Sulfonic acid derivative compounds containing oxathionium ions as photoacid generators in resist applications

Abstract

A sulfonic acid derivative compound represented by chemical formula (I): [Formula 1] JPEG2024522530000016.jpg54128In the formula, R is a substituted or unsubstituted C1 to C 12 is an alkyl group, Z is a substituted or unsubstituted polycyclic C 30 Cycloalkyl groups, substituted or unsubstituted monocyclic C3-C 30 Cycloalkyl groups and substituted or unsubstituted monocyclic C3-C 30 The compounds and compositions disclosed herein are useful as photoactive components in chemically amplified resist compositions for a variety of microfabrication applications.

Description

[Technical field]

[0001] The present disclosure relates to novel photoacid generator compounds ("PAGs") and compositions containing such PAG compounds. In particular, the PAG compounds of the present disclosure have excellent solubility in organic solvents and exhibit higher sensitivity and better performance in photolithography processes than conventional PAG compounds. [Background technology]

[0002] Photoresists are light-sensitive films for transferring images to a substrate. They form either negative or positive images. After coating the photoresist on a substrate, the coating is exposed to a source of activating energy, such as ultraviolet light, through a patterned photomask to form a latent image in the photoresist coating. The photomask has areas that are opaque and transparent to activating radiation that define the image desired to be transferred to the underlying substrate.

[0003] Chemically amplified photoresists have proven useful in achieving high sensitivity in the process of forming ultrafine patterns in semiconductor manufacturing. These photoresists are prepared by blending PAG with a polymer matrix having an acid-labile structure. According to the reaction mechanism of such photoresists, upon irradiation with a light source, a photoacid generator generates acid, and in the so-called "post-exposure bake" (PEB), the main chain or branch of the polymer matrix in the exposed or irradiated area reacts with the generated acid and is decomposed or crosslinked, resulting in a change in the polarity of the polymer. This polarity change creates a difference in the solubility in the developer between the irradiated and unexposed areas, thereby forming a positive or negative image of the mask on the substrate. The diffusion of acid is important not only to increase the sensitivity and throughput of the photoresist, but also to limit the line edge roughness due to the statistical value of the shot noise.

[0004] In chemically amplified photoresists, the solubility conversion chemical reaction required for imaging is not directly attributable to the exposure, but rather the exposure generates stable catalytic species that drive the solubility conversion chemical reaction during the subsequent PEB step. The term "chemical amplification" arises from the fact that each photochemically generated catalytic molecule can drive multiple solubility conversion reaction events. The apparent quantum efficiency of this conversion reaction is the quantum efficiency of catalyst generation multiplied by the average catalytic chain length. The original exposure dose is "amplified" by the chain of subsequent chemical reaction events. The catalytic chain length of the catalyst can be very long (up to hundreds of reaction events), thereby significantly amplifying the exposure dose.

[0005] Chemical amplification is beneficial in that it can dramatically increase resist sensitivity, but it is not without potential drawbacks. For example, the catalyst molecules are not necessarily restricted to the areas exposed to the imaging radiation, since they can roam to hundreds of reaction sites. There is a potential trade-off between resist sensitivity and imaging fidelity. For example, an amplified photoresist is exposed through a photomask to generate acid catalyst in the exposed areas. The acid latent image created in the first step is converted to an image of soluble and insoluble areas by increasing the temperature of the wafer in the PEB, thereby initiating a chemical reaction. Some of the acid migrates outside the originally exposed areas, causing a "finite dimension bias" problem. After baking, the image is developed with a solvent. Diffusion of acid from exposed to unexposed areas can cause the width of the developed features to be larger than the nominal mask dimension. For most of the history of amplification resists, this tradeoff was of little concern because catalyst diffusion lengths were insignificant compared to the size of the features being printed; however, as feature sizes have decreased, diffusion lengths have remained roughly the same and catalyst diffusion has emerged as a major concern.

[0006] A certain exposure time is required to generate enough acid to change the solubility of the polymer. For known PAG molecules such as N-hydroxynaphthalimide triflate ("NIT"), this exposure time is rather long (due to the low absorption above 365 nm). However, increasing the concentration of such PAGs does not lead to a faster exposure time, since the solubility of the PAG is the limiting factor. Another possibility is to add a sensitizer that absorbs light and transfers energy to the PAG, thus liberating acid. However, such sensitizers must be used in fairly high concentrations to be able to transfer energy to the adjacent PAG. At such high concentrations, the sensitizers often absorb too much, adversely affecting the shape of the resist profile after development. Summary of the Invention [Problem to be solved by the invention]

[0007] Thus, there is a need in the art for PAGs with improved solubility (meaning that more active molecules are brought into the formulation) and photoresist compositions containing these compounds that have increased sensitivity to electromagnetic radiation, in particular electromagnetic radiation with wavelengths between 200 and 500 nm, while at the same time allowing the production of patterned structures with higher resolution compared to photoresist compositions known from the prior art.

[0008] This need is met by the compounds and compositions disclosed herein.

[0009] Embodiment 1. A sulfonic acid derivative compound represented by Formula I: [ka] In the formula, R is a substituted or unsubstituted C-C 12 alkyl group, Z is a substituted or unsubstituted polycyclic C-C 30 Cycloalkyl groups, substituted or unsubstituted monocyclic C3-C 30 Cycloalkyl groups and substituted or unsubstituted C3-C 30monocyclic heteroalkyl groups.

[0010] Embodiment 2. The sulfonic acid derivatized compound of embodiment 1, wherein R is a substituted or unsubstituted C1-C6 alkyl group.

[0011] Embodiment 3. The sulfonic acid derivatized compound of embodiment 1 or 2, wherein R is isobutyl.

[0012] Embodiment 4. Z is a substituted or unsubstituted polycyclic C-C 30 The sulfonic acid derivatized compound of any of the preceding embodiments, which is a cycloalkyl group.

[0013] Embodiment 5. The sulfonic acid derivative compound of embodiment 4, wherein Z is selected from the group consisting of adamantyl, norbornyl, cubyl, octahydro-indenyl, decahydro-naphthyl, bicyclo[3.2.1]octyl, bicyclo[3.3.2]decyl, bicyclo[2.2.2]octyl, bicyclo[2.2.1]heptyl, and bicyclo[3.3.1]nonyl.

[0014] Embodiment 6. The sulfonic acid derivative compound of embodiment 5, wherein Z is norbornyl.

[0015] Embodiment 7. The sulfonic acid derivatized compound of embodiment 5, wherein Z is adamantyl.

[0016] Embodiment 8. Z is a substituted or unsubstituted monocyclic C-C 30 The sulfonic acid derivatized compound of any one of embodiments 1, 2 and 3, wherein the group is a cycloalkyl group.

[0017] Embodiment 9. The sulfonic acid derivatized compound of embodiment 8, wherein Z is selected from the group consisting of cyclopropyl, cyclobutyl, cycloheptyl, cyclopentyl, and cyclohexyl groups.

[0018] Embodiment 10. Z is a substituted or unsubstituted C3-C 30The sulfonic acid derivatized compound of any one of embodiments 1, 2 and 3, which is a monocyclic heteroaryl group.

[0019] Embodiment 11. The sulfonic acid derivative compound of embodiment 10, wherein Z is selected from the group consisting of morpholinyl, thiomorpholinyl, pyrrolidinyl, imidazolinyl, oxazolinyl, piperidinyl, piperazinyl, tetrahydrofuranyl, aziridinyl, azetidinyl, indolinyl, and isoindolinyl.

[0020] Embodiment 12. The compound of formula (I) is [ka] The sulfonic acid derivatized compound of embodiment 1,

[0021] Embodiment 13. A photoresist composition comprising: (i) at least one sulfonic acid derivatized compound according to any one of the preceding embodiments; (ii) at least one polymer or copolymer that can be given altered solubility in aqueous solution in the presence of an acid; (iii) an organic solvent; and, optionally, (iv) an additive.

[0022] Embodiment 14. The composition of embodiment 13, wherein the organic solvent is propylene glycol monomethyl ether acetate (PGMEA).

[0023] Embodiment 15. The composition of embodiment 13 or 14 comprising 0.05-15 wt.% of a sulfonic acid derivatized compound, 5-50 wt.% of at least one polymer or copolymer, 0-10 wt.% of an additive, the balance being propylene glycol monomethyl ether acetate.

[0024] Embodiment 16. The at least one sulfonic acid derivatized compound comprises: [ka] 17. The composition of one of embodiments 13-16, wherein

[0025] Embodiment 17. A process for producing a patterned structure on a surface of a substrate, comprising the steps of: (a) applying a layer of the composition according to any one of embodiments 13 to 16 to the surface of the substrate and at least partially removing the organic solvent (iv), (b) exposing the layer to electromagnetic radiation, thereby releasing acid from the sulfonic acid derivative compound (i) in the areas exposed to the electromagnetic radiation, (c) optionally heating the layer to bring compound (ii) to the areas where the acid was released, improving its solubility in aqueous solutions, and (d) at least partially removing the layer with the aqueous solutions in these areas.

[0026] Embodiment 18. At least one sulfonic acid derivative in the composition is [ka] 18. The process of embodiment 17, wherein

[0027] Embodiment 19. The composition of any one of embodiments 13-16, wherein the additive is a basic quencher.

[0028] Embodiment 20. The basic quencher is selected from linear and cyclic amides and derivatives thereof, such as N,N-bis(2-hydroxyethyl)pivalamide, N,N-diethylacetamide, N1,N1,N3,N3-tetrabutylmalonamide, 1-methylazepan-2-one, 1-allylazepan-2-one, and tert-butyl 1,3-dihydroxy-2-(hydroxymethyl)propan-2-ylcarbamate; aromatic amines, such as pyridine and di-tert-butylpyridine; triisopropanolamine, n-tert-butyldiethanolamine, tris(2-acetoxyethyl)amine, 2,2',2 The composition of embodiment 19, wherein the amine is selected from the group consisting of aliphatic amines such as, 2'''-(ethane-1,2-diylbis(azanetriyl))tetraethanol and 2-(dibutylamino)ethanol, 2,2',2''-nitrilotriethanol; cyclic aliphatic amines such as 1-(tert-butoxycarbonyl)-4-hydroxypiperidine, tert-butyl 1-pyrrolidinecarboxylate, tert-butyl 2-ethyl-1H-imidazole-1-carboxylate, di-tert-butylpiperazine-1,4-dicarboxylate, and N(2-acetoxyethyl)morpholine.

[0029] Embodiment 21. The composition of embodiment 20, wherein the basic quencher is selected from the group consisting of 1-(tert-butoxycarbonyl)-4-hydroxypiperidine and triisopropanolamine.

[0030] Embodiment 22. The process of embodiment 17 or 18, wherein the applying step is carried out by a method selected from the group consisting of spin coating, spray coating, dip coating, and doctor blading.

[0031] Embodiment 23. The process of embodiment 17 or 18, wherein the substrate is selected from the group consisting of silicon, silicon dioxide, silicon-on-insulator (SOI), strained silicon, gallium arsenide, and coated substrates, and the coating is selected from the group consisting of silicon nitride, silicon oxynitride, titanium nitride, tantalum nitride, hafnium oxide, titanium, tantalum, copper, aluminum, tungsten, alloys thereof, and combinations thereof. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0032] definition Unless otherwise stated, the following terms used in this application, including the specification and claims, have the definitions given below. It must be noted that as used in this specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise.

[0033] All numerical designations, including ranges, such as weight, pH, temperature, time, concentration, and molecular weight, are approximate values ​​that vary by 10%. It is to be understood, although not necessarily expressly indicated, that all numerical designations are preceded by the word "about". It is also to be understood, although not necessarily expressly indicated, that the reagents described herein are merely exemplary, and that equivalents of such reagents are known in the art.

[0034] For the purposes of this disclosure, technical and scientific terms used in the specification of the invention shall have the meanings that are commonly understood by those of ordinary skill in the art, unless specifically defined otherwise. Accordingly, the following terms are intended to have the following meanings:

[0035] As used herein, the term "moiety" refers to a defined portion or functional group of a molecule. A chemical moiety is a recognized chemical entity that is often incorporated into or appended to a molecule.

[0036] As used herein, the term "aliphatic" includes the terms alkyl, alkenyl, alkynyl, each of which is optionally substituted as defined below.

[0037] As used herein, an "alkyl" group refers to a saturated aliphatic hydrocarbon group containing 1 to 20 (e.g., 2 to 18, 3 to 18, 1 to 8, 1 to 6, 1 to 4, or 1 to 3) carbon atoms. Alkyl groups can be linear, branched, cyclic, or any combination thereof. Examples of alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-heptyl, or 2-ethylhexyl. Alkyl groups can be substituted (i.e., optionally substituted) with one or more substituents, as defined below, or can be polycyclic.

[0038] "Halogen" refers to an atom in Group 17 of the periodic table and includes fluorine, chlorine, bromine and iodine.

[0039] As used herein, an "aryl" group used alone or as part of a larger moiety, as in "aralkyl," "aralkoxy," or "aryloxyalkyl," refers to monocyclic (e.g., phenyl); bicyclic (e.g., indenyl, naphthalenyl, tetrahydronaphthyl, tetrahydroindenyl); and tricyclic (e.g., fluorenyl, tetrahydrofluorenyl, or tetrahydroanthracenyl, anthracenyl) ring systems, where the monocyclic ring system is aromatic or at least one ring of the bicyclic or tricyclic ring system is aromatic. Bicyclic and tricyclic groups include 2-3 membered benzo-fused carbocyclic rings. For example, a benzo-fused group is a group having two or more C 4~8 It includes phenyl fused to a carbocyclic moiety. Aryl is optionally substituted with one or more substituents as described below.

[0040] As used herein, "monocyclic C-C 30The term "cycloalkyl group" refers to a monocyclic aliphatic alkyl group having 3 to 30 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclopentyl, and cyclohexyl groups.

[0041] As used herein, “polycyclic C-C 30 The term "cycloalkyl group" refers to a carbocyclic moiety having two or more rings (e.g., fused or bridged bicyclic) having 3 to 30 carbon atoms. Examples include adamantyl, norbornyl, cubyl, octahydro-indenyl, decahydro-naphthyl, bicyclo[3.2.1]octyl, bicyclo[2.2.2]octyl, bicyclo[3.3.1]nonyl, bicyclo[3.3.2]decyl, bicyclo[2.2.2]octyl, ((aminocarbonyl)cycloalkyl)cycloalkyl, bicyclo[2.2.1]heptane, bicyclo[3.2.1]octane, and bicyclo[3.3.1]nonane.

[0042] As used herein, "C3-C 30 The term "monocyclic heteroalkyl group" means a 3- to 30-membered monocyclic alkyl group as defined above, except that the ring system contains at least one heteroatom selected from a nitrogen atom, an oxygen atom, and a sulfur atom. Examples of such groups are monovalent groups derived from, for example, morpholine, thiomorpholine, pyrrolidine, imidazoline, oxazoline, piperidine, piperazine, tetrahydrofuran, aziridine, azetidine, indoline, isoindoline, and the like.

[0043] As used herein, the term "heteroaryl" group refers to a monocyclic, bicyclic, or tricyclic ring system having 4 to 18 ring atoms, in which one or more of the ring atoms is a heteroatom (e.g., N, O, S, or combinations thereof) and in which the monocyclic ring system is aromatic or at least one ring of the bicyclic or tricyclic ring system is aromatic.

[0044] The phrase "optionally substituted" is used synonymously with the phrase "substituted or unsubstituted." As described herein, the compounds of the present disclosure may be optionally substituted with one or more substituents, as generally set forth above or as illustrated by the particular classes, subclasses and species of compounds of the present disclosure. As described herein, any of the moieties above or below may be optionally substituted with one or more substituents as described herein. Each substituent of a particular group is optionally further substituted with 1-3 halo, cyano, oxoalkoxy, hydroxy, amino, nitro, aryl, haloalkyl, and alkyl. For example, an alkyl group may be substituted with an alkylsulfanyl, which may be optionally substituted with 1-3 halo, cyano, oxoalkoxy, hydroxy, amino, nitro, aryl, haloalkyl, and alkyl.

[0045] In general, the term "substituted", whether or not preceded by the term "optionally", refers to the replacement of hydrogen radicals in a given structure with the radical of a given substituent. Specific substituents are described above in the definitions and below in the compound descriptions and examples. Unless otherwise indicated, an optionally substituted group can have a substituent at each substitutable position of the group, and when more than one position in any given structure can be substituted with more than one substituent selected from a given group, the substituents can be the same or different at all positions. A ring substituent, such as a heterocycloalkyl, can be bonded to another ring, such as a cycloalkyl, to form a spiro-bicyclic ring system, e.g., both rings share one common atom. As will be recognized by one of skill in the art, the combinations of substituents contemplated by this disclosure are those that result in the formation of stable or chemically feasible compounds.

[0046] Modified forms or derivatives of the compounds disclosed throughout this specification are contemplated as useful with the methods and compositions of this disclosure. Derivatives may be prepared and the properties of such derivatives may be assayed for their desired properties by any method known to those skilled in the art. In certain aspects, a "derivative" refers to a chemically modified compound that retains the desired activity of the compound prior to the chemical modification.

[0047] Sulfonic acid derivatives as photoacid generator compounds Disclosed herein are novel photoacid generators (herein PAGs) that have low outgassing properties when exposed to actinic radiation, particularly when used in photoresist compositions exposed to advanced lithographic radiation such as electron beam, x-ray, and extreme ultraviolet (EUV) radiation having a wavelength of 13.5 nm. The photoacid generators are salts of oxathionium cations that have high sensitivity to these actinic radiation, but the decomposition products of these PAGs are reduced compared to conventional PAGs under similar conditions of photoresist composition, exposure, and processing.

[0048] The PAGs disclosed herein are based on a cation-anion structure in which the cation is an aryl-substituted oxathiane cation. As used herein, "oxathiane" refers to a sulfonium cation having the following structure (Ia): [ka]

[0049] In formula (Ia), R is a substituted or unsubstituted C1-C 12 It is an alkyl group. Examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-octyl and 2-ethylhexyl groups.

[0050] The PAGs disclosed herein are oxacid salts of sulfonic acid derivatives and are represented by formula (I). [ka] In the formula, R is a substituted or unsubstituted C1-C 12 is an alkyl group, Z is a substituted or unsubstituted polycyclic C 30 Cycloalkyl groups, substituted or unsubstituted monocyclic C3-C 30 Cycloalkyl groups and substituted or unsubstituted C3-C 30 Monocyclic heteroaryl groups are selected from the group consisting of:

[0051] In formula I, R is a substituted or unsubstituted C1-C 12 It is an alkyl group, preferably a C1 to C6 alkyl group. Examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-octyl and 2-ethylhexyl groups.

[0052] In some embodiments, Z is a substituted or unsubstituted polycyclic C-C 30 is a cycloalkyl group selected from the group consisting of adamantyl, norbornyl, cubyl, octahydro-indenyl, decahydro-naphthyl, bicyclo[3.2.1]octyl, bicyclo[3.3.2]decyl, bicyclo[2.2.2]octyl, bicyclo[2.2.1]heptyl, and bicyclo[3.3.1]nonyl.

[0053] In other embodiments, Z is a substituted or unsubstituted monocyclic C-C 30 It is a cycloalkyl group selected from the group consisting of a cyclopropyl group, a cyclobutyl group, a cycloheptyl group, a cyclopentyl group, and a cyclohexyl group.

[0054] In yet another embodiment, Z is a substituted or unsubstituted C-C 30It is a monocyclic heteroaryl group and is selected from the group consisting of morpholinyl, thiomorpholinyl, pyrrolidinyl, imidazolinyl, oxazolinyl, piperidinyl, piperazinyl, tetrahydrofuranyl, aziridinyl, azetidinyl, indolinyl, and isoindolinyl.

[0055] In a preferred embodiment, the anion is 5-norbornyl octafluoro-3-oxapentanesulfonate, [ka] and the oxacyanium ion is [ka] It is.

[0056] The sulfonic acid derivative compounds disclosed herein can be used as photoacid generators, as described in more detail below. Surprisingly, it has been discovered that the PAG compounds disclosed herein are characterized by excellent solubility and photoreactivity to electromagnetic radiation, particularly to electromagnetic radiation having wavelengths in the range of 150-500 nm, preferably in the range of 300-450 nm, more preferably in the range of 350-440 nm, and more preferably at wavelengths of 365 nm (i-line), 405 nm (h-line) and 436 nm (g-line).

[0057] The PAGs of the present disclosure impart a high degree of efficiency to the photolithography process, improving contrast and resolution between exposed and unexposed areas of the resist composition. The amount of energy provided by the PAG and UV radiation is selected to be sufficient to enable the desired polycondensation.

[0058] The PAGs of the present disclosure may be suitably used in positive- or negative-tone chemically amplified photoresists, i.e., negative-tone resist compositions in which a photoacid promotes a crosslinking reaction such that the exposed regions of a coating layer of the resist are less soluble in a developer than the unexposed regions, and positive-tone resist compositions in which a photoacid promotes a deprotection reaction of acid labile groups of one or more composition components such that the exposed regions of a coating layer of the resist are more soluble in an aqueous developer than the unexposed regions.

[0059] Preferred imaging wavelengths of the photoresists disclosed herein include wavelengths less than 300 nm, such as 248 nm, and wavelengths less than 200 nm, such as 193 nm and EUV, more preferably in the range of 200-500 nm, preferably in the range of 300-450 nm, even more preferably in the range of 350-440 nm, and most preferably 365 nm (i-line), 405 nm (h-line) and 436 nm (g-line).

[0060] Photoresist Composition The photoresist compositions disclosed herein include a photoresist composition comprising: (i) at least one photoacid generator selected from formula (I); (ii) at least one photoresist polymer or copolymer, which may be base soluble or insoluble; (iii) an organic solvent; and, optionally, (iv) an additive.

[0061] Photoresist compositions according to the present disclosure that include a photoacid generator of formula (I) are suitable for use as photoresists in a variety of applications, particularly in the fabrication of electronic devices, including flat panel displays (where the photoresist can be coated glass substrates or layers of indium tin oxide), and semiconductor devices (where the photoresist can be coated onto silicon wafer substrates). A variety of exposure radiations can be used, including exposure with electromagnetic radiation having a wavelength of 200-500 nm, preferably in the range of 300-450 nm, more preferably in the range of 350-440 nm, even more preferably 365 nm (i-line), 436 nm (g-line) or 405 nm (h-line), with electromagnetic radiation having a wavelength of 365 nm being particularly preferred.

[0062] The photoresist composition disclosed herein comprises, as component (ii), one or more photoresist polymers or copolymers that may be soluble or insoluble in a developer. The photoresist composition disclosed herein may be for a positive tone or negative tone composition. In the case of a positive tone composition, the solubility of component (ii) is improved when reacting with an acid released from the compound(s) disclosed herein. In this case, a photoresist polymer or copolymer having an acid labile group is used as component (ii) that is insoluble in an aqueous base solution but becomes soluble in the solution when deprotected by a catalyst in the presence of an acid. In the case of a negative tone composition, the solubility of component (ii) is decreased when reacting with an acid released from the compound disclosed herein. In this case, a photoresist polymer or copolymer is used as component (ii) that is soluble in a developer solution but becomes insoluble in an aqueous base solution when crosslinked in the presence of an acid. That is, the photoresist polymer or copolymer can change its solubility in the developer solution in the presence of an acid. Preferably, the developer solution is an aqueous solution, more preferably an aqueous base solution.

[0063] Examples of photoresist polymers that may be used as component (ii) of the positive tone composition include, but are not limited to, aromatic polymers such as homopolymers or copolymers of hydroxystyrene protected with acid labile groups, acrylic acid esters such as poly(meth)acrylic acid esters having at least one unit containing a pendant alicyclic group and having acid labile groups branched from the polymer backbone and / or from the alicyclic group, cycloolefin polymers, cycloolefin maleic anhydride copolymers, cycloolefin vinyl ether copolymers, siloxanes, silsesquioxanes, carbosilanes, and oligomers including polyhedral oligomeric silsesquioxanes, carbohydrates and other cage compounds. The above polymers or oligomers are appropriately functionalized with aqueous base soluble groups, acid labile groups, polar functional groups and silicon-containing groups, as appropriate.

[0064] Examples of copolymers that may be used as component (ii) of the positive tone compositions of the present disclosure include, but are not limited to, poly(p-hydroxystyrene)-methyl adamantyl methacrylate (PHS-MAdMA), poly(p-hydroxystyrene)-2-ethyl-2-adamantyl methacrylate (PHS-EAdMA), poly(p-hydroxystyrene)-2-ethyl-2-cyclopentyl methacrylate (PHS-ECpMA), poly(p-hydroxystyrene)-2-methyl-2-cyclopentyl methacrylate (PHS-mCPMA) or PHS-EVE.

[0065] Preferably, at least one component (ii) of the positive tone composition is a poly(hydroxystyrene) resin in which at least some of the hydroxy groups are replaced by a protecting group. Preferred protecting groups are selected from the group consisting of tert-butoxycarbonyloxy, tert-butyloxy, tert-amyloxycarbonyloxy and acetal groups. Furthermore, suitable as component ii) are all the polymers and copolymers described as "acid-labile group-containing resins" in paragraphs

[0068] to

[0114] of EP1586570A1. The disclosure of EP1586570A1 regarding these resins is incorporated herein by reference and forms part of the present disclosure.

[0066] A preferred negative tone composition comprises a mixture of materials that cure, crosslink or harden when exposed to acid. A preferred negative tone composition comprises a polymeric binder such as a phenolic or non-aromatic polymer as component (ii), a crosslinker component as additive (iv), and a photoacid generator component as disclosed herein as component (i). Suitable polymeric binders and crosslinkers for such negative tone photoresist compositions and their use are disclosed in EP-A-0164248 and US 5,128,232. Preferred phenolic polymers for use as component (ii) include novolaks and poly(vinylphenols). Novolak resins are thermoplastic condensation products of phenols and aldehydes. Examples of phenols suitable for condensation with aldehydes, particularly formaldehyde, to form novolak resins include phenol, m-cresol, o-cresol, p-cresol, 2,4-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol and thymol. An acid-catalyzed condensation reaction forms suitable novolak resins whose molecular weights can vary from about 500 to 100,000 Daltons. Polyvinylphenol resins are thermoplastic polymers that can be formed by block, emulsion or solution polymerization of the corresponding monomers in the presence of a cationic catalyst. Vinylphenols useful for making polyvinylphenol resins can be prepared, for example, by hydrolysis of commercially available coumarins or substituted coumarins followed by decarboxylation of the resulting hydroxycinnamic acids. Useful vinylphenols can also be prepared by dehydrating the corresponding hydroxyalkylphenols or by decarboxylation of hydroxycinnamic acids obtained from the reaction of substituted or unsubstituted hydroxybenzaldehydes with malonic acid. Preferred polyvinylphenol resins prepared from such vinylphenols have molecular weights in the range of about 2,000 to about 60,000 Daltons. Preferred crosslinkers for use as component (iv) include amine-based materials including melamine, glycolurils, benzoguanamine-based materials and urea-based materials. Melamine-formaldehyde polymers are often particularly suitable.Such crosslinkers are commercially available, for example, melamine polymers, glycoluril polymers, urea-based polymers and benzoguanamine polymers, such as those sold by Cytec under the trade names Cymel™ 301, 303, 1170, 1171, 1172, 1123 and 1125, and Beetle™ 60, 65 and 80.

[0067] As component (iii), the composition disclosed herein includes at least one organic solvent. The organic solvent may be any solvent capable of dissolving component (ii) and component (i) to form a homogeneous solution, and one or more solvents selected from among known materials used as solvents for conventional chemically amplified resists may be used. Specific examples of organic solvents include ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, and 2-heptanone; polyhydric alcohols and derivatives thereof such as ethylene glycol, ethylene glycol monoacetate, diethylene glycol, diethylene glycol monoacetate, propylene glycol, propylene glycol monoacetate, dipropylene glycol, or monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether, or monophenyl ether of dipropylene glycol monoacetate; cyclic ethers such as dioxane; and esters such as methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, and ethyl ethoxypropionate. These organic solvents can be used alone or as a mixed solvent containing two or more different solvents. Particularly preferred organic solvents (iii) are selected from the group consisting of ketones, ethers and esters.

[0068] Additionally, compositions according to the present disclosure may optionally include at least one additive different from components (i), (ii), and (iii). For example, other optional additives may include actinic and contrast dyes, anti-striation agents, plasticizers, rate enhancers, sensitizers, etc. Such optional additives will typically be present in low concentrations in photoresist compositions, with the exception of fillers and pigments, which may be present in relatively high concentrations (e.g., amounts of 5-30 weight percent of the total weight of the dry components of the resist).

[0069] One of the additives typically used in the photoresist composition according to the present disclosure is a basic quencher. The basic quencher is intended to neutralize the acid generated in the surface area of ​​the underlying photoresist layer by the backlight reaching the area intended to be the unexposed area (dark area) of the photoresist layer. This allows the depth of focus and exposure latitude of the defocused area to be improved by controlling the undesired deprotection reaction in the unexposed area. As a result, irregularities in the profile, such as necking and T-topping in the formed resist pattern, can be minimized or avoided.

[0070] In order to allow effective interaction of the basic quencher with the generated acid in the dark areas of the underlying photoresist layer, the basic quencher must be of the non-surfactant type. That is, the basic quencher must not be of the type that migrates to the top surface of the overcoat layer, for example, because its surface free energy is lower than the other components of the overcoat composition. In such a case, the basic quencher will not be present at the photoresist layer interface in a significant amount to interact with the generated acid and prevent acid-induced deprotection. Thus, the basic quencher must be of the type that is present at the overcoat layer / photoresist layer interface, whether it is distributed uniformly throughout the overcoat layer or forms a graded or separate layer at the overcoat layer / photoresist layer interface. Such a separate layer can be achieved by selecting a basic quencher that has a high surface free energy compared to the other components of the overcoat composition.

[0071] Suitable basic quenchers include, for example, linear and cyclic amides and derivatives thereof such as N,N-bis(2-hydroxyethyl)pivalamide, N,N-diethylacetamide, N1,N1,N3,N3-tetrabutylmalonamide, 1-methylazepan-2-one, 1-allylazepan-2-one, and tert-butyl 1,3-dihydroxy-2-(hydroxymethyl)propan-2-ylcarbamate, aromatic amines such as pyridine and di-tert-butylpyridine, triisopropanolamine, n-tert-butyldiethanolamine, tris(2-acetoxyethyl) ... aliphatic amines such as 2,2',2'',2'''-(ethane-1,2-diylbis(azanetriyl))tetraethanol, 2-(dibutylamino)ethanol, and 2,2',2''-nitrilotriethanol; and cyclic aliphatic amines such as 1-(tert-butoxycarbonyl)-4-hydroxypiperidine, tert-butyl 1-pyrrolidinecarboxylate, tert-butyl 2-ethyl-1H-imidazole-1-carboxylate, di-tert-butylpiperazine-1,4-dicarboxylate, and N(2-acetoxyethyl)morpholine. Among these basic quenchers, 1-(tert-butoxycarbonyl)-4-hydroxypiperidine and triisopropanolamine are preferred. The content of the basic quencher depends, for example, on the content of the photoacid generator in the underlying photoresist layer, but is typically present in an amount of 0.1 to 5 wt %, preferably 0.5 to 3 wt %, and more preferably 1 to 3 wt %, based on the total solids content of the overcoat composition.

[0072] Another idea is to attach a basic moiety to the PAG molecule. In this case, the quencher is part of the PAG and is in close proximity to the acid formed upon irradiation. These compounds have a high sensitivity to electromagnetic radiation, in particular to electromagnetic radiation with a wavelength in the range of 200-500 nm, more particularly to electromagnetic radiation with a wavelength of 365 nm (i-line), and at the same time allow the production of patterned structures with a higher resolution compared to photoresist compositions known from the prior art that contain a quencher as an additive.

[0073] The resin binder component of the resists of the present disclosure is typically used in an amount sufficient to render an exposed coating layer of the resist developable, such as by an aqueous alkaline solution. More specifically, the resin binder will preferably comprise from 50 to about 90 weight percent of the total solids of the resist. The photoactive component should be present in an amount sufficient to form a latent image in a coating layer of the resist. More specifically, the photoactive component will preferably be present in an amount of from about 1 to 40 weight percent of the total solids of the resist. Typically, lower amounts of photoactive component are preferred for chemically amplified resists.

[0074] According to a preferred embodiment, the compositions disclosed herein comprise:

[0075] (i) 0.05 to 15 wt %, preferably 0.1 to 12.5 wt %, and most preferably 1 to 10 wt % of at least one photoacid generator compound of formula (I);

[0076] (ii) 5-50% by weight, preferably 7.5-45% by weight, most preferably 10-40% by weight of at least one photoresist polymer or copolymer, which may be base soluble or insoluble;

[0077] (iv) 0 to 10% by weight, preferably 0.01 to 7.5% by weight, most preferably 0.1 to 5% by weight of further additives, with the remainder of the composition being the organic solvent (iii).

[0078] In the compounds according to the present disclosure, the basic functional groups acting as quenchers for the acid groups released upon exposure to electromagnetic radiation are part of the photoacid generator compound, so that it is not necessary to add a separate basic component as a quencher (as is necessary in photoresist compositions known from the prior art). According to a preferred embodiment of the composition according to the present disclosure, the composition preferably contains less than 5 wt. %, more preferably less than 1 wt. %, even more preferably less than 0.1 wt. %, and most preferably 0 wt. % of basic compounds different from components (i)-(iv), such as hydroxides, carboxylates, amines, imines and amides.

[0079] Photoresists of the present disclosure are generally prepared according to known procedures, except that the PAGs of the present disclosure are substituted for conventional photoactive compounds used in formulating similar photoresists. For example, resists of the present disclosure can be prepared as coating compositions by dissolving the components of the photoresist in a suitable solvent, such as, for example, glycol ethers such as 2-methoxyethyl ether (diglyme), ethylene glycol monomethyl ether, propylene glycol monomethyl ether, lactates such as ethyl lactate or methyl lactate, but ethyl lactate is preferred, propionates, particularly methyl propionate and ethyl propionate, cellosolve esters such as methyl cellosolve acetate, aromatic hydrocarbons such as toluene, xylene, or ketones such as methyl ethyl ketone, cyclohexanone, and 2-heptanone. Typically, the solids content of the photoresist varies between 5 and 35 weight percent of the total weight of the photoresist composition.

[0080] The photoresist compositions of the present disclosure can be used according to known procedures. The photoresists of the present disclosure can be applied as dry films, but are preferably applied as liquid coating compositions onto a substrate, dried by heating to remove solvent, preferably until the coating layer is tack-free, exposed to activating radiation through a photomask, and optionally post-exposure baked to create or increase the solubility difference between exposed and unexposed areas of the resist coating layer, and then developed, preferably with an aqueous alkaline developer, to form a relief image. The substrate onto which the resist of the present disclosure is applied and treated can suitably be any substrate used in processes involving photoresists, such as microelectronic wafers. For example, the substrate can be a silicon, silicon dioxide or aluminum-aluminum oxide microelectronic wafer. Gallium arsenide, ceramic, quartz or copper substrates can also be used. Substrates used in liquid crystal display applications and other flat panel display applications, such as glass substrates, indium tin oxide coated substrates, and the like, are also suitably used. The liquid coating resist compositions can be applied by any standard means, such as spinning, dipping or roller coating. The exposure energy must be sufficient to effectively activate the photoactive components of the radiation-sensitive system to form a patterned image in the resist coating layer. Suitable exposure energies are typically about 1 to 300 mJ / cm. 2As mentioned above, preferred exposure wavelengths include wavelengths less than 200 nm, such as 193 nm. Suitable post-exposure bake temperatures are about 50° C. or higher, more specifically about 50-140° C. For acid-hardening negative resists, a post-development bake can be used, if desired, at a temperature of about 100-150° C. for several minutes or more to further harden the relief image formed during development. After development and optional post-development hardening, the substrate surface exposed by development may be selectively treated, for example by chemical etching or plating of the exposed substrate areas from which the photoresist has been removed, according to procedures known in the art. Suitable etchants include hydrofluoric acid etchants and plasma gas etchants, such as oxygen plasma etchants.

[0081] Complex The present specification provides a process for fabricating a composite comprising a substrate and a coating applied in a patterned structure on the substrate, the process comprising:

[0082] (a) applying a layer of a composition according to the present disclosure onto a surface of a substrate and at least partially removing the organic solvent (iii);

[0083] (b) exposing selected areas of the layer to electromagnetic radiation, thereby releasing acid from compound (i) in the areas exposed to the electromagnetic radiation;

[0084] (c) optionally heating the bed to bring compound (ii) to the areas where the acid was released and to change its solubility in aqueous solutions; and

[0085] (d) at least partially removing the layer.

[0086] In process step (a), a layer of a composition according to the present disclosure is applied onto the surface of a substrate, followed by at least partial removal of the organic solvent (iii).

[0087] The substrate may be of any size and shape, and is preferably a substrate useful for photolithography, such as silicon, silicon dioxide, silicon-on-insulator (SOI), strained silicon, gallium arsenide, coated substrates (including substrates coated with silicon nitride, silicon oxynitride, titanium nitride, tantalum nitride), ultra-thin gate oxides such as hafnium oxide, metal or metal coated substrates (including substrates coated with titanium, tantalum, copper, aluminum, tungsten, alloys thereof), and combinations thereof. Preferably, the surface of the substrate herein includes the micro-scale layer to be patterned, including one or more gate level layers or other micro-scale layers on the substrate, for example, for semiconductor manufacturing. Such substrates may preferably include silicon, SOI, strained silicon, and other similar substrate materials formed as circular wafers, with dimensions such as, for example, 20 cm, 30 cm or more in diameter, or other dimensions useful for fab production of wafers.

[0088] The composition according to the present disclosure may be applied onto a substrate by any suitable method, including spin coating, spray coating, dip coating, doctor blading, and the like. The photoresist layer is preferably applied by spin coating the photoresist using a coating track that dispenses the photoresist onto the spinning wafer. During the spin coating process, the wafer may be spun at a speed of up to 4,000 rpm, preferably about 500-3,000 rpm, more preferably 1,000-2,500 rpm. The coated wafer is spun to remove the organic solvent (iii) and baked on a hotplate to remove residual solvent and free volume from the film and to homogenize the density of the film.

[0089] In process step (b), selected areas of the layer are exposed to electromagnetic radiation, thereby releasing acid from compound (i) in the areas exposed to the electromagnetic radiation. As noted above, various exposure radiations can be used, including exposure to electromagnetic radiation having a wavelength of 365 nm (i-line), 436 nm (g-line) or 405 nm (h-line), with electromagnetic radiation having a wavelength of 365 nm being particularly preferred.

[0090] Such patternwise exposure can be performed using an exposure tool such as a stepper, where the film is irradiated through a pattern mask and thereby patternwise exposed. The method preferably uses an advanced exposure tool that generates activating radiation at a wavelength that allows high resolution, including extreme ultraviolet (EUV) or electron beam radiation. It will be apparent that exposure with activating radiation decomposes the components according to the present disclosure contained in the photoresist layer in the exposed areas to generate acid and decomposition by-products, and the acid then causes a chemical change in the polymer compound (ii) (either deblocking acid-sensitive groups to generate base-soluble groups in the exposed areas or catalyzing crosslinking reactions). The resolution of such exposure tools can be less than 30 nm.

[0091] In process step (c), the layer can be optionally heated to bring compound (ii) to the areas where the acid was released, changing its solubility in aqueous solutions. This so-called "post-exposure bake" creates or increases the solubility difference between exposed and unexposed areas of the coating layer. Typically, post-exposure bake conditions include a temperature of about 50° C. or higher, more specifically about 50° C. to about 160° C., for 10 seconds to 30 minutes, preferably 30 to 200 seconds. According to certain embodiments of the process according to the present disclosure, no heat treatment is performed before process step (b) and after process step (d).

[0092] In process step (d), the layer is at least partially removed with an aqueous solution, preferably an aqueous base solution. This can be done by treating the exposed photoresist layer with a suitable developer capable of selectively removing the exposed parts of the film (in this case the photoresist is positive tone) or removing the unexposed parts of the film (in this case the photoresist is negative tone). Preferably the photoresist is a polymer-based positive tone with acid-sensitive groups (deprotectable groups) and the developer is preferably a metal ion-free tetraalkylammonium hydroxide solution.

[0093] A composite made according to the present disclosure comprises a substrate and a coating applied in a patterned structure onto a surface of the substrate, the coating comprising a compound according to the present disclosure.

[0094] It is also within the scope of the present disclosure to use the photoacid generator compounds of formula (I) for photoinduced polymerization, photoinduced crosslinking, photoinduced decomposition and photoinduced transformation of functional groups.The compounds according to the present disclosure are particularly suitable for use in protective coatings, smart cards, 3D rapid prototyping or additive manufacturing, sacrificial coatings, adhesives, anti-reflective coatings, holograms, galvano masks and plating masks, ion implantation masks, etching resists, chemically amplified resists, light sensing applications, PCB (printed circuit board) patterning, MEMS fabrication, TFT layer patterning in flat panel displays, TFT layer patterning in flexible displays, pixel patterning in color filters or black matrices for displays or LCDs, or semiconductor patterning in packaging processes, and semiconductor manufacturing protective coatings, smart cards, 3D rapid prototyping or additive manufacturing, sacrificial coatings, adhesives, anti-reflective coatings, holograms, galvano masks and plating masks, ion implantation masks, etching resists, chemically amplified resists, light sensing applications or TSV-related patterning in color filters.

[0095] The following examples are intended to illustrate the above disclosure and should not be interpreted to narrow its scope. Those skilled in the art will easily recognize that these examples suggest many other ways in which the present disclosure can be implemented. It should be understood that many variations and modifications can be made while remaining within the scope of the present disclosure. EXAMPLES

[0096] solubility Solubility is an important factor in the evaluation of PAGs. High solubility not only allows the PAG to be easily purified, but also allows the PAG to be used in a wide range of concentrations in photoresists and various solvent systems. To test the solubility of a PAG, solvent is added slowly until the PAG is completely dissolved and no turbidity is observed in the clear solution. Table 1 lists the solubility (w / w%) of representative oxacyanium-containing PAGs according to the present disclosure relative to compounds disclosed in U.S. Pat. No. 9,507,259.

[0097] [Table 1] *=Propylene glycol monomethyl ether acetate

[0098] As shown in Table 1, Compound A exhibits higher solubility in various solvents, including PGMEA, the most used solvent for photoresists, than the comparative compounds from the prior art, indicating that Compound A is a potentially useful photoacid generator (PAG) for ArF (193 nm) photoresist applications.

[0099] synthesis The following is a non-limiting example of a synthesis for producing compound A above. Bis(t-butylphenyl)iodonium 5-(2-norbornyl)octafluoro-3-oxapentanesulfonate (I) was similarly synthesized according to a literature approach (US 9,507,259). Synthesis of Compound A [ka]

[0100] A 1 L 4-neck round bottom flask was fitted with a mechanical stirrer, thermometer, condenser, and N2 gas inlet. 100 g (127 mmol) of bis(t-butylphenyl)iodonium 5-(2-norbornyl)octafluoro-3-oxapentanesulfonate (I), 14.6 g (140 mmol) of 1,4-thioxane, and 1.16 g (6.4 mmol) of copper acetate were mixed in 402 g of anhydrous chlorobenzene. The reaction mixture was heated to 120° C. for 4 hours and cooled overnight. The chlorobenzene was removed by rotary evaporation at 60° C. 200 g of t-butyl methyl ether (MTBE) was added to the reaction flask. The resulting precipitate was collected by filtration and the solid was redissolved in 200 g of methylene chloride. Undissolved copper acetate was filtered off. The solution was washed with 2% HCl, 3% aqueous ammonium hydroxide, 10% citric acid solution, and then deionized water. The methylene chloride solution was removed by rotary evaporation. Then, 600 g of MTBE was added to precipitate the solid. The recovered solid was recrystallized from i-propanol and dried in a vacuum oven at 45° C. for 24 hours to obtain 40 g of compound A (yield: 50%). Melting point: 129.5°C. 1 H NMR(300MHz,CDCl3)δ:1.12-1.23(m,3H),1.33(s,9H),1.43-1.52(m,4H),1.65-1.69(m,1H),2.08-2.22(m,1 H),2.27(s,1H),2.56(s,1H),3.67(t,2H),3.93(d,2H),4.07(t,2H),4.35(d,2H),7.66(d,2H),7.87(d,2H). 13 C NMR (75.4 MHz, CDCl3) δ: 27.8, 30.3, 30.8, 31.7, 35.4, 35.6, 36.8, 39.0, 42.6 (t, 20.8 Hz, Fc coupling, 1C), 64.0, 108-122 (m, Fc coupling, 4C), 118.8, 128.5, 129.7, 158.8. 19F NMR(282.2MHz, CDCl3)δ:-120.1(m,AB,2F),-118.0(s,2F),-86.0(m,AB,2F),-82.8(m,2F).

[0101] Although shown and described above with reference to certain specific embodiments and examples, the present disclosure is not intended to be limited to the details shown. Rather, various modifications in details can be made without departing from the spirit of the present disclosure, within the scope and range of equivalents of the claims. For example, all broad ranges described herein are expressly intended to include all narrow ranges that are included in the broad ranges. In addition, features of one embodiment can be incorporated into another embodiment.

Claims

1. Represented by the following chemical formula I: 【Chemistry 1】 In the formula, R is a substituted or unsubstituted C １ -C １２ is an alkyl group, Z is a substituted or unsubstituted polycyclic C ３ ~C ３０ Cycloalkyl groups, substituted or unsubstituted monocyclic C ３ ~C ３０ Cycloalkyl groups and substituted or unsubstituted C ３ ~C ３０ A sulfonic acid derivative compound selected from the group consisting of monocyclic heteroalkyl groups.

2. R is a substituted or unsubstituted C １ ~C ６ The sulfonic acid derivatized compound of claim 1 , which is an alkyl group.

3. 3. The sulfonic acid derivative compound of claim 1 or 2, wherein R is isobutyl.

4. Z is a substituted or unsubstituted polycyclic C ３ ~C ３０ The sulfonic acid derivative compound of claim 1 or 2, which is a cycloalkyl group.

5. 5. The sulfonic acid derivative compound of claim 4, wherein Z is selected from the group consisting of adamantyl, norbornyl, cubyl, octahydro-indenyl, decahydro-naphthyl, bicyclo[3.2.1]octyl, bicyclo[3.3.2]decyl, bicyclo[2.2.2]octyl, bicyclo[2.2.1]heptyl, and bicyclo[3.3.1]nonyl.

6. The sulfonic acid derivative compound of claim 5 , wherein Z is norbornyl.

7. 6. The sulfonic acid derivative compound of claim 5, wherein Z is adamantyl.

8. Z is a substituted or unsubstituted monocyclic C ３ ~C ３０ The sulfonic acid derivative compound of claim 1 or 2, which is a cycloalkyl group.

9. 9. The sulfonic acid derivative compound of claim 8, wherein Z is selected from the group consisting of a cyclopropyl group, a cyclobutyl group, a cycloheptyl group, a cyclopentyl group, and a cyclohexyl group.

10. Z is a substituted or unsubstituted monocyclic C ３ ~C ３０ 3. The sulfonic acid derivative compound of claim 1 or 2, which is a heteroaryl group.

11. 11. The sulfonic acid derivative compound of claim 10, wherein Z is selected from the group consisting of morpholinyl, thiomorpholinyl, pyrrolidinyl, imidazolinyl, oxazolinyl, piperidinyl, piperazinyl, tetrahydrofuranyl, aziridinyl, azetidinyl, indolinyl, and isoindolinyl.

12. The compound represented by formula (I) is 【Chemistry 2】 2. The sulfonic acid derivatized compound of claim 1 ,

13. (i) at least one sulfonic acid derivatized compound according to claim 1; (ii) at least one polymer or copolymer that can be given altered solubility in aqueous solution in the presence of an acid; (iii) an organic solvent, and optionally (iv) A photoresist composition comprising an additive.

14. 14. The composition of claim 13, wherein the organic solvent is propylene glycol monomethyl ether acetate (PGMEA).

15. 0.05 to 15 weight percent of said sulfonic acid derivatized compound; 5 to 50% by weight of said at least one polymer or copolymer, and 0 to 10% by weight of said additive, 15. The composition of claim 13 or 14, wherein the remainder is propylene glycol monomethyl ether acetate.

16. The at least one sulfonic acid derivatized compound is 【Chemistry 3】 The composition of claim 13, wherein

17. A process for fabricating a patterned structure on a surface of a substrate, comprising the steps of: (a) applying a layer of the composition according to any one of claims 13 to 16 to a surface of the substrate and at least partially removing the organic solvent (iv); (b) exposing said layer to electromagnetic radiation, thereby releasing acid from said sulfonic acid derivatized compound (i) in the areas exposed to said electromagnetic radiation; (c) optionally heating the bed to bring compound (ii) to the areas where the acid was released, making it more soluble in aqueous solutions; (d) at least partially removing said layer with the aqueous solution in these areas.

18. The at least one sulfonic acid derivative in the composition is 【Chemistry 4】 20. The process of claim 17, wherein

19. The composition of claim 13, wherein the additive is a basic quencher.

20. The basic quencher may be selected from linear and cyclic amides and derivatives thereof, such as N,N-bis(2-hydroxyethyl)pivalamide, N,N-diethylacetamide, N1,N1,N3,N3-tetrabutylmalonamide, 1-methylazepan-2-one, 1-allylazepan-2-one, and tert-butyl 1,3-dihydroxy-2-(hydroxymethyl)propan-2-ylcarbamate; aromatic amines, such as pyridine and di-tert-butylpyridine; triisopropanolamine, n-tert-butyldiethanolamine, tris(2-acetoxyethyl)amine, 2,2',2' 20. The composition of claim 19, wherein the amine is selected from the group consisting of aliphatic amines such as 2',2'''-(ethane-1,2-diylbis(azanetriyl))tetraethanol, 2-(dibutylamino)ethanol, 2,2',2''-nitrilotriethanol, 1-(tert-butoxycarbonyl)-4-hydroxypiperidine, tert-butyl 1-pyrrolidine carboxylate, tert-butyl 2-ethyl-1H-imidazole-1-carboxylate, di-tert-butylpiperazine-1,4-dicarboxylate, and N(2-acetoxyethyl)morpholine.

21. 21. The composition of claim 20, wherein the basic quencher is selected from the group consisting of 1-(tert-butoxycarbonyl)-4-hydroxypiperidine and triisopropanolamine.

22. 19. The process of claim 17 or 18, wherein the applying step is carried out by a method selected from the group consisting of spin coating, spray coating, dip coating, and doctor blading.

23. 19. The process of claim 17 or 18, wherein the substrate is selected from the group consisting of silicon, silicon dioxide, silicon-on-insulator (SOI), strained silicon, gallium arsenide, and coated substrates, and the coating is selected from the group consisting of silicon nitride, silicon oxynitride, titanium nitride, tantalum nitride, hafnium oxide, titanium, tantalum, copper, aluminum, tungsten, alloys thereof, and combinations thereof.

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