TWI823901B - Enhanced euv photoresist materials, formulations and processes - Google Patents

Abstract

The present disclosure relates to novel negative-type photoresist composition and methods of their use. The disclosure further relates to multiple trigger photoresist processes which allow for the improvement in contrast, resolution, and/or line edges roughness in some systems without giving up sensitivity. The photoresist compositions and the methods of the current disclosure are ideal for fine patent processing using, for example, ultraviolet radiation, extreme ultraviolet radiation, beyond extreme ultraviolet radiation, X-rays and changed particle. The disclosure further relates to sensitivity enhancing materials useful in the disclosed compositions and methods.

Description

Enhanced EUV photoresist materials, formulations and methods

This disclosure relates to novel negative photoresist compositions and methods of use. This disclosure also relates to methods of multiple triggering photoresists that allow for 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 use with sophisticated proprietary methods, such as ultraviolet radiation, extreme ultraviolet radiation, ultra-extreme ultraviolet radiation, X-rays, and altered particles. This disclosure document also relates to sensitivity enhancing materials for use in the disclosed compositions and methods.

Extreme UV (EUV) lithography (EUVL), with a wavelength of 13.5nm, is considered to be one of the most promising candidates to replace the current 193nm lithography tools to meet future semiconductor manufacturing needs. Smaller and smaller lines and spaces to create smaller and smaller semiconductor features.

To meet the new EUV requirements for suitable photoresist materials, photoresist manufacturers initially reformulated existing 193nm resist systems - through formulation adjustments, additives and photoacid generator (PAG) loading - for EUV. use. Although this is a cost-effective method, it yields a penalty in line width roughness (LWR), sensitivity, and resolution. limit. LWR is defined by random fluctuations in the width of the patterned lithographic features along their length. As photoresists are used to print smaller and smaller patterns, defects in the sidewalls become a larger portion of patterning error. Furthermore, in several previous studies, these high LWR values were attributed to the polymer used in the photoresist matrix. Other factors that influence the LWR value are shot noise (e.g. flux variation, which is increasingly important as the dose per photon increases significantly in EUV schemes), PAG in bulk film ), the acid diffusion (or blurring) during chemical amplification, and the degree of developer selectivity. As a result, a large number of new materials have been introduced to support new technologies, but to date, no photoresist can simultaneously meet the resolution, linewidth roughness and sensitivity (RLS) specified in the international semiconductor technology roadmap. )Require.

In addition to achieving current resist targets for next-generation devices; new material platforms must also have the potential to exceed outlined specifications to that point to ensure the longevity of next-generation lithography processes. Traditional chemically amplified resist (CAR) materials have been expanded to try to meet this need, but as resolution has improved, the typical CAR dose at 14nm half pitch (hp) is 30-40mJ/ Sizes in the ^cm range result in significant sensitivity reduction. In order to increase the absorption of EUV photons, there has been a lot of research and significant work on metal-based resist materials to alleviate industry concerns about integrating metal resists with factory-friendly processes. Doses of less than 25 mJ/ ^cm at 16 nm half pitch and less than 35 mJ/ ^cm at 13 nm hp have been reported. Industry is increasingly calling for new approaches and more innovative chemistries to address RLS issues. Studies of metal additives to conventional chemically amplified resists to increase optical density have shown that the sensitivity of contact hole patterning increases from 50 to 43 mJ/cm for 22 nm half-pitch contact holes, but at ^a higher cost with increased hole size. at the expense of variability. The PSCAR process using pan-UV exposure to amplify acids generated through earlier EUV exposure has demonstrated a ^significant reduction in dose requirements from 30mJ/cm to 17mJ/ ^cm at 18nm hp, but at a significantly reduced exposure range and has also shown an increase in LWR .

For many years, extreme ultraviolet (EUV) lithography has been considered the next enabling technology for lithography patterning. However, a number of technical stumbling blocks (i.e., issues with EUV optics, mask infrastructure, and photoresist materials) have delayed the widespread introduction and implementation of this technology. For example, scanner optics for patterning systems and reticles have changed from transmission to reflection optics. This change has proven to be a rather challenging transition, but great progress has now been made and EUV scanner shipments are accelerating. EUV film development is also progressing (requiring mitigation measures to address defect issues), and the masking infrastructure is evolving both externally and internally for mask procurement.

35-40mJ/cm²來印刷合理的接觸孔(具有可用的製程窗口)。 Very few commercially available materials have LWR below about 3nm. There is a need to develop photoresists that can meet these LWR parameters while improving the high sensitivity of the photoresist. For example, most commercially available photoresist systems require

35-40mJ/ ^cm2 to print reasonable contact holes (with available process window).

As semiconductor dimensions decrease to the nanometer scale, traditional thinking about materials, formulations, and mechanisms needs to be revisited and reassessed.

This article reveals new materials, new formulations, new additives and new processes that meet and exceed current requirements for sensitivity, line edge roughness and resolution.

In a first embodiment, disclosed and claimed herein is a method of forming a patterned resist, comprising: providing a substrate, applying a multi-trigger resist composition comprising at least one polymer, oligomer or monomer , each multi-trigger resist composition contains two or more cross-linkable functional groups, wherein substantially all of the functional groups are attached to an acid-labile protecting group, at least one acid-activatable cross-linker, at least one photoacid generator, and at least one solvent, wherein the composition does not contain any additional acid diffusion controlling ingredients , heating the coated substrate to form a substantially dry coating to obtain the desired thickness, imagewise exposing the coated substrate to actinic radiation, and developing using an aqueous developer, a solvent developer, or a combined water-solvent The agent composition removes unexposed areas of the coating, wherein the remaining photoimageable pattern is selectively heated.

In a second embodiment, disclosed and claimed herein are methods as described above, wherein at least about 90% of the crosslinkable functional groups are attached to acid labile protecting groups.

In a third embodiment, the present invention discloses and claims any of the above methods, wherein the at least one photoacid generator includes an onium salt compound, a sulfonium salt, a triphenylsulfonium salt, a sulfonimide, a halogen-containing compound, , tereimine, sulfonate, quinonediazide, diazomethane, iodonium salt, oxime sulfonate, dicarboxyliminyl sulfate, ylidene aminooxy sulfonate, sulfonyl diazo Methane, or mixtures thereof, is capable of producing acids when exposed to at least one of UV, deep UV, extreme UV, X-ray or electron beam actinic radiation.

In a fourth embodiment, any of the methods described above are disclosed and claimed herein, wherein the at least one acid-activatable cross-linker comprises an aliphatic, aromatic or aralkyl monomer, oligomer, resin or polymer, It includes glycidyl ether, glycidyl ester, oxycyclobutane, glycidylamine, methoxymethyl, ethoxymethyl, butoxymethyl, benzyloxymethyl, dimethylaminomethyl, Diethylaminomethylamino, dialkylmethylamino, dibutoxymethylamino, dihydroxymethylmethylamino, dihydroxyethylmethylamino, dihydroxybutylmethylamino, morpholinomethyl , at least one of acetyloxymethyl, benzyloxymethyl, formyl, acetyl, vinyl or isopropenyl, and wherein the acid-labile protecting group includes a third alkoxycarbonyl group.

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

In a sixth embodiment, any of the methods described above are disclosed and claimed herein, wherein the composition further includes at least one metallic component, wherein the metallic component exhibits high EUV light absorption cross-section, moderate to high inelastic electron scattering and low High to moderate elastic scattering coefficient.

Cross-references to related applications:

This application claims the rights and interests under 35 U.S.C 119(e) of U.S. Patent Provisional Application No. 62/634,827 filed on February 24, 2018, titled "Enhanced EUV Photoresist Materials, Formulation and Methods" , which application is incorporated herein by reference in its entirety.

Figure 1 shows a diagram regarding the structure of xMT molecules useful in the present disclosure.

Figure 2 illustrates alternative xMT molecules that may be used in the present disclosure.

Figure 3 shows the infrared spectrum of phenol overlaid on the infrared spectrum of t-BOC protected phenol.

Figure 4 shows the infrared spectra of comparative materials before and during this process.

Figure 5 shows the infrared spectra of the present composition at different stages of the process.

Figure 6 shows the infrared spectra of the cross-linker at various stages of the process.

Figure 7 shows the proposed mechanism for various processes, including this process.

Figure 8 compares the SEM of this process B and the standard process A.

Figure 9 shows the chemical structures of the ingredients used in the examples.

Figure 10 further compares the SEM of this process B and the standard process A.

Figure 11 shows an SEM of a contact hole pattern using the present composition and process.

As used herein, unless otherwise stated, 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," "including," and similar terms are open-ended terms that indicate the presence of stated elements or features but do not exclude other elements or features. The articles "a", "an" and "the" are intended to include the plural as well as the singular unless the context clearly indicates otherwise.

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

As used herein, the term "protected polymer" refers to a polymer containing functional groups capable of cross-linking with a cross-linking agent, which functional groups are protected from reaction with the cross-linking agent by acid-labile functional groups, and therefore when exposed to acid, the acid-labile functional groups have been removed.

As used herein, the term "metal" includes neutral, unoxidized species and any type of oxidation state in which metals may exist.

As used herein, line edge roughness (LER) refers to areas on a light-defining line that are not aligned with the rest of the line. This also refers to line geometry and line width roughness.

Traditional semiconductor materials are based on chemically amplified resist (CAR) materials. In a positive-working system, a typical formulation includes a photoacid generator (PAG), a polymer with developer-sensitive groups that are at least partially blocked by acid-labile groups, and a base quencher. When the coated formulation is exposed to actinic radiation, the PAG emits acid functional groups, which react with the acid-labile groups to deprotect the developer-sensitive functional groups. A developer is then applied, traditionally an aqueous base, which reacts with the now unprotected polymer, dissolving it and removing it, leaving the desired lines, spaces, vias, etc. Post exposure bake (PEB) is required because the radiation-generated acid reacts with conventional acid-labile groups to detach developer-sensitive groups from the activation energy required for protection. Traditionally, the developer-sensitive group is phenolic OH (phenolic OH), which easily reacts with aqueous alkali.

Over the years, as finer lines and spaces have become desirable, acid migration of photogenerated acids has been found to be a problem. Here, during PEB, the heat required to deprotect the polymer also activates the photogenerated acid, causing it to migrate throughout the system, especially in areas where it is not needed, such as under a mask, where it then no longer Areas exposed to radiation cause the polymer to become unprotected, an undesirable result. This is also called a "dark reaction". This results in thinner lines than desired (in a positive working resist). To compensate for this undesirable effect, it is well known and often required that the resist formulation must contain an ingredient that reduces the effect of the migrating acid by binding to it. These ingredients are usually acid diffusion control agents, usually in the form of groups. Form exists.

Similar problems arise in negative-working resists based on polymers containing reactive functional groups protected by acid-labile groups. In these resists, the reactive functional groups obtained when deprotected by photogenerated acids are designed to cross-link with the cross-linker component of the formulation. In these resists, the cross-linker is usually protected with an acid-labile protecting group, such as hexamethoxymethylmelamines (HMMM), or through activation with photogenerating agents, such as epoxy resins and oxybutanes. When these resists undergo exposure and PEB, the exposed areas become cross-linked and insoluble in the developer, which removes the unexposed areas. In these resists, acid migration results in line growth as the acid diffuses under the mask and initiates cross-linking reactions in undesirable areas, specifically affecting line width growth and roughness as well as line edge roughness.

In this disclosure, we surprisingly find that removal of base quenching alone or when combined with other innovative approaches presented here, has resulted in improvements in resolution, line edge roughness, and sensitivity. This is an unexpected result because all current resists have base quenchers, and research has clearly shown that base quenchers are absolutely necessary to obtain small developed features.

We also found that eliminating post-exposure bake (PEB) results in low thermal migration of photogenerated acids, allowing for improvements in line width growth and roughness as well as line edge roughness. Again, this is an unexpected result since all resist processes include PEB.

Based on these findings, without being bound by theory, we believe that the processes and formulations revealed so far have captured the physical and chemical properties of nanofeatures that have so far not been solved; in the macroscopic world, line edge roughness and line Wide growth and roughness issues also arise with current materials, formulations and processes. However, in the nanometer world, these problems have become apparent, and current technology cannot solve the problem of nanometer features. We found that PEB is necessary for deprotection using currently available phenolic OH-based t-butoxycarbonyl (t-BOC) protected materials.

Furthermore, we found that t-BOC-protected phenolic OH acts as a self-quencher because the photogenerated acid can theoretically coordinate with molecules with high electron density, e.g., any oxygen atom of the carbonate functional group to form a metastable ( metastable) state complex (a possible example is shown as Scheme 1). When not heated, the complex remains in this metastable state, or reverts to an inactive photoproduct, while upon heating, tBOC will unblock the phenol.

Substrates useful in the present disclosure are those well known in the art for fabricating electronic components, including, for example, silicon substrates that have been coated with other materials, such as 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 containing two or more cross-linkable functional groups. Such polymers, oligomers and monomers are known in the art and include, for example, novolak resins and polyhydroxystyrenes. Two or more cross-linkable functional groups useful in the disclosed methods are known in the industry and include, for example, hydroxyl, amino, oxime, and the like. The functional groups in the presence of acid and acid-activated cross-linking agent will undergo a cross-linking reaction. These functional groups are attached to polymers, oligomers or monomers containing these groups, such as aryl groups, which may be substituted or unsubstituted divalent aromatic groups, including, for example, phenylene (-C ₆ H ₄ -), condensed divalent aromatic groups (such as naphthylene (-C ₁₀ H ₆ -), anthracenyl (-C ₁₄ H ₈ -), etc.) and heteroaromatic groups (such as nitrogen Cyclic compounds: pyridine, quinoline, pyrrole, indole, pyrazole, triazine and other nitrogen-containing aromatic heterocycles known in the art) and oxygen heterocycles: furan, oxazole and other oxygen-containing aromatic heterocycles, and Sulfur aromatic heterocyclic heterocyclic rings, such as thiophene. Trivalent and tetravalent aromatic compounds may also be used.

The aryl groups may be in the form of oligomers or polymers with molecular weights between about 1000 daltons and 100,000 daltons or higher, depending on the desired pattern of the cured negative resist. Properties, such as etching resistance. Examples include phenol-based novolacs, cresols, resorcinols, pyrogallols, and the like, including copolymers prepared therefrom. Furthermore, polyhydroxystyrene-based polymers and derivatives or copolymers thereof may be used in these photoresist compositions.

As mentioned above, the crosslinkable functional groups are blocked or protected by acid-labile protecting groups. Acid labile protecting groups include, for example, substituted methyl, 1-substituted ethyl, 1-substituted alkyl, silyl, germyl, alkoxycarbonyl, hydroxyl, and cyclic acids Dissociable radical. Substituted methyl groups include, for example, methoxymethyl, methylthiomethyl, ethoxymethyl, ethylthiomethyl, methoxyethoxymethyl, benzyloxymethyl, benzylthio Methyl, benzyl, bromobenzyl, methoxybenzyl, methylthiobenzyl, α-methylbenzyl, cyclopropylmethyl, benzyl, diphenyl Methyl, triphenylmethyl, bromobenzyl, nitrobenzyl, methoxybenzyl, methylthiobenzyl, ethoxybenzyl, ethylthiobenzyl, piperonyl, methoxycarbonylmethyl base, ethoxycarbonylmethyl, N-propoxycarbonylmethyl, isopropoxycarbonylmethyl, N-butoxycarbonylmethyl and tert-butoxycarbonylmethyl. 1-Substituted ethyl groups include, for example, 1-methoxyethyl, 1-methylthioethyl, 1,1-dimethoxyethyl, 1-ethoxyethyl, 1-ethylthio Ethyl, 1,1-diethoxyethyl, 1-phenoxyethyl, 1-phenylthioethyl, 1,1-diphenoxyethyl, 1-benzyloxyethyl, 1 -Benzylthioethyl, 1-cyclopropylethyl, 1-phenylethyl, 1,1-diphenylethyl, 1-methoxycarbonylethyl, 1-ethoxycarbonylethyl, 1-N-propoxycarbonylethyl, 1-isopropoxycarbonylethyl, 1-N-butoxycarbonylethyl and 1-tert-butoxycarbonylethyl. 1-Substituted alkyl groups include isopropyl, sec-butyl, tert-butyl, 1,1-dimethylpropyl, 1-methylbutyl and 1,1-dimethylbutyl.

Acid labile protecting groups may contain silyl functionality, including, for example, trimethylsilyl, ethyldimethylsilyl, methyldiethylsilyl, triethylsilyl, isopropyldimethyl Silica, methyldiisopropylsilyl, triisopropylsilyl, tert-butyldimethylsilyl, methyldi-tert-butylsilyl silyl, tri-tert-butylsilyl, phenyldimethylsilyl, methyldiphenylsilyl and triphenylsilyl. Trihydrogengermanyl groups include, for example, trimethyltrihydrogengermanyl, ethyldimethyltrihydrogengermanyl, methyldiethyltrihydrogengermanyl, triethyltrihydrogengermanyl, isopropyldimethyl Trihydrogengermanyl, methyldiisopropyltrihydrogengermanyl, triisopropyltrihydrogengermanyl, tert-butyldimethyltrihydrogengermanyl, methyldi-tertiarybutyltrihydrogengermanyl, trihydrogengermanyl tert-butyltrihydrogengermanyl, phenyldimethyltrihydrogengermanyl, methyldiphenyltrihydrogengermanyl and triphenyltrihydrogengermanyl.

Other acid labile protecting groups include alkoxycarbonyl acid labile protecting groups including, for example, methoxycarbonyl, ethoxycarbonyl, isopropoxycarbonyl and tert-butoxycarbonyl. Acid-labile protecting groups may be used, including, for example, acetyl, propionyl, butyl, heptyl, hexyl, pentyl, trimethylacetyl, isopentyl, lauryl Base, myristyl, palmityl, stearyl, ethylenediyl, malonyl, succinyl, glutadiyl, hexadiyl, piperonyl, suberyl, nonyl Diacyl, decanediyl, acrylic, propynyl, methacryl, crotonyl, oleyl, maleyl, fumaryl, mesaconoyl ), camphordiyl, benzyl, phthalyl, isophthalyl, terephthalyl, naphthyl, toluoyl, atropyl hydrate Hydroatropoyl, atropoyl, cinnamonyl, furanyl, thiophenyl, nicotinyl, isonicotinyl, p-toluenesulfonyl and methanesulfonyl.

Additional acid labile protecting groups include cyclic acid labile protecting groups including, for example, cyclopropyl, cyclopentyl, cyclohexyl, cyclohexyl, 4-methoxycyclohexyl, tetrahydropyranyl, tetrahydrofuran base, tetrahydrothiopyranyl, tetrahydrothiofuranyl, 3-bromotetrahydropyranyl, 4-methoxytetrahydropyranyl, 4-methoxytetrahydrothiopyranyl Phenyl and 3-tetrahydrothiophene-1,1-dioxy.

Acid-activated cross-linking agents suitable for use in the present disclosure constitute compounds capable of cross-linking with the cross-linkable functional groups described above during the process such that when deprotected to provide, for example, phenol or the like, the cross-linking agent will be located in the phenol or Reacts similarly to the currently unprotected -OH group on the base. Cross-linking agents can be polymers, oligomers or monomers. Without being bound by theory, it is believed that the acid generated by exposure to actinic radiation reacts not only with the acid-labile protecting groups of the polymer, oligomer, or monomer, but also with the cross-linking agent acting as a secondary trigger. A curing reaction occurs when the two materials are brought close enough. This curing reaction reduces the solubility of the developer in the exposed and now reacted areas, thereby creating a pattern of cured material. Examples of cross-linking agents include compounds containing at least one substituent having cross-linking reactivity with hydroxyl groups, for example from phenols, amines or similar groups from polymers, oligomers or monomers. Specific examples of acid-activated cross-linking agents include glycidyl ether group, glycidyl ester group, glycidyl amino group, methoxymethyl group, ethoxymethyl group, benzyloxymethyl group, dimethylaminomethyl group , diethylaminomethyl, dihydroxymethylaminomethyl, diethanolaminomethyl, morpholinomethyl, acetyloxymethyl, benzyloxymethyl, formyl, acetyl, ethylene base and isopropenyl.

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

Melamine-based acid-activated crosslinkers useful in the present disclosure include, for example, hydroxymethyl-containing melamine compounds, hydroxymethyl-containing benzoguanamine compounds, hydroxymethyl-containing urea compounds, hydroxymethyl-containing urea compounds, Phenolic compounds, alkoxyalkyl-containing melamine compounds, alkoxyalkyl-containing benzoguanamine compounds, alkoxyalkyl-containing urea compounds, alkoxyalkyl-containing phenolic compounds, carboxymethyl-containing Melamine resin, carboxymethyl-containing benzoguanamine resin, carboxymethyl-containing urea resin, Carboxymethyl-containing phenolic resin, carboxymethyl-containing melamine compound, carboxymethyl-containing benzoguanamine compound, carboxymethyl-containing urea compound, carboxymethyl-containing phenol compound, hydroxymethyl-containing phenol compound, Methoxymethyl-containing melamine compounds, methoxymethyl-containing phenol compounds, methoxymethyl-containing ethylene glycol-urea compounds, methoxymethyl-containing urea compounds and acetyloxymethyl-containing of phenolic compounds. Melamine compounds containing methoxymethyl groups are commercially available, such as CYMEL300, CYMEL301, CYMEL303, CYMEL305 (manufactured by Mitsui Cyanamid), and methoxymethyl-containing ethylene glycol-urea compounds are commercially available, such as CYMEL1174 (manufactured by Mitsui Cyanamid), and urea compounds containing methoxymethyl groups are commercially available, such as MX290 (manufactured by Sanwa Chemicals).

Other acid-activated cross-linkers include epoxy cross-linkers. Illustrations of epoxy resins for use within the scope of the present invention include aliphatic and aromatic epoxy resins in polymeric, oligomeric and monomeric forms, including, for example, cycloaliphatic epoxy resins, bisphenol A Epoxy resin, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarboxylate, etc. Also included are epoxy resin formulations based on the glycidyl ether of p-aminophenol, as described in U.S. Patent No. 5,514,729. Other suitable epoxy resins useful in practicing the present invention include, but are not limited to, epoxy resins derived from bisphenol S, bisphenol F, novolak resins, and epoxy resins derived from the reaction of bisphenol A and epihalohydrins. Such epoxy resins are described in US Patent No. 5,623,031. Other suitable epoxy resins useful in practicing the present invention are disclosed in U.S. Patent Nos. 5,602,193; 5,741,835; and 5,910,548. Other examples of epoxy resins useful in the present disclosure are glycidyl ethers and glycidyl esters of novolak-based polymers, oligomers, and monomers, and oxybutanes.

Photoacid generators (PAGs) suitable for the multi-trigger negative-working photoresist disclosed in the present disclosure include onium salt compounds, styrene imine compounds, halogen-containing compounds, styrene compounds, and ester sulfonates. acid salt compounds, quinonediazide compounds and diazomethane compounds. Specific examples of these acid generators are shown below.

Examples of onium salt compounds include sulfonium salts, iodonium salts, phosphonium salts, diazonium salts, and pyridinium salts. Specific examples of onium salt compounds include diphenyl(4-phenylthiophenyl)sulfonate hexafluoroantimonate, 4,4′-bis[diphenylsulfonylphenylsulfide bishexafluoroantimonate, and Their combinations, triphenylsonium nonafluorobutane sulfonate, triphenylsonium trifluoromethanesulfonate, triphenylsonium pyrene sulfonate, triphenylsonium dodecylbenzene sulfonate, triphenylsonium dodecylbenzene sulfonate, Phenylsonium p-toluenesulfonate, triphenylsonium benzene sulfonate, triphenylsonium 10-camphorsulfonate, triphenylsonium octane sulfonate, triphenylsonium 2-trifluoromethyl Benzenesulfonate, triphenylsonium hexafluoroantimonate, triarylsonium hexafluoroantimonate, triarylsonium hexafluorophosphate, triarylsonium tetrafluoroborate and other tetrafluoroborates, triphenylsulfonate Naphthalene sulfonate, tris (4-hydroxyphenyl) nonafluorobutane sulfonate, tris (4-hydroxyphenyl) sulfonate trifluoromethane sulfonate, tris (4-hydroxyphenyl) pyrene sulfonate Salt, tris(4-hydroxyphenyl)sulfonium dodecyl sulfonate, tris(4-hydroxyphenyl)sulfonium p-toluenesulfonate, tris(4-hydroxyphenyl)sulfonium benzene sulfonate, tris(4-hydroxyphenyl)sulfonium benzene sulfonate (4-Hydroxyphenyl)sonium camphorsulfonate, tris(4-hydroxyphenyl)sonium octane sulfonate, tris(4-hydroxyphenyl)sonium 2-trifluoromethylbenzenesulfonate, tris( 4-hydroxyphenyl)sulfonium hexafluoroantimonate, tris(4-hydroxyphenyl)sulfonium naphthalenesulfonate, diphenyliodonium nonafluorobutanesulfonate, diphenyliodonium trifluoromethanesulfonate Salt, diphenyliodonium pyrene sulfonate, diphenyliodonium dodecyl benzene sulfonate, diphenyliodonium p-toluene sulfonate, diphenyl iodonium benzene sulfonate, diphenyl Ionium 10-camphorsulfonate, diphenyliodonium octane sulfonate, diphenyliodonium 2-trifluoromethylbenzenesulfonate, bis(4-tert-butylphenyl)iodonium Nonafluorobutane sulfonate, bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate, bis(4-tert-butylphenyl)iodonium pyrene sulfonate, bis(4- tert-butylphenyl)iodonium dodecylbenzene sulfonate, bis(4-tert-butylphenyl)iodonium p-toluenesulfonate, bis(4-tert-butylphenyl)iodide Onium benzene sulfonate, bis(4-tert-butylphenyl)iodonium 10-camphorsulfonate, bis(4-tert-butyl) Phylphenyl)iodonium octane sulfonate, bis(4-tert-butylphenyl)iodonium 2-trifluoromethylbenzenesulfonate, 4-hydroxy-1-naphthyltetrahydrothiophene trifluoromethane Sulfonate and 4,7-dihydroxy-1-naphthyltetrahydrothiophene trifluoromethanesulfonate.

Specific examples of the styrylimine compound include N-(trifluoromethylsulfonyloxy)succinimide, N-(trifluoromethylsulfonyloxy)phthalimide, N-( Trifluoromethylsulfonyloxy)diphenylmaleimide, N-(trifluoromethylsulfonyloxy)bicyclo[2.2.1]hept-5-en-2,3-dicarboxylimide Amine, N-(trifluoromethylsulfonyloxy)-7-oxisobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylimine, N-(trifluoromethylsulfonate) acyloxy)bicyclo[2.2.1]heptane-5,6-oxo-2,3-dicarboxylimide, N-(trifluoromethylsulfonyloxy)naphthodimide, N-(10 -Camhor-sulfonyloxy)succinimide, N-(10-camphor-sulfonyloxy)phthalimide, N-(10-camphor-sulfonyloxy)diphenylma Lesimide, N-(10-camphor-sulfonyloxy)bicyclo[2.2.1]hept-5-en-2,3-dicarboxylimide, N-(10-camphor-sulfonyloxy) )-7-oxisobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylimine, N-(10-camphor-sulfonyloxy)bicyclo[2.2.1]heptane- 5,6-Oxy-2,3-dicarboxylimine, N-(10-camphor-sulfonyloxy)naphthodiamide, N-(p-toluenesulfonyloxy)succinimide , N-(p-toluenesulfonyloxy)phthalimide, N-(p-toluenesulfonyloxy)diphenylmaleimide, N-(p-toluenesulfonyloxy) )bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylimide, N-(p-toluenesulfonyloxy)-7-oxisobicyclo[2.2.1]hept-5- En-2,3-dicarboxylimine, N-(p-toluenesulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxy-2,3-dicarboxylimine, N -(p-toluenesulfonyloxy)naphthodiamide, N-(2-trifluoromethylbenzenesulfonyloxy)succinimide, N-(2-trifluoromethylbenzenesulfonyloxy) )phthalimide, N-(2-trifluoromethylbenzenesulfonyloxy)diphenylmaleimide, N-(2-trifluoromethylbenzenesulfonyloxy)bicyclo[ 2.2.1]Hept-5-ene-2,3-dicarboxylimine, N-(2-trifluoromethylbenzenesulfonyloxy)-7-oxoisobicyclo[2.2.1]Hept-5 -En-2,3-dicarboxylimine, N-(2-trifluoromethylbenzenesulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxy-2,3-dicarboxylic acyl imine, N-(2-trifluoromethylbenzenesulfonyloxy)naphthodiamide, N-(4-fluorobenzenesulfonyloxy)succinimide, N-(4-fluorobenzenesulfonyloxy) Phthalamide, N-(4-fluorobenzenesulfonyloxy)diphenylmaleimide, N-(4-fluorobenzenesulfonyloxy)bicyclo[2.2.1]hept-5 -En-2,3-dicarboxylidene, N-(4-fluorobenzenesulfonyloxy)-7-oxoisobicyclo[2.2.1]hept-5-en-2,3-dicarboxylidene Imine, N-(4-fluorobenzenesulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxy-2,3-dicarboxylic acid imine, N-(4-fluorobenzenesulfonyloxy) Oxy) naphthyl imine, N-(nonafluorobutylsulfonyloxy)succinimide, N-(nonafluorobutylsulfonyloxy)phthalimide, N-(nonafluorobutylsulfonyloxy)succinimide Fluorobutylsulfonyloxy)diphenylmaleimide, N-(nonafluorobutylsulfonyloxy)bicyclo[2.2.1]hept-5-en-2,3-dicarboxylimide , N-(nonafluorobutylsulfonyloxy)-7-oxisobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylimide, N-(nonafluorobutylsulfonyloxy) base) bicyclo[2.2.1]heptane-5,6-oxy-2,3-dicarboxylimide and N-(nonafluorobutylsulfonyloxy)naphthodimide.

Examples of the halogen-containing compound include, for example, halogenated alkyl group-containing hydrocarbon compounds and halogenated alkyl group-containing heterocyclic compounds. Specific examples of halogen-containing compounds include (poly)trichloromethyl-s-triazine derivatives, such as phenyl-bis(trichloromethyl)-s-triazine, 4-methoxyphenylbis(trichloro Methyl)-s-triazine and 1-naphthyl-bis(trichloromethyl)-s-triazine and 1,1-bis(4-chlorophenyl)-2,2,2-trichloroethane .

Examples of triane compounds include, for example, β-ketotriane and β-sulfonate triane, and α-diazo compounds thereof. Specific examples of the benzenesulfonate compound include benzoylbenzene, 2,4,6-tritolylphenone, bis(benzenesulfonyl)methane, 1,1-bis(benzenesulfonyl)cyclobutane, 1, 1-bis(benzenesulfonyl)cyclopentane, 1,1-bis(benzenesulfonyl)cyclohexane and 4-trityltrityltriene.

Examples of sulfonate compounds include alkyl sulfonates, haloalkylsulfonates, arylsulfonates, and iminosulfonates. Specific examples of the sulfonate compound include benzoin tosylate, pyrogallol tritrifluoromethanesulfonate, pyrogallol trinonafluorobutanesulfonate, pyrogallol methanesulfonate triester, pyrogallol trifluoromethanesulfonate, Benzyl-9,10-diethoxyanthracene-2-sulfonate, α-hydroxymethyl benzoin tosylate, α-hydroxy Methyl benzoin octane sulfonate, alpha-hydroxybenzoin trifluoromethanesulfonate and alpha-hydroxymethyl benzoin dodecyl sulfonate.

Examples of quinodiazine compounds include compounds containing a 1,2-quinonediazide sulfonyl group, such as 1,2-benzoquinonediazide-4-sulfonyl group, 1,2-naphthoquinonediazide- 4-sulfonyl, 1,2-naphthoquinonediazide-4-sulfonyl, 1,2-naphthoquinonediazide-5-sulfonyl and 1,2-naphthoquinonediazide-6- Sulfonyl group. Specific examples of quinonediazide compounds include 1,2-quinonediazide sulfonate esters of (poly)hydroxyphenyl aryl 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',4,4',5'-hexahydroxybenzophenone, 2,3',4,4', 5',6-Hexahydroxybenzophenone; 1,2-quinonediazide sulfonate ester of bis[(poly)hydroxyphenyl]alkane, such as bis(4-hydroxyphenyl)methane, bis(2, 4-dihydroxyphenyl)methane, bis(2,3,4-trihydroxyphenyl)methane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(2,4-dihydroxy) Phenyl)propane and 2,2-bis(2,3,4-trihydroxyphenyl)propane; 1,2-quinonediazide sulfonates of (poly)hydroxytriphenylalkanes, such as 4,4' -Dihydroxytriphenylmethane, 4,4',4"-trihydroxytriphenylmethane, 2,2',5,5'-tetramethyl-2",4,4'-trihydroxytriphenyl Methane, 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-hydroxybenzene ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 1,1-bis(4-hydroxyphenyl)-1-[4-{1-(4-hydroxy Phenyl)-1-methylethyl}phenyl]ethane, 1,1,3-tris(2,5-dimethyl-4-hydroxyphenyl)propane, 1,1,3-tris(2 ,5-dimethyl-4-hydroxyphenyl)butane and 1,3,3-tris(2,5-dimethyl-4-hydroxyphenyl)butane; and (poly)hydroxyphenylflavans 1,2-quinonediazide sulfonate, such as 2,4,4-trimethyl-2',4',7-trihydroxy-2-phenylflavan and 2,4,4-trimethyl Base-2',4',5',6',7-pentahydroxy-2-phenylflavan.

Specific examples of the diazomethane compound include bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(benzenesulfonyl)diazomethane, bis(p-toluene) Sulfonyl)diazomethane, methylsulfonyl-p-toluenesulfonyldiazomethane, 1-cyclohexylsulfonyl-1-(1,1-dimethylethylsulfonyl)diazo Methane and bis(1,1-dimethylethylsulfonyl)diazomethane.

Compositions of the present disclosure may include one or more photoacid generators described above.

Examples of suitable solvents for use in the present disclosure include ethers, esters, ether esters, ketones, and ketone esters, and, more specifically, ethylene glycol monoalkyl ethers, diethylene glycol dialkyl ethers, propylene glycol monoalkanes Ether, propylene glycol dialkyl ether, acetate, glycol acetate, lactate, ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, alkoxy acetate, ( Non)cyclic ketones, acetoacetates, pyruvates and propionates. 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 Alcohol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, methyl cellulosulfate acetate, ethyl cellulosulfate acetate, propylene glycol monomethyl ether acetate, propylene glycol Monoethyl ether acetate, propylene glycol monopropyl ether acetate, isopropenyl acetate, isopropenyl propionate, methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone , 4-Heptanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethoxyethyl acetate, ethyl glycolate, 2-hydroxy-3-methylmethylbutanate acid ester, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl ethyl ester, 3-methyl-3-methoxybutylpropionate, 3-methyl- 3-Methoxybutylbutyrate, ethyl acetate, propyl acetate, butyl acetate, methyl acetyl acetate, ethyl acetyl acetate, methyl 3-methoxypropionate, 3-methoxy Ethyl propionate, methyl 3-ethoxypropionate and ethyl 3-ethoxypropionate. The above-mentioned solvents may be used alone, or two or more types may be mixed and used. In addition, at least one high boiling point solvent, such as benzyl ether, dihexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, acetonylacetone, isophorone (isoholon), caproic acid, Decanoic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate Ester, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethyl carbonate, propyl carbonate and phenyl cellosu acetate can be added to the above solvent.

In a typical resist formulation, various additives for acid diffusion control agents are added to prevent acid from migrating to unexposed areas of the coating. We have found that through appropriate selection of acid labile protecting groups and appropriate selection of acid activatable cross-linking agents, such acid diffusing agents can be eliminated. That is, acid-labile protecting groups and acid-activated cross-linkers will complex with the photogenerated acid without migrating. Not all acid-labile protecting groups or acid-activatable cross-linkers will complex with photoacid and therefore need to act as acid diffusion control agents.

The cross-linkable functional groups are all blocked by acid-labile protecting groups, and the blocking is about 90% to about 100%. The acid labile group is selected for the ability to complex with the photogenerated acid.

The photoresist composition may be applied to a substrate, such as a silicon wafer or any of a variety of semiconductor materials or nitrides or other substrates well known in the semiconductor industry, or coated with silicon dioxide, aluminum, alumina, copper, nickel, A substrate having an organic film thereon, such as an underlying anti-reflective film, etc. The photoresist composition is applied through processes such as spin coating, curtain coating, slot coating, dip coating, roller coating, and blade coating. After application, the solvent is removed to the extent that the coating can be properly exposed. In some cases, residual 5% solvent may remain in the coating, while in other cases, less than 1% is required. Drying can be accomplished through hot plate heating, convection heating, infrared heating, etc. The coating is image-exposed through markings containing the desired pattern.

Radiation suitable for use in the photoresist composition includes, for example, ultraviolet (UV), such as the bright line spectrum of a mercury lamp (254 nm), KrF excimer laser (248 nm) and ArF excimer laser (193 nm), extreme Ultraviolet (EUV) (such as 13.5nm from plasma discharge and synchrotron light sources), beyond extreme ultraviolet (BEUV) (such as 6.7nm exposure), X-rays (such as synchrotron radiation). Ion beam imaging and charged particle rays such as electron beams may also be used.

In the current method embodiment, after exposure, the exposed coated substrate is not subjected to a post-exposure bake, thereby preventing photogenerated acid migration and thus dark reactions that cause line edge roughness and other undesirable pattern defects.

Next use developer to move the unexposed areas. These developers often include organic solvents. The developing solvent is less aggressive than the solvent used to prepare the photoresist composition.

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

In further disclosure, we have developed a new material, xMT, which can be used in the composition of the disclosed method. These materials are described in U.S. Patent No. 9,122,156, U.S. Patent No. 9,229,322, and U.S. Patent No. 9,519,215, which are incorporated herein by reference, including those of the general formula:

And the above general formula (xMT ester) includes a compound with one of the following structures:

Wherein R ₁ is a saturated or unsaturated group having 1 to 4 carbon atoms, R ₂ is selected from hydrogen or a saturated or unsaturated group having 1 to 4 carbon atoms, and R ₃ is a saturated or unsaturated group having 1 to 4 carbon atoms. A saturated or unsaturated group of atoms, R ₄ is a saturated or unsaturated group having 1 to 4 carbon atoms; the group -N=R ₃ ' is used here to represent an amine double bonded to the R ₃ part. In addition, m is 1 to 4, and n is 1 to 4. Furthermore, at least one of X or Y contains -(alkyl) _j -(aryl) _k -(O) _p -(COO) _q -LG.

where j, k, p and q take the values in the table of Figure 1; wherein the alkyl group is branched or unbranched, substituted or unsubstituted and contains 1-16 of 0-16 heteroatoms substituted into the chain carbon atom divalent Alkyl chain, the aryl group is a substituted or unsubstituted divalent phenyl group, a divalent heteroaromatic group, or a divalent fused aromatic or fused heteroaromatic group, where LG is the third alkyl group or the third Cycloalkyl, cycloaliphatic, ketal or cyclic aliphatic ketal, or acetal which is a leaving group.

Surprisingly, these materials were found to improve resolution, sensitivity and line geometries such as line edge roughness and sensitivity. Other more recently developed xMT materials available for use in this disclosure surprisingly provide better LER and sensitivity improvements, including those in Figure 2. Both variants are designed to reduce LER by stiffening the molecules before and after the photoreaction, where they are cross-linked with a cross-linking agent. A variation, shown in Figure 8B, that includes additional functional groups designed to increase photosensitivity, may be used in the present disclosure. The xMT materials are based on protected malonates and amidines as described in the aforementioned references. reaction product.

Metallic compositions useful in the present disclosure include those exhibiting high EUV light absorption cross-sections, moderate to high inelastic electron scattering, and low to moderate elastic scattering coefficients, including, for example, selected from elements 3-3 of the Periodic Table of Elements. Metals in column 17 and columns 3-6, which include scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, arsenic, selenium, bromine, yttrium, zirconium, niobium, molybdenum , titanium, ruthenium, rhodium, palladium, silver, cadmium, indium, tin, antimony, tellurium, iodine, lanthanides, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, mercury, lead, bismuth, polonium , and columns 13-17, column 3, including aluminum, silicon, phosphorus, sulfur and chlorine or salts or coordination complexes or these selected metals, the selected metals containing monomeric, oligomeric or polymeric ligands. These materials are described in U.S. Patent No. 9,632,409, which is incorporated herein by reference.

In some embodiments, the exposed resist may undergo a post-exposure bake step. This optional step includes a selected temperature for a selected period of time. The time and temperature are selected to optimize exposure curing prior to development, depending on the aggressiveness of the developer and also on the complexation of the photogenerated acid with the component, such as at least one polymer, oligomer, or monomer. The strength of the complex, each polymer, oligo The polymer or monomer contains two or more cross-linkable functional groups, with at least 90% of the functional groups attached to acid-labile protecting groups and/or at least one acid-activatable cross-linking agent.

Example:

tBOC protected phenol was formulated with a photoacid generator (PAG) and exposed to EUV radiation. After 15 minutes of holding, almost no tBOC reacted with the photogenerated acid, and no phenolic OH was produced. Figure 3 shows the IR spectra of phenol and tBOC protected phenol, showing a significant extension of the carbonyl moiety of the tBOC functionality at 1774 cm ⁻¹ . Figure 4 shows that after UV exposure and a holding time of 15 minutes, no carbonyl reduction of the tBOC functionality occurred. The significant extension of the t-BOC functional group at 1774 cm ^-1 is essentially the same. Further evidence is shown in Figure 5, where no OH appears in the IR after protected phenol and PAG exposure and after a 15 min hold, and would be expected if tBOC reacted with the photogenerated acid to unblock the phenolic oxygen. This can be proven by a small or no change at about 3000 cm ^-1 (where -OH is strongly absorbed).

Additionally, we were surprised to find that typical cross-linkers found in negative photoresists, such as epoxies, also require heat to complete their curing step. Figure 6 shows the infrared spectrum, line A, of a typical epoxy cross-linker mixed with a typical PAG. It can be seen that after UV irradiation, some epoxy resin has reacted, line B, but the reaction does not occur until the PEB reaction is completed, line C.

Without being bound by theory, we believe that, based on the foregoing, tBOC functional groups and epoxy resins serve as self-quenching materials because the photogenerated acid will coordinate with the oxygen atoms of the tBOC protected material and the cross-linker. ), or coordinate with any other position on these molecules with high electron density.

The proposed mechanism is shown in Figure 7, A-E. This schematic illustrates the newly revealed process. In Figure 7A, the photogenerated acid will form a metastable complex with tBOC, and only heating can Can produce phenol. The photogenerated acid will also form a metastable complex with the cross-linker, as shown in Figure 7B. However, some epoxies will open and partially cross-link, as shown in Figure 7B. It is believed that at ambient temperature, only small chains are produced, ending with chain termination via a chain transfer mechanism of photoproducts from PAG, as shown in Figure 7C. Figure 7D shows the mechanism of a typical photoresist where PEB has been applied, tBOC deprotects the phenol, and then the phenol reacts with the growing chain from the thermally activated chain-growing cross-linker. Because there is little control over the reaction once PEB is applied, chain and cross-linking as well as acid migration produce line edge roughness, line width growth and roughness. In the new unintended process shown in Figure 7E, the metastable material remains unreacted until the tBOC complex and cross-linker complex are close enough for them to react, and in the case of epoxy, the chains will Start growing. Because two events need to occur simultaneously, multiple triggering processes, line and space geometries, will be controlled simultaneously. Figure 8A shows an SEM of a standard photoresist containing additional acid diffusion control components using typical methods, compared to a resist using the non-PEB composition and process disclosed so far, as shown in Figure 8B. You can easily see the improvements in the geometry of line and space. The photoacid will activate the matrix molecules, but the reaction will only proceed if the base molecule and cross-linker are activated simultaneously in very close proximity to each other. Therefore, it is surprising to find that new processes that eliminate PEB produce surprisingly superior results in photoresist formulations.

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

example 1:

The materials for the examples are shown in Figure 9.

Composition 1:

The xMT molecular resin compound in Figure 9 was mixed with a molecular cross-linker and a photoacid generator in ethyl lactate at a weight ratio of 0.2:2:1. The composition was spin-coated on specialized carbon-coated silicon wafer and heated on a hot plate at 75°C for 5 minutes to obtain a film of approximately 25 nm. The coated wafers were then imagewise exposed to synchrotron-based EUV light at 13-14 nm wavelength and post-exposure baked at 90°C for 3 minutes. Unexposed areas were removed by puddle development in a 50:50 mixture of monochlorobenzene and isopropyl alcohol for 20 seconds, followed by a rinse with isopropyl alcohol. Remove unexposed areas by immersion developing in a 50:50 mixture of monochlorobenzene and isopropyl alcohol for 20 seconds, then rinsing with isopropyl alcohol.

Composition 2:

Repeat Composition 1 but add 2.5% quencher.

The results are shown in Figure 10, comparing Composition 1 (Figure 10A) and Composition 2 (Figure 10B). As can be seen in Figure 10A, the resist without quencher has a higher sensitivity of 18.9 mJ/ ^cm compared to 40.4 mJ/ ^cm while the line edge roughness is essentially the same. The line edge roughness of Composition 1 is approximately 50% higher than that of Composition 2 under the same exposure.

Example 2:

Few commercially available materials have LWR below about 3 nm, and there is a need to develop higher-sensitivity photoresists. For example, most commercially available photoresist systems require 35-40mJ/ ^cm to print reasonable contact holes (with available process window).

Composition 1 was used to print samples with contact hole patterns (see Figure 11) using Lawrence Berkeley National Laboratory’s Microfield Exposure tool, which has the highest resolution in the world EUV development tool (0.3 numerical aperture). In particular, the exposure patterning dose is less than 17mJ/cm ² and the critical size target is a dense 25nm contact hole structure.

The results show the complete resolution of pores using current methods using the compositions of the present disclosure. When post-exposure baking is used, the holes are unresolved or have worse resolution.

Claims (9)

A method of forming a patterned resist, comprising: (a) providing a substrate, (b) applying a multi-trigger resist composition comprising: 1 at least one polymer, each comprising two or more cross-linkable Functional groups, of which at least 90% of the functional groups are attached to acid-labile protecting groups, II at least one acid-activatable cross-linker, III at least one photoacid generator, IV at least one solvent, and V at least one xMT ester , which contains compounds with one of the following structures:

Wherein R ₁ is a saturated or unsaturated group having 1 to 4 carbon atoms, R ₂ is selected from hydrogen or a saturated or unsaturated group having 1 to 4 carbon atoms, and R ₃ is a saturated or unsaturated group having 1 to 4 carbon atoms. A saturated or unsaturated group of atoms, R ₄ is a saturated or unsaturated group with 1 to 4 carbon atoms; the group -N=R ₃ ' is used here to represent the amine connected to the double bond of the R ₃ part; Also, at least one of X or Y includes: -(alkyl) _j -(aryl) _k -(O) _p -(COO) _q -LG where j, k, p and q take the values in the table:

wherein alkyl is a branched or unbranched, substituted or unsubstituted divalent alkyl chain of 1 to 16 carbon atoms substituted to 0 to 16 heteroatoms in the chain, and aryl is substituted or unsubstituted Divalent phenyl, divalent heteroaromatic, or divalent fused aromatic or fused heteroaromatic, where LG is the third alkyl or third cycloalkyl, alicyclic group, ketal or cyclic aliphatic ketals, or acetals that are leaving groups; wherein the composition does not contain any additional acid diffusion control components, (c) heating the coated substrate to form a substantially dry coating, to obtaining the desired thickness, (d) imagewise exposing the coated substrate to actinic radiation, (e) removing unexposed areas of the coating using an aqueous developer, a solvent developer, or a combined aqueous-solvent developer composition, and The remaining photoimaged pattern is selectively heated, and the exposed resist is selectively heated prior to development. The method of claim 1, wherein the at least one photoacid generator includes an onium salt compound, a sulfonium salt, a triphenylsulfonium salt, a sulfonium salt, a halogen-containing compound, sulfonate, a sulfonium salt, a sulfonate ester , quinonediazide, diazomethane, iodonium salt, oxime sulfonate, dicarboxyliminosulfate, ylidene aminooxysulfonate, sulfonyldiazomethane, or mixtures thereof, when Acid can be generated upon exposure to at least one of UV, deep UV, extreme UV, X-ray or electron beam actinic radiation. The method of claim 1, wherein the at least one acid-activatable cross-linking agent includes aliphatic, aromatic or aralkyl monomers, oligomers, resins or polymers including glycidyl ether, glycidyl Esters, oxybutane, glycidylamine, methoxymethyl, ethoxymethyl, butoxymethyl, benzyloxymethyl, dimethylaminomethyl, diethylaminomethylamino, Dialkylmethylamino, dibutoxymethylamino, dihydroxymethylmethylamino, dihydroxyethylmethylamino, dihydroxybutylmethylamino, morpholinomethyl, acetyloxymethyl, At least one of benzyloxymethyl, formyl, acetyl, vinyl or isopropenyl. The method of claim 1, wherein the xMT ester contains a compound with one of the following structures:

wherein m is 1 to 4, and n is 1 to 4; and at least one of X or Y includes: -(alkyl) _j -(aryl) _k -(O) _p -(COO) _q -LG where j, k, p and q take the values in the table:

wherein alkyl is a branched or unbranched, substituted or unsubstituted divalent alkyl chain of 1 to 16 carbon atoms substituted to 0 to 16 heteroatoms in the chain, and aryl is substituted or unsubstituted Divalent phenyl, divalent heteroaromatic, or divalent fused aromatic or fused heteroaromatic, where LG is the third alkyl or third cycloalkyl, alicyclic group, ketal or Cyclic aliphatic ketals, or acetals with leaving groups. The method of claim 4, wherein the at least one photoacid generator includes an onium salt compound, a sulfonium salt, a triphenylsulfonium salt, a sulfonium salt, a halogen-containing compound, sulfonate, a sulfonium salt, a sulfonate ester , quinonediazide, diazomethane, iodonium salt, oxime sulfonate, dicarboxyliminosulfate, ylidene aminooxysulfonate, sulfonyldiazomethane, or mixtures thereof, when capable of generating acid upon exposure to at least one of UV, deep UV, extreme UV, body, oligomer, resin or polymer, which includes glycidyl ether, glycidyl ester, oxycyclobutane, glycidylamine, methoxymethyl, ethoxymethyl, butoxymethyl, benzyloxy Methyl, dimethylaminomethyl, diethylaminomethylamino, dialkylmethylamino, dibutoxymethylamino, dihydroxymethylmethylamino, dihydroxyethylmethylamino, At least one of dihydroxybutylmethylamino, morpholinomethyl, acetyloxymethyl, benzyloxymethyl, formyl, acetyl, vinyl or isopropenyl. The method of claim 1, wherein the composition further includes at least one metal component, wherein the metal component exhibits high EUV light absorption cross-section, moderate to high inelastic electron scattering and low to moderate elastic scattering coefficient, Wherein the at least one metal is selected from columns 3-17 and 3-6 of the periodic table of elements, including scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, arsenic , selenium, bromine, yttrium, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, silver, cadmium, indium, tin, antimony, tellurium, iodine, lanthanides, hafnium, tantalum, tungsten, rhenium, osmium, iridium , platinum, gold, mercury, lead, bismuth, polonium, and column 3 of columns 13-17 columns, including aluminum, silicon, phosphorus, sulfur and chlorine or salts or coordination complexes of selected metals, or monomeric, oligomeric or polymeric ligands containing selected metals. The method of claim 6, wherein the at least one photoacid generator includes an onium salt compound, a sulfonium salt, a triphenylsulfonium salt, a sulfonium salt, a halogen-containing compound, sulfonate, a sulfonium salt, a sulfonate ester , quinonediazide, diazomethane, iodonium salt, oxime sulfonate, dicarboxyliminosulfate, ylidene aminooxysulfonate, sulfonyldiazomethane, or mixtures thereof, when capable of generating acid upon exposure to at least one of UV, deep UV, extreme UV, body, oligomer, resin or polymer, which includes glycidyl ether, glycidyl ester, oxycyclobutane, glycidylamine, methoxymethyl, ethoxymethyl, butoxymethyl, benzyloxy Methyl, dimethylaminomethyl, diethylaminomethylamino, dialkylmethylamino, dibutoxymethylamino, dihydroxymethylmethylamino, dihydroxyethylmethylamino, At least one of dihydroxybutylmethylamino, morpholinomethyl, acetyloxymethyl, benzyloxymethyl, formyl, acetyl, vinyl or isopropenyl. The method of claim 4, wherein the composition further includes at least one metal component, wherein the metal component exhibits high EUV light absorption cross-section, moderate to high inelastic electron scattering and low to moderate elastic scattering coefficient, Wherein the at least one metal is selected from columns 3-17 and 3-6 of the periodic table of elements, including scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, arsenic , selenium, bromine, yttrium, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, silver, cadmium, indium, tin, antimony, tellurium, iodine, lanthanides, hafnium, tantalum, tungsten, rhenium, osmium, iridium , platinum, gold, mercury, lead, bismuth, polonium, and columns 13-17, column 3, including aluminum, silicon, phosphorus, sulfur and chlorine or salts or coordination complexes of selected metals, or containing selected Monomeric, oligomeric or polymeric ligands of metals. The method of claim 8, wherein the at least one photoacid generator includes an onium salt compound, a sulfonium salt, a triphenylsulfonium salt, a sulfonium salt, a halogen-containing compound, sulfonate, a sulfonium salt, a sulfonate ester , quinonediazide, diazomethane, iodonium salt, oxime sulfonate, dicarboxyliminosulfate, ylidene aminooxysulfonate, sulfonyldiazomethane, or mixtures thereof, when capable of generating acid upon exposure to at least one of UV, deep UV, extreme UV, body, oligomer, resin or polymer, which includes glycidyl ether, glycidyl ester, oxycyclobutane, glycidylamine, methoxymethyl, ethoxymethyl, butoxymethyl, benzyloxy Methyl, dimethylaminomethyl, diethylaminomethylamino, dialkylmethylamino, dibutoxymethylamino, dihydroxymethylmethylamino, dihydroxyethylmethylamino, At least one of dihydroxybutylmethylamino, morpholinomethyl, acetyloxymethyl, benzyloxymethyl, formyl, acetyl, vinyl or isopropenyl.