Polyimide containing a novel bis-o-aminophenol, photosensitive composition, dielectric film, and buffer coating containing the same

Abstract

Polyimide containing a novel indan bis-o-aminophenol and the preparation of a functional polyimide and a photosensitive composition obtained therefrom are described.

Description

Technology Field

[0001] Cross-reference regarding related applications

[0002] This application claims priority to U.S. Provisional Application No. 63 / 608,471 filed on December 11, 2023, the entire contents of which are incorporated herein by reference.

[0003] Technology field

[0004] The present disclosure relates to a polyimide comprising indan bis-o-aminophenol as a diamine monomer, and a dielectric film-forming composition prepared therefrom. Background Technology

[0005] The requirements for dielectric materials in semiconductor packaging applications are continuously evolving. Trends in electronic packaging are moving toward faster processing speeds, increased complexity, and higher packaging densities while maintaining high levels of reliability. As electronic packaging technology advances and chip sizes continue to shrink, the demand for innovative, high-performance resin compositions is growing.

[0006] The present disclosure provides a polyimide comprising an indan bis-o-aminophenol as a diamine monomer and a dielectric film-forming composition prepared therefrom. The dielectric film-forming composition of the present disclosure meets the very demanding requirements of the microelectronics industry. In some embodiments of the disclosure, a dielectric film-forming composition is provided comprising (a) at least one polyimide comprising at least one indan bis-o-aminophenol of formula Ia as a diamine monomer:

[0007]

[0008] In the chemical formula, R 1 , R 2 , R 3 , R 4 , and R 5Each is independently a hydrogen atom, a substituted or unsubstituted C1-C 12 Alkyl, partially halogen-substituted, or fully halogen-substituted C1-C 12 Alkyl, substituted, or unsubstituted C4-C 18 Cycloalkyl, substituted or unsubstituted C6-C 22 Aryl, or substituted or unsubstituted C5-C 22 It is heteroaryl; R 11 and R 12 are, respectively, hydrogen atoms, linear or branched C1-C4 alkyls, and C4-C 12 Cycloalkyl, C6-C 18 Aryl, C5-C 18 It is a heteroaryl group, a C1-C4 alkoxy group, or a halogen atom.

[0009] of the present disclosure Polyimide can be used in different photosensitive compositions to provide positive tone or negative tone photosensitive compositions, both of which are soluble in alkaline aqueous solutions, can form fine patterns, and can achieve high resolution.

[0010] In some embodiments of the present disclosure, a dielectric layer that can be cast from the composition of the present disclosure is provided. The dielectric layer of the present disclosure can form a uniform film, which can be developed after exposure to a relatively long UV wavelength (e.g., about 365 nm) to form a patterned dielectric film. When the dielectric layer of the present disclosure is present in a microelectronic device, the dielectric layer imparts excellent reliability to the device.

[0011] A dielectric layer can be cast from the dielectric film-forming composition of the present disclosure. The composition of the present disclosure can form a uniform film, which can be developed after exposure to a relatively long UV wavelength (e.g., about 365 nm) to form a patterned dielectric film, and the patterned dielectric film can exhibit desirable characteristics according to one or more reliability tests.

[0012] In some embodiments, the present disclosure provides a composition comprising a fully imidized polyimide comprising at least one indan bis-o-aminophenol compound and at least one solubility switching compound comprising a vinyl group, an allyl group, a vinyl ether group, a propene ether group, a (meth)acryloyl group, a SiH group, or a thiol group, and the dielectric composition is suitable for providing a dielectric layer that imparts excellent reliability to a microelectronic device when the dielectric layer is present in the device.

[0013] Other aspects, embodiments, and advantages are as follows. Specific details for implementing the invention

[0014] Generally, the present disclosure relates to polyimides, dielectric film-forming compositions, as well as related processes, dry films, and dielectric films. In some embodiments, the dielectric film-forming composition described herein comprises (a) at least one polyimide comprising at least one indan bis-o-aminophenol as a diamine monomer. In some embodiments, the dielectric film-forming composition described herein may be photosensitive and / or thermosetting.

[0015] The present disclosure provides a polyimide containing at least one indan bis-o-aminophenol monomer. Such monomers are suitable for manufacturing polymers that meet the very demanding requirements of the microelectronics industry. The presence of the indan bis-o-aminophenol monomer of the present disclosure in the polyimide provides a fully cyclized polyimide that is easily soluble and has high-temperature stability. The present disclosure also provides a fully cyclized polyimide containing a functional group, the functional group being selected from substituted or unsubstituted linear alkenyl groups, substituted or unsubstituted linear alkynyl groups, (meth)acrylic groups, or hydroxyl groups.

[0016] The present disclosure provides an indan bis-o-aminophenol compound comprising an indan moiety of structure Ia:

[0017]

[0018] In the chemical formula, R 1 , R 2 , R 3 , R 4 , and R 5 Each is independently a hydrogen atom, a substituted or unsubstituted C1-C 12 Alkyl, partially halogen-substituted, or fully halogen-substituted C1-C 12 Alkyl, substituted, or unsubstituted C4-C 18 Cycloalkyl, substituted or unsubstituted C6-C 22 Aryl, or substituted or unsubstituted C5-C 22 It is heteroaryl; R 11 and R 12 are, respectively, hydrogen atoms, linear or branched C1-C4 alkyls, C5-C 12 Cycloalkyl, C6-C 18 Aryl, C5-C 18 It is a heteroaryl group, a C1-C4 alkoxy group, or a halogen atom.

[0019] In some embodiments, the dielectric film-forming composition presented herein comprises at least one fully imidized polyimide. In some embodiments, the fully imidized polyimide has a structure (II):

[0020]

[0021] In the structure, R 21 Silver, hydrogen, or C1-C 12 It is an alkenyl group, and R 22 is hydrogen or C1-C 12 Alkyl, C2-C 12 Alkenyl, C4-C 18 Cycloalkyl, C6-C 22 Aryl, or C5-C 22 It is a heteroaryl group; R 23 is a terminal group, and at least one monohydric compound is added to the polymerization system to terminate the chain growth of the polyamic acid, n1 is an integer greater than 1 (e.g., 1 to 200), and n2 is an integer greater than or equal to 2 (e.g., 2 to 200). R 21 Examples of include, but are not limited to, hydrogen, acetyl, trifluoroacetyl, propionyl, trimethylacetyl, etc. R 22 Examples of include, but are not limited to, hydrogen, methyl, ethyl, allyl, phenyl, etc. R 23 Examples of such end groups include, but are not limited to, acetyl, trifluoroacetyl, propionyl, trimethylacetyl, etc. Examples of such end groups (e.g., functional or non-functional end groups) are disclosed, for instance, in U.S. Patent No. 10,781,341, the entire contents of which are incorporated herein by reference.

[0022] In Structure II, B1 is the nucleus of the precursor diamine, and A1 and A2 are each independently the nucleus of the precursor dianhydride, and A1 and A2 may be the same or different. When referring to the precursor diamine as used herein, "nucleus" refers to the moiety between two amine functional groups. When referring to the precursor dianhydride, "nucleus" refers to the moiety between two anhydride functional groups.

[0023] Examples of such diamines and dianhydrides are disclosed, for instance, in U.S. Patent No. 9,695,284, the entire contents of which are incorporated herein by reference. Functional or non-functional acid anhydrides or acid chlorides may be used for terminal-capping of unreacted amine functional groups on amino-terminal polyamic acids.

[0024] In some embodiments, the dielectric film forming composition comprises at least one fully imidized polyimide of structure (III), and R 22 , R 23 , n1 and n2 have the same meaning as defined above. R 24 is a reactive functional group such as a substituted or unsubstituted linear alkenyl group, a substituted or unsubstituted linear alkynyl group, or a (meth)acryloyl group, and these functional groups react additionally with the crosslinking agent. Other groups have the same meaning as defined above.

[0025]

[0026] Examples of suitable diamine B1 that can be used to prepare polymers of structure (II or III) are 1-(4-aminophenyl)-1,3,3-trimethylindane-5-amine (alternative names include 4,4'-[1,4-phenylene-bis(1-methylethylidene)]bisaniline, 1-(4-aminophenyl)-1,3,3-trimethyl-2H-indene-5-amine, 1-(4-aminophenyl)-1,3,3-trimethyl-indane-5-amine, and [1-(4-aminophenyl)-1,3,3-trimethyl-indane-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-trimethylindane, 4-amino-6-methyl-1-(3'-amino-4'-methylphenyl)-1,3,3-trimethylingan, 5,7-diamino-1,1-dimethylingan, 4,7-diamino-1,1-dimethylingan, 5,7-diamino-1,1,4-trimethylingan, 5,7-diamino-1,1,6-trimethylingan, 5,7-diamino-1,1-dimethyl-4-ethylingan, p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 3-methyl-1,2-benzene-diamine, 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-Diaminodecane, 1,2-Diaminocyclohexane, 1,4-Diaminocyclohexane, 1,3-CyclohexaneBis(Methylamine), 5-Amino-1,3,3-TrimethylcyclohexaneMethanolamine, 2,5-Diaminobenzotrifluoride, 3,5-Diaminobenzotrifluoride, 1,3-Diamino-2,4,5,6-Tetrafluorobenzene, 4,4'-Oxidianiline, 3,4'-Oxidianiline, 3,3'-Oxidianiline, 3,3'-Diaminodiphenylsulfone, 4,4'-Diaminodiphenylsulfone, 4,4'-Isopropylidendianiline, 4,4'-Diaminodiphenylmethane, 2,2-Bis(4-Aminophenyl)propane, 4,4'-Diaminodiphenylpropane, 4,4'-Diaminodiphenyl Sulfide, 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-beta-amino-t-butylphenyl)ether, p-Bis-2-(2-methyl-4-aminopentyl)benzene, p-Bis(1,1-dimethyl-5-aminopentyl)benzene, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diaminobenzophenone, 3'-dichlorobenzidine, 2,2-Bis[4-(4-aminophenoxy)phenyl]propane, 4,4'-[1,3-phenylenebis(1-methyl-ethylidene)]bisaniline, 4,4'-[1,4-phenylenebis(1-methyl-ethylidene)]bisaniline, 2,2-Bis[4-(4-aminophenoxy)phenyl]sulfone, Includes, but is not limited to, 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, H-fluorene-2,6-diamine, bis(aminopropyl)tetramethyldisiloxane (BATMS), bis(aminopropyl)tetraphenyldisiloxane, bis(4-aminophenoxy)dimethylsilane, etc.

[0027] Examples of such diamines are disclosed, for instance, in U.S. Patents No. 10,604,628; No. 10,781,341; and No. 10,793,676, the entire contents of which are incorporated herein by reference. Any of these diamines may be used individually or may be used in combination in any suitable ratio to form the polyimide described herein.

[0028] Suitable for use in manufacturing polymers of structure (II or III) Examples of dianhydrides are 1-(3',4'-dicarboxyphenyl)-1,3,3-trimethylindane-5,6-dicarboxylic acid dianhydride, 1-(3',4'-dicarboxyphenyl)-1,3,3-trimethylindane-6,7-dicarboxylic acid dianhydride, 1-(3',4'-dicarboxyphenyl)-3-methylindane-5,6-dicarboxylic acid dianhydride, 1-(3',4'-dicarboxyphenyl)-3-methylindane-6,7-dicarboxylic acid dianhydride, pyromellitic acid dianhydride, benzene-1,2,3,4-tetracarboxylic acid dianhydride, 2,3,5,6-naphthalenetetracarboxylic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 1,4,5,8-Naphthalene tetracarboxylic acid dianhydride, 2,6-Dichloronaphthalene-1,4,5,8-tetracarboxylic acid dianhydride, 2,7-Dichloronaphthalene-1,4,5,8-tetracarboxylic acid dianhydride, 2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic acid dianhydride, Phenanthrene-8,9,10-tetracarboxylic acid dianhydride, 3,4,9,10-Perylene tetracarboxylic acid dianhydride, Pyrazine-2,3,5,6-tetracarboxylic acid dianhydride, Thiophene-2,3,4,5-tetracarboxylic acid dianhydride, 2,3,5,6-pyridine tetracarboxylic acid dianhydride, Butane-1,2,3,4-tetracarboxylic acid dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride, cyclobutane-1,2,3,4-tetracarboxylic acid dianhydride, cyclopentane-1,2,3,4-tetracarboxylic acid dianhydride, cyclohexane-1,2,4,5-tetracarboxylic acid dianhydride, norbornan-2,3,5,6-tetracarboxylic acid dianhydride, bicyclo[2.2.2]oct-7-en-3,4,8,9-tetracarboxylic acid dianhydride, tetracyclo[4.4.1.0 2,5 .0 7,10] Undecane-1,2,3,4-tetracarboxylic acid dianhydride, 3,3',4,4'-benzophenone tetracarboxylic acid dianhydride, 2,2',3,3'-benzophenone tetracarboxylic acid dianhydride, 2,3,3',4'-benzophenone tetracarboxylic acid dianhydride, 3,3',4,4'-diphenylsulfone tetracarboxylic acid dianhydride, 2,2',3,3'-diphenylsulfone tetracarboxylic acid dianhydride, 2,3,3',4'-diphenylsulfone tetracarboxylic acid dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic acid dianhydride, 2,2',3,3'-diphenyl ether tetracarboxylic acid dianhydride, 2,3,3',4'-diphenyl ether tetracarboxylic acid dianhydride, 2,2-[bis(3,4-dicarboxyphenyl)]hexafluoropropane dianhydride, ethylene glycol bis(anhydrotrimellitate), and 5-(2,5-dioxotetrahydro)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride are included, but not limited thereto. Examples of such dianhydrides are disclosed, for instance, in U.S. Patents No. 10,604,628; No. 10,781,341; and No. 10,793,676, the whole contents of which are incorporated herein by reference. Any of these tetracarboxylic acid dianhydrides may be used individually or may be used in any suitable ratio to form the polyimide described herein.

[0029] In some embodiments, the second step of polyamic acid synthesis may be performed by reacting an amino-terminal polyamic acid with a monohydride to yield a terminal-capped polyamic acid. In some embodiments, the terminal-capped polyamic acid may be used in further reactions without isolation. In other embodiments, when a cyclic monohydride is used for the termination of the amino group, an amic acid is formed. The amic acid is subsequently cyclized to an imide terminal group during the imidation of the polyamic acid into a fully cyclized polyimide. The monohydrides considered for use in these aspects of the disclosure include, for example, aliphatic acid anhydrides such as acetic anhydride, trifluoroacetic anhydride, pivalic anhydride, or cyclic anhydrides such as 1,1-cyclopentanediacetic anhydride, succinic anhydride, or maleic anhydride. Additional examples of end-capping devices are disclosed, for instance, in U.S. Patent No. 9,695,284, the entire contents of which are incorporated herein by reference.

[0030] In some embodiments, the fully imidized polyimide described herein is imidized by at least about 90% (e.g., at least about 95%, at least about 98%, at least about 99%, or about 100%). Evidence of the imidization level and polyimide structure formation is attributed to the imide ring structure at 1770 and 1700 cm⁻¹. -1 Within the infrared spectrum at It is confirmed by the observation of characteristic absorption.

[0031] 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 up to about 100,000 daltons (e.g., up to about 95,000 daltons, up to about 90,000 daltons, up to about 85,000 daltons, up to about 80,000 daltons, up to about 75,000 daltons, up to about 70,000 daltons, up to about 65,000 daltons, or up to about 60,000 daltons).

[0032] In some embodiments, the molar ratio of diamine component(s) to tetracarboxylic acid dianhydride component(s) is 1.01 to 1.20. In some embodiments, a molar ratio of diamine to diacid chloride of about 1.02 to 1.10 is used. It should be noted that when the molar ratio of diamine component(s) to tetracarboxylic acid dianhydride component(s) is greater than 1.00, the resulting species is an amino-terminal polyamic acid, which can further react with a terminal-capping monomer to form a terminal-capping polymer.

[0033] The present disclosure provides a polyimide comprising indan bis-o-aminophenol as a diamine monomer in the diamine component of a fully cyclized polyimide, wherein the indan bis-o-aminophenol represented by formula (Ia) is 1.0 to 90 mol% of the total amount of the diamine component incorporated into the polyimide chain as a diamine monomer. In some embodiments, the indan bis-o-aminophenol represented by formula (Ia) is 5 to 50 mol% of the total amount of the diamine component incorporated into the polyimide chain as a diamine monomer.

[0034] In some embodiments, the fully imidized polyimide is prepared by the reaction of at least one diamine with at least one tetracarboxylic acid dianhydride. In some embodiments, the resulting polymer is soluble in the organic solvent of this disclosure, thereby facilitating the formation of dielectric films, such as dielectric films having a flattened surface (e.g., the difference between the highest and lowest points on the upper surface of the dielectric film is less than about 2 microns). Examples of methods for preparing the fully imidized polyimide are known in the art, for example, as described in U.S. Patent Publication No. 2019 / 0077913, the entire contents of which are incorporated herein by reference.

[0035] Methods for synthesizing end-capping and non-end-capping polyimide (PI) precursor polymers are well known to those skilled in the art. Examples of such methods and PI precursor polymers are, for example, U.S. Patents No. 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, US5,478,915, US5,773,559, US5,783,656. Disclosed in US Patent No. 5,969,055, US Patent No. 9,617,386 and US Patent Publications No. 2004 / 0265731, US Patent No. 2004 / 0235992 and US Patent No. 2007 / 0083016, the entire contents of which are incorporated herein by reference.

[0036] In some embodiments, (a) a method of providing an organic solution containing a fully imidized polyimide polymer in at least one polar aprotic polymerization solvent; (b) a method of adding at least one purification solvent to the organic solution to form a diluted organic solution, wherein at least one purification solvent is less polar than at least one polymerization solvent and has a lower water solubility than at least one polymerization solvent at 25°C; (c) a method of washing the diluted organic solution with an acidified aqueous solution to obtain a washed organic solution; (d) a method of repeatedly washing the diluted organic solution with water to obtain a washed organic solution free of polymerization solvent; (e) a method of removing at least a portion of at least one purification solvent from the washed organic solution to obtain a solution containing a purified fully imidized polyimide polymer, wherein this method avoids precipitation of the fully imidized polyimide polymer.

[0037] 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 group 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 on the side chains of the polymer). As used herein, the term “alkali-soluble” means that the solubility in an aqueous solution of 2.38 wt% tetramethylammonium hydroxide at 25°C is about 0.1 g / 100 mL or more.

[0038] In some embodiments, the amount of indan bis-o-aminophenol-containing polyimide present in the dielectric film-forming composition of the present disclosure is at least about 0.1 wt% (e.g., 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 up to about 55 wt% (e.g., up to about 50 wt%, up to about 45 wt%, up to about 40 wt%, up to about 35 wt%, up to about 30 wt%, up to about 25 wt%, up to about 20 wt%, up to about 15 wt%, or up to about 10 wt%) of the solid weight of the dielectric film-forming composition described herein.

[0039] In some embodiments, the dielectric film-forming compositions described herein comprise at least one solubility-converting compound (SSC) having at least one functional group capable of reacting with other functional groups present on the polyimide. Such functional groups present on the polyimide include, for example, substituted or unsubstituted linear alkenyl groups, substituted or unsubstituted linear alkynyl groups, (meth)acrylic groups, or hydroxyl groups. In some embodiments, the solubility-converting compound may react on its own when there are no reactive functional groups on the polyimide polymer. In such cases, the composition typically comprises an initiator to facilitate the self-crosslinking of the solubility-converting compound.

[0040] Solubility-switching compounds generally help create a contrast in dissolution rates between unexposed and exposed areas after exposure to photochemical radiation. In some embodiments, the solubility-switching compound may be a crosslinking agent, which can crosslink the polymer in the exposed area after photochemical radiation exposure, thereby reducing the solubility of the exposed area in the developer.

[0041] The solubility-changing compound generally has at least one functional group or pendant reactive functional group capable of reacting with a terminal functional group on the polyimide polymer. The solubility-changing compound may be a monomer or an oligomer. The oligomer may contain many monomer units and may undergo further reactions to be incorporated into the final composition. Examples of such monomer units / oligomers include acrylates, esters, vinyl alcohols, urethanes, ureas, imides, amides, carboxazoles, carbonates, pyranoses, siloxanes, urea-formaldehyde, and melamine-formaldehyde. The solubility-changing compound generally contains at least one terminal and / or pendant reactive functional group capable of radical, thermal, or acid-catalyzed reactions with at least one functional group on the polyimide polymer.

[0042] Additional examples of solubility-switching compounds include, but are not limited to, compounds having vinyl groups, allyl groups, vinyl ether groups, propenyl ether groups, hydrophobic polyfunctional (meth)acrylates, epoxy groups, -SiH groups, and -SH (thiol) groups.

[0043] In some embodiments, the dielectric film-forming composition described herein comprises at least one (e.g., two, three, or four) hydrophobic polyfunctional (meth)acrylate as a solubility-switching compound. In some embodiments, the hydrophobic polyfunctional (meth)acrylate compound may comprise an ethylenically unsaturated polymerizable compound (e.g., an ethylenically unsaturated photopolymerizable compound), a metal-containing (meth)acrylate compound, or a mixture thereof.

[0044] In some embodiments, the hydrophobic polyfunctional (meth)acrylate compound described herein may comprise an ethylenically unsaturated polymerizable compound containing at least two (meth)acrylate groups. In some embodiments, the polyfunctional (meth)acrylate compound is 1,6-hexanediol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propoxylated (3) glycerol tri(meth)acrylate or tri-propoxylated glycerol triacrylate, ethoxylated bisphenol-A-di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol It is selected from the group consisting of tetra(meth)acrylate, dipentaerythritol penta- / hexa-(meth)acrylate, isocyanurate tri(meth)acrylate, bis(2-hydroxyethyl)-isocyanurate di(meth)acrylate, 1,3-butanediol tri(meth)acrylate, 1,4-butanediol tri(meth)acrylate, neopentyl glycol di(meth)acrylate, (meth)acrylate modified-urea-formaldehyde resin, (meth)acrylate modified melamine-formaldehyde resin, and (meth)acrylate modified cellulose. Other examples of such compounds are disclosed, for instance, in U.S. Patents No. 10,036,952 and 10,563,014 and U.S. Patent Publication No. 2015 / 0219990 and European Patent No. 3,492,982; the entire contents thereof are incorporated herein by reference.

[0045] In some embodiments, the crosslinking agent may be a metal-containing (meth)acrylate (MCA) compound. As used herein, the term “(meth)acrylate” refers to both acrylate compounds and methacrylate compounds. Examples of suitable MCAs include titanium tetra(meth)acrylate, zirconium tetra(meth)acrylate, hafnium tetra(meth)acrylate, titanium butoxide tri(meth)acrylate, titanium (meth)acryloxyethylacetoacetate triisopropoxide, titanium tris(2-ethylhexanoate) (carboxyethyl (meth)acrylate), titanium tetra(carboxyethyl (meth)acrylate), zirconium tetra(carboxyethyl (meth)acrylate), hafnium tetra(carboxyethyl (meth)acrylate), titanium butoxide tri(carboxyethyl (meth)acrylate), titanium dibutoxide di(carboxyethyl (meth)acrylate), titanium tributoxide (carboxyethyl (meth)acrylate), titanium oxide di(carboxyethyl (meth)acrylate), and zirconium butoxide tri(carboxyethyl (meth)acrylate), zirconium dibutoxide di(carboxyethyl (meth)acrylate), zirconium tributoxide (carboxyethyl (meth)acrylate), zirconium oxide di(carboxyethyl (meth)acrylate), zirconium bis(2-ethylhexanoate) di(carboxyethyl (meth)acrylate), and zirconium bis(2-ethylhexanoate) di(carboxyethyl (meth)acrylate) are included but not limited thereto. Other examples of such compounds are disclosed, for example, in U.S. Patent Publication No. 2021 / 104398; the whole of which is incorporated herein by reference.

[0046] In some embodiments, the crosslinking agent described herein may be present in an amount of 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 a maximum of about 35 wt% (e.g., a maximum of about 30 wt%, a maximum of about 28 wt%, a maximum of about 26 wt%, a maximum of about 24 wt%, a maximum of about 22 wt%, a maximum of about 20 wt%, a maximum of about 18 wt%, a maximum of about 16 wt%, a maximum of about 15 wt%, a maximum of about 14 wt%, a maximum of about 12 wt%, a maximum of about 10 wt%, a maximum of about 8 wt%, a maximum of about 6 wt%, or a maximum of about 5 wt%) of the solid weight of the dielectric film forming composition described herein.

[0047] The dielectric film-forming compositions described herein may optionally contain at least one (e.g., two, three, or four) radical initiators. As used herein, a radical initiator refers to a compound capable of generating free radicals capable of initiating radical polymerization or crosslinking upon heating or irradiation with light of a specific wavelength range (e.g., about 150 nm (e.g., about 157 nm) to about 600 nm). In some embodiments, the wavelength range is selected such that the radical initiator is absorbent and the radical polymerizable monomer is not substantially absorbent. 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.

[0048] In some embodiments, the amount of 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 a maximum of about 10 wt% (e.g., a maximum of about 9 wt%, a maximum of about 8 wt%, a maximum of about 7 wt%, a maximum of about 6 wt%, a maximum of about 5 wt%, a maximum of about 4 wt%, a maximum of about 3 wt%, a maximum of about 2 wt%, or a maximum of about 1 wt%) of the solid weight of the dielectric film forming composition described herein.

[0049] In some embodiments, the photoinitiator is photosensitized to light in the ultraviolet to visible light range. In some embodiments, the photoinitiator may be an activator that produces free radicals through some interaction with a photo-excited photosensitizer. In some embodiments, the photoinitiator is selected from the group consisting of oxime esters, titanocene, acyl germanium compounds, peroxides, and mixtures thereof.

[0050] An example of a photoinitiator is an oxime ester of structure (IV):

[0051]

[0052] In the structure, R 31 and R 32 are independently substituted or unsubstituted C1-C 12 Alkyl, substituted, or unsubstituted C4-C 18 Cycloalkyl, substituted or unsubstituted C6-C 22 Aryl, or substituted or unsubstituted C6-C 22 It is heteroaryl; R 33 UV absorbing functional groups (e.g., substituted or unsubstituted C6-C 22 Aryl or substituted or unsubstituted C6-C 22It is a heteroaryl. In some embodiments, the alkyl, cycloalkyl, aryl, or heteroaryl described above is optionally substituted by at least one (e.g., two or three) C1-C4 alkyl, halogen, C1-C4 haloalkyl, -OR', -OC(O)R', or -COOR', where R' is H, C1-C4 alkyl, C5-C 12 Cycloalkyl, C6-C 18 Aryl, or C6-C 18 It is a heteroaryl.

[0053] Another example of a photoinitiator is an organic titanocene compound of structure (V):

[0054]

[0055] In the structure, M is selected from the group consisting of titanium atoms, zirconium atoms, and hafnium atoms; R 34 and R 35 are independently substituted or unsubstituted C1-C 12 Alkyl, substituted, or unsubstituted C4-C 18 Cycloalkyl, substituted or unsubstituted C6-C 22 Aryl, substituted or unsubstituted C6-C 22 Heteroaryl, substituted or unsubstituted C6-C 22 Heteroaryl, or substituted or unsubstituted alkylsulfonyloxy groups (e.g., substituted or unsubstituted C1-C 12 It is selected from the group consisting of alkylsulfonyloxy groups. In some embodiments, the alkyl, cycloalkyl, aryl, or heteroaryl described above is optionally substituted by at least one (e.g., two or three) C1-C4 alkyl, halogen, C1-C4 haloalkyl, -OR', -OC(O)R', or -COOR', where R' is H, C1-C4 alkyl, C5-C 12 Cycloalkyl, C6-C 18 Aryl, or C6-C 18 It is a heteroaryl.

[0056] Commercial examples of photoinitiators include, but are not limited to, IRGACURE-784, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04, and IRGACURE OXE 05 available from BASF; and ADEKA OPTOMER N-1919, ADEKA ARKLS NCI-831, and ADEKA ARKLS NCI-930 available from ADEKA Corporation. Examples of other photoinitiators are disclosed, for instance, in European Patent No. 3,492,982, the entire contents of which are incorporated herein by reference.

[0057] Examples of thermal initiators include, but are not limited to, benzoyl peroxide, cyclohexanone peroxide, lauroyl peroxide, tert-amyl peroxybenzoate, tert-butyl hydroperoxide, di(tert-butyl)peroxide, dicumyl peroxide, cumene hydroperoxide, succinic acid peroxide, di(n-propyl)peroxydicarbonate, 2,2-azobis(isobutyronitrile), 2,2-azobis(2,4-dimethylvaleronitrile), dimethyl-2,2-azobis(isobutyrate), 4,4-azobis(4-cyanopentanic acid), azobiscyclohexanecarbonitrile, 2,2-azobis(2-methylbutyronitrile).

[0058] In some embodiments, an acyl germanium compound can be used as a photoinitiator. Suitable examples of acyl germanium compounds include, but are not limited to, (2,4,6-trimethylbenzoyl)triethylgermanium, (2,4,6-trimethylbenzoyl)tripropylgermanium, (2,4,6-trimethylbenzoyl)tribubutylgermanium, (2,6-dimethoxybenzoyl)triethylgermanium, (2,6-dimethoxybenzoyl)tripropylgermanium, (2,6-dimethoxybenzoyl)tribubutylgermanium, bisbenzoyldiethylgermanium, bisbenzoyldipropylgermanium, bis(4-methoxybenzoyl)diethylgermanium, bis(2,4,6-trimethylbenzoyl)diethylgermanium, trisbenzoylethylgermanium, tris(2,4,6-trimethylbenzoyl)ethylgermanium. A commercial example of an acyl germanium compound is ibocerin (i.e., bis(4-methoxybenzoyl)diethylgermanium). Other examples of such acyl germanium compounds are disclosed, for instance, in U.S. Patents No. 7,605,190 and No. 9,532,930, the entire contents of which are incorporated herein by reference.

[0059] In some embodiments, the dielectric film-forming composition described herein may comprise at least one (e.g., two, three, or four) photosensitive agent different from the acyl germanium compound, and the photosensitive agent may absorb light in a wavelength range of about 150 nm to about 600 nm (e.g., about 405 nm). Examples of suitable photosensitive agents that may be used in the dielectric film-forming composition include benzophenone compounds, thioxantone compounds, anthraquinone compounds, anthracene compounds, coumarin compounds, and mixtures thereof. Specific examples of photosensitive agents include, but are not limited to, 9-methylanthracene, 9,10-dibutoxycyanthracene, 9,10-diethoxycyanthracene, anthracene methanol, acenaphtylene, thioxantone, methyl-2-naphthyl ketone, 4-acetylbiphenyl, and 1,2-benzofluorene. Examples of other photosensitizers are disclosed, for instance, in U.S. Patent Publication No. 2022 / 0171285, the entire contents of which are incorporated herein by reference. In some embodiments, the acyl germanium compounds described herein may serve as photosensitizers.

[0060] In some embodiments, the amount of photosensitive material 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 a maximum of about 1 wt% (e.g., a maximum of about 0.8 wt%, a maximum of about 0.6 wt%, a maximum of about 0.5 wt%, a maximum of about 0.4 wt%, a maximum of about 0.2 wt%, or a maximum of about 0.1 wt%) of the solid weight of the dielectric film forming composition described herein.

[0061] In some embodiments, the dielectric film-forming composition described herein may further comprise an organic solvent or a mixture of organic solvents (e.g., two, three, or four). In another embodiment, the solvent is selected from the group consisting of alkylene carbonates, lactones, cycloketones, linear ketones, alkyl esters; alkyl ester alcohols, alkyl ether alcohols, alkyl ether esters, glycol esters; glycol ethers, cyclic ethers, pyrrolidone, and dialkyl sulfoxides and mixtures thereof. Examples of organic solvents suitable for the dielectric film-forming composition described herein include alkylene carbonates, such as ethylene carbonate, propylene carbonate, butylene carbonate, and glycerin carbonate; lactones, such as gamma-butyrolactone, ε-caprolactone, γ-caprolactone, and γ-valerolactone; cycloketones, such as cyclopentanone and cyclohexanone; Linear ketones, e.g., methyl ethyl ketone (MEK) and methyl isobutyl ketone (MIBK); esters, e.g., n-butyl acetate; ester alcohols, e.g., ethyl lactate; ether alcohols, e.g., tetrahydrofurfuryl alcohol; ether esters, e.g., (tetrahydrofuran-2-yl)methyl acetate, methyl-3-methoxypropionate, ethyl-3-ethoxypropionate and 3-methoxybutyl acetate; glycol esters, e.g., propylene glycol methyl ether acetate; glycol ethers, e.g., propylene glycol methyl ether (PGME); cyclic ethers, e.g., tetrahydrofuran (THF); pyrrolidones, e.g., N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or N-butyl-2-pyrrolidone or TamiSolve™ NxG; and dialkyl sulfoxides, such as dimethyl sulfoxide, are included but not limited thereto.

[0062] In some embodiments, the total amount of solvent is at least about 20 wt% (e.g., 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 up to about 98 wt% (e.g., up to about 95 wt%, up to about 90 wt%, up to about 85 wt%, up to about 80 wt%, up to about 75 wt%, up to about 70 wt%, or up to about 60 wt%) of the total amount of the dielectric film forming composition described herein.

[0063] In some embodiments, the dielectric film-forming composition described herein optionally comprises at least one (e.g., two, three, or four) filler (e.g., inorganic filler or inorganic particle). In some embodiments, the inorganic filler is selected from the group consisting of silica, alumina, titania, zirconia, hafnium oxide, CdSe, CdS, CdTe, CuO, zinc oxide, lanthanum oxide, niobium oxide, tungsten oxide, strontium oxide, calcium titanium oxide, sodium titanate, barium sulfate, barium titanate, barium zirconate, and potassium niobate. Preferably, the inorganic filler exists in a granular form with an average size of about 0.1 to 2.0 microns. In some embodiments, the filler is an inorganic particle containing a ferromagnetic material. Suitable ferromagnetic materials are elemental metals (e.g., iron, nickel, and cobalt) or their oxides, sulfides, and oxyhydroxides, and intermetallic compounds, such as awaruite (Ni3Fe), wararuite (CoFe), and Co 17 Sm2 and Nd2Fe 14 Includes B.

[0064] In some embodiments, the amount of 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 up to about 30 wt% (e.g., up to about 25 wt%, up to about 20 wt%, or up to about 15 wt%) of the solid weight of the dielectric film forming composition described herein.

[0065] In some embodiments, the dielectric film-forming compositions described herein may optionally further comprise at least one (e.g., two, three, or four) adhesion promoter. Suitable adhesion promoters are described in the literature ["Silane Coupling Agent" by Edwin P. Plueddemann, 1982, Plenum Press, New York]. Examples of such adhesion promoters are disclosed, for instance, in U.S. Patents No. 10,036,952 and 10,563,014, U.S. Patent Publication No. 2015 / 0219990, and European Patent No. 3,492,982, the entire contents of which are incorporated herein by reference.

[0066] In some embodiments, the amount of 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 up to about 4 wt% (e.g., up to about 3.5 wt%, up to about 3 wt%, up to about 2.5 wt%, or up to about 2 wt%) of the solid weight of the dielectric film forming composition described herein.

[0067] 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 whole of which is incorporated herein by reference.

[0068] In some embodiments, the amount of 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 up to about 1 wt% (e.g., up to about 0.5 wt% or up to about 0.2 wt%) of the solid weight of the dielectric film-forming composition described herein.

[0069] In some embodiments, the dielectric film-forming composition described herein may optionally contain at least one (e.g., two, three, or four) corrosion inhibitor.

[0070] Examples of suitable corrosion inhibitors include triazole compounds, imidazole compounds, and tetrazole compounds. Triazole compounds may include triazole, benzotriazole, substituted triazole, and substituted benzotriazole. A dielectric film forming composition containing a corrosion inhibitor prevents corrosion and discoloration of copper or copper alloys when a photosensitive layer is used on top of copper or copper alloys. The corrosion inhibitor additive plays a significant role in improving the HAST stability of TEG chips by effectively bonding to copper.

[0071] Examples of tetrazole compounds include 1-H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-(ethylthio)-1H-tetrazole, 5-(benzylthio)-1H-tetrazole, ethyl 1H-tetrazole-5-acetate, ethyl 1H-tetrazole-5-carboxylate, 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, 5-amino-1H-tetrazole, 1-methyl-1H-tetrazole, etc.

[0072] Examples of triazole compounds include, but are not limited to, 1,2,4-triazole, 1,2,3-triazole, or C1-C8 alkyl (e.g., 5-methyltriazole), and triazoles substituted with substituents such as amino, thiol, mercapto, imino, carboxyl, and nitro groups.

[0073] Additional examples of triazoles include 1,2,4-triazole, 1,2,3-triazole, 5-methyl-1,2,4-triazole, 3-amino-5-mercapto-1,2,4-triazole, 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, etc.

[0074] Examples of benzotriazoles include 1-H benzotriazole, tolyltriazole, 5-phenyl-benzotriazole, 5-nitro-benzotriazole, hydroxybenzotriazole, 2-(5-amino-pentyl)-benzotriazole, 5-phenylthiol-benzotriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, 4-carboxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole, etc. Examples of benzotriazoles include 2-hydroxy-5-acrylyloxyphenyl-2H-benzotriazole, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-(3-t-butyl-phenyl)5-methyl-2-hydroxy-benzotriazole, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-hydroxy-3-chloro-5-acrylyloxyphenyl-2H-benzotriazole, etc.

[0075] 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-imidazole methanol hydrochloride, and 2-mercapto-1-methylimidazole.

[0076] If used, the amount of 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 up to about 3.0 wt% (e.g., up to about 2.0 wt% or up to about 1.0 wt%) of the solid weight of the dielectric film-forming composition described herein. If the amount of corrosion inhibitor exceeds this range, storage stability is reduced, and if the amount of corrosion inhibitor is less than the above range, there is a possibility of voids occurring between the copper or copper alloy surfaces.

[0077] In some embodiments, the dielectric film-forming compositions described herein include one or more (e.g., two, three, or four) other optional components such as dyes, pigments, plasticizers, or antioxidants. Examples of such components are described in U.S. Patent Publication No. 2022 / 0127459, the entire contents of which are incorporated herein by reference.

[0078] In some embodiments, the dielectric film-forming compositions described herein are substantially fluorine-free compositions, and the fully imidized polyimide, solubility-switching compound, photoinitiator, photosensitizer, adhesion promoter, surfactant, solvent, corrosion inhibitor, and additives are substantially fluorine-free. In another embodiment, the dielectric film-forming compositions described herein are substantially fluorine-free perfluoroalkyl and polyfluoroalkyl materials (PFAS). Accordingly, the fully imidized polyimide, solubility-switching compound, photoinitiator, photosensitizer, adhesion promoter, surfactant, solvent, corrosion inhibitor, and additives are all fluorine-free perfluoroalkyl and polyfluoroalkyl materials (PFAS). In some embodiments, the dielectric film-forming compositions described herein are substantially halogen-free, and the fully imidized polyimide, solubility-switching compound, photoinitiator, photosensitizer, adhesion promoter, surfactant, solvent, corrosion inhibitor, and additives are all substantially halogen-free.

[0079] In some embodiments, a dielectric film may be prepared from a dielectric film forming composition described herein by a method comprising the following steps: (a) forming a dielectric film by coating the dielectric film forming composition described herein onto a substrate (e.g., a semiconductor substrate); and (b) optionally baking the film at an elevated 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).

[0080] Coating methods for manufacturing dielectric films include, but are not limited to, (1) spin coating, (2) spray coating, (3) roll coating, (4) rod coating, (5) rotary coating, (6) slit coating, (7) compression coating, (8) curtain coating, (9) die coating, (10) wire bar coating, (11) knife coating, and (12) dry film lamination. For coating methods (1) to (11), the dielectric film forming composition is typically provided in solution form. Those skilled in the art will select an appropriate solvent type and solvent concentration based on the coating type.

[0081] The substrate may have a circular, square, or rectangular shape, such as wafers or panels of various dimensions. Examples of suitable substrates are epoxy molded compound (EMC), silicon, glass, copper, stainless steel, copper clad laminate (CCL), aluminum, silicon oxide, and silicon nitride. The substrate may be flexible, such as polyimide, PEEK, polycarbonate, and polyester films. The substrate may have surface-mounted or embedded chips, dyes, or packages. The substrate may be sputtered or pre-coated with a combination of a seed layer and a passivation layer. In some embodiments, the substrate mentioned herein may be a semiconductor substrate. A semiconductor substrate used herein is a substrate (e.g., a silicon or copper substrate or wafer) that becomes part of a final electronic device.

[0082] The thickness of the dielectric film of the present disclosure is not particularly limited. In some embodiments, the dielectric film has a film thickness of 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 up to about 100 microns (e.g., up to about 90 microns, up to about 80 microns, up to about 70 microns, up to about 60 microns, up to about 50 microns, up to about 40 microns, or up to 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 2.0 microns).

[0083] In some embodiments, when the dielectric film forming composition is photosensitive, a method for manufacturing a patterned photosensitive dielectric film includes the step of converting the photosensitive dielectric film into a patterned dielectric film by a lithography method. In such cases, the conversion may include the step of exposing the photosensitive dielectric film to high-energy radiation (e.g., electron beam, ultraviolet, and X-ray) using a patterned mask.

[0084] After exposure, the dielectric film may be heat-treated from at least about 50°C (e.g., at least about 55°C, at least about 60°C, or at least about 65°C) to a maximum of about 100°C (e.g., at most about 95°C, 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 (e.g., at least about 65 seconds, or at least about 70 seconds) to a maximum of about 240 seconds (e.g., at most about 180 seconds, at most about 120 seconds, or at most about 90 seconds). Heat treatment is typically achieved using a hot plate or an oven.

[0085] After exposure and heat treatment, the dielectric film is developed using a developer to remove unexposed areas, thereby forming openings or relief images on the substrate. Development can be performed, for example, by immersion or spraying methods. Microholes and fine lines are developed It can be formed on a dielectric film on a stacked substrate.

[0086] In some embodiments, the dielectric film may be developed by using an organic developer. Examples of such developers include suitable organic solvents, such as gamma - Butyrolactone (GBL), gamma-valerolactone, cyrene, 2-methyl tetrahydrofuran, dimethyl sulfoxide (DMSO), N,N-diethylacetamid, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), 2-heptanone, cyclopentanone (CP), cyclohexanone, n-butyl acetate (nBA), propylene glycol methyl ether acetate (PGMEA), propylene glycol methyl ether (PGME), ethyl lactate (EL), propyl lactate, 3-methyl-3-methoxybutanol, tetralin, isophorone, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, triethylene glycol monoethyl ether, Dipropylene glycol monomethyl ether, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, diethyl malonate, ethylene glycol, 1,4:3,6-dianhydrosorbitol, isosorbide dimethyl ether, 1,4:3,6-dianhydrosorbitol 2,5-diethyl ether (2,5-diethylisosorbide), and mixtures thereof may be included, but are not limited thereto. A preferred developer is gamma-valerolactone, syrene, 2-methyl tetrahydrofuran , gamma- Butyrolactone (GBL), cyclopentanone (CP), cyclohexanone, ethyl lactate (EL), n-butyl acetate (nBA), and dimethyl sulfoxide (DMSO). These developers may be used individually or in combination of two or more to optimize image quality for compositions and lithography methods.

[0087] In some embodiments, the dielectric film may be developed by using an aqueous developer. When the developer is an aqueous solution, it preferably contains one or more aqueous bases. Examples of suitable bases are inorganic alkalis (e.g., potassium hydroxide, sodium hydroxide), primary amines (e.g., ethylamine, n -propylamine), secondary amines (e.g., diethylamine, di- n 2-propylamine), tertiary amines (e.g., triethylamine), alcoholamines (e.g., triethanolamine), quaternary ammonium hydroxides (e.g., tetramethylammonium hydroxide or tetraethylammonium hydroxide), and mixtures thereof, but are not limited thereto. The concentration of the base used will depend, for example, on the base solubility of the polymer used. The most preferred aqueous developer is one containing tetramethylammonium hydroxide (TMAH). Suitable concentrations of TMAH are in the range of about 1% to about 5%.

[0088] In some embodiments, after development with an organic developer, an optional rinsing treatment may be performed with an organic rinsing solvent to remove residues. Suitable examples of organic rinsing solvents include, but are not limited to, alcohols such as isopropyl alcohol, methyl isobutyl carbinol (MIBC), propylene glycol monomethyl ether (PGME), and amyl alcohol; esters such as n-butyl acetate (nBA), ethyl lactate (EL), and propylene glycol monomethyl ether acetate (PGMEA); ketones such as methyl ethyl ketone, and mixtures thereof.

[0089] In some embodiments, after a developing step or an optional rinsing step, an optional baking step (e.g., a developing-post-baking) may be performed at a temperature ranging from at least about 120°C (e.g., 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 a maximum of about 250°C (e.g., a maximum of about 240°C, a maximum of about 230°C, a maximum of about 220°C, a maximum of about 210°C, a maximum of about 200°C, or a maximum of about 190°C). The baking time is at least about 5 minutes (e.g., 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 up to about 5 hours (e.g., up to about 4 hours, up to about 3 hours, up to about 2 hours, or up to about 1.5 hours). This baking step can remove residual solvent from the residual dielectric film and further crosslink the residual dielectric film. Baking after development can be performed in air or, preferably under a nitrogen blanket, and can be performed by any suitable heating means.

[0090] In some embodiments, the patterned dielectric film comprises at least one element having a feature size of up to about 10 microns (e.g., up to about 9 microns, up to about 8 microns, up to about 7 microns, up to about 6 microns, up to about 5 microns, up to about 4 microns, up to about 3 microns, up to about 2 microns, or up to about 1 micron). One important embodiment of the present disclosure is that a dielectric film prepared from the dielectric film forming composition described herein can produce a patterned film having a feature size of up to about 3 microns (e.g., up to 2 microns or up to 1 micron) by a laser ablation method.

[0091] In some embodiments, the embodiment ratio (ratio of height to width) of a feature (e.g., the smallest feature) of the patterned dielectric film of the present disclosure is at least about 1 / 3 (e.g., 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).

[0092] In some embodiments (e.g., when the dielectric film forming composition is non-photosensitive), a method for manufacturing a patterned dielectric film includes the step of converting the dielectric film into a patterned dielectric film by laser ablation technology. A direct laser ablation method using an excimer laser beam is generally a dry, one-step material removal method for forming an opening (or pattern) in the dielectric film. In some embodiments, the wavelength of the laser is 640 nm or less (e.g., 157 nm, 193 nm, 248 nm, 308 nm, 351 nm, 405 nm, 445 nm, 470 nm, 520 nm, 528 nm, 555 nm, or 640 nm). Examples of suitable laser ablation methods include, but are not limited to, the methods described in U.S. Patents No. 7,598,167, 6,667,551, and 6,114,240, the contents of which are incorporated herein by reference.

[0093] In an embodiment, when the dielectric film forming composition is non-photosensitive, the composition may be used to form the lower layer of a double-layer photoresist. In this embodiment, the upper layer of the double-layer photoresist may be a photosensitive layer and may be patterned upon exposure to high-energy radiation. The pattern of the upper layer may be transferred to the lower dielectric layer (e.g., by etching). Afterward, the upper layer may be removed (e.g., by using a wet chemical etching method) to form a patterned dielectric film.

[0094] In some embodiments, the present disclosure features a method for depositing a metal layer (e.g., to create an embedded copper trace structure), the method comprising: (a) forming a patterned dielectric film having an opening; and (d) depositing a metal layer (e.g., an electrically conductive metal layer) at least one opening of the patterned dielectric film. For example, the method comprises: (a) forming a dielectric film by depositing a dielectric film forming composition described herein onto a substrate (e.g., a semiconductor substrate); (b) exposing the dielectric film to a radiation source or a heat source or a combination thereof (e.g., through a mask); (c) patterning the dielectric film to form a patterned dielectric film having an opening; and (d) depositing a metal layer (e.g., an electrically conductive metal layer) at least one opening of the patterned dielectric film. In some embodiments, steps (a) through (d) may be repeated one or more times (e.g., two, three, or four times).

[0095] In some embodiments, the present disclosure features a method for depositing a metal layer (e.g., an electrically conductive copper layer for creating an embedded copper trace structure) on a semiconductor substrate. In some embodiments, to achieve this, a conformal seed layer is first deposited on a patterned dielectric film (e.g., outside the openings of the film). The seed layer may contain a barrier layer and a metal seed layer (e.g., a copper seed layer). In some embodiments, the barrier layer is manufactured using a material capable of preventing the diffusion of an electrically conductive metal (e.g., copper) through the dielectric layer. Suitable materials that may be used for the barrier layer include, but are not limited to, tantalum (Ta), titanium (Ti), tantalum nitride (TiN), tungsten nitride (WN), and Ta / TaN. A suitable method for forming the barrier layer is sputtering (e.g., PVD or physical vapor deposition). Sputtering deposition offers several advantages as a metal deposition technique because it can be used to deposit many conductive materials at high deposition rates with excellent uniformity and low ownership costs. Conventional sputtering fill yields relatively poor results for deeper and narrower (high implementation ratio) features. The fill factor of sputtering deposition has been improved by collimating the sputtered flux. Typically, this is achieved by inserting a collimator plate with a hexagonal cell array between the target and the substrate.

[0096] The next step of this method is metal seed deposition. To enhance the deposition of the metal layer (e.g., a copper layer) formed in subsequent steps, a thin metal seed layer (e.g., an electrically conductive metal such as copper) may be formed on top of the barrier layer.

[0097] The next step of this method is to deposit an electrically conductive metal layer (e.g., a copper layer) on top of a metal seed layer within the openings of a patterned dielectric film, such that the metal layer is sufficiently thick to fill the openings of the patterned dielectric film. The metal layer filling the openings of the patterned dielectric film can be deposited by plating (e.g., electroless plating or electrolytic plating), sputtering, plasma vapor deposition (PVD), and chemical vapor deposition (CVD). Electrochemical deposition is generally a preferred method because it is more economical than other deposition methods and can completely fill the interconnect features with copper. The copper deposition method must generally meet the stringent requirements of the semiconductor industry. For example, the copper deposit must be uniform and capable of completely filling small interconnect features of devices, for example, having openings of 100 nm or less. This technology is described, for example, in U.S. Patents No. 5,891,804, 6,399,486, and 7,303,992, the contents of which are incorporated herein by reference.

[0098] In some embodiments, the method for depositing an electrically conductive metal layer further includes the step of removing the overburden of the electrically conductive metal or removing a seed layer (e.g., a barrier layer and a metal seed layer). In some embodiments, the overburden of the electrically conductive metal layer (e.g., a copper layer) is up to about 3 microns (e.g., up to about 2.8 microns, up to about 2.6 microns, up to about 2.4 microns, up to about 2.2 microns, up to about 2.0 microns, or up to about 1.8 microns) and at least about 0.4 microns (e.g., 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 copper overburden include aqueous solutions containing copper chloride and hydrochloric acid or aqueous mixtures of ferric nitrate and hydrochloric acid. Other suitable copper etchants include, but are not limited to, the copper etchants described in U.S. Patents No. 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. Patent Publication No. 2017 / 0175274, the contents of which are incorporated herein by reference.

[0099] In some embodiments, the present disclosure describes a method of surrounding a metal-structured substrate containing a conductive metal (e.g., copper) wire structure forming a line and an interconnection network with a dielectric film as described herein. This method is, for example,

[0100] a) A step of providing a substrate containing a conductive metal wire structure that forms a line and an interconnection network on the substrate;

[0101] b) A step of forming a dielectric film (e.g., a film surrounding a conductive metal line and an interconnection network) by depositing a dielectric film forming composition described herein onto a substrate; and

[0102] c) Step of exposing the dielectric film to a radiation source, a heat source, or a combination of radiation and heat (regardless of whether a mask is used)

[0103] It can be performed by.

[0104] The above steps can be repeated multiple times (e.g., 2, 3, or 4 times) to form a complex multilayer three-dimensional object.

[0105] In some embodiments, the present disclosure features a method for manufacturing a dry film structure. The method

[0106] a) A step of coating a carrier substrate (e.g., a substrate comprising at least one polymer or plastic film) with a dielectric film forming composition as described herein;

[0107] b) A step of drying a coated dielectric film forming composition to form a dielectric layer (e.g., a photosensitive dielectric layer); and

[0108] c) Optionally, a step of applying a protective layer to a dry film structure

[0109] Includes

[0110] In some embodiments, the carrier substrate is a single-layer or multilayer polymer or plastic film that may comprise one or more polymers (e.g., polyethylene terephthalate). In some embodiments, the carrier substrate has excellent optical transparency, which is substantially transparent to light irradiation used to form a relief pattern on the polymer layer. The thickness of the carrier substrate is preferably in the range of 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 a maximum of about 150 μm (e.g., a maximum of about 140 μm, a maximum of about 120 μm, a maximum of about 100 μm, a maximum of about 90 μm, a maximum of about 80 μm, or a maximum of about 70 μm).

[0111] In some embodiments, the protective layer is a single-layer or multilayer film, which may comprise one or more polymers (e.g., polyethylene or polypropylene). Examples of carrier substrates and protective layers are, for example, described in U.S. Patent Publication No. 2016 / 0313642, the contents of which are incorporated herein by reference.

[0112] When the dielectric layer of the present disclosure is present in a microelectronic device, the dielectric layer imparts excellent reliability to the device. Reliability is the probability that an electronic component performs a required function under stress conditions for a specified period. Preconditioning, temperature humidity bias (THB), biased humidity stress test (bHAST), unbiased HAST (uHAST), and high temperature storage (HTS) are stress tests commonly applied to semiconductor packaging materials. Reliability is measured as the ratio of devices that have not failed from time 0 to a specified time 't'.

[0113] The highly accelerated stress test (HAST) combines high temperature, high humidity, high pressure, and time to measure component reliability, with or without electrical bias. In a controlled environment, the HAST test accelerates the stress of more conventional tests. It essentially functions as a corrosion failure test. Corrosion-type failures are accelerated, allowing for the detection of defects such as packaging seals, materials, and joints within a shorter timeframe.

[0114] The biased highly accelerated stress test (bHAST) utilizes the same variables (high pressure, high temperature, and time) as the HAST test but adds voltage bias. The goal of the bHAST test is to accelerate corrosion within the device, thereby increasing the test duration. In the non-biased HAST test, humidity accelerates failure mechanisms associated with the presence of moisture in non-hermetic packages. Bias voltage under high humidity conditions causes galvanic and electrochemical corrosion in non-hermetic packages during the biased humidity stress test (bHAST). For advanced / emerging package technologies, board-level reliability (BLR) testing is conducted using a daisy-chain test vehicle to determine the reliability of solder joint interconnects. Failure analysis is performed on defective samples to determine the cause.

[0115] As an accelerated version of the conventional non-condensing THB (temperature and humidity bias) test, the HAST test has the advantage of accelerating temperature and humidity-induced failures to about one-tenth the time of the THB test by adding high pressure and high temperature (up to 149°C). HAST and BHAST tests are typically conducted at 130°C / 85%RH, but conditions may also vary.

[0116] Typical HAST test conditions consist of a temperature of 110°C or 130°C, 85% RH humidity, and a test duration of 96 or 200 hours. Once the high-acceleration stress test is completed, the test samples are analyzed by microscopy and SEM for changes that occurred during the HAST conditions. HAST testing generally follows JEDEC standard JESD22 A110, "High-Acceleration Temperature and Humidity Stress Test (HAST)." Biased Humidity Stress Testing (bHAST) is the most sensitive stress test for the reliability of microelectronic devices using organic dielectric film compositions. Examples of bHAST methods used for semiconductor device evaluation are described in U.S. Patent No. 9,874,813 and U.S. Patent Application No. 2021 / 0272898, the contents of which are incorporated herein by reference.

[0117] TEG (test element group) wafers plated with Cu posts (pillars) have been used by inspection methods for wafer evaluation, such as material development and package stability under HAST conditions. Examples of TEG wafers used for semiconductor device evaluation are described in U.S. Patents No. 8,237,450 and No. 9,082,708, the contents of which are incorporated herein by reference.

[0118] In some embodiments, the dielectric film of the dry film structure can be peeled off from the carrier layer as a self-supporting dielectric film. A self-supporting 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 self-supporting dielectric film is not cross-linked or cured and may include the components of the dielectric film forming composition described above, excluding the solvent.

[0119] In some embodiments, the dielectric loss tangent or dissipation factor of a dielectric film produced 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 a maximum of about 0.1 (e.g., a maximum of about 0.08, a maximum of about 0.06, a maximum of about 0.05, a maximum of about 0.04, a maximum of about 0.02, a maximum of about 0.01, a maximum of about 0.008, a maximum of about 0.006 or a maximum of about 0.005).

[0120] In some embodiments, the dielectric film of the dry film structure may be pre-laminated by planar compression or hot roll compression and then laminated onto a substrate (e.g., a semiconductor substrate such as a wafer) using a vacuum laminator at about 50°C to about 140°C. When hot roll lamination is used, the dry film structure may be placed in the hot roll laminator, an optional protective layer may be peeled off from the dielectric film / carrier substrate, and the dielectric film may be contacted with the substrate and laminated using a roller applying heat and pressure to form an article containing the substrate, the dielectric film, and the carrier substrate. Subsequently, the dielectric film may be exposed to a radiation source or a heat source (e.g., through the carrier substrate) to form a cross-linked dielectric film. In some embodiments, the carrier substrate may be removed before exposing the dielectric film to the radiation source or heat source.

[0121] Some embodiments of the present disclosure describe a method for forming a planarized dielectric film on a substrate having a copper pattern. In some embodiments, the method comprises the step of forming a dielectric film by depositing a dielectric film forming composition on a substrate having a copper pattern. In some embodiments, the method

[0122] a. The step of providing a dielectric film forming composition of the present disclosure, and

[0123] b. The method includes the step of forming a dielectric film by depositing a dielectric film forming composition on a substrate having a copper pattern, wherein the difference between the highest point and the lowest point on the surface of the dielectric film is up to about 2 microns (e.g., up to about 1.5 microns, up to about 1 micron, or up to about 0.5 microns).

[0124] In some embodiments, the present disclosure features an article (or three-dimensional object) comprising 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 insulators, wire coatings, wire enamels, and ink-treated substrates. In some embodiments, the present disclosure features a semiconductor device comprising one or more of such articles. Examples of semiconductor devices that may be made from such articles include integrated circuits, light-emitting diodes, solar cells, and transistors.

[0125] The present disclosure is illustrated in more detail with reference to the following examples, but these are for illustrative purposes only and should not be construed as limiting the scope of the present disclosure.

[0126] Examples

[0127] Synthesis Example 1: Preparation of a Fully Imidified Polyimide Polymer (PI-I)

[0128] Solid 4,4'-oxydiphthalic dianhydride (ODPA) (122.22 g) at 25°C in NMP (N-methylpyrrolidone) (640 g) 1-(4-aminophenyl)-1,3,3-trimethylindane-5-amine [also known as 4,4'-[1,4-phenylene-bis(1-methylethylidene)]bisaniline (DAPI)] (53.28 g), 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP) (41.05 g), and 6-amino-3-(3'-amino-4'-hydroxyphenyl)-1,1,3-trimethyl-2,3-dihydro-1 H - Added to a solution of inden-5-ol (indane bis-o-aminophenol) (29.84 g). The dianhydride was rinsed into the solution using additional NMP (100 g). The reaction temperature was increased to 40°C, and the mixture was reacted for 3 hours. Next, acetic anhydride (89.8 g) and pyridine (17.4 g) were added, the reaction temperature was increased to 100°C, and the mixture was reacted for 12 hours.

[0129] The solution is diluted with 300 g of tetrahydrofuran (THF). Afterward, the solution is precipitated in 8 L of distilled water. After filtration, the wet cake is air-dried. The crude polymer is dissolved in 500 g of THF and precipitated in 8 L of distilled water. After filtration, the wet cake is air-dried, and then air-dried under vacuum at 60°C for 12 hours to completely remove moisture. The weight-average molecular weight (Mw) is measured by GPC.

[0130] Synthesis Example 2: Preparation of a Fully Imidified Polyimide Polymer (PI-II)

[0131] Solid 4,4'-oxydiphthalic dianhydride (ODPA) (122.22 g) is added to a solution of DAPI (53.28 g), BAPP (41.05 g), and indan bis-o-aminophenol (29.84 g) in NMP (640 g) at 25°C. The dianhydride is rinsed into the solution using additional NMP (100 g). The reaction temperature is increased to 40°C, and the mixture is reacted for 3 hours. Afterward, methacrylic anhydride (30.8 g) and pyridine (15.8 g) are added, and the mixture is stirred for 2 hours. Next, acetic anhydride (89.8 g) and pyridine (17.4 g) are added, the reaction temperature is increased to 100°C, and the mixture is reacted for 12 hours.

[0132] The solution is diluted with 300 g of tetrahydrofuran (THF). Afterward, the solution is precipitated in 8 L of distilled water. After filtration, the wet cake is air-dried. The crude polymer is dissolved in 500 g of THF and precipitated in 8 L of distilled water.

[0133] After filtration, the wet cake is dried in air, and then under vacuum at 60°C for 12 hours to completely remove moisture. The weight-average molecular weight (Mw) is measured by GPC.

[0134] Synthesis Example 3: Preparation of Fully Imidified Polyimide (PI-III)

[0135] Solid 2,2',3,3'-benzophenone tetracarboxylic acid dianhydride (BTDA) (127.3 g) is added to a solution of DAPI (79.91 g) and indan bis-o-aminophenol (29.84 g) in NMP (445 g) at 25°C. The dianhydride is rinsed into the solution using an additional 100 g of NMP. The reaction temperature is increased to 40°C, and the mixture is reacted for 3 hours. To perform the terminal-capping reaction, 2.97 g of 4-methacryloxyethyl trimellitic anhydride (META) and 2.0 g of pyridine are added to the flask. The mixture is shaken at 60°C for 3 hours.

[0136] Next, acetic anhydride (60.4 g) and pyridine (23.43 g) are added, the reaction temperature is increased to 100°C, and the mixture is reacted for 12 hours.

[0137] The processing method is according to Example 1, and the weight average molecular weight (Mw) is measured by GPC.

[0138] The following designations should be used with reference to the photosensitive composition examples presented below.

[0139] (B) Multifunctional (meth)acrylate crosslinking agent

[0140] B-1: Tetra(ethylene glycol)diacrylate, D048 (trademark, available from Green Chemical, South Korea)

[0141] B-2: Pentaerythritol triacrylate, SR295 (trademark, available from Sartomer)

[0142] B-3: Hexanediol diacrylate SR238 (trademark, available from Sartomer)

[0143] B-4: Tricyclodecane dimethanol diacrylate SR833S (trademark, available from Sartomer)

[0144] B-5: 1,6-Bisphenol A (EO)2 diacrylate (manufactured by Sigma Aldrich Corp.)

[0145] B-6: 2-(tricyclo[5.2.1.02,6]deck-3-en-8-yloxy)ethyl acrylate (manufactured by Sigma Aldrich Corp.)

[0146] B-7: Tris(2-hydroxyethyl)isocyanurate triacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0147] B-8: 1,9-Nonanediol diacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0148] B-9: 1,10-Decyldiol Diacrylate SR595 (trademark, available from Sartomer)

[0149] (C) Photo-radical polymerization initiator

[0150] C-1: NCI-831 (trademark, available from ADEKA Corporation),

[0151] C-2: IRGACURE OXE 01 (Manufactured by BASF)

[0152] C3: IRGACURE OXE O2 (Manufactured by BASF)

[0153] C4: KEYCURE VIS-831 ​​(Titanium (4+) 2,4-Cyclopentadienide 1-(2,4-Difluorophenyl)-1H-pyrrole-3-ide (1:2:2)) (Manufactured by KING BROTHER CHEM CO., LTD)

[0154] (D) Adhesion promoter

[0155] D-1: gamma - Glycidoxypropyltrimethoxysilane (available from Gelest Corporation)

[0156] D-2: Gamma-glycidoxypropyltrimethoxysilane or SilQuest A-187 (available from Gelest Corporation)

[0157] D-3: 3-(trimethoxysilyl)propyl methacrylate (available from Gelest Corporation)

[0158] (E) Polymerization inhibitor

[0159] E-1: Monomethyl ether hydroquinone (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0160] E-2: Parabenzoquinone (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0161] E-3: t-butylcatechol (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0162] (F) Copper corrosion inhibitor

[0163] F-1: 5-methylbenzotriazole (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0164] F-2: 2-hydroxy-5-acrylyloxyphenyl-2H-benzotriazole (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0165] F-3: 1H Tetrazole (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0166] F-4: 5-phenyl 1H tetrazole (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0167] F-5: Ethyl 1H-tetrazole-5-acetate (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0168] F-6: Ethyl 1H-tetrazole-5-carboxylate (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0169] F-7: 3-amino-1,2,4-triazole (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0170] F-8: 3,5-diamino-1,2,4-triazole (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0171] (G) Surfactant

[0172] G-1: PolyFox 6320 from GBL (available from OMNOVA Solutions)

[0173] G-2: 0.5 wt% solution of PolyFox 6320 (available from OMNOVA Solutions) in propylene carbonate

[0174] G-3: Troysol S366 in 0.5% GBL (available from Troy Corp. Inc.)

[0175] (H) solvent

[0176] H-1: Gamma-butyrolactone (manufactured by Eastman)

[0177] H-2: Cyclopentanone (manufactured by Solvay)

[0178] H-3: Propylene carbonate (manufactured by Huntsman)

[0179] H-4: Dimethyl sulfoxide (manufactured by Sigma Aldrich Corp.)

[0180] H-5: N-methyl-2-pyrrolidone (manufactured by Ashland)

[0181] (I) Additives

[0182] I-1: 50% solution of XU 378 in cyclopentanone (prepared by Huntsman)

[0183] I-2: 50% solution of 2,2-bis(4-cyanatophenyl)propane in cyclopentanone (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0184] photosensitive Composition Example 1

[0185] A photosensitive composition (FE-1) is mixed with 80 g of a polymer solution (PI-I), 14.69 g of GBL (H-1), a 0.5 wt% solution of PolyFox 6320 (available from OMNOVA Solutions) in 1.42 g of GBL (G-1), 0.71 g of 3-(trimethoxysilyl)propyl methacrylate (D-3), 0.71 g of NCI-831E (trademark, available from ADEKA corporation) (C-1), and 0.05 g of blue It is prepared using benzoquinone (E-2), 8.00 g of tetra(ethylene glycol) diacrylate (B-1), and 2.67 g of pentaerythritol triacrylate (B-2). After mechanical stirring for 24 hours, the solution is filtered using a 0.2 micron filter.

[0186] photosensitive Composition Example 2

[0187] A photosensitive composition (FE-2) comprising 100 parts of a 32.46 percent solution of a polyimide polymer (PI-II), 93.2 parts of cyclopentanone (manufactured by Solvay) (H-2), 27.5 parts of gamma-butyrolactone (manufactured by Eastman) (H-1), 5.9 parts of PolyFox 6320 in GBL (available from OMNOVA Solutions) (G-1), 5 parts of 3-(trimethoxysilyl)propyl methacrylate (available from Gelest Corporation) (D-3), 3.0 parts of IRGACURE OXE 01 (manufactured by BASF) (C-2), 0.1 parts of t-butylcatechol (manufactured by Tokyo Chemical Industry Co., Ltd.) (E-3), and 32.5 parts of tetra(ethylene glycol) diacrylate, It is prepared using D048 (trademark, available from Green Chemical, South Korea), 12.5 parts of pentaerythritol triacrylate (SR295, trademark, available from Sartomer) (B-2), 5.0 parts of 2-(tricyclo[5.2.1.02,6]dek-3-en-8-yloxy)ethyl acrylate (manufactured by Sigma Aldrich Corp) (B-6), and 0.62 parts of 5-methyl benzotriazole (manufactured by Tokyo Chemical Industry Co., Ltd.) (F-1). After mechanical stirring for 24 hours, the solution is filtered using a 0.2 micron filter (Ultradyne from Meissner Corporation, catalog number CLTM0.2-552).

[0188] photosensitive Composition Example 3

[0189] The photosensitive composition (FE-3) comprises 100 parts of a 29.19% solution of polyimide polymer (PI-III), 9.5 parts of cyclopentanone (manufactured by Solvay) (H-2), 142 parts of propylene carbonate (manufactured by Huntsman) (H-3), 0.5 wt% solution of PolyFox 6320 (available from OMNOVA Solutions) in 6.0 parts of propylene carbonate (G-2), 5.0 parts of 3-(trimethoxysilyl)propyl methacrylate (available from Gelest Corporation) (D-3), 3.0 parts of IRGACURE OXE 01 (manufactured by BASF) (C-2), 0.2 parts of hydroquinone (E-1), 37.5 parts of tetra(ethylene glycol) diacrylate, D048 (trademark, from Green Chemical, South Korea). (Available)(B-1), 12.5 parts tetra(ethylene glycol)diacrylate, D048 (trademark, available from Green Chemical, South Korea)(B-2), 50% solution of 2,2-bis(4-cyanatophenyl)propane in 10.0 parts cyclopentanone (manufactured by Tokyo Chemical Industry Co., Ltd.)(I - 2) and 0.5 parts of 5-methylbenzotriazole (manufactured by Tokyo Chemical Industry Co., Ltd.) (F-1) are prepared. After mechanical stirring for 24 hours, the solution is filtered using a 0.2 micron filter (Ultradyne from Meissner Corporation, catalog number CLTM0.2-552).

[0190] photosensitive Composition Example 4

[0191] The photosensitive composition (FE-4) comprises 100 parts of a 29.19% solution of a polyimide polymer (PI-III), 9.5 parts of cyclopentanone (manufactured by Solvay) (H-2), 142 parts of propylene carbonate (manufactured by Huntsman) (H-3), 2.0 parts by weight of Troysol S366 in 0.5% GBL (available from Troy Corp. Inc.) (G-3), 5.0 parts of 3-(trimethoxysilyl)propyl methacrylate (available from Gelest Corporation) (D-3), 3.0 parts of IRGACURE OXE 01 (manufactured by BASF) (C-2), 0.2 parts of hydroquinone (E-1), 37.5 parts of tetra(ethylene glycol) diacrylate, D048 (trademark, available from Green Chemical, South Korea) (Available)(B-1), 12.5 parts tetra(ethylene glycol) diacrylate, D048 (trademark, available from Green Chemical, South Korea)(B-2), 50% solution of 2,2-bis(4-cyanatophenyl)propane in 10.0 parts cyclopentanone (manufactured by Tokyo Chemical Industry Co., Ltd.)(I - 2) and 0.5 parts of 5-methylbenzotriazole (manufactured by Tokyo Chemical Industry Co., Ltd.) (F-1) are prepared. After mechanical stirring for 24 hours, the solution is filtered using a 0.2 micron filter (Ultradyne from Meissner Corporation, catalog number CLTM0.2-552).

[0192] Lithography Method Example 1

[0193] A photosensitive composition FE-1 is spin-coated onto a silicon wafer and baked at 95°C for 6 minutes using a hot plate to form a coating with a thickness of 7.95 microns.

[0194] A photosensitive polyimide film is exposed to various levels of exposure energy using a Canon 4000 IE i-line stepper.

[0195] Remove non-exposed areas using cyclopentanone as the developer (dynamic development once for 40 seconds), and then rinse the developed film with PGMEA for 15 seconds to form a pattern. 200 mJ / cm² 2 Achieves a resolution of 4 microns at the sensitivity. The film thickness loss is 20%.

[0196] General procedure for measuring the mechanical properties of films

[0197] The filtered polymer solution is applied onto a silicon oxide wafer via spin coating to obtain a film approximately 12.0 to 15.0 microns thick. The coating is dried in a 90°C hot plate oven for 10 minutes. Afterward, the film is subjected to 500 mJ / cm² 2 It is exposed to [the element]. Finally, the film is baked using a YES oven under vacuum at 230°C for 3 hours. The film is peeled off from the silicon oxide layer using a 2% hydrofluoric acid solution and air-dried at 50°C for 2 hours. After cooling to room temperature, the film is characterized by DMA for Tg measurement.

[0198] Reliability test example

[0199] The dielectric film forming composition of Examples FE 1-3 is spin-coated at 1200 rpm onto a TEG chip having copper-plated line / space patterns ranging from 2 / 2 micron, 8 / 8 micron, and 15 / 15 micron in thickness from 6 to 12 microns, and baked using a hot plate at 95°C for 5 minutes to form a coating layer approximately 13 microns thick. Subsequently, the dielectric film forming composition is applied using an LED i-line exposure tool at 500 mJ / cm² 2The blanket is exposed to the surface. The composition is cured in a YES oven at 170°C to 230°C for 3 hours.

Claims

Claim 1 A polyimide comprising reaction products of components (a), (b), and (c), wherein components (a), (b), and (c) are at least one bis-o-aminophenol selected from the group consisting of diamines of formula Ia: In the chemical formula, R 1 , R 2 , R 3 , R 4 , and R 5 Each is independently a hydrogen atom, a substituted or unsubstituted C1-C 12 Alkyl, partially halogen-substituted, or fully halogen-substituted C1-C 12 Alkyl, substituted, or unsubstituted C4-C 18 Cycloalkyl, substituted or unsubstituted C6-C 22 Aryl, or substituted or unsubstituted C5-C 22 It is heteroaryl; R 11 and R 12 are, respectively, hydrogen atoms, linear or branched C1-C4 alkyls, and C4-C 12 Cycloalkyl, C6-C 18 Aryl, C5-C 18 A polyimide that is a heteroaryl group, a C1-C4 alkoxy group, or a halogen atom; (b) at least one other diamine; and (c) at least one tetracarboxylic acid dianhydride. Claim 2 A polyimide comprising reaction products of components (a), (b), (c), and (d), wherein components (a), (b), (c), and (d) are at least one diamine selected from the group consisting of (a) an indan bis-o-aminophenol of formula (Ia): In the chemical formula, R 1 , R 2 , R 3 , R 4 , and R 5 Each is independently a hydrogen atom, a substituted or unsubstituted C1-C 12 Alkyl, partially halogen-substituted, or fully halogen-substituted C1-C 12 Alkyl, substituted, or unsubstituted C4-C 18 Cycloalkyl, substituted or unsubstituted C6-C 22 Aryl, or substituted or unsubstituted C5-C 22 It is heteroaryl; R 11 and R 12 are, respectively, hydrogen atoms, linear or branched C1-C4 alkyls, and C4-C 12 Cycloalkyl, C6-C 18 Aryl, C5-C 18 (b) a heteroaryl group, a C1-C4 alkoxy group, or a halogen atom; (c) at least one other diamine; (d) at least one tetracarboxylic acid dianhydride; and (d) at least one diamine selected from the group consisting of diamines of structure (Ia), wherein the phenolic hydroxyl group is functionalized to a reactive functional group selected from substituted or unsubstituted linear alkenyl groups, substituted or unsubstituted linear alkynyl groups, and (meth)acryloyl groups. Claim 3 (a) at least one polyimide of claim 1 or 2; (b) at least one solubility switching compound comprising at least one functional group selected from the group consisting of vinyl group, allyl group, vinyl ether group, propenyl ether group, (meth)acryloyl group, SiH group, and thiol group; (c) at least one initiator; and (d) at least one solvent comprising a photosensitive composition. Claim 4 A photosensitive composition according to paragraph 3, wherein the composition further comprises at least one member selected from the group consisting of at least one plasticizer compound, at least one adhesion promoter, at least one surfactant, at least one filler, at least one pigment, at least one dye, and at least one metal-containing (meth)acrylate compound. Claim 5 A method comprising the steps of: coating a substrate with the composition of claim 4 to form a coated substrate having a film on the substrate; and baking the coated substrate to form a coated substrate having a dried film. Claim 6 In claim 5, the coated substrate is baked at a temperature of about 50°C to about 200°C. Claim 7 A method according to claim 6, further comprising the step of exposing a dried film to radiation through a mask to form a coated substrate having a dried and pattern-wise exposed film. Claim 8 A method according to claim 7, further comprising the step of baking the dried and patterned exposed film at a temperature of about 50°C to about 150°C in a second baking step. Claim 9 A method according to claim 8, further comprising the step of developing a portion of the dried and exposed film in a developer to produce a relief image on a substrate. Claim 10 A method according to claim 9, further comprising the step of rinsing a relief image on a substrate with a solvent or a solvent mixture. Claim 11 A method according to claim 10, further comprising the step of baking a substrate having a relief image at a temperature of about 50°C to about 200°C in a third baking step. Claim 12 An article formed by the method of claim 11, wherein the article is a semiconductor substrate, a flexible film for electronic products, a wire insulator, a wire coating, a wire enamel, or an ink-treated substrate. Claim 13 A semiconductor device comprising the article of paragraph 12. Claim 14 In paragraph 13, the semiconductor device is an integrated circuit, a light-emitting diode, a solar cell, or a transistor. Claim 15 A dry film structure comprising a carrier substrate, a protective layer, and a polymer layer of claim 4 disposed between the carrier substrate and the protective layer. Claim 16 (a) a step of removing a protective layer from the dry film structure of claim 15; and (b) a step of applying the structure obtained in step (a) onto an electronic product substrate to form a laminate. Claim 17 A method according to claim 16, further comprising the step of removing the carrier substrate before or after exposing the polymer layer. Claim 18 A method according to claim 17, further comprising the step of removing non-exposed portions within the polymer layer using a developer. Claim 19 A method according to claim 18, further comprising the step of curing the residual polymer layer. Claim 20 An article formed by the method of paragraph 19, wherein the article is a semiconductor substrate, a flexible film for electronic products, a wire insulator, a wire coating, a wire enamel, or an ink-treated substrate. Claim 21 A semiconductor device comprising the article of paragraph 20. Claim 22 In paragraph 21, the device is a semiconductor device that is an integrated circuit, a light-emitting diode, a solar cell, or a transistor. Claim 23 In paragraph 4, a photosensitive composition substantially free of fluorine. Claim 24 (a) A photosensitive composition comprising at least one polyimide of claim 1, wherein the monomer represented by chemical formula (Ia) comprises 1.0 to 90 mol% of the total amount of diamine monomer incorporated into the polyimide. Claim 25 (a) A photosensitive composition comprising at least one polyimide of claim 2, wherein the monomer represented by chemical formula (Ia) comprises 1.0 to 90 mol% of the total amount of diamine monomer incorporated into the polyimide.

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