Poly-O-hydroxyamide comprising a novel indan bis-O-aminophenol, a photosensitive composition containing the same, a dielectric film, and a buffer coating

Abstract

The present disclosure describes a novel highly soluble poly-o-hydroxyamide containing a novel indan bis-o-aminophenol, a photosensitive composition containing the same, and a method and articles for using the same.

Description

Technology Field

[0001] Cross-reference regarding related applications

[0002] This application claims priority to U.S. Provisional Application No. 63 / 608,475 filed December 11, 2023 and U.S. Application No. 18 / 960,615 filed November 26, 2024, the entire contents of which are incorporated herein by reference. Background Technology

[0003] Dielectric material requirements for semiconductor packaging applications are constantly evolving. Trends in electronic packaging continue to advance toward faster processing speeds, increased complexity, and higher packing densities while maintaining high levels of reliability. As electronic packaging technology advances and chip sizes continue to shrink, the demand for innovative, high-performance resin compositions is also increasing. The problem to be solved

[0004] The present disclosure provides a dielectric film-forming composition comprising a polymer comprising at least one indan bis-o-aminophenol compound as a diamine monomer. The dielectric film-forming compositions described herein meet the very demanding requirements of the microelectronics industry. In some embodiments, the present disclosure provides a dielectric film-forming composition comprising a poly-o-hydroxyamide having at least one indan bis-o-aminophenol compound as a diamine monomer. In certain embodiments, the present disclosure provides a composition comprising a poly-o-hydroxyamide comprising an indan bis-o-aminophenol monomer of formula Ia:

[0005] Ia

[0006] In the above equation, R 1 , R 2 , R 3 , R 4 and R 5 Each is independently a hydrogen atom, a substituted or unsubstituted C1-C 12Alkyl, partially halogen-substituted or completely halogen-substituted C1-C 12 Alkyl, substituted or unsubstituted C4-C 18 Cycloalkyl, substituted or unsubstituted C6-C 22 Aryl or substituted or unsubstituted C5-C 22 It is heteroaryl; R 11 and R 12 Each is independently a hydrogen atom, a linear or branched C1-C4 alkyl group, a partially or completely halogen-substituted C1-C4 alkyl group, or a C5-C 12 Cycloalkyl group, C6-C 18 Aryl group, C5-C 18 It is a heteroaryl group, a C1-C4 alkoxy group, or a halogen atom. means of solving the problem

[0007] The poly-o-hydroxyamide of the present disclosure can be used in a photosensitive composition to provide a positive tone, wherein the photosensitive composition can be dissolved in an alkaline aqueous solution to form a fine pattern and achieve high resolution.

[0008] In some embodiments of the present disclosure, a dielectric layer that can be formed from the composition of the present disclosure is provided. The dielectric layer of the present disclosure may form a uniform film, which may be developed after exposure to a relatively long UV wavelength (e.g., about 365 nm) to form a patterned dielectric film. After the photolithography process, the patterned layer is converted into a heat-resistant polybenzoxazole film by applying additional heating, wherein the patterned cured dielectric film may exhibit desirable properties according to one or more reliability tests. The film formed from the photosensitive composition has good mechanical properties even when the composition is cured at a low temperature. Specific details for implementing the invention

[0009] The present disclosure provides a dielectric film forming composition, a related process, a dry film, and a dielectric film. In some embodiments, the dielectric film forming composition described herein comprises (a) at least one polymer comprising at least one indan bis-o-aminophenol compound as a diamine monomer. In some embodiments, the dielectric film forming composition described herein may be photosensitive and / or thermosetting.

[0010] In some embodiments, a poly-o-hydroxyamide suitable for manufacturing a photosensitive composition that meets the very demanding requirements of the microelectronics industry is provided.

[0011] In some embodiments of the present disclosure, a poly-o-hydroxyamide represented by the general formula (2) is provided:

[0012] (2)

[0013] In the above equation, R 1 , R 2 , R 3 , R 4 , R 5 , R 11 and R 12 has the same meaning as described above, and Ar1 and Ar2 are each independently a divalent aromatic group, an aliphatic group, a heterocyclic group, or a mixture thereof; Ar 11 Department A 12is a divalent aromatic, aliphatic, heterocyclic, or siloxane group; E is a terminal 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; p2 is any positive number up to about 0.9, and p1 is any value from about 0.1 to about 0.8, provided that (p1+p2) = 1; A is any suitable monovalent acid labile group and includes acetals, ketals, carbonates, ethers, silyl ethers, t-butyl ester-containing portions, and mixtures thereof. Examples of such acid labile groups include, but are not limited to, parts of the following formula:

[0014]

[0015] In some embodiments of the present disclosure, a poly-o-hydroxyamide represented by the general formula (3) is provided:

[0016] (3)

[0017] In the above equation, 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 A have the same meaning as described above.

[0018] In some embodiments of the present disclosure, a poly-o-hydroxyamide represented by the general formula (4) is provided:

[0019] (4)

[0020] In the above equation, R 1 , R 2 , R 3 , R4 , R 5 , R 11 , R 12 , Ar1, Ar2, Ar 11 , n 1 , n 2 , n 3 , n 4 , p1, p2 and A have the same meaning as described above.

[0021] As used herein, the “end-capping group” refers to the reaction product of an amino terminal group of poly-o-hydroxyamide and a monoanhydride compound. When the monoanhydride compound is added to a polymerization system, it facilitates the termination of the poly-o-hydroxyamide chain, thereby limiting the growth of the polymer chain.

[0022] In some implementations, Ar1 and Ar2 include the following parts:

[0023]

[0024] In the above formula, 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 - and, where X3 is unsubstituted or substituted phenyl, diphenylsulfone, isopropylidene diphenyl, hexafluoroisopropylidene diphenyl, Z is H or a C1-C6 alkyl group, m is an integer from 1 to 6, and Ra is each independently a hydrogen atom, an alkoxy group, a fluoroalkoxy group, a cycloalkyl group, a cycloalkoxy group, a cycloalkylsulfonyl group, an aryloxy group, an alkylaryloxy group, an arylsulfonyl group, or an alkylarylsulfonyl group.

[0025] In some embodiments, the poly-o-hydroxyamide may contain one or more different Ar1 and Ar2 groups.

[0026] In some implementations, Ar 11 It includes the following parts:

[0027]

[0028] In the above formula, 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 - and X4 is an unsubstituted or substituted phenyl, diphenyl sulfone, isopropylidene diphenyl, or hexafluoroisopropylidene diphenyl, and Z and m have the same meaning as described above.

[0029] The dicarboxylic acid chlorides of the present disclosure are, for example, aromatic dicarboxylic acid chlorides such as isophthalic acid chloride, terephthalic acid chloride, 4,4'-hexafluoroisopropylidenedibenzoic acid chloride, 4,4'-biphenyldicarboxylic acid chloride, 4,4'-dicarboxydiphenyl ether chloride, 4,4'-dicarboxytetraphenylsilane chloride, bis(4-carboxyphenyl)sulfone chloride, 2,2-bis(p-carboxyphenyl)propane chloride, 5-tert-butylisophthalic acid chloride, 5-bromoisophthalic acid chloride, 5-fluoroisophthalic acid chloride, 5-chloroisophthalic acid chloride, 2,6-naphthalenedicarboxylic acid chloride, etc.; It includes 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, sebacoyl chloride, etc. Examples of these diacid chlorides are disclosed, for example, in U.S. Patents No. 6,143,467 and No. 7,803,510, the entire contents of which are incorporated herein by reference. Any of these dicarboxylic acid chlorides may be used individually or in combination in any suitable proportions to form the poly-o-hydroxyamide described herein.

[0030] Examples of indan bis-o-aminophenol compounds (Ia) include, but are not limited to:

[0031]

[0032]

[0033] 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. Patents No. 6,143,467 and No. 7,803,510, the entire contents of which are incorporated herein by reference. Any of these bis-o-hydroxyamines may be used individually or in combination in any suitable proportions to form the poly-o-hydroxyamide described herein.

[0034] Examples of suitable diamines containing an Ar12 structure that can be used to prepare a poly-o-hydroxyamide polymer of structure (2) include 1-(4-aminophenyl)-1,3,3-trimethylindane-5-amine (alternative names include 4,4'-[1,4-phenylene-bis(1-methylethylidene)]bisaniline, 1-(4-aminophenyl)-1,3,3-trimethyl-2H-indene-5-amine, 1-(4-aminophenyl)-1,3,3-trimethyl-indane-5-amine and [1-(4-aminophenyl)-1,3,3-trimethyl-indane-5-yl]amine), 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-indene-5-amine, 5-amino-6-methyl-1-(3'-amino-4'-methylphenyl)-1,3,3-trimethylingan, 4-amino-6-methyl-1-(3'-amino-4'-methylphenyl)-1,3,3-trimethylingan, 5,7-diamino-1,1-dimethylingan, 4,7-diamino-1,1-dimethylingan, 5,7-diamino-1,1,4-trimethylingan, 5,7-diamino-1,1,6-trimethylingan, 5,7-diamino-1,1-dimethyl-4-ethylingan, p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 3-methyl-1,2-benzenediamine, 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-Diaminohexane, 1,7-Diaminoheptane, 1,8-Diaminooctane, 1,9-Diaminononane, 1,10-Diaminodecane, 1,2-Diaminocyclohexane, 1,4-Diaminocyclohexane, 1,3-Cyclohexanebis(methylamine), 5-Amino-1,3,3-Trimethylcyclohexanemethaneamine, 2,5-Diaminobenzotrifluoride, 3,5-Diaminobenzotrifluoride, 1,3-Diamino-2,4,5,6-Tetrafluorobenzene, 4,4'-Oxidianiline, 3,4'-Oxidianiline, 3,3'-Oxidianiline, 3,3'-Diaminodiphenylsulfone, 4,4'-Diaminodiphenylsulfone, 4,4'-Isopropylidendianiline, 4,4'-Diaminodiphenylmethane, 2,2-Bis(4-aminophenyl)propane, 4,4'-Diaminodiphenylpropane, 4,4'-Diaminodiphenylsulfide, 4,4'-Diaminodiphenylsulfone, 4-aminophenyl-3-aminobenzoate, 2,2'-Dimethyl-4,4'-Diaminobiphenyl, 3,3'-Dimethyl-4,4'-Diaminobiphenyl, 2,2'-Bis(trifluoromethyl)benzidine, 3,3'-Bis(trifluoromethyl)benzidine, 2,2-Bis[4-(4-aminophenoxyphenyl)]hexafluoropropane, 2,2-Bis(3-amino-4-methylphenyl)-hexafluoropropane, 2,2-Bis(3-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 1,3-Bis-(4-aminophenoxy)benzene, 1,3-Bis-(3-aminophenoxy)benzene, 1,4-Bis-(4-aminophenoxy)benzene, 1,4-Bis-(3-aminophenoxy)benzene, 1-(4-aminophenoxy)-3-(3-aminophenoxy)benzene, 2,2'-Bis-(4-phenoxyaniline)isopropylidene, bis(p-beta-amino-t-butylphenyl)ether, p-Bis-2-(2-methyl-4-aminopentyl)benzene, p-Bis(1,1-dimethyl-5-aminopentyl)benzene, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diaminobenzophenone, 3'-dichlorobenzidine, 2,2-Bis[4-(4-aminophenoxy)phenyl]propane, 4,4'-[1,3-phenylenebis(1-methyl-ethylidene)]bisaniline, 4,4'-[1,4-phenylenebis(1-methyl-ethylidene)]bisaniline, 2,2-Bis[4-(4-aminophenoxy)phenyl]sulfone, 2,2-bis[4-(3-aminophenoxy)benzene], 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3'-bis(3-aminophenoxy)benzene, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, H-fluorene-2,6-diamine, 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., are included but not limited thereto. Any of these diamines may be used individually or in combination in any suitable proportions to form the poly-o-hydroxyamide described herein.

[0035] The poly-o-hydroxyamide structure (2a) can be synthesized through a number of synthesis procedures, and variations of these procedures are known to those skilled in the art:

[0036] (2a)

[0037] In the above equation, 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 described above.

[0038] Generally, the synthesis procedure involves contacting one or more bis-o-hydroxyamines with one or more chlorides of dioxide in the presence of a solvent suitable for dissolving the monomer and desirable for dissolving the resulting poly-o-hydroxyamide, and optionally a base or a mixture thereof. Examples of suitable bases include, but are not limited to, pyridine, triethylamine, tripropylamine, tributylamine, dicyclohexylmethylamine, 2,6-rutidine, 3,5-rutidine, picoline, 4-dimethylaminopyridine (DMAP), etc. If used, the basic catalyst used may be the same or different from the basic catalyst used in the terminal capping reaction.

[0039] In some embodiments, to produce poly-o-hydroxyamide, the bis-o-hydroxyamine component and the chloride dioxide component are introduced into a reaction vessel by slowly adding one of the components in solid or solution form to a solution of the other component (where not all substances may be completely dissolved) or by adding both components simultaneously. The molar ratio of bis-o-hydroxyamine component(s) to chloride dioxide component(s) is preferably 1.01 to 1.50. More preferably, the molar ratio of diamine to chloride dioxide is adopted to be about 1.05 to 1.30. Generally, the reaction is carried out at about -15°C to about 50°C for about 1 hour to about 48 hours. Note that when the molar ratio of bis-o-hydroxyamine component(s) to chloride dioxide component(s) is greater than 1.00, the resulting species is an amino-terminated poly-o-hydroxyamide, which can further react with a terminal capping monomer to form a terminally capped polymer.

[0040] Suitable polymerization solvents useful for the present invention include, but are not limited to, N-methyl-2-pyrrolidone, N,N-dimethylformamide, dimethyl sulfoxide, gamma-butyrolactone, N,N-dimethylacetamide, tetramethylene sulfone, 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 may be used alone or in combination of two or more. Among these solvents, N-methyl-2-pyrrolidone, gamma-butyrolactone, and N,N-dimethylacetamide are preferred, and N-methyl-2-pyrrolidone is more preferred. In some embodiments, a poor solvent for poly-o-hydroxyamide may be used in combination with these solvents in an amount such that the poly-o-hydroxyamide is not precipitated. Examples of such poor solvents include hexane, heptane, benzene, toluene, xylene, chlorobenzene, and o-dichlorobenzene. It is preferable that the amount of poor solvent to be used be 50% by weight or less (including 0) based on the total amount of solvent. The poly-o-hydroxyamide thus produced can be separated by precipitation in a non-solvent or poor solvent and can be collected by filtration.

[0041] The second step of the polymer synthesis process of the structure (2a) mentioned above is to end-cap the poly-o-hydroxyamide of the structure (2b) synthesized in the first step, i.e., the amino-terminal poly-o-hydroxyamide (uncapped structure (2a)):

[0042] (2b)

[0043] In the above equation, 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 described above.

[0044] In some embodiments, the second step may be carried out by reacting the amino-terminal poly-o-hydroxyamide of structure (2a) with a single anhydride to produce the terminal-capped poly-o-hydroxyamide of structure (2b). In some embodiments, the terminal-capped poly-o-hydroxyamide structure (2b) thus formed may be used for further reactions without separation. The single anhydrides considered for use in this aspect of the disclosure include, for example, aliphatic anhydrides such as acetic anhydride, trifluoroacetic anhydride, pivalic 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-en-2,3-dicarboxylic anhydride, etc. Additional examples of end capping devices are disclosed, for example, in U.S. Patent No. 9,695,284, the full contents of which are incorporated herein by reference.

[0045] In some embodiments, the second step may be carried out by reacting an amino-terminated poly-o-hydroxyamide (structure 2a) and an unreacted diamine monomer with a single anhydride to produce a terminally capped poly-o-hydroxyamide structure (2b) and an adduct, wherein the amine value of the poly-o-hydroxyamide polymer precursor structure (2b) is about 0.0010 to 0.0300 mmol / g; if the amine value is higher than these values, the amine group will interfere with the photoacid generated by exposure of a photoacid generator. The weight-average molecular weight (Mw) of poly-o-hydroxyamide can be measured by standard methods such as membrane osmometry or gel permeation chromatography, as described, for example, in Jan Rabek’s Experimental Methods in Polymer Chemistry, John Wiley & Sons, New York, 1983.

[0046] The weight average molecular weight (Mw) range suitable for the poly-o-hydroxyamide of structure (2) is about 1,000 g / mol to about 80,000 g / mol. The preferred molecular weight range may vary depending on the application of the specific product, the solvent used, and the method of application to the underlying substrate. For example, a weight average molecular weight value suitable 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 up to about 60,000 g / mol (e.g., up to about 50,000 g / mol, up to about 40,000 g / mol).

[0047] Where the term “solvent(s)” is used, it refers to a single organic solvent or a combination of two or more organic solvents unless specifically stated otherwise. The purification or separation of poly-o-hydroxyamide can be carried out by numerous of these procedures known to those skilled in the art. The solution separation procedure of poly-o-hydroxyamide polymers is one of the efficient and environmentally friendly processes for producing poly-o-hydroxyamide polymers with improved purity.

[0048] The purification process may include: (a) providing an organic solution containing poly-o-hydroxyamide in at least one polar, aprotic polymerization solvent; (b) adding at least one purification solvent to the organic solution to form a diluted organic solution, wherein at least one purification solvent has lower polarity than at least one polymerization solvent and lower water solubility than at least one polymerization solvent at 25°C; (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 at least one purification solvent from the washed organic solution to obtain a solution containing purified poly-o-hydroxyamide.

[0049] While not wishing to be bound by theory, the two key functions of purification solvent(s) are considered to be (1) maintaining the poly-o-hydroxyamide polymer in a solution state and (2) forming a two-phase mixture with an aqueous solution containing water and / or additives. In the context of the present disclosure, a two-phase mixture refers to a mixture containing two distinct separate phases (e.g., two distinct liquid phases).

[0050] In some embodiments, the purification solvent(s) may optionally include an ester, ether, ketone, or hydrocarbon substituted with at least one chloride. Examples of suitable purification solvent(s) include 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, pentyl formate, epsilon-caprolactone, diethyl ether, dipropyl ether, dibutyl ether, dicyclohexyl ether, cyclopentyl methyl ether, methyl tert-butyl ether, ethyl tert-butyl ether, anisole, phenyl ethyl ether, diphenyl ether, 1,2-dimethoxypropane, 1,2-dimethoxyethane, 2-butanone, 2-Pentanone, 3-Pentanone, methyl isobutyl ketone, ethyl isobutyl ketone, methyl isopropyl ketone, cyclopentanone, cyclohexanone, acetophenone, isophorone, mesethyl oxide, benzene, toluene, xylene, ethylbenzene, chlorobenzene, 1,2-dichlorobenzene, α,α,α- It includes, but is not limited to, trifluorotoluene, pentane, hexane, heptane, octane, cyclohexane, methylcyclohexane, cyclohexene, and mixtures thereof.

[0051] Depending on the solubility characteristics of the poly-o-hydroxyamide polymer, the purification solvent(s) may be used as the sole solvent(s) in the dilution / purification step. However, in some embodiments, purification co-solvent(s) may be used in addition to the purification solvent(s). 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(s). Generally, the purification co-solvent(s) are not used alone but are used in combination with one or more purification solvent(s). In some embodiments, the purification solvent may be a solvent that does not mix with water.

[0052] Examples of suitable purification cosolvents include, but are not limited to, acetone, gamma-butyrolactone (GBL), furan, tetrahydrofuran, methyl tetrahydrofuran, tetrahydrofuryl methyl ether, 1,4-dioxane, and mixtures thereof. In some embodiments, the purification cosolvent may be a solvent that is miscible with water.

[0053] If an aqueous solution containing additives is used at this stage, the solution may contain additional components such as acids, bases, or chelating agents in sufficient concentrations to remove impurities (e.g., polymerization byproducts), thereby increasing the purity of the poly-o-hydroxyamide polymer. The concentration of the acid, base, or other additives in this aqueous solution may be in the range of 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 a maximum of about 10 wt% (e.g., a maximum of about 8 wt%, a maximum of about 7 wt%, or a maximum of about 5 wt%).

[0054] In some embodiments, the washing step may include the step of adding water or an aqueous solution to the diluted organic solution obtained in the above dilution step. In such embodiments, the washing step may include the step of forming a mixture having an organic phase and an aqueous phase (e.g., by separating the organic phase and the aqueous phase from each other). The washing step may also further include the step of removing the aqueous phase. Generally, washing the diluted solution can substantially remove at least one polymerization solvent or other impurities in the diluted organic solution.

[0055] To improve the effectiveness of the washing step, the diluted organic solution containing the poly-o-hydroxyamide polymer obtained from step 2 and the aqueous washing medium (e.g., water or an aqueous solution) may be mixed by stirring. This stirring may take the form of stirring, agitation, inversion, or any other method that enables effective mixing of the organic phase and the aqueous phase.

[0056] After mixing, the mixture may be left as is until two distinct phases are formed. Once the distinct phases are formed, the aqueous phase may be removed and discarded to remove impurities (e.g., polymerization solvent). Step 3 (and optionally together with Step 2 as needed) may be repeated any number of times to achieve the desired polymer purity. In some embodiments, the number of aqueous washes is 1 to 5 (i.e., 1, 2, 3, 4, or 5).

[0057] A wide range of stirring speeds, times, temperatures, and separation conditions may be adopted. While it is not desirable to be bound by theory, the basic aspect of this step is considered to be to sufficiently mix the mixture to extract a significant amount of polymerization solvent(s) and other impurities into the aqueous phase, and then perform phase separation. These conditions may vary depending on the vessels used for mixing and separation. In some embodiments, the stirring time is about 1 minute to about 24 hours (e.g., about 10 minutes to about 6 hours). In some embodiments, the stirring temperature is about 10°C to about 40°C (e.g., about 15°C to about 30°C). In some embodiments, the separation time is about 10 minutes to about 24 hours (e.g., about 15 minutes to about 12 hours). In some embodiments, the separation temperature is about 10°C to about 40°C (e.g., about 15°C to about 30°C).

[0058] In some embodiments, when forming and purifying the poly-o-hydroxyamide polymer, the amount of residual polymerization solvent(s) remaining after the final aqueous wash is up to about 1 weight% (e.g., up to about 0.5 weight%) of the weight of the poly-o-hydroxyamide polymer.

[0059] After washing an organic solution containing a poly-o-hydroxyamide polymer with an aqueous medium (e.g., water), at least some (e.g., substantially all) of the purification solvent(s) in the organic solution can be removed or replaced with at least one separation solvent(s) to obtain a solution containing a purified poly-o-hydroxyamide polymer (i.e., a purified polymer solution).

[0060] In some embodiments, a solution containing purified poly-o-hydroxyamide polymer (i.e., purified polymer solution) is treated with an ion exchange resin (an acidic and basic ion exchange resin or a mixture of an acidic ion exchange resin and a basic ion exchange resin) to remove trace amounts of acid or base from the purified polymer solution. In certain embodiments, the poly-o-hydroxyamide solution purified by ion exchange is filtered through a filtration medium (pad, cartridge) to remove any gel that may be present in the polymer solution.

[0061] In some embodiments, at least some (e.g., substantially all) of the purification solvent(s) (and essentially all residual water) in the purified polymer solution may be solvent exchanged with separation solvent(s). In some embodiments, the separation solvent(s) are a solvent with a boiling point equal to or higher than that of the purification solvent(s) or a combination of two or more solvents. In certain embodiments, the separation solvent(s) may be the same as the purification solvent(s) or the polymerization solvent(s). In other embodiments, the separation solvent(s) may be different from the purification solvent(s) or the polymerization solvent(s). In some embodiments, the separation solvent(s) are compatible with various coating and application methods used in many industrial applications.

[0062] In some embodiments, the separation solvent(s) may comprise a ketone, ester, hydrocarbon, sulfoxide, ether, or a mixture thereof. Examples of suitable separation solvent(s) include, but are not limited to, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), 2-heptanone, cyclopentanone, cyclohexanone, xylene, gamma-butyrolactone, dimethyl sulfoxide, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), ethyl lactate (EL), and mixtures thereof.

[0063] In some embodiments, the separation solvent(s) may first be added to a washed and purified organic solution containing a poly-o-hydroxyamide polymer. In these embodiments, the purification solvent(s) may be removed by evaporation or distillation. In some embodiments, the amount of residual purification solvent(s) remaining after this step may be up to about 2 weight% (e.g., up to about 1 weight%) of the weight of the poly-o-hydroxyamide polymer. While not wishing to be bound by theory, it is believed that adding a separation solvent(s) with a boiling point higher than that of the purification solvent(s) can facilitate the removal of the purification solvent(s) during distillation.

[0064] Although I do not wish to be bound by theory, aside from exchanging the purification solvent(s) for the separation solvent(s), this step is also believed to serve to dry the final polymer solution by removing residual water along with the purification solvent (e.g., through distillation).

[0065] In some embodiments, after exchanging at least some (e.g., substantially all) of the purification solvent(s) with the separation solvent(s), the solution containing the poly-o-hydroxyamide polymer can be concentrated to form a solution suitable for the next step, the blocking reaction of the poly-o-hydroxyamide.

[0066] Distillation conditions may be any temperature and pressure at which the polymer is stable and the desired result is obtained. In some embodiments, the distillation temperature is about 20°C to about 70°C (e.g., about 25°C to about 45°C). In some embodiments, the distillation pressure is about 760 Torr to about 0.1 Torr (e.g., about 100 Torr to about 0.1 Torr). It should be noted that while a poly-o-hydroxyamide polymer with improved purity is produced by the process described above, additional process steps, including but not limited to ion exchange and filtration, may be included before and / or after steps 3 and 4 of this process.

[0067] In some embodiments, the purified poly-o-hydroxyamide polymer can be separated from the purified polymer solution obtained above by any suitable method known in the art (e.g., solvent removal by precipitation or distillation).

[0068] The poly-o-hydroxyamide precursor of the present invention has a hydroxyl group concentration of 3.35 mol / kg or more when it does not contain fluorine atoms. When it contains fluorine atoms, the hydroxyl group concentration is 4.0 to 10.0 mol / kg, and when it contains fluorine atoms, the hydroxyl group concentration is 2.00 mol / kg or more, preferably 3.0 to 10.0 mol / kg. If the hydroxyl concentration is lower than these values, there is a disadvantage that the poly-o-hydroxyamide polymer is not sufficiently soluble in an alkaline aqueous solution.

[0069] In another embodiment, an unexposed photosensitive film having a poly-o-hydroxyamide structure (2) has a dissolution rate of less than 0.05 μm / sec in an alkaline aqueous solution with a pH greater than 8.0. In some embodiments, an unexposed photosensitive film having a poly-o-hydroxyamide structure (2) has a dissolution rate of less than 0.01 μm / sec in a 2.38% aqueous solution of tetramethylammonium hydroxide.

[0070] In an embodiment in which the dielectric film-forming composition described herein comprises a protected poly-o-hydroxyamide precursor having an acid-unstable functional group,

[0071] The poly-o-hydroxyamide precursor having the acid-unstable functional group shown in structure (2) is the poly-o-hydroxyamide precursor of the present disclosure and the formula CH2=CH-OR in the presence of an acid catalyst. 21 It can be derived from the reaction of a vinyl ether having, where R 21 is a linear, branched, or cyclic alkyl group, an aralkyl group, or a cycloalkyl group, a substituted cycloalkyl group, an aryl group, and a linear or branched alkyl group having a substituted aryl group, preferably having 1 to 10 carbon atoms.

[0072] Another suitable method for preparing a poly-o-hydroxyamide precursor having an acid-unstable functional group is through the reaction of a poly-o-hydroxyamide precursor with di-t-butyl dicarbonate in the presence of a base. A poly-o-hydroxyamide precursor having an acid-unstable functional group can also be synthesized by reacting a poly-o-hydroxyamide precursor with an alcohol and t-butyl vinyl ether in the presence of an acid.

[0073] A typical synthesis reaction mechanism for preparing an acetal-protected poly-o-hydroxyamide precursor is shown in reaction (1):

[0074]

[0075] In the above equation, Ar1, Ar2, n4, n5, and R 21 has the same meaning as defined above, and A has the same meaning as defined above. In some embodiments, R 21 It may be t-butyl, isobutyl, ethyl, propyl, butyl, cyclohexyl, ethylcyclohexyl, or phenethyl.

[0076] In some embodiments, the purified poly-o-hydroxyamide polymer solution is solvent exchanged with a solvent that is immiscible with water to remove trace amounts of water via azeotropic distillation before partial acetal protection of the OH groups of the poly-o-hydroxyamide polymer. Examples of suitable separation solvent(s) include, but are not limited to, 2-heptanone, cyclopentanone, cyclohexanone, xylene, propylene glycol monomethyl ether acetate (PGMEA), ethyl acetate, n-butyl acetate, and mixtures thereof. The solution is cooled to about 5°C to about 20°C (e.g., about 0°C to about 25°C). Then, less than stoichiometric amount of alkyl vinyl ether is added to the dried solution while stirring. A dilute solution of organic sulfonic acid in the reaction solvent is added to the alkyl vinyl ether and poly-o-hydroxyamide polymer solution as a catalyst for the acetylation reaction. Examples of suitable sulfonic acids include, but are not limited to, toluenesulfonic acid, benzenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, and mixtures thereof. The blocking reaction is terminated by quenching the reaction with a dilute solution of trialkylamine. Examples of suitable isolated trialkylamines include, but are not limited to, triethylamine, triisopropylamine, tributylamine, and mixtures thereof.

[0077] In some embodiments, a solution containing a blocked poly-o-hydroxyamide polymer solution (i.e., a polymer solution blocked by acetal) is treated with an ion exchange resin (a basic ion exchange resin or a mixture of an acidic and a basic ion exchange resin) to remove trace amounts of acid from the blocked polymer solution. In certain embodiments, the blocked poly-o-hydroxyamide solution purified by ion exchange is filtered through a filtration medium (pad, cartridge) to remove any gel that may be present in the polymer solution.

[0078] In some embodiments, the washing step may include the step of adding water to the diluted organic solution obtained in the dilution step by adding the same solvent or hydrocarbon solvent. Examples of suitable hydrocarbon solvents that do not mix with water include, but are not limited to, hexane, heptane, xylene, and mixtures thereof. In such embodiments, the washing step may include the step of forming a mixture having an organic phase and an aqueous phase (e.g., by separating the organic phase and the aqueous phase from each other). The washing step may further include the step of removing the aqueous phase. Generally, washing the diluted solution can substantially remove salt impurities (salts of sulfonic acids and bases) in the diluted organic solution through stirring. This stirring may take the form of stirring, agitation, inversion, or any other method that enables effective mixing of the organic phase and the aqueous phase.

[0079] After mixing, the mixture may be left as is until two distinct phases are formed. Once the distinct phases are formed, the aqueous phase may be removed and discarded to remove impurities (e.g., salts). Step 2 may be repeated any number of times to achieve the desired blocked polymer purity. In some embodiments, the number of aqueous washes is 1 to 5 (i.e., 1, 2, 3, 4, or 5).

[0080] A wide range of stirring speeds, times, temperatures, and separation conditions may be adopted. While it is not desirable to be bound by theory, the basic aspect of this step is considered to be to sufficiently mix the mixture to extract a significant amount of polymerization solvent(s) and other impurities into the aqueous phase, and then perform phase separation. These conditions may vary depending on the vessels used for mixing and separation. In some embodiments, the stirring time is about 1 minute to about 24 hours (e.g., about 10 minutes to about 6 hours). In some embodiments, the stirring temperature is about 10°C to about 25°C (e.g., about 15°C to about 22°C). In some embodiments, the separation time is about 10 minutes to about 24 hours (e.g., about 15 minutes to about 12 hours). In some embodiments, the separation temperature is about 10°C to about 25°C (e.g., about 15°C to about 22°C).

[0081] In some embodiments, a solution containing a poly-o-hydroxyamide polymer can be concentrated to form a solution suitable for formulating poly-o-hydroxyamide.

[0082] Distillation conditions may be any temperature and pressure at which the polymer is stable and the desired result is obtained. In some embodiments, the distillation temperature is about 20°C to about 50°C (e.g., about 25°C to about 45°C). In some embodiments, the distillation pressure is about 760 Torr to about 0.1 Torr (e.g., about 100 Torr to about 0.1 Torr).

[0083] In an embodiment in which the dielectric film-forming composition described herein comprises a protected poly-o-hydroxyamide precursor having an acid-unstable functional group, the composition may comprise at least one photogenerator (PAG) and at least one solvent. After exposure, the photogenerated acid catalyzes a deblocking reaction of the protected poly-o-hydroxyamide precursor, converting it into an aqueous base-soluble poly-o-hydroxyamide precursor as illustrated in reaction (2):

[0084]

[0085] Generally, any suitable PAG compound can be used to remove acid-unstable functional groups. For example, suitable PAG compounds include triazine compounds, sulfonates, disulfones, onium salts, and mixtures thereof. Examples of suitable onium salts include iodonium, sulfonium, phosphonium, diazonium, sulfoxonium, and mixtures thereof. In some embodiments, photogenerators include those that can be used for g-line, i-line, 248 nm, and broadband lithography.

[0086] In one embodiment, the aqueous base solubility of poly-o-hydroxyamide is reduced by the attachment of acid-unstable groups. In this case, the alkali solubility of the polymer is restored through the action of the acid generated by the photodegradation of the photogenerator (PAG). The protecting group may be any suitable acid-unstable group, such as acetals, ketals, carbonates, ethers, silyl ethers, t-butyl ester-containing portions, and mixtures thereof. Using this concept, a positive photosensitive composition comprising poly-o-hydroxyamide having acid-unstable functional groups, a photogenerator, and a solvent can be prepared. After the photolithography process, the patterned layer obtained therefrom can be converted into a heat-resistant polybenzoxazole coating by applying additional heating.

[0087] Other examples of poly-o-hydroxyamide precursors, PBO polymers, and reagents for forming poly-o-hydroxyamide precursors and PBO polymers are described, for example, in U.S. Patents No. 6,143,467 and No. 5,883,221, the contents of which are incorporated herein by reference.

[0088] In some embodiments, the positive photosensitive composition of the present disclosure contains one or more compounds that emit acid upon exposure. Such materials are generally referred to as photogenerators (PAGs). The PAGs used in the composition of the present disclosure are active to radiation with wavelengths of about 300 nm to about 460 nm. The PAGs may be dissolved in the photosensitive composition and generate strong acids upon irradiation. Examples of such strong acids include hydrogen halides or sulfonic acids. Types of such PAGs include, but are not limited to, oxime sulfonates, triazines, diazoquinone sulfonates, aromatic sulfonylimides, or sulfonium or iodonium salts of sulfonic acids. Examples of such photogenerators are described, for example, in U.S. Patents No. 6,143,467 and No. 9,519,216, the entire contents of which are incorporated herein by reference. Other suitable photogenerators are perfluoroalkyl sulfonyl methide and perfluoroalkyl sulfonyl imide as disclosed in U.S. Patent No. 5,554,664, which are incorporated herein by reference.

[0089] Other suitable examples of photogenerative agents are triphenylsulfonium bromide, triphenylsulfonium chloride, triphenylsulfonium iodide, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroarsenate, triphenylsulfonium hexafluoroarsenate, triphenylsulfonium trifluoromethanesulfonate, diphenylethylsulfonium chloride, phenacyl dimethylsulfonium chloride, phenacyl tetrahydrothiophenium chloride, 4-nitrophenacyl tetrahydrothiophenium chloride, and 4-hydroxy-2-methylphenylhexahydrothiopyrillium chloride.

[0090] Additional examples of photogenerators suitable for use in the compositions of the present disclosure are triphenylsulfonium perfluorooctanesulfonate, triphenylsulfonium perfluorobutanesulfonate, methylphenyldiphenylsulfonium perfluorooctanesulfonate, methylphenyldiphenylsulfonium perfluorooctanesulfonate, 4-n-butoxyphenyldiphenylsulfonium perfluorobutanesulfonate, 2,4,6-trimethylphenyldiphenylsulfonium perfluorobutanesulfonate, 2,4,6-trimethylphenyldiphenylsulfonium benzenesulfonate, 2,4,6-trimethylphenyldiphenylsulfonium 2,4,6-triisopropylbenzenesulfonate, phenylthiophenyldiphenylsulfonium 4-dodecylbenzenesulfonic acid, tris(-t-butylphenyl)sulfonium perfluorooctanesulfonate, tris(-t-butylphenyl)sulfonium perfluorobutanesulfonate, It includes tris(-t-butylphenyl)sulfonium 2,4,6-triisopropylbenzenesulfonate, tris(-t-butylphenyl)sulfonium benzenesulfonate and phenylthiophenyldiphenylsulfonium perfluorooctanesulfonate.

[0091] Examples of iodium salts suitable for use in the present invention include, but are not limited to, diphenyl iodium perfluorobutanesulfonate, bis-(t-butylphenyl)iodonium perfluorobutanesulfonate, bis-(t-butylphenyl)iodonium perfluorooctanesulfonate, diphenyl iodium perfluorooctanesulfonate, bis-(t-butylphenyl)iodonium benzenesulfonate, bis-(t-butylphenyl)iodonium 2,4,6-triisopropylbenzenesulfonate and diphenyl iodium 4-methoxybenzenesulfonate.Additional examples of photogenerators suitable for use in the present invention include bis(p-toluenesulfonyl)diazomethane, methylsulfonyl p-toluenesulfonyldiazomethane, 1-cyclo-hexylsulfonyl-1-(1,1-dimethylethylsulfonyl)diazomethane, bis(1,1-dimethylethylsulfonyl)diazomethane, bis(1-methylethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, 1-p-toluenesulfonyl-1-cyclohexylcarbonyldiazomethane, 2-methyl-2-(p-toluenesulfonyl)propiophenone, 2-methanesulfonyl-2-methyl-(4-methylthiopropiophenone, 2,4-methyl-2-(p-toluenesulfonyl)pent-3-one, 1-Diazoo-1-methylsulfonyl-4-phenyl-2-butanone, 2-(cyclohexylcarbonyl-2-(p-toluenesulfonyl)propane, 1-cyclohexylsulfonyl-1-cyclohexylcarbonyldiazomethane, 1-Diazoo-1-cyclohexylsulfonyl-3,3-dimethyl-2-butanone, 1-Diazoo-1-(1,1-dimethylethylsulfonyl)-3,3-dimethyl-2-butanone, 1-acetyl-1-(1-methylethylsulfonyl)diazomethane, 1-Diazoo-1-(p-toluenesulfonyl)-3,3-dimethyl-2-butanone, 1-Diazoo-1-benzenesulfonyl-3,3-dimethyl-2-butanone, The photogenerators are 1-diazo-1-(p-toluenesulfonyl)-3-methyl-2-butanone, cyclohexyl 2-diazo-2-(p-toluenesulfonyl)acetate, tert-butyl 2-diazo-2-benzenesulfonylacetate, isopropyl-2-diazo-2-methanesulfonylacetate, cyclohexyl 2-diazo-2-benzenesulfonylacetate, tert-butyl 2-diazo-2-(p-toluenesulfonyl)acetate, 2-nitrobenzyl p-toluenesulfonate, 2,6-dinitrobenzyl p-toluenesulfonate, and 2,4-dinitrobenzyl p-trifluoromethylbenzenesulfonate. Photogenerators are described, for example, in U.S. Patents No. 6,143,467 and No. 5,883,221, the contents of which are incorporated herein by reference. It is included.

[0092] The composition of the present disclosure may optionally include a basic compound selected from the group consisting of tertiary amines having alkyl and / or aromatic groups, sterically hindered secondary amines, non-aromatic cyclic amines, and quaternary ammonium hydroxides. Examples of tertiary amines include, but are not limited to, N,N-dimethylcyclohexylamine, N,N-diethylcyclohexylamine, N-methyldicyclohexylamine, N,N-dimethylethanolamine, etc. Examples of sterically hindered secondary amines include, but are not limited to, diphenylamine, dicyclohexylamine, di-t-butylamine, t-butylphenylamine, t-butylcyclohexylamine, diisopropylamine, di-t-amylamine, phenyl-cyclohexylamine, phenyl-naphthylamine, dinaphthylamine, dianthracenylamine, etc. Examples of suitable non-aromatic cyclic amines include morpholine, N-methylmorpholine, 2,6-dimethylmorpholine, 2,2,6,6-tetramethylmorpholine, N-hydroxyethylmorpholine, N-ethylmorpholine, thiomorpholine, N-methylthiomorpholine, 2,6-dimethylthiomorpholine, 2,2,6,6-tetramethylthiomorpholine, piperidine, N-hydroxyethylpiperidine, 2,6-dimethylpiperidine, 2,2,6,6-tetramethylpiperidine, pyrrolidine, N-methylpyrrolidine, N-ethylpyrrolidine, 2,5-dimethylpyrrolidine, 2,2,5,5-tetramethylpyrrolidine, piperazine, N,N'-dimethylpiperazine, and N,N'-diethylpiperazine, but to It is not limited.

[0093] Examples of sterically hindered cyclic amines include 5-diazabicyclo[4,3,0]non-5-ene and 1,8-diazabicyclo[5,4,0]undek-7-ene, etc. Examples of amines include 1-phenylpiperidine, N,N-diethylaniline, N-phenyldiethanolamine, N-phenyldipropanolamine, tripropylamine, N-(diethoxymethyl)aniline, N-(ethoxymethyl)-N-methylaniline, N-phenyldiethoxyethanolamine, etc. Examples of such amines are described, for example, in heading 9,519 216, the whole contents of which are incorporated herein by reference.

[0094] The amount of the basic compound is in the range of about 0.5 to about 80% (mol) based on the amount of PAG. A preferred amount of the basic compound is about 1 to about 40% (mol) based on the amount of PAG. A more preferred amount of the basic compound is about 2 to about 20% (mol) based on the amount of PAG. The most preferred amount of the basic compound is about 3 to about 10% (mol) based on the amount of PAG.

[0095] 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 up to about 55 wt% (e.g., up to about 50 wt%, up to about 45 wt%, up to about 40 wt%, up to about 35 wt%, up to about 30 wt%, up to about 25 wt%, up to about 20 wt%, up to about 15 wt%, or up to about 10 wt%) of the solid weight of the dielectric film forming composition described herein.

[0096] In some embodiments, the dielectric film-forming composition described herein may comprise at least one (e.g., two, three, or four) photobase generator. For example, if the dielectric film-forming composition comprises a photosensitive polymer having an acid-unstable functional group, the composition may include a photobase generator (such as that described above) to remove the acid-unstable functional group and create a solubility contrast. To control acid diffusion, the composition may include a photobase generator to create a solubility contrast by quenching an additional acid. Examples of suitable photobase generators include 9-anthrylmethyl N,N-diethylcarbamate (WPBG-018), 1,2-dicyclohexyl-4,4,5,5-tetramethylbiguanidium, n-butyltriphenylborate (WPBG-300), etc. In some embodiments, the photobase generator described herein may be present in an amount of at least about 0.1 wt% (e.g., at least about 0.2 wt%, at least about 0.4 wt%, at least about 0.5 wt%, at least about 0.6 wt%, at least about 0.8 wt% or at least about 1 wt%) to a maximum of about 2 wt% of the weight of the solids of the dielectric film forming composition described herein.

[0097] In some embodiments, the dielectric film-forming compositions described herein may comprise at least one (e.g., two, three, or four) photosensitizer, wherein the photosensitizer may absorb light in a wavelength range of about 150 nm to about 600 nm (e.g., about 405 nm). Examples of suitable photosensitizers that may be used in the dielectric film-forming compositions of the present disclosure include benzophenone compounds, thioxantone compounds, anthraquinone compounds, anthracene compounds, coumarin compounds, and mixtures thereof. Some examples of photosensitizers include, but are not limited to, 9-methylanthracene, 9,10-dibutoxycyanthracene, 9,10-diethoxycyanthracene, anthracene methanol, acenaphtylene, thioxantone, methyl-2-naphthyl ketone, 4-acetyl biphenyl, and 1,2-benzofluorene. Examples of other photosensitizers are disclosed, for example, in U.S. Application Publication No. 2022 / 0171285, the entire contents of which are incorporated herein by reference. In some embodiments, the acyl germanium compounds described herein may serve as photosensitizers.

[0098] In some embodiments, the amount of photosensitive material is at least about 0.01 wt% (e.g., at least about 0.05 wt%, at least about 0.1 wt%, or at least about 0.5 wt%) to a maximum of about 1 wt% (e.g., a maximum of about 0.8 wt%, a maximum of about 0.6 wt%, a maximum of about 0.5 wt%, a maximum of about 0.4 wt%, a maximum of about 0.2 wt%) of the weight of the solids of the dielectric film forming composition described herein.

[0099] In some embodiments, the dielectric film-forming composition described herein may further comprise one of organic solvents or a mixture of (e.g., two, three, or four types). In some embodiments, the solvent is selected from the group consisting of alkylene carbonates, lactones, cycloketones, linear ketones, alkyl esters; alkyl ester alcohols, alkyl ether alcohols, alkyl ether esters, glycol esters; glycol ethers, cyclic ethers, pyrrolidone, dialkyl sulfoxides, and mixtures thereof. Examples of organic solvents suitable for the dielectric film-forming composition described herein include alkylene carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate, and glycerin carbonate; lactones such as gamma-butyrolactone, ε-caprolactone, γ-caprolactone, and γ-valerolactone; and cycloketones such as cyclopentanone and cyclohexanone. Linear ketones such as methyl ethyl ketone (MEK) and methyl isobutyl ketone (MIBK); esters such as n-butyl acetate; ester alcohols such as ethyl lactate; ether alcohols such as tetrahydrofurfuryl alcohol; 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 includes, but is not limited to, dialkyl sulfoxides such as dimethyl sulfoxide.In addition, gamma-valerolactone, a bio-derived lactone that may be derived from corn and sugarcane; syrene, a bio-derived ketone that may be derived from corn and sugarcane; 2-methyl tetrahydrofuran, a bio-derived ether that may be derived from lignocellulosic biomass; glycerol, a bio-derived alcohol that may be derived from vegetable oils; limonene (e.g., d-limonene) and pinene (e.g., .) that may be derived from oil waste or citrus waste. α- Bio-derived alkyl aliphatic ring compounds including pinene; bio-derived alkyl aliphatic ring compounds including cymene (e.g., p-cymene) which may be derived from oil waste or citrus waste are suitable solvents or cosolvents for dielectric film-forming compositions containing poly-o-hydroxyamide.

[0100] In some embodiments, the total amount of solvent is at least about 20 wt% (e.g., at least about 25 wt%, at least about 30 wt%, at least about 35 wt%, at least about 40 wt%, at least about 45 wt%, at least about 50 wt%, at least about 55 wt%, at least about 60 wt% or at least about 65 wt%) and / or up to about 98 wt% (e.g., up to about 95 wt%, up to about 90 wt%, up to about 85 wt%, up to about 80 wt%, up to about 75 wt%, up to about 70 wt% or up to about 60 wt%) of the total weight of the dielectric film forming composition described herein.

[0101] In some embodiments, the dielectric film forming composition described herein optionally comprises at least one (e.g., two, three, or four) filler (e.g., inorganic filler or inorganic particle). In some embodiments, the inorganic filler is selected from the group consisting of silica, alumina, titania, zirconia, hafnium oxide, CdSe, CdS, CdTe, CuO, zinc oxide, lanthanum oxide, niobium oxide, tungsten oxide, strontium oxide, calcium titanium oxide, sodium titanate, barium sulfate, barium titanate, barium zirconate, and potassium niobate. The inorganic filler is in the form of granules having an average size of about 0.1 to 2.0 microns. In some embodiments, the filler is an inorganic particle containing a ferromagnetic material. Suitable ferromagnetic materials are elemental metals (e.g., iron, nickel, and cobalt) or their oxides, sulfides, and oxyhydroxides, as well as awaruite (Ni3Fe), wararuite (CoFe), and Co 17 Sm2 and Nd2Fe 14 It includes intermetallic compounds such as B.

[0102] In some embodiments, the amount of inorganic filler (e.g., silica filler) is at least about 1 wt% (e.g., at least about 2 wt%, at least about 5 wt%, at least about 8 wt%, or at least about 10 wt%) and / or up to about 30 wt% (e.g., up to about 25 wt%, up to about 20 wt%, or up to about 15 wt%) of the weight of the solids of the dielectric film forming composition described herein.

[0103] In some embodiments, the dielectric film-forming compositions described herein may optionally further comprise at least one (e.g., two, three, or four) adhesion promoter. Any suitable adhesion promoter may be used in the compositions and methods of the present disclosure. Types of suitable adhesion promoters include, but are not limited to, vinylalkoxysilane, methacryloxalkoxysilane, mercaptoalkoxysilane, epoxyalkoxysilane, and glycidoxyalkoxysilane. Examples of suitable adhesion promoters include, but are not limited to, gamma-glycidoxypropylmethyldimethoxysilane, gamma-glycidoxypropyl-methyldiethoxysilane, gamma-mercaptopropylmethyldimethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, gamma-glycidoxypropylmethyldimethoxysilane, etc. Suitable adhesion promoters are described in the literature ["Silane Coupling Agent Edwin P. Plueddemann, 1982 Plenum Press, New York"]. Examples of such adhesion promoters are disclosed, for example, in U.S. Patents No. 10,036,952 and No. 10,563,014, U.S. Application Publication No. 2015 / 0219990, and European Patent No. 3,492,982, the full contents of which are incorporated herein by reference.

[0104] In some embodiments, the amount of selective adhesion promoter is at least about 0.5 wt% (e.g., at least about 0.8 wt%, at least about 1 wt%, or at least about 1.5 wt%) and / or up to about 4 wt% (e.g., up to about 3.5 wt%, up to about 3 wt%, up to about 2.5 wt%, or up to about 2 wt%) of the weight of the solids of the dielectric film forming composition described herein.

[0105] In some embodiments, the dielectric film-forming compositions described herein may optionally contain at least one (e.g., two, three, or four) surfactant. Examples of suitable surfactants include, but are not limited to, 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 full contents of which are incorporated herein by reference.

[0106] In some embodiments, the amount of surfactant is at least about 0.005 wt% (e.g., at least about 0.01 wt% or at least about 0.1 wt%) and / or up to about 1 wt% (e.g., up to about 0.5 wt% or up to about 0.2 wt%) of the weight of the solids of the dielectric film-forming composition described herein.

[0107] In some embodiments, the dielectric film-forming composition described herein may optionally contain at least one (e.g., two, three, or four) corrosion inhibitor.

[0108] Examples of suitable corrosion inhibitors include triazole compounds, imidazole compounds, and tetrazole compounds. Triazole compounds may include triazoles, benzotriazoles, substituted triazoles, and substituted benzotriazoles. When a dielectric film-forming composition containing a corrosion inhibitor is used as a photosensitive layer on top of copper or a copper alloy, it prevents corrosion and discoloration of the copper or copper alloy. Corrosion inhibitor additives play an important role in improving the HAST stability of TEG chips by effectively binding to copper.

[0109] Examples of tetrazol 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.

[0110] Examples of triazole compounds include, but are not limited to, 1,2,4-triazole, 1,2,3-triazole, or triazoles substituted with substituents such as C1-C8 alkyl groups (e.g., 5-methyltriazole), amino groups, thiol groups, mercapto groups, imino groups, carboxyl groups, and nitro groups.

[0111] 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.

[0112] Examples of benzotriazoles are 1-H-benzotriazole, tolyltriazole, 5-phenyl-benzotriazole, 5-nitro-benzotriazole, hydroxybenzotriazole, 2-(5-amino-pentyl)-benzotriazole, 5-phenylthiol-benzotriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, 4-carboxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole, 2-hydroxy-5-acrylyloxyphenyl-2H-benzotriazole, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-(3-t-butyl-phenyl)5-methyl-2-hydroxy-benzotriazole, Includes 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-hydroxy-3-chloro-5-acrylyloxyphenyl-2H-benzotriazole, etc.

[0113] Examples of imidazoles include, but are not limited to, 2-alkyl-4-methylimidazole, 2-phenyl-4-alkylimidazole, 2-methyl-4(5)-nitroimidazole, 5-methyl-4-nitroimidazole, 4-imidazole methanol hydrochloride, and 2-mercapto-1-methylimidazole.

[0114] When used, the amount of selective corrosion inhibitor is at least about 0.1 wt% (e.g., at least about 0.2 wt% or at least about 0.5 wt%) and / or up to about 3.0 wt% (e.g., up to about 2.0 wt% or up to about 1.0 wt%) of the solid weight of the dielectric film-forming composition described herein. If the amount of corrosion inhibitor exceeds the said range, storage stability is reduced, and if the amount of corrosion inhibitor is less than the said range, there is a high probability that voids will form between the copper or copper alloy surfaces.

[0115] In some embodiments, the genome membrane-forming compositions described herein comprise one or more (e.g., two, three, or four) other optional components, such as dyes, pigments, plasticizers, or antioxidants. Examples of such components are described, for example, in U.S. Application Publication No. 2022 / 0127459, the entire contents of which are incorporated herein by reference.

[0116] In some embodiments, the positive formulation of the present disclosure comprises a plasticizer, wherein the amount of plasticizer present in the composition is an amount effective in reducing the sidewall angle of the imaged and cured features in the coated film on the substrate to prevent stress failure in the subsequent metallization process of the substrate due to the steep angle of the imaged feature.

[0117] For some applications, microelectronics manufacturers and technicians require coating compositions that provide shallower or smoother sidewall geometries. If the sidewalls of features generated by a photoimaging process are too vertical and / or form too sharp an angle with the top surface of the coating, a metal layer with high induced stress may be formed due to the subsequent metallization process of the feature. In high-stress regions, cracking and delamination of the metal layer may occur. These cracks can propagate through the metal layer structure to the extent that they result in functional failure of the device due to open circuits. Additionally, wire bonding can be difficult with bond pads containing coatings with vertical sidewalls because the bonding head may not fit between the vertical walls. Clearly, tapered sidewalls with rounded edges are required. The present invention discloses a novel photosensitive composition containing a poly-o-hydroxyamide precursor polymer and a plasticizer having a low vapor pressure at the typical soft bake temperature (100 to 150°C) of the film. The presence of such plasticizers in the formulation helps to provide shallower wall angles or more rounded corners and edges. For the purposes of the present invention, a plasticizer is defined as a compound capable of producing such shallower wall angles and / or more rounded corners and edges within photoimaging features of a coating cast from the composition of the present invention during the curing cycle of a poly-o-hydroxyamide precursor when present in the composition of the present invention.

[0118] In one embodiment of the present invention regarding a positive working photosensitive poly-o-hydroxyamide precursor composition containing a monovalent acid instability group, the plasticizer is at least one polyhydroxy compound having at least two OH groups, and its boiling point is higher than the boiling point of the solvent of the positive working photosensitive poly-o-hydroxyamide precursor composition. 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-oxepanone and 2-ethyl-2-(hydroxymethyl)-1,3-propanediol, and silanediols such as diarylsilanediol or dialkylsilanediol. In some embodiments, polyhydroxy compounds having at least two OH groups are provided, such as diethylene glycol, tripropylene glycol, and copolymers of 2-oxepanone and 2-ethyl-2-(hydroxymethyl)-1,3-propanediol. In some embodiments, the polyhydroxy compound having at least two OH groups is a copolymer of tripropylene glycol and 2-oxepanone and 2-ethyl-2-(hydroxymethyl)-1,3-propanediol.

[0119] Any suitable phenolic plasticizer, such as methylolated and / or methylolated, etc., may be used in this application. Specific examples of hydroxymethyl-substituted polyfunctional phenols used as crosslinking agent precursors are 4,4'-[1,4-phenylenebis(methylidene)]bis(3,5-dihydroxymethylphenol), 4,4'-[1,4-phenylenebis(1-ethylidene)]bis(3,5-dihydroxymethylphenol), 4,4'-[1,4-phenylenebis(1-propylidene)]bis(3,5-dihydroxymethylphenol), 4,4'-[1,4-phenylenebis(1-butylidene)]bis(3,5-dihydroxymethylphenol), 4,4'-[1,4-phenylenebis(1-pentylidene)]bis(3,5-dihydroxymethylphenol), 4,4'-[1,4-phenylenebis(1-methylethylidene)]bis(3,5-dihydroxymethylphenol), 4,4'-[1,4-phenylenebis(1-ethylpropylidene)]bis(3,5-dihydroxymethylphenol), 4,4'-[1,4-phenylenebis(1-propylbutylidene)]bis(3,5-dihydroxymethylphenol), 4,4'-[1,4-phenylenebis(1-butylpentylidene)]bis(3,5-dihydroxymethylphenol), 4,4'-[1,3-phenylenebis(methylidene)]bis(3,5-dihydroxymethylphenol), 4,4'-[1,3-phenylenebis(1-methylethylidene)]bis(3,5-dihydroxymethylphenol), 4,4'-[1,3-phenylenebis(1-ethylpropylidene)]bis(3,5-dihydroxymethylphenol), 4,4'-[1,3-phenylenebis(1-propylbutylidene)]bis(3,5-dihydroxymethylphenol) and 4,4'-[1,3-phenylenebis(1-butylpentylidene)]bis(3,5-dihydroxymethylphenol) are presented as specific examples of hydroxymethyl-substituted polyfunctional phenols used as crosslinking agent precursors. More examples of crosslinking agents in which G is a methylol or an etherified methylol group are presented. The crosslinking agents used in this disclosure may be commercially available or may be prepared by hydroxymethylating or alkoxymethylating the corresponding phenol using standard techniques known to those skilled in the art.

[0120] The amount of plasticizer used in the positive-type photosensitive poly-o-hydroxyamide precursor composition containing a monovalent acid instability group of the present invention is about 0.1 weight percent to about 20 weight percent, preferably about 1 weight percent to about 10 weight percent, more preferably about 1.25 weight percent to about 7.5 weight percent, and most preferably about 1.5 weight percent to about 5 weight percent of the total weight of the composition. The plasticizer may be mixed in any suitable proportion.

[0121] In some embodiments, the dielectric film-forming composition described herein is a composition that is substantially free of fluorine, wherein the acid instability-blocked poly-o-hydroxyamide, photogenerator, basic compound, photobase generator, photosensitizer, adhesion promoter, surfactant, solvent, corrosion inhibitor, plasticizer, and additive are substantially free of fluorine. In other embodiments, the dielectric film-forming composition described herein is substantially free of perfluoroalkyl and polyfluoroalkyl substances (PFAS). Here, the poly-o-hydroxyamide, photogenerator, basic compound, photobase generator, photosensitizer, adhesion promoter, surfactant, solvent, corrosion inhibitor, plasticizer, and additive are not perfluoroalkyl and polyfluoroalkyl substances (PFAS). In some embodiments, the dielectric film forming compositions described herein are substantially halogen-free, wherein poly-o-hydroxyamide, photogenerator, basic compound, photobase generator, photosensitizer, adhesion promoter, surfactant, solvent, corrosion inhibitor, plasticizer and additive are substantially halogen-free.

[0122] In another embodiment, the present disclosure provides a method of using the composition of the present disclosure and a manufactured article, in particular an electronic component, obtained by a combination of the composition and the method of use according to the present disclosure. The method of the present disclosure includes a method for forming a patterned image on a substrate. The method comprises the following steps:

[0123] (a) a step of providing a substrate;

[0124] (b) a step of coating a negative photosensitive composition comprising one or more poly-o-hydroxyamide precursors having a structure (2), at least one solvent, and at least one dissolution rate regulator (all as described above) on the substrate, wherein, if the potential crosslinking agent is highly reactive, the dissolution rate regulator does not contain a carboxylic acid group, thereby forming a coated substrate;

[0125] (c) a step of exposing the coated substrate to actinic radiation;

[0126] (d) a step of baking the coated substrate after exposure at a high temperature;

[0127] (e) a step of forming a relief image by developing the coated substrate with an aqueous developer; and

[0128] (f) A step of baking the substrate at a high temperature to cure the relief image and form a heat-resistant film.

[0129] In some embodiments, a dielectric film may be prepared from a dielectric film forming composition described herein by a method comprising the following steps: (a) forming a dielectric film by coating the dielectric film forming composition described herein onto a substrate (e.g., a semiconductor substrate); and (b) optionally baking the film at a high temperature (e.g., about 50°C to about 150°C) for a certain period of time (e.g., about 20 seconds to about 600 seconds).

[0130] Coating methods for manufacturing dielectric films include, but are not limited to, (1) spin coating, (2) spray coating, (3) roll coating, (4) rod coating, (5) spin coating, (6) slit coating, (7) compression coating, (8) curtain coating, (9) die coating, (10) wire bar coating, (11) knife coating, and (12) dry film lamination. For coating methods (1) to (11), the dielectric film forming composition is generally provided in the form of a solution. Those skilled in the art will select an appropriate solvent type and solvent concentration depending on the coating type.

[0131] The substrate may have a circular, square, or rectangular shape, such as a wafer or panel of various dimensions. Examples of suitable substrates are epoxy molded compound (EMC), silicon, glass, copper, stainless steel, copper clad laminate (CCL), aluminum, silicon oxide, and silicon nitride. The substrate may be flexible, such as polyimide, PEEK, polycarbonate, and polyester films. The substrate may have a surface-mounted or embedded chip, dye, or package. The substrate may be sputtered or pre-coated with a combination of a seed layer and a passivation layer. In some embodiments, the substrate mentioned herein may be a semiconductor substrate. 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.

[0132] The thickness of the dielectric film of the present disclosure is not particularly limited. In some embodiments, the dielectric film has a film thickness of at least about 1 micron (e.g., at least about 2 microns, at least about 3 microns, at least about 4 microns, at least about 5 microns, at least about 6 microns, at least about 8 microns, at least about 10 microns, at least about 15 microns, at least about 20 microns, or at least about 25 microns) and / or up to about 100 microns (e.g., up to about 90 microns, up to about 80 microns, up to about 70 microns, up to about 60 microns, up to about 50 microns, up to about 40 microns, or up to about 30 microns). In some embodiments, the thickness of the dielectric film is less than about 5 microns (e.g., less than about 4.5 microns, less than about 4.0 microns, less than about 3.5 microns, less than about 3.0 microns, less than about 2.5 microns, or less than about 2.0 microns).

[0133] In some embodiments, when the dielectric film forming composition is photosensitive, a method for manufacturing a patterned photosensitive dielectric film comprises the step of converting the photosensitive dielectric film into a patterned dielectric film by a lithography method. In such cases, the conversion may include the step of exposing the photosensitive dielectric film to high-energy radiation (e.g., electron beam, ultraviolet and X-ray) using a patterned mask.

[0134] 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 a maximum of 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 a maximum of 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 generally performed using a hot plate or an oven.

[0135] After photolithography and heat treatment, the dielectric film can be developed using a developer to remove unexposed areas, thereby forming apertures or relief images on the substrate. Development can be performed, for example, by an immersion method or a spraying method. After development, microholes and fine lines can be created in the dielectric film on the laminated substrate.

[0136] In some embodiments, the dielectric film may be developed using an aqueous developer. When the developer is an aqueous solution, it is preferable to contain one or more aqueous bases. Examples of suitable bases are inorganic alkalis (e.g., potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate), and primary amines (e.g., ethylamine, n -propylamine), secondary amines (e.g., diethylamine, di -n-propylamine), tertiary amines (e.g., triethylamine), alcoholamines (e.g., triethanolamine), quaternary ammonium hydroxides (e.g., tetramethylammonium hydroxide or tetraethylammonium hydroxide), and mixtures thereof are included but not limited thereto. The concentration of the base used will depend, for example, on the base solubility of the polymer used. The most preferred aqueous developer is an aqueous developer containing tetramethylammonium hydroxide (TMAH). A suitable concentration of TMAH is in the range of about 1% to about 5%.

[0137] In some embodiments, after a developing step or an optional rinsing step, an optional baking step (e.g., post-development baking) may be performed at a temperature ranging from at least about 120°C (e.g., at least about 130°C, at least about 140°C, at least about 150°C, at least about 160°C, at least about 170°C, or at least about 180°C) to a maximum of about 250°C (e.g., a maximum of about 240°C, a maximum of about 230°C, a maximum of about 220°C, a maximum of about 210°C, a maximum of about 200°C, or a maximum of about 190°C). The baking time is at least about 5 minutes (e.g., at least about 10 minutes, at least about 20 minutes, at least about 30 minutes, at least about 40 minutes, at least about 50 minutes, or at least about 60 minutes) and / or up to about 5 hours (e.g., up to about 4 hours, up to about 3 hours, up to about 2 hours, or up to about 1.5 hours). This baking step can remove residual solvent from the remaining dielectric film and further crosslink the remaining dielectric film. Baking after development can be performed in air or preferably under a nitrogen blanket and can be carried out by any suitable heating means.

[0138] Then, by curing the uncured relief pattern, benzoxazole rings are formed, ultimately obtaining a pattern with high heat resistance. Curing is performed on the developed uncured relief pattern at the glass transition temperature (T) of the photosensitive composition. g This is performed by baking at a temperature above ) to obtain a benzoxazole ring that provides high heat resistance. Generally, a temperature higher than about 200°C is used. In some embodiments, a temperature of about 250°C to about 400°C is applied. The curing time is about 15 minutes to about 24 hours depending on the heating method used. In some embodiments, the curing time is about 20 minutes to about 5 hours. In some embodiments, the curing time is about 30 minutes to about 3 hours. Curing can be performed in air or under a nitrogen blanket, and can be carried out by any suitable heating means, including baking on a hot plate or in a convection oven.

[0139] In some embodiments, curing comprises the step of curing a poly-O-hydroxyamide precursor at a temperature sufficient to perform cyclodehydration to form a benzoxazole ring, wherein A1 and A2 are substituted or unsubstituted alkyl groups or aromatic groups:

[0140]

[0141] Curing poly-O-hydroxyamide precursors 2 and 3 will convert them into 2c and 3c.

[0142] (2c)

[0143] (3c)

[0144] In the above equation, R 1 , R 2 , R 3 , R 4 , R 5 , R 11 , R 12 , Ar1, Ar2, Ar 11 , n 1 , n2 , n 3 , n 4 and E have the same meaning as described above.

[0145] In some embodiments, the patterned dielectric film comprises at least one element having a feature size of up to about 10 microns (e.g., up to about 9 microns, up to about 8 microns, up to about 7 microns, up to about 6 microns, up to about 5 microns, up to about 4 microns, up to about 3 microns, up to about 2 microns, or up to about 1 micron). In specific embodiments of the present disclosure, a dielectric film prepared from the dielectric film forming composition described herein can produce a patterned film having a feature size of up to about 3 microns (e.g., up to 2 microns or up to 1 micron) by a laser ablation method.

[0146] In some embodiments, the aspect ratio (ratio of height to width) of a feature (e.g., the smallest feature) of the patterned dielectric film of the present disclosure is at least about 1 / 3 (e.g., at least about 1 / 2, at least about 1 / 1, at least about 2 / 1, at least about 3 / 1, at least about 4 / 1, or at least about 5 / 1).

[0147] In some embodiments (e.g., when the dielectric film forming composition is non-photosensitive), a method for manufacturing a patterned dielectric film comprises the step of converting a dielectric film into a patterned dielectric film by a laser ablation technique. A direct laser ablation method using an excimer laser beam is generally a dry one-step material removal that forms an opening (or pattern) in the dielectric film. In some embodiments, the wavelength of the laser is 640 nm or less (e.g., 157 nm, 193 nm, 248 nm, 308 nm, 351 nm, 405 nm, 445 nm, 470 nm, 520 nm, 528 nm, 555 nm, or 640 nm). Examples of suitable laser ablation methods include, but are not limited to, the methods described in U.S. Patents No. 7,598,167, 6,667,551, and 6,114,240, the contents of which are incorporated herein by reference.

[0148] In an embodiment where the dielectric film forming composition is non-photosensitive, the composition can be used to form a bottom layer on a bilayer photoresist. In this embodiment, the top layer of the bilayer photoresist may be a photosensitive layer and may be patterned when exposed to high-energy radiation. The pattern of the top layer may be transferred to the bottom dielectric layer (e.g., by etching). Then, the top layer may be removed (e.g., by using a wet chemical etching method) to form a patterned dielectric film.

[0149] In some embodiments, the present disclosure features a method for depositing a metal layer (e.g., to create an embedded copper trace structure) comprising: (a) forming a patterned dielectric film having an opening; and (d) depositing a metal layer (e.g., an electrically conductive metal layer) at least one opening of the patterned dielectric film. In some embodiments, the method may comprise: (a) forming a dielectric film by depositing the dielectric film forming composition described herein onto a substrate (e.g., a semiconductor substrate); (b) exposing the dielectric film to a radiation source, a heat source, or a combination thereof (e.g., through a mask); (c) patterning the dielectric film to form a patterned dielectric film having an opening; and (d) depositing a metal layer (e.g., an electrically conductive metal layer) at least one opening of the patterned dielectric film. In some embodiments, steps (a) through (d) may be repeated one or more times (e.g., two, three, or four times).

[0150] In some embodiments, the present disclosure features a method for depositing a metal layer (e.g., an electrically conductive copper layer for creating an embedded copper trace structure) on a semiconductor substrate. In some embodiments, a seed layer conformal to the patterned dielectric film is first deposited on the patterned dielectric film (e.g., outside the openings of the film). The seed layer may contain a barrier layer and a metal seeding layer (e.g., a copper seeding layer). In some embodiments, the barrier layer is manufactured using a material capable of preventing the diffusion of an electrically conductive metal (e.g., copper) through the dielectric layer. Suitable materials that may be used for the barrier layer include, but are not limited to, tantalum (Ta), titanium (Ti), tantalum nitride (TiN), tungsten nitride (WN), and Ta / TaN. A suitable method for forming the barrier layer is sputtering (e.g., PVD or physical vapor deposition). Sputtering deposition offers several advantages as a metal deposition technique because it can be used to deposit many conductive materials at high deposition rates with good uniformity and low ownership costs. Conventional sputtering fill results in relatively poor performance for deeper and narrower (high aspect ratio) features. The fill factor of sputtering deposition has been improved by collimating the sputtered flux. Generally, this is achieved by inserting a collimator plate with a hexagonal cell array between the target and the substrate.

[0151] The next step of this method is metal seeding deposition. To improve the deposition of the metal layer (e.g., copper layer) formed in subsequent steps, a thin metal (e.g., an electrically conductive metal such as copper) seeding layer can be formed on top of the barrier layer.

[0152] The next step of this method is to deposit an electrically conductive metal layer (e.g., a copper layer) on top of a metal seeding layer within the openings of the patterned dielectric film, wherein the metal layer is sufficiently thick to fill the openings of the patterned dielectric film. The metal layer for filling the openings of the patterned dielectric film can be deposited by plating (e.g., electroless 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 completely fill the copper within interconnect features. Copper deposition methods generally must meet the stringent requirements of the semiconductor industry. For example, the copper deposit must be uniform and capable of completely filling small interconnect features of devices, for example, with openings of 100 nm or less. This technology is described, for example, in U.S. Patents No. 5,891,804, 6,399,486 and 7,303,992, the contents of which are incorporated herein by reference.

[0153] In some embodiments, the method for depositing an electrically conductive metal layer further includes the step of removing the overburden of the electrically conductive metal or removing a seed layer (e.g., a barrier layer and a metal seeding layer). In some embodiments, the overburden of the electrically conductive metal layer (e.g., a copper layer) is up to about 3 microns (e.g., up to about 2.8 microns, up to about 2.6 microns, up to about 2.4 microns, up to about 2.2 microns, up to about 2.0 microns, or up to about 1.8 microns) and at least about 0.4 microns (e.g., at least about 0.6 microns, at least about 0.8 microns, at least about 1.0 microns, at least about 1.2 microns, at least about 1.4 microns, or at least about 1.6 microns). Examples of copper etchants for removing copper overburden include aqueous solutions containing cupric chloride and hydrochloric acid or aqueous mixtures of ferric nitrate and hydrochloric acid. Other suitable copper etchants include, but are not limited to, the copper etchants described in U.S. Patents No. 4,784,785, 3,361,674, 3,816,306, 5,524,780, 5,650,249, 5,431,776 and 5,248,398, and U.S. Application Publication No. 2017 / 0175274, the contents of which are incorporated herein by reference.

[0154] Some embodiments describe a method for surrounding a metal-structured substrate, comprising a conductive metal (e.g., copper) wire structure forming a network of wiring and interconnects, with a dielectric film as described herein. This method includes the following:

[0155] a) providing a substrate including a conductive metal wire structure that forms a network of wiring and interconnects on the substrate;

[0156] b) a step of forming a dielectric film (e.g., surrounding conductive metal wiring and interconnects) by depositing a dielectric film forming composition described herein on a substrate; and

[0157] c) A step of exposing a dielectric film to a radiation source, a heat source, or a combination of radiation and heat (with or without a mask).

[0158] The above steps can be repeated several times (e.g., 2, 3, or 4 times) to form a complex multilayer three-dimensional object.

[0159] In some embodiments, the present disclosure features a method for manufacturing a dry film structure. The method includes the following:

[0160] a) a step of coating a carrier substrate (e.g., a substrate comprising at least one polymer film or plastic film) with a dielectric film forming composition as described herein;

[0161] b) drying a coated dielectric film forming composition to form a dielectric layer (e.g., a photosensitive dielectric layer); and

[0162] c) Optionally, a step of applying a protective layer to the dry film structure.

[0163] In some embodiments, the carrier substrate is a single-layer or multi-layer polymer or plastic film that may comprise one or more polymers (e.g., polyethylene terephthalate). In some embodiments, the carrier substrate has excellent optical transparency and is substantially transparent to chemical lines used to form a relief pattern on the polymer layer. The thickness of the carrier substrate is preferably in the range of at least about 10 μm (e.g., at least about 15 μm, at least about 20 μm, at least about 30 μm, at least about 40 μm, at least about 50 μm, or at least about 60 μm) to a maximum of about 150 μm (e.g., a maximum of about 140 μm, a maximum of about 120 μm, a maximum of about 100 μm, a maximum of about 90 μm, a maximum of about 80 μm, or a maximum of about 70 μm).

[0164] In some embodiments, the protective layer is a single or multilayer film that may comprise one or more polymers (e.g., polyethylene or polypropylene). Examples of carrier substrates and protective layers are described, for example, in U.S. Application Publication No. 2016 / 0313642, the contents of which are incorporated herein by reference.

[0165] Reliability is the probability that an electronic component performs the required function under stress conditions over a specified period. Preconditioning, temperature and humidity bias (THB), biased humidity stress test (bHAST), unbiased HAST (uHAST), and high temperature storage (HTS) are commonly used stress tests applied to semiconductor packaging materials. Reliability is measured as the proportion of devices that will not fail from time 0 to a given time 't'.

[0166] Highly Accelerated Stress Testing (HAST) measures component reliability with or without electrical bias by combining high temperature, high humidity, high pressure, and time. In a controlled environment, HAST testing accelerates the stress of more traditional tests. It essentially functions as a corrosion failure test. As corrosion-type failures are accelerated, defects such as those in packaging seals, materials, and joints become apparent within a short period.

[0167] Biased High Acceleration Stress Testing (bHAST) uses the same variables (high pressure, high temperature, and time) as HAST testing but adds voltage bias. The goal of BHAST testing is to shorten test duration by accelerating corrosion within the device. In unbiased HAST testing, humidity accelerates failure mechanisms associated with the presence of moisture in non-hermetic packages. In Biased Humidity Stress Testing (bHAST), bias voltage under high humidity induces galvanic and electrochemical corrosion in non-hermetic packages. For advanced / emerging packaging technologies, board-level reliability (BLR) testing is performed using daisy-chained test vehicles to measure the reliability of solder joint interconnects. Failure analysis is performed on failed samples to identify the cause.

[0168] As an accelerated version of the traditional non-condensing THB (temperature and humidity bias) test, the HAST test applies high pressure and high temperature (up to 149°C) to accelerate failure due to temperature and humidity in about 1 / 10 of the THB time. HAST and BHAST tests are typically run at 130°C / 85%RH, but conditions may vary.

[0169] Typical HAST test conditions consist of a temperature of 110°C or 130°C, 85% RH humidity, and a test run time of 96 or 200 hours. Once the high-acceleration stress test is completed, the tested samples are analyzed using a microscope and SEM to identify changes that occurred during the HAST conditions. HAST testing generally follows JEDEC standard JESD22 A110, "High-Acceleration Temperature and Humidity Stress Test (HAST)." Biased Humidity Stress Testing (bHAST) is the most sensitive stress test for measuring the reliability of microelectronic devices using organic dielectric film compositions. Examples of bHAST methods used for semiconductor device evaluation are described, for instance, in U.S. Patent No. 9,874,813 and U.S. Patent Application No. 2021 / 0272898, the contents of which are incorporated herein by reference.

[0170] The material development and package stability of the wafer were evaluated under HAST conditions using a test element group (TEG) wafer with Cu post (pillar) plating through an inspection method. Examples of TEG wafers used for semiconductor device evaluation are described, for example, in U.S. Patents No. 8,237,450 and No. 9,082,708, the contents of which are incorporated herein by reference.

[0171] In some embodiments, the dielectric film of the dry film structure can be peeled off from the carrier layer as a self-supporting dielectric film. A self-supporting dielectric film is a film that can maintain its physical integrity without using any support layer, such as a carrier layer. In some embodiments, the self-supporting dielectric film is not cross-linked or cured and may comprise the components of the dielectric film forming composition described above, excluding the solvent.

[0172] In some embodiments, the dielectric loss tangent or dissipation factor of a dielectric film prepared from the dielectric film forming composition described herein, measured at 10 GHz, 15 GHz, and / or 35 GHz, is in the range of at least about 0.001 (e.g., at least about 0.002, at least about 0.003, at least about 0.004, at least about 0.005, at least about 0.01, or at least about 0.05) to a maximum of about 0.1 (e.g., a maximum of about 0.08, a maximum of about 0.06, a maximum of about 0.05, a maximum of about 0.04, a maximum of about 0.02, a maximum of about 0.01, a maximum of about 0.008, a maximum of about 0.006, or a maximum of about 0.005).

[0173] In some embodiments, after pre-laminating a dielectric film of a dry film structure, the dielectric film of the dry film structure can be laminated onto a substrate (e.g., a semiconductor substrate such as a wafer) using a vacuum laminator at a temperature of about 50°C to about 140°C by a planar compression method or a hot roll compression method. When hot roll lamination is used, the dry film structure can be placed inside the hot roll lamination machine, an optional protective layer can be peeled off from the dielectric film / carrier substrate, the dielectric film can be brought into contact with the substrate, and heat and pressure can be applied and laminated onto the substrate using a roller to form an article comprising a substrate, a dielectric film, and a carrier substrate. Then, the dielectric film can be exposed to a radiation source or a heat source (e.g., through the carrier substrate) to form a cross-linked dielectric film. In some embodiments, the carrier substrate can be removed before exposing the dielectric film to a radiation source or a heat source.

[0174] Some embodiments of the present disclosure describe a method for forming a planarized dielectric film on a substrate having a copper pattern. In some embodiments, the method comprises the step of forming a dielectric film by depositing a dielectric film forming composition on a substrate having a copper pattern. In some embodiments, the method comprises,

[0175] a. A step of providing a dielectric film forming composition of the present disclosure, and

[0176] b. A step of forming a dielectric film by depositing a dielectric film forming composition on a substrate having a copper pattern, wherein the difference between the highest point and the lowest point on the surface of the dielectric film is up to about 2 microns (e.g., up to about 1.5 microns, up to about 1 micron, or up to about 0.5 microns).

[0177] In some embodiments, the present disclosure features an article (or three-dimensional object) comprising at least one patterned dielectric film formed by the method described herein. Examples of such articles include semiconductor substrates, flexible films for electronic devices, wire isolation, wire coating, wire enamel, and inked substrates. In some embodiments, the present disclosure features a semiconductor device comprising one or more of such articles. Examples of semiconductor devices that can be manufactured from such articles include integrated circuits, light-emitting diodes, solar cells, and transistors.

[0178] The present disclosure is further illustrated in detail with reference to the following embodiments, which are for illustrative purposes only and should not be construed as limiting the scope of the present disclosure.

[0179] Examples

[0180] Synthesis Example 1: Synthesis of Poly-o-Hydroxyamide Precursor

[0181] 13.23 g of indan bis-o-aminophenol[6-amino-3-(3'-amino-4'-hydroxyphenyl)-1,1,3-trimethyl-2,3-dihydro-1 H- [Inden-5-ol], 3.71 g of pyridine, and 70 g of NMP were added. The solution was stirred at room temperature until clear, then cooled to -5°C to -9°C. To this solution, 3.85 g of isophthalyl chloride (IC) dissolved in 21 g of NMP and 5.60 g of 4,4'-oxydibenzoyl chloride were added dropwise. After addition, the resulting mixture was stirred at room temperature for 18 hours. Then, 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 then washed with a 50 / 50 water / methanol mixture. The polymer was dried under vacuum at 60°C for 24 hours to obtain a poly-o-hydroxyamide precursor. The weight-average molecular weight (Mw) measured by GPC was 13,200.

[0182]

[0183] Synthesis Example 2: Synthesis of Poly-o-Hydroxyamide Precursor

[0184] 66.21 g of indan bis-o-aminophenol, 34.3 g of pyridine, and 266 g of NMP were added to a 1000 mL three-necked round-bottom jacketed flask equipped with a mechanical stirrer, a nitrogen inlet, and an addition funnel. The solution was stirred at room temperature until clear, then cooled to -5°C to -9°C. To this solution, 18.14 g of isophthalyl chloride dissolved in 188 g of NMP, 26.37 g of 4,4'-oxydibenzoyl chloride, and 2.67 g of sebacoyl chloride were added dropwise. After 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 then washed with a 50 / 50 water / methanol mixture. A poly-o-hydroxyamide precursor was obtained by drying the polymer under vacuum at 60°C for 24 hours.

[0185] Synthesis Example 3: Synthesis of Poly-o-Hydroxyamide Precursor

[0186] 62.93 g of indan 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 are added to a 1000 mL three-necked round-bottom jacketed flask equipped with a mechanical stirrer, a nitrogen inlet, and an addition funnel. The solution is stirred at room temperature until clear, then cooled to -5°C to -9°C. To this solution, 18.03 g of isophthalyl chloride dissolved in 200 g of NMP, 26.4 g of 4,4'-oxydibenzoyl chloride, and 2.03 g of adipoyl chloride are added dropwise. After addition, the resulting mixture is stirred at room temperature for 18 hours. The viscous solution is precipitated in 3000 mL of deionized water. The polymer is collected by filtration, washed with deionized water, and then washed with a 50 / 50 water / methanol mixture. The polymer is dried under vacuum at 60°C for 24 hours to obtain a poly-o-hydroxyamide precursor.

[0187] Synthesis Example 4: Synthesis of an ethyl vinyl ether-protected poly-o-hydroxyamide precursor

[0188] 7.5 g of the poly-o-hydroxyamide precursor obtained from the reaction of Synthesis Example 1 and 100 g of PGMEA are added to a 250 mL three-necked flask equipped with a nitrogen inlet and a magnetic stirrer. After the polymer is dissolved, the solution is distilled to remove water and the additional amount of PGMEA. After cooling the solution to 25°C, 3.0 g of ethyl vinyl ether is added. After stirring for 10 minutes, the reaction mixture is cooled to 0 to 5°C using an ice bath, and then 0.15 g of p-toluenesulfonic acid is slowly added. Then, the reaction temperature is raised to room temperature. After stirring at room temperature for 2 hours, 0.3 g of triethylamine is added to 6 g of PGMEA to quench the reaction. The reaction mixture is precipitated in 1200 mL of hexane. The polymer is collected by filtration and washed twice with hexane. The polymer is dried in a vacuum oven at 60°C for 24 hours. The protection of phenolic hydroxyl groups is confirmed by 1H-NMR. Approximately 65% ​​of the hydroxyl groups of the poly-o-hydroxyamide precursor are protected by 1-ethoxy ether.

[0189] Synthesis Example 5: Synthesis of an ethyl vinyl ether-protected poly-o-hydroxyamide precursor

[0190] 30 g of the poly-o-hydroxyamide precursor obtained from the reaction of Synthesis Example 1 and 400 g of PGMEA are added to a 1000 mL three-necked flask equipped with a nitrogen inlet and a magnetic stirrer. After the polymer is dissolved, the solution is distilled to remove water and the additional amount of PGMEA. After cooling the solution to 25°C, 12.0 g of ethyl vinyl ether is added. After stirring for 10 minutes, the reaction mixture is cooled to 0 to 5°C using an ice bath, and then 2 g of a 1% p-toluenesulfonic acid solution in PGMEA is slowly added. Then, the reaction temperature is raised to room temperature. After stirring at room temperature for 2 hours, 1.0 g of 1% triethylamine in PGMEA is added to quench the reaction. The reaction mixture is treated with washed CR-20 resin (DIAION™ CR20 is a polyamine-type chelate resin available from Mitsubishi Chemical Corp) for 6 hours, and then filtered to remove the solid resin.

[0191] Dilute the reaction solution with 100 g of hexane and wash with water for 1 hour. After stopping stirring, let the mixture stand for 3 hours. When phase separation occurs, remove the aqueous phase. Wash the organic phase twice with water.

[0192] The solution is concentrated by vacuum distillation (distillation temperature of about 30°C to 40°C, distillation pressure of 100 Torr to about 1 Torr) to obtain a polymer solution containing a poly-o-hydroxyamide precursor protected by ethyl vinyl ether. The solid content % of the final polymer is 40%.

[0193] Photosensitive Composition Example 1

[0194] A positively active photosensitive composition was prepared by mixing 100 parts by weight of a polymer solution prepared by the method described in Synthesis Example 4, 3 parts by weight of triethoxysilylpropyl ethoxycarbamate, 0.102 parts by weight of 1,8-diazabicyclo[5.4.0]undek-7-ene (DBU), 5 parts by weight of (5-propylsulfonylmino-5H-thiophene-2-ylidene)-2-methylphenyl-acetonitrile, 10 parts by weight of tripropylene glycol, 0.1 parts by weight of 5-methyl-1H-benzotriazole, 0.1 parts by weight of Troysol S366 (available from Troy Corp. Inc.) in 0.5% GBL, 20 parts by weight of additional PGMEA, and 211 parts by weight of GBL, and filtered with a 0.2 micrometer Teflon filter.

[0195] Then, a silicon wafer is coated with the photosensitive composition and baked on a hot plate at 125°C for 3 minutes to produce a film thickness of 9 micrometers. The film is exposed using an i-line stepper equipped with a patterned exposure array. Film segments on the wafer are exposed at various levels of exposure energy using a Canon 4000 IE i-line stepper. The wafer is exposed at 130°C for 90 seconds and then baked. The wafer is developed with a 2.38 percent TMAH aqueous solution using two 30-second puddle development steps, and the used developer is removed using a spin step between developer applications. The developed film is rinsed with deionized water and dried by rotating at 5000 rpm for 10 seconds to provide a relief pattern. No loss of unexposed film thickness is observed. Each 200 mJ / cm² 2 and 175 mJ / cm² 2 2 micrometer and 8 micrometer features are resolved at the exposure energy.

[0196] Photosensitive Composition Example 2

[0197] A positively active photosensitive composition is prepared by mixing 100 parts by weight of a polymer solution prepared by the method described in Synthesis Example 4, 7 parts by weight of (3-glycidoxypropyl)trimethoxysilane, 0.59 parts by weight of N-phenyldiethanolamine, 5 parts by weight of (5-propylsulfonylmino-5H-thiophene-2-ylidene)-2-methylphenyl-acetonitrile, 10 parts by weight of propylene carbonate, 10 parts by weight of tripropylene glycol, 0.1 parts by weight of 1-tetrazole, 0.1 parts by weight of Troysol S366 (available from Troy Corp. Inc.) in 0.5% GBL, 24 parts by weight of PGMEA, and 207 parts by weight of GBL, and filtered through a 0.2 micrometer Teflon filter.

[0198] Then, a silicon wafer is coated with the photosensitive composition and baked on a hot plate at 115°C for 3 minutes to produce a film thickness of 8.64 micrometers. The film is exposed using an i-line stepper with a patterned exposure array. Film segments on the wafer are exposed at various levels of exposure energy using a Canon 4000 IE i-line stepper. The wafer is exposed at 135°C for 90 seconds and then baked. The wafer is developed in a 2.38 percent aqueous TMAH solution using a single 60-second standing puddle development step. The developed film is rinsed with deionized water and dried by rotating at 5000 rpm for 10 seconds to provide a relief pattern. The film thickness after development is 8.49 micrometers. The unexposed film thickness loss is 1.70 percent. 335 mJ / cm² 2 At the exposure energy of 8 micrometers, features are resolved. When these features were carefully examined with SEM, no chemical undercuts were observed.

[0199] Photosensitive composition Example 3

[0200] A positively acting photosensitive composition was prepared by mixing 100 parts by weight of a polymer solution prepared by the method described in Synthesis Example 4, 3 parts by weight of triethoxysilylpropyl ethoxycarbamate, 0.217 parts by weight of 1,8-diazabicyclo[5.4.0]undek-7-ene (DBU), 5 parts by weight of the additive CLR-19-MF available from Honshu Chemicals, 5 parts by weight of (5-propylsulfonylmino-5H-thiophene-2-ylidene)-2-methylphenyl-acetonitrile, 10 parts by weight of tripropylene glycol, 0.1 parts by weight of 5-methyl-1H-benzotriazole, 0.1 parts by weight of Troysol S366 (available from Troy Corp. Inc.) in 0.5% GBL, 26 parts by weight of additional PGMEA, and 205 parts by weight of GBL, and filtered through a 0.2 micrometer Teflon filter Filters.

[0201] Photosensitive formulation 3 is spin-coated onto a silicon wafer. The coated wafer is baked at 120°C for 4 minutes. The thickness of the resulting film is approximately 10.3 µm. Then, the coated silicon wafer is subjected to broadband radiation measured with a 400 nm probe at 5.5 MW / cm² 2 Exposed pattern-wise at an intensity of 300 mJ / cm² for 54.5 seconds. 2 Exposure energy is obtained. The wafer is baked at 120°C for 180 seconds, and then developed using multiple immersion development in 0.262 N aqueous TMAH. The first immersion is for 100 seconds, the second immersion is for 250 seconds, and the wafer is rinsed with deionized water between and after the development steps. After development is complete, the thickness of the remaining film is 9.6 microns. 200 micrometer vias (square holes) are resolved.

[0202] Photosensitive composition Example 4

[0203] 100 parts by weight of a polymer solution prepared by the method described in Synthesis Example 4, 3 parts by weight of (3-glycidoxypropyl)trimethoxysilane, and 0.08 parts by weight of AM 3662 2-{2-[2-(2,6-dimethoxyphenoxy)ethoxy]ethoxy}- N,N- A positively active photosensitive composition is prepared by mixing bis(2-methoxyethyl)ethanolamine, 4 parts by weight of TPG (tripropylene glycol), 4.4 parts by weight of (5-propylsulfonylmino-5H-thiophene-2-ylidene)-2-methylphenyl-acetonitrile, 4.4 parts by weight of propylene carbonate, 26 parts by weight of additional PGMEA, and 205 parts by weight of GBL, and filtered through a 0.2 micrometer Teflon filter.

[0204] Photosensitive formulation 4 is spin-coated onto a silicon wafer. The coated wafer is baked at 120°C for 4 minutes. The thickness of the resulting film is approximately 10.3 µm. Then, the coated silicon wafer is subjected to broadband radiation measured with a 400 nm probe at 5.5 MW / cm² 2 Exposed in a patterned manner at an intensity of 300 mJ / cm² for 54.5 seconds. 2 Exposure energy is obtained. The wafer is baked at 120°C for 180 seconds, and then developed using multiple immersion development in 0.262 N aqueous TMAH. The first immersion is for 100 seconds, the second immersion is for 250 seconds, and the wafer is rinsed with deionized water between and after the development steps. After development is complete, the thickness of the remaining film is 9.6 microns. 200 micrometer vias (square holes) are resolved.

[0205] Photosensitive composition Example 5

[0206] A positively active photosensitive composition is prepared by mixing 100 parts by weight of a polymer solution prepared by the method described in Synthesis Example 4, 3 parts by weight of (3-glycidoxypropyl)trimethoxysilane, 0.1 parts by weight of N-phenyldiethanolamine, 4 parts by weight of TPG (tripropylene glycol), 4.4 parts by weight of (5-propylsulfonylmino-5H-thiophene-2-ylidene)-2-methylphenylacetonitrile, 4.4 parts by weight of propylene carbonate, 0.1 parts by weight of 1-tetrazole, 0.1 parts by weight of Troysol S366 (available from Troy Corp. Inc.) in 0.5% GBL, 26 parts by weight of additional PGMEA, and 205 parts by weight of GBL, and filtered through a 0.2 micrometer Teflon filter.

[0207] Photosensitive agent 5 is spin-coated onto a silicon wafer. The coated wafer is baked at 120°C for 4 minutes. The thickness of the resulting film is approximately 10.3 µm. Then, the coated silicon wafer is subjected to broadband radiation measured with a 400 nm probe at 5.5 MW / cm² 2 Exposed in a patterned manner at an intensity of 300 mJ / cm² for 54.5 seconds. 2 Exposure energy is obtained. The wafer is baked at 120°C for 180 seconds, and then developed using multiple immersion development in 0.262 N aqueous TMAH. The first immersion is for 100 seconds, the second immersion is for 250 seconds, and the wafer is rinsed with deionized water between and after the development steps. After development is complete, the thickness of the remaining film is 9.6 microns. 200 micrometer vias (square holes) are resolved.

[0208] Adhesion test

[0209] The coated wafer is baked at 120°C for 3 minutes. The thickness of the resulting film is 7 to 8 micrometers. Then, it is exposed in a patterned manner for 108.2 seconds using broadband mercury lamp light with a Karl Suss MA-56 broadband exposure system (the lamp output at 400 nm during the exposure time is 1000 mJ / cm²). 2 In this way, a 10×10 grid consisting of 2 mm squares is created. The wafer is then baked at 120°C for 2 minutes and developed using puddle development (2 puddles, 25 seconds each) in a 0.262 N aqueous solution of tetramethylammonium hydroxide. The patterned film is cured at 350°C for 1 hour under an N2 atmosphere. The wafer is then placed in a pressure cooker pot and exposed to saturated steam at 121°C for 100 hours. Subsequently, the adhesion of the film to the wafer is tested using a tape peel test with 3M Tape #720 as described in ASTM D-3359-83. Since the squares of the grid did not peel off, the formulation passes the test. Even after 1,000 hours of testing, both films show no loss of adhesion.

[0210] Although the present invention has been described in detail with reference to specific embodiments thereof, modifications and variations will be understood to be within the spirit and scope of what is described and claimed.

Claims

Claim 1 In a polymer comprising poly-o-hydroxyamide represented by the following structure (2), (2) R in the above formula 1 , R 2 , R 3 , R 4 and R 5 Each is independently a hydrogen atom, a substituted or unsubstituted C1-C 12 Alkyl, partially halogen-substituted or completely halogen-substituted C1-C 12 Alkyl, substituted or unsubstituted C4-C 18 Cycloalkyl, substituted or unsubstituted C6-C 22 Aryl or substituted or unsubstituted C5-C 22 It is heteroaryl; R 11 and R 12 Each is independently a hydrogen atom, a linear or branched C1-C4 alkyl group, a partially or completely halogen-substituted C1-C4 alkyl group, or a C5-C 12 Cycloalkyl group, C6-C 18 Aryl group, C5-C 18 It is a heteroaryl group, a C1-C4 alkoxy group, or a halogen atom; Ar1 ​​and Ar2 are each independently a divalent aromatic group, an aliphatic group, a heterocyclic group, or a mixture thereof; Ar 11 Department A 12 A polymer comprising poly-o-hydroxyamide, wherein each is independently a divalent aromatic group, an aliphatic group, a heterocyclic group, or a siloxane group; E is a terminal 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; A is an acid labile group selected from acetals, ketals, carbonates, ethers, silyl ethers, t-butyl ester-containing portions, and mixtures thereof; p2 is any positive number up to about 0.5, and p1 is any value from about 0.5 to about 1, provided that (p1+p2) = 1. Claim 2 A positive photosensitive composition comprising (a) a polymer according to claim 1, (b) a photoacid generator, (c) a solvent, and optionally a photosensitizer. Claim 3 A positive photosensitive composition, wherein the monovalent acid unstable group A is selected from the group consisting of acetal, ketal, carbonate, ether, silyl ether, a t-butyl ester group-containing portion, and mixtures thereof. Claim 4 In paragraph 3, the photo-generating agent is a positive photosensitive composition selected from the group consisting of triazine compounds, sulfonates, disulfones, onium salts, and mixtures thereof. Claim 5 A positive photosensitive composition according to claim 4, wherein the photogenerator is an onium salt selected from the group consisting of iodonium salts, sulfonium salts, phosphonium salts, diazonium salts, sulfoxonium salts, and mixtures thereof. Claim 6 A positive photosensitive composition according to claim 2, further comprising at least one polyhydroxy compound having at least two OH groups as a plasticizer, wherein the boiling point is higher than the boiling point of the solvent of the positive working photosensitive poly-o-hydroxyamide precursor composition. Claim 7 A positive photosensitive composition according to paragraph 2, further comprising at least one adhesion promoter. Claim 8 A positive photosensitive composition according to claim 2, further comprising at least one amino or phenolic crosslinking agent. Claim 9 A positive photosensitive composition according to claim 2, further comprising a basic compound selected from the group consisting of tertiary amines having alkyl and / or aromatic groups, sterically hindered secondary amines, non-aromatic cyclic amines, and quaternary ammonium hydroxide. Claim 10 A positive photosensitive composition according to paragraph 2, further comprising at least one component selected from the group consisting of at least one photobase generator, at least one corrosion inhibitor, at least one surfactant, at least one filler, at least one pigment, and at least one dye. Claim 11 A positive photosensitive composition according to paragraph 2, wherein at least one polymer is present in an amount of about 0.1 weight% to about 55 weight% based on the solid weight of the composition. Claim 12 A method for producing a heat-resistant relief image comprising: a) coating a heat-resistant positive photosensitive composition of any one of claims 2 to 11 onto a substrate; b) exposing the coated substrate to actinic radiation; c) baking the coated substrate at a high temperature after exposure; d) developing the coated substrate with an aqueous developer to form a developed substrate; and e) baking the developed substrate at a high temperature to convert a poly-o-hydroxyamide precursor into polybenzoxazole. Claim 13 A method for producing a heat-resistant relief image, wherein the chemical line is selected from the group consisting of X-rays, electron beams, ultraviolet rays, and visible light. Claim 14 In claim 13, a method for producing a heat-resistant relief image, wherein the chemical line has wavelengths of 436 nm and 365 nm. Claim 15 A method for producing a heat-resistant relief image according to claim 12, wherein the aqueous developer is a solution selected from the group consisting of alkali, primary amine, secondary amine, tertiary amine, alcohol amine, quaternary ammonium salt, and mixtures thereof. Claim 16 A method for producing a heat-resistant relief image according to claim 15, wherein the alkaline aqueous developer is selected from the group consisting of sodium carbonate, potassium carbonate, potassium hydroxide and ammonium hydroxide. Claim 17 An article formed by the method of claim 16, wherein the article is a semiconductor device, a flexible film for electronic devices, a wire isolation, a wire coating, a wire enamel, or an inked substrate. Claim 18 In paragraph 17, the semiconductor device is an article that is an integrated circuit, a light-emitting diode, a solar cell, or a transistor. Claim 19 In paragraph 1, Ar1 and Ar2 each independently comprise a component selected from the group consisting of the following: In the above formula, 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 - and, where X3 is unsubstituted or substituted phenyl, diphenylsulfone, isopropylidene diphenyl, hexafluoroisopropylidene diphenyl; Z is H or a C1-C6 alkyl group; m is an integer from 1 to 6; and Ra is a hydrogen atom, an alkoxy group, a fluoroalkoxy group, a cycloalkyl group, a cycloalkoxy group, a cycloalkylsulfonyl group, an aryloxy group, an alkylaryloxy group, an arylsulfonyl group, or an alkylarylsulfonyl group, a polymer comprising a poly-o-hydroxyamide. Claim 20 In paragraph 1, Ar 11 ... comprises a component selected from the group consisting of the following: In the above formula, 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 - and, where X4 is an unsubstituted or substituted phenyl, diphenyl sulfone, isopropylidene diphenyl, hexafluoroisopropylidene diphenyl; Z is an H or C1-C6 alkyl group; and m is an integer from 1 to 6, a polymer comprising poly-o-hydroxyamide. Claim 21 In the polybenzoxazole obtained by curing the poly-o-hydroxyamide of claim 1, the polybenzoxazole has the following structure: In the above equation, R 1 , R 2 , R 3 , R 4 and R 5 Each is independently a hydrogen atom, a substituted or unsubstituted C1-C 12 Alkyl, partially halogen-substituted or completely halogen-substituted C1-C 12 Alkyl, substituted or unsubstituted C4-C 18 Cycloalkyl, substituted or unsubstituted C6-C 22 Aryl or substituted or unsubstituted C5-C 22 It is heteroaryl; R 11 and R 12 Each is independently a hydrogen atom, a linear or branched C1-C4 alkyl group, a partially or completely halogen-substituted C1-C4 alkyl group, or a C5-C 12 Cycloalkyl group, C6-C 18 Aryl group, C5-C 18 It is a heteroaryl group, a C1-C4 alkoxy group, or a halogen atom; Ar1 ​​and Ar2 are each independently a divalent aromatic group, an aliphatic group, a heterocyclic group, or a mixture thereof; Ar 11 Department A 12 Polybenzoxazole, wherein each is independently a divalent aromatic group, an aliphatic group or a heterocyclic group or a siloxane group; E is a terminal 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. Claim 22 In paragraph 2, the composition is a positive photosensitive composition that substantially does not contain fluorine. Claim 23 A positive photosensitive composition comprising at least one polymer of claim 1, at least one photogenerator, at least one basic compound, at least one photobase generator, optionally at least one selected from a photosensitive agent, an adhesion promoter, a surfactant, a solvent, a corrosion inhibitor, a plasticizer, and an additive, wherein each component of the composition substantially does not contain fluorine.

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