KR20220082781A - How to form a patterned resist for EUV - Google Patents

Abstract

The present disclosure relates to novel negative photoresist compositions and methods of using the same. The present disclosure further relates to multiple trigger photoresist methods that allow improvements in contrast, resolution, and/or line edge roughness in some systems without sacrificing sensitivity. The photoresist compositions and methods of the present disclosure are ideal for micropatent processing using, for example, ultraviolet, extreme ultraviolet, ultra-ultraviolet, X-ray and modified particles. The present disclosure further relates to sensitivity enhancing materials useful in the disclosed compositions and methods.

Description

How to form a patterned resist for EUV

field of invention

The present disclosure relates to novel negative photoresist compositions and methods of using the same. The present disclosure further relates to multiple trigger photoresist methods that allow improvements in contrast, resolution, and/or line edge roughness in some systems without sacrificing sensitivity. The photoresist compositions and methods of the present disclosure are ideal for micropatent processing using, for example, ultraviolet, extreme ultraviolet, beyond extreme ultraviolet radiation, X-rays, and modified particles. The present disclosure further relates to sensitivity enhancing materials useful in the disclosed compositions and methods.

See earlier filed applications

This application is filed on February 24, 2018, entitled "Enhanced EUV Photoresist Materials, Formulations and Processes," in 35 U.S.C. Priority under 119(e), this provisional application is hereby incorporated by reference in its entirety.

background

EUV (extreme ultraviolet) lithography (EUVL), i.e. lithography at 13.5 nm wavelength, is the current 193 nm photolithography tool for increasingly smaller lines and spaces to create smaller and smaller semiconductor features, a future semiconductor manufacturing demand. considered to be one of the most promising candidates to replace

To meet the requirements of new EUV-compliant photoresist materials, photoresist manufacturers originally reworked existing 193 nm resist systems for EUV use - through the use of formulation adjustments, additives, and photoacid generator (PGA) loadings. was formulated. Although this is a cost-effective approach, it introduces line width roughness (LWR), sensitivity, and resolution limitations. LWR is defined by the random variation of the width of the patterned lithographic feature along the length of the patterned lithographic feature. As photoresist is used to print smaller and smaller patterns, sidewall imperfections become a larger proportion of patterning errors. Moreover, in some previous studies, these high LWR values were attributed to the use of polymers in the photoresist matrix. Other contributing factors to the LWR value are shot noise (e.g., flux change, which becomes increasingly important as the dose per photon substantially increases in the EUV regime), PAG location (relative to acid sensitive protecting groups) in bulk films. , acid diffusion (or smearing) during the chemical amplification process, and the level of developer selectivity. As such, a number of new materials have been introduced to support the new technology, but so far photoresists have not been able to simultaneously meet the resolution, line width roughness and sensitivity (RLS) requirements designed by the International Technology Roadmap for Semiconductors.

In addition to fulfilling current resist goals for next-generation devices, new material platforms should also have the potential to meet rough specifications beyond that point to ensure the useful lifetime of next-generation lithography. Although traditional chemically amplified resist (CAR) materials have been extended to meet this need, resolution improvements have resulted in significant sensitivity reductions, and representative CAR doses range from 30 to 40 mJ/cm2 at 14 nm half pitch (hp). Metal-based resist materials have been heavily studied to increase the absorption of EUV photons, and significant work has been undertaken to alleviate industry concerns about the integration of metal resists into fab-friendly processes. Doses of less than 25 mJ/cm 2 at 16 nm half pitch and less than 35 mJ/cm 2 at 13 nm hp have been reported. The industry is increasingly in need of new approaches and more fundamental chemistry to address the RLS debate. Studies of metal additives to traditional chemically amplified resists to increase optical density show increased sensitivity in contact hole patterning from 50 mJ/cm2 to 43 mJ/cm2 for 22 nm half-pitch contact holes. However, it comes at the cost of increased variability in hole size. The PSCAR process, which uses flood UV exposure to amplify the acid produced through earlier EUV exposure, demonstrated a significant reduction in the dose requirement from 30 mJ/cm2 to 17 mJ/cm2 at 18 nm hp, but allowed exposure to A significant decrease in degree and an increase in LWR were also reported.

For many years, extreme ultraviolet (EUV) lithography has been discussed as the next realization technique for lithographic patterning. However, many technical obstacles (ie, debates regarding EUV optics, photomask infrastructure, and photoresist materials) have delayed widespread adoption and implementation of this technology. For example, scanner optics used in patterning systems and photomasks have changed from transmissive optics to reflective optics. Although this shift has proven to be a rather challenging transition, it has now made tremendous strides and EUV scanner shipments are occurring at an accelerated pace. EUV pellicle development is also progressing (a mitigation step is needed to address defect concerns), and mask infrastructure is being developed in both merchant and in-house mask shops.

Very few commercially available materials have an LWR of less than about 3 nm. A photoresist capable of meeting these LWR parameters while improving photoresist sensitivity should be developed. For example, most commercial photoresist systems require 35-40 mJ/cm 2 to print a reasonable contact hole (with usable process window).

As semiconductor dimensions decrease to the nanometer scale, conventional thinking regarding materials, formulations, and mechanisms must be reconsidered and reevaluated.

Brief description of the drawing
1 shows a chart of the structure of an xMT molecule useful in the disclosure herein.
2 shows an alternative xMT molecule useful in the disclosure herein.
3 shows the infrared spectrum of phenol overlaid on the infrared spectrum of t-BOC protected phenol.
4 shows an infrared spectrum comparing the material before the method herein and the material during the method herein.
5 shows an infrared spectrum of a composition herein at different stages of the method herein.
6 shows infrared spectra of cross-linking agents at various stages of the process herein.
7 shows the proposed mechanism of various methods including the methods herein.
8 compares the SEM of Method B herein and Standard Method A.
9 shows the chemical structures of components used in Examples.
10 further compares the SEM of method B herein and standard method A.
11 shows a SEM of a pattern of contact holes using a composition herein and a method herein.

Summary of Disclosure

Disclosed herein are new materials, new formulations, new additives and new processes that meet and exceed existing requirements of sensitivity, line edge roughness and resolution.

In a first embodiment, providing a substrate, at least one polymer, oligomer or monomer, each comprising two or more crosslinkable functional groups and essentially all functional groups attached to an acid labile protecting group, at least one acid activatable crosslinking agent, applying a multi-trigger resist composition comprising at least one photoacid generator and at least one solvent and free of any additional acid diffusion controlling component, heating the coated substrate to form a substantially dry coating to a desired thickness exposing the coated substrate imagewise to actinic radiation, removing the unexposed areas of the coating using an aqueous developer, solvent developer, or combination of an aqueous-solvent developer composition, and A method of forming a patterned resist comprising optionally heating a photoimaged pattern is disclosed and claimed herein.

In a second embodiment, disclosed and claimed herein, said method wherein at least about 90% of the crosslinkable functional groups are attached to an acid labile protecting group.

In a third embodiment, the onium salt compound, sulfonium salt, tri Phenylsulfonium salt, sulfonimide, halogen-containing compound, sulfone, sulfonimide, sulfonate ester, quinone-diazide, diazomethane, iodonium salt, oxime sulfonate, dicarboxyimidyl sulfate ester, ylideneaminooxy Any of the above methods comprising a sulfonic acid ester, a sulfonyldiazomethane, or a mixture thereof is disclosed and claimed herein.

In a fourth embodiment, the at least one acid activatable crosslinking agent is glycidyl ether, glycidyl ester, oxetane, glycidyl amine, methoxymethyl group, ethoxymethyl group, butoxymethyl group, benzyloxymethyl group, dimethylamino Methyl group, diethylamino methylamino group, dialkylolmethyl amino group, dibutoxymethyl amino group, dimethylolmethyl amino group, diethylolmethyl amino group, dibutylolmethyl amino group, morpholinomethyl group, acetoxymethyl group, benzyloxymethyl group, phospho aliphatic, aromatic or aralkyl monomers, oligomers, resins or polymers comprising at least one of a mil group, an acetyl group, a vinyl group or an isopropenyl group, wherein the acid labile protecting group comprises a tertiary alkoxycarbonyl group. Any of the methods are disclosed and claimed herein.

In a fifth embodiment, any of the above methods wherein the polymer, oligomer or monomer is at least one xMT ester is disclosed and claimed herein.

In a sixth embodiment, wherein the composition further comprises at least one metal component, wherein the metal component exhibits a high EUV light absorption cross-section, a medium to high inelastic electron scattering and a low to medium elastic scattering coefficient. Any method is disclosed and claimed herein.

DETAILED DESCRIPTION OF THE DISCLOSURE

As used herein, unless otherwise indicated, the conjunction "and" is intended to be inclusive, and the conjunction "or" is not intended to be exclusive. For example, the phrase “or, alternatively” is intended to be exclusive.

As used herein, the terms "having," "containing," "including," "comprising," and the like, indicate the presence of the stated element or feature, but not the additional element or feature. It is an open-ended term that does not exclude . The articles "a", "an" and "the" are intended to include the singular as well as the plural unless the context clearly dictates otherwise.

As used herein, the terms “dry”, “dried” and “dried coating” mean having less than 8% residual solvent.

As used herein, the term “protected polymer” refers to a polymer containing a functional group capable of crosslinking with a crosslinking agent, such functional group being protected from reaction with the crosslinking agent by an acid labile functional group, and thus being resistant to acid. When exposed, the acid labile functional group is removed.

As used herein, the term metal includes neutral, non-oxidized species, as well as any of the representative oxidation states a metal may possess.

As used herein, line edge roughness (LER) refers to an area on a photodefined line that does not line up with the rest of the line. It also refers to line geometry and line width roughness.

Traditional semiconductor materials have been based on chemically amplified resist (CAR) materials. In positive systems, representative agents include photoacid generators (PAGs), polymers having at least some developer sensitive groups blocked by acid labile groups, and base quenchers. When the coated formulation is exposed to actinic radiation, the PAG releases acid functional groups, which react with the acid labile groups to deprotect the developer sensitive functional groups. A developer, traditionally an aqueous base, is then applied and reacted with the just deprotected polymer to solubilize it and remove it, leaving the desired lines, spaces, vias, etc. Post-exposure baking (PEB) is required because of the activation energy required for radiation-generated acids to react with traditional acid labile groups to deprotect developer sensitive groups. Traditionally the developer sensitive group is phenolic OH, which reacts readily with aqueous bases.

Over the years, it has been discovered that acid transport of light-generated acids has become problematic as finer lines and spaces are becoming desirable. Here, during PEB, the heat required to deprotect the polymer also energizes the photo-generated acid to cause it to migrate throughout the system and in particular under undesirable areas such as the mask, which then It deprotects the polymer in areas that have not been exposed to radiation, which is an undesirable result. This is also referred to as a "dark reaction". This made the line thinner than desired (in positive-working resist). In order to compensate for this undesirable effect, it is well known and generally required that a component that reduces the action of transporting an acid should be included in the resist formulation in combination therewith, and such component is typically an acid in the general form of a base. It is a diffusion modulating agent.

Similar problems arise with negative resists based on polymers containing reactive functional groups that are protected by acid labile groups. In these resists, the reactive functional groups obtained when deprotected by the photogenerated acid are designed to crosslink with the crosslinker component of the formulation. In these resists, the crosslinking agent is usually protected with an acid labile protecting group such as for example hexamethoxymethylmelamine (HMMM) or activated by photogenerated such as for example epoxy and oxetane. When these resists are subjected to exposure and PEB, the exposed areas are crosslinked and insoluble in the developer, and the developer removes the unexposed areas. In these resists, acid migration causes line growth as the acid diffuses under the mask and initiates crosslinking reactions in undesirable areas, particularly achieving line width growth and roughness as well as line edge roughness.

In the present disclosure, Applicants surprisingly found that removal of base quench resulted in improved resolution, line edge roughness and sensitivity when alone or in combination with other innovations presented herein. This is an unexpected result since all resists herein have a base quencher, and research has made it clear that a base quencher is absolutely necessary to obtain small lithographic features.

Applicants have also found that the removal of post-exposure bake (PEB) results in low heat transfer of the photogenerated acid and allows for improved line width growth and roughness as well as line edge roughness. Again, this is an unexpected result since all resist processes involve PEB.

Based on these findings and without wishing to be bound by theory, Applicants have captured the physics and chemistry of nanometer features that the disclosed methods and formulations herein have not addressed to this point; As in the macro world, we believe that the debates of line edge roughness and line width growth and roughness have been satisfied with existing materials. However, in the nano world, these debates are prominent, and the existing technology cannot solve the nano-feature controversy. Applicants have discovered that for currently available materials based on t-butoxycarbonyl (t-BOC) protection of phenolic OH, PEB is required for deprotection.

In addition, Applicants have claimed that a t-BOC protected phenolic OH in that it can theoretically coordinate with a high electron density molecule, such as any of the oxygens of the carbonate functional group, for example, to form a metastable complex. was found to act as a self-quencher (one possible example is shown in Scheme 1). When no heat is applied, the complex will remain in this metastable state or it will be reverted back to a non-reactive photo product, while on the other hand heat will deblock the phenol by tBOC.

Scheme 1

Substrates useful in this disclosure are substrates well known in the art for making electronic components and include, for example, silicon substrates coated with other materials such as, for example, silicon dioxide, other oxides, organic and/or inorganic coatings, and the like. .

The multi-trigger resist composition contains at least one polymer, oligomer or monomer, each comprising two or more crosslinkable functional groups. Such polymers, oligomers and monomers are well known in the art and include, for example, novolac resins and polyhydroxy-styrene. Two or more crosslinkable functional groups useful in the disclosed methods are well known in the industry and include, for example, hydroxy, amino, oxime, and the like. The functional groups will react and crosslink in the presence of an acid and an acid activated crosslinking agent. These functional groups are attached, for example, to polymers, oligomers or monomers containing groups such as, for example, aryl groups, and the aryl groups may be substituted or unsubstituted divalent aromatic groups, such aromatic groups being, for example, phenylene (-C ₆ H ₄ -), fused divalent aromatic groups such as for example naphthylene (-C ₁₀ H ₆ -), anthracenylene (-C ₁₄ H ₈ -), etc. as well as heteroaromatic groups such as for example nitrogen hetero Cycles: pyridine, quinoline, pyrrole, indole, pyrazole, triazine and other nitrogen-containing aromatic heterocycles well known in the art, as well as oxygen heterocycles: furan, oxazole and other oxygen-containing aromatic heterocycles, as well as sulfur containing aromatic heterocycles such as for example thiophene. Trivalent and tetravalent aromatics may also be used.

The aryl group may be in the form of an oligomeric or polymer having a molecular weight of between about 1000 Daltons and 100,000 Daltons depending on the desired properties of the cured negative resist pattern, such as etch resistance. Examples include novolac resins based on phenol, cresol, resorcinol, pyrogallol, and the like, and also include copolymers prepared therefrom. Polyhydroxystyrene based polymers and their derivatives or copolymers may also be used in these photoresist compositions.

As noted above, the crosslinkable functional group is blocked or protected with an acid labile protecting group. Acid labile protecting groups include, for example, substituted methyl groups, 1-substituted ethyl groups, 1-substituted alkyl groups, silyl groups, germanyl groups, alkoxycarbonyl groups, acyl groups and cyclic acid-dissociable groups. The substituted methyl group is, for example, a methoxymethyl group, a methylthiomethyl group, an ethoxymethyl group, an ethylthiomethyl group, a methoxyethoxymethyl group, a benzyloxymethyl group, a benzylthiomethyl group, a phenacyl group, a bromophenacyl group, a methoxyphenacyl group, Methylthiophenacyl group, α-methylphenacyl group, cyclopropylmethyl group, benzyl group, diphenyl methyl group, triphenylmethyl group, bromobenzyl group, nitrobenzyl group, methoxybenzyl group, methylthiobenzyl group, ethoxybenzyl group , ethylthiobenzyl group, piperonyl group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group, N-propoxy carbonylmethyl group, isopropoxy carbonylmethyl group, N-butoxycarbonylmethyl group and t-butoxycarr Contains a bornylmethyl group. The 1-substituted ethyl group is, for example, 1-methoxyethyl group, 1-methylthioethyl group, 1,1-dimethoxyethyl group, 1-ethoxyethyl group, 1-ethylthioethyl group, 1,1-diethoxyethyl group, 1 -Phenoxyethyl group, 1-phenylthioethyl group, 1,1-diphenoxyethyl group, 1-benzyloxyethyl group, 1-benzylthioethyl group, 1-cyclopropylethyl group, 1-phenylethyl group, 1,1-diphenyl ethyl group , 1-methoxycarbonylethyl group, 1-ethoxycarbonylethyl group, 1-N-propoxycarbonylethyl group, 1-isopropoxycarbonylethyl group, 1-N-butoxycarbonylethyl group and 1-t- butoxycarbonylethyl group. The 1-substituted alkyl group includes isopropyl group, sec-butyl group, t-butyl group, 1,1-dimethylpropyl group, 1-methylbutyl group and 1,1-dimethylbutyl group.

The acid labile protecting group may contain a silyl functional group, for example, trimethyl silyl group, ethyldimethylsilyl group, methyldiethylsilyl group, triethylsilyl group, isopropyldimethylsilyl group, methyldiisopropylsilyl group, triiso and a propylsilyl group, a t-butyldimethylsilyl group, a methyldi-t-butylsilyl group, a tri-t-butylsilyl group, a phenyldimethylsilyl group, a methyldiphenylsilyl group, and a triphenylsilyl group. The germanyl group is, for example, a trimethyl germanyl group, an ethyldimethylgermyl group, a methyldiethylgermyl group, a triethylgermyl group, an isopropyldimethylgermyl group, a methyldiisopropylgermyl group, a triisopropylgermyl group, and a t-butyldimethylgermyl group. and a mil group, a methyldi-t-butylgermyl group, a tri-t-butylgermyl group, a phenyldimethylgermyl group, a methyldiphenylgermyl group and a triphenylgermyl group.

Other acid labile protecting groups include alkoxycarbonyl acid labile protecting groups, and include, for example, methoxycarbonyl groups, ethoxy carbonyl groups, isopropoxy carbonyl groups and t-butoxycarbonyl groups. Acyl acid labile protecting groups can be used, for example, acetyl group, propionyl group, butyryl group, heptanoyl group, hexanoyl group, valeryl group, pivaloyl group, isovaleryl group, lauroyl group, myristoyl group, palmitoyl group , stearoyl group, oxalyl group, malonyl group, succinyl group, glutaryl group, adipoyl group, piperoyl group, suberoyl group, azelayl group, sebacoyl group, acrylyl group, propioloyl group, methacryloyl group , crotonoyl group, oleoyl group, maleoyl group, fumaroyl group, mesaconoyl group, camphoroyl group, benzoyl group, phthaloyl group, isophthaloyl group, terephthaloyl group, naphthoyl group, toluyl group, hydroa tropoyl group, atropoyl group, cinnamoyl group, furoyl group, tenoyl group, nicotinoyl group, isonicotinoyl group, p-toluene sulfonyl group and mesyl group.

Additional acid labile protecting groups include cyclic acid labile protecting groups, for example, cyclopropyl group, cyclopentyl group, cyclohexyl group, cyclohexanyl group, 4-methoxycyclohexyl group, tetrahydropyranyl group, tetrahydrofura Nyl group, tetrahydrothiopyranyl group, tetrahydrothiofuranyl group, 3-bromotetrahydropyranyl group, 4-methoxy tetrahydropyranyl group, 4-methoxy tetrahydrothiopyranyl group and 3-tetrahydrothiophene-1 , 1-deoxy group.

When acid activated crosslinking agents suitable for the present disclosure constitute a compound capable of crosslinking with the above-mentioned crosslinkable functional groups during processing, and thus deprotected to provide, for example, a phenol or similar group, the crosslinking agent is a phenol or similar group. It will react with the just deprotected -OH group located there. The crosslinking agent may be a polymer, oligomer or monomer. Without wishing to be bound by theory, it is believed that the acid generated by exposure to actinic radiation not only reacts with the acid labile protecting group of the polymer, oligomer or monomer, but also reacts with the crosslinker as a second trigger to cause a curing reaction when the two materials are in close enough proximity. Believe. Such curing reactions reduce developer solubility in areas that have just been exposed to light, resulting in a pattern of cured material. Examples of crosslinking agents include compounds comprising at least one type of substituted group having crosslinking reactivity with a hydroxyl group of a polymer, oligomer or monomer, such as a hydroxyl group from a phenol, an amine or a similar group. Specific examples of the acid-activated crosslinking agent include glycidyl ether group, glycidyl ester group, glycidyl amino group, methoxymethyl group, ethoxymethyl group, benzyloxymethyl group, dimethylamino methyl group, diethylamino methyl group, dimethylol amino methyl group , a diethylol amino methyl group, a morpholino methyl group, an acetoxymethyl group, a benzyloxy methyl group, a formyl group, an acetyl group, a vinyl group and an isopropenyl group.

Examples of compounds having the above-mentioned acid-activated crosslinking agents include, for example, bisphenol A-based epoxy compounds, bisphenol F-based epoxy compounds, bisphenol S-based epoxy compounds, novolac resin-based epoxy compounds, resol resin-based epoxies compounds, and poly(hydroxystyrene)-based epoxy compounds.

Acid-activated crosslinking agents based on melamine are useful in the present disclosure, for example, melamine compounds containing methylol groups, benzoguanamine compounds containing methylol groups, urea compounds containing methylol groups, phenolic compounds containing methylol groups, melamine compounds containing alkoxyalkyl groups Compound, alkoxyalkyl group-containing benzoguanamine compound, alkoxyalkyl group-containing urea compound, alkoxyalkyl group-containing phenol compound, carboxymethyl group-containing melamine resin, carboxymethyl group-containing benzoguanamine resin, carboxymethyl group-containing urea resin, carboxymethyl group-containing phenol resin, carboxymethyl group A melamine compound containing a carboxymethyl group, a benzoguanamine compound containing a carboxymethyl group, a urea compound containing a carboxymethyl group, and a phenol compound containing a carboxymethyl group, a phenol compound containing a methylol group, a melamine compound containing a methoxymethyl group, a methoxymethyl group containing phenol compound, a methoxymethyl group containing glycol -A uryl compound, a urea compound containing a methoxymethyl group, and a phenol compound containing an acetoxymethyl group are included. A melamine compound containing a methoxymethyl group is commercially available as, for example, CYMEL300, CYMEL301, CYMEL303, CYMEL305 (manufactured by Mitsui Cyanamid), and a glycol-uril compound containing a methoxymethyl group is, for example, CYMEL117 4 (manufactured by Mitsui Cyanamid) The urea compound containing a methoxymethyl group is commercially available as, for example, MX290 (manufactured by Sanwa Chemicals).

Other acid activated crosslinkers include epoxy crosslinkers. Examples of epoxies used within the scope of the present invention include polymeric, oligomeric and monomeric aliphatic and aromatic epoxies, such as cycloaliphatic epoxies, bisphenol A epoxies, 3,4-epoxycyclohexyl methyl 3,4-epoxy cyclo hexyl carboxylate; and the like. Also included are epoxy formulations based on glycidyl ethers of para amino phenols as described in US Pat. No. 5,514,729. Other suitable epoxies that may be used in practicing the present invention include, but are not limited to, those derived from bisphenol S, bisphenol F, novolac resins, and epoxies obtained from the reaction of bisphenol A and epihalohydrin. Such epoxies are described in US Pat. No. 5,623,031. Other suitable epoxies that may be used in practicing the present invention are described in U.S. Patent Nos. 5,602,193; 5,741,835; and 5,910,548. Additional examples of epoxies useful in this disclosure are glycidyl ethers and glycidyl esters of novolac based polymers, oligomers, and monomers, and oxetane.

Suitable photoacid generators (PAGs) for the multiple trigger negative working photoresists of the present disclosure include onium salt compounds, sulfonimide compounds, halogen containing compounds, sulfone compounds, ester sulfonate compounds, quinonediazide compounds, and dia crude methane compounds. Specific examples of these acid generators are indicated below.

Examples of the onium salt compound include sulfonium salts, iodonium salts, phosphonium salts, diazonium salts and pyridinium salts. Specific examples of the onium salt compound include diphenyl (4-phenylthiophenyl) sulfonium hexafluoroantimonate, 4,4'-bis [diphenylsulfonylphenyl sulfide bis hexafluoroantimonate and combinations thereof, tri Phenylsulfonium nonafluorobutanesulfonate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium pyrenesulfonate, triphenylsulfonium dodecylbenzenesulfonate, triphenylsulfonium p-toluenesulfonate, tri Phenylsulfonium benzenesulfonate, triphenylsulfonium 10-camphor-sulfonate, triphenylsulfonium octanesulfonate, triphenylsulfonium 2-trifluoromethyl benzenesulfonate, triphenylsulfonium hexafluoroantimo nate, triarylsulfonium hexafluoroantimonate, triarylsulfonium hexafluorophosphate, triarylsulfonium tetrafluoroborate as well as other tetrafluoroborates, triphenylsulfonium naphthalenesulfonate, tri(4- Hydroxyphenyl)sulfonium nonafluorobutanesulfonate, tri(4-hydroxyphenyl)sulfonium trifluoromethanesulfonate, tri(4-hydroxyphenyl)sulfonium pyrenesulfonate, tri(4-hydroxyl Phenyl)sulfoniumdodecylbenzenesulfonate, tri(4-hydroxyphenyl)sulfonium p-toluene sulfonate, tri(4-hydroxyphenyl)sulfonium benzenesulfonate, tri(4-hydroxyphenyl)sulfonium l0-camphor-sulfonate, tri(4-hydroxyphenyl)sulfonium octanesulfonate, tri(4-hydroxyphenyl)sulfonium 2-trifluoromethylbenzenesulfonate, tri(4-hydroxyphenyl) Sulfonium hexafluoroantimonate, tri(4-hydroxyphenyl)sulfonium naphthalenesulfonate, diphenyliodonium nonafluorobutanesulfonate, diphenyliodonium trifluoromethanesulfonate, diphenylio Donium pyrenesulfonate, diphenyliodonium dodecylbenzenesulfonate, diphenyliodonium p-toluene sulfonate, diphenyliodonium benzenesulfonate, diphenyliodonium 10-camphor-sulfonate, Diphenyliodonium octanesulfonate, diphenyliodonium 2-trifluoromethylbenzenesulfonate, bis(4-t-butylphenyl)iodonium nonafluorobutanesulfonate, bis(4-t-butyl Phenyl)iodonium trifluoromethanesulfonate, bis(4-t-butylphenyl)io Donium pyrenesulfonate, bis(4-t-butylphenyl)iodonium dodecylbenzenesulfonate, bis(4-t-butylphenyl)iodonium p-toluene sulfonate, bis(4-t-butylphenyl) iodonium benzenesulfonate, bis(4-t-butylphenyl)iodonium 10-camphor-sulfonate, bis(4-t-butylphenyl)iodonium octanesulfonate, bis(4-t-butyl Phenyl)iodonium 2-trifluoromethylbenzenesulfonate, 4-hydroxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate and 4,7-dihydroxy-1-naphthyl tetrahydro thiophenium trifluoromethanesulfonate.

Specific examples of the sulfonimide compound include N-(trifluoromethylsulfonyloxy)succinimide, N-(trifluoromethylsulfonyloxy)phthalimide, N-(trifluoromethylsulfonyloxy)di Phenylmaleimide, N-(trifluoromethylsulfonyloxy)bicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide, N-(trifluoromethylsulfonyloxy)-7- oxabicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide, N-(trifluoromethylsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxy-2, 3-Dicarboxyimide, N-(trifluoromethylsulfonyloxy)naphthylimide, N-(10-camphor-sulfonyloxy)succinimide, N-(10-camphor-sulfonyloxy) Phthalimide, N-(10-camphor-sulfonyloxy)diphenyl maleimide, N-(10-camphor-sulfonyloxy)bicyclo[2.2.1]hepto-5-ene-2,3- Dicarboxyimide, N-(10-camphor-sulfonyloxy)-7-oxabicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide, N-(10-camphor-sulfonyloxy) Ponyloxy)bicyclo[2.2.1]heptane-5,6-oxy-2,3-dicarboxyimide, N-(10-camphor-sulfonyloxy)naphthylimide, N-(p-toluenesulf Ponyloxy) succinimide, N-(p-toluenesulfonyloxy)phthalimide, N-(p-toluenesulfonyloxy)diphenyl maleimide, N-(p-toluenesulfonyloxy)bicyclo[2.2 .1]hepto-5-ene-2,3-dicarboxyimide, N-(p-toluenesulfonyloxy)-7-oxabicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyi mide, N-(p-toluenesulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxy-2,3-dicarboxyimide, N-(p-toluenesulfonyloxy)naphthylimide; N-(2-trifluoromethylbenzenesulfonyloxy)succinimide, N-(2-trifluoromethylbenzenesulfonyloxy)phthalimide, N-(2-trifluoromethylbenzenesulfonyloxy) Diphenyl maleimide, N-(2-trifluoromethylbenzenesulfonyloxy)bicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide, N-(2-trifluoromethylbenzene Sulfonyloxy)-7-oxabicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide, N-(2-trifluoromethylbenzenesulfonyloxy)bicyclo[2. 2.1]Heptane-5,6-oxy-2,3-dicarboxyimide, N-(2-trifluoromethylbenzenesulfonyloxy)naphthylimide, N-(4-fluorobenzenesulfonyloxy)succinic Imide, N-(4-fluorobenzenesulfonyloxy)phthalimide, N-(4-fluorobenzenesulfonyloxy)diphenyl maleimide, N-(4-fluorobenzenesulfonyloxy)bicyclo [2.2.1]hepto-5-ene-2,3-dicarboxyimide, N-(4-fluorobenzenesulfonyloxy)-7-oxabicyclo[2.2.1]hepto-5-ene-2, 3-Dicarboxyimide, N-(4-fluorobenzenesulfonyloxy) bicyclo[2.2.1]heptane-5,6-oxy-2,3-dicarboxyimide, N-(4-fluorobenzenesulfonyl) Ponyloxy)naphthylimide, N-(nonafluorobutylsulfonyloxy)succinimide, N-(nonafluorobutylsulfonyloxy)phthalimide, N-(nonafluorobutylsulfonyloxy)di Phenyl maleimide, N-(nonafluorobutylsulfonyloxy)bicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide, N-(nonafluorobutylsulfonyloxy)-7- oxabicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide, N-(nonafluorobutylsulfonyloxy)bicyclo[2.2.1]heptane-5, 6-oxy-2, 3-dicarboxyimide and N-(nonafluorobutylsulfonyloxy)naphthylimide.

Examples of the halogen-containing compound include, for example, a haloalkyl group-containing hydrocarbon compound and a haloalkyl group-containing heterocyclic compound. Specific examples of halogen-containing compounds include (poly)trichloromethyl-s-triazine derivatives such as phenyl-bis(trichloromethyl)-s-triazine, 4-methoxyphenyl-bis(trichloromethyl)-s-tri azine and 1-naphthyl-bis(trichloromethyl)-s-triazine, and 1,1-bis(4-chlorophenyl)-2,2,2-trichloroethane.

Examples of the sulfone compound include, for example, β-ketosulfone and β-sulfonylsulfone, and α-diazo compounds thereof. Specific examples of the sulfone compound include phenacyl phenylsulfone, mesitylphenacyl sulfone, bis(phenylsulfonyl)methane, 1,1-bis(phenylsulfonyl)cyclobutane, 1,1-bis(phenylsulfonyl)cyclopentane, 1,1-bis(phenylsulfonyl)cyclohexane, and 4-trisphenacylsulfone.

Examples of the sulfonate ester compound include alkylsulfonate esters, haloalkyl sulfonate esters, aryl sulfonate esters and imino sulfonates. Specific examples of the sulfonate ester compound include benzoin tosylate, pyrogallol tristrifluoromethanesulfonate, pyrogallol trisnonafluorobutanesulfonate, pyrogallol methanesulfonate triester, nitrobenzyl-9,10-diethoxy anthracene-2-sulfonate, α-methylol benzoin tosylate, α-methylol benzoin octanesulfonate, α-methylol benzoin trifluoromethanesulfonate and α-methylol benzoin dodecylsulfonate include

Examples of the quinine diazide compound include a 1,2-quinone diazide sulfonyl group such as a 1,2-benzoquinone diazide-4-sulfonyl group, a 1,2-naphthoquinone diazide-4-sulfonyl group, 1,2- and compounds containing a naphthoquinine diazide-5-sulfonyl group and a 1,2-naphthoquinone diazide-6-sulfonyl group. Specific examples of the quinone diazide compound include (poly)hydroxyphenylaryl ketones such as 2,3,4-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,3,4,4′- Tetrahydroxybenzophenone, 2,2',3,4-tetrahydroxybenzophenone, 3'-methoxy-2,3,4,4'-tetrahydroxybenzophenone, 2,2',4,4 '-tetrahydroxybenzophenone, 2,2'3,4,4'-pentahydroxybenzophenone, 2,2'3,4,6'-pentahydroxybenzophenone, 2,3,3'4, 1,2-quinone diazidesulfonate ester of 4',5'-hexahydroxybenzophenone, 2,3'4,4',5',6-hexahydroxybenzophenone; bis[(poly)hydroxyphenyl]alkanes such as bis(4-hydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)methane, bis(2,3,4-trihydroxyphenyl)methane, 2 1 of ,2-bis(4-hydroxyphenyl)propane, 2,2-bis(2,4-dihydroxyphenyl)propane and 2,2-bis(2,3,4-trihydroxyphenyl)propane ,2-quinone diazide sulfonate esters; (poly)hydroxytriphenylalkanes such as 4,4′-dihydroxytriphenylmethane, 4,4′,4″-trihydroxytriphenylmethane, 2,2′,5,5′-tetramethyl-2 ",4,4'-trihydroxytriphenylmethane, 3,3',5,5'-tetramethyl-2",4,4'-trihydroxytriphenylmethane, 4,4',5,5 '-Tetramethyl-2,2',2"-trihydroxytriphenylmethane, 2,2',5,5'-tetramethyl-4,4',4"-trihydroxytriphenylmethane, 1, 1,1-tris(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 1,1-bis(4-hydroxyphenyl)-1-[4- {1-(4-hydroxyphenyl)-1-methylethyl}phenyl)ethane, 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl)propane, 1,1,3-tris( 1,2-quinone diazide sulfonate esters of 2,5-dimethyl-4-hydroxyphenyl)butane and 1,3,3-tris(2,5-dimethyl-4-hydroxyphenyl)butane; and (poly ) hydroxyphenylflavans such as 2,4,4-trimethyl-2',4',7-trihydroxy-2-phenylflavan and 2,4,4-trimethyl-2',4',5', 1,2-quinone diazide sulfonate ester of 6',7-pentahydroxy-2-phenylflavan.

Specific examples of the diazomethane compound include bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl) Diazomethane, methylsulfonyl-p-toluenesulfonyldiazomethane, 1-cyclohexylsulfonyl-1-(1,1-dimethylethylsulfonyl)diazomethane and bis(1,1-dimethylethylsulfonyl) ), including diazomethane.

The composition of the present disclosure may contain one or more of the above-mentioned photoacid generators.

Examples of suitable solvents of the present disclosure include ethers, esters, etheresters, ketones and ketoneesters and more specifically ethylene glycol monoalkyl ethers, diethylene glycol dialkyl ethers, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, acetates esters, hydroxyacetate esters, lactate esters, ethylene glycol monoalkylether acetates, propylene glycol monoalkylether acetates, alkoxyacetate esters, (non-)cyclic ketones, acetoacetate esters, pyruvate esters and propionate esters include Specific examples of these solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, Diethylene glycol dibutyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, isopropenyl acetate, isopropenyl propionate , methylethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-hydroxypropionate ethyl, 2-hydroxy-2-methylpropionate ethyl, ethoxy acetate ethyl , ethyl hydroxyacetate, 2-hydroxy-3-methyl methylbutyrate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, 3- Methyl-3-methoxybutyl butyrate, ethyl acetate, propyl acetate, butyl acetate, methyl acetoacetate, ethyl acetoacetate, methyl 3-methoxypropionate, ethyl 3-methoxy propionate, 3-ethoxy propionate cypionate methyl and 3-ethoxy propionate ethyl. The solvents mentioned above may be used independently or as a mixture of two or more types. In addition, high boiling solvents such as benzylethyl ether, dihexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, acetonylacetone, isoholone, caproic acid, capric acid, 1-octanol, 1-no At least one type of nanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate and phenylcellosolve acetate is mentioned above It can be added to the used solvent.

In typical resist formulations, various additives are added for acid diffusion control agents that retard migration of acid to unexposed areas of the coating. Applicants have discovered that with proper selection of acid labile protecting groups and appropriate selection of acid activatable crosslinker agents, such acid diffusion agents are not required. That is, the acid labile protecting group and the acid activated crosslinking agent will complex with the photogenerated acid without migration. Not all acid labile protecting groups or acid activatable crosslinkers will complex with the photoacid and therefore require acid diffusion modulating agents.

All crosslinkable functional groups are blocked by acid labile protecting groups, and from about 90% to about 100% blocked. The acid labile group is selected to have the property of being able to complex with the photogenerated acid.

The photoresist composition may be a substrate such as a silicon wafer or a wafer coated with silicon dioxide, aluminum, aluminum oxide, copper, nickel, many semiconductor materials or nitrides or other substrates well known in the semiconductor industry, or an organic film such as for example a bottom layer antireflective It may be coated on a substrate having a film or the like thereon. The photoresist composition is applied by methods such as spin coating, curtain coating, slot coating, dip coating, roller coating, blade coating, and the like. After coating, the solvent is removed to a certain level, where the coating can be properly exposed. In some cases, a 5% solvent residue may remain in the coating, while in other cases less than 1% is required. Drying can be achieved by hot plate heating, convection heating, infrared heating, and the like. The coating is exposed image-by-image through marks containing the desired pattern.

Suitable radiation for the photoresist compositions described include, for example, the bright spectrum of ultraviolet (UV) such as mercury lamps (254 nm), KrF excimer lasers (248 nm), and ArF excimer lasers (193 nm), extreme ultraviolet (EUV) such as 13.5 nm, extreme ultraviolet (BEUV) eg 6.7 nm exposure from a plasma discharge and synctron light source, X-rays eg syncron radiation. Ion beam lithography and charged particle beams such as electron beams may also be used.

In this method embodiment, after exposure, the exposed coated substrate does not undergo post-exposure baking, thus preventing the photogenerated acid from migrating and thus preventing dark reactions leading to line edge roughness and other undesirable pattern defects. do.

The unexposed areas are then moved using a developer. Such developers generally include an organic solvent. The developing solvent is less aggressive than the solvent used to prepare the photoresist composition.

After development, a final baking step may be included to further enhance curing of the just exposed and developed pattern. The heating process may be, for example, about 30 to about 300° C. for about 10 to about 120 seconds, and may be achieved by hot plate heating, convection heating, infrared heating, and the like.

In a further disclosure, Applicants have developed a new material, xMT, useful in the compositions of the disclosed methods. These materials are described in US Pat. No. 9,122.156, US Pat. No. 9,229,322, and US Pat. No. 9,519,215, which are incorporated herein by reference, and have the formula:

wherein at least one of X or Y is

-(alkyl) _j -(aryl) _k -(O) _p -(COO) _q -LG

wherein j, k, p and q take the values shown in the table of FIG. 1 ; wherein alkyl is a branched or unbranched, substituted or unsubstituted divalent alkyl chain of 1 to 16 carbon atoms having 0 to 16 heteroatoms substituted in the chain, and aryl is a substituted or unsubstituted 2 is a phenyl group, a divalent heteroaromatic group, or a divalent fused aromatic or fused heteroaromatic group, wherein LG is a tertiary alkyl or tertiary cycloalkyl group, an alicyclic group, a ketal or cyclic aliphatic ketal, or an acetal, leaving it's gi

These materials have surprisingly been shown to improve resolution, sensitivity and line geometry, such as line edge roughness and sensitivity. Surprisingly, other more newly developed xMT materials useful in this disclosure provided much better improvements in LER and sensitivity, including that of FIG. 2 . Both variants are designed to reduce LER by stiffening molecules before and after photoreaction, where they crosslink with added crosslinkers. One variant, Figure 8b, includes additional functional groups designed to increase photosensitivity. The xMT materials useful in this disclosure are based on the reaction product of a protected malonic acid ester and an amidine as described in the references cited above.

Metal components useful in the present disclosure include metals exhibiting high EUV light absorption cross-sections, moderate to high inelastic electron scattering and low to moderate elastic scattering coefficients, for example, scandium, titanium, vanadium, chromium, manganese, iron, Cobalt, nickel, copper, zinc, gallium, germanium, arsenic, selenium, bromine, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, cadmium, indium, tin, antimony, tellurium , iodine, lanthanide, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, mercury, lead, bismuth, polonium, columns 3 to 17 and rows 3 to 6, and aluminum, silicon , phosphorus, sulfur and chlorine, a metal selected from column 13-17, row 3 of the Periodic Table of the Elements, or a salt or coordination complex or a selected metal, selected metal containing monomer, oligomer or polymer ligand. These materials are described in US Pat. No. 9,632,409, which is incorporated herein by reference.

In some embodiments, the exposed resist may be subjected to a post-exposure baking step. This optional step includes a selected temperature for a selected length of time. The time and temperature will depend on the aggressiveness of the developer and also with the photogenerated acid and components such as at least one polymer, oligomer or monomer each comprising two or more crosslinkable functional groups and at least 90% of the functional groups attached to acid labile protecting groups. , and/or the strength of the complex obtained as a result of complexation with at least one acid activatable crosslinking agent is selected to optimize exposure curing prior to development.

Example

The tBOC protected phenol was formulated with a PAG (photoacid generator) and exposed to EUV radiation. After holding for 15 minutes, tBOC did little to no reaction with the photogenerated acid and no phenolic OH was obtained. 3 shows the IR spectra of phenol and tBOC protected phenol, showing significant stretching at 1774 cm ⁻¹ of the carbonyl moiety of the tBOC functional group. Figure 4 shows that the reduction carbonyl of the tBOC functional group did not occur after UV exposure and 15 min holding time. The 1774 cm ⁻¹ significant stretching of the t-BOC functional group is essentially the same. Figure 5 shows additional evidence, where IR after exposure and 15 min hold of the protected phenol and PAG as evidenced by little to no change in stretching at approximately 3000 cm ^-1 that -OH would have strongly absorbed. no OH appears, which would have been expected if tBOC had reacted with photogenerated acid to deblock phenolic oxygen.

Additionally, Applicants have surprisingly discovered that typical crosslinking agents found in negative photoresists such as epoxies also require heat to complete their curing step. 6 shows line A, the infrared spectrum of a representative epoxy crosslinker blended with a representative PAG. In line B, part of the epoxy reacted after UV exposure, but in line C, it can be seen that the reaction was completed only after PEB.

Without wishing to be bound by theory, based on the foregoing, the tBOC functional group and It is believed that epoxies act as self-quenching materials.

The proposed mechanism is shown in Figs. 7, a-e. This summary exemplifies the newly disclosed method. In Figure 7a, the photogenerated acid will form a metastable complex with tBOC, and phenol will be obtained only by heat. The photogenerated acid will also form a metastable complex with the crosslinking agent as shown in Figure 7b. However, some of the epoxies will be ring-opened and partially crosslinked, as shown in Figure 7b. At ambient temperature, very few chains are obtained, and we believe that the chain transfer mechanism of the photoproduct from the PAG ends with chain termination as shown in Fig. 7c. In the mechanism of the representative photoresist of FIG. 7D with PEB applied, tBOC deprotects the phenol, which then reacts with the propagating chain from the thermally activated chain propagating crosslinker. Since the reaction is hardly controlled once PEB is applied, chain and crosslinking as well as acid migration cause line edge roughness, and line width growth and roughness. In the novel and unexpected method of Figure 7e, the metastable material will remain unreacted until both the tBOC complex and the crosslinker complex are in close enough proximity that they can react, and in the case of epoxies the chains will start to propagate. . Because both events must occur simultaneously, the multi-trigger process, line and space geometry is controlled. 8A shows a SEM of a standard photoresist containing additional acid diffusion control components using a representative method compared to the resist using the non-PEB compositions and methods disclosed herein shown in FIG. 8B. Improvements in line and space geometry are readily apparent. The photoacid will activate the matrix molecules, but the reaction will proceed only if the base molecule and the crosslinker are in close proximity to each other and are activated simultaneously. Therefore, it has been surprisingly found that the novel method of removing PEB provides surprisingly superior results in photoresist formulations.

In some embodiments of the present disclosure, the high Z metallic and/or non-metal and xMT materials may each be used alone in the disclosed resist compositions, or they may be combined.

Example 1

Examples of materials are shown in FIG. 9 .

composition 1

The xMT molecular resin compound of FIG. 9 was mixed with a molecular crosslinking agent and a photoacid generator and ethyl lactate in a weight ratio of 0.2:2:1. The composition was spin coated onto a dedicated carbon coated silicon wafer and heated on a 75° C. hot plate for 5 min to give a film of approximately 25 nm. Then, the coated wafer was image-exposed to synctron-based EUV light of 13-14 nm wavelength, and post-exposure baking was performed at 90° C. for 3 min. The unexposed areas were removed by puddle development in a 50:50 blend of monochlorobenzene and isopropyl alcohol for 20 sec followed by rinsing with isopropyl alcohol. Unexposed areas are removed by poodle development in a 50:50 blend of monochlorobenzene and isopropyl alcohol followed by rinsing with isopropyl alcohol.

composition 2

Composition 1 was repeated except that 2.5% quencher was added.

The results are shown in FIG. 10 by comparing Composition 1 (FIG. 10A) and Composition 2 (FIG. 10B). As can be seen in FIG. 10A , the resist without quencher had higher sensitivity, 18.9 mJ/cm ² versus 40.4 mJ/cm ² , while at the same time the line edge roughness was essentially the same. At equivalent exposure, composition 1 has about 50% higher line edge roughness than composition 2.

Example 2

Very few commercially available materials have LWRs less than about 3 nm, and there is a need to develop higher sensitivity photoresists. For example, most commercial photoresist systems require 35-40 mJ/cm ² to print a reasonable contact hole (with the available process window).

Composition 1 was used to print patterned samples into contact holes using Lawrence Berkeley National Laboratory's Microfield Exposure Tool (see FIG. 11 ), which is the world's highest resolution EUV lithography tool (0.3 numerical aperture). In particular, the patterning dose for this exposure was less than 17 mJ/cm ² , and the critical dimension target was a dense 25 nm contact hole structure.

The results show the full resolution of the hole when the method herein is used with the disclosed composition. When post-exposure baking was used, the holes either did not resolve or had much poorer resolution.

Claims (18)

A method of forming a patterned resist comprising:
a. providing a substrate;
at least one polymer, oligomer or monomer wherein each bi comprises at least two crosslinkable functional groups and essentially all functional groups are attached to acid labile protecting groups;
ii. at least one acid activatable crosslinking agent,
iii. at least one photoacid generator, and
iv. at least one solvent
applying a multi-trigger resist composition comprising
c. heating the coated substrate to form a substantially dried coating to obtain a desired thickness;
d. imagewise exposing the coated substrate to actinic radiation;
e. Unexposed areas of the coating may be removed using an aqueous developer, solvent developer, or combination of an aqueous-solvent developer composition, the remaining photoimaged pattern optionally heated, and the exposed resist optionally heated prior to development. step there. The method of claim 1 , wherein at least about 90% of the crosslinkable functional groups are attached to an acid labile protecting group. The onium salt compound, sulfonium salt of claim 1 , wherein the at least one photoacid generator is capable of generating an acid when exposed to at least one of UV, deep ultraviolet, extreme ultraviolet, x-ray, or e-beam actinic radiation; Triphenylsulfonium salt, sulfonimide, halogen-containing compound, sulfone, sulfonimide, sulfonate ester, quinone-diazide, diazomethane, iodonium salt, oxime sulfonate, dicarboxyimidyl sulfate ester, ylideneamino oxy sulfonic acid ester, sulfonyldiazomethane, or mixtures thereof. 2. The method of claim 1, wherein said at least one acid activatable crosslinking agent is glycidyl ether, glycidyl ester, oxetane, glycidyl amine, methoxymethyl group, ethoxymethyl group, butoxymethyl group, benzyloxymethyl group, dimethyl aminomethyl group, diethylamino methylamino group, dialkylolmethyl amino group, dibutoxymethyl amino group, dimethylolmethyl amino group, diethylolmethyl amino group, dibutylolmethyl amino group, morpholinomethyl group, acetoxymethyl group, benzyloxymethyl group, A method comprising an aliphatic, aromatic or aralkyl monomer, oligomer, resin or polymer containing at least one of a formyl group, an acetyl group, a vinyl group, or an isopropenyl group. The method of claim 1 , wherein the acid labile protecting group comprises a tertiary alkoxycarbonyl group. 6. The method of claim 5, wherein said at least one acid activatable crosslinking agent comprises one or more glycidyl ether groups attached to an aryl monomer, oligomer or polymer. 4. The method of claim 3, wherein said polymer, oligomer or monomer is at least one xMT ester. 8. The structure of claim 7, wherein the xMT ester has the structure:

wherein at least one of X or Y is
-(alkyl) _j -(aryl) _k -(O) _p -(COO) _q -LG
wherein j, k, p, and q are the values listed in the following table;

wherein alkyl is a branched or unbranched, substituted or unsubstituted divalent alkyl chain of 1 to 16 carbon atoms having 0 to 16 heteroatoms substituted in the chain, and aryl is a substituted or unsubstituted 2 is a phenyl group, a divalent heteroaromatic group, or a divalent fused aromatic or fused heteroaromatic group, wherein LG is a tertiary alkyl or tertiary cycloalkyl group, cycloaliphatic group, ketal or cyclic aliphatic ketal, or acetal, leaving How to sign. 9. The structure of claim 8, wherein the xMT ester has the structure:

wherein at least one of X or Y is
-(alkyl) _j -(aryl) _k -(O) _p -(COO) _q -LG
wherein j, k, p, and q are the values listed in the following table:

wherein alkyl is a branched or unbranched, substituted or unsubstituted divalent alkyl chain of 1 to 16 carbon atoms having 0 to 16 heteroatoms substituted in the chain, and aryl is a substituted or unsubstituted 2 is a phenyl group, a divalent heteroaromatic group, or a divalent fused aromatic or fused heteroaromatic group, wherein LG is a tertiary alkyl or tertiary cycloalkyl group, cycloaliphatic group, ketal or cyclic aliphatic ketal, or acetal, leaving How to sign. 10. The method of claim 9, wherein at least about 90% of said crosslinkable functional groups are attached to acid labile protecting groups. 11. The compound of claim 10, wherein the at least one photoacid generator is capable of generating an acid when exposed to at least one of UV, deep ultraviolet, extreme ultraviolet, x-ray, or e-beam actinic radiation; Triphenylsulfonium salt, sulfonimide, halogen-containing compound, sulfone, sulfonimide, sulfonate ester, quinone-diazide, diazomethane, iodonium salt, oxime sulfonate, dicarboxyimidyl sulfate ester, ylideneamino oxy sulfonic acid ester, sulfonyldiazomethane, or mixtures thereof. 12. The method of claim 11 wherein said at least one acid activatable crosslinking agent is glycidyl ether, glycidyl ester, oxetane, glycidyl amine, methoxymethyl group, ethoxymethyl group, butoxymethyl group, benzyloxymethyl group, dimethyl aminomethyl group, diethylamino methylamino group, dialkylolmethyl amino group, dibutoxymethyl amino group, dimethylolmethyl amino group, diethylolmethyl amino group, dibutylolmethyl amino group, morpholinomethyl group, acetoxymethyl group, benzyloxymethyl group, A method comprising an aliphatic, aromatic or aralkyl monomer, oligomer, resin or polymer containing at least one of a formyl group, an acetyl group, a vinyl group, or an isopropenyl group. 4. The method of claim 3, wherein the composition further comprises at least one metal component, wherein the metal component exhibits a high EUV light absorption cross-section, a medium to high inelastic electron scattering and a low to medium elastic scattering coefficient. 14. The method of claim 13, wherein said at least one metal is selected from the group consisting of scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, arsenic, selenium, bromine, yttrium, zirconium, niobium, Molybdenum, technetium, ruthenium, rhodium, palladium, silver, cadmium, indium, tin, antimony, tellurium, iodine, lanthanide, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, mercury , Columns 3 to 17 and rows 3 to 6 of the Periodic Table of the Elements, containing lead, bismuth, polonium, and columns 13 to 17, rows 3, containing aluminum, silicon, phosphorus, sulfur and chlorine, or a salt or coordination complex of a selected metal; or selected from selected metal containing monomers, oligomers or polymeric ligands. 15. The method of claim 14, wherein said at least one acid activatable crosslinking agent is glycidyl ether, glycidyl ester, oxetane, glycidyl amine, methoxymethyl group, ethoxymethyl group, butoxymethyl group, benzyloxymethyl group, dimethyl aminomethyl group, diethylamino methylamino group, dialkylolmethyl amino group, dibutoxymethyl amino group, dimethylolmethyl amino group, diethylolmethyl amino group, dibutylolmethyl amino group, morpholinomethyl group, acetoxymethyl group, benzyloxymethyl group, A method comprising an aliphatic, aromatic or aralkyl monomer, oligomer, resin or polymer containing at least one of a formyl group, an acetyl group, a vinyl group, or an isopropenyl group. 10. The method of claim 9, wherein the composition further comprises at least one metal component, wherein the metal component exhibits a high EUV light absorption cross-section, a medium to high inelastic electron scattering and a low to medium elastic scattering coefficient. 17. The method of claim 16, wherein said at least one metal is selected from the group consisting of scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, arsenic, selenium, bromine, yttrium, zirconium, niobium, Molybdenum, technetium, ruthenium, rhodium, palladium, silver, cadmium, indium, tin, antimony, tellurium, iodine, lanthanide, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, mercury , Columns 3 to 17 and rows 3 to 6 of the Periodic Table of the Elements, containing lead, bismuth, polonium, and columns 13 to 17, rows 3, containing aluminum, silicon, phosphorus, sulfur and chlorine, or containing a salt, coordination complex, or metal a method selected from monomeric, oligomeric or polymeric ligands. 18. The method of claim 17, wherein said at least one acid activatable crosslinking agent is glycidyl ether, glycidyl ester, oxetane, glycidyl amine, methoxymethyl group, ethoxymethyl group, butoxymethyl group, benzyloxymethyl group, dimethyl aminomethyl group, diethylamino methylamino group, dialkylolmethyl amino group, dibutoxymethyl amino group, dimethylolmethyl amino group, diethylolmethyl amino group, dibutylolmethyl amino group, morpholinomethyl group, acetoxymethyl group, benzyloxymethyl group, A method comprising an aliphatic, aromatic or aralkyl monomer, oligomer, resin or polymer containing at least one of a formyl group, an acetyl group, a vinyl group, or an isopropenyl group.

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