Acceptor-substituted EUV PAG with high electron affinity

Abstract

A compound of structure (I), wherein R1, R2, R 1a and R 2a R1, R2, R 1a and R 2a At least two of these are independently selected from nitro, cyano, and alkylsulfonyl, and X - The disclosed compounds are not halides, tosylates, trifluoromethylsulfonates, tetrafluoroborates, aryl-substituted borates, hexafluorophosphates, hexafluoroarcenates, acetates, trifluoroacetates, methanesulfonates, C2-C20 linear unsubstituted alkyl sulfonates, naphthalene sulfonates, and camphor sulfonates. Also disclosed are EUV negative and positive chemically amplified photoresist compositions containing the compounds, as well as methods for using these photoresists to pattern substrates.

Description

[Technical Field]

[0001] The disclosed and claimed inventions relate to a chemically amplified organic resist material comprising a certain type of photoacid generator (PAG) designed to enhance sensitivity to high-resolution patterning using an electron beam or 13.5 nm EUV radiation, and a method of using the same. [Background technology]

[0002] Chemically amplified resists are the dominant resist type used in 248 nm, 193 nm, and 193 nm immersion lithography. In these chemically amplified resists, the change in resist solubility is divided into two reactions. The first step is a photoreaction, in which photons are absorbed by a photoacid generator (PAG), which decomposes to form photoacid. This photoacid then catalyzes a chemical reaction that results in a change in the solubility of the photoresist, for example, in the case of positivetone photoresists, making the exposed area more easily soluble in the developer. The change in solubility can be caused by the deprotection reaction of groups suspended from the polymer backbone, such as acetal-protected phenols or tertiary alcohol esters of carboxylic acids, which results in the formation of phenol-OH groups or carboxylic acids, making the polymer soluble in aqueous base developers or insoluble in organic solvent-based developers. These reactions often occur during the post-exposure bake (PEB) step. Since photoacids act solely as catalysts and are not consumed in the reaction, they can catalyze many such reactions; the original photo-catalyzed phenomenon is amplified by the number of reactions catalyzed per acid, and is therefore called chemical amplification.

[0003] Commonly used PAGs include strong acids, such as triphenylsulfonium and diphenyliodonium salts of strong acids, including, but not limited to, perfluoroalkylsulfonic acids or their derivatives. In the case of the UV wavelength mentioned above, the generation of photoacid occurs via the absorption of a photon into one of the absorption bands of the PAG, which is then transitioned to an unstable excited state and decomposed into a radical and a radical cation. The latter then reacts further to generate the proton necessary to produce the catalytic chemical species. This mechanism is described in some detail in the literature [John L. Dektar and Nigel P. Hacker, J. Am. Chem. Soc. 1990, 112, 6004-6015 (Non-Patent Literature 1)].

[0004] The use of chemically amplified resists has extended to extreme UV (EUV) wavelengths of 13.5 nm or photon energies of 91.6 eV. At this wavelength, photon absorption leads to primary ionization, where electrons are emitted from atoms at high energies. These electrons then collide with other atoms, leading to further ionization, generating secondary electrons. In this electron cascade, the energy of the original photon is dissipated in a limited region around the original absorption event, in the form of electrons and positively charged chemical species ("holes") as well as electrons and thermal excitations. The size of this region is limited by the path lengths of the primary and secondary electrons, which are estimated to be on the order of 2 to 3 nanometers.

[0005] At lower energy UV lithography wavelengths (i.e., 248 and 193 nm), the polymer components of the resist are almost transparent at these exposure wavelengths, and absorption occurs mainly by PAG. However, at EUV energy, everything exhibits absorption. Specifically, photon absorption and subsequent ionization can occur not only in PAG but also in any atom constituting the photoresist. This absorption occurs almost independently of the chemical environment of the ionized atom; instead, it depends solely on the atomic composition of the photoresist. The absorbance of EUV resists can be directly calculated from the individual atomic absorption cross-sections and film density without considering the chemical environment of the atoms [Roberto Fallica, Jarich Haitjema, Lianjia Wu, Sonia Castellanos, Albert M. Brouwer, Yasin Ekinci, J. Micro / Nanolith.MEMS MOEMS 17(2), 023505(2018), doi:10.1117 / 1.JMM.17.2.023505 (Non-Patent Literature 2)].

[0006] This leads to a significant difference in the mechanism of acid generation between EUV and longer UV lithography wavelengths; in EUV, direct absorption of photons by PAGs is no longer the primary mechanism of photoacid generation. During exposure, EUV photon absorption generates steady states of electrons and holes, in which case electrons lose energy in a series of collisions until they reach an energy close to thermal equilibrium or recombine with holes. PAGs begin to act again at relatively low energies in the electron cascade when their cations can capture electrons, leading to the formation of free radicals. These free radicals are unstable and decompose into non-charge reaction products, as shown in equation (1) for triphenylsulfonium and diphenyliodonium cations as parent compounds.

[0007] [ka] As a result of electron capture, electrons are removed from the electron / hole equilibrium formed during the exposure period, leaving behind holes. These holes then react further with the corresponding cation species to generate the protons necessary to form the catalytic species (i.e., dissociated or undissociated photoacid). The dynamics of this process have been validated in the literature, and the rate of acid formation predicted by the dynamic model matches experimentally well [Craig D. Higgins, Charles R. Szmanda1, Alin Antohe, Greg Denbeaux, Jacque Georger2, and Robert L. Brainard, Japanese Journal of Applied Physics 50(2011)036504,10.1143 / JJAP.50.036504,DOI:10.1143 / JJAP.50.036504 (Non-Patent Literature 3)].

[0008] In the aforementioned dynamic model, hole type R + The concentration of the acid is determined by equation (2) by the formation of the acid or by recombination with electrons, resulting in a steady-state concentration F[R + ,e - It decreases from ].

[0009] [ka] From the perspective of acid production, electron / hole recombination is a parasitic process that reduces the efficiency of acid production. The number of recombination events can be reduced by the removal of electrons from the steady state via electron capture by PAGs. All electron capture events leave behind a hole, which is free to react further to produce photoacid. The more effective electron capture, the greater the acid yield.

[0010] One parameter that can be used to predict the efficiency of electron capture by PAGs is the energy balance during electron capture, also known as its electron affinity. According to a widely accepted generalization of Koopmans' theorem [Tjalling Koopmans, Physica.1(1-6):104-113.doi:10.1016 / S0031-8914(34)90011-2 (Non-Patent Literature 4)], electron affinity can be estimated by the LUMO energy obtained from quantum chemical calculations within the limits of the single-electron self-consistent field (SCF) model. Table 1 lists the calculated LUMO values ​​for a series of sulfonium and iodonium PAGs. Examining this table shows that iodonium salts generally have higher electron affinity than sulfonium salts.

[0011] The calculation results summarized in Table 1 show that iodonium salts have significantly higher electron affinity than sulfonium salts. Another advantage of iodonium salts is that the iodine atom has a very broad EUV absorption cross-section. Since PAG is only a small portion of the total mass of the resist film, this may be of little importance in increasing the overall EUV absorbance of the resist film, but it may contribute to an improved photospeed to some extent due to the direct contribution of the absorbance of initial photons into PAG.

[0012] In the above dynamics study [Higgins et al. (Non-Patent Literature 3)], the acid production efficiencies of the two PAGs, bis(4-(tert-butyl)phenyl)iodonium nonafluorobutanesulfonate and triphenylsulfonium nonafluorobutanesulfonate, were determined to be 5.6 and 4.6 acids per absorbed photon, respectively. This is in reference to other studies that have shown that diphenyliodonium salts result in faster EUV photospeed than triphenylsulfonium salts [Martin Glodde, Dario L. Goldfarb, David R. Medeiros, Gregory M. Wallraff, and Gregory P. Denbeaux, Journal of Vacuum Science & Technology B: Microelectronics and Nanometer Structures Processing, Measurement, and Phenomena 25, 2496 (2007); doi: 10.1116 / 1.2779045 (Non-Patent Literature 5)], [Dario L. Goldfarb, Ali Afzali-Ardakani, Martin Glodde, Proc. SPIE 9779, Advances in Patterning Materials and Processes XXXIII, 97790A (25 March)]. This matches [2016);doi:10.1117 / 12.2218457 (Non-Patent Literature 6)], and this result is consistent with the EA values ​​listed in Table 1.

[0013] [Table 1]

[0014] In one of the studies mentioned above [Goldfarb et al. (Non-Patent Literature 5)], the electron affinity EA and electrochemical reduction potential Ep of PAGs were validated as predictors of EUV photospeed. A high correlation was found between the EA value determined from the LUMO value and the experimentally determined Ep value, both of which exhibited a linear relationship. However, not all PAG photospeeds were accurately predicted by either the EA or Ep value. The authors concluded that "although a correlation between such basic research and actual EUV photospeed could not be established, a significant improvement in EUV sensitivity compared to DUV performance was observed in the PAG group with photoelectron trapping properties." Therefore, based on the estimated electron trapping mechanism when acid is formed from PAGs during EUV exposure and available literature data, it can be concluded that while electron affinity values ​​can serve as a criterion for pre-selecting highly efficient EUV PAGs, other factors also influence PAG performance. [Brief explanation of the drawing]

[0015] [Figure 1] Examples of specific compounds with structures (I), (Ia), (Ib), and (Ic) are shown. [Figure 2] Examples of specific compounds with structures (I), (Ia), (Ib), and (Ic) are shown. [Prior art documents] [Patent Documents]

[0016] [Patent Document 1] US7,655,379B2 [Patent Document 2] US2009181319A1 [Patent Document 3] US8,617,791B2 [Patent Document 4] WO2009 / 087027A2 [Patent Document 5] US20060216643A1 [Patent Document 6] US7,087,356

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Non-licensed literature

[0017] [Non-licensed document 1] John L.Dektar and Nigel P.Hacker, J.Am.Chem.Soc.1990,112,6004-6015 [Non-licensed document 2] Roberto Fallica,Jarich Haitjema,Lianjia Wu,Sonia Castellanos,Albert M.Brouwer,Yasin Ekinci,J.Micro / Nanolith.MEMS MOEMS 17(2),023505(2018),doi:10.1117 / 1.JMM.17.2.023505 [Non-licensed document 3] Craig D.Higgins, Charles R.Szmanda1, Alin Antohe, Greg Denbeaux, Jacque Georger 2, and Robert L.Brainard, Japanese Journal of Applied Physics 50(2011)036504,10.1143 / JJAP.50.036504,DOI:10.1143 / JJAP.50.036504

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[0018] The present invention relates to a compound of structure (I), wherein in structure (I), R1, R2, R 1a and R 2a R1, R2, R2 are independently selected from H, nitro, cyano, and alkylsulfonyl, where R1, R2, R2 are R1, R2 1a and R 2a At least two of these are independently selected from nitro, cyano, and alkylsulfonyl, and X -The compounds are not halides, tosylates, trifluoromethylsulfonates, tetrafluoroborates, aryl-substituted borates, tetrafluorophosphates, hexafluoroarcenates, acetates, trifluoroacetates, methanesulfonates, C2-C20 linear unsubstituted alkylsulfonates, naphthalene sulfonates, and / or camphor sulfonates. Another aspect of the present invention is EUV negative and positive chemically amplified photoresist compositions comprising the compounds, and methods for using these photoresists to pattern substrates.

[0019] [ka] This invention describes PAGs that exhibit higher efficiency in acid generation upon exposure to ionizing radiation, the higher efficiency resulting from the improved electron affinity exhibited by these PAGs as a result of acceptor substitution of their PAG cations. A greater number of catalytic acids generated per EUV photon or per electron bombardment is desirable, as this increases photoresist sensitivity, increases throughput, and reduces the stochastic effect on linewidth roughness.

[0020] Another aspect of the present invention is the use of the compound of structure (I) and any of the embodiments thereof disclosed herein as a photoacid generator. Yet another aspect of the present invention is the use of any one of the compositions disclosed herein as a photoresist on a substrate. [Detailed explanation] Both the general description above and the detailed description below are illustrative and explanatory, and should be understood not to limit the invention described in the claims. In this application, unless otherwise specifically stated, the use of the singular form includes the plural, the singular form means "at least one (or one kind)", and the use of "or" means "and / or". Furthermore, the use of "includes" and other verb forms such as "includes" is not limiting. Also, unless otherwise specifically stated, descriptions such as "element" or "component" include both elements and components containing one constituent unit, and elements or components containing more than one constituent unit. Unless otherwise indicated, the conjunction "and" used herein is intended to be compatible, and the conjunction "or" is not intended to be exclusive. For example, the phrase "or instead" is intended to be exclusive. The use of "and / or" used herein refers to any combination of the aforementioned elements, including the use of a single element.

[0021] The term C1-C4 alkyl includes methyl, C2-C4 linear alkyl, and C3-C4 branched alkyl moieties, such as methyl (-CH3), ethyl (-CH2-CH3), n-propyl (-CH2-CH2-CH3), isopropyl (-CH(CH3)2), n-butyl (-CH2-CH2-CH2-CH3), tert-butyl (-C(CH3)3), isobutyl (CH2-CH(CH3)2), and 2-butyl (-CH(CH3)CH2-CH3). Similarly, the designation C1-C8 includes methyl, C2-C8 linear alkyl, C3-C8 branched alkyl, C4-C8 cycloalkyl (e.g., cyclopentyl, cyclohexyl, etc.), or C5-C8 alkylene cycloalkyl (e.g., -CH2-cyclohexyl, CH2-CH2-cyclopentyl, etc.).

[0022] The term C2-C8 alkylene encompasses both C2-C8 linear alkylene moieties (e.g., ethylene, propylene, etc.) and C3-C8 branched alkylene moieties (e.g., -CH(CH3)-, -CH(CH3)-CH2-, etc.).

[0023] The term "C2-C4 alkylene" includes a C2-C4 linear alkylene moiety and a C3-C4 branched alkylene moiety.

[0024] The term "C2-C8 perfluoroalkylene" includes a C2-C8 linear perfluoroalkylene moiety and a C3-C8 branched perfluoroalkylene moiety.

[0025] The term "C2-C4 perfluoroalkylene" includes a C2-C4 linear perfluoroalkylene moiety and a C3-C4 branched perfluoroalkylene moiety.

[0026] The term "alkylsulfonyl", unless otherwise indicated, includes a C1-C8 alkyl moiety, which in turn includes C1-C8 linear alkyl, C3-C8 branched alkyl, C3-C8 cyclic alkyl and C4-C8 cycloalkyl bonded to the sulfonyl.

[0027] As used herein, the statement "X - is the anion of an acid having a pK less than 0" excludes acids (e.g., HI, HCl, HBr, HF) that have a pK less than 0 but also have a corresponding nucleophilic anion. Such nucleophilic anions attack the intermediate carbocation to form a stable compound (e.g., an alkyl halide such as tert-butyl halide), stop the chemical amplification chain reaction, and consume the catalytic proton (H a a + is also excluded. Such nucleophilic anions attack the intermediate carbocation to form a stable compound (e.g., an alkyl halide such as tert-butyl halide), stop the chemical amplification chain reaction, and consume the catalytic proton (H +This will prevent the regeneration of ). The following references describe the mechanism of chemical amplification (Polymers for Microelectronics ACS Symposium Series ACS, (1993), Chapter 1 Chemically Amplification Mechanisms for Microlithography, E. Reichmanis et al, p.3 (Non-Patent Literature 7) (Chemical Amplification Resists for Microlithography Adv Polymer Sci, Hiroshi Ito (2005) 172, p.37 (Non-Patent Literature 8)). Examples of suitable non-nucleophilic anions are listed below.

[0028] The present invention relates to a PAG designed for ionizing radiation, such as X-rays, EUV, particle beams, or electron beams, and shown to exhibit high photospeed for these radiations, wherein the PAG generates electrons that can be captured by an iodonium salt as a result of an energy dissipation mechanism. The iodonium derivative is selectively substituted with an acceptor substituent to increase electron capture efficiency by increasing electron affinity compared to the parent compound (i.e., a compound without acceptor substituents).

[0029] Among these acceptor substitutions, nitro, cyano, and alkylsulfonyl substituents at positions 3 and 4 were found to be particularly effective. However, not only the properties of the substituents but also their positions are important. Nitro substituents at position 2 have relatively small EA calculations and slow photospeed. The (2-nitrophenyl)phenyliodonium ion has a lower electron affinity than its parent diphenyliodonium ion, and the electron affinity of the 2,2'-dinitrophenyl derivative is very close to that of the parent, despite the substitution of two strong acceptors. The n-butylsulfonyl group, which acts as a weak electron donor at positions 3 and 4, is a strong electron donor when at position 2. This "ortho effect" is presumed to be a result of the negative charge of the oxygen atom in the nitro- or sulfonium group adjacent to the central iodonium, which donates electron density to the iodonium, thus reducing its positive charge and, consequently, its electron affinity. The aforementioned ortho effect can also contribute to the electron affinity of 2,2'-dicyano derivatives, however, in this case, the partial negative charge moves further away from the central iodine and does not interact with the lone pair of electrons. It is noteworthy that 3- and 4-acceptor substitutions result in nearly equivalent increases in electron affinity, which is not usually expected from typical substitution effects seen in aromatic systems. Here, n-butylsulfonyl substituents, which are chosen as a general substitute for all alkylsulfonyl substituents, decrease electron affinity when monosubstituted (Table 1), but when positioned at the 4-position and combined with a 4'-nitro substituent, they result in high electron affinity. Alkylsulfonyl substituents are important because they can improve the solubility of iodonium salts by selecting an appropriate length of alkyl chain. Trifluoromethyl CF3 substituents act as strong acceptors at the 3- and 4-positions, but also result in a significant improvement in electron affinity at the 2-position; as "hard" substituents (i.e., substituents with low polarizability), they are considerably less affected by the ortho effect.

[0030] Table 1 lists several compounds for which EA is not a valid predictor of the observed EUV photospeed. Tests of bis(2,4,6-trifluorophenyl)iodonium PAG have been reported in the literature and confirmed to have a very low EUV photospeed [Goldfarb et al. (Non-Patent Literature 5)]. In the same literature, PAGonium 1, 2, 3, and 5 were found to have slower or equivalent photospeeds compared to their parent compounds, despite calculations predicting considerably higher EAs.

[0031] EUV PAG components Iodonium ions combine with suitable counteranions to form iodonium salts. For the purpose of high-resolution photolithography, these anions need to be non-nucleophilic strong acids with low diffusivity and volatility. In terms of their acidity, photoacids should have a pKa of -1 or less on the 1,2-dichloroethane acidity scale [Eno Paenurk, Karl Kaupmees, Daniel Himmel, Agnes Kuett, Ivari Kaljurand, Ilmar A. Koppel, Ingo Krossing and Ivo Leito, Chem. Sci., 2017, 8, 6964 (Non-Patent Literature 9)]. Sulfonic acids are preferred because they exhibit low nucleophilicity and do not react with cationic intermediates generated during solubility change reactions. The absence of such side reactions is important because the addition of an acid anion to a cationic species results in a neutral molecule, i.e., the acid catalyst is consumed and the chain reaction of chemical amplification terminates.

[0032] Early chemically amplified resists used antimony hexafluoride, arsenic hexafluoride, or hexafluorophosphate anions. Among these, phosphorus is the dopant, hence PF6 - This is undesirable, and also due to the high toxicity of arsenic, AsF6 - That is undesirable.

[0033] For high-resolution applications, it is desirable that the acid does not exhibit high diffusivity. For example, trifluoromethanesulfonic acid is a strong catalyst with low nucleophilicity, but it is highly diffusive and has a high vapor pressure, which may lead to redeposition of the acid from highly exposed areas to areas intended not to be exposed [Thomas Wallow, Marina Plat, Zhanping Zhang, Brian MacDonald, Joffre Bernard, Jeremias Romero, Bruno La Fontaine, Harry J. Levinson, Proc. SPIE 6519, Advances in Resist Materials and Processing Technology XXIV, 65190T, 2007; doi:10.1117 / 12.712338 (Non-patent Literature 10)]. Therefore, trifluoromethanesulfonic acid is not a good candidate for high-resolution resists.

[0034] In one embodiment of the PAG, composition, and method of the present invention, suitable counterions include, but are not limited to, antimony hexafluoride; per and polyfluoroalkanesulfonates, for example, but are not limited to, perfluorobutanesulfonate (PFBS), hexafluoropropanesulfonate, or oxa-substituted derivatives, for example, but are not limited to, 1,1,2-trifluoro-2-(trifluoromethoxy)ethanesulfonate (TTES); Examples include anions of methides and imido superacids, such as tris(perfluoroalkylsulfonyl)methides, particularly tris[(trifluoromethyl)sulfonyl]methide (C1) and tris[(nonafluoro-n-butyl)sulfonyl]methide (C4), bis(perfluoroalkylsulfonyl)imide anions, particularly bis(trifluoromethanesulfonyl)imide anions (N1), bis(nanofluoro-n-butanesulfonyl)imide anions (N4), and cyclic 4,4,5,5,6,6-hexafluorodihydro-1,1,3,3-tetraoxide-4H-1,3,2-dithiazine (NC3).

[0035] [ka] In another aspect of this embodiment, other suitable counteranions are acid anions including fluorinated aromatics, such as, but are not limited to, fully or partially substituted benzenesulfonates having fluorine and trifluoromethyl substituents.

[0036] In another aspect of this embodiment, the other suitable counteranion is a polymer-bonded acid in which a sulfonate anion is linked to the polymer main chain by a linker group, wherein the linker group is SO3 - The group does not contain aromatic rings directly bonded to it. In one preferred embodiment, the linker group includes a CF2 group on the carbon atom following the sulfonate. In one of the other preferred embodiments, the suspended anion is a bissulfonylimide anion having one perfluoroalkyl substituent, most preferably CF3 or C4F9, and a linker group that bonds it to the polymer main chain, the linker group optionally includes a carbon atom that is also per- or polyfluorinated.

[0037] Non-PFAS anions, such as polycyano-substituted cyclopentadienide anions, particularly pentacyano, tetracyano-monocarboxylate, and tetracyanomethoxycyclopentadienide anions [Martin Glodde, Sen Liu and Pushkara Rao Varnasi, J. Photopol. Sci. Techn. 23(2), 173-184 (2010) (Non-Patent Document 11) and US7,655,379B2 (Patent Document 1)], or acceptor-substituted thiophenesulfonates as described in Liu et al. [Sen Liu, Martin Glodde and Pushkara Varanasi, Proc. SPIE 7639, 76390D (2010); DOI: 10.1117 / 12.846600 (Non-Patent Document 12)], US2009181319A1 (Patent Document 2) and US8,617,791B2 (Patent Document 3).

[0038] In one other aspect of this embodiment, formula P + A -Other suitable counter anions described in WO2009 / 087027A2 (Patent Document 4) disclosing PAG, in the formula, A - The group includes pentacyanopentadienides and various tetracyanocarboxylate ions, P + is an onium salt, particularly an iodonium salt, which may be optionally nitro-substituted. However, WO2009 / 087027A2 (Patent Document 4) does not teach or suggest combinations of the cations of the present invention with these anions, because the document states P + This is because nitro is listed as one of the many substituents above (both electron-donating and electron-withdrawing), and substitutions at the 2, 3, or 4 positions are not distinguished. The present invention has inadvertently found that only nitro substitutions at the 3- and 4- positions, and especially nitro disubstitutions, result in higher electron affinity, and therefore higher acid yields for such PAGs, while 2-substitutions are actually detrimental to them, and 2,2'-disubstitutions are ineffective.

[0039] As stated here, pK a When describing a range, these values ​​pK a This is ACD / pK for Microsoft Windows. a This prediction was made by software version 4.0 (Advanced Chemistry development Inc., 8 King Street East, Suite 107, Toronto, Ontario, Canada).

[0040] One aspect of the present invention is a compound of structure (I), wherein in structure (I), R1, R2, R 1a and R 2a R1, R2, R2 are independently selected from H, nitro, cyano, and alkylsulfonyl, where R1, R2, R2 are R1, R2 1a and R 2a At least two of these are independently selected from nitro, cyano, and alkylsulfonyl, and X -This does not include halides, tosylates, trifluoromethylsulfonates, tetrafluoroborates, aryl-substituted borates, hexafluorophosphates, hexafluoroarcenates, acetates, trifluoroacetates, methanesulfonates, C2-C20 linear unsubstituted alkylsulfonates, naphthalene sulfonates, and / or camphor sulfonates.

[0041] [ka] Another aspect of the present invention is R1 and R 1a , or R2 and R 2a , or R 1a and R2, or R1 and R 2a However, independently selected from nitro, cyano, and alkylsulfonyl, and X - However, it is a compound of structure (I) that is not a halide, tosylate, trifluoromethylsulfonate, tetrafluoroborate, aryl-substituted borate, hexafluorophosphate, hexafluoroarsenate, acetate, trifluoroacetate, methanesulfonate, C2-C20 linear unsubstituted alkylsulfonate, naphthalene sulfonate and / or camphor sulfonate.

[0042] [ka] In one aspect of the compound of the present invention having the structure (I) described above, it more specifically has structure (Ia). In one aspect of this embodiment, R1 and R 1a Both are nitro. In one other aspect of this embodiment, R1 and R 1a Both are cyanoides. In one of the other aspects of this embodiment, R1 and R 1a Both are alkylsulfonyl. In one other aspect of this embodiment, R1 is nitro, and R 1a R is cyano. In one other aspect of this embodiment, R1 is nitro, and R 1a R is an alkylsulfonyl. In one other aspect of this embodiment, R1 is an alkylsulfonyl, and R 1aIt is cyano.

[0043] [ka] In one aspect of the present invention, the compound of the present invention having structure (I) described above, more specifically, has structure (Ib). In one aspect of this embodiment, R2 and R 2a Both are nitro. In one other aspect of this embodiment, R2 and R 2a Both are cyanoides. In one of the other aspects of this embodiment, R2 and R 2a Both are alkylsulfonyl. In one other aspect of this embodiment, R2 is nitro, and R 2a R is cyano. In one other aspect of this embodiment, R2 is nitro, and R 2a R is an alkylsulfonyl. In one other aspect of this embodiment, R2 is an alkylsulfonyl, and R 2a It is cyano.

[0044] [ka] In one aspect of the compound of the present invention having the structure (I) described above, it more specifically has structure (Ic). In one aspect of this embodiment, R1 and R 2a Both are nitro. In one other aspect of this embodiment, R1 and R 2a Both are cyanoides. In one of the other aspects of this embodiment, R1 and R 2a Both are alkylsulfonyl. In one other aspect of this embodiment, R1 is nitro, and R 2a R is cyano. In one other aspect of this embodiment, R1 is nitro, and R 2a R is an alkylsulfonyl. In one other aspect of this embodiment, R1 is an alkylsulfonyl, and R 2a It is cyano.

[0045] [ka] In one aspect of any one of the compounds of the present invention with structures (I), (Ia), (Ib), and (Ic), X - pK is less than 0 a It is an anion of an acid having X. In one other aspect of this embodiment, X - pK is less than 1 a It is an anion of an acid that possesses [a certain characteristic].

[0046] In another aspect of the compounds of the present invention with structures (I), (Ia), (Ib), and (Ic), X - X is an anion which is a perfluorinated or partially fluorinated alkyl sulfonate having more than three carbon atoms, where the alkyl is linear, branched or cyclic alkyl. In one other aspect of this embodiment, X - The anion is a perfluorinated or partially fluorinated alkyl sulfonate having more than three carbon atoms, where the alkyl is a linear, branched, or cyclic alkyl containing a heteroatom selected from -O-, -C(=O)-, and -S(=O)2-.

[0047] In one aspect of any one of the compounds of the present invention with structures (I), (Ia), (Ib), and (Ic), X - It is antimony hexafluoride.

[0048] In one aspect of any one of the compounds of the present invention with structures (I), (Ia), (Ib), and (Ic), X - This is an anion of a methide or imido perfluoride superacid. In one aspect of this embodiment, this is an anion of a methide perfluoride superacid. In another aspect of this embodiment, this is an anion of an imido perfluoride superacid.

[0049] In one aspect of any one of the compounds of the present invention with structures (I), (Ia), (Ib), and (Ic), X - These are perfluorobutanesulfonate (PFBS) or hexafluoropropanesulfonate.

[0050] In one aspect of any one of the compounds of the present invention with structures (I), (Ia), (Ib), and (Ic), X - This is tris(perfluoroalkylsulfonyl)methide.

[0051] In one aspect of any one of the compounds of the present invention with structures (I), (Ia), (Ib), and (Ic), X - This is an anion selected from the group consisting of tris[(trifluoromethyl)sulfonyl]methide (C1) and tris[(nonafluoro-n-butyl)sulfonyl]methide (C4), bis(perfluoroalkylsulfonyl)imide anions, particularly bis(trifluoromethanesulfonyl)imide anions (N1), bis(nonafluoro-n-butanesulfonyl)imide anions (N4), and cyclic 4,4,5,5,6,6-hexafluorodihydro-1,1,3,3-tetraoxide-4H-1,3,2-dithiazine (NC3).

[0052] [ka] In one aspect of any one of the compounds of the present invention with structures (I), (Ia), (Ib), and (Ic), X - This is an aryl sulfonate fluoride, which is partially or completely substituted with substituents selected from fluorine or perfluoroalkyl groups.

[0053] In one aspect of any one of the compounds of the present invention with structures (I), (Ia), (Ib), and (Ic), X - This is a sulfonate moiety (-SO3) connected to the polymer main chain by a linker group. - ) and the linker group is the (-SO3 - ) This does not include aromatic rings directly bonded to the portion. In one other aspect of this embodiment, the -SO3 -The portion is directly bonded to the polymer main chain via a C1-C8 linear perfluoroalkyl linker group. In another aspect of this embodiment, the perfluoroalkylene linker group is selected from the group consisting of difluoromethylene (-CF2-), tetrafluoroethylene (-CF2-CF2-), and hexafluoropropylene (-CF2-CF2-CF2-). In another aspect of this embodiment, the linker group has a methylene portion directly bonded to the sulfonate portion, and the other end of it is directly bonded to the polymer or bonded via a C1-C4 perfluoroalkylene portion.

[0054] In one aspect of any one of the compounds of the present invention with structures (I), (Ia), (Ib), and (Ic), X - The perfluoroalkylamide moiety (-N(perfluoroalkyl)) is directly or via a linker group attached to the polymer backbone. - The linker group is selected from the group consisting of C1-C8 alkylene, C1-C8 perfluorinated alkylene, and C1-C8 partially fluorinated alkylene.

[0055] In one aspect of any one of the compounds of the present invention with structures (I), (Ia), (Ib), and (Ic), X - This is a diperfluoroalkyl carbide moiety (-C(perfluoroalkyl)2) that is directly or via a linker group attached to the polymer backbone. - The linker group is selected from the group consisting of C1-C8 alkylene, C1-C8 perfluorinated alkylene, and C1-C8 partially fluorinated alkylene.

[0056] In one aspect of any one of the compounds of the present invention with structures (I), (Ia), (Ib), and (Ic), X -is a polycyanosubstituted cyclopentadienyl anion. In one other aspect of this embodiment, the polycyanosubstituted cyclopentadienyl anion is selected from the group consisting of pentacyanocyclopentadienyl anion, tetracyanomonocarboxylate cyclopentadienyl anion, and tetracyanomethoxycyclopentadienyl anion. Figures 1 and 2 show non-limiting examples of specific compounds of structures (I), (Ia), (Ib), and (Ic).

[0057] Resin components suitable for EUV Polymer resin for photoresists The photoresist composition according to the present invention described herein comprises an acid-sensitive imaging polymer and an acceptor-substituted photoacid generator described above. The imaging polymer is preferably one that undergoes chemical transformation upon exposure of the photoresist composition to ionizing radiation, thereby producing differential solubility of the polymer in either the exposed or unexposed regions. That is, the base polymer used in the present invention comprises any acid-sensitive polymer having acid-sensitive side chains that can undergo catalytic cleavage in the presence of an acid generated by the photoacid generator according to the present invention. The imaging polymer may be either a positive-tone imaging polymer or a negative-tone imaging polymer. In such polymers, acid sensitivity exists due to the presence of acid-sensitive side chains bonded to the polymer main chain. Such acid-sensitive polymers containing acid-sensitive side chains are conventional and well known in the art. Preferably, the imaging polymer is suitable for use in 13.4 nm (EUV) lithography. A resist composition that operates as a positive tone when developed with an aqueous base developer may operate as a negative tone resist when developed with a solvent. One non-limiting example of such a solvent is n-butyl acetate.

[0058] In some embodiments of these compositions of the present invention, the acid-sensitive side chains of the acid-sensitive polymer are protected with a variety of acid-instability protecting groups well known to those skilled in the art. For example, the acid-sensitive side chains may be protected with high-activity-energy protecting groups such as t-butyl esters or t-butylcarbonyl groups, low-activity-energy protecting groups such as acetals, ketals, or silieethers of phenolic chemical species, or a combination of both low and high-activity-energy protecting groups may be used. More preferably, the image-forming polymer of the present invention comprises a lactone moiety, more preferably a suspended lactone moiety. Examples of image-forming polymers comprising lactone moieties are well known in the art. For example, see US20060216643A1 (Patent Document 5), and US7,087,356 (Patent Document 6), US7,063,931 (Patent Document 7), US6,902,874 (Patent Document 8), US6,730,452 (Patent Document 9), US6,627,391 (Patent Document 10), US6,635,401 (Patent Document 11), and US6,756,180 (Patent Document 12). Some lactone-containing monomer units preferred for inclusion in image-forming polymers are as follows:

[0059] [ka] In one embodiment of these compositions according to the present invention, the preferred image-forming polymer contains at least about 5 mol%, more preferably about 10 to 50 mol%, and most preferably 15 to 35 mol%, of lactone-containing monomer units based on the total monomer units in the image-forming polymer.

[0060] The image-forming polymer may also include mono- or poly-hydroxysubstituted derivatives of adamantyl methacrylate or acrylate.

[0061] Negative molecular glass photoresist resin In another embodiment of these compositions of the present invention, they may be based on a recently reported class of EUV photoresists, which are negative-tone molecular glass photoresists based on crosslinking of monomolecular epoxides [C. Popescu; G. O'Callaghan; A. McClelland; J. Roth; T. Lada; T. Kudo; R. Dammel; M. Moinpour; Y. Cao; APGRobinson, Proc. SPIE11612, Advances in Patterning Materials and Processes XXXVIII, 116120K (5 April 2021); doi:10.1117 / 12.2583888 (Non-Patent Literature 13)], [Richard A. Lawson, Clifford L. Henderson, Journal of Micro / Nanolithography, MEMS, and MOEMS, Vol.9, Issue 1, 013016 (January)]. [2010).DOI:10.1117 / 1.3358383 (Non-Patent Literature 14)], [RALawson, CTLee, CLHenderson, R.Whetsell, L.Tolbert, and Y.Wang, J.Vac.Sci.Technol.B, 25(6), 2140-2144 (2007).DOI 10.1116 / 1.2801885 (Non-Patent Literature 15)]. In these resist systems, a strong acid, often hexafluoroantimonic acid generated from the PAG during exposure, catalyzes the crosslinking of difunctional, trifunctional, or more polyfunctional monocrystalline epoxides. In EUV exposure, the higher the acid yield from the acceptor-substituted PAG of the present invention, the faster the photospeed of this type of photoresist.

[0062] Acid Quencher A suitable acid quencher, but not limited to, has a boiling point above 100°C and at least 1 pK at atmospheric pressure. aExamples of basic materials or combinations of materials include amine compounds having the structure (XIIa), (XIIb), (XIIc), (XIId), (XIIe), (XIIf), (XIIg), (XIIh), (XIIi), (XIIj), (XIIk), and (XIIl), or mixtures of several compounds from this group, provided that R b1 R is a C1-C20 saturated alkyl chain or a C2-C20 unsaturated alkyl chain, b2 , R b3 , R b4 , R b5 , R b6 , R b7 , R b8 , R b9 , R b10 , R b11 , R b12 , and R b13 These are independently selected from the group consisting of H and C1-C20 alkyl groups, as shown below.

[0063] [ka] Other suitable acid quenchers are tetraalkylammonium or trialkylammonium salts of carboxylic acids. Specific non-limiting examples include mono(tetraalkylammonium) of dicarboxylic acids, di(tetraalkylammonium) salts of dicarboxylic acids, mono(trialkylammonium) of dicarboxylic acids, or di(trialkylammonium) salts of dicarboxylic acids. Non-limiting examples of suitable dicarboxylic acids for these salts include oxalic acid, maleic acid, malonic acid, fumaric acid, phthalic acid, and analogues. Structures (XIIma) to (XIImd) give general structures of such materials, where Rqa to Rqd are independently C4-C8 alkyl groups, Rqe is a valence bond, an arylene moiety, a C1-C4 alkylene moiety, and an alkenyl moiety (-C(Rqf)=C(Rqg)-, where Rqf and Rqg are independently H or C1-C4 alkyl. Structure (XIIme) gives specific examples of such materials.

[0064] [ka] Organic spin coating solvents Suitable organic spin-coating solvents for dissolving the above EUV composition include: glycol ether derivatives, such as ethyl cellosolve, methyl cellosolve, propylene glycol monomethyl ether (PGME), diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol dimethyl ether, propylene glycol n-propyl ether, or diethylene glycol dimethyl ether; glycol ether ester derivatives, such as ethyl cellosolve acetate, methyl cellosolve acetate, or propylene glycol monomethyl ether acetate (PGMEA); carboxylates, such as ethyl acetate, n-butyl acetate, and amyl acetate; carboxylates of dibasic acids, such as diethyl oxylate and dimethyl malonate; dicarboxylates of glycols, such as ethylene glycol diacetate and propylene glycol diacetate; and hydroxycarboxylates, such as methyl lactate, ethyl lactate (EL), ethyl glycolate, and ethyl 3-hydroxypropionate; ketone esters, such as methyl pyruvate or ethyl pyruvate; Examples include alkoxycarboxylic acid esters, such as methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 2-hydroxy-2-methylpropionate, or methyl ethoxypropionate; ketone derivatives, such as methyl ethyl ketone, acetylacetone, cyclopentanone, cyclohexanone, or 2-heptanone; ketone ether derivatives, such as methyl diacetone alcohol; ketone alcohol derivatives, such as acetol or diacetone alcohol; ketals or acetals, such as 1,3-dioxalane and diethoxypropane; lactones, such as butyrolactone; amide derivatives, such as dimethylacetamide or dimethylformamide, anisole, and mixtures thereof. These solvents may also be used as "organic solvent-based developers" in part of the process for using the photoresist of the present invention when exposed to electron beam or EUV radiation as described below.

[0065] Optional cross-linking components The EUV and electron beam compositions described herein, intended for negative tone development using organic solvents, may additionally include crosslinking agents as optional components. These materials are polyfunctional compounds containing a portion that forms crosslinks in the photoresist film under the influence of a photogenerated acid. Examples of such components are polyfunctional alkyl and aryl epoxides that form crosslinks via ring-opening of epoxides, or N-methoxymethylated melamine-based crosslinking agent derivatives, benzyl alcohol derivatives, or vinyl cyclic acetal derivatives that form crosslinks via the formation of reactive carbocations (Polymers for Microelectronics ACS Symposium Series ACS, (1993), Chapter 1 Chemically Amplification Mechanisms for Microlithography, E. Reichmanis et al, p.3 (Non-Patent Literature 16)) and (Chemical Amplification Resists for Microlithography Adv Polymer Sci, Hiroshi Ito (2005) 172, p.37 (Non-Patent Literature 17)).

[0066] Other optional components In addition, the EUV and electron beam compositions described herein may further include additives selected from the group consisting of surfactants, inorganic polymers; additives such as small molecules, inorganic molecules, surfactants, other photoacid generators, thermoacid generators, curing agents, crosslinking agents, chain extenders, and similars; and combinations containing at least one of these.

[0067] Positive-type chemically amplified photoresist and processing according to the present invention Positive-type chemically amplified photoresist composition By using such materials described herein, another aspect of the present invention is a positive chemically amplified EUV or electron beam photoresist composition, 1) Any one of the compounds of the invention of structures (I), (Ia), (Ib) and (Ic) described herein, 2) A photoresist resin that undergoes chemically amplified deprotection catalyzed by a photoacid generator and releases a resin soluble in an aqueous base, 3) An optional acid quencher component, 4) An organic spin coating solvent, which is a positive chemically amplified EUV or electron beam photoresist composition.

[0068] In another aspect of this embodiment, the optional acid quencher component is present, which can be selected from suitable materials described herein. In yet another aspect of this embodiment, the organic spin coating solvent may be selected from any one of the organic spin coating solvents described herein, or a mixture of at least two such solvents.

[0069] By using such materials described herein, another aspect of the invention is a positive chemically amplified EUV or electron beam photoresist composition, 1a) A compound of structure (I), provided that R1, R2, R 1a and R 2a are independently selected from H, nitro, cyano and alkylsulfonyl, where at least two of R1, R2, R 1a and R 2a are independently selected from nitro, cyano and alkylsulfonyl, and X - is an anion of an acid having a pK a less than 0;

[0070]

Chemical formula

[0071] In yet another aspect of this embodiment, the optional acid quencher component is present, which can be selected from suitable materials described herein.

[0072] In yet another aspect of this embodiment, the organic spin coating solvent may be selected from any one of the organic spin coating solvents described herein, or a mixture of at least two such solvents.

[0073] By using such materials described herein, one other aspect of the present invention is a positive chemically amplified EUV or electron beam photoresist composition, 1b) A compound of structure (I), provided that R1 and R 1a or R2 and R 2a or R 1a and R2, or R1 and R 2a are independently selected from nitro, cyano and alkylsulfonyl, and X - is not a halide, tosylate, trifluoromethylsulfonate, tetrafluoroborate, aryl-substituted borate, hexafluorophosphate, hexafluoroarsenate, acetate, trifluoroacetate, methanesulfonate, C2-C20 linear unsubstituted alkylsulfonate, naphthalenesulfonate and / or camphorsulfonate, and X - is an anion of an acid having a pKa smaller than 0;

[0074]

Chemical formula

[0075] In other aspects of this embodiment, the positive-type photoresist resin described herein may be used specifically.

[0076] In yet another aspect of this embodiment, the optional acid quencher component is present, which may be selected from the appropriate materials described herein. In yet another aspect of this embodiment, the organic spin coating solvent may be selected from any one of the organic spin coating solvents described herein, or a mixture of at least two such solvents.

[0077] Method using positive-type chemically amplified photoresist Another aspect of the present invention is a method for forming a positive image on a substrate by EUV or electron beam exposure using a positive chemically amplified photoresist, the following steps i) to iv); i) A step of coating a substrate with any one of the positive chemically amplified EUV or electron beam photoresist compositions of the present invention described above to form a coating film. ii) A step of baking the coating film to form a baked coating film, iii) The baked coating region is exposed to EUV or electron beam radiation through a mask to form exposed and unexposed regions. iv) Optional post-exposure bake step v) Developing and removing the exposed area using an aqueous base developer to form a positive image pattern in the coated photoresist on the substrate. vi) Using the positive image pattern as a mask, etching the substrate with plasma or a chemical etching agent to form a positive image in the substrate. The method includes the above.

[0078] In one aspect of this embodiment, process step iv) is not optional. In one aspect of this embodiment, the aqueous base developer in step v) is 0.26N TMAH at room temperature.

[0079] A method using a positive-type chemically amplified photoresist to form a negative image. Another aspect of the present invention is a method for forming a negative image in a substrate by EUV or electron beam exposure using a positive chemically amplified photoresist, which proceeds from step ia) to via); ia) A step of forming a coating film by coating a substrate with any one of the positive chemically amplified EUV or electron beam photoresist compositions of the present invention described above. iia) A step of baking the coating film to form a baked coating film, iiia) A step of passing the baked coating film through a mask and exposing it with EUV or electron beam radiation to form exposed and unexposed regions. iva) Optional post-exposure bake step, va) A step of developing and removing unexposed areas using an organic solvent-based developer to form a negative image pattern in the coated photoresist on the substrate. via) The step of etching the substrate with plasma or a chemical etching agent using the negative image pattern as a mask to form a negative image in the substrate, The method includes the above.

[0080] In one aspect of this embodiment, process step iva) is not optional. In another aspect of this embodiment, the organic solvent developer in step va) is n-butyl acetate at room temperature.

[0081] Negative type chemically amplified photoresist composition By using such materials described herein, another aspect of the present invention is a negative chemically amplified EUV or electron beam photoresist composition, 1c) Any one of the compounds of the present invention having structures (I), (Ia), (Ib), and (Ic) described herein, 2c) A photoresist resin soluble in aqueous base that undergoes chemical amplification and crosslinking in the presence of a photogenerating acid. 3c) Optional crosslinking component, 4c) Optional acid quenching component, 5c) Organic spin coating solvent, This is a negative-type chemically amplified EUV or electron beam photoresist composition containing [the specified element].

[0082] In yet another aspect of this embodiment, the optional acid quencher component is present, which may be selected from the appropriate materials described herein. In yet another aspect of this embodiment, the organic spin coating solvent may be selected from any one of the organic spin coating solvents described herein, or a mixture of at least two such solvents.

[0083] By using such materials described herein, another aspect of the present invention is a negative chemically amplified EUV or electron beam photoresist composition, 1d) Compounds of structure (I), However, R1, R2, R 1a and R 2a R1, R2, R 1a and R 2a At least two of these are independently selected from nitro, cyano, and alkylsulfonyl, and X - pK is less than 0 a It is an anion of an acid that has,

[0084] [ka] 2d) A photoresist resin soluble in aqueous base that undergoes chemical amplification and crosslinking in the presence of a photogenerating acid. 3d) Optional crosslinking component, 4d) Optional acid quenching component, 5d) Organic spin coating solvent, This is a negative-type chemically amplified EUV or electron beam photoresist composition containing [the specified element].

[0085] In yet another aspect of this embodiment, the optional acid quencher component is present, which may be selected from the appropriate materials described herein. In yet another aspect of this embodiment, the organic spin coating solvent may be selected from any one of the organic spin coating solvents described herein, or a mixture of at least two such solvents.

[0086] By using such materials described herein, another aspect of the present invention is a negative chemically amplified EUV or electron beam photoresist composition, 1e) Compounds of structure (I), However, R1, R2, R 1a and R 2a R1, R2, R 1a and R 2a At least two of these are independently selected from nitro, cyano, and alkylsulfonyl, and X - pK is less than 0 a It is an anion of an acid that possesses the following properties;

[0087] [ka] 2e) A photoresist resin soluble in aqueous base that undergoes chemical amplification and crosslinking in the presence of a photogenerating acid, 3e) crosslinking component, 4e) Optional acid quenching component, 5e) Organic spin coating solvents, This is a negative-type chemically amplified EUV or electron beam photoresist composition containing [the specified element].

[0088] In yet another aspect of this embodiment, the optional acid quencher component is present, which may be selected from the appropriate materials described herein. In yet another aspect of this embodiment, the organic spin coating solvent may be selected from any one of the organic spin coating solvents described herein, or a mixture of at least two such solvents.

[0089] By using such materials described herein, another aspect of the present invention is a negative chemically amplified EUV or electron beam photoresist composition, 1f) Compounds of structure (I), However, R1 and R 1a , or R2 and R 2a , or R 1a and R2, or R1 and R 2a These are independently selected from nitro, cyano, and alkylsulfonyl, and X - This does not include halides, tosylates, trifluoromethylsulfonates, tetrafluoroborates, aryl-substituted borates, hexafluorophosphates, hexafluoroarcenates, acetates, trifluoroacetates, methanesulfonates, C2-C20 linear unsubstituted alkyl sulfonates, naphthalene sulfonates, and / or camphor sulfonates;

[0090] [ka] 2f) A photoresist resin soluble in aqueous base that undergoes chemical amplification and crosslinking in the presence of a photogenerating acid. 3f) Optional crosslinking component, 4f) Optional acid quenching component, 5f) Organic spin coating solvent, This is a negative-type chemically amplified EUV or electron beam photoresist composition containing [the specified element].

[0091] In yet another aspect of this embodiment, the optional quencher component exists, which may be selected from the appropriate materials described herein. In yet another aspect of this embodiment, the organic spin-coating solvent may be selected from any one of the organic spin-coating solvents described herein or a mixture of at least two such solvents.

[0092] Method using negative chemically amplified photoresist Another aspect of the present invention is a method for forming a negative image on a substrate by EUV or electron beam exposure using a negative chemically amplified photoresist, the following steps from ib) to vib); ib) A step of coating a substrate with any one of the negative chemically amplified EUV photoresist compositions of the present invention described above to form a coating film. iib) A step of baking the coating film to form a baked coating film, iiib) A step of exposing the baked film region to EUV or electron beam radiation through a mask to form exposed and unexposed regions. ivb) Optional post-exposure bake step, vb) A step of developing and removing unexposed areas using an aqueous base or organic solvent-based developer to form a negative image pattern in the coated photoresist on the substrate. vib) A step of etching the substrate with plasma or a chemical etching agent using the negative image pattern as a mask to form a negative image in the substrate. The method includes the above.

[0093] In one aspect of this method, process step ivb) is not optional. In one aspect of this process step vb), the developer is an aqueous base; in one aspect of another aspect of this method, the developer is 0.26N TMAH at room temperature. In one aspect of another aspect of this method, in step vb), the developer is an organic solvent; in one aspect of another aspect of this method, the developer is n-butyl acetate at room temperature.

[0094] Composition containing crosslinkable molecular glass Another aspect of the present invention is a negative-type chemically amplified EUV or electron beam photoresist composition, 1g) Compound of structure (I), however, R1, R2, R 1a and R 2a R1, R2, R 1a and R 2a At least two of these are independently selected from nitro, cyano, and alkylsulfonyl, and X - pK is less than 0 a It is an anion of an acid that possesses the following properties;

[0095] [ka] A molecular glass compound comprising 3 to 5 crosslinkable moieties selected from oxiranes, oxetanes, or mixtures thereof, which are crosslinked under the influence of an acid formed by irradiation of component 1a) 2g), 3g) Optional acid quencher ingredients, 4g) Organic spin coating solvent, This is a negative-type chemically amplified EUV or electron beam photoresist composition containing [the specified element].

[0096] In one aspect of this embodiment, the molecular glass compound has structure (II).

[0097] [ka] Method using negative crosslinkable molecular glass Another aspect of the present invention is a method for forming a negative image on a negative-type photoresist by EUV or electron beam, comprising steps ic) to vic) using the composition comprising a molecular glass compound, ic) A step of forming a coating film by coating a substrate with the negative chemically amplified EUV photoresist or electron beam composition described above, which contains a molecular glass compound. iic) A step of baking the coating film to form a baked coating film, ii) A step of passing the baked coating film region through a mask and exposing it with EUV or electron beam radiation to form exposed and unexposed regions. IVC) Optional post-exposure bake step, vc) A step of developing and removing unexposed areas using an organic solvent-based developer to form a negative image pattern in the coated molecular glass on the substrate, vic) A step of etching the substrate with plasma or a chemical etching agent using the negative image pattern as a mask to form a negative image in the substrate. The method includes the above.

[0098] In addition, the EUV composition may further include surfactants, inorganic polymers; additives such as small molecules, inorganic molecules, surfactants, other photoacid generators, thermoacid generators, quenchers, curing agents, crosslinking agents, chain extenders, and similars; and additives selected from the group consisting of combinations of at least one of the above. [Examples]

[0099] Chemicals and Characterization Unless otherwise stated, all chemicals were purchased from Sigma-Aldrich Ltd. (3050 Spruce Street, St. Louis, 63103 Missouri) as the highest quality products, and were used as delivered, unless otherwise noted.

[0100] Characterization Method NMR spectra were recorded using a 400 MHz or 500 MHz Bruker Advance II+ spectrometer with a deuterated solvent from Sigma-Aldrich (Merck). Chemical shifts were recorded as d-values ​​(ppm) and calibrated according to the internal standard Si(OMe)4 (0.00 ppm).

[0101] [Table 2] JPEG2026509744000023.jpg248170TIFF2026509744000024.tif66170

[0102] Synthesis Example 1: Synthesis of bis(4-nitrophenyl)iodonium tetrafluoroborate (PAG-1)

[0103] [ka] Meta-chloroperoxybenzoic acid (mCPBA, CAS: 937-14-4, 3.8 g, 22 mmol) was dissolved in 100 mL of DCM and treated with 1-iodo-4-nitrobenzene (CAS: 636-98-6, 5.1 g, 20 mmol). Boron trifluoride etherate (CAS: 109-63-7, 7.1 g, 50 mmol) was added dropwise, and the mixture was stirred at room temperature for 1 hour. The mixture was then cooled to 0°C, and 4-nitrophenylboronic acid (CAS: 24067-17-2, 3.7 g, 22 mmol) was added in several batches, stirred at room temperature for 2 hours, and purified using a silica plug. The crude product was isolated by first eluting impurities with DCM, and then with DCM / methanol (20:1). The product fraction was concentrated, and tert-butyl methyl ether (MTBE) was added to precipitate it. The solid was washed twice with MTBE and then dried under vacuum to obtain bis(4-nitrophenyl)iodonium tetrafluoroborate in 36% yield (3.3 g).

[0104] 1H-NMR (500MHz, DMSO-d6): δ = 8.55 (d, J = 9.0 Hz, 4H), 8.34 (d, J = 9.0, 4H) ppm. 13 C-NMR (126MHz, DMSO-d6): δ = 150.1, 137.3, 126.9, 123.4, 49.1ppm. 19 F-NMR (377MHz, DMSO-d6): δ=-100.0,-146.2,-148.3ppm.

[0105] Synthesis Example 2: Synthesis of bis(4-nitrophenyl)iodonium 4,4,5,5,6,6-hexafluoro-1,3,2-dithiadinane-2-ide 1,1,3,3-tetraoxide (PAG-2)

[0106] [ka] Bis(4-nitrophenyl)iodonium tetrafluoroborate (1 g, 2.1 mmol) was dissolved in 150 mL of ethyl acetate and treated with 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonimide potassium salt (abcr, CAS: 588668-97-7, 0.87 g, 2.6 mmol), and the mixture was stirred at room temperature for 2 hours. The reaction mixture was washed with water (3 × 100 mL), dried over Na₂SO₄, filtered, and reduced in volume under vacuum to obtain 1.2 g (84%) of the product as a white solid.

[0107] 1 H-NMR (500MHz, DMSO-d6): δ = 8.55 (d, J = 9.0 Hz, 4H), 8.34 (d, J = 9.0, 4H) ppm.

[0108] 19 F-NMR (377MHz, DMSO-d6): δ=-119.5,-125.8 ppm.

[0109] Synthesis Example 3: Synthesis of bis(3-nitrophenyl)iodonium tetrafluoroborate (PAG-3)

[0110] [ka] The same procedure as in Synthesis Example 1 was followed using 1-iodo-3-nitrobenzene (CAS: 645-00-1) and 3-nitrophenylboronic acid (CAS: 13331-27-6). Yield: 25% (white solids). 1 H-NMR (500MHz, DMSO-d6): δ=9.29(t,J=1.9Hz,2H),8.74(dt,J=8.1,1.1Hz 2H),8.48(ddd,J=8.3,2.3,0.9Hz,2H),7.85(t,J=8.1Hz,2H)ppm.

[0111] Synthesis Example 4: Synthesis of bis(3-nitrophenyl)iodonium 4,4,5,5,6,6-hexafluoro-1,3,2-dithiadinane-2-ide 1,1,3,3-tetraoxide

[0112] [ka] Follow the same procedure as in Synthesis Example 2. Yield: 95% (white solids). 1 H-NMR (500MHz, DMSO-d6): δ=9.29(t,J=1.9Hz,2H),8.73(dt,J=8.0,1.3Hz 2H),8.48(ddd,J=8.3,2.3,0.9Hz,2H),7.85(t,J=8.1Hz,2H)ppm. 13 C-NMR (126MHz, DMSO-d6): δ = 148.9, 141.8, 133.4, 130.6, 127.5, 117.3ppm. 19 F-NMR (377MHz, DMSO-d6): δ=-119.5,-125.8ppm.

[0113] Synthesis Example 5: Synthesis of bis(2-nitrophenyl)iodonium tetrafluoroborate (PAG-5)

[0114] [ka] The same procedure as in Synthesis Example 1 was followed using 1-iodo-2-nitrobenzene (CAS: 609-73-4) and 2-nitrophenylboronic acid (CAS: 5570-19-4). Yield: 28% (white solids). 1 H-NMR (500MHz, DMSO-d6): δ=8.55(dd,J=8.1,1.6Hz,2H),8.29(dd,J=8.1,1.3Hz 2H),8.02(td,J=7.7,1.3Hz,2H),7.93(td,J=7.7,1.6Hz,2H)ppm.

[0115] Synthesis Example 6: Synthesis of bis(2-nitrophenyl)iodonium 4,4,5,5,6,6-hexafluoro-1,3,2-dithiadinane-2-ide 1,1,3,3-tetraoxide (PAG-6)

[0116] [ka] Follow the same procedure as in Synthesis Example 2. Yield: 98% (white solids). 1 H-NMR (500MHz, DMSO-d6): δ=8.55(dd,J=8.1,1.5Hz,2H),8.29(dd,J=7.9,1.3Hz 2H),8.02(td,J=7.8,1.2Hz,2H),7.93(td,J=7.7,1.6Hz,2H)ppm. 13 C-NMR (126MHz, DMSO-d6): δ=147.6,138.0,134.6,127.9,110.1ppm. 19 F-NMR (377MHz, DMSO-d6): δ=-119.5,-125.8ppm.

[0117] Synthesis Example 7: Synthesis of (3-nitrophenyl)(4-nitrophenyl)iodonium tetrafluoroborate PAG-7

[0118] [ka] The same procedure as in Synthesis Example 1 was followed using 1-iodo-4-nitrobenzene (CAS: 636-98-6) and 3-nitrophenylboronic acid (CAS: 13331-27-6). Yield: 29% (white solids). 1 H-NMR(500MHz,DMSO-d6):δ=9.28(t,J=2.01H),8.72(ddd,J=8.0,1.7,0.9Hz 1H),8.60-8.54(m,2H),8.48(ddd,J=8.3,2.3,0.9Hz,1H),8.37-8.31(m,2H),7.85(t,J=8.2Hz,1H)ppm.

[0119] Synthesis Example 8: Synthesis of (3-nitrophenyl)(4-nitrophenyl)iodonium 4,4,5,5,6,6-hexafluoro-1,3,2-dithiadinane-2-ide 1,1,3,3-tetraoxide PAG-8

[0120] [ka] Follow the same procedure as in Synthesis Example 2. Yield: 99% (white solids). 1 H-NMR(500MHz,DMSO-d6):δ=9.28(t,J=1.81H),8.72(dt,J=8.1,1.3Hz 1H),8.59-8.53(m,2H),8.52-8.44(m,1H),8.36-8.30(m,2H),7.85(td,J=8.2,1.1Hz,1H)ppm. 13 C-NMR (126MHz, DMSO-d6): δ=150.0,149.0,141.9,137.2,133.4,130.7,127.6,126.9,123.6,117.2ppm. 19 F-NMR (377MHz, DMSO-d6): δ=-119.5,-125.8ppm.

[0121] Synthesis Example 9: Synthesis of bis(4-cyanophenyl)iodonium tetrafluoroborate (PAG-9)

[0122] [ka] The same procedure as in Synthesis Example 1 was followed using 4-iodobenzonitrile (CAS: 3058-39-7) and (4-cyanophenyl)boronic acid (CAS: 126747-14-6). Yield: 30% (white solids). 1 H-NMR (500MHz, DMSO-d6): δ = 8.50-8.44 (m, 4H), 8.07-8.01 (m, 4H) ppm.

[0123] Synthesis Example 10: Synthesis of bis(4-cyanophenyl)iodonium 4,4,5,5,6,6-hexafluoro-1,3,2-dithiadinane-2-ide 1,1,3,3-tetraoxide

[0124] [ka] Follow the same procedure as in Synthesis Example 2. Yield: 99% (white solids). 1 H-NMR (500MHz, DMSO-d6): δ = 8.50-8.45 (m, 4H), 8.07-7.97 (m, 4H) ppm. 13 C-NMR (126MHz, DMSO-d6): δ = 136.5, 135.7, 122.0, 117.9, 115.5ppm. 19 F-NMR (377MHz, DMSO-d6): δ=-119.5,-125.8ppm. Synthesis Example 11: Synthesis of bis(2-methyl-5-nitrophenyl)iodonium bromide (PAG-11) (Scheme 1)

[0125] [ka] 4-nitrotoluene (7.70 g, 55.6 mmol, 2.6 equivalents; 30% excess) was dissolved in 30 ml of concentrated sulfuric acid (98%), and the stirred mixture was slowly heated to 55°C. Sodium metaperiodate (4.62 g, 21.4 mmol, 1.0 equivalent) was added in several portions over 2 hours while stirring and maintaining the given temperature. Stirring was continued for another 2 hours while maintaining the temperature at approximately 55°C, and then the mixture was cooled to room temperature. The cooled final reaction mixture was stopped by pouring it into a 400 mL beaker of crushed ice. All precipitates were filtered and removed, and the cold filtrate was extracted three times with diethyl ether to remove unreacted 4-nitrotoluene (3 × 125 ml; the ether extract was discarded). Potassium bromide (6.36 g, excess) was added to the remaining aqueous solution while stirring. The poorly water-soluble precipitated bis(2-methyl-5-nitrophenyl)iodonium bromide (C-1) was collected by filtration, thoroughly washed with cold water until the filtrate was neutral, and then air-dried in the dark to obtain a pale yellow powder (7.85 g, yield 76.6%); mp = 159°C (decomposition); 1 H NMR(400MHz,DMSO) δ=9.37,8.36,8.35,7.84,7.82,2.74; 13 C NMR (101MHz, DMSO) δ=148.78,146.54,132.26,131.93,127.25,120.79,25.29.

[0126] Synthesis Example 12: Synthesis of bis(2-methyl-5-nitrophenyl)iodonium tris(trifluoromethanesulfonyl)methanide (PAG-12) (Scheme 2)

[0127] [ka] The compound obtained in Example 11 (6.03 g, 12.6 mmol, 1.0 equivalent) was added to 400 mL of nitromethane, and then 100 mL of water and 6.23 g (13.8 mmol, 1.1 equivalents) of potassium tris(trifluoromethanesulfonyl)methanide were added, and the mixture was stirred overnight at room temperature. The water was then separated, and the organic solution was dried over anhydrous sodium sulfate. Finally, the nitromethane was removed under vacuum at 50°C to obtain the desired product, bis(2-methyl-5-nitrophenyl)iodonium tris(trifluoromethanesulfonyl)methanide (8.11 g, yield 79.5%); mp = 165°C; 1 H NMR(400MHz,MeOD) δ=9.27,9.26,8.44,8.42,7.84,7.82,2.81; 19 F NMR (377 MHz, MeOD) δ = -78.22; 13 C NMR (101MHz, MeOD) δ=149.99,148.27,133.79,133.02,128.77,126.17,122.94,119.69,119.46,116.46,83.83,25.81.

[0128] Synthesis Example 13: Synthesis of bis(3-nitrophenyl)iodonium bromide (PAG-13) (Scheme 3)

[0129] [ka] Nitrobenzene (14.20 g, 115.3 mmol, 2.6 equivalents; 30% excess) was dissolved in 60 ml of concentrated sulfuric acid (98%), and the stirred mixture was slowly heated to 55°C. Sodium metaperiodate (9.59 g, 44.4 mmol, 1 equivalent) was added in several portions over 2 hours while stirring and maintaining the given temperature. Stirring was continued for several more hours while maintaining the temperature at 55°C, and then the mixture was cooled to room temperature. The cooled final reaction mixture was stopped by pouring it into a beaker (600 mL) filled with crushed ice. All precipitates were filtered and removed, and the cold filtrate was extracted three times with diethyl ether to remove unreacted nitrobenzene (3 × 150 ml; the ether extract was discarded). Potassium bromide (13.2 g, excess) was added to the remaining aqueous solution while stirring. The precipitated bis(3-nitrophenyl)iodonium bromide (C-2) was collected by filtration, thoroughly washed with cold water until the filtrate was neutral, and then air-dried in the dark to obtain a pale yellow powder (15.82 g, yield 79.1%); 1 H NMR(400MHz,DMSO) δ=9.21,8.68,8.66,8.41,8.38,7.78,7.76,7.74; 13 C NMR (101MHz, DMSO) δ=148.59,141.42,132.81,130.20,126.72,120.15.

[0130] Synthesis Example 14: Synthesis of bis(3-nitrophenyl)iodonium tris(trifluoromethanesulfonyl)methanide (PAG-14) (Scheme 4)

[0131] [ka] The compound obtained in Synthesis Example 13 (5.30 g, 11.8 mmol, 1.0 equivalent) was added to 400 mL of nitromethane, and then 100 mL of water and 6.35 g (14.1 mmol, 1.2 equivalents) of potassium tris(trifluoromethanesulfonyl)methanide were added. The mixture was stirred overnight at room temperature. The water was then separated, and the organic solution was dried over anhydrous sodium sulfate. Finally, the nitromethane was removed under vacuum at 50°C to obtain the desired product, bis(3-nitrophenyl)iodonium tris(trifluoromethanesulfonyl)methanide (8.23 g, yield 89.5%); mp = 205°C (decomposition); 1 H NMR(400MHz,MeOD) δ=9.20,8.63,8.61,8.54,8.52,7.83,7.81,7.79; 19 F NMR (377 MHz, MeOD) δ = -78.14; 13 C NMR (101MHz, MeOD) δ=140.99,132.70,124.73,122.01,119.11,116.87,113.63,110.40,107.16,106.39.

[0132] Synthesis Example 15: Synthesis of bis(4-nitrophenyl)iodonium tetrafluoroborate (alternative synthesis PAG-1) (Scheme 5)

[0133] [ka] In a 400 mL volume EasyMax automatic reactor, meta-chloroperoxybenzoic acid (m-CPBA) (>70%, 16.95 g, 68.8 mmol, 1.1 eq) was dissolved in 200 mL of dichloromethane, and then 1-iodo-4-nitrobenzene (15.89 g, 62.52 mmol, 1.0 eq) was added. The solution changed to red. After stirring at room temperature for 30 minutes, boron trifluoride etherate BF3·Et2O (20.7 mL, 23.81 g, 164.4 mmol, 2.6 eq) was added to the reaction mixture using a syringe. Some precipitate formed on the inner wall of the reactor glass. The solution was then stirred vigorously for 2 hours and then cooled to 0 °C for approximately 30 minutes. 4-Nitrobenzeneboronic acid (12.08 g, 68.8 mmol, 1.1 eq) was added to the cold reaction mixture, stirred at 0 °C for 6 hours, and then equilibrated at room temperature overnight. The crude mixture was filtered off, and the crude product was washed three times with dichloromethane and five times with diethyl ether until the TLC test showed no trace amounts of reactants. The product was filtered off and dried in an air stream in a fume hood for two days to obtain bis(4-nitrophenyl)iodonium tetrafluoroborate as a gray powder (13.94 g, yield: 48.7%); mp = 134 °C; 1 1H NMR (400 MHz, DMSO) δ = 8.56, 8.54, 8.34, 8.32; 19 19F NMR (377 MHz, DMSO) δ = -148.17; 13 13C NMR (101 MHz, DMSO) δ = 149.72, 136.69, 126.58, 123.16.

[0134] Synthesis Example 16: Synthesis of bis(4-nitrophenyl)iodonium tris(trifluoromethane-sulfonyl)methanide (PAG-15) (Scheme 6)

[0135]

Chemical Structure

[0136] Synthesis Example 17: Synthesis of bis(4-cyanophenyl)iodonium tetrafluoroborate (Alternative Synthesis PAG-9) (Scheme 7)

[0137]

Chemical Structure

[0138] Synthesis Example 18: Synthesis of bis(4-cyanophenyl)iodonium tris(trifluoromethanesulfonyl)methanide (PAG-16) (Scheme 8)

[0139] [ka] The compound obtained in Synthesis Example 17 (3.55 g, 8.5 mmol, 1.0 equivalent) was added to 100 mL of nitromethane, and then 25 mL of water and 4.21 g (9.3 mmol, 1.1 equivalents) of potassium tris(trifluoromethanesulfonyl)methanide were added. The mixture was stirred overnight at room temperature. The water was then separated, and the organic solution was dried over anhydrous sodium sulfate. Finally, the nitromethane was removed under vacuum at 50°C to obtain the desired product, bis(4-cyanophenyl)iodonium tris(trifluoromethanesulfonyl)methanide (6.23 g, yield 98.8%); mp = 166°C; 1 H NMR(400MHz,MeOD) δ=8.37,8.35,7.88,7.86; 19 F NMR (377 MHz, MeOD) δ = -78.04; 13 C NMR (101MHz, MeOD) δ=137.37,136.39,126.32,123.08,120.28,119.84,117.86,117.72,116.60,84.04.

[0140] Synthesis Example 19: Synthesis of bis(4-cyanophenyl)iodonium 4,4,5,5,6,6-hexafluoro-1,3,2-dithiadinane-2-ide 1,1,3,3-tetraoxide (alternative synthesis PAG-10) (Scheme 9)

[0141] [ka] The compound obtained in Synthesis Example 18 (3.54 g, 8.47 mmol, 1.00 equivalent) was added to 100 mL of nitromethane, and then 25 mL of water and 3.15 g (9.52 mmol, 1.12 equivalents) of potassium cyclohexafluoropropane-1,3-bis(sulfonyl)imide were added. The mixture was stirred overnight at room temperature. The water was then separated, and the organic solution was dried over anhydrous sodium sulfate. Finally, the nitromethane was removed under vacuum at 50°C to obtain the desired product, bis(4-cyanophenyl)iodonium cyclohexafluoropropane-1,3-bis(sulfonyl)imide (4.20 g, yield 79.6%); mp=220o C; 1 H NMR(400MHz,DMSO) δ=8.44,8.42,7.98,7.96; 19 F NMR(377MHz) δ=-119.61,-125.81; 13 C NMR (101MHz, DMSO) δ=136.31,135.36,121.62,117.60,115.65,115.30,112.69,109.57,106.86.

[0142] Synthesis Example 20: Synthesis of bis(3-nitrophenyl)iodonium 4,4,5,5,6,6-hexafluoro-1,3,2-dithiadinane-2-ide 1,1,3,3-tetraoxide (alternative synthesis PAG-4) (Scheme 10)

[0143] [ka] The compound obtained in Synthesis Example 14 (5.00 g, 11.09 mmol, 1.00 equivalent) was added to 400 mL of nitromethane, and then 100 mL of water and 4.13 g (9.52 mmol, 1.12 equivalents) of potassium cyclohexafluoropropane-1,3-bis(sulfonyl)imide were added. The mixture was stirred overnight at room temperature. The water was then separated, and the organic solution was dried over anhydrous sodium sulfate. Finally, the nitromethane was removed under vacuum at 50°C to obtain the desired product, bis(3-nitrophenyl)iodonium cyclohexafluoropropane-1,3-bis(sulfonyl)imide (7.25 g, yield 98.6%); mp = 175°C; 1 H NMR(400MHz,MeOD) δ=9.20,8.65,8.63,8.53,8.50,7.83,7.81,7.79; 19 F NMR(377MHz,MeOD) δ=-120.99,-127.50; 13 C NMR (101MHz, MeOD) δ=150.41,142.29,134.21,131.52,128.55,117.16,115.74,114.22,110.93,108.21.

[0144] Synthesis Example 21: Synthesis of bis(4-nitrophenyl)iodonium 4,4,5,5,6,6-hexafluoro-1,3,2-dithiadinane-2-ide 1,1,3,3-tetraoxide (alternative synthesis 2) (Scheme 11)

[0145] [ka] The obtained compound C-3 (3.80 g, 8.30 mmol, 1.00 equivalent) was added to 200 mL of nitromethane, and then 50 mL of water and 3.09 g (9.33 mmol, 1.12 equivalents) of potassium cyclohexafluoropropane-1,3-bis(sulfonyl)imide were added, and the mixture was stirred overnight at room temperature. The water was then separated, and the organic solution was dried over anhydrous sodium sulfate. Finally, the nitromethane was removed under vacuum at 50°C to obtain the desired product, bis(4-nitrophenyl)iodonium cyclohexafluoropropane-1,3-bis(sulfonyl)imide (4.40 g, yield 79.9%); mp = 231°C; 1 H NMR(400MHz,DMSO) δ=8.56,8.54,8.33,8.31; 19 F NMR(377MHz,DMSO) δ=-119.55,-125.84; 13 C NMR (101MHz, DMSO) δ=149.65,136.86,126.48,123.05,115.45,112.48,109.39,106.67.

[0146] Lithography Example 1: Electron Beam Contrast Curve of Negatone Molecular Glass Resist The PAGs of Synthesis Examples 1, 8, and 10, as well as the iodonium-hydride diphenyliodonium 4,4,5,5,6,6-hexafluoro-1,3,2-dithiadinane-2-oid 1,1,3,3-tetraoxide (prepared from diphenyliodonium tetrafluoroborate in a manner similar to Synthesis Example 2), were compounded into a photoresist using the trifunctional epoxide 2,2',2''-[methylidinetris(4,1-phenyleneoxymethylene)]tris[oxirane](II) (prepared as described in the reference Shou Zhao, Xiangning Huang, Andrew J.Whelton, and Mahdi M.Abu-Omar, ACS Sustainable Chem.Eng. 2018, 6, 7600-7608; DOI:10.1021 / acssuschemeng.8b0044 (Non-Patent Document 18)).

[0147] [ka] 4 g of the epoxide was dissolved in 100 ml of ethyl lactate. 0.0536 g of PAG was dissolved in 4 ml of ethyl lactate and mixed with the epoxide solution, then stirred for at least 2 hours. This solution was then filtered through a 20 nm PTFE syringe filter to obtain a resist preparation. 3 mL of the resist preparation was deposited onto a 4-inch silicon wafer and spin-coated at 1,000 rpm using a Suss Microtec spin coater to obtain a film approximately 30 nm thick after a soft bake at 75°C for 300 seconds. The initial film thickness was determined using a DECTAC profilometer after scratching the photoresist film. These wafers were exposed using a Tescan SEM MIRA with an accelerating voltage of 20 keV and a beam intensity setting of 8. The exposed films were developed by immersion in n-butyl acetate for 3 minutes and then dried using a nitrogen stream. The residual film thickness in each region exposed to different doses was measured using the same profilometer, and the contrast curve was determined. 50% film retention rate (E 1 / 2) The dose at that time was as follows (Table 3). This table shows that the PAGs of the present invention having specific electron-withdrawing substituents exhibit unexpectedly high sensitivity to electron beams, and as a result, will also exhibit unexpectedly high sensitivity to EUV exposure. This is because in both cases, the generation of acid from the PAG proceeds by electron capture, and both EUV and electron beams generate secondary electrons that can be captured in this way.

[0148]

Table 3

[0149] Lithography Example 2: Electron Beam Contrast Curve of a Positive Tone Chemically Amplified Resist 5 g of a PGME solution with a 50% w / w solids content of a ternary copolymer (monomer ratio 6:2:2) consisting of hydroxystyrene, styrene, and t-butyl acrylate, having a molecular weight of approximately 10,000 daltons, was mixed with 130.8 mmol of PAG (cyclohexafluoropropane-1,3-bis(sulfonyl)imide salt of iodonium cation as described in Table 4) and 0.39 g of 0.1N triethanolamine in PGMEA. This solution was diluted with PGMEA to a total concentration of 9.12% w / w solids content (approximately 28.3 g PGMEA). Each bottle containing this solution was placed on a roller overnight, and then the solution was filtered through a 20 nm PTFE syringe filter to obtain a resist preparation. 3 mL of the resist formulation was deposited onto a 4-inch silicon wafer and spin-coated at 1,000 rpm using a Suss Microtec spin coater to obtain films with thicknesses ranging from 346 nm to 388 nm after a soft bake at 110°C for 90 seconds. The initial film thickness was determined using a DECTAC profilometer after scratching the photoresist film. These wafers were exposed using a Tescan SEM MIRA with an acceleration voltage of 20 keV and a beam intensity setting of 8. After exposure, these wafers were baked at 130°C for 90 seconds. The baked films were developed by immersion in a 2.38% w / w TMAH solution, washed with water, and dried with a nitrogen stream. The residual film thickness in each region exposed to different doses was measured using the same profilometer, and the contrast curves were determined. The open point dose E0 was as follows (Table 4):

[0150] [Table 4]

[0151] The above results demonstrate that the PAG of the present invention provides unexpectedly high sensitivity to positive-tone chemically amplified photoresists in electron beam and, consequently, EUV.

[0152] While the disclosed and claimed inventions have been described and explained with a certain degree of detail, it should be understood that this disclosure is merely illustrative, and that a person skilled in the art may rely on numerous variations in the conditions and order of each step without departing from the spirit and scope of the disclosed and claimed inventions.

Claims

1. A compound of structure (I), wherein R １ , R ２ , R １ａ and R ２ａ are independently selected from H, nitro, cyano and alkylsulfonyl, provided that at least two of R １ , R ２ , R １ａ and R ２ａ are independently selected from nitro, cyano and alkylsulfonyl, and X － is not a halide, tosylate, trifluoromethylsulfonate, tetrafluoroborate, aryl-substituted borate, hexafluorophosphate, hexafluoroarsenate, acetate, trifluoroacetate, methanesulfonate, C2-C20 linear unsubstituted alkylsulfonate, naphthalenesulfonate and / or camphorsulfonate, a compound. 【Chemistry 1】

2. A compound of structure (I), R １ and R １ａ , or R ２ and R ２ａ , or R １ａ and R ２ , or R １ and R ２ａ These are independently selected from nitro, cyano, and alkylsulfonyl, and X － This refers to compounds that are not halides, tosylates, trifluoromethylsulfonates, tetrafluoroborates, aryl-substituted borates, hexafluorophosphates, hexafluoroarcenates, acetates, trifluoroacetates, methanesulfonates, C2-C20 linear unsubstituted alkyl sulfonates, naphthalene sulfonates, and / or camphor sulfonates. 【Chemistry 2】

3. A compound according to claim 1 or 2, having structure (Ia). 【Transformation 3】

4. R １ and R １ａ The compound according to claim 3, wherein both are nitro.

5. R １ and R １ａ The compound according to claim 3, wherein both are cyano compounds.

6. R １ and R １ａ The compound according to claim 3, wherein both are alkylsulfonyl.

7. R １ It is nitro, R １ａ The compound according to claim 3, wherein is cyano.

8. R １ It is nitro, R １ａ The compound according to claim 3, wherein is an alkylsulfonyl.

9. R １ is alkylsulfonyl, R １ａ The compound according to claim 3, wherein is cyano.

10. A compound according to claim 1 or 2, having structure (Ib). 【Chemistry 4】

11. R ２ and R ２ａ The compound according to claim 10, wherein both are nitro.

12. R ２ and R ２ａ The compound according to claim 10, wherein both are cyano compounds.

13. R ２ and R ２ａ The compound according to claim 10, wherein both are alkylsulfonyl.

14. R ２ It is nitro, R ２ａ The compound according to claim 10, wherein is cyano.

15. R ２ It is nitro, R ２ａ The compound according to claim 10, wherein is an alkylsulfonyl.

16. R ２ is alkylsulfonyl, R ２ａ The compound according to claim 10, wherein is cyano.

17. A compound according to claim 1 or 2, having structure (Ic). 【Transformation 5】

18. R １ and R ２ａ The compound according to claim 17, wherein both are nitro.

19. R １ and R ２ａ The compound according to claim 17, wherein both are cyano compounds.

20. R １ and R ２ａ The compound according to claim 17, wherein both are alkylsulfonyl.

21. R １ It is nitro, R ２ａ The compound according to claim 17, wherein is cyano.

22. R １ It is nitro, R ２ａ The compound according to claim 17, wherein is an alkylsulfonyl.

23. R １ is alkylsulfonyl, R ２ａ The compound according to claim 17, wherein is cyano.

24. X － However, pK is less than 0 ａ A compound according to any one of claims 1 to 23, which is an anion of an acid having [a specific characteristic].

25. X － However, pK less than 1 ａ A compound according to any one of claims 1 to 23, which is an anion of an acid having [a specific characteristic].

26. X － However, the anion is a perfluorinated or partially fluorinated alkyl sulfonate having more than 3 carbon atoms, and the alkyl is linear, branched or cyclic; or the anion is a perfluorinated or partially fluorinated alkyl sulfonate having more than 3 carbon atoms, and the alkyl is -O-, -C(=O)- and -S(=O) ２ The compound according to any one of claims 1 to 23, which is a linear, branched, or cyclic alkyl group containing a heteroatom group selected from -.

27. X － The compound according to any one of claims 1 to 23, wherein the compound is antimony hexafluoride.

28. X － The compound according to any one of claims 1 to 23, wherein the compound is a methide or an imido perfluorinated superacid.

29. X － The compound according to any one of claims 1 to 23, wherein the compound is perfluorobutanesulfonate (PFBS) or hexafluoropropanesulfonate.

30. X － The compound according to any one of claims 1 to 23, wherein the compound is tris(perfluoroalkylsulfonyl)methide.

31. X － The compound according to any one of claims 1 to 23, wherein the compound is a bis(perfluoroalkylsulfonyl)imide anion.

32. X － The compound according to any one of claims 1 to 23, wherein the anion is selected from the group consisting of tris[(trifluoromethyl)sulfonyl]methide (C1), tris[(nonafluoro-n-butyl)sulfonyl]methide (C4), bis(trifluoromethanesulfonyl)imide anion (N1), bis(nonafluoro-n-butanesulfonyl)imide anion (N4), and cyclic 4,4,5,5,6,6-hexafluorodihydro-1,1,3,3-tetraoxide-4H-1,3,2-dithiazine (NC3). 【Transformation 6】

33. X － The compound according to any one of claims 1 to 23, wherein the compound is an aryl sulfonate fluoride that is partially or completely substituted with a substituent selected from fluorine or perfluoroalkyl.

34. X － However, the sulfonate moiety (-SO) connected to the polymer main chain by the linker group ３ － ) and the linker group is the -SO ３ － The compound according to any one of claims 1 to 23, which does not contain an aromatic ring directly bonded to the portion.

35. The aforementioned -SO ３ － The compound according to claim 34, wherein the portion is directly bonded to the polymer main chain via C1-C8 linear perfluoroalkylene linker groups.

36. The perfluoroalkylene linker group is difluoromethylene (-CF ２ -), tetrafluoroethylene (-CF ２ -CF ２ -), and hexafluoropropylene (-CF ２ -CF ２ -CF ２ A compound according to claim 35, selected from the group consisting of -).

37. The compound according to claim 36, wherein the linker group is a methylene moiety directly bonded to the sulfonate moiety, and the other end is bonded to the polymer directly or via a C1-C4 perfluoroalkylene moiety.

38. X － However, the perfluoroalkylamide moiety (-N(perfluoroalkyl)) is directly attached to the polymer main chain or by a linker group. － The compound according to any one of claims 1 to 23, wherein the linker group is selected from the group consisting of C1-C8 alkylene, C1-C8 perfluorinated alkylene, and C1-C8 partially fluorinated alkylene.

39. X － However, the diperfluoroalkyl carbide moiety (-C(perfluoroalkyl)) is directly attached to the polymer main chain or by a linker group. ２ － The compound according to any one of claims 1 to 23, wherein the linker group is selected from the group consisting of C1-C8 alkylene, C1-C8 perfluorinated alkylene, and C1-C8 partially fluorinated alkylene.

40. X － The compound according to any one of claims 1 to 23, wherein the compound is a polycyanosubstituted cyclopentadienyl anion.

41. The compound according to claim 40, wherein the polycyanosubstituted cyclopentadienyl anion is selected from the group consisting of pentacyanocyclopentadienyl anion, tetracyanomonocarboxylatecyclopentadienyl anion, and tetracyanomethoxycyclopentadienyl anion.

42. A positive-type chemically amplified EUV or electron beam photoresist composition, 1) A compound according to any one of claims 1 to 41, 2) A photoresist resin that releases a resin soluble in aqueous base after undergoing chemical amplification and deprotection catalyzed by a photogenerated acid, 3) Optional acid quenching component, 4) Organic spin coating solvents, A positive-type chemically amplified EUV or electron beam photoresist composition comprising:

43. A positive-type chemically amplified EUV or electron beam photoresist composition, 1a) A compound of structure (I), provided that R １ 、R ２ 、R １ａ and R ２ａ are, independently, selected from H, nitro, cyano and alkylsulfonyl, where R １ 、R ２ 、R １ａ and R ２ａ at least two of which are, independently, selected from nitro, cyano and alkylsulfonyl, and X － is the anion of an acid having a pK ａ less than 0; 【Transformation 7】 2a) A photoresist resin that releases a resin soluble in aqueous base after undergoing chemical amplification and deprotection catalyzed by a photogenerating acid, 3a) Optional acid quenching component, 4a) Organic spin coating solvent, A positive-type chemically amplified EUV or electron beam photoresist composition comprising:

44. A positive-type chemically amplified EUV or electron beam photoresist composition, 1b) A compound of structure (I), provided that R １ and R １ａ , or R ２ and R ２ａ , or R １ａ and R ２ , or R １ and R ２ａ are independently selected from nitro, cyano and alkylsulfonyl, and X － is not a halide, tosylate, trifluoromethylsulfonate, tetrafluoroborate, aryl-substituted borate, hexafluorophosphate, hexafluoroarsenate, acetate, trifluoroacetate, methanesulfonate, C2-C20 linear unsubstituted alkylsulfonate, naphthalenesulfonate and / or camphorsulfonate, and X － is the anion of an acid having a pKa less than 0; 【Transformation 8】 2b) A photoresist resin that releases a resin soluble in aqueous base after undergoing chemical amplification and deprotection catalyzed by a photogenerating acid. 3b) Optional acid quenching component, 4b) Organic spin coating solvents, A positive-type chemically amplified EUV or electron beam photoresist composition comprising:

45. A method for forming a positive image using a positive-type chemically amplified photoresist by EUV or electron beam exposure, the following steps i) to vi); i) A step of coating a substrate with a positive-type chemically amplified EUV or electron beam photoresist composition according to any one of claims 42 to 44 to form a coating film, ii) A step of baking the coating film to form a baked coating film, iii) The step of exposing the baked coating area to EUV or electron beam radiation through a mask to form exposed and unexposed areas, iv) Optional post-exposure bake step, v) Developing and removing the exposed area using an aqueous base developer to form a positive image pattern in the coated photoresist on the substrate. vi) Using the positive image pattern as a mask, etching the substrate with plasma or a chemical etching agent to form a positive image in the substrate. The method, including the method described above.

46. A method for forming a negative image using a positive-type chemically amplified photoresist by EUV or electron beam exposure, the following steps ia) to via); ia) A step of coating a substrate with a positive-type chemically amplified EUV or electron beam photoresist composition according to any one of claims 42 to 44 to form a coating film, ii) A step of baking the coating film to form a baked coating film, iiia) The step of exposing the baked coating area to EUV or electron beam radiation through a mask to form exposed and unexposed areas, iva) Optional post-exposure bake step, va) A step of developing and removing unexposed areas using an organic solvent-based developer to form a negative image pattern in the coated photoresist on the substrate. via) A step of etching the substrate with plasma or a chemical etching agent using the negative image pattern as a mask to form a negative image in the substrate. The method, including the method described above.

47. A negative-type chemically amplified EUV or electron beam photoresist composition, 1c) A compound according to any one of claims 1 to 41, 2c) A photoresist resin soluble in an aqueous base that undergoes chemical amplification and crosslinking in the presence of a photogenerating acid. 3c) Optional crosslinking component, 4c) Optional acid quenching component, 5c) Organic spin coating solvent, The negative-type chemically amplified EUV or electron beam photoresist composition comprising the above.

48. A negative-type chemically amplified EUV or electron beam photoresist composition, 1d) Compounds of structure (I), however, R １ , R ２ , R １ａ and R ２ａ R is independently selected from H, nitro, cyano, and alkylsulfonyl, where R １ , R ２ , R １ａ and R ２ａ At least two of these are independently selected from nitro, cyano, and alkylsulfonyl, and X － pK is less than 0 ａ It is an anion of an acid that has; 【Chemistry 9】 2d) A photoresist resin soluble in an aqueous base that undergoes chemically amplified crosslinking in the presence of a photogenerating acid, 3d) Optional crosslinking component, 4d) Optional acid quenching component, 5d) Organic spin coating solvent, The negative-type chemically amplified EUV or electron beam photoresist composition comprising the above.

49. A negative-type chemically amplified EUV or electron beam photoresist composition, 1e) Compounds of structure (I), however, R １ , R ２ , R １ａ and R ２ａ R is independently selected from H, nitro, cyano, and alkylsulfonyl, where R １ , R ２ , R １ａ and R ２ａ At least two of these are independently selected from nitro, cyano, and alkylsulfonyl, and X － pK is less than 0 ａ It is an anion of an acid that has; 【Chemistry 10】 2e) A photoresist resin soluble in an aqueous base that undergoes chemical amplification and crosslinking in the presence of a photogenerating acid. 3e) crosslinking component, 4e) Optional acid quenching component, 5e) Organic spin coating solvents, The negative-type chemically amplified EUV or electron beam photoresist composition comprising the above.

50. A negative-type chemically amplified EUV or electron beam photoresist composition, 1f) Compounds of structure (I), however, R １ and R １ａ , or R ２ and R ２ａ , or R １ａ and R ２ , or R １ and R ２ａ These are independently selected from nitro, cyano, and alkylsulfonyl, and X － This does not include halides, tosylates, trifluoromethylsulfonates, tetrafluoroborates, aryl-substituted borates, hexafluorophosphates, hexafluoroarcenates, acetates, trifluoroacetates, methanesulfonates, C2-C20 linear unsubstituted alkyl sulfonates, naphthalene sulfonates, and / or camphor sulfonates; 【Chemistry 11】 2f) A photoresist resin soluble in an aqueous base that undergoes chemical amplification and crosslinking in the presence of a photogenerating acid. 3f) Optional crosslinking component, 4f) Optional acid quenching component, 5f) Organic spin coating solvent, The negative-type chemically amplified EUV or electron beam photoresist composition comprising the above.

51. A method for forming a negative image using a negative-type photoresist by EUV or electron beam exposure, the following steps ib) to vib); ib) A step of coating a substrate with a negative chemically amplified EUV or electron beam photoresist composition according to any one of claims 47 to 50 to form a coating film, ii) A step of baking the coating film to form a baked coating film, iiib) The step of exposing the region of the baked coating film to EUV or electron beam radiation through a mask to form exposed and unexposed regions. ivb) Optional post-exposure bake step, vb) A step of developing and removing unexposed areas using an aqueous base or organic solvent-based developer to form a negative image pattern in the coated photoresist on the substrate. vib) A step of etching the substrate with plasma or a chemical etching agent using the negative image pattern as a mask to form a negative image in the substrate. The method, including the method described above.

52. A negative-type chemically amplified EUV or electron beam photoresist composition, 1 g) Compound of structure (I), however, R １ , R ２ , R １ａ and R ２ａ R is independently selected from H, nitro, cyano, and alkylsulfonyl, where R １ , R ２ , R １ａ and R ２ａ At least two of these are independently selected from nitro, cyano, and alkylsulfonyl, and X － pK is less than 0 ａ It is an anion of an acid that has; 【Chemistry 12】 A molecular glass compound comprising 3 to 5 crosslinkable moieties selected from oxiranes, oxetanes, or mixtures thereof, which are crosslinked under the influence of an acid formed by irradiation of component 1a) 2g), 3g) Optional acid quenching ingredients, 4g) Organic spin coating solvent, A negative-type chemically amplified EUV or electron beam photoresist composition comprising [the specified element].

53. The composition according to claim 52, wherein the molecular glass compound has structure (II). 【Chemistry 13】

54. A method for forming a negative image using a negative-type photoresist by EUV or electron beam exposure, comprising the following steps ic) to vic); ic) A step of forming a coating film by coating a substrate with the negative chemically amplified EUV photoresist or electron beam composition described in claim 52 or 53, iic) A step of baking the coating film to form a baked coating film, iii) The step of exposing the region of the baked coating film with EUV or electron beam radiation through a mask to form exposed and unexposed regions. IVC) Optional post-exposure bake step, vc) A step of developing and removing unexposed areas using an organic solvent-based developer to form a negative image pattern in the coated molecular glass on the substrate. (vic) A step of etching the substrate with plasma or a chemical etching agent using the negative image pattern as a mask to form a negative image in the substrate. The method, including the method described above.

55. Use of any one of the compounds described in claims 1 to 41 as a photoacid generator.

56. Use of the composition according to any one of claims 42-44, 47-50, 52, or 53 as a photoresist on a substrate.

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