Dielectric film-forming composition

Abstract

The present disclosure pertains to a dielectric film-forming composition comprising: (a) at least one resin selected from the group consisting of: i) a fully imidized polyimide polymer; ii) a polyamic acid ester; iii) a cyclized polydiene resin; and iv) a mixture of a cyclized polydiene resin and a cyanate ester compound; and (b) at least one additive selected from the group consisting of: i) a polybenzoxazole (PBO) precursor; ii) a PBO particle; iii) a mixture of PBO and silica particles; and iv) a PBO resin containing at least two reactive functional groups.

Description

Cross-references to related applications

[0001] This application claims priority to U.S. Provisional Application Serial No. 63 / 533,731, filed August 21, 2023, the contents of which are incorporated herein by reference in their entirety. Background Technology

[0002] Dielectric materials with low dielectric constant (Dk) and low dielectric loss tangent (Df) can reduce transmission loss in materials used in high-frequency bands. The purpose of this disclosure is to provide dielectric material compositions suitable for suppressing transmission loss of electrical signals in next-generation high-frequency (10 GHz or higher) applications. Summary of the Invention

[0003] In one aspect, the present disclosure is characterized by a dielectric film forming composition comprising: (a) at least one resin selected from the group consisting of: i) a fully imidized polyimide polymer; ii) a polyamic acid ester; iii) a cyclized polydiene resin; and iv) a mixture of a cyclized polydiene resin and a cyanate ester compound; and (b) at least one additive selected from the group consisting of: i) a polybenzoxazole (PBO) precursor; ii) PBO particles; iii) a mixture of PBO and silica particles; and iv) a PBO resin containing at least two reactive functional groups.

[0004] In another aspect, this disclosure is characterized by a method for preparing a dielectric film, the method comprising: a) coating a substrate with the dielectric film forming composition described herein to form a film; and b) optionally baking the film at a temperature of about 50°C to about 150°C for about 20 seconds to about 240 seconds.

[0005] In another aspect, this disclosure features a method for preparing a dry film, the method comprising: a) coating a carrier substrate with a dielectric film forming composition described herein to form a coated composition; b) drying the coated composition to form a dielectric film; and c) optionally coating a protective layer onto the dielectric film.

[0006] In another aspect, the present disclosure is characterized by a dielectric film comprising: (a) at least one resin selected from the group consisting of: i) a fully imidized polyimide polymer; ii) a polyamic acid ester; iii) a cyclized polydiene resin; and iv) a mixture of a cyclized polydiene resin and a cyanate ester compound; and (b) at least one additive selected from the group consisting of: i) a polybenzoxazole (PBO) precursor; ii) PBO particles; iii) a mixture of PBO and silica particles; and iv) a PBO polymer containing at least two reactive functional groups. Detailed Implementation

[0007] Generally, this disclosure relates to dielectric film forming compositions, related methods, dry films, and dielectric films. In some embodiments, the dielectric film forming compositions described herein include (a) at least one resin and (b) at least one additive (e.g., an additive that enhances dielectric properties). In some embodiments, the dielectric film forming compositions described herein may be photosensitive and / or thermosetting.

[0008] In some embodiments, the dielectric film forming compositions described herein include at least one (e.g., two, three, or four) additives. In some embodiments, the additives are selected from the group consisting of: i) polybenzoxazole (PBO) precursors; ii) PBO particles; iii) mixtures of PBO and silica particles; and iv) PBO resins containing at least two reactive functional groups. Without wishing to be bound by theory, it is believed that including additives in the dielectric film forming compositions described herein can improve their electrical properties, such as reducing Df and / or Dk.

[0009] In some embodiments, the additive may include a curable PBO precursor (e.g., a photosensitive PBO precursor), such as a chemically amplified PBO precursor. The alkaline aqueous solution solubility of the PBO precursor is reduced by protecting the aromatic hydroxyl groups in the PBO precursor using acid-insecure groups. The recovery of the polymer's alkaline solubility is achieved by the action of the acid generated by the photolysis of the photoacid generator (PAG). The protecting group may be any suitable acid-insecure group, such as acetals, ketals, carbonates, ethers, silyl ethers, tert-butyl ester-containing moieties, and mixtures thereof. Using this concept, a positive photosensitive resin composition comprising a PBO precursor having acid-insecure functional groups, a photoacid generator, and a solvent can be prepared. After photolithography, the patterned layer can be transformed into a heat-resistant polybenzoxazole coating by applying additional heat.

[0010] In some embodiments, the PBO precursor described herein may include acid-labile functional groups and may have the following structure (I): (I), Where k1 is an integer of 0, 1, or 2, k2 is an integer of 0 or 1, and the sum of k1 and k2 is 0 or 2; Ar1 ​​is a tetravalent aromatic group, aliphatic group, or heterocyclic group, or a mixture of a tetravalent aromatic group, aliphatic group, or heterocyclic group and a divalent aromatic group, aliphatic group, or heterocyclic group, wherein the fraction of divalent groups in Ar1 is 0 to 60 mol% and the sum of tetravalent and divalent groups in Ar1 is 100 mol%; Ar2 is a divalent aromatic group, aliphatic group, heterocyclic group, or siloxane group; D is a monovalent acid unstable group, and the combination of it with the oxygen atom attached thereto is selected from the group consisting of: acetal, ketal, carbonate, ether, part containing tert-butyl ester group and mixture thereof; and n is an integer from 20 to 200.

[0011] In some embodiments, Ar1 includes the following portions: , , , , , , and , Where X1 is -O-, -S-, -C(CF3)2-, -C(CH3)2-, -CH2-, -SO2-, -NHCO-, -C(O)-, -C(O)-C(O)-, -C(O)O-, or -(CH2). m -Si(Z)2-O-Si(Z)2-(CH2) m -, Z is H or C1-C6 alkyl and m is an integer from 1 to 6.

[0012] In some embodiments, Ar2 includes the following portions: , , , , , , , , , , and , Where X2 is -C(O)-C(O)-, -C(O)O-, or -(CH2). p -Si(Z)2-O-Si(Z)2-(CH2) p - Z is H or C1-C6 alkyl and p is an integer from 1 to 6. In some embodiments, the PBO precursor may contain one or more different Ar1 and Ar2 groups.

[0013] In some embodiments, D is any suitable monovalent acid unstable group, such as acetal, ketal, carbonate, ether, silyl ether, tert-butyl ester-containing moiety, or mixtures thereof, including but not limited to the moiety of the following: , , , , , , and .

[0014] In embodiments, when the dielectric film forming composition described herein includes a protected PBO precursor with acid-insecure functional groups, the composition may also include a photoacid generator and a solvent. Alternatively, the composition may contain photosensitizers, adhesion promoters, leveling agents, or other additives. After exposure, the photoacid catalyzes the deblocking of the protected PBO precursor and converts it into an alkaline aqueous solution-soluble PBO precursor, as shown in reaction (1): Reaction (1) .

[0015] Generally, any suitable photoacid generating compound can be used to remove acid-instable functional groups. For example, suitable photoacid generating compounds include triazine compounds, sulfonates, disulfones, onium salts, and mixtures thereof. Examples of suitable onium salts include monazonium, sulfonium, phosphonium, diazonium, sulfoxonium, and mixtures thereof. In some embodiments, the photoacid generating agent includes those suitable for use in g-line, i-line, 248 nm, and broadband lithography.

[0016] The PBO precursor with acid-instable functional groups shown in formula (A) can be derived from the PBO precursor and the precursor with formula R. 1 =CH-OR 2 The reaction of vinyl ether in the presence of an acid catalyst, wherein R 1 The preferred form is (a) a straight-chain, branched, or cyclic alkylene group having 1 to 10 carbon atoms, (b) a straight-chain, branched, or cyclic haloalkylene group having 1 to 10 carbon atoms, or (c) an arylalkylene group. 2 The precursor is a straight-chain, branched, cyclic alkyl, aralkyl, or a straight-chain or branched alkyl group containing cycloalkyl, substituted cycloalkyl, aryl, or substituted aryl groups, preferably having 1 to 10 carbon atoms. Another suitable method for preparing PBO precursors with acid-unstable functional groups is by reacting the PBO precursor with di-tert-butyl dicarbonate in the presence of a base. PBO precursors with acid-unstable functional groups can also be synthesized by reacting the PBO precursor, an alcohol, and tert-butyl vinyl ether in the presence of an acid.

[0017] In some embodiments, the PBO precursor described herein may not include acid-labile functional groups and may have the structure (II) shown below: (II), Ar1 is a tetravalent aromatic group, aliphatic group, or heterocyclic group, or a mixture of a tetravalent aromatic group, aliphatic group, or heterocyclic group and a divalent aromatic group, aliphatic group, or heterocyclic group, wherein the fraction of divalent groups in Ar1 is 0 to 60 mol%, and the total fraction of tetravalent and divalent groups in Ar1 is 100 mol%; Ar2 It is a divalent aromatic group, aliphatic group, heterocyclic group, siloxane group or a mixture thereof; and n is an integer from 20 to 200. In these embodiments, the PBO precursor may be a non-photosensitive PBO precursor.

[0018] Acetal-protected PBO precursors can be prepared by an acid-catalyzed addition reaction of a vinyl ether with a PBO precursor. Any suitable acid catalyst can be used for the reaction. Examples of suitable acid catalysts include hydrochloric acid, p-toluenesulfonic acid, and pyridium-p-toluene sulfonate. The acid catalyst can be added in amounts ranging from about 0.001 wt% to about 3.0 wt%. Several vinyl ethers with a range of activation energies for acid-induced deprotection can be used in this reaction. In some embodiments, the protected PBO precursor can be prepared using an acid-catalyzed reaction comprising a PBO precursor, tert-butyl vinyl ether, and an alkyl alcohol, alkylene alcohol, cycloalkyl alcohol, or aralkyl alcohol.

[0019] The typical synthetic reaction mechanism for generating acetal-protected PBO precursors is shown in reaction (2): Where k1, k2, n, R 1 and R 2 As previously defined, and D as previously defined but excluding tert-butoxycarbonyl, ethers, silyl ethers, and carbonates. In some embodiments, R 2 It can be tert-butyl, isobutyl, ethyl, cyclohexyl, ethylcyclohexyl or phenylethyl.

[0020] In some embodiments, the PBO precursor can be prepared by reacting one or more aromatic diaminodihydroxy compounds, or any one or more aromatic or aliphatic diamines, with one or more aromatic or aliphatic acids or acid halides. For example, the diaminodihydroxy compound may be a portion of the structure (I) described herein. Or part of structure (II) described herein Compounds. Examples of suitable acids or acid halides include aromatic or aliphatic dicarboxylic acids and dicarboxylic acid chlorides. For example, the acid or acid halide may be a part of the structure (I) or (II) described herein. The acid or acid halide. The synthesized PBO precursor can be a homopolymer or copolymer.

[0021] Other examples of PBO precursors, PBO polymers, and reagents for forming PBO precursors and PBO polymers are described, for example, in U.S. Patent Nos. 6,143,467 and 5,883,221, the contents of which are incorporated herein by reference.

[0022] In some embodiments, PBO polymers can be generated by chemical or thermal cyclization of a PBO precursor (e.g., polyhydroxyamide (PHA)), which can be prepared from a diamine (e.g., an aromatic diamine) and a diacid or diacid (e.g., an aromatic, aliphatic diacid or diacid, or a mixture of aromatic and aliphatic diacids or diacids) in various organic solvents. PBO polymers, PBO particles, and PBO polymers containing at least two reactive functional groups (e.g., having a low molecular weight) can be generated after reaction (3) shown below, wherein R... 1 It is an aromatic group, an aliphatic group, or a mixture thereof; Y is an OH group or a halogen atom; X is a divalent group or a single bond; R 2 It is hydrogen or alkyl (e.g., C1-C6 alkyl).

[0023] A single diamine diphenol or a mixture thereof can be used in the above reactions to form the PBO precursor or PBO polymer described herein.

[0024] As shown in reaction (3) above, in some embodiments, the PBO precursor described herein can be cured to form an oxazole ring, thereby forming a PBO polymer. Curing can be performed by baking the PBO precursor at a suitable temperature (e.g., from about 150°C to about 450°C) to convert the PBO precursor into PBO.

[0025] As shown in reaction (3) above, in some embodiments, the PBO precursor described herein can form PBO particles when cured at a relatively high temperature. For example, the PBO precursor can be prepared in particle form and subsequently cured at a relatively high temperature to form PBO particles. In some embodiments, the PBO particles thus formed do not include particles made of other materials and include only the PBO polymer.

[0026] In some embodiments, the PBO precursor described herein may be coated onto inorganic particles (e.g., silica particles). The coated particles may then be cured to form PBO-coated particles. In some embodiments, the PBO precursor described herein may be mixed with inorganic particles (e.g., silica particles). The mixture may then be cured to form a mixture of PBO particles and silica particles.

[0027] As shown in reaction (3) above, in some embodiments, the PBO precursor described herein can react with a capping compound (e.g., a compound containing carbon-carbon double or triple bonds) to form a PBO polymer containing at least two reactive functional groups. Examples of such capping compounds include acrylate (alkyl) ester compounds.

[0028] In some embodiments, the amount of additive may be from at least about 5% by weight (e.g., at least about 10% by weight, at least about 15% by weight, at least about 20% by weight, at least about 25% by weight, at least about 30% by weight, at least about 35% by weight, or at least about 40% by weight) to at most about 50% by weight (e.g., at most about 45% by weight, at most about 40% by weight, at most about 35% by weight, at most about 30% by weight, at most about 25% by weight, at most about 20% by weight, at most about 15% by weight, or at most about 10% by weight) of the dielectric film forming composition described herein.

[0029] In some embodiments, in addition to the additives described above, the dielectric film forming compositions described herein further include at least one (e.g., two, three, or four) resins. In some embodiments, the resins may be selected from the group consisting of: i) fully imidized polyimide polymers; ii) polyamic acid esters; iii) cyclized polydiene resins; and iv) mixtures of cyclized polydiene resins and cyanate ester compounds. In some embodiments, the dielectric film forming compositions described herein may include any combination of polymers i) to iv). As used herein, the term “fully imidized” means that the polyimide polymers of this disclosure are at least about 90% (e.g., at least about 95%, at least about 98%, at least about 99%, or about 100%) imidized. Imidization of the polyimide can be confirmed by observing characteristic absorptions in the infrared spectra at 1770 and 1700 cm⁻¹ at indices attributable to the imide ring structure.

[0030] In some embodiments, at least one fully imidized polyimide described herein is prepared by reacting at least one diamine as a monomer with at least one dianhydride (e.g., at least one tetracarboxylic dianhydride) as another monomer.Examples of diamines include, but are not limited to, p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 3-methyl-1,2-phenylenediamine, 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,2-diaminocyclohexane, 1,4-diaminocyclohexane, 1,3-cyclohexanebis(methylamine), 5-amino-1,3,3-trimethylcyclohexanemethylamine, 2,5-diaminotrifluorotoluene, 3,5-diaminotrifluorotoluene, 1,3-diamino-2,4,5,6-tetrafluorobenzene, 4,4'- -Oxydiphenylamine, 3,4'-Oxydiphenylamine, 3,3'-Oxydiphenylamine, 3,3'-Diaminodiphenyl sulfone, 4,4'-Diaminodiphenyl sulfone, 4,4'-Isopropylidene diphenylamine, 4,4'-Diaminodiphenylmethane, 2,2-bis(4-aminophenyl)propane, 4,4'-Diaminodiphenylpropane, 4,4'-Diaminodiphenylsulfone, 4,4'-Diaminodiphenyl sulfone, 4-Aminophenyl-3-aminobenzoate, 2,2'-Dimethyl-4,4'-Diaminobiphenyl, 3,3'-Dimethyl-4,4'-Diaminobiphenyl, 2,2'-bis(trifluoromethyl)benzidine, 3,3'-bis(trifluoromethyl)benzidine, 2,2-bis[4-( 4-Aminophenoxyphenyl)hexafluoropropane, 2,2-bis(3-amino-4-methylphenyl)hexafluoropropane, 2,2-bis(3-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 1,3-bis-(4-aminophenoxy)benzene, 1,3-bis-(3-aminophenoxy)benzene, 1,4-bis-(4-aminophenoxy)benzene, 1,4-bis-(3-aminophenoxy)benzene, 1-(4-aminophenoxy)-3-(3-aminophenoxy)benzene, 2,2'-bis-(4-phenoxyaniline)isopropylidene, bis(p-β-amino-tert-butylphenyl) ether, p-bis-2-(2-methyl-4-aminopentyl)benzene, p-bis(1,1-dimethyl-5- Aminopentylbenzene, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diaminodiphenyl ketone, 3'-dichlorobenzidine, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 4,4'-[1,3-phenylenebis(1-methyl-ethylene)]bisaniline, 4,4'-[1,4-phenylenebis(1-methyl-ethylene)]bisaniline, 2,2-bis[4-(4-aminophenoxy)phenyl]sulfone, 2,2-bis[4-(3-aminophenoxy)benzene], 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, (1,3'-bis(3-aminophenoxy)benzene and 9H-fluorene-2,6-diamine.

[0031] In some embodiments, at least one diamine comprises a compound selected from the group consisting of diamines of structure (IIIa) and diamines of structure (IIIb): (IIIa) and (IIIb) Where R 1 R 2 R 3 R 4 R 5 R 11 R 12 R 13 and R 14 Each is independently H, a substituted or unsubstituted C1-C6 straight-chain or branched alkyl group or a C5-C7 cycloalkyl group.

[0032] R 1 R 2 R 3 R 4 R 5 R 11 R 12 R 13 and R 14 Examples of substituted or unsubstituted C1-C6 straight-chain or branched alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, and 2-methylhexyl. 1 R 2 R 3 R 4 R 5 R 11 R 12 R 13 and R 14 Examples of C5-C7 cycloalkyl groups include (but are not limited to) cyclopentyl, cyclohexyl, and cycloheptyl.

[0033] Examples of diamines with structures (IIIa) or (IIIb) include (but are not limited to) 1-(4-aminophenyl)-1,3,3-trimethyldihydroindene-5-amine (also known as 4,4'-[1,4-phenylene-bis(1-methylethylene)]bisphenylamine, 1-(4-aminophenyl)-1,3,3-trimethyl-2H-indene-5-amine, 1-(4-aminophenyl)-1,3,3-trimethyl-dihydroindene-5-amine, [1-(4-aminophenyl)-1,3,3-trimethyl-dihydroindene-5-yl]amine and 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-trimethyldihydroindene, 4-amino-6-methyl-1-(3'-amino-4'-methylphenyl)-1,3,3-trimethyldihydroindene, 5,7-diamino-1,1-dimethyldihydroindene, 4,7-diamino-1,1-dimethyldihydroindene, 5,7-diamino-1,1,4-trimethyldihydroindene, 5,7-diamino-1,1,6-trimethyldihydroindene and 5,7-diamino-1,1-dimethyl-4-ethyldihydroindene.

[0034] In some embodiments, at least one diamine comprises (a) a compound selected from the group consisting of diamines of structure (IIIa) and diamines of structure (IIIb), and (b) at least one diamine of structure (IV): (IV), Where R 15 R 16 R 17 and R 18 Each can independently be H, a substituted or unsubstituted C1-C6 straight-chain or branched alkyl group or a C5-C7 cycloalkyl group, subject to the condition R. 15 R 16 R 17 and R 18 At least two of them are not hydrogen.

[0035] R 15 R 16 R 17 and R 18 Examples of substituted or unsubstituted C1-C6 straight-chain or branched alkyl groups include (but are not limited to) methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, and 2-methylhexyl. 15 R 16 R 17 and R 18 Examples of C5-C7 cycloalkyl groups include (but are not limited to) cyclopentyl, cyclohexyl, and cycloheptyl.

[0036] Examples of diamines with structure (IV) include (but are not limited to) 2,3,5,6-tetramethylphenylenediamine, 2,4-diamino-1,3,5-trimethylbenzene, 2,4-diamino-1,3,5-triethylbenzene, 2,4-diamino-3,5-dimethyl-1-ethylbenzene, 2,4-diamino-1,5-dimethyl-3-ethylbenzene, 2,4-diamino-1,3,5-triisopropylbenzene, 2,3,5,6-tetraisopropylphenylenediamine, and 2,4-diamino-1,3,5,6-tetramethylbenzene.

[0037] In some embodiments, the molar percentage of the diamines of structures (IIIa) and (IIIb) in the total amount of diamines (e.g., diamines of structures (IIIa), (IIIb) and (IV) is at least about 10% (e.g., at least about 20%, at least about 25%, at least about 30%, at least about 35%, at least about 40%, at least about 45%, or at least about 50%) to at most about 90% (e.g., at most about 85%, at most about 80%, at most about 75%, at most about 70%, at most about 65%, or at most about 60%).

[0038] In some embodiments, the molar percentage of the diamine of structure (IV) in the total amount of diamines (e.g., diamines of structures (IIIa), (IIIb) and (IV) is at least about 10% (e.g., at least about 20%, at least about 25%, at least about 30%, at least about 35%, at least about 40%, at least about 45% or at least about 50%) to at most about 90% (e.g., at most about 85%, at most about 80%, at most about 75%, at most about 70%, at most about 65% or at most about 60%).

[0039] Generally, in order to form the polyimide polymer described herein, a diamine can be reacted with at least one dianhydride (such as at least one tetracarboxylic dianhydride).

[0040] Examples of tetracarboxylic anhydrides include, but are not limited to, 1-(3',4'-dicarboxyphenyl)-1,3,3-trimethyldihydroindene-5,6-dicarboxylic anhydride, 1-(3',4'-dicarboxyphenyl)-1,3,3-trimethyldihydroindene-6,7-dicarboxylic anhydride, 1-(3',4'-dicarboxyphenyl)-3-methyldihydroindene-5,6-dicarboxylic anhydride, 1-(3', 4'-Dicarboxyphenyl)-3-methyldihydroindene-6,7-dicarboxylic anhydride, benzopyrene dianhydride, benzo-1,2,3,4-tetracarboxylic anhydride, 2,3,5,6-naphthalenetetracarboxylic anhydride, 2,3,6,7-naphthalenetetracarboxylic anhydride, 1,4,5,8-naphthalenetetracarboxylic anhydride, 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic anhydride, 2,7-dichloronaphthalene-1,4,5, 8-Tetracarboxylic dianhydride, 2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, phenanthrene-8,9,10-tetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride, thiophene-2,3,4,5-tetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, butane-1,2,3,4-tetracarboxylic dianhydride Anhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, cyclobutane-1,2,3,4-tetracarboxylic dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride, norbornene-2,3,5,6-tetracarboxylic dianhydride, bicyclo[2.2.2]oct-7-ene-3,4,8,9-tetracarboxylic dianhydride, tetracyclo[4.4.1.0] 2,5 .0 7,10 Undecane-1,2,3,4-Tetracarboxylic dianhydride, 3,3',4,4'-Diphenylketone tetracarboxylic dianhydride, 2,2',3,3'-Diphenylketone tetracarboxylic dianhydride, 2,3,3',4'-Diphenylketone tetracarboxylic dianhydride, 3,3',4,4'-Diphenylsulfone tetracarboxylic dianhydride, 2,2',3,3'-Diphenylsulfone tetracarboxylic dianhydride, 2,3,3',4'-Diphenylsulfone tetracarboxylic dianhydride Anhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 2,2',3,3'-diphenyl ether tetracarboxylic dianhydride, 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride, 2,2-[bis(3,4-dicarboxyphenyl)]hexafluoropropane dianhydride, ethylene glycol bis(dehydrated trimellitate) and 5-(2,5-dioxytetrahydro)-3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride.

[0041] Other fully imidized polyimide polymers are described, for example, in WO 2016 / 172089, U.S. Patent Nos. 10,036,952 and 10,563,014 and U.S. Application Publication No. 2015 / 0219990, the contents of which are incorporated herein by reference.

[0042] In some embodiments, at least one polyamic acid ester described herein may be prepared using methods known in the art by employing the diamine and dianhydride described herein as monomers. In some embodiments, one or more diamines and one or more tetracarboxylic dianhydrides are combined in at least one (e.g., two, three or more) polymerization solvents to form a polyamic acid (PAA) polymer. In some embodiments, the PAA polymer thus formed may be esterified to form a polyamic acid ester, which remains soluble in the polymerization solvent. Examples of suitable polyamic acid esters and their compositions have been described, for example, in U.S. Patent Nos. 6,511,789 and 8,288,656, the contents of which are incorporated herein by reference.

[0043] In some embodiments, the cyclized polydiene resins described herein (e.g., substituted or unsubstituted) may comprise homopolymers of conjugated dienes such as isoprene, butadiene, pentadiene, etc. In other embodiments, the cyclized polydiene resins comprise copolymers of such conjugated dienes with olefins (e.g., ethylene or propylene), styrene, or acrylates. Cyclization of polydienes occurs under the influence of heat, light, ultraviolet light, or nuclear radiation, or in the presence of a cationic donor catalyst (e.g., an inorganic acid, organic acid, or Lewis acid). For example, two adjacent polymer structural units may participate in cis-olefin-catalyzed cyclization, which can produce a monocyclic structure by eliminating a double bond. As cyclization continues, bicyclic or tricyclic structures may be produced in later stages. Gradually, the unsaturation and elasticity of the polydiene decrease due to the continuous cyclization of the cis-double bond, and the toughness of the polydiene increases. In some embodiments, cyclization in polyisoprene may be more efficient than in polybutadiene. By controlling the temperature, catalyst concentration, and / or reaction time, a degree of cyclization of approximately 50% to approximately 95% can be achieved. Examples of this cyclization process have been described, for example, in U.S. Patent Nos. 4,678,841 and 4,248,986 and European Patent No. 0063043, the contents of which are incorporated herein by reference.

[0044] Depending on the specific product application, the solvent used, and the method of coating onto the underlayer substrate, cyclic polydiene resins can have any suitable weight-average molecular weight (Mw). For example, the weight-average molecular weight of cyclic polydiene resins can be at least about 5,000 Daltons (e.g., at least about 25,000 Daltons, at least about 50,000 Daltons, at least about 75,000 Daltons, at least about 100,000 Daltons, at least about 125,000 Daltons, or at least about 150,000 Daltons) and / or at most about 500,000 Daltons (e.g., at most about 400,000 Daltons, at most about 300,000 Daltons, or at most about 200,000 Daltons).

[0045] In some embodiments, the dielectric film forming composition described herein may include a mixture of cyclized polydiene resins. The mixture may include: a) At least one cyclic polydiene resin having a weight-average molecular weight of about 5,000 Daltons to about 20,000 Daltons. b) At least one cyclic polydiene resin having a weight-average molecular weight of about 25,000 Daltons to about 60,000 Daltons; and c) At least one cyclic polydiene resin having a weight-average molecular weight of about 70,000 Daltons to about 200,000 Daltons.

[0046] Without being bound by theory, it is believed that dielectric film forming compositions containing mixtures of cyclized polydiene resins with different molecular weights can produce dielectric films with excellent coating quality and film properties.

[0047] In some embodiments, the double bond content in uncyclized polyisoprene is 14.7 mmol unsaturation / 1 gram of polyisoprene, i.e., the reciprocal of the molecular weight of the isoprene unit (i.e., 68 g / mol). Generally, the double bond content in cyclized polyisoprene decreases with increasing degree of cyclization. In some embodiments, after cyclization, the amount of double bonds or unsaturation in the cyclized polydiene resin (e.g., in xylene) can range from at least about 1 mmol (e.g., at least about 2 mmol, at least about 3 mmol, at least about 4 mmol, or at least about 5 mmol) to at most about 12 mmol (e.g., at most about 11 mmol, at least about 10 mmol, at least about 9 mmol, or at least about 8 mmol) / 1 gram of polyisoprene.

[0048] Generally, the increase of bicyclic and tricyclic structures in cyclic polydiene resins increases the glass transition temperature (Tg) of the polydiene resin. In some embodiments, the Tg of the cyclic polydiene resins disclosed herein may be at least about 0°C (e.g., at least about 5°C, at least about 10°C, at least about 15°C, at least about 20°C, or at least about 25°C) and / or at most about 100°C (e.g., at most about 90°C, at most about 80°C, at most about 70°C, at most about 60°C, or at most about 50°C). In some embodiments, two or more cyclic polydiene resins with different properties (e.g., different degrees of unsaturation or Tg) may be used together in the dielectric film forming compositions described herein.

[0049] In some embodiments, the cyclized polydiene resins described herein may include one or more substituted or unsubstituted alkenyl groups. As used herein, possible substituents on substituted groups (e.g., substituted alkyl, alkenyl, alkylene, cycloalkyl, cycloalkylene, aryl, aralkyl, or heteroaryl) or substituted compounds include C1-C10 alkyl groups (e.g., methyl, ethyl, or propyl), halogens (F, Cl, Br, or I), cyano groups, and phenyl groups.

[0050] In some embodiments, the cyclized polydiene resin described herein may be present in an amount from at least about 2% by weight (e.g., at least about 3%, at least about 4%, at least about 5%, at least about 8%, or at least 10% by weight) to at most about 40% by weight (e.g., at most about 35%, at most about 30%, at most about 25%, at most about 20%, or at most about 15% by weight) of the dielectric film forming composition described herein.

[0051] In embodiments of the dielectric film forming composition described herein comprising a cyclic polydiene resin, the composition may further comprise at least one cyanate ester compound as part of the resin containing the cyclic polydiene. In some embodiments, the cyanate ester compound may have structure (V): A-(OC≡N) m (V), Where m is an integer of at least 2 (i.e., m ≥ 2), and A is a divalent organic group containing a substituted or unsubstituted aromatic group (e.g., a cyanate group -OC≡N directly bonded to a substituted or unsubstituted aromatic organic group). In some embodiments, the aromatic group may include aryl and heteroaryl groups. The term "aryl" as used herein refers to a hydrocarbon moiety having one or more aromatic rings. Examples of aryl moieties include phenyl (Ph), phenylene, naphthyl, naphthylene, pyrene, anthracene, and phenanthrene. The term "heteroaryl" as used herein refers to a moiety having one or more aromatic rings containing at least one heteroatom (e.g., N, O, or S). Examples of heteroaryl moieties include furanyl, furinyl, fluorenyl, pyrroleyl, thiopheneyl, oxazolyl, imidazolyl, thiazolyl, pyridinyl, pyrimidinyl, quinazolinyl, quinolinyl, isoquinolinyl, and indoleyl. Examples of suitable cyanate compounds have been described, for example, in U.S. Patents 3,595,900, 4,894,414, and 4,785,034, the contents of which are incorporated herein by reference. In some embodiments, two or more cyanate compounds may be used together in the dielectric film forming compositions described herein.

[0052] In some embodiments, the cyanate compound described herein may be present in an amount from at least about 1% by weight (e.g., at least about 2%, at least about 3%, at least about 4%, or at least about 5% by weight) to at most about 25% by weight (e.g., at most about 20%, at most about 15%, at most about 10%, or at most about 8% by weight) of the dielectric film forming composition described herein.

[0053] In some embodiments, the resin containing polyimide, polyamic acid ester, cyclized polydiene resin and / or cyanate ester compound may be present in an amount of at least about 50% by weight (e.g., at least about 55% by weight, at least about 60% by weight, at least about 65% by weight, at least about 70% by weight, at least about 75% by weight, at least about 80% by weight, at least about 85% by weight or at least about 90% by weight) to at most about 95% by weight (e.g., at most about 90% by weight, at most about 85% by weight, at most about 80% by weight, at most about 75% by weight, at most about 70% by weight, at most about 65% by weight or at most about 60% by weight) of the dielectric film forming composition described herein.

[0054] In some embodiments, the dielectric film forming compositions described herein may optionally include at least one (e.g., two, three, or four) crosslinking agents. In some embodiments, the crosslinking agents described herein may include at least two (e.g., three or four) functional groups capable of reacting with substituted or unsubstituted alkenyl groups on a cyclized polydiene resin to form a crosslinked dielectric film. Examples of crosslinking agents are compounds containing at least two (meth)acrylate groups, at least two olefin groups, at least two cyclic olefin groups, or at least two alkynyl groups. Examples of compounds containing at least two cyclic olefin groups include, but are not limited to, dicyclopentadiene, norbornene, etc. Examples of compounds containing two olefin groups include divinylbenzene, ethylidene norbornene, etc. In some embodiments, compounds containing at least two (meth)acrylate groups include unsubstituted or substituted linear, branched, or cyclic C1-C14 groups. 10Alkyl di(meth)acrylates and unsubstituted or substituted aromatic di(meth)acrylates. Examples of such compounds include, but are not limited to, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, cyclohexanediethanol di(meth)acrylate, tricyclodecanediethanol di(meth)acrylate, 1,4-phenylene di(meth)acrylate, 2,2-bis[4-(2-hydroxy-3-methacryloyloxypropoxy)phenyl]propane, tricyclodecanediethanol di(meth)acrylate, and trimethylolpropane ethoxide tri(meth)acrylate. Other examples of crosslinking agents have been described, for example, in U.S. Patent Nos. 10,036,952, 10,563,014, and U.S. Application Publication No. 2015219990, the contents of which are incorporated herein by reference. In some embodiments, two or more crosslinking agents may be used together in the dielectric film forming compositions described herein.

[0055] In some embodiments, the amount of at least one crosslinking agent may be from at least about 1% by weight (e.g., at least about 2%, at least about 3%, at least about 4%, or at least 5% by weight) to at most about 25% by weight (e.g., at most about 20%, at most about 15%, at most about 10%, or at most about 8% by weight) of the total weight of the dielectric film forming composition described herein. Without being bound by theory, it is believed that the crosslinking agent can induce crosslinking in the dielectric film (e.g., upon exposure to radiation or heat), which contributes to the formation of a solubility contrast before and after exposure. Furthermore, without being bound by theory, it is believed that dielectric film forming compositions containing a relatively large amount of crosslinking agent can produce dielectric films with relatively high Tg.

[0056] In some embodiments, the dielectric film forming compositions described herein may optionally include at least one (e.g., two, three, or four) catalyst (e.g., an initiator). When exposed to heat (thermal initiator) and / or a radiation source (photoinitiator), the catalyst is capable of inducing a crosslinking or polymerization reaction. Specific examples of thermal initiators include, but are not limited to, benzoyl peroxide, dicumyl peroxide, 2,2-azobis(2-methylbutyronitrile), etc. Other examples of thermal initiators have been described, for example, in U.S. Patent No. 10,563,014, the contents of which are incorporated herein by reference. Specific examples of photoinitiators include, but are not limited to, 2-(benzoyloxyimino)-1-[4-(phenylthio)phenyl]-1-octanone (Irgacure OXE-01 from BASF), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl] ethyl ketone 1-(O-acetyl oxime) (Irgacure OXE-2 from BASF), ethoxy(2,4,6-trimethylbenzoyl)phenylphosphine oxide (Lucerin TPO-L from BASF), NCI-831 (ADEKA), NCI-930 (ADEKA), N-1919 (ADEKA), etc. Other examples of photoinitiators have been described, for example, in U.S. Patent Nos. 10,036,952 and 10,563,014 and U.S. Patent Application Nos. 2015 / 0219990 and 2019 / 0018321, the contents of which are incorporated herein by reference.

[0057] In some embodiments, the amount of catalyst is at least about 0.2% by weight (e.g., at least about 0.5% by weight, at least about 0.8% by weight, at least about 1.0% by weight, or at least about 1.5% by weight) and / or at most about 3.0% by weight (e.g., at most about 2.8% by weight, at most about 2.6% by weight, at most about 2.4% by weight, or at most about 2.0% by weight) of the total weight of the dielectric film forming composition described herein.

[0058] In some embodiments, the dielectric film forming compositions described herein may optionally include at least one (e.g., two, three, or four) solvents (e.g., organic solvents).

[0059] Examples of suitable organic solvents include (but are not limited to) alkylene carbonates, such as ethylene carbonate, propylene carbonate, butyl carbonate, and glyceryl carbonate; lactones, such as γ-butyrolactone, ε-caprolactone, γ-caprolactone, and δ-valerolactone; cyclic ketones, such as cyclopentanone and cyclohexanone; straight-chain ketones, such as methyl ethyl ketone (MEK) and methyl isobutyl ketone (MIBK); esters, such as n-butyl acetate; ester alcohols, such as ethyl lactate; ether alcohols, such as tetrahydrofurfuryl alcohol; glycol esters, such as propylene glycol methyl ether acetate; glycol ethers, such as propylene glycol methyl ether (PGME); cyclic ethers, such as tetrahydrofuran (THF); aromatic hydrocarbons, such as toluene, xylene, mesitylene, and tetrahydronaphthalene; and pyrrolidones, such as N-methyl-2-pyrrolidone.

[0060] In some embodiments, the amount of solvent is at least about 40% by weight (e.g., at least about 45% by weight, at least about 50% by weight, at least about 55% by weight, at least about 60% by weight, or at least about 65% by weight) and / or at most about 98% by weight (e.g., at most about 95% by weight, at most about 90% by weight, at most about 85% by weight, at most about 80% by weight, or at most about 75% by weight) of the total weight of the dielectric film forming composition described herein.

[0061] 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 (e.g., an alkoxy-containing silane). Suitable adhesion promoters are described in “Silane Coupling Agent”, Edwin P. Plueddemann, 1982 Plenum Press, New York; and U.S. Patent No. 9,519,216, the contents of which are incorporated herein by reference.

[0062] In some embodiments, the amount of the chosen adhesion promoter is at least about 0.5% by weight (e.g., at least about 0.8% by weight, at least about 1% by weight, or at least about 1.5% by weight) and / or at most about 4% by weight (e.g., at most about 3.5% by weight, at most about 3% by weight, at most about 2.5% by weight, or at most about 2% by weight) of the total weight of the dielectric film forming composition described herein.

[0063] In some embodiments, the dielectric film forming compositions described herein may optionally include at least one (e.g., two, three, or four) fillers. These fillers are generally inorganic or organic in nature. In some embodiments, the fillers are selected from the group consisting of: silica, alumina, titanium dioxide, zirconium oxide, hafnium oxide, CdSe, CdS, CdTe, CuO, zinc oxide, lanthanum oxide, niobium oxide, tungsten oxide, carbon black, graphene, carbon nanotubes (CNTs), etc. Preferably, the inorganic fillers are in the form of particles with an average size of about 0.1 micrometers to 2.0 micrometers. In some embodiments, the fillers are inorganic particles containing ferromagnetic materials. Suitable ferromagnetic materials include elemental metals (such as iron, nickel, and cobalt) or their oxides, sulfides, and hydroxyl oxides, and intermetallic compounds such as awaruite (Ni3Fe), wairaruite (CoFe), and Co. 17 Sm2 and Nd2Fe 14 B. In some embodiments, the organic filler may be selected from the group consisting of: rubber particles, polyimide particles, polyester particles, etc. In some embodiments, the dielectric film forming composition may include a thermally conductive filler selected from the group consisting of: Cu particles, diamond particles, gold particles, etc. In some embodiments, two or more fillers may be used together in the dielectric film forming composition described herein.

[0064] Mechanical milling (MM) is essentially a mixing process achieved through repeated high-intensity plastic deformation. Particle size reduction and the incorporation of particles into a new phase, along with the disruption of long-range order to produce an amorphous phase, are several key objectives of this technique. Without being bound by theory, this technique is believed to improve the dispersion of various fillers, enhance polymer properties, regulate the morphology of polymer blends, and improve compatibility within polymer blends. In some embodiments, mechanical milling methods can be used for the direct solid-state mixing of PBO fillers with other inorganic fillers or PBO-inorganic filler composites to produce filler components with particle sizes ranging from 10 to 500 nm in diameter. In some embodiments, mechanical milling methods in the solution stage of a dielectric film forming composition containing the PBO additives described herein can achieve target particle sizes ranging from 5 to 200 nm in diameter for uniform coating on various substrates, such as PET films, Si, SiO2, SiON, Cu, and Al wafers, and copper-clad laminates (CCLs).

[0065] In some embodiments, the amount of filler (e.g., organic filler) may be at least about 1% by weight (e.g., at least about 2% by weight, at least about 3% by weight, at least about 4% by weight, or at least 5% by weight) and / or at most about 50% by weight (e.g., at most about 40% by weight, at most about 30% by weight, at most about 20% by weight, or at most about 10% by weight) of the total weight of the dielectric film forming composition described herein.

[0066] In some embodiments, this disclosure describes a composition comprising: a) At least one resin selected from the group consisting of: i) fully imidized polyimide polymers; ii) polyamic acid esters; iii) cyclized polydiene resins; and iv) mixtures of cyclized polydiene resins and cyanate ester compounds; b) At least one additive selected from the group consisting of: i) polybenzoxazole (PBO) precursor; ii) PBO particles; iii) a mixture of PBO and silica particles; and iv) a PBO resin containing at least two reactive functional groups. c) At least one crosslinking agent; d) At least one catalyst; e) at least one adhesive aid of choice; and f) At least one solvent of your choice.

[0067] In some embodiments, this disclosure is characterized by a dielectric film (e.g., a cross-linked dielectric film) comprising: (a) at least one resin selected from the group consisting of: i) a fully imidized polyimide polymer; ii) a polyamic acid ester; iii) a cyclized polydiene resin; and iv) a mixture of a cyclized polydiene resin and a cyanate ester compound; and (b) at least one additive selected from the group consisting of: i) a polybenzoxazole (PBO) precursor; ii) PBO particles; iii) a mixture of PBO and silica particles; and iv) a PBO polymer containing at least two reactive functional groups.

[0068] In some embodiments, the dielectric film can be prepared by a method comprising: a) coating a substrate (e.g., a semiconductor substrate, such as a wafer) with the dielectric film forming composition described herein to form a film (e.g., a dielectric film); b) optionally baking the film at a high temperature (e.g., from about 50°C to about 150°C) for a period of time (e.g., from about 20 seconds to about 240 seconds); and c) optionally exposing the film (e.g., floododexposing without the use of a mask, such as a patterned mask) to radiation, heat, or a combination of both. In some embodiments, the dielectric film prepared by the above method (which may use broad exposure without a mask) may be crosslinked but does not include patterned or textured images.

[0069] Coating methods for preparing dielectric films include, but are not limited to, spin coating, spray coating, roll coating, bar coating, rotational coating, slot coating, compression coating, curtain coating, mold coating, wire rod coating, blade coating, and dry film lamination. The semiconductor substrate may have a circular shape, such as a wafer, or may be a plate. In some embodiments, the semiconductor substrate may be a silicon substrate, copper substrate, aluminum substrate, silicon oxide substrate, silicon nitride substrate, glass substrate, organic substrate, copper-clad laminate, or dielectric material substrate.

[0070] The thickness of the dielectric film disclosed herein is not specifically limited. In some embodiments, the dielectric film has the following thicknesses: at least about 1 micrometer (e.g., at least about 2 micrometers, at least about 3 micrometers, at least about 4 micrometers, at least about 5 micrometers, at least about 7 micrometers, at least about 10 micrometers, at least about 15 micrometers, at least about 20 micrometers, at least about 25 micrometers, at least 50 micrometers, or at least 100 micrometers) and / or at most about 5000 micrometers (5 mm) (e.g., at most about 4000 micrometers, at most about 3000 micrometers, at most about 2000 micrometers, at most about 1000 micrometers, at most about 500 micrometers, at most about 400 micrometers, at most about 300 micrometers, or at least 200 micrometers).

[0071] In some embodiments, the dielectric film forming composition of this disclosure is photo-patternable. In such embodiments, a method of preparing a patterned dielectric film includes converting a dielectric film prepared from the dielectric film forming composition into a patterned dielectric film using a photolithography method. In this case, the conversion may include exposing the dielectric film to high-energy radiation (such as electron beams, ultraviolet light, and X-rays) using a patterned mask.

[0072] Following exposure, the dielectric film may optionally be heat-treated to a temperature of at least about 50°C (e.g., at least about 55°C, at least about 60°C, or at least about 65°C) to at most about 100°C (e.g., at most about 95°C, or at most about 90°C, at most about 85°C, at most about 80°C, at most about 75°C, or at most about 70°C) for at least about 60 seconds (e.g., at least about 80 seconds or at least about 100 seconds) to at most about 240 seconds (e.g., at most about 180 seconds, at most about 120 seconds, or at most about 90 seconds). The heat treatment is typically performed using a heating plate or an oven.

[0073] After exposure and / or heat treatment, the dielectric film can be developed using a developer to remove unexposed portions, thereby forming openings or textured images on the substrate. Development can be performed, for example, by immersion or spraying. After development, micropores and fine lines can be created in the dielectric film on the laminated substrate.

[0074] In some embodiments, the dielectric film can be developed using an organic developer. Examples of such developers include, but are not limited to, cyclohexanone, xylene, toluene, tetrahydronaphthalene, γ-butyrolactone (GBL), dimethyl sulfoxide (DMSO), N,N-diethylacetamide, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), 2-heptanone, cyclopentanone (CP), cyclohexanone, n-butyl acetate (nBA), propylene glycol methyl ether acetate (PGMEA), propylene glycol methyl ether (PGME), ethyl lactate (EL), propyl lactate, 3-methyl-3-methoxybutanol, tetrahydronaphthalene, Isophorone, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, triethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, diethyl malonate, ethylene glycol, 1,4:3,6-didesorbitol, isosorbide dimethyl ether, 1,4:3,6-didesorbitol 2,5-diethyl ether (2,5-diethyl isosorbitol), and mixtures thereof. Preferred developers include cyclohexanone, xylene, toluene, and tetrahydronaphthalene. These developers can be used alone or in combination of two or more to optimize the image quality of a particular composition and photolithography method.

[0075] In some embodiments, the dielectric film described herein is not photo-patternable. In this case, patterning can be achieved by mechanical laser drilling or by a two-layer method. Laser drilling typically involves using a fixed laser beam with high power density to melt or vaporize the material of a target substrate or workpiece. In principle, laser drilling is controlled by an energy balance between the irradiation energy of the laser beam and the conductive heat entering the substrate, the energy loss dissipated into the environment, and the energy required for phase transitions in the workpiece. Examples of mechanical laser drilling are described, for example, in U.S. Patent No. 6,353,999, the contents of which are incorporated herein by reference.

[0076] In some embodiments, the dielectric film described herein may have a relatively low loss factor (Df). For example, when measured at 5 GHz after curing, the dielectric film described herein may have a Df of up to about 0.01 (e.g., up to about 0.008, up to about 0.006, up to about 0.005, up to about 0.004, up to about 0.002, or up to about 0.001) and at least about 0.0001.

[0077] In some embodiments, this disclosure features a method for preparing a dry film. In some embodiments, the method includes a) coating a carrier substrate with a dielectric film forming composition described herein to form a coated composition; b) drying the coated composition to form a dielectric film; and c) optionally coating a protective layer onto the dielectric film. In some embodiments, the dry film may include a carrier substrate, a dielectric film, and an optional protective layer.

[0078] In some embodiments, the carrier substrate is a single-layer or multi-layer plastic film, which may include one or more polymers (e.g., polyethylene terephthalate). In some embodiments, the carrier substrate has excellent optical transparency and is substantially transparent to photochemical radiation used to form a textured pattern in the polymer layer. The thickness of the carrier substrate is preferably in the range of at least about 10 micrometers (e.g., at least about 15 micrometers, at least about 20 micrometers, at least about 30 micrometers, at least about 40 micrometers, at least about 50 micrometers, or at least about 60 micrometers) to at most about 150 micrometers (e.g., at most about 140 micrometers, at most about 120 micrometers, at most about 100 micrometers, at most about 90 micrometers, at most about 80 micrometers, or at most about 70 micrometers).

[0079] In some embodiments, the protective layer is a single-layer or multi-layer film, which may include one or more polymers (e.g., polyethylene or polypropylene). Examples of carrier substrates and protective layers have been described, for example, in U.S. Application Publication No. 2016 / 0313642, the contents of which are incorporated herein by reference.

[0080] In some embodiments, the dielectric film of the dry film can be peeled off from the carrier layer as a freestanding dry film. A freestanding dry film is a film that can maintain its physical integrity without the use of any support layer, such as a carrier layer. In some embodiments, the freestanding dielectric dry film is not cross-linked or cured and may include components other than solvents of the dielectric film forming compositions described herein.

[0081] In some embodiments, dielectric films prepared from the dielectric film forming compositions described herein may have relatively low dielectric loss tangents. For example, measured at 10 GHz, the dielectric loss tangent of dielectric films (e.g., crosslinked or uncrosslinked dielectric films) prepared from the dielectric film forming compositions of this disclosure may range from at least about 0.001 (e.g., at least about 0.005, at least about 0.01, or at least about 0.05) to at most about 0.1 (e.g., at most about 0.08, at most about 0.06, at most about 0.05, at most about 0.04, or at most about 0.02). At variable frequencies from 1 GHz to 75 GHz, the dielectric constant (Dk) and loss factor (Df) are measured using a discrete cylindrical resonator according to the method of IPC TM-650 2.5.5.13.

[0082] In some embodiments, this disclosure features a three-dimensional object comprising at least one (e.g., two or three) conductive metal layers and at least one (e.g., two or three) dielectric film (e.g., a cross-linked patterned dielectric film) formed using the dielectric film forming composition of this disclosure. In some embodiments, the three-dimensional object may include dielectric films in at least two stacks (e.g., at least three stacks).

[0083] The following examples are provided to more clearly illustrate the principles and practices of this disclosure. It should be understood that this disclosure is not limited to the examples described.

[0084] Example Synthesis Example 1: Synthesis of PBO Precursor 3.66 g (0.010 mol) of hexafluoro-2,2-bis(3-amino-4-hydroxyphenyl)propane, 1.70 g (0.021 mol) of pyridine, and 15 g of N-methylpyrrolidone (NMP) were added to a 100 mL three-necked round-bottom flask equipped with a mechanical stirrer, nitrogen inlet, and feeding funnel. The solution was stirred at room temperature until it became clear and then cooled in an ice-water bath at 0 to 5 °C. 2.03 g (0.010 mol) of isophthalyl chloride dissolved in 5 g of NMP was added dropwise to this solution. After the addition, the mixture was stirred at room temperature for 18 hours. The viscous solution was allowed to precipitate in 800 mL of deionized water. The polymer was collected by filtration and washed with deionized water, followed by washing with a 50 / 50 water / methanol mixture. The polymer was dried under vacuum at 105 °C for 24 hours to obtain the PBO precursor.

[0085] The yield was almost quantitative, and the intrinsic viscosity of the polymer, measured at 25°C and in NMP at a concentration of 0.5 g / dL, was 0.28 dL / g.

[0086] Synthesis Example 2: Synthesis of PBO Particles Under vacuum conditions at 350°C, a mixture of 5 g of the PBO precursor prepared in Synthesis Example 1 and 5 g of molten silica particles (Accuratus) was cured in a YES oven for 4 hours to form silica particles coated with PBO.

[0087] Example 1: Preparation and coating of dielectric film forming composition 1 The dielectric film forming composition of this example was prepared by mixing cyclopentadiene (SC rubber supplied by Fujifilm Electronic Materials USA, 57.90 g in a 28.5% xylene solution), PBO particles prepared in Synthesis Example 2 (6.6 g), tricyclodecanedimethylethanol diacrylate (6.60 g), 2,2-bis(4-cyanophenyl)propane (8.25 g), dicumyl peroxide (0.50 g), and xylene (1.75 g) using a mechanical mixer with a toothed saw blade to obtain a homogeneous solution. The solution was then filtered using a 10.0-micron PTFE filter to obtain dielectric film forming composition 1.

[0088] In this example, SC rubber is used as a cyclized polydiene, PBO particles are used as a low Df additive, tricyclodecanediethanol diacrylate is used as a reactive functional compound, 2,2-bis(4-cyanophenyl)propane is used as a cyanate compound, dicumyl peroxide is used as a thermal initiator, and xylene is used as a solvent.

[0089] Dielectric film forming composition 1 was applied to a 35-micron-thick PET film using an applicator to form a film. The film was baked at 105°C for 7 minutes using a hot plate to remove most of the solvent. The film was then baked at 160°C under nitrogen for 185 minutes to obtain a stable dielectric film with a thickness of 90 microns. After peeling the dielectric film off the PET film, it was placed on a 25-micron-thick KAPTON film and subsequently baked at 210°C under nitrogen for 1 hour.

[0090] After cooling to room temperature, the dielectric film was removed from the KAPTON film and cut into 3 mm wide films. The thermomechanical properties of the films were analyzed using a TMA 450 (available from TA Instruments, USA). The linear coefficient of thermal expansion (CTE) was measured to be 80 ppm / K over a temperature range of 25°C to 120°C.

[0091] Other aspects, embodiments, and features are within the scope of the following claims.

Claims

1. A dielectric film forming composition comprising: a) At least one resin selected from the group consisting of: i) Fully imidized polyimide polymers; ii) Polyamate; iii) Cyclated polydiene resins; and iv) A mixture of cyclized polydiene resin and cyanate ester compound; and b) At least one additive selected from the group consisting of: i) Polybenzoxazole (PBO) precursor; ii) PBO particles; iii) A mixture of PBO and silica particles; and iv) PBO resin containing at least two reactive functional groups.

2. The composition of claim 1, wherein the at least one resin is about 50% to about 95% by weight of the composition.

3. The composition of claim 1 or 2, wherein the at least one additive is about 5% to about 50% by weight of the composition.

4. The composition according to any one of claims 1 to 3 further comprises at least one crosslinking agent, at least one catalyst, at least one adhesive agent, or at least one solvent.

5. A method for preparing a dielectric film, comprising: a) Coating a dielectric film forming composition as described in any one of claims 1 to 4 onto a substrate to form a film; and b) Selectively bake the film at a temperature of about 50°C to about 150°C for about 20 seconds to about 240 seconds.

6. The method of claim 5, further comprising exposing the membrane to radiation, heat, or a combination thereof without a mask.

7. A method for preparing a dry film, comprising: a) Coating a carrier substrate with the dielectric film forming composition as described in any one of claims 1 to 4 to form the coated composition; b) Dry the coated composition to form a dielectric film; and c) Optionally coat the dielectric film with a protective layer.

8. A dielectric film comprising: (a) At least one resin selected from the group consisting of: i) Fully imidized polyimide polymers; ii) Polyamate; iii) Cyclated polydiene resins; and iv) A mixture of cyclized polydiene resin and cyanate ester compound; and b) At least one additive selected from the group consisting of: i) Polybenzoxazole (PBO) precursor; ii) PBO particles; iii) A mixture of PBO and silica particles; and iv) PBO resin containing at least two reactive functional groups.

9. The dielectric film of claim 8, wherein the dielectric film has a loss factor (Df) of up to 0.01 at 5 GHz after curing.

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