Poly-o-hydroxyamides containing novel indane bis-o-aminophenols, photosensitive compositions containing the same, dielectric films and buffer coatings

Abstract

The present disclosure describes novel highly soluble poly-ortho-hydroxyamides containing indane bis-o-aminophenols, photosensitive compositions containing the same, and methods and articles of use.

Description

Cross-reference to related applications

[0001] This application claims priority to U.S. Provisional Application No. 63 / 608,475, filed December 11, 2023, and U.S. Application No. 18 / 960,640, filed November 26, 2024, the contents of which are incorporated herein by reference in their entirety. Background Technology

[0002] The requirements for dielectric materials in semiconductor packaging applications are constantly evolving. Electronic packaging trends are moving towards faster processing speeds, greater complexity, and higher packaging densities, while maintaining high levels of reliability. As electronic packaging technologies advance and chip sizes continue to shrink, the demand for innovative and high-performance resin compositions is growing. Summary of the Invention

[0003] This disclosure provides a dielectric film forming composition comprising a polymer containing at least one indane bis-o-aminophenol compound as a diamine monomer. The dielectric film forming compositions described herein meet the extremely stringent requirements of the microelectronics industry. In some embodiments, this disclosure provides a dielectric film forming composition comprising a poly-o-hydroxyamide containing at least one indane bis-o-aminophenol compound as a diamine monomer. In some embodiments, this disclosure provides a composition comprising a poly-o-hydroxyamide containing an indane bis-o-aminophenol monomer of formula Ia: Ia Where R 1 R 2 R 3 R 4 and R 5 Each of the atoms in the equation is independently a hydrogen atom, substituted or unsubstituted C1-C. 12 Alkyl groups, partially or completely halogenated C1-C 12 Alkyl, substituted or unsubstituted C4-C 18 cycloalkyl, substituted or unsubstituted C6-C 22 Aryl or substituted or unsubstituted C5-C 22 heteroaryl; R 11 and R 12 Each of these elements is independently a hydrogen atom, a straight-chain or branched C1-C4 alkyl group, a C1-C4 alkyl group partially or completely halogenated, or a C5-C... 12 cycloalkyl, C6-C 18 Aryl, C5-C 18 Heteroaryl groups, C1-C4 alkoxy groups, or halogen atoms.

[0004] The poly-o-hydroxyamide disclosed herein can be used in various photosensitizing compositions to provide a positive tone, wherein the photosensitizing composition is soluble in an aqueous alkaline solution, can form fine patterns, and achieve high resolution. In some embodiments, the photosensitivity of the composition is chemically amplified as described herein.

[0005] In some embodiments of this disclosure, a dielectric layer is provided that can be cast from the compositions of this disclosure. The dielectric layer of this disclosure can form a uniform film that can be developed after exposure to ultraviolet light at a relatively long wavelength (e.g., about 365 nm) to form a patterned dielectric film. After photolithography, the patterned layer is converted into a heat-resistant polybenzoxazole film by applying additional heating, wherein the patterned cured dielectric film exhibits desired properties according to one or more reliability tests. Even when the composition is cured at low temperatures, the film formed from this photosensitive composition exhibits good mechanical properties. Detailed Implementation

[0006] This disclosure provides dielectric film forming compositions, related methods, dry films, and dielectric films. In some embodiments, the dielectric film forming compositions described herein comprise (a) at least one polymer containing at least one indane bis-o-aminophenol compound as a diamine monomer. In some embodiments, the dielectric film forming compositions described herein may be photosensitive and / or thermosetting.

[0007] In some embodiments, a poly-o-hydroxyamide is provided, which is suitable for preparing photosensitive compositions that meet the extremely demanding requirements of the microelectronics industry.

[0008] In some embodiments of this disclosure, poly-o-hydroxyamides represented by general formula (2) are provided: (2) Where R 1 R 2 R 3 R 4 R 5 R 11 and R 12 Having the same meaning as above, Ar1 and Ar2 are each independently a divalent aromatic, aliphatic, or heterocyclic group, or a mixture thereof; Ar 11 and A 12E is a divalent aromatic, aliphatic, or heterocyclic group or a siloxane group; E is a capped group; n1 is an integer from 5 to 200; n3 is an integer from 0 to 200; n5 is an integer from 0 to 200; n2 is an integer from 5 to 200, and n4 is an integer from 0 to 200; p2 is any positive value up to about 0.9, p1 is any value from about 0.1 to about 0.8, provided that (p1+p2) = 1; D is selected from the group consisting of one of the following parts, where R 31 Choose from the group consisting of: hydrogen, halogens, C1-C4 alkyl groups, C1-C4 alkoxy groups, substituted or unsubstituted C4-C 18 Cycloalkyl: In some embodiments of this disclosure, poly-o-hydroxyamides represented by general formula (3) are provided: (3) Where R 1 R 2 R 3 R 4 R 5 R 11 R 12 Ar1, Ar2, Ar 11 n 1 n 2 n 3 n 4 p1, p2 and D have the same meaning as above.

[0009] In this article, "terminated group" refers to the reaction product of the amino-terminal group of a poly-o-hydroxyamide and a monohydric anhydride compound. When added to the polymerization system, the monohydric anhydride compound promotes the termination of the poly-o-hydroxyamide chain, thereby limiting polymer chain growth.

[0010] In some embodiments, Ar1 and Ar2 include the following components: Where X1 is -C(O)-C(O)-, -C(O)O-, C5-C7 cyclic aliphatic group, fluorenyl group, -O-X3-O, -OC(O)-X3-C(O)-O-, -C(O)-O-X3-OC(O)- or -(CH2). m -Si(Z)2-O-Si(Z)2-(CH2) m- where X3 is an unsubstituted or substituted phenyl, diphenyl sulfone, isopropylidene diphenyl, hexafluoroisopropylidene diphenyl, and Z is H or a C1-C6 alkyl group, and m is an integer from 1 to 6, and Ra is independently a hydrogen atom, alkoxy, fluoroalkoxy, cycloalkyl, cycloalkoxy, cycloalkylsulfonyl, aryloxy, alkylaryloxy, arylsulfonyl or alkylarylsulfonyl group.

[0011] In some embodiments, the poly-o-hydroxyamide may contain one or more different Ar1 and Ar2 groups.

[0012] In some embodiments, Ar 11 Includes the following parts: Where X2 is -O-, -S-, -C(CF3)2-, -C(CH3)2-, -CH2-, -SO2-, -NHCO-, -C(O)-, -C(O)-C(O)-, -C(O)O-, C5-C7 cyclic aliphatic group, fluorenyl group, -O-X4-O, -OC(O)-X4-C(O)-O-, -C(O)-O-X4-OC(O)-, or -(CH2). m -Si(Z)2-O-Si(Z)2-(CH2) m -, X4 represents unsubstituted or substituted phenyl, diphenyl sulfone, isopropylidene diphenyl, hexafluoroisopropylidene diphenyl, and Z and m have the same meaning as above.

[0013] The dicarboxylic acid chlorides disclosed herein include, for example, aromatic dicarboxylic acid chlorides, such as isophthalic acid chloride, terephthalic acid chloride, 4,4'-hexafluoroisopropylbenzene dibenzoic acid chloride, 4,4'-biphenyl dicarboxylic acid chloride, 4,4'-dicarboxylic diphenyl ether chloride, 4,4'-dicarboxylic tetraphenylsilane chloride, bis(4-carboxyphenyl) sulfone chloride, 2,2-bis(p-carboxyphenyl) propane chloride, 5- Chlorides of tert-butylisophthalic acid, 5-bromoisophthalic acid, 5-fluoroisophthalic acid, 5-chloroisophthalic acid, and 2,6-naphthalenedicarboxylic acid, etc.; aliphatic dicarboxylic acid chlorides, such as 1,2-cyclobutanedicarboxylic acid chloride, 1,4-cyclohexanedicarboxylic acid chloride, 1,3-cyclopentanedicarboxylic acid chloride, malonic acid chloride, succinic acid chloride, adipic acid chloride, sebacic acid chloride, etc. Examples of such dicarboxylic acid chlorides are disclosed, for example, in U.S. Patent Nos. 6,143,467 and 7,803,510, the entire contents of which are incorporated herein by reference. Any of these dicarboxylic acid chlorides may be used alone or in combination in any suitable ratio to form the poly-o-hydroxyamides described herein.

[0014] Examples of indane bis-o-aminophenol compounds (Ia) include, but are not limited to: Exemplary bis-o-hydroxyamines include, but are not limited to, 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, bis(3-amino-4-hydroxyphenyl)propane, bis(4-amino-3-hydroxyphenyl)propane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(4-amino-3-hydroxyphenyl)sulfone, bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(4-amino-3-hydroxyphenyl)hexafluoropropane, etc. Examples of such bis-o-hydroxyamines are disclosed, for example, in U.S. Patent Nos. 6,143,467; 7,803,510, the entire contents of which are incorporated herein by reference. Any of these bis-o-hydroxyamines may be used alone or in combination in any suitable ratio to form the poly-o-hydroxyamides described herein.

[0015] Examples of suitable diamines containing an Ar12 structure that can be used to prepare poly-o-hydroxyamide polymers of structure (2) include, but are not limited to, 1-(4-aminophenyl)-1,3,3-trimethylindane-5-amine (also known as 4,4'-[1,4-phenylene-bis(1-methylethylene)]bisphenylamine, 1-(4-aminophenyl)-1,3,3-trimethyl-2H-indane-5-amine, 1-(4-aminophenyl)-1,3,3-trimethyl-indane-5-amine and [1-(4-aminophenyl)-1,3,3-trimethyl-indane-5-yl]amine), 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-indane-5-amine, 5-amino-6-methyl-1-(3'-aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-indane-5-amine, and 5-amino-6-methyl-1-(3'-aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-indane-5-amine. (-4'-methylphenyl)-1,3,3-trimethylindane, 4-amino-6-methyl-1-(3'-amino-4'-methylphenyl)-1,3,3-trimethylindane, 5,7-diamino-1,1-dimethylindane, 4,7-diamino-1,1-dimethylindane, 5,7-diamino-1,1,4-trimethylindane, 5,7-diamino-1,1,6-trimethylindane, 5,7-diamino-1,1-dimethyl-4-ethylindane, p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 3-methyl-1,2-phenylenediamine, 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane 1,8-Diaminooctane, 1,9-Diaminononane, 1,10-Diaminodecane, 1,2-Diaminocyclohexane, 1,4-Diaminocyclohexane, 1,3-Cyclohexanebis(methylamine), 5-Amino-1,3,3-Trimethylcyclohexanemethylamine, 2,5-Diaminotrifluoromethylbenzene, 3,5-Diaminotrifluoromethylbenzene, 1,3-Diamino-2,4,5,6-Tetrafluorobenzene, 4,4'-Oxydiphenylamine, 3,4'-Oxydiphenylamine, 3,3'-Oxydiphenylamine, 3,3'-Diaminodiphenylsulfone, 4,4'-Diaminodiphenylsulfone, 4,4'-Isopropylidenediphenylamine, 4,4'-Diaminodiphenylmethane, 2,2-Bis(4-aminophenyl)propane, 4,4'-Diaminodiphenylpropane 4,4'-Diaminodiphenyl sulfide, 4,4'-Diaminodiphenyl sulfone, 4-aminophenyl-3-aminobenzoate, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)benzidine, 3,3'-bis(trifluoromethyl)benzidine, 2,2-bis[4-(4-aminophenoxyphenyl)]hexafluoropropane, 2,2-bis(3-amino-4-methylphenyl)hexafluoropropane, 2,2-bis(3-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 1,3-bis-(4-aminophenoxy)benzene, 1,3-bis-(3-aminophenoxy)benzene, 1,4-bis-(4-aminophenoxy)benzene, 1,4-bis-(3-aminophenoxy)benzene, 1-(4-aminophenoxy)-3-(3-aminophenoxy)benzene, 2,2'-bis-(4-phenoxyaniline)isopropylidene, bis(p-β-amino-tert-butylphenyl) ether, p-bis-2-(2-methyl-4-aminopentyl)benzene, p-bis(1,1-dimethyl-5-aminopentyl)benzene, 3,3'-dimethyl-4,4'-diaminobenzene Benzene, 4,4'-diaminobenzophenone, 3'-dichlorobenzidine, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 4,4'-[1,3-phenylenebis(1-methyl-ethylene)]bisaniline, 4,4'-[1,4-phenylenebis(1-methyl-ethylene)]bisaniline, 2,2-bis[4-(4-aminophenoxy)phenyl]sulfone, 2,2-bis[4-(3-)phenylenebis(1-methyl-ethylene)]bisaniline [-aminophenoxy)benzene], 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3'-bis(3-aminophenoxy)benzene, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, H-fluorene-2,6-diamine, 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-ditert-butylaniline), 3,5-diaminobenzoic acid, 3,4-diaminobenzoic acid, bis(aminopropyl)tetramethyldisiloxane (BATMS), bis(aminopropyl)tetraphenyldisiloxane, bis(4-aminophenoxy)dimethylsilane, etc. Any of these diamines may be used alone or in combination in any suitable ratio to form the poly-o-hydroxyamides described herein.

[0016] Poly-o-hydroxyamide (structure 2a) can be synthesized by a number of synthetic methods, variations of which are known to those skilled in the art.

[0017] (2a) Where R 1 R 2 R 3 R 4 R 5 R 11 R 12 Ar1, Ar2, A 11 Ar 12 n1, n2, n3, n4 and n5 have the same meaning as above.

[0018] Typically, the synthesis method involves contacting one or more bis-o-hydroxyamines with one or more diacid chlorides in the presence of a solvent and an optional base or mixture thereof, said solvent and optional base or mixture thereof being suitable for dissolving the monomer, and preferably suitable for dissolving the resulting poly-o-hydroxyamide. Examples of suitable bases include, but are not limited to, pyridine, triethylamine, tripropylamine, tributylamine, dicyclohexylmethylamine, 2,6-dimethylpyridine, 3,5-dimethylpyridine, methylpyridine, 4-dimethylaminopyridine (DMAP), etc. If used, the basic catalyst employed may be the same as or different from the basic catalyst used in the end-capping reaction.

[0019] In some embodiments, to prepare poly-o-hydroxyamides, a bis-o-hydroxyamine component and a diacid chloride component are loaded into a reaction vessel by means of: gradually adding one of the two components, which are in solid or solution form, into a solution of the other component (all materials may not completely dissolve), or simultaneously loading the two components. The molar ratio of the bis-o-hydroxyamine component to the diacid chloride component is preferably 1.01 to 1.50. More preferably, a molar ratio of about 1.05 to 1.30 for the diamine to the diacid chloride is used. Typically, the reaction is carried out at about -15°C to about 50°C for about 1 to about 48 hours. It should be noted that when the molar ratio of the bis-o-hydroxyamine component to the diacid chloride component is greater than 1.00, the resulting substance is an amino-terminated poly-o-hydroxyamide, which can further react with a capping monomer to form a capped polymer.

[0020] Suitable polymerization solvents that can be used in this invention include, but are not limited to, N-methyl-2-pyrrolidone, N,N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, N,N-dimethylacetamide, sulfolane, p-chlorophenol, m-cresol, diethylene glycol methyl ether, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, cyclohexanone, propylene glycol monomethyl ether acetate, and 2-chloro-4-hydroxytoluene. These solvents can be used alone or in combination of two or more. Among these solvents, N-methyl-2-pyrrolidone, γ-butyrolactone, and N,N-dimethylacetamide are preferred, with N-methyl-2-pyrrolidone being more preferred. In some embodiments, undesirable solvents for poly-o-hydroxyamides can be used in combination with these solvents in amounts that do not precipitate the poly-o-hydroxyamide. Examples of such undesirable solvents include hexane, heptane, benzene, toluene, xylene, chlorobenzene, and o-dichlorobenzene. The amount of undesirable solvent to be used, based on the total amount of the solvent, is preferably 50% by weight or less (including zero). The resulting poly-o-hydroxyamide can be isolated by precipitation in a non-solvent or undesirable solvent and collected by filtration.

[0021] The second step in the synthesis method of the polymer of structure 2 mentioned above is to end-cap the poly-o-hydroxyamide synthesized in the first step.

[0022] (2b) Where R 1 R 2 R 3 R 4 R 5 R 11 R 12 Ar1, Ar2, A 11 Ar 12 n1, n2, n3, n4, n5 and E have the same meaning as above.

[0023] In some embodiments, the second step can be carried out by reacting the amino-terminated poly-o-hydroxyamide of structure 2a with a monohydric anhydride to generate the terminally capped poly-o-hydroxyamide of structure 2b. In some embodiments, the terminally capped poly-o-hydroxyamide thus formed can be used for further reactions without being isolated. Monohydric anhydrides contemplated for use in this aspect of the present disclosure include, for example, aliphatic anhydrides such as acetic anhydride, trifluoroacetic anhydride, neopentanoic anhydride, or cyclic anhydrides such as 1,1-cyclopentanediacetic anhydride, succinic anhydride, maleic anhydride, exo-3,6-epoxy-1,2,3,6-tetrahydrophthalic anhydride, cis-1,2-cyclohexanedicarboxylic anhydride, cis-4-cyclohexene-1,2-dicarboxylic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride, etc. Further examples of capping groups are disclosed, for example, in U.S. Patent No. 9,695,284, the entire contents of which are incorporated herein by reference.

[0024] In some embodiments, the second step can be carried out by reacting an amino-terminated poly-o-hydroxyamide and unreacted diamine monomer with a monohydric anhydride to generate a capped poly-o-hydroxyamide and an adduct, wherein the amine value of the poly-o-hydroxyamide polymer precursor is about 0.0010 to 0.0300 mmol / g. When the amine value is higher than these values, the amino group will interfere with the decomposition process of the diazonium quinone residues.

[0025] In some embodiments, in the third reaction step, the poly-o-hydroxyamide is reacted with about 1% to about 50% (based on the number of OH groups in the monomer) of a diazonium quinone compound (DCI) in the presence of a base to generate the poly-o-hydroxyamide according to the following reaction: Suitable DCI compounds include: The weight-average molecular weight (Mw) of poly-o-hydroxyamides can be determined by standard methods such as membrane osmotic pressure measurement or gel permeation chromatography as described, for example, in Jan Rabek, Experimental Methods in Polymer Chemistry, John Wiley & Sons, New York, 1983.

[0026] The suitable weight-average molecular weight (Mw) range for the poly-o-hydroxyamide of structure 2 is from about 1,000 g / mol to about 80,000 g / mol. The preferred molecular weight range may depend on the specific product application, the solvent used, and the method of application to the underlying substrate. For example, a suitable weight-average molecular weight value for coating applications may be at least about 1,000 g / mol (e.g., at least about 9,000 g / mol, at least about 12,000 g / mol, at least about 15,000 g / mol, at least about 20,000 g / mol, at least about 25,000 g / mol, or at least about 35,000 g / mol) and / or may be at most about 50,000 g / mol (e.g., at most about 40,000 g / mol, at most about 35,000 g / mol, at most about 30,000 g / mol, at most about 25,000 g / mol, at most about 20,000 g / mol, at most about 15,000 g / mol, at most about 12,000 g / mol).

[0027] Wherever the term "solvent" is used, unless specifically specified, it refers to a single organic solvent or a combination of two or more organic solvents. The purification or isolation of poly-o-hydroxyamides can be achieved through many processes known to those skilled in the art. Solution isolation processes for poly-o-hydroxyamide polymers are efficient and environmentally friendly methods for producing poly-o-hydroxyamide polymers with improved purity.

[0028] The purification method may include (a) providing an organic solution containing a poly-o-hydroxyamide polymer in at least one polar, aprotic polymerizing solvent; (b) adding at least one purification solvent to the organic solution to form a diluted organic solution, the at least one purification solvent being less polar than the at least one polymerizing solvent and having lower water solubility at 25ºC than the at least one polymerizing solvent; (c) washing the diluted organic solution with an acidified aqueous solution to obtain a washed organic solution; and (d) removing at least a portion of the at least one purification solvent from the washed organic solution to obtain a solution containing the purified poly-o-hydroxyamide.

[0029] Without being bound by theory, it is believed that two key functions of the purification solvent are: (1) to retain the poly-o-hydroxyamide polymer in solution, and (2) to form a two-phase mixture with water and / or an aqueous solution containing additives. In the context of this disclosure, a two-phase mixture refers to a mixture containing two distinct and separate phases (e.g., two different liquid phases).

[0030] In some embodiments, the purification solvent may include esters, ethers, ketones, and hydrocarbons optionally substituted with at least one chloride. Examples of suitable purification solvents include, but are not limited to, methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, cyclohexyl acetate, ethyl lactate, propylene glycol monomethyl ether acetate (PGMEA), tetrahydrofurfuryl acetate, propyl formate, butyl formate, isobutyl formate, amyl formate, ε-caprolactone, diethyl ether, dipropyl ether, dibutyl ether, dicyclohexyl ether, cyclopentyl methyl ether, methyl tert-butyl ether, ethyl tert-butyl ether, and benzyl acetate. Ethers, phenyl ethyl ethers, diphenyl ethers, 1,2-dimethoxypropane, 1,2-dimethoxyethane, 2-butanone, 2-pentanone, 3-pentanone, methyl isobutyl ketone, ethyl isobutyl ketone, methyl isopropyl ketone, cyclopentanone, cyclohexanone, acetophenone, isoflavone, isopropylidene acetone, benzene, toluene, xylene, ethylbenzene, chlorobenzene, 1,2-dichlorobenzene, α,α,α-trifluorotoluene, pentane, hexane, heptane, octane, cyclohexane, methylcyclohexane, cyclohexene, and mixtures thereof.

[0031] Depending on the solubility characteristics of the poly-o-hydroxyamide polymer, the purification solvent may be used as the sole solvent in the dilution / purification step. However, in some embodiments, a purification co-solvent may be used in addition to the purification solvent. The purification co-solvent is an organic solvent that has a higher (e.g., significantly higher) solubility in water at 25°C than the purification solvent. Typically, the purification co-solvent is not used alone but in combination with one or more purification solvents. In some embodiments, the purification solvent may be a solvent immiscible with water.

[0032] Examples of suitable purification cosolvents include, but are not limited to, acetone, γ-butyrolactone (GBL), furan, tetrahydrofuran, methyltetrahydrofuran, tetrahydrofurfuryl methyl ether, 1,4-dioxane, and mixtures thereof. In some embodiments, the purification cosolvent may be a solvent miscible with water.

[0033] When an aqueous solution containing additives is used in this step, the solution may contain sufficient concentrations of acids, bases, or additional components, such as chelating agents, to improve the purity of the poly-o-hydroxyamide polymer by removing impurities (e.g., polymerization byproducts). The concentration of acids, bases, or other additives in this aqueous solution may range from at least about 0.1 wt% (e.g., at least about 0.3 wt%, at least about 0.5 wt%, or at least about 1 wt%) to at most about 10 wt% (e.g., at most about 8 wt%, at most about 7 wt%, or at most about 5 wt%).

[0034] In some embodiments, the washing step may include adding water or an aqueous solution to the diluted organic solution obtained in the dilution step described above. In such embodiments, the washing step may include forming a mixture having an organic phase and an aqueous phase (e.g., by allowing the organic and aqueous phases to be separated from each other). The washing step may further include removing the aqueous phase. Typically, washing the diluted solution substantially removes at least one polymerization solvent or other impurities from the diluted organic solution.

[0035] To improve the effectiveness of the washing step, the diluted organic solution containing the poly-o-hydroxyamide polymer and the aqueous washing medium (e.g., water or an aqueous solution) can be mixed by agitation. This agitation can take the form of stirring, shaking, inverting, or any other method that allows the organic phase and the aqueous phase to mix effectively.

[0036] After mixing, the mixture can be allowed to stand undisturbed until two distinct and separate phases form. Once the distinct and separate phases have formed, the aqueous phase can be removed and discarded to remove impurities (e.g., polymerization solvents). In some embodiments, the number of aqueous washes is one to five (i.e., one, two, three, four, or five).

[0037] A wide range of agitation speeds, times, temperatures, and separation conditions can be used. It is not desirable to be limited by theory; a key aspect of this step is believed to be ensuring thorough mixing to extract significant amounts of polymerization solvent and other impurities to the aqueous phase, followed by phase separation. These conditions may vary depending on the vessel used for mixing and separation. In some embodiments, agitation time is from about 1 minute to about 24 hours (e.g., from about 10 minutes to about 6 hours). In some embodiments, agitation temperature is about 10... o C to approximately 40 o C (for example, about 15) o C to approximately 30 o C). In some embodiments, the separation time is from about 10 minutes to about 24 hours (e.g., from about 15 minutes to about 12 hours). In some embodiments, the separation temperature is about 10°C. o C to approximately 40 o C (for example, about 15) oC to approximately 30 o C).

[0038] In some embodiments, when the poly-o-hydroxyamide polymer is formed and purified, the amount of residual polymerization solvent remaining after the final aqueous wash is up to about 1 wt% (e.g., up to about 0.5 wt%) of the weight of the poly-o-hydroxyamide polymer.

[0039] After the organic solution containing the poly-o-hydroxyamide polymer is washed with an aqueous medium (e.g., water), at least a portion (e.g., substantially all) of the purification solvent in the organic solution may be removed or exchanged with at least one single solvent to obtain a solution containing the purified poly-o-hydroxyamide polymer (i.e., a purified polymer solution).

[0040] In some embodiments, a solution containing a purified poly-o-hydroxyamide polymer (i.e., a purified polymer solution) is treated with an ion exchange resin (an acidic, a basic, or a mixture of acidic and basic ion exchange resins) to remove trace amounts of acid or base from the purified polymer solution. In some embodiments, the ion-exchange purified poly-o-hydroxyamide solution is filtered through a filter medium (a filter pad, a filter cartridge) to remove any gel that may be present in the polymer solution.

[0041] In some embodiments, at least a portion (e.g., substantially all) of the purified solvent (and substantially all of the residual water) in the purified polymer solution may be solvent-exchanged with a single-electrode solvent. In some embodiments, the single-electrode solvent is one solvent or a combination of two or more solvents having a boiling point equal to or greater than that of the purified solvent. In some embodiments, the single-electrode solvent may be the same as the purified solvent or the polymerization solvent. In other embodiments, the single-electrode solvent may be different from the purified solvent or the polymerization solvent. In some embodiments, the single-electrode solvent may be compatible with a variety of coating and application methods used in many industry applications.

[0042] In some embodiments, the isolating solvent may include ketones, esters, hydrocarbons, sulfoxides, ethers, or mixtures thereof. Examples of suitable isolating solvents include, but are not limited to, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), 2-heptanone, cyclopentanone, cyclohexanone, xylene, γ-butyrolactone, dimethyl sulfoxide, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), ethyl lactate (EL), and mixtures thereof.

[0043] In some embodiments, a separate solvent may be added first to a washed, purified organic solution containing the poly-o-hydroxyamide polymer. In such embodiments, the purified solvent may then be removed by evaporation or distillation. In some embodiments, the amount of residual purified solvent remaining after this step may be up to about 2 wt% (e.g., up to about 1 wt%) of the weight of the poly-o-hydroxyamide polymer. It is not intended to be theoretically limited, but it is believed that adding a separate solvent with a higher boiling point than the purified solvent during distillation can facilitate the removal of the purified solvent.

[0044] Not wanting to be limited by theory, it is believed that, in addition to replacing the purification solvent with a single-dissociation solvent, this step is also used to dry the final polymer solution by removing residual water along with the purification solvent (e.g., via distillation).

[0045] In some embodiments, after at least a portion (e.g., substantially all) of the purified solvent is exchanged with a single solvent, the solution containing the poly-o-hydroxyamide polymer can be concentrated to form a solution suitable for coating onto a substrate.

[0046] Distillation conditions can be any temperature and pressure that stabilizes the polymer and achieves the desired end result. In some embodiments, the distillation temperature is from about 20°C to about 70°C (e.g., from about 25°C to about 45°C). In some embodiments, the distillation pressure is from about 760 Torr to about 0.1 Torr (e.g., from about 100 Torr to about 0.1 Torr). Although the methods detailed above can yield poly-o-hydroxyamide polymers with improved purity, it should be noted that additional method steps, including but not limited to ion exchange and filtration, may be included before and / or after steps 3 and 4 in this method.

[0047] In some embodiments, this disclosure is characterized by a purified poly-o-hydroxyamide polymer solution obtained by the methods described above. In some embodiments, the purified poly-o-hydroxyamide polymer can be isolated from the purified polymer solution obtained above by any suitable method known in the art (e.g., by precipitation or by removing the solvent via distillation).

[0048] In one embodiment, a poly-o-hydroxyamide polymer with improved purity prepared using the methods of this disclosure may be incorporated into a composition (e.g., a film-forming composition, a thermosetting composition, a photosensitive composition).

[0049] The polybenzoxazole precursor of this invention has a hydroxyl group concentration of 3.35 mol / Kg or greater when it does not contain fluorine atoms. When it is 4.0-10.0 mol / Kg and contains fluorine atoms, the hydroxyl group concentration is not less than 2.00 mol / Kg, preferably 3.0-10.0 mol / Kg. When the hydroxyl group concentration is lower than these values, there is a disadvantage that the poly-o-hydroxyamide polymer is not sufficiently soluble in alkaline aqueous solutions.

[0050] In another embodiment, the unexposed photosensitive membrane having poly-o-hydroxyamide (I) dissolves at a rate of less than 0.05 μm / s in an aqueous alkaline solution with a pH greater than 8.0. In some embodiments, the unexposed photosensitive membrane having poly-o-hydroxyamide (I) dissolves at a rate of less than 0.01 μm / s in a 2.38% tetramethylammonium hydroxide aqueous solution.

[0051] In some embodiments, the indane bis-o-aminophenol of this disclosure can be used to prepare soluble poly-o-hydroxyamides. During photolithography, the aqueous alkali solubility of the poly-o-hydroxyamide present in the photosensitive composition is suppressed and subsequently re-established using at least one photoactive compound (PAC). In some embodiments, a diazonoquinone PAC is used to suppress the solubility of the poly-o-hydroxyamide in an aqueous alkali. After exposure, the diazonoquinone compound undergoes photodecomposition and is converted to indenecarboxylic acid, which promotes the aqueous alkali solubility of the poly-o-hydroxyamide. In some embodiments, the diazonoquinone PAC is used as a dissolution inhibitor. Intermediates generated by capping the aromatic hydroxyl groups of the poly-o-hydroxyamide with a PAC are known as capped poly-o-hydroxyamides. Examples of such diazonoquinone PACs are listed below, where D has the same meaning as above. Examples of such diazonoquinone PACs are also described, for example, in 7,803,510, the entire contents of which are incorporated herein by reference.

[0052] Capped poly-o-hydroxyamides can be prepared using one or more diazonium quinone compounds, one or more dihydropyridines, or mixtures thereof. The amount of the diazonium quinone compound used in this composition is about 1% to 20% by weight, about 2% to about 10% by weight, and about 3% to about 5% by weight of the total weight of the composition. The amount of the dihydropyridine compound used in this composition is about 1% to 20% by weight, about 2% to about 10% by weight, and about 3% to about 5% by weight of the total weight of the composition. If both diazonium quinone and dihydropyridine are used, the amounts of the diazonium quinone compound and dihydropyridine in this composition are about 1% to 20% by weight, about 2% to about 10% by weight, and about 3% to about 5% by weight of the total weight of the composition.

[0053] In some embodiments, a crosslinking agent is used in the compositions disclosed herein. Any suitable amino or phenolic crosslinking agent may be used in this application, such as hydroxymethylated and / or hydroxymethylated and etherified guanidine, hydroxymethylated and / or hydroxymethylated and etherified melamine, etc. These types of crosslinking agents act as latent crosslinkers, which generate intermediates in the presence of heat or in the presence of thermally or photo-generated acids. These reactive intermediates react with themselves (to form a crosslinked interpenetrating network (IPN)) or with the hydroxyl functional groups of poly-o-hydroxyamides to form crosslinked polymeric materials.

[0054] Any suitable amino or phenolic crosslinking agent can be used in this application, such as hydroxymethylated and / or hydroxymethylated and etherified guanidine, hydroxymethylated and / or hydroxymethylated and etherified melamine, etc. Examples of suitable melamine crosslinking agents are methoxyalkyl melamines, such as hexamethoxymethyl melamine, trimethoxymethyl melamine, hexamethoxyethyl melamine, tetramethoxyethyl melamine, hexamethoxypropyl melamine, pentamethoxypropyl melamine, etc. In some embodiments, the melamine crosslinking agent is hexamethoxymethyl melamine. In some embodiments, the amino crosslinking agent is MW100LM melamine crosslinking agent from Sanwa Chemical Co. Ltd., Kanaxawa-ken, Japan; Cymel 303, Cymel 1171, and Powderlink 1174 from Cytec Industries, West Patterson, New Jersey. Examples of suitable phenolic crosslinking agents are disclosed in U.S. Patent Nos. 5,488,182 and 6,777,161 and U.S. Patent Application No. 2005 / 0238997. Specific examples of hydroxymethyl-substituted polyfunctional phenols used as crosslinking agent precursors are 4,4'-[1,4-phenylbis(methylene)]bis(3,5-dihydroxymethylphenol), 4,4'-[1,4-phenylbis(1-ethylidene)]bis(3,5-dihydroxymethylphenol), 4,4'-[1,4-phenylbis(1-propylidene)]bis(3,5-dihydroxymethylphenol), 4,4'-[1,4-phenylbis(1-butylidene)]bis(3,5-dihydroxymethylphenol), 4,4'-[1,4-phenylbis(1-pentylidene)]bis(3,5-dihydroxymethylphenol), 4,4'-[1, [4-Phenylidene bis(1-methylethylidene)]bis(3,5-dihydroxymethylphenol), 4,4'-[1,4-Phenylidene bis(1-ethylpropylidene)]bis(3,5-dihydroxymethylphenol)), 4,4'-[1,4-Phenylidene bis(1-propylbutylidene)]bis(3,5-dihydroxymethylphenol), 4,4'-[1,4-phenylenebis(1-butylpentane)]bis(3,5-dihydroxymethylphenol), 4,4'-[1,3-phenylenebis(methylene)]bis(3,5-dihydroxymethylphenol), 4,4'-[1,3-phenylenebis(1-methylethylene)]bis(3,5-dihydroxymethylphenol), 4,4'-[1,3-phenylenebis(1-ethylpropylene)]bis(3,5-dihydroxymethylphenol), 4,4'-[1,3-phenylenebis(1-propylbutylene)]bis(3,5-dihydroxymethylphenol] and 4,4'-[1,3-phenylenebis(1-butylpentane)]bis(3,5-dihydroxymethylphenol] are specific examples of hydroxymethyl-substituted polyfunctional phenols provided as crosslinking agent precursors.

[0055] Further examples of crosslinking agents are provided below, wherein G is a hydroxymethyl or etherified hydroxymethylated group. The crosslinking agents used in this disclosure are commercially available or can be prepared using standard techniques known to those skilled in the art via hydroxymethylation or alkoxymethylation of the corresponding phenol.

[0056] Other examples of crosslinking agents are described, for example, in U.S. Patent Nos. 5,488,182 and 6,777,161 and 8,153,346, the contents of which are incorporated herein by reference.

[0057] Uncapped or capped poly-o-hydroxyamides may be formulated with one or more amino or phenolic crosslinking agents or mixtures thereof. The amount of the amino or phenolic crosslinking agent used is from about 1% to about 25% by weight, from about 2% to about 15% by weight, or from about 3% to about 10% by weight of the total weight of the composition.

[0058] In some embodiments, the amount of poly-o-hydroxyamide resin is at least about 0.1 wt.% (e.g., at least about 0.5 wt.%, at least about 1 wt%, at least about 2 wt%, at least about 5 wt%, at least about 10 wt%, at least about 15 wt%, or at least about 20 wt%) and / or at most or about 55 wt% (e.g., at most about 50 wt%, at most about 45 wt%, at most about 40 wt%, at most about 35 wt%, at most about 30 wt%, at most about 25 wt%, at most about 20 wt%, at most about 15 wt%, or at most about 10 wt%) of the solid weight of the dielectric film forming composition described herein.

[0059] In some embodiments, the amount of photosensitizer is at least about 0.01 wt% (e.g., at least about 0.05 wt%, at least about 0.1 wt%, or at least about 0.5 wt%) to at most about 1 wt% (e.g., at most about 0.8 wt%, at most about 0.6 wt%, at most about 0.5 wt%, at most about 0.4 wt%, at most about 0.2 wt%) of the solid weight of the dielectric film forming composition described herein.

[0060] In some embodiments, the dielectric film forming compositions described herein may include at least one (e.g., two, three, or four) photosensitizer, wherein the photosensitizer absorbs light in a wavelength range of about 150 nm to about 600 nm (e.g., at about 405 nm). Examples of suitable photosensitizers that can be used in the dielectric film forming compositions of this disclosure include benzophenone compounds, thioxanthone compounds, anthraquinone compounds, anthracene compounds, coumarin compounds, and mixtures thereof.

[0061] Examples of photosensitizers include, but are not limited to, 9-methylanthracene, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, anthracene methanol, acenaphthene, thioxanthone, methyl-2-naphthyl ketone, 4-acetylbiphenyl, and 1,2-benzofluorene. Other examples of photosensitizers are disclosed, for example, in U.S. Patent Application Publication No. 2022 / 0171285, the entire contents of which are incorporated herein by reference. In some embodiments, the acylgermanium compounds described herein may be used as photosensitizers.

[0062] In some embodiments, the dielectric film forming compositions described herein may further include one or a mixture of organic solvents (e.g., two, three, or four). In some embodiments, the solvent is selected from the group consisting of: alkylene carbonates, lactones, cyclic ketones, straight-chain ketones, alkyl esters; alkyl ester alcohols, alkyl ether alcohols, alkyl ether esters, glycol esters; glycol ethers, cyclic ethers, pyrrolidones, and dialkyl sulfoxides and mixtures thereof. Examples of organic solvents suitable for the dielectric film forming compositions described herein include, but are not limited to, alkylene carbonates such as ethylene carbonate, propylene carbonate, butenyl carbonate, and glyceryl carbonate; lactones such as γ-butyrolactone, ε-caprolactone, γ-caprolactone, and γ-valerolactone; cyclic ketones such as cyclopentanone and cyclohexanone; straight-chain ketones such as methyl ethyl ketone (MEK) and methyl isobutyl ketone (MIBK); esters such as n-butyl acetate; ester alcohols such as ethyl lactate; ether alcohols such as tetraethyl ether... Hydrofurfuryl alcohol; ether esters, such as (tetrahydrofuran-2-yl)methyl acetate, methyl-3-methoxypropionate, ethyl-3-ethoxypropionate and 3-methoxybutyl acetate; glycol esters, such as propylene glycol methyl ether acetate; glycol ethers, such as propylene glycol methyl ether (PGME); cyclic ethers, such as tetrahydrofuran (THF); pyrrolidones, such as N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or N-butyl-2-pyrrolidone or TamiSolve™ NxG; and dialkyl sulfoxides, such as dimethyl sulfoxide.

[0063] In some embodiments, the total amount of solvent is at least about 20 wt.% (e.g., at least about 25 wt.%, at least about 30 wt.%, at least about 35 wt.%, at least about 40 wt.%, at least about 45 wt.%, at least about 50 wt.%, at least about 55 wt.%, at least about 60 wt.% or at least about 65 wt.%) and / or at most about 98 wt.% (e.g., at most about 95 wt.%, at most about 90 wt.%, at most about 85 wt.%, at most about 80 wt.%, at most about 75 wt.%, at most about 70 wt.% or at most about 60 wt.%) of the total weight of the dielectric film forming composition described herein.

[0064] In some embodiments, the dielectric film forming compositions described herein optionally include at least one (e.g., two, three, or four) filler (such as inorganic fillers or inorganic particles). In some embodiments, the inorganic filler is selected from the group consisting of: silicon oxide, aluminum oxide, titanium oxide, zirconium oxide, hafnium oxide, CdSe, CdS, CdTe, CuO, zinc oxide, lanthanum oxide, niobium oxide, tungsten oxide, strontium oxide, calcium titanium oxide, sodium titanate, barium sulfate, barium titanate, barium zirconate, and potassium niobate. The inorganic filler is in the form of particles with an average size of about 0.1–2.0 micrometers. In some embodiments, the filler is inorganic particles containing ferromagnetic material. Suitable ferromagnetic materials include elemental metals (such as iron, nickel, and cobalt) or their oxides, sulfides, and hydroxyl oxides, as well as intermetallic compounds such as Awaruite (Ni3Fe), Wairaruite (CoFe), and Co 17 Sm2 and Nd2Fe 14 B.

[0065] In some embodiments, the amount of inorganic filler (e.g., silica filler) is at least about 1 wt.% (e.g., at least about 2 wt.%, at least about 5 wt.%, at least about 8 wt.%, or at least about 10 wt.%) and / or at most about 30 wt.% (e.g., at most about 25 wt.%, at most about 20 wt.%, or at most about 15 wt.%) of the solid weight of the dielectric film forming composition described herein.

[0066] In some embodiments, the dielectric film forming composition described herein may optionally further include at least one (e.g., two, three, or four) adhesion promoters.

[0067] Suitable cooperating agents are described in “Silane Coupling Agent”, Edwin P. Plueddemann, 1982 Plenum Press, New York. Examples of such cooperating agents are disclosed, for example, in U.S. Patent Nos. 10,036,952 and 10,563,014, U.S. Application Publication No. 2015 / 0219990, and EP Patent No. 3,492,982; the entire contents of which are incorporated herein by reference.

[0068] In some embodiments, the amount of the selected adhesion promoter is at least about 0.5 wt.% (e.g., at least about 0.8 wt.%, at least about 1 wt.%, or at least about 1.5 wt.%) and / or at most about 4 wt.% (e.g., at most about 3.5 wt.%, at most about 3 wt.%, at most about 2.5 wt.%, or at most about 2 wt.%) of the solid weight of the dielectric film forming composition described herein.

[0069] 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, the surfactants described in JP-A-62-36663, JP-A-61-226746, JP-A-61-226745, JP-A-62-170950, JP-A-63-34540, JP-A-7-230165, JP-A-8-62834, JP-A-9-54432, and JP-A-9-5988, the entire contents of which are incorporated herein by reference.

[0070] In some embodiments, the amount of surfactant is at least about 0.005 wt.% (e.g., at least about 0.01 wt.% or at least about 0.1 wt.%) and / or at most about 1 wt.% (e.g., at most about 0.5 wt.% or at most about 0.2 wt.%) of the solid weight of the dielectric film forming composition described herein.

[0071] In some embodiments, the dielectric film forming compositions described herein may optionally contain at least one (e.g., two, three, or four) corrosion inhibitors.

[0072] Examples of suitable corrosion inhibitors include triazole, imidazole, and tetraazole compounds. Triazole compounds may include triazoles, benzotriazoles, substituted triazoles, and substituted benzotriazoles. Dielectric film forming compositions containing corrosion inhibitors prevent corrosion and discoloration of copper or copper alloys when used as a photosensitive layer on top of copper or copper alloys. Corrosion inhibitor additives play an important role in improving the HAST stability of TEG chips through effective binding with copper.

[0073] Examples of tetrazolium include 1-H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-(ethylthio)-1H-tetrazole, 5-(benzylthio)-1H-tetrazole, ethyl 1H-tetrazole-5-acetate, ethyl 1H-tetrazole-5-carboxylate, 5-amino-1H-tetrazole, 1-phenyl-5-mercapto-1H-tetrazole, 5,5'-bis-1H-tetrazole, 1-methyl-5-ethyltetrazole, 1-methyl-5-mercaptotetrazole, 1-carboxymethyl-5-mercaptotetrazole, 5-amino-1H-tetrazole, 1-methyl-1H-tetrazole, etc.

[0074] Examples of triazole compounds include, but are not limited to, 1,2,4-triazole, 1,2,3-triazole, or triazoles substituted with substituents such as C1-C8 alkyl (e.g., 5-methyltriazole), amino, thiol, mercapto, imino, carboxyl, and nitro groups.

[0075] 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, etc.

[0076] Examples of benzotriazoles include 1-H benzotriazole, tolyltriazole, 5-phenyl-benzotriazole, 5-nitro-benzotriazole, hydroxybenzotriazole, 2-(5-amino-pentyl)-benzotriazole, 5-phenylthiobenzotriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, 4-carboxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole, 2-hydroxy-5-acryloyloxyphenyl-2H-benzotriazole, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-(3-tert-butyl-phenyl)-5-methyl-2-hydroxy-benzotriazole, 2-(3,5-di-tert-pentyl-2-hydroxyphenyl)benzotriazole, 2-hydroxy-3-chloro-5-acryloyloxyphenyl-2H-benzotriazole, etc.

[0077] Examples of imidazoles include, but are not limited to, 2-alkyl-4-methylimidazolium, 2-phenyl-4-alkylimidazolium, 2-methyl-4(5)-nitroimidazolium, 5-methyl-4-nitroimidazolium, 4-imidazolium methanol hydrochloride and 2-mercapto-1-methylimidazolium.

[0078] If used, the amount of any corrosion inhibitor shall be at least about 0.1 wt.% (e.g., at least about 0.2 wt.% or at least about 0.5 wt.%) and / or at most about 3.0 wt.% (e.g., at most about 2.0 wt.% or at most about 1.0 wt.%) of the solid weight of the dielectric film forming composition described herein. If the amount of corrosion inhibitor is greater than this range, storage stability is reduced; if the amount of corrosion inhibitor is less than the above range, porosity is likely to occur between the copper or copper alloy surfaces.

[0079] In some embodiments, the dielectric film forming compositions described herein include other optional components, such as one or more (e.g., two, three, or four) dyes, pigments, plasticizers, or antioxidants. Examples of such components have been described, for example, in U.S. Application Publication No. 2022 / 0127459, the entire contents of which are incorporated herein by reference.

[0080] In some embodiments, the positive formulation of this disclosure includes a plasticizer, wherein the amount of plasticizer present in the composition is such that it effectively reduces the sidewall angle of the imaged and cured morphology in the coated film on the substrate to prevent stress failure in subsequent metallization of the substrate due to the steep angle of the imaged morphology.

[0081] For some applications, microelectronics manufacturers and technicians desire coating compositions with gentler or more gradual sidewall geometries. If the sidewalls of the topography obtained by the photoimaging process are too vertical and / or form excessively sharp angles with the top surface of the coating, subsequent metallization of the topography can result in a metal layer with high induced stress. Cracks and delamination of the metal layer may form in high-stress areas. These cracks can extend through the metal layer structure, potentially leading to device failure due to open circuits. Furthermore, bonding pads of coatings with vertical sidewalls may be difficult to wire bond because the bonding heads may not fit between the vertical walls. Clearly, tapered sidewalls with rounded edges are desired. This invention discloses novel photosensitive compositions containing a poly-o-hydroxyamide precursor polymer and a plasticizer with a low vapor pressure at typical soft-baking temperatures (100-150 degrees Celsius). The presence of these plasticizers in the formulation helps to provide gentler corners or smoother edges and corners. For the purposes of this invention, a plasticizer is defined as a compound that, when present in the compositions of this invention, is capable of producing such gentler corners and / or smoother edges and corners in the photo-imaged morphology of a coating cast from the compositions of this invention during the curing cycle of the poly-o-hydroxyamide precursor.

[0082] In one embodiment of the present invention relating to a positive working photosensitive poly-o-hydroxyamide precursor composition containing diazonium quinone, the plasticizer is at least one polyhydroxy compound having at least two OH groups, and its boiling point is higher than that of the solvent of the positive working photosensitive poly-o-hydroxyamide precursor composition containing diazonium quinone. Examples of polyhydroxy compounds having at least two OH groups include, but are not limited to, ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, tripropylene glycol, polypropylene glycol, glycerol, butanediol, hexanediol, sorbitol, cyclohexanediol, 4,8-bis(hydroxymethyl)-tricyclo(5.2.1.0 / 2,6)decane, and copolymers of 2-oxahepane and 2-ethyl-2-(hydroxymethyl)-1,3-propanediol. Preferred polyhydroxy compounds having at least two OH groups are diethylene glycol, tripropylene glycol, and copolymers of 2-oxahepane and 2-ethyl-2-(hydroxymethyl)-1,3-propanediol. More preferably, the polyhydroxy compound having at least two OH groups is tripropylene glycol and a copolymer of 2-oxohepanone and 2-ethyl-2-(hydroxymethyl)-1,3-propanediol.

[0083] The amount of plasticizer used in the positive working photosensitive poly-o-hydroxyamide precursor composition containing diazonium quinone of the present invention is from about 0.1% to about 20% by weight of the total weight of the composition, preferably from about 1% to about 10% by weight, more preferably from about 1.25% to about 7.5% by weight, and most preferably from about 1.5% to about 5% by weight. The plasticizer can be mixed in any suitable ratio.

[0084] In some embodiments, the positive formulation disclosed herein includes silanediols, such as diarylsilanediol or dialkylsilanediol, as additives as dissolution inhibitors. Diphenylsilanediol is most preferred. Silanediols are included in the composition in amounts from about 0.1% to 10.0% by weight, preferably from about 0.5% to 7.5% by weight, and most preferably from about 1% to 5% by weight.

[0085] In some embodiments, the dielectric film forming compositions described herein are substantially fluorine-free compositions, wherein the poly-o-hydroxyamide photosensitive diazonium quinone compound, sensitizer, adhesion promoter, surfactant, solvent, corrosion inhibitor, plasticizer, and additives are substantially fluorine-free. In another embodiment, the dielectric film forming compositions described herein are free of perfluoroalkyl substances and polyfluoroalkyl substances (PFAS), wherein the poly-o-hydroxyamide, photoacid generator, basic compound, photoalkali generator, sensitizer, adhesion promoter, surfactant, solvent, corrosion inhibitor, plasticizer, and additives are substantially free of perfluoroalkyl substances and polyfluoroalkyl substances (PFAS). In some embodiments, the dielectric film forming compositions described herein are substantially halogen-free, wherein the poly-o-hydroxyamide, photoacid generator, basic compound, photoalkali generator, sensitizer, adhesion promoter, surfactant, solvent, corrosion inhibitor, plasticizer, and additives are substantially halogen-free.

[0086] In other embodiments, this disclosure provides methods of using the compositions of this disclosure, and manufactured articles, particularly electronic components, obtained from a combination of the compositions and methods of use according to this disclosure. The methods of this disclosure include a method for forming a patterned image on a substrate. This method includes the following steps: (a) Provide a substrate. (b) A negative photosensitive composition is coated onto the substrate, the composition comprising one or more poly-o-hydroxyamide precursors having structure (2), at least one solvent and at least one dissolution rate modifier (all as described above), provided that the dissolution rate modifier does not contain a carboxylic acid group when the potential crosslinking agent has high reactivity, thereby forming a coated substrate. (c) Exposing the coated substrate to photochemical radiation; (d) Expose the coated substrate to high temperature and then bake it; (e) The coated substrate is developed with an aqueous developer to form an embossed image; and (f) The substrate is baked at a high temperature to solidify the embossed image and form a heat-resistant film.

[0087] In some embodiments, the dielectric film may be prepared by a method comprising the steps of: (a) applying the dielectric film forming composition described herein onto a substrate (e.g., a semiconductor substrate) to form the dielectric film; and (b) optionally baking the film at a high temperature (e.g., from about 50°C to about 150°C) for a period of time (e.g., from about 20 seconds to about 600 seconds).

[0088] Coating methods for preparing dielectric films include, but are not limited to, (1) spin coating, (2) spray coating, (3) roll coating, (4) bar coating, (5) spin coating, (6) slot coating, (7) compression coating, (8) curtain coating, (9) mold coating, (10) wire rod coating, (11) blade coating, and (12) lamination of dry films. In the case of coating methods (1)–(11), the dielectric film forming composition is typically provided in solution form. Those skilled in the art will select an appropriate solvent type and solvent concentration based on the coating type.

[0089] The substrate can have a circular, square, or rectangular shape, such as wafers or panels of various sizes. Examples of suitable substrates include epoxy molding compounds (EMC), silicon, glass, copper, stainless steel, copper-clad laminates (CCL), aluminum, silicon oxide, and silicon nitride. The substrate can be flexible, such as polyimide, PEEK, polycarbonate, and polyester films. The substrate can have surface-mount or embedded chips, dies, or packages. The substrate can be sputtered or pre-coated with a combination of seed layers and passivation layers. In some embodiments, the substrate mentioned herein can be a semiconductor substrate. As used herein, a semiconductor substrate is a substrate (e.g., a silicon or copper substrate or wafer) that becomes part of the final electronic device.

[0090] The thickness of the dielectric film disclosed herein is not particularly limited. In some embodiments, the dielectric film has a thickness of at least about 1 micrometer (e.g., at least about 2 micrometers, at least about 3 micrometers, at least about 4 micrometers, at least about 5 micrometers, at least about 6 micrometers, at least about 8 micrometers, at least about 10 micrometers, at least about 15 micrometers, at least about 20 micrometers, or at least about 25 micrometers) and / or at most about 100 micrometers (e.g., at most about 90 micrometers, at most about 80 micrometers, at most about 70 micrometers, at most about 60 micrometers, at most about 50 micrometers, at most about 40 micrometers, or at most about 30 micrometers). In some embodiments, the thickness of the dielectric film is less than about 5 micrometers (e.g., less than about 4.5 micrometers, less than about 4.0 micrometers, less than about 3.5 micrometers, less than about 3.0 micrometers, less than about 2.5 micrometers, or less than about 2.0 micrometers).

[0091] In some embodiments, when the dielectric film forming composition is photosensitive, the method of preparing a patterned photosensitive dielectric film includes converting the photosensitive dielectric film into a patterned dielectric film by photolithography. In such cases, the conversion may include exposing the photosensitive dielectric film to high-energy radiation (such as electron beams, ultraviolet light, and X-rays) using a patterned mask.

[0092] After exposure, the dielectric film may be heat-treated at a temperature of at least about 50°C (e.g., at least about 55°C, at least about 60°C, or at least about 65°C) to at most about 100°C (e.g., at most about 95°C, or at most about 90°C, at most about 85°C, at most about 80°C, at most about 75°C, or at most about 70°C) for at least about 60 seconds (e.g., at least about 65 seconds or at least about 70 seconds) to at most about 240 seconds (e.g., at most about 180 seconds, at most about 120 seconds, or at most about 90 seconds). The heat treatment is typically performed using a hot plate or an oven.

[0093] After exposure and heat treatment, a developer can be used to develop the dielectric film to remove unexposed portions, thereby forming openings or embossed images on the substrate. Development can be performed, for example, by immersion or spraying. After development, micropores and fine lines can be generated in the dielectric film on the laminated substrate.

[0094] In some embodiments, an aqueous developer can be used to develop the dielectric film. When the developer is an aqueous solution, it preferably contains one or more aqueous bases. Examples of suitable bases include, but are not limited to, inorganic bases (e.g., potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate), primary amines (e.g., ethylamine, n-propylamine), secondary amines (e.g., diethylamine, di-n-propylamine), tertiary amines (e.g., triethylamine), alkanolamines (e.g., triethanolamine), quaternary ammonium hydroxides (e.g., tetramethylammonium hydroxide or tetraethylammonium hydroxide), and mixtures thereof. The concentration of the base used will depend, for example, on the base solubility of the polymer used. The most preferred aqueous developer is a developer containing tetramethylammonium hydroxide (TMAH). Suitable concentrations of TMAH range from about 1% to about 5%.

[0095] In some embodiments, after the developing step or optional rinsing step, at least about 120 o C (for example, at least about 130) o C. At least approximately 140 o C. At least approximately 150 o C. At least approximately 160 o C. At least approximately 170 o C or at least approximately 180 o C) Up to approximately 250 o C (for example, at most about 240) o C. At most about 230o C. At most approximately 220 o C. At most about 210 o C. At most about 200 o C or at most about 190 o The baking step (e.g., post-development baking) is performed at a temperature within the range of (C). The baking time is at least about 5 minutes (e.g., at least about 10 minutes, at least about 20 minutes, at least about 30 minutes, at least about 40 minutes, at least about 50 minutes, or at least about 60 minutes) and / or at most about 5 hours (e.g., at most about 4 hours, at most about 3 hours, at most about 2 hours, or at most about 1.5 hours). This baking step can remove residual solvent from the remaining dielectric film and can further crosslink the remaining dielectric film. Post-development baking can be performed in air or preferably under a nitrogen atmosphere and can be performed by any suitable heating method.

[0096] Subsequently, benzoxazole rings are formed through the curing of this uncured embossed pattern to obtain the final high-heat-resistant pattern. This is achieved by curing the photosensitive composition at its glass transition temperature (T0). g The embossed pattern is cured by baking (or baking at a temperature of 200°C or higher) to obtain a benzoxazole ring that provides high heat resistance. Typically, temperatures above about 200°C are used. In some embodiments, temperatures are applied from about 250°C to about 400°C. Depending on the heating method used, the curing time is from about 15 minutes to about 24 hours. In some embodiments, the curing time is from about 20 minutes to about 5 hours. In some embodiments, the curing time is from about 30 minutes to about 3 hours. Curing can be performed in air or under a nitrogen atmosphere and can be carried out using any suitable heating method, including baking on a hot plate or in a convection oven.

[0097] In some embodiments, the poly-o-hydroxyamide precursor is cured at a temperature sufficient to affect cyclization and dehydration to form a benzoxazole ring, wherein A1 and A2 are substituted or unsubstituted alkyl or aromatic groups.

[0098] Poly-o-hydroxyamide precursors 2 and 3 are converted into 2c and 3c after curing.

[0099] (2c) (3c) Where R 1 R 2 R 3 R 4 R 5 R 11 R12 Ar1, Ar2, Ar 11 n 1 n 2 n 3 and n 4 And E has the same meaning as previously stated.

[0100] In some embodiments, the patterned dielectric film includes at least one element having a morphology size of up to about 10 micrometers (e.g., up to about 9 micrometers, up to about 8 micrometers, up to about 7 micrometers, up to about 6 micrometers, up to about 5 micrometers, up to about 4 micrometers, up to about 3 micrometers, up to about 2 micrometers, or up to about 1 micrometer). In some embodiments of this disclosure, the dielectric film prepared from the dielectric film forming composition described herein can be patterned by laser ablation to produce a morphology size of up to about 3 micrometers (e.g., up to 2 micrometers or up to 1 micrometer).

[0101] In some embodiments, the aspect ratio (height-to-width ratio) of the patterned dielectric film of this disclosure (e.g., the minimum aspect ratio) is at least about 1 / 3 (e.g., at least about 1 / 2, at least about 1 / 1, at least about 2 / 1, at least about 3 / 1, at least about 4 / 1 or at least about 5 / 1).

[0102] In some embodiments (e.g., when the dielectric film forming composition is non-photosensitive), methods for preparing a patterned dielectric film include converting the dielectric film into a patterned dielectric film using laser ablation techniques. Direct laser ablation methods using an excimer laser beam are typically dry, one-step material removal to form openings (or patterns) in the 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. Patent Nos. 7,598,167, 6,667,551, and 6,114,240, the contents of which are incorporated herein by reference.

[0103] In embodiments where the dielectric film forming composition is non-photosensitive, the composition can be used to form the bottom layer of a bilayer photoresist. In such embodiments, the top layer of the bilayer photoresist can be a photosensitive layer and can be patterned after exposure to high-energy radiation. The pattern in the top layer can be transferred to the bottom dielectric layer (e.g., by etching). The top layer can then be removed (e.g., by using a wet chemical etching method) to form a patterned dielectric film.

[0104] In some embodiments, this disclosure features a method for depositing a metal layer (e.g., to create 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. In some embodiments, the method may include the steps of: (a) depositing the dielectric film forming composition described herein on a substrate (e.g., a semiconductor substrate) to form a dielectric film; (b) exposing the dielectric film (e.g., through a mask) to a source of radiation or heat, or a combination thereof; (c) patterning the dielectric film to form a patterned dielectric film with 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)-(d) may be repeated once or more (e.g., two, three, or four times).

[0105] In some embodiments, this disclosure features a method for depositing a metal layer (e.g., a conductive copper layer to create an embedded copper trace structure) on a semiconductor substrate. In some embodiments, a seed layer conformally to a patterned dielectric film is first deposited on the patterned dielectric film (e.g., outside an opening in the film). The seed layer may contain a barrier layer and a metal seed layer (e.g., a copper seed layer). In some embodiments, the barrier layer is prepared by using a material capable of preventing the diffusion of conductive metal (e.g., copper) through the dielectric layer. Suitable materials for the barrier layer include, but are not limited to, tantalum (Ta), titanium (Ti), tantalum nitride (TiN), tungsten nitride (WN), and Ta / TaN. A suitable method for forming the barrier layer is sputtering (e.g., PVD or physical vapor deposition). Sputtering deposition has several advantages as a metal deposition technique because it can be used to deposit many conductive materials at high deposition rates, good uniformity, and low cost of ownership. For deeper and narrower (high specificity) topologies, conventional sputtering fill produces relatively poor results. The fill factor of sputtered deposition has been improved by collimating the sputtering flux. Typically, this is achieved by inserting a collimating plate with a hexagonal cell array between the target and the substrate.

[0106] The next step in this method is metal seed deposition. A thin metal (e.g., a conductive metal such as copper) seed layer may be formed on top of the barrier layer to improve the deposition of the metal layer (e.g., a copper layer) formed in subsequent steps.

[0107] The next step of the method is to deposit a conductive metal layer (e.g., a copper layer) on top of a metal seed layer in the openings of a patterned dielectric film, wherein the metal layer is thick enough to fill the openings in the patterned dielectric film. The metal layer used to fill the openings in the patterned dielectric film can be deposited by plating (such as electroless plating or electrolytic plating), sputtering, plasma vapor deposition (PVD), and chemical vapor deposition (CVD). Electrochemical deposition is generally the preferred method for applying copper because it is more economical than other deposition methods and can fill the interconnect topology with copper without voids. 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 topologies of the device without voids, such as openings of 100 nm or smaller. This technique has been described in, for example, U.S. Patent Nos. 5,891,804, 6,399,486, and 7,303,992, the contents of which are incorporated herein by reference.

[0108] In some embodiments, the method of 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 at most about 3 micrometers (e.g., at most about 2.8 micrometers, at most about 2.6 micrometers, at most about 2.4 micrometers, at most about 2.2 micrometers, at most about 2.0 micrometers, or at most about 1.8 micrometers) and at least about 0.4 micrometers (e.g., at least about 0.6 micrometers, at least about 0.8 micrometers, at least about 1.0 micrometers, at least about 1.2 micrometers, at least about 1.4 micrometers, or at least about 1.6 micrometers). Examples of copper etchants used to remove the copper overburden include aqueous solutions containing copper chloride and hydrochloric acid or aqueous mixtures of ferric nitrate and hydrochloric acid. Other examples of suitable copper etchants 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, and U.S. Application Publication No. 2017 / 0175274, the contents of which are incorporated herein by reference.

[0109] Some embodiments describe a method of surrounding a metal-structured substrate containing a conductive metal (e.g., copper) wire structure with a dielectric film as described herein, the conductive metal wire structure forming a network of circuits and interconnects. The method includes: a) Provides a substrate containing a conductive metal wire structure, wherein the conductive metal wire structure forms a network of circuits and interconnects on the substrate; b) Deposit the dielectric film forming composition described herein on the substrate to form (e.g., surrounding the conductive metal lines and interconnects) a dielectric film; and c) Exposing the dielectric film (with or without a mask) to a source of radiation or heat, or a combination of radiation and heat.

[0110] The above steps can be repeated multiple times (e.g., two, three, or four times) to form complex, multi-layered three-dimensional objects.

[0111] In some embodiments, this disclosure features a method for preparing a dry film structure. The method includes: a) Coating a carrier substrate (e.g., a substrate comprising at least one polymeric or plastic film) with the dielectric film forming composition described herein; b) Dry the coated dielectric film forming composition to form a dielectric layer (e.g., a photosensitive dielectric layer); and c) Apply the protective layer to the dry film at any location.

[0112] In some embodiments, the carrier substrate is a single-layer or multi-layer polymeric film or plastic film, which may comprise one or more polymers (e.g., polyethylene terephthalate). In some embodiments, the carrier substrate has excellent optical transparency and is substantially transparent to photochemical radiation used to form an embossed pattern in the polymer layer. The thickness of the carrier substrate is preferably in the range of at least about 10 µm (e.g., at least about 15 µm, at least about 20 µm, at least about 30 µm, at least about 40 µm, at least about 50 µm, or at least about 60 µm) to at most about 150 µm (e.g., at most about 140 µm, at most about 120 µm, at most about 100 µm, at most about 90 µm, at most about 80 µm, or at most about 70 µm).

[0113] In some embodiments, the protective layer is a single-layer or multi-layer film, which may include one or more polymers (e.g., polyethylene or polypropylene). Examples of carrier substrates and protective layers have been described, for example, in U.S. Application Publication No. 2016 / 0313642, the contents of which are incorporated herein by reference.

[0114] Reliability is the probability that an electronic component will perform its intended function under stress conditions within a specified time period. Preconditioning, temperature and humidity bias (THB), bias humidity stress test (bHAST), unbiased HAST (uHAST), and high-temperature storage (HTS) are commonly used stress tests for semiconductor packaging materials. Reliability is measured by the proportion of devices that have not failed within a given time 't' after being used from time zero.

[0115] High Accelerated Stress Testing (HAST) combines high temperature, high humidity, high pressure, and time to measure the reliability of components with or without electrical bias. In a controlled environment, HAST testing accelerates stress compared to conventional testing. Essentially, it functions as a corrosion failure test. Corrosion-induced failure is accelerated, thus exposing defects such as those in encapsulation seals, materials, and connectors within a short period.

[0116] Bias-accelerated high-stress testing (bHAST) utilizes the same variables as HAST testing (high voltage, high temperature, and time), but adds a voltage bias. The goal of bHAST testing is to accelerate corrosion within the device, thereby speeding up the test cycle. In unbiased HAST testing, humidity accelerates failure mechanisms associated with the presence of moisture in non-hermetic packages. In bias-humidity stress testing (bHAST), the bias voltage under high humidity conditions leads to galvanic and electrochemical corrosion in non-hermetic packages. For advanced / emerging packaging technologies, board-level reliability (BLR) testing using daisy-chain test carriers is used to determine solder joint interconnect reliability. Failure analysis is performed on failed samples to determine the causes.

[0117] As an accelerated version of the traditional non-condensing THB (Temperature and Humidity Bias) test, the HAST test has the advantage of increasing the pressure and temperature (up to 149°C) to accelerate temperature and moisture-induced failures, taking approximately one-tenth the time of THB. HAST and BHAST tests are typically run at 130°C / 85%RH, but conditions can vary.

[0118] Typical HAST test conditions consist of a temperature of 110°C or 130°C and a humidity of 85% RH, with a test run time of 96 hours or 200 hours. Once the high-accelerated stress test is completed, the changes in the test samples during the HAST conditions are analyzed using microscopy and scanning electron microscopy (SEM). HAST testing generally follows JEDEC specification JESD22 A110, "High-Accelerated Temperature and Humidity Stress Test (HAST)". Bias-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 for evaluating semiconductor devices have been described, for example, in U.S. Patent 9,874,813 and U.S. Patent Application 2021 / 0272898, the contents of which are incorporated herein by reference.

[0119] TEG (Test Element Group) wafers with Cu pillar (pillar) plating are used to evaluate wafers by detection methods, such as for materials development and packaging stability under HAST conditions. Examples of TEG wafers used for evaluating semiconductor devices have been described, for example, in U.S. Patents 8,237,450 and 9,082,708, the contents of which are incorporated herein by reference.

[0120] In some embodiments, the dielectric film of a dry film structure can be delaminated from the carrier layer to become a self-standing dielectric film. A self-standing dielectric film is a film that can maintain its physical integrity without the use of any support layer, such as a carrier layer. In some embodiments, the self-standing dielectric film is uncrosslinked or uncured and may include components other than the solvent of the dielectric film forming composition described above.

[0121] In some embodiments, the dielectric loss tangent or dissipation factor of the dielectric film prepared by the dielectric film forming composition described herein, measured at 10 GHz, 15 GHz and / or 35 GHz, is in the range of at least about 0.001 (e.g., at least about 0.002, at least about 0.003, at least about 0.004, at least about 0.005, at least about 0.01 or at least about 0.05) to at most about 0.1 (e.g., at most about 0.08, at most about 0.06, at most about 0.05, at most about 0.04, at most about 0.02, at most about 0.01, at most about 0.008, at most about 0.006 or at most about 0.005).

[0122] In some embodiments, after pre-laminating the dielectric film of the dry film structure, the dielectric film of the dry film structure can be laminated using a vacuum laminator at approximately 50°C. o C to approximately 140 o C is laminated onto a substrate (e.g., a semiconductor substrate, such as a wafer) using planar compression or hot roll lamination. When using hot roll lamination, a dry film structure can be placed in a hot roll laminator, an optional protective layer can be peeled off from the dielectric film / carrier substrate, and rollers with heat and pressure can be used to bring the dielectric film into contact with and laminate it to form an article containing the substrate, the dielectric film, and the carrier substrate. The dielectric film can then be exposed to a source of radiation or heat (e.g., through the carrier substrate) to form a cross-linked dielectric film. In some embodiments, the carrier substrate can be removed before exposing the dielectric film to a source of radiation or heat.

[0123] Some embodiments of this disclosure describe a method for forming a planarized dielectric film on a substrate with a copper pattern. In some embodiments, the method includes depositing a dielectric film forming composition on the substrate with the copper pattern to form a dielectric film. In some embodiments, the method includes the following steps: a. Provides the dielectric film forming composition of this disclosure, and b. The dielectric film forming composition is deposited on a substrate having a copper pattern to form a dielectric film, wherein the difference between the highest and lowest points on the surface of the dielectric film is at most about 2 micrometers (e.g., at most about 1.5 micrometers, at most about 1 micrometer, or at most about 0.5 micrometers).

[0124] In some embodiments, this disclosure is characterized by 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 insulators, wire coatings, enameled wire enamels, and ink-coated substrates. In some embodiments, this disclosure is characterized by a semiconductor device comprising one or more of these articles. Examples of semiconductor devices that can be made from such articles include integrated circuits, light-emitting diodes, solar cells, and transistors.

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

[0126] Example Synthesis Example 1: Synthesis of Poly-o-hydroxyamide precursor 13.23 g of indane bis-o-aminophenol [6-amino-3-(3'-amino-4'-hydroxyphenyl)-1,1,3-trimethyl-2,3-dihydro-1-aminophenol] was added to a 250 mL three-necked round-bottom jacketed flask equipped with a mechanical stirrer, nitrogen inlet, and feeding funnel. H [Indene-5-ol], 13.71 g pyridine, and 70 g NMP (N-methylpyrrolidone). The solution was stirred at room temperature until clear, and then cooled at -5 to -9°C. To this solution, 3.85 g isophthaloyl dichloro and 5.60 g 4,4'-oxybenzoyl chloride dissolved in 21 g NMP were added dropwise. After the addition, the resulting mixture was stirred at room temperature for 18 hours. Subsequently, 1.06 g pyridine and 2.20 g nadic anhydride were added to the flask, and the temperature was raised to 90°C and stirred for 12 hours. After cooling to room temperature, the viscous solution was precipitated in 1000 mL deionized water. The polymer was collected by filtration, washed with deionized water, and subsequently washed with a 50 / 50 water / methanol mixture. The polymer was dried under vacuum at 60°C for 24 hours to give the poly-o-hydroxyamide precursor. The weight-average molecular weight (Mw) measured by GPC was 13,200.

[0127] Synthesis Example 2: Synthesis of Poly-o-hydroxyamide precursor To a 1000 mL three-necked round-bottom jacketed flask equipped with a mechanical stirrer, nitrogen inlet, and feeding funnel, 66.21 g of indane bis-o-aminophenol, 34.3 g of pyridine, and 266 g of NMP were added. The solution was stirred at room temperature until clear, and then cooled at -5 to -9°C. To this solution, 18.14 g of isophthaloyl dichloride, 26.37 g of 4,4'-oxydibenzoyl chloride, and 2.67 g of sebacyl chloride dissolved in 188 g of NMP were added dropwise. After the addition, the resulting mixture was stirred at room temperature for 18 hours. The viscous solution was precipitated in 3000 mL of deionized water. The polymer was collected by filtration, washed with deionized water, and subsequently washed with a 50 / 50 water / methanol mixture. The polymer was dried under vacuum at 60°C for 24 hours to obtain the poly-o-hydroxyamide precursor.

[0128] Synthesis Example 3: Synthesis of Poly-o-hydroxyamide precursor To a 1000 mL three-necked round-bottom jacketed flask equipped with a mechanical stirrer, nitrogen inlet, and feeding funnel, add 62.93 g of indane bis-o-aminophenol, 4.56 g of 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP), 17.5 g of pyridine, and 255 g of NMP. Stir the solution at room temperature until clear, then cool at -5 to -9°C. Add dropwise to this solution 18.03 g of isophthaloyl dichloride, 26.4 g of 4,4'-oxydibenzoyl chloride, and 2.03 g of adipyl chloride dissolved in 200 g of NMP. After addition, stir the resulting mixture at room temperature for 18 hours. Precipitate the viscous solution in 3000 mL of deionized water. Collect the polymer by filtration, wash with deionized water, and then with a 50 / 50 water / methanol mixture. The polymer was dried under vacuum at 60°C for 24 hours to obtain the poly-o-hydroxyamide precursor.

[0129] Synthesis Example 4: Synthesis of poly-o-hydroxyamide precursors with DNQ capping To a 100 mL three-necked round-bottom flask equipped with a mechanical stirrer, add 5.0 g (17.5 mmol) of the polymer obtained in Synthesis Example 1 and 50 mL of tetrahydrofuran (THF). Stir the mixture for 10 minutes until the solids are completely dissolved. Then add 0.92 g (3.5 mmol) of Example 1, 1-naphthoquinone diazide-5-sulfonyl chloride, and stir the mixture for another 10 minutes. Gradually add 0.36 g (3.5 mmol) of triethylamine over 15 minutes, and then stir the reaction mixture for 5 hours. The reaction mixture is then gradually added to 500 mL of vigorously stirred deionized water. The precipitated product is separated by filtration and washed with 200 mL of deionized water. Add another 600 mL of deionized water to the product and stir the mixture vigorously for 30 minutes. After filtration, wash the product with 100 mL of deionized water. Allow the isolated product to stand at 40 °C. o Dry overnight at C. Yield: 90%.

[0130] D = DNQ, attached to the polymer via the sulfonyl moiety. Synthesis Example 5: Synthesis of Poly-o-hydroxyamide precursor 13.23 g of indane bis-o-aminophenol, 13.71 g of pyridine, and 70 g of NMP were added to a 250 mL three-necked round-bottom jacketed flask equipped with a mechanical stirrer, nitrogen inlet, and feeding funnel. The solution was stirred at room temperature until clear, and then cooled at -5 to -9°C. 3.94 g of isophthaloyl dichloroisocyanurate and 5.73 g of 4,4'-oxybenzoyl chloride dissolved in 21 g of NMP were added dropwise to this solution. After the addition, the resulting mixture was stirred at room temperature for 18 hours. Subsequently, 1.06 g of pyridine and 2.20 g of nadic anhydride were added to the flask, and the temperature was raised to 90°C and stirred for 12 hours. After cooling to room temperature, the viscous solution was precipitated in 1000 mL of deionized water. The polymer was collected by filtration, washed with deionized water, and subsequently washed with a 50 / 50 water / methanol mixture. The polymer was dried under vacuum at 60°C for 24 hours to obtain the poly-o-hydroxyamide precursor. The weight-average molecular weight (Mw) measured by GPC was 14,500.

[0131] Photosensitive Composition Example 1 The positively acting photosensitizing composition was prepared by mixing 100 parts by weight of the polymer solid prepared by the method described in Synthesis Example 1, 3 parts by weight of γ-ureidopropyltrimethoxysilane (Silquest A 1524, available from Momentive Performance Materials Inc.), 2.5 parts by weight of diphenylsilanediol, 13.5 parts by weight of the mixed ester PAC (Bisphenol AP PAC), and 230.5 parts by weight of GBL, and filtering the mixture through a 0.2-micron Teflon filter.

[0132] Photosensitive Composition Example 2 The positively acting photosensitizing composition was prepared by mixing 100 parts by weight of the polymer solid prepared by the method described in Synthesis Example 1, 3 parts by weight of γ-ureidopropyltrimethoxysilane (Silquest A 1524, available from Momentive Performance Materials Inc.), 2.5 parts by weight of diphenylsilanediol, 13.5 parts by weight of the mixed ester PAC (Bisphenol AP PAC), and 230.5 parts by weight of GBL, and filtering the mixture through a 0.2-micron Teflon filter.

[0133] The aforementioned photosensitive composition was then coated onto a silicon wafer and baked on a hot plate at 125°C for 3 minutes to obtain a film thickness of 9 micrometers. The film was exposed using an i-line stepper with a patterned exposure array. Sections of the film on the wafer were exposed to various levels of exposure energy using a Canon 4000 IE i-line stepper. The wafer was exposed at 130°C followed by baking for 90 seconds. The wafer was developed with a 2.38% aqueous TMAH solution using two 30-second over-solvent development steps, with a spin step used to remove the used developer between developer applications. The developed film was rinsed with deionized water and dried by spinning at 5000 rpm for 10 seconds to provide an embossed pattern. No loss of film thickness was observed in unexposed areas. (The last sentence appears to be incomplete and possibly refers to a measurement or measurement at 200 mJ / cm².) 2 and 175 mJ / cm 2 The morphologies of 2-micrometer and 8-micrometer bodies were analyzed under the exposure energy.

[0134] Photosensitive Composition Example 3 The positively active photosensitizing composition was prepared by mixing 100 parts by weight of the polymer solid prepared by the method described in Synthesis Example 1, 17 parts by weight of P17 PAC, 2.4 parts by weight of Surfynol 440 (available from Evonik) in CPO 0.5% and 270.6 parts by weight of GBL, and filtering through a 5.0-micron Teflon filter.

[0135] PS17 (D-S215) The silicon wafer was then coated with a photosensitive composition (Photosensitive Composition Example 3) and baked on a hot plate at 90°C for 2 minutes to obtain a film thickness of 9 micrometers. The film was exposed using an i-line stepper with a patterned exposure array. Sections of the film on the wafer were exposed to various levels of exposure energy using a Canon 4000 IE i-line stepper. The wafer was developed with a 2.38% aqueous TMAH solution (OPD 4262) using two 20-second in-liquid development steps, with used developer removed using a spin step between developer applications. The developed film was rinsed with deionized water and dried by spinning at 5000 rpm for 20 seconds to provide an embossed pattern. No loss of unexposed film thickness was observed. (1350 mJ / cm) 2 The 3-micron pattern was analyzed under the exposure energy.

[0136] Adhesion test The coated wafer was baked at 120°C for 3 minutes. The resulting film thickness was 7-8 micrometers. Subsequently, the wafer was patterned and exposed for 108.2 seconds using a Karl Suss MA-56 broadband exposure tool and a broadband mercury lamp (during the exposure time, the lamp output at 400 nm was 1000 mJ / cm²). 2 This resulted in a 10x10 grid of 2 mm squares. The wafer was then baked at 120°C for 2 minutes and developed using a coating solution in 0.262 N aqueous tetramethylammonium hydroxide (2 coatings, 25 seconds each). The patterned film was then cured at 350°C for 1 hour in a nitrogen atmosphere. The wafer was then placed in an autoclave and exposed to saturated steam at 121°C for 100 hours. The adhesion of the film to the wafer was then tested using 3M tape #720 as described in ASTM D-3359-83 using a tape peel test. No squares in the grid were peeled off, and the formulation passed the test. After 1000 hours of testing, neither film showed any loss of adhesion.

[0137] Although this disclosure has been described in detail with reference to certain embodiments thereof, it should be understood that modifications and variations fall within the spirit and scope of what is described and claimed.

Claims

1. A polymer comprising a poly-o-hydroxyamide represented by the following structure: Where R 1 R 2 R 3 R 4 and R 5 Each of the atoms in the equation is independently a hydrogen atom, substituted or unsubstituted C1-C. 12 Alkyl groups, partially or completely halogenated C1-C 12 Alkyl, substituted or unsubstituted C4-C 18 cycloalkyl, substituted or unsubstituted C6-C 22 Aryl or substituted or unsubstituted C5-C 22 heteroaryl; R 11 and R 12 Each of these elements is independently a hydrogen atom, a straight-chain or branched C1-C4 alkyl group, a C1-C4 alkyl group partially or completely halogenated, or a C5-C... 12 cycloalkyl, C6-C 18 Aryl, C5-C 18 Heteroaryl groups, C1-C4 alkoxy groups, or halogen atoms; Ar1 ​​and Ar2 are each independently a divalent aromatic, aliphatic, or heterocyclic group, or a mixture thereof; Ar 11 and A 12 It is a divalent aromatic, aliphatic, or heterocyclic group or a siloxane group; E is a capping group; n1 is an integer from 5 to 200; n3 is an integer from 0 to 200; n5 is an integer from 0 to 200; n2 is an integer from 5 to 200, and n4 is an integer from 0 to 200.

2. The polymer of claim 1, having the following structure: D is selected from the group consisting of one of the following parts: And R 31 Choose from the group consisting of: hydrogen atoms, halogens, C1-C4 alkyl groups, C1-C4 alkoxy groups, substituted or unsubstituted C4-C 18 Cycloalkyl; p2 is any positive value up to about 0.5, p1 is any value from about 0.5 to about 1, provided that (p1+p2) = 1.

3.

3. A positive photosensitizing composition comprising: (a) The polymer as claimed in claim 1 or claim 2 (b) Photoactive compounds, and (c) Solvent.

4. The composition of claim 3, wherein the amount of at least one polymer is from about 0.1% to about 55% by weight of the solid weight of the composition.

5. The positive photosensitizing composition of claim 3, wherein the photoactive compound is a diazonoquinone compound that generates an acid upon exposure, thereby increasing the dissolution rate of the polymer in an aqueous alkaline solution relative to the dissolution rate of the unexposed polymer.

6. The positive photosensitizing composition of claim 3, further comprising at least one polyhydroxy compound having at least two OH groups as a plasticizer, wherein the boiling point of the polyhydroxy compound is higher than the boiling point of the solvent of the positive working photosensitizing poly-o-hydroxyamide precursor composition containing the diazonium quinone.

7. The positive photosensitizing composition of claim 3, further comprising at least one adhesive agent.

8. The positive photosensitizing composition of claim 3, further comprising at least an amino or phenolic crosslinking agent that acts as a potential crosslinking agent, which generates an intermediate in the presence of heat or in the presence of an acid generated by heat or by light.

9. The positive photosensitizing composition of claim 3, further comprising at least one member selected from the group consisting of corrosion inhibitors, sensitizers, surfactants, fillers, pigments, and dyes.

10. A method for forming an embossed image on a substrate, comprising the following steps: (a) The positive photosensitizing composition as described in claim 3 is coated onto a suitable substrate to form a coated substrate; (b) Pre-baking the coated substrate; (c) Exposing the pre-baked coated substrate to photochemical radiation; (e) The exposed coated substrate is developed with an aqueous developer to form an uncured relief image on the coated substrate; and (e) The developed and coated substrate is baked at a high temperature to solidify the relief image.

11. An article formed by the method of claim 10, wherein the article is a semiconductor device, a flexible film for electronic devices, a wire insulator, a wire coating, an enameled wire varnish, or an inkd substrate.

12. The article of manufacture as claimed in claim 11, wherein the semiconductor device is an integrated circuit, a light-emitting diode, a solar cell, or a transistor.

13. The polymer of claim 1 or claim 2, wherein Ar1 and Ar2 each independently comprise a member selected from the group consisting of: Where X1 is -C(O)-C(O)-, -C(O)O-, C5-C7 cyclic aliphatic group, fluorenyl group, -O-X3-O, -OC(O)-X3-C(O)-O-, -C(O)-O-X3-OC(O)- or -(CH2). m -Si(Z)2-O-Si(Z)2-(CH2) m - where X3 is an unsubstituted or substituted phenyl, diphenyl sulfone, isopropylidene diphenyl, hexafluoroisopropylidene diphenyl, and Z is H or a C1-C6 alkyl group, and m is an integer from 1 to 6, and Ra is independently a hydrogen atom, alkoxy, fluoroalkoxy, cycloalkyl, cycloalkoxy, cycloalkylsulfonyl, aryloxy, alkylaryloxy, arylsulfonyl or alkylarylsulfonyl group.

14. The polymer of claim 1 or claim 2, wherein Ar 11 Includes a member selected from the following groups: Where X2 is -O-, -S-, -C(CF3)2-, -C(CH3)2-, -CH2-, -SO2-, -NHCO-, -C(O)-, -C(O)-C(O)-, -C(O)O-, C5-C7 cyclic aliphatic group, fluorenyl group, -O-X4-O, -OC(O)-X4-C(O)-O-, -C(O)-O-X4-OC(O)-, or -(CH2). m -Si(Z)2-O-Si(Z)2-(CH2) m -, X4 represents unsubstituted or substituted phenyl, diphenyl sulfone, isopropylidene diphenyl, hexafluoroisopropylidene diphenyl, and Z and m have the same meaning as above.

15. A method comprising: (a) Provide an organic solution containing the poly-o-hydroxyamide polymer as described in claim 1 or claim 2 in at least one polar, aprotic polymerizing solvent; (b) add at least one purified solvent to the organic solution to form a diluted organic solution, the at least one purified solvent being less polar than the at least one polymerizing solvent and having lower water solubility at 25ºC than the at least one polymerizing solvent; (c) wash the diluted organic solution with an acidified aqueous solution to obtain a washed organic solution. (d) Removing at least a portion of the at least one purified solvent from the washed organic solution to obtain a solution containing the purified poly-o-hydroxyamide, wherein the method avoids precipitation of the poly-o-hydroxyamide.

16. A polybenzoxazole obtained by curing a poly-o-hydroxyamide as described in claim 1, wherein the polybenzoxazole has the following structure: Where R 1 R 2 R 3 R 4 and R 5 Each of the atoms in the equation is independently a hydrogen atom, substituted or unsubstituted C1-C. 12 Alkyl groups, partially or completely halogenated C1-C 12 Alkyl, substituted or unsubstituted C4-C 18 cycloalkyl, substituted or unsubstituted C6-C 22 Aryl or substituted or unsubstituted C5-C 22 heteroaryl; R 11 and R 12 Each of these elements is independently a hydrogen atom, a straight-chain or branched C1-C4 alkyl group, a C1-C4 alkyl group partially or completely halogenated, or a C5-C... 12 cycloalkyl, C6-C 18 Aryl, C5-C 18 Heteroaryl groups, C1-C4 alkoxy groups, or halogen atoms; Ar1 ​​and Ar2 are each independently a divalent aromatic, aliphatic, or heterocyclic group, or a mixture thereof; Ar 11 and A 12 It is a divalent aromatic, aliphatic, or heterocyclic group or a siloxane group; E is a capping group; n1 is an integer from 5 to 200; n3 is an integer from 0 to 200; n5 is an integer from 0 to 200; n2 is an integer from 5 to 200 and n4 is an integer from 0 to 200.

17. The photosensitizing composition of claim 3, wherein the composition is substantially free of fluorine.

18. A photosensitive composition comprising: at least one polymer as claimed in claim 1, at least one sensitizer, at least one adhesion promoter, at least one surfactant, at least one solvent, at least one corrosion inhibitor, at least one plasticizer, and at least one additive, wherein each component is independently substantially free of fluorine.

Images