Dielectric film-forming composition containing acyl germanium compound

Abstract

The present disclosure relates to a dielectric film forming composition including at least one resin; and at least one acyl germanium compound; and related methods, films, dry film structures, and articles.

Description

[0001] Cross - Reference to Related Applications

[0002] This application claims priority to U.S. Provisional Application Serial No. 63 / 437,151, filed on January 5, 2023, the content of which is incorporated herein by reference in its entirety. Technical Field

[0003] This disclosure relates to a dielectric film - forming composition containing an acylgermanium compound, and related methods, films, dry - film structures, and articles. Background Art

[0004] The requirements for dielectric materials in semiconductor packaging applications are constantly evolving. The trend in electronic packaging is continuously towards faster processing speed, greater complexity, and higher packing density while maintaining a high level of reliability. With the development of electronic packaging technology and the continuous reduction of chip size, the demand for innovative and high - performance resin compositions is also increasing. To meet high resolution, various suggestions have been made for photosensitive dielectric compositions. When used in photosensitive compositions using laser direct imaging (LDI) technology, photoinitiators with high sensitivity at longer wavelengths can be beneficial in some cases. Summary of the Invention

[0005] This disclosure is based on the unexpected discovery that certain acylgermanium compounds can be used as photoinitiators or photosensitizers in photosensitive dielectric film - forming compositions, such that the compositions can 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. Therefore, the dielectric films thus formed can have excellent pattern shapes and film hardness.

[0006] In one aspect, this disclosure provides a dielectric film - forming composition containing at least one resin (e.g., a polymer); and at least one acylgermanium compound.

[0007] In some embodiments, the dielectric film - forming compositions described herein may further include at least one ethylenically unsaturated polymerizable compound, at least one thiol compound, at least one siloxane compound, or a mixture thereof.

[0008] In some embodiments, the dielectric film - forming compositions described herein may further contain a radical initiator (e.g., a photoinitiator) different from the acylgermanium compound. In some embodiments, the radical initiator does not generate radicals when exposed to the 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 can act as sensitizers and help generate radicals from the above - mentioned radical initiators by a synergistic effect.

[0009] In some embodiments, the dielectric film-forming composition described herein may further contain a photosensitizer different from the acyl germanium compound, wherein the photosensitizer may absorb light in the wavelength range of about 150 nm to about 600 nm (e.g., at about 405 nm).

[0010] In some embodiments, the resin described herein may include a fully imidized polyimide optionally containing a functional group, a cyclized rubber, a cycloolefin polymer optionally containing a functional group, a polyphenylene ether, an acrylic compound, a cyanate compound, a polybenzoxazole precursor polymer, a novolak polymer, an epoxy novolak polymer, or an alkali-soluble polyimide. In some embodiments, the resin is selected from the group consisting of non-fully imidized polyimide resins (which may be referred to as precursor polyimides in the present disclosure), and the resin may contain a functional group.

[0011] In some embodiments, the dielectric film-forming composition described herein may optionally include one or more of the following components:

[0012] a) One or more adhesion promoters;

[0013] b) One or more corrosion inhibitors;

[0014] c) One or more surfactants;

[0015] d) One or more fillers or particles;

[0016] e) One or more additives, which include dyes, dye mixtures, pigments, or pigment mixtures; and

[0017] f) One or more metal (meth) acrylate compounds.

[0018] In another aspect, the present disclosure provides a process for preparing a patterned dielectric film, the process comprising: a) depositing the 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; and c) patterning the dielectric film to form a patterned dielectric film having openings.

[0019] In another aspect, the present disclosure provides a process for forming a three-dimensional object, the process comprising: a) providing a substrate containing a metal wire structure (which may contain copper), the metal wire structure forming a network structure of wires and interconnects on the substrate; b) depositing the 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.

[0020] In another aspect, the present disclosure provides a process for preparing a three-dimensional object (e.g., an object containing a metal layer), the process comprising: a) depositing a dielectric film-forming composition as 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 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.

[0021] In another aspect, the present disclosure provides a dry film structure comprising a carrier substrate and a dielectric film supported by the carrier substrate, wherein the dielectric film is prepared from a dielectric film-forming composition as described herein.

[0022] In another aspect, the present disclosure provides a process for preparing a dry film structure, the process comprising: (a) coating a carrier substrate with a dielectric film-forming composition as 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 a dry film structure.

[0023] In another aspect, the present disclosure provides a process for producing a dielectric film on a substrate having a copper pattern, the process comprising: depositing a dielectric film-forming composition as described herein on a substrate having a copper pattern to form a dielectric film, wherein the height difference between the highest point and the lowest point on the surface of the dielectric film is at most about 2 microns.

[0024] In yet another aspect, the present disclosure describes a method for manufacturing a cured film, the method comprising: exposing a photosensitive dielectric film as described herein to electromagnetic radiation, an electron beam, or X-rays in the range of about 150 to about 600 nm; developing the exposed dielectric film with a developer to obtain a pattern; and obtaining a cured film by heating the patterned film.

[0025] In yet another aspect, the present disclosure provides a three-dimensional object prepared by the method as described herein. In some embodiments, the object comprises dielectric films in the form of at least two or three laminations. Detailed Description

[0026] Generally, the present disclosure relates to dielectric film-forming compositions. In some embodiments, the dielectric film-forming compositions described herein may be photosensitive. For example, the dielectric film-forming compositions described herein may be sensitive to electromagnetic or actinic radiation, an electron beam, or X-rays in the wavelength range of about 150 nm to 600 nm (e.g., 405 nm), thereby producing a solubility change (e.g., an increase or decrease in solubility) in a suitable developer (e.g., a TMAH solution).

[0027] In some embodiments, the present disclosure provides a dielectric film-forming composition containing at least one (e.g., two, three, or four) resin (e.g., a polymer, such as a dielectric polymer) and at least one (e.g., two, three, or four) acylgermanium compound according to the following structure (I),

[0028]

[0029] wherein R 1 is a 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 are each independently a C1-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 a C1-C4 alkyl, C5-C 12 cycloalkyl, C6-C 18 aryl, or C6-C 18 heteroaryl; and the alkyl, alkenyl, cycloalkyl, aryl, or heteroaryl is each independently optionally substituted with at least one (e.g., two or three) of the following groups: C1-C4 alkyl, halogen, C1-C4 haloalkyl, -OR 5 , -OC(O)R 5 , or -COOR 5 , where R 5 is H, C1-C4 alkyl, C5-C 12 cycloalkyl, C6-C 18 aryl, or C6-C 18 heteroaryl. In some embodiments, the acylgermanium compounds described herein may include 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).

[0030] Examples of the alkyl groups described herein include methyl, ethyl, propyl, isopropyl, and butyl. Examples of the alkenyl groups described herein include vinyl and allyl. Examples of the cycloalkyl groups described herein include cyclopentyl and cyclohexyl. Examples of the aryl groups described herein include phenyl, naphthyl, pyrenyl, anthracenyl, and phenanthrenyl. Examples of the heteroaryl groups described herein include furyl, furylene, fluorenyl, pyrrolyl, thienyl, oxazolyl, imidazolyl, thiazolyl, pyridyl, pyrimidinyl, quinazolinyl, quinolinyl, isoquinolinyl, and indolyl.

[0031] Suitable examples of the compounds of structure (I) include, but are not limited to, (2,4,6-trimethylbenzoyl)triethylgermane, (2,4,6-trimethylbenzoyl)tripropylgermane, (2,4,6-trimethylbenzoyl)tributylgermane, (2,6-dimethoxybenzoyl)triethylgermane, (2,6-dimethoxybenzoyl)tripropylgermane, (2,6-dimethoxybenzoyl)tributylgermane, dibenzoyldiethylgermane, dibenzoyldipropylgermane, bis(4-methoxybenzoyl)diethylgermane, bis(2,4,6-trimethylbenzoyl)diethylgermane, tribenzoylethylgermane, tris(2,4,6-trimethylbenzoyl)ethylgermane, and the like. A commercial example of the acylgermane compound is Ivocerin (i.e., bis(4-methoxybenzoyl)diethylgermane). Other examples of such acylgermane compounds are disclosed, for example, in U.S. Patent Nos. 7,605,190 and 9,532,930, the entire contents of which are incorporated herein by reference.

[0032] In some embodiments, the amount of the acylgermane compound is at least about 0.05 wt% (e.g., at least about 0.1 wt%, at least about 0.2 wt%, at least about 0.4 wt%, at least about 0.5 wt%, at least about 0.6 wt%, at least about 0.8 wt%, at least about 1 wt%, at least about 1.5 wt%, or at least about 2 wt%) to at most about 20 wt% (e.g., at most about 18 wt%, at most about 16 wt%, at most about 15 wt%, at most about 14 wt%, at most about 12 wt%, at most about 10 wt%, at most about 8 wt%, at most about 6 wt%, at most about 5 wt%, at most about 4 wt%, at most about 2 wt%, or at most about 1 wt%) of the solid weight of the dielectric film-forming composition described herein. As used herein, the solid weight of the dielectric film-forming composition refers to the total weight of the solids in such composition (i.e., without any solvent).

[0033] Without wishing to be bound by theory, it is believed that a dielectric film-forming composition containing the acyl germanium compounds described herein (alone or in combination with initiators different from the acyl germanium compounds) can be developed at a relatively long UV wavelength (e.g., about 405 nm) to form a dielectric film. Unexpectedly, the dielectric film thus formed has significantly improved resolution and excellent pattern shape, while being non-toxic to the environment.

[0034] The dielectric film-forming composition described herein may optionally contain at least one (e.g., two, three, or four) radical initiator different from the acyl germanium described herein. As used herein, a radical initiator refers to a compound capable of generating radicals, which can initiate radical polymerization or crosslinking after heating or irradiation with light in a specific 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 has an absorption effect and the radical polymerizable monomer does not have a substantial absorption effect. Photo radical initiators (also referred to herein as photoinitiators) and thermal radical initiators (also referred to herein as thermal initiators) are examples of radical initiators. In some embodiments, photo radical initiators are preferred.

[0035] In some embodiments, the amount of the radical initiator (e.g., photoinitiator) is at least about 0.1 wt% (e.g., at least about 0.2 wt%, at least about 0.5 wt%, at least about 0.8 wt%, at least about 1 wt%, at least about 1.5 wt%, at least about 2 wt%, at least about 3 wt%, at least about 4 wt%, or at least about 5 wt%) to at most about 10 wt% (e.g., at most about 9 wt%, at most about 8 wt%, at most about 7 wt%, at most about 6 wt%, at most about 5 wt%, at most about 4 wt%, at most about 3 wt%, at most about 2 wt%, or at most about 1 wt%) of the solid weight of the dielectric film-forming composition described herein.

[0036] In some embodiments, the photoinitiator is photosensitive to radiation in the ultraviolet to visible light range. In some embodiments, the photoinitiator can be an activator that generates radicals due to some effects of the photoexcited sensitizer.

[0037] An example of a photoinitiator is an oxime ester of the following structure (II),

[0038]

[0039] wherein R 11 and R 12 are each independently a substituted or unsubstituted C1-C 12 alkyl, a substituted or unsubstituted C4-C 18 cycloalkyl, a substituted or unsubstituted C6-C 22An aryl or a substituted or unsubstituted C6-C 22 heteroaryl; and R 13 is a UV-absorbing functional group (e.g., a substituted or unsubstituted C6-C 22 aryl or a substituted or unsubstituted C6-C 22 heteroaryl). In some embodiments, the alkyl, cycloalkyl, aryl or heteroaryl described above is optionally substituted with at least one (e.g., two or three) C1-C4 alkyl groups, halogen, C1-C4 haloalkyl groups, -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 heteroaryl.

[0040] Examples of the oxime ester of formula (II) include (but are not limited to)

[0041]

[0042]

[0043] Another example of a photoinitiator is an organic compound of the following structure (III):

[0044]

[0045] wherein M is selected from the group consisting of a titanium atom, a zirconium atom and a hafnium atom; and R 14 and R 15 [[ID=3 : 6]]are each independently selected from the group consisting of: a substituted or unsubstituted C1-C 12 alkyl, a substituted or unsubstituted C4-C 18 cycloalkyl, a substituted or unsubstituted C6-C 22 aryl, a substituted or unsubstituted C6-C 22 heteroaryl, a substituted or unsubstituted C6-C 22 heteroaryloxy and a substituted or unsubstituted alkylsulfonyloxy (e.g., a substituted or unsubstituted C1-C 12 alkylsulfonyloxy). In some embodiments, the alkyl, cycloalkyl, aryl or heteroaryl described above is optionally substituted with at least one (e.g., two or three) C1-C4 alkyl groups, halogen, C1-C4 haloalkyl groups, -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 heteroaryl.

[0046] Specific examples of thermal initiators include (but are not limited to) benzoyl peroxide, cyclohexanone peroxide, lauroyl peroxide, tertiary amyl peroxybenzoate, tertiary butyl hydroperoxide, di(tertiary butyl) peroxide, dicumyl peroxide, cumene hydroperoxide, succinic peroxide, di(n-propyl) peroxydicarbonate, 2,2-azobis(isobutyronitrile), 2,2-azobis(2,4-dimethylvaleronitrile), dimethyl 2,2-azobisisobutyrate, 4,4-azobis(4-cyanovaleric acid), azobis(cyclohexanecarbonitrile), 2,2-azobis(2-methylbutyronitrile), and the like.

[0047] Specific examples of thermal initiators include (but are not limited to) benzoyl peroxide, cyclohexanone peroxide, lauroyl peroxide, tertiary amyl peroxybenzoate, tertiary butyl hydroperoxide, di(tertiary butyl) peroxide, dicumyl peroxide, cumene hydroperoxide, succinic peroxide, di(n-propyl) peroxydicarbonate, 2,2-azobis(isobutyronitrile), 2,2-azobis(2,4-dimethylvaleronitrile), dimethyl 2,2-azobisisobutyrate, 4,4-azobis(4-cyanovaleric acid), azobis(cyclohexanecarbonitrile), 2,2-azobis(2-methylbutyronitrile), and the like.

[0048] Other examples of free radical photoinitiators include benzophenone derivatives such as benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl ketone; benzhydryl ketone and fluorenone; acetophenone derivatives such as 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone; thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, and the like; benzyl derivatives such as benzyl, benzyl dimethyl ketal, benzyl-β-methoxyethyl acetal, and the like; benzoin derivatives such as benzoin, benzoin methyl ether, and the like; benzoin derivatives such as benzoin, benzoin methyl ether, and the like; 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, oximes such as 3-diphenylpropanetrione-2-(o-ethoxycarbonyl)oxime, 1-phenyl-3-ethoxypropanetrione-2-(o-benzoyl)oxime; N-aryl glycine such as N-phenylglycine; peroxides such as benzoyl peroxide, aromatic diimidazoles, and the like. In addition, these initiators can be used alone or in the form of a mixture of two or more types.

[0049] In some embodiments, the dielectric film-forming composition described herein may include at least one (e.g., two, three, or four) photosensitizer different from the acylgermanium compound, wherein the photosensitizer may absorb light in the wavelength range of about 150 nm to about 600 nm (e.g., at about 405 nm). Examples of suitable photosensitizers that can be used in the dielectric film-forming composition 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. Examples of other photosensitizers are disclosed in, for example, U.S. Application Publication No. 2022 / 0171285, the entire content of which is incorporated herein by reference. In some embodiments, the acylgermanium compound described herein may act as a photosensitizer.

[0050] In some embodiments, the amount of the photosensitizer other than the acylgermanium compound is at least about 0.01 wt% (e.g., at least about 0.05 wt%, at least about 0.1 wt%, or at least about 0.5 wt%) to at most about 1 wt% (e.g., at most about 0.8 wt%, at most about 0.6 wt%, at most about 0.5 wt%, at most about 0.4 wt%, at most about 0.2 wt%, or at most about 0.1 wt%) of the solid weight of the dielectric film-forming composition described herein.

[0051] In some embodiments, the dielectric film-forming composition described herein may optionally include at least one (e.g., two, three, or four) crosslinking agent. In some embodiments, the crosslinking agent may include an ethylenically unsaturated polymerizable compound (e.g., an ethylenically unsaturated photo-polymerizable compound), a thiol compound, a siloxane compound, a metal-containing (meth)acrylate compound, or a mixture thereof.

[0052] In some embodiments, the crosslinking agent described herein may include a polyfunctional 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 hexa(3-mercaptopropionate), tris[2-(3-mercaptopropionyloxy)ethyl] isocyanurate, ethoxylated trimethylolpropane tris-3-mercaptopropionate, propylene glycol-3-mercaptopropionate 800, trimethylolpropane tris(4-mercaptocyclohexanecarboxylate), pentaerythritol tetrakis(4-mercaptocyclohexanecarboxylate), and the like. Other examples of such thiol compounds are disclosed in, for example, U.S. Patent No. 9,695,284, the entire content of which is incorporated herein by reference.

[0053] In some embodiments, the crosslinking agents described herein may include ethylenically unsaturated polymerizable compounds containing at least two (meth)acrylate groups. In some embodiments, the crosslinking agent is selected from the group consisting of: 1,6 - hexanediol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, 1,12 - dodecanediol di(meth)acrylate, 1,3 - butanediol 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, di(trimethylolpropane)tetra(meth)acrylate, neopentyl glycol tri(meth)acrylate, neopentyl glycol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate / hexa(meth)acrylate, isocyanuric acid tri(meth)acrylate, bis(2 - hydroxyethyl)-isocyanuric acid 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. Patent Nos. 10,036,952 and 10,563,014 and U.S. Patent Application Publication Nos. 2015 / 0219990, European Patent No. 3,492,982; the entire contents of which are incorporated herein by reference.

[0054] 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 is 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 is independently an - O - Si(R 24 )2H group, and each R 24 is independently a C1 - C4 alkyl group.

[0055]

[0056] In some embodiments, the crosslinking agent described herein may be a metal (meth) acrylate (MCA) compound. As used herein, the term "(meth) acrylate" refers to acrylate compounds 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, butoxytitanium (meth) acrylate, titanium (meth) acryloyloxyethyl acetoacetate triisopropanol, titanium tris (2-ethylhexanoate) (carboxyethyl (meth) acrylate), dibutoxytitanium di (meth) acrylate, tributoxytitanium (meth) acrylate, titanium oxide di (meth) acrylate, zirconium tributoxide (meth) acrylate, zirconium dibutoxide di (meth) acrylate, zirconium tributoxide (meth) acrylate, zirconium oxide di (meth) acrylate, hafnium tributoxide (meth) acrylate, hafnium dibutoxide di (meth) acrylate, hafnium tributoxide (meth) acrylate, hafnium oxide di (meth) acrylate, titanium tris (carboxyethyl (meth) acrylate) (2,4-pentanedioate), titanium tetra (carboxyethyl (meth) acrylate), zirconium tetra (carboxyethyl (meth) acrylate), hafnium tetra (carboxyethyl (meth) acrylate), titanium tributoxide tris (carboxyethyl (meth) acrylate), dibutoxytitanium di (carboxyethyl (meth) acrylate), tributoxytitanium (carboxyethyl (meth) acrylate), titanium oxide di (carboxyethyl (meth) acrylate), zirconium tributoxide tris (carboxyethyl (meth) acrylate), zirconium dibutoxide di (carboxyethyl (meth) acrylate), zirconium tributoxide (carboxyethyl (meth) acrylate), zirconium oxide di (carboxyethyl (meth) acrylate), zirconium bis (carboxyethyl (meth) acrylate) bis (2-ethylhexanoate), zirconium bis (carboxyethyl (meth) acrylate) bis (2,4-pentanedioate), hafnium tributoxide tris (carboxyethyl (meth) acrylate), hafnium dibutoxide di (carboxyethyl (meth) acrylate), hafnium tributoxide (carboxyethyl (meth) acrylate), and hafnium oxide di (carboxyethyl (meth) acrylate).

[0057] In some embodiments, the amount of the crosslinking agent described herein may be at least about 0.5 wt% (e.g., at least about 1 wt%, at least about 2 wt%, at least about 3 wt%, at least about 4 wt%, at least about 5 wt%, at least about 6 wt%, at least about 7 wt%, at least about 8 wt%, at least about 9 wt%, at least about 10 wt%) to at most about 25 wt% (e.g., at most about 24 wt%, at most about 22 wt%, at most about 20 wt%, at most about 18 wt%, at most about 16 wt%, at most about 15 wt%, at most about 14 wt%, at most about 12 wt%, at most about 10 wt%, at most about 8 wt%, at most about 6 wt% or at most about 5 wt%) of the solid weight of the dielectric film-forming composition described herein.

[0058] In some embodiments, the dielectric film-forming composition described herein includes at least one (e.g., two, three, or four) resin (e.g., a polymeric resin). In some embodiments, the resin may include a fully imidized polyimide optionally containing a functional group; a cyclized rubber; a cycloolefin polymer optionally containing a functional group; a polyphenylene ether; an acrylic compound; a cyanate ester compound; a polybenzoxazole precursor polymer; a novolac polymer; an epoxy novolac polymer; or an alkali-soluble polyimide. In some embodiments, the functional group on the polymer may be an acid group, such as a carboxylic acid group, a hydroxyl group, or a sulfonic acid group.

[0059] In some embodiments, the fully imidized polyimide described herein may be a polymer of structure (V):

[0060]

[0061] wherein R 31 is a terminal group (e.g., a functional or non-functional terminal group), n is an integer greater than 5 (e.g., 5 - 100), B1 is the nucleus of the precursor diamine and A1 is the nucleus of the precursor dianhydride. As used herein, when referring to a precursor diamine, "nucleus" refers to the portion between two amine functional groups. When referring to a precursor dianhydride, "nucleus" refers to the portion between two anhydride functional groups. Examples of such diamines and dianhydrides are disclosed, for example, in U.S. Patent No. 9,695,284, the entire content of which is incorporated herein by reference. A functional or non-functional acid anhydride or acyl chloride may be used to cap unreacted amine functional groups on the amine-terminated polyamic acid.

[0062] Examples of suitable diamines that can be used to prepare the polymers of structure (V) include (but are not limited to) 1-(4-aminophenyl)-1,3,3-trimethylindan-5-amine (alternative names include 4,4'-[1,4-phenylenebis(1-methylethylidene)]dianiline, 1-(4-aminophenyl)-1,3,3-trimethyl-2H-indene-5-amine, 1-(4-aminophenyl)-1,3,3-trimethylindan-5-amine, and [1-(4-aminophenyl)-1,3,3-trimethylindan-5-yl]amine), 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-indene-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, 5,7-diamino-1,1-dimethyl-4-ethylindan, p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 3-methyl-1,2-benzenediamine, 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-cyclohexanebis(methylamine), 5-amino-1,3,3-trimethylcyclohexanemethylamine, 2,5-diaminotrifluorobenzene, 3,5-diaminotrifluorobenzene, 1,3-diamino-2,4,5,6-tetrafluorobenzene, 4,4'-oxydianiline, 3,4'-oxydianiline, 3,3'-oxydianiline, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 4,4'-isopropylidenedianiline, 4,4'-diaminodiphenylmethane, 2,2-bis(4-aminophenyl)propane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfone, 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-tert-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-phenylene bis(1-methyl-ethylidene)]dianiline, 4,4'-[1,4-phenylene bis(1-methyl-ethylidene)]dianiline, 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 one of these diamines can be used alone or in combination at any suitable ratio to form the polyimide described herein.,

[0063] Examples of suitable dianhydrides useful for preparing the polymers of structure (V) include, but are not limited to, 1-(3',4'-dicarboxyphenyl)-1,3,3-trimethyldihydroindene-5,6-dianhydride, 1-(3',4'-dicarboxyphenyl)-1,3,3-trimethyldihydroindene-6,7-dianhydride, 1-(3',4'-dicarboxyphenyl)-3-methyldihydroindene-5,6-dianhydride, 1-(3',4'-dicarboxyphenyl)-3-methyldihydroindene-6,7-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, 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 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, 3,3',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(trimellitate), and 5-(2,5-dioxotetrahydro)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride. Any of these tetracarboxylic dianhydrides can be used alone or in combination in any suitable ratio to form the polyimides described herein.

[0064] In some embodiments, the fully imidized polyimides referred to herein are imidized by at least about 90% (such as at least about 95%, at least about 98%, at least about 99% or about 100%).

[0065] In some embodiments, the weight average molecular weight of the fully imidized polyimide is at least about 20,000 Daltons (e.g., at least about 25,000 Daltons, at least about 30,000 Daltons, at least about 35,000 Daltons, at least about 40,000 Daltons, at least about 45,000 Daltons, at least about 50,000 Daltons, or at least about 55,000 Daltons) and / or at most about 100,000 Daltons (e.g., at most about 95,000 Daltons, at most about 90,000 Daltons, at most about 85,000 Daltons, at most about 80,000 Daltons, at most about 75,000 Daltons, at most about 70,000 Daltons, at most about 65,000 Daltons, or at most about 60,000 Daltons).

[0066] In some embodiments, the fully imidized polyimide is prepared by the reaction of at least one diamine with at least one dianhydride of a tetracarboxylic acid. 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 point and the lowest point 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 have been described, for example, in U.S. Application Publication No. 2019 / 0077913, the entire content of which is incorporated herein by reference.

[0067] Methods for synthesizing capped and uncapped PI precursor polymers are well known to those skilled in the art. Examples of such methods and PI precursor polymers are disclosed in, for example, U.S. Pat. Nos. US2,731,447, US3,435,002, US3,856,752, US3,983,092, US4,026,876, US4,040,831, US4,579,809, US4,629,777, US4,656,116, US4,960,860, US4,985,529, US5,006,611, US5,122,436, US5,252,534, US5,4789,15, US5,773,559, US5,783,656, US5,969,055, US9,617,386 and U.S. Application Publication Nos. US2004 / 0265731, US2004 / 0235992 and US2007 / 0083016, the entire content of the said documents being incorporated herein by reference.

[0068] In some embodiments, the fully imidized polyimide described herein may be an alkali-soluble polyimide having at least one (e.g., two or three) functional groups such as a carboxylic acid group, a hydroxyl group (e.g., a phenolic hydroxyl group), a sulfonic acid group, or a thiol group (e.g., at one or both ends of the main chain or at the side chain of the polymer). The term "alkali-soluble" as used herein means a solubility of not less than about 0.1 g / 100 mL in a 2.38 weight percent aqueous solution of tetramethylammonium hydroxide at 25 °C.

[0069] In some embodiments, the polymer resin suitable for the dielectric film-forming composition described herein may include at least one (e.g., two, three, or four) dielectric polymer such as a dielectric polymer containing an epoxy resin, a novolak resin, or a mixture of an epoxy resin and a novolak resin, a polybenzoxazole (PBO) precursor polymer, or a mixture thereof.

[0070] Examples of suitable epoxy resins that can be used as dielectric film materials are known to those skilled in the art and include those disclosed in, for example, U.S. Patent No. 4,882,245 and U.S. Patent Application Publication No. 2006 / 0257785, the entire contents of which are incorporated herein by reference.

[0071] Examples of suitable novolak polymers described herein include polymers containing at least one photosensitive diazoquinone compound and are known to those skilled in the art. Examples of such novolak 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.

[0072] In some embodiments, the resin in the dielectric film-forming composition described herein may include a polyamide ester. The polyamide ester of the present disclosure has a number average degree of polymerization of 5 to 100 and is synthesized by polycondensation of monomer A and B as follows:

[0073] (Formula 1)

[0074]

[0075] Monomer A is obtained by reacting a dianhydride compound with an alcohol, i.e., R'OH, to obtain a diester-diacid, and then converting the diacid-diester to a diester-diacid chloride with the aid of a suitable reagent (Formula 2):

[0076] (Formula 2)

[0077]

[0078] The group R represents a tetravalent aromatic group containing at least one 6-membered carbon ring, wherein four carbonyl groups are directly connected to different carbon atoms of R and wherein each of two pairs of the four carbonyl groups is connected to adjacent carbon atoms. The dianhydride compounds can be the same as those shown previously. The tetracarboxylic dianhydrides can be used alone or in combination, and the selection of the dianhydride compounds is not limited to the compounds listed above. The group R' contains at least one unsaturated group, and the at least one unsaturated group can be vinyl, allyl, acryloyl, methacryloyl, ethynyl, cyano or other suitable radiation-crosslinkable groups.

[0079] Monomer B is a divalent diamine. Suitable diamines are the same as those discussed previously.

[0080] In some embodiments, the resin in the dielectric film-forming composition described herein can include a curable polybenzoxazole (PBO) precursor, such as a chemically amplified PBO precursor. The aqueous alkali solubility of the PBO precursor is reduced by protecting the aromatic hydroxyl groups in the PBO precursor by attachment of acid-labile groups. The restoration of the polymer alkali solubility is achieved by the action of the acid generated by the photolysis of a photoacid generator (PAG). The protecting group can be any suitable acid-labile group, such as acetal, ketal, carbonate, ether, silyl ether, a moiety containing a tert-butyl ester, and combinations thereof. Using this concept, a positive photosensitive resin composition containing a PBO precursor with acid-labile functional groups, a photoacid generator, and a solvent can be prepared and used to form a dielectric film. In some embodiments, after photolithography, the patterned layer can be converted into a heat-resistant polybenzoxazole coating by additional heating.

[0081] In some embodiments, the PBO precursor described herein can include an acid-labile functional group having the following structure (VI):

[0082]

[0083] wherein 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, aliphatic or heterocyclic group, or a mixture of a tetravalent aromatic, aliphatic or heterocyclic group and a divalent aromatic, aliphatic or heterocyclic group, wherein the proportion of Ar1 in the divalent group is 0 - 60 mol% and the sum of Ar1 in the tetravalent group and the divalent group is 100 mol%; Ar2 is a divalent aromatic, aliphatic or heterocyclic group or a siloxanyl group; D is a monovalent acid-labile group, and in combination with the oxygen atom to which it is attached, is selected from the group consisting of acetal, ketal, carbonate, ether, a moiety containing a tert-butyl ester group, and combinations thereof; and n is an integer from 20 to 200.

[0084] In some embodiments, Ar1 includes the following moiety:

[0085] 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 a C1-C6 alkyl group and m is an integer from 1 to 6.

[0086] In some embodiments, Ar2 comprises the following moieties:

[0087]

[0088] 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 a C1-C6 alkyl group and p is an integer from 1 to 6. In some embodiments, the PBO precursor may contain one or more different Ar1 and Ar2 groups.

[0089] In some embodiments, D is any suitable monovalent acid-labile group, such as an acetal, ketal, carbonate, ether, silyl ether, a moiety containing a tert-butyl ester, and combinations thereof. By way of example, D may include (but is not limited to) moieties of the following formula:

[0090] In some embodiments, D may be a monovalent diazoquinone ester compound formed between a PBO precursor having one or more phenolic hydroxyl groups and 1,2-diazidonaphthoquinone-4-sulfonic acid, 1,2-diazidonaphthoquinone-5-sulfonic acid, or a mixture thereof.

[0091] In some embodiments, when the dielectric film-forming composition described herein comprises a protected PBO precursor having an acid-labile functional group, the composition may also include a photoacid generator and a solvent. Optionally, the composition may contain a photosensitizer, an adhesion promoter, a leveling agent, or other additives. After exposure, the photo-generated acid catalyzes the removal of the blocking group from the protected PBO precursor and converts it into an alkali aqueous solution-soluble PBO precursor, as shown in reaction (1):

[0092] Reaction (1)

[0093]

[0094] Generally, any suitable photoacid generator compound can be used to remove acid-labile functional groups. 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.

[0095] The PBO precursor with an acid-labile functional group shown in formula (VI) can be prepared by reacting a PBO precursor with a vinyl ether having the formula R 1 =CH-OR 2 in the presence of an acid catalyst, where R 1 is (a) a straight-chain, branched-chain, or cyclic alkylene group having 1 to 10 carbon atoms, (b) a straight-chain, branched-chain, or cyclic haloalkylene group having 1 to 10 carbon atoms, or (c) an aralkyl group; R 2 is a straight-chain, branched-chain, cyclic alkyl, aralkyl group having 1 to 10 carbon atoms, or a straight-chain or branched-chain alkyl group with cycloalkyl, substituted cycloalkyl, aryl, and substituted aryl. Another suitable method for preparing a PBO precursor with an acid-labile functional group is from the reaction of a PBO precursor with di-tert-butyl dicarbonate in the presence of a base. The PBO precursor with an acid-labile functional group can also be synthesized by reacting a PBO precursor, an alcohol, and tert-butyl vinyl ether in the presence of an acid.

[0096] In some embodiments, the PBO precursors described herein may not include acid-labile functional groups and may have the structure (VII) shown below:

[0097]

[0098] where Ar1, Ar2, and n are as defined above.

[0099] The acetal-protected PBO precursor can be prepared by an acid-catalyzed addition reaction of a vinyl ether with a PBO precursor. Any suitable acid catalyst can be used for the reaction. Examples of suitable acid catalysts include hydrochloric acid, p-toluenesulfonic acid, and pyridinium p-toluenesulfonate. The acid catalyst can be added in an amount in the range of about 0.001 wt% to about 3.0 wt%. A number of vinyl ethers with a range of activation energies for acid-induced deprotection can be used in this reaction. In some embodiments, the acetal-protected PBO precursor can be prepared using a process that includes an acid-catalyzed reaction of a PBO precursor, tert-butyl vinyl ether, and an alkyl alcohol, alkylene alcohol, cycloalkyl alcohol, or aralkyl alcohol.

[0100] Methods for synthesizing polybenzoxazole precursor polymers are known to those skilled in the art. Examples of such methods and PBO precursor polymers are disclosed, for example, in U.S. Patent No. 6,143,467, U.S. Patent No. 7,195,849, U.S. Patent No. 7,129,011, and U.S. Patent No. 9,519,216, the entire contents of which are incorporated herein by reference.

[0101] In some embodiments, the resin in the dielectric film-forming composition described herein may include at least one (e.g., two or three) polyphenylene ether (PPE). In some embodiments, the PPE may be a polymer of structure (VIII):

[0102]

[0103] where each R 51 independently represents an aliphatic hydrocarbon group having 1 to 6 carbon atoms; each R 52 independently represents a hydrogen atom, a halogen atom, or an aliphatic hydrocarbon group having 1 to 6 carbon atoms; each R 53 independently represents an ethylenically unsaturated organic group; each of n1 and n2 independently represents an integer from 0 to 20; and P represents a divalent group.

[0104] In some embodiments, the PPE may include at least one vinylbenzyl ether group or at least one methyl (acrylate) group (e.g., in the end group R 53 ). Examples of suitable PPEs 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.

[0105] In some embodiments, the resin in the dielectric film-forming composition described herein may include at least one (e.g., two or three) cyclic rubbers. In some embodiments, the cyclized rubber is selected from the group of cyclized polydienes. In some embodiments, the cyclized polydiene includes a homopolymer of a conjugated diene (such as isoprene, butadiene, and pentadiene). In other embodiments, the cyclized polydiene includes a copolymer of such a conjugated diene with an olefin, styrene, or acrylate. 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 (such as an inorganic acid, an organic acid, or a Lewis acid). For example, two adjacent polymer structural units may participate in cis-olefin-catalyzed cyclization to produce a monocyclic structure while one double bond will disappear. Generally, bicyclic or tricyclic structures are formed in subsequent cyclization stages. Gradually, the degree of unsaturation and elasticity decrease due to the continuous cyclization of the cis-polyene, and its toughness increases. Cyclization is generally more effective in polyisoprene than in 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 have been described, for example, in U.S. Patent 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 of their types. In some embodiments, the cyclized rubber is polyisoprene.

[0106] In some embodiments, the resin in the dielectric film-forming composition described herein may include at least one (e.g., two or three) cyanate ester compounds (e.g., a cyanate ester compound having at least two cyanate groups in one molecule).

[0107] In some embodiments, the cyanate ester compound described herein may have structure (IX):

[0108] Ar-(O-C≡N) m (IX)

[0109] wherein m is an integer of at least 2 (m≥2), and Ar is a substituted or unsubstituted aromatic organic group, wherein the cyanate group is directly bonded to the substituted or unsubstituted aromatic organic group. In some embodiments, the aromatic organic group described above is optionally substituted with at least one (e.g., two or three) C1-C4 alkyl groups, halogens, C1-C4 haloalkyl groups, -OR', -OC(O)R', or -COOR', wherein R' is H, C1-C4 alkyl, C5-C 12 cycloalkyl, C6-C 18 aryl, or C6-C 18 heteroaryl.

[0110] In some embodiments, the cyanate ester compounds described herein may have structure (X):

[0111]

[0112] wherein R is a hydrogen atom, a C1-C3 alkyl group, a C1-C3 alkyl group that is fully or partially halogen-substituted, or a halogen atom; X is a single bond, an O or S atom, -(C=O)-, -(C=O)-O-, -O-(C=O)-, -(S=O)-, -(SO2)-, or -CH2CH2-O- group, a substituted or unsubstituted C1-C 10 alkylene group, a C1-C4 alkylene group that is partially or fully fluorine-substituted, or a substituted or unsubstituted C3-C 10 cycloalkylene group.

[0113] Specific examples of suitable cyanate ester compounds may include 2-bis(4-cyanatophenyl)propane, hexafluorobisphenol A dicyanate, bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatophenyl-1-(methylethylidene))benzene, bis(4-cyanatophenyl) sulfide, bis(4-cyanatophenyl) ether, and polyfunctional cyanate ester resins derived from phenol novolac, cresol novolac, or dicyclopentadiene-containing phenol resins. Other examples of such cyanate ester compounds have been described, for example, in U.S. Patent 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, although the weight average molecular weight of the cyanate ester resin or polymer is not particularly limited, it is at least about 500 Daltons (e.g., at least about 600 Daltons) to at most about 4,500 Daltons (e.g., at most about 3,000 Daltons).

[0114] Without wishing to be bound by theory, it is believed that the cyanate ester compounds can be cyclized and / or crosslinked thermally or under irradiation (e.g., in the presence or absence of a catalyst) to form an interpenetrating network structure with the dielectric polymer in the composition for forming the dielectric film described herein. Further, without wishing to be bound by theory, it is believed that including the cyanate ester compounds in the composition for forming the dielectric film described herein can reduce the dielectric constant (K) and / or the dissipation factor (DF) of the film formed from the composition.

[0115] In some embodiments, the resin of the present disclosure is a polyimide precursor. In some embodiments, the polyimide precursor is a heterocyclic-containing polyimide precursor, wherein the heterocyclic-containing polymer precursor is selected from polyimide (PI) precursors of formula (3)

[0116]

[0117] wherein A 1 and A 2 each independently represents an oxygen atom or NH, and R 111 represents a divalent organic group, and R 115 represents a tetravalent organic group, and R 113 and R 114 each independently represents a hydrogen atom or a monovalent organic group.

[0118] In some embodiments, the amount of the resin or dielectric polymer is at least about 0.1 wt% (such as at least about 0.5 wt%, at least about 1 wt%, at least about 2 wt%, at least about 5 wt%, at least about 10 wt%, at least about 15 wt%, or at least about 20 wt%) and / or at most about 55 wt% (such as at most about 50 wt%, at most about 45 wt%, at most about 40 wt%, at most about 35 wt%, at most about 30 wt%, at most about 25 wt%, at most about 20 wt%, at most about 15 wt%, or at most about 10 wt%) of the solid weight of the dielectric film-forming composition described herein.

[0119] In some embodiments, the dielectric film-forming composition described herein may include at least one (such as 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, when the dielectric film-forming composition includes a photosensitive polymer having an acid-labile functional group, the composition may include a photoacid generator (such as those photoacid generators described above) to remove the acid-labile functional group and create a solubility contrast. As another example, when the dielectric film-forming composition includes a photosensitive polymer having a base-labile functional group (such as an epoxy group), the composition may include a photobase generator to remove the base-labile functional group to 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, tributylphenyl borate (WPBG-300), and the like. 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about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about at least about 0.1 wt% (such as at least about 0.2 wt%, at least about 0.4 wt%, at least about 0.5 wt%, at least about 0.6 wt%, at least about 0.8 wt%, or at least about 1 wt%) to at most about 5 wt% (such as at most about 4 wt%, at most about 3 wt%, at most about 2 wt%, or at most about 1 wt%) of the solid weight of the dielectric film-forming composition described herein.

[0120] It seems there is some repetition and potential error in the "at least about" and "at most about" parts in the original text for the amount range description in ID=21. I've tried to translate it as accurately as possible while keeping the original structure. If you have any further clarifications or corrections regarding the original text, please let me know.In some embodiments, the dielectric film-forming composition described herein may optionally further include an organic solvent or a mixture of organic solvents (such as two, three, or four). Examples of organic solvents suitable for the dielectric film-forming composition described herein include (but are not limited to) alkylene carbonates, such as ethylene carbonate, propylene carbonate, butylene carbonate, and glycerol carbonate; lactones, such as γ-butyrolactone, ε-caprolactone, γ-caprolactone, and γ-valerolactone; cycloalkanones, such as cyclopentanone and cyclohexanone; straight-chain ketones, such as methyl ethyl ketone (MEK) and methyl isobutyl ketone (MIBK); esters, such as n-butyl acetate; ester alcohols, such as ethyl lactate; ether alcohols, such as tetrahydrofurfuryl alcohol; ether esters, such as (tetrahydrofuran-2-yl)methyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, and butyl 3-methoxyacetate; glycol esters, such as propylene glycol methyl ether acetate; glycol ethers, such as propylene glycol methyl ether (PGME); cyclic ethers, such as tetrahydrofuran (THF); pyrrolidinones, such as N-methyl-2-pyrrolidinone, N-ethyl-2-pyrrolidinone, or N-butyl-2-pyrrolidinone or TamiSolve TM NxG; and dialkyl sulfoxides, such as dimethyl sulfoxide.

[0121] In some embodiments, the total amount of the solvent is at least about 20 wt% (such as at least about 25 wt%, at least about 30 wt%, at least about 35 wt%, at least about 40 wt%, at least about 45 wt%, at least about 50 wt%, at least about 55 wt%, at least about 60 wt%, or at least about 65 wt%) and / or at most about 98 wt% (such as at most about 95 wt%, at most about 90 wt%, at most about 85 wt%, at most about 80 wt%, at most about 75 wt%, at most about 70 wt%, or at most about 60 wt%) of the total weight of the dielectric film-forming composition described herein.

[0122] In some embodiments, the dielectric film-forming composition described herein optionally includes at least one (such as two, three, or four) filler (such as an inorganic filler or inorganic particles). In some embodiments, the inorganic filler is selected from the group consisting of: silica, alumina, titanium dioxide, zirconium oxide, hafnium oxide, CdSe, CdS, CdTe, CuO, zinc oxide, lanthanum oxide, niobium oxide, tungsten oxide, strontium oxide, calcium titanate, 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 size of about 0.1 - 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 hydroxides, as well as intermetallic compounds, such as awaruite (Ni3Fe), wairaruite (CoFe), Co 17 Sm2 and Nd2Fe14 B.

[0123] In some embodiments, the amount of the inorganic filler (e.g., silica filler) is at least about 1 wt% (e.g., at least about 2 wt%, at least about 5 wt%, at least about 8 wt%, or at least about 10 wt%) and / or at most about 30 wt% (e.g., at most about 25 wt%, at most about 20 wt%, or at most about 15 wt%) of the solid weight of the dielectric film-forming composition described herein.

[0124] In some embodiments, the dielectric film-forming composition described herein may optionally further include at least one (e.g., two, three, or four) adhesion promoter. Suitable adhesion promoters are described in "Silane Coupling Agent" by Edwin P. Plueddemann, 1982, Plenum Press, New York. Examples of such adhesion promoters are disclosed, for example, in U.S. Patent No. 10,036,952 and U.S. Patent No. 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.

[0125] In some embodiments, the amount of the optional adhesion promoter is at least about 0.5 wt% (e.g., at least about 0.8 wt%, at least about 1 wt%, or at least about 1.5 wt%) and / or at most about 4 wt% (e.g., at most about 3.5 wt%, at most about 3 wt%, at most about 2.5 wt%, or at most about 2 wt%) of the solid weight of the dielectric film-forming composition described herein.

[0126] In some embodiments, the dielectric film-forming composition 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) the surfactants described in JP-A-62-36663, JP-A-61-226746, JP-A-61-226745, JP-A-62-170950, JP-A-63-34540, JP-A-7-230165, JP-A-8-62834, JP-A-9-54432, and JP-A-9-5988; the entire contents of which are incorporated herein by reference.

[0127] In some embodiments, the amount of the surfactant is at least about 0.005 wt% (e.g., at least about 0.01 wt% or at least about 0.1 wt%) and / or at most about 1 wt% (e.g., at most about 0.5 wt% or at most about 0.2 wt%) of the solid weight of the dielectric film-forming composition described herein.

[0128] In some embodiments, the dielectric film-forming composition 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 triazoles, and substituted benzotriazoles. 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 (e.g., 5-methyltriazole), amino, thiol, mercapto, imino, carboxyl, 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 their analogs. 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-benzotetrazole, 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 their analogs. If used, the amount of the optional corrosion inhibitor is at least about 0.1 wt% (e.g., at least about 0.2 wt% or at least about 0.5 wt%) and / or at most about 3.0 wt% (e.g., at most about 2.0 wt% or at most about 1.0 wt%) of the solid weight of the dielectric film-forming composition described herein.

[0129] In some embodiments, the dielectric film-forming composition described herein includes other optional components, such as one or more (e.g., two, three, or four) dyes, pigments, plasticizers, or antioxidants. Examples of such components have been described, for example, in U.S. Application Publication No. 2022 / 0127459, the entire content of which is incorporated herein by reference.

[0130] In some embodiments, the dielectric film can be prepared from the dielectric film-forming composition described herein by a method comprising the following steps: (a) coating the dielectric film-forming composition described herein on a substrate (e.g., a semiconductor substrate) to form a dielectric film; and (b) optionally baking the film at a high temperature (e.g., about 50 °C to about 150 °C) for a certain period of time (e.g., about 20 seconds to about 600 seconds).

[0131] Coating methods for preparing dielectric films include (but are not limited to) (1) spin coating, (2) spraying, (3) roll coating, (4) bar coating, (5) spin coating, (6) slot coating, (7) compression coating, (8) curtain coating, (9) die coating, (10) wire bar coating, (11) knife coating, and (12) dry film lamination. In the case of coating methods (1) to (11), the dielectric film-forming composition is usually provided in solution form. Those skilled in the art will select an appropriate solvent type and solvent concentration based on the coating type.

[0132] The substrate can have a circular, square, or rectangular shape, such as wafers or panels of various sizes. Examples of suitable substrates are epoxy molding compounds (EMC), silicon, glass, copper, stainless steel, copper-clad laminates (CCL), aluminum, silicon oxide, and silicon nitride. The substrate can be flexible, such as polyimide, PEEK, polycarbonate, and polyester films. The substrate can have surface-mounted or embedded chips, dies, or packages. The substrate can be sputter-coated or pre-coated with a combination of a seed layer and a passivation layer. In some embodiments, the substrate mentioned herein can be a semiconductor substrate. As used herein, a semiconductor substrate is a substrate (e.g., a silicon or copper substrate or wafer) that becomes part of the final electronic device.

[0133] The thickness of the dielectric film of the present disclosure is not particularly limited. In some embodiments, the film thickness of the dielectric film is at least about 1 micron (e.g., at least about 2 microns, at least about 3 microns, at least about 4 microns, at least about 5 microns, at least about 6 microns, at least about 8 microns, at least about 10 microns, at least about 15 microns, at least about 20 microns, or at least about 25 microns) and / or at most about 100 microns (e.g., at most about 90 microns, at most about 80 microns, at most about 70 microns, at most about 60 microns, at most about 50 microns, at most about 40 microns, or at most about 30 microns). 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).

[0134] In some embodiments, when the dielectric film-forming composition is photosensitive, a method of preparing a patterned photosensitive dielectric film includes converting the photosensitive dielectric film into a patterned dielectric film by a lithography method. In such cases, the conversion can include exposing the photosensitive dielectric film to high energy radiation (such as electron beams, ultraviolet light, and X-rays) using a patterned mask.

[0135] After exposure, the dielectric film can be subjected to a heat treatment at at least about 50 °C (such as at least about 55 °C, at least about 60 °C, or at least about 65 °C) to at most about 100 °C (such as at most about 95 °C, or at most about 90 °C, at most about 85 °C, at most about 80 °C, at most about 75 °C, or at most about 70 °C) for at least about 60 seconds (such as at least about 65 seconds or at least about 70 seconds) to at most about 240 seconds (such as at most about 180 seconds, at most about 120 seconds, or at most about 90 seconds). The heat treatment is typically accomplished by using a hot plate or an oven.

[0136] After exposure and heat treatment, the dielectric film can be developed by using a developer to remove the unexposed portions to form an opening or a relief image on the substrate. The development can be carried out, for example, by an immersion method or a spraying method. After development, micropores and fine lines can be generated in the dielectric film laminated on the substrate.

[0137] In some embodiments, the dielectric film can be developed by using an organic developer. Examples of such developers can include (but are not limited to) suitable organic solvents, such as γ-butyrolactone (GBL), γ-valerolactone, cyrene, 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 monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), ethyl lactate (EL), propyl lactate, 3-methyl-3-methoxybutanol, tetralin, isophorone, ethylene glycol monobutyl ether, 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-dianhydrohexitol, isosorbide dimethyl ether, 1,4:3,6-dianhydrohexitol 2,5-diethyl ether (2,5-diethylisosorbide), and mixtures thereof. Preferred developers are γ-valerolactone, cyrene, 2-methyltetrahydrofuran, γ-butyrolactone (GBL), cyclopentanone (CP), cyclohexanone, ethyl lactate (EL), n-butyl acetate (nBA), and dimethyl sulfoxide (DMSO). These developers can be used individually or in combination of two or more to optimize the image quality of a specific composition and lithography process.

[0138] In some embodiments, the dielectric film may be developed by using an aqueous developer solution. When the developer is an aqueous solution, it may contain one or more aqueous bases. Examples of suitable bases include (but are not limited to) inorganic bases (such as potassium hydroxide, sodium hydroxide), primary amines (such as ethylamine, n-propylamine), secondary amines (such as diethylamine, di-n-propylamine), tertiary amines (such as triethylamine), alkanolamines (such as triethanolamine), quaternary ammonium hydroxides (such as tetramethylammonium hydroxide or tetraethylammonium hydroxide), and mixtures thereof. The base concentration used will vary depending on, for example, the base solubility of the polymer used. The optimal aqueous developer is an aqueous developer containing tetramethylammonium hydroxide (TMAH). A suitable concentration of TMAH is in the range of about 1% to about 5%.

[0139] In some embodiments, after development by an organic developer, a rinsing process may optionally be performed with an organic rinsing solvent to remove residues. Suitable examples of the organic rinsing solvent 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.

[0140] In some embodiments, after the development step or the optional rinsing process step, a baking step (such as post-development baking) may optionally be performed at a temperature in the range of at least about 120 °C (such as at least about 130 °C, at least about 140 °C, at least about 150 °C, at least about 160 °C, at least about 170 °C, or at least about 180 °C) to at most about 250 °C (such as at most about 240 °C, at most about 230 °C, at most about 220 °C, at most about 210 °C, at most about 200 °C, or at most about 190 °C). The baking time is at least about 5 minutes (such as at least about 10 minutes, at least about 20 minutes, at least about 30 minutes, at least about 40 minutes, at least about 50 minutes, or at least about 60 minutes) and / or at most about 5 hours (such as at most about 4 hours, at most about 3 hours, at most about 2 hours, or at most about 1.5 hours). This baking step can remove residual solvents from the remaining dielectric film and can further crosslink the remaining dielectric film. Post-development baking can be carried out in air or under a nitrogen blanket and can be performed by any suitable heating device.

[0141] In some embodiments, the patterned dielectric film includes at least one component having a feature size of at most about 10 microns (such as at most about 9 microns, at most about 8 microns, at most about 7 microns, at most about 6 microns, at most about 5 microns, at most about 4 microns, at most about 3 microns, at most about 2 microns, or at most about 1 micron). An important aspect of the present disclosure is that a dielectric film prepared from a composition for forming a dielectric film described herein can produce a patterned film having a feature size of at most about 3 microns (such as at most 2 microns or at most 1 micron) by a laser ablation method.

[0142] In some embodiments, the aspect ratio (ratio of height to width) of a component (such as the smallest component) of the patterned dielectric film of the present disclosure is at least about 1 / 3 (such as at least about 1 / 2, at least about 1 / 1, at least about 2 / 1, at least about 3 / 1, at least about 4 / 1, or at least about 5 / 1).

[0143] In some embodiments (such as when the dielectric film-forming composition is non-photosensitive), the method of preparing a patterned dielectric film includes converting the dielectric film into a patterned dielectric film by a laser ablation technique. A direct laser ablation method using an excimer laser beam is generally a one-step dry material removal for forming an opening (or pattern) in the dielectric film. In some embodiments, the wavelength of the laser is 640 nm or less (such as, 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 methods include (but are not limited to) the methods 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.

[0144] In an embodiment, when the dielectric film-forming composition is non-photosensitive, the composition can be used to form a bottom layer in a bilayer photoresist. In such embodiments, the top layer of the bilayer photoresist can be a photosensitive layer and can be patterned after exposure to high-energy radiation. The pattern in the top layer can be transferred to the bottom dielectric layer (such as by etching). Subsequently, the top layer can be removed (such as by using a wet chemical etching method) to form a patterned dielectric film.

[0145] In some embodiments, the present disclosure provides a method for depositing a metal layer (e.g., to create an embedded copper trace structure), which includes 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 of 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 to a radiation source or a heat source or a combination thereof (e.g., via a mask); (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 of the patterned dielectric film. In some embodiments, steps (a) to (d) may be repeated one or more times (e.g., two, three, or four times).

[0146] In some embodiments, the present disclosure provides a method for depositing a metal layer (e.g., a conductive copper layer to create an embedded copper trace structure) on a semiconductor substrate. In some embodiments, to achieve this, a seed layer conformal to the patterned dielectric film is first deposited on the patterned dielectric film (e.g., outside the opening of the film). The seed layer may 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 capable of preventing the diffusion of a conductive metal (e.g., copper) through the dielectric layer. Suitable materials 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, as a metal deposition technique, has certain advantages because it can be used to deposit a variety of conductive materials, has a high deposition rate, good uniformity, and low cost. For deeper, narrower (high aspect ratio) components, the results of conventional sputtering filling are relatively poor. The filling factor of sputtering deposition has been improved by calibrating the sputtering flux. Typically, this is achieved by inserting a collimator plate having an array of hexagonal pores between the target and the substrate.

[0147] 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 top of the barrier layer to improve the deposition of the metal layer (e.g., a copper layer) formed in subsequent steps.

[0148] The next step in the method is to deposit a conductive metal layer (such as a copper layer) on top of the metal seed layer in the opening of the patterned dielectric film, where the thickness of the metal layer is sufficient to fill the opening in the patterned dielectric film. The metal layer filling the opening in the patterned dielectric film can be deposited by electroplating (such as electroless or electrolytic electroplating), sputtering, plasma vapor deposition (PVD), and chemical vapor deposition (CVD). Electrochemical deposition is generally a better method for coating copper because it is more economical than other deposition methods and can fill copper into the interconnect components flawlessly. The copper deposition method should generally meet the strict requirements of the semiconductor industry. For example, the copper deposit should be uniform and capable of filling the small interconnect components of the device flawlessly, such as openings of 100 nm or less. This technology has been described in, for example, U.S. Patent Nos. 5,891,804, 6,399,486, and 7,303,992, the contents of which are incorporated herein by reference.

[0149] In some embodiments, the method of depositing the conductive metal layer further includes removing the capping layer of the conductive metal or removing the seed layer (such as the barrier layer and the metal seed layer). In some embodiments, the capping layer of the conductive metal layer (such as the copper layer) is at most about 3 microns (such as at most about 2.8 microns, at most about 2.6 microns, at most about 2.4 microns, at most about 2.2 microns, at most about 2.0 microns, or at most about 1.8 microns) and at least about 0.4 microns (such as at least about 0.6 microns, at least about 0.8 microns, at least about 1.0 microns, at least about 1.2 microns, at least about 1.4 microns, or at least about 1.6 microns). Examples of copper etchants for removing the copper capping layer include an aqueous solution containing copper chloride and hydrochloric acid, or an aqueous mixture of iron nitrate and hydrochloric acid. Examples of other suitable copper etchants include (but are not limited to) the copper etchants described in U.S. Patent Nos. 4,784,785, 3,361,674, 3,816,306, 5,524,780, 5,650,249, 5,431,776, and 5,248,398, and U.S. Application Publication No. 2017 / 0175274, the contents of which are incorporated herein by reference.

[0150] Some embodiments describe a method of surrounding a metal-structured substrate containing a conductive metal (such as copper) wire structure with the dielectric film described herein, where the conductive metal wire structure forms a network structure of wires and interconnects. The method may include the following steps:

[0151] a) Providing a substrate containing a conductive metal wire structure, where the metal wire structure forms a network structure of wires and interconnects on the substrate.

[0152] b) Depositing the dielectric film-forming composition described herein on the substrate to form a dielectric film (such as surrounding the conductive metal wires and interconnects); and

[0153] c) Exposing the dielectric film to a radiation source or a heat source or a combination of radiation and heat (with or without shielding).

[0154] The above steps can be repeated multiple times (e.g., twice, three times or four times) to form a complex multi-layer three-dimensional object.

[0155] In some embodiments, the present disclosure provides a method for preparing a dry film structure. The method may include:

[0156] a) Coating a carrier substrate (e.g., a substrate including at least one polymeric or plastic film) with a composition comprising the dielectric film described herein.

[0157] b) Drying the coated composition of the dielectric film to form a dielectric layer (e.g., a photosensitive dielectric layer); and

[0158] c) Optionally, applying a protective layer to the dry film structure.

[0159] In some embodiments, the carrier substrate is a single-layer or multi-layer polymeric 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 actinic radiation for forming a relief pattern in the polymer layer. The thickness of the carrier substrate ranges from at least about 10 μm (e.g., at least about 15 μm, at least about 20 μm, at least about 30 μm, at least about 40 μm, at least about 50 μm or at least about 60 μm) to at most about 150 μm (e.g., at most about 140 μm, at most about 120 μm, at most about 100 μm, at most about 90 μm, at most about 80 μm or at most about 70 μm).

[0160] In some embodiments, the protective layer is a single-layer or multi-layer film, which may include one or more polymers (e.g., polyethylene or polypropylene). Examples of the carrier substrate and the protective layer are described in, for example, U.S. Application Publication No. 2016 / 0313642, the content of which is incorporated herein by reference.

[0161] In some embodiments, the dielectric film of the dry film structure can be peeled off from the carrier layer as a free-standing dielectric film. A free-standing dielectric film is a film that can maintain its physical integrity without using any support layer (such as a carrier layer). In some embodiments, the free-standing dielectric film is not crosslinked or cured and may contain the components of the dielectric film-forming composition described above other than the solvent.

[0162] In some embodiments, the dielectric loss tangent or loss factor of a dielectric film prepared from the dielectric film-forming composition described herein, measured at 10 GHz, 15 GHz, and / or 35 GHz, is in the range of at least about 0.001 (e.g., at least about 0.002, at least about 0.003, at least about 0.004, at least about 0.005, at least about 0.01, or at least about 0.05) to at most about 0.1 (e.g., at most about 0.08, at most about 0.06, at most about 0.05, at most about 0.04, at most about 0.02, at most about 0.01, at most about 0.008, at most about 0.006, or at most about 0.005).

[0163] In some embodiments, after pre-laminating the dielectric film of the dry film structure by a planar compression method or a hot roll compression method, the dielectric film of the dry film structure can be laminated to a substrate (e.g., a semiconductor substrate such as a wafer) at about 50 °C to about 140 °C using a vacuum laminator. When hot roll lamination is employed, the dry film structure can be placed in a hot roll laminator, an optional protective layer can be peeled off from the dielectric film / carrier substrate, and the dielectric film can be brought into contact with the substrate and laminated to the substrate under heat and pressure using a roll to form a product containing the substrate, the dielectric film, and the carrier substrate. The dielectric film can then be exposed to a radiation source or a heat source (e.g., via 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 source or the heat source.

[0164] 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 the following steps:

[0165] a. providing the dielectric film-forming composition of the present disclosure, and

[0166] 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 at most about 2 microns (e.g., at most about 1.5 microns, at most about 1 micron, or at most about 0.5 micron).

[0167] In some embodiments, the present disclosure provides an article (or three-dimensional object) containing at least one patterned dielectric film formed by the method described herein. Examples of such articles include semiconductor substrates, flexible films for electronic devices, wire insulation layers, wire coatings, enamel paints for magnet wires, or ink-printed substrates. In some embodiments, the present disclosure provides a semiconductor device including one or more of such articles. Examples of semiconductor devices that can be made from such articles include integrated circuits, light-emitting diodes, solar cells, and transistors.

[0168] The contents of all publications (e.g., patents, patent application publications, and papers) cited herein are incorporated herein by reference in their entirety.

[0169] The present disclosure will be described in more detail with reference to the following examples, which are for illustrative purposes only and should not be construed as limiting the scope of the present disclosure.

[0170] Synthesis Example 1: Preparation of fully imidized polyimide (I)

[0171]

[0172] Structure of polymer (I)

[0173] At 25 °C, solid 4,4'-(hexafluoroisopropylidene)bis(phthalic anhydride) (6FDA) (2.370 kg, 5.33 mol) was fed into a solution of 1-(4-aminophenyl)-1,3,3-trimethylindan-5-amine (also known as 4,4'-[1,4-phenylene-bis(1-methylethylidene)]bis-aniline (DAPI)) (1.465 kg, 5.51 mol) in NMP (9.86 kg). The temperature of the reaction mixture was raised to 40 °C and allowed to react for 6 hours. Subsequently, 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.

[0174] The above reaction mixture was cooled to room temperature and transferred to a larger container equipped with a mechanical stirrer. The reaction solution was diluted with ethyl acetate and washed with water for one hour. After stopping the stirring, the mixture was allowed to stand. Once phase separation occurred, the aqueous phase was removed. The organic phase was diluted with a combination of ethyl acetate and acetone and washed with water twice. The amounts of the organic solvents (ethyl acetate and acetone) and water used in all washes are shown in Table 1.

[0175] Table 1

[0176] The 1st washing The 2nd washing The 3rd washing Ethyl acetate (kg) 20.5 4.1 4.1 Acetone (kg) --- 2.3 2.3 Water (kg) 22.0 26.0 26.0

[0177] 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 solid % of the final polymer was 29.19% and the weight average molecular weight (Mw) measured by GPC was 54,000 daltons.

[0178] Synthesis Example 2: Preparation of fully imidized polyimide (II)

[0179] The following is an example of preparing a polyimide (PI) polymer using a diamine and a dianhydride, where the separation solvent (i.e., lactone) is different from the purification solvents (i.e., ketone and ester).

[0180] At 25 °C, solid 4,4'-oxydiphthalic anhydride (ODPA, 664.5 g) was fed into a solution of 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl (TFMB, 722.1 g) in NMP (3296 g). The dianhydride was rinsed into the solution using additional NMP (1346 g). The reaction temperature was raised to 40 °C and the mixture was reacted for 3 hours. Subsequently, acetic anhydride (507.2 g) and pyridine (98.3 g) were added, the reaction temperature was raised to 100 °C, and the mixture was reacted for 12 hours.

[0181] 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 using a combination of cyclopentanone and n-butyl acetate and washed with water for one hour. Stirring was stopped and the mixture was allowed to stand. Once phase separation occurred, the aqueous phase was removed. The organic phase was diluted with cyclopentanone and washed with water three more times. The amounts of the purification solvents (i.e., cyclopentanone and n-butyl acetate) and water used in all washes are shown in Table 2.

[0182] Table 2

[0183] The 1st washing The 2nd washing The 3rd washing The 4th washing Cyclopentanone (g) 1385 202 --- --- n-Butyl acetate (g) 892 --- --- --- Water (g) 1329 1628 1631 1630

[0184] The washed organic phase was concentrated by vacuum distillation. γ-Valerolactone (605 g) was added as a separation solvent and vacuum distillation was continued. The final polymer solution contained polyimide (II) (FCP-2) at a concentration of 24.99 wt%.

[0185] [[ID=*17]]Synthesis Example 3: Preparation of fully imidized polyimide (III)

[0186] At 25 °C, solid ODPA (14.73 g) was fed into a solution of TFMB (16.01 g) in 1:1 bio-derived γ-valerolactone:cyrene (73.18 g). Additional 1:1 bio-derived γ-valerolactone:cyrene (29.75 g) was used to rinse the dianhydride into the solution. The reaction temperature was raised to 40 °C and the mixture was reacted for 3 hours. Subsequently, acetic anhydride (11.32 g) and pyridine (2.21 g) were added, the reaction temperature was raised to 100 °C, and the mixture was reacted for 12 hours.

[0187] The treatment method followed Example 2, and the polyimide (III) (FCP-3) thus formed was separated in cyclopentanone.

[0188] [[ID=*26]]Synthesis Example 4: Preparation of fully imidized polyimide (IV)

[0189] At 25 °C, a mixture of solid ODPA (94.78 g) and 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride (6FDA) (45.25 g) was fed into a solution of TFMB (135.5 g) in NMP (819 g). Additional NMP (100 g) was used to rinse the dianhydride into the solution. The reaction temperature was raised to 40 °C and the mixture was reacted for 3 hours. Subsequently, acetic anhydride (94.25 g) and pyridine (18.27 g) were added, the reaction temperature was raised to 100 °C, and the mixture was reacted for 12 hours.

[0190] The treatment method followed Example 2, and the polyimide (IV) (FCP-4) thus formed was separated in cyclopentanone.

[0191] Synthesis Example 5: Preparation of fully imidized polyimide (V)

[0192] At 25 °C, a mixture of solid ODPA (117.6 g) and 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride (6FDA) (8.87 g) was fed into a solution of TFMB (134.5 g) in NMP (819 g). Additional NMP (100 g) was used to rinse the dianhydride into the solution. The reaction temperature was raised to 40 °C and the mixture was reacted for 3 hours. Subsequently, acetic anhydride (94.25 g) and pyridine (18.27 g) were added, the reaction temperature was raised to 100 °C, and the mixture was reacted for 12 hours.

[0193] The treatment method followed Example 2, and the polyimide (V) (FCP-5) thus formed was separated in cyclopentanone.

[0194] Photosensitive composition Example 1

[0195] By using a 32% solution of 100 parts of a polyimide polymer (V) with a weight average molecular weight of 51,000 daltons in cyclopentanone (CPO); 44.26 parts of propylene carbonate (PC); a 0.5 wt% solution of 1.75 parts 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); 10.22 parts of tetraethylene glycol diacrylate (a reactive functional compound, Komerate D048); 1.46 parts of neopentyl glycol triacrylate (a reactive functional compound, SR295); 0.15 parts of 5-methylbenzotriazole (a copper corrosion inhibitor); 2.92 parts of 2,2-bis(4-cyanatophenyl)propane (a 50% solution of cyanate ester in cyclopentanone), a photosensitive dielectric film-forming composition (PSC-1) was prepared. After mechanical stirring for 24 hours, the solution was filtered using a 0.2-micron filter (Ultradyne from Meissner Corporation, catalog number CLTM0.2-552).

[0196] Examples 2 to 5 of photosensitive compositions

[0197] Photosensitive dielectric film-forming compositions 2-5 (i.e., PSC-2 to PSC-5) were prepared by using the same method as described in Example 1 of the photosensitive composition. The components and their amounts in these compositions are summarized in Table 3 below.

[0198] Table 3

[0199]

[0200]

[0201] Example 6 of photosensitive composition

[0202] By using 100 parts of a 32% solution of a 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 PolyFox6320 (a surfactant available from OMNOVA Solutions) in cyclopentanone; 1.46 parts of methacryloxypropyltrimethoxysilane (an adhesion promoter); 0.87 part of Ivocerin (an acylgermanium photoinitiator); 0.29 part of Irgacure 784 (a photoinitiator available from BASF); 0.06 part of monomethyl ether hydroquinone (an antioxidant); 10.22 parts of tetraethylene glycol diacrylate (a reactive functional compound, Komerate D048); 1.46 parts of neopentyl glycol triacrylate (a reactive functional compound, SR295); 0.15 part of 5-methylbenzotriazole (a copper corrosion inhibitor); 2.92 parts of 2,2-bis(4-cyanatophenyl)propane (a 50% solution of cyanate ester in cyclopentanone), a photosensitive dielectric film-forming composition (PSC-6) was prepared. After mechanical stirring for 24 hours, the solution was filtered using a 0.2-micron filter (Ultradyne from Meissner Corporation, catalog number CLTM0.2-552).

[0203] Example 7 of the photosensitive composition

[0204] By using 100 parts of a 29.19% solution of a polyimide polymer (I) having a weight average molecular weight of 54,000 daltons in cyclopentanone; 44.26 parts of cyclopentanone; 1.75 parts of a 0.5 wt% solution of PolyFox6320 (a surfactant available from OMNOVA Solutions) in cyclopentanone; 1.46 parts of methacryloxypropyltrimethoxysilane (an adhesion promoter); 0.88 part of Ivocerin (an acylgermanium photoinitiator); 0.06 part of monomethyl ether hydroquinone (an antioxidant); 10.95 parts of tetraethylene glycol diacrylate (a reactive functional compound); 3.65 parts of neopentyl glycol triacrylate (a reactive functional compound); 2.92 parts of 2,2-bis(4-cyanatophenyl)propane (a 50% solution of cyanate ester in cyclopentanone); and 0.15 part of 5-methylbenzotriazole (a copper corrosion inhibitor), a photosensitive dielectric film-forming composition (PSC-7) was prepared. After mechanical stirring for 24 hours, the solution was filtered using a 0.2-micron filter (Ultradyne from Meissner Corporation, catalog number CLTM0.2-552).

[0205] Example 8 of the photosensitive composition

[0206] A photosensitive dielectric film-forming composition (PSC-8) was prepared by using 100 parts of a 29.19% solution of a 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 bioderived γ-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); 0.88 parts of Ivocerin (an acylgermanium photoinitiator); 0.06 parts of monomethyl ether hydroquinone (an antioxidant); 10.95 parts of tetraethylene glycol diacrylate (a reactive functional compound); 3.65 parts of pentaerythritol triacrylate (a reactive functional compound); 2.92 parts of 2,2-bis(4-cyanatophenyl)propane (a 50% solution of cyanate in cyclopentanone); and 0.15 parts of 5-methylbenzotriazole (a copper corrosion inhibitor). After mechanical stirring for 24 hours, the solution was filtered using a 0.2-micron filter (Ultradyne from Meissner Corporation, catalog number CLTM0.2-552).

[0207] Example 9 of photosensitive composition

[0208] A photosensitive dielectric film-forming composition (PSC-9) was prepared by using 100 parts of a 29.19% solution of a 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 bioderived γ-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); 0.88 parts of 2-(O-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione (Irgacure OXE 01, a photoinitiator available from BASF), 0.22 parts of Ivocerin (an acylgermanium photoinitiator); 0.06 parts of monomethyl ether hydroquinone (an antioxidant); 10.95 parts of tetraethylene glycol diacrylate (a reactive functional compound); 3.65 parts of pentaerythritol triacrylate (a reactive functional compound); 2.92 parts of 2,2-bis(4-cyanatophenyl)propane (a 50% solution of cyanate in cyclopentanone); and 0.15 parts of 5-methylbenzotriazole (a copper corrosion inhibitor). After mechanical stirring for 24 hours, the solution was filtered using a 0.2-micron filter (Ultradyne from Meissner Corporation, catalog number CLTM0.2-552).

[0209] Example 10 of Photosensitive Composition

[0210] By mixing 200 parts by weight of EPON TM Resin SU-8 (a 40 wt% solution in butyl carbitol, supplied by Hexion), 3 parts by weight of triethoxysilylpropyl ethylcarbamate, 5 parts by weight of TPS-C1 (supplied by Heraeus) [salt of triphenylsulfonium and tris[(trifluoromethyl)sulfonyl]-methane (1:1)], and 1 part by weight of Ivocerin were used to prepare a negative photosensitive dielectric film-forming composition (PSC-10), and it was filtered through a 0.2-μm Teflon filter.

[0211] Subsequently, a silicon wafer was coated with the above photosensitive composition and baked on a hot plate at 95 °C for 3 minutes to obtain a film. The film was exposed using a patterned exposure array with a 405-nm exposure tool. The wafer was post-exposure baked at 95 °C for 90 seconds. The wafer was developed with PGMEA using two 30-second puddle development steps, and a spin step was used to remove the used developer between the two coatings of the developer. The developed film was rinsed with n-butyl acetate and dried by spinning at 5000 rpm for 10 seconds to provide a relief pattern.

[0212] Example 11 of Photosensitive Composition

[0213] By mixing 200 parts by weight of polymer solution RD09-07 (supplied by Fujifilm Electronic Materials U.S.A.), 3 parts by weight of triethoxysilylpropyl ethylcarbamate, 0.102 part 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, 1 part of Ivocerin, 10 parts by weight of tripropylene glycol, 20 parts by weight of additional PGMEA, and 30 parts by weight of GBL, a positive photosensitive composition was prepared, and it was filtered through a 0.2-μm Teflon filter.

[0214] Subsequently, a silicon wafer was coated with the above photosensitive composition and baked on a hot plate at 125 °C for 3 minutes to obtain a film. The film was exposed using a patterned exposure array with a 405-nm exposure tool. The wafer was post-exposure baked at 130 °C for 90 seconds. The wafer was developed with a 2.38 wt% aqueous TMAH solution using two 30-second puddle development steps, and a spin step was used to remove the used developer between the two coatings of the developer. The developed film was rinsed with deionized water and dried by spinning at 5000 rpm for 10 seconds to provide a relief pattern.

[0215] Example 12 of Photosensitive Composition

[0216] A dielectric film-forming composition was prepared by obtaining a homogeneous solution by mixing SC rubber (which is cyclized polyisoprene and supplied by Fujifilm Electronic Materials U.S.A.) (62.60 g, in a 28.5 wt% xylene solution), tricyclodecane dimethanol diacrylate (7.14 g, a reactive functional compound), and Ivocerin (0.53 g, a photoinitiator). The solution was filtered using a 5.0 micron PTFE filter.

[0217] Subsequently, a silicon wafer was coated with the above photosensitive composition and baked on a hot plate at 95 °C for 3 minutes to obtain a film. The film was exposed using a patterned exposure array with a 405 nm exposure tool. The wafer was post-exposure baked at 95 °C for 90 seconds. The wafer was developed with xylene using two 30-second puddle development steps, and a spin step was used to remove the used developer between the two coatings of the developer. The developed film was rinsed with PGMEA and dried by spinning at 5000 rpm for 10 seconds to provide a relief pattern.

[0218] Photosensitive composition Example 13

[0219] By mixing 28.48 g of PBO precursor polymer (I):

[0220]

[0221] Structure of polymer (1)

[0222] 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 were used to prepare a photosensitive composition. This composition was easily filtered using a 0.2 μm filter.

[0223]

[0224] Structure of PAC (II)

[0225] Subsequently, a silicon wafer was coated with the above photosensitive composition and baked on a hot plate at 95 °C for 3 minutes to obtain a film. The film was exposed using a patterned exposure array with a 405 nm exposure tool. The wafer was post-exposure baked at 130 °C for 90 seconds. The wafer was developed with a 2.38 wt% aqueous solution of TMAH using two 30-second puddle development steps, and a spin step was used to remove the used developer between the two coatings of the developer. The developed film was rinsed with deionized water and dried by spinning at 5000 rpm for 10 seconds to provide a relief pattern.

[0226] Photosensitive composition Example 14

[0227] A photosensitive composition was prepared by mixing 29.82 g of PD-1630 polymer (Durite Resin supplied by Hexion), 5.06 g of PS-9PAC (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.

[0228] Subsequently, a silicon wafer was coated with the above photosensitive composition and baked on a hot plate at 95 °C for 3 minutes to obtain a film. The film was exposed using a patterned exposure array with a 405 nm exposure tool. The wafer was post-exposure baked at 130 °C for 90 seconds. The wafer was developed using a 2.38 wt% aqueous TMAH solution in two 30-second puddle development steps, and the used developer was removed using a spin step between the two puddle developers. The developed film was rinsed with deionized water and dried by spinning at 5000 rpm for 10 seconds to provide a relief pattern.

[0229] Dry Film Example 1

[0230] A photosensitive dielectric film-forming composition was prepared by using a 31.69% solution of 1345.24 g of a polyimide polymer (I) (FCP-1) with a weight average molecular weight of 54,000 daltons in cyclopentanone; 1021.91 g of bio-derived γ-valerolactone (GVL); a 0.5 wt% solution of 102.31 g of PolyFox6320 in cyclopentanone; 21.31 g of methacryloxypropyltrimethoxysilane; a 50% solution of 34.11 g 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 diisopropylbenzene peroxide, and 0.426 g of 5-methylbenzotriazole. After mechanical stirring for 24 hours, the solution was filtered using a 0.2 micron filter (Ultradyne from Meissner Corporation, catalog number CLTM0.2-552).

[0231] The photosensitive dielectric film-forming composition obtained above was coated onto a polyethylene terephthalate (PET) film (TCH21, manufactured by DuPont Teijin Films USA) having a width of 16.2" and a thickness of 36 microns (which serves as a carrier substrate) using a slot die coater at a line speed of about 2 feet / minute (61 cm / minute) and a gap of 60 microns, and dried at 194°F to obtain a photosensitive polymer layer. On this polymer layer, a biaxially oriented polypropylene film (BOPP, manufactured by Impex Global, Houston, TX) having a width of 16" and a thickness of 30 microns was laid by roll pressing to serve as a protective layer. The carrier substrate, the photosensitive polymer layer, and the protective layer together form a dry film (i.e., DF1).

[0232] Three-dimensional object instance 1

[0233] The photosensitive dielectric film-forming composition described in the dry film instance 1 was converted into a film deposited on various substrates used in microelectronics and packaging applications. The film was deposited on a 100 mm silicon wafer by spin coating about 5 g of the solution at a rotational speed of about 2000 rpm. The film was dried on a hot plate at a temperature of 105°C for 3 minutes to obtain a 12-micron permeable and transparent film. The film quality in terms of transparency, defect count, and uniformity was expected to meet the requirements of semiconductor packaging applications.

[0234] The above procedure was repeated on aluminum, copper, and silicon nitride wafers. All the films obtained thereby were expected to meet the requirements of semiconductor packaging applications.

Claims

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

2. The composition according to claim 1, wherein, The at least one acyl germanium compound comprises a compound of structure (I): Wherein 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 and R 4 each independently is C1-C 12 alkyl, C2-C 12 alkenyl, C4-C 18 cycloalkyl, C6-C 22 aryl, C6-C 22 heteroaryl or -C(O)R, wherein R is C1-C4 alkyl, C5-C 12 cycloalkyl, C6-C 18 aryl or C6-C 18 heteroaryl; and The alkyl, alkenyl, cycloalkyl, aryl or heteroaryl is each independently optionally substituted by at least one of the following groups: C1-C4 alkyl, halogen, C1-C4 haloalkyl, -OR 5 , -OC(O)R 5 or -COOR 5 , wherein R 5 is H, C1-C4 alkyl, C5-C 12 cycloalkyl, C6-C 18 aryl or C6-C 18 heteroaryl.

3. The composition according to claim 1 or 2, wherein, The at least one acyl germanium compound comprises (2,4,6-trimethylbenzoyl)triethylgermane, (2,4,6-trimethylbenzoyl)tripropylgermane, (2,4,6-trimethylbenzoyl)tributylgermane, (2,6-dimethoxybenzoyl)triethylgermane, (2,6-dimethoxybenzoyl)tripropylgermane, (2,6-dimethoxybenzoyl)tributylgermane, dibenzoyldiethylgermane, dibenzoyldipropylgermane, bis(4-methoxybenzoyl)diethylgermane, bis(2,4,6-trimethylbenzoyl)diethylgermane, tribenzoylethylgermane, tris(2,4,6-trimethylbenzoyl)ethylgermane.

4. The composition according to any one of claims 1 to 3, wherein, Based on the solid weight of the composition, the amount of the at least one acyl germanium compound is about 0.05 wt% to about 20 wt%.

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

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

7. The composition according to claim 6, wherein, The radical initiator is an oxime ester of structure (II): Wherein R 11 and R 12 each independently is a substituted or unsubstituted C1-C 12 alkyl group, a substituted or unsubstituted C4-C 18 cycloalkyl group, a substituted or unsubstituted C6-C 22 aryl group or a substituted or unsubstituted C6-C 22 heteroaryl group; and R 13 is a UV absorption functional group.

8. The composition according to claim 5, wherein The at least one radical initiator comprises a compound of structure (III): Wherein M is a metal selected from the group consisting of titanium, zirconium or hafnium; and R 14 and R 15 each independently selected from the group consisting of: 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 and substituted or unsubstituted alkylsulfonyloxy.

9. The composition according to any one of claims 1 to 8, wherein, The at least one resin comprises: a fully imidized polyimide optionally containing a functional group; a cyclized rubber; a cycloolefin polymer optionally containing a functional group; a polyphenylene ether; an acrylic compound; a cyanate ester compound; a polybenzoxazole precursor polymer; a novolak polymer; an epoxy novolak polymer; or an alkali-soluble polyimide.

10. The composition according to any one of claims 1 to 9, wherein, Based on the solid weight of the composition, the amount of the at least one resin is about 0.1 wt% to about 55 wt%.

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 according to any one of claims 1 to 11, further comprising a photosensitizer selected from the group consisting of benzophenone, thioxanthone, anthraquinone, anthracene and coumarin.

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

16. A patterned dielectric film produced by the process according to claim 15.

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

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

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

20. A process for preparing a three-dimensional object, comprising: a) depositing a dielectric film-forming composition according to any one of claims 1 to 14 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 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.

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

22. A process for forming a three-dimensional object, comprising: a) providing a substrate having a metal wire structure that forms a network structure of wires and interconnects on the substrate; b) depositing a dielectric film-forming composition according to any one of claims 1 to 14 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.

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

24. The semiconductor device according to claim 23, wherein, The semiconductor device is an integrated circuit, a light-emitting diode, a solar cell, or a transistor.

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

26. A method for preparing a dry film structure, comprising: (a) coating a carrier substrate with a composition according to 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.

27. The method according to claim 26, further comprising: The dry film structure is applied to an electronic substrate to form a laminate, wherein, The dielectric layer in the laminate is between the electronic substrate and the carrier substrate.

28. A process for producing a dielectric film on a substrate having a copper pattern, comprising: depositing a composition according to any one of claims 1 to 14 on a substrate having a copper pattern to form a dielectric film, Among them, The height difference between the highest and lowest points on the surface of the dielectric film is at most about 2 microns.

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