Fabrication of integrated circuits using positive photopatternable dielectrics including high silicon content polysilsesquioxanes

Abstract

A 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, and a photoacid generator wherein the catalyst is inactivated due to the presence of an acid; exposing a portion of the first layer of the dielectric precursor composition to radiation at a first image level to produce an acid in the portion exposed to the radiation; heating the exposed first layer to form a cured dielectric resin in portions of the first layer that are not exposed to the radiation; after heating, removing the dielectric precursor composition in the portion exposed to the radiation; and filling the portion from which the dielectric precursor has been removed with a metal. The dielectric precursor composition may be characterized in that the resin cured after curing comprises greater than 42 weight percent of elemental silicon.

Description

Technical Field

[0001] The present invention relates to a method of forming metal patterns in dielectric materials, in particular to forming interconnects for integrated circuits. Background Art

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

[0003] For example, as shown in Figures 1(a)-(c), a photoresist 11 is applied to a non-photosensitive dielectric material 12 on a substrate 13. The substrate 13 may include, for example, a metal, a semiconductor, or a dielectric material, or a combination of two or more thereof. For example, the substrate may have a metal top layer or may include a metal feature (e.g., a line) in a dielectric, to which a subsequent metal feature is connected using a method as shown. In Figure 1(a), the photoresist 11 has been exposed to an activating radiation wavelength in an image-level manner and developed to remove a portion of the photoresist 11 to expose a portion of the non-photosensitive dielectric material 12. In Figure 1(b), the non-photosensitive dielectric material 12 has been etched (e.g., by reactive ion etching, RIE) to form a void 14 (e.g., a via or trench) extending to the substrate 13. The etching also removes the photoresist. In Figure 1(c), the void 14 has been filled with metal 15 to form a portion of an interconnect.

[0004] As another example, in Figures 2(a)-(f), a dual damascene method is shown. In Figure 2(a), the photoresist 11 has been exposed to an activating radiation wavelength and developed to remove a portion of the photoresist 11 to expose a portion of the non-photosensitive dielectric material 12. In Figure 2(b), the non-photosensitive dielectric material 12 has been etched (e.g., by reactive ion etching, RIE) to remove the photoresist 11 and form a void 14 for the via. In Figure 2(c), a second photoresist 11 has been applied on the non-photosensitive dielectric material 12 and fills the void 14. In Figure 2(d), the photoresist 11 has been exposed to an activating radiation wavelength in an image-level manner and developed to remove a portion of the photoresist 11 to expose a portion of the non-photosensitive dielectric material 12. In FIG2(e), the photoresist 11 and a portion of the non-photosensitive dielectric material 12 have been removed by etching to form a void 14 having a first region 14v for a via and a second region 14t for a trench. In FIG2(f), the void has been filled with metal 15.

[0005] Examples of photoresists include hydrocarbon-based photoresists (eg, polyhydroxystyrene and polymethacrylate-based compositions including photosensitive compounds or moieties) and silicon hardmasks (see, eg, US 2010 / 0261097, the contents of which are incorporated herein by reference in their entirety). The process can be time consuming and expensive.

[0006] Various methods using photopatternable dielectrics have been proposed to eliminate the need for photoresists and etching. See, for example, US 8,029,971, WO 2005 / 109490 and WO 2011 / 057832, the contents of which are incorporated herein by reference in their entirety. However, the methods of US 8,029,971 and WO 2011 / 057832 using silicon-based dielectrics are still cumbersome because they require a baking step after exposing the dielectric material and before developing, and a curing step after developing the dielectric layer. WO 2005 / 109490 relates to a decomposable photosensitive trench layer material that is at least partially removed by heating, decomposing and diffusing through the top layer to form air gaps in the trench layer.

[0007] There remains a need for a more efficient method of forming integrated circuits. Summary of the invention

[0008] Disclosed herein is a method for forming metal interconnects in a dielectric material, 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 a condensation reaction of the silicon-containing polymer resin, and a photoacid generator, wherein the catalyst can be deactivated by the presence of an acid so that it loses the ability to catalyze the condensation reaction; exposing a first portion of the first layer of the dielectric precursor composition to radiation in a first image-level manner to generate an acid in the first portion exposed to the radiation 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 not exposed to the radiation; after the heating, removing the dielectric precursor composition in the first portion exposed to the radiation; and filling the first portion from which the dielectric precursor has been removed with a metal.

[0009] An article made by such a method is also disclosed. The cured dielectric resin in the article may have a dielectric constant of less than 4, preferably less than 3. The cured dielectric resin layer having a thickness of up to 1.5 microns resists cracking at temperatures up to 400°C.

[0010] Also disclosed herein is a composition comprising: a curable silicon-containing polymer resin, a catalyst capable of catalyzing a condensation reaction of the silicon-containing polymer resin, a photoacid generator, and an organic solvent, wherein, when cured, the silicon-containing polymer resin comprises greater than 42, preferably at least 42.5, and more preferably at least 43 weight percent of elemental silicon based on the total weight of the cured resin. BRIEF DESCRIPTION OF THE DRAWINGS

[0011] Reference is now made to the drawings, which are exemplary embodiments, and in which like elements are numbered like throughout.

[0012] Figures 1(a)-(c) illustrate an example of a prior art method of forming metal features in a dielectric using photoresist.

[0013] 2(a)-(f) illustrate an example of a dual damascene prior art method of forming metal features in a dielectric using photoresist.

[0014] 3(a)-(c) illustrate an example of a method of forming metal interconnects using a positive photo-patternable dielectric as disclosed herein.

[0015] 4(a)-(e) illustrate an example of a dual damascene method for forming metal interconnects using a positive photo-patternable dielectric as disclosed herein.

[0016] 5(a)-(f) illustrate an example of a method of forming metal interconnects using a positive photo-patternable dielectric as disclosed herein. DETAILED DESCRIPTION

[0017] The method described herein includes forming a layer of a photo-patternable dielectric precursor composition on a substrate, exposing the layer to an activating radiation wavelength, heating to cure portions of the layer not exposed to the radiation, removing exposed portions of the layer to form void regions, and filling the void regions with a metal.

[0018] The method can avoid the need for RIE, avoiding the need for a photoresist removal process step and the associated equipment and materials.

[0019] The substrate may include a metal, a semiconductor, a dielectric material, or a combination of two or more thereof. The substrate may include a metal film or a metal feature in a dielectric material on its top layer so that the additional metal incorporated into the method disclosed herein contacts such metal. For example, the substrate may include a semiconductor material such as Si, SiGe, SiGeC, SiC, GaAs, InAs, InP or other III / V or II / VI compound semiconductors. The substrate may include, for example, a silicon wafer or a process wafer, such as a wafer produced 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, for example, Si / SiGe, Si / SiC, silicon on insulator (SOI) or silicon germanium on insulator (SGOI). A substrate including a combination of at least one of the foregoing may be used.

[0020] The silicon dielectric precursor composition may include a silicon-containing resin, a catalyst capable of catalyzing a condensation reaction of the silicon-containing resin, and a photoacid generator, wherein the catalyst can be deactivated by the presence of an acid such that it loses the ability to catalyze the condensation reaction. Thus, when an area of ​​a coating of the silicon dielectric precursor composition is exposed to activating radiation, an acid is formed and the catalyst is deactivated. Subsequent curing occurs in one or more unexposed areas. Development in a suitable developing solution removes the one or more exposed areas. Thus, the silicon dielectric precursor composition is a positive-working composition.

[0021] The silicon-containing polymer resin may be prepared from one or more monomers having the following molecular structures or a combination of two or more thereof:

[0022] (a)

[0023]

[0024] or (b)

[0025]

[0026] or (c)

[0027]

[0028] Preferably (a), (b), or (a) and (b). Each R is independently hydrogen or an alkyl group of 1 to 4 carbon atoms, preferably 1 to 3 carbon atoms and more preferably 1 or 2 carbon atoms at each occurrence, R is preferably an alkyl group of 1 or 2 carbon atoms, and each R1 is independently a monovalent organic group having 1 to 30 carbon atoms and optionally including 1 to 5 heteroatoms selected from N, O, P, S or a combination of two or more thereof at each occurrence. For example, R1 can be an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an olefin group having 2 to 30 carbon atoms or an alicyclic group having 3 to 30 carbon atoms, each of which optionally includes -O-, -CO-, -OCO-, -COO- or -OCOO- as part of its structure. R1 can be further substituted by one or more epoxy groups. R1 is preferably an alkyl group of 1 or 2 carbon atoms, to provide a cured resin having a silicon content higher than 42 weight percent based on the gross weight of the cured resin.

[0029] 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, cyclohexenyltriethoxysilane, triethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, trimethylmethoxysilane, dimethylethylmethoxysilane, dimethylbenzylmethoxysilane, dimethylphenethylmethoxysilane, or the like, or a combination of two or more thereof.

[0030] The polymerization of monomers can be carried out in an organic solvent. Exemplary organic solvents used 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 amyl ketone, butanediol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanediol 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, 3-methoxy methyl propionate, 3-ethoxy ethyl propionate, tert-butyl acetate, tert-butyl propionate, propylene glycol monotert-butyl ether acetate, γ-butyrolactone, etc., or a combination of two or more thereof. The organic solvent may be propylene glycol methyl ether or propylene glycol methyl ether acetate.

[0031] The polymerization of the monomers can be carried out in the presence of one or more polymerization catalysts. The polymerization catalyst can be an acid catalyst. Exemplary acid catalysts include organic acids such as formic acid, acetic acid, oxalic acid, maleic acid, methanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, etc., or a combination of two or more thereof; or inorganic acids such as hydrofluoric acid, hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, perchloric acid, phosphoric acid, etc., or a combination of two or more thereof. The acid catalyst can be acetic acid. The acid catalyst can be used in any suitable amount, such as 1 to 10 weight percent of the total content in the reactor.

[0032] The polymerization may be 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.

[0033] The volatile alkanol formed during the condensation reaction can be removed by distillation as the reaction proceeds. The distillate may also include an acid catalyst, water and / or a solvent. A stream of nitrogen flushed through the reactor may assist the distillation. The removal of the volatile alkanol may be carried out during or after the polymerization reaction.

[0034] The silicon-containing polymer resin thus formed may include polysiloxane, polysilsesquioxane, or a combination thereof. For example, the silicon-containing polymer resin includes both polysiloxane and polysilsesquioxane. The silicon-containing polymer resin may include a cross-linked network structure. The network may include a complex and diverse set of molecular structures of polysiloxane and polysilsesquioxane. For example, the network structure may include a variety of structures, including the following molecular structures:

[0035]

[0036] wherein R and R1 are as defined herein. However, the above simplified structure is not necessarily an accurate and complete description of the silicon-containing polymer resin, such that the monomers and polymerization process provide the most accurate description of the polymer.

[0037] The weight average molecular weight (M) of the silicone-containing polymer resin before curing w ) may be 1,000 to 50,000 grams per mole (g / mol), 1,500 to 30,000 g / mol, 2,000 to 20,000 g / mol, or 3,000 to 10,000 g / mol. w It can be determined using gel permeation chromatography (GPC) with polystyrene standards as described in Williams and Ward, J. Polymer. Sci., Polymer. Letters, 6, 621 (1968), the contents of which are incorporated herein by reference in their entirety.

[0038] Exemplary silicon-containing polymer resins may include substituted siloxanes, substituted silsesquioxanes, substituted polysiloxanes, or substituted polysilsesquioxanes, such as substituted methylsiloxanes, substituted methylsilsesquioxanes, substituted phenylsiloxanes, substituted phenylsilsesquioxanes, substituted methylphenylsiloxanes, substituted methylphenylsilsesquioxanes, substituted dimethylsiloxanes, substituted diphenylsiloxanes, substituted methylphenylsiloxanes, substituted polyphenylsilsesquioxanes, substituted polyphenylsiloxanes, substituted polymethylphenylsiloxanes, substituted polymethylphenylsilsesquioxanes, substituted polymethylsiloxanes, substituted polymethylsiloxanes, or combinations thereof.

[0039] The silicon-containing polymer resin can be included in the dielectric precursor composition in an amount of, for example, 2 to 50, 4 to 40, or 10 to 30 weight percent based on the total weight of the dielectric precursor composition. Compositions having a silicon-containing polymer resin within this weight range can produce a film thickness of 100 nanometers to 4 micrometers at a typical spin coating speed, for example, 500 to 2000 revolutions per minute (RPM).

[0040] The catalyst in the silicon dielectric precursor composition is capable of catalyzing 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. As used herein, an acid-deactivated catalyst refers to a catalyst that is deactivated in the presence of an acid. Such a catalyst may be referred to as a curing catalyst.

[0041] The curing catalyst may include a quaternary ammonium and / or amine such as, 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. 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.

[0042] The amount of the curing catalyst may be about 0.0005 to about 0.2 or about 0.001 to about 0.05 weight percent (wt%) based on the total weight of the dielectric precursor composition. The amount of the catalyst may be about 0.045 to about 4 or 0.01 to about 0.5 wt% based on the weight of the silicon-containing polymer resin.

[0043] The photoacid generator is a compound that generates an organic acid by irradiation with actinic rays or radiation, and a known compound can be used. The sensitive wavelength of the photoacid generator can be, for example, a wavelength of 10 to 450 or 300 to 450 nanometers (nm). In other words, the photoacid generator can be a compound that generates an acid in response to actinic rays within the above wavelength range. In addition, the pKa of the acid generated by the photoacid generator can be 4.0 or less or 3.0 or less.

[0044] The photoacid generator may include an onium salt, a triazine compound (such as a halomethylated triazine compound, and more particularly, for example, a trichloromethyl-s-triazine compound), an oxime sulfonate compound, a bissulfonyldiazomethane compound, an imide sulfonate compound, a diazodisulfone compound, a disulfone compound, or a nitrobenzylsulfonate compound (such as an o-nitrobenzylsulfonate compound). The photoacid generator may include a sulfonium or iodonium salt, such as a compound including a sulfonium cation or a sulfonate or a methide or an iodonium cation or a sulfonate. Exemplary sulfonium cations include triphenylsulfonium and tris (4-tert-butoxyphenyl) sulfonium. Exemplary sulfonates include trifluoromethanesulfonate and perfluoro-1-butanesulfonate. Exemplary methyl anions include tris (trifluoromethyl) methyl anions. Exemplary iodonium cations are aryliodonium cations, including diphenyliodonium and bis(4-tert-butylphenyl)iodonium. Exemplary sulfonates include trifluoromethanesulfonate and perfluoro-1-butanesulfonate.

[0045] Exemplary photoacid generators include onium salts such as triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate, 4-methoxyphenyldiphenylsulfonium trifluoroacetate, 4-phenylphenylthiodiphenylsulfonium trifluoromethanesulfonate, 4-phenylphenylthiodiphenylsulfonium trifluoromethanesulfonate, diphenyliodonium trifluoromethanesulfonate, (p-tert-butoxyphenyl)phenyliodonium trifluoromethanesulfonate, diphenyliodonium p-toluenesulfonate, (p-tert-butoxyphenyl)phenyliodonium 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 nonafluorobutanesulfonate, triphenylsulfonium butanesulfonate, trimethylsulfonium trifluoromethanesulfonate, trimethylsulfonium p-toluenesulfonate, cyclohexylmethyl (2 1-(2-oxyylidenecyclohexyl)sulfonium trifluoromethanesulfonate, cyclohexylmethyl (2-oxyylidenecyclohexyl)sulfonium p-toluenesulfonate, dimethylphenylsulfonium trifluoromethanesulfonate, dimethylphenylsulfonium p-toluenesulfonate, dicyclohexylphenylsulfonium trifluoromethanesulfonate, dicyclohexylphenylsulfonium p-toluenesulfonate, trinaphthylsulfonium trifluoromethanesulfonate, cyclohexylmethyl (2-oxyylidenecyclohexyl)sulfonium trifluoromethanesulfonate, (2-norbornyl)methyl (2-oxyylidenecyclohexyl)sulfonium trifluoromethanesulfonate, ethylenebis[methyl (2-oxyylidenecyclopentyl)sulfonium trifluoromethanesulfonate salt], 1,2'-naphthylcarbonylmethyltetrahydrothiophenium trifluoromethanesulfonate, diphenyliodonium trifluoroacetate, diphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium trifluoromethanesulfonate, phenyl-4-(2'-hydroxy-1'-tetradecyloxy)phenyliodonium trifluoromethanesulfonate, 4-(2'-hydroxy-1'-tetradecyloxy)phenyliodonium hexafluoroantimonate, phenyl-4-(2'-hydroxy-1'-tetradecyloxy)phenyliodonium p-toluenesulfonate, and the like, or a combination of two or more thereof.

[0046] Exemplary diazomethane compounds include bis(benzenesulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(xylenesulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(cyclopentylsulfonyl)diazomethane, bis(n-butylsulfonyl)diazomethane, bis(isobutylsulfonyl)diazomethane, bis(isopentylsulfonyl)diazomethane, 1-tert-amylsulfonyl-1-(tert-butylsulfonyl)diazomethane, and the like, or a combination of two or more thereof.

[0047] Exemplary triazine compounds include 2-(3-chlorophenyl)-bis(4,6-trichloromethyl)-s-triazine, 2-(4-methoxyphenyl)-bis(4,6-trichloromethyl)-s-triazine, 2-(4-methylthiophenyl)-bis(4,6-trichloromethyl)-s-triazine, 2-(4-methoxy-β-phenylphenyl)-bis(4,6-trichloromethyl)-s-triazine, 2-piperonyl-bis(4,6-trichloromethyl)-s-triazine, 2-[2 -(furan-2-yl)vinyl]-bis(4,6-trichloromethyl)-s-triazine, 2-[2-(5-methyl)furan-2-yl)vinyl]-bis(4,6-trichloromethyl)-s-triazine, 2-[2-(4-diethylamino-2-methylphenyl)vinyl]-bis(4,6-trichloromethyl)-s-triazine, 2-(4-methoxynaphthyl)-bis(4,6-trichloromethyl)-s-triazine, and the like, or a combination of two or more thereof.

[0048] Exemplary imidosulfonate compounds include trifluoromethylsulfonyloxybicyclo[2.2.1]-hept-5-ene-dicarboxyimide, succinimidyl trifluoromethylsulfonate, phthalimide trifluoromethylsulfonate, N-hydroxynaphthalimide methanesulfonate, N-hydroxy-5-norbornene-2,3-dicarboxyimido propanesulfonate, and the like, or a combination of two or more thereof.

[0049] A specific example of a photoacid generator is 2-(4-methoxyphenyl)([((4-methylphenyl)sulfonyl)oxy]imino)acetonitrile.

[0050] The photoacid generator may be included in an amount of about 0.05 to 3, or 0.1 to 2, or 0.1 to 1, or 0.2 wt %, based on the total solid content of the composition.

[0051] The molar ratio of the photoacid generator to the catalyst in the composition can be, for example, 0.5:1 to 10:1, or 0.5:1 to 5:1, or 0.5:1 to 1.5:1.

[0052] The cured silicon-containing dielectric can have a high silicon atomic content, for example, greater than 35, greater than 38, greater than 39, greater than 40, greater than 41, greater than 42, at least 42.5, or at least 43 weight percent, up to 46, or up to 45 weight percent atomic silicon based on the total weight of the cured silicon-containing dielectric.

[0053] Forming a layer of the photo-patternable dielectric precursor composition on the substrate may include applying a coating composition to the substrate. The composition may include a silicon-containing polymer resin, a catalyst (ie, an acid-deactivated curing catalyst), a photoacid generator, and a coating solvent.

[0054] Exemplary coating solvents include solvents that are not part of the hydrocarbon solvent compound family, such as ketones, including acetone, diethyl ketone, methyl ethyl ketone, etc., alcohols, esters, ethers or amines. Examples of solvents include propylene glycol methyl ether (PGME), propylene glycol methyl ether acetate (PGMEA), propylene glycol propyl ether (PGPE) and ethyl lactate (EL).

[0055] The solvent may be 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.

[0056] Suitable application methods may include spin coating, spray coating, etc. The solvent is removed to form a solid layer of the photo-patternable dielectric precursor composition.

[0057] Additional optional components of the coating composition may include film modifiers for controlling diffusion of ingredients in the film, surfactants, and the like, or a combination of two or more thereof.

[0058] The membrane modifier can be a polymer, oligomer or non-polymer compound. wIt can be less than 5,000g / mol, or can be less than 2,000g / mol, such as 200 to 5,000g / mol, or 500 to 2,000g / mol. The molecules of the membrane modifier must be small enough to fill the membrane pores. The membrane modifier can be a hydrocarbon compound, and preferably can be a silicon-containing compound. On the one hand, at least one hydroxyl group is connected to each molecule of the membrane modifier. The hydroxyl group can participate in the condensation reaction of the membrane resin. Exemplary hydrocarbon membrane modifiers include polyols, such as polyether glycols, glycerol, 2-(hydroxymethyl)-1,3-propanediol, dihydrogen phosphate 1,3-dihydroxypropane-2-yl ester, ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol and / or the like. Examples of the branched alkylene glycol may 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-tri(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, and 1,2,3-butanetriol. triol, 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-cyclohexanetrimethanol, butane-1,2,3,4-tetrol, 2,2-bis(hydroxymethyl)-1,3-propanediol, pentane-1,2,4,5-tetrol, and the like, or a combination of two or more thereof. The film modifier can 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(hydroxydimethylsilane)benzene, 4-vinylphenylsilanediol, etc., or a combination of two or more thereof. The film modifier can be no more than 30wt% of the total weight of the resin, or no more than 10wt%. The concentration of the film modifier in the composition is used to control the diffusion length of the catalyst, the photoacid generator and the quencher.The use of various membrane modifying agents in the composition is mentioned.

[0059] The removal of the solvent can be performed as part of the coating (e.g., spin coating) process. If the solvent is not sufficiently removed in the process, an additional step can be performed, such as baking (e.g., on a hot plate surface) at 40 to 120° C., 50 to less than 100° C., or 60 to less than 80° C. for 15 to 120 seconds or 30 to 60 seconds. The baking step must not be long enough or hot enough to cause curing of the silicon-containing polymer resin so that the dried film remains soluble in the developer solution.

[0060] The exposure may include exposure to an activating radiation wavelength. To produce a pattern in the photopatternable dielectric precursor, the exposure is an image-level exposure. This may be done through a mask or by direct addressing with a laser. The activating wavelength may be, for example, in the range of 10 to 400 nm, or a specific wavelength such as 365 nm, 248 nm, 193 nm, or 13.5 nm. A combination comprising at least one of the foregoing wavelengths may be used.

[0061] Exposure deactivates the catalyst. During subsequent heating to induce curing, the silicon-containing resin precursor cures (eg, crosslinks) only in areas not exposed to radiation. Curing may be performed at a temperature of 60 to 120° C. or 80 to 110° C. for 30 to 120 seconds.

[0062] The exposed and cured silicon-containing dielectric may be developed with a solution including an organic solvent (particularly a polar organic solvent) or an alkaline aqueous solution. Examples of organic solvents include, but are not limited to, cyclohexanone, methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, methoxyethyl acetate, ethoxyethyl acetate, 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, carbonate The developer may be an aqueous developer, such as ethyl ester, 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, or the like, or a combination of two or more thereof. Examples of alkaline developers may include aqueous solutions of organic or inorganic bases, including tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, ethanolamine, propylamine, ethylenediamine, choline, potassium hydroxide, or sodium hydroxide. A specific example of a developer is an aqueous solution of tetramethylammonium hydroxide in a concentration range of 2.5 to 25 g / L. Development is performed under appropriately determined conditions; for example, at a temperature of 5 to 50° C. and for a time of 10 to 600 seconds.

[0063] The thickness of the dielectric layer can be selected to be suitable for the interconnect structure being manufactured. For example, the thickness of the dielectric layer can be from 2, 5 or 10 nm to 10,000, to 5,000, to 1,000, to 900, to 800, to 700, to 600, to 500, to 400, to 300, to 200 or to 100 nm. The size of the through hole can be a cross-section or diameter of about 140 nm to 10 microns, or 40 to 1 micron. The width of the groove or line can be from 10 nm or from 100 nm to 10 microns or to 5 microns.

[0064] Filling with metal may include sputtering, physical vapor deposition, chemical vapor deposition, plasma enhanced vapor deposition, atomic layer deposition, electroless plating, or a combination of two or more thereof. The metal may include tungsten, nickel, cobalt, copper, aluminum, gold, or silver.

[0065] After filling, the layer may be planarized, for example using chemical mechanical polishing to planarize the surface of the layer.

[0066] Referring to Figures 3(a)-(c), as an example of a method as disclosed herein, a layer 20 of a photo-patternable dielectric precursor composition 21 is formed on a substrate 13. In Figure 3(b), the photo-patternable dielectric precursor has been image-wise exposed to activating radiation, and the layer 20 has been heated to form a cured dielectric 22, and the portion of the layer exposed to the activating radiation (the "first portion") is removed (e.g., using a developing solution) to form voids 14 between areas (the "second portion") of the cured dielectric 22. In Figure 3(c), metal 15 has been filled into the voids 14.

[0067] Referring to Figures 4(a)-(e), as an example of a method as disclosed herein, a layer 20 of a photo-patternable dielectric precursor composition 21 is formed on a substrate 13. In Figure 4(b), the photo-patternable dielectric precursor has been image-wise exposed to activating radiation, and the layer 20 has been heated to form a cured dielectric 22, and the portion of the layer exposed to the activating radiation (the "first portion") is removed (e.g., using a developer solution) to form voids 14v (e.g., vias) between regions of the cured dielectric 22 (the "second portion"). In Figure 4(c), additional photo-patternable dielectric precursor composition 21 is applied, filling the voids and covering the cured dielectric 22. In Figure 4(d), additional photo-patternable dielectric precursor 21 has been image-wise exposed to activating radiation and heated to form a cured dielectric 22, and the regions of the layer exposed to the activating radiation (the "first region") are removed (e.g., using a developer solution) to form voids 14t (e.g., trenches). The voids 14v and 14t are fluidly connected to each other to form a continuous void region. In FIG4(e), metal 15 has been filled into the voids 14t and 14v.

[0068] As an alternative to this approach, rather than removing the first portion of the first layer exposed to activating radiation as shown in FIG4( b) to form voids 14v, a second layer of photo-patternable dielectric precursor composition 21 can be formed on the exposed and cured (but not developed) photo-patternable dielectric precursor composition. The second layer can then be exposed and cured, and both the exposed, uncured first layer and the second layer are simultaneously developed to yield a structure as shown in FIG4( d).

[0069] Referring to Figures 5(a)-(f), as an example of a method as disclosed herein, a layer 20 of a photo-patternable dielectric precursor composition 21 is formed on a substrate 13. In Figure 5(b), the photo-patternable dielectric precursor has been image-wise exposed to activating radiation, and the layer 20 has been heated to form a cured dielectric 22, and the portion of the layer exposed to the activating radiation (the "first portion") is removed (e.g., using a developing solution) to form voids 14v (e.g., vias) between areas of the cured dielectric 22 (the "second portion"). In Figure 5(c), metal 15 has been filled into the voids 14v. Optionally, the top surface can be planarized after metallization and before proceeding to the next step. In Figure 5(d), additional photo-patternable dielectric precursor composition 21 is applied over the metal 15 and over the cured dielectric 22. In FIG. 5( e), the additional photo-patternable dielectric precursor has been image-wise exposed to activating radiation and heated to form a cured dielectric 22, and the portion of the layer exposed to the activating radiation (the "first region") is removed (e.g., using a developing solution) to form trenches 14t (e.g., trenches). As shown in FIG. 5( e), at least a portion of trench 14t covers at least a portion of metal 15. However, in other embodiments, there is no such overlap. In FIG. 5( f), metal 15 has been filled into trench 14t.

[0070] The process steps of applying, exposing, curing, developing and filling may be repeated for subsequent layers forming a multi-layer interconnect.

[0071] Planarization may be performed to ensure a level surface for initiation of the next layer. In particular, planarization using chemical mechanical polishing may be performed after the metallization step.

[0072] After curing, the dielectric is resistant to chemicals. In addition, once cured, there is no or substantially no outgassing from the dielectric material.

[0073] The cured dielectric film may have a dielectric constant of less than 4 or less than 3.5 and greater than 2 or greater than 2.5. The dielectric constant may be measured according to ASTM D150 on an impedance analyzer such as model E4990A from Keysight.

[0074] Articles comprising metal features and a cured dielectric made by the methods disclosed herein can resist cracking. For example, such articles do not exhibit cracking after being heated to 400° C. In particular, a cured dielectric having a thickness of 1.5 microns baked at 400° C. for 30 minutes was cooled, and no cracks were observed visually and microscopically.

[0075] The article of manufacture can be an electronic device, such as a chip or integrated circuit, or a system including such a device. Examples of such systems include computers, cellular phones, transportation vehicles, appliances, manufacturing systems, robotic devices, etc.

[0076] Example

[0077] Example 1: Synthesis of Silicon-Containing Polymer Resins and Formulation of Photo-Patternable Dielectrics

[0078] In a 500-mL round-bottom flask, 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 combined, mixed thoroughly, and distilled for 5 hours. The temperature of the flask contents was raised to boiling point. The silicon-containing polymer resin was recovered from the flask.

[0079] Example 2: Preparation of a photo-patternable dielectric and process conditions for forming a dielectric pattern.

[0080] Six grams of the silicon-containing polymer resin obtained in Example 1, 0.5 grams of 1-methoxy-2-propanol acetate, 1 gram of 1-propoxy-2-propanol, 0.001 grams of benzyltrimethylammonium chloride and 0.01 grams of 2-(4-methoxyphenyl)([((4-methylphenyl)sulfonyl)oxy]imino)acetonitrile were combined in a container and mixed until all ingredients were dissolved. The solution was spin-coated on a silicon wafer at a rotation speed of 1000 revolutions per minute. A film having a thickness of about 200 nm was formed on the surface of the wafer. No baking was required after spin coating. The film was a photo-patternable dielectric having a thickness of 200 nanometers. The wafers having these coatings were image-wise exposed to radiation having a wavelength of 365 nm to generate acid in the exposed areas. The wafers were then baked on a hot surface at a temperature of 120° C. for 60 seconds. After this baking, the wafer was immersed in a 2.38 weight percent (wt%) tetramethylammonium hydroxide aqueous solution for 10 to 40 seconds to form a desired pattern on the dielectric film. The pattern was then cured on a hot plate at 200° C. for 120 seconds.

[0081] Example 3

[0082] The dielectric resin as obtained in Example 1 was tested by forming a 1.5 micron spin coating on a substrate, followed by baking at 400° C. for 30 minutes and then cooling. Visual inspection with and without a microscope showed no cracks.

[0083] Example 4

[0084] The silicon-containing polymer resin obtained in Example 1 was formed into a film and cured and the dielectric constant was measured on an E4990A impedance analyzer from Keysight. The measured dielectric constant was 3.0.

[0085] Example 5

[0086] The silicone resin cured from the resin as obtained in Example 1 was tested by inductively coupled plasma mass spectrometry (ICPMS) to determine the silicon content. It was found to have a silicon content of about 43 weight percent based on the total weight of the resin.

[0087] The present disclosure further encompasses the following aspects.

[0088] Aspect 1: A method for forming metal interconnects in a dielectric material, 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 a condensation reaction of the silicon-containing polymer resin, and a photoacid generator, wherein the catalyst can be deactivated by the presence of an acid so that it loses the ability to catalyze the condensation reaction; exposing a portion of the first layer of the dielectric precursor composition to radiation in a first image-level manner to generate acid in the portion exposed to the radiation; heating the exposed first layer to form a cured dielectric resin in the portion of the first layer not exposed to the radiation; after heating, removing the dielectric precursor composition in the portion exposed to the radiation; and filling the portion from which the dielectric precursor has been removed with a metal.

[0089] Aspect 2: The method according to Aspect 1 further includes, 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 area of ​​the second layer of the dielectric precursor composition to radiation in a second image-level manner to generate acid in the first area exposed to the radiation, heating the exposed second layer to form a cured dielectric resin in a second area of ​​the second layer not exposed to the radiation; removing the dielectric precursor composition in the first area of ​​the second layer exposed to the radiation; and filling the first area of ​​the second layer from which the dielectric precursor has been removed with the metal.

[0090] Aspect 3: The method according to Aspect 1 further includes, after removing the dielectric precursor composition in the first portion of the first layer exposed to radiation, applying a second layer of the dielectric composition, exposing a first area of ​​the second layer of the dielectric precursor composition to radiation in an image-level manner, the first area of ​​the second layer overlapping the removed first area of ​​the first layer to generate acid in the first area of ​​the second layer exposed to the radiation, heating the exposed second layer to form a cured dielectric resin in a second area of ​​the second layer not exposed to the radiation; removing the dielectric precursor composition in the first area of ​​the second layer, forming a continuous void area in the area where the first area of ​​the first layer is removed and the area where the second layer is removed, and filling the continuous void area with the metal.

[0091] Aspect 4: The method according to Aspect 1 further includes, after heating the exposed first layer to form a cured dielectric resin in a second portion of the first layer but before removing the first portion of the first layer exposed to the radiation, applying a second layer of the dielectric composition on the first layer, exposing a first area of ​​the second layer of the dielectric precursor composition to radiation in an image-level manner, the first area of ​​the second layer overlapping the first portion of the first layer to generate acid in the first area of ​​the second layer exposed to the radiation, heating the exposed second layer to form a cured dielectric resin in a second area of ​​the second layer not exposed to the radiation; removing the exposed first portion of the first layer and the dielectric precursor composition in the first area of ​​the layer to form a continuous void area, and filling the continuous void area with the metal.

[0092] Aspect 5: The method according to any of the preceding aspects, wherein the cured dielectric resin comprises at least 38, preferably at least 40, more preferably at least 42 weight percent silicon based on the total weight of the cured dielectric resin.

[0093] Aspect 6: The method according to any one of the preceding aspects, wherein the silicon-containing polymer resin is prepared from monomers having the following molecular structures or combinations thereof:

[0094]

[0095] wherein R at each occurrence is independently hydrogen or an alkyl group of 1 to 4, preferably 1 to 3 and more preferably 1 or 2 carbon atoms, R is preferably an alkyl group of 1 or 2 carbon atoms, and R1 at each occurrence is independently alkyl, aryl, olefin, alicyclic, epoxy-alkyl or epoxy-cycloalkyl, R1 is preferably an alkyl group of 1 or 2 carbon atoms, and the monomer is polymerized in the presence of a polymerization catalyst in an organic solvent at a temperature of 80° C. to 110° C., removing volatile alkanol during polymerization to form the silicon-containing resin.

[0096] Aspect 7: The method according to any one of the preceding aspects, wherein the catalyst comprises a quaternary ammonium and / or an amine, preferably benzyltriethylammonium chloride (BTEAC), tetramethylammonium chloride (TMAC), guanidine carbonate or tetramethylammonium hydroxide (TMAH).

[0097] Aspect 8: A method according to any one of the preceding aspects, wherein the catalyst is present in an amount of 0.0005 to 0.2, preferably 0.001 to 0.05 weight percent based on the weight of the dielectric precursor composition, or in an amount of 0.005 to 4, preferably 0.01 to 0.5 weight percent based on the weight of the silicon-containing polymer resin.

[0098] Aspect 9: The method according to any one of the preceding aspects, wherein the photoacid generator comprises an onium salt, preferably a sulfonium or iodonium salt, more preferably a compound of a sulfonium cation and a sulfonate or a methyl anion, or an iodonium cation and a sulfonate.

[0099] Aspect 10: The method according to any one of the preceding aspects, wherein the molar ratio of the photoacid generator to the catalyst is 0.5:1 to 10:1.

[0100] Aspect 11: The method according to any of the preceding aspects, wherein the radiation has a wavelength of 10 to 400 nm.

[0101] Aspect 12: The method according to any of the preceding aspects, wherein the layer is exposed to the radiation in an image-wise manner through a mask or by laser addressing.

[0102] Aspect 13: The method according to any one of the preceding aspects, wherein filling with metal comprises sputtering, vapor deposition, atomic layer deposition, or a combination of two or more thereof.

[0103] Aspect 14: The method according to aspect 1, wherein after filling with metal, planarization is performed to remove excess metal and form a flat surface.

[0104] Aspect 15: An article formed by the method of any one of aspects 1-14.

[0105] Aspect 16: The article of aspect 15, wherein the cured dielectric resin has a dielectric constant less than 4, preferably less than 3.5.

[0106] Aspect 17: The article of aspect 15 or 16, wherein the cured dielectric resin layer does not crack at temperatures up to 400°C.

[0107] Aspect 18: A composition comprising: a curable silicon-containing polymer resin, a catalyst capable of catalyzing a condensation reaction of the silicon-containing polymer resin, a photoacid generator, and one or more organic solvents, characterized in that when cured, the resin comprises greater than 42, preferably at least 42.5, and more preferably at least 43 weight percent elemental silicon based on the total weight of the cured resin. Aspect 19: The composition according to Aspect 18, wherein the curable silicon-containing polymer resin is a reaction product of monomers consisting of methyltrimethoxysilane, tetraethoxysilane, and combinations thereof.

[0108] All ranges disclosed herein are inclusive of the endpoints, and the endpoints are independently combinable with each other (e.g., the range of "up to 25 wt.%, or more specifically, 5 wt.% to 20 wt.%" includes the endpoints of the range of "5 wt.% to 25 wt.%" and all intermediate values, etc.). In addition, the upper and lower limits can be combined to form ranges (e.g., "at least 1 or at least 2 weight percent" and "up to 10 or 5 weight percent" can be combined into the ranges "1 to 10 weight percent" or "1 to 5 weight percent" or "2 to 10 weight percent" or "2 to 5 weight percent").

[0109] The present disclosure may alternatively include, consist of, or consist essentially of any suitable component disclosed herein. Additionally or alternatively, the present disclosure may be formulated to lack or be substantially free of any component, material, ingredient, adjuvant, or substance used in prior art compositions or otherwise not necessary for achieving the functions and / or purposes of the present disclosure.

[0110] All cited patents, patent applications, and other references are incorporated herein by reference in their entirety. However, if a term in the present application contradicts or conflicts with a term in the incorporated reference, the term in the present application takes precedence over the conflicting term in the incorporated reference.

[0111] Unless specified to the contrary herein, all test standards are the most current standards in effect as of the filing date of this application or, if priority is claimed, the filing date of the earliest priority application in which such test standard appears.

Claims

1. A method for forming a metal interconnect in a dielectric material, 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 a condensation reaction of the silicon-containing polymer resin, and a photoacid generator, wherein the catalyst can be deactivated by the presence of an acid so that it loses the ability to catalyze the condensation reaction; exposing a first portion of the first layer of the dielectric precursor composition to radiation in a first image-wise manner to generate acid in the first portion exposed to the radiation 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 not exposed to the radiation; after said heating, removing the dielectric precursor composition in said first portion exposed to radiation; as well as The first portion from which the dielectric precursor has been removed is filled with metal.

2. The method according to claim 1, further comprising: applying a second layer of the dielectric precursor composition after filling the first portion of the first layer from which the dielectric precursor has been removed with the metal, exposing first areas of the second layer of the dielectric precursor composition to radiation in a second image-wise manner to generate acid in the portions exposed to the radiation, heating the exposed second layer to form a cured dielectric resin in second areas of the second layer not exposed to the radiation; removing the dielectric precursor composition in the first region of the second layer exposed to the radiation; as well as The first region of the second layer from which the dielectric precursor has been removed is filled with metal.

3. The method of claim 1, further comprising, after removing the dielectric precursor composition in the first portion of the first layer exposed to radiation, applying a second layer of the dielectric composition, exposing a first region of a second layer of the dielectric precursor composition to radiation in an image-wise manner, the first region of the second layer overlapping the removed first portion of the first layer, to generate acid in the first portion of the second layer exposed to the radiation, heating the exposed second layer to form a cured dielectric resin in second areas of the second layer not exposed to the radiation; removing the dielectric precursor composition in the first region of the second layer to form a continuous void region in the region where the portion of the first layer is removed and the portion of the second layer is removed, and The continuous void region is filled with the metal.

4. The method according to claim 1, further comprising: applying a second layer of the dielectric composition on the first layer after heating the exposed first layer to form a cured dielectric resin in a second portion of the first layer but before removing the first portion of the first layer exposed to the radiation, exposing a first region of a second layer of the dielectric precursor composition to radiation in an image-wise manner, the first region of the second layer overlapping a first portion of the first layer, to generate 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 second areas of the second layer not 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, and The continuous void region is filled with the metal.

5. A method according to any one of the preceding claims, wherein: The cured dielectric resin includes at least 38, preferably at least 40, and more preferably at least 42 weight percent silicon based on the total weight of the cured dielectric resin.

6. A method according to any one of the preceding claims, wherein: The silicon-containing polymer resin is prepared from monomers having the following molecular structures or combinations thereof: wherein each R at each occurrence is independently hydrogen or an alkyl group of 1 to 4, preferably 1 to 3 and more preferably 1 or 2 carbon atoms, R is preferably an alkyl group of 1 or 2 carbon atoms, and R1 at each occurrence is independently alkyl, aryl, olefin, alicyclic, epoxy-alkyl or epoxy-cycloalkyl, R1 is preferably an alkyl group of 1 or 2 carbon atoms, and the monomer is polymerized in an organic solvent at a temperature of 80°C to 110°C in the presence of a polymerization catalyst, and volatile alkanol is removed during the polymerization to form the silicon-containing resin.

7. A method according to any one of the preceding claims, wherein: The catalyst comprises a quaternary ammonium and / or an amine, preferably benzyltriethylammonium chloride (BTEAC), tetramethylammonium chloride (TMAC), guanidine carbonate or tetramethylammonium hydroxide (TMAH).

8. A method according to any one of the preceding claims, wherein: The catalyst is present in an amount of 0.0005 to 0.2 weight percent, preferably 0.001 to 0.05 weight percent, based on the total weight of the dielectric precursor composition, or 0.005 to 4, preferably 0.01 to 0.5 weight percent, based on the total weight of the silicon-containing polymer resin.

9. A method according to any one of the preceding claims, wherein: The photoacid generator includes an onium salt, preferably a sulfonium or iodonium salt, more preferably a sulfonium cation or sulfonate, or a methyl anion or an iodonium cation or sulfonate compound.

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

1.

11. A method according to any one of the preceding claims, wherein: The radiation has a wavelength of 10 to 400 nanometers.

12. A method according to any one of the preceding claims, wherein: The layer is exposed to the radiation in an image-wise manner through a mask or by laser addressing.

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

14. A method according to any one of the preceding claims, wherein: After said filling with metal, planarization is performed to remove excess metal and form a flat surface.

15. An article formed by the method of any one of claims 1-14.

16. The article of claim 15, wherein: The cured dielectric resin has a dielectric constant of less than 4, preferably less than 3.

5.

17. The article according to claim 15 or 16, wherein The cured dielectric resin layer does not crack at temperatures up to 400°C.

18. A composition comprising: Curable silicone-containing polymer resin, A catalyst capable of catalyzing the condensation reaction of a silicon-containing polymer resin, Photoacid generators, and Organic solvents, Wherein, when cured, the silicon-containing polymer resin comprises greater than 42, preferably at least 42.5, and more preferably at least 43 weight percent elemental silicon based on the total weight of the cured resin.

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.

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