Microelectronic devices with good reliability, as well as related compositions and methods.

Abstract

This disclosure generally relates to microelectronic devices with good reliability, as well as related compositions and methods. In some embodiments, the method comprises providing a composition comprising a hydrophobic polyfunctional (meth)acrylate crosslinking agent and a polymer, and reacting the composition to provide a dielectric layer, the microelectronic device exhibiting good reliability when the dielectric layer is present in the device. In certain embodiments, the composition comprises a fully imidized polyimide and a hydrophobic polyfunctional (meth)acrylate crosslinking agent, and the dielectric composition is suitable for providing a dielectric layer that imparts good reliability to a microelectronic device when the dielectric layer is present in the device.

Description

[Technical Field]

[0001] Related applications This application claims priority to U.S. Provisional Patent Application No. 63 / 529,819, filed on 31 July 2023, the contents of which are incorporated herein by reference in their entirety.

[0002] Technical field This disclosure generally relates to microelectronic devices having good reliability, as well as related compositions and methods. In some embodiments, the method comprises providing a composition comprising a hydrophobic polyfunctional (meth)acrylate crosslinker and a polymer, and reacting the composition to provide a dielectric layer, the microelectronic device exhibiting good reliability when the dielectric layer is present in the microelectronic device. In certain embodiments, the composition comprises a fully imidized polyimide and a hydrophobic polyfunctional (meth)acrylate crosslinker, and the dielectric composition is suitable for providing a dielectric layer that imparts good reliability to the microelectronic device when the dielectric layer is present in the microelectronic device. Optionally, the polymer comprises at least one polybenzoxazole precursor polymer, at least one polyimide precursor polymer, or at least one fully imidized polyimide polymer, or a mixture thereof, and at least one hydrophobic polyfunctional (meth)acrylate crosslinker. [Background technology]

[0003] In general, the various desirable properties of dielectric materials for semiconductor packaging applications are continuously evolving. Generally, trends in electronic packaging continue to move towards faster processing speeds, increased complexity, and higher packaging density while maintaining a high level of reliability.

[0004] Often, reliability is a parameter considered when developing advanced integrated circuit (IC) packaging technology. Typically, component level reliability (CLR) and board level reliability (BLR) are two reliability steps in IC packaging technology. If a semiconductor chip can pass these two levels of reliability tests, it can often be used in the desired applications. For advanced / emerging package technologies, BLR tests may be performed to determine the reliability of solder joint interconnects using daisy chain-connected test vehicles. Failure analysis is performed on failed samples to identify the causes. Preconditioning, temperature humidity bias (THB), highly accelerated stress test (HAST), biased humidity stress test (bHAST), unbiased HAST (uHAST), and high temperature storage (HTS) are commonly used stress tests applied to semiconductor packaging materials to determine board level reliability (BLR). BLR is the ratio of devices that have not failed among the devices used from time zero to a given time "t". bHAST is a test of electrical insulation reliability under highly accelerated temperature, humidity, and bias voltage. Summary of the Invention

[0005] In some embodiments, the present disclosure provides a method comprising providing a composition comprising a hydrophobic polyfunctional (meth)acrylate crosslinker and a polymer, and reacting the composition to provide a dielectric layer, wherein when the dielectric layer is present in a microelectronic device, the microelectronic device exhibits good reliability. In certain embodiments, the present disclosure provides a composition comprising a fully imidized polyimide and a hydrophobic polyfunctional (meth)acrylate crosslinker, wherein the dielectric composition is suitable for providing a dielectric layer that imparts good reliability to a microelectronic device when the dielectric layer is present in the microelectronic device. The polymer can include one or more polybenzoxazole precursor polymers, polyimide precursor polymers, and / or fully imidized polyimide polymers. The dielectric layer can be cast from such a composition. The compositions of the present disclosure can form relatively uniform films, 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 properties according to one or more reliability tests.

[0006] In one aspect, the present disclosure provides a method comprising providing a composition comprising a hydrophobic polyfunctional (meth)acrylate crosslinker and a polymer, and processing the composition to provide a dielectric layer, wherein when the dielectric layer is present in a microelectronic device, the microelectronic device exhibits good reliability.

[0007] In some embodiments, the hydrophobic polyfunctional (meth)acrylate crosslinker has a logP value of at least 0.5.

[0008] The hydrophobic polyfunctional (meth)acrylate crosslinker includes at least one species selected from difunctional (meth)acrylates, trifunctional (meth)acrylates, tetrafunctional (meth)acrylates, and hexafunctional (meth)acrylates, and each of the hydrophobic polyfunctional (meth)acrylate crosslinkers has a logP value of from about 0.5 to about 8.0.

[0009] In some embodiments, the composition further comprises a corrosion inhibitor. In certain embodiments, the corrosion inhibitor has a logP value of about -1.0 to about 6.0.

[0010] In some embodiments, the composition further comprises a photopolymerization initiator. In certain embodiments, the photopolymerization initiator comprises at least one species selected from oxime esters, titanocene, acylgermanium compounds, and peroxides.

[0011] In some embodiments, the composition further comprises an organic solvent. In certain embodiments, the organic solvent comprises at least one species selected from alkylene carbonates, lactones, cycloketones, linear ketones, alkyl esters, alkyl ester alcohols, alkyl ether alcohols, alkyl ether esters, glycol esters, glycol ethers, cyclic ethers, pyrrolidones, and dialkyl sulfoxides.

[0012] In some embodiments, the polymer comprises at least one species selected from polybenzoxazole precursor polymers, polyimide precursor polymers, or fully imidized polyimide polymers. In certain embodiments, the polymer comprises a fully imidized polyimide polymer. In certain embodiments, the fully imidized polyimide polymer comprises a functional group. In certain embodiments, the fully imidized polyimide polymer comprises an alkali-soluble polymer. In certain embodiments, the fully imidized polyimide polymer comprises a fluorine atom-free polymer.

[0013] In some embodiments, the polymer is present in an amount of about 0.1% to about 55% by weight relative to the solids weight of the composition.

[0014] In some embodiments, the hydrophobic polyfunctional (meth)acrylate crosslinking agent is present in an amount of about 0.5% to about 25% by weight relative to the solids weight of the composition.

[0015] In some embodiments, the composition further comprises at least one selected from the group consisting of adhesion promoters, surfactants, fillers, pigments, dyes, and metal-containing (meth)acrylate compounds.

[0016] In some embodiments, the composition further comprises at least one photosensitizer selected from the group consisting of benzophenones, thioxanthones, anthraquinones, anthracenes, and coumarins.

[0017] In some embodiments, the composition is substantially fluorine-free.

[0018] In some embodiments, if the dielectric layer is present in a microelectronic device, the microelectronic device passes at least one test selected from the group consisting of HAST, bHAST, HTS, and TCT.

[0019] In some embodiments, the method further includes: depositing a composition on a substrate to form a film; exposing the film to radiation, heat, or a combination of radiation and heat to crosslink a hydrophobic polyfunctional (meth)acrylate crosslinking agent to provide a dielectric layer; and patterning the dielectric layer to form a patterned dielectric layer having openings. In some embodiments, the present disclosure provides a patterned dielectric layer produced by such embodiments.

[0020] In some embodiments, the method further includes: incorporating a dielectric layer into a microelectronic device.

[0021] In some embodiments, the substrate includes at least one type selected from organic films, epoxy molded compounds (EMC), silicon, glass, copper, stainless steel, copper-clad laminates (CCL), aluminum, silicon oxide, and silicon nitride.

[0022] In some embodiments, the method further includes: optionally depositing a seed layer on a patterned dielectric film; and depositing a metal layer within openings in the patterned dielectric film to form a metal pattern.

[0023] In some embodiments, the semiconductor device is an integrated circuit, a light-emitting diode, a solar cell, or a transistor.

[0024] In some embodiments, the method further includes supporting the dielectric film with a carrier layer.

[0025] In some embodiments, the method further includes: coating a carrier substrate with a composition to form a coated composition; drying the coated composition to form a dielectric layer; and optionally applying a protective layer to the dielectric layer to form a dry film structure.

[0026] In some embodiments, the method further includes applying a dry film structure onto an electronic substrate to form a laminate, and arranging a dielectric layer in the laminate between the electronic substrate and the carrier substrate.

[0027] In some embodiments, the method further includes depositing a dielectric film on a substrate having a copper pattern to form a dielectric film, wherein the height difference between the highest and lowest points on the surface of the dielectric film is at most about 2 microns.

[0028] In one embodiment, the present disclosure provides a composition comprising a fully imidized polyimide and a hydrophobic polyfunctional (meth)acrylate crosslinking agent, wherein the dielectric composition is suitable for providing a dielectric layer that imparts good reliability to a microelectronic device when the dielectric layer is present in the microelectronic device.

[0029] In some embodiments, the hydrophobic polyfunctional (meth)acrylate crosslinking agent has a logP value of at least 0.5.

[0030] In some embodiments, the hydrophobic polyfunctional (meth)acrylate crosslinking agent comprises at least one species selected from difunctional (meth)acrylate, trifunctional (meth)acrylate, tetrafunctional (meth)acrylate, and hexafunctional (meth)acrylate, each of which has a logP value of about 0.5 to about 8.0.

[0031] In some embodiments, the composition further comprises a corrosion inhibitor. In certain embodiments, the corrosion inhibitor has a logP value of about -1.0 to about 6.0.

[0032] In some embodiments, the composition further comprises a photopolymerization initiator. In certain embodiments, the photopolymerization initiator comprises at least one species selected from oxime esters, titanocene, acylgermanium compounds, and peroxides.

[0033] In some embodiments, the composition further comprises an organic solvent. In certain embodiments, the organic solvent comprises at least one species selected from alkylene carbonates, lactones, cycloketones, linear ketones, alkyl esters, alkyl ester alcohols, alkyl ether alcohols, alkyl ether esters, glycol esters, glycol ethers, cyclic ethers, pyrrolidones, and dialkyl sulfoxides.

[0034] In some embodiments, the polymer comprises at least one species selected from polybenzoxazole precursor polymers, polyimide precursor polymers, or fully imidized polyimide polymers. In certain embodiments, the polymer comprises a fully imidized polyimide polymer. In certain embodiments, the fully imidized polyimide polymer comprises a functional group. In certain embodiments, the fully imidized polyimide polymer comprises an alkali-soluble polymer. In certain embodiments, the fully imidized polyimide polymer comprises a fluorine atom-free polymer.

[0035] In some embodiments, the polymer is present in an amount of about 0.1% to about 55% by weight relative to the solids weight of the composition.

[0036] In some embodiments, the hydrophobic polyfunctional (meth)acrylate crosslinking agent is present in an amount of about 0.5% to about 25% by weight relative to the solids weight of the composition.

[0037] In some embodiments, the composition further comprises at least one selected from the group consisting of adhesion promoters, surfactants, fillers, pigments, dyes, and metal-containing (meth)acrylate compounds.

[0038] In some embodiments, the composition further comprises at least one photosensitizer selected from the group consisting of benzophenones, thioxanthones, anthraquinones, anthracenes, and coumarins.

[0039] In some embodiments, the composition is substantially fluorine-free.

[0040] In some embodiments, if the dielectric layer is present in a microelectronic device, the microelectronic device passes at least one test selected from the group consisting of HAST, bHAST, HTS, and TCT. [Brief explanation of the drawing]

[0041] [Figure 1] Figure 1 shows an example plot of resistance [ohms] versus time (hours) in a successful bHAST plot of formulation FE-33. [Figure 2] Figure 2 shows an example plot of resistance [ohms] versus time (hours) for a failed bHAST plot of formulation FE-9. [Modes for carrying out the invention]

[0042] This disclosure relates to methods and compositions that can be used to provide microelectronic devices with good reliability. In some embodiments, the compositions described herein may be photosensitive. For example, the compositions described herein may be sensitive to electromagnetic radiation or active light in the wavelength range of about 150 nm to 600 nm (e.g., 405 nm), thereby resulting in a change in solubility (e.g., increase or decrease in solubility) in a suitable developer (e.g., cyclopentanone).

[0043] In some embodiments, the dielectric film-forming composition used by the methods described herein comprises at least one fully imidized polyimide. The fully imidized polyimide may be a polymer of structure (I), [ka] In structure (I), R 1 is hydrogen, or C1~C 12 Alkyl, C2~C 12 Alkenyl, C4~C 18 Cycloalkyl, C6~C 22 Aryl, or C6~C 22 It is a heteroaryl group; R 2 is a terminal group (e.g., a functional or non-functional terminal group), n is an integer greater than 5 (e.g., 5 to 200), 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 contents of which are incorporated herein by reference. Functional or non-functional acid anhydrides or acid chlorides may be used for end-capturing of unreacted amine functional groups on amino-terminated polyamic acids.

[0044] Examples of suitable diamines that can be used to prepare polymers of structure (I) include 1-(4-aminophenyl)-1,3,3-trimethylindan-5-amine (also known as 4,4'-[1,4-phenylene-bis(1-methylethylidene)]bisaniline, 1-(4-aminophenyl)-1,3,3-trimethyl-2H-inden-5-amine, 1-(4-aminophenyl)-1,3,3-trimethylindan-5-amine, and [1-(4-aminophenyl)-1,3,3-trimethylindan-5-yl]amine), 1-(4-A Minophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-inden-5-amine, 5-amino-6-methyl-1-(3'-amino-4'-methylphenyl)-1,3,3-trimethylindan, 4-amino-6-methyl-1-(3'-amino-4'-methylphenyl)-1,3,3-trimethylindan, 5,7-diamino-1,1-dimethylindan, 4,7-diamino-1,1-dimethylindan, 5,7-diamino-1,1,4-trimethylindan, 5,7-diamino-1,1,6-trimethylindan, 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-trimethylcyclohexanemethaneamine, 2,5-diaminobenzotrifluoride, 3,5-diaminobenzotrifluoride, 1,3-diamino-2,4,5,6-tetrafluorobenzene, 4,4'-oxydianiline, 3,4'-oxydianiline, 3,3'-oxydianiline, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 4,4'-isopropylidenedianiline, 4,4'-diaminodiphenylmethane, 2,2-bis(4-aminophenyl)propane, 4,4'-diaminodiphenylpropane, 4,4'-Diaminodiphenyl sulfide, 4,4'-Diaminodiphenyl sulfone, 4-Aminophenyl-3-Aminobenzoate, 2,2'-Dimethyl-4,4'-Diaminobiphenyl, 3,3'-Dimethyl-4,4'-Diaminobiphenyl, 2,2'-Bis(trifluoromethyl)benzidine, 3,3'-Bis(trifluoromethyl)benzidine, 2,2-Bis[4-(4-Aminophenoxyphenyl)]Hexafluoropropane, 2,2-Bis(3-Amino-4-methyl Phenyl)-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)iso Propyridene, 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-methylethylidene)]bis Dilin, 4,4'-[1,4-phenylenebis(1-methylethylidene)]bisaniline, 2,2-bis[4-(4-aminophenoxy)phenyl]sulfone, 2,2-bis[4-(3-aminophenoxy)benzene], 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3'-bis(3-aminophenoxy)benzene, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, H-fluorene-2,Examples include, but are not limited to, 6-diamines, bis(aminopropyl)tetramethyldisiloxane (BATMS), bis(aminopropyl)tetraphenyldisiloxane, bis(4-aminophenoxy)dimethylsilane, and similar materials. Any of these diamines can be used individually or in combination in any suitable ratio to form the polyimides described herein.

[0045] Examples of suitable dianhydrides that can be used to prepare the polymer of structure (I) include 1-(3’,4’-dicarboxyphenyl)-1,3,3-trimethylindane-5,6-dicarboxylic dianhydride, 1-(3’,4’-dicarboxyphenyl)-1,3,3-trimethylindane-6,7-dicarboxylic dianhydride, 1-(3’,4’-dicarboxyphenyl)-3-methylindane-5,6-dicarboxylic dianhydride, 1-(3’,4’-dicarboxyphenyl)-3-methylindane-6,7-dicarboxylic anhydride, 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]octa-7-ene-3,4,8,9-tetracarboxylic dianhydride, tetracyclo[4.4.1.0 2,5 .0 7,10Undecane-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 Examples include, but are not limited to, '-diphenyl ether tetracarboxylic dianhydride, 2,2',3,3'-diphenyl ether tetracarboxylic dianhydride, 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride, 2,2-[bis(3,4-dicarboxyphenyl)]hexafluoropropane dianhydride, ethylene glycol bis(anhydrotrimellitate), and 5-(2,5-dioxotetrahydro)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride. Any of these tetracarboxylic dianhydrides can be used individually or in combination in any suitable ratio to produce the polyimides described herein.

[0046] In some embodiments, the fully imidized polyimides referred to herein are imidized by about 90% or more (e.g., about 95% or more, about 98% or more, about 99% or more, or about 100%).

[0047] In some embodiments, at least one diamine comprises a compound selected from the group consisting of diamines of structure (II), [ka] In structure (II), R 11 , R 12 , R 13 , R 14 and R 15 Each of these is independently H, a substituted or unsubstituted C1-C6 linear or branched alkyl group, or a C5-C7 cycloalkyl group.

[0048] R 11 , R 12 , R 13 , R 14 and R 15 Examples of substituted or unsubstituted C1-C6 linear or branched alkyl groups in include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, amyl, hexyl, and 2-methylhexyl. 11 , R 12 , R 13 , R 14 and R 15 Examples of C5-C7 cycloalkyl groups in this context include, but are not limited to, cyclopentyl, cyclohexyl, and cycloheptyl.

[0049] Examples of preferred diamine(II) in this embodiment include 1-(4-aminophenyl)-1,3,3-trimethylindan-5-amine (also known as 4,4'-[1,4-phenylene-bis(1-methylethylidene)]bisaniline, 1-(4-aminophenyl)-1,3,3-trimethyl-2H-inden-5-amine, 1-(4-aminophenyl)-1,3,3-trimethyl-indan-5-amine, [1-(4-aminophenyl)-1,3,3-trimethyl-indan-5-yl]amine, and 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl- Examples include, but are not limited to, 1H-inden-5-amine, 5-amino-6-methyl-1-(3'-amino-4'-methylphenyl)-1,3,3-trimethylindan, 4-amino-6-methyl-1-(3'-amino-4'-methylphenyl)-1,3,3-trimethylindan, 5,7-diamino-1,1-dimethylindan, 4,7-diamino-1,1-dimethylindan, 5,7-diamino-1,1,4-trimethylindan, 5,7-diamino-1,1,6-trimethylindan, and 5,7-diamino-1,1-dimethyl-4-ethylindan.

[0050] In some embodiments, the fully imidized polyimide may be a partially fluorinated polyimide. Examples of suitable diamines that can be used to prepare the polymer of structure (I) include 2,5-diaminobenzotrifluoride, 3,5-diaminobenzotrifluoride, 1,3-diamino-2,4,5,6-tetrafluorobenzene, 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- Examples include, but are not limited to, bis(3-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 1,4-bis(4'-amino-3'-trifluoromethylphenoxy)benzene, 1,1-bis[4'-(4''-amino-2''-trifluoromethylphenoxy)phenyl]cyclopentane, 1,1-bis[4'-(4''-amino-2''-trifluoromethylphenoxy)phenyl]cyclohexane, and similar products. Similarly, an example of a fluorinated dianhydride is 2,2-[bis(3,4-dicarboxyphenyl)]hexafluoropropane dianhydride. Any of these fluorinated diamines can be used individually or in combination in any suitable ratio to produce the polyimides described herein.

[0051] In another embodiment, the fully imidized polyimide is a polyimide polymer that is completely free of fluorine atoms.

[0052] Suitable diamines that can be used to prepare fluorine atom-free polyimide polymers include 1-(4-aminophenyl)-1,3,3-trimethylindan-5-amine (also known as 4,4'-[1,4-phenylene-bis(1-methylethylidene)]bisaniline, 1-(4-aminophenyl)-1,3,3-trimethyl-2H-inden-5-amine, 1-(4-aminophenyl)-1,3,3-trimethylindan-5-amine, and [1-(4-aminophenyl)-1,3,3-trimethylindan-5-yl] (Containing amine), 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-inden-5-amine, 5-amino-6-methyl-1-(3'-amino-4'-methylphenyl)-1,3,3-trimethylindan, 4-amino-6-methyl-1-(3'-amino-4'-methylphenyl)-1,3,3-trimethylindan, 5,7-diamino-1,1-dimethylindan, 4,7-diamino-1,1-dimethylindan, 5,7-diamino-1,1,4-trimethylindan, 5,7-diamino-1,1,6-trimethylin Dan, 5,7-diamino-1,1-dimethyl-4-ethylindan, p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 3-methyl-1,2-benzene-diamine, 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,2-diaminocyclohexane, 1,4-diaminocyclohexane, 1,3-cyclohexanebis( Methylamine), 5-amino-1,3,3-trimethylcyclohexanemethaneamine, 2,5-diaminobenzotrifluoride, 3,5-diaminobenzotrifluoride, 1,3-diamino-2,4,5,6-tetrafluorobenzene, 4,4'-oxydianiline, 3,4'-oxydianiline, 3,3'-oxydianiline, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 4,4'-isopropylidenedianiline, 4,4'-diaminodiphenylmethane, 2,2-bis(4-aminophenyl)propane, 4,4'-Diaminodiphenylpropane, 4,4'-Diaminodiphenyl sulfide, 4,4'-Diaminodiphenyl sulfone, 4-Aminophenyl-3-Aminobenzoate, 2,2'-Dimethyl-4,4'-Diaminobiphenyl, 3,3'-Dimethyl-4,4'-Diaminobiphenyl, 1,3-Bis-(4-Aminphenoxy)benzene, 1,3-Bis-(3-Aminphenoxy)benzene, 1,4-Bis-(4-Aminphenoxy)benzene, 1,4-Bis-(3-Aminphenoxy)benzene, 1-(4-Amin Nophenoxy)-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-methylethylidene)]bisaniline, 4,4'-[1,4-phenylenebis(1-methylethylidene)]bisaniline, 2,2-bis[4-(4-aminophenoxy)phenyl]sulfone, 2,2-bis[4-(3-aminophenoxy)benzene], 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3'-bis(3-aminophenoxy)benzene, H-fluorene-2,6-diamine, bis(aminopropyl) Examples include, but are not limited to, tramethyldisiloxane (BATMS), 4,4'-methylenebis(2,6-diethylaniline), 4,4'-methylenebis(2,6-dimethylaniline), 4,4'-methylenebis(2,6-diisopropylaniline), 4,4'-methylenebis(2,6-dipropylaniline), 4,4'-methylenebis(2,6-di-tert-butylaniline), bis(aminopropyl)tetraphenyldisiloxane, bis(4-aminophenoxy)dimethylsilane, and similar materials. Any of these diamines can be used individually or in combination in any suitable ratio to form the polyimides described herein.

[0053] Suitable dianhydrides that can be used to prepare fluorine atom-free polyimides include: 1-(3',4'-dicarboxyphenyl)-1,3,3-trimethylindan-5,6-dicarboxylic acid dianhydride, 1-(3',4'-dicarboxyphenyl)-1,3,3-trimethylindan-6,7-dicarboxylic acid dianhydride, 1-(3',4'-dicarboxyphenyl)-3-methylindan-5,6-dicarboxylic acid dianhydride, 1-(3',4'-dicarboxyphenyl)-3-methylindan-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, and 1,4,5,8-naphthalenetetracarboxylic acid 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]octa-7-ene-3,4,8,9-tetracarboxylic dianhydride, tetracyclo[4.4.1.0 2,5 .0 7,10Examples include, but are not limited to, undecane-1,2,3,4-tetracarboxylic acid dianhydride, 3,3',4,4'-benzophenonetetracarboxylic acid dianhydride, 2,2',3,3'-benzophenonetetracarboxylic acid dianhydride, 2,3,3',4'-benzophenonetetracarboxylic acid dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic acid dianhydride, 2,2',3,3'-diphenylsulfonetetracarboxylic acid dianhydride, 2,3,3',4'-diphenylsulfonetetracarboxylic acid dianhydride, 3,3',4,4'-diphenylethertetracarboxylic acid dianhydride, 2,2',3,3'-diphenylethertetracarboxylic acid dianhydride, 2,3,3',4'-diphenylethertetracarboxylic acid dianhydride, and 5-(2,5-dioxotetrahydro)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride. Any of these tetracarboxylic dianhydrides can be used individually or in combination in any suitable ratio to produce the polyimides described herein.

[0054] In some embodiments, the weight-average molecular weight of the fully imidized polyimide is about 20,000 daltons or more (e.g., about 25,000 daltons or more, about 30,000 daltons or more, about 35,000 daltons or more, about 40,000 daltons or more, about 45,000 daltons or more, about 50,000 daltons or more, or about 55,000 daltons or more) and / or about 100,000 daltons or less (e.g., about 95,000 daltons or less, about 90,000 daltons or less, about 85,000 daltons or less, about 80,000 daltons or less, about 75,000 daltons or less, about 70,000 daltons or less, about 65,000 daltons or less, or about 60,000 daltons or less).

[0055] In some embodiments, fully imidized polyimides are prepared by the reaction of at least one diamine with at least one tetracarboxylic dianhydride. In some embodiments, the resulting polymers are soluble in the organic solvents of this disclosure to facilitate the formation of dielectric films, such as dielectric films having a planarized 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 fully imidized polyimides are known in the art, for example, described in U.S. Patent Application Publication 2019 / 0077913, which is incorporated herein by reference in its entirety.

[0056] Methods for synthesizing end-capped and end-uncapped 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 Nos. 2,731,447, 3,435,002, 3,856,752, 3,983,092, 4,026,876, 4,040,831, 4,579,809, 4,629,777, 4,656,116, 4,960,860, 4,985,529, and 5,006,611. This is disclosed in U.S. Patent Applications Nos. 5,122,436, 5,252,534, 5,478,915, 5,773,559, 5,783,656, 5,969,055, 9,617,386, and U.S. Patent Publications Nos. 2004 / 0265731, 2004 / 0235992, and 2007 / 0083016, the full contents of which are incorporated herein by reference.

[0057] In some embodiments, the fully imidized polyimides described herein may be alkali-soluble polyimides having at least one (e.g., two or three) functional groups (e.g., one or both ends of the main chain or in the side chains of the polymer), such as carboxylic acid groups, hydroxyl groups (e.g., phenolic hydroxyl groups), sulfonic acid groups, or thiol groups. As used herein, the term "alkali-soluble" means that the solubility in a 2.38 wt% aqueous solution of tetramethylammonium hydroxide at 25°C is about 0.1 g / 100 mL or more.

[0058] In some embodiments, the polymer resin suitable for the dielectric film-forming compositions described herein may include at least one (e.g., two, three, or four) other dielectric polymers, such as epoxy resins, novolac resins, or dielectric polymers comprising a mixture of epoxy resins and novolac resins, polybenzoxazole (PBO) precursor polymers, or mixtures thereof.

[0059] Examples of suitable epoxy resins that can be used as dielectric film materials are known to those skilled in the art, for example, as disclosed in 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.

[0060] Examples of suitable novolac polymers described herein include those comprising at least one photoactive o-quinone diazide compound, which are known to those skilled in the art. Examples of such novolac polymers are disclosed in U.S. Patents No. 5,413,894; No. 5,306,594; No. 4,959,292; No. 8,334,092; and No. 8,492,067; and U.S. Patent Publications 2012 / 0296053 and 2012 / 0052438, the entire contents of which are incorporated herein by reference.

[0061] In some embodiments, the resin in the dielectric film-forming composition described herein may include at least one (e.g., two or three) cyclized rubbers. In some embodiments, the cyclized rubber is selected from the group of cyclized polydienes. In some embodiments, the cyclized polydiene includes homopolymers of conjugated dienes such as isoprene, butadiene, and pentadiene. In other embodiments, the cyclized polydiene includes copolymers of such conjugated dienes with olefins, styrene, or acrylates. In some embodiments, the cyclization of the rubber occurs under the influence of heat, light, ultraviolet or nuclear radiation, and / or in the presence of a cation-donating catalyst (e.g., mineral acid, organic acid, or 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 disappears. Generally, bicyclic or tricyclic structures are produced in later cyclization steps. Gradually, the degree of unsaturation and elasticity decreases as a result of the successive cyclization of cis-polydienes, while their toughness increases. Cyclization is generally more efficient 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 methods are described, for example, in U.S. Patents 4,678,841 and 4,248,986, and European Patent No. 0063043, which are incorporated herein by reference. These cyclized rubbers may be used individually or in combination of two or more. In some embodiments, the cyclized rubber is polyisoprene.

[0062] 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., cyanate ester compounds having at least two cyanate groups in one molecule).

[0063] In some embodiments, the cyanate ester compounds described herein may have structure (III), Ar-(OC≡N) m (III) In structure (III), m is at least an integer of 2 (m≧2), and Ar is a substituted or unsubstituted aromatic organic group in which the cyanate ester group is directly bonded to the substituted or unsubstituted aromatic organic group. In some embodiments, the above aromatic organic group may be optionally substituted with at least one (e.g., two or three) C1-C4 alkyl, halogen, C1-C4 haloalkyl, -OR', -OC(O)R', or -COOR', where R' is H, C1-C4 alkyl, C5-C 12 Cycloalkyl, C6~C 18 Aryl, or C6~C 18 It is a heteroaryl compound.

[0064] In some embodiments, the cyanate ester compounds described herein may have structure (IV), [ka] In structure (IV), R is a hydrogen atom, a C1-C3 alkyl group, a C1-C3 alkyl group that is completely or partially halogen-substituted, or a halogen atom; X is a single bond, an O atom or an S atom, a -(C=O)-, -(C=O)-O-, -O-(C=O)-, -(S=O)-, -(SO2)-, -CH2CH2-O- group, or a substituted or unsubstituted C1-C3 alkyl group. 10 Alkylene groups, partially or completely fluorine-substituted C1-C4 alkylene groups, substituted or unsubstituted C3-C 10 It is a cycloalkylene group.

[0065] Specific examples of suitable cyanate ester compounds include 2-bis(4-cyanatophenyl)propane, hexafluorobisphenol A dicyanate, bis(4-cyanato-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatophenyl-1-(methylethylidene))benzene, bis(4-cyanatophenyl) thioether, bis(4-cyanatophenyl) ether, and polyfunctional cyanate resins derived from phenol novolac, cresol novolac, or dicyclopentadiene-containing phenol resins. Other examples of such cyanate ester compounds are described, for example, in U.S. Patent Nos. 3,595,900, 4,894,414, and 4,785,034, and U.S. Patent Application Publications 2022 / 0002463 and 2022 / 0127459, which are incorporated herein by reference. In some embodiments, the weight-average molecular weight of the cyanate ester resin or polymer is not particularly limited, but is between approximately 500 daltons or more (e.g., approximately 600 daltons or more) and approximately 4,500 daltons or less (e.g., approximately 3,000 daltons or less).

[0066] While we do not wish to be bound by theory, it is conceivable that cyanate ester compounds can be cyclized and / or crosslinked thermally or under irradiation (e.g., with or without a catalyst) to form interpenetrating networks with dielectric polymers in the dielectric film-forming compositions described herein. Furthermore, while we do not wish to be bound by theory, it is conceivable that the inclusion of cyanate ester compounds in the dielectric film-forming compositions described herein can reduce the dielectric constant (K) and / or dielectric loss tangent (DF, dissipation factor) of the film formed from the composition.

[0067] In some embodiments, the amount of resin or dielectric polymer is about 0.1% by weight or more (e.g., about 0.5% by weight or more, about 1% by weight or more, about 2% by weight or more, about 5% by weight or more, about 10% by weight or more, about 15% by weight or more, or about 20% by weight or more) and / or about 55% by weight or less (e.g., about 50% by weight or less, about 45% by weight or less, about 40% by weight or less, about 35% by weight or less, about 30% by weight or less, about 25% by weight or less, about 20% by weight or less, about 15% by weight or less, or about 10% by weight or less) of the solids content of the dielectric film-forming composition described herein.

[0068] LogP is a crucial molecular physical property that influences a wide range of parameters in a formulation. LogP is a measure of the preference for solubility in either water or an organic solvent (such as octanol) when a compound is uncharged. More technically, it is the logarithm of the partition coefficient (P) of a molecule between the aqueous and lipophilic phases. LogP predicts the partition coefficient, a measure of hydrophobicity, from the structure.

[0069] The logP value is a constant defined in the following way: LogP = log10(partition coefficient of organic) / (partition coefficient of water), P = [organic] / [aqueous] In the formula, [ ] indicates the concentration of the solute in the organic and aqueous partitions.

[0070] A negative value of logP means the compound has a higher affinity for the aqueous phase (is more hydrophilic); if logP=0, the compound is equally distributed between the lipid phase and the aqueous phase; a positive value of logP indicates a higher concentration in the lipid phase (i.e., the compound is more lipophilic). LogP=1 means there is a 10:1 distribution between the organic phase and the aqueous phase.

[0071] logP is a constant, but its value depends on the choice of organic partition solvent and, to a lesser extent, on the measurement conditions. The ACD / Labs logP algorithm specifically calculates the partition between octan-1-ol and water, the most commonly used system.

[0072] In some embodiments, the dielectric film-forming compositions described herein may optionally contain at least one (e.g., two, three, or four) hydrophobic polyfunctional (meth)acrylate crosslinking agents, wherein the logP (octanol / water partition coefficient) value of the hydrophobic polyfunctional (meth)acrylate crosslinking agent is 0.5 or greater and less than 8.0. In some embodiments, the hydrophobic polyfunctional (meth)acrylate crosslinking agent may include ethylenically unsaturated polymerizable compounds (e.g., ethylenically unsaturated photopolymerizable compounds), metal-containing (meth)acrylate compounds, or mixtures thereof.

[0073] In some embodiments, the dielectric film-forming compositions described herein may optionally contain at least one (e.g., two, three, or four) hydrophobic polyfunctional (meth)acrylate crosslinking agents, the logP (octanol / water partition coefficient) value of the hydrophobic polyfunctional (meth)acrylate crosslinking agents being 0.5 or greater and less than 7.0. A hydrophobic polyfunctional (meth)acrylate crosslinking agent means a compound having one or more unsaturated (meth)acryloyloxy groups in its molecule. A typical example of a (meth)acrylate compound is a (meth)acrylic acid ester.

[0074] If the logP value is too low, it affects the stability of the film-forming properties of the photosensitive composition, and tends to result in a non-uniform film. In addition, if the logP value is too high, separation of the photopolymerizable compound (B) and the film-forming resin (A) may occur, which can cause the resin to aggregate.

[0075] In some embodiments, the hydrophobic polyfunctional (meth)acrylate crosslinking agents described herein may include ethylenically unsaturated polymerizable compounds containing at least two (meth)acrylate groups. In some embodiments, the crosslinking agents include 1,6-hexanediol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propoxylated (3)glycerol tri(meth)acrylate, ethoxylated bisphenol-A di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, The following are selected from the group consisting of pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta- / hexa-(meth)acrylate, isocyanurate tri(meth)acrylate, bis(2-hydroxyethyl)-isocyanurate di(meth)acrylate, 1,3-butanediol tri(meth)acrylate, 1,4-butanediol tri(meth)acrylate, neopentyl glycol di(meth)acrylate, (meth)acrylate-modified urea-formaldehyde resin, (meth)acrylate-modified melamine-formaldehyde resin, and (meth)acrylate-modified cellulose. Other examples of such compounds are disclosed, for example, in U.S. Patent Nos. 10,036,952 and 10,563,014, as well as in U.S. Patent Application Publication No. 2015 / 0219990 and European Patent No. 3,492,982; the full contents thereof are incorporated herein by reference.

[0076] Examples of LogP values ​​for hydrophobic polyfunctional (meth)acrylate crosslinking agents include tris(2-hydroxyethyl) isocyanurate triacrylate (LogP -0.26), pentaerythritol triacrylate (LogP 0.56), tetraethylene glycol dimethacrylate (LogP 1.45), tripropylene glycol diacrylate (LogP 1.75), dipropylene glycol diacrylate (LogP 1.76), neopentyl glycol diacrylate (LogP 1.86), 1,4-butanediol diacrylate (LogP 2.2), ethylene glycol dimethacrylate (LogP 2.78), 1,6-hexanediol diacrylate (LogP 2.96), 2-(tricyclo[5.2.1.02,6]deca-3-en-8-yloxy)ethyl acrylate (LogP 3.01), and trimethylolpropane trimethacrylate (LogP 3.15), Neopentyl glycol diacrylate (LogP 3.56), Bisphenol A (EO) 2-diacrylate (LogP 5.89), Pentaerythritol tetraacrylate (LogP -0.13), Tetraethylene glycol diacrylate (LogP 0.34), Triethylene glycol diacrylate (LogP 0.70), Trimethylolpropane triacrylate (LogP 1.50), Triethylene glycol dimethacrylate (LogP 1.81), 1,6-Hexanediol diacrylate (LogP 2.35), Dipentaerythritol hexaacrylate (LogP 2.47), Dipentaerythritol pentaacrylate (LogP 2.55), Trimethylolpropane (EO) 3-triacrylate (LogP 2.79), Trimethylolpropane (EO) 9-trimethacrylate (LogP 2.79), neopentyl glycol dimethacrylate (LogP 2.96), 1,6-hexanediol dimethacrylate (LogP 4.06), tricyclodecanedimethanol diacrylate (LogP 4.22), ditrimethylolpropanetetraacrylate (LogP 4.26), 1,9-nonanediol diacrylate (LogP 4.55), and 1,10-decanediol diacrylate (LogP 5.08).

[0077] In some embodiments, the crosslinking agents described herein may be metal-containing (meth)acrylate (MCA) compounds. As used herein, the term "(meth)acrylate" refers to both acrylate compounds and methacrylate compounds. Suitable examples of MCAs include titanium tetra(meth)acrylate, zirconium tetra(meth)acrylate, hafnium tetra(meth)acrylate, titanium butoxide tri(meth)acrylate, titanium (meth)acrylooxyethyl acetoacetate triisopropoxide, titanium tris(2-ethylhexanoate)(carboxyethyl(meth)acrylate), titanium tetra(carboxyethyl(meth)acrylate), zirconium tetra(carboxyethyl(meth)acrylate), hafnium tetra(carboxyethyl(meth)acrylate), and titanium butoxide tri(carboxyethyl(meth)acrylate). Examples of such compounds include, but are not limited to, titanium dibutoxide di(carboxyethyl (meth)acrylate), titanium tributoxide (carboxyethyl (meth)acrylate), titanium oxide di(carboxyethyl (meth)acrylate), zirconium butoxide tri(carboxyethyl (meth)acrylate), zirconium dibutoxide di(carboxyethyl (meth)acrylate), zirconium tributoxide (carboxyethyl (meth)acrylate), zirconium oxide di(carboxyethyl (meth)acrylate), and zirconium bis(2-ethylhexanoate) di(carboxyethyl (meth)acrylate). Other examples of such compounds are disclosed, for example, in U.S. Patent Application Publication No. 2021 / 104398, the entire contents of which are incorporated herein by reference.

[0078] In some embodiments, the crosslinking agent described herein may be in an amount of about 0.5% by weight or more (e.g., about 1% by weight or more, about 2% by weight or more, about 3% by weight or more, about 4% by weight or more, about 5% by weight or more, about 6% by weight or more, about 7% by weight or more, about 8% by weight or more, about 9% by weight or more, about 10% by weight or more) to about 35% by weight or less (e.g., about 30% by weight or less, about 28% by weight or less, about 26% by weight or less, about 24% by weight or less, about 22% by weight or less, about 20% by weight or less, about 18% by weight or less, about 16% by weight or less, about 15% by weight or less, about 14% by weight or less, about 12% by weight or less, about 10% by weight or less, about 8% by weight or less, about 6% by weight or less, or about 5% by weight or less) of the solids weight of the dielectric film-forming composition described herein.

[0079] The dielectric film-forming compositions described herein may optionally contain at least one (e.g., two, three, or four) radical initiators. When used herein, a radical initiator represents a compound that can generate free radicals that can initiate radical polymerization or crosslinking upon heating or irradiation with light in a specific wavelength range (e.g., from 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 absorption and the radically polymerizable monomer has substantial absorption. Photoradical initiators (also referred herein as photopolymerization initiators) and thermal radical initiators (also referred herein as thermal initiators) are examples of radical initiators. In some embodiments, photoradical initiators are preferred.

[0080] In some embodiments, the amount of radical initiator (e.g., photopolymerization initiator) is from about 0.1% by weight or more (e.g., about 0.2% by weight or more, about 0.5% by weight or more, about 0.8% by weight or more, about 1% by weight or more, about 1.5% by weight or more, about 2% by weight or more, about 3% by weight or more, about 4% by weight or more, or about 5% by weight or more) to about 10% by weight or less (e.g., about 9% by weight or less, about 8% by weight or less, about 7% by weight or less, about 6% by weight or less, about 5% by weight or less, about 4% by weight or less, about 3% by weight or less, about 2% by weight or less, or about 1% by weight or less) of the solids weight of the dielectric film-forming composition described herein.

[0081] In some embodiments, the photopolymerization initiator is photosensitive to light ranging from the ultraviolet region to the visible region. In some embodiments, the photopolymerization initiator may be an activator that generates free radicals through some interaction with a photoexcited sensitizer. In some embodiments, the photopolymerization initiator is selected from the group consisting of oxime esters, titanocene, acylgermanium compounds, peroxides, and mixtures thereof.

[0082] One example of a photopolymerization initiator is an oxime ester of structure (V), [ka] In structure (V), R 21 and R 22 Each of these can be independently substituted or not substituted 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 a heteroaryl; R 23 This refers to UV-absorbing functional groups (e.g., substituted or unsubstituted C6-C6). 22 Aryl, substituted, or unsubstituted C6~C 22 (heteroaryl). In some embodiments, the alkyl, cycloalkyl, aryl, or heteroaryl may be substituted with at least one (e.g., two or three) C1-C4 alkyl, halogen, C1-C4 haloalkyl, -OR', -OC(O)R', or -COOR', where R' is H, C1-C4 alkyl, C5-C 12 Cycloalkyl, C6~C 18 Aryl, or C6~C 18 It is a heteroaryl compound.

[0083] Examples of oxime esters of formula (II) include, but are not limited to, the following. [ka]

[0084] Another example of a photopolymerization initiator is an organic titanocene compound of structure (VI), [ka] In structure (VI), M is selected from the group consisting of titanium atoms, zirconium atoms, and hafnium atoms; R 14 and R 15 Each of these can be independently substituted or not substituted 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 Selected from the group consisting of alkylsulfonyloxy groups. In some embodiments, the alkyl, cycloalkyl, aryl, or heteroaryl may be substituted with at least one (e.g., two or three) C1-C4 alkyl, halogen, C1-C4 haloalkyl, -OR', -OC(O)R', or -COOR', where R' is H, C1-C4 alkyl, C5-C 12 Cycloalkyl, C6~C 18 Aryl, or C6~C 18 It is a heteroaryl compound.

[0085] Examples of commercially available photopolymerization initiators include, but are not limited to, IRGACURE-784, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04, and IRGACURE OXE 05 from BASF; and ADEKA OPTOMER N-1919, ADEKA ARKLS NCI-831, and ADEKA ARKLS NCI-930 from ADEKA Corporation. Other examples of photopolymerization initiators are disclosed, for example, in European Patent No. 3,492,982, which is incorporated herein by reference in its entirety.

[0086] 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, succinate peroxide, di(n-propyl) peroxydicarbonate, 2,2-azobis(isobutyronitrile), 2,2-azobis(2,4-dimethylvaleronitrile), dimethyl-2,2-azobisisobutyrate, 4,4-azobis(4-cyanopentanoic acid), azobiscyclohexanecarbonitrate, 2,2-azobis(2-methylbutyronitrile), and similar substances.

[0087] In some embodiments, acylgermanium compounds can be used as photopolymerization initiators. Suitable examples of acylgermanium compounds include, but are not limited to, (2,4,6-trimethylbenzoyl)triethylgermanium, (2,4,6-trimethylbenzoyl)tripropylgermanium, (2,4,6-trimethylbenzoyl)tributylgermanium, (2,6-dimethoxybenzoyl)triethylgermanium, (2,6-dimethoxybenzoyl)tripropylgermanium, (2,6-dimethoxybenzoyl)tributylgermanium, bisbenzoyldiethylgermanium, bisbenzoyldipropylgermanium, bis(4-methoxybenzoyl)diethylgermanium, bis(2,4,6-trimethylbenzoyl)diethylgermanium, trisbenzoylethylgermanium, tris(2,4,6-trimethylbenzoyl)ethylgermanium, and similar compounds. A commercially available example of an acylgermanium compound is Ivocerin (i.e., bis(4-methoxybenzoyl)diethylgermanium). Other examples of such acylgermanium compounds are disclosed, for example, in U.S. Patents 7,605,190 and 9,532,930, the full contents of which are incorporated herein by reference.

[0088] In some embodiments, the dielectric film-forming compositions described herein may contain at least one (e.g., two, three, or four) photosensitizers different from the acylgermanium compound, the photosensitizers capable of absorbing light in the wavelength range of about 150 nm to about 600 nm (e.g., about 405 nm). Examples of suitable photosensitizers that can be used in the dielectric film-forming compositions include benzophenone compounds, thioxanthone compounds, anthraquinone compounds, anthracene compounds, coumarin compounds, and mixtures thereof. Specific examples of photosensitizers include, but are not limited to, 9-methylanthracene, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, anthracene methanol, acenaphthylene, thioxanthone, methyl-2-naphthylketone, 4-acetylbiphenyl, and 1,2-benzofluorene. Other examples of photosensitizers are disclosed, for example, in U.S. Patent Application Publication No. 2022 / 0171285, which is incorporated herein by reference in its entirety. In some embodiments, the acylgermanium compounds described herein can function as photosensitizers.

[0089] In some embodiments, the amount of photosensitizer other than the acylgermanium compound is from about 0.01% by weight or more (e.g., about 0.05% by weight or more, about 0.1% by weight or more, or about 0.5% by weight or more) to about 1% by weight or less (e.g., about 0.8% by weight or less, about 0.6% by weight or less, about 0.5% by weight or less, about 0.4% by weight or less, about 0.2% by weight or less, or about 0.1% by weight or less) of the solid content weight of the dielectric film-forming composition described herein.

[0090] In some embodiments, the dielectric film-forming compositions described herein may further comprise an organic solvent or a mixture of organic solvents (e.g., two, three, or four). In other embodiments, 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, pyrrolidones, and dialkyl sulfoxides, as well as mixtures thereof. Examples of organic solvents suitable for dielectric film-forming compositions described herein include alkylene carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate, and glycerin carbonate; lactones such as γ-butyrolactone, ε-caprolactone, γ-caprolactone, and γ-valerolactone; cycloketones such as cyclopentanone and cyclohexanone; linear ketones such as methyl ethyl ketone (MEK) and methyl isobutyl ketone (MIBK); esters such as n-butyl acetate; ester alcohols such as ethyl lactate; ether alcohols such as tetrahydrofurfuryl alcohol; (tetrahydrofurfuryl alcohol) Examples include, but are not limited to, ether esters such as n-2-yl)methyl acetate, methyl-3-methoxypropionate, ethyl-3-ethoxypropionate, and 3-methoxybutyl acetate; glycol esters such as propylene glycol methyl ether acetate; glycol ethers such as propylene glycol methyl ether (PGME); cyclic ethers such as tetrahydrofuran (THF); pyrrolidones such as N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, or N-butyl-2-pyrrolidone, or TamiSolve® NxG; and dialkyl sulfoxides such as dimethyl sulfoxide.

[0091] Examples of solvents with LogP values ​​include γ-butyrolactone (LogP -0.76), sylen (LogP -0.71), propylene carbonate (LogP -0.41), γ-valerolactone (LogP -0.27), ethyl lactate (LogP -0.19), cyclopentanone (LogP 0.2), furfuryl alcohol (LogP 0.2), 3-methoxybutyl acetate (LogP 0.75), cyclohexanone (LogP 0.76), TamiSolve® NxG (LogP 1.2), and Dottisol (LogP -0.65).

[0092] In some embodiments, the total amount of solvent is about 20% by weight or more (e.g., about 25% by weight or more, about 30% by weight or more, about 35% by weight or more, about 40% by weight or more, about 45% by weight or more, about 50% by weight or more, about 55% by weight or more, about 60% by weight or more, or about 65% by weight or more) and / or about 98% by weight or less (e.g., about 95% by weight or less, about 90% by weight or less, about 85% by weight or less, about 80% by weight or less, about 75% by weight or less, about 70% by weight or less, or about 60% by weight or less) of the total weight of the dielectric film-forming composition described herein.

[0093] In some embodiments, the dielectric film-forming compositions described herein optionally include at least one (e.g., two, three, or four) fillers (such as inorganic fillers or inorganic particles). 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 titanate, sodium titanate, barium sulfate, barium titanate, barium zirconate, and potassium niobate. Preferably, the inorganic filler is in granular form with an average size of about 0.1 to 2.0 microns. In some embodiments, the filler is inorganic particles containing a ferromagnetic material. Suitable ferromagnetic materials include elemental metals (such as iron, nickel, and cobalt) or their oxides, sulfides, and oxyhydroxides, as well as awaluite (Ni3Fe), weiralite (CoFe), Co 17 Sm2 and Nd2Fe14 Examples include intermetallic compounds such as B.

[0094] In some embodiments, the amount of inorganic filler (e.g., silica filler) is about 1% by weight or more (e.g., about 2% by weight or more, about 5% by weight or more, about 8% by weight or more, or about 10% by weight or more) and / or about 30% by weight or less (e.g., about 25% by weight or less, about 20% by weight or less, or about 15% by weight or less) of the solids weight of the dielectric film-forming composition described herein.

[0095] In some embodiments, the dielectric film-forming compositions described herein may optionally further include at least one (e.g., two, three, or four) adhesion promoters. 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 Nos. 10,036,952 and 10,563,014, as well as U.S. Patent Application Publication No. 2015 / 0219990 and European Patent No. 3,492,982; the full contents thereof are incorporated herein by reference.

[0096] In some embodiments, the amount of optional adhesion promoter used is about 0.5% by weight or more (e.g., about 0.8% by weight or more, about 1% by weight or more, or about 1.5% by weight or more) and / or about 4% by weight or less (e.g., about 3.5% by weight or less, about 3% by weight or less, about 2.5% by weight or less, or about 2% by weight or less) of the solids content of the dielectric film-forming composition described herein.

[0097] In some embodiments, the dielectric film-forming compositions described herein may optionally contain at least one (e.g., two, three, or four) surfactants. Examples of suitable surfactants include, but are not limited to, those described in Japanese Patent Publication Nos. 62-36663, 61-226746, 61-226745, 62-170950, 63-34540, 7-230165, 8-62834, 9-54432, and 9-5988, the full contents of which are incorporated herein by reference.

[0098] In some embodiments, the amount of surfactant is about 0.005% by weight or more (e.g., about 0.01% by weight or about 0.1% by weight or more) and / or about 1% by weight or less (e.g., about 0.5% by weight or about 0.2% by weight or less) of the solids weight of the dielectric film-forming composition described herein.

[0099] In some embodiments, the dielectric film-forming compositions described herein may optionally contain at least one (e.g., two, three, or four) corrosion inhibitors. Examples of suitable corrosion inhibitors include triazole compounds, imidazole compounds, and tetrazole compounds. Triazole compounds may include triazole, benzotriazole, substituted triazole, and substituted benzotriazole. Dielectric film-forming compositions containing corrosion inhibitors prevent corrosion and discoloration of copper or copper alloys when the photosensitive layer is used on copper or copper alloys. The corrosion inhibitor additive plays an important role in improving the HAST stability of the TEG chip by effectively binding to the copper. Examples of suitable corrosion inhibitors include structures (VII), (VIII), (IX), (X), and (XI). [ka] In the structure, R 31 , R 32 , R 33 , R 34 , R35 , R 36 This includes hydrogen atoms, functional or non-functional C1-C6 alkyl groups, t-alkyl groups having 4-6 carbon atoms, or functional or non-functional C6-C6 alkyl groups. 22 It is an aromatic group; R 37 and R 38 R is a hydrogen atom, a C1-C4 alkyl group, a t-alkyl group having 4-6 carbon atoms, or an allyl group; 39 R is hydrogen, a C1-C4 alkyl group, or a polymerizable group; 40 It is either hydrogen or a halogen.

[0100] Examples of tetrazole compounds of structure (VII) include 1-H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-(ethylthio)-1H-tetrazole, 5-(benzylthio)-1H-tetrazole, 1H-tetrazole-5-ethyl acetate, 1H-tetrazole-5-carboxylate ethyl acetate, 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, and similar compounds.

[0101] Examples of triazole compounds of structures (VIII) and (IX) include, but are not limited to, 1,2,4-triazoles, 1,2,3-triazoles, or triazoles substituted with substituents such as C1-C8 alkyl groups (e.g., 5-methyltriazole), amino, thiol, mercapto, imino, carboxy, and nitro groups.

[0102] Specific 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, and similar compounds.

[0103] Examples of benzotriazoles of structure (X) 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, and similar. Examples of benzotriazoles of structure (XI) include 2-hydroxy-5-acrylyloxyphenyl-2H-benzotriazole, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-(3-t-butylphenyl)5-methyl-2-hydroxybenzotriazole, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-hydroxy-3-chloro-5-acrylyloxyphenyl-2H-benzotriazole, and similar.

[0104] 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.

[0105] If used, the amount of optional corrosion inhibitor is about 0.1% by weight or more (e.g., about 0.2% by weight or about 0.5% by weight or more) and / or about 3.0% by weight or less (e.g., about 2.0% by weight or about 1.0% by weight or less) of the solids weight of the dielectric film-forming composition described herein. If the amount of corrosion inhibitor is greater than the range, the storage stability will decrease, and if the amount of corrosion inhibitor is less than the above range, voids are more likely to form between the copper or copper alloy surfaces. The dielectric film-forming composition contains at least one corrosion inhibitor having a logP of about -1.0 to about 6. If the logP value of the corrosion inhibitor is too low, this will affect the stability of the film-forming properties of the photosensitive composition and tend to result in a non-uniform film. In addition, if the logP value of the corrosion inhibitor is too high, separation of the photopolymerizable compound (B) and the film-forming resin (A) may occur, which may cause the resin to aggregate.

[0106] In some embodiments, the dielectric film-forming compositions described herein include at least one (e.g., two, three, or four) corrosion inhibitors having a logP (octanol / water partition coefficient) value of -0.8 or greater and less than 5. In some embodiments, the dielectric film-forming compositions described herein include at least one (e.g., two, three, or four) corrosion inhibitor compounds having a logP (octanol / water partition coefficient) value of -0.6 or greater and less than 3.0.

[0107] Examples of corrosion inhibitors with logP values ​​include 1H-tetrazole (logP -0.6), 5-(ethylthio)-1H-tetrazole (logP 0.6), 5-(benzylthio)-1H-tetrazole (logP 1.574), 5-phenyltetrazole (logP 1.91), 1H-tetrazole-5-ethyl acetate (logP 0.03), 1H-tetrazole-5-ethyl carboxylate (logP -0.1), 5-methyl-1H-benzotriazole (logP 1.8), 3-amino-1,2,4-triazole (logP -1.25), 3,5-diamino-1,2,4-triazole (logP -1.61), 1H-benzotriazole (logP 1.34), and 2-hydroxy-5-acrylyloxyphenyl-2H-benzotriazole (logP 5.16).

[0108] In some embodiments, the dielectric film-forming compositions described herein include one or more (e.g., two, three, or four) dyes, pigments, plasticizers, or other optionally used components such as antioxidants. Examples of such components are given, for example, in U.S. Patent Application Publication No. 2022 / 0127459, which is incorporated herein by reference in its entirety.

[0109] In some embodiments, the dielectric film-forming compositions described herein are completely fluorine-free compositions, and the fully imidized polyimides, soluble switching compounds, photopolymerization initiators, sensitizers, adhesion promoters, surfactants, solvents, corrosion inhibitors, and additives are completely fluorine-free materials.

[0110] In some embodiments, a dielectric film can be prepared from a dielectric film-forming composition described herein by a method comprising: (a) coating a substrate (e.g., a semiconductor substrate) with a dielectric film-forming composition described herein 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).

[0111] Coating methods for preparing dielectric films include, but are not limited to, (1) spin coating, (2) spray coating, (3) roll coating, (4) rod coating, (5) rotational coating, (6) slit coating, (7) compression coating, (8) curtain coating, (9) die coating, (10) wire bar coating, (11) knife coating, and (12) dry film lamination. In coating methods (1) to (11), the dielectric film-forming composition is typically provided in the form of a solution. Those skilled in the art will select an appropriate type and concentration of solvent based on the type of coating.

[0112] The substrate can have a circular, square, or rectangular shape, such as a wafer or panel of various dimensions. Suitable substrate examples include epoxy molding compound (EMC), silicon, glass, copper, stainless steel, copper-clad laminate (CCL), aluminum, silicon oxide, and silicon nitride. The substrate may be flexible, such as polyimide, PEEK, polycarbonate, and polyester film. The substrate may have surface-mounted or embedded chips, coatings, or packages. The substrate may be sputtered or pre-coated with a combination of seed and passivation layers. In some embodiments, the substrate referred to herein may be a semiconductor substrate. As used herein, a semiconductor substrate refers to a substrate (e.g., a silicon or copper substrate or wafer) that will become part of a final electronic device.

[0113] The thickness of the dielectric film of this disclosure is not particularly limited. In some embodiments, the dielectric film has a thickness of about 1 micron or more (e.g., about 2 microns or more, about 3 microns or more, about 4 microns or more, about 5 microns or more, about 6 microns or more, about 8 microns or more, about 10 microns or more, about 15 microns or more, about 20 microns or more, or about 25 microns or more) and / or about 100 microns or less (e.g., about 90 microns or less, about 80 microns or less, about 70 microns or less, about 60 microns or less, about 50 microns or less, about 40 microns or less, or about 30 microns or less). In some embodiments, the thickness of the dielectric film is less than about 5 microns (e.g., less than about 4.5 microns, less than about 4.0 microns, less than about 3.5 microns, less than about 3.0 microns, less than about 2.5 microns, or less than about 2.0 microns).

[0114] In some embodiments, when the dielectric film-forming composition is photosensitive, a method for preparing a patterned photosensitive dielectric film includes converting the photosensitive dielectric film into a patterned dielectric film by lithography. In such cases, the conversion may include exposing the photosensitive dielectric film to high-energy radiation (such as electron beams, ultraviolet rays, and X-rays) using a patterned mask.

[0115] After exposure, the dielectric film can be heat-treated at a temperature of approximately 50°C or higher (e.g., approximately 55°C or higher, approximately 60°C or higher, or approximately 65°C or higher) to approximately 100°C or lower (e.g., approximately 95°C or lower, or approximately 90°C or lower, approximately 85°C or lower, approximately 80°C or lower, approximately 75°C or lower, or approximately 70°C or lower) for approximately 60 seconds or higher (e.g., approximately 65 seconds or higher, or approximately 70 seconds or higher) to approximately 240 seconds or lower (e.g., approximately 180 seconds or lower, approximately 120 seconds or lower, or approximately 90 seconds or lower). Heat treatment is usually achieved by using a hot plate or oven.

[0116] After exposure and heat treatment, the dielectric film can be developed using a developer to remove unexposed areas, thereby forming openings or relief images on the substrate. Development can be carried out, for example, by immersion or spraying. After development, micropores and fine lines can be generated in the dielectric film on the laminated substrate.

[0117] In some embodiments, the dielectric film can be developed using an organic developer. Examples of such developers include γ-butyrolactone (GBL), γ-valerolactone, silene, 2-methyltetrahydrofuran, dimethyl sulfoxide (DMSO), N,N-diethylacetamide, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), 2-heptanone, cyclopentanone (CP), cyclohexanone, n-butyl acetate (nBA), propylene glycol methyl ether acetate (PGMEA), propylene glycol methyl ether (PGME), ethyl lactate (EL), propyl lactate, 3-methyl-3-methoxybutanol, tetralin, isophorone, ethylene glycol monobutyl ether, and diethylene glycol. Suitable organic solvents include, but are not limited to, methyl ether 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-diethyl isosorbide), and mixtures thereof. Preferred developers are γ-valerolactone, silene, 2-methyltetrahydrofuran, γ-butyrolactone (GBL), cyclopentanone (CP), cyclohexanone, ethyl lactate (EL), n-butyl acetate (nBA), and dimethyl sulfoxide (DMSO). These developers can be used alone or in combination of two or more to optimize the image quality of the composition and lithography method.

[0118] In some embodiments, the dielectric film can be developed using an aqueous developer. When the developer is an aqueous solution, it preferably contains one or more aqueous bases. Suitable bases include, but are not limited to, inorganic alkalis (e.g., potassium hydroxide, sodium hydroxide), primary amines (e.g., ethylamine, n-propylamine), secondary amines (e.g., diethylamine, di-n-propylamine), tertiary amines (e.g., triethylamine), alcohol amines (e.g., triethanolamine), quaternary ammonium hydroxides (e.g., tetramethylammonium hydroxide or tetraethylammonium hydroxide), and mixtures thereof. The concentration of the base used varies, for example, depending on the base solubility of the polymer used. The most preferred aqueous developer contains tetramethylammonium hydroxide (TMAH). A suitable concentration of TMAH is in the range of about 1% to about 5%.

[0119] In some embodiments, after development with an organic developer, an optional rinsing treatment with an organic rinsing solvent may be performed to remove residue. Suitable examples of organic rinsing solvents include, but are not limited to, alcohols such as isopropyl alcohol, methyl isobutylcarbinol (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.

[0120] In some embodiments, after the developing step or an optionally present rinsing step, an optionally present baking step (e.g., post-developing bake) can be carried out at a temperature in the range of approximately 120°C or higher (e.g., approximately 130°C or higher, approximately 140°C or higher, approximately 150°C or higher, approximately 160°C or higher, approximately 170°C or higher, or approximately 180°C or higher) to approximately 250°C or lower (e.g., approximately 240°C or lower, approximately 230°C or lower, approximately 220°C or lower, approximately 210°C or lower, approximately 200°C or lower, or approximately 190°C or lower). The baking time is approximately 5 minutes or more (e.g., approximately 10 minutes or more, approximately 20 minutes or more, approximately 30 minutes or more, approximately 40 minutes or more, approximately 50 minutes or more, or approximately 60 minutes or more) and / or approximately 5 hours or less (e.g., approximately 4 hours or less, approximately 3 hours or less, approximately 2 hours or less, or approximately 1.5 hours or less). This baking process can remove residual solvent from the remaining dielectric film and further crosslink the remaining dielectric film. The post-development bake can be carried out in air, or preferably under a nitrogen blanket, and may be carried out by any suitable heating means.

[0121] In some embodiments, the patterned dielectric film includes at least one element having a feature size of about 10 microns or less (e.g., about 9 microns or less, about 8 microns or less, about 7 microns or less, about 6 microns or less, about 5 microns or less, about 4 microns or less, about 3 microns or less, about 2 microns or less, or about 1 micron or less). One key embodiment of the present disclosure is that dielectric films prepared from the dielectric film-forming compositions described herein can be produced by laser ablation to create patterned films having a feature size of about 3 microns or less (e.g., 2 microns or less or 1 micron or less).

[0122] In some embodiments, the aspect ratio (height-to-width ratio) of the feature (e.g., minimum feature) of the patterned dielectric film of the Disclosure is about 1 / 3 or greater (e.g., about 1 / 2 or greater, about 1 / 1 or greater, about 2 / 1 or greater, about 3 / 1 or greater, about 4 / 1 or greater, or about 5 / 1 or greater).

[0123] In some embodiments (for example, when the dielectric film-forming composition is non-photosensitive), the method for preparing a patterned dielectric film includes converting a dielectric film into a patterned dielectric film by laser ablation technique. Direct laser ablation using an excimer laser beam is generally a dry, one-step material removal method for forming apertures (or patterns) in a dielectric film. In some embodiments, the laser wavelength 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 7,598,167, 6,667,551, and 6,114,240, the contents of which are incorporated herein by reference.

[0124] In embodiments where the dielectric film-forming composition is non-photosensitive, the composition can be used to form the lower layer in a two-layer photoresist. In such embodiments, the upper layer of the two-layer photoresist may be a photosensitive layer that can be patterned upon exposure to high-energy radiation. The pattern in the upper layer can be transferred to the lower dielectric layer (e.g., by etching). The upper layer can then be removed (e.g., by using a wet chemical etching method) to form the patterned dielectric film.

[0125] In some embodiments, the Disclosure features a method for depositing a metal layer (for example, for producing an embedded copper trace structure), comprising the steps of: (a) forming a patterned dielectric film having openings; and (d) depositing a metal layer (e.g., a conductive metal layer) in at least one opening in the patterned dielectric film. For example, the method may include: (a) depositing a dielectric film-forming composition described herein onto 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., through a mask); (c) patterning the dielectric film to form a patterned dielectric film having openings; and (d) depositing a metal layer (e.g., a conductive metal layer) in at least one opening in the patterned dielectric film. In some embodiments, steps (a) to (d) may be repeated one or more times (e.g., two, three, or four times).

[0126] In some embodiments, the disclosure features a method for depositing a metal layer (e.g., a conductive copper layer for fabricating an embedded copper trace structure) onto a semiconductor substrate. In some embodiments, to achieve this, a conformal seed layer is first deposited on a patterned dielectric film (e.g., outside of openings in 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 by using a material that can prevent the diffusion of a conductive metal (e.g., copper) through the dielectric layer. Suitable materials that can be used for the barrier layer include, but are not limited to, tantalum (Ta), titanium (Ti), tantalum nitride (TiN), tungsten nitride (WN), and Ta / TaN. A suitable method for forming the barrier layer is sputtering (e.g., PVD or physical vapor deposition). Sputtering deposition has several advantages as a metal deposition technique because it can be used to deposit many conductive materials at high deposition rates, with good uniformity and low ownership costs. Conventional sputtering fill yields relatively poor results for deeper, narrower (higher aspect ratio) features. Filling efficiency by sputtering deposition has been improved by collimating the sputtered flux. Typically, this is achieved by inserting a collimator plate with an array of hexagonal cells between the target and the substrate.

[0127] The next step in the method is metal seed deposition. A thin metal (e.g., a conductive metal such as copper) seed layer can be formed on top of the barrier layer to improve the deposition of the metal layer (e.g., a copper layer) that will be formed in a subsequent step.

[0128] The next step in the method is to deposit a conductive metal layer (e.g., a copper layer) on top of a metal seed layer within the openings of the patterned dielectric film, the metal layer being thick enough to fill the openings in the patterned dielectric film. The metal layer for filling the openings in the patterned dielectric film can be deposited by plating (such as electroless or electroplating), sputtering, plasma deposition (PVD), and chemical deposition (CVD). Electrochemical deposition is generally more economical than other deposition methods and is a preferred method for applying copper because it can fill interconnect features with copper without defects. Copper deposition methods should generally meet the stringent requirements of the semiconductor industry. For example, the copper deposit should be uniform and able to fill small interconnect features of the device, e.g., openings of 100 nm or less, without defects. This technique is described, for example, in U.S. Patents 5,891,804, 6,399,486, and 7,303,992, which are incorporated herein by reference.

[0129] In some embodiments, the method for depositing a conductive metal layer further includes removing the overburden of the conductive metal or removing a seed layer (e.g., a barrier layer and a metal seed layer). In some embodiments, the overburden of the conductive metal layer (e.g., a copper layer) is about 3 microns or less (e.g., about 2.8 microns or less, about 2.6 microns or less, about 2.4 microns or less, about 2.2 microns or less, about 2.0 microns or less, or about 1.8 microns or less) and about 0.4 microns or more (e.g., about 0.6 microns or more, about 0.8 microns or more, about 1.0 micron or more, about 1.2 microns or more, about 1.4 microns or more, or about 1.6 microns or more). Examples of copper etching solutions for removing copper overburden include aqueous solutions containing cupric chloride and hydrochloric acid, or aqueous mixtures of ferric nitrate and hydrochloric acid. Other suitable copper etching solutions include, but are not limited to, those 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, as well as U.S. Patent Application Publication No. 2017 / 0175274. These are incorporated herein by reference.

[0130] Several embodiments describe methods for surrounding a metal-structured substrate containing conductive metal (e.g., copper) wire structures with dielectric films described herein to form networks of lines and interconnections. The method is: a) Prepare a substrate containing a conductive metal wire structure that forms a network of lines and interconnections on the substrate; b) Depositing a dielectric film-forming composition described herein onto a substrate to form a dielectric film (for example, surrounding conductive metal lines and interconnections); c) Exposure of the dielectric film to a radiation source, a heat source, or a combination of radiation and heat (with or without a mask), This includes the above process, which can be repeated multiple times (for example, two, three, or four times) to form a complex multilayered three-dimensional object.

[0131] In some embodiments, the present disclosure features a method for preparing a dry film structure. The method is: a) Coating a carrier substrate (e.g., a substrate comprising at least one polymer or plastic film) with a dielectric film-forming composition described herein; b) Drying the coated dielectric film-forming composition to form a dielectric layer (e.g., a photosensitive dielectric layer); c) Optionally, apply a protective layer to the dry film structure. Includes.

[0132] In some embodiments, the carrier substrate is a single-layer or multi-layer polymer or plastic film that may contain one or more polymers (e.g., polyethylene terephthalate). In some embodiments, the carrier substrate has excellent optical transparency and is substantially transparent to irradiation with active light used to form a relief pattern in the polymer layer. The thickness of the carrier substrate is preferably in the range of about 10 μm or more (e.g., about 15 μm or more, about 20 μm or more, about 30 μm or more, about 40 μm or more, about 50 μm or more, or about 60 μm or more) to about 150 μm or less (e.g., about 140 μm or less, about 120 μm or less, about 100 μm or less, about 90 μm or less, about 80 μm or less, or about 70 μm or less).

[0133] In some embodiments, the protective layer is a single-layer or multilayer film that may contain one or more polymers (e.g., polyethylene or polypropylene). Examples of carrier substrates and protective layers are described, for example, in U.S. Patent Application Publication No. 2016 / 0313642, which are incorporated herein by reference.

[0134] Reliability is the probability that an electronic component will perform the required function under stress conditions for a specified period of time. Preconditioning, temperature and humidity bias (THB), biased humidity stress test (bHAST), unbiased HAST (uHAST), and high temperature storage (HTS) are commonly used stress tests applied to semiconductor packaging materials. This is the percentage of devices that have not failed by a given time "t" out of devices used from time zero.

[0135] Highly accelerated stress testing (HAST) measures the reliability of components with and without electrical bias by combining high temperature, high humidity, high pressure, and time. In a controlled environment, HAST testing accelerates the stress of more traditional tests. It essentially functions as a corrosion failure test. Corrosion-type failures are accelerated, revealing defects such as packaging seals, materials, and joints in a short period of time.

[0136] Biased Highly Accelerated Stress Test (bHAST) utilizes the same variables as the HAST test (high voltage, high temperature, and time) but adds a voltage bias. The purpose of the bHAST test is to accelerate corrosion within the device, thereby shortening the test period. In the unbiased HAST test, humidity accelerates failure mechanisms related to the presence of moisture in non-airtight packages. In the biased humidity stress test (bHAST), the bias voltage under high humidity causes galvanic and electrochemical corrosion in non-airtight packages. For advanced / emerging packaging technologies, board-level reliability (BLR) testing is performed using daisy-chained test vehicles to determine the reliability of solder joint interconnects. Failure analysis is performed on failed samples to identify the cause.

[0137] As an accelerated version of the conventional non-condensing THB (temperature-humidity biased) test, the HAST test has the advantage of accelerating temperature and moisture-induced failures in approximately one-tenth the time of THB by applying high pressure and higher temperatures (below 149°C). HAST and bHAST tests are typically performed at 130°C / 85%RH, but conditions may vary.

[0138] Typical HAST test conditions consist of a temperature of 110°C or 130°C, a humidity of 85% RH, and a test run time of 96 or 200 hours. Upon completion of the highly accelerated stress test, the tested sample is analyzed by microscopy and SEM for changes that occurred during the HAST conditions. HAST tests generally follow the JEDEC standard JESD22 A110, “Highly Accelerated 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 to evaluate semiconductor devices are described, for example, in U.S. Patent No. 9,874,813 and U.S. Patent Application Publication No. 2021 / 0272898, which are incorporated herein by reference.

[0139] TEG (Test Element Group) wafers with Cu post (pillar) plating were used for material development by inspection methods and for wafer evaluation, including package stability under HAST conditions. Examples of TEG wafers used for evaluating semiconductor devices are described, for example, in U.S. Patent Nos. 8,237,450 and 9,082,708, which are incorporated herein by reference.

[0140] In some embodiments, the dielectric film of a dry film structure can be exfoliated 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 supporting layer, such as a carrier layer. In some embodiments, the self-supporting dielectric film is not crosslinked or cured and may contain components of the above-described dielectric film forming composition, except for the solvent.

[0141] In some embodiments, the dielectric loss loss tangent or dissipation coefficient of a dielectric film prepared from the dielectric film forming compositions described herein, measured at 10 GHz, 15 GHz, and / or 35 GHz, is in the range of about 0.001 or more (e.g., about 0.002 or more, about 0.003 or more, about 0.004 or more, about 0.005 or more, about 0.01 or more, or about 0.05 or more) to about 0.1 or less (e.g., about 0.08 or less, about 0.06 or less, about 0.05 or less, about 0.04 or less, about 0.02 or less, about 0.01 or less, about 0.008 or less, about 0.006 or less, or about 0.005 or less).

[0142] In some embodiments, the dielectric film of a dry film structure can be laminated to a substrate (e.g., a semiconductor substrate such as a wafer) using a vacuum laminator at approximately 50°C to approximately 140°C, after pre-lamination of the dielectric film of the dry film structure by a planar compression method or a hot roll compression method. When hot roll lamination is employed, the dry film structure can be placed in a hot roll laminator, the protective layer can optionally be peeled off from the dielectric film / carrier substrate, and the dielectric film can be laminated to the substrate using rollers with heat and pressure to form an article containing the substrate, dielectric film, and carrier substrate. The dielectric film can then be exposed to a radiation source or heat source (e.g., via the carrier substrate) to form a crosslinked dielectric film. In some embodiments, the carrier substrate can be removed before the dielectric film is exposed to a radiation source or heat source.

[0143] Some embodiments of this disclosure describe methods for forming a planar dielectric film on a substrate having a copper pattern. In some embodiments, the method includes depositing a dielectric film-forming composition onto a substrate having a copper pattern to form a dielectric film. In some embodiments, the method is: a. A step of preparing the dielectric film forming composition of the present disclosure, and b. A step of depositing a dielectric film-forming composition onto a substrate having a copper pattern to form a dielectric film. Includes, The height difference between the highest and lowest points on the surface of the dielectric film is approximately 2 microns or less (for example, approximately 1.5 microns or less, approximately 1 micron or less, or approximately 0.5 microns or less).

[0144] In some embodiments, the Disclosure features an article (or three-dimensional object) comprising at least one patterned dielectric film formed by the methods described herein. Examples of such articles include semiconductor substrates, flexible films for electronic devices, wire insulation, wire coatings, wire enamels, and ink-coated substrates. In some embodiments, the Disclosure features a semiconductor device comprising one or more of these articles. Examples of semiconductor devices that can be fabricated from such articles include integrated circuits, light-emitting diodes, solar cells, and transistors.

[0145] All publications cited herein (e.g., patents, patent application publications, and articles) are incorporated herein by reference in their entirety. [Examples]

[0146] The present disclosure is illustrated in more detail below with reference to the following examples, which are illustrative and should not be construed as limiting the scope of the present disclosure.

[0147] Synthesis Example 1: Preparation of fully imidized polyimide (PI-I) [ka] Solid 4,4'-(hexafluoroisopropylidene)bis(phthalic anhydride) (6FDA) (2.370 kg, 5.33 mol) was charged at 25°C into a solution of 1-(4-aminophenyl)-1,3,3-trimethylindan-5-amine (also known as 4,4'-[1,4-phenylene-bis(1-methylethylidene)]bisaniline (DAPI)) (1.465 kg, 5.51 mol) in NMP (9.86 kg). The temperature of the reaction mixture was raised to 40°C and the reaction was allowed to proceed for 6 hours. Next, acetic anhydride (1.125 kg) and pyridine (0.219 kg) were added, and the temperature of the reaction mixture was raised to 100°C and the reaction was allowed to proceed for 12 hours.

[0148] The 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 1 hour. After stopping the stirring, the mixture was allowed to stand. When phase separation occurred, the aqueous phase was removed. The organic phase was diluted with a combination of ethyl acetate and acetone and washed twice with water. The amounts of organic solvents (ethyl acetate and acetone) and water used in all washes are shown in Table 1. [Table 1]

[0149] 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) (PI-I). The solids content of the final polymer was 29.19%, and the weight-average molecular weight (Mw) measured by GPC was 54,000 daltons.

[0150] Synthesis Example 2: Preparation of fully imidized polyimide (PI-II) The following is an example of the preparation of polyimide (PI) polymers using one diamine and one dianhydride, where the isolation solvent (i.e., lactone) was different from the purification solvent (i.e., ketone and ester).

[0151] Solid 4,4'-oxydiphthalic anhydride (ODPA, 664.5 g) was charged at 25°C into a solution of 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl (TFMB, 722.1 g) in NMP (3296 g). The dianhydride was washed into the solution using additional NMP (1346 g). The reaction temperature was raised to 40°C and the mixture was reacted for 3 hours. Next, acetic anhydride (507.2 g) and pyridine (98.3 g) were added, and the reaction temperature was raised to 100°C and the mixture was reacted for 12 hours.

[0152] The reaction mixture was cooled to room temperature, and a portion of it (899 g) was transferred to a 5 L container equipped with a mechanical stirrer. The reaction solution was diluted using a combination of cyclopentanone and n-butyl acetate and washed with water for 1 hour. Stirring was stopped, and the mixture was allowed to stand. When phase separation occurred, the aqueous phase was removed. The organic phase was diluted with cyclopentanone and washed three more times with water. The amounts of purified solvents (i.e., cyclopentanone and n-butyl acetate) and water used in all washings are shown in Table 2. [Table 2]

[0153] The washed organic phase was concentrated by vacuum distillation. γ-butyrolactone (605 g) was added as an isolation solvent, and vacuum distillation was continued. The final polymer solution contained polyimide(II) (PI-II) at a concentration of 24.99 wt%, and the weight-average molecular weight (Mw) measured by GPC was 45,000 daltons.

[0154] Synthesis Example 3: Preparation of fully imidized polyimide (PI-III) A mixture of solid ODPA (94.78 g) and 6FDA (45.25 g) was charged at 25°C into a solution of TFMB (135.5 g) in NMP (819 g). The dianhydride was washed into the solution using an additional NMP (100 g). The reaction temperature was raised to 40°C and the mixture was reacted for 3 hours. Next, 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.

[0155] The processing method was followed in Example 2, and the resulting polyimide(III)(PI-III) was isolated in cyclopentanone. The weight-average molecular weight (Mw) measured by GPC was 47,000 daltons.

[0156] Synthesis Example 4: Preparation of fully imidized polyimide (PI-IV) Solid ODPA (170.24 g) was charged at 25°C into a solution of DAPI (74.59 g) and 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP) (114.94 g) in NMP (979 g). The dianhydride was washed into the solution using an additional NMP (100 g). The reaction temperature was raised to 40°C and the mixture was reacted for 3 hours. Next, acetic anhydride (125.6 g) and pyridine (24.4 g) were added, the reaction temperature was raised to 100°C, and the mixture was reacted for 12 hours.

[0157] The processing method was followed in Example 2, and the resulting polyimide(IV) (PI-IV) was isolated in a GBL (solids content 30.60%). The weight-average molecular weight (Mw) measured by GPC was 42,000 daltons.

[0158] Synthesis Example 5: Preparation of fully imidized polyimide (PI-V) Solid ODPA (203.7g) was charged at 25°C into a solution of DAPI (133.2g) and BAPP (68.4g) in NMP (1115g). The dianhydride was washed into the solution using an additional NMP (100g). The reaction temperature was raised to 40°C and the mixture was reacted for 3 hours. Next, acetic anhydride (150g) and pyridine (9g) were added, the reaction temperature was raised to 100°C, and the mixture was reacted for 12 hours.

[0159] The processing method was followed in Example 2, and the resulting polyimide(IV)(PI-V) was isolated in cyclopentanone (solid content 30.26%). The weight-average molecular weight (Mw) measured by GPC was 43,000 daltons.

[0160] Synthesis Example 6: Preparation of fully imidized polyimide (PI-VI) Solid 2,2',3,3'-benzophenonetetracarboxylic dianhydride (BTDA) (127.3 g) was charged into a solution of DAPI (106.55 g) in NMP (445 g) at 25°C. The dianhydride was washed into the solution using an additional NMP (100 g). The reaction temperature was raised to 40°C and the mixture was reacted for 3 hours. To carry out the end-capturing reaction, 2.97 g of 4-methacryloxyethyl trimellitic anhydride (META) and 2.0 g of pyridine were charged into a flask. The mixture was stirred at 60°C for 3 hours.

[0161] Next, acetic anhydride (60.4g) and pyridine (23.43g) were added, the reaction temperature was raised to 100°C, and the mixture was reacted for 12 hours.

[0162] The processing method was followed in Example 2, and the resulting polyimide (VI) (PI-VI) was isolated in cyclopentanone (solid content 30.26%). The weight-average molecular weight (Mw) measured by GPC was 20,400 daltons.

[0163] Synthesis Example 7: Preparation of fully imidized polyimide (PI-VII) Solid 6FDA (61.08 g) was charged into a solution of DAPI (39.95 g) in NMP (500 g) at 25°C. The dianhydride was washed into the solution using an additional NMP (100 g). The reaction temperature was raised to 40°C and the mixture was reacted for 3 hours. To carry out the end-capturing reaction, 4.2 g of exo-3,6-epoxy-1,2,3,6-tetrahydrophthalic anhydride (oxonadic anhydride) and 2.0 g of pyridine were charged into a flask. The mixture was stirred at 60°C for 3 hours.

[0164] Next, acetic anhydride (10.2g) and pyridine (2.0g) were added, the reaction temperature was raised to 100°C, and the mixture was reacted for 12 hours.

[0165] The processing method was followed in Example 2, and the resulting polyimide (VII) (PI-VII) was isolated in cyclopentanone (30.5% solids content). The weight-average molecular weight (Mw) measured by GPC was 13,200 daltons.

[0166] Synthesis Example 7: Preparation of fully imidized polyimide (PI-VIII) PI-VIII was a 31.7% solution of polyimide polymers of ODPA, 6FDA, and TFMB, and was prepared on a large scale in cyclopentanone to have a weight-average molecular weight of 44,786 daltons, similar to Example PI-III. [ka]

[0167] Synthesis Example 9: Preparation of fully imidized polyimide (PI-IX) Solid ODPA (132.90 g) was charged at 25°C into a solution of TFMB (128.09 g) and 3,5-diaminobenzoic acid (6.09 g) in NMP (793 g). The dianhydride was washed into the solution using an additional NMP (100 g). The reaction temperature was raised to 40°C and the mixture was reacted for 3 hours. Next, acetic anhydride (98.74 g) and pyridine (19.2 g) were added, the reaction temperature was raised to 100°C, and the mixture was reacted for 12 hours.

[0168] The solution was diluted with 300 g of tetrahydrofuran (THF). The solution was then precipitated in 8 L of distilled water. After filtration, the wet cake was dried in air. The crude polymer was dissolved in 500 g of THF and precipitated in 8 L of distilled water. After filtration, the wet cake was dried in air, and then dried under vacuum at 60°C for 12 hours to completely remove moisture. The weight-average molecular weight (Mw) measured by GPC was 50,000 daltons.

[0169] Synthesis Example 10: Preparation of fully imidized polyimide (PI-X) Solid ODPA (118.83 g) was charged at 25°C into a solution of DAPI (128.09 g) and 3,5-diaminobenzoic acid (5.92 g) in NMP (544 g). The dianhydride was washed into the solution using an additional NMP (100 g). The reaction temperature was raised to 40°C and the mixture was reacted for 3 hours. Next, acetic anhydride (87.3 g) and pyridine (16.9 g) were added, the reaction temperature was raised to 100°C, and the mixture was reacted for 12 hours.

[0170] The polymer was treated in the same manner as in Example PI-IX. The weight-average molecular weight (Mw) measured by GPC was 30,000 daltons.

[0171] Synthesis Example 11: Preparation of fully imidized polyimide (PI-XI) PI-XI is a 32.2% solution of polyimide polymers of 6FDA, DAPI, and BAPP, prepared on a large scale in cyclopentanone to have a weight-average molecular weight of 54,000 daltons. [ka]

[0172] Synthesis Example 12: Preparation of fully imidized polyimide (PI-XII) PI-XII is a 33.65% solution of polyimide polymers of 6FDA, DAPI, and BAPP, prepared on a large scale in cyclopentanone to have a weight-average molecular weight of 74,000 daltons. [ka]

[0173] Synthesis Example 13: Preparation of fully imidized polyimide (PI-XIII) PI-XIII is a blend of 49% PI-XI and 51% PI-XII.

[0174] Synthesis Example 14: Preparation of fully imidized polyimide (PI-XIV) Solid ODPA (123.46 g) was charged at 25°C into a solution of DAPI (79.91 g) and 4,4'-methylenebis(2,6-diethylaniline) (31.05 g) in NMP (603 g). The dianhydride was washed into the solution using an additional NMP (100 g). The reaction temperature was raised to 40°C and the mixture was reacted for 3 hours. Next, acetic anhydride (122.1 g) and pyridine (23.7 g) were added, the reaction temperature was raised to 100°C, and the mixture was reacted for 12 hours.

[0175] The polymer was treated in the same manner as in Example PI-IX. The weight-average molecular weight (Mw) measured by GPC was 41,000 daltons.

[0176] The abbreviations listed in Table 4 below are as follows: (A) Resin component Resins synthesized in Synthesis Examples 1-13 (fully imidized polyimides) (PI I-XIII) (B) Polyfunctional (meth)acrylate crosslinking agent B-1: Tetra(ethylene glycol) diacrylate, D048 (Trade name, Green Chemical, available from South Korea) B-2: Pentaerythritol triacrylate, SR295 (product name, available from Sartomer) B-3: Hexanediol diacrylate SR238 (product name, available from Sartomer) B-4: Tricyclodecanedimethanol diacrylate SR833S (trade name, available from Sartomer) B-5: 1,6-Bisphenol A(EO)2 diacrylate (manufactured by Sigma Aldrich Corp.) B-6:2-(Tricyclo[5.2.1.02,6]deca-3-en-8-yloxy)ethyl acrylate (manufactured by Sigma Aldrich Corp.) B-7: Tris(2-hydroxyethyl) isocyanurate triacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) B-8: 1,9-nonanediol diacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) B-9:1,10-decyldiol diacrylate SR595 (product name, available from Sartomer) (C) Photoradical polymerization initiator C-1: NCI-831 (product name, available from ADEKA Corporation) C-2: IRGACURE OXE 01 (BASF) C3: IRGACURE OXE 02 (BASF) 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)) (D) Adhesion promoter D-1: γ-Glycidoxypropyltrimethoxysilane (available from Gelest Corporation) D-2: γ-Glycidoxypropyltrimethoxysilane or SilQuest A-187 (available from Gelest Corporation) (E) Polymerization inhibitors E-1: Monomethyl ether hydroquinone (manufactured by Tokyo Chemical Industry Co., Ltd.) E-2: Parabenzoquinone (manufactured by Tokyo Chemical Industry Co., Ltd.) E-3: t-butylcatechol (manufactured by Tokyo Chemical Industry Co., Ltd.) (F) Copper corrosion inhibitor F-1: 5-Methylbenzotriazole (manufactured by Tokyo Chemical Industry Co., Ltd.) F-2: 2-Hydroxy-5-acrylyloxyphenyl-2H-benzotriazole (manufactured by Tokyo Chemical Industry Co., Ltd.) F-3: 1H Tetrazole (manufactured by Tokyo Chemical Industry Co., Ltd.) F-4:5-phenyl-1H-tetrazole (manufactured by Tokyo Chemical Industry Co., Ltd.) F-5: 1H-tetrazole-5-ethyl acetate (manufactured by Tokyo Chemical Industry Co., Ltd.) F-6: 1H-tetrazole-5-carboxylate ethyl (manufactured by Tokyo Chemical Industry Co., Ltd.) F-7: 3-amino-1,2,4-triazole (manufactured by Tokyo Chemical Industry Co., Ltd.) F-8:-3,5-diamino-1,2,4-triazole (manufactured by Tokyo Chemical Industry Co., Ltd.) (G) Surfactants G-1: PolyFox 6320 during GBL (available from OMNOVA Solutions) G-2: 0.5 wt% solution of PolyFox 6320 (available from OMNOVA Solutions) in propylene carbonate. (H) solvent H-1: γ-butyrolactone (manufactured by Eastman) H-2: Cyclopentanone (Solvay brand) H-3: Propylene Carbonate (Huntsman) H-4: Dimethyl sulfoxide (manufactured by Sigma Aldrich Corp.) H-5: N-methyl-2-pyrrolidone (manufactured by Ashland) (I) Additives I-1: 50% solution of XU 378 in cyclopentanone (Huntsman) I-2: 50% solution of 2,2-bis(4-cyanatophenyl)propane in cyclopentanone (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0177] Photosensitive composition Example 1 Photosensitive composition (FE-1) was prepared using 80 g of polymer solution (PI-I), 14.69 g of GBL (H-1), 1.42 g of a 0.5 wt% solution of PolyFox 6320 (available from OMNOVA Solutions) in GBL (G-1), 0.71 g of γ-glycidoxypropyltrimethoxysilane (D-1), 0.71 g of NCI-831E (trade name, available from ADEKA Corporation) (C-1), 0.05 g of para-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 was filtered using a 0.2 micron filter.

[0178] Photosensitive composition example 2 A photosensitive composition (FE-2) was prepared using a 32.46 percent solution of 100 parts of polyimide polymer (PI-XI), 93.2 parts of H-2, 27.5 parts of H-1, 5.9 parts of G-1, 5 parts of D-1, 3.0 parts of C-2, 0.1 parts of E-3, 32.5 parts of B-1, 12.5 parts of B-2, 5.0 parts of B-6, and 0.62 parts of F-1. After 24 hours of mechanical stirring, the solution was filtered using a 0.2 micron filter (Ultradyne, Meissner Corporation, catalog number CLTM0.2-552).

[0179] Photosensitive composition example 3 The photosensitive composition (FE-3) was prepared using 100 parts of a 29.19% solution of a polyimide polymer (PI-XI) having a weight-average molecular weight of 54,000 daltons in cyclopentanone, 9.5 parts H-2, 142 parts H-3, 6.0 parts G-2, 5.0 parts D-1, 3.0 parts C-2, 0.2 parts hydroquinone E-1, 37.5 parts B-1, 12.5 parts B-2, 10.0 parts I-2, and 0.5 parts F-1. After mechanical stirring for 24 hours, the solution was filtered using a 0.2 micron filter (Ultradyne, Meissner Corporation, catalog number CLTM0.2-552).

[0180] Composition Examples FE-4 to FE-35 A photosensitive polyimide film-forming composition was prepared based on 100 parts of polymer. After thorough mixing as in Example FE-1, the solution was filtered using a 0.2 micron filter (Ultradyne, Meissner Corporation, catalog number CLTM0.2-552).

[0181] Composition Examples FE-41~FE-42 A photosensitive polyimide film-forming composition is prepared based on 100 parts of polymer. After thorough mixing as in Example FE-1, the solution is filtered using a 0.2 micron filter (Ultradyne, Meissner Corporation, catalog number CLTM0.2-552).

[0182] Table 4 provides the compositions of formulations FE-4 to FE-35 and FE-41 to FE-42.

[0183] Dry film example 1 The photosensitive dielectric film-forming composition consists of 1345.24 g of a 31.69% solution of polyimide polymer (I) (PI-I) having a weight-average molecular weight of 54,000 in cyclopentanone (H-2), 1021.91 g of propylene carbonate (H-3), 102.31 g of a 0.5 wt% solution of PolyFox 6320 (G-1) in cyclopentanone, 21.31 g of methacryloxypropyltrimethoxysilane (D-1), 34.11 g of a 50% solution of XU-378 (bisphenol M cyanate ester available from Huntsman) (I-1) in cyclopentanone, and 2-(O-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione (Irgacure available from BASF). The solution was prepared using 12.79 g of OXE-1)(C-2), 0.43 g of monomethyl ether hydroquinone (E-1), 138.55 g of tetraethylene glycol diacrylate (B-1), 53.39 g of pentaerythritol triacrylate (B-2), 26 g of dicumyl peroxide, and 0.426 g of 5-methylbenzotriazole (F-1). After mechanical stirring for 24 hours, the solution was filtered using a 0.2 micron filter (Ultradyne, Meissner Corporation, catalog number CLTM0.2-552).

[0184] The photosensitive dielectric film-forming composition obtained above was applied to a polyethylene terephthalate (PET) film (TCH21, manufactured by DuPont Teijin Films USA) having a width of 16.2 inches and a thickness of 36 microns (this was used as a carrier substrate) using a slot die coater at a line speed of approximately 2 feet / min (61 cm per minute) and a clearance of 60 microns, and dried at 194°F to obtain a photosensitive polymer layer. A biaxially oriented polypropylene film (BOPP, manufactured by Impex Global, Houston, Texas) having a width of 16 inches and a thickness of 30 microns was overlaid on this polymer layer by roll compression to function as a protective layer. The carrier substrate, photosensitive polymer layer, and protective layer together form a dry film (i.e., DF-1).

[0185] Lithography Method Example 1 Photosensitive composition FE-1 was 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. The photosensitive polyimide film was exposed at various exposure energy levels using a Canon 4000 IE i-line stepper.

[0186] Unexposed areas were removed using cyclopentanone as the developer (dynamic development for 1 × 40 seconds), and then the developed film was rinsed with PGMEA for 15 seconds to form a pattern. 100 mJ / cm 2 A resolution of 4 microns was achieved at a sensitivity (photospeed). The film thickness reduction was 17.9%.

[0187] General procedure for measuring the mechanical properties of films The filtered polymer solution was applied to a silicon oxide wafer by spin coating to obtain a film with a thickness of approximately 12.0 to 15.0 microns. The coating was dried on a hot plate oven at 90°C for 10 minutes. The film was then subjected to a 500 mJ / cm² test. 2 The film was exposed to light until [a certain point]. Finally, the film was baked in a YES oven under vacuum at 230°C for 3 hours. The film was peeled from the silicon oxide layer using a 2% hydrofluoric acid solution and dried in air at 50°C for 2 hours. After cooling to room temperature, the film was characterized by DMA for Tg measurement.

[0188] Three-dimensional object example 1 The photosensitive dielectric film-forming composition described in Dry Film Example 1 is converted into a film deposited on various substrates used in microelectronics and packaging applications. The film is deposited on a 100 mm silicon wafer by spin-coating approximately 5 g of the solution at a spin speed of approximately 2000 rpm. The film is dried on a hot plate at a temperature of 105°C for 3 minutes to obtain a 12 micron transparent film. The film quality in terms of transparency, defect count, and uniformity is expected to meet the requirements for semiconductor packaging applications.

[0189] The above procedure is repeated on aluminum, copper, and silicon nitride wafers. All films obtained in this way are expected to meet the requirements for semiconductor packaging applications.

[0190] Reliability Test Examples The dielectric film-forming compositions of Examples FE21-35 were spin-coated to a thickness of 6-12 microns at 1200 rpm onto TEG chips having copper-plated line / space patterns in the range of 2 / 2 microns, 8 / 8 microns, and 15 / 15 microns, and then baked at 95°C for 5 minutes using a hot plate to form a coating with a thickness of approximately 13 microns. The dielectric film-forming compositions were then exposed to 500 mJ / cm² using an LED i-line exposure tool. 2 The entire surface was exposed (blanket exposure). The composition was cured in a YES oven at 170-230°C for 3 hours.

[0191] Next, reliability tests were conducted as described below and summarized in Table 3.

[0192] Unbiased Highly Accelerated Stress Test (uHAST) (JESD22-A118) The purpose of uHSAT is to simulate extreme operating conditions (similar to an autoclave). Description: The device is baked for various periods in a chamber with extreme temperature and humidity. The device is then subjected to ATE evaluation for electrical failures. Variables: Temperature = 130°C / Humidity = 85%RH / Time = 96 hours or 210 hours. TEG chips were heated in an ESPEC reliability test chamber at 130°C and 85%RH for 96 hours, 168 hours, and 210 hours for unbiased humidity stress testing (uHAST). Cracks or delamination were checked at 96 hours, 168 hours, and 210 hours using an optical microscope, or by cross-sectional SEM after cutting and ion milling of the samples at 96 hours, 168 hours, and 210 hours.

[0193] Biased High-Accelerated Stress Test (bHAST) (JESD22-A110) The purpose of the bHAST test is to simulate extreme operating conditions (very similar to uHAST). Description: The device is baked for various periods in a chamber with extreme temperature and humidity. While the device is in the chamber, it is biased. The device is then electrically tested for electrical faults using an ATE (Electron-Technical Test). Variables: Temperature = 130°C / Humidity = 85%RH / Time = 96 hours or 264 hours, Voltage bias level between 5 volts and 20 volts.

[0194] TEG chips were heated for 96 hours at 130°C, 85% RH, and 5–20 volts in an ESPEC reliability test chamber for biased humidity stress testing (bHAST). Cracks or delamination were checked at 96 hours using an optical microscope or by cross-sectional SEM after cutting and ion milling of the sample at 96 hours.

[0195] High temperature operating life (HTS) The failure rate period during the operating life generally lasts for a considerable amount of time. HTS is used to determine a device's tolerance to long-term operating stress, including both electrical and thermal mechanisms. HTS is typically a reliability measure for device design / layout in a given manufacturing (fab) method.

[0196] The purpose of the test is to simulate the operating life under a specified set of conditions. Variables: Temperature = 175°C / Time = 1000 hours.

[0197] Cracks or delamination were checked at 100, 500, and 1000 hours using an optical microscope, or by cross-sectional SEM after cutting and ion milling of the sample at 100, 500, and 1000 hours.

[0198] Thermal cycling (TCT) (JESD22-A104 / IPC-9701) The purpose of the TCT test is to accelerate the effects of thermal expansion mismatch between the solder joints of the components and the system board. Description: The thermal cycle is defined by the temperature extremes, the residence / immersion time at the extremes, and the temperature gradient (ramp rate). The resistance of all daisy-chain nets is measured in situ or according to predefined reading points and compared to the initial resistance. Variables: Temperature = 150°C (upper limit) and -40°C (lower limit) / approximately 60 minutes per cycle, number of cycles = 1000.

[0199] Cracks or delamination were checked using an optical microscope at cycles 100, 500, and 1000, or by cross-sectional SEM after cutting and ion milling of the sample at cycles 100, 500, and 1000.

[0200] Biased humidity stress testing (bHAST) is the most sensitive stress test for assessing the reliability of microelectronic devices using organic dielectric film compositions.

[0201] [Table 3] conditions: HAST: 130℃ / 85%RH / 96 hours bHAST: 5-15 volts, 130°C / 85%RH / 96 hours HTS: 175℃ / 1000 hours TCT: -40℃ to 150℃ / 1000 cycles.

[0202] Table 4.Formula FE-4~FE-42 [Table 4] [Table 5] Table 6 Table 7

Claims

1. To prepare a composition containing a hydrophobic polyfunctional (meth)acrylate crosslinking agent and polymer; The process includes processing the composition to provide a dielectric layer, When the dielectric layer is present in the microelectronic device, the microelectronic device exhibits good reliability. method.

2. The method according to claim 1, wherein the hydrophobic polyfunctional (meth)acrylate crosslinking agent has a logP value of at least 0.

5.

3. The method according to claim 1 or claim 2, wherein the hydrophobic polyfunctional (meth)acrylate crosslinking agent comprises at least one species selected from the group consisting of at least one difunctional (meth)acrylate, trifunctional (meth)acrylate, tetrafunctional (meth)acrylate, and hexafunctional (meth)acrylate, and each of the hydrophobic polyfunctional (meth)acrylate crosslinking agents has a logP value of about 0.5 to about 8.

0.

4. The method according to any one of claims 1 to 3, wherein the composition further comprises a corrosion inhibitor.

5. The method according to claim 4, wherein the corrosion inhibitor has a logP value of about -1.0 to about 6.

0.

6. The method according to any one of claims 1 to 5, wherein the composition further comprises a photopolymerization initiator.

7. The method according to claim 6, wherein the photopolymerization initiator comprises at least one species selected from the group consisting of oxime esters, titanocene, acylgermanium compounds, and peroxides.

8. The method according to any one of claims 1 to 7, wherein the composition further comprises an organic solvent.

9. The method according to claim 8, wherein the organic solvent comprises at least one species 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, pyrrolidones, and dialkyl sulfoxides.

10. The method according to any one of claims 1 to 9, wherein the polymer comprises at least one species selected from the group consisting of polybenzoxazole precursor polymers, polyimide precursor polymers, and fully imidized polyimide polymers.

11. The method according to any one of claims 1 to 9, wherein the polymer comprises a fully imidized polyimide polymer.

12. The method according to claim 11, wherein the fully imidized polyimide polymer contains a functional group.

13. The method according to claim 11, wherein the fully imidized polyimide polymer includes an alkali-soluble polymer.

14. The method according to claim 11, wherein the fully imidized polyimide polymer includes a polymer that does not contain fluorine atoms.

15. The method according to any one of claims 1 to 14, wherein the polymer is present in an amount of about 0.1% to about 55% by weight relative to the solid content weight of the composition.

16. The method according to any one of claims 1 to 15, wherein the hydrophobic polyfunctional (meth)acrylate crosslinking agent is present in an amount of about 0.5% to about 25% by weight relative to the solid content weight of the composition.

17. The method according to any one of claims 1 to 16, wherein the composition further comprises at least one selected from the group consisting of adhesion promoters, surfactants, fillers, pigments, dyes, and metal-containing (meth)acrylate compounds.

18. The method according to any one of claims 1 to 17, wherein the composition further comprises at least one photosensitizer selected from the group consisting of benzophenones, thioxanthones, anthraquinones, anthracenes, and coumarins.

19. The method according to any one of claims 1 to 18, wherein the composition is substantially fluorine-free.

20. The method according to any one of claims 1 to 19, wherein, if the dielectric layer is present in the microelectronic device, the microelectronic device passes at least one test selected from the group consisting of HAST, bHAST, HTS, and TCT.

21. Depositing the composition onto a substrate to form a film; The film is exposed to radiation, heat, or a combination of radiation and heat to crosslink the hydrophobic polyfunctional (meth)acrylate crosslinking agent and provide the dielectric layer; The dielectric layer is patterned to form a patterned dielectric layer having an opening, The method according to any one of claims 1 to 20, further comprising:

22. A patterned dielectric layer manufactured by the method of claim 21.

23. Incorporating the dielectric layer into the microelectronic device, The method according to any one of claims 1 to 21, further comprising:

24. The method according to claim 21 or claim 23, wherein the substrate comprises at least one selected from the group consisting of organic film, epoxy molding compound (EMC), silicon, glass, copper, stainless steel, copper-clad laminate (CCL), aluminum, silicon oxide, and silicon nitride.

25. Optionally, deposit a seed layer on the patterned dielectric film; A metal layer is deposited within the openings of the patterned dielectric film to form a metal pattern. The method according to any one of claim 21, claim 23, or claim 24, further comprising:

26. The method according to any one of claims 1 to 21 or 23 to 25, wherein the semiconductor device is an integrated circuit, a light-emitting diode, a solar cell, or a transistor.

27. The dielectric film is supported by the carrier layer. The method according to any one of claims 1 to 20, further comprising:

28. The carrier substrate is coated with the composition to form the coated composition; The coated composition is dried to form the dielectric layer; Optionally, a protective layer may be applied to the dielectric layer to form a dry film structure. The method according to any one of claims 1 to 20, further comprising:

29. The dry film structure is applied to an electronic substrate to form a laminate. It further includes, The dielectric layer in the laminate is placed between the electronic substrate and the carrier substrate. The method according to claim 28.

30. Depositing the dielectric film on a substrate having a copper pattern to form a dielectric film, It further includes, The height difference between the highest and lowest points on the surface of the dielectric film is approximately 2 microns at most. The method according to any one of claims 1 to 20.

31. Fully imidized polyimides; and Hydrophobic polyfunctional (meth)acrylate crosslinking agent A composition containing, The dielectric composition is suitable for providing a dielectric layer that imparts good reliability to a microelectronic device when the dielectric layer is present in the microelectronic device. composition.

32. The composition according to claim 31, wherein the hydrophobic polyfunctional (meth)acrylate crosslinking agent has a logP value of at least 0.

5.

33. The composition according to claim 31 or claim 32, wherein the hydrophobic polyfunctional (meth)acrylate crosslinking agent comprises at least one species selected from the group consisting of at least one difunctional (meth)acrylate, trifunctional (meth)acrylate, tetrafunctional (meth)acrylate, and hexafunctional (meth)acrylate, and each of the hydrophobic polyfunctional (meth)acrylate crosslinking agents has a logP value of about 0.5 to about 8.

0.

34. The composition according to any one of claims 31 to 33, further comprising a corrosion inhibitor.

35. The composition according to claim 34, wherein the corrosion inhibitor has a logP value of about -1.0 to about 6.

0.

36. The composition according to any one of claims 31 to 35, further comprising a photopolymerization initiator.

37. The composition according to claim 36, wherein the photopolymerization initiator comprises at least one species selected from the group consisting of oxime esters, titanocene, acylgermanium compounds, and peroxides.

38. The composition according to any one of claims 31 to 37, further comprising an organic solvent.

39. The composition according to claim 38, wherein the organic solvent comprises at least one species selected from the group consisting of alkylene carbonate, lactone, cycloketone, linear ketone, alkyl ester, alkyl ester alcohol, alkyl ether alcohol, alkyl ether ester, glycol ester, glycol ether, cyclic ether, pyrrolidone, and dialkyl sulfoxide.

40. The composition according to any one of claims 31 to 39, wherein the polymer comprises at least one species selected from the group consisting of polybenzoxazole precursor polymers, polyimide precursor polymers, and fully imidized polyimide polymers.

41. The composition according to any one of claims 31 to 39, wherein the polymer comprises a fully imidized polyimide polymer.

42. The composition according to claim 41, wherein the fully imidized polyimide polymer comprises a functional group.

43. The composition according to claim 41, wherein the fully imidized polyimide polymer comprises an alkali-soluble polymer.

44. The composition according to claim 41, wherein the fully imidized polyimide polymer includes a polymer that does not contain fluorine atoms.

45. The composition according to any one of claims 31 to 44, wherein the polymer is present in an amount of about 0.1% to about 55% by weight relative to the solid content weight of the composition.

46. The composition according to any one of claims 31 to 45, wherein the hydrophobic polyfunctional (meth)acrylate crosslinking agent is present in an amount of about 0.5% to about 25% by weight relative to the solid content weight of the composition.

47. The composition according to any one of claims 31 to 46, further comprising at least one selected from the group consisting of adhesion promoters, surfactants, fillers, pigments, dyes, and metal-containing (meth)acrylate compounds.

48. The composition according to any one of claims 31 to 47, further comprising at least one photosensitizer selected from the group consisting of benzophenones, thioxanthones, anthraquinones, anthracenes, and coumarins.

49. The composition according to any one of claims 31 to 48, wherein the composition is substantially fluorine-free.

50. The composition according to any one of claims 31 to 49, wherein, if the dielectric layer is present in the microelectronic device, the microelectronic device passes at least one test selected from the group consisting of HAST, bHAST, HTS, and TCT.

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