Dielectric film forming composition

Abstract

Cyclized polyisoprene has a low Tg and poor mechanical properties, which hinders its use as a dielectric material in packaging applications. [Solution] This disclosure relates to a dielectric film-forming composition comprising at least one cyclized polydiene resin and one or both of at least one reactive functional compound and at least one catalyst.

Description

[Technical Field]

[0001] This invention relates to a dielectric film forming composition. [Background technology]

[0002] Cross-references to related applications This application claims priority from U.S. Provisional Application No. 63 / 047,560, filed 2 July 2020. The contents of said U.S. Provisional Application are incorporated in their entirety by reference.

[0003] Dielectric materials possessing balanced electrical properties (e.g., dielectric constant Dk less than 2.8 and dielectric loss tangent Df less than 0.007), low thermal expansion coefficient (e.g., less than 100 ppm), low hygroscopicity, and good adhesion to copper are essential for good antenna performance and for delivering outstanding signal transmission to ensure high speed and low latency for 5G communication devices. Various engineering plastics with such properties are being developed for use in emerging 5G networks and high-power devices. However, designing dielectric materials based on balanced electrical, mechanical, and thermal properties remains a significant challenge.

[0004] Various classes of materials, including polytetrafluoroethylene (PTFE), epoxy resins, polycycloolefins, and cyanate ester resins, with or without fillers, have been proposed for applications requiring good insulation. While PTFE and filler-added PTFE are excellent dielectric materials, their poor mechanical properties and lack of film-forming ability on most substrates when using conventional film-forming techniques make them impractical for use in manufacturing environments.

[0005] Filler-added epoxy resins and filler-free epoxy resins are widely used in the PCB industry. However, poor electrical properties due to the presence of a large number of polar groups in the material, and a low glass transition temperature (Tg), limit the use of epoxy resins in high-speed communications.

[0006] Cyanate ester resins produce polytriazines as thermosetting products during high-temperature curing. These possess good heat resistance, hardness, electrical properties, dimensional stability, corrosion resistance, and chemical resistance. Cyanate ester resins are useful as adhesives and as coatings for substrates. However, these materials are not very suitable for dielectric films where good mechanical properties are essential to the performance of the material. Cyanate ester resins have been blended with thermoplastics and elastomers to form blended resins. Disadvantages include the fact that these blends have been found to produce a semi-interpenetrating network rather than a uniform resin. The formation of such a semi-interpenetrating network often results in phase separation between cyanate domains and modifier domains. Furthermore, various elastomer-modified cyanate esters exhibit low Tg and high tackiness, and therefore... It is considered suitable.

[0007] Cyclized polydiene resins, such as cyclized polyisoprene, possess desirable electrical properties. However, cyclized polyisoprene has a low Tg and poor mechanical properties, which hinders its use as a dielectric material in packaging applications.

[0008] Therefore, designing materials with an appropriate balance of electrical, thermal, and mechanical properties remains a challenge. [Overview of the project]

[0009] This disclosure is based on the unexpected discovery that certain dielectric films comprising a cyclized polydiene (e.g., cyclized polyisoprene) and a reactive functional compound, or a cyclized polydiene and a cyanate ester, or both a cyclized polydiene and a cyanate ester and a reactive functional compound, can address the above-mentioned problems. The resulting “hybrid” dielectric films described herein have a higher Tg and a lower coefficient of thermal expansion (CTE) compared to cyclized polydiene without the cyanate ester or reactive functional compound.

[0010] In one aspect, this disclosure is: a) At least one cyclized polydiene resin having a substituted or unsubstituted alkenyl group; b) At least one reactive functional compound having at least two functional groups that can react with the substituted or unsubstituted alkenyl groups on the cyclized polydiene resin; and c) At least one catalyst capable of inducing the reaction between the cyclized polydiene resin and the reactive functional compound. One of its features is a dielectric film forming composition that includes [a specific element].

[0011] In another aspect, this disclosure is a) at least one cyclopolydiene resin; and b) At least one cyanate ester compound having at least two cyanate groups (i.e., having at least two cyanate groups in one molecule) A dielectric film-forming composition containing [a specific element] is one of its features.

[0012] In yet another aspect, this disclosure is a) At least one cyclized polydiene resin having a substituted or unsubstituted alkenyl group; b) At least one reactive functional compound having at least two functional groups that can react with the substituted or unsubstituted alkenyl groups on the cyclized polydiene resin; c) At least one cyanate ester compound having at least two cyanate groups (i.e., having at least two cyanate groups in one molecule); d) At least one catalyst capable of inducing the reaction between the cyclized polydiene resin and the reactive functional compound; and e) Optionally, at least one solvent A dielectric film-forming composition containing [a specific element] is one of its features.

[0013] In yet another aspect, the present disclosure features a process for preparing a dielectric film. The process is: a) Coating a substrate with the dielectric film-forming composition described in the present disclosure to form a film; b) Optionally, baking the film at a temperature of about 50 °C to about 150 °C for about 20 seconds to about 240 seconds; c) Exposing the film to radiation, heat, or a combination thereof without a mask (e.g., a patterned mask) may be included.

[0014] In yet another aspect, the present disclosure features a process for a dry film. The process is a) Coating a carrier substrate with the dielectric film-forming composition described in the present disclosure; b) Drying the coated dielectric film-forming composition to form a dry film; and c) Optionally, applying a protective film to the dry film may be included.

[0015] In yet another aspect, the present disclosure features a process for depositing a conductive metal layer. The process is a) Depositing the dielectric film-forming composition described in the present disclosure on a substrate to form a dielectric film; b) Exposing the dielectric film to radiation, heat, or a combination of radiation and heat; c) Patterning the dielectric film to form a patterned dielectric film having openings; d) Optionally, depositing a seed layer on the patterned dielectric film; e) Depositing a conductive metal layer in at least one opening in the patterned dielectric film; and f) Optionally, repeating steps a) to e) at least once may be included.

[0016] In yet another aspect, the present disclosure features a process for forming a dielectric film on a substrate. The process is a) To provide a substrate that includes a conductive metal wire structure forming a network of lines and interconnects on the substrate; b) Depositing the dielectric film-forming composition described herein onto the substrate to form a dielectric film; c) Exposing the dielectric film to radiation, heat, or a combination of radiation and heat; d) Optionally, repeat steps a) to c) at least once. It may include.

[0017] In yet another embodiment, the Disclosure features a three-dimensional object comprising at least one layer of a conductive metal and a crosslinked dielectric film formed using the dielectric film forming composition of the Disclosure. [Modes for carrying out the invention]

[0018] In some embodiments, this disclosure is, a) At least one (e.g., two, three, or four) cyclopolydiene resin having substituted or unsubstituted alkenyl groups; b) at least one (e.g., two, three, or four) reactive functional compounds having at least two functional groups that can react with the substituted or unsubstituted alkenyl or olefin groups on the cyclized polydiene resin; and c) At least one (e.g., two, three, or four) catalyst capable of inducing the reaction between the cyclized polydiene resin and the reactive functional compound. A dielectric film forming composition (for example, a photosensitive dielectric film forming composition) containing Regarding.

[0019] In some embodiments, the substituted or unsubstituted cyclized polydienes may include homopolymers of conjugated dienes such as isoprene, butadiene, pentadiene, and so on. In other embodiments, the cyclized polydienes may include 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 or nuclear radiation, or in the presence of a cation donor catalyst (e.g., mineral acid, organic acid, or Lewis acid). For example, two adjacent polymer structural units can participate in cis-olefin catalyzed cyclization, which can produce a monocyclic structure by eliminating one double bond. If cyclization continues, a bicyclic or tricyclic structure can be produced in later steps. As cis double bonds are successively cyclized, the unsaturation and elasticity of the polydiene gradually decrease, and the toughness of the polydiene increases. In some embodiments, cyclization may be more efficient in polyisoprene than in polybutadiene. By adjusting the temperature, catalyst concentration, and / or reaction time, a degree of cyclization of approximately 50% to approximately 95% can be achieved. Examples of such cyclization processes 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 by reference in this disclosure.

[0020] In some embodiments, the viscosity of the cyclized polydiene resin in the xylene at a 26% solid content may be about 400 cSt or more (e.g., about 450 cSt or more, about 500 cSt or more, about 550 cSt or more, or about 600 cSt or more) to about 900 cSt or less (e.g., about 850 cSt or less, about 800 cSt or less, about 750 cSt or less, or about 700 cSt or less).

[0021] The cyclized polydiene resin may have any appropriate weight-average molecular weight (Mw) depending on the specific product application, the solvent used, and the method of application to the substrate located below. For example, the cyclized polydiene resin may have a weight-average molecular weight of about 5,000 daltons or more (e.g., 25,000 daltons or more, about 50,000 daltons or more, about 75,000 daltons or more, about 100,000 daltons or more, about 125,000 daltons or more, or about 150,000 daltons or more) and / or about 500,000 daltons or less (e.g., about 400,000 daltons or less, about 300,000 daltons or less, or about 200,000 daltons or less).

[0022] In some embodiments, the dielectric film-forming composition described herein may include a mixture of cyclized polydiene resins. The mixture is a) At least one cyclized polydiene resin having a weight-average molecular weight of approximately 5,000 Daltons to approximately 20,000 Daltons; b) At least one cyclized polydiene resin having a weight-average molecular weight of approximately 25,000 Daltons to approximately 60,000 Daltons; c) At least one cyclized polydiene resin having a weight-average molecular weight of approximately 70,000 Daltons to approximately 200,000 Daltons; It may include.

[0023] While we do not wish to be 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.

[0024] In some embodiments, the double bond content in uncyclized polyisoprene is 14.7 mmol of unsaturated polyisoprene per gram, i.e., per the reciprocal of the molecular weight of isoprene units (i.e., 68 g / mol). Generally, the double bond content in cyclized polyisoprene decreases as the degree of cyclization increases. In some embodiments, the amount of double bonds or unsaturated polyisoprene in cyclized polydiene resin (e.g., in xylene) may range from about 1 mmol or more (e.g., about 2 mmol or more, about 3 mmol or more, about 4 mmol or more, or about 5 mmol or more) to about 12 mmol or less (e.g., about 11 mmol or less, about 10 mmol or less, about 9 mmol or less, or about 8 mmol or less) per gram of cyclized polyisoprene.

[0025] Generally, an increase in bicyclic and tricyclic structures in a cyclized polydiene resin increases the glass transition temperature (Tg) of the polydiene resin. In some embodiments, the Tg of the cyclized polydiene resins disclosed herein may be about 0°C or higher (e.g., about 5°C or higher, about 10°C or higher, about 15°C or higher, about 20°C or higher, or about 25°C or higher) and / or about 100°C or lower (e.g., about 90°C or lower, about 80°C or lower, about 70°C or lower, about 60°C or lower, or about 50°C or lower). In some embodiments, two or more cyclized polydiene resins having different properties (e.g., different degrees of unsaturation or Tg) may be used together in the dielectric film-forming composition described herein.

[0026] In some embodiments, the cyclized polydiene resins described herein may comprise one or more substituted or unsubstituted alkenyl groups. As used herein, options for substituted groups (e.g., substituted alkyl groups, substituted alkenyl groups, substituted alkynyl groups, substituted cycloalkyl groups, substituted cycloalkylene groups, substituted aryl groups, substituted arylalkyl groups, or substituted heteroaryl groups) or substituents on the substituted compound include C1-C10 alkyl groups (e.g., methyl, ethyl, or propyl), halogens (F, Cl, Br, or I), cyano, and phenyl.

[0027] In some embodiments, the cyclized polydiene resin described herein may be present in an amount of about 2% by weight or more (e.g., about 3% by weight or more, about 4% by weight or more, about 5% by weight or more, about 8% by weight or more, or about 10% by weight or more) to about 40% by weight or less (e.g., about 35% by weight or less, about 30% by weight or less, about 25% by weight or less, about 20% by weight or less, or about 15% by weight or less) of the total weight of the dielectric film-forming composition. While we do not wish to be bound by theory, it is believed that dielectric films prepared from cyclized polydiene resins may have desirable electrical properties (e.g., low dielectric loss tangent or low dielectric loss tangent (dissipation factor)).

[0028] In some embodiments, the reactive functional compounds described herein may have two or more (e.g., three or four) functional groups that can react with substituted or unsubstituted alkenyl groups on the cyclized polydiene resin to form a crosslinked dielectric film. Examples of reactive functional compounds include compounds comprising at least two (meth)acrylate groups, at least two olefin groups, at least two cycloolefin groups, or at least two alkynyl groups. As used herein, the term "(meth)acrylate" encompasses both acrylate and methacrylate. Examples of compounds comprising at least two cycloolefin groups include, but are not limited to, dicyclopentadiene and norbornadiene. Examples of compounds comprising two olefin groups include divinylbenzene and ethylenenorbornene. In some embodiments, compounds comprising at least two (meth)acrylate groups include di(meth)acrylates of unsubstituted or substituted linear, branched, or cyclic C1-C10 alkyl groups, and di(meth)acrylates of unsubstituted or substituted aromatic groups. Examples of such compounds include, but are not limited to, 1,3-butylene glycol 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, cyclohexanedimethanol di(meth)acrylate, tricyclodecanedimethanol diacrylate, 1,4-phenylenedi(meth)acrylate, 2,2-bis[4-(2-hydroxy-3-methacryloxypropoxy)phenyl]propane, tricyclodecanedimethanol di(meth)acrylate, and trimethylolpropane ethoxylate tri(meth)acrylate. Other examples of reactive functional compounds have been described, for example, in U.S. Patent Publication No. 10,036,952, U.S. Patent Publication No. 10,563,014, and U.S. Patent Application Publication No. 2015 / 219990, the contents of which are incorporated by reference in this disclosure.In some embodiments, two or more reactive functional compounds may be used together in the dielectric film-forming composition described herein.

[0029] In some embodiments, the amount of the at least one reactive functional compound may be about 1% by weight or more (e.g., about 2% by weight or more, about 3% by weight or more, about 4% by weight or more, or about 5% by weight or more) to about 25% by weight or less (e.g., about 20% by weight or less, about 15% by weight or less, about 10% by weight or less, or about 8% by weight or less) of the total weight of the dielectric film forming composition of the present disclosure. Although we do not wish to be bound by theory, it is thought that the reactive functional compound can cause crosslinking in the dielectric film (e.g., by exposure to radiation or heat), which is thought to facilitate the formation of a solubility contrast before and after exposure. In addition, although we do not wish to be bound by theory, it is thought that a dielectric film forming composition containing a relatively large amount of the reactive functional compound may produce a dielectric film having a relatively high Tg.

[0030] In some embodiments, this disclosure is, a) at least one (e.g., two, three, or four) cyclopolydiene resin; and b) At least one (e.g., two, three, or four) cyanate ester compound having at least two cyanate groups (i.e., having them in one molecule) This relates to a dielectric film forming composition containing [a specific component].

[0031] In some embodiments, the cyanate ester compound has structure (I) [ka] It may have a substituted or unsubstituted aromatic group (e.g., a cyanate ester group), where m is an integer of 2 or more (i.e., m≧2), and A is a substituted or unsubstituted aromatic group (e.g., a cyanate ester group). [ka] The group is a divalent organic group (which is directly bonded to the substituted or unsubstituted aromatic group). In some embodiments, the aromatic group may include aryl and heteroaryl groups. As used in this disclosure, “aryl” refers to a hydrocarbon moiety having one or more aromatic rings. Examples of aryl moieties include phenyl (Ph), phenylene, naphthyl, naphthylene, pyrenyl, anthryl, and phenanthryl. As used in this disclosure, “heteroaryl” 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 furyl, furylene, fluorenyl, pyrrolyl, thienyl, oxazolyl, imidazolyl, thiazolyl, pyridinyl, pyrimidinyl, quinazolinyl, quinolyl, isoquinolyl, and indolyl.

[0032] In some embodiments, the cyanate ester compound of structure (I) may be the cyanate ester compound of structure (II): [ka] Here, R is a hydrogen atom, a C1-C3 alkyl group, a C1-C3 alkyl group that is completely or partially substituted with a halogen (F, Cl, Br, or I) (e.g., substituted with one, two, or three halogens), or a halogen atom; X is a single bond, -O-, -S-, -(C=O)-, -(C=O)-O-, -O-(C=O)-, -(S=O)-, -(SO2)-, -CH2CH2-O-, a substituted or unsubstituted C1-C10 alkylene, a fluorosubstituted (e.g., partially or completely fluorosubstituted) C1-C4 alkylene (e.g., substituted with one, two, or three fluoros), a substituted or unsubstituted C3-C10 cycloalkylene, or one of the following groups: [ka] That is the case.

[0033] In some embodiments, the cyanate ester compound may have structure (III): [Chemical formula] Here, n 1 is an integer of 2 or more (that is, n 1 ≧2), n 2 and n 3 are independently 0 or an integer from 1 to 100, R 1 is a C1-C10 alkyl group or a C1-C20 arylalkyl group (for example, an acid-sensitive / acid-degradable substituted alkyl group or an acid-sensitive / acid-degradable substituted arylalkyl group), R 2 is a substituted or unsubstituted C1-C10 alkyl, a substituted or unsubstituted C3-C10 cycloalkyl, a substituted or unsubstituted aryl group, or a -(C=O)-OR 4 group, where R 4 is a non-acid-sensitive substituted alkyl group or a non-acid-sensitive substituted arylalkyl group, and R 3 is a substituted or unsubstituted C1-C10 alkyl, or a fluoro-substituted (for example, partially or completely fluoro-substituted) C1-C4 alkyl.

[0034] Specific examples of suitable cyanate ester compounds include 2,2-bis(4-cyanatophenyl)propane, hexafluorobisphenol A dicyanate, bis(4-cyanato-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatophenyl-1-(methylethylidene))benzene, bis(4-cyanatophenyl) thioether, and bis(4-cyanatophenyl) ether; polyfunctional cyanate esters derived from phenol novolacs, cresol novolacs, or dicyclopentanediene structure-containing phenolic resins, and so on. Other examples of cyanate ester compounds have been described, for example, in U.S. Publications 3,595,900, 4,894,414, and 4,785,034, the contents of which are incorporated by reference in this disclosure. In some embodiments, two or more cyanate ester compounds may be used together in the dielectric film-forming compositions described in this disclosure.

[0035] In general, the weight-average molecular weight of a cyanate ester compound is not particularly limited. In some embodiments, the cyanate ester compound may have a weight-average molecular weight in the range of about 500 daltons or more (e.g., about 600 daltons or more or about 1,000 daltons or more) to about 4,500 daltons or less (e.g., about 4,000 daltons or less or about 3,000 daltons or less).

[0036] In some embodiments, the cyanate ester compound described herein may be present in an amount of about 1% by weight or more (e.g., about 2% by weight or more, about 3% by weight or more, about 4% by weight or more, or about 5% by weight or more) to about 25% by weight or less (e.g., about 20% by weight or less, about 15% by weight or less, about 10% by weight or less, or about 8% by weight or less) of the total weight of the dielectric film-forming composition described herein.

[0037] While we do not wish to be bound by theory, it is believed that by including one or more cyanate ester compounds in the dielectric film-forming composition described herein (for example, by heating such as heating in the post-development baking step), polymerization can be carried out to form an interpenetrating polymer network with the cyclized polydiene resin, thereby producing a dielectric film with improved mechanical and thermal properties (e.g., higher Tg and lower coefficient of thermal expansion (CTE)), which would lead to good reliability when incorporated into microelectronic devices.

[0038] In some embodiments, the dielectric film-forming compositions of the present disclosure may include at least one (e.g., two, three, or four) catalysts (e.g., initiators). The catalysts are capable of inducing a crosslinking or polymerization reaction when exposed to heat (in the case of a thermal initiator) and / or a radiation source (in the case of a photoinitiator). Specific examples of thermal initiators include, but are not limited to, benzoyl peroxides, dicumyl peroxides, 2,2-azobis(2-methylbutyronitrile), and the like. Other examples of thermal initiators have been described, for example, in U.S. Patent No. 10,563,014, the contents of which are incorporated by reference into the present disclosure. Specific examples of photoinitiators include, but are not limited to, 2-(benzoyloxyimino)-1-[4-(phenylthio)phenyl]-1-octanone (Irgacure OXE-01 available from BASF), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]etanone 1-(O-acetyloxime) (Irgacure OXE-2 available from BASF), ethoxy(2,4,6-trimethylbenzoyl)phenylphosphine oxide (Lucerin TPO-L available 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 Applications 10,036,952 and 10,563,014, and U.S. Patent Applications 2015 / 0219990 and 2019 / 0018321, the contents of which are incorporated herein by reference.

[0039] In some embodiments, the amount of the catalyst is about 0.2% by weight or more (about 0.5% by weight or more, about 0.8% by weight or more, about 1.0% by weight or more, or 1.5% by weight or more) and / or about 3.0% by weight or less (about 2.8% by weight or less, about 2.6% by weight or less, about 2.4% by weight or less, or 2.0% by weight or less) of the total weight of the dielectric film forming composition. While we do not wish to be constrained by theory, it is conceivable that the catalyst can induce a reaction between the alkenyl groups on the cyclized polydiene resin and the functional groups on the reactive functional compound in order to form a crosslinked dielectric film.

[0040] In some embodiments, the dielectric film-forming composition of the present disclosure may contain at least one (e.g., two, three, or four) solvents (e.g., organic solvents).

[0041] Examples of the aforementioned organic solvents include, but are not limited to, alkylene carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate, and glycerin carbonate; lactones such as gamma-butyrolactone, ε-caprolactone, γ-caprolactone, and δ-valerolactone; cycloketones such as cyclopentanone and cyclohexanone; linear ketones such as methyl ethyl ketone (MEK) and methyl isobutyl ketone (MIBK); esters such as n-butyl acetate; ester alcohols such as ethyl lactate; ether alcohols such as tetrahydrofurfuryl alcohol; 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 tetralin; and pyrrolidones such as N-methyl-2-pyrrolidone. Preferred solvents are cyclohexanone, xylene, toluene, and tetralin, as well as mixtures thereof.

[0042] In some embodiments, the amount of the solvent is about 40% by weight or more (for example, about 45% by weight or more, about 50% by weight or more, about 55% by weight or more, about 60% by weight or more, or about 65% by weight or more) and / or about 98% by weight or less (for example, about 95% by weight or less, about 90% by weight or less, about 85% by weight or less, about 80% by weight or less, or about 75% by weight or less).

[0043] In some embodiments, a photosensitizer capable of absorbing light in the wavelength range of 193 to 405 nm can be used in the dielectric film-forming composition. Examples of photosensitizers include, but are not limited to, 9-methylanthracene, anthracenemethanol, acenaphthylene, thioxanthone, methyl-2-naphthylketone, 4-acetylbiphenyl, and 1,2-benzofluorene.

[0044] In some embodiments, the dielectric film-forming composition described herein comprises at least one filler. These fillers may generally be inorganic or organic in nature. In some embodiments, the 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, carbon black, graphene, carbon nanotubes (CNTs), and the like. Preferably, the inorganic filler is in granular form having an average particle size of about 0.1 to 2.0 microns. In some embodiments, the filler is inorganic particles containing a ferromagnetic material. Suitable ferromagnetic materials include elemental metals (e.g., iron, nickel, and cobalt) or their oxides, sulfides, and oxyhydroxides, as well as awaruite (Ni3Fe), weirauite (CoFe), Co 17 Sm2 and Nd2Fe 14Examples include intermetallic compounds such as B. In other embodiments, the organic filler is selected from the group consisting of rubber particles, polyimide particles, polyester particles, and so on. In some embodiments, the dielectric film-forming composition may also include a thermally conductive filler selected from the group consisting of Cu particles, diamond particles, gold particles, and so on. In some embodiments, two or more fillers may be used together in the dielectric film-forming composition described herein.

[0045] In some embodiments, the filler (e.g., organic filler) may be in an amount of about 1% by weight or more (e.g., about 2% by weight or more, about 3% by weight or more, about 4% by weight or more, or about 5% by weight or more) and / or about 50% by weight or less (e.g., about 40% by weight or less, about 30% by weight or less, about 20% by weight or less, or about 10% by weight or less) of the total weight of the dielectric film forming composition.

[0046] In some embodiments, the dielectric film-forming compositions of the present disclosure may optionally further contain one or more (e.g., two, three, or four) adhesion promoters (e.g., silane-containing alkoxy groups). Suitable adhesion promoters are described in Edwin P. Plueddemann, "Silane Coupling Agents" (1982, Plenum Press, New York), and U.S. 9,519,216, the contents of which are incorporated by reference into the present disclosure.

[0047] In some embodiments, the amount of the optional adhesion promoter is about 0.5% by weight or more (e.g., about 0.8% by weight or more, about 1% by weight or more, or about 1.5% by weight or more) and / or about 4% by weight or less (e.g., about 3.5% by weight or less, about 3% by weight or less, about 2.5% by weight or less, or about 2% by weight or less) of the total weight of the dielectric film-forming composition of the Disclosure.

[0048] The dielectric film-forming compositions of this disclosure may optionally include one or more (e.g., two, three, or four) surfactants (e.g., ionic or nonionic surfactants). Examples of suitable surfactants include, but are not limited to, those described in U.S. 9,519,216 and U.S. 10,036,952, the contents of which are incorporated by reference into this disclosure.

[0049] In some embodiments, the amount of the optional surfactant is about 0.005% by weight or more (e.g., about 0.01% by weight or about 0.1% by weight or more) and / or about 1% by weight or less (e.g., about 0.5% by weight or about 0.2% by weight or less) of the total weight of the dielectric film-forming composition.

[0050] The dielectric film-forming compositions of this disclosure may optionally contain one or more (e.g., two, three, or four) copper passivation reagents. Examples of suitable copper passivation reagents include triazole compounds, imidazole compounds, and tetrazole compounds. Examples of triazole compounds include triazole, benzotriazole, substituted triazole, and substituted benzotriazole. Examples of such copper passivation triazoles and tetrazoles have been described in U.S. Patent Application No. 2019 / 016999 and U.S. Patent Application No. 2020 / 173013, the contents of which are incorporated by reference into this disclosure.

[0051] The amount of the optional copper passivation reagent, if used, is about 0.05% by weight or more (for example, about 0.1% by weight or more, about 0.2% by weight or more, or about 0.5% by weight or more) and / or about 3.0% by weight or less (for example, about 2.0% by weight or less, or about 1.0% by weight or less) of the total weight of the dielectric film forming composition of the present disclosure.

[0052] In some embodiments, the dielectric film-forming composition of the present disclosure may optionally include one or more (e.g., two, three, or four) dyes and / or one or more colorants.

[0053] In some embodiments, the dielectric film-forming composition of the present disclosure may contain one or more (e.g., two, three, or four) low dielectric loss resins. Examples of suitable low dielectric loss resins include, but are not limited to, polycarbonate, polystyrene, polytetrafluoroethylene, polycycloolefin, functionalized polycycloolefin, and the like.

[0054] In some embodiments, the dielectric film-forming compositions of the present disclosure may optionally include one or more (e.g., two, three, or four) cyanate curing catalysts to reduce the curing temperature of the dielectric film. The cyanate curing catalysts may be selected from the group consisting of metal carboxylate salts, metal acetylacetonate salts, phenol derivatives, or alcohols. The metals of the metal carboxylate salts and metal acetylacetonate salts may be selected from the group consisting of zinc, copper, manganese, cobalt, iron, nickel, aluminum, titanium, zirconium, and mixtures thereof. Examples of cyanate curing catalysts include zinc octanoate, zinc naphthenate, cobalt naphthenate, copper octanoate, copper naphthenate, manganese octanoate, and iron acetylacetone; phenol compounds such as octylphenol and nonylphenol; alcohols such as 1-butanol and 2-ethylhexanol; imidazole derivatives such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, and 2-phenyl-4,5-dihydroxymethylimidazole; benzotriazole derivatives such as 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2H-benzotriazole-2-yl)-4-methyl-6-(2-propenyl)phenol, 2-tert-butyl-6-(5-chloro-2H-benzotriazole-2-yl)-4-methylphenol, and 2-[3-2H-benzotriazole-2-yl)-4-hydroxyphenyl]ethyl methacrylate. Other examples of suitable cyanate curing catalysts have been described, for example, in U.S. Patent Application No. 2018 / 0105488 and U.S. Patent No. 9,822,226, the contents of which are incorporated by reference into this disclosure.

[0055] In some embodiments, the film formed by the dielectric film-forming composition may have a glass transition temperature (Tg) of about 25°C or higher (e.g., about 30°C or higher, about 40°C or higher, or about 50°C or higher) and / or about 100°C or lower (e.g., about 90°C or lower, about 80°C or lower, or about 70°C or lower) before crosslinking.

[0056] In some embodiments, the dielectric film is a) Forming a film (e.g., a dielectric film) by coating a substrate (e.g., a semiconductor substrate) with the dielectric film forming composition of the present disclosure; b) Optionally, bake the film at the elevated temperature (e.g., approximately 50°C to approximately 150°C) for a period of time (e.g., approximately 20 seconds to approximately 240 seconds); c) Exposing the film to radiation, heat, or a combination of radiation and heat (for example, flood exposure without using a mask such as a patterned mask). It can be prepared by the above process. In some embodiments, the dielectric film prepared by the above process (using broad exposure without a mask) can be crosslinked but does not contain a pattern or relief image.

[0057] In some embodiments, a crosslinked dielectric film formed by a dielectric film-forming composition described herein (e.g., including a cyanate ester) can have a relatively high Tg. For example, a crosslinked dielectric film described herein may have a Tg of about 120°C or higher (e.g., about 140°C or higher, about 150°C or higher, about 160°C or higher, about 180°C or higher, or 200°C or higher) and / or about 300°C or lower (e.g., about 290°C or higher, about 280°C or higher, about 270°C or higher, about 260°C or higher, or about 250°C or higher).

[0058] In some embodiments, a crosslinked dielectric film formed by a dielectric film-forming composition described in this disclosure (e.g., including a cyanate ester) may have a relatively low coefficient of thermal expansion (CTE). For example, a crosslinked dielectric film described in this disclosure may have a CTE of about 100 ppm / °C or less (e.g., about 95 ppm / °C or less, about 90 ppm / °C or less, about 85 ppm / °C or less, about 80 ppm / °C or less, about 75 ppm / °C or less, about 70 ppm / °C or less, about 65 ppm / °C or less, about 60 ppm / °C or less, about 55 ppm / °C or less, or about 50 ppm / °C or less) when measured in a temperature range of 50°C to 150°C, and may have a CTE of about 10 ppm / °C or more (e.g., about 20 ppm / °C or more, about 30 ppm / °C or more, or about 40 ppm / °C or more).

[0059] In some embodiments, a crosslinked dielectric film formed by a dielectric film-forming composition described in this disclosure (e.g., including a cyanate ester) can have relatively low moisture permeability. For example, a crosslinked dielectric film described in this disclosure may have a moisture permeability of about 3 WVT / μm or less (e.g., about 2.5 WVT / μm or less, about 2 WVT / μm or less, about 1.5 WVT / μm or less, about 1 WVT / μm or less, or about 0.8 WVT / μm or less) and about 0.01 WVT / μm or more (e.g., about 0.02 WVT / μm or more, about 0.03 WVT / μm or more, about 0.04 WVT / μm or more, or about 0.05 WVT / μm or more).

[0060] In some embodiments, the present disclosure features a process for depositing a conductive metal layer (for example, to fabricate an embedded copper trace structure). a) A step of depositing the dielectric film-forming composition described herein onto a substrate (e.g., a semiconductor substrate) to form a dielectric film; b) Exposing the dielectric film to a radiation source, a heat source, or a source of a combination of radiation and heat (for example, through a mask such as a patterned mask); c) Patterning the dielectric film to form a patterned dielectric film having openings; d) optionally depositing a seed layer on the patterned dielectric film; e) the step of depositing a conductive metal layer in at least one opening in the patterned dielectric film; and f) Optionally, repeat steps a) through e) at least once (for example, two, three, or four times). It may include.

[0061] Coating methods for preparing the dielectric film include, but are not limited to, spin coating, spray coating, roll coating, rod coating, rotation coating, slit coating, compression coating, curtain coating, die coating, wire bar coating, knife coating, and lamination of a dried film. The semiconductor substrate may be circular, such as a wafer, or it may be a panel. In some embodiments, the semiconductor substrate may be a silicon substrate, a copper substrate, an aluminum substrate, a silicon oxide substrate, a silicon nitride substrate, a glass substrate, an organic substrate, a copper clad laminate, or a dielectric material substrate.

[0062] The thickness of the dielectric film of the present disclosure is not particularly limited. In some embodiments, the dielectric film has a thickness of about 1 micron or more (for example, about 2 microns or more, about 3 microns or more, about 4 microns or more, about 5 microns or more, about 7 microns or more, about 10 microns or more, about 15 microns or more, about 20 microns or more, about 25 microns or more, about 50 microns or more, or about 100 microns or more) and / or about 5000 microns (5 mm) or less (for example, about 4000 microns or less, about 3000 microns or less, about 2000 microns or less, about 1000 microns or less, about 500 microns or less, about 400 microns or less, about 300 microns or less, or about 200 microns or more).

[0063] In some embodiments, the dielectric film-forming compositions of the present disclosure are photo-patternable. In such embodiments, the process for preparing a patterned dielectric film includes converting the dielectric film prepared from the dielectric film-forming composition into a patterned dielectric film by a lithography process. In such cases, the conversion may include exposing the dielectric film to high-energy radiation (e.g., electron beams, ultraviolet rays, and X-rays) using a patterned mask.

[0064] After the exposure, the dielectric film may optionally be heat-treated at a temperature of approximately 50°C or higher (e.g., approximately 55°C or higher, approximately 60°C or higher, or approximately 65°C or higher) to approximately 100°C or lower (e.g., approximately 95°C or lower, approximately 90°C or lower, approximately 85°C or lower, approximately 80°C or lower, approximately 75°C or lower, or approximately 70°C or lower) for approximately 60 seconds or higher (e.g., approximately 80 seconds or higher or approximately 100 seconds or higher) to approximately 240 seconds or lower (e.g., approximately 180 seconds or lower, approximately 120 seconds or lower, or approximately 90 seconds or lower). The heat treatment is usually achieved using a hot plate or oven.

[0065] After the exposure and / or heat treatment, the dielectric film can be developed using a developer to remove unexposed areas and form apertures or relief images on the substrate. Development can be performed, for example, by immersion or spraying. After development, microholes and fine lines can be created in the dielectric film on the laminated substrate.

[0066] In some embodiments, the dielectric film can be developed using an organic developer. Examples of such developers include cyclohexanone, xylene, toluene, tetralin, gamma-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, tetralin, isophorone, ethylene glycol monobutyl ether, and ethyl acetate. Examples of suitable developers include, but are not limited to, ethylene 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-dianehydrosorbitol, isosorbide dimethyl ether, 1,4:3,6-dianehydrosorbitol 2,5-diethyl ether (2,5-diethyl isosorbide), and mixtures thereof. Preferred developers are cyclohexanone, xylene, toluene, and tetralin. These developers can be used individually or in combination of two or more to optimize image quality for specific compositions and lithography processes.

[0067] In some embodiments, the compositions of this disclosure are not optically patternable. In such cases, patterning can be achieved by mechanical laser drilling or a bilayer process. Laser drilling generally uses a static laser beam with its own high power density to dissolve or evaporate material from a target substrate or workpiece. In principle, laser drilling is governed by the energy balance between the irradiation energy from the laser beam and the heat conducted to the substrate, energy loss to the environment, and the energy required for phase change in the workpiece. Examples of mechanical laser drilling have been described, for example, in U.S. Patent No. 6,353,999, the contents of which are incorporated by reference in this disclosure.

[0068] In some embodiments, the pattern formation is achieved using a bilayer process. In such cases, a photoresist film may be deposited on the upper surface of the dielectric film of the Disclosure. This photoresist film can be patterned, and the pattern can be transferred to the dielectric film of the Disclosure by etching. Suitable examples of photoresists have been described, for example, in U.S. Patent Applications 6,803,434 and 6,830,870, and U.S. Patent Publications 2003 / 022097 and 2019 / 018321, the contents of which are incorporated by reference into the Disclosure.

[0069] In a preferred embodiment, the upper layer of the bilayer is a silicon-containing resist layer. In some embodiments, the silicon-containing resist layer described herein can be prepared from a resist-forming composition comprising a) at least one silicon-containing polymer, b) at least one solvent (e.g., the solvent described herein), and c) at least one photoacid generator (PAG).

[0070] A radiosensitive photoresist composition can be prepared using any suitable photoacid generator (particularly nitrobenzyl esters and onium sulfonate salts) that generates acid under the influence of active radiation from exposure sources ranging from electron beams, ArF excimer lasers, and KrF excimer lasers, together with the silicon-containing polymer described herein.

[0071] Suitable onium sulfonate salts include arylsulfonium and iodonium sulfonates, particularly triarylsulfonium and iodonium sulfonates. The aryl group of the sulfonium or iodonium moiety may be optionally substituted with one or more substituents such as halogens, C1-C4 alkyl groups, C1-C4 alkoxy groups, -OH groups, and / or nitro groups, or it may be a substituted or unsubstituted aryl group such as phenyl or naphthyl. The aryl groups (plural) or substituents on each aryl group may be the same or different from each other.

[0072] The anion of the photoacid generator may be any suitable anion of a suitable organic sulfonic acid, such as an aliphatic sulfonic acid, a cycloaliphatic sulfonic acid, a carbocyclic aromatic sulfonic acid, a heterocyclic aromatic sulfonic acid, or an arylaliphatic sulfonic acid. These anions may be substituted or unsubstituted. Partially fluorinated or fully fluorinated sulfonic acid derivatives, or sulfonic acid derivatives substituted at positions adjacent to each acid group, are preferred. Examples of substituents include halogens (e.g., F or Cl), alkyls (e.g., methyl, ethyl, or n-propyl), and alkoxys (e.g., methoxy, ethoxy, or n-propoxy).

[0073] Preferably, the anion of the photoacid generator is a monovalent anion obtained from a partially fluorinated or fully fluorinated sulfonic acid, such as a fluorinated alkyl sulfonate anion.

[0074] Suitable onium salts include triphenylsulfonium bromide, triphenylsulfonium chloride, triphenylsulfonium iodide, triphenylsulfonium methanesulfonate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium hexafluoropropanesulfonate, triphenylsulfonium nonafluorobutanesulfonate, triphenylsulfonium phenylsulfonate, triphenylsulfonium 4-methylphenylsulfonate, triphenylsulfonium 4-methoxyphenylsulfonate, triphenylsulfonium 4-chlorophenylsulfonate, triphenylsulfonium camphorsulfonate, 4-methylphenyl-diphenylsulfonium trifluoromethanesulfonate, bis(4-methylphenyl)-phenylsulfonium trifluoromethanesulfonate, tris-4-methylphenylsulfonium trifluoromethanesulfonate, 4-tert-butylphenyl-diphenylsulfonium trifluoromethanesulfonate, and 4-methoxyphenyl-diphenylsulfonium. Trifluoromethanesulfonate, mesityl-diphenylsulfonium Trifluoromethanesulfonate, 4-chlorophenyldiphenylsulfonium Trifluoromethanesulfonate, bis-(4-chlorophenyl)-phenylsulfonium Trifluoromethanesulfonate, tris(4-chlorophenyl)sulfonium Trifluoromethanesulfonate, 4-methylphenyl-diphenylsulfonium Hexafluoropropanesulfonate, bis(4-methylphenyl)-phenylsulfonium Hexafluoropropanesulfonate, tris-4-methylphenylsulfonium Hexafluoropropanesulfonate, 4-tert-butylphenyl-diphenylsulfonium Hexafluoropropanesulfonate, 4-methoxyphenyl-diphenylsulfonium Hexafluoropropanesulfonate, mesityl-diphenylsulfonium Hexafluoropropanesulfonate, mesityl-diphenylsulfonium Nonafluorooctanesulfonate, mesityl-diphenylsulfoniumExamples include perfluorobutanesulfonate, 4-chlorophenyl-diphenylsulfonium hexafluoropropanesulfonate, bis-(4-chlorophenyl)-phenylsulfonium hexafluoropropanesulfonate, tris(4-chlorophenyl)sulfonium hexafluoropropanesulfonate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium hexafluoropropanesulfonate, diphenyliodonium 4-methylphenylsulfonate, bis-(4-tert-butylphenyl)iodonium trifluoromethanesulfonate, bis-(4-tert-butylphenyl)iodonium hexafluoropropanesulfonate, bis-(4-cyclohexylphenyl)iodonium trifluoromethanesulfonate, tris(4-tert-butylphenyl)sulfonium perfluorooctanesulfonate, and bis-(4-cyclohexylphenyl)iodonium hexafluoropropanesulfonate. A preferred example is triphenylsulfonium trifluoromethanesulfonate (triphenylsulfonium triflate).

[0075] In some embodiments, the amount of PAG is about 0.1% by weight or more (for example, about 0.2% by weight or more, about 0.5% by weight or more, about 1% by weight or more, about 2% by weight or more, or about 3% by weight or more) and / or about 10% by weight or less (for example, about 9% by weight or less, about 8% by weight or less, about 7% by weight or less, about 6% by weight or less, or 5% by weight or less).

[0076] An example of the aforementioned silicon-containing polymer is a tetrapolymer containing the following four monomer repeating units. [ka] Here, n is an integer from 1 to 5, and R 5 R is a methyl group or a trimethylsiloxy group, 6 is a tert-butyl group, and R 7 and R 8Each of these is independently selected from hydrogen and methyl groups. Preferably, n is 1.

[0077] In some embodiments, the silicon-containing polymer can be prepared by polymerization of one or more of the following monomers. [ka]

[0078] Other examples of suitable silicon-containing polymers are described by reference in U.S. 6,929,897, U.S. 6,916,543, and U.S. 6,165,682, which are incorporated herein by reference.

[0079] In some embodiments, the amount of the silicon-containing polymer is about 1% by weight or more (for example, about 2% by weight or more, about 5% by weight or more, about 8% by weight or more, about 10% by weight or more, or about 12% by weight or more) and / or about 30% by weight or less (for example, about 27% by weight or less, about 25% by weight or less, about 23% by weight or less, about 20% by weight or less, or about 15% by weight or less) of the total weight of the resist-forming composition.

[0080] In some embodiments, the amount of the solvent is about 60% by weight or more (for example, about 65% by weight or more, about 70% by weight or more, about 75% by weight or more, about 80% by weight or more, or about 85% by weight or more) and / or about 98% by weight or less (for example, about 96% by weight or less, about 94% by weight or less, about 92% by weight or less, about 90% by weight or less, or about 85% by weight or less).

[0081] Some embodiments of this disclosure describe a process for depositing a metal layer (e.g., a conductive copper layer for creating an embedded copper trace structure) on a semiconductor substrate. In some embodiments, to achieve this, a seed layer conforming to a patterned dielectric film is first deposited on the patterned dielectric film (e.g., outside the openings of the film). The seed layer may include a barrier layer and a metal seeding layer (e.g., a copper seeding layer). In some embodiments, the barrier layer is prepared using a material capable of preventing a conductive metal (e.g., copper) from diffusing through the dielectric layer. Suitable materials that can be used for the barrier layer include, but are not limited to, tantalum (Ta), titanium (Ti), tantalum nitride (TiN), tungsten nitride (WN), and Ta / TaN. A suitable method for forming the barrier layer is sputtering (e.g., PVD or physical vapor deposition). Sputtering deposition has several advantages as a metal deposition technique. This is because sputtering deposition can be used to deposit many conductive materials at high deposition rates, with good uniformity, and at low ownership costs. Conventional sputtering fills produce relatively poor results for deeper and narrower (high aspect ratio) features. The fill factor of sputtering deposition has been improved by collimating the sputtered flux. Typically, this is achieved by inserting a collimator plate with an array of hexagonal cells between the target and the substrate.

[0082] The next step in the process described above is metal seeding deposition. To improve the deposition of the metal layer (e.g., copper layer) formed in the subsequent step, a thin metal (e.g., a conductive metal such as copper) seeding layer can be formed on the upper surface of the barrier layer.

[0083] The next step in the process is to deposit a conductive metal layer (e.g., a copper layer) on the upper surface of the metal seeding layer within the openings of the patterned dielectric film, where the metal layer is thick enough to fill the openings in the patterned dielectric film. The metal layer for filling the openings in the patterned dielectric film can be deposited by plating (e.g., electroless plating or electrolytic plating), sputtering, plasma deposition (PVD), and chemical deposition (CVD). Electrochemical deposition is generally preferred for copper deposition because it is more economical than other deposition methods and can fill interconnect features with copper without defects. Copper deposition methods generally need to meet the stringent requirements of the semiconductor industry. For example, the copper deposits need to be uniform and able to fill small interconnect features of the device, such as interconnect features with openings of 100 nm or less, without defects. This technology has been described, for example, in U.S. Publication No. 5,891,804 (Havemann et al.), U.S. Publication No. 6,399,486 (Tsai et al.), and U.S. Publication No. 7,303,992 (Paneccasio et al.), the contents of which are incorporated by reference into this disclosure.

[0084] In some embodiments, the process of depositing a conductive metal layer further includes removing an overburden of conductive metal or a seed layer (e.g., a barrier layer and a metal seeding layer). In some embodiments, the overburden of the conductive metal layer (e.g., a copper layer) is about 3 microns or less (e.g., about 2.8 microns or less, about 2.6 microns or less, about 2.4 microns or less, about 2.2 microns or less, about 2.0 microns or less, or about 1.8 microns or less) and about 0.4 microns or more (e.g., about 0.6 microns or more, about 0.8 microns or more, about 1.0 micron or more, about 1.2 microns or more, about 1.4 microns or more, or about 1.6 microns or more). Examples of copper etchants for removing copper overburdens include aqueous solutions containing copper(II) chloride and hydrochloric acid, or aqueous mixtures of iron(III) nitrate and hydrochloric acid. Other suitable examples of copper etchants include, but are not limited to, those described in U.S. Patent Applications 4,784,785, 3,361,674, 3,816,306, 5,524,780, 5,650,249, 5,431,776, and 5,248,398 and U.S. Patent Application Publication 2017 / 175274, the contents of which are incorporated by reference into this disclosure.

[0085] Some embodiments describe a process of surrounding a metal-structured substrate, which includes conductive metal (e.g., copper) wire structures forming a network of lines and interconnects, with a dielectric film of the present disclosure. a) A step of providing a substrate including a conductive metal wire structure that forms a network of lines and interconnects on the substrate; b) A step of depositing the dielectric film-forming composition of the present disclosure onto the substrate to form a dielectric film (for example, a dielectric film covering the conductive metal line and interconnect); c) Exposing the film to a radiation source, a heat source, or a source of a combination of radiation and heat (capable of crosslinking the film); d) Optionally, repeat steps a) to c) at least once (for example, two, three, or four times). It may include. In some embodiments, the above process may further include patterning the dielectric film by a suitable process such as a lithography process, a laser ablation process or a laser drilling process, or a bilayer process (e.g., the process described herein).

[0086] In some embodiments, the present disclosure features a method for preparing a dry film structure. The method is as follows: a) Coating a carrier substrate (e.g., a substrate comprising at least one plastic film) with the dielectric film forming composition described herein; b) drying the coated dielectric film-forming composition to form a dry film; and c) Optionally, apply a protective film to the dried film. It may include.

[0087] In some embodiments, the carrier substrate is a single-layer or multilayer plastic film and may contain one or more polymers (e.g., polyethylene terephthalate). In some embodiments, the carrier substrate has good optical transparency and is substantially transparent to actinic irradiation used to form a relief pattern in the polymer layer. The thickness of the carrier substrate is preferably in the range of about 10 microns or more (e.g., about 15 microns or more, about 20 microns or more, about 30 microns or more, about 40 microns or more, about 50 microns or more, or about 60 microns or more) to about 150 microns or less (e.g., about 140 microns or less, about 120 microns or less, about 100 microns or less, about 90 microns or less, about 80 microns or less, or about 70 microns or less).

[0088] In some embodiments, the protective layer may be a single or multilayer film and may contain one or more polymers (e.g., polyethylene or polypropylene). Examples of carrier substrates and protective layers have been described, for example, in U.S. Patent Application Publication 2016 / 0313642, the contents of which are incorporated by reference into this disclosure.

[0089] In some embodiments, the dielectric film of the dried film may be peeled from the carrier layer as a self-standing dry film. A self-standing dry film is a film that can maintain its physical integrity without the use of a support layer such as a carrier layer. In some embodiments, the self-standing dielectric dry film is not crosslinked or cured and may contain components of the dielectric film forming composition described in this disclosure, except for the solvent.

[0090] In some embodiments, dielectric films prepared from the dielectric film-forming compositions described herein may have a relatively low dielectric loss tangent. For example, the dielectric loss tangent of a dielectric film (e.g., a crosslinked or uncrosslinked dielectric film) prepared from the dielectric film-forming compositions of this disclosure, measured at 10 GHz, may be in the range of about 0.001 or more (e.g., about 0.005 or more, about 0.01 or more, or about 0.05 or more) to about 0.1 or less (e.g., about 0.08 or less, about 0.06 or less, about 0.05 or less, about 0.04 or less, or about 0.020 or less).

[0091] In some embodiments, the Disclosure features a three-dimensional object comprising at least one layer of a conductive metal and a dielectric film (e.g., a crosslinked and patterned dielectric film) formed using the film-forming composition of the Disclosure. In some embodiments, the three-dimensional object may comprise two or more stacks (e.g., three or more stacks) of the dielectric film.

[0092] The entire contents of all publications cited in this disclosure (e.g., patents, patent application publications, and articles) are incorporated into this disclosure by reference. The following embodiments are given to more clearly illustrate the principles and practices of this disclosure. It should be understood that this disclosure is not limited to the embodiments described. [Examples]

[0093] ●Example 1: Preparation and application of dielectric film forming composition 1 The dielectric film-forming composition in this example was prepared by mixing cyclized polyisoprene (62.60 g of a 28.5% solution in xylene) supplied by Fujifilm Electronic Materials USA, tricyclodecanedimethanol diacrylate (7.14 g), and dicumyl peroxide (0.53 g) to obtain a homogeneous solution. This solution was filtered using a 5.0 micron PTFE filter.

[0094] In this example, SC rubber was used as the cyclized polydiene, tricyclodecanedimethanol diacrylate was used as the reactive functional compound, dicumyl peroxide was used as the thermal initiator, and xylene was used as the solvent.

[0095] Dielectric film-forming composition 1 was applied to a 35-micron thick PET film using an applicator to form a film. This film was baked at 95°C for 10 minutes using a hot plate to remove most of the solvent. Then, the film was baked under nitrogen at 150°C for 1 hour to obtain a stable dielectric film with a thickness of 130 microns. After lifting the dielectric film from the PET film, the dielectric film was placed on a 25-micron KAPTON film and then baked under nitrogen at 200°C for another 1 hour.

[0096] After cooling to room temperature, the dielectric film was removed from the KAPTON film and cut into slits to form a 3 mm wide film. This film was analyzed for its thermomechanical properties using TMA. The dielectric film in this embodiment had a Tg at 120°C and a CTE of 88 ppm / °C when measured in the range of 50°C to 150°C.

[0097] ●Example 2: Preparation and application of dielectric film forming composition 2 The dielectric film-forming composition of this example was prepared by mixing cyclized polyisoprene (43.6 g of a 28.5% solution in xylene), tricyclodecanedimethanol diacrylate (5.0 g), dicumyl peroxide (0.37 g), silica (46.9 g, silica nanoparticles dispersed in 20% xylene, SUPSIL® PREMIUM, monodisperse, charge-stabilized, supplied by Superior Silica), and xylene (3.5 g) to obtain a homogeneous solution. This solution was filtered using a 5.0 micron PTFE filter.

[0098] In this example, SC rubber was used as the cyclized polydiene, tricyclodecanedimethanol diacrylate was used as the reactive functional compound, dicumyl peroxide was used as the thermal initiator, silica nanoparticles were used as the filler, and xylene was used as the solvent.

[0099] Dielectric film-forming composition 2 was applied to a 35-micron thick PET film using an applicator to form a film. This film was baked at 95°C for 10 minutes using a hot plate to remove most of the solvent. Then, the film was baked under nitrogen at 150°C for 1 hour to obtain a stable dielectric film with a thickness of 130 microns. After lifting the dielectric film from the PET film, the dielectric film was placed on a 25-micron KAPTON film and then baked under nitrogen at 200°C for another 1 hour.

[0100] After cooling to room temperature, the dielectric film was removed from the KAPTON film and cut into slits to form a 3 mm wide film. This film was then analyzed for its thermomechanical properties using a thermomechanical analyzer (TMA). The dielectric film in this embodiment had a Tg at 120°C and a CTE of 58 ppm / °C when measured in the range of 50°C to 150°C.

[0101] ●Example 3: Preparation and application of dielectric film forming composition 3 The dielectric film-forming composition of this example is prepared by mixing cyclized polyisoprene (57.9g of a 28.5% solution in xylene supplied by Fujifilm Electronic Materials USA), 2,2-bis(4-cyanatophenyl)propane (8.25g), dicumyl peroxide (0.50g), and xylene (1.75g) to obtain a homogeneous solution. This solution is filtered using a 5.0 micron PTFE filter.

[0102] In this embodiment, SC rubber is used as the cyclized polydiene, 2,2-bis(4-cyanatophenyl)propane is used as the cyanate ester compound, dicumyl peroxide is used as the thermal initiator, and xylene is used as the solvent.

[0103] The dielectric film-forming composition 3 is applied to a 35-micron thick PET film using an applicator to form a film. This film is baked at 95°C for 10 minutes using a hot plate to remove most of the solvent. This film is then baked at 150°C for 1 hour under nitrogen to obtain a stable dielectric film with a thickness of 120 microns. After lifting the dielectric film from the PET film, the dielectric film is placed on a 25-micron KAPTON film and then baked for another 1 hour at 200°C under nitrogen.

[0104] After cooling to room temperature, the dielectric film is removed from the KAPTON film and cut into slits to form a 3 mm wide film. This film is then analyzed for its thermomechanical properties using TMA.

[0105] ●Example 4: Preparation and application of dielectric film forming composition 4 The dielectric film-forming composition of this example was prepared by mixing cyclized polyisoprene (57.90 g of a 28.5% solution in xylene supplied by Fujifilm Electronic Materials USA), tricyclodecanedimethanol diacrylate (6.60 g), 2,2-bis(4-cyanatophenyl)propane (8.25 g), dicumyl peroxide (0.50 g), and xylene (1.75 g) to obtain a homogeneous solution. This solution was filtered using a 5.0 micron PTFE filter.

[0106] In this example, SC rubber was used as the cyclized polydiene, tricyclodecanedimethanol diacrylate as the reactive functional compound, 2,2-bis(4-cyanatophenyl)propane as the cyanate ester compound, dicumyl peroxide as the thermal initiator, and xylene as the solvent.

[0107] Dielectric film-forming composition 4 was applied to a 30-micron thick PET film using an applicator to form a film. This film was baked at 95°C for 12 minutes using a hot plate to remove most of the solvent. This film was then baked under nitrogen at 200°C for 70 minutes to obtain a stable dielectric film with a thickness of 250 microns. After lifting the dielectric film from the PET film, the dielectric film was placed on a 25-micron KAPTON film and then baked further under nitrogen at 250°C for 1 hour.

[0108] After cooling to room temperature, the dielectric film was removed from the KAPTON film and cut into slits to form a 3 mm wide film. This film was then analyzed for its thermomechanical properties using a thermomechanical analyzer (TMA). The dielectric film in this embodiment had a Tg of 167°C and a CTE of 76 ppm / °C when measured in the range of 50°C to 150°C.

[0109] ●Example 5: Preparation and application of dielectric film forming composition 5 The dielectric film-forming composition of this example was prepared by mixing cyclized polyisoprene (57.90 g of a 28.5% solution in xylene supplied by Fujifilm Electronic Materials USA), tricyclodecanedimethanol diacrylate (4.1 g), 2,2-bis(4-cyanatophenyl)propane (11.0 g), dicumyl peroxide (0.50 g), and xylene (1.75 g) to obtain a homogeneous solution. This solution was filtered using a 5.0 micron PTFE filter.

[0110] In this example, SC rubber was used as the cyclized polydiene, tricyclodecanedimethanol diacrylate as the reactive functional compound, 2,2-bis(4-cyanatophenyl)propane as the cyanate ester compound, dicumyl peroxide as the thermal initiator, and xylene as the solvent.

[0111] Dielectric film-forming composition 5 was applied to a 30-micron thick PET film using an applicator to form a film. This film was baked at 95°C for 12 minutes using a hot plate to remove most of the solvent. Then, the film was baked under nitrogen at 200°C for 70 minutes to obtain a stable dielectric film with a thickness of 250 microns. After lifting the dielectric film from the PET film, the dielectric film was placed on a 25-micron KAPTON film and then baked further under nitrogen at 250°C for 1 hour.

[0112] After cooling to room temperature, the dielectric film was removed from the KAPTON film and cut into slits to form a 3 mm wide film. This film was then analyzed for its thermomechanical properties using TMA. The dielectric film in this embodiment had a Tg of 175°C and a CTE of 67 ppm / °C when measured in the range of 50°C to 150°C.

[0113] ●Example 6: Preparation and application of dielectric film forming composition 6 The dielectric film-forming composition of this example consists of: cyclized polyisoprene (57.90 g of a 28.5% solution in xylene supplied by Fujifilm Electronic Materials USA as SC rubber), tricyclodecanedimethanol diacrylate (6.60 g), 2,2-bis(4-cyanatophenyl)propane (8.25 g), silica (12.0 g, silica nanoparticles SUPSIL® PREMIUM, monodisperse, charge-stabilized, Superior Silica) The solution was prepared by mixing dicumyl peroxide (0.50 g) and xylene (1.75 g) (supplied from [source]) to obtain a homogeneous solution. This solution was filtered using a 5.0 micron PTFE filter.

[0114] In this example, SC rubber was used as a cyclized polydiene, silica nanoparticles were used as an inorganic particle filler, tricyclodecanedimethanol diacrylate was used as a reactive functional compound, 2,2-bis(4-cyanatophenyl)propane was used as a cyanate ester compound, dicumyl peroxide was used as a thermal initiator, and xylene was used as a solvent.

[0115] A dielectric film-forming composition 6 was applied to a 35-micron thick PET film using an applicator to form a film. This film was baked on a hot plate at 105°C for 7 minutes to remove most of the solvent. Then, the film was baked under nitrogen at 160°C for 185 minutes to obtain a stable dielectric film with a thickness of 350 microns. After lifting the dielectric film from the PET film, the dielectric film was placed on a 25-micron KAPTON film and then baked under nitrogen at 210°C for a further 1 hour.

[0116] After cooling to room temperature, the dielectric film was removed from the KAPTON film and cut into slits to form a 3 mm wide film. This film was then analyzed for its thermomechanical properties using TMA. The dielectric film in this embodiment had a Tg of 173°C and a CTE of 67 ppm / °C when measured in the range of 50°C to 150°C.

[0117] ●Example 7: Preparation and application of dielectric film forming composition 7 The dielectric film-forming composition of this example was prepared by mixing cyclized polyisoprene (57.90 g of a 28.5% solution in xylene supplied by Fujifilm Electronic Materials USA as SC rubber), tricyclodecanedimethanol diacrylate (6.60 g), 2,2-bis(4-cyanatophenyl)propane (8.25 g), dicumyl peroxide (0.50 g), 2-hydroxy-5-acryloyloxyphenyl-2H-benzotriazole (0.11 g), and xylene (1.75 g) to obtain a homogeneous solution. This solution was filtered using a 5.0 micron PTFE filter.

[0118] In this example, SC rubber was used as a cyclized polydiene, tricyclodecanedimethanol diacrylate as a reactive functional compound, 2,2-bis(4-cyanatophenyl)propane as a cyanate ester compound, dicumyl peroxide as a thermal initiator, 2-hydroxy-5-acryloyloxyphenyl-2H-benzotriazole as a Cu rust inhibitor and cyanate curing catalyst, and xylene as a solvent.

[0119] A dielectric film-forming composition 7 was applied to a 30-micron thick PET film using an applicator to form a film. This film was baked at 95°C for 12 minutes using a hot plate to remove most of the solvent. Then, the film was baked under nitrogen at 200°C for 70 minutes to obtain a stable dielectric film with a thickness of 250 microns. After lifting the dielectric film from the PET film, the dielectric film was placed on a 25-micron KAPTON film and then baked further under nitrogen at 250°C for 1 hour.

[0120] After cooling to room temperature, the dielectric film was removed from the KAPTON film and cut into slits to form a 3 mm wide film. The thermomechanical properties of this film were analyzed using TMA.

[0121] ●Example 8: Preparation and application of dielectric film forming composition 8 The dielectric film-forming composition of this example was prepared by mixing cyclized polyisoprene (62.60 g of a 28.5% solution in xylene supplied by Fujifilm Electronic Materials USA as SC Rubber), tricyclodecanedimethanol diacrylate (7.14 g), 2,2-bis(4-cyanatophenyl)propane (4.46 g), 2-(benzoyloxyimino)-1-[4-(phenylthio)phenyl]-1-octanone (Irgacure OXE-01 available from BASF) (0.53 g), and xylene (0.25 g) to obtain a homogeneous solution. This solution was filtered using a 5.0 micron PTFE filter.

[0122] In this example, SC rubber was used as the cyclized polydiene, tricyclodecanedimethanol diacrylate as the reactive functional compound, 2,2-bis(4-cyanatophenyl)propane as the cyanate ester compound, Irgacure® OXE01 as the photoinitiator, and xylene as the solvent.

[0123] A dielectric film-forming composition 8 was applied to a 35-micron thick PET film using an applicator to form a film. This film was baked at 95°C for 10 minutes using a hot plate to remove most of the solvent. Then, the film was baked under nitrogen at 150°C for 1 hour to obtain a stable dielectric film with a thickness of 130 microns. After lifting the dielectric film from the PET film, the dielectric film was placed on a 25-micron KAPTON film and then baked under nitrogen at 200°C for another 1 hour.

[0124] After cooling to room temperature, the dielectric film was removed from the KAPTON film and cut into slits to form a 3 mm wide film. The thermomechanical properties of this film were analyzed using TMA.

[0125] ●Example 9: Preparation and application of dielectric film forming composition 9 The dielectric film-forming composition of this example is prepared by mixing cyclized polyisoprene (77.2 g of a 28.5% solution in xylene supplied by Fujifilm Electronic Materials USA as SC rubber), hexane diacrylate (4.40 g), 2,2-bis(4-cyanatophenyl)propane (11.00 g), Irgacure® OXE-01 (0.66 g), 5-methylbenzotriazole (MBTA, 0.11 g), methacrylate / oxypropyltrimethoxysilane (0.33 g), and xylene (6.5 g) to obtain a homogeneous solution. This solution is filtered using a 5.0 micron PTFE filter.

[0126] In this embodiment, SC rubber is used as a cyclized polydiene, hexanediacrylate is used as a reactive functional compound, 2,2-bis(4-cyanatophenyl)propane is used as a cyanate ester, Irgacure® OXE01 is used as a photoinitiator, 5-methylbenzotriazole is used as a copper passivation reagent, methacrylateoxypropyltrimethoxysilane is used as an adhesion promoter, and xylene is used as a solvent.

[0127] The dielectric film-forming composition 9 is applied to a 35-micron thick PET film using an applicator to form a film. This film is baked at 90°C for 8 minutes using a hot plate to remove most of the solvent. Then the film is baked under nitrogen at 175°C for 90 minutes to obtain a stable dielectric film with a thickness of 100 microns. After lifting the dielectric film from the PET film, the dielectric film is placed on a 25-micron KAPTON film and then baked under nitrogen at 220°C for a further 1 hour.

[0128] After cooling to room temperature, the dielectric film is removed from the KAPTON film and cut into slits to form a 3 mm wide film. This film is then analyzed for its thermomechanical properties using TMA.

[0129] ●Example 10: Preparation and application of dielectric film forming composition 10 The dielectric film-forming composition of this example is prepared by mixing cyclized polyisoprene (77.20 g of a 28.5% solution in xylene supplied by Fujifilm Electronic Materials USA as SC Rubber), tricyclodecanedimethanol diacrylate (4.40 g), 2,2-bis(4-cyanatophenyl)propane (11.00 g), Mitsubishi silica (5.50 g), Irgacure® OXE-01 (0.67 g), 2-[3-2H-benzotriazol-2-yl)-4-hydroxyphenyl]ethyl methacrylate (BTZ-AC, 0.11 g), methacryloxypropyltrimethoxysilane (0.33 g), and xylene (6.7 g) to obtain a homogeneous solution. This solution is filtered using a 5.0 micron PTFE filter.

[0130] In this embodiment, SC rubber is used as a cyclized polydiene, tricyclodecanedimethanol diacrylate is used as a reactive functional compound, 2,2-bis(4-cyanatophenyl)propane is used as a cyanate ester, Mitsubishi silica is used as a filler, Irgacure® OXE01 is used as a photoinitiator, 2-[3-2H-benzotriazole-2-yl)-4-hydroxyphenyl]ethyl methacrylate is used as a copper rust inhibitor, methacryloxypropyltrimethoxysilane is used as an adhesion promoter, and xylene is used as a solvent.

[0131] The dielectric film-forming composition 10 is applied to a 35-micron thick PET film using an applicator to form a film. This film is baked at 85°C for 15 minutes using a hot plate to remove most of the solvent. Then the film is baked under nitrogen at 180°C for 75 minutes to obtain a stable dielectric film having a thickness of 150 microns. After lifting the dielectric film from the PET film, the dielectric film is placed on a 25-micron KAPTON film and then baked under nitrogen at 250°C for a further 30 minutes.

[0132] After cooling to room temperature, the dielectric film is removed from the KAPTON film and cut into slits to form a 3 mm wide film. This film is then analyzed for its thermomechanical properties using TMA.

[0133] ●Example 11: Preparation and application of dielectric film forming composition 11 The dielectric film-forming composition of this example is prepared by mixing cyclized polyisoprene (77.20 g of a 28.5% solution in xylene supplied by Fujifilm Electronic Materials USA as SC Rubber), tricyclodecanedimethanol diacrylate (4.40 g), 2,2-bis(4-cyanatophenyl)propane (11.00 g), Mitsubishi silica (5.50 g), Irgacure® OXE-01 (0.67 g), BTZ-AC (0.11 g), methacrylate oxypropyltrimethoxysilane (0.33 g), titanium carboxyethyl acrylate (0.11 g), and xylene (6.70 g) to obtain a homogeneous solution. This solution is filtered using a 5.0 micron PTFE filter.

[0134] In this embodiment, SC rubber is used as a cyclized polydiene, tricyclodecanedimethanol diacrylate is used as a reactive functional compound, 2,2-bis(4-cyanatophenyl)propane is used as a cyanate ester, Mitsubishi silica is used as a filler, Irgacure® OXE01 is used as a photoinitiator, BTZ-AC is used as a copper rust inhibitor, methacrylate oxypropyltrimethoxysilane is used as an adhesion promoter, titanium carboxyethyl acrylate is used as a curing catalyst, and xylene is used as a solvent.

[0135] The dielectric film-forming composition 11 is applied to a 35-micron thick PET film using an applicator to form a film. This film is baked at 100°C for 12 minutes using a hot plate to remove most of the solvent. Then the film is baked under nitrogen at 160°C for 80 minutes to obtain a stable dielectric film with a thickness of 200 microns. After lifting the dielectric film from the PET film, the dielectric film is placed on a 25-micron KAPTON film and then baked under nitrogen at 240°C for a further 45 minutes.

[0136] After cooling to room temperature, the dielectric film is removed from the KAPTON film and cut into slits to form a 3 mm wide film. This film is then analyzed for its thermomechanical properties using TMA.

[0137] ●Example 12: Preparation and application of dielectric film forming composition 12 The dielectric film-forming composition of this example is prepared by mixing cyclized polyisoprene (77.20 g of a 28.5% solution in xylene supplied by Fujifilm Electronic Materials USA), tricyclodecanedimethanol diacrylate (4.40 g), AroCy® XU366 (11.00 g), Mitsubishi Silica (5.50 g), Irgacure® OXE-01 (0.67 g), BTZ-AC (0.11 g), methacrylate oxypropyltrimethoxysilane (0.33 g), titanium carboxyethyl acrylate (0.11 g), and xylene (6.7 g) to obtain a homogeneous solution. This solution is filtered using a 5.0 micron PTFE filter.

[0138] In this embodiment, SC rubber is used as a cyclized polydiene, tricyclodecanedimethanol diacrylate is used as a reactive functional compound, AroCy® XU366 is used as a cyanate ester compound, Mitsubishi silica is used as a filler, Irgacure® OXE01 is used as a photoinitiator, BTZ-AC is used as a copper rust inhibitor, methacrylate oxypropyl trimethoxysilane is used as an adhesion promoter, titanium carboxyethyl acrylate is used as a curing catalyst, and xylene is used as a solvent.

[0139] The dielectric film-forming composition 12 is applied to a 35-micron thick PET film using an applicator to form a film. This film is baked on a hot plate at 80°C for 15 minutes to remove most of the solvent. Then the film is baked under nitrogen at 190°C for 50 minutes to obtain a stable dielectric film with a thickness of 130 microns. After lifting the dielectric film from the PET film, the dielectric film is placed on a 25-micron KAPTON film and then baked under nitrogen at 210°C for a further 1 hour.

[0140] After cooling to room temperature, the dielectric film is removed from the KAPTON film and cut into slits to form a 3 mm wide film. This film is then analyzed for its thermomechanical properties using TMA.

[0141] ●Example 13: Preparation and application of dielectric film forming composition 13 The dielectric film-forming composition of this example is prepared by mixing cyclized polyisoprene (77.20 g of a 28.5% solution in xylene supplied by Fujifilm Electronic Materials USA as SC rubber), tricyclodecanedimethanol diacrylate (4.40 g), novolac (AroCy® XU371) (11.00 g), Mitsubishi silica (5.50 g), Irgacure® OXE-01 (0.67 g), BTZ-AC (0.11 g), methacrylate oxypropyltrimethoxysilane (0.33 g), titanium carboxyethyl acrylate (0.11 g), and xylene (6.7 g) to obtain a homogeneous solution. This solution is filtered using a 5.0 micron PTFE filter.

[0142] In this embodiment, SC rubber is used as a cyclized polydiene, tricyclodecanedimethanol diacrylate is used as a reactive functional compound, novolac (AroCy® XU371) is used as a cyanate ester compound, Mitsubishi silica is used as a filler, Irgacure® OXE01 is used as a photoinitiator, BTZ-AC is used as a copper rust inhibitor, methacrylate oxypropyltrimethoxysilane is used as an adhesion promoter, titanium carboxyethyl acrylate is used as a curing catalyst, and xylene is used as a solvent.

[0143] The dielectric film-forming composition 13 is applied to a 50-micron thick PET film using an applicator to form a film. This film is baked at 100°C for 12 minutes using a hot plate to remove most of the solvent. Then the film is baked at 250°C for 1 hour under nitrogen to obtain a stable dielectric film with a thickness of 320 microns. After lifting the dielectric film from the PET film, the dielectric film is placed on a 25-micron KAPTON film and then baked at 250°C for a further 70 minutes under nitrogen.

[0144] After cooling to room temperature, the dielectric film is removed from the KAPTON film and cut into slits to form a 3 mm wide film. This film is then analyzed for its thermomechanical properties using TMA.

[0145] ●Example 14: Preparation and application of dielectric film forming composition 14 The dielectric film-forming composition of this example is prepared by mixing cyclized polyisoprene (77.20 g of a 28.5% solution in xylene supplied by Fujifilm Electronic Materials USA as SC Rubber), tricyclodecanedimethanol diacrylate (4.40 g), novolac (product Primaset® DT-4000) (11.00 g), Mitsubishi silica (5.50 g), Irgacure® OXE-01 (0.67 g), BTZ-AC (0.11 g), methacrylate / oxypropyltrimethoxysilane (0.33 g), titanium carboxyethyl acrylate (0.11 g), and xylene (6.7 g) to obtain a homogeneous solution. This solution is filtered using a 5.0 micron PTFE filter.

[0146] In this embodiment, SC rubber is used as a cyclized polydiene, tricyclodecanedimethanol diacrylate is used as a reactive functional compound, novolac (product Primaset® DT-4000) is used as a cyanate ester compound, Mitsubishi silica is used as a filler, Irgacure® OXE01 is used as a photoinitiator, BTZ-AC is used as a copper rust inhibitor, methacrylate oxypropyltrimethoxysilane is used as an adhesion promoter, titanium carboxyethyl acrylate is used as a curing catalyst, and xylene is used as a solvent.

[0147] The dielectric film-forming composition 14 is applied to a 45-micron thick PET film using an applicator to form a film. This film is baked on a hot plate at 75°C for 12 minutes to remove most of the solvent. Then the film is baked under nitrogen at 160°C for 55 minutes to obtain a stable dielectric film with a thickness of 100 microns. After lifting the dielectric film from the PET film, the dielectric film is placed on a 25-micron KAPTON film and then baked under nitrogen at 210°C for a further 1 hour.

[0148] After cooling to room temperature, the dielectric film is removed from the KAPTON film and cut into slits to form a 3 mm wide film. This film is then analyzed for its thermomechanical properties using TMA.

[0149] ●Example 15: Preparation and application of dielectric film forming composition 15 The dielectric film-forming composition of this example is prepared by mixing cyclized polyisoprene (Resiprene, 11.00 g), tricyclodecanedimethanol diacrylate (4.40 g), novolac (product Primaset® DT-4000) (11.00 g), Mitsubishi silica (5.50 g), Irgacure® OXE-01 (0.67 g), BTZ-AC (0.11 g), methacrylate / oxypropyltrimethoxysilane (0.33 g), titanium carboxyethyl acrylate (0.11 g), and xylene (72.9 g) to obtain a homogeneous solution. This solution is filtered using a 5.0 micron PTFE filter.

[0150] In this embodiment, Resiprene is used as a cyclized polydiene, tricyclodecanedimethanol diacrylate is used as a reactive functional compound, novolac (product Primaset® DT-4000) is used as a cyanate ester compound, Mitsubishi Silica is used as a filler, Irgacure® OXE01 is used as a photoinitiator, BTZ-AC is used as a copper rust inhibitor, methacrylate oxypropyltrimethoxysilane is used as an adhesion promoter, titanium carboxyethyl acrylate is used as a curing catalyst, and xylene is used as a solvent.

[0151] The dielectric film-forming composition 15 is applied to a 40-micron thick PET film using an applicator to form a film. This film is baked at 115°C for 8 minutes using a hot plate to remove most of the solvent. Then the film is baked under nitrogen at 170°C for 70 minutes to obtain a stable dielectric film having a thickness of 120 microns. After lifting the dielectric film from the PET film, the dielectric film is placed on a 25-micron KAPTON film and then baked under nitrogen at 210°C for a further 80 minutes.

[0152] After cooling to room temperature, the dielectric film is removed from the KAPTON film and cut into slits to form a 3 mm wide film. This film is then analyzed for its thermomechanical properties using TMA.

[0153] ●Example 16: Preparation and application of dielectric film forming composition 16 The dielectric film-forming composition of this example consists of cyclopolymerized polyisoprene (38.60 g of a 28.5% solution in xylene supplied by Fujifilm Electronic Materials USA), and Resiprene (11.00 g, ESINE ITALIANE). The solution is prepared by mixing tricyclodecanedimethanol diacrylate (2.2g), hexanediacrylate (2.2g), novolac (AroCy® XU371) (11.00g), Primaset PT-3 (5.5g), Mitsubishi silica (3.30g), electrostatically stabilized silica (2.20g), Irgacure® OXE-01 (0.33g), dicumyl peroxide (3.30g), 5-methylbenzotriazole (BTZ-AC, 0.11g), methacrylateoxypropyltrimethoxysilane (0.33g), xylene (27.60g), and cyclopentanone (6.70g) to obtain a homogeneous solution. This solution is filtered using a 5.0 micron PTFE filter.

[0154] In this embodiment, SC Rubber and Resiprene are used as two different cyclized polydiene polymers, tricyclodecane dimethanol diacrylate and hexane diacrylate are used as reactive functional compounds, novolac (AroCy® XU371) and Primaset® PT-3 are used as cyanate ester compounds, Mitsubishi Silica and electrostatically stabilized silica are used as fillers, Irgacure® OXE01 is used as a photoinitiator, dicumyl peroxide is used as a thermal initiator, BTZ-AC is used as a copper rust inhibitor, methacrylate oxypropyl trimethoxysilane is used as an adhesion promoter, and xylene and cyclopentanone are used as solvents.

[0155] The dielectric film-forming composition 16 is applied to a 40-micron thick PET film using an applicator to form a film. This film is baked at 100°C for 9 minutes using a hot plate to remove most of the solvent. Then the film is baked under nitrogen at 160°C for 75 minutes to obtain a stable dielectric film having a thickness of 130 microns. After lifting the dielectric film from the PET film, the dielectric film is placed on a 25-micron KAPTON film and then baked under nitrogen at 250°C for a further 75 minutes.

[0156] After cooling to room temperature, the dielectric film is removed from the KAPTON film and cut into slits to form a 3 mm wide film. This film is then analyzed for its thermomechanical properties using TMA.

[0157] ●Example 17: Preparation and application of dielectric film forming composition 17 The dielectric film-forming composition of this example is prepared by mixing cyclized polyisoprene (38.60 g of a 28.5% solution in xylene supplied by Fujifilm Electronic Materials USA as SC Rubber), Resiprene 35 (11.00 g, supplied by ESINE ITALIANE SrI), ALPEX CK514 / PAST (5.5 g, supplied by Allnex), tricyclodecanedimethanol diacrylate (2.2 g), hexane diacrylate (2.2 g), novolac (AroCy® XU371, 11.00 g), electrostatically stabilized silica (2.20 g), dicumyl peroxide (3.30 g), 5-methylbenzotriazole (BTZ-AC, 0.11 g), methacrylatexpropyltrimethoxysilane (0.33 g), and cyclohexanone (26.70 g) to obtain a homogeneous solution. This solution is filtered using a 5.0 micron PTFE filter.

[0158] In this embodiment, SC rubber, Resiprene, and ALPEX CK514 / PAST are used as three different cyclized polydiene polymers, tricyclodecane dimethanol diacrylate and hexane diacrylate are used as reactive functional compounds, novolac (AroCy® XU371) is used as a cyanate ester compound, electrostatically stabilized silica is used as a filler, dicumyl peroxide is used as a thermal initiator, BTZ-AC is used as a copper rust inhibitor, methacrylateoxypropyltrimethoxysilane is used as an adhesion promoter, and cyclohexanone is used as a solvent.

[0159] The dielectric film-forming composition 17 is applied to a 40-micron thick PET film using an applicator to form a film. This film is baked at 100°C for 9 minutes using a hot plate to remove most of the solvent. Then the film is baked under nitrogen at 160°C for 75 minutes to obtain a stable dielectric film having a thickness of 130 microns. The dielectric film is lifted from the PET film and placed on a 25-micron KAPTON film, and then baked under nitrogen at 250°C for a further 75 minutes.

[0160] After cooling to room temperature, the dielectric film is removed from the KAPTON film and cut into slits to form a 3 mm wide film. This film is then analyzed for its thermomechanical properties using TMA.

[0161] ●Example 18: Preparation and application of dielectric film forming composition 18 The dielectric film-forming composition of this example consists of: cyclized polyisoprene (38.60 g of a 28.5% solution in xylene supplied by Fujifilm Electronic Materials USA), b-stage methacrylate-functionalized cycloolefin thermosetting resin (Proxima®) (11.00 g), tricyclodecanedimethanol diacrylate (2.20 g), hexanediacrylate (2.20 g), and Primaset® DT-4000 (11.00 g). The solution is prepared by mixing Primaset PT-3 (5.50g), carbon black (3.30g), electrostatically stabilized silica (2.20g), Irgacure® OXE-01 (0.33g), dicumyl peroxide (DCP, 3.30g), 5-methylbenzotriazole (BTZ-AC, 0.11g), methacrylateoxypropyltrimethoxysilane (0.33g), xylene (27.60g), and cyclopentanone (6.70g) to obtain a homogeneous solution. This solution is filtered using a 5.0 micron PTFE filter.

[0162] In this embodiment, SC rubber and b-stage methacrylate-functionalized cycloolefin thermosetting resin (polyolefin dielectric polymer) are used as two different cyclized polydiene polymers, tricyclodecane dimethanol diacrylate and hexane diacrylate are used as reactive functional compounds, Primaset® DT-4000 and Primaset® PT-3 are used as cyanate ester compounds, carbon black and electrostatically stabilized silica are used as fillers, Irgacure® OXE01 is used as a photoinitiator, dicumyl peroxide is used as a thermal initiator, BTZ-AC is used as a copper rust inhibitor, methacrylateoxypropyltrimethoxysilane is used as an adhesion promoter, and xylene and cyclopentanone are used as solvents.

[0163] The dielectric film-forming composition 18 is applied to a 55-micron thick PET film using an applicator to form a film. This film is baked at 90°C for 15 minutes using a hot plate to remove most of the solvent. Then the film is baked under nitrogen at 170°C for 70 minutes to obtain a stable dielectric film with a thickness of 220 microns. After lifting the dielectric film from the PET film, the dielectric film is placed on a 25-micron KAPTON film and then baked under nitrogen at 250°C for a further 70 minutes.

[0164] After cooling to room temperature, the dielectric film is removed from the KAPTON film and cut into slits to form a 3 mm wide film. This film is then analyzed for its thermomechanical properties using TMA.

[0165] ●Example 19: Preparation and application of dielectric film forming composition 19 The dielectric film-forming composition of this example is prepared by mixing cyclized polyisoprene (77.20 g of a 28.5% solution in xylene supplied by Fujifilm Electronic Materials USA), tricyclodecanedimethanol diacrylate (4.40 g), Primaset® DT-4000 (11.00 g), polydiene particles (5.50 g), Irgacure® OXE-01 (0.67 g), BTZ-AC (0.11 g), methacrylate oxypropyltrimethoxysilane (0.33 g), titanium carboxyethyl acrylate (0.11 g), and xylene (6.70 g) to obtain a homogeneous solution. This solution is filtered using a 5.0 micron PTFE filter.

[0166] In this embodiment, SC rubber is used as a cyclized polydiene, Primaset® DT-4000 is used as a cyanate ester compound, polydiene particles are used as a filler, tricyclodecanedimethanol diacrylate is used as a reactive functional compound, Irgacure® OXE01 is used as a photoinitiator, BTZ-AC is used as a copper rust inhibitor and catalyst, methacryloxypropyltrimethoxysilane is used as an adhesion promoter, titanium carboxyethyl acrylate is used as a curing catalyst, and xylene is used as a solvent.

[0167] The dielectric film-forming composition 19 is applied to a 60-micron thick PET film using an applicator to form a film. This film is baked at 120°C for 6 minutes using a hot plate to remove most of the solvent. Then the film is baked under nitrogen at 200°C for 50 minutes to obtain a stable dielectric film having a thickness of 350 microns. After lifting the dielectric film from the PET film, the dielectric film is placed on a 25-micron KAPTON film and then baked under nitrogen at 250°C for a further 50 minutes.

[0168] After cooling to room temperature, the dielectric film is removed from the KAPTON film and cut into slits to form a 3 mm wide film. This film is then analyzed for its thermomechanical properties using TMA.

[0169] ●Example 20: Preparation and application of dielectric film forming composition 20 The dielectric film-forming composition of this example is prepared by mixing cyclized polyisoprene (77.20 g of a 28.5% solution in xylene supplied by Fujifilm Electronic Materials USA), tricyclodecanedimethanol diacrylate (4.40 g), Primaset® DT-4000 (11 g), carbon nanotubes (CNTs) (5.5 g), Irgacure® OXE-01 (0.67 g), BTZ-AC (0.11 g), methacrylate oxypropyltrimethoxysilane (0.33 g), titanium carboxyethyl acrylate (0.11 g), and xylene (6.7 g) to obtain a homogeneous solution. This solution is filtered using a 5.0 micron PTFE filter.

[0170] In this embodiment, SC rubber is used as a cyclized polydiene, novolac (product Primaset® DT-4000) is used as a cyanate ester compound, carbon nanotubes are used as a filler, Irgacure® OXE01 is used as a photoinitiator, BTZ-AC is used as a copper rust inhibitor, methacrylate oxypropyltrimethoxysilane is used as an adhesion promoter, titanium carboxyethyl acrylate is used as a curing catalyst, and xylene is used as a solvent.

[0171] The dielectric film-forming composition 20 is applied to a 40-micron thick PET film using an applicator to form a film. This film is baked on a hot plate at 85°C for 11 minutes to remove most of the solvent. Then the film is baked under nitrogen at 200°C for 1 hour to obtain a stable dielectric film having a thickness of 400 microns. After lifting the dielectric film from the PET film, the dielectric film is placed on a 25-micron KAPTON film and then baked under nitrogen at 250°C for another 1 hour.

[0172] After cooling to room temperature, the dielectric film is removed from the KAPTON film and cut into slits to form a 3 mm wide film. This film is then analyzed for its thermomechanical properties using TMA.

[0173] ●Example 21: Preparation and application of dielectric film forming composition 21 The dielectric film-forming composition of this example is prepared by mixing cyclized polyisoprene (77.20 g of a 28.5% solution in xylene supplied by Fujifilm Electronic Materials USA as SC rubber), tricyclodecanedimethanol diacrylate (4.40 g), Primaset® DT-4000 (11.00 g), Mitsubishi particles (Fe3O4, 5.50 g), Irgacure® OXE-01 (0.67 g), BTZ-AC (0.11 g), methacrylate oxypropyltrimethoxysilane (0.33 g), zirconium carboxyethyl acrylate (0.11 g), and xylene (6.70 g) to obtain a homogeneous solution. This solution is filtered using a 5.0 micron PTFE filter.

[0174] In this embodiment, SC rubber is used as a cyclized polydiene polymer, Primaset® DT-4000 is used as a cyanate ester compound, Mitsubishi particles are used as a filler, Irgacure® OXE01 is used as a photoinitiator, BTZ-AC is used as a copper rust inhibitor, methacrylate oxypropyl trimethoxysilane is used as an adhesion promoter, zirconium carboxyethyl acrylate is used as a curing catalyst, and xylene is used as a solvent.

[0175] The dielectric film-forming composition 21 is applied to a 50-micron thick PET film using an applicator to form a film. This film is baked at 85°C for 13 minutes using a hot plate to remove most of the solvent. Then the film is baked at 160°C for 1 hour under nitrogen to obtain a stable dielectric film with a thickness of 180 microns. After lifting the dielectric film from the PET film, the dielectric film is placed on a 25-micron KAPTON film and then baked at 220°C for a further 75 minutes under nitrogen.

[0176] After cooling to room temperature, the dielectric film is removed from the KAPTON film and cut into slits to form a 3 mm wide film. This film is then analyzed for its thermomechanical properties using TMA.

[0177] ●Example 22: Preparation and application of dielectric film forming composition 22 The dielectric film-forming composition of this example is prepared by mixing cyclized polyisoprene (77.20 g of a 28.5% solution in xylene supplied by Fujifilm Electronic Materials USA as SC Rubber), tricyclodecanedimethanol diacrylate (4.40 g), Primaset® DT-4000 (11.00 g), alumina (5.50 g), Irgacure® OXE-01 (0.67 g), BTZ-AC (0.11 g), glycidoxypropyltrimethoxysilane (Silquest A-187, 0.33 g), zirconium carboxyethyl acrylate (0.11 g), and xylene (6.70 g) to obtain a homogeneous solution. This solution is filtered using a 5.0 micron PTFE filter.

[0178] In this embodiment, SC rubber is used as a cyclized polydiene, tricyclodecanedimethanol diacrylate is used as a reactive functional compound, Primaset® DT-4000 is used as a cyanate ester compound, alumina is used as a filler, Irgacure® OXE01 is used as a photoinitiator, BTZ-AC is used as a copper rust inhibitor, glycidoxypropyltrimethoxysilane is used as an adhesion promoter, zirconium carboxyethyl acrylate is used as a curing catalyst, and xylene is used as a solvent.

[0179] The dielectric film-forming composition 22 is applied to a 45-micron thick PET film using an applicator to form a film. This film is baked at 95°C for 10 minutes using a hot plate to remove most of the solvent. Then the film is baked at 180°C for 1 hour under nitrogen to obtain a stable dielectric film having a thickness of 100 microns. After lifting the dielectric film from the PET film, the dielectric film is placed on a 25-micron KAPTON film and then baked at 225°C for a further 65 minutes under nitrogen.

[0180] After cooling to room temperature, the dielectric film is removed from the KAPTON film and cut into slits to form a 3 mm wide film. This film is then analyzed for its thermomechanical properties using TMA.

[0181] ●Example 23: Preparation and application of dielectric film forming composition 23 The dielectric film-forming composition of this example is prepared by mixing cyclized polyisoprene (77.2 g of a 28.5% solution in xylene supplied by Fujifilm Electronic Materials USA as SC rubber), tricyclodecanedimethanol diacrylate (4.40 g), novolac (AroCy® XU371) (11.00 g), copper particles (5.50 g), Irgacure® OXE-01 (0.67 g), BTZ-AC (0.11 g), methacrylate (0.33 g), zirconium carboxyethyl acrylate (0.11 g), and xylene (6.70 g) to obtain a homogeneous solution. This solution is filtered using a 5.0 micron PTFE filter.

[0182] In this embodiment, SC rubber is used as a cyclized polydiene, tricyclodecanedimethanol diacrylate is used as a reactive functional compound, novolac (AroCy® XU371) is used as a cyanate ester compound, copper particles are used as a filler, Irgacure® OXE01 is used as a photoinitiator, BTZ-AC is used as a copper rust inhibitor, methacrylate oxypropyltrimethoxysilane is used as an adhesion promoter, zirconium carboxyethyl acrylate is used as a curing catalyst, and xylene is used as a solvent.

[0183] The dielectric film-forming composition 23 is applied to a 50-micron thick PET film using an applicator to form a film. This film is baked on a hot plate at 100°C for 12.5 minutes to remove most of the solvent. Then the film is baked under nitrogen at 175°C for 75 minutes to obtain a stable dielectric film with a thickness of 180 microns. After lifting the film from the PET film, the film is placed on a 25-micron KAPTON film and then baked under nitrogen at 225°C for a further 75 minutes.

[0184] After cooling to room temperature, the dielectric film is removed from the KAPTON film and cut into slits to form a 3 mm wide film. This film is then analyzed for its thermomechanical properties using TMA.

[0185] ●Example 24: Preparation and application of dielectric film forming composition 24 The dielectric film-forming composition of this example consists of: cyclized polyisoprene (38.60 g of a 28.5% solution in xylene supplied by Fujifilm Electronic Materials USA as SC rubber), Resiprine (5.50 g), tricyclodecanedimethanol diacrylate (2.20 g), hexane diacrylate (2.20 g), 2,2-bis(4-cyanatophenyl)propane (3.60 g), Primaset® DT-4000 (3.66 g), Primaset® PT30 (3.66 g), Irgacure® OXE01 (0.33 g), dicumyl peroxide (DCP, 3.30 g), 5-methylbenzotriazole (MBTA, 0.11 g), BTZ-AC (0.11 g), methacrylate oxypropyltrimethoxysilane (0.11 g), and glycidoxypropyltrimethoxysilane (Silquest). This solution is prepared by mixing A-187 (0.22g), titanium carboxyethyl acrylate (0.11g), a 0.5% solution of Polyfox 3260 in cyclopentanone (0.11g), a 0.015% solution of Victoria Blue naphthalene sulfonate in cyclopentanone (1.00g solution), poly(bisphenol A carbonate) (1.00g), xylene (6.70g), mesitylene (20.00g), and cyclohexanone (7.60g) to obtain a homogeneous solution. This solution is filtered using a 5.0 micron PTFE filter.

[0186] In this embodiment, SC Rubber and Resiprene are used as two different cyclized polydiene polymers, tricyclodecane dimethanol diacrylate and hexane diacrylate are used as reactive functional compounds, 2,2-bis(4-cyanatophenyl)propane, Primaset® DT-4000, and Primaset® PT30 are used as cyanate ester compounds, Irgacure® OXE01 is used as a photoinitiator, dicumyl peroxide is used as a thermal initiator, MBTA and BTZ-AC are used as copper rust inhibitors, methacrylate oxypropyl trimethoxysilane and glycidoxypropyl trimethoxysilane are used as adhesion promoters, titanium carboxyethyl acrylate is used as a curing catalyst, Polyfox 3260 is used as a surfactant, naphthalene sulfonate of Victoria Blue dye is used as a dye, poly(bisphenol A carbonate) is used as a binder to reduce dielectric loss, and xylene, mesitylene, and cyclohexanone are used as solvents.

[0187] The dielectric film-forming composition 24 is applied to a 40-micron thick PET film using an applicator to form a film. This film is baked at 100°C for 10 minutes using a hot plate to remove most of the solvent. Then the film is baked under nitrogen at 175°C for 70 minutes to obtain a stable dielectric film with a thickness of 140 microns. After lifting the dielectric film from the PET film, the dielectric film is placed on a 25-micron KAPTON film and then baked under nitrogen at 220°C for a further 1 hour.

[0188] After cooling to room temperature, the dielectric film is removed from the KAPTON film and cut into slits to form a 3 mm wide film. This film is then analyzed for its thermomechanical properties using TMA.

[0189] ●Example 25: Preparation and application of dielectric film forming composition 25 The dielectric film-forming composition of this example is prepared by mixing cyclized polyisoprene (Resiprene, 11.00 g) and AroCy® L-10 (11.00 g) and heating to 50°C to obtain a homogeneous solution. After cooling to room temperature, the solution is filtered using a 5.0 micron PTFE filter.

[0190] In this embodiment, Resiprene is used as the cyclized polydiene polymer, and AroCy(registered trademark)L-10 is used as the cyanate ester compound.

[0191] The dielectric film-forming composition 25 is applied to a 40-micron thick PET film using an applicator to form a film. This film is baked at 115°C for 8 minutes using a hot plate to remove most of the solvent. Then the film is baked under nitrogen at 170°C for 70 minutes to obtain a stable dielectric film having a thickness of 120 microns. After lifting the dielectric film from the PET film, the dielectric film is placed on a 25-micron KAPTON film and then baked under nitrogen at 210°C for a further 80 minutes.

[0192] After cooling to room temperature, the dielectric film is removed from the KAPTON film and cut into slits to form a 3 mm wide film. This film is then analyzed for its thermomechanical properties using TMA.

[0193] ●Example 26: Preparation of fine Cu lines and ultrafine Cu lines in polyolefin cyanate ester dielectrics The dielectric film-forming composition is prepared by mixing cyclized polyisoprene (57.90 g of a 28.5% solution in xylene supplied by Fujifilm Electronic Materials USA as SC rubber), tricyclodecanedimethanol diacrylate (3.30 g), 2,2-bis(4-cyanatophenyl)propane (8.25 g), dicumyl peroxide (0.50 g), and xylene (25.20 g) to obtain a homogeneous solution. This solution is filtered using a 5.0 micron PTFE filter.

[0194] This solution is spin-coated onto a 100 mm PVD-copper wafer to form a film. Then, this film is baked at 115°C for 6 minutes using a hot plate. After that, the film is baked under nitrogen at 250°C for 2 hours to form a dielectric film with a thickness of approximately 3 microns.

[0195] TIS193IL-A01 supplied by Fujifilm Electronic Materials USA is spin-coated onto the upper surface of the dielectric film in this embodiment to form a silicon-containing resist layer. The silicon-containing resist layer is baked on a hot plate at 135°C for 90 seconds to remove most of the solvent, completing the preparation of the laminate of the dielectric film and the silicon-containing resist layer.

[0196] The TIS193L-A01 layer was tested using a Canon 248nm stepper (NA 0.65, Sigma 2 (cyclic)) through trench test pattern reticle 1, yielding 77 mJ / cm². 2 The wafer is exposed with a fixed exposure dose and a fixed focus of 0 μm. The exposed silicon-containing resist layer is then baked at 125°C for 90 seconds and developed in 2.38 N TMAH for 60 seconds to resolve trenches with dimensions of 10 μm when observed with an optical microscope, and containing an ultrafine 2 μm trench pattern beneath them. The wafer is cut into 2-inch x 2-inch square coupons. The ultrafine trench pattern is transferred to the dielectric film by etching with an oxygen plasma at 250 W Rf and an oxygen gas flow rate of 15 sccm for 5 minutes.

[0197] ●Example 27: Preparation of a dried film The dielectric film-forming composition of this example was prepared by mixing cyclized polyisoprene (360 g of a 28.5% solution in xylene supplied by Fujifilm Electronic Materials USA), tricyclodecanedimethanol diacrylate (20.52 g), 2,2-bis(4-cyanatophenyl)propane (51.30 g), dicumyl peroxide (3.08 g), methacrylateoxypropyltrimethoxysilane (3.08 g), BTZ-AC (1.03 g), and xylene (162.1 g) to obtain a homogeneous solution. This solution was filtered using a 0.2 micron PTFE filter.

[0198] The above dielectric film-forming composition was applied to a 16.2-inch wide and 36-micron thick polyethylene terephthalate (PET) film (TCH21, manufactured by DuPont Teijin Films USA) used as a carrier substrate, at a line speed of 2 feet / min (61 cm / min) and a clearance of 60 microns, using a slot die coater obtained from Fujifilm USA (Greenwood, South Carolina). The film was dried at 194 degrees Fahrenheit to obtain a film (dried film 1) with a thickness of approximately 32.3 microns. A biaxially oriented polypropylene film (BOPP, manufactured by Impex Global in Houston, Texas) with a width of 16 inches and a thickness of 30 microns was then layered on top of this polymer layer by roll compression to act as a protective layer.

[0199] After removing the protective layer by peeling, the two dry films (Dry Film 1) (6 inches x 6 inches) were stacked together and placed on a 12-inch x 12-inch steel plate. The films were successfully laminated by vacuum lamination (0.2-0.4 Torr) for 20 seconds, subjected to both a pressure of 40 psi and a vacuum of 0.2-0.4 Torr for 180 seconds. The lamination temperature was 60°C. The lamination process was performed using a DPL-24A differential pressure laminator manufactured by OPTEK, Inc. in New Jersey. This process was repeated 11 times.

[0200] A thick film was obtained by laminating 12 layers of the dried film 1. The film was then baked under nitrogen at 150°C for 1 hour to obtain a stable dielectric film with a thickness of 350 microns. After lifting the dielectric film from the PET film, the dielectric film was placed on a 25-micron KAPTON film and then baked under nitrogen at 200°C for another 1 hour.

[0201] This thick film is used for measuring dielectric properties (Dk and Df).

[0202] ●Example 28: Formation of a 3D object The dielectric film-forming composition of Example 4 is spin-coated at 1200 rpm onto a silicon oxide wafer having a copper plating pattern with line / space / height in the range of 8 / 8 / 6 microns to 15 / 15 / 6 microns. The coated film is baked at 95°C for 5 minutes using a hot plate to form a film with a thickness of approximately 13 microns. Then, the photosensitive composition is exposed to 500 mJ / cm using an LED i-line exposure system. 2 Blanket exposure is performed. The photosensitive composition is cured in a YES oven at 170°C for 2 hours. In this way, a three-dimensional object is prepared in which individual copper structures are surrounded by a dielectric film.

[0203] ●Example 29: Copper deposition The dielectric film-forming composition of Example 4 is spin-coated onto a PVD copper wafer at 1200 rpm. This film is baked using a hot plate at 95°C for 6 minutes to form a photosensitive composition film with a thickness of 8 microns. The photosensitive composition film is subjected to a trench test test using a Canon i-line stepper (NA 0.45, Sigma 0.7) through a trench test pattern reticle at 500 mJ / cm². 2The photosensitive film is exposed with a fixed exposure dose and a fixed focus of -1 micron. The exposed photosensitive film is then developed for 40 seconds using cyclopentanone dynamic development and observed with an optical microscope (and confirmed by a scanning electron microscope (SEM)) to resolve trenches with dimensions of 50 microns and containing an ultrafine 4-micron trench pattern beneath them. The photosensitive composition is cured in a YES oven at 170°C for 2 hours.

[0204] Then, the wafer is electroplated, and when observed with a SEM, copper lines with a height of 3.0 microns are formed in all the trenches. Copper electrodeposition is achieved using an electrolyte composition consisting of copper ions (30 g / L), sulfuric acid (50 g / L), chloride ions (40 ppm), poly(propylene glycol) (500 ppm), 3,3-dithiobis(1-propanesulfonate) disodium (200 ppm), and bis(sodium sulfopropyl) disulfide (100 ppm). Electroplating is carried out in a beaker with stirring under the following conditions: Anode: Copper; Plating temperature: 25°C; Current density: 10mA / cm² 2 ; and time: 2 minutes. After electroplating, the micro trenches are cut, and the copper filling is examined using an optical microscope and a scanning electron microscope to confirm that the copper is completely filled without voids. The deposition time is also adjusted to avoid the formation of excess deposition.

[0205] ●Example 30: Moisture permeability test 25 g of desiccant (CaCl2) was placed in an EZ cup and covered with a dielectric film prepared in Example 1, 4, or 8 having a diameter of 63.5 mm. The EZ cup was sealed using a screw-in flanged ring between two neoprene gaskets and placed in a climate chamber (40°C; 90% RH) for 24 hours. The weight of the dielectric film and the assembled EZ cup was measured before and after storage in the climate chamber. The water vapor transmission rate (WVT) was calculated using the following formula. WVT = G / (t × A) Here, G is the weight change (g), t is time (h), and A is the area of ​​the dielectric film (m²). 2 ) where G / t = slope of the line, grains / h, and WVT = water vapor transmission rate, grains / h·m 2 That is the case.

[0206] [Table 1]

[0207] As shown in Table 2, the films prepared in Examples 1, 4, and 8 exhibited low water vapor permeability or moisture permeability.

Claims

1. a) At least one cyclized polydiene resin having a substituted or unsubstituted alkenyl group; b) At least one reactive functional compound having at least two functional groups that can react with the substituted or unsubstituted alkenyl groups on the cyclized polydiene resin; and c) At least one catalyst capable of inducing the reaction between the cyclized polydiene resin and the reactive functional compound. A dielectric film forming composition containing the following:

2. The composition according to claim 1, wherein the at least one cyclized polydiene resin comprises cyclized polyisoprene, cyclized polybutadiene, cyclized polypentadiene, or a copolymer thereof.

3. The composition according to claim 1, wherein the at least one cyclized polydiene resin has a weight-average molecular weight (Mw) of about 5,000 daltons or more and about 500,000 daltons or less.

4. The at least one cyclized polydiene resin is a) Cyclic polydiene resins having a weight-average molecular weight of approximately 5,000 Daltons to approximately 20,000 Daltons; b) Cyclic polydiene resins having a weight-average molecular weight of approximately 25,000 Daltons to approximately 60,000 Daltons; c) Cyclic polydiene resin having a weight-average molecular weight of approximately 70,000 Daltons to approximately 200,000 Daltons The composition according to claim 1, which is a mixture of the following.

5. The composition according to claim 1, wherein the at least one cyclized polydiene resin is present in an amount of about 2% to about 40% by weight of the composition.

6. The dielectric film forming composition is capable of forming a dielectric film having a Tg of about 120°C or higher, as described in claim 1.

7. The composition according to claim 1, wherein the at least one reactive functional compound comprises a compound having at least two functional groups selected from the group consisting of a (meth)acrylate group, an olefin group, a cycloolefin group, an alkynyl group, and combinations thereof.

8. The composition according to claim 1, wherein the at least one reactive functional compound is present in an amount of about 1% to about 25% by weight of the composition.

9. The composition according to claim 1, wherein the at least one catalyst is present in an amount of about 0.2% to about 3% by weight of the composition.

10. a) Forming a film by coating a substrate with the dielectric film forming composition described in claim 1; b) Optionally, bake the film at a temperature of approximately 50°C to approximately 150°C for approximately 20 seconds to approximately 240 seconds; c) Exposing the film to radiation, heat, or a combination thereof without a mask. A process for preparing dielectric films, including [specific components / methods].

11. a) Coating the carrier substrate with the dielectric film forming composition described in claim 1; b) Drying the coated dielectric film-forming composition to form a dry film; and c) Optionally, apply a protective film to the dried film. A process for preparing a dried film, including [specific components / methods].

12. A dried film prepared by the process described in claim 11.

13. a) Depositing the composition described in claim 1 onto a substrate to form a dielectric film; b) Exposing the dielectric film to radiation, heat, or a combination of radiation and heat; c) Patterning the dielectric film to form a patterned dielectric film having openings; d) Optionally, deposit a seed layer on the patterned dielectric film; e) Depositing a conductive metal layer in at least one opening in the patterned dielectric film; and f) Optionally, repeat steps a) through e) at least once. A process for depositing a conductive metal layer, including [a specific component].

14. a) Providing a substrate including a conductive metal wire structure that forms a network of lines and interconnects on the substrate; b) A step of depositing the composition described in claim 1 onto the substrate to form a dielectric film; c) Exposing the dielectric film to radiation, heat, or a combination of radiation and heat; d) Optionally, a step in which steps a) to c) are repeated at least once. A process that includes forming a dielectric film on a substrate.

15. A three-dimensional object formed by the process described in claim 14.

16. The object according to claim 15, comprising two or more stacks of dielectric films.

17. a) at least one cyclized polydiene resin; and b) At least one cyanate ester compound having at least two cyanate groups A dielectric film forming composition containing the following:

18. The above-mentioned at least one cyanate ester compound has structure (I) 【Chemistry 1】 The composition according to claim 17, wherein m is an integer of 2 or more, and A is a divalent organic group containing a substituted or unsubstituted aromatic group.

19. The above-mentioned at least one cyanate ester compound has structure (II) 【Chemistry 2】 The following are the components, where R is a hydrogen atom, a C1-C3 alkyl group, a C1-C3 alkyl group completely or partially substituted with a halogen, or a halogen atom; X is a single bond, -O-, -S-, -(C=O)-, -(C=O)-O-, -O-(C=O)-, -(S=O)-, -(SO ２ ) -, -CH ２ CH ２ -O-, substituted or unsubstituted C1-C10 alkylenes, fully or partially fluorosubstituted C1-C4 alkylenes, substituted or unsubstituted C3-C10 cycloalkylenes, or one of the following groups: 【Transformation 3】 The composition according to claim 18.

20. The above-mentioned at least one cyanate ester compound has structure (III) 【Chemistry 4】 having, where n １ is an integer of 2 or more, and n ２ and n ３ are independently 0 or an integer of 1 to 100, and R １ is a C1-C10 alkyl group or a C1-C20 arylalkyl group, and R ２ is a substituted or unsubstituted C1-C10 alkyl, a substituted or unsubstituted C3-C10 cycloalkyl, a substituted or unsubstituted aryl group, or a -(C=O)-OR ４ group, where R ４ is a substituted alkyl group not sensitive to acids or a substituted arylalkyl group not sensitive to acids, and R ３ is a substituted or unsubstituted C1-C10 alkyl or a fluoro-substituted C1-C4 alkyl, the composition according to claim 17.

21. The composition according to claim 17, wherein the at least one cyanate ester compound is present in an amount of about 1% to about 25% by weight of the composition.

22. a) At least one cyclized polydiene resin having a substituted or unsubstituted alkenyl group; b) At least one reactive functional compound having at least two functional groups that can react with the substituted or unsubstituted alkenyl groups on the cyclized polydiene resin; c) At least one cyanate ester compound having at least two cyanate groups; d) At least one catalyst capable of inducing the reaction between the cyclized polydiene resin and the reactive functional compound; and e) Optionally, at least one solvent A dielectric film forming composition containing the following:

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