Polyphenolethers as molecular glass material for molecular resists

Abstract

A compound of structure (1), wherein A is linking moiety where nA is either 0, where said linking moiety A' is not present, or nA is 1 and said linking moiety (A') is present and is either a single valence bond or a divalent moiety. R1, R2, R3 and R4 are individually selected from the group consisting of moieties having structures (i) and (ii), where * designates the attachment point of these moieties to structure (A), R5, R6, R7 and R8 are individually selected from a C-1 to C-10 linear alkyl, a C-3 to C-10 branched alkyl, a C-3 to C-12 alicyclic alkyl, an aryl, a heteroaryl and a halogen.

Description

AZ75295PC POLYPHENOLETHERS AS MOLECULAR GLASS MATERIAL FOR MOLECULAR RESISTS RELATED APPLICATIONS

[0001] The present application claims the benefit of priority of U.S. Provisional PatentApplication No. 63 / 653,327, filed May 30, 2024, the entire contents of which is incorporated herein by reference. FIELD

[0002] The disclosed and claimed subject matter relates to a chemically amplifiedorganic resist material that contains new polyphenolethers as molecular glasses whichare designed towards forming precise patterns on substrates such as silicon wafers usingUV, e-beam or EUV radiation of 13.5 nm wavelength, and processes for using the same.BACKGROUND

[0003] Chemically amplified resists are the dominant resist type used in 248 nm, 193nm dry, and 193 nm immersion lithography. In these chemically amplified resists, thesolubility change of the resist is split into two reactions. The first step is aphotoreaction, in which a photon is absorbed by a photoacid generator (PAG) which decomposes with formation of a photoacid. The photoacid then catalyzes a chemical reaction which leads to the solubility change of the photoresist, for example, making the exposed areas more soluble in a developer for the case of a positive-tone photoresist. The solubility change may be caused by a deprotection reaction of a group pendant from a polymer backbone, for example, an acetal-protected phenol or a tertiary alcohol ester of a carboxylic acid, which leads to the formation of a phenolic OH group or acarboxylic acid, rendering the polymer soluble in aqueous base developers or insolublein an organic solvent developer. These reactions often occur during a post exposure bake (PEB) step. Since the photoacid acts as a catalyst only and is not consumed in the reaction, it can catalyze many such reactions: the original photo-event is amplified bythe number of reactions catalyzed per acid - hence the name chemical amplification.

[0004] Commonly used PAGs include triphenylsulfonium and diphenyliodonium saltsof strong acids, including but not limited to perfluoroalkyl sulfonic acids, and theirderivatives. For the above-mentioned UV wavelengths, the photoacid formation occursvia absorption of a photon into one of the absorption bands of the PAG, transitioning it into an excited state which is unstable and decomposes into a radical and a radical cation, with the latter reacting further to generate the proton needed to form the catalytic 1AZ75295PC species. This mechanism has been described in some detail in the literature. [John L.Dektar and Nigel P. Hacker, J. Am. Chem. Soc. 1990, 112, 6004-6015]

[0005] The use of chemically amplified resists has been extended to Extreme UV(EUV) with a wavelength of 13.5 nm or a photon energy of 91.6 eV. At thiswavelength, the absorption of the photon leads to a primary ionization event in whichan electron is ejected from an atom at high energy. This electron then collides with other atoms, leading to further ionization events which generate secondary electrons. In this electron cascade the energy of the original photon is dissipated over a limited area around the original absorption event in the form of electron and positively chargedspecies (“holes”) as well as electronic and thermal excitations. The size of this area islimited by the path length of the primary and secondary electrons, which has been estimated to be of the order of 2-3 nanometers.

[0006] Several small molecules have been reported as potential resist materials.Among these are polyphenols in combination with glycoluril (Chem. Mater.2006, 18,3404-3411 and R. Soc. Open Sci. 8, 202132) which is a two-component system whichforms relatively big patterns of 50 nm and where smaller size could not be achieved.

[0007] Calixarenes alone and as additives have been used in Chemically amplified(CAR) resists alone and in combination with polymers (Proc. of SPIE Vol. 8679,867912 and J. Photopolym. Sci. Technol. 2008, 21, 443). These calixarenes arecompound mixtures with undefined composition; the main resist material is a polymerwhich has the same drawbacks stated above.

[0008] Extensive work has been done on small polyphenolic molecules fully orpartially substituted with polymerizable epoxy-groups. The studies from Henderson et. al. served as proof of principle for the use of small molecules as molecular resistmaterials for EUV lithography ("Methods of controlling cross-linking in negative-toneresists, "Proc. SPIE 9051, Advances in Patterning Materials and ProcessesXXXI,90510Q (27 March 2014); J. Vac. Sci. Technol. B 37, 011604 (2019); "Negative- tone molecular resists based on cationic polymerization," Proc.SPIE 7273, Advances in Resist Materials and Processing Technology XXVI, 72733E (1 April 2009) and "Base developable negative tone molecular resist based on epoxide cross-linking," Proc. SPIE 9425, Advances in Patterning Materials and Processes XXXII, 94251S (20 March 2015).

[0009] US 9152043 describes the epoxy-substituted compounds shown below (4-AP),2AZ75295PC(3-AP) and (2-AP) as crosslinker compounds for EUV resists which are nowcommercially available. Other fluorenyl-type compounds as crosslinkers for EUVlithography were developed and reported in non- and patent literature, MicroelectronicEngineering 86 (2009) 734–737; KR101600658; US 2014 / 0175343 A1. For instance,KR101600658 discloses “Chemical Formula 15,” which similarly to 2-AP only has twocrosslinking epoxy groups.DETAILED DESCRIPTION OF DRAWINGS

[0010] FIG. 1 illustrates the 1H-NMR Spectrum of EX01;

[0011] FIG. 2 illustrates the 1H-NMR Spectrum of EX02;

[0012] FIG. 3 illustrates the 1H-NMR Spectrum of EX03;

[0013] FIG. 4 illustrates the 1H-NMR Spectrum of EX04;

[0014] FIG. 5 illustrates the 1H-NMR Spectrum of EX05;

[0015] FIG. 6 illustrates the 1H-NMR Spectrum of EX06;

[0016] FIG. 7 illustrates the 1H-NMR Spectrum of EX07;

[0017] FIG. 8 illustrates the 1H-NMR Spectrum of EX08;3AZ75295PC

[0018] FIG. 9 illustrates the 1H-NMR Spectrum of EX09;

[0019] FIG. 10 illustrates the exposure response curves for comparative examplesComp EX01 and Comp EX02;

[0020] FIG. 11 illustrates the expanded view of exposure response curves forcomparative examples Comp EX01 and Comp EX02.

[0021] FIG. 12 illustrates the exposure response curves for photoresist compositioncontaining molecular glass compound EX01 and EX02;

[0022] FIG. 13 illustrates the exposure response curves for photoresist compositioncontaining molecular glass compound EX05 and EX07;

[0023] FIG. 14 illustrates the exposure response curve for photoresist compositioncontaining molecular glass compound EX06; and

[0024] FIG. 15 illustrates the exposure response curves for photoresist compositioncontaining molecular glass compound EX08 and EX09.SUMMARY OF INVENTION

[0025] This patent application introduces novel resist materials, tailored for advancedlithographic processes, specifically EUV lithography. The disclosed materials addressthe limitations of existing technologies described above by utilizing pure, small molecules with meticulous control over their molecular architecture and composition. Through this innovation, improved resolution, sensitivity, and LWR can be achieved, meeting the demanding requirements of the industry for manufacturing high- performance electronic and semiconductor devices.

[0026] It has been found that previously disclosed molecular glass compounds, asdisclosed in the Background section above, have problematic issues which arediscussed in more detail in the Example section. In summary, 4-AP is insoluble in ethyllactate, the most common and green solvent for EUV lithography and is also insolublein PGMEA. Compound 3-AP shows poor coating properties and slow photospeed.Compound 2-AP is insoluble in ethyl lactate and PGMEA. Additionally, Compound2-AP exhibits slow photospeed. Without being bond by theory, it is believed that thatthe poor performance of 2-AP is caused by this compound only having two cross-linkable functional groups. Based on what was found for 2-AP, other fluorenyl-typecompounds as crosslinkers for EUV / e-beam which only have two crosslinking groupssuch as “Chemical Formula 15” will also have this issue.

[0027] Specifically, without being bound by theory, it is believed molecular glass4AZ75295PCcrosslinking compounds with only two epoxy-groups have poor ability for crosslinkingand lead to linear-type polymers. These linear polymers lacking a dense crosslinkednetwork display poor performance (LER, LWR) and mechanical strength, which is contrary to the lithography industry’s needs. Thus, the problems to be solved by thecurrently disclosed and claimed matter is the lack non-polymeric resist materials whichsimultaneously have cross-linking ability to form non-linear polymers which are crosslinker molecules with precise molecular weight, compositional andstereochemical architecture which are high Tg crosslinker molecules, which also arecrosslinker molecules with good solubility in green solvents suitable for EUV and e-beam lithography.

[0028] This patent application pertains to the field of electronic and semiconductordevice manufacturing, specifically focusing on the photolithographic process used to create precise patterns on substrates such as silicon wafers. As device feature sizes continue to shrink, novel lithographic patterning processes are being developed,necessitating the use of advanced resist materials to meet the rigorous requirements forresolution, sensitivity, and line width roughness (LWR) in the industry.

[0029] Among these processes, extreme ultraviolet (EUV) lithography has emerged asthe leading technology for next-generation electronic and semiconductor device manufacturing. EUV lithography employs light with a wavelength of 13.5 nm to induce a chemical reaction in the lithographic process, enabling the formation of nano-sized patterns. Current photoresist technologies for EUV lithography primarily rely on a combination of photoacid generators (PAG) and polymeric chemically amplified resist (CAR) materials. However, these materials have reached their performance limits and are unable to meet the industry's targets for resolution, sensitivity, and LWR and more.

[0030] Given that the desired pattern sizes are now comparable to those of largerorganic molecules and polymers, it becomes evident that new resist materials must be based on pure, small molecules, offering precise control over the molecular architectureand composition of the resist to meet the industries demand for high performance resistmaterials.

[0031] Specifically the disclosed and claimed subject matter describes Fluorenyl-typecrosslinker compounds with epoxy-groups or oxetane groups as polymerizable groupswhich have spherical shape and spatial orientation of polymerizable groups, which are also single molecule crosslinker compounds with precise molecular weight, perfect 5AZ75295PC compositional and stereochemical control, and are also High Tg crosslinker molecules which simultaneously have great solubility in EUV lithography solvents such as n-butylacetate (nBA), Ethyl lactate (EL), and Propylene glycol monomethyl ether acetate(PGMEA).

[0032] One aspect of the disclosed and claimed subject matter pertains to novelpolyphenolethers, molecular glasses which have structure (A) wherein A’ is a linkingmoiety where nAis either 0, where said linking moiety A’ is not present, or nAis 1 andsaid linking moiety A’ is present and is either a single valent bond or a divalent moietyselected from the group consisting of a methylene moiety (-CH2-), a mono substituted methylene moiety (-CHR9-), a disubstituted methylene moiety (-CR9R10-), an oxymoiety (-O-), an amino moiety (-NR9-), a thio moiety (-S-), a sulfoxide moiety (-S(=O)-), a sulfone moiety (-S(=O)2-), a silyl moiety (-SiR9R10-), a phosphine moiety (-PR9-),a phosphine oxide moiety (-P(=O)R9-), where R9and R10are individually selected froma C-1 to C-10 linear alkyl, a C-3 to C-10 branched alkyl, a C-3 to C-12 alicyclic alkyl,an alkenyl (-CH=CH-R11) where R11 is a C-1 to C-10 linear alkyl, a C-3 to C-10branched alkyl, a C-3 to C-12 alicyclic alkyl, an aryl, a heteroaryl and e, f, g and h areindividually selected from an integer ranging from 0 to 2, R1, R2, R3and R4are individually selected from the group consisting of moieties having structures (i) and (ii), where ^designates the attachment point of these moieties to structure (A), a and b are independently 1 or 2, c and d are independently an integer ranging from 0 to 2, and where the sum of c and d is an integer ranging from 1 to 4, n and n’ are individuallyselected from an integer ranging from 1 to 5, m, m’ are individually selected from aninteger ranging from 1 to 5, R12 and R12’ are individually selected from H, a C-1 to C- 6 linear alkyl, and a C-1 to C-6 linear hydroxyalkylene (HO-alkylene-), and R5, R6, R7 and R8 are individually selected from a C-1 to C-10 linear alkyl, a C-3 to C-10 branched alkyl, a C-3 to C-12 alicyclic alkyl, an aryl, a heteroaryl and a halogen,and e, f, g and h are individually selected from an integer ranging from 0 to 2.6AZ75295PC

[0033] Another aspect of the disclosed and claimed subject matter is a negativechemically amplified EUV or e-beam photoresist composition comprising said novel polyphenolethers, molecular glasses which have structure (A). Yet another aspect ofthe disclosed and claimed subject matter is a process of forming negative image withthis photoresist. Yet another aspect of the disclosed and claimed subject matter is theuse of said compounds of structure (A) in photoresist compositions. DETAILED DESCRIPTION

[0034] It is to be understood that both the foregoing general description and thefollowing detailed description are illustrative and explanatory, and are not restrictive of the subject matter, as claimed. In this application, the use of the singular includes the plural, the word "a" or "an" means "at least one", and the use of "or" means "and / or," unless specifically stated otherwise. Furthermore, the use of the term "including," as well as other forms such as "includes" and "included," is not limiting. Also, terms such as "element" or "component" encompass both elements and components comprising one unit and elements or components that comprise more than one unit, unless specifically stated otherwise. As used herein, the conjunction "and" is intended to beinclusive and the conjunction "or" is not intended to be exclusive unless otherwiseindicated. For example, the phrase "or, alternatively" is intended to be exclusive. As used herein, the term "and / or" refers to any combination of the foregoing elements including using a single element.

[0035] The term “PAG,” unless otherwise described, refers to a photoacid generator thatcan generate acid (a.k.a. photoacid) under e-beam, deep UV or UV irradiation such as 200-300 nm, i-line, h-line, g-line and / or broadband irradiation and EUV radiation (13.5 nm).

[0036] The term C-1 to C-4 alkyl embodies methyl and C-2 to C-4 linear alkyls and C-3 to C-4 branched alkyl moieties, for example as follows: methyl(-CH3), ethyl (-CH2- CH3), n-propyl (-CH2-CH2-CH3), isopropyl (-CH(CH3)2, n-butyl (-CH2-CH2-CH2- 7AZ75295PC CH3), tert-butyl (-C(CH3)3), isobutyl (CH2-CH(CH3)2, 2-butyl (-CH(CH3)CH2-CH3).Similarly, the term C-1 to C-6 alkyl embodies methyl, C-2 to C-6 linear alkyls, C-3 toC-6 branched alkyls, C-4 to C-6 cycloalkyls (e.g., cyclopentyl, cyclohexyl etc) or C-5- C-8 alkylenecycloalkyls (e.g. -CH2-cyclohexyl, CH2-CH2-cyclopentyl etc.). Similarly,the term C-1 to C-8 alkyl embodies methyl, C-2 to C-8 linear alkyls, C-3 to C-8branched alkyls, C-4 to C-8 cycloalkyls (e.g., cyclopentyl, cyclohexyl etc) or C-5-C-8 alkylenecycloalkyls (e.g. -CH2-cyclohexyl, CH2-CH2-cyclopentyl etc.). Similarly, the terms C-1 to C-10 alkyl and C-1 to C-20 alkyl, encompass within their scope branched alkyls, linear alkyls, cyclic alkyls including multicyclic alkyls having higher numbers of carbons such as adamantyl, norbornyl and the like.

[0037] The term C-2 to C-8 alkylene embodies C-2 to C-8 linear alkylene moieties(e.g., ethylene, propylene etc.), 1,1-ethylene and C-3 to C-8 branched alkylene moieties(e.g., -CH(CH3)-, -CH(CH3)-CH2-, etc.).

[0038] The term C-2 to C-4 alkylene embodies C-2 to C-4 linear alkylene moieties,1,1-ethylene and C-3 to C-4 branched alkylene moieties.

[0039] The term C-2 to C-8 perfluoroalkylene embodies C-2 to C-8 linearperfluoroalkylene moieties, 1,1-perfluoroethylene and C-3 to C-8 branchedperfluoroalkylene moieties.

[0040] The term C-2 to C-4 perfluoroalkylene embodies C-2 to C-4 linearperfluoroalkylene moieties, 1,1-perfluoroethylene and C-3 to C-4 branchedperfluoroalkylene moieties.

[0041] The term alkylsulfonyl unless otherwise indicated encompasses C-1 to C-8 alkylmoieties, which in turn encompasses C-1 to C-8 linear alkyls, C-3 to C-8 branched alkyls, C-3 to C-8 cyclic alkyls and C-4 to C-8 alicyclic alkyls, attached to sulfonyl. Compounds

[0042] One aspect of the disclosed and claimed subject matter is a compound ofstructure (A), wherein A’is a linking moiety where nA is either 0, where said linkingmoiety A’ is not present, or nA is 1 and said linking moiety A’ is present and is either a single valent bond or a divalent moiety selected from the group consisting of a methylene moiety (-CH2-), a mono substituted methylene moiety (-CHR9-), a disubstituted methylene moiety (-CR9R10-), an oxy moiety (-O-), an amino moiety (- NR9-), a thio moiety (-S-), a sulfone moiety (-S(=O)2-), a sulfoxide moiety (-S(=O)-), a silyl moiety (-SiR9R10-), a phosphine moiety (-PR9-), a phosphine oxide moiety (- 8AZ75295PC P(=O)R9-), where R9 and R10 are individually selected from a C-1 to C-10 linear alkyl,a C-3 to C-10 branched alkyl, a C-3 to C-12 alicyclic alkyl, an alkenyl (-CH=CH-R11)where R11is a C-1 to C-10 linear alkyl, a C-3 to C-10 branched alkyl, a C-3 to C-12alicyclic alkyl, an aryl, a heteroaryl and e, f, g and h are individually selected from aninteger ranging from 0 to 2, R1, R2, R3 and R4 are individually selected from the groupconsisting of moieties having structures (i) and (ii), where ^ designates the attachmentpoint of these moieties to structure (A), a and b are independently 1 or 2, c and d are independently an integer ranging from 0 to 2, and where the sum of c and d is an integer ranging from 1 to 4, n and n’ are individually selected from an integer ranging from 1to 5, m, m’ are individually selected from an integer ranging from 1 to 5, R12 and R12’are individually selected from H, a C-1 to C-6 linear alkyl, and a C-1 to C-6 linear hydroxyalkylene (HO-alkylene-), and R5, R6, R7 and R8 are individually selected froma C-1 to C-10 linear alkyl, a C-3 to C-10 branched alkyl, a C-3 to C-12 alicyclic alkyl,an aryl, a heteroaryl and a halogen, and e, f, g and h are individually selected from an integer ranging from 0 to 2,

[0043] Another aspect of said disclosed and claimed compound of structure (A) iswhere it has it has structure (I) or structure (I-1), where R5a is selected from the groupconsisting of H, a C-1 to C-10 linear alkyl, a C-3 to C-10 branched alkyl, a C-3 to C-12 alicyclic alkyl, an aryl, a heteroaryl and a halogen.

[0044] Another aspect of said disclosed and claimed compound of structures (A), (I)9AZ75295PCand (I-1), is one wherein R1, R2, R3 and R4 have structure (i).

[0045] Another aspect of said disclosed and claimed compound of structures (A), (I)and (I-1), is one wherein R1, R2, R3 and R4 have structure (ii).

[0046] Another aspect of said disclosed and claimed compound of structures (A), (I)and (I-1), is one where it has structure (Ia) or structure (Ia-1), where R5a is selected fromthe group consisting of H, a C-1 to C-10 linear alkyl, a C-3 to C-10 branched alkyl, aC-3 to C-12 alicyclic alkyl, an aryl, a heteroaryl and a halogen.

[0047] Another aspect of said disclosed and claimed compound of structures (A), (I)and (I-1), is where it has structure (Ib) or structure (Ib-1), where R5a is selected fromthe group consisting of H, a C-1 to C-10 linear alkyl, a C-3 to C-10 branched alkyl, aC-3 to C-12 alicyclic alkyl, an aryl, a heteroaryl and a halogen.

[0048] Another aspect of said disclosed and claimed compound of structures (A), (I)and (I-1), is where it has structure (Ic) or structure (Ic-1), where R5a is selected from thegroup consisting of H, a C-1 to C-10 linear alkyl, a C-3 to C-10 branched alkyl, a C-3to C-12 alicyclic alkyl, an aryl, a heteroaryl and a halogen.

[0049] Another aspect of said disclosed and claimed compound of structures (A), (I)and (I-1), is where it has structure (Id) or structure (Id-1), where R5a is selected from10AZ75295PCthe group consisting of H, a C-1 to C-10 linear alkyl, a C-3 to C-10 branched alkyl, aC-3 to C-12 alicyclic alkyl, an aryl, a heteroaryl and a halogen, and where Riv and Riv’, are independently selected from H, a C-1 to C-10 linear alkyl, a C-3 to C-10 branchedalkyl, a C-3 to C-12 alicyclic alkyl.

[0050] Another aspect of said disclosed and claimed compound of structures (A), (I)and (I-1), is where it has structure (Ie) or structure (Ie-1), where R5a is selected from thegroup consisting of H, a C-1 to C-10 linear alkyl, a C-3 to C-10 branched alkyl, a C-3to C-12 alicyclic alkyl, an aryl, a heteroaryl and a halogen.

[0051] Another aspect of said disclosed and claimed compounds of structure (A), (I),(I-1), (Ia), (Ia-1), (Ib), (Ib-1), (Ic), (Ic-1), (Id), (Id-1), (Ie) or (Ie-1), is where these structures are ones wherein R1, R2, R3 and R4 have structure (ia).

[0052] Another aspect of said disclosed and claimed compounds of structure (A), (I),(I-1), (Ia), (Ia-1), (Ib), (Ib-1), (Ic), (Ic-1), (Id), (Id-1), (Ie) or (Ie-1), is where thesestructures are ones wherein R1, R2, R3 and R4 have structure (ib).

[0053] Another aspect of said disclosed and claimed compounds of structure (A), (I),(I-1), (Ia), (Ia-1), (Ib), (Ib-1), (Ic), (Ic-1), (Id), (Id-1), (Ie) or (Ie-1), is where thesestructures are ones wherein R1, R2, R3 and R4 have structure (ic).

[0054] Another aspect of said disclosed and claimed compounds of structure (A), (I),(I-1), (Ia), (Ia-1), (Ib), (Ib-1), (Ic), (Ic-1), (Id), (Id-1), (Ie) or (Ie-1), is where thesestructures are ones wherein R1, R2, R3 and R4 have structure (id).

[0055] Another aspect of said disclosed and claimed compounds of structure (A), (I),11AZ75295PC(I-1), (Ia), (Ia-1), (Ib), (Ib-1), (Ic), (Ic-1), (Id), (Id-1), (Ie) or (Ie-1), is where thesestructures are ones wherein R1, R2, R3 and R4 have structure (iia).

[0056] Another aspect of said disclosed and claimed compounds of structure (A), (I),(I-1), (Ia), (Ia-1), (Ib), (Ib-1), (Ic), (Ic-1), (Id), (Id-1), (Ie) or (Ie-1), is where thesestructures are ones wherein R1, R2, R3 and R4 have structure (iib).

[0057] Another aspect of said disclosed and claimed compounds of structure (I), (I-1),(Ia), (Ia-1), (Ib), (Ib-1), (Ic), (Ic-1), (Id), (Id-1), (Ie) or (Ie-1), and their embodimentswhere R1, R2, R3 and R4 are selected from structures (i), (ii), (ia), (ib), (ic), (id), (iia) and (iib) is one wherein R5ais H.

[0058] Another aspect of said disclosed and claimed compounds of structure (I), (I-1),(Ia), (Ia-1), (Ib), (Ib-1), (Ic), (Ic-1), (Id), (Id-1), (Ie) or (Ie-1), and their embodimentswhere R1, R2, R3and R4are selected from structures (i), (ii), (ia), (ib), (ic), (id), (iia) and (iib) is one wherein R5a is an aryl.

[0059] Another aspect of said disclosed and claimed compounds of structure (I), (I-1),(Ia), (Ia-1), (Ib), (Ib-1), (Ic), (Ic-1), (Id), (Id-1), (Ie) or (Ie-1), and their embodimentswhere R1, R2, R3 and R4 are selected from structures (i), (ii), (ia), (ib), (ic), (id), (iia)and (iib) is one wherein R5a is phenyl.

[0060] Another aspect of said disclosed and claimed compound of structure (A) iswhere it has structure (II) or structure (II-1), where R5a is selected from the groupconsisting of H, a C-1 to C-10 linear alkyl, a C-3 to C-10 branched alkyl, a C-3 to C-12 alicyclic alkyl, an aryl, a heteroaryl and a halogen.

[0061] Another aspect of said disclosed and claimed compound of structures (A), (II)12AZ75295PC and (II-1), is one wherein R1, R2, R3 and R4 have structure (i).

[0062] Another aspect of said disclosed and claimed compound of structures (A), (II)and (II-1), is one wherein R1, R2, R3and R4have structure (ii).

[0063] Another aspect of said disclosed and claimed compound of structures (A), (II)and (II-1), is one where it has structure (IIa) or structure (IIa-1), where R5a is selectedfrom the group consisting of H, a C-1 to C-10 linear alkyl, a C-3 to C-10 branchedalkyl, a C-3 to C-12 alicyclic alkyl, an aryl, a heteroaryl and a halogen.

[0064] Another aspect of said disclosed and claimed compound of structures (A), (II)and (II-1), is one where it has structure (IIb) or structure (IIb-1), where R5a is selectedfrom the group consisting of H, a C-1 to C-10 linear alkyl, a C-3 to C-10 branchedalkyl, a C-3 to C-12 alicyclic alkyl, an aryl, a heteroaryl and a halogen.

[0065] Another aspect of said disclosed and claimed compound of structures (A), (II)and (II-1), is one where it has structure (IIc) or structure (IIc-1), where R5ais selected from the group consisting of H, a C-1 to C-10 linear alkyl, a C-3 to C-10 branchedalkyl, a C-3 to C-12 alicyclic alkyl, an aryl, a heteroaryl and a halogen.

[0066] Another aspect of said disclosed and claimed compound of structures (A), (II)and (II-1), is one where it has structure (IId) or structure (IId-1), where R5a is selected from the group consisting of H, a C-1 to C-10 linear alkyl, a C-3 to C-10 branched 13AZ75295PCalkyl, a C-3 to C-12 alicyclic alkyl, an aryl, a heteroaryl and a halogen and where Rivand Riv’, are independently selected from H, a C-1 to C-10 linear alkyl, a C-3 to C-10branched alkyl, a C-3 to C-12 alicyclic alkyl.

[0067] Another aspect of said disclosed and claimed compound of structures (A), (II)and (II-1), is one where it has structure (IIe) or structure (IIe-1), where R5ais selected from the group consisting of H, a C-1 to C-10 linear alkyl, a C-3 to C-10 branchedalkyl, a C-3 to C-12 alicyclic alkyl, an aryl, a heteroaryl and a halogen.

[0068] Another aspect of said disclosed and claimed compounds of structure (A), (II),(II-1), (IIa), (IIa-1), (IIb), (IIb-1), (IIc), (IIc-1), (IId), (IId-1), (IIe) or (IIe-1), is wherethese structures are ones wherein R1, R2, R3 and R4 have structure (ia).

[0069] Another aspect of said disclosed and claimed compounds of structure (A), (II),(II-1), (IIa), (IIa-1), (IIb), (IIb-1), (IIc), (IIc-1), (IId), (IId-1), (IIe) or (IIe-1), is wherethese structures are ones wherein R1, R2, R3 and R4 have structure (ib).

[0070] Another aspect of said disclosed and claimed compounds of structure (A), (II),(II-1), (IIa), (IIa-1), (IIb), (IIb-1), (IIc), (IIc-1), (IId), (IId-1), (IIe) or (IIe-1), is wherethese structures are ones wherein R1, R2, R3 and R4 have structure (ic).

[0071] Another aspect of said disclosed and claimed compounds of structure (A), (II),(II-1), (IIa), (IIa-1), (IIb), (IIb-1), (IIc), (IIc-1), (IId), (IId-1), (IIe) or (IIe-1), is wherethese structures are ones wherein R1, R2, R3 and R4 have structure (id).

[0072] Another aspect of said disclosed and claimed compounds of structure (A), (II),(II-1), (IIa), (IIa-1), (IIb), (IIb-1), (IIc), (IIc-1), (IId), (IId-1), (IIe) or (IIe-1), is wherethese structures are ones wherein R1, R2, R3 and R4 have structure (iia).

[0073] Another aspect of said disclosed and claimed compounds of structure (A), (II),14AZ75295PC(II-1), (IIa), (IIa-1), (IIb), (IIb-1), (IIc), (IIc-1), (IId), (IId-1), (IIe) or (IIe-1), is wherethese structures are ones wherein R1, R2, R3 and R4 have structure (iib).

[0074] Another aspect of said disclosed and claimed compounds of structure (II), (II-1), (IIa), (IIa-1), (IIb), (IIb-1), (IIc), (IIc-1), (IId), (IId-1), (IIe) or (IIe-1), and theirembodiments where R1, R2, R3and R4are selected from structures (i), (ii), (ia), (ib),(ic), (id), (iia) and (iib) is one wherein R5a is H.

[0075] Another aspect of said disclosed and claimed compounds of structure (II), (II-1), (IIa), (IIa-1), (IIb), (IIb-1), (IIc), (IIc-1), (IId), (IId-1), (IIe) or (IIe-1), and theirembodiments where R1, R2, R3and R4are selected from structures (i), (ii), (ia), (ib),(ic), (id), (iia) and (iib) is one wherein R5a is an aryl.

[0076] Another aspect of said disclosed and claimed compounds of structure (II), (II-1), (IIa), (IIa-1), (IIb), (IIb-1), (IIc), (IIc-1), (IId), (IId-1), (IIe) or (IIe-1), and theirembodiments where R1, R2, R3 and R4 are selected from structures (i), (ii), (ia), (ib),(ic), (id), (iia) and (iib) is one wherein R5a is phenyl.

[0077] Another aspect of said disclosed and claimed compound of structure (A) iswhere it has structure (III) or structure (III-1), where R5a is selected from the groupconsisting of H, a C-1 to C-10 linear alkyl, a C-3 to C-10 branched alkyl, a C-3 to C-12 alicyclic alkyl, an aryl, a heteroaryl and a halogen.

[0078] Another aspect of said disclosed and claimed compound of structures (A), (III)and (III-1), is one wherein R1, R2, R3 and R4 have structure (i).

[0079] Another aspect of said disclosed and claimed compound of structures (A), (III)15AZ75295PCand (III-1), is one wherein R1, R2, R3 and R4 have structure (ii).

[0080] Another aspect of said disclosed and claimed compound of structures (A), (III)and (III-1), is one where it has structure (IIIa) or structure (IIIa-1), where R5a is selectedfrom the group consisting of H, a C-1 to C-10 linear alkyl, a C-3 to C-10 branchedalkyl, a C-3 to C-12 alicyclic alkyl, an aryl, a heteroaryl and a halogen.

[0081] Another aspect of said disclosed and claimed compound of structures (A), (III)and (III-1), is one where it has structure (IIIb) or structure (IIIb-1), where R5a is selectedfrom the group consisting of H, a C-1 to C-10 linear alkyl, a C-3 to C-10 branched

[0082] Another aspect of said disclosed and claimed compound of structures (A), (III)and (III-1), is one where it has structure (IIIc) or structure (IIIc-1), where R5a is selectedfrom the group consisting of H, a C-1 to C-10 linear alkyl, a C-3 to C-10 branchedalkyl, a C-3 to C-12 alicyclic alkyl, an aryl, a heteroaryl and a halogen.

[0083] Another aspect of said disclosed and claimed compound of structures (A), (III)and (III-1), is one where it has structure (IIId) or structure (IIId-1), where R5a is selectedfrom the group consisting of H, a C-1 to C-10 linear alkyl, a C-3 to C-10 branched16AZ75295PCalkyl, a C-3 to C-12 alicyclic alkyl, an aryl, a heteroaryl and a halogen and where Rivand Riv’, are independently selected from H, a C-1 to C-10 linear alkyl, a C-3 to C-10branched alkyl, a C-3 to C-12 alicyclic alkyl.

[0084] Another aspect of said disclosed and claimed compound of structures (A), (III)and (III-1), is one where it has structure (IIIa) or structure (IIIa-1), where R5a is selectedfrom the group consisting of H, a C-1 to C-10 linear alkyl, a C-3 to C-10 branchedalkyl, a C-3 to C-12 alicyclic alkyl, an aryl, a heteroaryl and a halogen.

[0085] Another aspect of said disclosed and claimed compounds of structure (A), (III),(III-1), (IIIa), (IIIa-1), (IIIb), (IIIb-1), (IIIc), (IIIc-1), (IIId), (IIId-1), (IIIe) or (IIIe-1),is where these structures are ones wherein R1, R2, R3and R4have structure (ia).

[0086] Another aspect of said disclosed and claimed compounds of structure (A), (III),(III-1), (IIIa), (IIIa-1), (IIIb), (IIIb-1), (IIIc), (IIIc-1), (IIId), (IIId-1), (IIIe) or (IIIe-1),is where these structures are ones wherein R1, R2, R3and R4have structure (ib).

[0087] Another aspect of said disclosed and claimed compounds of structure (A), (III),(III-1), (IIIa), (IIIa-1), (IIIb), (IIIb-1), (IIIc), (IIIc-1), (IIId), (IIId-1), (IIIe) or (IIIe-1),is where these structures are ones wherein R1, R2, R3and R4have structure (ic).

[0088] Another aspect of said disclosed and claimed compounds of structure (A), (III),(III-1), (IIIa), (IIIa-1), (IIIb), (IIIb-1), (IIIc), (IIIc-1), (IIId), (IIId-1), (IIIe) or (IIIe-1),is where these structures are ones wherein R1, R2, R3 and R4 have structure (id).

[0089] Another aspect of said disclosed and claimed compounds of structure (A), (III),(III-1), (IIIa), (IIIa-1), (IIIb), (IIIb-1), (IIIc), (IIIc-1), (IIId), (IIId-1), (IIIe) or (IIIe-1),17AZ75295PC is where these structures are ones wherein R1, R2, R3 and R4 have structure (id).

[0090] Another aspect of said disclosed and claimed compounds of structure (A), (III),(III-1), (IIIa), (IIIa-1), (IIIb), (IIIb-1), (IIIc), (IIIc-1), (IIId), (IIId-1), (IIIe) or (IIIe-1),is where these structures are ones wherein R1, R2, R3and R4have structure (iia).

[0091] Another aspect of said disclosed and claimed compounds of structure (A), (III),(III-1), (IIIa), (IIIa-1), (IIIb), (IIIb-1), (IIIc), (IIIc-1), (IIId), (IIId-1), (IIIe) or (IIIe-1),is where these structures are ones wherein R1, R2, R3and R4have structure (iib).

[0092] Another aspect of said disclosed and claimed compounds of structure (III), (III-1), (IIIa), (IIIa-1), (IIIb), (IIIb-1), (IIIc), (IIIc-1), (IIId), (IIId-1), (IIIe) or (IIIe-1) andtheir embodiments where R1, R2, R3and R4are selected from structures (i), (ii), (ia), (ib), (ic), (id), (iia) and (iib), is one wherein R5a is H.

[0093] Another aspect of said disclosed and claimed compounds of structure (III), (III-1), (IIIa), (IIIa-1), (IIIb), (IIIb-1), (IIIc), (IIIc-1), (IIId), (IIId-1), (IIIe) or (IIIe-1) andtheir embodiments where R1, R2, R3 and R4 are selected from structures (i), (ii), (ia), (ib), (ic), (id), (iia) and (iib), is one wherein R5a is an aryl.

[0094] Another aspect of said disclosed and claimed compounds of structure (III), (III-1), (IIIa), (IIIa-1), (IIIb), (IIIb-1), (IIIc), (IIIc-1), (IIId), (IIId-1), (IIIe) or (IIIe-1) andtheir embodiments where R1, R2, R3 and R4 are selected from structures (i), (ii), (ia), (ib), (ic), (id), (iia) and (iib), is one wherein R5ais phenyl.Structure (I) and (I-1) nA=0 where A’ is not present

[0095] More specific examples of the disclosed and claimed compounds havingstructure (Ia) and (Ia-1) where in structure (I) and (I-1) nA=0, where A’ is not present,which are shown as follows, and are a few non-limiting representative examples of thespecific structures which are covered for the disclosed and claimed compounds ofstructures (I) and (I-1), when nA=0 and consequently where the linking moiety A’ isnot present. 18AZ75295PCStructure (I) and (I-1) nA=1 where A’ is a direct valence bond

[0096] The structures which are shown as follows are a few non-limiting representativeexamples of the specific structures which are covered for the disclosed and claimedcompounds of structures (I) and (I-1), when nA=1 and where the linking moiety A’ is adirect valence bond and are substructures of structures (Ib) or (Ib-1).21AZ75295PC .Structure (I) and (I-1) nA=1 where A’ is a -O-

[0097] The structures which are shown as follows are a few non-limiting representativeexamples of the specific structures which are covered for the disclosed and claimedcompounds of structures (I) and (I-1), when nA=1 and where the linking moiety A’ is -O-, and are substructures of structures (Ic) or (Ic-1)24AZ75295PCStructure (I) and (I-1) nA=1 where A’ is a -CH2-

[0098] The structures which are shown as follows are a few non-limiting representative27AZ75295PC examples of the specific structures which are covered for the disclosed and claimedcompounds of structures (I) and (I-1), when nA=1 and where the linking moiety A’ is -CH2-, which are substructures of structures (Id) or (Id-1).28AZ75295PCStructure (I) and (I-1) nA=1 where A’ is a -S-

[0099] The structures which are shown as follows are a few non-limiting representativeexamples of the specific structures which are covered for the disclosed and claimedcompounds of structures (I) and (I-1), when nA=1 and where the linking moiety A’ is -S-, and are substructures of structures (Ie) or (1e-1).31AZ75295PCStructure (II) and (II-1) nA=0 where A’ is not present or when nA=1 and A’ is adirect valence bond, -O-, -CH2- or -S

[0100] The structures which are shown as follows are a few non-limiting representativeexamples for the disclosed and claimed compounds which have structure (II) and (II-1), when nA=0, where the linking moiety A’ is not present or where were nA=1 andlinking moiety A’ is present either as a direct valence bond, -O-, -CH2- or -S-, whichare respectively substructures of structures (IIa) or (IIa-1), structures (IIb) or (IIb-1), structures (IIc) or (IIc-1), structures (IId) or (IId-1), or structures (IIe) or (IIe-1):35AZ75295PCStructure (III) and (III-1) nA=0 where A’ is not present or when nA=1 and A’ is adirect valence bond, -O-, -CH2- or -S-,

[0101] The structures which are shown as follows are a few non-limiting representativeexamples for the disclosed and claimed compounds which have structure (III) and (III-1), when nA=0, where the linking moiety A’ is not present and where were nA=1 andand linking moiety A’ is present either as a direct valence bond, -O-, -CH2- or -S-,which are respectively substructures of structures (IIIa) or (IIIa-1), structures (IIIb) or (IIIb-1), structures (IIIc) or (IIIc-1), structures (IIId) or (IIId-1), or structures (IIIe) or (IIIe-1):37AZ75295PC

[0102] In another aspect of said disclosed and claimed compound of structures (A) it isone which is selected from the group consisting of structure (I), (I-1), (II), (II-1), (III)and (III-1). More specifically, said disclosed and claimed compounds of (A) is onewhich is selected from the group consisting of the any of the substructures of thecompounds having structures (I), (I-1), (II), (II-1), (III) and (III-1) as described herein.

[0103] In another aspect of said disclosed and claimed compound of structure (A) asdescribed herein is one which is selected from the group consisting of compounds ofstructure (I), (I-1), (II), and (II-1)). More specifically, said disclosed and claimedcompounds of (A) is one which is selected from the group consisting of the any of the substructures of the compounds having structures (I), (I-1), (II), and (II-1).

[0104] In another aspect of this disclosed and claimed compound, it is selected from acompound of structures (A) and any of its described substructures described herein, but also has the negative limitation that it excludes the following compound: 41AZ75295PCNegative Chemically Amplified Photoresist Compositions

[0105] Another aspect of the disclosed and claimed subject matter is a negativechemically amplified EUV or e-beam photoresist composition comprising thefollowing component:1a) a molecular glass component crosslinker which comprises at least one compoundof structure (A), or any one of its substructures described herein (“component A)”),2a) at least one photoacid generator (PAG) component (“component B)”),3a) an optional additional crosslinking component (“component C)”),4a) an optional acid quencher component (“component D)”),5a) an organic spin coating solvent (“component E)”).

[0106] Another aspect of the disclosed and claimed subject matter is a process offorming negative image with a negative photoresist by EUV or e beam exposure, comprising step i) to vi) i) coating the negative chemically amplified EUV photoresist or beam compositiondescribed herein on a substrate, to form a coated film,ii) baking said coated film to form a baked coated film,iii) exposing regions of the baked coated film through a mask with EUV or e-beamradiation, forming exposed and unexposed regions, iv) an optional post exposure baking step, v) developing away the unexposed regions with an organic solvent developer forming a negative image pattern in said coated photoresist on the substrate, vi) etching the substrate with a plasma or a chemical etchant using said negative image pattern as a mask, forming a negative image in the substrate.

[0107] For the disclosed and claimed negative chemically amplified EUV or e-beamphotoresist composition described above in addition to the disclosed and claimed compound the other components or optional component are described as follows: Component B): PAG

[0108] Component B) in said negative chemically amplified EUV or e-beamphotoresist composition is present in an amount from about 10 mol% to about 30 mol%42AZ75295PCcompared to the number of moles of Component A) said molecular glass crosslinkercomponent which comprises at least one compound of structure (A). In anotherembodiment it is present in an amount from about 15 mol% to about 30 mol%. Inanother embodiment it is present in an amount from about 15 mol% to about 25 mol%.In another embodiment it is present in an amount from about 16 mol% to about 24mol%.%. In another embodiment it is present in an amount from about 17 mol% toabout 23 mol%.%. In another embodiment it is present in an amount from about 18mol% to about 22 mol%.%. In another embodiment it is present in an amount about 20mol%.

[0109] Component B) these may include, for example, photoacid generators thatproduce acids by light (e.g., UV, Deep UV, EUV) or radiation (e-beam) preferably onesthat which produce or irradiation an acid with a very low pKa such as triflic acid, perfluoroalkylsulfonic acid, HSbF6, HAsF6as described in more detail as follows:

[0110] Acid generators component B) are preferably iodonium salts,tetrahydrothiophenium salts, sulfonium salts, it is selected from groups consisting of diazonium salts, and pyridinium salts, for example diphenyliodoniumtrifluoromethanesulfonate, diphenyliodonium nonafluoro-n- butanesulfonate,diphenyliodonium perfluoro-n-octanesulfonate, diphenyliodonium 2-bicyclonal [2.2.1] hepta-2-il-1,2,2-ethofluoronate bis(4-t-butyl phenyl) iodonium trifluoromethanesulfonate, bis(4-t-butyl phenyl) iodonium nonafluoro-n- butanesulfonate, bis(4-t-butyl phenyl) iodonium perfluoro-n-octanesulfonate, bis(4-t- butyl phenyl Cyclohexyl 2-oxocyclohexyl methylsulfonium trifluoromethanesulfonate, Dicyclohexyl 2-oxocyclohexylsulfonium trifluoromethanesulfonate, 2-oxocyclohexyl dimethylsulfonium trifluoromethanesulfonate, and so on.

[0111] Acid generators are preferably sulfonium salts, preferably triphenylsulfoniumsalts, and preferably expressed by the following structure (B).

[0112] In structure (B), Rb1 contains C-1 to C-6 alkyl, C-1 to C-6 alkoxy, C6-12 aryl, C-6 to C-12 arylthio, or C6-12 aryloxy, preferably methyl, ethyl, t-butyl, methoxy, ethoxy,43AZ75295PC phenylthio, or phenyloxy, more preferably, t-butyl, methoxy, ethoxy, phenylthio, or phenyloxy, nb1 is 0, 1, 2 or 3, independently for each occurrence.

[0113] It is a preferred form that all nb1s are 1. It is also preferable that all nb1s areidentical. The fact that all nb1s are 0 is also a good form. One nb1 is 3 and the othertwo nb1 is 0 is also a good form. Specific examples of cations in structure (B) are asfollows:

[0114] A- is a monovalent anion, examples of anions in structure (B) include forexample, hexafluoroantimonate ion, hexafluorophosphate ion, the following ions are represented by equations (BA1) through (BA4), preferably hexafluoroantimonic acid ions, ions represented by structure (BA1), or ions represented by equations (BA2).

[0115] The structure of (BA1) is as follows:

[0116] In structure (BA1), Rb5 is independently C1-6 fluorine substituted alkyl, C1-6fluorine substituted alkoxy, or C1-6 alkyl. For example, -CF3means that all hydrogen in methyl (C1) has been substituted with fluorine. In the disclosed and claimed subject matter, fluorine substitution means that some or all of the hydrogen present in the alkyl or in the alkyl portion of an alkoxy is substituted by fluorine, preferably all of which is substituted by fluorine.

[0117] Rb5 is preferably fluorinated or unsubstituted, methyl, ethyl, t-butyl, methoxy,ethoxy, or t-butoxy, preferably fluorosubstituted or non-substituted methyl. Rb5is preferably fluorine-substituted alkyl; more preferably -CF3. 44AZ75295PC

[0118] The following is a specific example of structure (BA1).

[0119] Another example of an anion is one of structure (BA2), as follows, where Rb6is C1-10 fluorine substituted alkyl, C1-6 fluorine substituted alkoxy, and C6-12 fluorine substituted aryl, C2-12 fluorine substituted acyl, C6-12 fluorine substituted alkoxyaryl, or C6-12 alkyl substituted aryl; preferably C1-10 fluorine substituted alkyl or C6-12alkyl substituted aryl. In Rb6 the alkyl or the alkyl portion is preferable to be linear orcyclic and is also preferably C1-6 fluorine substituted alkyl; more preferably C2-6 fluorine substituted alkyl.

[0120] The following are specific examples of equation (BA2):

[0121] Another example of an anion is one of structure (BA3), as follows, where Rb7is independently selected from C1-6 fluorosubstituted alkyl, C1-6 fluorosubstituted alkoxy, C6-12 fluorosubstituted aryl, C2-12 fluorine substituted acyl, or C6-12 fluorine substituted alkoxyaryl; preferably C2-6 fluorine substituted alkyl. Two Rb7s may be connected to each other to form a fluorine-substituted heteroring structure. The heteroring structure is preferably a saturated ring. The heteroring structure, including N and S, is preferably a monocyclic structure of 5 to 8; more preferably a five- membered or six-membered ring; more preferably a six-membered ring.

[0122] The following are specific examples of equation (BA3):45AZ75295PC

[0123] Another example of a suitable anion is one of structure (BA4), as follows, whereRb8is hydrogen, C1-6 alkyl, C1-6 alkoxy, or hydroxy; preferably hydrogen, methyl, ethyl, methoxy, or hydroxy; preferably hydrogen or hydroxy. Lbcan be methylene, ethylene, carbonyl, oxy or carbonyloxy; preferably ethylene or carbonyl. Ybcan beeither hydrogen or fluorine independently of each other; preferably 1 or more Yb isfluorine. Further, in structure (BA4), nb4 is an integer from 0 to 10; preferably 0, 1 or2. nb5 is an integer from 0 to 21; preferably 4, 5, or 6.

[0124] The following are specific examples of structure (BA4):

[0125] Component B) may be one or more type of photoacid generator, preferably twoor more, preferably two. In the preferred form, the (B) component consists of two types of photoacid generators. In component (B) when there are two components, the molarratio of the first photoacid generator and the second acid generator is in the range of0.1 to 9.0 where pKa (in H2O) of the photochemically released acid from the firstphotoacid generator is smaller than the pKa (in H2O) of the photochemically releasedacid from the second photoacid generator.Component C): Optional Additional Crosslinking Component

[0126] The EUV and e-beam compositions described herein intended for negative tonedevelopment with an organic solvent may additionally contain as an optional component crosslinkers. These material are multifunctional compounds containing a moiety which under the influence of photogenerated acid form crosslinks in the photoresist film.

[0127] Examples of such components are multifunctional alkyl and aryl epoxides,which form crosslinking through ring opening of epoxides or N-methoxymethylated melamine crosslinker derivatives, benzyl alcohol derivatives or vinyl cyclic acetal derivatives which form crosslinks through the formation of reactive carbocations (Polymers for Microelectronics ACS Symposium Series ACS, (1993), Chapter 1 Chemically Amplification Mechanisms for Microlithography, E. Reichmanis et al, 46AZ75295PC pages 3) and (Chemical Amplification Resists for Microlithography Adv Polymer Sci,Hiroshi Ito (2005) 172, page 37).

[0128] Other examples of optional additional crosslinking components are recentlydescribed monomolecular epoxide [C. Popescu; G. O'Callaghan; A. McClelland; J. Roth; T. Lada; T. Kudo; R. Dammel; M. Moinpour; Y. Cao; A. P. G. Robinson, Proc. SPIE 11612, Advances in Patterning Materials and Processes XXXVIII, 116120K (5 April 2021); doi: 10.1117 / 12.2583888], [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], [R. A. Lawson, C. T. Lee, C. L. Henderson,R. Whetsell, L. Tolbert, and Y. Wang, J. Vac. Sci. Technol. B, 25 (6), 2140 –2144 (2007).DOI 10.1116 / 1.2801885]. Component D): Optional Acid Quencher Component

[0129] The composition comprising the molecular glass crosslinker compounds ofstructure (A) of the disclosed and claimed subject matter may additionally contain an acid quencher component which may be either a non-photodecomposable acidquencher, a photodecomposable acid quencher or a mixture of the two type of acidquencher. When the acid quencher component Component D) is present it may rangefrom about 10 to about 40 mol% compared to the molar amount of Component A), themolecular glass crosslinker compounds of structure (A). In another embodiment itranges from about 20 to about 40 mol% compared to the molar amount of theComponent A) molecular glass crosslinker compounds of structure (A). In anotherembodiment it ranges from about 25 to about 40 mol% compared to the molar amountof Component A) the molecular glass crosslinker compounds of structure (A). Inanother embodiment it ranges from about 30 to about 40 mol% compared to the molaramount of component A), the molecular glass crosslinker compounds of structure (A).In another embodiment it ranges from about 31 to about 39 mol% compared to themolar amount of the PAG component. In another embodiment it ranges from about 32to about 38 mol% compared to the molar amount compared to the molar amount ofcomponent A), the molecular glass crosslinker compounds of structure (A). In anotherembodiment it ranges from about 33 to about 37 mol% compared to the molar amountof component A), the molecular glass crosslinker compounds of structure (A). Inanother embodiment it ranges from about 34 to about 36 mol% compared to the molaramount of component A), the molecular glass crosslinker compounds of structure (A).47AZ75295PCIn another embodiment it is about 35 mol% compared to the molar amount ofcomponent A), the molecular glass crosslinker compounds of structure (A).

[0130] Without being bound by theory, non-photodecomposable quencher have theeffect of suppressing the diffusion of acid generated in the exposed area and are thought to contribute to the improvement of resolution.

[0131] Without being bound by theory, photo-decomposable quenchers are alsomaterial when formulated into chemically amplified photoresist of suppressing the diffusion of acid in the radiation exposed area, but because they are photodecomposable the concentration of the quencher in the exposed area is lower than in the unexposed area than in the unexposed area, creating a greater contrast between the concentrationof quencher in unexposed and exposed areas which is thought to contribute further inthe improvement of resolution.

[0132] Photo-decomposable quenchers are different from the photo acid generatorcomponent (PAG) component. As a preferred form of the disclosed and claimedsubject matter, PAG are for instance onium salts of the conjugate base of very strongacid (a.k.a. anion). In a photoresist formulation photodecomposition of these oniumsalts releases in the areas exposed to radiation a very strong super acid released fromthe PAG (e.g., perfluoralkylsulfonic acid such as triflic acid which have a pka of ~ -6.85 as predicted by ACD / LABS*, also see above detailed description of PAG component). As a preferred from of the disclosed and claimed subject matter photodecomposition quencher are also onium salts of stronger conjugate bases (a.k.a. anions of weaker acids), which on irradiation releases a proton which protonates the conjugate base anion and thus removing this conjugate base as an acid quencher in the photoresist areas exposed to radiation.

[0133] An example of photo-decomposable quenchers are photosensitive onium salt(e.g., diaryliodonium, triarylsulfonium) of a weak acid such as an photosensitive oniumcarboxylate or a photosensitive onium sulfonate of a weaker sulfonic acid, where thephotodecomposition of the onium cation during lithographic exposure releasesrespectively converts a carboxylate anion to a free carboxylic acid, or converts thissulfonate anion into a weak sulfonic acid having a pKa of higher than -2 (as predictedby ACD / Labs*). Examples of such weak sulfonic are alkyl sulfonic acid (e.g., mesicacid, butylsulfonic acid), arylsulfonic acids (e.g., tosic acid, 4-ethylbenzenesulfonicacid) aminosulfonic acid (e.g., cyclamic acid) and the like. *(ACD / pKa software48AZ75295PC version 4.0 for Microsoft windows, Advanced Chemistry development Inc 8 King Street East, Suite 107, Toronto, Ontario Canada).

[0134] . These weak acids preferably have an acid dissociation constant pKa aspredicted by ACD / Labs* of -1.9 to 8 (preferably 1.5 to 5).

[0135] The photoreaction quencher consists of cations and anions, and illustrativeexamples of specific cations and anions of weak acids are as follows:49AZ75295PC

[0136] Component D), the acid quencher, may also be a non-photodecomposablequencher component in the disclosed and claimed composition containing the disclosedand claimed compound having structure (A) or any of its substructures described herein,if present, may be any suitable acid quenchers including amine compound amidecompouds or a mixture of amine and amide compounds or any other type of acidquencher with a pKafor its conjugated acid of at least 1 and up to 9, and having aboiling point above 100°C at atmospheric pressure or non-photolabile onium salts ofan acid having a pKa of at least -1.9 such as ammonium salts of carboxylic acids with apKa of at least 0.5 or weak sulfonic acids as described above with a pKa of at least -1.9.

[0137] The amine acid quenchers include, but are not limited to, C-1 to C-16 primaryaliphatic amine compound, C2-32 aromatic secondary aliphatic amine compound, C-3 to C-48 tertiary aliphatic amine compound, C6-30. Another examples are aminecompounds, are C-5 to C-30 heterocyclic amine compounds. Preferably selected fromthe group consisting of C-1 to C-16 primary aliphatic amine compound, C-2 to C-32secondary aliphatic amine compound, C-3 to C-48 tertiary aliphatic amine compound,C-6 to C-30 aromatic amine compound and C-5 to C-30 heterocyclic amine compoundsand amine compounds having structures (XIIa), (XIIb), (XIIc), (XIId), (XIIe), (XIIf),(XIIg), (XIIh), (XIIi) (XIIj), (XIIk) and (XIIl)or a mixture of compounds from this group; wherein Rb1is C-1 to C-20 saturated alkyl chain or a C-2 to C-20 unsaturated alkyl chain; Rb2, Rb3, Rb4, Rb5, Rb6, Rb7, Rb8, Rb9, Rb10, Rb11, Rb12 and Rb13 are independently selected from the group of H, and a C-1 to C-20 alkyl as shown below:

[0138] C1-16 primary aliphatic amine compound, C-2 to C-32 aromatic secondaryaliphatic amine compound, C-3 to C-48 tertiary aliphatic amine compound, C-6 to C-30. Another examples of amine compounds, are C-5 to C-30 heterocyclic aminecompounds.

[0139] Exemplified embodiments of the basic compound are preferably selected fromthe group consisting of C-1 to C-16 primary aliphatic amine compound, C-2 to C-32secondary aliphatic amine compound, C-3 to C-48 tertiary aliphatic amine compound,C-6 to C-30 aromatic amine compound and C-5 to C-30 heterocyclic amine compounds.

[0140] In one embodiment of the amine compound, where said component D) said acidquencher is present, it may be an amine or a mixture of amine compounds having aboiling point above 100°C, at atmospheric pressure, and which have a pKa of at least 1.50AZ75295PC Such acid quenchers include, but are not limited to, amine compounds having structures (XIIa), (XIIb), (XIIc), (XIId), (XIIe), (XIIf),(XIIg), (XIIh), (XIIi) (XIIj), (XIIk) and (XIIl)or a mixture of compounds from this group; wherein Rb1is C-1 to C-20 saturatedalkyl chain or a C-2 to C-20 unsaturated alkyl chain; Rb2, Rb3, Rb4, Rb5, Rb6, Rb7, Rb8,Rb9, Rb10, Rb11, Rb12 and Rb13 are independently selected from the group of H, and a C-1 to C-20 alkyl as shown below:

[0141] In one particular embodiment of Component D), when it is present, is wheresaid acid is a non-photo-decomposable onium salt such as tetraalkylammonium or 51AZ75295PC trialkylammonium salts of carboxylic acid. Specific non limiting examples are mono(tetraalkyl ammonium) of dicarboxylic acid, di(tetraalkyl ammonium) salts of dicarboxylic acid, mono(trialkyl ammonium) of dicarboxylic acid, or di(trialkyl ammonium) salts of dicarboxylic acid. Non-limiting examples of suitable dicarboxylic acid for these salts are oxalic acid, maleic acid, malonic acid, fumaric acid, phthalic acid and the like. Structure (XIIma) to (XIImd) gives a general structure for such materials wherein Rqa to Rqd are independently a C-4 to C-8 alkyl group, Rqe is a valence bond, an arylene moiety, a C-1 to C-4 alkylene moiety, an alkenyl moiety(- C(Rqf)=C(Rqg)-, wherein Rqf and Rqg are independently H or a C-1 to C-4 alkyl). Structure (XIIme) gives a specific example of such a material. (XIIma), (XIImb), (XIImc), (XIImd)(XIIme) Component E): Organic spin coating solvent

[0142] The organic spin coating solvent component in the disclosed and claimedcomposition containing the disclosed and claimed compound having structure (A) or anyof its substructures described herein, is any organic spin coating solvents suitable fordissolving the above-described EUV compositions include a glycol ether derivative such as ethyl cellosolve, methyl cellosolve, propylene glycol monomethyl ether (PGME), diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 52AZ75295PC dipropylene glycol dimethyl ether, propylene glycol n-propyl ether, or diethylene glycol dimethyl ether; a glycol ether ester derivative 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 di- basic acids such as diethyloxylate and diethylmalonate; dicarboxylates of glycols such as ethylene glycol diacetate and propylene glycol diacetate; and hydroxy carboxylates such as methyl lactate, ethyl lactate (EL), ethyl glycolate, and ethyl-3-hydroxy propionate; a ketone ester such as methyl pyruvate or ethyl pyruvate; an alkoxycarboxylic acid ester such as methyl 3-methoxypropionate, ethyl 3- ethoxypropionate, ethyl 2-hydroxy-2-methylpropionate, or methylethoxypropionate; a ketone derivative such as methyl ethyl ketone, acetyl acetone, cyclopentanone, cyclohexanone or 2-heptanone; a ketone ether derivative such as diacetone alcohol methyl ether; a ketone alcohol derivative such as acetol or diacetone alcohol; a ketal or acetal like 1,3 dioxalane and diethoxypropane; lactones such as butyrolactone; an amide derivative such as dimethylacetamide or dimethylformamide, anisole, and mixtures thereof. Preferred organic spin coating solvent are ethyl lactate, PGME, PGMEA and mixtures thereof.

[0143] Also, theses organic spin coating solvents may also be used as “organic solventdeveloper” for developing the negative photoresist compositions comprisingComponent A), said glass crosslinking compound of structure (A) after it is coated ona substrate and exposed through a mask to e-beam or EUV radiation as describedbelow, the unexposed regions of the coated film as delineated by the mask pattern areremovable by using development using these “organic solvent developers,” while theexposed regions of this coated film are crosslinked and not removable by this solvent development, forming a negative image. Preferred “organic solvent developer” are ethyl lactate, PGME, PGMEA, n-butyl acetate (BuAC). Other Optional components

[0144] Additionally, the EUV and e-beam compositions described herein, may furthercomprise additives selected from the group consisting of surfactants, inorganic- containing polymers; additives including small molecules, inorganic-containing molecules, surfactants, other photoacid generators, thermal acid generators, hardeners, cross-linkers, chain extenders, and the like; and combinations comprising at least one of the foregoing. 53AZ75295PC Preferred Composition Embodiments

[0145] In one aspect of the disclosed and claimed subject matter, it is a formulationwhich contains 1.0 to 1.5% w / w (preferentially 1.0 to 1.25% w / w) solution of solidcompounds in an organic spin coating solvent such as ethyl lactate, PGME, cyclohexanone or a mixture thereof.

[0146] The following are preferred solid components and their preferred ranges:

[0147] For component A), at least one claimed disclosed and claimed molecular glasscrosslinker of structure (A) or any of its substructures described herein wherein itcomprises 100 mol% compared to the other solid components.

[0148] For component B), at least one photoacid generator (PAG) as described herein.In one embodiment this is triarylsulfonium salt of a diaryiodonium salt PAG whichreleases upon exposure a superacid having a pKa smaller than -7, such as triflic acid, nonafluorobutanesulonic, acid, HAsF6or HSbF6, (as described in more detail in thesection on Component B), where this component is present in an amount from 15-25mol% compared to the number of moles of Component A) the molecular glasscomponent of structure (A). In another embodiment the formulation comprisespreferably about 20 mol%. In one preferred embodiment it is a triphenylsulfonium saltof a super acid. In another it is it triphenylsulfonium hexafluoroantimonate (PAG-1).

[0149] In this preferred embodiment Component C), the acid quencher component, asdescribed herein, is present in an amount from about 30 to about 40 mol% compared tothe molar amount of the PAG component. In one embodiment the amount is about 35mol%. In one embodiment the acid quencher component is at least onephotodecomposable acid quencher, as described herein, which is a triarylsulfonium ordiaryliodonium salt of a weak acid as described herein. In one embodiment it is a triphenylsulfonium salt of a weak sulfonic acid, as described herein. In oneembodiment it is triphenylsulfonium tosylate (Quencher-1). In one aspect of thisembodiment, it is preferred if Component E) said organic spin coating solvent isselected from ethyl lactate, PGMEA, PGME and mixtures thereof. In one particular embodiment the solvent is Ethyl lactate. 54AZ75295PC(Quencher 1) EXAMPLES

[0150] Reference will now be made to more specific embodiments of the presentdisclosure and experimental results that provide support for such embodiments. Theexamples are given below to more fully illustrate the disclosed subject matter and shouldnot be construed as limiting the disclosed subject matter in any way.

[0151] It will be apparent to those skilled in the art that various modifications andvariations can be made in the disclosed subject matter and specific examples providedherein without departing from the spirit or scope of the disclosed subject matter. Thus, itis intended that the disclosed subject matter, including the descriptions provided by the following examples, covers the modifications and variations of the disclosed subject matter that come within the scope of any claims and their equivalents. Chemicals and Characterization 7-dihydroxy-9H-fluoren-9-one, 97%, CAS: 42523-29-5 from abcr;Triphenylsulfonium hexafluoro antimonate (TPS-103) CAS 603-36-1 from Sigma-Aldrich; Triphenylsulfonium tosylate (TPS-1000) CAS 13891-29-7 from Alfa; Kr-17B Underlayer from AZ Electronic Materials (EMD Electronics); Phenol, for synthesis, CAS: 108-95-2 from Sigma-Aldrich; 2-Phenylphenole, 99%, CAS:90-43-7 from Sigma-Aldrich;2,2',7,7'-Tetrabromo-9,9'-spirobi[9H-fluorene], 97%, CAS: 128055-74-3 from abcr;4-Bromphenole, 99%, CAS:106-41-2 from Sigma-Aldrich; 2-Hydroxy-9-fluorenone, 97%, CAS: 6949-73-1 from abcr; Epibromhydrin 98%, CAS: 3132-64-7 from Sigma-Aldrich; 55AZ75295PC 2-(2-Bromoethyl)oxirane, 95%, CAS: 13287-42-8 from abcr; 3-(bromomethyl)-3-methyloxetane, CAS: 78385-26-9, from Sigma-Aldrich BBE; [3-(bromomethyl)-3-oxetanyl]methanol, CAS: 22633-44-9, from Sigma-Aldrich BBE; Caesium carbonate, reagent plus, CAS: 534-17-8, from Sigma-Aldrich;Tetra-n-butylammonium iodide, fro synthesis, CAS: 311-28-4, from Sigma Aldrich;N,N-Dimethylformamid, anhydrous 99.8%, CAS:64-12-2, from Sigma Aldrich; Methansulfonic acid, >99.0%, CAS: 75-75-2, Sigma-Aldrich; Sodium methoxide, reagent grade 95% powder, CAS: 124-41-4, Sigma-Aldrich; Copper(I) iodide, for synthesis, CAS: 7681-65-4, Sigma-Aldrich; 2,2’-((((9H-fluorene-9,9-diyl)bis(4,1- phenylene))bis(oxy))bis(methylene))bis(oxirane); CAS: 47758-37-2 (2-AP) was obtained from Merck KGaA;Tris(4-(oxiran-2-ylmethoxy)phenyl)methane (3-AP), CAS: 43224-82-4 was obtainedfrom ABClabtory (China); and Solvents for extraction and chromatography were purchased from Sigma-Aldrich in the highest purity available. Unless otherwise indicated all other chemical were obtain from Sigma-Aldrich. Application process conditions:Substrate : SiUL : KrF-17B, 64 nm FTBake : 180°C / 60sPR : Samples, 26nm FT, MRX-2002-27PAB : 80°C / 60sExposure : Canon / FPA-3000EX5, NA / Sigma=0.63 / 0.65Mask : Open frame 10x10PEB : 90°C / 60sDevelop : nBA single puddle, 30sCharacterization Methods

[0152] NMR spectra were recorded either on a 400 MHz or a 500 MHz BrukerAdvance II+ spectrometer using deuterated solvents from Sigma-Aldrich (Merck).Chemical shifts were reported as δ values (ppm) and were calibrated according toresidual solvent signal (CDCl3: 7.26 ppm; DMSO-d6: 2.50 ppm). Examples: 56AZ75295PC

[0153] The compounds for comparative making the Comparative Examples which hadstructures (2-AP), (3-AP) as shown below, were obtained commercially as indicatedabove. The compound (4-AP) was by synthesis as follows:Synthesis of compound Comp EX03 (4-AP)].

[0154] 4,4’-Dihydrobenzophenone (10.0 g, 46.7 mmol, 1.0 eq.) was dissolved in dryTHF (200 ml) and treated with Zn dust (7.32 g; 112 mmol, 2.4 eq). The mixture was cooled to -78 °C and treated with TiCl4 (10.6 g, 56.0 mmol, 1.2 eq.) in a dropwisemanner to keep the temperature below – 70 °C. After stirring for 1h at -78 °C, themixture was stirred 1h at room temperature and then at refluxing conditions for 16h. After cooling to room temperature, the mixture was carefully treated with aq. K2CO3solution (10% w / w; 200 ml) and extracted three times with ethyl acetate. The combinedorganics were dried of MgSO4, filtered and the solvent was evaporated. Purification by column chromatography (silica gel; heptane / ethyl acetate) gave 6.54 g (71%) of intermediate 1.

[0155] Intermediate 1 (8.79 g, 22.2 mmol) was dissolved in THF (350 ml) and treatedwith Pd / C (3.00 g, 5% w / w). The mixture stirred at room temperature under 1.013 bar H2-atmosphere for 72 h. After removal of all H2, the solvent was evaporated to yieldpure Intermediate 2 (8.80 g, 99%).

[0156] Intermediate 2 (5.73 g, 14.4 mmol, 1.0 eq.) and tetrabutylammonium iodine(531 mg, 1.44 mmol, 0.1 eq.) were dissolved in dry DMF (50 ml) at room temperature. Sodium hydride (60% w / w; 2.76 g, 69.0 mmol, 4.8 eq.) was added carefully in 5 equal portions over 30 min and the mixture was stirred at room temperature until gas evolution ceased. Epibromohydrin (11.8 g, 86.3 mmol, 6.0 eq.) was added carefully over 5 min and the mixture was stirred at room temperature for 30 min. Then the mixture was stirred at 50 °C for 18h. The mixture was cooled to room temperature, poured into water (500 ml) and extracted three times with ethyl acetate. The combined organic phases were washed 3 times with brine, dried over Na2SO4, filtered and the solvent was evaporated. The crude was subjected to column chromatography (silica, 57AZ75295PCcyclohexane / acetone) to yield Comp. Ex 03 (2.47 g, 28%).The identity of the substance was confirmed by1H NMR (500 MHz, DMSO-d6) δ 7.27 (d, J = 8.6 Hz, 8H), 6.67 (d, J = 8.8 Hz, 8H), 4.92 (s, 2H), 4.14 (dd, J = 11.3, 2.8Hz, 4H), 3.67 (dd, J = 11.3, 6.5 Hz, 4H), 3.24 – 3.13 (m, 4H), 2.77 (dd, J = 5.1, 4.3Hz, 4H), 2.62 (dd, J = 5.2, 2.6 Hz, 4H). Tg = 44.4 °C. The compound was insoluble inEL, PGMEA.Solubility testing of (2-AP), (3-AP) and (4-AP)

[0157] It was found that the compound (2-AP) was insoluble in the following spincasting solvents ethyl lactate and PGMEA, PGME, and mixtures of these solvent, andcould only be dissolved in a mixture of or PGMEA / cyclohexanone (Wt. ratio 50 / 50) ina concentration sufficient enough to spin coat a coating of sufficient thickness of about26 nm needed for lithographic evaluation. Thus, the inclusion of the undesirablesolvent, cyclohexanone, was required.

[0158] It was found that the compound (3-AP), was soluble in ethyl lactate, but as notedin Table 3 it had a low Tg compared to the Tg’s of compounds EX01 to EX10 as notedin Table 2.

[0159] It was found the compound (4-AP), was insoluble in the following spin castingsolvents ethyl lactate and PGMEA, PGME, cyclohexanone and mixtures of thesesolvent, which preclude them to be formulated in these spin casting solvent at a needed concentration to spin coat a coating of sufficient thickness of about 26 nm needed for lithographic evaluation.(4-AP) (3-AP)58AZ75295PC(2-AP) (Chemical Formula 15)

[0160] The following are the chemical structures of the disclosed and claimed glasscompounds EX01 to EX.10:59AZ75295PC Synthesis of EX01:

[0161] In A 250 mL round bottom flask equipped with mechanical stirrer, thermometerand condenser 2,7-dihydroxy-9-fluorenone (10.0 g, 47.2 mmol, 1.0 eq.) and phenol(44.4 g, 471 mmol, 10 eq.) were mixed with methane sulfonic acid (18.1 g, 189 mmol,4.0 eq.) and stirred at 80 °C for 18 h under argon atmosphere. Water was added andthe mixture was extracted with ethyl acetate. The combined organic phases was washedwith brine, dried over Na2SO4, filtered and the solvent was evaporated. The resultingsolid was purified by column chromatography (silica gel; heptane / ethyl acetate / ethanol)to give 17.7 g (98%) of EX01-OH.

[0162] The identity of the substance was confirmed by 1HNMR: (500 MHz, DMSO-d6) δ 9.27 (s, 2H), 9.27 (s, 2H), 7.47 (d, J = 8.2 Hz, 2H), 6.95 – 6.81 (m, 4H), 6.68 (dd,J = 8.2, 2.3 Hz, 2H), 6.66 – 6.49 (m, 6H).

[0163] In a 500ml 3-neck flask, equipped with a stir bar, reflux condenser, thermometerand, EX01-OH (17.7 g, 46.3 mmol, 1.0 eq), cesium carbonate (72.4 g, 222 mmol, 4.8eq) and tetrabutylammonium iodide (1.71 mg, 4.63 mmol, 0.1 eq) were treated withDMF (227 mL) Epibromohydrin (38.0 g, 278 mmol, 6.0 eq) was added and theobtained suspension was stirred at 50 °C for 18 h under argon atmosphere. Water wasadded to give a clear solution and the aqueous phase was extracted three times withethyl acetate. The combined organic phases were washed with brine, dried overNa2SO4, filtered and the solvent was evaporated. The resulting crude product waspurified by column chromatography to give 23.2 g (82.6%) of EX01.

[0164] The identity of the substance was confirmed by 1H NMR (500 MHz, DMSO-d6) δ 7.72 (d, J = 8.4 Hz, 2H), 7.02 (dt, J = 9.0, 2.4 Hz, 4H), 6.95 (dd, J = 8.4, 2.4 Hz,2H), 6.90 – 6.82 (m, 6H), 4.26 (td, J = 11.1, 2.7 Hz, 4H), 3.78 (ddd, J = 11.0, 6.5, 4.2Hz, 4H), 3.29 (dq, J = 6.6, 2.8 Hz, 4H), 2.81 (ddd, J = 5.4, 4.2, 1.4 Hz, 4H), 2.68 (ddd, J = 6.4, 5.1, 2.6 Hz, 4H). Tg= 33.2 °C. FIG.1 shows the1H-NMR Spectrum of EX01. 60AZ75295PC Synthesis of EX02

[0165] In A 100 mL round bottom flask equipped with mechanical stirrer, thermometerand condenser, 2,7-dihydroxy-9-fluorenone (10.0 g, 47.1 mmol, 1.0 eq.) and o-phenylphenol (80.2 g, 471 mmol, 10 eq.) were mixed with methane sulfonic acid (18.1g, 189 mmol, 4.0 eq.) and stirred at 80 °C for 19 h under argon atmosphere. Aftercooling to ambient temperature, water was added, and the mixture was extracted threetimes with ethyl acetate.

[0166] The combined organic phases were washed with brine, dried over Na2SO4,filtered, and the solvent was evaporated. The resulting solid was purified by columnchromatography (silica gel; heptane / ethyl acetate / ethanol) to give 10.97 g (43.5%) ofEX02-OH.

[0167] The identity of the substance was confirmed by 1H NMR (500 MHz, DMSO-d6) δ 9.51 (s, 2H), 9.32 (s, 2H), 7.50 (d, J = 8.1 Hz, 2H), 7.42 – 7.31 (m, 8H), 7.25 (t, J= 7.3 Hz, 2H), 7.01 (d, J = 2.4 Hz, 2H), 6.87 (dd, J = 8.4, 2.3 Hz, 2H), 6.82 (d, J = 8.5Hz, 2H), 6.76 (d, J = 2.2 Hz, 2H), 6.69 (dd, J = 8.1, 2.2 Hz, 2H).

[0168] In a 100 ml 3-neck flask, equipped with a stir bar, reflux condenser,thermometer, EX02-OH (3.81 g, 7.13 mmol, 1.0 eq), cesium carbonate (11.2 g, 34.2mmol, 4.8 eq) and tetrabutylammonium iodide (263 mg, 0.71 mmol, 0.1 eq) weretreated with DMF (35 mL). Epibromohydrin (5.86 g, 42.8 mmol, 6.0 eq) was addedand the mixture was stirred at 50 °C for 18 h under argon atmosphere. Water was addedand the aqueous phase was extracted three times with ethyl acetate. The combinedorganic phases were washed with brine, dried over Na2SO4, filtered and the solvent wasevaporated. The resulting solid was purified by column chromatography (silica gel,heptane / ethylacetate / ethanol) to give 3.0 g (55.5%) of EX02.

[0169] The identity of the substance was confirmed by 1H NMR (500 MHz, DMSO-d6) δ 7.73 (d, J = 8.3 Hz, 2H), 7.40 – 7.33 (m, 8H), 7.31 – 7.25 (m, 2H), 7.12 (dd, J =8.6, 2.6 Hz, 2H), 7.07 – 6.99 (m, 6H), 6.96 (dd, J = 8.3, 2.4 Hz, 2H), 4.30 (ddd, J =12.3, 10.0, 2.6 Hz, 4H), 3.84 (ddd, J = 20.3, 11.4, 6.2 Hz, 4H), 3.31 – 3.26 (m, 1H), 3.2561AZ75295PC– 3.20 (m, 2H), 2.79 (t, J = 4.7 Hz, 2H), 2.75 (dd, J = 5.2, 4.2 Hz, 2H), 2.67 (dd, J =5.1, 2.6 Hz, 2H), 2.61 (dd, J = 5.2, 2.6 Hz, 2H). Tg = 49.7 °C, FIG 2 show the 1H-NMRSpectrum of EX02. Synthesis of EX03

[0170] In a 500 mL round bottom flask equipped with stir bar, condenser 2,2',7,7'-Tetrabromo-9,9'-spiro[9H-fluorene] (5.90 g, 9.34 mmol, 1.0 eq.) was dissolved underargon atmosphere in a mixture of 118 mL DMF and 12 ml methanol. Sodiummethoxide (19.2 g, 355 mmol, 38.0 eq) was added while stirring. After 5 mincopper(I)iodide (1.78 g, 9.34 mmol, 1.0 eq) was added and the green suspension wasstirred at 120 °C for 18 h. After cooling to room temperature, water was added, and thesolution was acidified with 2 M HCl. The resulting crude product was collected byfiltration, washed with water, and dried under vacuum at 30 °C overnight. Purification of the crude product by column chromatography (silica gel, heptane / ethylacetate / ethanol) gives 3.8 g (93%) of EX03-OMe.

[0171] The identity of the substance was confirmed by 1H NMR (500 MHz, DMSO-d6) δ 7.82 (d, J = 8.4 Hz, 4H), 6.95 (dd, J = 8.4, 2.4 Hz, 4H), 6.05 (d, J = 2.4 Hz, 4H), 3.59 (s, 12H).

[0172] In a 500 mL 3-neck round bottom flask equipped with stir bar, thermometer,Septum, EX03-OMe (10.3 g; 23.6 mmol; 1.0 eq.) was dissolved in 150 mL drydichloromethane under argon atmosphere. After cooling to 0°C boron tribromide (24.8g, 9.40 mL, 99.1 mmol, 4.2 eq) was added dropwise while keeping the temperaturebelow 5 °C. After addition, stirring was continued for 18 h at room temperature.

[0173] The reaction was quenched by addition of 40 mL of saturated NaHCO3 and thendiluted with water. The formed precipitate was collected by filtration, washed withwater and dried in a vacuum oven at 30 °C for 14 h. The crude solid product waspurified by column chromatography (silica gel, heptane / ethanol / ethyl acetate) to give 8.9 g (99%) of EX03-OH.

[0174] The identity of the substance was confirmed by 1H NMR (500 MHz, DMSO-d6) δ 9.14 (s, 4H), 7.59 (d, J = 8.2 Hz, 4H), 6.71 (dd, J = 8.2, 2.2 Hz, 4H), 5.98 (d, J =2.2 Hz, 4H). 62AZ75295PC

[0175] In a 250ml 3-neck flask, equipped with a stir bar, reflux condenser,thermometer, EX03-OH (6.00 g, 15.8 mmol, 1.0 eq), cesium carbonate (24.7 g, 75.7mmol, 4.8 eq) and tetrabutylammonium iodide (583 mg, 1.58 mmol, 0.1 eq) weretreated with 72 mL DMF. Epibromohydrin (12.9 g, 95.6 mmol, 6.0 eq) was added andthe obtained suspension was stirred at 50 °C for 23 h under argon atmosphere. Waterwas added and the mixture heated to 45 °C. The warm suspension was filtered, and theprecipitate was washed with water. The solid was crystallized first from ethyl acetateand then from ethanol to give 6.04 g (63%) of EX03.

[0176] The identity of the substance was confirmed by 1H NMR (500 MHz, DMSO-d6) δ 7.82 (d, J = 8.4 Hz, 4H), 7.04 – 6.93 (m, 4H), 6.08 (d, J = 2.5 Hz, 4H), 4.15 (ddt,J = 11.2, 2.7, 1.4 Hz, 4H), 3.70 – 3.54 (m, 4H), 3.23 – 3.09 (m, 4H), 2.73 (t, J = 4.7 Hz,4H), 2.61 (dd, J = 5.2, 2.6 Hz, 4H). Tg = 55.0 °C, FIG.3 shows the1H-NMR Spectrum of EX03. Synthesis of EX04

[0177] In a 100ml 3-neck flask, equipped with a stir bar, reflux condenser,thermometer, EX03-OH (2.47 g, 6.49 mmol, 1.0 eq), cesium carbonate (10.2 g, 31.2mmol, 4.8 eq) and tetrabutylammonium iodide (239 mg, 0.65 mmol, 0.1 eq) weretreated with 30 mL DMF. 2-(2-Bromoethyl)oxiran (5.88 g, 38.9 mmol, 6.0 eq) wasadded and the obtained suspension was stirred at 50 °C for 18 h. Water was added andthe mixture extracted with ethyl acetate. The organic extracts were washed with water,then brine, dried of Na2SO4 and filtered. The crude product was obtained after removalof the solvent. Purification of the crude by column chromatography gives 3.10 g (72.3%) of EX04.

[0178] The identity of the substance was confirmed by 1H NMR (500 MHz, DMSO-d6) δ 7.81 (d, J = 8.4 Hz, 4H), 6.96 (dt, J = 8.5, 1.9 Hz, 4H), 6.07 (d, J = 2.2 Hz, 4H),3.90 (t, J = 6.3 Hz, 9H), 3.00 – 2.91 (m, 4H), 2.64 (t, J = 4.7 Hz, 4H), 2.45 – 2.41 (m,4H), 1.84 – 1.73 (m, 8H). FIG. 4 shows the 1H NMR of EXO4. Tg = 49.5 °C. Thecompound was soluble in EL, nBA, PGMEA. FIG. 4 shows the 1H-NMR Spectrum of63AZ75295PC EX04 Synthesis of EX05

[0179] In A 250 mL round bottom flask equipped with mechanical stirrer, thermometerand condenser 2-hydroxy-9H-fluoren-9-one (5.0 g, 25.5 mmol, 1.0 eq.) and phenol(23.9 g, 255 mmol, 10 eq.) were mixed with methane sulfonic acid (9.80 g, 102 mmol,4.0 eq.) and stirred at 80 °C for 20.5 h under argon atmosphere. Water was added andthe mixture was extracted with ethyl acetate. The organic phase was washed withwater, 1 M HCl, water and brine, dried over Na2SO4, filtered and the solventevaporated. The resulting solid was purified by column chromatography to give 8.83g (94.6%) of EX05-OH.

[0180] The identity of the compound was confirmed by 1H NMR (500 MHz, DMSO-d6) δ 9.50 (s, 1H), 9.27 (s, 2H), 7.72 – 7.67 (m, 1H), 7.65 (d, J = 8.2 Hz, 1H), 7.31 –7.24 (m, 2H), 7.15 (td, J = 7.4, 1.2 Hz, 1H), 6.90 – 6.83 (m, 4H), 6.75 (dd, J = 8.2, 2.2Hz, 1H), 6.70 (d, J = 2.2 Hz, 1H), 6.65 – 6.59 (m, 4H).

[0181] In a 100ml 3-neck flask, equipped with a stir bar, reflux condenser,thermometer, EX05-OH (3.88 g, 10.6 mmol, 1.0 eq), cesium carbonate (12.4 g, 38.1mmol, 3.6 eq) and tetrabutylammonium iodide (391 mg, 1.06 mmol, 0.1 eq) weresuspended in 50 mL DMF. Epibromohydrine (6.53 g, 47.7 mmol, 4.5 eq) was addedand the obtained suspension was stirred at 50 °C for 20 h. Water was added, and themixture extracted with ethyl acetate. The organic extracts were washed with water,then brine, dried of Na2SO4 and filtered. The crude product was obtained after removalof the solvent. Purification of the crude by column chromatography gives 4.28 g (75.6%) of EX05.

[0182] The identity of the substance was confirmed by 1H NMR (500 MHz, DMSO-d6) δ 7.81 (t, J = 8.0 Hz, 2H), 7.33 (t, J = 7.9 Hz, 2H), 7.22 (td, J = 7.3, 1.2 Hz, 1H),7.05 – 6.97 (m, 5H), 6.93 (d, J = 2.3 Hz, 1H), 6.88 – 6.80 (m, 4H), 4.30 (dd, J = 11.3,2.7 Hz, 1H), 4.25 (dd, J = 11.3, 2.7 Hz, 2H), 3.88 – 3.73 (m, 3H), 3.31 – 3.24 (m, 3H),64AZ75295PC2.84 – 2.78 (m, 3H), 2.69 (dd, J = 5.1, 2.7 Hz, 1H), 2.67 (dd, J = 5.1, 2.7 Hz, 2H). FIG.5 shows the 1H-NMR Spectrum of EX05, Tg = 27.6 °C. The compound was soluble inEL, nBA, PGMEA. Synthesis of EX06

[0183] In a 1000 mL 4-neck round bottom flask equipped with mechanical stirrer,condenser and thermometer, 2,7-dibromo-9-fluorenone (8.79 g, 26.0 mmol, 1.0 eq), 4-bromophenol (45.0 g, 260 mmol, 10.0 eq) and methane sulfonic acid (10.0 g, 104 mmol,4.0 eq.) were mixed and stirred at 70 °C for 4 h and additional 16 h at 100 °C undernitrogen atmosphere. After cooling down to room temperature methanol (600 ml) wasadded and the mixture was stirred for 1 h. The resulting precipitate was collected byfiltration, washed with cold methanol and dried under vacuum to give 14.3 g (85%) of EX06-Br.The identity of the substance was confirmed by 1H NMR (500 MHz, CDCl3) δ 7.65 (d,J = 8.1 Hz, 2H), 7.56 (dd, J = 8.1, 1.8 Hz, 2H), 7.34 (dd, J = 8.7, 2.4 Hz, 2H), 7.22 (d, J = 1.8 Hz, 2H), 7.12 (d, J = 8.8 Hz, 2H), 6.43 (d, J = 2.4 Hz, 2H).

[0184] In a 1 L 4-neck round bottom flask equipped with mechanical stirrer, condenserand thermometer EX06-Br (17.4 g, 26.9 mmol, 1.0 eq) was dissolved in DMF (322 mL)and methanol (32 mL) was added. Sodium methoxide (55.1 g, 1.02 mol, 38 eq) wasadded portion wise over 30 min. Then copper (I) iodide (5.11 g, 26.9 mmol, 1.0 eq)was added and the mixture was stirred at 120 °C for 18 h. Under cooling, water andthen 2 M HCl were added. The resulting precipitate was collected by filtration, washedwith water and dried in vacuum. This crude material was purified by columnchromatography to give 6.21 g (51%) of EX06-OMe as a colorless solid.

[0185] The identity of the substance was confirmed via 1H NMR (500 MHz, CDCl3) δ7.57 (dd, J = 8.3, 6.0 Hz, 2H), 7.23 – 7.09 (m, 4H), 6.87 (dt, J = 8.4, 2.9 Hz, 2H), 6.7665AZ75295PC (dt, J = 8.9, 4.3 Hz, 2H), 6.67 (d, J = 2.6 Hz, 2H), 3.70 (s, 6H), 3.52 (s, 6H).

[0186] In a 250 mL 4-neck round bottom flask equipped with stir bar and condenserEX06-OMe (6.20 g, 13.7 mmol, 1.0 eq) was dissolved in dichloromethane 20 mL underargon atmosphere. At 0 °C boron tribromide (5.72 mL, 15.1 g, 60.3 mmol, 4.4 eq) wasadded. After stirring overnight at RT the solution was poured into ice and the resultingprecipitate was collected by filtration. This crude material was purified by columnchromatography to give 4.55 g (84%) of EX06-OH as a colorless solid.

[0187] The identity of the substance was confirmed by 1H NMR (500 MHz, DMSO-d6) δ 9.31 (s, 2H), 8.91 (s, 2H), 7.58 (d, J = 8.2 Hz, 2H), 7.04 (dd, J = 8.9, 1.5 Hz, 2H),6.73 (dd, J = 8.3, 2.1 Hz, 2H), 6.61 (dd, J = 8.9, 2.7 Hz, 2H), 6.45 – 6.36 (m, 2H), 5.75– 5.72 (m, 2H).

[0188] In a 100ml 4-neck flask, equipped with a stir bar, reflux condenser,thermometer, EX06-OH (2.60 g, 6.56 mmol, 1.0 eq), cesium carbonate (10.3 g, 31.5mmol, 4.8 eq) and tetrabutylammonium iodide (242 mg, 0.66 mmol, 0.1 eq) weretreated with 33 mL dry DMF. Epibromohydrin (5.39 g, 39.4 mmol, 6.0 eq) was addedand the obtained suspension was stirred at 50 °C for 18 h. After cooling to roomtemperature, water and ethylacetate were added. After phase separation the organicphase was washed three times with brine. After that the aqueous phases were extractedtwo times with ethyl acetate. The combined organic phases were dried over Na2SO4,filtered and the solvent was evaporated. The resulting solid was purified by columnchromatography (silica gel, dichloromethane) to give 3.00 g (74%) of EX06.

[0189] The identity of the compound was confirmed by 1H NMR (500 MHz, DMSO-d6) δ 7.81 (dt, J = 8.4, 1.2 Hz, 2H), 7.23 (d, J = 8.9 Hz, 2H), 7.01 (dq, J = 8.6, 2.1 Hz,2H), 6.94 – 6.86 (m, 2H), 6.57 (td, J = 3.7, 2.3 Hz, 2H), 5.78 (q, J = 2.5 Hz, 2H), 4.22(dd, J = 11.2, 2.6 Hz, 2H), 4.02 (dd, J = 11.2, 2.8 Hz, 2H), 3.77 – 3.68 (m, 2H), 3.56(dd, J = 11.1, 6.4 Hz, 2H), 3.26 – 3.18 (m, 2H), 3.13 (M, 2H), 2.76 (dd, J = 5.1, 4.3 Hz,2H), 2.70 (t, J = 4.7 Hz, 2H), 2.64 (dd, J = 5.2, 2.6 Hz, 2H), 2.56 (dd, J = 5.1, 2.7 Hz,2H). Tg = 35.7 °C. The compound was soluble in EL, PGMEA and nBA. FIG. 6 showsthe1H-NMR Spectrum of EX06. 66AZ75295PC Synthesis of EX07

[0190] In a 100 ml 3-neck flask, equipped with a stir bar, reflux condenser,thermometer, EX05-OH (3.95 g, 10.8 mmol, 1.0 eq), cesium carbonate (12.6 g, 38.8mmol, 3.6 eq) and tetrabutylammonium iodide (400 mg, 1.08 mmol, 0.1 eq) weretreated with 52 mL DMF. 2-(2-bromoethyl)oxirane (7.33 g, 48.5 mmol, 4.5 eq) wasadded and the obtained suspension was stirred at 50 °C for 19 h. Water was added andthe mixture extracted with ethyl acetate. The organic extracts were washed with water,then brine, dried of Na2SO4 and filtered. The crude product was obtained after removalof the solvent. Purification of the crude by column chromatography gives 4.46 g (72%) of EX07.

[0191] The identity of the substance was confirmed by 1H NMR (500 MHz, DMSO-d6) δ 7.80 (t, J = 8.3 Hz, 2H), 7.37 – 7.29 (m, 2H), 7.21 (t, J = 7.5 Hz, 1H), 7.04 – 6.95(m, 5H), 6.89 (d, J = 2.3 Hz, 1H), 6.86 – 6.78 (m, 4H), 4.05 – 3.96 (m, 6H), 3.09 – 2.97(m, 3H), 2.71 (t, J = 4.7 Hz, 3H), 2.53 – 2.50 (m, 4H), 1.97 – 1.88 (m, 2H), 1.89 – 1.76(m, 3H). Tg = 8.21 °C. The compound was soluble in EL, nBA, PGMEA. FIG. 7 showsthe1H-NMR Spectrum of EX-07. Synthesis of EX08

[0192] In a 100 ml 3-neck flask, equipped with a stir bar, reflux condenser,thermometer, EX02-OH (3.00 g, 5.61 mmol, 1.0 eq), cesium carbonate (8.78 g, 26.9mmol, 4.8 eq) and tetrabutylammonium iodide (207 mg, 0.56 mmol, 0.1 eq) weretreated with DMF (27 mL). 3-(Bromomethyl)-3-methyloxetane (5.56 g, 33.7 mmol,6.0 eq) was added and the obtained suspension was stirred at 50 °C for 22 h under argon67AZ75295PCatmosphere. Water was added and the aqueous phase was extracted three times withethyl acetate. The combined organic phases were extracted with brine, dried overNa2SO4, filtered and the solvent was evaporated. The resulting solid was purified bycolumn chromatography (silica gel, heptane / ethyl acetate / ethanol) to give 4.19 g (86%) of EX02.

[0193] The identity of the substance was confirmed by 1H NMR (500 MHz, DMSO-d6) δ 7.74 (d, J = 8.3 Hz, 2H), 7.37 – 7.30 (m, 8H), 7.29 – 7.23 (m, 2H), 7.18 (dd, J =8.7, 2.5 Hz, 2H), 7.12 – 7.06 (m, 4H), 7.04 (d, J = 2.3 Hz, 2H), 6.99 (dd, J = 8.4, 2.3Hz, 2H), 4.47 (d, J = 5.8 Hz, 4H), 4.35 (d, J = 5.7 Hz, 4H), 4.28 (d, J = 5.8 Hz, 4H),4.17 (d, J = 5.7 Hz, 4H), 4.06 (s, 4H), 4.02 (s, 4H), 1.34 (s, 6H), 1.21 (s, 6H). Tg = 65.4°C. The compound was soluble in EL, nBA, PGMEA. FIG. 8 shows the 1H-NMRSpectrum of EX08. Synthesis of EX09

[0194] In a 100 ml 3-neck flask, equipped with a stir bar, reflux condenser,thermometer, EX02-OH (2.69 g, 5.03 mmol, 1.0 eq), cesium carbonate (7.87 g, 24.2mmol, 4.8 eq) and tetrabutylammonium iodide (186 mg, 0.50 mmol, 0.1 eq) weretreated with DMF (24 mL). [3-(Bromomethyl)-3-oxetanyl]methanol (5.47 g, 30.2mmol, 6.0 eq) was added and the obtained suspension was stirred at 50 °C for 20 hunder argon atmosphere. Water was added and the aqueous phase was extracted threetimes with ethyl acetate. The combined organic phases were extracted with brine, driedover Na2SO4, filtered and the solvent was evaporated. The resulting solid was purifiedby column chromatography (silica gel, heptane / ethyl acetate / ethanol) to give 3.82 g (81%) of EX09.

[0195] The identity of the substance was confirmed by 1H NMR (500 MHz, DMSO-d6) δ 7.74 (d, J = 8.4 Hz, 2H), 7.37 – 7.30 (m, 8H), 7.29 – 7.23 (m, 2H), 7.17 (dd, J =8.8, 2.5 Hz, 2H), 7.12 – 7.07 (m, 4H), 7.03 (d, J = 2.3 Hz, 2H), 6.99 (dd, J = 8.4, 2.3Hz, 2H), 4.97 (t, J = 5.4 Hz, 2H), 4.89 (t, J = 5.4 Hz, 2H), 4.41 (d, J = 5.9 Hz, 4H), 4.37 (d, J = 5.9 Hz, 4H), 4.29 (d, J = 5.9 Hz, 4H), 4.26 (d, J = 5.9 Hz, 4H), 4.14 (s, 4H), 4.12 68AZ75295PC (s, 4H), 3.69 (d, J = 5.3 Hz, 4H), 3.55 (d, J = 5.3 Hz, 4H). Tg = 117.7 °C. The compoundwas soluble in EL, nBA, PGMEA. FIG. 9 shows the 1H-NMR Spectrum of EX09.Synthesis of EX10

[0196] In a 100 ml 3-neck flask, equipped with a stir bar, reflux condenser,thermometer, EX02-OH (1.66 g, 3.11 mmol, 1.0 eq), cesium carbonate (4.86 g, 14.9mmol, 4.8 eq) and tetrabutylammonium iodide (115 mg, 0.31 mmol, 0.1 eq) weretreated with DMF (15 mL). {6-oxabicyclo[3.1.0]hexan-3-yl}methyl 4-methylbenzene-1-sulfonate (5.00 g, 18.6 mmol, 6.0 eq; prepared according to the known literatureknown procedures see below) was added and the obtained suspension was stirred at 50°C for 21 h under argon atmosphere. Water was added and the aqueous phase wasextracted three times with ethyl acetate. The combined organic phases were extractedwith brine, dried over Na2SO4, filtered and the solvent was evaporated. The resultingsolid was purified by column chromatography (silica gel, heptane / ethyl acetate / ethanol)to give 2.26 g (79%) of EX10.

[0197] The identity of the substance was confirmed by 1H NMR (500 MHz, DMSO-d6) δ 7.67 (d, J = 8.4 Hz, 2H), 7.39 – 7.30 (m, 15H), 7.29 – 7.25 (m, 3H), 7.12 – 7.07(m, 2H), 7.05 – 6.94 (m, 6H), 6.94 – 6.87 (m, 6H), 3.87 (dd, J = 17.4, 4.7 Hz, 13H),3.46 (s, 6H), 3.41 (s, 7H), 2.10 – 2.01 (m, 10H), 1.98 – 1.90 (m, 17H), 1.52 – 1.43 (m,3H), 1.43 – 1.34 (m, 4H) Tg = 82.1 °C. The compound was soluble in EL, nBA,PGMEA. Synthesis of 6-oxabicyclo[3.1.0]hexan-3-yl}methyl 4-methylbenzene-1-sulfonate

[0198] The bicyclic epoxy linker was synthesized according to literature knownprocedures: Chem. Ber.1981, 114, 346-358 and Bioorg. Med. Chem.2003, 11, 3633- 3639. To a solution of 3-cyclopenten-1-methanol (5.00 g, 51.0 mmol, 1.0 eq.) indichloromethane (50 ml) at 0 °C was added mCPBA (70 w%, 15.1 g, 61.1 mmol, 1.269AZ75295PCeq.) and the mixture was stirred for 19h while warming to room temperature. Thereaction mixture was filtered over Celite® and rinsed with dichloromethane. The filtrate was treated with aq. Na2S2O3solution (10 w%, 20ml) and stirred for 1 h at roomtemperature. The organic phase was separated, and the aqueous phase extracted threetimes with dichloromethane. The combined organic phases were dried over MgSO4, filtered and the solvent evaporated. This crude material was subjected to the next step without further purification. The crude material was dissolved in dichloromethane (50 ml) at 0 °C and treated with pyridine (30 ml) and pTsCl (12.6 g, 66.3 mmol, 1.3 eq.). The mixture was stirred at room temperature for 2 h, then diluted with dichloromethane (100 ml), washed with water, then brine, dried over Na2SO4and filtered. The solventwas evaporated, and the crude product was purified by column chromatography (silica,hexane / ethyl acetate) to give the pure product (70%, 9.56 g) as a mixture ofdiastereoisomers. The identity of the product was confirmed by 1H NMR.Major isomer: 1H NMR (500 MHz, DMSO-d6): 7.78 (d, J = 7.8 Hz, 2H), 7.48 (d, J =7.8 Hz, 2H), 3.97 (d, J = 5.35 Hz, 2H), 3.48 – 3.37 (m, 2H), 2.65 – 2.52 (m, 1H), 2.42(s, 3H) 1.92 – 1.68 (m, 4H),Photoresist Preparation and EvaluationPreparation of formulation with comparative compounds

[0199] It was attempted to prepare comparative formulation examples based on thecommercially available crosslinking compounds Comp EX01, Comp EX02 and CompEX03. The initially targeted comparative formulations were ones which employed thesame loading of the crosslinkers, the same PAG component and loading, the samequencher component and loading the same solvent component, as used as employed inthe corresponding formulations made with EX01 to EX10. Thus, it was attempted toprepare a formulation which contained 1.25% w / w of total solids in ethyl lactate, which in terms of molar rations containing 100 mol% of the crosslinker component, 20 mol% of the PAG component relative to the crosslinker and 35 mol% of the quenchercomponent relative to the crosslinker component. It was found that Comp Ex03 wasinsoluble in ethyl lactate, and PGMEA and could only be dissolved in the undesirablesolvent cyclohexanone. Comp Ex01 was also insoluble in ethyl lactate, and PGMEA,and could only be dissolved in the undesirable solvent cyclohexanone. Comp Ex02could be dissolved only in a mixture of cyclohexanone and PGMEA (50:50 wt. ratio)however the formulation based on this material formed poor coatings when attempts70AZ75295PC were made to spin coat it on a substrate. Consequently, in order to further evaluatethese materials formulations were prepared that contained the much more aggressivenon-green solvent cyclohexanone which yellows upon storage by the formation ofperoxides which may be deleterious in maintaining photoresist stability and consistencyof performance upon storage of photoresist formulated with this solvent. This was dueto its ketone functional group (C=O). Oxidation reactions involve the loss of electrons, leading to the formation of new chemical species.

[0200] Exposure to oxygen (O2) in the air can cause cyclohexanone to undergo slowoxidation. This process may result in the formation of peroxides, which contribute toyellowing and other color changes and can have undesirable effects on the lithographicperformance of photoresist using this solvent.

[0201] The disclosed and claimed compounds EX01 to EX02 unexpectedly do notrequire the use of the undesirable solvent cyclohexanone alone or in mixture with othersolvent to form solution which were concentrated enough (about 1.0 to about 1.5%w / w) to be enable the formation of a coating on a substrate by spin casting, which werein the target region of 20 to 30 nm required for a negative photoresist of this type.

[0202] After dissolution of the components for these comparative examples thesolution were filtered through a Nylon or Poly Tetra Fluoro Ethylene (PTFE): PTFE0.2 micron filter before spin coating to form a film with a thickness of 26 nmindividually using a spin speed of between 1500 to 2000 rpm for each sample to achievethe target thickness after post applied bake (PAB).Preparation of formulation with compounds EX01 to EX09

[0203] Formulations EX01 to EX09 were formed respectively from molecular glass71AZ75295PCcrosslinking compounds EX01 to EX09 contained 1.25% w / w of total solids in ethyllactate, which in terms of molar rations containing 100 mol% of the crosslinker component, 20 mol% of the PAG component relative to the crosslinker and 35 mol%of the quencher component relative to the crosslinker component.

[0204] For the comparative formulations prepared with compounds Comp EX01 andComp EX02, were prepared in the same manner as described for crosslinking glasscompound EX01 to EX10, except that the for the preparation the comparativeformulation Comp EX02, which was based compound (2-AP) a more aggressivemixture of PGMEA and the undesirable solvent cyclohexanone had to be employedbecause of the insolubility of compound (2-AP) in the spin casting solvent ethyl lactate, PGMEA, PGME and mixtures thereof. Evaluation of Photoresist Formulations

[0205] The general processing conditions for formulations based on Comp EX01,Comp EX02 and EX01 to EX09 used are as follows and spin coating these negativephotoresist formulations on silicon coated with KrF-17B targeted a film thickness of 26 nm.^ Substrate : Si^ UL : KrF-17B, 65 nm FT^ Bake : 180 °C / 60s^ PR : Samples, 26nm FT, MRX-2002-27^ Post applied bake (PAB) : 80 °C / 60s^ Exposure : Canon / FPA-3000EX5, NA / Sigma=0.63 / 0.65^ Mask : Open flame 10x10^ Post Exposure bake (PEB) : 90 °C / 60s^ Develop : nBA single puddle, 30s

[0206] Spin speeds for the examples and comparative exampled were between 1500-2000 rpm where the spin speed for each sample was individually adjusted within thisrange to obtain a film thickness of 26 nm after the PAB.

[0207] Tables 1 summarize the EUV lithographic results for the negative photoresistformulations comparative crosslinking compounds (Comp EX01, Comp EX02), thesematerials have very large film losses in exposed and also have poor EUV sensitivitybased on their dose to image (DtG) and thickness loss in exposed areas were measuredby their EUV exposure response curves compared to the corresponding negative72AZ75295PC photoresist formulation which were prepared with the novel crosslinking compound EX01 to EX10.

[0208] FIG. 10 and 11 shows the EUV exposure response curves for the formulationprepared with Comp EX01 and Comp EX02 illustrates in more detail the poorperformance of these materials.

[0209] Specifically, for the very poor performance of Comp EX01, without beingbound by theory, it is believed that molecular glass crosslinking compounds such asEX01 with only epoxy-groups have poor ability for crosslinking and lead to linear-typepolymers. These linear polymers lacking a dense crosslinked network also display poorperformance (LER, LWR).

[0210] Table 2 summarizes the EUV performance of the negative photoresistformulation prepared with compounds EX01, EX02, EX05, EX07, EX08 and EX09,unexpectedly showed much better EUV photosensitivity and also, unexpectedly, havelittle or no film loss in the exposed area compared to the formulation prepared withComp 01 and Comp 02 based on their dose to image (DtG) and thickness loss inexposed areas were measured by their EUV exposure response curves.

[0211] FIG. 12 shows the EUV exposure response curves for the formulation preparedwith EX01 and EX02 illustrated in more detail the poor performance of these materials.

[0212] FIG. 13 shows the EUV exposure response curves for the formulation preparedwith EX05 and EX07 which illustrated the unexpected high contrast, sensitivity and film thickness retention of these materials.

[0213] FIG. 14 shows the EUV exposure response curve for the formulation preparedwith EX06 which illustrated the unexpected the high contrast, sensitivity and filmthickness retention of this materials.

[0214] FIG. 15 shows the EUV exposure response curves for the formulation preparedwith EX08 and EX09 which illustrated the unexpected the high contrast, sensitivity and film thickness retention of these materials.

[0215] Additionally, it has been found that these formulation when exposed to EUVwere able to resolve fine features which also unexpectedly achieved low LWR valuescompared to other crosslinking molecular glasses which do not have the architecture embodied in disclosed structure (A). Table 1 73AZ75295PCTable 2Comment: A: Higher photo-speed, high contrast and less film loss

[0216] Table 3 shows a comparison of the Tg of the comparative examples, compoundsComp EX01 (2-AP), Comp EX02 (3-AP), Comp EX03 (4-AP), to the disclosed andclaimed compounds EX01 to EX10. While Comp EX01 and Comp EX03 have Tgcomparable to the of the disclosed and claimed compounds EX01 to EX10, it was foundthat Comp EX03 was insoluble in any spin casting solvent tested, Comp EX01 was onlysoluble in a solvent mixtures containing the undesirable solvent cyclohexanone.Although Comp EX02(2-AP) was soluble enough in the green solvent ethyl lactate sothat it could be tested its Tg was very low and this low Tg combined with only havingtwo crosslinking group resulted in a material as shown in FIG. 1 which has poorcontrast. In contrast all the inventive compounds tested showed very good contrast,little if any film loss in the exposed areas. Thus, the disclosed and claimed compoundstested unexpectedly combine the properties of high solubility in desirable spin casting solvent coupled with high Tgwhile having more than two crosslinking moieties per molecule and were found to give negative photoresist with high contrast and no film loss in exposed areas. Table 374AZ75295PC

[0217] Although the disclosed and claimed subject matter has been described andillustrated with a certain degree of particularity, it is understood that the disclosure has been made only by way of example, and that numerous changes in the conditions and order of steps can be resorted to by those skilled in the art without departing from the spirit and scope of the disclosed and claimed subject matter. 75

Claims

AZ75295PC CLAIMS1. A compound of structure (A), whereinA’ is a linking moiety where nAis either 0, where said linking moiety A’ is not present, or nAis 1 and said linking moiety A’ is present and is either a single valent bond or a divalent moiety selected from the group consisting of a methylene moiety (-CH2-), a mono substituted methylene moiety (-CHR9-), a disubstituted methylene moiety (- CR9R10-), an oxy moiety (-O-), an amino moiety (-NR9-), a thio moiety (-S-), a sulfone moiety (-S(=O)2-), a sulfoxide moiety (-S(=O)-), a silyl moiety (-SiR9R10-), a phosphine moiety (-PR9-), a phosphine oxide moiety (-P(=O)R9-), where R9 and R10 are individually selected from a C-1 to C-10 linear alkyl, a C-3 to C-10 branched alkyl, aC-3 to C-12 alicyclic alkyl, an alkenyl (-CH=CH-R11) where R11 is a C-1 to C-10 linearalkyl, a C-3 to C-10 branched alkyl, a C-3 to C-12 alicyclic alkyl, an aryl, a heteroaryland e, f, g and h are individually selected from an integer ranging from 0 to 2, R1, R2, R3 and R4 are individually selected from the group consisting of moieties havingstructures (i) and (ii), where ^ designates the attachment point of these moieties tostructure (A), a and b are independently 1 or 2, c and d are independently an integer ranging from 0 to 2, and where the sum of c and d is an integer ranging from 1 to 4, n and n’ are individually selected from an integer ranging from 1 to 5, m, m’ are individually selected from an integer ranging from 1 to 5, R12 and R12’ are individually selected from H, a C-1 to C-6 linear alkyl, and a C-1 to C-6 linear hydroxyalkylene (HO-alkylene-), and R5, R6, R7and R8are individually selected from a C-1 to C-10 linear alkyl, a C-3 to C-10 branched alkyl, a C-3 to C-12 alicyclic alkyl, an aryl, a heteroaryl and a halogen,and e, f, g and h are individually selected from an integer ranging from 0 to 2,76AZ75295PC.

2. The compound of claim 1 which has structure (I) or structure (I-1), where R5a isselected from the group consisting of H, a C-1 to C-10 linear alkyl, a C-3 to C-10branched alkyl, a C-3 to C-12 alicyclic alkyl, an aryl, a heteroaryl and a halogen,3. The compound of claim 1 or 2, wherein R1, R2, R3 and R4 have structure (i).

4. The compound of claim 1 or 2, wherein R1, R2, R3 and R4 have structure (ii).

5. The compound of claim 1 or 2, which has structure (Ia) or structure (Ia-1), whereR5ais selected from the group consisting of H, a C-1 to C-10 linear alkyl, a C-3 to C-10branched alkyl, a C-3 to C-12 alicyclic alkyl, an aryl, a heteroaryl and a halogen,6. The compound of claim 1 or 2, which has structure (Ib) or structure (Ib-1),where R5a is selected from the group consisting of H, a C-1 to C-10 linear alkyl, a C-3to C-10 branched alkyl, a C-3 to C-12 alicyclic alkyl, an aryl, a heteroaryl and a halogen,7. The compound of claim 1 or 2, which has structure (Ic) or structure (Ic-1),77AZ75295PC where R5a is selected from the group consisting of H, a C-1 to C-10 linear alkyl, a C-3to C-10 branched alkyl, a C-3 to C-12 alicyclic alkyl, an aryl, a heteroaryl and a halogen,8. The compound of claim 1 or 2, which has structure (Id) or structure (Id-1),where R5a is selected from the group consisting of H, a C-1 to C-10 linear alkyl, a C-3to C-10 branched alkyl, a C-3 to C-12 alicyclic alkyl, an aryl, a heteroaryl and a halogen,and where Rivand Riv’, are independently selected from H, a C-1 to C-10 linear alkyl,a C-3 to C-10 branched alkyl, a C-3 to C-12 alicyclic alkyl,9. The compound of claim 1 or 2, which has structure (Ie) or structure (Ie-1),where R5a is selected from the group consisting of H, a C-1 to C-10 linear alkyl, a C-3to C-10 branched alkyl, a C-3 to C-12 alicyclic alkyl, an aryl, a heteroaryl and a halogen,10. The compound of claim 1, which has structure (II) or structure (II-1), where R5ais selected from the group consisting of H, a C-1 to C-10 linear alkyl, a C-3 to C-10branched alkyl, a C-3 to C-12 alicyclic alkyl, an aryl, a heteroaryl and a halogen,78AZ75295PC11. The compound of any one of claims 1 to 10, wherein R1, R2, R3 and R4 havestructure (ia),.

12. The compound of any one of claims 1 to 10, wherein R1, R2, R3 and R4 havestructure (ib),.

13. The compound of any one of claims 1 to 10, wherein R1, R2, R3 and R4 havestructure (ic),.

14. The compound of any one of claims 1 to 10, wherein R1, R2, R3 and R4 havestructure (id),. The compound of any one of claims 1 to 10, wherein R1, R2, R3 and R4 havestructure (iia),.

16. The compound of any one of claims 1 to 10, wherein R1, R2, R3 and R4 have79AZ75295PC structure (iib),.

17. The compound of any one of claims 1 to 16, wherein R5a is H.

18. The compound of any one of claims 1 to 16, wherein R5a is an aryl.

19. The compound of any one of claims 1 to 16 and 18, wherein R5a is phenyl.

20. The compound of claim 1 which has structure (II) or structure (II-1), where R5ais selected from the group consisting of H, a C-1 to C-10 linear alkyl, a C-3 to C-10branched alkyl, a C-3 to C-12 alicyclic alkyl, an aryl, a heteroaryl and a halogen,21. The compound of claim 1 or 20, wherein R1, R2, R3 and R4 have structure (i).

22. The compound of claim 1 or 20, wherein R1, R2, R3 and R4 have structure (ii).

23. The compound of claim 1 or 20, which has structure (IIa) or structure (IIa-1),where R5ais selected from the group consisting of H, a C-1 to C-10 linear alkyl, a C-3to C-10 branched alkyl, a C-3 to C-12 alicyclic alkyl, an aryl, a heteroaryl and a halogen,24. The compound of claim 1 or 20, which has structure (IIb) or structure (IIb-1),where R5ais selected from the group consisting of H, a C-1 to C-10 linear alkyl, a C-3to C-10 branched alkyl, a C-3 to C-12 alicyclic alkyl, an aryl, a heteroaryl and a halogen,80AZ75295PC25. The compound of claim 1 or 20, which has structure (IIc) or structure (IIc-1),where R5a is selected from the group consisting of H, a C-1 to C-10 linear alkyl, a C-3to C-10 branched alkyl, a C-3 to C-12 alicyclic alkyl, an aryl, a heteroaryl and a halogen,26. The compound of claim 1 or 20, which has structure (IId) or structure (IId-1),where R5ais selected from the group consisting of H, a C-1 to C-10 linear alkyl, a C-3to C-10 branched alkyl, a C-3 to C-12 alicyclic alkyl, an aryl, a heteroaryl and a halogen,and where Rivand Riv’, are independently selected from H, a C-1 to C-10 linear alkyl,a C-3 to C-10 branched alkyl, a C-3 to C-12 alicyclic alkyl,27. The compound of claim 1 or 20, which has structure (IIe) or structure (IIe-1),where R5a is selected from the group consisting of H, a C-1 to C-10 linear alkyl, a C-3to C-10 branched alkyl, a C-3 to C-12 alicyclic alkyl, an aryl, a heteroaryl and a halogen,28. The compound of any one of claims 1, 20 to 27, wherein R1, R2, R3 and R4 have81AZ75295PC structure (ia),.

29. The compound of any one of claims 1, 20 to 27, wherein R1, R2, R3 and R4 havestructure (ib),.

30. The compound of any one of claims 1, 20 to 27, wherein R1, R2, R3 and R4 havestructure (ic),.

31. The compound of any one of claims 1, 20 to 27, wherein R1, R2, R3 and R4 havestructure (id),.

32. The compound f any one of claims 1, 20 to 27, wherein R1, R2, R3 and R4 havestructure (iia),.

33. The compound of any one of claims 1, 20 to 27, wherein R1, R2, R3 and R4 havestructure (iib),.

34. The compound of any one of claims 1, 20 to 33, wherein R5a is H.

35. The compound of any one of claims 1, 20 to 33, wherein R5a is an aryl.

36. The compound of any one of claims 1, 20 to 33, and 35, wherein R5a is phenyl.

37. The compound of claim 1, which has structure (III) or structure (III-1), where82AZ75295PC R5a is selected from the group consisting of H, a C-1 to C-10 linear alkyl, a C-3 to C-10branched alkyl, a C-3 to C-12 alicyclic alkyl, an aryl, a heteroaryl and a halogen,39. The compound of claim 1 or 37, wherein R1, R2, R3 and R4 have structure (ii).

40. The compound of claim 1 or 37, which has structure (IIIa) or structure (IIIa-1),where R5ais selected from the group consisting of H, a C-1 to C-10 linear alkyl, a C-3to C-10 branched alkyl, a C-3 to C-12 alicyclic alkyl, an aryl, a heteroaryl and a halogen,41. The compound of claim 1 or 37, which has structure (IIIb) or structure (IIIb-1),where R5ais selected from the group consisting of H, a C-1 to C-10 linear alkyl, a C-3to C-10 branched alkyl, a C-3 to C-12 alicyclic alkyl, an aryl, a heteroaryl and a halogen,42. The compound of claim 1 or 37, which has structure (IIIc) or structure (IIIc-1),where R5ais selected from the group consisting of H, a C-1 to C-10 linear alkyl, a C-3to C-10 branched alkyl, a C-3 to C-12 alicyclic alkyl, an aryl, a heteroaryl and a halogen,83AZ75295PC43. The compound of claim 1 or 37, which has structure (IIId) or structure (IIId-1),where R5a is selected from the group consisting of H, a C-1 to C-10 linear alkyl, a C-3to C-10 branched alkyl, a C-3 to C-12 alicyclic alkyl, an aryl, a heteroaryl and a halogen,and where Riv and Riv’, are independently selected from H, a C-1 to C-10 linear alkyl,a C-3 to C-10 branched alkyl, a C-3 to C-12 alicyclic alkyl,44. The compound of claim 1 or 37, which has structure (IIIa) or structure (IIIa-1),where R5a is selected from the group consisting of H, a C-1 to C-10 linear alkyl, a C-3to C-10 branched alkyl, a C-3 to C-12 alicyclic alkyl, an aryl, a heteroaryl and a halogen,45. The compound of any one of claims 1 and 37 to 44, wherein R1, R2, R3 and R4have structure (ia),.

46. The compound of any one of claims 1 and 37 to 44, wherein R1, R2, R3 and R4have structure (ib), 84AZ75295PC.

47. The compound of any one of claims 1 and 37 to 44, wherein R1, R2, R3 and R4have structure (ic),.

48. The compound of any one of claims 1 and 37 to 44, wherein R1, R2, R3 and R4have structure (id),.

49. The compound of any one of claims 1 and 37 to 44, wherein R1, R2, R3 and R4have structure (iia),.

50. The compound of any one of claims 1 and 37 to 44, wherein R1, R2, R3 and R4have structure (iib),.

51. The compound of any one of claims 1 and 37 to 50, wherein R5a is H.

52. The compound of any one of claims 1 and 37 to 50, wherein R5a is an aryl.

53. The compound of any one of claims 1 and 37 to 50, and 52, wherein R5a isphenyl.

54. A negative chemically amplified EUV or e-beam photoresist compositioncomprising, 1a) a compound of any one of claims 1 to 53,2a) a photoacid generator component3a) an optional additional crosslinking component, 85AZ75295PC 4a) an optional acid quencher component, 5a) an organic spin coating solvent.

55. A process of forming negative image with a negative photoresist by EUV or ebeam exposure, comprising step i) to vi) i) coating the negative chemically amplified EUV photoresist or beam composition ofany one of claim 54 on a substrate, to form a coated film,ii) baking said coated film to form a baked coated film, iii) exposing regions of the baked coated film through a mask with EUV or e-beam radiation, forming exposed and unexposed regions, iv) an optional post exposure baking step,v) developing away the unexposed regions with an organic solvent developer forminga negative image pattern in said coated photoresist on the substrate, vi) etching the substrate with a plasma or a chemical etchant using said negative imagepattern as a mask, forming a negative image in the substrate.

56. The use of the compound of any one of claims 1 to 53 in a photoresistcomposition. 86

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