Photolithography using silicon photoresist

Abstract

1. A method of forming a pattern, comprising: providing a substrate on which a pattern is to be formed; forming a silicon photoresist layer on the substrate; exposing the silicon photoresist to radiation at an activating wavelength; hardening the silicon photoresist; developing the hardened silicon photoresist to remove portions of the photoresist exposed to radiation at the activating wavelength; and etching the substrate to form the pattern.

Description

Technical Field

[0001] The present invention relates to photolithography for manufacturing microelectronic components.

Background Art

[0002] In photolithography, a photoresist is applied to a substrate including a layer where formation of features such as lines or via holes is desired. The photoresist is exposed image-wise to radiation of an activation wavelength, cured, and developed. Thereby, uncured portions are removed, leaving a pattern of the cured portions. Development can be performed by applying a developer for removing the uncured portions. Commonly used photoresists include hydrocarbon-based polymer materials. Hydrocarbon photoresists are usually spin-coated onto a thick organic BARC that is bonded to a bare substrate, a thin organic underlayer anti-reflection coating (BARC), and a thin silicon BARC (sometimes called a hard mask).

[0003] BARC is desired to reduce reflection of radiation from the substrate, which may adversely affect the accuracy of the formed image. There is still a need for an improved method of forming a pattern of lines or via holes.

Summary of the Invention

[0004] This specification discloses a method of forming a pattern, the method including providing a substrate on which the pattern is to be formed, forming a silicon photoresist layer on the substrate, exposing a part of the silicon photoresist to radiation of an activation wavelength, curing the silicon photoresist, developing the cured silicon photoresist to remove the portion of the photoresist exposed to the radiation of the activation wavelength, and etching the substrate to form the pattern.

Brief Description of the Drawings

[0005] [Figure 1] Figures 1(a) to 1(c) show a conventional method for forming patterns using hydrocarbon photoresist and hydrocarbon BARC. [Figure 2] Figures 2(a) to 2(d) show a conventional method for forming patterns using hydrocarbon photoresists and silicon-containing BARCs in combination with hydrocarbon-containing BARCs. [Figure 3] Figures 3(a) to 3(c) show examples of methods for forming patterns using hydrocarbon-containing BARC and silicon photoresist. [Figure 4] Figures 4(a) to 4(c) show examples of methods for forming patterns using silicon BARC and silicon photoresist. [Figure 5] Figures 5(a) to 5(c) show examples of methods for forming patterns using thick hydrocarbon BARC and silicon photoresist. [Figure 6] Figures 6(a) to 6(c) show examples of methods for forming patterns on a silicon substrate using silicon photoresist. [Figure 7] Figures 7(a) to 7(c) show examples of methods for forming patterns on a silicon substrate using photosensitive hydrocarbon BARC and silicon photoresist. [Modes for carrying out the invention]

[0006] Next, we refer to the drawings. These drawings are illustrative embodiments, and the same reference numerals are used for the same elements.

[0007] In photolithography, the base anti-reflective coating (BARC) contains a chromophore that strongly absorbs radiation at activation wavelengths. BARC can reduce the reflection of radiation from the substrate, which can negatively affect the accuracy of the resulting image. Furthermore, BARC can adjust the adhesion of the photoresist to the substrate.

[0008] BARC may be a hydrocarbon-based material (also called a hydrocarbon-containing material or hydrocarbon BARC). However, while "hydrocarbon" usually refers to a compound having only C and H atoms, as used in this specification, "hydrocarbon group," "hydrocarbon-containing," and "hydrocarbon BARC" may include compounds having only C and H atoms, compounds containing C atoms, H atoms and heteroatoms such as O, N, and S, or combinations thereof.

[0009] Hydrocarbon-containing BARCs include hydrocarbon-containing polymers that can be cured to ensure that the hydrocarbon BARCs are resistant to the developer for photoresists. This curing occurs, for example, at about 200°C. Due to the high curing temperature, it is preferable that the chromophore be grafted onto the polymer chains to avoid migration (e.g., gas release) during curing at high temperatures. For example, as shown in Figure 1(a), a thin cured hydrocarbon BARC 11 is formed on a substrate containing a polycrystalline silicon layer 13 on silicon oxide 14. A hydrocarbon photoresist layer is applied to the hydrocarbon BARC 11, exposed to radiation of an activation wavelength, and developed to form a patterned hydrocarbon photoresist 16.

[0010] After developing the photoresist, the exposed BARC is at least partially removed by reactive ion etching (referred to as "RIE" in this specification). The substrate can also be patterned by etching (e.g., RIE). As shown in Figure 1(b), the hydrocarbon BARC 11 is etched using RIE to expose the polycrystalline silicon layer 13. Next, as shown in Figure 1(c), the polycrystalline silicon layer 13 is etched using RIE to form a pattern protected by hydrocarbon photoresist 16, and the remaining photoresist 16 and hydrocarbon BARC 11 are removed. The residual photoresist can also be removed using a stripping solution.

[0011] The lack of etching selectivity between hydrocarbon photoresist and hydrocarbon BARC limits the effective use of hydrocarbon photoresist and thick hydrocarbon BARC layers. Therefore, when thick hydrocarbon BARC is used, an additional thin silicon BARC (also called a hard mask) is usually used. For example, as shown in Figure 2(a), a hydrocarbon photoresist is applied, exposed, and developed to form a pattern of hydrocarbon photoresist 16 on a laminate consisting of metal 15, silicon oxide 14, a thick hydrocarbon BARC 11, and a thin silicon BARC 12 from bottom to top. As shown in Figure 2(b), the silicon BARC 12 is etched by RIE and the hydrocarbon photoresist is removed. As shown in Figure 2(c), the hydrocarbon BARC 11 is etched using the silicon BARC as a mask and the silicon BARC is removed. As shown in Figure 2(d), the pattern is etched onto the silicon oxide 14 using the hydrocarbon BARC 11 as a mask and the hydrocarbon BARC 11 is removed.

[0012] Due to insufficient resistance to etching, hydrocarbon photoresists cannot be effectively used alone with silicon-containing BARC. Although silicon-containing hard masks are disclosed, for example, in US8911932, US8728710, CN102236253, and JP6144000, improved methods for simplifying and / or enhancing photolithography processes are desired.

[0013] To address these and other drawbacks, the method disclosed herein includes the step of providing a substrate including portions on which a pattern is to be formed. A silicon photoresist is applied to the substrate, exposed to imagewise radiation of an activation wavelength, cured and developed, and the exposed portions of the silicon photoresist are removed. The activation wavelength radiation may be in the range of 10 nm to 400 nm, such as 13.5 nm, 193 nm, 248 nm, and 365 nm. In the development step, a portion of the substrate may be directly exposed (see, for example, Figure 6). Alternatively, a BARC may be formed on the substrate before applying the silicon photoresist. In this case, the BARC is exposed by developing the photoresist, and then the BARC is etched (e.g., using reactive ion etching, RIE) to expose a portion of the substrate (see, for example, Figures 3-5, 7). Once the substrate is exposed, a pattern can be etched onto the substrate using the silicon photoresist and / or interposed BARC as a mask (e.g., using RIE).

[0014] The substrate may include metals, semiconductors, dielectric materials, or combinations of two or more of these. For example, the substrate may include semiconductor materials such as Si, SiGe, SiGeC, SiC, GaAs, InAs, InP, or other III / V or II / VI compound semiconductors. The substrate may include process wafers, such as silicon wafers or wafers manufactured in various steps of a semiconductor manufacturing process, such as integrated semiconductor wafers. The substrate may include multiple layers or a single layer. The substrate may include layered substrates such as Si / SiGe, Si / SiC, silicon-on-insulator (SOI), and silicon-germanium-on-insulator (SGOI). The substrate may include silicon, polycrystalline silicon, silicon dioxide or aluminum-aluminum oxide microelectronic wafers, gallium arsenide, silicon carbide, ceramics, quartz, metals, or combinations of two or more of these. For example, the substrate may include a polycrystalline silicon layer on a silicon dioxide layer. As another example, the substrate may include silicon dioxide on a metal layer. As another example, the substrate may include a silicon substrate, consist substantially of a silicon substrate, or consist of a silicon substrate. When a substantially bare silicon substrate is used, the silicon substrate can be surface-treated before applying the silicon photoresist. For example, the silicon substrate can be treated with an adhesion promoter such as a silylation agent (e.g., an alkylsilylamine such as bis(trimethylsilyl)amine, also known as hexamethyldisilazane or HMDS).

[0015] A silicon photoresist composition comprises a silicon-containing resin, a catalyst capable of catalyzing the condensation reaction of the silicon-containing resin but deactivated in the presence of an acid and losing its ability to catalyze the condensation reaction, and a photoacid generator. This catalyst is also called a condensation catalyst or curing catalyst. Therefore, when the coated area of ​​the silicon photoresist composition is exposed to radiation of an activation wavelength, acid is generated and the catalyst is deactivated. Subsequently, curing occurs in the unexposed area. Then, the exposed area is removed by developing with an appropriate developer. For this reason, the silicon photoresist may also be a positive-type photoresist.

[0016] Silicon-containing polymer resins can be prepared from one or more monomers having the following molecular structures or combinations of two or more thereof.

[0017] [ka]

[0018] In each appearance, 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. Preferably, R is an alkyl group having 1 or 2 carbon atoms. In each appearance, R1 is independently a monovalent hydrocarbon group having 1 to 30 carbon atoms and optionally 1 to 5 heteroatoms selected from N, O, P, S or two or more combinations thereof. Combinations containing at least one of the above can be used. For example, each R1 may be an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an alkene 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. Each R1 may further independently be substituted with one or more epoxy groups. Preferably, R1 is an alkyl group having one or two carbon atoms in order to provide a cured resin having a silicon content of more than 42% by weight relative to the total weight of the cured resin.

[0019] 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, and cyclohexenyl Examples include trimethoxysilane, 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 of these. Combinations containing at least one of the above can be used.

[0020] 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. Combinations containing at least one of the above can be used. The organic solvent may be propylene glycol monomethyl ether or propylene glycol methyl ether acetate.

[0021] 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 combinations of two or more thereof, or inorganic acids such as, for example, hydrofluoric acid, hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, perchloric acid, phosphoric acid, or combinations of two or more thereof. Combinations containing at least one of the above can be used. The acid catalyst may be acetic acid. The acid catalyst can be used in any suitable amount, for example, 1 wt% to 10 wt% (weight %), 2 to 8 wt%, 3 to 7 wt%, etc., based on the total weight of the reactor contents.

[0022] 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.

[0023] The volatile alkanol formed during the reaction can be removed by distillation as the reaction proceeds. The distillate may also contain the catalyst, water and / or 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.

[0024] Examples of the silicon-containing polymer resin thus formed include polysiloxane, polysilsesquioxane or combinations thereof. For example, the silicon-containing polymer resin contains both polysiloxane and polysilsesquioxane. The silicon-containing polymer resin may contain a crosslinked or 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.

[0025]

Chemical formula

[0026] However, each R and R1 is defined independently in this specification. Nevertheless, the above structure is not necessarily an accurate and complete description of the silicon-containing polymer resin. The selected monomer and polymerization process provide the most accurate description of the polymer.

[0027] The weight-average molecular weight (Mw) of the silicon-containing polymer resin before curing may be 1,000 to 50,000 g / mol, 1,500 to 30,000 g / mol, 2,000 to 20,000 g / mol, or 3,000 to 10,000 g / mol. The weight-average molecular weight can be determined by gel permeation chromatography (GPC) using standard polystyrene, and all of the details thereof are incorporated by reference into this specification, as described in WilliamsandWard, J. Polymer. Sci., Polymer. Letters, 6, 621 (1968).

[0028] Examples of silicon-containing resins include siloxanes, silsesquioxanes, polysiloxanes, or polysilsesquioxanes, such as methylsiloxane, methylsilsesquioxane, phenylsiloxane, phenylsilsesquioxane, methylphenylsiloxane, methylphenylsilsesquioxane, dimethylsiloxane, diphenylsiloxane, methylphenylsiloxane, polyphenylsilsesquioxane, polyphenylsiloxane, polymethylphenylsilsesquioxane, polymethylphenylsilsesquioxane, and substituted polymethylsilsesquioxane, or combinations of two or more of these. Combinations containing at least one of the above can be used. These resins may be substituted or unsubstituted.

[0029] The amount of silicon-containing resin that can be included in the photoresist precursor composition is 0.5 wt% to 40 wt%, 1 wt% to 30 wt%, or 2 wt% to 20 wt%, relative to the total weight of the dielectric precursor composition, corresponding to a film thickness of 10 nm to 2 μm at a typical spin-coding speed (e.g., 500 rpm to 2000 rpm).

[0030] Examples of catalysts (curing catalysts or condensation catalysts) in silicon photoresist compositions include 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, Examples include quaternary ammonium and / or amines such as N-dimethylpyridine-4-amine, 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 combinations of two or more of these. Combinations containing at least one of the above can be used.

[0031] The amount of curing catalyst may be 0.0005 wt% to 0.2 wt%, or 0.001 wt% to 0.05 wt%, relative to the total weight of the dielectric precursor composition. The amount of catalyst may be 0.045 wt% to 4 wt%, or 0.01 wt% to 0.5 wt%, relative to the total weight of the silicon-containing polymer resin.

[0032] The photoacid generator is preferably a compound that generates organic acids upon irradiation with active light or radiation. The photosensitive wavelength of the photoacid generator is preferably, for example, 10 nm to 450 nm, or 300 nm to 450 nm. In other words, the photoacid generator is preferably a compound that generates acid in response to active light in the above wavelength range. Furthermore, the pKa of the acid generated by the photoacid generator is preferably 4.0 or less, and more preferably 3.0 or less.

[0033] Examples of photoacid generators include onium salts, triazine compounds (preferably halomethylated triazine compounds, more preferably trichloromethyl-s-triazine compounds), oxime sulfonate compounds, bissulfonyldiazomethane compounds, imidosulfonate compounds, diazodisulfone compounds, disulfone compounds, or nitrobenzyl sulfonate compounds (preferably o-nitrobenzyl sulfonate compounds). Sulfonium salts or iodonium salts are preferred as photoacid generators, and compounds of sulfonium cations with sulfonates or methides, or compounds of iodonium cations with sulfonates, are more preferred. Exemplary sulfonium cations include triphenylsulfonium and tris(4-tert-butoxyphenyl)sulfonium. Exemplary sulfonates include trifluoromethanesulfonate and nonafluorobutane-1-sulfonate. Exemplary methides include tris(trifluoromethyl)methide. Examples of iodonium cations include iodonium cations having an aryl group, such as diphenyliodonium and bis(4-tert-butylphenyl)iodonium. Examples of sulfonates include trifluoromethanesulfonate and nonafluorobutane-1-sulfonate. A combination containing at least one of the above can be used.

[0034] Examples of photoacid generators include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate, (4-methoxyphenyl)diphenylsulfonium trifluoromethanesulfonate, (4-methoxyphenyl)diphenylsulfonium trifluoroacetate, [4-(phenylthio)phenyl]diphenylsulfonium trifluoromethanesulfonate, [4-(phenylthio)phenyl]diphenylsulfonium trifluoroacetate, diphenyliodonium trifluoromethanesulfonate, and Triflu. Oromethanesulfonic acid (p-tert-butoxyphenyl)phenyliodonium, p-toluenesulfonic acid diphenyliodonium, p-toluenesulfonic acid (p-tert-butoxyphenyl)phenyliodonium, trifluoromethanesulfonic acid triphenylsulfonium, trifluoromethanesulfonic acid (p-tert-butoxyphenyl)diphenylsulfonium, trifluoromethanesulfonic acid bis(p-tert-butoxyphenyl)phenylsulfonium, trifluoromethanesulfonic acid tris(p-tert-butoxyphenyl) Phenyl sulfonium, p-toluenesulfonate triphenylsulfonium, p-toluenesulfonate (p-tert-butoxyphenyl)diphenylsulfonium, p-toluenesulfonate bis(p-tert-butoxyphenyl)phenylsulfonium, p-toluenesulfonate tris(p-tert-butoxyphenyl)sulfonium, nonafluoro-1-butanesulfonate triphenylsulfonium, 1-butanesulfonate triphenylsulfonium, trifluoromethanesulfonate trimethylsulfonium, p-toluenesulfonate Trimethylsulfonium, 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-norbonyl)methyl(2-oxocyclohexyl)sulfonium trifluoromethanesulfonate, ethylenebis[methyl(2-oxocyclopentyl)sulfonium trifluoromethanesulfonate], 1,2'-naphthylcarbonylmethyltetrahydrothiophenium triflate, diphenyliodonium trifluoroacetate, diphenyliodonium trifluoromethanesulfonate, trifluoromethanesulfonate (4-methyl Examples include onium salts such as toxyphenyl)phenyliodonium, trifluoroacetic acid (4-methoxyphenyl)phenyliodonium, [4-[(2-hydroxytetradecyl)oxy]phenyl]phenyliodonium trifluoromethanesulfonate, [4-[(2-hydroxytetradecyl)oxy]phenyl]phenyliodonium hexafluoroantimonate, [4-[(2-hydroxytetradecyl)oxy]phenyl]phenyliodonium p-toluenesulfonate, or combinations of two or more of these. A combination containing at least one of the above may be used.

[0035] Examples of 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, or combinations of two or more of these. Combinations containing at least one of the above can be used.

[0036] 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, and 2- Examples include [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, or combinations of two or more of these. Any combination containing at least one of the above may be used.

[0037] Examples of imidosulfonate compounds include trifluoromethylsulfonyloxy-bicyclo-[2.2.1]-hept-5-ene-dicarboximide, succinimide trifluoromethylsulfonate, phthalimide trifluoromethylsulfonate, N-hydroxynaphthalimide methylsulfonate, N-hydroxy-5-norbornene-2,3-dicarboximidopropylsulfonate, or combinations of two or more of these. A combination containing at least one of the above can be used.

[0038] A specific example of a photoacid generator is 2-(4-methoxyphenyl)([((4-methylphenyl)sulfonyl)oxy]imino)acetonitrile.

[0039] The preferred content of the photoacid generator is 0.01 wt% to 3 wt%, 0.05 wt% to 2 wt%, 0.1 wt% to 1 wt%, or 0.2 wt% relative to the total solid content of the composition.

[0040] The molar ratio of the photoacid generator to the catalyst may be, for example, 0.5:1 to 10:1, 0.5:1 to 5:1, or 0.5:1 to 1.5:1.

[0041] Silicon photoresists may have a high silicon content. For example, the silicon content may be more than 35 wt%, more than 38 wt%, more than 39 wt%, more than 40 wt%, more than 41 wt%, or at least 42 wt% and 46 wt% or less, or 45 wt% or less, relative to the total weight of the photoresist composition.

[0042] Silicon photoresists can offer superior protection against ionic bombardment compared to hydrocarbon photoresists. This characteristic is particularly beneficial when the photoresist is applied to a bare (treated or untreated) silicon substrate.

[0043] The step of forming a silicon photoresist layer on a substrate includes applying a coating composition to the substrate, which comprises a silicon-containing resin, a catalyst, a photoacid generator, optional additives, and a coating solvent.

[0044] Examples of paint solvents include ketones such as acetone, diethyl ketone, and methyl ethyl ketone, as well as solvents that do not belong to the hydrocarbon category, such as alcohols, esters, ethers, and amines. Examples of solvents include propylene glycol monomethyl ether (PGME), propylene glycol methyl ether acetate (PGMEA), propylene glycol monopropyl ether (PGPE), and ethyl lactate (EL).

[0045] The paint solvent is included in the dielectric precursor composition in amounts of 50 wt% to 99 wt%, 55 wt% to 95 wt%, 60 wt% to 90 wt%, or 65 wt% to 85 wt%, relative to the total weight of the dielectric precursor composition.

[0046] Suitable coating methods include spin coating and spray coating. The solvent is removed to form a solid layer of the photo-patternable dielectric precursor composition.

[0047] Optional additional components of the coating composition include film modifiers for controlling the diffusion of components in the film, or a combination of two or more of these.

[0048] The membrane modifier may be a polymer, oligomer, or nonpolymer compound. The weight-average molecular weight (Mw) of the polymer or oligomer used as the membrane modifier is preferably less than 5000 g / mol, more preferably less than 2000 g / mol, and is determined, for example, by GPC. The molecules of the membrane modifier must be small enough to fill the pores of the membrane. The membrane modifier may be a compound containing only C and H, a hydrocarbon, and preferably a silicon-containing compound. At least one hydroxyl group is bonded to each molecule of the membrane modifier. The hydroxyl group can participate in the condensation reaction of the resin membrane. Examples of exemplary hydrocarbon film modifiers include polyols such as polyetherdiol, 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, and 1,10-decanediol, or combinations of two or more of these.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- Examples include 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, or combinations of two or more of these. The membrane modifier may also be 1,1,1-tris(hydroxymethyl)ethane, pentaerythritol, or a combination thereof.Examples of silicon-containing film modifiers include silanols such as diphenylsilanediol, diisobutylsilanediol, 1,4-bis(dimethylhydroxysilyl)benzene, and 4-vinylphenylsilanediol, or combinations of two or more of these. The content of the film modifier is 30 wt% or less of the total weight of the resin, preferably 10 wt% or less. Alternatively, it may be 0.01 wt% to 15 wt%, or 0.1 wt% to 10 wt% of the total weight of the resin. The diffusion length of the catalyst, photoacid generator, and quencher is controlled by the concentration of the film modifier in the composition. Various film modifiers can be used.

[0049] The removal of the solvent may include a baking step of 15 to 120 seconds or 30 to 60 seconds at 40°C to 120°C, 50 to less than 100°C, or 60 to less than 80°C (e.g., on a hot plate surface). This baking step should not be long or hot enough to cure the silicon-containing resin so that the dried film remains soluble in the developer. Exposure may involve exposing the material to radiation at an activation wavelength. Exposure is imagewise exposure to generate a pattern on a silicon photoresist. Exposure can be performed via a mask or by direct laser addressing. The wavelength may be in the range of, for example, 10 nm to 400 nm, or it may be a specific wavelength such as 365 nm, 248 nm, 193 nm, or 13.5 nm.

[0050] Exposure deactivates the catalyst. Therefore, during the subsequent heating and curing period, the silicon-containing resin precursor hardens (e.g., crosslinks) only in the areas not exposed to the radiation. Curing is performed at a temperature of 60°C to 120°C or 80°C to 111°C for 30 to 120 seconds.

[0051] Silicon photoresists can be developed using organic solvents, particularly polar organic solvents or basic aqueous solutions.Examples of organic solvents include cyclohexanone, propylene glycol monomethyl ether, methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, ethyl methoxyethyl acetate, ethyl ethoxyethyl acetate, propylene glycol monomethyl ether acetate, 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 Coal monopropyl ether acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxyamyl acetate, 3-methoxyamyl acetate, 4-methoxyamyl acetate, 2-methyl-3-methoxyamyl acetate, 3-methyl-3-methoxyamyl acetate, 3-methyl-4-methoxyamyl acetate, 4-methyl-4-methoxyamyl acetate, propylene glycol diaacetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, ethyl carbonate, propyl carbonate, carbonate Examples include, but are not limited to, butyl, 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 combinations of two or more of these. A combination containing at least one of the above can be used.The organic solvent may be propylene glycol monomethyl ether (PGME), propylene glycol methyl ether acetate (PGMEA), ethyl lactate (EL), or cyclohexanone. Examples of alkaline (basic) developers include aqueous solutions of organic or inorganic bases such as tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, ethanolamine, propylamine, ethylenediamine, choline, potassium hydroxide, sodium hydroxide, or combinations thereof. A specific example of a developer is an aqueous solution of tetramethylammonium hydroxide with a concentration of 2.5 to 25 g / L. Development is carried out under appropriately determined conditions, namely a temperature of 5 to 50°C and a time of 10 to 600 seconds.

[0052] Due to its high resistance to etching, silicon photoresist can be made thinner than typical hydrocarbon photoresist thicknesses. This is beneficial because thinner photoresist allows for more precise patterns. The thickness of the photoresist must be sufficient to protect the substrate when used with a thin BARC layer. Photoresist thicknesses can range from 2nm, 5nm, 10nm to 1000nm, 900nm, 800nm, 700nm, 600nm, 500nm, 400nm, 300nm, 200nm, or 100nm. When used with a thin BARC layer (e.g., approximately 2-200nm thick), silicon photoresist thicknesses can range from 5nm, 10nm to 1000nm, 900nm, 800nm, 700nm, 600nm, 500nm, 400nm, 300nm, or 200nm. Any suitable combination of the above thicknesses can be used. When silicon photoresist is used with a thick hydrocarbon BARC (for example, having a thickness of 10 nm to 2000 nm), the silicon photoresist can be thinned to a range of 2 nm, 5 nm, 10 nm, 200 nm, 100 nm, 90 nm, 80 nm, 70 nm, or 60 nm.

[0053] Hydrocarbon BARC (when used) may include polymers and light-absorbing groups, such as chromophores. Chromophores can be bonded to the polymer backbone. Examples of polymers include epoxy cresol novolac resins, phenol novolac resins, acrylic polymers, polyesters, polysaccharides, polyethers, polyacetates, styrene polymers (e.g., polystyrene or copolymers of styrene with other monomers such as acrylonitrile), and polyimides. Compositions for forming a layer of hydrocarbon BARC include, for example, aminoplasts. TIFF0007900839000003.tif9166 may contain crosslinking agents such as epoxy resins, polyols, anhydrides, glycidyl ethers, vinyl ethers, or combinations thereof. The polymer may contain epoxide rings in its repeating units. For example, epoxide groups account for about 20 wt% to 80 wt%, preferably about 20 wt% to 40 wt%, of the total weight of the polymer. The chromophore contains an aromatic or heterocyclic light-absorbing moiety. The chromophore can be covalently bonded to the polymer. For example, the chromophore may have the following chemical formula:

[0054] [ka]

[0055] However, R is selected from the group consisting of H and substituted and unsubstituted alkyl groups (preferably C1-C8, more preferably C1-C4), X 1 This is an aromatic or heterocyclic light-absorbing moiety. This includes chromophores having phenol-OH, -COOH, or -NH2 functional groups. Examples of chromophores include phenyl groups, thiophenes, naphthoic acid, anthracene, naphthalene, benzene, chalcone, phthalimide, pamoic acid, acridine, azo compounds, dibenzofuran, or derivatives thereof.

[0056] Hydrocarbon BARC does not need to be crosslinked. Hydrocarbon BARC can be applied by spin coating, for example, from a composition containing hydrocarbon BARC in a solvent. The solvent can be removed by baking (for example, at a temperature of 30°C to 150°C or 50°C to less than 100°C for 10 seconds, 30 seconds to 120 seconds, or 90 seconds).

[0057] The hydrocarbon BARC may be thin (for example, having a thickness of 2 nm to 200 nm, preferably 5 nm to 60 nm), as shown in Figure 3, for example, or thick (for example, having a thickness of 10 nm to 2000 nm, preferably 20 nm to 1000 nm), as shown in Figure 5.

[0058] Silicon BARC (if used) may contain silicon-containing polymers and light-absorbing functional groups (e.g., chromophores). For example, Silicon BARC may contain oligomers or polymers of alkylsiloxanes, alkylsilsesquioxanes, arylsiloxanes, arylsilsesquioxanes, alkenylsiloxanes, alkenylsilsesquioxanes, or combinations thereof. In the above, the number of carbon atoms in the alkyl group may be, for example, 1, 2, 3, 4, 5, 6, 7, or 8. In the above, the number of carbon atoms in the aryl group may be, for example, 6 to 16. Examples of chromophores include phenyl groups, thiophenes, naphthoic acid, anthracene, naphthalene, benzene, chalcone, phthalimide, pamoic acid, acridine, azo compounds, dibenzofuran, or derivatives thereof.

[0059] Silicone BARC can be applied by spin coating, for example, from a composition containing silicone BARC in a solvent. The solvent can be removed by baking (for example, at a temperature of 30°C to 150°C or 50°C to less than 100°C for 10 seconds, 30 seconds to 120 seconds, or 90 seconds).

[0060] The silicon BARC may have a thickness in the range of 2 nm to 200 nm, preferably 5 nm to 60 nm.

[0061] As shown in Figures 3(a) to 3(c), an example of the method described herein involves forming a thin hydrocarbon BARC 11 (e.g., 2 nm to 200 nm) on a substrate containing a polycrystalline silicon layer 13 on silicon oxide 14. As shown in Figure 3(a), a silicon photoresist composition is applied, exposed to imagewise radiation of an activation wavelength, and cured and developed to remove the photoresist composition in the exposed area, leaving a silicon photoresist 20 that exhibits a pattern on the hydrocarbon BARC 11. As shown in Figure 3(b), the hydrocarbon BARC 11 is etched using the silicon photoresist 20 as a mask to expose the polycrystalline silicon layer 13. As shown in Figure 3(c), the polycrystalline silicon layer 13 is etched using the remaining silicon photoresist 20 and the hydrocarbon BARC 11 beneath it as a mask.

[0062] As shown in Figures 4(a) to 4(c), another example of the method described herein involves forming a thin silicon BARC 12 (e.g., 2 nm to 200 nm) on a substrate including a polycrystalline silicon layer 13 on silicon oxide 14. As shown in Figure 4(a), a silicon photoresist composition is applied, exposed to imagewise radiation of an activation wavelength, and cured and developed to remove the photoresist composition in the exposed area, leaving a silicon photoresist 20 that exhibits a pattern on the silicon BARC 12. As shown in Figure 4(b), the silicon BARC 12 is etched using the silicon photoresist 20 as a mask to expose the polycrystalline silicon layer 13. As shown in Figure 4(c), the polycrystalline silicon layer 13 is etched using the remaining silicon photoresist 20 and the silicon BARC 12 beneath it as a mask.

[0063] As shown in Figures 5(a) to 5(c), another example of the method described herein involves forming a thick hydrocarbon BARC 11 (e.g., 10 nm to 2000 nm) on a substrate containing silicon oxide 14 on a metal 15. As shown in Figure 5(a), a silicon photoresist composition is applied, exposed to imagewise radiation of an activation wavelength, and cured and developed to remove the photoresist composition in the exposed area, leaving a silicon photoresist 20 that exhibits a pattern on the hydrocarbon BARC 11. As shown in Figure 5(b), the hydrocarbon BARC 11 is etched using the silicon photoresist 20 as a mask to expose the silicon oxide 14. As shown in Figure 5(c), the silicon oxide 14 is etched using the remaining silicon photoresist 20 and the hydrocarbon BARC 11 beneath it as a mask.

[0064] As shown in Figures 6(a) to 6(c), another example of the method described in this specification includes coating a silicon photoresist layer 20 onto a silicon substrate 21. As shown in Figure 6(b), after imagewise exposure, curing, and development, the silicon photoresist pattern 20 remains on the silicon substrate 21 as a mask. The silicon substrate (21) is then etched using the silicon photoresist 20 as a mask. As shown in Figure 6(c), residue of the silicon photoresist 20 can be left, or it can be completely removed during etching (not shown). The remaining silicon photoresist can function as a mask when ion implantation is subsequently performed on the exposed portion of the silicon substrate.

[0065] As shown in Figures 7(a) to 7(c), another example of the method described herein involves forming a thin photosensitive hydrocarbon BARC 10 (e.g., 2 nm to 200 nm) on a substrate comprising a polycrystalline silicon layer 13 on silicon oxide 14. The photosensitive BARC is positive in nature, because its dissolution rate in the developer increases when exposed to radiation of an activation wavelength.

[0066] Such photosensitive hydrocarbon BARC compositions may contain an aromatic polymer resin and a photoactivator. For example, aromatic polymer resins include novolac resin (a polymer derived from phenol and formaldehyde), polyamic acid, polyamic acid ester resin, or a combination thereof. For example, a hydrocarbon BARC composition may contain a novolac resin and diazonaphthoquinone (DNQ). DNQ inhibits the dissolution of the novolac resin, and when exposed, its dissolution rate increases, potentially exceeding the dissolution rate of the underlying novolac resin. A hydrocarbon BARC composition may contain a novolac resin, DNQ, a polyamic acid, or a polyamic acid ester. The amount of polyamic acid or polyamic acid ester may be 2 wt% to 20 wt% or 5 wt% to 10 wt% of the total weight of the hydrocarbon BARC composition. A photosensitive hydrocarbon BARC containing a novolac resin and DNQ can be developed with a basic or alkaline developer. Examples of alkaline (basic) developers include aqueous solutions of organic or inorganic bases such as tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, ethanolamine, propylamine, ethylenediamine, choline, potassium hydroxide, sodium hydroxide, or combinations thereof. Specific examples of developers may include 0.1 to 0.4 N tetraalkylammonium hydroxide (e.g., C1 to C4 tetraalkylammonium hydroxide such as tetramethylammonium hydroxide).

[0067] Polyamic acids or polyamic acid esters can protect hydrocarbon BARC from mixed solvents used in silicon photoresists. Polyamic acids or polyamic acid esters may also be reaction products of dianhydrides, particularly aromatic dianhydrides, with diamines, particularly aromatic diamines.

[0068] Examples of aromatic dianhydrides include pyromellitic dianhydride, biphenyltetracarboxylic acid dianhydride, pyromellitic dianhydride, benzophenonetetracarboxylic acid dianhydride, diphenyl ethertetracarboxylic acid dianhydride, (p-phenylenedioxy)diphthalic anhydride, (isopropylidene diphenoxy)bis(phthalic anhydride), (hexafluoroisopropylidene)diphthalic anhydride, or combinations of two or more of these. Alternatively, combinations containing at least one of the above can be used. Examples of diamines include phenylenediamine, oxydianiline, or combinations thereof.

[0069] Figure 7(a) shows a film laminate comprising a silicon photoresist 20 on a photosensitive hydrocarbon BARC 10 on a polycrystalline silicon layer 13 on a silicon dioxide layer 14. As shown in Figure 7(b), the silicon photoresist composition and the photosensitive hydrocarbon BARC are exposed to radiation at an activation wavelength in an imagewise manner, and then cured and developed to remove the photoresist composition and photosensitive hydrocarbon BARC in the exposed areas, leaving the silicon photoresist 20 exhibiting a pattern on the photosensitive hydrocarbon BARC 10. Exposure involves exposing the area of ​​the silicon photoresist 20 with radiation, which simultaneously exposes the photosensitive hydrocarbon BARC 10 beneath it with radiation. Development can be performed sequentially, first developing the silicon photoresist and then developing the photosensitive BARC beneath it. Alternatively, both layers can be developed simultaneously using a mixed solution of alkaline developers as described in this specification. As shown in Figure 7(c), the polycrystalline silicon layer 13 is etched using the silicon photoresist 20 and the photosensitive hydrocarbon BARC 10 beneath it as a mask.

[0070] This specification further discloses products manufactured by the methods described herein. For example, the products may be electronic devices such as chips and integrated circuits, display devices, or systems including such devices. Examples of such systems include computers, mobile phones, transport vehicles, electrical appliances, manufacturing systems, and robotic devices.

[0071] Examples Example 1: Synthesis of silicon-containing polymer resin for use in silicon photoresists In a 500 mL round-bottom flask, 65 g of methyltrimethoxysilane, 30 g of tetraethoxysilane, 10 g of phenyltrimethoxysilane, 250 g of 1-methoxy-2-propanol acetate, 48 g of water, and 10 g of acetic acid were placed and thoroughly mixed. The mixture was then distilled for 5 hours. The flask was removed from the heating distiller and transferred to a rotary evaporator. Under a vacuum of 20 Torr and at a temperature of 80°C, all solvents were removed over 40 minutes. The silicon-containing resin was recovered from the flask.

[0072] Example 2: Preparation of a thin silicon photoresist coating composition 5 g of the silicon-containing polymer resin obtained in Example 1 was placed in a container with 90 g of n-butanol, 10 g of propylene carbonate, 0.004 g of benzyltrimethylammonium chloride, and 0.12 g of a triarylsulfonium hexafluoroantimonate mixture (TR-PAG-201, TronlyNewElectrionicMaterialsCo.,Ltd, Changzhou, China), and mixed until all components were dissolved. This solution is a liquid, dilute silicon photoresist.

[0073] Example 3: Preparation of a thick silicon photoresist coating composition 20 g of the silicon-containing polymer resin obtained in Example 1 was placed in a container with 30 g of n-butanol, 10 g of propylene carbonate, 0.008 g of benzyltrimethylammonium chloride, and 0.24 g of a triarylsulfonium hexafluoroantimonate mixture (TR-PAG-201, Changzhou Strong Electronic New Materials Co., Ltd., China), and mixed until all components were dissolved. This solution is a thick liquid silicon photoresist.

[0074] Example 4: Preparation of a dilute hydrocarbon BARC composition Two g of polystyrene resin with a weight-average molecular weight of 50,000 daltons was dissolved in 200 g of 1-methoxy-2-propanol acetate. This solution is a liquid dilute hydrocarbon (BARC).

[0075] Example 5: Preparation of a thick hydrocarbon BARC composition 180 g of acrylonitrile-styrene copolymer resin with a weight-average molecular weight of 50,000 daltons was dissolved in 720 g of 1-methoxy-2-propanol acetate. This solution is a thick hydrocarbon BARC of liquid acrylonitrile-styrene.

[0076] Example 6: Preparation of another thick hydrocarbon BARC composition 40 g of novolac resin with a weight-average molecular weight of 9000 daltons, 4 g of hexakis(methoxymethyl)melamine, and 0.4 g of p-toluenesulfonic acid were dissolved in 92 g of 1-methoxy-2-propanol acetate and 40 g of 1-methoxy-2-propanol. This solution is a liquid novolac resin thick hydrocarbon BARC.

[0077] Example 7: Preparation of a thin silicon BARC composition In a 500 mL round-bottom flask, 52 g of methyltrimethoxysilane, 8 g of phenyltrimethoxysilane, 24 g of β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 240 g of 1-methoxy-2-propanol acetate, 40 g of water, and 8 g of acetic acid were added and thoroughly mixed. The mixture was then distilled for 5 hours. A silicon-containing polymer resin was formed in the flask. 10 g of this silicon-containing polymer resin was combined with 0.08 g of p-toluenesulfonic acid and 590 g of n-butanol and mixed until all components were dissolved. This solution is a liquid, dilute silicon BARC.

[0078] Example 8: Process of thick silicon photoresist and thin hydrocarbon BARC The thin hydrocarbon BARC composition obtained in Example 4 was spin-coated onto a silicon wafer at a rotational speed of 2000 rpm and baked at 120°C for 60 seconds to obtain a film with a thickness of 17 nm. The thick silicon photoresist composition obtained in Example 3 was spin-coated onto the thin hydrocarbon BARC film at a rotational speed of 1000 rpm to form a film with a thickness of approximately 800 nm. The wafer having such a coating was exposed to radiation with a wavelength of 365 nm in an imagewise manner to generate acid in the exposed area. Next, the wafer was baked on a high-temperature surface at 120°C for 60 seconds. Following this bake, the wafer was immersed in a 2.38 wt% aqueous solution of tetramethylammonium hydroxide for 20 seconds to form the desired pattern on the silicon photoresist film.

[0079] Example 9: Process of thick silicon photoresist and thin silicon BARC The thin silicon BARC composition obtained in Example 7 was spin-coated onto a silicon wafer at a rotational speed of 2000 rpm and baked at 150°C for 60 seconds to obtain a film with a thickness of approximately 20 nm. Next, the thick silicon photoresist composition obtained in Example 3 was spin-coated onto the thin hydrocarbon BARC film at a rotational speed of 1000 rpm to form a film with a thickness of 800 nm. The wafer having such a coating was exposed to radiation with a wavelength of 365 nm in an imagewise manner to generate acid in the exposed area. Next, the wafer was baked on a high-temperature surface at 120°C for 60 seconds. Following this bake, the wafer was immersed in a 2.38 wt% aqueous solution of tetramethylammonium hydroxide for 20 seconds to form the desired pattern on the silicon photoresist film.

[0080] Example 10: Process of thin silicon photoresist and thick hydrocarbon BARC The thick hydrocarbon BARC composition obtained in Example 5 was spin-coated onto a silicon wafer at a rotational speed of 3000 rpm, and then baked at 150°C for 60 seconds to obtain a film with a thickness of approximately 2000 nm. Next, the thin silicon photoresist obtained in Example 2 was spin-coated onto the thick hydrocarbon BARC film at a rotational speed of 2000 rpm to form a film with a thickness of approximately 100 nm. The wafer having such a coating was exposed to radiation with a wavelength of 365 nm in an imagewise manner to generate acid in the exposed area. Next, the wafer was baked on a high-temperature surface at 120°C for 60 seconds. Following this bake, the wafer was immersed in a 2.38 wt% aqueous solution of tetramethylammonium hydroxide for 20 seconds to form the desired pattern on the silicon photoresist film.

[0081] Example 11: Process of thin silicon photoresist and another thick hydrocarbon BARC The thick hydrocarbon BARC obtained in Example 6 was spin-coated onto a silicon wafer at a rotational speed of 3000 rpm, and then baked at 150°C for 60 seconds to obtain a film with a thickness of approximately 2000 nm. The thin silicon photoresist obtained in Example 2 was spin-coated onto the thick hydrocarbon BARC film at a rotational speed of 2000 rpm to form a film with a thickness of approximately 100 nm. The wafer having such a coating was exposed to radiation with a wavelength of 365 nm in an imagewise manner to generate acid in the exposed area. Next, the wafer was baked on a high-temperature surface at 120°C for 60 seconds. Following this bake, the wafer was immersed in a 2.38 wt% aqueous solution of tetramethylammonium hydroxide for 20 seconds to form the desired pattern on the silicon photoresist film.

[0082] Example 12: Process for a thick silicon photoresist on a silicon surface treated with HMDS. A thick silicon photoresist obtained in Example 3 was spin-coated onto the surface of a silicon wafer pre-treated with HMDS at a rotation speed of 1000 rpm to form a film of approximately 800 nm. The wafer having this coating was exposed to radiation with a wavelength of 365 nm in an imagewise manner to generate acid in the exposed area. Next, the wafer was baked on a high-temperature surface of 120°C for 60 seconds. Following this bake, the wafer was immersed in a 2.38 wt% aqueous solution of tetramethylammonium hydroxide for 20 seconds to form the desired pattern on the silicon photoresist film.

[0083] Example 13: Process for thick silicon photoresist on a bare silicon surface A thick silicon photoresist obtained in Example 3 was spin-coated onto the surface of a pre-cleaned and dried silicon wafer at a rotational speed of 1000 rpm to form a film of approximately 800 nm. The wafer with this coating was exposed to radiation with a wavelength of 365 nm in an imagewise manner to generate acid in the exposed area. Next, the wafer was baked on a high-temperature surface of 120°C for 60 seconds. Following this bake, the wafer was immersed in a 2.38 wt% aqueous solution of tetramethylammonium hydroxide for 20 seconds to form the desired pattern on the silicon photoresist film.

[0084] This disclosure further includes the following aspects:

[0085] Aspect 1 A method for forming a pattern includes the steps of: providing a substrate on which the pattern is formed; forming a silicon photoresist layer on the substrate; exposing a portion of the silicon photoresist with radiation of an activation wavelength; curing the silicon photoresist; developing the cured silicon photoresist to remove the portion of the photoresist exposed with radiation of the activation wavelength; and etching the substrate to form the pattern.

[0086] Aspect 2 In the method described in the above-mentioned section 1, the silicon photoresist comprises, before curing, 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 its ability to catalyze the condensation reaction, and a photoacid generator.

[0087] Aspect 3 In the method described in aspect 1 or 2 above, the silicon photoresist contains at least 35 wt%, preferably at least 40 wt%, and more preferably more than 41 wt%, of silicon relative to the total weight of the silicon photoresist.

[0088] Aspect 4 In the method described above, the substrate includes a microelectronic wafer of silicon, polycrystalline silicon, silicon dioxide or aluminum-aluminum oxide, gallium arsenide, silicon carbide, ceramics, quartz, metal, or a combination of two or more of these.

[0089] Aspect 5 The method described above further includes the steps of forming an underlayer anti-reflective film containing a polymer on the substrate, forming the silicon photoresist layer on the underlayer anti-reflective film and developing the cured silicon photoresist to expose a portion of the underlayer anti-reflective film, and etching the exposed portion of the underlayer anti-reflective film to expose a portion of the substrate before etching the substrate.

[0090] Aspect 6 In the method described in paragraph 5 above, the lower anti-reflective film is characterized by one or two of the following: the polymer is not crosslinked, and it contains a chromophore that is not grafted onto the polymer.

[0091] Aspect 7 In the method described in paragraph 5 or 6 above, the lower anti-reflective film comprises a hydrocarbon-containing polymer.

[0092] Aspect 8 In the method described in aspect 5 or 6 above, the lower anti-reflective film comprises a silicon-containing polymer.

[0093] Aspect 9 In the method described in paragraph 8 above, the lower anti-reflective film is derived from alkylsiloxane, alkylsilsesquioxane, arylsiloxane, arylsilsesquioxane, alkenylsiloxane, alkenylsilsesquioxane, or a combination of two or more thereof.

[0094] Aspect 10 In the method described in any of the above sections 5 to 7, the lower anti-reflective coating is not crosslinked.

[0095] Aspect 11 In the method described in section 5, 8, or 9 above, the lower anti-reflective coating is crosslinked.

[0096] Aspect 12 In the method described above, the silicon photoresist layer has a thickness of 2 nm to 1000 nm.

[0097] Aspect 13 In the method described in any of the above sections 5 to 11, the silicon photoresist layer has a thickness of 2 nm to 1000 nm, and the underlying anti-reflective film has a thickness of 2 nm to 200 nm.

[0098] Aspect 14 In the method described in any of the above sections 5 to 11, the silicon photoresist layer has a thickness of 2 nm to 200 nm, preferably 3 nm to 90 nm, more preferably 5 nm to 60 nm, and the lower anti-reflective film has a thickness of 10 nm to 2000 nm, preferably 85 nm to 1000 nm.

[0099] Aspect 15 In the method described above, the substrate includes a layer on which a pattern is formed, and the layer includes polycrystalline silicon or silicon oxide.

[0100] Aspect 16 In the method described in the above-mentioned section 1, the layer in the substrate consists substantially of silicon or silicon treated with an adhesion promoter.

[0101] Aspect 17 In the method described in the above section 16, the adhesion promoter is a silylating agent.

[0102] Aspect 18 The method described in any of the above aspects 1 to 4 further includes the steps of forming an underlayer anti-reflective film containing a positive-type photosensitive hydrocarbon composition on the substrate and forming the silicon photoresist layer on the underlayer anti-reflective film; exposing the silicon photoresist with radiation of an activation wavelength and exposing a part of the underlayer anti-reflective film with radiation of the activation wavelength; and developing the exposed underlayer anti-reflective film to remove the exposed portion of the photosensitive underlayer anti-reflective film and expose a part of the substrate.

[0103] Aspect 19 In the method described in the above section 18, the photosensitive hydrocarbon-containing composition comprises a novolac resin and a diazonaphthoquinone.

[0104] Aspect 20 In the method described in paragraph 18 or 19 above, the development of the lower anti-reflective film and the development of the silicon photoresist are carried out simultaneously in a basic solution.

[0105] Aspect 21 The product was manufactured by any one of the methods described in Sections 1 to 20. All ranges disclosed in this specification include endpoints, and each point can be independently combined with others. For example, the range "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. Furthermore, ranges can be formed by combining the above upper and lower limits. For example, by stating "at least 1 wt% or at least 2 wt%" and "10 wt% or less or 5 wt% or less," ranges such as "1 wt% to 10 wt%", "1 wt% to 5 wt%", "2 wt% to 10 wt%", and "2 wt% to 5 wt%" can be combined.

[0106] The terms used in this specification are merely descriptive and not limiting to specific embodiments. The terms “one,” “one,” “the / the said,” and “at least one” used in this specification are not quantitative and include both singular and plural forms unless specifically defined above or below. For example, “element” and “at least one element” have the same meaning unless specifically defined above or below. “At least one” should not be interpreted as limiting “one” or “one.” “Or” means “and / or.” The term “and / or” used in this specification includes all or any combination of one or more related enumeration items. Furthermore, terms such as “include” or “incorporate,” when used in this specification, indicate the presence of a described feature, area, integer, step, operation, element, and / or component, but do not imply the exclusion of the presence or addition of one or more other features, areas, integers, steps, operations, elements, components, and / or groups thereof.

[0107] Unless otherwise specified, all terms used in this specification (including technical and scientific terms) have the meanings that a person skilled in the art of the field to which this disclosure belongs would ordinarily understand. Terms defined in general dictionaries should be understood to have the same meaning as in the relevant field and the context of this disclosure, and should not be interpreted as having an ideal or overly formal meaning unless specifically defined in this specification.

[0108] This disclosure may include, consist of, or substantially consist of, any suitable elements disclosed herein. This disclosure may be formulated, additionally or alternatively, to exclude, or substantially exclude, any elements, materials, components, auxiliaries, or substances used in prior art compositions or not necessary for achieving the functions and / or purposes of this disclosure.

[0109] All cited patents, patent applications, and other documents are incorporated into this specification by reference in their entirety. However, if any terminology in this specification conflicts with or is inconsistent with any terminology in a cited document, the terminology in this specification shall prevail over that of the cited document.

[0110] Unless otherwise specified in this specification, all test standards are the most current standards in effect as of the filing date of this application. Or, if priority is claimed, the test standards are the most current standards in effect as of the filing date of the earliest priority application listed.

Claims

1. The steps include providing a substrate on which a pattern is formed, The steps include forming a silicon photoresist layer made of polysiloxane on the substrate, The steps include exposing a portion of the silicon photoresist with radiation of an activation wavelength, The steps include curing the silicon photoresist, The steps include developing the cured silicon photoresist to remove the portion of the photoresist exposed with the radiation of the activation wavelength, The step of etching the substrate to form the pattern includes, Furthermore, the process includes the step of forming an underlayer anti-reflective film containing a polymer on the substrate, The silicon photoresist layer is formed on the underlying anti-reflective film, and the cured silicon photoresist is developed to expose a portion of the underlying anti-reflective film. The process further includes the step of etching the exposed portion of the lower anti-reflective film to expose a part of the substrate before etching the substrate, The aforementioned underlayer anti-reflective film is derived from alkylsiloxane, alkylsilsesquioxane, arylsiloxane, arylsilsesquioxane, alkenylsiloxane, alkenylsilsesquioxane, or a combination of two or more of these. The silicon photoresist comprises, before curing, 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 its ability to catalyze the condensation reaction, and a photoacid generator. The catalyst consists of 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-dimethylpyridine-4-amine, 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), quaternary ammonium compounds and / or amines, or combinations of two or more of these. The thickness of the aforementioned lower anti-reflective film is greater than the thickness of the silicon photoresist layer. The silicon photoresist layer has a thickness of 2 nm to 200 nm, and the underlying anti-reflective film has a thickness of 10 nm to 2000 nm. A method for forming a pattern characterized by the above.

2. The silicon photoresist contains at least 35 wt% silicon relative to the total weight of the silicon photoresist. The method according to claim 1.

3. The substrate includes a microelectronic wafer of silicon, polycrystalline silicon, silicon dioxide or aluminum-aluminum oxide, gallium arsenide, silicon carbide, ceramics, quartz, metal, or a combination of two or more of these. The method according to claim 1 or 2.

4. The aforementioned lower anti-reflective film includes chromophores that are not grafted onto the polymer. The method according to claim 1.

5. The aforementioned lower anti-reflective coating is not crosslinked. The method according to claim 1.

6. The aforementioned lower anti-reflective coating is crosslinked The method according to claim 1.

7. The substrate includes a layer on which a pattern is formed, and the layer includes polycrystalline silicon or silicon oxide. The method according to claim 1 or 2.

8. The layer in the substrate is made of silicon, or silicon treated with an adhesion promoter. The method according to claim 1.

9. The aforementioned adhesion promoter is a silylater. The method according to claim 8.

10. The steps include forming an underlayer anti-reflective film on the substrate and forming the silicon photoresist layer on the underlayer anti-reflective film, The steps include exposing the silicon photoresist with radiation of the activation wavelength and exposing a portion of the underlying anti-reflective coating with radiation of the activation wavelength, The step further includes developing the exposed lower anti-reflective film to remove the exposed portion of the lower anti-reflective film and expose a part of the substrate. The method according to claim 1 or 2.

11. The development of the aforementioned lower anti-reflective coating and the development of the silicon photoresist are carried out simultaneously in a basic solution. The method according to claim 10.

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