Manufacture of integrated circuits using a positive photopatternable dielectric containing polysilsesquioxane with a high silicon content

Abstract

The method includes forming a first layer of a dielectric precursor composition on a substrate, the dielectric precursor composition including a silicon-containing polymer resin, a catalyst capable of catalyzing a condensation reaction of the silicon-containing polymer resin but deactivated in the presence of an acid, and a photoacid generator; irradiating a portion of the first layer of the dielectric precursor composition with radiation in a first imagewise manner to generate an acid in the irradiated portion; heating the exposed first layer to form a cured dielectric resin in the portion of the first layer that has not been irradiated with the radiation; after heating, removing the dielectric precursor composition in the portion irradiated with the radiation; and filling the portion from which the dielectric precursor has been removed with a metal. The dielectric precursor composition is characterized in that the cured resin after curing contains more than 42% by weight of silicon.

Description

Technical Field

[0001] The present invention relates to a method of forming a metal pattern on a dielectric material, and more particularly to a method of forming interconnects used in integrated circuits.

Background Art

[0002] An integrated circuit includes a semiconductor substrate having one or more layers of dielectric material. The semiconductor substrate has conductive interconnects formed by metal via holes or metal trenches formed in the dielectric material. A typical process for forming such a structure includes steps of forming a dielectric layer, applying a photoresist or a photosensitive hard mask, imaging and developing the photoresist to expose a part (or region) of the dielectric layer, etching the dielectric layer to form via holes and / or trenches, and filling the via holes and / or trenches with metal.

[0003] For example, as shown in FIGS. 1(a) to 1(c), a photoresist 11 is applied to a non-photosensitive dielectric material 12 on a substrate 13. The substrate 13 includes, for example, metal, semiconductor, dielectric material, or a combination of two or more of these. For example, the substrate may have a metal top layer, or may include a metal feature (e.g., a line) in the dielectric that can be connected to subsequent metal features by the method shown. As shown in FIG. 1(a), the photoresist 11 is imagewise exposed and developed with radiation of an activation wavelength to remove a part of the photoresist 11 and expose a part of the non-photosensitive dielectric material 12. As shown in FIG. 1(b), the non-photosensitive dielectric material 12 is etched, for example, by reactive ion etching (RIE), to form a void 14 (e.g., a via hole or a trench) down to the substrate 13. Also, the photoresist is removed by the etching. As shown in FIG. 1(c), the void 14 is filled with metal 15 to form a part of the interconnect. Also, as another example, FIGS. 2(a) to 2(f) show the dual damascene process. As shown in FIG. 2(a), the photoresist 11 was exposed and developed with radiation of the activation wavelength so as to remove a part of the photoresist 11 and expose a part of the non-photosensitive dielectric material 12. As shown in FIG. 2(b), the non-photosensitive dielectric material 12 was etched, for example, by reactive ion etching (RIE), the photoresist 11 was removed, and a void 14 for a via hole was formed. As shown in FIG. 2(c), the second photoresist 11 was applied to the non-photosensitive dielectric material 12 to fill the void 14. As shown in FIG. 2(d), the photoresist 11 was exposed and developed with radiation of the activation wavelength imagewise so as to remove a part of the photoresist 11 and expose a part of the non-photosensitive dielectric material 12. As shown in FIG. 2(e), a part of the photoresist 11 and the non-photosensitive dielectric material 12 were removed by etching, and a void 14 having a first region 14v for a via hole and a second region 14t for a trench was formed. As shown in FIG. 2(f), the void was filled with metal 15.

[0004] Examples of the photoresist include hydrocarbon-based photoresists (e.g., polyhydroxystyrene and polymethacrylate-based compositions containing a photosensitive compound or a part thereof) and silicon hard masks (see, for example, US2010 / 0261097, the entire contents of which are incorporated herein by reference). This process is time-consuming and costly.

[0005] Various methods of using a photo-patternable dielectric have been proposed to eliminate the need for photoresist and etching. See, for example, US8029971, WO2005 / 109490, and WO2011 / 057832, the entire contents of all of which are incorporated herein by reference. However, the methods of US8029971 and WO2011 / 057832 that use silicon-based dielectrics are still cumbersome because they require a bake step before developing the exposed dielectric material and a curing step after developing the dielectric layer. WO2005 / 109490 relates to a decomposable photosensitive trench layer material that can be at least partially removed through the top layer by heating, decomposition, and diffusion to form an air gap in the trench layer.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Summary of the Invention

Problems to be Solved by the Invention

[0007] However, there is still a need for a more efficient method of forming integrated circuits.

Means for Solving the Problems

[0008] This specification discloses a method of forming metal interconnects in a dielectric material, the method comprising: forming a first layer of a dielectric precursor composition on a substrate, the dielectric precursor composition comprising a silicon-containing polymer resin, a catalyst capable of catalyzing the condensation reaction of the silicon-containing polymer resin but deactivated in the presence of an acid and losing its ability to catalyze the condensation reaction, and a photoacid generator; exposing a first portion of the first layer of the dielectric precursor composition to radiation in a first imagewise manner to generate an acid in the exposed first portion and form an exposed first layer; heating the exposed first layer to form a cured dielectric resin in a second portion of the first layer that is not exposed to the radiation; removing the dielectric precursor composition of the first portion exposed to the radiation after the heating; and filling the first portion from which the dielectric precursor has been removed with metal.

[0009] Further disclosed is a product manufactured by such a method. The cured dielectric resin in the product may have a dielectric constant of less than 4, preferably less than 3. A cured dielectric resin layer having a maximum thickness of 1.5 μm has resistance to cracking at a temperature of up to 400°C.

[0010] This specification further discloses a composition comprising a curable silicon-containing polymer resin, a catalyst capable of catalyzing the condensation reaction of the silicon-containing polymer resin, a photoacid generator, and an organic solvent, which composition, upon curing, has the silicon-containing polymer resin containing more than 42% by weight, preferably more than at least 42.5% by weight, more preferably more than at least 43% by weight of silicon based on the total weight of the cured resin.

Brief Description of the Drawings

[0011] Next, reference is made to the drawings. These drawings are exemplary embodiments and the same reference numerals are used for the same elements.

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

DETAILED DESCRIPTION OF THE INVENTION

[0012] The method of the present application includes the steps of forming a layer of a photo-patternable dielectric precursor composition on a substrate, exposing the layer to radiation of an activation wavelength, heating and curing the portions of the layer not exposed to the radiation, removing the exposed portions of the layer to form void regions, and filling the void regions with metal. According to this method, RIE is not required, and the steps of removing the photoresist and the related equipment and materials are also not required. The substrate may include a metal, a semiconductor, a dielectric material, or a combination of two or more of these. The substrate may include a metal film or metal feature in its topmost dielectric material so as to contact additional metal incorporated into the method of the present application. For example, the substrate may include a semiconductor material such as Si, SiGe, SiGeC, SiC, GaAs, InAs, InP, or other group III / V or II / VI compound semiconductors. The substrate may include a process wafer such as a silicon wafer or a wafer manufactured in various steps of a semiconductor manufacturing process such as an integrated semiconductor wafer. The substrate may include multiple layers or may be a single layer. The substrate may include a layered substrate such as Si / SiGe, Si / SiC, silicon-on-insulator (SOI), silicon-germanium-on-insulator (SGOI), etc. A substrate composed of a combination including at least one of the above can be used.

[0013] The silicon dielectric precursor composition includes a silicon-containing resin, a catalyst that can catalyze the condensation reaction of the silicon-containing resin but is deactivated in the presence of an acid and loses the ability to catalyze the condensation reaction, and a photoacid generator. Therefore, when the coating region of the silicon dielectric precursor composition is exposed to radiation of the activation wavelength, an acid is generated and the catalyst is deactivated. Thereafter, curing occurs in one or more unexposed regions. Then, development is carried out with an appropriate developer to remove one or more exposed regions. Therefore, the silicon dielectric precursor composition is a positive-type composition.

[0014] The silicon-containing polymer resin can be prepared by one or more monomers having the following molecular structures or a combination of two or more of these.

[0015]

Chemical formula

[0016] Preferably (a), (b), or (a) and (b). R at each occurrence is independently hydrogen or an alkyl group having 1 to 4 carbon atoms, preferably 1 to 3 carbon atoms, more preferably 1 or 2 carbon atoms. Preferably, R is an alkyl group having 1 or 2 carbon atoms. R1 at each occurrence is independently a monovalent organic group having 1 to 30 carbon atoms and optionally 1 to 5 heteroatoms selected from N, O, P, S, or a combination of two or more thereof. For example, R1 may be an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an alkene group having 2 to 30 carbon atoms, or an alicyclic group having 3 to 30 carbon atoms. Each may optionally contain -O-, -CO-, -OCO-, -COO-, or -OCOO- as part of its structure. R1 may further be substituted with one or more epoxy groups. Preferably, R1 is an alkyl group having 1 or 2 carbon atoms in order to provide a cured resin having a silicon content of more than 42% by weight based on the total weight of the cured resin.

[0017] Examples of preferred monomers include methyltrimethoxysilane, tetraethoxysilane, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, cyclohexenyltrimethoxysilane, cyclohexenyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, benzyltrimethoxysilane, benzyltriethoxysilane, phenethyltrimethoxysilane, phenethyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, dipropyldimethoxysilane, dibutyldimethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, trimethylmethoxysilane, dimethylethylmethoxysilane, dimethylphenylmethoxysilane, dimethylbenzylmethoxysilane, dimethylphenethylmethoxysilane, etc., or combinations of two or more thereof.

[0018] The polymerization of the monomer can be carried out in an organic solvent. Exemplary organic solvents for use in the polymerization include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, acetone, acetonitrile, tetrahydrofuran, toluene, hexane, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl normal pentyl ketone, butylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butylene glycol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, propylene glycol mono-tert-butyl ether acetate, γ-butyrolactone, or a combination of two or more thereof. The organic solvent may be propylene glycol monomethyl ether or propylene glycol methyl ether acetate.

[0019] The polymerization of the monomer can be carried out in the presence of one or more polymerization catalysts. The polymerization catalyst may be an acid catalyst. Exemplary acid catalysts include, for example, organic acids such as formic acid, acetic acid, oxalic acid, maleic acid, methanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, or a combination of two or more thereof, or, for example, inorganic acids such as hydrofluoric acid, hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, perchloric acid, phosphoric acid, or a combination of two or more thereof. The acid catalyst may be acetic acid. The acid catalyst can be used in any suitable amount, such as 1 to 10% by weight of the reactor contents.

[0020] The polymerization is carried out at a temperature of 0°C to 110°C, 20°C to 110°C, 50°C to 110°C, or 80°C to 110°C.

[0021] The volatile alkanol formed during the condensation reaction can be removed by distillation as the reaction proceeds. The distillate may also contain an acid catalyst, water, and / or a solvent. The nitrogen gas flowing through the reactor contributes to the distillation. The removal of the volatile alkanol can be carried out during or after the polymerization reaction.

[0022] Examples of the silicon-containing polymer resin thus formed include polysiloxane, polysilsesquioxane, or a combination thereof. For example, the silicon-containing polymer resin contains both polysiloxane and polysilsesquioxane. The silicon-containing polymer resin may include a crosslinked network structure. The network structure may include a series of complex and diverse molecular structures of polysiloxane and polysilsesquioxane. For example, the network structure may include diverse structures such as the following molecular structures.

[0023]

Chemical formula

[0024] However, R and R1 are as defined in the present specification. However, the above simplified structure is not necessarily an accurate and complete description of the silicon-containing polymer resin. The monomers and the polymerization process provide the most accurate description of the polymer.

[0025] The weight average molecular weight Mw of the silicon-containing polymer resin before curing may be 1000 - 50000 g / mol, 1500 - 30000 g / mol, 2000 - 20000 g / mol, or 3000 - 10000 g / mol. The weight average molecular weight can be determined by gel permeation chromatography (GPC) using standard polystyrene, and all of its contents are incorporated herein by reference as described in Williams and Ward, J. Polymer. Sci., Polymer Letters, 6, 621 (1968).

[0026] Exemplary silicon-containing polymer resins include substituted methyl siloxane, substituted methyl silsesquioxane, substituted phenyl siloxane, substituted phenyl silsesquioxane, substituted methyl phenyl siloxane, substituted methyl phenyl silsesquioxane, substituted dimethyl siloxane, substituted diphenyl siloxane, substituted methyl phenyl siloxane, substituted polyphenyl silsesquioxane, substituted polyphenyl siloxane, substituted polymethyl phenyl siloxane, substituted polymethyl phenyl silsesquioxane, substituted polymethyl siloxane, substituted polymethyl silsesquioxane and other substituted siloxanes, substituted silsesquioxanes, substituted polysiloxanes or substituted polysilsesquioxanes, or combinations thereof.

[0027] The silicon-containing polymer resin is included in the dielectric precursor composition in an amount of, for example, 2 to 50 wt%, 4 to 40 wt% or 10 to 30 wt% based on the total weight of the dielectric precursor composition. A composition having a silicon-containing polymer resin within this weight range can produce a film thickness of 100 nm to 4 μm at a typical spin coating speed, for example, 500 to 2000 rpm.

[0028] The catalyst in the silicon dielectric precursor composition can catalyze the condensation reaction of the silicon-containing resin. That is, the silicon-containing resin can be further cross-linked by condensation. The catalyst is deactivated by an acid such as a photoacid generated by a photoacid generator. The acid-deactivatable catalyst used in the present specification refers to a catalyst that is deactivated in the presence of an acid. Such a catalyst is called a curing catalyst.

[0029] The curing catalyst may contain quaternary ammonium and / or amines. For example, methylamine, ethylamine, propylamine, butylamine, ethylenediamine, hexamethylenediamine, dimethylamine, diethylamine, ethylmethylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, cyclohexylamine, dicyclohexylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, hexamethylenetetramine, aniline, N,N-dimethylaniline, N,N-dimethylaminopyridine, pyrrole, piperazine, pyrrolidine, piperidine, benzyltriethylammonium chloride (BTEAC), tetramethylammonium chloride (TMAC), guanidine carbonate, tetramethylammonium hydroxide (TMAH), tetramethylammonium acetate (TMAA), tetrabutylammonium hydroxide (TBAH), tetrabutylammonium acetate (TBAA), cetyltrimethylammonium acetate (CTAA), tetramethylammonium nitrate (TMAN), or a combination of two or more thereof may be mentioned. Other exemplary catalysts include (2-hydroxyethyl)trimethylammonium chloride, (2-hydroxyethyl)trimethylammonium hydroxide, (2-hydroxyethyl)trimethylammonium acetate, (2-hydroxyethyl)trimethylammonium formate, (2-hydroxyethyl)trimethylammonium nitrate, (2-hydroxyethyl)trimethylammonium benzoate, tetramethylammonium formate or a combination of two or more thereof.

[0030] The amount of the curing catalyst may be about 0.0005 wt% to about 0.2 wt%, or about 0.001 wt% to about 0.05 wt% based on the total weight of the dielectric precursor composition. The amount of the catalyst may be about 0.045 wt% to about 4 wt%, or 0.01 wt% to about 0.5 wt% based on the weight of the silicon-containing polymer resin. A photoacid generator is a compound that generates an organic acid upon irradiation with actinic rays or radiation, and known compounds can be used. The photosensitive wavelength of the photoacid generator may be, for example, a wavelength of 10 nm to 450 nm, or 300 nm to 450 nm. In other words, the photoacid generator may be a compound that generates an acid in response to actinic rays within the above wavelength range. Also, the pKa of the acid generated by the photoacid generator may be 4.0 or less, or 3.0 or less.

[0031] Examples of photoacid generators include onium salts, triazine compounds (halomethylated triazine compounds, more particularly, for example, trichloromethyl-s-triazine compounds), oxime sulfonate compounds, bissulfonyldiazomethane compounds, imide sulfonate compounds, diazodisulfone compounds, disulfone compounds, nitrobenzyl sulfonate compounds (for example: o-nitrobenzyl sulfonate compounds). Examples of photoacid generators include sulfonium salts or iodonium salts such as compounds of sulfonium cations with sulfonates or methides, or compounds of iodonium cations with sulfonates. Exemplary sulfonium cations include triphenylsulfonium and tris(4-tert-butoxyphenyl)sulfonium. Exemplary sulfonates include trifluoromethanesulfonate and nonafluorobutane-1-sulfonate. An exemplary methide is tris(trifluoromethyl)methide. Exemplary iodonium cations are iodonium cations having aryl groups such as diphenyliodonium and bis(4-tert-butylphenyl)iodonium. Exemplary sulfonates include trifluoromethanesulfonate and nonafluorobutane-1-sulfonate.

[0032] Exemplary photoacid generators include, for example, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate, (4-methoxyphenyl)diphenylsulfonium trifluoromethanesulfonate, (4-methoxyphenyl)diphenylsulfonium trifluoroacetate, [4-(phenylthio)phenyl]diphenylsulfonium trifluoromethanesulfonate, [4-(phenylthio)phenyl]diphenylsulfonium trifluoroacetate, diphenyliodonium trifluoromethanesulfonate, (p-tert-butoxyphenyl)phenyl iodonium trifluoromethanesulfonate, diphenyliodonium p-toluenesulfonate, (p-tert-butoxyphenyl)phenyl iodonium p-toluenesulfonate, triphenylsulfonium trifluoromethanesulfonate, (p-tert-butoxyphenyl)diphenylsulfonium trifluoromethanesulfonate, bis(p-tert-butoxyphenyl)phenylsulfonium trifluoromethanesulfonate, tris(p-tert-butoxyphenyl)sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, (p-tert-butoxyphenyl)diphenylsulfonium p-toluenesulfonate, bis(p-tert-butoxyphenyl)phenylsulfonium p-toluenesulfonate, tris(p-tert-butoxyphenyl)sulfonium p-toluenesulfonate, triphenylsulfonium nonafluoro-1-butanesulfonate, triphenylsulfonium 1-butanesulfonate, trimethylsulfonium trifluoromethanesulfonate, trimethylsulfonium p-toluenesulfonate, cyclohexylmethyl(2-oxocyclohexyl)sulfonium trifluoromethanesulfonate, cyclohexylmethyl(2-oxocyclohexyl)sulfonium p-toluenesulfonate, dimethylphenylsulfonium trifluoromethanesulfonate, dimethylphenylsulfonium p-toluenesulfonate, dicyclohexylphenylsulfonium trifluoromethanesulfonate, dicyclohexylphenylsulfonium p-toluenesulfonate, trinaphthylsulfonium trifluoromethanesulfonate,Cyclohexylmethyl(2-oxocyclohexyl)sulfonium trifluoromethanesulfonate, (2-norbornyl)methyl(2-oxocyclohexyl)sulfonium trifluoromethanesulfonate, ethylenebis[methyl(2-oxocyclopentyl)sulfonium trifluoromethanesulfonate], 1,2'-naphthylcarbonylmethyltetrahydrothiophenium triflate, diphenyliodonium trifluoroacetate, diphenyliodonium trifluoromethanesulfonate, (4-methoxyphenyl)phenyl iodonium trifluoromethanesulfonate, (4-methoxyphenyl)phenyl iodonium trifluoroacetate, [4-[(2-hydroxy-tetradecyl)oxy]phenyl]phenyl iodonium trifluoromethanesulfonate, [4-[(2-hydroxy-tetradecyl)oxy]phenyl]phenyl iodonium hexafluoroantimonate, [4-[(2-hydroxy-tetradecyl)oxy]phenyl]phenyl iodonium p-toluenesulfonate and other onium salts, or combinations of two or more thereof.

[0033] Exemplary diazomethane compounds include bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(xylenesulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(cyclopentylsulfonyl)diazomethane, bis(n-butylsulfonyl)diazomethane, bis(isobutylsulfonyl)diazomethane, bis(isoamylsulfonyl)diazomethane, 1-tert-amylsulfonyl-1-(tert-butylsulfonyl)diazomethane, etc., or combinations of two or more thereof.

[0034] Exemplary triazine compounds include 2-(3-chlorophenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methylthiophenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxy-β-styryl)-4,6-bis(trichloromethyl)-s-triazine, 2-piperonyl-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(5-methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(4-diethylamino-2-methylphenyl)vinyl]-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, etc., or combinations of two or more of these.

[0035] Exemplary imide sulfonate compounds include trifluoromethylsulfonyloxy-bicyclo-[2.2.1]-hept-5-ene-dicarboximide, succinimide trifluoromethylsulfonate, phthalimide trifluoromethylsulfonate, N-hydroxynaphthalimide methylsulfonate, N-hydroxy-5-norbornene-2,3-dicarboximide propylsulfonate, etc., or combinations of two or more of these.

[0036] A specific example of the photoacid generator is 2-(4-methoxyphenyl)([((4-methylphenyl)sulfonyl)oxy]imino)acetonitrile. The content of the photoacid generator may be about 0.05 wt% to 3 wt%, 0.1 wt% to 2 wt%, 0.1 wt% to 1 wt%, or 0.2 wt% based on the total solids of the composition. The molar ratio of the photoacid generator to the catalyst in the composition may be, for example, 0.5:1 to 10:1, 0.5:1 to 5:1, or 0.5:1 to 1.5:1. The cured silicon-containing dielectric may have a high silicon content. For example, silicon is more than 35 wt%, more than 38 wt%, more than 39 wt%, more than 40 wt%, more than 41 wt%, more than 42 wt%, at least 42.5 wt%, or at least 43 wt%, 46 wt% or less, or 45 wt% or less based on the total weight of the cured silicon-containing dielectric.

[0037] The step of forming a layer of the photo-patternable dielectric precursor composition on a substrate includes applying a coating composition to the substrate. This composition includes a silicon-containing polymer resin, a catalyst (i.e., a curing catalyst deactivated by an acid), a photoacid generator, and a coating solvent.

[0038] Exemplary coating solvents include solvents that do not belong to hydrocarbon-based solvents such as ketones (e.g., acetone, diethyl ketone, methyl ethyl ketone), alcohols, esters, ethers, amines, etc. Examples of solvents include propylene glycol monomethyl ether (PGME), propylene glycol methyl ether acetate (PGMEA), propylene glycol monopropyl ether (PGPE), and ethyl lactate (EL).

[0039] The solvent is included in the composition in an amount of 50 wt% to 98 wt%, 55 wt% to 95 wt%, or 65 wt% to 90 wt% based on the total weight of the dielectric precursor composition. Suitable coating methods include spin coating, spray coating, etc. The solvent is removed to form a solid layer of the photo-patternable dielectric precursor composition. Additional optional components of the coating composition include film modifiers, surfactants, etc. for controlling the diffusion of components in the film, or combinations of two or more of these.

[0040] The film modifier may be a polymer, an oligomer, or a non-polymeric compound. The Mw of the polymer or oligomer used as the film modifier may be less than 5000 g / mol or less than 2000 g / mol, for example, 200 to 5000 g / mol, or 500 to 2000 g / mol. The molecules of the film modifier must be small enough to fill the pores of the film. The film modifier may be a hydrocarbon, preferably a silicon-containing compound. On the other hand, at least one hydroxy group is bonded to each molecule of the film modifier. The hydroxy group can participate in the condensation reaction of the resin film. Exemplary hydrocarbon film modifiers include, for example, polyol and / or analogs such as polyether diol, glycerin, 2-(hydroxymethyl)-1,3-propanediol, 1,3-dihydroxypropan-2-yl dihydrogen phosphate, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, etc.Examples of branched alkylene glycols include neopentyl glycol, 2,4-diethyl-1,5-pentanediol, 2,4-dibutyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, 1-methylethylene glycol, 1-ethylethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, 1,1,1-tris(hydroxymethyl)ethane, 2-hydroxymethyl-1,3-propanediol, 2-ethyl-2-(hydroxymethyl)-1,3-propanediol, 2-hydroxymethyl-2-propyl-1,3-propanediol, 2-hydroxymethyl-1,4-butanediol, 2-hydroxyethyl-2-methyl-1,4-butanediol, 2-hydroxymethyl-2-propyl-1,4-butanediol, 2-ethyl-2-hydroxyethyl-1,4-butanediol, 1,2,3-butanetriol, 1,2,4-butanetriol, 3-(hydroxymethyl)-3-methyl-1,4-pentanediol, 1,2,5-pentanetriol, 1,3,5-pentanetriol, 1,2,3-trihydroxyhexane, 1,2,6-trihydroxyhexane, 2,5-dimethyl-1,2,6-hexanetriol, tris(hydroxymethyl)nitromethane, 2-methyl-2-nitro-1,3-propanediol, 2-bromo-2-nitro-1,3-propanediol, 1,2,4-cyclopentanetriol, 1,2,3-cyclopentanetriol, 1,3,5-cyclohexanetriol, 1,3,5-cyclohexanetricarbinol, butane-1,2,3,4-tetrol, 2,2-bis(hydroxymethyl)-1,3-propanediol, pentane-1,2,4,5-tetrol, etc., or combinations of two or more thereof. The film modifier may be 1,1,1-tris(hydroxymethyl)ethane, pentaerythritol, or a combination of two or more thereof.Exemplary silicon-containing film modifiers include silanols such as diphenylsilanediol, diisobutylsilanediol, 1,4-bis(dimethylhydroxysilyl)benzene, 4-vinylphenylsilanediol, or combinations of two or more thereof. The film modifier may be 30 wt% or less, or 10 wt% or less of the total weight of the resin. The diffusion lengths of the catalyst, photoacid generator, and quencher are controlled by the concentration of the film modifier in the composition. Also, embodiments in which multiple film modifiers are used in the composition are mentioned.

[0041] Removal of the solvent can be carried out as part of the coating (e.g., spin coating) process. If the solvent cannot be sufficiently removed in this process, additional steps such as baking at 40°C to 120°C, 50°C or more and less than 100°C, or 60°C or more and less than 80°C (e.g., on the surface of a hot plate) for 15 seconds to 120 seconds or 30 seconds to 60 seconds may be performed. This baking step should not be at a time and temperature sufficient to cure the silicon-containing polymer resin such that the dried film remains soluble in the developer.

[0042] Exposure may include exposure to radiation of an activation wavelength. Exposure is imagewise exposure to generate a pattern in the photo-patternable dielectric precursor. Exposure can be carried out through a mask or directly by laser addressing. The activation wavelength may be, for example, in the range of 10 nm to 400 nm, or may be a specific wavelength such as 365 nm, 248 nm, 193 nm, 13.5 nm, etc. Combinations including at least one of the above wavelengths can be used.

[0043] Exposure deactivates the catalyst. During the subsequent heat-curing period, the silicon-containing resin precursor cures (e.g., crosslinks) only in the regions not exposed to the radiation. Curing is carried out at a temperature of 60°C to 120°C or 80°C to 110°C for 30 to 120 seconds.

[0044] The exposed and cured silicon-containing dielectric can be developed using an organic solvent (especially a polar organic solvent) or a basic aqueous solution. Examples of organic solvents include cyclohexanone, methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, ethyl methoxyacetate, ethyl ethoxyacetate, propylene glycol monomethyl ether (PGME), ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, 4-methyl-4-methoxypentyl acetate, propylene glycol diacetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, propyl 3-methoxypropionate, etc., or combinations of two or more of these, but are not limited thereto.Examples of the alkaline developer include aqueous solutions of organic bases or inorganic bases such as tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, ethanolamine, propylamine, ethylenediamine, choline, potassium hydroxide, and sodium hydroxide. A specific example of the developer is an aqueous solution of tetramethylammonium hydroxide in a concentration range of 2.5 g / L to 25 g / L. The development is carried out under appropriately determined conditions, for example, at a temperature of 5°C to 50°C and for a time of 10 seconds to 600 seconds.

[0045] The thickness of the dielectric layer can be appropriately selected according to the structure of the interconnect to be manufactured. For example, the thickness of the dielectric layer can range from 2 nm, 5 nm, or 10 nm to 10000 nm, 5000 nm, 1000 nm, 900 nm, 800 nm, 700 nm, 600 nm, 500 nm, 400 nm, 300 nm, 200 nm, or 100 nm. The size of the via hole may have a cross-section or diameter of about 140 nm to 10 μm, or 40 to 1 μm. The width of the trench or line can range from 10 nm or 100 nm to 10 μm or 5 μm.

[0046] Examples of the method for filling the metal include sputtering, physical vapor deposition, chemical vapor deposition, plasma CVD, atomic layer deposition, electroless plating, or a combination of two or more of these. Examples of the metal include tungsten, nickel, cobalt, copper, aluminum, gold, and silver.

[0047] After filling, the layer is planarized, for example, the surface of the layer is planarized using chemical mechanical polishing. As shown in FIGS. 3(a) to 3(c), in an example of the method disclosed in the present specification, a layer 20 of a photo-patternable dielectric precursor composition 21 is formed on a substrate 13. As shown in FIG. 3(b), the photo-patternable dielectric precursor is exposed imagewise with radiation of an activation wavelength, the layer 20 is heated, and a cured dielectric 22 is formed. A portion of the layer exposed to the radiation of the activation wavelength (the "first portion") is removed using, for example, a developer, and voids 14 are formed between regions of the cured dielectric 22 (the "second portion"). As shown in FIG. 3(c), a metal 15 fills the voids 14.

[0048] As shown in FIGS. 4(a) to 4(e), in an example of the method disclosed in the present specification, a layer 20 of a photo-patternable dielectric precursor composition 21 is formed on a substrate 13. As shown in FIG. 4(b), the photo-patternable dielectric precursor is exposed imagewise with radiation of an activation wavelength, the layer 20 is heated, and a cured dielectric 22 is formed. A portion of the layer exposed to the radiation of the activation wavelength (the "first portion") is removed using, for example, a developer, and voids 14v (e.g., via holes) are formed between regions of the cured dielectric 22 (the "second portion"). As shown in FIG. 4(c), an additional photo-patternable dielectric precursor composition 21 is applied to fill the voids and cover the cured dielectric 22. As shown in FIG. 4(d), the additional photo-patternable dielectric precursor 21 is exposed imagewise with radiation of an activation wavelength and further heated, and a cured dielectric 22 is formed. A region of the layer exposed to the radiation of the activation wavelength (the "first region") is removed using, for example, a developer, and voids 14t (e.g., trenches) are formed. Voids 14v and 14t are in fluid communication with each other and form a continuous void region. As shown in FIG. 4(e), a metal 15 fills the voids 14t and 14v.

[0049] As an alternative to this method, instead of removing the first portion of the first layer exposed to radiation of the activation wavelength shown in FIG. 4(b) to form void 14v, a second layer of the photo-patternable dielectric precursor composition 21 is formed on the exposed and cured (undeveloped) photo-patternable dielectric precursor composition. Then, the second layer is exposed and cured, and both the unexposed and uncured first and second layers are developed simultaneously to obtain the structure shown in FIG. 4(d).

[0050] As shown in FIGS. 5(a) to 5(f), an example of the method disclosed in the present specification is that a layer 20 of a photo-patternable dielectric precursor composition 21 is formed on a substrate 13. As shown in FIG. 5(b), the photo-patternable dielectric precursor is imagewise exposed to radiation of the activation wavelength, the layer 20 is heated, and a cured dielectric 22 is formed. The portion of the layer exposed to radiation of the activation wavelength (the "first portion") is removed, for example, using a developer, and a void 14v (for example, a via hole) is formed between the regions of the cured dielectric 22 (the "second portion"). As shown in FIG. 5(c), the metal 15 fills the void 14v. Optionally, after metallization, the upper surface may be planarized before proceeding to the next step. As shown in FIG. 5(d), an additional photo-patternable dielectric precursor composition 21 is applied over the metal 15 and covers the cured dielectric 22. As shown in FIG. 5(e), the additional photo-patternable dielectric precursor is imagewise exposed to radiation of the activation wavelength, further heated, and a cured dielectric 22 is formed. The portion of the layer exposed to radiation of the activation wavelength (the "first region") is removed, for example, using a developer, and a trench 14t (for example, a trench) is formed. As shown in FIG. 5(e), at least a portion of the trench 14t covers at least a portion of the metal 15. However, in other embodiments, such an overlap does not exist. As shown in FIG. 5(f), the metal 15 fills the trench 14t.

[0051] For subsequent layers forming the multi-layer interconnect, the steps of coating, exposure, curing, development, and filling can be repeated.

[0052] To ensure a horizontal surface for starting the creation of the next layer, planarization can be performed. In particular, planarization using chemical mechanical polishing can be carried out after the metallization step.

[0053] After curing, the dielectric is resistant to chemicals. Once cured, there is no or substantially no release of gas from the dielectric material.

[0054] The cured dielectric film may have a dielectric constant less than 4 or less than 3.5 and greater than 2 or 2.5. The dielectric constant can be measured with an impedance analyzer (e.g., E4990A type manufactured by Keysight) according to ASTM D150.

[0055] Products containing metal features and the cured dielectrics manufactured by the methods disclosed in this specification have resistance to cracking. For example, such products do not crack even when heated to 400 °C. In particular, when a 1.5 μm thick cured dielectric baked at 400 °C for 30 minutes was cooled, no cracks were found visually and under a microscope.

[0056] The product may be an electronic device such as a chip or an integrated circuit, or a system including such devices. Examples of such systems include computers, mobile phones, transportation vehicles, electrical products, manufacturing systems, robotic devices, etc.

[0057] Examples Example 1: Synthesis of a silicon-containing polymer resin and preparation of a photo-patternable dielectric 60 g of methyltrimethoxysilane, 30 g of tetraethoxysilane, 250 g of 1-methoxy-2-propanol acetate, 42 g of water, and 9 g of acetic acid were placed in a 500 mL round-bottom flask, mixed well, and distilled for 5 hours. The temperature of the flask contents was raised to the boiling point. The silicon-containing polymer resin was recovered from the flask.

[0058] Example 2: Preparation of a photo-patternable dielectric and process conditions for forming a dielectric pattern. 6 g of the silicon-containing polymer resin obtained in Example 1, 0.5 g of 1-methoxy-2-propanol acetate, 1 g of 1-propoxy-2-propanol, 0.001 g of benzyltrimethylammonium chloride, and 0.01 g of 2-(4-methoxyphenyl)([((4-methylphenyl)sulfonyl)oxy]imino)acetonitrile were placed in a container and mixed until all the components were dissolved. This solution was spin-coated onto a silicon wafer at a rotational speed of 1000 rpm. A film with a thickness of approximately 200 nm was formed on the surface of the wafer. Baking after spin-coating was not required. This film is a photo-patternable dielectric with a thickness of 200 nm. The wafer thus coated was exposed imagewise to radiation having a wavelength of 365 nm to generate acid in the exposed areas. Next, the wafer was baked on a 120 °C surface for 60 seconds. Following this baking, the wafer was immersed in a 2.38 wt% aqueous solution of tetramethylammonium hydroxide for 10 - 40 seconds to form a desired pattern in the dielectric film. Thereafter, the pattern was cured on a 200 °C hot plate for 120 seconds.

[0059] Example 3 For the dielectric resin obtained in Example 1, a 1.5 μm spin-coated layer was formed on a substrate, baked at 400 °C for 30 minutes, and then cooled to conduct the test. No cracks were found in the visual inspection with and without using a microscope.

[0060] Example 4 After forming and curing a film of the silicon-containing polymer resin obtained in Example 1, the dielectric constant was measured using an E4990A impedance analyzer manufactured by Keysight. The measured dielectric constant was 3.0.

[0061] Example 5 The cured silicon resin derived from the resin obtained in Example 1 was tested by inductively coupled plasma mass spectrometry (ICPMS) to measure its silicon content. The silicon content was approximately 43 wt% based on the total weight of the resin.

[0062] The present disclosure further includes the following aspects.

[0063] Aspect 1 A method of forming a metal interconnect in a dielectric material includes forming a first layer of a dielectric precursor composition on a substrate, the dielectric precursor composition including a silicon-containing polymer resin, a catalyst capable of catalyzing a condensation reaction of the silicon-containing polymer resin but deactivated in the presence of an acid to lose the ability to catalyze the condensation reaction, and a photoacid generator; irradiating a portion of the first layer of the dielectric precursor composition imagewise with radiation to generate an acid in the irradiated portion; heating the exposed first layer to form a cured dielectric resin in the portion of the first layer not irradiated with the radiation; removing the dielectric precursor composition in the portion irradiated with the radiation after heating; and filling the portion from which the dielectric precursor has been removed with a metal.

[0064] Aspect 2 In the method according to Aspect 1, after filling a first portion of the first layer from which the dielectric precursor has been removed with the metal, the method further includes applying a second layer of the dielectric precursor composition; irradiating a first region of the second layer of the dielectric precursor composition imagewise with radiation to generate an acid in the irradiated first region; heating the exposed second layer to form a cured dielectric resin in a second region of the second layer not irradiated with the radiation; removing the dielectric precursor composition in the first region of the second layer irradiated with the radiation; and filling the first region of the second layer from which the dielectric precursor has been removed with a metal.

[0065] Aspect 3 In the method described in Aspect 1, after removing the dielectric precursor composition of the first portion of the first layer exposed to the radiation, a step of applying a second layer of the dielectric composition; a step of imagewise exposing a first region of the second layer of the dielectric precursor composition to radiation, the first region of the second layer overlapping the removed first region of the first layer, and generating an acid in the first region of the second layer exposed to the radiation; a step of heating the exposed second layer to form a cured dielectric resin in a second region of the second layer not exposed to the radiation; a step of removing the dielectric precursor composition of the first region of the second layer to form a continuous void region in the removed region of the first region of the first layer and the region of the second layer; and a step of filling the continuous void region with the metal.

[0066] Aspect 4 In the method described in Aspect 1, heating the exposed first layer to form a cured dielectric resin in a second portion of the first layer, and after that and before removing the first portion of the first layer exposed to the radiation, a step of applying a second layer of the dielectric composition to the first layer; a step of imagewise exposing a first region of the second layer of the dielectric precursor composition to radiation, the first region of the second layer overlapping the first portion of the first layer, and generating an acid in the first region of the second layer exposed to the radiation; a step of heating the exposed second layer to form a cured dielectric resin in a second region of the second layer not exposed to the radiation; a step of removing the dielectric precursor composition of the exposed first portion of the first layer and the first region of the layer to form a continuous void region; and a step of filling the continuous void region with the metal.

[0067] Aspect 5 In the method described above, the cured dielectric resin contains at least 38% by weight, preferably at least 40% by weight, more preferably at least 42% by weight of silicon based on the total weight of the cured dielectric resin.

[0068] Aspect 6 In the method described above, the silicon-containing polymer resin is

[0069]

Chemical formula

[0070] Aspect 7 In the method described above, the catalyst contains quaternary ammonium and / or amine, preferably including benzyltriethylammonium chloride (BTEAC), tetramethylammonium chloride (TMAC), guanidine carbonate, and tetramethylammonium hydroxide (TMAH).

[0071] Aspect 8 In the method described above, the amount of the catalyst relative to the weight of the dielectric precursor composition is 0.0005 wt% to 0.2 wt%, preferably 0.001 wt% to 0.05 wt%, or the amount of the catalyst relative to the weight of the silicon-containing polymer resin is 0.005 wt% to 4 wt%, preferably 0.01 wt% to 0.5 wt%.

[0072] Aspect 9 In the method described above, the photoacid generator contains an onium salt, preferably a sulfonium salt or an iodonium salt, more preferably a compound of a sulfonium cation and a sulfonate or methide, or a compound of an iodonium cation and a sulfonate.

[0073] Situation 10 In the method described above, the molar ratio of the photoacid generator to the catalyst is 0.5:1 to 10:1.

[0074] Situation 11 In the method described above, the radiation has a wavelength of 10 nm to 400 nm.

[0075] Situation 12 In the method described above, the layer is exposed to the radiation imagewise through a mask or by laser addressing.

[0076] Situation 13 In the method described above, the filling with metal includes sputtering, vapor deposition, atomic layer deposition, or a combination of two or more of these.

[0077] Situation 14 In the method described above, after filling with metal, the excess metal is removed and planarized to form a flat surface.

[0078] Situation 15 A product formed by the method according to any one of Situations 1 to 14.

[0079] Situation 16 In the product described in Situation 15 above, the cured dielectric resin has a dielectric constant of less than 4, preferably less than 3.5.

[0080] Situation 17 In the product described in Situation 16 above, the cured dielectric resin layer does not crack at a temperature of up to 400 °C.

[0081] Situation 18 The composition contains a curable silicon-containing polymer resin, a catalyst capable of catalyzing the condensation reaction of the silicon-containing polymer resin, a photoacid generator, and one or more organic solvents. When cured, the resin contains more than 42% by weight, preferably more than at least 42.5% by weight, more preferably more than at least 43% by weight of silicon based on the total weight of the cured resin.

[0082] Situation 19 In the composition described in the above Situation 18, the curable silicon-containing polymer resin is a reaction product of monomers consisting of methyltrimethoxysilane, tetraethoxysilane or a combination thereof.

[0083] All ranges disclosed in this specification include endpoints, and each point can be independently combined with others. For example, the range of "25 wt.% or less, particularly 5 wt.% to 20 wt.% " includes both ends of "5 wt.% to 25 wt.% " and all values within this range. It should be noted that ranges can also be formed by combining the above upper and lower limits. For example, the descriptions of "at least 1% by weight or at least 2% by weight" and "10% by weight or less or 5% by weight or less" can be combined to form ranges of "1% by weight to 10% by weight", "1% by weight to 5% by weight", "2% by weight to 10% by weight", and "2% by weight to 5% by weight".

[0084] This disclosure alternately includes, consists of, or consists essentially of any suitable elements disclosed in this specification. This disclosure can additionally or alternatively be formulated so as not to contain, or substantially not contain, any element, material, component, adjuvant or substance used in prior art compositions or not necessary for the achievement of the functions and / or purposes of this disclosure.

[0085] All cited patents, patent applications, and other documents are hereby incorporated by reference in their entirety. However, if the terms in this specification conflict with or are contrary to the terms in the cited documents, the terms in this specification shall prevail over the terms in the cited documents.

[0086] In this specification, unless otherwise limited, all test standards are the latest valid standards as of the filing date of this application. Or, if a priority is claimed, the test standards are the latest valid standards as of the filing date of the earliest published priority application.

Claims

1. Forming a first layer of a dielectric precursor composition on a substrate, the composition comprising a silicon-containing polymer resin, a catalyst capable of catalyzing the condensation reaction of the silicon-containing polymer resin but deactivated in the presence of an acid and losing its ability to catalyze the condensation reaction, and a photoacid generator; Exposing a first portion of the first layer of the dielectric precursor composition in a first imagewise manner to radiation, generating an acid in the exposed first portion, and forming an exposed first layer; Heating the exposed first layer to form a cured dielectric resin in a second portion of the first layer that has not been exposed to the radiation; Removing the dielectric precursor composition in the first portion exposed to the radiation after the heating; Filling the first portion from which the dielectric precursor has been removed with a metal, A method for forming a metal interconnect in a dielectric material.

2. After filling the first portion of the first layer from which the dielectric precursor has been removed with the metal, applying a second layer of the dielectric precursor composition; Exposing a first region of the second layer of the dielectric precursor composition in a second imagewise manner to radiation and generating an acid in the exposed portion; Heating the exposed second layer to form a cured dielectric resin in a second region of the second layer that has not been exposed to the radiation; Removing the dielectric precursor composition in the first region of the second layer exposed to the radiation; Filling the first region of the second layer from which the dielectric precursor has been removed with a metal, further comprising The method according to claim 1.

3. After removing the dielectric precursor composition in the first portion of the first layer exposed to the radiation, applying a second layer of the dielectric composition; Exposing a first region of the second layer of the dielectric precursor composition in an imagewise manner to radiation, wherein the first region of the second layer overlaps with the removed first portion of the first layer, and generating an acid in the first region of the second layer exposed to the radiation; Heating the exposed second layer to form a cured dielectric resin in a second region of the second layer that has not been exposed to the radiation; Removing the dielectric precursor composition in the first region of the second layer and forming a continuous void region in a region where a part of the first layer and a part of the second layer have been removed; Filling the continuous void region with the metal, further comprising The method according to claim 1.

4. Heating the exposed first layer, applying a second layer of the dielectric composition to the first layer after forming a cured dielectric resin in a second portion of the first layer and before removing the first portion of the first layer exposed by the radiation; Imagewise exposing a first region of the second layer of the dielectric precursor composition to radiation, the first region of the second layer overlapping the first portion of the first layer, and generating an acid in the first region of the second layer exposed by the radiation; Heating the exposed second layer and forming a cured dielectric resin in a second region of the second layer that has not been exposed to the radiation; Removing the exposed first portion of the first layer and the dielectric precursor composition in the first region of the layer to form a continuous void region; Further comprising filling the continuous void region with the metal. The method according to claim 1.

5. The cured dielectric resin contains at least 38% by weight, preferably at least 40% by weight, more preferably at least 42% by weight of silicon, based on the total weight of the cured dielectric resin. The method according to any one of claims 1 to 4.

6. The silicon-containing polymer resin 【Chemical 1】 is prepared from monomers having a molecular structure of, or combinations thereof, However, in each occurrence, R is independently hydrogen or an alkyl group having 1 to 4 carbon atoms, preferably 1 to 3 carbon atoms, more preferably 1 or 2 carbon atoms, and preferably, R is an alkyl group having 1 or 2 carbon atoms, and R in the occurrence １ is independently an alkyl group, an aryl group, an alkene group, an alicyclic group, an epoxyalkyl group, or an epoxycycloalkyl group, and preferably, R １ is an alkyl group having 1 or 2 carbon atoms, and the monomer undergoes polymerization in an organic solvent at a temperature of 80°C to 110°C in the presence of a polymerization catalyst, and a volatile alkanol is removed during the polymerization to form the silicon-containing resin The method according to any one of claims 1 to 5.

7. The catalyst contains a quaternary ammonium and / or an amine, preferably benzyltriethylammonium chloride (BTAC), tetramethylammonium chloride (TMAC), guanidine carbonate, tetramethylammonium hydroxide (TMAH). The method according to any one of claims 1 to 6.

8. The amount of the catalyst relative to the total weight of the dielectric precursor composition is 0.0005% to 0.2% by weight, preferably 0.001% to 0.05% by weight, or the amount of the catalyst relative to the total weight of the silicon-containing polymer resin is 0.005% to 4% by weight, preferably 0.01% to 0.5% by weight. The method according to any one of claims 1 to 7.

9. The photoacid generator contains an onium salt, preferably a sulfonium salt or an iodonium salt, more preferably a compound of a sulfonium cation and a sulfonate or a methide, or a compound of an iodonium cation and a sulfonate. The method according to any one of claims 1 to 8.

10. The method according to any one of claims 1 to 9, wherein the molar ratio of the photoacid generator to the catalyst is 0.5:1 to 10:

1.

11. The method according to any one of claims 1 to 10, wherein the radiation has a wavelength of 10 nm to 400 nm.

12. The method according to any one of claims 1 to 11, wherein the layer is imagewise exposed to the radiation through a mask or by laser addressing.

13. The method according to any one of claims 1 to 12, wherein the filling with the metal includes sputtering, vapor deposition, atomic layer deposition, or a combination of two or more thereof.

14. The method according to any one of claims 1 to 13, wherein after filling with the metal, excess metal is removed and planarized to form a flat surface.

15. A product formed by the method according to any one of claims 1 to 14.

16. The product according to claim 15, wherein the cured dielectric resin has a dielectric constant of less than 4, preferably less than 3.

5.

17. The product according to claim 15 or claim 16, wherein the cured dielectric resin layer does not crack at a temperature of up to 400 °C.

18. A curable silicon-containing polymer resin, a catalyst capable of catalyzing the condensation reaction of the silicon-containing polymer resin, a photoacid generator, and an organic solvent, wherein upon curing, the silicon-containing polymer resin contains more than 42% by weight, preferably at least more than 42.5% by weight, more preferably at least more than 43% by weight of silicon based on the total weight of the cured resin. Composition.

19. The composition according to claim 18, wherein the curable silicon-containing polymer resin is a reaction product of monomers consisting of methyltrimethoxysilane, tetraethoxysilane, or a combination thereof. The composition according to claim 18.

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