent Nos. 6,143,467, 7,195,849, 7,129,011, and 9,519,216, the entire contents of which are incorporated herein by reference.

[0067] In some embodiments, the resin in the dielectric film-forming compositions described herein can include at least one (e.g., two or three) polyphenylene ether (PPE). In some embodiments, the PPE can be a polymer of structure (VIII): [ka] In the formula, each R 51 each independently represents an aliphatic hydrocarbon group having 1 to 6 carbon atoms; 52 each independently represents a hydrogen atom, a halogen atom, or an aliphatic hydrocarbon group having 1 to 6 carbon atoms; 53 each independently represents an ethylenically unsaturated organic group; n1 and n2 each independently represents an integer of 0 to 20; and P represents a divalent group.

[0068] In some embodiments, the PPE comprises at least one vinylbenzyl ether group or at least one meth(acrylate) group (e.g., a terminal group R 53 Examples of suitable PPE are disclosed, for example, in U.S. Patent Nos. 9,402,310, 10,774,210, and 3,306,874, the entire contents of which are incorporated herein by reference.

[0069] In some embodiments, the resin in the dielectric film-forming composition described herein can include at least one (e.g., two or three) cyclized rubber. In some embodiments, the cyclized rubber is selected from the group of cyclized polydienes. In some embodiments, the cyclized polydienes include homopolymers of conjugated dienes such as isoprene, butadiene, and pentadiene. In other embodiments, the cyclized polydienes include copolymers of such conjugated dienes with olefins, styrenes, or acrylates. In some embodiments, the cyclization of the rubber occurs under the influence of heat, light, ultraviolet light, or nuclear radiation and / or in the presence of a cation donor catalyst (e.g., a mineral acid, an organic acid, or a Lewis acid). For example, two adjacent polymer structural units can participate in a cis-olefin-catalyzed cyclization reaction to form a monocyclic structure, concomitantly resulting in the elimination of one double bond. Generally, further cyclization steps result in the formation of bicyclic or tricyclic structures. Gradually, the continued cyclization of the cis-polydienes results in a decrease in unsaturation and elasticity, and an increase in toughness. Generally, polyisoprene exhibits a higher cyclization efficiency than polybutadiene. By controlling the temperature, catalyst concentration, and reaction time, a degree of cyclization of about 50% to about 95% can be achieved. Examples of such cyclization processes are described, for example, in U.S. Pat. Nos. 4,678,841 and 4,248,986, and European Patent No. 0063043, the contents of which are incorporated herein by reference. These cyclized rubbers can be used alone or in combination of two or more types. In some embodiments, the cyclized rubber is polyisoprene.

[0070] In some embodiments, the resin in the dielectric film-forming composition described herein can include at least one (e.g., two or three) cyanate ester compound (e.g., a cyanate ester compound having at least two cyanate groups in one molecule).

[0071] In some embodiments, the cyanate ester compounds described herein may have structure (IX): [ka] wherein m is an integer of at least 2 (m≧2), Ar is a substituted or unsubstituted aromatic organic group, and the cyanate ester group is directly bonded to the substituted or unsubstituted aromatic organic group. In some embodiments, the aromatic organic group is optionally substituted with at least one (e.g., two or three) C1-C4 alkyl, halogen, C1-C4 haloalkyl, —OR′, —OC(O)R′, or —COOR′, where R′ is H, C1-C4 alkyl, C5-C 12 Cycloalkyl, C6-C 18 Aryl or C6-C 18 It is heteroaryl.

[0072] In some embodiments, the cyanate ester compounds described herein may have the structure (X): [ka] In the formula, R is a hydrogen atom, a C1-C3 alkyl group, a fully or partially halogen-substituted C1-C3 alkyl group, or a halogen atom; X is a single bond, an O or S atom, a -(C=O)-, -(C=O)-O-, -O-(C=O)-, -(S=O)-, -(SO2)-, or -CH2CH2-O- group, a substituted or unsubstituted C1-C 10 an alkylene group, a partially or fully fluorinated C1-C4 alkylene group, or a substituted or unsubstituted C3-C 10 It is a cycloalkylene group.

[0073] Specific examples of suitable cyanate ester compounds include 2-bis(4-cyanatophenyl)propane, hexafluorobisphenol A dicyanate, bis(4-cyanato-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatophenyl-1-(methylethylidene))benzene, bis(4-cyanatophenyl)thioether, bis(4-cyanatophenyl)ether, and polyfunctional cyanate resins derived from phenol novolac, cresol novolac, or dicyclopentadiene-containing phenolic resins. Other examples of such cyanate ester compounds are described, for example, in U.S. Pat. Nos. 3,595,900, 4,894,414, and 4,785,034, and U.S. Patent Application Publication Nos. 2022 / 0002463 and 2022 / 0127459, the contents of which are incorporated herein by reference. In some embodiments, the weight average molecular weight of the cyanate ester resin or polymer is, but is not limited to, about 500 daltons or more (e.g., about 600 daltons or more) to about 4,500 daltons or less (e.g., about 3,000 daltons or less).

[0074] Without being bound by theory, it is believed that the cyanate ester compounds can cyclize and / or crosslink thermally or under irradiation (e.g., with or without a catalyst) to form an interpenetrating network with the dielectric polymer in the dielectric film-forming compositions described herein. Further, without being bound by theory, it is believed that the inclusion of cyanate ester compounds in the dielectric film-forming compositions described herein can lower the dielectric constant (K) and / or dissipation factor (DF) of films formed from the compositions.

[0075] In some embodiments, the resin of the present disclosure is a polyimide precursor. In some embodiments, the polyimide precursor is a heterocycle-containing polyimide precursor, and the heterocycle-containing polymer precursor is selected from a polyimide (PI) precursor comprising formula (3): [ka] In the formula, A1 and A2 each independently represent an oxygen atom or NH, R111 represents a divalent organic group, R115 represents a tetravalent organic group, and R113 and R114 each independently represent a hydrogen atom or a monovalent organic group.

[0076] In some embodiments, the amount of the resin or dielectric polymer is about 0.1 wt % or more (e.g., about 0.5 wt % or more, about 1 wt % or more, about 2 wt % or more, about 5 wt % or more, about 10 wt % or more, about 15 wt % or more, or about 20 wt % or more) and / or about 55 wt % or less (e.g., about 50 wt % or less, about 45 wt % or less, about 40 wt % or less, about 35 wt % or less, about 30 wt % or less, about 25 wt % or less, about 20 wt % or less, about 15 wt % or less, or about 10 wt % or less) based on the solids weight of the dielectric film-forming composition described herein.

[0077] In some embodiments, the dielectric film-forming compositions described herein may contain at least one (e.g., two, three, or four) photoacid generator or photobase generator, or a mixture of at least one photoacid generator and at least one photobase generator. For example, if the dielectric film-forming composition includes a photopolymer having an acid-labile functional group, the composition may include a photoacid generator (such as those described above) to remove the acid-labile functional group and create a solubility contrast. As another example, if the dielectric film-forming composition includes a photopolymer having a base-labile functional group (e.g., an epoxy group), the composition may include a photobase generator to remove the base-labile functional group and create a solubility contrast. Examples of suitable photobase generators include 9-anthrylmethyl N,N-diethylcarbamate (WPBG-018), 1,2-dicyclohexyl-4,4,5,5-tetramethylbiguanidinium, n-butyltriphenylborate (WPBG-300), and the like. In some embodiments, the photoacid generator or photobase generator described herein can be in an amount of about 0.1 wt % or more (e.g., about 0.2 wt % or more, about 0.4 wt % or more, about 0.5 wt % or more, about 0.6 wt % or more, about 0.8 wt % or more, or about 1 wt % or more) to about 5 wt % or less (e.g., about 4 wt % or less, about 3 wt % or less, about 2 wt % or less, or about 1 wt % or less) based on the solids weight of the dielectric film-forming composition described herein.

[0078] In some embodiments, the dielectric film-forming compositions described herein may optionally further comprise an organic solvent or a mixture of (e.g., two, three, or four) organic solvents. Examples of organic solvents suitable for the dielectric film-forming compositions described herein include, but are not limited to, alkylene carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate, and glycerin carbonate; lactones such as γ-butyrolactone, ε-caprolactone, γ-caprolactone, and γ-valerolactone; cycloketones such as cyclopentanone and cyclohexanone; linear ketones such as methyl ethyl ketone (MEK) and methyl isobutyl ketone (MIBK); esters such as n-butyl acetate; ester alcohols such as ethyl lactate; and ether alcohols such as tetrahydrofurfuryl alcohol. ether esters such as (tetrahydrofuran-2-yl)methyl acetate, methyl-3-methoxypropionate, ethyl-3-ethoxypropionate, and 3-methoxybutyl acetate; glycol esters such as propylene glycol methyl ether acetate; glycol ethers such as propylene glycol methyl ether (PGME); cyclic ethers such as tetrahydrofuran (THF); pyrrolidones such as N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, or N-butyl-2-pyrrolidone or TamiSolve™ NxG; and dialkyl sulfoxides such as dimethyl sulfoxide.

[0079] In some embodiments, the total amount of the solvent is about 20% by weight or more (e.g., about 25% by weight or more, about 30% by weight or more, about 35% by weight or more, about 40% by weight or more, about 45% by weight or more, about 50% by weight or more, about 55% by weight or more, about 60% by weight or more, or about 65% by weight or more) and / or about 98% by weight or less (e.g., about 95% by weight or less, about 90% by weight or less, about 85% by weight or less, about 80% by weight or less, about 75% by weight or less, about 70% by weight or less, or about 60% by weight or less), based on the total weight of the dielectric film-forming composition described herein.

[0080] In some embodiments, the dielectric film-forming compositions described herein optionally include at least one (e.g., two, three, or four) filler (e.g., inorganic filler or inorganic particle). In some embodiments, the inorganic filler is selected from the group consisting of silica, alumina, titania, zirconia, hafnium oxide, CdSe, CdS, CdTe, CuO, zinc oxide, lanthanum oxide, niobium oxide, tungsten oxide, strontium oxide, calcium titanium oxide, sodium titanate, barium sulfate, barium titanate, barium zirconate, and potassium niobate. In some embodiments, the inorganic filler is in the form of particles having an average particle size of about 0.1 to 2.0 microns. In some embodiments, the filler is an inorganic particle containing a ferromagnetic material. Suitable ferromagnetic materials include elemental metals (such as iron, nickel, and cobalt) or their oxides, sulfides, and oxyhydroxides, as well as awaruite (NiFe), wairauite (CoFe), Co 17 Sm2 and Nd2Fe 14 Examples include intermetallic compounds such as B.

[0081] In some embodiments, the amount of the inorganic filler (e.g., silica filler) is about 1 wt % or more (e.g., about 2 wt % or more, about 5 wt % or more, about 8 wt % or more, or about 10 wt % or more) and / or about 30 wt % or less (e.g., about 25 wt % or less, about 20 wt % or less, or about 15 wt % or less) based on the solids weight of the dielectric film-forming composition described herein.

[0082] In some embodiments, the dielectric film-forming compositions described herein may optionally further comprise at least one (e.g., two, three, or four) adhesion promoter. Suitable adhesion promoters are described in "Silane Coupling Agent," Edwin P. Plueddemann, 1982, Plenum Press, New York. Other examples of such adhesion promoters are disclosed, for example, in U.S. Pat. Nos. 10,036,952 and 10,563,014, U.S. Patent Application Publication No. 2015 / 0219990, and European Patent No. 3,492,982, the entire contents of which are incorporated herein by reference.

[0083] In some embodiments, the optional adhesion promoter is present in an amount of about 0.5 wt % or more (e.g., about 0.8 wt % or more, about 1 wt % or more, or about 1.5 wt % or more) and / or about 4 wt % or less (e.g., about 3.5 wt % or less, about 3 wt % or less, about 2.5 wt % or less, or about 2 wt % or less) based on the solids weight of the dielectric film-forming composition described herein.

[0084] In some embodiments, the dielectric film-forming compositions described herein may optionally contain at least one (e.g., two, three, or four) surfactant. Examples of suitable surfactants include, but are not limited to, those described in Japanese Patent Application Laid-Open Nos. 62-36663, 61-226746, 61-226745, 62-170950, 63-34540, 7-230165, 8-62834, 9-54432, and 9-5988, the entire contents of which are incorporated herein by reference.

[0085] In some embodiments, the amount of surfactant is about 0.005 wt % or more (e.g., about 0.01 wt % or more or about 0.1 wt % or more) and / or about 1 wt % or less (e.g., about 0.5 wt % or less or about 0.2 wt % or less) based on the solids weight of the dielectric film-forming composition described herein.

[0086] In some embodiments, the dielectric film-forming compositions described herein may optionally contain at least one (e.g., two, three, or four) corrosion inhibitor. Examples of suitable corrosion inhibitors include triazole compounds, imidazole compounds, and tetrazole compounds. Triazole compounds may include triazole, benzotriazole, substituted triazole, and substituted benzotriazole. Examples of triazole compounds include, but are not limited to, 1,2,4-triazole, 1,2,3-triazole, or triazoles substituted with substituents such as C1-C8 alkyl groups (e.g., 5-methyltriazole), amino groups, thiol groups, mercapto groups, imino groups, carboxy groups, and nitro groups. Specific examples include benzotriazole, tolyltriazole, 5-methyl-1,2,4-triazole, 5-phenyl-benzotriazole, 5-nitro-benzotriazole, 3-amino-5-mercapto-1,2,4-triazole, hydroxybenzotriazole, 2-(5-amino-pentyl)-benzotriazole, 1-amino-1,2,3-triazole, 1-amino-5-methyl-1,2,3-triazole, 3-amino-1,2,4-triazole, 3-mercapto-1,2,4-triazole, 3-isopropyl-1,2,4-triazole, 5-phenylthiol-benzotriazole, halo-benzotriazole (halo = F, Cl, Br, or I), naphthotriazole, and the like. Examples of imidazoles include, but are not limited to, 2-alkyl-4-methylimidazole, 2-phenyl-4-alkylimidazole, 2-methyl-4(5)-nitroimidazole, 5-methyl-4-nitroimidazole, 4-imidazolemethanol hydrochloride, and 2-mercapto-1-methylimidazole. Examples of tetrazoles include 1-H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole, 1-phenyl-5-mercapto-1H-tetrazole, 5,5'-bis-1H-tetrazole, 1-methyl-5-ethyltetrazole, 1-methyl-5-mercaptotetrazole, 1-carboxymethyl-5-mercaptotetrazole, and the like.If used, the amount of optional corrosion inhibitor is about 0.1 wt % or more (e.g., about 0.2 wt % or more or about 0.5 wt % or more) and / or about 3.0 wt % or less (e.g., about 2.0 wt % or less or about 1.0 wt % or less) based on the solids weight of the dielectric film-forming composition described herein.

[0087] In some embodiments, the dielectric film-forming compositions described herein include other optional ingredients, such as one or more (e.g., two, three, or four) dyes, pigments, plasticizers, or antioxidants. Examples of such ingredients are described, for example, in U.S. Patent Application Publication No. 2022 / 0127459, the entire contents of which are incorporated herein by reference.

[0088] In some embodiments, a dielectric film can be prepared from a dielectric film-forming composition described herein by a method comprising the steps of: (a) coating a dielectric film-forming composition described herein onto a substrate (e.g., a semiconductor substrate) to form a dielectric film; and (b) optionally baking the film at an elevated temperature (e.g., from about 50°C to about 150°C) for a period of time (e.g., from about 20 seconds to about 600 seconds).

[0089] Coating methods for preparing dielectric films include, but are not limited to, (1) spin coating, (2) spray coating, (3) roll coating, (4) rod coating, (5) rotary coating, (6) slit coating, (7) compression coating, (8) curtain coating, (9) die coating, (10) wire bar coating, (11) knife coating, and (12) dry film lamination. In the coating methods (1) to (11), the dielectric film-forming composition is typically provided in the form of a solution. Those skilled in the art will select the appropriate solvent type and solvent concentration depending on the type of coating.

[0090] The substrate may have a circular, square, or rectangular shape, such as a wafer or panel of various sizes. Examples of suitable substrates are epoxy molding compound (EMC), silicon, glass, copper, stainless steel, copper clad laminate (CCL), aluminum, silicon oxide, and silicon nitride. The substrate may be flexible, such as polyimide, PEEK, polycarbonate, and polyester film. The substrate may have surface-mounted or embedded chips, dyes, or packages. The substrate may be sputtered or pre-coated with a combination of seed and passivation layers. In some embodiments, the substrate referred to herein may be a semiconductor substrate. As used herein, a semiconductor substrate is a substrate (e.g., a silicon or copper substrate or wafer) that will become part of a final electronic device.

[0091] The thickness of the dielectric film of the present disclosure is not particularly limited. In some embodiments, the dielectric film has a film thickness of about 1 micron or more (e.g., about 2 microns or more, about 3 microns or more, about 4 microns or more, about 5 microns or more, about 6 microns or more, about 8 microns or more, about 10 microns or more, about 15 microns or more, about 20 microns or more, or about 25 microns or more) and / or about 100 microns or less (e.g., about 90 microns or less, about 80 microns or less, about 70 microns or less, about 60 microns or less, about 50 microns or less, about 40 microns or less, or about 30 microns or less). In some embodiments, the thickness of the dielectric film is less than about 5 microns (e.g., less than about 4.5 microns, less than about 4.0 microns, less than about 3.5 microns, less than about 3.0 microns, less than about 2.5 microns, or less than about 2.0 microns).

[0092] In some embodiments, when the dielectric film-forming composition is photosensitive, the method of preparing a patterned photosensitive dielectric film comprises converting the photosensitive dielectric film into a patterned dielectric film by a lithographic process, In such cases, the conversion may comprise exposing the photosensitive dielectric film to high-energy radiation (such as electron beam, ultraviolet light, and X-rays) using a patterned mask.

[0093] After the exposure, the dielectric film may be heat-treated at about 50°C or higher (e.g., about 55°C or higher, about 60°C or higher, or about 65°C or higher) to about 100°C or lower (e.g., about 95°C or lower, or about 90°C or lower, about 85°C or lower, about 80°C or lower, about 75°C or lower, or about 70°C or lower) for about 60 seconds or longer (e.g., about 65 seconds or longer or about 70 seconds or longer) to about 240 seconds or shorter (e.g., about 180 seconds or shorter, about 120 seconds or shorter, or about 90 seconds or shorter). The heat treatment is typically achieved by using a hot plate or an oven.

[0094] After the exposure and heat treatment, the dielectric film can be developed using a developer to remove unexposed portions and form openings or relief images on the substrate. Development can be performed, for example, by immersion or spraying. After development, micropores and fine lines can be generated in the dielectric film on the laminated substrate.

[0095] In some embodiments, the dielectric film may be developed using an organic developer, examples of which include, but are not limited to, gamma-butyrolactone (GBL), gamma-valerolactone, silane, 2-methyltetrahydrofuran, dimethyl sulfoxide (DMSO), N,N-diethylacetamide, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), 2-heptanone, cyclopentanone (CP), cyclohexanone, n-butyl acetate (nBA), propylene glycol methyl ether acetate (PGMEA), propylene glycol methyl ether (PGME), ethyl lactate (EL), propyl lactate, 3-methyl-3-methoxybutanol, tetralin, isophorone, ethylene glycol monobutyl ether, and the like. Suitable organic solvents may include ethanol, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, triethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, diethyl malonate, ethylene glycol, 1,4:3,6-dianhydrosorbitol, isosorbide dimethyl ether, 1,4:3,6-dianhydrosorbitol 2,5-diethyl ether (2,5-diethylisosorbide), and mixtures thereof. Preferred developers are γ-valerolactone, silane, 2-methyltetrahydrofuran, γ-butyrolactone (GBL), cyclopentanone (CP), cyclohexanone, ethyl lactate (EL), n-butyl acetate (nBA), and dimethyl sulfoxide (DMSO). These developers may be used alone or in combination of two or more to optimize image quality for the composition and lithographic process.

[0096] In some embodiments, the dielectric film can be developed using an aqueous developer. When the developer is an aqueous solution, it can contain one or more aqueous bases. Examples of suitable bases include, but are not limited to, inorganic alkalis (e.g., potassium hydroxide, sodium hydroxide), primary amines (e.g., ethylamine, n-propylamine), secondary amines (e.g., diethylamine, di-n-propylamine), tertiary amines (e.g., triethylamine), alcohol amines (e.g., triethanolamine), quaternary ammonium hydroxides (e.g., tetramethylammonium hydroxide or tetraethylammonium hydroxide), and mixtures thereof. The concentration of the base used will vary depending, for example, on the base solubility of the polymer used. The most preferred aqueous developer contains tetramethylammonium hydroxide (TMAH). A suitable concentration of TMAH is in the range of about 1% to about 5%.

[0097] In some embodiments, development with an organic developer may optionally be followed by a rinse with an organic rinse solvent to remove residues. Suitable examples of organic rinse solvents include, but are not limited to, alcohols such as isopropyl alcohol, methyl isobutyl carbinol (MIBC), propylene glycol monomethyl ether (PGME), and amyl alcohol; esters such as n-butyl acetate (nBA), ethyl lactate (EL), and propylene glycol monomethyl ether acetate (PGMEA); ketones such as methyl ethyl ketone, and mixtures thereof.

[0098] In some embodiments, after the development step or the optional rinsing step, a baking step (e.g., post-development baking) may be optionally performed at a temperature ranging from about 120°C or higher (e.g., about 130°C or higher, about 140°C or higher, about 150°C or higher, about 160°C or higher, about 170°C or higher, or about 180°C or higher) to about 250°C or lower (e.g., about 240°C or lower, about 230°C or lower, about 220°C or lower, about 210°C or lower, about 200°C or lower, or about 190°C or lower). The baking time is about 5 minutes or longer (e.g., about 10 minutes or longer, about 20 minutes or longer, about 30 minutes or longer, about 40 minutes or longer, about 50 minutes or longer, or about 60 minutes or longer) and / or about 5 hours or shorter (e.g., about 4 hours or shorter, about 3 hours or shorter, about 2 hours or shorter, or about 1.5 hours or shorter). The baking step can remove residual solvent from the remaining dielectric film and can also crosslink the remaining dielectric film. Post-development baking can be performed in air or under a nitrogen blanket and can be performed by any suitable heating means.

[0099] In some embodiments, the patterned dielectric film comprises at least one element having a feature size of about 10 microns or less (e.g., about 9 microns or less, about 8 microns or less, about 7 microns or less, about 6 microns or less, about 5 microns or less, about 4 microns or less, about 3 microns or less, about 2 microns or less, or about 1 micron or less). One important aspect of the present disclosure is that the dielectric films prepared from the dielectric film-forming compositions described herein are capable of producing patterned films having feature sizes of about 3 microns or less (e.g., 2 microns or less or 1 micron or less) by a laser ablation process.

[0100] In some embodiments, the aspect ratio (height to width ratio) of the features (e.g., smallest features) of the patterned dielectric films of the present disclosure is about 1 / 3 or greater (e.g., about 1 / 2 or greater, about 1 / 1 or greater, about 2 / 1 or greater, about 3 / 1 or greater, about 4 / 1 or greater, or about 5 / 1 or greater).

[0101] In some embodiments (e.g., when the dielectric film-forming composition is non-photosensitive), a method for preparing a patterned dielectric film includes converting a dielectric film to the patterned dielectric film by laser ablation. Direct laser ablation processes using an excimer laser beam generally involve dry, one-step material removal to form openings (or patterns) in the dielectric film. In some embodiments, the laser has a wavelength of 640 nm or less (e.g., 157 nm, 193 nm, 248 nm, 308 nm, 351 nm, 405 nm, 445 nm, 470 nm, 520 nm, 528 nm, 555 nm, or 640 nm). Examples of suitable laser ablation processes include, but are not limited to, those described in U.S. Patent Nos. 7,598,167, 6,667,551, and 6,114,240, the contents of which are incorporated herein by reference.

[0102] In embodiments in which the dielectric film-forming composition is non-photosensitive, the composition can be used to form the bottom layer of a bilayer photoresist. In such embodiments, the top layer of the bilayer photoresist can be a photosensitive layer and can be patterned by exposure to high-energy radiation. The pattern in the top layer can be transferred (e.g., by etching) to the bottom dielectric layer. The top layer can then be removed (e.g., by using wet chemical etching) to form a patterned dielectric film.

[0103] In some embodiments, the present disclosure features a method for depositing a metal layer (e.g., for creating a buried copper trace structure) including the following steps: (a) forming a patterned dielectric film having an opening; and (d) depositing a metal layer (e.g., a conductive metal layer) in at least one opening in the patterned dielectric film. For example, the method may include the following steps: (a) depositing a dielectric film-forming composition described herein on a substrate (e.g., a semiconductor substrate) to form a dielectric film; (b) exposing the dielectric film (e.g., through a mask) to a radiation source, a heat source, or a combination thereof; (c) patterning the dielectric film to form a patterned dielectric film having an opening; and (d) depositing a metal layer (e.g., a conductive metal layer) in at least one opening in the patterned dielectric film. In some embodiments, steps (a) through (d) may be repeated one or more times (e.g., two, three, or four times).

[0104] In some embodiments, the present disclosure features a method for depositing a metal layer (e.g., a conductive copper layer for creating a buried copper trace structure) on a semiconductor substrate. To achieve this, in some embodiments, a seed layer conformal to the patterned dielectric film is first deposited on the patterned dielectric film (e.g., outside the openings in the film). The seed layer can include a barrier layer and a metal seed layer (e.g., a copper seed layer). In some embodiments, the barrier layer is prepared using a material that can prevent the diffusion of a conductive metal (e.g., copper) through the dielectric layer. Suitable materials that can be used for the barrier layer include, but are not limited to, tantalum (Ta), titanium (Ti), tantalum nitride (TiN), tungsten nitride (WN), and Ta / TaN. A suitable method for forming the barrier layer is sputtering (e.g., PVD or physical vapor deposition). Sputtering deposition has several advantages as a metal deposition method because it can be used to deposit many conductive materials at high deposition rates, with good uniformity and low cost of ownership. Conventional sputtering fill yields relatively poor results in deeper, narrower (high aspect ratio) features. The fill factor of sputtering deposition has been improved by collimating the sputtered flux. This improvement is typically achieved by inserting a collimator plate with an array of hexagonal cells between the target and the substrate.

[0105] The next step in the method is metal seed deposition: a thin metal (e.g., a conductive metal such as copper) seed layer may be formed on the barrier layer to improve the deposition of a metal layer (e.g., a copper layer) formed in a subsequent step.

[0106] The next step in the method is to deposit a conductive metal layer (e.g., a copper layer) over the metal seed layer in the openings of the patterned dielectric film, the metal layer being thick enough to fill the openings of the patterned dielectric film. The metal layer for filling the openings of the patterned dielectric film can be deposited by plating (e.g., electroless plating or electrolytic plating), sputtering, plasma-enhanced vapor deposition (PVD), and chemical vapor deposition (CVD). Electrochemical deposition is generally the preferred method for copper applications because it is more economical than other deposition methods and can completely fill interconnect features with copper. Copper deposition methods generally meet the stringent requirements of the semiconductor industry. For example, copper deposits must be uniform and capable of completely filling small interconnect features in devices, e.g., openings of 100 nm or less. This technique is described, for example, in U.S. Patent Nos. 5,891,804, 6,399,486, and 7,303,992, the contents of which are incorporated herein by reference.

[0107] In some embodiments, the method of depositing a conductive metal layer further includes removing an overburden of the conductive metal or removing the seed layer (e.g., the barrier layer and the metal seed layer). In some embodiments, the excess portion of the conductive metal layer (e.g., a copper layer) is about 3 microns or less (e.g., about 2.8 microns or less, about 2.6 microns or less, about 2.4 microns or less, about 2.2 microns or less, about 2.0 microns or less, or about 1.8 microns or less) and about 0.4 microns or more (e.g., about 0.6 microns or more, about 0.8 microns or more, about 1.0 microns or more, about 1.2 microns or more, about 1.4 microns or more, or about 1.6 microns or more). Examples of copper etchants for removing the copper excess include an aqueous solution containing cupric chloride and hydrochloric acid, or an aqueous mixture of ferric nitrate and hydrochloric acid. Other suitable copper etchants include, but are not limited to, those described in U.S. Pat. Nos. 4,784,785, 3,361,674, 3,816,306, 5,524,780, 5,650,249, 5,431,776, and 5,248,398, the contents of which are incorporated herein by reference, and U.S. Patent Application Publication No. 2017 / 0175274.

[0108] Some embodiments describe a method of surrounding a metal structured substrate containing a conductive metal (e.g., copper) wire structure forming a network of lines and interconnects with a dielectric film as described herein, the method comprising: a) providing a substrate containing a conductive metal wire structure forming a network of lines and interconnects on the substrate; b) depositing a dielectric film-forming composition described herein onto the substrate to form a dielectric film (e.g., surrounding the conductive metal lines and interconnects); and c) exposing the dielectric film to a source of radiation or heat, or a combination of radiation and heat (with or without a mask); may include:

[0109] The above steps may be repeated multiple times (eg, two, three, or four times) to form complex multi-layer three-dimensional objects.

[0110] In some embodiments, the disclosure features a method of preparing a dry film structure, the method comprising: a) coating a carrier substrate (e.g., a substrate comprising at least one polymer or plastic film) with a dielectric film-forming composition described herein; b) drying the coated dielectric film-forming composition to form a dielectric layer (e.g., a photosensitive dielectric layer); and c) optionally applying a protective layer to the dry film structure; may include:

[0111] In some embodiments, the carrier substrate is a single-layer or multi-layer polymer or plastic film, which may include one or more polymers (e.g., polyethylene terephthalate). In some embodiments, the carrier substrate has excellent optical transparency and is substantially transparent to the actinic radiation used to form the relief pattern in the polymer layer. The thickness of the carrier substrate is within a range from about 10 μm or more (e.g., about 15 μm or more, about 20 μm or more, about 30 μm or more, about 40 μm or more, about 50 μm or more, or about 60 μm or more) to about 150 μm or less (e.g., about 140 μm or less, about 120 μm or less, about 100 μm or less, about 90 μm or less, about 80 μm or less, or about 70 μm or less).

[0112] In some embodiments, the protective layer is a monolayer or multilayer film, which may include one or more polymers (e.g., polyethylene or polypropylene). Examples of carrier substrates and protective layers are described, for example, in U.S. Patent Application Publication No. 2016 / 0313642, the contents of which are incorporated herein by reference.

[0113] In some embodiments, the dielectric film of the dry film construction can be peeled from the carrier layer as a free-standing dielectric film. A free-standing dielectric film is one that can maintain its physical integrity without the use of any supporting layer, such as a carrier layer. In some embodiments, the free-standing dielectric film is not crosslinked or cured and can comprise the components of the dielectric film-forming composition described above, excluding solvent.

[0114] In some embodiments, the dielectric films prepared from the dielectric film-forming compositions described herein have a dielectric loss tangent or dissipation factor in the range of about 0.001 or more (e.g., about 0.002 or more, about 0.003 or more, about 0.004 or more, about 0.005 or more, about 0.01 or more, or about 0.05 or more) to about 0.1 or less (e.g., about 0.08 or less, about 0.06 or less, about 0.05 or less, about 0.04 or less, about 0.02 or less, about 0.01 or less, about 0.008 or less, about 0.006 or less, or about 0.005 or less) when measured at 10 GHz, 15 GHz, and / or 35 GHz.

[0115] In some embodiments, the dielectric film of the dry film structure can be pre-laminated by planar compression or hot roll compression, and then laminated to a substrate (e.g., a semiconductor substrate such as a wafer) using a vacuum laminator at about 50°C to about 140°C. When hot roll lamination is used, the dry film structure can be placed in the hot roll laminator, the optional protective layer can be peeled from the dielectric film / carrier substrate, and the dielectric film can be contacted and laminated to the substrate using a roller with heat and pressure to form an article containing the substrate, the dielectric film, and the carrier substrate. The dielectric film can then be exposed to a radiation or heat source (e.g., through the carrier substrate) to form a crosslinked dielectric film. In some embodiments, the carrier substrate can be removed before exposing the dielectric film to the radiation or heat source.

[0116] Some embodiments of the present disclosure describe a method for producing a planarized dielectric film on a substrate having a copper pattern. In some embodiments, the method includes depositing a dielectric film-forming composition on a substrate having a copper pattern to form a dielectric film. In some embodiments, the method includes: a. providing a dielectric film-forming composition of the present disclosure; and b. depositing the dielectric film-forming composition on a substrate having a copper pattern to form a dielectric film, wherein the difference between the highest point and the lowest point on the surface of the dielectric film is about 2 microns or less (e.g., about 1.5 microns or less, about 1 micron or less, or about 0.5 microns or less); Includes.

[0117] In some embodiments, the disclosure features articles (or three-dimensional objects) containing at least one patterned dielectric film formed by the methods described herein. Examples of such articles include semiconductor substrates, flexible films for electronics, wire isolation, wire coatings, wire enamels, and inked substrates. In some embodiments, the disclosure features semiconductor devices that include one or more of these articles. Examples of semiconductor devices that can be fabricated from such articles include integrated circuits, light-emitting diodes, solar cells, and transistors.

[0118] The contents of all publications (eg, patents, patent application publications, and articles) cited herein are hereby incorporated by reference in their entirety.

[0119] The present disclosure will now be described in more detail with reference to the following examples, which are for illustrative purposes and should not be construed as limiting the scope of the present disclosure. [Example]

[0120] Synthesis Example 1: Preparation of fully imidized polyimide (I) [ka] Solid 4,4'-(hexafluoroisopropylidene)bis(phthalic anhydride) (6FDA) (2.370 kg, 5.33 mol) was charged to a solution of 1-(4-aminophenyl)-1,3,3-trimethylindan-5-amine (also known as 4,4'-[1,4-phenylene-bis(1-methylethylidene)]bisaniline (DAPI)) (1.465 kg, 5.51 mol) in NMP (9.86 kg) at 25°C. The temperature of the reaction mixture was raised to 40°C and allowed to react for 6 hours. Next, acetic anhydride (1.125 kg) and pyridine (0.219 kg) were added, and the temperature of the reaction mixture was raised to 100°C and allowed to react for 12 hours.

[0121] The reaction mixture was cooled to room temperature and transferred to a large vessel equipped with a mechanical stirrer. The reaction solution was diluted with ethyl acetate and washed with water for 1 hour. After stirring was stopped, the mixture was allowed to stand undisturbed. Upon phase separation, the aqueous phase was removed. The organic phase was diluted with a combination of ethyl acetate and acetone and washed twice with water. The amounts of organic solvents (ethyl acetate and acetone) and water used for all washes are listed in Table 1. [Table 1]

[0122] Cyclopentanone (10 kg) was added to the washed organic phase, and the solution was concentrated by vacuum distillation to obtain a polymer solution containing polyimide (I) (FCP-1). The solids content of the final polymer was 29.19%, and the weight average molecular weight (Mw) measured by GPC was 54,000 Daltons.

[0123] Synthesis Example 2: Preparation of fully imidized polyimide (II) Below is an example of the preparation of polyimide (PI) polymers using one diamine and one dianhydride, where the isolation solvent (i.e., lactone) was different from the purified solvent (i.e., ketone and ester).

[0124] Solid 4,4'-oxydiphthalic anhydride (ODPA, 664.5 g) was charged to a solution of 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl (TFMB, 722.1 g) in NMP (3296 g) at 25°C. Additional NMP (1346 g) was used to rinse the dianhydride into the solution. The reaction temperature was increased to 40°C, and the mixture was allowed to react for 3 hours. Next, acetic anhydride (507.2 g) and pyridine (98.3 g) were added, the reaction temperature was increased to 100°C, and the mixture was allowed to react for 12 hours.

[0125] The reaction mixture was cooled to room temperature, and a portion (899 g) was transferred to a 5 L vessel equipped with a mechanical stirrer. The reaction solution was diluted with a combination of cyclopentanone and n-butyl acetate and washed with water for 1 hour. The stirring was stopped, and the mixture was allowed to stand undisturbed. Upon phase separation, the aqueous phase was removed. The organic phase was diluted with cyclopentanone and washed three more times with water. The amounts of purified solvents (i.e., cyclopentanone and n-butyl acetate) and water used for all washes are listed in Table 2. [Table 2]

[0126] The washed organic phase was concentrated by vacuum distillation. γ-Valerolactone (605 g) was added as an isolation solvent, and vacuum distillation was continued. The final polymer solution contained polyimide (II) (FCP-2) at a concentration of 24.99 wt%.

[0127] Synthesis Example 3: Preparation of fully imidized polyimide (III) Solid ODPA (14.73 g) was charged to a solution of TFMB (16.01 g) in 1:1 bio-derived γ-valerolactone:silane (73.18 g) at 25° C. An additional 1:1 bio-derived γ-valerolactone:silane (29.75 g) was used to rinse the dianhydride into the solution. The reaction temperature was increased to 40° C., and the mixture was allowed to react for 3 hours. Next, acetic anhydride (11.32 g) and pyridine (2.21 g) were added, the reaction temperature was increased to 100° C., and the mixture was allowed to react for 12 hours.

[0128] The treatment method was the same as in Example 2, and the polyimide (III) (FCP-3) thus formed was isolated in cyclopentanone.

[0129] Synthesis Example 4: Preparation of fully imidized polyimide (IV) A mixture of solid ODPA (94.78 g) and 2,2-[bis(3,4-dicarboxyphenyl)]hexafluoropropane dianhydride (6FDA) (45.25 g) was charged to a solution of TFMB (135.5 g) in NMP (819 g) at 25° C. Additional NMP (100 g) was used to rinse the dianhydride into the solution. The reaction temperature was increased to 40° C., and the mixture was allowed to react for 3 hours. Next, acetic anhydride (94.25 g) and pyridine (18.27 g) were added, the reaction temperature was increased to 100° C., and the mixture was allowed to react for 12 hours.

[0130] The treatment method was the same as in Example 2, and the polyimide (IV) (FCP-4) thus formed was isolated in cyclopentanone.

[0131] Synthesis Example 5: Preparation of fully imidized polyimide (V) A mixture of solid ODPA (117.6 g) and 2,2-[bis(3,4-dicarboxyphenyl)]hexafluoropropane dianhydride (6FDA) (8.87 g) was charged to a solution of TFMB (134.5 g) in NMP (819 g) at 25° C. Additional NMP (100 g) was used to rinse the dianhydride into the solution. The reaction temperature was increased to 40° C., and the mixture was allowed to react for 3 hours. Next, acetic anhydride (94.25 g) and pyridine (18.27 g) were added, the reaction temperature was increased to 100° C., and the mixture was allowed to react for 12 hours.

[0132] The treatment method was the same as in Example 2, and the polyimide (V) (FCP-5) thus formed was isolated in cyclopentanone.

[0133] Photosensitive composition example 1 A photosensitive dielectric film-forming composition (PSC-1) was prepared by mixing 100 parts of a 32% solution of polyimide polymer (V) having a weight average molecular weight of 51,000 daltons in cyclopentanone (CPO), 44.26 parts of propylene carbonate (PC), 1.75 parts of a 0.5 wt % solution of PolyFox 6320 (a surfactant available from OMNOVA Solutions) in cyclopentanone, 1.46 parts of methacryloxypropyltrimethoxysilane (an adhesion promoter), 1.168 parts of Ivocerin (an acylgermanium photoinitiator), 0.06 parts of monomethyl ether hydroquinone (an antioxidant), tetraethylene glycol diacrylate (a reactive functional compound, Komerate), and 1.168 parts of Ivocerin (an acylgermanium photoinitiator). A solution was prepared using 10.22 parts of erythritol triacrylate (a reactive functional compound, SR295), 1.46 parts of pentaerythritol triacrylate (a reactive functional compound, SR295), 0.15 parts of 5-methylbenzotriazole (a copper corrosion inhibitor), and 2.92 parts of 2,2-bis(4-cyanatophenyl)propane (a cyanate ester of a 50% solution in cyclopentanone). After stirring with a mechanical stirrer for 24 hours, the solution was filtered using a 0.2 micron filter (Ultradyne from Meissner Corporation, catalog number CLTM0.2-552).

[0134] Photosensitive composition examples 2-5 Photosensitive dielectric film-forming compositions 2 through 5 (i.e., PSC-2 through PSC-5) were prepared using the same method as described in Photosensitive Composition Example 1. The components and amounts thereof in these compositions are summarized in Table 3 below. [Table 3]

[0135] Photosensitive composition example 6 A photosensitive dielectric film-forming composition (PSC-6) was prepared by mixing 100 parts of a 32% solution of polyimide polymer (V) having a weight average molecular weight of 51,000 daltons in cyclopentanone, 44.26 parts of propylene carbonate, 1.75 parts of a 0.5 wt % solution of PolyFox 6320 (a surfactant available from OMNOVA Solutions) in cyclopentanone, 1.46 parts of methacryloxypropyltrimethoxysilane (an adhesion promoter), 0.87 parts of Ivocerin (an acylgermanium photoinitiator), 0.29 parts of Irgacure 784 (a photoinitiator available from BASF), 0.06 parts of monomethyl ether hydroquinone (an antioxidant), tetraethylene glycol diacrylate (a reactive functional compound, Komerate). A solution is prepared using 10.22 parts of erythritol triacrylate (reactive functional compound, SR295), 1.46 parts of pentaerythritol triacrylate (reactive functional compound, SR295), 0.15 parts of 5-methylbenzotriazole (copper corrosion inhibitor), and 2.92 parts of 2,2-bis(4-cyanatophenyl)propane (cyanate ester of a 50% solution in cyclopentanone). After stirring with a mechanical stirrer for 24 hours, the solution is filtered using a 0.2 micron filter (Ultradyne from Meissner Corporation, catalog number CLTM0.2-552).

[0136] Photosensitive composition example 7 A photosensitive dielectric film-forming composition (PSC-7) was prepared by dissolving 100 parts of a 29.19% solution of polyimide polymer (I) having a weight average molecular weight of 54,000 daltons in cyclopentanone, 44.26 parts of cyclopentanone, 44.26 parts of PolyFox 6320 (OMNOVA) in cyclopentanone, and 100 parts of a 29.19% solution of polyimide polymer (I) having a weight average molecular weight of 54,000 daltons in cyclopentanone. A 0.5 wt% solution of 1.75 parts of a 0.5 wt% solution of 1,2-dimethyl-2,4-trimethyl-2,4-trimethyl-1 ...1,4-trimethyl-2,4-trimethyl-1,4-trimethyl-1,4-trimethyl-2,4-trimethyl-1,4-trimethyl-1,4-trimethyl-1,4-trimethyl-1,4-trimethyl-1,4-trimethyl-1,4-trimethyl-1,4-trimethyl-1,4-trimethyl-1,4-trimethyl-1,4-trimethyl-1,4-trimethyl-1,4-trimethyl-1,4-trimethyl-1,4-trimethyl-1,4-trimethyl-1,4-trimethyl-1,4-trimethyl-1,4-trimethyl-1,4-trimethyl-1,4-trimethyl-1,4-trimethyl-1,4-trimethyl-1,4-trimethyl-1,4-trimethyl-1

[0137] Photosensitive composition example 8 A photosensitive dielectric film-forming composition (PSC-8) was prepared by dissolving 100 parts of a 29.19% solution of polyimide polymer (I) (FCP-1) having a weight average molecular weight of 54,000 daltons in cyclopentanone, 2.76 parts of cyclopentanone, 41.5 parts of bio-derived γ-valerolactone (GVL), 1.5 parts of PolyFox 6320 (OMNOVA) in cyclopentanone. A 0.5 wt% solution of 1.75 parts of a 0.5 wt% solution of 1,2-dimethyl-2,4-trimethyl-2,4-trimethyl-1 ...1,4-trimethyl-2,4-trimethyl-1,4-trimethyl-1,4-trimethyl-2,4-trimethyl-1,4-trimethyl-1,4-trimethyl-1,4-trimethyl-1,4-trimethyl-1,4-trimethyl-1,4-trimethyl-1,4-trimethyl-1,4-trimethyl-1,4-trimethyl-1,4-trimethyl-1,4-trimethyl-1,4-trimethyl-1,4-trimethyl-1,4-trimethyl-1,4-trimethyl-1,4-trimethyl-1,4-trimethyl-1,4-trimethyl-1,4-trimethyl-1,4-trimethyl-1,4-trimethyl-1,4-trimethyl-1,4-trimethyl-1,4-trimethyl-1

[0138] Photosensitive composition example 9 A photosensitive dielectric film-forming composition (PSC-9) was prepared by mixing 100 parts of a 29.19% solution of polyimide polymer (I) (FCP-1) having a weight average molecular weight of 54,000 daltons in cyclopentanone, 2.76 parts of cyclopentanone, 41.5 parts of bio-derived gamma-valerolactone (GVL), 1.75 parts of a 0.5 wt % solution of PolyFox 6320 (a surfactant available from OMNOVA Solutions) in cyclopentanone, 1.46 parts of methacryloxypropyltrimethoxysilane (an adhesion promoter), 2-(O-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione (Irgacure OXE), and 1.46 parts of methylparaben. A solution is prepared using 0.88 parts of BASF 01 (photoinitiator available from BASF), 0.22 parts of Ivocerin (acylgermanium photoinitiator), 0.06 parts of monomethyl ether hydroquinone (antioxidant), 10.95 parts of tetraethylene glycol diacrylate (reactive functional compound), 3.65 parts of pentaerythritol triacrylate (reactive functional compound), 2.92 parts of 2,2-bis(4-cyanatophenyl)propane (cyanate ester of a 50% solution in cyclopentanone), and 0.15 parts of 5-methylbenzotriazole (copper corrosion inhibitor). After stirring for 24 hours with a mechanical stirrer, the solution is filtered using a 0.2 micron filter (Ultradyne from Meissner Corporation, catalog number CLTM0.2-552).

[0139] Photosensitive composition example 10 A negative-working photosensitive dielectric film-forming composition (PSC-10) was prepared by mixing 200 parts by weight of EPON™ Resin SU-8 (40% by weight in butyl carbitol supplied by Hexion), 3 parts by weight of triethoxysilylpropylethoxycarbamate, 5 parts by weight of TPS-C1 [a 1:1 salt of tris[(trifluoromethyl)sulfonyl]-methane and triphenylsulfonium] supplied by Heraeus, and 1 part by weight of Ivocerin, and filtering through a 0.2 micron Teflon filter.

[0140] A silicon wafer is then coated with the photosensitive composition and baked on a hotplate at 95°C for 3 minutes to yield a film. The film is exposed using a 405 nm exposure tool with a patterned exposure array. The wafer is post-exposure baked at 95°C for 90 seconds. The wafer is developed with PGMEA using two 30-second puddle development steps with a spin step between developer applications to remove the spent developer. The developed film is rinsed with n-butyl acetate and spin-dried at 5000 rpm for 10 seconds to yield a relief pattern.

[0141] Photosensitive composition example 11 A positive-working photosensitive composition was prepared by mixing 200 parts by weight of polymer solution RD09-07 supplied by Fujifilm Electronic Materials USA, 3 parts by weight of triethoxysilylpropylethoxycarbamate, 0.102 parts by weight of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 5 parts by weight of (5-propylsulfonyloxyimino-5H-thiophen-2-ylidene)-2-methylphenyl-acetonitrile, and 1 part by weight of Ivocerin, 10 parts by weight of tripropylene glycol, 20 parts by weight of additional PGMEA, and 30 parts by weight of GBL, and filtering through a 0.2 micron Teflon filter.

[0142] The photosensitive composition is then coated onto a silicon wafer and baked on a hotplate at 125°C for 3 minutes to yield a film. The film is exposed using a 405 nm exposure tool with a patterned exposure array. The wafer is post-exposure baked at 130°C for 90 seconds. The wafer is developed with a 2.38 wt% aqueous TMAH solution using two 30-second puddle development steps with a spin step between developer applications to remove the spent developer. The developed film is rinsed with deionized water and spin-dried at 5000 rpm for 10 seconds to yield a relief pattern.

[0143] Photosensitive composition example 12 A dielectric film-forming composition is prepared by mixing SC Rubber (62.60 g of a 28.5 wt % solution in xylene), a cyclized polyisoprene supplied by Fujifilm Electronic Materials USA, tricyclodecane dimethanol diacrylate (7.14 g, a reactive functional compound), and Ivocerin (0.53 g, a photoinitiator) to obtain a homogeneous solution, which is then filtered using a 5.0 micron PTFE filter.

[0144] A silicon wafer is then coated with the photosensitive composition and baked on a hotplate at 95°C for 3 minutes to yield a film. The film is exposed using a 405 nm exposure tool with a patterned exposure array. The wafer is post-exposure baked at 95°C for 90 seconds. The wafer is developed in xylene using two 30-second puddle development steps with a spin step between developer applications to remove the spent developer. The developed film is rinsed with PGMEA and spin-dried at 5000 rpm for 10 seconds to yield a relief pattern.

[0145] Photosensitive composition example 13 The photosensitive composition was prepared by dissolving 28.48 g of PBO precursor polymer (I): [ka] A mixture of 46.10 g of bio-derived γ-butyrolactone, 0.87 g of γ-ureidopropyltrimethoxysilane, 0.70 g of diphenylsilanediol, 3.85 g of PAC of structure (II), and 0.56 g of Ivocerin is prepared. This composition is easily filtered using a 0.2 μm filter. [ka]

[0146] The photosensitive composition is then coated onto a silicon wafer and baked on a hotplate at 95°C for 3 minutes to yield a film. The film is exposed using a 405 nm exposure tool with a patterned exposure array. The wafer is post-exposure baked at 130°C for 90 seconds. The wafer is developed with a 2.38 wt% aqueous TMAH solution using two 30-second puddle development steps with a spin step between developer applications to remove the spent developer. The developed film is rinsed with deionized water and spin-dried at 5000 rpm for 10 seconds to yield a relief pattern.

[0147] Photosensitive composition example 14 A photosensitive composition was prepared by mixing 29.82 g of PD-1630 Polymer (Durite Resin supplied by Hexion), 5.06 g of PS-9 PAC (supplied by SEQENS), 0.052 g of Silwet L-7210 Surfactant, and 0.59 g of Ivocerin in 65 g of cyclopentanone. This composition was easily filtered using a 0.2 μm filter.

[0148] The photosensitive composition is then coated onto a silicon wafer and baked on a hotplate at 95°C for 3 minutes to yield a film. The film is exposed using a 405 nm exposure tool with a patterned exposure array. The wafer is post-exposure baked at 130°C for 90 seconds. The wafer is developed with a 2.38 wt% aqueous TMAH solution using two 30-second puddle development steps with a spin step between developer applications to remove the spent developer. The developed film is rinsed with deionized water and spin-dried at 5000 rpm for 10 seconds to yield a relief pattern.

[0149] Dry film example 1 The photosensitive dielectric film-forming composition was prepared by mixing 1345.24 g of a 31.69% solution of polyimide polymer (I) (FCP-1) having a weight average molecular weight of 54,000 in cyclopentanone, 1021.91 g of bio-derived gamma-valerolactone (GVL), 1021.91 g of PolyFox in cyclopentanone, and 1021.91 g of hydroxybenzoates. A solution of 102.31 g of a 0.5 wt% solution of 6320, 21.31 g of methacryloxypropyltrimethoxysilane, 34.11 g of a 50% solution of XU-378 (bisphenol M cyanate ester available from Huntsman) in cyclopentanone, 12.79 g of Ivocerin, 0.43 g of monomethyl ether hydroquinone, 138.55 g of tetraethylene glycol diacrylate, 53.39 g of pentaerythritol triacrylate, 21.32 g of ethylene glycol dicyclopentenyl ether acrylate, 4.26 g of dicumyl peroxide, and 0.426 g of 5-methylbenzotriazole was prepared. After stirring for 24 hours with a mechanical stirrer, the solution was filtered using a 0.2 micron filter (Ultradyne from Meissner Corporation, catalog number CLTM0.2-552).

[0150] The photosensitive dielectric film-forming composition obtained above was applied to a polyethylene terephthalate (PET) film (TCH21, manufactured by DuPont Teijin Films USA) (used as a carrier substrate) having a width of 16.2 inches and a thickness of 36 microns using a slot die coater with a clearance of 60 microns and a line speed of approximately 2 feet / minute (61 cm / minute) and dried at 194°F to obtain a photosensitive polymer layer. A biaxially oriented polypropylene film (BOPP, manufactured by Impex Global, Houston, TX) having a width of 16 inches and a thickness of 30 microns was then roll-compressed onto the polymer layer to serve as a protective layer. The carrier substrate, the photosensitive polymer layer, and the protective layer together formed a dry film (i.e., DF-1).

[0151] Three-dimensional object example 1 The photosensitive dielectric film-forming composition described in Dry Film Example 1 is converted into films deposited on a variety of substrates used in microelectronics and packaging applications. Films are deposited on 100 mm silicon wafers by spin-coating approximately 5 g of the solution at a spin speed of approximately 2000 rpm. The films are dried on a hot plate at a temperature of 105°C for 3 minutes, resulting in clear, transparent films of 12 microns. Film quality in terms of transparency, defect count, and uniformity is expected to meet the requirements for semiconductor packaging applications.

[0152] The above procedure is repeated on aluminum, copper, and silicon nitride wafers, and all the resulting films are expected to meet the requirements for semiconductor packaging applications.

Claims

1. at least one resin, and at least one acylgermanium compound; 1. A dielectric film-forming composition comprising:

2. the at least one acylgermanium compound comprises a compound of structure (I): 【Chemistry 1】 During the ceremony, R １ is C １ ~C １２ Alkyl, C ２ ~C １２ Alkenyl, C ４ ~C １８ Cycloalkyl, C ６ ~C ２２ Aryl, or C ６ ~C ２２ is heteroaryl, R ２ , R ３ , and R ４ Each of the groups independently represents C １ ~C １２ Alkyl, C ２ ~C １２ Alkenyl, C ４ ~C １８ Cycloalkyl, C ６ ~C ２２ Aryl, C ６ ~C ２２ heteroaryl, or —C(O)R, where R is C １ ~C ４ Alkyl, C ５ ~C １２ Cycloalkyl, C ６ ~C １８ Aryl, or C ６ ~C １８ is heteroaryl, and Each of the alkyl, alkenyl, cycloalkyl, aryl, or heteroaryl independently contains at least one C １ ~C ４ Alkyl, halogen, C １ ~C ４ Haloalkyl, -OR ５ , -OC(O)R ５ , or -COOR ５ wherein R ５ is H, C １ ~C ４ Alkyl, C ５ ~C １２ Cycloalkyl, C ６ ~C １８ Aryl, or C ６ ~C １８ is heteroaryl, The composition of claim 1.

3. 3. The composition of claim 1 or claim 2, wherein the at least one acylgermanium compound comprises (2,4,6-trimethylbenzoyl)triethylgermanium, (2,4,6-trimethylbenzoyl)tripropylgermanium, (2,4,6-trimethylbenzoyl)tributylgermanium, (2,6-dimethoxybenzoyl)triethylgermanium, (2,6-dimethoxybenzoyl)tripropylgermanium, (2,6-dimethoxybenzoyl)tributylgermanium, bisbenzoyldiethylgermanium, bisbenzoyldipropylgermanium, bis(4-methoxybenzoyl)diethylgermanium, bis(2,4,6-trimethylbenzoyl)diethylgermanium, trisbenzoylethylgermanium, or tris(2,4,6-trimethylbenzoyl)ethylgermanium.

4. The composition of any one of claims 1 to 3, wherein the at least one acylgermanium compound is present in an amount of from about 0.05% to about 20% by weight based on the solids weight of the composition.

5. The composition according to any one of claims 1 to 4, further comprising at least one radical initiator different from the acylgermanium compound.

6. The composition of claim 5 , wherein the at least one radical initiator comprises an oxime ester.

7. the radical initiator is an oxime ester of structure (II): 【Chemistry 2】 During the ceremony, R １１ and R １２ each independently represents a substituted or unsubstituted C １ ~C １２ Alkyl, substituted or unsubstituted C ４ ~C １８ Cycloalkyl, substituted or unsubstituted C ６ ~C ２２ Aryl, or substituted or unsubstituted C ６ ~C ２２ is heteroaryl, R １３ is a UV absorbing functional group, The composition of claim 6.

8. the at least one radical initiator comprises a compound of structure (III): 【Transformation 3】 During the ceremony, M is a metal selected from the group consisting of titanium, zirconium, or hafnium; R １４ and R １５ each independently represents a substituted or unsubstituted C １ ~C １２ Alkyl, substituted or unsubstituted C ４ ~C １８ Cycloalkyl, substituted or unsubstituted C ６ ~C ２２ Aryl, substituted or unsubstituted C ６ ~C ２２ selected from the group consisting of heteroaryl, and substituted or unsubstituted alkylsulfonyloxy groups; The composition of claim 5.

9. The composition of any one of claims 1 to 8, wherein the at least one resin comprises a fully imidized polyimide optionally containing functional groups; a cyclized rubber; a cyclic olefin polymer optionally containing functional groups; a polyphenylene ether; an acrylic compound; a cyanate ester compound; a polybenzoxazole precursor polymer; a novolac polymer; an epoxy phenol novolac polymer; or an alkali-soluble polyimide.

10. The composition of any one of claims 1 to 9, wherein the at least one resin is present in an amount of from about 0.1% to about 55% by weight based on the solids weight of the composition.

11. The composition according to any one of claims 1 to 10, further comprising at least one ethylenically unsaturated polymerizable compound, at least one thiol compound, at least one siloxane compound, at least one metal-containing (meth)acrylate compound, or a mixture thereof.

12. The composition of any one of claims 1 to 11, further comprising a photosensitizer selected from the group consisting of benzophenones, thioxanthones, anthraquinones, anthracenes, and coumarins.

13. The composition of any one of claims 1 to 12, further comprising at least one photoacid generator or photobase generator, or a mixture of at least one photoacid generator and at least one photobase generator.

14. The composition of any one of claims 1 to 13, further comprising at least one adhesion promoter, at least one corrosion inhibitor, at least one surfactant, at least one filler, at least one pigment, at least one dye, or a mixture thereof.

15. 1. A method for preparing a patterned dielectric film, comprising: a) depositing the dielectric film-forming composition of any one of claims 1 to 14 onto a substrate to form a dielectric film; b) exposing the dielectric film to radiation or heat or a combination of radiation or heat; and c) patterning the dielectric film to form a patterned dielectric film having openings; A method comprising:

16. 16. A patterned dielectric film produced by the method of claim 15.

17. 17. A three-dimensional object comprising at least one patterned dielectric film according to claim 16 and at least one substrate.

18. 20. The three-dimensional object of claim 17, wherein the substrate comprises an organic film, an epoxy molding compound (EMC), silicon, glass, copper, stainless steel, copper clad laminate (CCL), aluminum, silicon oxide, silicon nitride, or a combination thereof.

19. The three-dimensional object of claim 18 , wherein the substrate comprises a metal pattern.

20. 1. A method for preparing a three-dimensional object, comprising: a) depositing the dielectric film-forming composition of any one of claims 1 to 14 onto a substrate to form a dielectric film; b) exposing the dielectric film to radiation or heat or a combination of radiation or heat; c) patterning the dielectric film to form a patterned dielectric film having openings; d) optionally depositing a seed layer on the patterned dielectric film; and e) depositing a metal layer in at least one opening in the patterned dielectric film to form a metal pattern; A method comprising:

21. 21. The method of claim 20, wherein the patterned dielectric film comprises a surrounding copper pattern.

22. 1. A method of forming a three-dimensional object, comprising: a) providing a substrate containing a metal wire structure forming a network of lines and interconnects on said substrate; b) depositing the dielectric film-forming composition of any one of claims 1 to 14 onto the substrate to form a dielectric film; and c) exposing the dielectric film to radiation or heat or a combination of radiation and heat; A method comprising:

23. A semiconductor device comprising the three-dimensional object according to any one of claims 17 to 19.

24. 24. The semiconductor device of claim 23, which is an integrated circuit, a light emitting diode, a solar cell, or a transistor.

25. a carrier layer, and A dielectric film prepared from the composition of any one of claims 1 to 14 supported on the carrier layer. A dry film structure comprising:

26. 1. A method for preparing a dry film structure, comprising: (a) coating a carrier substrate with the composition of any one of claims 1 to 14 to form a coated composition; (b) drying the coated composition to form a dielectric layer; and (c) optionally applying a protective layer to the dielectric layer to form the dry film structure; A method comprising:

27. applying the dry film structure onto an electronics substrate to form a laminate; 27. The method of claim 26, wherein the dielectric layer in the stack is between the electronics substrate and the carrier substrate.

28. 1. A method for producing a dielectric film on a substrate having a copper pattern, comprising: depositing the composition of any one of claims 1 to 14 onto a substrate having a copper pattern to form a dielectric film; wherein the difference in height between the highest and lowest points on the surface of the dielectric film is about 2 microns or less.

Images