BIO-based compositions for photoresists and patterning

Abstract

Compositions for use in lithographic pattern forming processes are described, along with methods of using such. The disclosure further contemplates bio-based solvents for use in lithographic processes as pre-wet solvents, edge removal solvents and in photoresist compositions, wherein the bio-based solvents are synthesized from biological or renewable sources.

Description

BIO-BASED COMPOSITIONS FOR PHOTORESISTS AND PATTERNINGCROSS-REFERENCE TO RELATED APPLICATIONS[1] This application claims the benefit of priority from U.S. Provisional Appl. No. 63 / 600,315, filed November 17, 2023, which is incorporated by reference as if fully set forth herein.FIELD OF THE DISCLOSURE[2] The field described in the disclosure comprises bio-based compositions for photoresists and methods of using such bio-based compositions. More particularly, the disclosure contemplates photoresist compositions comprising solvents that are synthesized from biological or renewable sources and further, employing such bio-based solvents as carriers and processing agents for photoresists to produce high resolution images.BACKGROUND OF THE DISCLOSURE[3] Photoresist materials are photosensitive compositions typically used for transferring an image to one or more underlying layers such as a metal, semiconductor or dielectric layer disposed on a semiconductor substrate. To increase the integration density of semiconductor devices and allow for the formation of structures having dimensions in the nanometer range, photoresists and photolithography processing tools having high-resolution capabilities have been and continue to be developed with a constant push for greater resolution and efficiency.[4] Both positive-tone and negative-tone chemically amplified photoresists are conventionally used for high-resolution processing. Such resists typically employ a polymer having acid-labile groups and a photoacid generator. Pattern-wise exposure to activating radiation through a photomask causes the acid generator to form an acid which, during post-exposure baking, causes cleavage of the acid- labile groups in exposed regions of the polymer, creating a difference in solubility characteristics between exposed and unexposed regions of the resist in a developer solution. In a positive tone development (PTD) process, exposed regions of the photoresist layer become soluble in the developer and are removed from the substrate surface, whereas unexposed regions, which are insoluble in the developer, remain after development to form a positive image. The resulting relief image permits selective processing of the substrate.[5] In a negative tone development (NTD) process, an organic solvent dissolves the unexposed areas and creates a negative image of the exposed chemically amplified photoresist. Processing of a chemically amplified resist in a NTD fashion utilizing anisole as the organic solvent developer was first reported by J. G. Maltabes, et al. in SPIE Vol. 1262, Advances in Resist Technology and Processing VII (1990), pp. 2-7.[6] Photoresist compositions generally include a solvent for dissolving the components of the composition and facilitating its coating on a substrate. Due to toxicological, environmental, and especially flammability issues, there are a limited number of organic solvents that are compatible with practical industrial-scale semiconductor manufacturing. Typical solvents include propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), hydroxyisobutyrate methyl ester (HBM), and cyclohexanone (CHO). The total solvent content inphotoresist compositions is typically 70 to 99 wt % based on total weight of the photoresist composition.[7] While the current solvents used in photoresist compositions are commercially viable, they are still not ideal and present additional problems for the semiconductor industry. These solvents are all manufactured from petrochemically-derived raw materials. Therefore, the cost of production is closely tied to the price of petroleum. Petrochemically-derived solvents contribute to greenhouse emissions due to their high petroleum derived carbon content. Furthermore, the need for low levels in impurities in these solvents means that recycling used solvents is difficult and not economically viable.[8] Thus, there exists an unmet need for solvents that are usable for photoresist compositions that are derived from renewable resources that share similar properties as petroleum-derived solvents. Further, because of the large investment costs associated with semiconductor development and fabrication, it would also be advantageous if the solvents derived from renewable resources can be processed through existing solvent manufacturing facilities.SUMMARY OF THE DISCLOSURE[9] The present disclosure comprises compositions, processes and products that address the foregoing needs, and provides environmental improvements, such as lower greenhouse gas emissions, to track based processes through the synthesis of bio-based organic solvents and utilization of such solvents.

[0010] A first aspect comprises a composition comprising: a polymer matrix comprising a group capable of decomposing under the action of an acid to produce an alkali-soluble group on either one or both of the main chain and the side chain of the polymer; a photo acid generator (PAG); and a biobased organic solvent; wherein the bio-based organic solvent comprises an amount of carbon-14 sufficient to produce a decay of at least 0.1 dpm / gC (disintegrations per minute per gram carbon).

[0011] In some embodiments of the first aspect, the bio-based organic solvent further comprises 10 parts per billion (ppb) or less of a concentration of one or more metal elements selected from group consisting of the metal elements: Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn. In some embodiments, the bio-based organic solvent comprises 10 ppb or less of a concentration of each metal element selected from group consisting of the metal elements: Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn. In some embodiments, the bio-based organic solvent comprises 1 ppb or less of a concentration of one or more metal elements selected from group consisting of the metal elements: Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn or the bio-based organic solvent comprises 1 ppb or less of a concentration of each metal element selected from group consisting of the metal elements: Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn.

[0012] In some embodiments of the first aspect, the bio-based organic solvent comprises a biobased propylene glycol monomethyl ether, a bio-based cyclohexanone, a bio-based methyl ethyl ketone, a bio-based solvent represented by the following Formula (1):wherein X1and X2each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxyl group, an alkoxycarbonyl group, a carboxyl group, a hydroxyl group, a cyano group or a halogen atom, and X1and X2may combine with each other to form a ring; a bio-based solvent represented by the following Formula (2):wherein X3and X5each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxyl group, an alkoxycarbonyl group, a carboxyl group, a hydroxyl group, a cyano group or a halogen atom, or X3and X5may combine with each other to form a ring, and X4is an alkyl, optionally substituted by a hydroxyl group, a carbonyl group, or a cyano group, or may have an ether bond in the alkylene chain; or a bio-based solvent represented by the following Formula (3):wherein X6and X8each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxyl group, an alkoxycarbonyl group, a carboxyl group, a hydroxyl group, a cyano group or a halogen atom, and Xsand X8or Xsand X7or and X7and X8may combine with each other to form a ring; and X7represents an alkylene group or a cycloalkylene group.

[0013] In some embodiments of the first aspect, the bio-based organic solvent comprises a bio-based propylene glycol monomethyl ether, a bio-based cyclohexanone, a bio-based methyl ethyl ketone. In some embodiments, the bio-based organic solvent comprises 50 wt% or more, or alternatively, 70 wt% or more, of a bio-based propylene glycol monomethyl ether, a bio-based cyclohexanone, or a biobased methyl ethyl ketone.

[0014] In some embodiments of the first aspect, the bio-based organic solvent comprises a bio-based solvent represented by Formula (1). Such embodiments may include a bio-based butyl acetate, biobased ethyl lactate, bio-based gamma-butyrolactone, bio-based gamma-valerolactone, or bio-based hydroxyisobutyrate methyl ester. In some embodiments, the bio-based organic solvent comprises 50 wt% or more, or alternatively, 70 wt% or more, of a bio-based butyl acetate, bio-based ethyl lactate, bio-based gamma-butyrolactone, bio-based gamma-valerolactone, or bio-based hydroxyisobutyrate methyl ester.

[0015] In some embodiments of the first aspect, the bio-based organic solvent comprises a bio-based solvent represented by Formula (2). Such embodiments may include a bio-based propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethylether acetate, propylene glycol monopropyl ether acetate, methyl-3-methoxypropionate, ethyl-3- methoxypropionate, ethyl-3-ethoxypropionate, propyl-3-methoxypropionate, ethyl methoxyacetate, ethyl ethoxyacetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3- methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, 2-ethoxybutyl acetate, 4- ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4- methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3- methyl-4-methoxypentyl acetate, or 4-methyl-4-methoxypentyl acetate. In some embodiments, the bio-based organic solvent comprises 50 wt% or more, or alternatively, 70 wt% or more, of a bio-based propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methyl-3- methoxypropionate, ethyl-3-methoxypropionate, ethyl-3-ethoxypropionate, propyl-3- methoxypropionate, ethyl methoxyacetate, ethyl ethoxyacetate, 2-methoxybutyl acetate, 3- methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3- methoxybutyl acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2- methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3- methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, or 4- methyl-4-methoxypentyl acetate.

[0016] In some embodiments of the first aspect, the bio-based organic solvent comprises a solvent represented by Formula (3). Such embodiments may include a bio-based methyl 4-methoxy valerate, bio-based ethyl 4-ethoxy valerate, or bio-based ethyl 3-ethoxypropionate. In some embodiments, the bio-based organic solvent comprises 50 wt% or more, or alternatively, 70 wt% or more, of a bio-based methyl 4-methoxy valerate, bio-based ethyl 4-ethoxy valerate, or bio-based ethyl 3-ethoxypropionate.

[0017] In some embodiments of the first aspect, the bio-based organic solvent comprises an amount of carbon-14 sufficient to produce a decay of at least 3.0 dpm / gC, at least 6.0 dpm / gC, 9.0 dpm / gC, or 12.0 dpm / gC. Further, some embodiments may comprise one or more of: 1 parts per billion (ppb) or less of a concentration of one or more metal elements selected from group consisting of the metal elements: Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn; 1 ppb or less of a concentration of each metal element selected from group consisting of the metal elements: Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn; 10 ppb or less of C1-22 alkane or C2-22 alkene; 1 ppb or less of C1-22 alkane or C2-22 alkene; less than 20 particles / mL of particles having a particle size of 0.15 pm or larger; a dispersion parameter of from 14.5017 Mpa05; or a boiling point from 50°C to 250°C

[0018] A second aspect comprises a pattern forming method comprising: providing a semiconductor substrate; optionally, applying a pre-wet solvent to the semiconductor substrate; forming a photoresist film comprising coating the semiconductor substrate with a photoresist composition comprising a polymer matrix comprising a group capable of decomposing under the action of an acid to produce an alkali-soluble group on either one or both of the main chain and the side chain of the polymer, a photo acid generator (PAG), and an organic solvent; optionally, performing an edge bead removal process wherein the peripheral portion of the photoresist film adjacent to the top or coated edge and the backside or bottom edge of the substrate, as well as any coated photoresist material lying over the edge of the substrate, is contacted with an edge bead removal solvent so as to dissolveand remove this unwanted material; exposing the resist film with actinic rays or electromagnetic radiation; and developing the resist film with a developer.

[0019] In a first embodiment of the second aspect comprises a photoresist composition characterized by the composition of any embodiment of the first aspect.

[0020] A second embodiment of the second aspect comprises applying a pre-wet solvent to the substrate, wherein the pre-wet solvent comprises a bio-based pre-wet solvent comprising an amount of carbon-14 sufficient to produce a decay of at least 0.1 dpm / gC. In some embodiments, the biobased pre-wet solvent is selected from propylene glycol monomethyl ether, cyclohexanone, methyl ethyl ketone, butyl acetate, ethyl lactate, gamma-butyrolactone, gamma-valerolactone, hydroxyisobutyrate methyl ester, propylene glycol monomethyl ether acetate, methyl 4-methoxy valerate, ethyl 4-ethoxy valerate, or ethyl 3-ethoxypropionate, or a combination thereof. In some embodiments, the bio-based pre-wet solvent comprises an amount of carbon-14 sufficient to produce a decay of at least 3.0, 6.0, 9.0, or 12.0 dpm / gC. In some embodiments, the bio-based pre-wet solvent further comprises one or more of: 1 ppb or less of a concentration of one or more metal elements selected from group consisting of the metal elements: Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn; 10 ppb or less of C1-22 alkane or C2-22 alkene; less than 20 particles / mL of particles having a particle size of 0.15 pm or larger; a dispersion parameter of from 14.5017 Mpa05; or a boiling point from 50°C to 250°C.

[0021] A third embodiment of the second aspect comprises an edge bead removal process, wherein the edge bead removal solvent comprises a bio-based edge bead removal solvent comprising an amount of carbon-14 sufficient to produce a decay of at least 0.1 dpm / gC. In some embodiments, the bio-based edge bead removal solvent comprises propylene glycol monomethyl ether, cyclohexanone, methyl ethyl ketone, butyl acetate, ethyl lactate, gamma-butyrolactone, gamma-valerolactone, hydroxyisobutyrate methyl ester, propylene glycol monomethyl ether acetate, methyl 4-methoxy valerate, ethyl 4-ethoxy valerate, or ethyl 3-ethoxypropionate, or a combination thereof. In some embodiments, bio-based edge bead removal solvent comprises an amount of carbon-14 sufficient to produce a decay of at least 3.0, 6.0, 9.0, or 12.0 dpm / gC. In some embodiments, the bio-based the edge bead removal solvent further comprises one or more of: 1 ppb or less of a concentration of one or more metal elements selected from group consisting of the metal elements: Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn; 10 ppb or less of C1-22 alkane or C2-22 alkene; less than 20 particles / mL of particles having a particle size of 0.15 pm or larger; a dispersion parameter of from 14.5017 Mpa05; or a boiling point from 50°C to 250°C.

[0022] A third aspect comprises a solvent comprising a bio-based propylene glycol monomethyl ether, a bio-based cyclohexanone, a bio-based methyl ethyl ketone, a bio-based solvent represented by the following Formula (1):wherein X1and X2each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxyl group, an alkoxycarbonyl group, a carboxyl group, a hydroxyl group, a cyano group or a halogen atom, and X1and X2may combine with each other to form a ring;a bio-based solvent represented by the following Formula (2):wherein X3and X5each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxyl group, an alkoxycarbonyl group, a carboxyl group, a hydroxyl group, a cyano group or a halogen atom, or X3and X5may combine with each other to form a ring, and X4is an alkyl, optionally substituted by a hydroxyl group, a carbonyl group, or a cyano group, or may have an ether bond in the alkylene chain; or a bio-based solvent represented by the following Formula (3):wherein X6and X8each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxyl group, an alkoxycarbonyl group, a carboxyl group, a hydroxyl group, a cyano group or a halogen atom, and Xsand X8or Xsand X7or and X7and X8may combine with each other to form a ring; and X7represents an alkylene group or a cycloalkylene group.

[0023] In some embodiments of the third aspect, the solvent comprises a bio-based propylene glycol monomethyl ether, a bio-based cyclohexanone, or a bio-based methyl ethyl ketone. In such embodiments, the solvent may comprises 50 wt% or more, or 70 wt% or more, of a bio-based propylene glycol monomethyl ether, a bio-based cyclohexanone, or a bio-based methyl ethyl ketone.

[0024] In some embodiments of the third aspect, the solvent comprises a bio-based propylene glycol monomethyl ether, a bio-based cyclohexanone, a bio-based methyl ethyl ketone. In some embodiments, the bio-based organic solvent comprises 50 wt% or more, or alternatively, 70 wt% or more, of a bio-based propylene glycol monomethyl ether, a bio-based cyclohexanone, or a bio-based methyl ethyl ketone.

[0025] In some embodiments of the third aspect, solvent comprises a bio-based solvent represented by Formula (1). Such embodiments may include a bio-based butyl acetate, bio-based ethyl lactate, biobased gamma-butyrolactone, bio-based gamma-valerolactone, or bio-based hydroxyisobutyrate methyl ester. In some embodiments, the bio-based organic solvent comprises 50 wt% or more, or alternatively, 70 wt% or more, of a bio-based butyl acetate, bio-based ethyl lactate, bio-based gammabutyrolactone, bio-based gamma-valerolactone, or bio-based hydroxyisobutyrate methyl ester.

[0026] In some embodiments of the third aspect, the solvent comprises 50 wt% or more, or alternatively, 70 wt% or more, of the bio-based organic solvent comprises a solvent represented by Formula (2). Such embodiments may include a bio-based propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propyleneglycol monopropyl ether acetate, methyl-3-methoxypropionate, ethyl-3-methoxypropionate, ethyl-3- ethoxypropionate, propyl-3-methoxypropionate, ethyl methoxyacetate, ethyl ethoxyacetate, 2- methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4- propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, or 4-methyl-4-methoxypentyl acetate. In some embodiments, the bio-based organic solvent comprises 50 wt% or more, or alternatively, 70 wt% or more, of a bio-based propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methyl-3-methoxypropionate, ethyl-3- methoxypropionate, ethyl-3-ethoxypropionate, propyl-3-methoxypropionate, ethyl methoxyacetate, ethyl ethoxyacetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3- methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, 2-ethoxybutyl acetate, 4- ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4- methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3- methyl-4-methoxypentyl acetate, or 4-methyl-4-methoxypentyl acetate.

[0027] In some embodiments of the third aspect, the solvent comprises a solvent represented by Formula (3). Such embodiments may include a bio-based methyl 4-methoxy valerate, bio-based ethyl 4-ethoxy valerate, or bio-based ethyl 3-ethoxypropionate. In some embodiments, the bio-based organic solvent comprises 50 wt% or more, or alternatively, 70 wt% or more, of a bio-based methyl 4- methoxy valerate, bio-based ethyl 4-ethoxy valerate, or bio-based ethyl 3-ethoxypropionate.

[0028] In some embodiments of the third aspect, the solvent comprises an amount of carbon-14 sufficient to produce a decay of at least 3.0 dpm / gC, at least 6.0 dpm / gC, 9.0 dpm / gC, or 12.0 dpm / gC. Further, some embodiments may comprise one or more of: 1 parts per billion (ppb) or less of a concentration of one or more metal elements selected from group consisting of the metal elements: Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn; 1 ppb or less of a concentration of each metal element selected from group consisting of the metal elements: Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn; 10 ppb or less of Ci.22alkane or C2.22alkene; 1 ppb or less of Ci.22alkane or C2.22alkene; less than 20 particles / mL of particles having a particle size of 0.15 pm or larger; a dispersion parameter of from 14.5017 Mpa05; or a boiling point from 50°C to 250°C.

[0029] A fourth aspect comprises any composition or method as substantially shown, described, or embodied in the application.DETAILED DESCRIPTION OF THE DISCLOSURE

[0030] The following description sets forth exemplary embodiments of the present technology. It should be recognized, however, that such description is not intended as a limitation on the scope of the present disclosure but is instead provided as a description of exemplary embodiments.

[0031] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as is commonly understood by one of ordinary skill in the art. As used herein, the belowterms have the following meanings unless specified otherwise. Any methods, devices and materials similar or equivalent to those described herein may also be used in the practice of the compositions and methods described herein. The following definitions are provided to facilitate understanding of certain terms used frequently herein and are not meant to limit the scope of the present disclosure. All references referred to herein are incorporated by reference in their entirety.

[0032] The term "comprise" and variations thereof, such as, "comprises" and "comprising" are to be construed in an open, inclusive sense, that is, as "including, but not limited to." The term "consisting essentially of" is construed to mean that the composition / process (a) necessarily includes the listed ingredients / steps and (b) is open to unlisted ingredients / steps that do not materially affect the basic and novel properties of the composition / process. The term "consisting of" is closed-ended and excludes any element, step, or ingredient not specifically mentioned after that phrase. Further, the singular forms "a," "an," and "the" include plural references unless the context clearly dictates otherwise. Thus, references to "the embodiment" includes a plurality of such embodiments.

[0033] In some embodiments, there are a number of possible alternatives that can be chosen. In such cases, the terminology "at least one of [A], [B] and [C]" or "one or more of [A], [B] and [C]" is used to mean "either [A], [B], [C] or any possible combination of [A], [B] and [C]," such as [A] and [B] or [A], [B], and [C], In cases where "[A] or [B]" is used, it should be interpreted as "either or both" and not as alternatives - e.g., "[A] or [B]" is equivalent to "[A] or [B] or the combination [A] and [B]." For sake of clarity, the disclosure may include "and combinations thereof" to further clarify that in cases where alternatives are listed, the list further comprises combinations thereof.

[0034] It is noted that the terms "substantially" and "about" may be utilized herein to represent the inherent degree of uncertainty that may be attributed to any quantitative comparison, value, measurement, or other representation. These terms are also utilized herein to represent the degree by which a quantitative representation may vary from a stated reference without resulting in a change in the basic function of the subject matter at issue. For example, reference to "about" a value or parameter herein includes (and describes) embodiments that are directed to that value or parameter per se. In certain embodiments, the term "about" includes the indicated amount ± 10%. In other embodiments, the term "about" includes the indicated amount ± 5%. In certain other embodiments, the term "about" includes the indicated amount ± 1%. Also, to the term "about X" includes description of "X."

[0035] "Ring," "cycle," "cyclic," "alicyclic", or like terms generally refer to at least one continuous closed loop, ring, or chain of atoms and can include, for example, saturated alicyclics, unsaturated alicyclics, aromatics, hetero-aromatics (heteroaryl), and like cyclic classifications, or combinations thereof, including monocyclic, bicyclic, tricyclic, and like conventional designations.

[0036] "Alkyl" includes linear alkyls and branched alkyls. "Substituted alkyl" or "optionally substituted alkyl" refers to an alkyl substituent, which can include, for example, a linear alkyl or a branched alkyl having from 1 to 4 optional substituents selected from, for example, hydroxyl (—OH), halogen, amino (—NHz or — NRj), nitro (—NO?), acyl (— C(=O)R), alkylsulfonyl (— S(=O)?R), alkoxy (—OR), (C3- io)cycloalkyl, and like substituents, where R is a hydrocarbyl, aryl, Het, or like moieties, such as a monovalent alkyl or a divalent alkylene having from 1 to about 10 carbon atoms. For example, a hydroxy substituted alkyl, can be a 2-hydroxy substituted propylene of the formula — CH?— CH(OH)— CH?—, an alkoxy substituted alkyl, can be a 2-methoxy substituted ethyl of the formula — CH?— CH?—O— CHg, an amino substituted alkyl, or can be a 1-dialkylamino substituted ethyl of the formula — CH(NR2)— CH3.

[0037] "Cycloalkyl" includes cyclic alkyls. "Substituted cycloalkyl" or "optionally substituted cycloalkyls" refers to a cycloalkyl substituent having from 1 to 4 optional substituents selected from, for example, alkyl, alkenyl, alkynyl, hydroxyl (—OH), halogen, amino (— NH2or — NR2), nitro (— NO2), acyl (— C(=O)R), alkylsulfonyl (— S(=O)2R), alkoxy (—OR), and like substituents .

[0038] "Alkoxyl" includes an alkyl group bound to the base structure via an oxygen atom, -O-R1, wherein R1can include optionally substituted linear alkyls or branched alkyls as described above.

[0039] "Alkoxylcarbonyl" includes an alkyl group bound the base structure via an oxygen, with a carbonyl group adjacent the oxygen, -O-C(=O)-R1, wherein R1can include optionally substituted linear alkyls or branched alkyls as described above.

[0040] "Carboxyl" means a moiety composed of carbon bonded to both an oxygen and a hydroxyl group, -C(=O)-O-H.

[0041] "Hydroxyl" mean an -O-H chemical moiety.

[0042] "Cyano" means a -CEN chemical moiety.

[0043] "Halogen" or "halo" includes fluoro (-F), chloro (-CI), bromo (-Br), or iodo (-1) moieties.

[0044] "Aryl" includes a mono- or divalent-phenyl radical or an ortho-fused bicyclic carbocyclic radical having about nine to twenty ring atoms in which at least one ring is aromatic. Aryl (Ar) can include substituted aryls, such as a phenyl radical having from 1 to 5 substituents, for example, alkyl, alkoxy, halo, and like substituents.

[0045] "Het" or "Heteroalkyl" includes a four-(4), five-(5), six-(6), or seven-(7) membered saturated or unsaturated heterocyclic ring having 1, 2, 3, or 4 heteroatoms selected from the group consisting of oxy, thio, sulfinyl, sulfonyl, selenium, tellurium, and nitrogen, which ring is optionally fused to a benzene ring. Het also includes "heteroaryl," which encompasses a radical attached via a ring carbon of a monocyclic aromatic ring containing five or six ring atoms consisting of carbon and 1, 2, 3, or 4 heteroatoms each selected from the group consisting of non-peroxide oxy, thio, and N(X) wherein X is absent or is H, O, (Ci-galkyl, phenyl, or benzyl, and a radical of an ortho-fused bicyclic heterocycle of about eight to ten ring atoms derived therefrom, particularly a benzo-derivative or one derived by fusing a propylene, trimethylene, or tetramethylene diradical thereto.

[0046] Alkyl, alkoxy, etc., include both straight and branched groups; but reference to an individual radical such as "propyl" embraces only the straight chain radical, a branched chain isomer such as "isopropyl" being specifically referred to.

[0047] The carbon atom content of various hydrocarbon-containing (i.e., hydrocarbyl) moieties can alternatively be indicated by a prefix designating a lower and upper number of carbon atoms in the moiety, i.e., the prefix Cj.j indicates a moiety of the integer "i" to the integer "j" carbon atoms, inclusive. Thus, for example, (Ci-Cg)alkyl or Ci-gal kyl refers to an alkyl of one to eight carbon atoms, inclusive, and hydrocarbyloxy such as (Ci-Cg)alkoxy or Ci.galkoxy refers to an alkoxy radical (—OR) having an alkyl group of one to eight carbon atoms, inclusive. Specifically, a Ci-galkyl can be, for example, methyl, ethyl, propyl, isopropyl, butyl, iso-butyl, sec-butyl, tert-butyl, pentyl, 3-pentyl, hexyl, heptyl, or octyl;(C3 i2)cycloalkyl can be cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, including bicyclic, tricyclic, or multi-cyclic substituents, and like substituents.

[0048] A specific "hydrocarbyl" can be, for example, (Cio-2o)hydrocarbyl, including all intermediate chain lengths and values, and (Cs-izjcyclohydrocarbyl including all intermediate values and ring sizes.

[0049] Ci-galkoxy can be, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, iso-butoxy, secbutoxy, pentoxy, 3-pentoxy, hexyloxy, 1-methylhexyloxy, heptyloxy, octyloxy, and like substituents.

[0050] A — C(=O)(C3-7)alkyl- or — (C2.7)alkanoyl can be, for example, acetyl, propanoyl, butanoyl, pentanoyl, 4-methylpentanoyl, hexanoyl, or heptanoyl. Aryl (Ar) can be, for example, phenyl, naphthyl, anthracenyl, phenanthrenyl, fluorenyl, tetrahydronaphthyl, or indanyl. Het can be, for example, pyrrolidinyl, piperidinyl, morpholinyl, thiomorpholinyl, or heteroaryl. Heteroaryl can be, for example, furyl, imidazolyl, triazolyl, triazinyl, oxazoyl, isoxazoyl, thiazolyl, isothiazoyl, pyrazolyl, pyrrolyl, pyrazinyl, tetrazolyl, pyridyl, (or its N-oxide), thienyl, pyrimidinyl (or its N-oxide), indolyl, isoquinolyl (or its N-oxide) or quinolyl (or its N-oxide).

[0051] Other conditions suitable for formation and modification of the compounds or like products of the disclosure, from a variety of starting materials or intermediates, as disclosed and illustrated herein are available. For example, see Feiser and Feiser, "Reagents for Organic Synthesis", Vol. 1, et seq., 1967; March, J. "Advanced Organic Chemistry," John Wiley & Sons, 4Supth / Suped. 1992; House, H. O., "Modem Synthetic Reactions," 2nded., W. A. Benjamin, New York, 1972; and Larock, R. C., "Comprehensive Organic Transformations," 2nded., 1999, Wiley-VCH Publishers, New York.

[0052] The present disclosure provides novel bio-based compounds for use in lithography and other patterning processes, along with methods of synthesizing such compounds and processes for using such compounds in lithographic processes. The term "bio-based," as used in this application, indicates the inclusion of some component that derives from at least one bio-based material. For example, a "bio-based NBA solvent" would be an NBA that is either partially or totally derived from at least one bio-based material. As used herein, "bio-based materials" refers to organic materials in which the carbon comes from non-fossil biological sources. Examples of bio-based materials include, but are not limited to, sugars, starches, corns, natural fibers, sugarcanes, beets, citrus fruits, woody plants, cellulosics, lignocelluosics, hemicelluloses, potatoes, plant oils, other polysaccharides such as pectin, chitin, levan, and pullulan, and a combination thereof. According to a particular embodiment, at least one bio-based material is selected from corn, sugarcane, beet, potato, starch, citrus fruit, woody plant, cellulosic lignin, plant oil, natural fiber, oily wood feedstock, and combinations thereof.

[0053] Fossil biological sources, or fossil fuels, as used herein, include hydrocarbon-containing materials, such as coal, crude oil, and natural gas, formed naturally in the earth's crust from the remains of dead plants and animals, as well as refined or synthesized materials stemming from such. The key differentiator of fossil biological sources from bio-based materials is that fossil biological sources stem from the anaerobic decomposition of buried dead organisms into high-carbon fossil fuels over millions of years.

[0054] Carbon-14 is a radioactive isotope of carbon that is formed in the upper layers of the troposphere and the stratosphere by thermal neutrons absorbed by nitrogen atoms. When cosmic rays enter the atmosphere, they undergo various transformations, including the production of neutrons. The resulting neutrons (In) participate in the following n-p reaction:14 / 7N + neutron -> 14 / 6C + protonAfter production in the upper atmosphere, the carbon-14 atoms react rapidly to form mostly (about 93%)14CO (carbon monoxide), which subsequently oxidizes at a slower rate to form14COz, radioactive carbon dioxide. The gas mixes rapidly and becomes evenly distributed throughout the atmosphere (the mixing timescale in the order of weeks) and is incorporated into biological organisms.

[0055] Carbon-14 (C-14) has a half-life of about 5,700 years, making it useful as a detector for determining the source of carbon in synthetic materials. C-14's relatively short half-life means that it can be found in bio-based materials, but not in fossil biological sources due to the fact that fossil sources take millions of years to form. As such, the novel bio-based solvents described herein comprise C-14 in detectable amounts that allow for distinguishing them from traditional, fossil-based solvents.

[0056] In some embodiments, C-14 levels in the bio-based solvents described herein are determined or measured via standard test methods as developed in one or more countries or by one or more standards organizations. In some embodiments, the C-14 levels in the bio-based solvents described herein are determined by ASTM D6866 - Standard Test Methods for Determining the Biobased Content of Solid, Liquid, and Gaseous Samples Using Radiocarbon Analysis; CEN / TS 16640:2014 - Biobased products - Determination of the bio based carbon content of products using the radiocarbon method; and / or CSN EN 16785-1 - Bio-based products - Bio-based content - Part 1: Determination of the bio-based content using the radiocarbon analysis and elemental analysis.

[0057] Bio-based solvents described herein have non-zero or detectable amounts of C-14. Example quantitatively measured levels of C-14 in the compositions include: a. a radioactive decay of at least 0.01, 0.1, 0.5, 1.0, 1.5, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, or 14 dpm / gC (disintegrations per minute per gram carbon) of carbon-14 (C-14). In some embodiments, the compositions described herein measure 0.1-14, 0.1-13, 0.1-12, 0.1-11, 0.1-10, 0.1-8, 0.1-6, 0.1-4, 0.1-2, 0.1-0.5, 0.5-14, 0.5-13, 0.5-12, 0.5-11, 0.5-10, 0.5-8, 0.5- 6, 0.5-4, 0.5-2, 1-14, 1-13, 1-12, 1-11, 1-10, 1-8, 1-6, 1-4, 1-2, 2-14, 2-13, 2-12, 2-11, 2-10, 2-8, 2-6, 2-4, 4-14, 4-13, 4-12, 4-11, 4-10, 4-8, 4-6, 6-14, 6-13, 6-12, 6-11, 6-10, 6-8, 8-14, 8-13, 8-12, 8-11, 8-10, 10-14, 10-13, 10-12, 10-11, 11-14, 11-13, 11-12, 12-14, 12-13, or 13-14 dpm / gC; b. measuring the ratio of14C to12C in a sample of the compound. A bio-based compound will comprise a14C / 12C ratio greater than zero. In some embodiments, the bio-based compound will have a14C / 12C ratio greater or equal to lxlO13, 2.5xl013, 5xl013, 7.5x10" 13, 9xl0"13, lxlO"12, l.lxlO"12, 1.2xl0"12, 1.3xl0"12, 1.4xl0"12, 1.45xl0"12, 1.5xl0"12. In some embodiments, the bio-based compound will have a14C / 12C ratio from 7.5xl0"13to 1.5x10" 12, 1.2xl0"12to 1.5xl0"12, 1.3xl0"12to 1.5xl0"12, 1.4xl0"12to 1.5xl0"12, or 1.45xl0"12to 1.5xl0"12. c. In some embodiments, the bio-based solvents described herein comprise a greater than 25, 50, 75, 100, 150, 175, 200, or 225 becquerels (Bq) of C-14 per kilogram (kg) of total carbon.

[0058] In some embodiments, the bio-based solvents described herein comprise a greater than 25, 50, 75, 100, 150, 175, 200, or 225 becquerels (Bq) of C-14 per kilogram (kg) of total carbon. In some embodiments, the C-14 / C-12 ratio of the carbon in the bio-based solvents described herein is greater than 0.10 x 1012, 0.15 x 1012, 0.20 x 1012, or 0.25 x 1012- such as, for example, a C-14 / C-12 ratio from 0.25x1012to 1.2xl012.

[0059] In some embodiments, the bio-based solvents emit greater than or equal to an average of 0.01, 0.025, 0.05, 0.075, or 0.1 dpm / gC (disintegrations per minute per gram carbon) as measured by standard techniques. Standard techniques to determine C-14 levels include, but are not limited to, beta ionization (Bl), liquid scintillation (LS) counting or accelerator mass spectroscopy (AMS). In some embodiments, liquid scintillation is used as the standard method for measuring C-14 levels.

[0060] In some embodiments there may be practical or economic reasons to use a solvent mixture or combination of solvents wherein at least only some of the solvents are bio-based. In some embodiments, the bio-based solvent comprises greater than 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 60, 70, 80, 90, 95, 98, 99, 99.5, or 99.9% by weight of the overall solvent mixture. In some embodiments, the bio-based solvent comprises from 5-99%, 10-99%, 20-99%, 30-99%, 40-99%, 50-99%, 60-99%, 70- 99%, 80-99%, 90-99%, 5-90%, 10-90%, 20-90%, 30-90%, 40-90%, 50-90%, 60-90%, 70-90%, 80-90%, 5- 80%, 10-80%, 20-80%, 30-80%, 40-80%, 50-80%, 60-80%, 70-80%, 5-70%, 10-70%, 20-70%, 30-70%, 40-70%, 50-70%, 60-70%, 5-60%, 10-60%, 20-60%, 30-60%, 40-60%, 50-60%, 5-50%, 10-50%, 20-50%, 30-50%, 40-50%, 5-40%, 10-40%, 20-40%, 30-40%, 5-30%, 10-30%, 20-30%, 5-20%, 10-20%, or 5-10% by weight of the overall solvent mixture.

[0061] Bio-based content is determined based on the amount of bio-based carbon in the material or product as a percent of weight of the total organic carbon in the material or product. In embodiments where the solvent is a mixture or combination of solvents wherein at least some of the solvents are bio-based, the bio-based content of the solvent may be approximated by several methods. For example, measuring the specific activity in dpm / gC of the mixture and applying the following equation can provide an estimate the bio-based content: wt% bio-based = 100 * (specific activity of mixture) / (specific activity of 100% bio-based)

[0062] As the global inventory of natural C-14 is approximately 75 tons, the specific activity is > 13.56 dpm / gC. The anticipated specific activity of a bio-based material can be approximated according to this value according to the following equation: specific activity of material X = (weight fraction of carbon in material) * 13.56 dpm / gCPHOTORESIST COMPOSITIONS COMPRISING BIO-BASED SOLVENTS

[0063] In one embodiment, the present disclosure relates to photoresist compositions that contain (A) a polymer matrix of which solubility in an alkali developer increases and solubility in an organic solvent decreases under the action of an acid; (B) a compound capable of generating an acid upon irradiation with actinic rays or radiation (sometimes referred to as a "photoacid generator"; (C) a biobased solvent which can be used for dissolving respective components of the photoresist composition that comprises at least 0.1 dpm / gC (disintegrations per minute per gram carbon) of carbon-14 (C-14), and optionally, one or more of the following: (D) basic compound, (E) surfactant, (F) photo- decomposable quencher, and (G) other additives .(A) Polymer Matrix

[0064] The polymer matrix of which solubility in an alkali developer increases and solubility in an organic solvent decreases under the action of an acid is a polymer having an acid-labile group capable of decomposing under the action of an acid to produce an alkali-soluble group on either one or both of the main chain and the side chain of the polymer. Acid-labile groups are also commonly referred to in the art as "acid-decomposable groups", "acid-cleavable groups," "acid-cleavable protecting groups," "acid-labile protecting groups," "acid-leaving groups," and "acid-sensitive groups;" and the resulting polymers are sometimes referred to as "acid-decomposable polymers", "acid-decomposable resins", or "resins".

[0065] In some embodiments, the polymer is preferably a polymer comprised of monomer units having a monocyclic or polycyclic alicyclic hydrocarbon structure and being capable of increasing the solubility in an alkali developer and decreasing the solubility in an organic solvent under the action of an acid, because the polarity of the polymer is greatly changed between before and after irradiation of actinic rays or radiation and when the resist film is developed using a positive developer (preferably an alkali developer) and a negative developer (preferably an organic solvent), the dissolution contrast is enhanced. Furthermore, the polymer having a monocyclic or polycyclic alicyclic hydrocarbon structure generally has high hydrophobicity and favors a high development rate at the time of developing the resist film in a region of weak light irradiation intensity with a negative developer (preferably an organic developer), and the developability on use of a negative developer is enhanced.

[0066] Examples of the alkali-soluble groups include groups having a phenolic hydroxyl group, a carboxylic acid group, a fluorinated alcohol group, a sulfonic acid group, a sulfonamide group, a sulfonylimide group, an (alkylsulfonyl)(alkylcarbonyl)methylene group, an (alkylsulfonyl)(alkylcarbonyl)imide group, a bis(alkylcarbonyl)methylene group, a bis(alkylcarbonyl)imide group, a bis(alkylsulfonyl)methylene group, a bis(alkylsulfonyl)-imide group, a tris(alkylcarbonyl)methylene group or a tris(alkylsulfonyl)methylene group. Among these alkali- soluble groups, a carboxylic acid group, a fluorinated alcohol group (preferably hexafluoroisopropanol) and a sulfonic acid group are preferred.

[0067] Acid-labile groups include, for example: tertiary alkyl ester groups, secondary or tertiary aryl ester groups, secondary or tertiary ester groups having a combination of alkyl and aryl groups, tertiary alkoxy groups, acetal groups, or ketal groups. Acid-labile groups are also commonly referred to in the art as "acid-decomposable groups", "acid-cleavable groups," "acid-cleavable protecting groups," "acid-labile protecting groups," "acid-leaving groups," and "acid-sensitive groups." As the acid-labile group, a cumyl ester group, an enol ester group, an acetal ester group, a tertiary alkyl ester group and the like are preferred. When the pattern forming method of the present disclosure is performed by exposure to KrF light or EUV light, or electron beam irradiation, an acid-decomposable group in which a phenolic hydroxyl group is protected with a group capable of leaving by an acid may be used.

[0068] The acid-labile group which, on decomposition, forms a carboxylic acid on the polymer is preferably a tertiary ester group of the formula — C(O)OC(R1)3 or an acetal group of the formula — C(O)OC(R2)2OR3, wherein: R1is each independently linear C1-20 alkyl, branched C3-20 alkyl, monocyclic or polycyclic C3-20 cycloalkyl, linear C2-20 alkenyl, branched C3-20 alkenyl, monocyclic or polycyclic C3- 20 cycloalkenyl, monocyclic or polycyclic Cg-2oaryl, or monocyclic or polycyclic C2-20 heteroaryl, preferably linear Ci-6 alkyl, branched C3-6 alkyl, or monocyclic or polycyclic C3-10 cycloalkyl, each of whichis substituted or unsubstituted, each R1optionally including as part of its structure one or more groups chosen from — O— , — C(O)— , — C(O)— O— , or — S— , and any two R1groups together optionally forming a ring; R2is independently hydrogen, fluorine, linear Ci-2oalkyl, branched C3-2oalkyl, monocyclic or polycyclic C3-20 cycloalkyl, linear C2-20 alkenyl, branched C3-20 alkenyl, monocyclic or polycyclic C3-20 cycloalkenyl, monocyclic or polycyclic Cg-2oaryl, or monocyclic or polycyclic C2- 20 heteroaryl, preferably hydrogen, linear Ci.g alkyl, branched C3-6 alkyl, or monocyclic or polycyclic C3- 10 cycloalkyl, each of which is substituted or unsubstituted, each R2optionally including as part of its structure one or more groups chosen from — O— , — C(O)— , — C(O)— O— , or — S— , and the R2groups together optionally forming a ring; and R3is linear C1-20 alkyl, branched C3-20 alkyl, monocyclic or polycyclic C3-20 cycloalkyl, linear C2-20 alkenyl, branched C3-20 alkenyl, monocyclic or polycyclic C3- 20 cycloalkenyl, monocyclic or polycyclic C6.2oaryl, or monocyclic or polycyclic C2-20 heteroaryl, preferably linear C1-6 alkyl, branched C3-6 alkyl, or monocyclic or polycyclic C3-10 cycloalkyl, each of which is substituted or unsubstituted, R3optionally including as part of its structure one or more groups chosen from — O— , — C(O)— , — C(O)— O— , or — S— , and one R2together with R3optionally forming a ring. Such monomer is typically a vinyl aromatic, (meth)acrylate, or norbornyl monomer. The total content of polymerized units comprising an acid-decomposable group which forms a carboxylic acid group on the polymer is typically from 10 to 100 mol %, more typically from 10 to 90 mol % or from 30 to 70 mol %, based on total polymerized units of the polymer.

[0069] The polymer can further include as polymerized a monomer comprising an acid-labile group, the decomposition of which group forms an alcohol group or a fluoroalcohol group on the polymer. Suitable such groups include, for example, an acetal group of the formula — COC(R2)2OR3— , or a carbonate ester group of the formula — OC(O)O— , wherein R is as defined above. Such monomer is typically a vinyl aromatic (including styrene and p-hydroxystyrene), an acrylate, a methacrylate, or a norbornene. If present in the polymer, the total content of polymerized units comprising an acid- decomposable group, the decomposition of which group forms an alcohol group or a fluoroalcohol group on the polymer, is typically from 10 to 90 mol %, more typically from 30 to 70 mol %, based on total polymerized units of the polymer.

[0070] The hydrocarbon-based acid-decomposable polymer for use in the present disclosure may contain, in addition to the above-described repeating units, various repeating structural units for the purpose of controlling dry etching resistance, suitability for standard developer, adhesion to substrate, resist profile and properties generally required of the resist, such as resolving power, heat resistance and sensitivity. Examples of such a repeating structural unit include, but are not limited to, repeating structural units corresponding to the monomers described below. By virtue of such a repeating structural unit, the performance required of the hydrocarbon-based acid-decomposable polymer, particularly, (1) solubility in coating solvent, (2) film-forming property (glass transition point), (3) solubility in positive or negative developer, (4) film loss (selection of hydrophilic, hydrophobic or alkali- soluble group), (5) adhesion of unexposed area to substrate, (6) dry etching resistance, and the like, can be subtly controlled.

[0071] The polymer may contain a repeating unit having a lactone structure or a sultone structure. The repeating unit having a lactone structure or a sultone structure may be used in combination of two or more kinds thereof. In the case where the polymer contains a repeating unit having a lactone structure or a sultone structure, the content of the repeating unit having a lactone structure or a sultone structure ranges preferably from 5 mol % to 60 mol %, more preferably from 5 mol % to 55mol %, and still more preferably from 10 mol % to 50 mol % based on all repeating units of the polymer. Further, the polymer may have a repeating unit having a cyclic carbonate ester structure, a repeating unit having a hydroxyl group or a cyano group.

[0072] The polymer may or may not contain a repeating unit having an acid group, but in the case of containing a repeating unit having an acid group, the content of the repeating unit having an acid group is preferably 25 mol % or less, and more preferably 20 mol % or less, based on all repeating units in the polymer. When the polymer contains a repeating unit having an acid group, the content of the repeating unit having an acid group in the polymer is usually 1 mol % or more.

[0073] The polymer may further have a repeating unit having an alicyclic hydrocarbon structure and / or an aromatic ring structure which have no polar group (for example, the acid group, the hydroxyl group, and the cyano group) and not exhibiting acid decomposability.

[0074] When the composition of the present disclosure is for ArF exposure, from the viewpoint of transparency to ArF light, the polymer used in the composition of the present disclosure preferably has substantially no aromatic ring (specifically, the ratio of a repeating unit having an aromatic group in the resin is preferably 5 mol % or less, more preferably 3 mol % or less, and ideally 0 mol %, that is, the resin does not have an aromatic group), and the polymer preferably has a monocyclic or polycyclic alicyclic hydrocarbon structure.

[0075] The form of the polymer in the present disclosure may be any form of a random type, a block type, a comb type, and a star type. The polymer may be synthesized, for example, by polymerization of radicals, cations, or anions of an unsaturated monomer, corresponding to each structure. Further, it is also possible to obtain a target resin by using an unsaturated monomer corresponding to a precursor of each structure to perform polymerization, and then performing a polymer reaction.

[0076] In the case where KrF excimer laser light, electron beam, X-ray or high-energy beam having a wavelength of 50 nm or less (EUV and the like) is irradiated on the composition of the present disclosure, the polymer may have a repeating unit having an aromatic ring. The repeating unit having an aromatic ring is not particularly limited and is exemplified in the above described descriptions of the repeating units. Examples thereof may include a styrene unit, a hydroxystyrene unit, a phenyl(meth)acrylate unit, and a hydroxyphenyl(meth)acrylate. More specifically, examples of the polymer may include a resin having a hydroxystyrene-based repeating unit, and a hydroxystyrene- based repeating unit protected by an acid-decomposable group, and a resin having a repeating unit having the aromatic ring, and a repeating unit in which a carboxylic acid moiety of (meth)acrylic acid is protected by an acid-decomposable group.

[0077] The polymer in the present disclosure may be synthesized and purified by a conventional method (e.g., radical polymerization). In regard to the synthesis and purification methods, see, e.g., the description in paragraphs 0201 to 0202 of Japanese Patent Application Laid-Open No. 2008- 292975. The weight average molecular weight of the polymer in the present disclosure is 7,000 or more as described above, preferably in a range of 7,000 to 200,000, more preferably 7,000 to 50,000, still more preferably 7,000 to 40,000, and particularly preferably 7,000 to 30,000, in terms of polystyrene by the GPC method. If the weight average molecular weight is less than 7,000, the solubility in an organic developer becomes higher, and thus, there is a concern that a fine pattern may not be formed.

[0078] The polydispersity (molecular weight distribution) is usually in a range of 1.0 to 3.0, preferably 1.0 to 2.6, more preferably 1.0 to 2.0, and particularly preferably 1.4 to 2.0. The smaller the molecular weight distribution is, the better the resolution and resist shape are, and the smoother the side wall of the resist pattern is, and thus roughness is excellent.

[0079] Examples of the monomer include a compound having one addition-polymerizable unsaturated bond selected from styrenics, acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers and vinyl esters. Other than these, an addition- polymerizable unsaturated compound copolymerizable with the monomers corresponding to the above-described various repeating structural units may be copolymerized.

[0080] In the hydrocarbon-based acid-decomposable polymer, the molar ratio of respective repeating structural units contained is appropriately determined to control the dry etching resistance of resist, suitability for standard developer, adhesion to substrate, resist profile and performances generally required of the resist, such as resolving power, heat resistance and sensitivity.

[0081] Specific example embodiments of monomer that can be polymerized into a polymer and act as a polymer matrix of which solubility in an alkali developer increases and solubility in an organic solvent decreases under the action of an acid include styrene, p-hydroxystyrene, other alkylsubstituted styrenes and p-hydroxystyrenes; monomers comprising alkyl-cyclopentyl (meth)acrylates or alkyl-adamantyl (meth)acrylates including 1-ethyl-l-cyclopentyl (meth)acrylate, 2-ethyl-2- adamantyl (meth)acrylate, 2-methyl-2-adamantyl acrylate, 2-methyl-2-adamantyl methacrylate, 2- ethyl-2-adamantyl acrylate, 2-ethyl-2-adamantyl methacrylate, 2-isopropyl-2-adamantyl acrylate and 2-isopropyl-2-adamantyl methacrylate are preferable and 2-methyl-2-adamantyl methacrylate, 2- ethyl-2-adamantyl methacrylate and 2-isopropyl-2-adamantyl methacrylate, 1-ethyl-l-cyclohexyl acrylate and 1-ethyl-l-cyclohexyl methacrylate; monomers comprising of a lactone structure, a cyclic carbonate structure, or a sultone structure, including a-gamma-butyrolactone methacrylate, 3- hydroxy-l-adamantyl methacrylate; and other functional monomers including 3-hydroxy-l-adamantyl acrylate, 3-hydroxy-l-adamantyl methacrylate, 3,5-dihydroxy-l-adamantyl acrylate, 3,5-dihydroxy-l- adamantyl methacrylate, (3,5-dihydroxy-l-adamantyloxycarbonyl)methyl acrylate and (3,5- dihydroxy-l-adamantyloxycarbonyl)methyl methacrylate; 2-methyl-2-adamantyloxycarbonylmethyl acrylate, adamantyloxycarbonylmethyl methacrylate, 2-ethyl-2-adamantyloxycarbonylmethyl acrylate, 2-ethyl-2-adamantyl methacrylate, hexahydro-2-oxo-3,5-methano-2H-cyclopenta[b]furan-6- ylacrylate, hexahydro-2-oxo-3,5-methano-2H-cyclopenta[b]furan-6-yl methacrylate, tetrahydro-2- oxo-3-furyl acrylate, tetrahydro-2-oxo-3-furyl methacrylate, 2-(5-oxo-4-oxatricyclo[4.2.1.03,7]nonan- 2-yloxy)-2-oxoethyl acrylate and 2-(5-oxo-4-oxatricyclo[4.2.1.03,7]nonan-2-yloxy)-2-oxoethyl methacrylate. Non-limiting examples of monomers and polymers are also described in US Pat. 8,507,176, US Pat. 9,557,641, US Pat. 10,705,428, and US Pat. Publ. 20220091506, which are incorporated herein by reference.(B) Compound Capable of Generating an Acid Upon Irradiation with Actinic Rays or Radiation

[0082] The positive resist composition of the present disclosure contains a compound capable of generating an acid upon irradiation with actinic rays or radiation (sometimes referred to as a "photoacid generator". The photoacid generator which can be used may be appropriately selected from a photoinitiator for photocationic polymerization, a photoinitiator for photoradical polymerization, a photo-decoloring agent for coloring matters, a photo-discoloring agent, a knowncompound used for microresist or the like and capable of generating an acid upon irradiation with actinic rays or radiation, and mixtures thereof. Any suitable photoacid generator may be used in the photosensitive compositions of the present disclosurechoice of PAG may be based upon such factors as acidity, catalytic activity, volatility, diffusivity, and solubility. Examples of embodied photoacid generators include a diazonium salt, a phosphonium salt, a sulfonium salt, an iodonium salt, an imidosulfonate, an oxime sulfonate, a diazodisulfone, a disulfone and an o-nitrobenzyl sulfonate.

[0083] Suitable classes of PAGs generating sulfonic acids include, but are not limited to, sulfonium or iodonium salts, oximidosulfonates, bissulfonyldiazomethanes, and nitrobenzylsulfonate esters. The PAG may be in non-polymerized or polymeric form, for example, present in a polymerized repeating unit of the polymer matrix. Suitable photoacid generator compounds are disclosed, for example, in U.S. Pat. Nos. 5,558,978, 5,468,589, 6,844,132, 6,855,476, and 6,911,297 which are incorporated herein by reference. In some embodiments, the preferred PAGs include one or more of tris(perfluoroalkylsulfonyl)methides, tris(perfluoroalkylsulfonyl)imides, and those generating perfluoroalkylsulfonic acids.

[0084] Additional examples of suitable photoacid generators include, but are not limited to, triphenylsulfonium perfluorooctanesulfonate, triphenylsulfonium perfluorobutanesulfonate, methylphenyldiphenylsulfonium perfluorooctanesulfonate, 4-n-butoxyphenyldiphenylsulfonium perfluorobutanesulfonate, 2,4,6-trimethylphenyldiphenylsulfonium perfluorobutanesulfonate, 2,4,6- trimethylphenyldiphenylsulfonium benzenesulfonate, 2,4,6-trimethylphenyldiphenylsulfonium 2,4,6- triisopropylbenzenesulfonate, phenylthiophenyldiphenylsulfonium 4-dodecylbenzensulfonic acid, tris(-t-butylphenyl)sulfonium perfluorooctanesulfonate, tris(-t-butylphenyl)sulfonium perfluorobutanesulfonate, tris(-t-butylphenyl)sulfonium 2,4,6-triisopropylbenzenesulfonate, tris(-t- butylphenyl)sulfonium benzenesulfonate, and phenylthiophenyldiphenylsulfonium perfluorooctanesulfonate.

[0085] Examples of suitable iodonium salts include, but are not limited to, diphenyl iodonium perfluorobutanesulfonate, bis-(t-butylphenyl)iodonium perfluorobutanesulfonate, bis-(t- butylphenyl)iodonium, perfluorooctanesulfonate, diphenyl iodonium perfluorooctanesulfonate, bis- (t-butylphenyl)iodonium benzenesulfonate, bis-(t-butylphenyl)iodonium 2,4,6- triisopropylbenzenesulfonate, and diphenyliodonium 4-methoxybenzensulfonate.

[0086] Examples of tris(perfluoroalkylsulfonyl)methide and tris(perfluoroalkylsulfonyl)imide PAGs can be found in U.S. Pat. Nos. 5,554,664 and 6,306,555, each of which is incorporated herein in its entirety. Additional examples of PAGs of this type can be found in Proceedings of SPIE, Vol. 4690, pp. 817-828 (2002). Suitable methide and imide PAGs include, but are not limited to, triphenylsulfonium tris(trifluoromethylsulfonyl)methide, methylphenyldiphenylsulfonium tris(perfluoroethylsulfonyl)methide, triphenylsulfonium tris(perfluorobutylsulfonyl)methide, triphenylsulfonium bis(trifluoromethylsulfonyl)imide, triphenylsulfonium bis(perfluoroethylsulfonyl)imide, and triphenylsulfonium bis(perfluorobutylsulfonyl)imide.

[0087] Further examples of suitable photoacid generators are bis(p-toluenesulfonyl)diazomethane, methylsulfonyl p-toluenesulfonyldiazomethane, l-cyclo-hexylsulfonyl-l-(l,l- dimethylethylsulfonyl)diazomethane, bis(l,l-dimethylethylsulfonyl)diazomethane, bis(l- methylethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, 1-p-toluenesulfonyl-l- cyclohexylcarbonyldiazomethane, 2-methyl-2-(p-toluenesulfonyl)propiophenone, 2-methanesulfonyl-2-methyl-(4-methylthiopropiophenone, 2,4-methyl-2-(p-toluenesulfonyl)pent-3- one, l-diazo-l-methylsulfonyl-4-phenyl-2-butanone, 2-(cyclohexylcarbonyl-2-(p- toluenesulfonyl)propane, 1-cyclohexylsulfonyl-lcyclohexylcarbonyldiazomethane, 1-diazo-l- cyclohexylsulfonyl-3,3-dimethyl-2-butanone, l-diazo-l-(l,l-dimethylethylsulfonyl)-3,3-dimethyl-2- butanone, l-acetyl-l-(l-methylethylsulfonyl)diazomethane, l-diazo-l-(p-toluenesulfonyl)-3,3- dimethyl-2-butanone, l-diazo-l-benzenesulfonyl-3,3-dirnethyl-2-butanone, l-diazo-l-(p- toluenesulfonyl)-3-methyl-2-butanone, cyclohexyl 2-diazo-2-(p-toluenesulfonyl)acetate, tert-butyl 2- diazo-2-benzenesulfonylacetate, isopropyl-2-diazo-2-methanesulfonylacetate, cyclohexyl 2-diazo-2- benzenesulfonylacetate, tert-butyl 2 diazo-2-(p-toluenesulfonyl)acetate, 2-nitrobenzyl p- toluenesulfonate, 2,6-dinitrobenzyl p-toluenesulfonate, 2,4-dinitrobenzyl p- trifluoromethylbenzenesulfonate.

[0088] More preferred PAGs are triarylsulfonium perfluoroalkylsulfonates and triarylsulfonium tris(perfluoroalkylsulfonyl)methides. Most preferred PAGs are triphenylsulfonium perfluorooctanesulfonate (TPS-PFOS), triphenylsulfonium perfluorobutanesulfonate (TPS-Nonaflate), methyiphenyldiphenylsulfonium perfluorooctanesulfonate (TDPS-PFOS), tris(-t- butylphenyl)sulfonium perfluorobutanesulfonate (TTBPS-Nonaflate), triphenylsulfonium tris(trifluoromethylsulfonyl)methide (TPS-C1) and methyiphenyldiphenylsulfonium tris(perfluoroethylsulfonyl)methide.

[0089] Additional PAG compounds include, for example: onium salts, for example, triphenylsulfonium trifluoromethanesulfonate, (p-tert-butoxyphenyl)diphenylsulfonium trifluoromethanesulfonate, tris(p-tert-butoxyphenyl)sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate; di-t-butyphenyliodonium perfluorobutanesulfonate, and di-t- butyphenyliodonium camphorsulfonate. Non-ionic sulfonates and sulfonyl compounds are also known to function as photoacid generators, e.g., nitrobenzyl derivatives, for example, 2-nitrobenzyl- p-toluenesulfonate, 2,6-dinitrobenzyl-p-toluenesulfonate, and 2,4-dinitrobenzyl-p-toluenesulfonate; sulfonic acid esters, for example, l,2,3-tris(methanesulfonyloxy)benzene, 1,2,3- tris(trifluoromethanesulfonyloxy)benzene, and l,2,3-tris(p-toluenesulfonyloxy)benzene; diazomethane derivatives, for example, bis(benzenesulfonyl)diazomethane, bis(p- toluenesulfonyl)diazomethane; glyoxime derivatives, for example, bis-O-(p-toluenesulfonyl)-a- dimethylglyoxime, and bis-O-(n-butanesulfonyl)-a-dimethylglyoxime; sulfonic acid ester derivatives of an N-hydroxyimide compound, for example, N-hydroxysuccinimide methanesulfonic acid ester, N- hydroxysuccinimide trifluoromethanesulfonic acid ester; and halogen-containing triazine compounds, for example, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-l,3,5-triazine, and 2-(4- methoxynaphthyl)-4,6-bis(trichloromethyl)-l,3,5-triazine. Suitable non-polymerized photoacid generators are further described in U.S. Pat. No. 8,431,325 to Hashimoto et al. in column 37, lines 11- 47 and columns 41-91. Other suitable sulfonate PAGs include sulfonated esters and sulfonyloxy ketones, nitrobenzyl esters, s-triazine derivatives, benzoin tosylate, t-butylphenyl a-(p- toluenesulfonyloxy)-acetate, and t-butyl a-(p-toluenesulfonyloxy)-acetate; as described in U.S. Pat. Nos. 4,189,323 and 8,431,325. PAGs that are onium salts typically comprise an anion having a sulfonate group or a non-sulfonate type group, such as a sulfonamidate group, a sulfonimidate group, a methide group, or a borate group.

[0090] The photoresist composition may optionally comprise a plurality of PAGs. The plural PAGs may be polymeric, non-polymeric, or may include both polymeric and non-polymeric PAGs. In someembodiments, each of the plurality of PAGs is non-polymeric. In some embodiments, when a plurality of PAGs are used, a first PAG comprises a sulfonate group on the anion and a second PAG comprises an anion that is free of sulfonate groups, such anion containing for example, a sulfonamidate group, a sulfonimidate group, a methide group, or a borate group such as described above.

[0091] In some embodiments, the PAG is a polymeric PAG, wherein the compound capable of generating an acid upon irradiation with actinic rays or radiation is introduced into the main or side chain of the polymer. Example embodiments include, for example, compounds described in U.S. Pat. No. 3,849,137, German Patent 3,914,407, JP-A-63-26653, JP-A-55-164824, JP-A-62-69263, JP-A-63- 146038, JP-A-63-163452, JP-A-62-153853 and JP-A-63-146029.

[0092] Typically, the photoresist composition may include a non-polymerized photoacid generator in an amount from about 1 to 65 wt %, from about 5 to 55 wt %, or from about 8 to 30 wt %, based on total solids of the photoresist composition. In some embodiments, the photoresist composition may include two or more different non-polymerized photoacid generators in a combined amount from about 1 to 65 wt %, from about 5 to 55 wt %, or from about 8 to 30 wt %, based on total solids of the photoresist composition. In some embodiments, the photoacid generator mixtures comprises 2 or 3 photoacid generators. Such mixtures may be of the same class or different classes. Examples of preferred mixtures include sulfonium salts with bis-sulfonyldiazomethane compounds, sulfonium salts and imidosulfonates, and two sulfonium salts.(C) Bio-Based Solvent

[0093] The photoresist composition further includes a bio-based solvent for dissolving the components of the composition and facilitating its coating on a substrate. Generally, the bio-based solvent may comprise one or more of a ketone-based solvent, an ester-based solvent, an alcohol- based solvent, an amide-based solvent, an ether-based solvent, and a hydrocarbon-based solvent.

[0094] The embodied bio-based solvent may have one or more of the following features: a. They are derived from biomaterials such that they comprise an amount of carbon-14 sufficient to produce a decay of at least 0.1 dpm / gC (disintegrations per minute per gram carbon); b. the bio-based photoresist solvent needs to be of high to ultra-high purity. Solvents must be purified to extremely low-level metal content. The metal element concentration may be measured according to inductively coupled plasma mass spectrometry (e.g., an inductively coupled plasma mass spectrometer, Agilent 7500cs (ICP-MS equipment) manufactured by Agilent Technologies, Inc.). In some embodiments, the bio-based solvent should comprise 1 parts per million (ppm) or less of metal element concentration of one or more of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn. In some embodiments, the biobased solvent should comprise 0.1 parts per million (ppm) or less of metal element concentration of one or more of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn. In some embodiments, the bio-based solvent should comprise 0.1 parts per million (ppm) or less of metal element concentration of each of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn. In some embodiments, the bio-based solvent should comprise 0.01 parts per million (ppm) or less of metal element concentration of each of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn. In some embodiments, the metal element concentration of each of Na, K,Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn is independently 5, 4, 3, 2, 1, 0.5, 0.1, 0.05, 0.01, 0.005, or 0.001 ppm or less. In some embodiments, the metal element concentration of each of Na and Ca is 0.75, 0.5, 0.1, 0.05, 0.01, 0.005, or 0.001 ppm or less, each of Al, K, Fe, Mg, and Zn is 0.25 ppm or less, and each of Cu, Mn, Li, Cr, and Ni is 0.1 ppm or less. In some embodiments, the bio-based solvent comprises 0.001-1 ppm of metal element concentration of each of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn. c. organic compounds or impurities may also create contamination issues in the semiconductor manufacturing process. In addition to minimizing the amounts of impurities in the solvent, it is necessary to reduce or eliminate organic impurities as well. In particular, relatively low molecular weight organic compounds pose a significant challenge to semiconductor processes as they can be challenging to remove via filtration techniques and form particle contamination, especially, a fine pattern (for example, 30 nm node or less). In some embodiments, the bio-based rinsing solution comprises 5 ppm or less of an alkane or alkene having a carbon number of 22 or less ("Ci.22alkane / alkene"). In some embodiments, the bio-based rinsing solution comprises 5, 4, 4, 2, 1, 0.5, 0.1, 0.05, or 0.01 ppm or less of Ci-22alkane / alkene. In some embodiments, the concentration of Cl-22 alkane / alkene is from 0.001-1 ppm. The content of Ci.22alkane / alkene may be measured according to a gas chromatography mass spectrometry (e.g., GCMS-QP2010 (a gas chromatography mass spectrometer) manufactured by Shimadzu Corporation) connected to a pyrolysis apparatus (e.g., PY2020D manufactured by Frontier Lab). d. in addition to metals and low molecular weight organics, general particle contamination comprising nano- to microscale particulates stemming from various other sources also results in device defects that negatively impact yield. Therefore, as noted above, it is critical that any trace particles be removed from the bio-based solvents. Specifically, according to the purification method, the number of particles having a particle size of 0.15 pm or more contained in the solvent can be, for example, 20 particles / mL or less, 10 particles / mL or less, or even 5 particles / mL or less. Particle count is measured by liquid particle count techniques as well as on wafer measurements. For example, after depositing a specified amount of solvent on a substrate and spinning it off at a specified number of revolutions, the wet particle amount is further dried at a specified number of revolutions, and then the number of defects on the substrate is determined by, for example, a KLA Surfscan SP7 unpatterned wafer inspection system; and e. The bio-based solvent can be characterized by its Hansen solubility parameters. The biobased solvent herein should have a dispersion parameter of about 14.5-17 MPa05, and the sum of a polarity parameter and a hydrogen bonding parameter is about 14-20 MPa05. More in particular, a selected solvent has a dispersion parameter value of about 15 to 16 MPa05, or for example from 15.4 to 15.9 MPa05; and a sum of the polarity parameter and the hydrogen bonding parameter is 15 to about 19 MPa05, more preferably from 15.5 to 18.5 MPa05. f. The boiling point of the solvent is preferably from 50° C to less than 250° C and the ignition point of the solvent used at the negative development is preferably 200° C or more.

[0095] Examples of the ketone-based solvent include 2-heptanone, 1-octanone, 2-octanone, 1- nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, 4-methyl-2-pentanone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methyl naphthyl ketone, isophorone, and dihydrolevoglucosenone. Preferred ketone- based solvents include 2-heptanone, cyclohexanone, cyclopentanone, methyl ethyl ketone, methyl isobutyl ketone, and dihydrolevoglucosenone.

[0096] Examples of the ester-based solvent include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, ethyl methoxyacetate, ethyl ethoxyacetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, 2- methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3- methyl-4-methoxypentyl acetate, 4-methyl-4-methoxypentyl acetate, propylene glycol diacetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, ethyl 2- hydroxypropionate, methyl-3-methoxypropionate, ethyl-3-methoxypropionate, ethyl-3- ethoxypropionate and propyl-3-methoxypropionate.

[0097] Examples of the alcohol-based solvent include an alcohol such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl methyl isobutyl carbinol, alcohol, n-heptyl alcohol, n-octyl alcohol, n-decanol and 3-methoxy-l-butanol; a glycol-based solvent such as ethylene glycol, diethylene glycol and triethylene glycol; and a hydroxyl group-containing glycol ether-based solvent such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methoxymethyl butanol, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol methyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether and propylene glycol monophenyl ether. Among these, a glycol ether-based solvent is preferred, with propylene glycol monomethyl ether being most preferred.

[0098] Examples of the ether-based solvent include, in addition to the hydroxyl group-containing glycol ether-based solvents above, a hydroxyl group-free glycol ether-based solvent such as propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol dimethyl ether and diethylene glycol diethyl ether; dioxane; tetrahydrofuran; anisole; perfluoro-2-butyltetrahydrofuran; and 1,4- dioxane. A glycol ether-based solvent is preferably used.

[0099] Examples of the hydrocarbon-based solvent include an aromatic hydrocarbon-based solvent such as toluene and xylene, an aliphatic hydrocarbon-based solvent such as pentane, hexane, octane, decane, 2,2,4-trimethylpentane, 2,2,3-trimethylhexane, perfluorohexane and perfluoroheptane, and an aromatic hydrocarbon-based solvent such as toluene, xylene, ethylbenzene, propylbenzene, 1- methylpropylbenzene, 2-methylpropylbenzene, dimethylbenzene, diethylbenzene, ethylmethylbenzene, trimethylbenzene, ethyldimethylbenzene and dipropylbenzene. Among these, an aromatic hydrocarbon-based solvent is preferred. Propylene carbonate is also preferable as a solvent.

[0100] In some embodiments, the bio-based solvent comprises a solvent represented by formula (1):O (1) x — c — o — X2In formula (1), X1and X2each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxyl group, an alkoxycarbonyl group, a carboxyl group, a hydroxyl group, a cyano group or a halogen atom, and X1and X2may combine with each other to form a ring. X1and X2each is preferably a hydrogen atom or an alkyl group, and the alkyl group of X1and X2may be substituted by a hydroxyl group, a carbonyl group, a cyano group or the like.

[0101] Examples of the solvent represented by formula (1) include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, hydroxyisobutyrate methyl ester, ethyl 2- hydroxypropionate, gamma-butyrolactone, and gamma-valerolactone.

[0102] In some embodiments, in the solvent represented by formula (1), X1and X2each is preferably an unsubstituted alkyl group, more preferably an alkyl acetate, still more preferably butyl acetate or ethyl lactate. In other embodiments wherein X1and X2combine with each other to form a ring, the solvent is most preferably gamma-butyrolactone and gamma-valerolactone. In other embodiments wherein X1and X2are each an alkyl group and are substituted by a hydroxyl group, the solvent is most preferably hydroxyisobutyrate methyl ester.

[0103] The solvent represented by formula (1) may be used in combination with one or more other solvents. In this case, the solvent used in combination is not particularly limited as long as it can be mixed with the solvent represented by formula (1) without causing separation, and the solvents represented by formula (1) may be used in combination with each other or the solvent represented by formula (1) may be used by mixing it with a solvent selected from other ester-based, ketone-based, alcohol-based, amide-based, ether-based and hydrocarbon-based solvents. As for the solvent used in combination, one or more species may be used but from the standpoint of obtaining a stable performance, one species is preferably used. In the case where one species of the solvent used in combination is mixed and used, the mixing ratio between the solvent represented by formula (1) and the solvent used in combination is usually from 20:80 to 99:1, preferably from 50:50 to 97:3, more preferably from 60:40 to 95:5, and most preferably from 60:40 to 90:10.

[0104] In some embodiments, the bio-based solvent comprises a solvent represented by formula (2):In formula (2), X3and X5each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxyl group, an alkoxycarbonyl group, a carboxyl group, a hydroxyl group, a cyano group or a halogen atom, and X3and X5may combine with each other to form a ring. X3and X5each is preferably a hydrogen atom or an alkyl group. X4represents an alkylene group or a cycloalkylene group. X4is an alkyl group. The alkyl group of X3, X4and X5may be substituted by a hydroxyl group, a carbonyl group, a cyano group or the like. In formula (2), the alkylene group of X4may have an ether bond in the alkylene chain.

[0105] Examples of the solvent represented by formula (2) include propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methyl-3-methoxypropionate, ethyl-3- methoxypropionate, ethyl-3-ethoxypropionate, propyl-3-methoxypropionate, ethyl methoxyacetate, ethyl ethoxyacetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3- methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, 2-ethoxybutyl acetate, 4- ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4- methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3- methyl-4-methoxypentyl acetate and 4-methyl-4-methoxypentyl acetate.

[0106] The bio-based solvent represented by formula (2) may be used in combination with one or more other solvents, the other solvents being optionally bio-based. In this case, the solvent used in combination is not particularly limited as long as it can be mixed with the bio-based solvent represented by formula (2) without causing separation, and the bio-based solvents represented by formula (2) may be used in combination with each other or the bio-based solvent represented by formula (2) may be used by mixing it with a solvent selected from other ester-based, ketone-based, alcohol-based, amide-based, ether-based and hydrocarbon-based solvents. As for the solvent used in combination, one or more species may be used, but from the standpoint of obtaining a stable performance, one species is preferably used. In the case where one species of the solvent used in combination is mixed and used, the mixing ratio between the bio-based solvent represented by formula (2) and the solvent used in combination is usually from 20:80 to 99:1, preferably from 50:50 to 97:3, more preferably from 60:40 to 95:5, and most preferably from 60:40 to 90:10.

[0107] A solvent represented by the following formula (3) may also be used as the solvent:wherein X6and X8each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxyl group, an alkoxycarbonyl group, a carboxyl group, a hydroxyl group, a cyano group or a halogen atom, and Xsand X8or Xsand X7or and X7and X8may combine with each other to form a ring; andX7represents an alkylene group or a cycloalkylene group. Examples of the solvent represented by formula (3) include ethyl 3-ethoxypropionate, methyl 4-methoxy valerate, or ethyl 4-ethoxy valerate.

[0108] The solvent represented by formula (3) may be used in combination with one or more other solvents. In this case, the solvent used in combination is not particularly limited as long as it can be mixed with the solvent represented by formula (3) without causing separation, and the solvents represented by formula (3) may be used in combination with each other or the solvent represented by formula (3) may be used by mixing it with a solvent selected from other ester-based, ketone-based, alcohol-based, amide-based, ether-based and hydrocarbon-based solvents. As for the solvent used in combination, one or more species may be used but from the standpoint of obtaining a stable performance, one species is preferably used. In the case where one species of the solvent used in combination is mixed and used, the mixing ratio between the solvent represented by formula (3) and the solvent used in combination is usually from 20:80 to 99:1, preferably from 50:50 to 97:3, more preferably from 60:40 to 95:5, and most preferably from 60:40 to 90:10.

[0109] Additional blends of bio-based solvents include the bio-based solvent described in any of (1)- (3) at about 20-80 wt% in combination with solvent compositions of about 10-70 wt% C1-C4 lactate ester and about 10-70 wt% Cj-Cgaliphatic alcohol as described in US Patent 7,754,104.

[0110] The total solvent content (i.e., cumulative solvent content for all solvents) in the photoresist compositions is typically from 40 to 99 wt %, more typically from 70 to 99 wt %, and still more typically from 85 to 99 wt %, based on total weight of the photoresist composition. The desired solvent content will depend, for example, on the desired thickness of the coated photoresist layer and coating conditions.(D) Basic Compound

[0111] The photoresist composition of the present disclosure may comprise (D) a basic compound or base additive for reducing the change of performance in aging from exposure until heating or to act as a diffusion control agent. One purpose of the base additive is to scavenge protons present in the photosensitive composition prior to being irradiated by the actinic radiation. The base prevents attack and cleavage of the acid labile groups by the undesirable acids, thereby increasing the performance and stability of the photosensitive composition. In addition, the base can act as a diffusion control agent to prevent the photogenerated acid from migrating too far after exposure and lowering resolution. The percentage of base in the photosensitive composition should be significantly lower than the photoacid generator or otherwise the photosensitivity becomes too low. The preferred range of the base compounds, when present, is from about 3 wt % to about 50 wt % of the photoacid generator compound.

[0112] Suitable examples of base additives include, but are not limited to, amine, guanidines, aminopyrrolidines, pyrazoles, pyrazolines, piperazines, aminomorpholines, aminoalkylmorpholines and piperidines. More preferred examples of the compound include a compound having an imidazole structure, a diazabicyclo structure, a trialkylamine structure, an aniline structure or a pyridinestructure; an alkylamine derivative having a hydroxyl group and / or an ether bond; and an aniline derivative having a hydroxyl group and / or an ether bond.

[0113] Suitable examples of base additives include, but are not limited to, cyclopropylamine, cyclobutylamine, cyclopentylamine, dicyclopentylamine, dicyclopentylmethylamine, dicyclopentylethylamine, cyclohexylamine, dimethylcyclohexylamine, dicyclohexylamine, dicyclohexylmethylamine, dicyclohexylethylamine, dicyclohexylbutylamine, cyclohexyl-t-butylamine, cycloheptylamine, cyclooctylamine, 1-adamantanamine, 1-dimethylaminoadamantane, 1- diethylaminoadamantane, 2-adamantanamine, 2-dimethylaminoadamantane, 2-aminonorbornene, and 3-noradamantanamine, 2-methylimidazole, tetramethyl ammonium hydroxide, tetrabutylammonium hydroxide, triisopropylamine, triocylamine, tridodecylamine, 4- dimethylaminopryidine, 4,4'-diaminodiphenyl ether, 2,4,5-triphenylimidazole, 1,4- diazabicyclo[4.3.0]non-5-ene and l,5-diazabicyclo[4.3.0]non-5-ene, and 1,8- diazabicyclo[5.4.0]undec-7-ene, guanidine, 1,1-dimethylguanidine, 1,1,3,3-tetramethylguanidine, 2- aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-dimethylaminopyridine, 4- dimethylaminopyridine, 2-diethylaminopyridine, 2-(aminomethyl)pyridine, 2-amino-3- methylpyridine, 2-amino-4-methylpyridine, 2-amino-5-methylpyridine, 2-amino-6-methylpyridine, 3- aminoethylpyridine, 4-aminoethylpyridine, 3-aminopyrrolidine, piperazine, N-(2- aminoethyl)piperazine, N-(2-aminoethyl)piperidine, 4-amino-2,2,6,6-tetramethylpiperidine, 4- piperidinopiperidine, 2-iminopiperidine, l-(2-aminoethyl)pyrrolidine, pyrazole, 3-amino-5- methylpyrazole, 5-amino-3-methyl-l-p-tolylpyrazole, pyrazine, 2-(aminomethyl)-5-methylpyrazine, pyrimidine, 2,4-diaminopyrimidine, 4,6-dihydroxypyrimidine, 2-pyrazoline, 3-pyrazoline, N- aminomorpholine, N-(2-aminoethyl)morpholine, trimethylimidazole, triphenylimidazole, and methyldiphenylimidazole. More preferred base additives are tridodecylamine, 2,4,5-triphenyl imidazole, l,5-diazobicyclo[4.3.0]non-5-ene and l,8-diazobicyclo[5.4.0]undec-7-ene.

[0114] The base additive may be in non-polymeric or polymer-bound form. When in polymeric form, the quencher is present in polymerized units on the first polymer or second polymer. The polymerized units containing the quencher are typically present in an amount of from 0.1 to 30 mole %, preferably from 1 to 10 mole %, and more preferably from 1 to 2 mole %, based on total repeating units of the polymer.(E) Surfactant

[0115] The photoresist composition of the present disclosure may further comprise (E) a surfactant, more preferably any one fluorine-containing and / or silicon-containing surfactant (a fluorine- containing surfactant, a silicon-containing surfactant or a surfactant containing both a fluorine atom and a silicon atom) or two or more species thereof.

[0116] When the photoresist composition of the present disclosure contains the surfactant (E), a resist pattern with good sensitivity, resolution and adhesion as well as less development defects can be obtained when an exposure light source of 250 nm or less, particularly 220 nm or less, is used.

[0117] Exemplary surfactants include fluorinated and non-fluorinated surfactants and can be ionic or non-ionic, with non-ionic surfactants being preferable. Examples of the fluorine-containing and / or silicon-containing surfactant include surfactants described in JP-A-62-36663, JP-A-61-226746, JP-A-61- 226745, JP-A-62-170950, JP-A-63-34540, JP-A-7-230165, JP-A-8-62834, JP-A-9-54432, JP-A-9-5988, JP-A-2002-277862 and U.S. Pat. Nos. 57405772075,360,692, 5,529,881, 5,296,330, 5,436,098, 5,576,143, 5,294,511 and 5,824,451. Examples of the commercially available surfactant which can be used include a fluorine-containing surfactant and a silicon-containing surfactant, such as EFtop EF301 and EF303 (produced by Shin-Akita Kasei K.K.); Florad FC430, 431 and 4430 (produced by Sumitomo 3M Inc.); Megafac F171, F173, F176, F189, F113, F110, F177, F120 and R08 (produced by Dainippon Ink & Chemicals, Inc.); Surfion S-382, SC101, 102, 103, 104, 105 and 106 (produced by Asahi Glass Co., Ltd.); Troysol S-366 (produced by Troy Chemical); GF-300 and GF-150 (produced by Toagosei Chemical Industry Co., Ltd.); Surftlon S-393 (produced by Seimi Chemical Co., Ltd.); Eftop EF121, EF122A, EF122B, RF122C, EF125M, EF135M, EF351, 352, EF801, EF802 and EF601 (produced by JEMCO Inc.); PF636, PF656, PF6320 and PF6520 (produced by OMNOVA); and FTX-204D, 208G, 218G, 230G, 204D, 208D, 212D, 218 and 222D (produced by NEOS Co., Ltd.). In addition, polysiloxane polymer KP-341 (produced by Shin-Etsu Chemical Co., Ltd.) may also be used as the silicon-containing surfactant. Exemplary fluorinated non-ionic surfactants include perfluoro C4surfactants such as FC-4430 and FC- 4432 surfactants, available from 3M Corporation; and fluorodiols such as POLYFOX PF-636, PF-6320, PF-656, and PF-6520 fluorosurfactants from Omnova. In an aspect, the photoresist composition further includes a surfactant polymer including a fluorine-containing repeating unit.(F) Photo-decomposable quencher

[0118] Photo-decomposable quenchers generate a weak acid upon irradiation. The acid generated from a photo-decomposable quencher is not strong enough to react rapidly with acid-labile groups that are present in the polymer binder. Exemplary photo-decomposable quenchers include, for example, photo-decomposable cations, and preferably those also useful for preparing strong acid generator compounds, paired with an anion of a weak acid (pKa>-l) such as, for example, an anion of a Ci-20 carboxylic acid or Ci.2osulfonic acid. Exemplary carboxylic acids include formic acid, acetic acid, propionic acid, tartaric acid, succinic acid, cyclohexanecarboxylic acid, benzoic acid, salicylic acid, and the like. Exemplary sulfonic acids include p-toluene sulfonic acid, camphor sulfonic acid and the like. In a preferred embodiment, the photo-decomposable quencher is a photo-decomposable organic zwitterion compound such as diphenyliodonium-2-carboxylate. Exemplary photo-decomposable quenchers are onium carboxylates, preferably an iodonium salt or a sulfonium salt. Furthermore, the carboxylate residue of the onium carboxylate for use in the present disclosure preferably contains no aromatic group and no carbon-carbon double bond. The anion moiety is preferably a linear, branched, monocyclic or polycyclic alkylcarboxylate anion having a carbon number of 1 to 30, more preferably an anion of the carboxylic acid with the alkyl group being partially or entirely fluorine-substituted. The alkyl chain may contain an oxygen atom. By virtue of such a construction, the transparency to light of 220 nm or less is ensured, the sensitivity and resolution are enhanced, and the defocus latitude depended on line pitch and the exposure margin are improved.

[0119] Examples of the anion of a fluorine-substituted carboxylic acid include anions of fluoroacetic acid, difluoroacetic acid, trifluoroacetic acid, pentafluoropropionic acid, heptafluorobutyric acid, nonafluoropentanoic acid, perfluorododecanoic acid, perfluoro-tridecanoic acid, perfluorocyclohexanecarboxylic acid and 2,2-bistrifluoromethylpropionic acid.

[0120] These onium carboxylates can be synthesized by reacting a sulfonium, iodonium or ammonium hydroxide and a carboxylic acid with silver oxide in an appropriate solvent. The content ofthe onium carboxylate in the composition is generally from 0.1 to 20 mass %, preferably from 0.5 to 10 mass %, more preferably from 1 to 7 mass %, based on the entire solid content of the composition.

[0121] The photo-decomposable quencher may be in non-polymeric or polymer-bound form. When in polymeric form, the photo-decomposable quencher is present in polymerized units on the first polymer or second polymer. The polymerized units containing the photo-decomposable quencher are typically present in an amount from 0.1 to 30 mole %, preferably from 1 to 10 mole %, and more preferably from 1 to 2 mole %, based on total repeating units of the polymer.(G) Other Additives

[0122] The positive resist composition of the present disclosure may further contain, for example, an actinic or contrast dye, an anti-striation agent, a plasticizer, a speed enhancer, a photosensitizer, a light absorbent, an alkali-soluble resin, a dissolution inhibitor, or a compound for accelerating dissolution in a developer (for example, a phenol compound having a molecular weight of 1,000 or less, or a carboxyl group-containing alicyclic or aliphatic compound), a resin having at least either a fluorine atom or a silicon atom, and the like, or combinations thereof. If present, the optional additives are typically present in the photoresist compositions in an amount from 0.01 to 10 wt %, based on total solids of the photoresist composition.

[0123] The phenol compound having a molecular weight of 1,000 or less can be easily synthesized by one skilled in the art with reference to the methods described, for example, in JP-A-4-122938, JP-A-2- 28531, U.S. Pat. No. 4,916,210 and European Patent 219294.

[0124] Specific examples of the carboxyl group-containing alicyclic or aliphatic compound include, but are not limited to, a carboxylic acid derivative having a steroid structure, such as cholic acid, deoxycholic acid and lithocholic acid, an adamantanecarboxylic acid derivative, an adamantanedicarboxylic acid, a cyclohexanecarboxylic acid and a cyclohexanedicarboxylic acid.

[0125] The photoresist compositions optionally contain additional additives including actinic and contrast dyes, anti-striation agents, plasticizers, speed enhancers, sensitizers, photo-decomposable quenchers (also known as photo-decomposable bases), basic quenchers, surfactants, a resin having at least either a fluorine atom or a silicon atom, an alkali-soluble resin, a dissolution inhibitor, and a compound for accelerating dissolution in a developer, and the like, or combinations thereof.PRODUCTION OF BIO-BASED SOLVENTS

[0126] As mentioned previously, the bio-based solvents can be derived from bio-based materials, including sugars, starches, corns, natural fibers, sugarcanes, beets, citrus fruits, woody plants, cellulosics, lignocelluosics, hemicelluloses, potatoes, plant oils, other polysaccharides such as pectin, chitin, levan, and pullulan, and combinations thereof. According to a particular embodiment, at least one bio-based material is selected from corn, sugarcane, beet, potato, starch, citrus fruit, woody plant, cellulosic lignin, plant oil, natural fiber, oily wood feedstock, and combinations thereof.

[0127] Use of bio-based materials to create homogenous chemicals involves dramatically different processes from fossil fuel feedstocks. Crude oil feedstock has low functionality which makes it directly suitable for use as a solvent or fuel after prior processing (for example cracking and isomerisation). Functional groups, such as C=O and OH, are added to crude oil derived feedstock to produce bulk andspecialty chemicals. Here, special care is taken to ensure selective addition of the functional group without over functionalization of the substrates. Contrastingly, biomass derived feedstocks, such as cellulose and hemicellulose, contain far too much functionality to use directly as fuels or bulk chemicals, and therefore require selective strategies for isolation and defunctionalization.

[0128] The three conversion technologies for carbohydrates and cellulose include biological conversion (enzymatic fermentation), catalytic conversion (dehydration, rehydration, hydrogenation, hydrolysis, aldo condensation, hydrogenolysis, oxidation, etc.), and thermochemical and thermocatalytic conversion. Although production of first-generation biofuels (bio-ethanol and biobutanol) is well established, this process relies on starch and sugar feeds which compete with the food chain. Hydrolysis of cellulosic feedstock to fermentable sugars has been achieved as alternative routes to bio-alcohols as fuels in order to avoid food sources as feedstock. However, slow reaction rate, high cost and sensitivity of enzymes and energy intensive subsequent distillation and drying steps remain challenges to achieving cost-effectiveness in these processes. Thermocatalytic conversions offer an alternative to enzymatic fermentation for transforming biomass (such as wood, sugarcane bagasse or corn stover) to aromatic compounds. For example, processes have been developed that uses zeolitebased catalysts to produce gases which are then converted to benzene, xylene and toluene (bio-BTX). Thermochemical processes such as gasification, pyrolysis, torrefaction and liquefaction require intense heating at elevated temperatures, therefore raising energy efficiency concerns. In addition, the selectivity in bio-oils produced from pyrolysis is extremely poor, therefore inevitably requiring expensive additional upgrading and separation steps. Finally, use of catalytic conversion of cellulosic biomass and cellulose derived intermediates to fuels, fuel additives and chemicals may be used. Multiple types of catalysts have shown potential in this space, for example noble metal catalyst systems for use in a variety of the key reaction steps, such as hydrolysis, dehydration, hydrodeoxygenation (HDO), hydrogenation and oxidation leading to value added products from cellulosic biomass. Examples of catalytically derived compounds include 5-hydroxymethylfurfural, furfural, and acetic acid. However, high catalyst costs and catalyst poisoning continue to pose issues for these processes.

[0129] Due to the ease and simplicity of fermentation, much of the research field has looked at microorganisms as a potentially ideal source for bio-product generation. However, as noted above, the fermentation process by natural microbes yields a low titer of products and the appearance of a multitude of by-products, which has ultimately led to very limited commercial bioproduct production and only in areas, such as fuels, where the impurities and byproducts are not a significant limitation. However, with the recent developments in genetic-engineering technologies, it is now possible to modify microbial strains to utilize alternative substrates via hydrolyzing the complex substrates into simple fermentable forms. In fact, applicants believe that the rapid progress in the fields of synthetic biology and metabolic engineering is leading to the generation of a wide range of advanced biomaterials that are economically viable due to the maximized yield and productivity and that these products will are sustainable with reduced carbon footprints.

[0130] In particular, the gene editing technology clustered regularly interspaced short palindromic repeats (CRISPR) and the CRISPR-associated system (Cas) is an RNA guided immune system in bacteria and archaea that has been engineered to be a high efficient genome editing tool that has been implemented in a broad range of organisms, such as bacteria, yeast, plants, mammal cells, and human cells. The recent development of CRISPR-Cas technology opens a new avenue in creating microbialbiorefineries for potentially enhanced biosolvent production. Example CRISPR technologies include inducible on / off genetic circuits in response to environmental stimuli that work through the regulation of targeted genome editing (TGE) by minimizing metabolic burden and maximizing fermentation efficiency. Genetic modification can include single gene knock-in or knock-out, but also successes have been reported for multiplex genome editing and transcriptional regulation, including repression and activation.

[0131] Clostridia are a type of bacteria that have long been studied for biobutanol production through its acetone-butanol-ethanol (ABE) fermentation pathway. Although tremendous efforts have been invested on the metabolic engineering of solventogenic clostridial strains for enhanced biobutanol production, only very limited success has been achieved. This is because, on one hand, there are several intrinsic byproducts in ABE fermentation including fatty acids, acetone and ethanol that are hard to eliminate; on the other, the ABE fermentation for butanol production goes through a biphasic process and is subjected to complicated metabolic regulation. Recent efforts have focused on modifying the ABE fermentation pathway of Clostridia in order to reduce unwanted byproducts while increasing overall yield of butanol. One method used to achieve these modifications involves the use of CRISPR-Cas9 systems.

[0132] In one process, as described in U.S. Pat. No. 11,142,751 B2, herein incorporated by reference, the endogenous CRISPR-Cas system of C. tyrobutyricum, was used to successfully engineer C. tyrobutyricum for enhanced butanol production. By introducing an adhE2 gene and inactivating the native catl gene, the obtained mutant produced a record high of 26.2 g / L butanol in a batch fermentation.

[0133] Additionally, production of bio-based butyl acetate has been demonstrated using microbial fermentation of glucose by butanol-producing Clostridium acetobutylicum NJ4 with the supplementation of exogenous acetic acid; by acetate-producing Actinobacillus succinogeneslBOz (! pflA) with the addition of exogenous butanol; and a microbial co-culture system of C. acetobutylicum NJ4 and A. succinogeneslBOz (! pflA) with the elimination of exogenous precursors (14 Biotechnol. Biofuels 203 (2021)).

[0134] Alternatively, bio-based butyl acetate has also been produced by leveraging pathways in solventogenic Clostridia for co-producing acyl-CoAs, acids and alcohols as precursors, combined with systematic metabolic engineering, resulting in strains that can produce 20.3 g / L butyl acetate (12 Nat. Commun. 4368 (2021)). Bio-based acetates such as n-butyl acetate can also be prepared from the corresponding bio-based alcohols, n-butanol, via direct Fischer esterification and transesterification reactions with bio-based acetic acid or acetate esters.

[0135] These fermentation processes produce mixtures of the desired butyl acetate along with significant levels of intermediates and impurities. For example, Yi Wang in a DOE Bioenergy Technologies Office (BETO), 2021 Project Peer Review, titled "Bioproduction and Evaluation of Renewable Butyl Acetate as a Desirable Bioblendstock for Diesel Fuel", and presented on March 16, 2021, disclosed the following composition in butyl acetate production:

[0136] A two-step biobased process, described in U.S. Pat. Publ. No. 2014 / 0329275, can convert glucose into methyl isobutyl ketone (MIBK), diisobutyl ketone (DIBK) or methyl isoamyl ketone (MIAK). The process utilizes a modified microbe that converts glucose into isovaleric acid and isocaproate. These intermediate chemicals can then be converted to the corresponding ketones. These ketones can then be reduced to the corresponding alcohols, methyl isobutyl carbinol (MIBC), diisobutyl carbinol (DIBC) or methyl isoamyl carbinol (MIAC).

[0137] U.S. Pat. 8,298,798 describes metabolically-modified microorganisms useful for producing biofuels including higher alcohols including C5-C8 alcohol from bio-based feedstocks like glucose. The methods are capable of producing C5 alcohols such as 2-methyl-l-butanol, 3-methyl-l-butanol, and 1-pentanol; C6 alcohols such as 3-methyl-l-pentanol, and 1-hexanol; C7 alcohols such as 2-isopropyl- 1-butanol, and the C8 alcohol 5-methyl-l-heptanol.

[0138] Bio-based alcohols such as hexanol can be produced by fermentation of syngas using Clostridium carboxidivorans P7 according to the methods described in 10 Front. Bioeng. Biotechnol., art. 850370 (2022). Bio-based heptanol can be prepared by catalytic hydrocracking -hydrogenation of Castor Oil fatty acid methyl esters as described in 1 ChemistrySelect 6396 (2016)).

[0139] Bio-based alcohols, acetic acid, and acetate esters can all be prepared by fermentation of sugars. Production of bio-based butyl acetate has also been demonstrated using microbial fermentation of glucose, by butanol-producing Clostridium acetobutylicum NJ4 with the supplementation of exogenous acetic acid; by acetate-producing Actinobacillus succinogeneslBOz (! pflA) with the addition of exogenous butanol; and a microbial co-culture system of C. acetobutylicum NJ4 and A. succinogeneslBOz (! pflA) with the elimination of exogenous precursors (Lv, Y., Jiang, Y., Lu, J. et al. Comprehensive evaluation for the one-pot biosynthesis of butyl acetate by using microbial mono- and co-cultures. Biotechnol Biofuels 14, 203 (2021). https: / / doi.org / 10.1186 / sl3068-Q21- 02053-2).

[0140] Bio-based butyl acetate has also been produced by leveraging pathways in solventogenic Clostridia for co-producing acyl-CoAs, acids and alcohols as precursors, combined with systematic metabolic engineering, resulting in strains that can produce 20.3 g / L butyl acetate (Feng, J., Zhang, J., Ma, Y. et al. Renewable fatty acid ester production in Clostridium. Nat Commun 12, 4368 (2021). https: / / doi.org / 10.1038 / s41467-021-24038-3).

[0141] Bio-based acetates such as n-butyl acetate can also be prepared from the corresponding biobased alcohols, n-butanol, via direct Fischer esterification and transesterification reactions with biobased acetic acid or acetate esters.

[0142] Bio-based processes can produce ketones. For example, a two-step biobased process, described in US2014 / 032927, can convert glucose into methyl isobutyl ketone (MIBK), diisobutyl ketone (DIBK) or methyl isoamyl ketone (MIAK). The process utilizes a modified microbe that converts glucose into isovaleric acid and isocaproate. These intermediate chemicals can then be converted to the corresponding ketones. These ketones can then be reduced to the corresponding alcohols, methyl isobutyl carbinol (MIBC), diisobutyl carbinol (DIBC) or methyl isoamyl carbinol (MIAC).

[0143] Gommo-valerolactone can be produced from levulinic acid, which is obtained from hexoses. In a typical process, cellulosic biomasses, such as corn stover, sawgrass, or wood, is hydrolysed intoglucose and other sugars using acid catalysts. The resulting glucose can then be dehydrated via hydroxymethylfurfural to yield formic acid and levulinic acid, which cyclises to intermediate unsaturated ring compounds, which can then be hydrogenated to gommo-valerolactone.Bio-based methyl 4-methoxy valerate and ethyl 4-ethoxy valerate can be prepared from the ring opening of gommo-valerolactone with methanol or ethanol, respectively, as described in US2007 / 0142664.

[0144] Bio-based propylene can be produced from bio-based ethanol, which in turn can be produced from biomass, such as sugarcane and corn. Bio-based propylene oxide can then be produced from biobased propylene using the chlorohydrin process or the hydroperoxide process. Bio-based propylene oxide can also be produced from bio-based propylene glycol derived from bio-based glycerol as described in Chem. Commun., 2009, 3934-3936. Bio-based propylene glycol monomethyl ether can be produced from bio-based propylene oxide. Bio-based propylene glycol monomethyl ether acetate can be produced from bio-based propylene glycol monomethyl ether.

[0145] Bio-based feedstocks, such as bio-methane and bio-naphtha, can also be used in place of traditional petrochemical feedstocks in manufacturing processes to produce solvents with bio-based content. Fisher-Tropsch processes can also convert bio-based feedstocks into valuable chemicals via condensation process using syngas (CO / H2).

[0146] Process steps not specifically described herein and additional synthetic methods may further be found in such references as, Synthesis and industrial production of bio-solvents is reviewed in Oklu, et al., Bio-Solvents: Synthesis, Industrial Production and Applications, in Solvents, Ionic Liquids and Solvent Effects, IntechOpen, London (2019).PURIFICATION OF BIO-BASED SOLVENTS

[0147] Solvents used in semiconductor manufacturing processes typically must be of high to ultra- high purity. It is critical that the semiconductor wafer surface is not contaminated with any metallic impurities present in the solvents as metals inhibit the functions of semiconductor elements. In fact, micro-contamination accounts for over 50% of yield loss in IC manufacturing. Therefore, minimizing the metal impurity content of materials used in these processes is demanded as a matter of course. Solvents must be purified to extremely low-level metal content, for example, several parts per billion (ppb) to several part per trillion (ppt), is required for each metal, e.g., sodium, iron, etc.

[0148] Organic compounds or impurities may also create contamination issues in the semiconductor manufacturing process. In addition to minimizing the amounts of impurities in the solvent, it is necessary to reduce or eliminate organic impurities as well. In particular, relatively low molecular weight organic compounds pose a significant challenge to semiconductor processes as they can be challenging to remove via filtration techniques and form particle contamination, especially, a fine pattern (for example, 30 nm node or less). Possible ways that these organic impurities are introduced is through impure or unpurified solvents, or through the containers or tubing used in transporting or semiconductor forming processes. Therefore, considerable thought is required in how the solvent is purified as well as how the solvent is stored and the materials it is contact with in order to avoid an increase of impurities during storage or transport, a degeneration of components, a quantitative change in the composition, an increase of impure metal elements, or a decrease in quality caused by a deterioration of a photosensitive component due to light.

[0149] In addition to metals and low molecular weight organics, general particle contamination comprising nano- to microscale particulates stemming from various other sources also results in device defects that negatively impact yield. Therefore, as noted above, it is critical that any trace particles be removed from the bio-based solvents. While ideally the number of particles on a semiconductor surface would be zero, the number of sources make this nigh impossible. Processes for monitoring and detecting particle contamination are described in ISO 14644-1:2015 and ISO 21501-4, herein incorporated by reference.

[0150] While not limited to the descriptions herein, purification of the bio-based solvents generally uses one or more of distillation, physical or chemisorptive filtration, or an ion exchange membrane. Ultimately, the process or processes are used in such a manner as to obtain the necessary purity and levels of metals and low molecular weight organics as disclosed herein.

[0151] Distillation processes may be employed to purify bio-based solvents. Depending on the composition of the primary product from the employed process, a multi-phase distillation may be employed including a first distillation device which removes low boiling point impurities, a second distillation device which removes high boiling point impurities, and a third distillation device which removes trace water. The distillation devices are selected from multiple stage type, packing type distillation towers, or spiral spinning band type distillation towers. Spinning band type distillation towers are particularly useful to separate compounds and remove trace water to produce an electronic-grade purity solvents. Inside the spinning band type distillation tower there is equipped a spiral stirring column made of metal or Teflon which rotates at high speed to maximize the contact area of the vapor components evaporated in the tower and the liquid component condensed in the tower, so that high separation and purification efficiency can be attained through fast and effective gas-liquid equilibrium. By varying the rotation speed of the spiral stirring column in the spinning band type distillation tower, the separation efficiency can be regulated appropriately. The resultant high separation and purification efficiency makes it possible to remove the trace water and easily separate and purify the individual components having similar boiling points into an electronic grade purity.

[0152] When necessary, a metal removing step is employed which typically comprises contacting the bio-based solvent with an acidic cation exchange resin. Various metals, such as alkali metals, alkaline earth metals, and transition metals, e.g., sodium, potassium, calcium, iron, nickel, etc., can be removed by the metal removing step. Commercially available strongly acidic cation exchange resins can be used in the present disclosure. Among them, cation exchange resins of sulfonated styrene- divinylbenzene cross-linked polymer are preferred. There are two types of strongly acidic cation exchange resins, one is the porous-type made of porous resins and the other one is the gel type which is made of nonporous resins. Suitable acidic exchange resins are available from Rohm and Haas Company, e.g. AMBERLYST 15 acidic ion exchange resin. These AMBERLYST resins typically contain as much as 80,000 to 200,000 ppb of sodium and iron. Before being utilized in the process of the disclosure, the ion exchange resin should be treated with water and then a mineral acid solution to reduce the metal ion level. It is important that the ion exchange resin be rinsed with a solvent that is the same as, or at least compatible with, the solvent being purified. The procedure in this step may be similar to those procedures disclosed in U.S. Pat. No. 5,284,930 and U.S. Pat. No. 5,288,850. Generally, the cation-exchange procedure is conducted at any temperature, pressure, and flow rate which accomplishes the desired end result. Liquid Purifiers such as PURASOL and PROTEGO purifiers may be employed to remove metal impurities.

[0153] Microfilters may be provided before and after the ion exchange resin treatment in order to remove by filtration insoluble impurities contained in the solvent or fine particles which might be flown out from the ion exchange resins. A filter device having a filter medium having a pore size of 0.05 pm or less is typically used, and the solvent is circulated in the filter device, whereby the filter medium is passed twice or more. Liquid filters based on a variety of membrane and media may be used, for example MICROGARD series filters from Entegris. In some embodiments, the microfilters comprise a polytetrfluoroethylene filter material. Such methods enable efficient removal of insoluble foreign matters, particles, and metal impurities having high polarity in the solvent. Specifically, according to the purification method, the number of particles having a particle size of 0.15 pm or more contained in the solvent can be, for example, 20 particles / mL or less, 10 particles / mL or less, or even 5 particles / mL or less. Particle count is measured by liquid particle count techniques as well as on wafer measurements. For example, after depositing a specified amount of solvent on a substrate and spinning it off at a specified number of revolutions, the wet particle amount is further dried at a specified number of revolutions, and then the number of defects on the substrate is determined by, for example, a KLA Surfscan SP7 unpatterned wafer inspection system.

[0154] In addition to the above methods for purifying the solvent, further steps may include storing or handling the solvent in materials comprising a perfluoro resin, wherein the perfluoro resin comprises a polytetrafluoroethylene resin (PTFE), a tetrafluoroethylene-perfluoroalkylvinyl ether copolymer (PFA), a tetrafluoroethylene-hexafluoropropylene copolymer resin (FEP), an ethylene tetrafluoroethylene copolymer resin (ETFE), an ethylene chlorotrifluoroethylene copolymer resin (ECTFE), a polyvinylidene resin (PVDF), a polychlorotrifluoroethylene copolymer resin (PCTFE), or a polyvinyl fluoride resin (PVF) may be exemplified. Such materials may reduce the amount of low molecular weight organics, metal impurities and other particles in the solvent.

[0155] Further, according to the purification method, the amount of metal element concentration of each of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn is preferably 5 ppm or less, and more preferably 3 ppm or less. It is most preferable that none of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn are present. However, if any one of these metal elements is present, a minimum of the concentration of the existing metal element is generally 0.001 ppm or more. The metal element concentration of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn may be measured according to an inductively coupled plasma mass spectrometry (e.g., an inductively coupled plasma mass spectrometer, Agilent 7500cs (ICP-MS equipment) manufactured by Agilent Technologies, Inc.).PATTERN FORMATIONS METHODS

[0156] Patterning methods using fossil fuel derived materials have been described in detail (see Mack, C.A. (2012) Fundamental Principles of Optical Lithography: The Science of Microfabrication. Wiley. DOI:10.1002 / 9780470723876). Methods using the photoresist compositions of the disclosure will now be described. Suitable substrates on which the photoresist compositions can be coated include electronic device substrates. A wide variety of electronic device substrates may be used in the present disclosure, such as: semiconductor wafers; polycrystalline silicon substrates; packaging substrates such as multichip modules; flat panel display substrates; substrates for light emitting diodes (LEDs) including organic light emitting diodes (OLEDs); and the like, with semiconductor wafers being typical. Such substrates are typically composed of one or more of silicon, poly silicon, silicon oxide, silicon nitride, silicon oxynitride, silicon germanium, gallium arsenide, aluminum, sapphire, tungsten,titanium, titanium-tungsten, nickel, copper, and gold. Suitable substrates may be in the form of wafers such as those used in the manufacture of integrated circuits, optical sensors, flat panel displays, integrated optical circuits, and LEDs. Such substrates may be any suitable size. Typical wafer substrate diameters are 200 to 300 millimeters (mm), although wafers having smaller and larger diameters may be suitably employed according to the present disclosure. The substrates may include one or more layers or structures which may optionally include active or operable portions of devices being formed.

[0157] Typically, one or more lithographic layers such as a hardmask layer, for example, a spin-on- carbon (SOC), amorphous carbon, or metal hardmask layer, a CVD layer such as a silicon nitride (SiN), a silicon oxide (SiO), or silicon oxynitride (SiON) layer, an organic or inorganic underlayer, or combinations thereof, are provided on an upper surface of the substrate prior to coating a photoresist composition of the present disclosure. Such layers, together with an overcoated photoresist layer, form a lithographic material stack.

[0158] Optionally, a layer of an adhesion promoter may be applied to the substrate surface prior to coating the photoresist compositions. If an adhesion promoter is desired, any suitable adhesion promoter for polymer films may be used, such as silanes, typically organosilanes such as trimethoxyvinylsilane, triethoxyvinylsilane, hexamethyldisilazane, or an aminosilane coupler such as gamma-aminopropyltriethoxysilane. Particularly suitable adhesion promoters include those sold under the AP 3000, AP 8000, and AP 9000S designations, available from DuPont Electronics & Imaging (Marlborough, Mass.).

[0159] The photoresist composition is then coated on the substrate by any suitable method, including spin coating, spray coating, dip coating, doctor blading, or the like. For example, applying the layer of photoresist may be accomplished by spin coating the photoresist in solvent using a coating track, in which the photoresist is dispensed on a spinning wafer. During dispensing, the wafer is typically spun at a speed of up to 4,000 rotations per minute (rpm), for example, from 200 to 3,000 rpm, for example, 1,000 to 2,500 rpm, for a period from 15 to 120 seconds to obtain a layer of the photoresist composition on the substrate. It will be appreciated by those skilled in the art that the thickness of the coated layer may be adjusted by changing the spin speed and / or the solids content of the composition. A photoresist layer formed from the compositions of the disclosure typically has a dried layer thickness from 10 to 1000 nanometers (nm), preferably from 15 to 500 nm, and more preferably from 20 to 200 nm.

[0160] In some embodiments, prior to coating the photoresist composition on the substrate, a "prewet solvent" can be applied to the substrate, which encourages a more even distribution of the photoresist composition over the substrate and provides a more uniform coating. The pre-wet solvent can be the same solvent or solvent blend used in the photoresist composition or a different solvent or blend of solvents. The pre-wet solvent can be a bio-based organic solvent comprising an amount of carbon-14 sufficient to produce a decay of at least 0.1 dpm / gC (disintegrations per minute per gram carbon). The pre-wet solvent can be applied to the substrate by spin coating, either while being rotated kept rotated or stopped, and then rotating the substrate applied with the solvent at a first rotational speed to diffuse the solvent through an entire area of one surface, followed by applying a predetermined amount of the photoresist composition at substantially the center of the substrate while rotating the substrate at a second rotational speed, thereby diffusing the photoresist composition to the entire area of one surface to form a coating film.

[0161] Preferably, the pre-wet solvent comprises a bio-based organic solvent comprising an amount of carbon-14 sufficient to produce a decay of at least 0.1 dpm / gC (disintegrations per minute per gram carbon). More preferably, the pre-wet solvent comprises propylene glycol monomethyl ether, cyclohexanone, methyl ethyl ketone, butyl acetate, ethyl lactate, gamma-butyrolactone, gammavalerolactone, hydroxyisobutyrate methyl ester, propylene glycol monomethyl ether acetate, methyl 4-methoxy valerate, ethyl 4-ethoxy valerate, or ethyl 3-ethoxypropionate, or a combination thereof.

[0162] After the photoresist film has been applied to the substrate, an edge bead removal process may be performed. In these steps, the peripheral portion of the photoresist film adjacent to the top or coated edge and the backside or bottom edge of the substrate, as well as any coated photoresist material lying over the edge of the substrate, is contacted with a solvent so as to dissolve this unwanted material and then it is removed. This unwanted material before removal is shown graphically in FIG. 1 of U.S. Pat. No. 4,113,492 (Sato et al). More specifically, conventional spin coating steps also sometimes form undesirable edge beads on the peripheral area between the coated or top surface of the substrate and the backside or bottom surface of the substrate. These edge beads are shown graphically in FIGS. 5 and 6 of U.S. Pat. No. 4,685,975 (Kottman et al). After this solvent contact and material removal, the desired partially coated substrate is best shown graphically by FIG. 3 of U.S. Pat. No. 4,518,678 (Allen).

[0163] The solvent employed in this edge bead removal process, commonly referred to as an "edge bead remover" or "EBR", can be the same solvent or solvent blend used in the photoresist composition or a different solvent or blend of solvents. The edge bead remover can be a bio-based organic solvent comprising an amount of carbon-14 sufficient to produce a decay of at least 0.1 dpm / gC (disintegrations per minute per gram carbon). More preferably, the pre-wet solvent comprises propylene glycol monomethyl ether, cyclohexanone, methyl ethyl ketone, butyl acetate, ethyl lactate, gamma-butyrolactone, gamma-valerolactone, hydroxyisobutyrate methyl ester, propylene glycol monomethyl ether acetate, methyl 4-methoxy valerate, ethyl 4-ethoxy valerate, or ethyl 3- ethoxypropionate, or a combination thereof.

[0164] The preferred method of contacting this peripheral coating material with the solvent mixture is by applying the solvent mixture from a pressurized container by means of a nozzle directed to the backside edge of the substrate as shown in FIGS. 3, 4, and 5 of U.S. Pat. No. 4,113,492 (Sato et al). The solvent mixture is dispersed for a period of about 2 to about 20 seconds, preferably about 5 to 15 seconds, while the wafer is spun at a predetermined speed depending upon the thickness of the coating film and the diameter of the wafer. The desired amount of edge bead remover will depend upon the particular application (e.g. type and size of substrate, type of photoresist and thickness of photoresist coating).

[0165] The speed used during this dispersing of the edge bead remover is preselected to permit migration of the solvent mixture around the edge of the substrate and onto the periphery of the top surface of the wafer. The slower the speed, the further inward migration of the chemical on the top surface resulting in a larger band of coating which will be removed. Of course, the removal of a larger band of peripheral coating material means that there will be a smaller useful area remaining on the substrate for further processing (e.g. lithographic imaging and developing). Accordingly, the desired size of the peripheral band removed should be large enough to remove any uneven areas of coated material on the periphery (thus leaving a substantially uniform film thickness throughout the coatedsurface) yet be minimized so as to maximize the useful surface area on the substrate. For most applications, it is desirable to remove a peripheral band from about 0.75 mm to about 2.0 mm, with the smallest possible bands being more preferred. Following the dispersing period, the wafer is typically spun at a higher speed e.g. above 2000 RPMs, more preferably about 2500 to about 3500 RPMs, to remove the dissolved coating in the desired peripheral areas by means of centrifugal force. A spin time of 2 to 20 seconds or longer may be used for this step.

[0166] The photoresist composition is typically next soft-baked to minimize the solvent content in the layer, thereby forming a tack-free coating and improving adhesion of the layer to the substrate. The soft bake is performed, for example, on a hotplate or in an oven, with a hotplate being typical. The soft bake temperature and time will depend, for example, on the particular photoresist composition and thickness. The soft bake temperature is typically from 90 to 170° C, and more typically from 110 to 150° C. The soft bake time is typically from 10 seconds to 20 minutes, more typically from 1 minute to 10 minutes, and still more typically from 1 minute to 5 minutes. The heating time can be readily determined by one of ordinary skill in the art based on the ingredients of the composition.

[0167] The photoresist layer is next pattern-wise exposed to activating radiation to create a difference in solubility between exposed and unexposed regions to form a latent image in the photoresist composition. The exposure is typically conducted through a patterned photomask that has optically transparent and optically opaque regions corresponding to regions of the resist layer to be exposed and unexposed, respectively. Such exposure may, alternatively, be conducted without a photomask in a direct writing method, typically used for e-beam lithography. The activating radiation typically has a wavelength of sub-400 nm, sub-300 nm or sub-200 nm, with 248 nm (KrF), 13.5 nm (EUV) wavelengths, or e-beam lithography being preferred. The methods find use in immersion or dry (non-immersion) lithography techniques. The exposure energy is typically from 1 to 200 millijoules per square centimeter (mJ / cm2), preferably from 10 to 100 mJ / cm2, and more preferably from 20 to 50 mJ / cm2, dependent upon the exposure tool and components of the photoresist composition.

[0168] Following exposure of the photoresist layer, a post-exposure bake (PEB) of the exposed photoresist layer is performed. The PEB can be conducted, for example, on a hotplate or in an oven, with a hotplate being typical. Conditions for the PEB will depend, for example, on the particular photoresist composition and layer thickness. The PEB is typically conducted at a temperature from 80 to 150° C, and a time from 30 to 120 seconds. A latent image defined by the polarity-switched (exposed regions) and unswitched regions (unexposed regions) is formed in the photoresist.

[0169] The exposed photoresist layer is then developed with a suitable developer to selectively remove those regions of the layer that are soluble in the developer while the remaining insoluble regions form the resulting photoresist pattern relief image. In the case of a positive-tone development (PTD) process, the exposed regions of the photoresist layer are removed during development and unexposed regions remain. Conversely, in a negative-tone development (NTD) process, the exposed regions of the photoresist layer remain, and unexposed regions are removed during development. Application of the developer may be accomplished by any suitable method such as described above with respect to application of the photoresist composition, with spin coating being typical. The development time is for a period effective to remove the soluble regions of the photoresist, with a time of from 5 to 60 seconds being typical. Development is typically conducted at room temperature.

[0170] Suitable developers for a PTD process include aqueous base developers, for example, quaternary ammonium hydroxide solutions such as tetramethylammonium hydroxide (TMAH), preferably 0.26 normal (N) TMAH, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and the like. Suitable developers for an NTD process are organic solvent-based, meaning the cumulative content of organic solvents in the developer is 50 wt % or more, typically 95 wt % or more, 98 wt % or more, or 100 wt %, based on total weight of the developer. Suitable organic solvents for the NTD developer include, for example, those chosen from ketones, esters, ethers, hydrocarbons, and mixtures thereof. The developer is typically 2-heptanone or n-butyl acetate. The NTD developer solvent can also be biobased.

[0171] A coated substrate may be formed from the photoresist compositions of the disclosure. Such a coated substrate includes: (a) a substrate having one or more layers to be patterned on a surface thereof; and (b) a layer of the photoresist composition over the one or more layers to be patterned.

[0172] The photoresist pattern may be used, for example, as an etch mask, thereby allowing the pattern to be transferred to one or more sequentially underlying layers by known etching techniques, typically by dry-etching such as reactive ion etching. The photoresist pattern may, for example, be used for pattern transfer to an underlying hardmask layer which, in turn, is used as an etch mask for pattern transfer to one or more layers below the hardmask layer. If the photoresist pattern is not consumed during pattern transfer, it may be removed from the substrate by known techniques, for example, oxygen plasma ashing. The photoresist compositions may, when used in one or more such patterning processes, be used to fabricate semiconductor devices such as memory devices, processor chips (CPUs), graphics chips, optoelectronic chips, LEDs, OLEDs, as well as other electronic devices.EXAMPLESExample 1. Photoresist Composition Preparation

[0173] Polymers Pl - P3 are prepared from monomers Ml - M6 using methods described in U.S. Pat. Pub. No. 2018 / 0284605 or other methods commonly available in the art. Polymer 1 is prepared from a mixture of monomers with a molar ratio of M1 / M2 / M3 / M4 / M5 = 1 / 4 / 2 / 2 / 1 and has a weightaverage molecular weight of 10,000 g / mol (relative to polystyrene standards). Polymer 2 is prepared from a mixture of monomers with a molar ratio of M1 / M2 / M5 = 4 / 4 / 2 and has a weight-average molecular weight of 10,000 g / mol. Polymer 3 is prepared from a mixture of monomers with a molar ratio of M1 / M2 / M5 / M6 = 30 / 35 / 15 / 20 and has a weight-average molecular weight of 10,000 g / mol.

[0174] Photoresist A. A positive chemically amplified photoresist composition was prepared by combining 4.54 g Polymer 1, 0.401 g of (4-t- butylphenyl)tetramethylene sulfonium norbornyl perfluoroethoxyethyl- sulfonate, 0.178 g triphenylsulfonium 4,4,5,5,6,6-hexafluorodihydro-4H- 1,3,2- dithiazine 1,1,3,3-tetraoxide, 0.039 g of l-(tertbutyoxycarbonyl)-4-hydroxypiperidine, 0.008 g of POLYFOX 656 surfactant (Omnova Solutions Inc.), 75.87 g bio-based propylene glycol methyl ether acetate and 18.97 g cyclohexanone. The resulting mixtures were shaken on a mechanical shaker and then filtered through a PTFE disk-shaped filter having a 0.2 micrometer pore size. Inductively coupled plasma mass spectroscopy shows the composition has less than 10 ppb of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn. Gas chromatography mass spectrometry shows the composition has a content ofC1-22 alkane / alkene less than 1 ppm. The photoresist solution also has an amount of carbon-14 sufficient to produce a decay greater than 1 dpm / gC.

[0175] Photoresist B. A positive chemically amplified photoresist composition was prepared by combining: 1.35 g Polymer 2 and 1.35 g Polymer 3, 0.51 g triphenylsulfonium-4-(3-hydroxy- adamantane-l-carbonyloxy) -1,1, 2, 2- tetrafluorobutane sulfonate, 0.07 g. trihydroxymethylcarbamic acid tert-butyl ester base quencher, 0.001 g POLYFOX 656 surfactant (Omnova Solutions Inc.), 19.34 g propylene glycol methyl ether and 77.36 g bio-based hydroxyisobutyrate methyl ester. The resulting mixtures were shaken on a mechanical shaker and then filtered through a PTFE disk - shaped filter having a 0.2 micrometer pore size. Inductively coupled plasma mass spectroscopy shows the composition has less than 10 ppb of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn. Gas chromatography mass spectrometry shows the composition has a content of C1-22 alkane / alkene less than 1 ppm. The photoresist solution has an amount of carbon-14 sufficient to produce a decay greater than 1 dpm / gC.Example 2. Photoresist Patterned Wafer Preparation

[0176] An 8-inch silicon wafer coated with an 80 nm BARC layer (AR 40A antireflectant, Dow Electronic Materials, Marlborough, Mass. USA) is treated with a pre-wet of bio-based propylene glycol methyl ether acetate (PGMEA), where the PGMEA has an amount of carbon-14 sufficient to producea decay greater than 1 dpm / gC, then spin-coated with Photoresist A, and then treated with a backside rinse using a 70 / 30 blend of bio-based propylene glycol methyl ether (PGME) and PGMEA, where the blend has an amount of carbon-14 sufficient to produce a decay greater than 1 dpm / gC. The wafer is then softbaked at 100° C for 60 seconds to provide a resist layer thickness of 900 A. The wafers are exposed using an ASML ArE 1100 scanner with NA=0.75, Dipole 35Y illumination (0.89 / 0.64sigma), using a mask having line and space patterns with PSM feature size of 120 nm 1:1 and 1:8, under dipole- 35Y with outer / inner sigma of 0.89 / 0.64. The exposed wafers are post-exposure baked at 100° C for 60 seconds and developed with a 0.26N aqueous tetramethylammonium hydroxide solution to form a 120 nm 1:1 line and space pattern imaged resist layer. Average critical dimension (CD) of 120 nm for the patterns are determined by processing the image captured by top-down Scanning electron microscopy (SEM) using a Hitachi 9380 CD-SEM, operating at an accelerating voltage of 500 volts (V), probe current of 5.0 picoamperes (pA), using 150 KX magnification.Example 3. Photoresist Patterned Wafer Preparation

[0177] A 12-inch silicon wafer coated with an organic bottom antireflective coating (BARC AR 12423 mm / AR 26N 77 nm (Rohm and Haas Electronic Materials LLC)) is treated with a pre-wet of bio-based PGMEA, where the PGMEA has an amount of carbon-14 sufficient to produce a decay greater than 1 dpm / gC, , then spin-coated with Photoresist B, and then treated with a backside rinse using a 70 / 30 blend of bio-based PGME and PGMEA, where the blend has an amount of carbon-14 sufficient to produce a decay greater than 1 dpm / gC. The coated wafer is then softbaked at 95° C for 60 seconds, to a thickness of 700 A. Opticoat OC2000 topcoat material (Rohm and Haas Electronic Materials LLC) is coated on the resist to form an immersion topcoat layer. The coated wafers are exposed with an ASMLArF 1900i immersion scanner with NA=1.35, Dipole 35Y illumination (0.9 / 0.635 Sigma), plus X polarization, and post-exposure baked (PEB) at 90° C for 60 seconds. The coated wafers are treated with 0.26N aqueous tetramethylammonium hydroxide solution to develop the imaged resist layers to form 45 nm 1:1 line and space resist patterns.

Claims

We claim:1) A composition comprising: a) a polymer matrix comprising a group that decomposes under the action of an acid to produce an alkali-soluble group on either one or both of a main chain and a side chain of the polymer; b) a photo acid generator (PAG); and c) a bio-based organic solvent; wherein the bio-based organic solvent comprises an amount of carbon-14 sufficient to produce a decay of at least 0.1 dpm / gC (disintegrations per minute per gram carbon).2) The composition of claim 1, wherein the bio-based organic solvent further comprises:10 parts per billion (ppb) or less of a concentration of one or more metal elements selected from group consisting of the metal elements: Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn.3) The composition of claim 2, wherein the bio-based organic solvent comprises 10 ppb or less of a concentration of each metal element selected from group consisting of the metal elements: Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn4) The composition of claim 2, wherein the bio-based organic solvent comprises 1 ppb or less of a concentration of one or more metal elements selected from group consisting of the metal elements: Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn.5) The composition of claim 4, wherein the bio-based organic solvent comprises 1 ppb or less of a concentration of each metal element selected from group consisting of the metal elements: Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn.6) The composition of any of claims 1-5, wherein the bio-based organic solvent comprises a biobased propylene glycol monomethyl ether, a bio-based cyclohexanone, a bio-based methyl ethyl ketone, a bio-based solvent represented by the following Formula (1):wherein X1and X2each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxyl group, an alkoxycarbonyl group, a carboxyl group, a hydroxyl group, a cyano group or a halogen atom, and X1and X2may combine with each other to form a ring; a bio-based solvent represented by the following Formula (2):wherein X3and X5each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxyl group, an alkoxycarbonyl group, a carboxyl group, a hydroxyl group, a cyano group or a halogen atom, or X3and X5may combine with each other to form a ring, andX4is an alkyl, optionally substituted by a hydroxyl group, a carbonyl group, or a cyano group, or may have an ether bond in the alkylene chain; or a bio-based solvent represented by the following Formula (3):wherein X6and X8each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxyl group, an alkoxycarbonyl group, a carboxyl group, a hydroxyl group, a cyano group or a halogen atom, and Xsand X8or Xsand X7or and X7and X8may combine with each other to form a ring; andX7represents an alkylene group or a cycloalkylene group.7) The composition of claim 6, wherein the bio-based organic solvent comprises a bio-based propylene glycol monomethyl ether, a bio-based cyclohexanone, a bio-based methyl ethyl ketone,8) The composition of claim 7, wherein the bio-based organic solvent comprises 50 wt% or more of a bio-based propylene glycol monomethyl ether, a bio-based cyclohexanone, or a bio-based methyl ethyl ketone.9) The composition of claim 7, wherein the bio-based organic solvent comprises 70 wt% or more of a bio-based propylene glycol monomethyl ether, a bio-based cyclohexanone, or a bio-based methyl ethyl ketone.10) The composition of claim 6, wherein the bio-based organic solvent comprises a bio-based solvent represented by Formula (1).11) The composition of claim 10, wherein the bio-based organic solvent comprises a bio-based butyl acetate, bio-based ethyl lactate, bio-based gamma-butyrolactone, bio-based gammavalerolactone, or bio-based hydroxyisobutyrate methyl ester.12) The composition of claim 11, wherein the bio-based organic solvent comprises 70 wt% or more of a bio-based methyl 4-methoxy valerate, bio-based ethyl 4-ethoxy valerate, or biobased ethyl 3-ethoxypropionate.13) The composition of claim 11, wherein the bio-based organic solvent comprises 50 wt% or more of a bio-based butyl acetate, bio-based ethyl lactate, bio-based gamma-butyrolactone, bio-based gamma-valerolactone, or bio-based hydroxyisobutyrate methyl ester.14) The composition of claim 11, wherein the bio-based organic solvent comprises 70 wt% or more of a bio-based butyl acetate, bio-based ethyl lactate, bio-based gamma-butyrolactone, bio-based gamma-valerolactone, or bio-based hydroxyisobutyrate methyl ester.15) The composition of claim 6, wherein the bio-based organic solvent comprises a solvent represented by Formula (2).16) The composition of claim 15, wherein the bio-based organic solvent comprises a bio-based propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methyl-3-methoxypropionate, ethyl-3-methoxypropionate, ethyl-3-ethoxypropionate, propyl-3-methoxypropionate, ethyl methoxyacetate, ethyl ethoxyacetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3- methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, 2-ethoxybutyl acetate, 4- ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3- methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, or 4-methyl-4-methoxypentyl acetate.17) The composition of claim 16, wherein the bio-based organic solvent comprises 50 wt% or more of a bio-based propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methyl-3-methoxypropionate, ethyl-3- methoxypropionate, ethyl-3-ethoxypropionate, propyl-3-methoxypropionate, ethyl methoxyacetate, ethyl ethoxyacetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4- methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, 2- ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, or 4-methyl-4-methoxypentyl acetate.18) The composition of claim 16, wherein the bio-based organic solvent comprises 70 wt% or more of a bio-based propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl etheracetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methyl-3-methoxypropionate, ethyl-3- methoxypropionate, ethyl-3-ethoxypropionate, propyl-3-methoxypropionate, ethyl methoxyacetate, ethyl ethoxyacetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4- methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, 2- ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, or 4-methyl- 4-methoxypentyl acetate.19) The composition of claim 6, wherein the bio-based organic solvent comprises a solvent represented by Formula (3).20) The composition of claim 19, wherein the bio-based organic solvent comprises a bio-based methyl 4-methoxy valerate, bio-based ethyl 4-ethoxy valerate, or bio-based ethyl 3- ethoxypropionate.21) The composition of claim 20, wherein the bio-based organic solvent comprises 50 wt% or more of a bio-based methyl 4-methoxy valerate, bio-based ethyl 4-ethoxy valerate, or biobased ethyl 3-ethoxypropionate.22) The composition of claim 1, wherein the polymer matrix comprises a polymer, wherein the polymer comprises one or more monomers selected from styrene, p-hydroxystyrene, acrylate, methacrylate, norbornene, or combinations thereof.23) The composition of claim 1, wherein the bio-based organic solvent comprises an amount of carbon-14 sufficient to produce a decay of at least 3.0 dpm / gC.24) The composition of claim 23, wherein the bio-based organic solvent comprises an amount of carbon-14 sufficient to produce a decay of at least 6.0 dpm / gC.25) The composition of claim 10, wherein the bio-based organic solvent comprises an amount of carbon-14 sufficient to produce a decay of at least 9.0 dpm / gC.26) The composition of claim 10, wherein the bio-based organic solvent comprises an amount of carbon-14 sufficient to produce a decay of at least 12.0 dpm / gC.27) The composition of claim 1, wherein the bio-based organic solvent further comprises 1 parts per billion (ppb) or less of a concentration of one or more metal elements selected from group consisting of the metal elements: Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn.28) The composition of claim 27, wherein the bio-based organic solvent comprises 1 parts per billion (ppb) or less of a concentration of each metal element selected from group consisting of the metal elements: Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn.29) The composition of claim 1, wherein the bio-based organic solvent further comprises 10 ppb or less of C1-22 alkane or C2-22 alkene.30) The composition of claim 29, wherein the bio-based organic solvent comprises 1 ppb or less of C1-22 alkane or C2-22 alkene.31) The composition of claim 1, wherein the bio-based organic solvent further comprises less than 20 particles / mL of particles having a particle size of 0.15 pm or larger.32) The composition of claim 1, wherein the bio-based organic solvent further comprises a dispersion parameter of from 14.5017 Mpa05.33) The composition of claim 1, wherein the bio-based organic solvent further comprises a boiling point from 50°C to 250°C.34) A pattern forming method comprising: a) providing a semiconductor substrate; b) optionally, applying a pre-wet solvent to the semiconductor substrate; c) forming a photoresist film comprising coating the semiconductor substrate with a photoresist composition comprising a polymer matrix comprising a group that decomposes under the action of an acid to produce an alkali-soluble group on either one or both of the main chain and the side chain of the polymer, a photo acid generator (PAG), and an organic solvent; d) optionally, performing an edge bead removal process wherein a peripheral portion of the photoresist film adjacent to a top or coated edge and a backside or bottom edge of the substrate, as well as any coated photoresist material lying over the top or coated edge of the substrate, is contacted with an edge bead removal solvent so as to dissolve and remove unwanted material; e) exposing the resist film with actinic rays or electromagnetic radiation; and f) developing the resist film with a developer.35) The pattern forming method of claim 34, wherein the photoresist composition comprises the composition of claim 1.36) The pattern forming method of claim 34 or claim 35 comprising applying a pre-wet solvent to the substrate, wherein the pre-wet solvent comprises a bio-based pre-wet solvent comprising an amount of carbon-14 sufficient to produce a decay of at least 0.1 dpm / gC.37) The pattern forming method of claim 36, wherein the bio-based pre-wet solvent is selected from propylene glycol monomethyl ether, cyclohexanone, methyl ethyl ketone, butyl acetate, ethyl lactate, gamma-butyrolactone, gamma-valerolactone, hydroxyisobutyrate methyl ester,propylene glycol monomethyl ether acetate, methyl 4-methoxy valerate, ethyl 4-ethoxy valerate, or ethyl 3-ethoxypropionate, or a combination thereof.38) The pattern forming method of claim 36, wherein the bio-based pre-wet solvent comprises an amount of carbon-14 sufficient to produce a decay of at least 3.0 dpm / gC.39) The pattern forming method of claim 38, wherein the bio-based pre-wet solvent comprises an amount of carbon-14 sufficient to produce a decay of at least 6.0 dpm / gC.40) The pattern forming method of claim 38, wherein the bio-based pre-wet solvent comprises an amount of carbon-14 sufficient to produce a decay of at least 9.0 dpm / gC.41) The pattern forming method of claim 38, wherein the bio-based pre-wet solvent comprises an amount of carbon-14 sufficient to produce a decay of at least 12.0 dpm / gC.42) The pattern forming method of claim 36, wherein the bio-based pre-wet solvent further comprises one or more of: a) 1 ppb or less of a concentration of one or more metal elements selected from group consisting of the metal elements: Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn; b) 10 ppb or less of Ci.22alkane or C2.22alkene; c) less than 20 particles / mL of particles having a particle size of 0.15 pm or larger; d) a dispersion parameter of from 14.5017 Mpa05; or e) a boiling point from 50°C to 250°C.43) The pattern forming method of claim 34 comprising performing an edge bead removal process, wherein an edge bead removal solvent comprises a bio-based edge bead removal solvent comprising an amount of carbon-14 sufficient to produce a decay of at least 0.1 dpm / gC.44) The pattern forming method of claim 41, wherein the bio-based edge bead removal solvent comprises propylene glycol monomethyl ether, cyclohexanone, methyl ethyl ketone, butyl acetate, ethyl lactate, gamma-butyrolactone, gamma-valerolactone, hydroxyisobutyrate methyl ester, propylene glycol monomethyl ether acetate, methyl 4-methoxy valerate, ethyl 4-ethoxy valerate, or ethyl 3-ethoxypropionate, or a combination thereof.45) The pattern forming method of claim 43, wherein the bio-based edge bead removal solvent comprises an amount of carbon-14 sufficient to produce a decay of at least 3.0 dpm / gC.46) The pattern forming method of claim 43, wherein the bio-based edge bead removal solvent comprises an amount of carbon-14 sufficient to produce a decay of at least 6.0 dpm / gC.47) The pattern forming method of claim 43, wherein the bio-based edge bead removal solvent comprises an amount of carbon-14 sufficient to produce a decay of at least 9.0 dpm / gC.48) The pattern forming method of claim 43, wherein the bio-based edge bead removal solvent comprises an amount of carbon-14 sufficient to produce a decay of at least 12.0 dpm / gC.49) The pattern forming method of claim 43, wherein the bio-based edge bead removal solvent further comprises one or more of: a) 1 ppb or less of a concentration of one or more metal elements selected from group consisting of the metal elements: Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn; b) 10 ppb or less of C1-22 alkane or C2-22 alkene; c) less than 20 particles / mL of particles having a particle size of 0.15 pm or larger; d) a dispersion parameter of from 14.5017 Mpa05; or e) a boiling point from 50°C to 250°C.50) A solvent comprising a bio-based propylene glycol monomethyl ether, a bio-based cyclohexanone, a bio-based methyl ethyl ketone, a bio-based solvent represented by the following Formula (1):wherein X1and X2each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxyl group, an alkoxycarbonyl group, a carboxyl group, a hydroxyl group, a cyano group or a halogen atom, and X1and X2may combine with each other to form a ring; a bio-based solvent represented by the following Formula (2):wherein X3and X5each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxyl group, an alkoxycarbonyl group, a carboxyl group, a hydroxyl group, a cyano group or a halogen atom, or X3and X5may combine with each other to form a ring, and X4is an alkyl, optionally substituted by a hydroxyl group, a carbonyl group, or a cyano group, or may have an ether bond in the alkylene chain; or a bio-based solvent represented by the following Formula (3):wherein X6and X8each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxyl group, an alkoxycarbonyl group, a carboxyl group, a hydroxyl group, a cyano group or a halogen atom, and Xsand X8or Xsand X7or and X7and X8may combine with each other to form a ring; and X7represents an alkylene group or a cycloalkylene group.51) The solvent of claim 50, wherein the solvent comprises a bio-based propylene glycol monomethyl ether, a bio-based cyclohexanone, a bio-based methyl ethyl ketone,52) The solvent of claim 51, wherein the solvent comprises 50 wt% or more of a bio-based propylene glycol monomethyl ether, a bio-based cyclohexanone, or a bio-based methyl ethyl ketone.53) The solvent of claim 51, wherein the solvent comprises 70 wt% or more of a bio-based propylene glycol monomethyl ether, a bio-based cyclohexanone, or a bio-based methyl ethyl ketone.54) The solvent of claim 50, wherein the solvent comprises a bio-based solvent represented by Formula (1).55) The solvent of claim 54, wherein the solvent comprises a bio-based butyl acetate, bio-based ethyl lactate, bio-based gamma-butyrolactone, bio-based gamma-valerolactone, or bio-based hydroxyisobutyrate methyl ester.56) The solvent of claim 55, wherein the solvent comprises 50 wt% or more of a bio-based butyl acetate, bio-based ethyl lactate, bio-based gamma-butyrolactone, bio-based gamma- valerolactone, or bio-based hydroxyisobutyrate methyl ester.57) The solvent of claim 55, wherein the solvent solvent comprises 70 wt% or more of a bio-based butyl acetate, bio-based ethyl lactate, bio-based gamma-butyrolactone, bio-based gamma- valerolactone, or bio-based hydroxyisobutyrate methyl ester.58) The solvent of claim 50, wherein the solvent comprises a solvent represented by Formula (2).59) The solvent of claim 58, wherein the solvent comprises a bio-based propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methyl-3-methoxypropionate, ethyl-3-methoxypropionate, ethyl- 3-ethoxypropionate, propyl-3-methoxypropionate, ethyl methoxyacetate, ethyl ethoxyacetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3- methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, 2-ethoxybutyl acetate, 4- ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, or 4-methyl-4-methoxypentyl acetate.60) The solvent of claim 58, wherein the solvent comprises 50 wt% or more of a bio-based propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methyl-3-methoxypropionate, ethyl-3-methoxypropionate, ethyl- 3-ethoxypropionate, propyl-3-methoxypropionate, ethyl methoxyacetate, ethyl ethoxyacetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3- methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, 2-ethoxybutyl acetate, 4- ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3- methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, or 4-methyl-4-methoxypentyl acetate.61) The solvent of claim 58, wherein the solvent comprises 70 wt% or more of a bio-based propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methyl-3-methoxypropionate, ethyl-3-methoxypropionate, ethyl-3-ethoxypropionate, propyl-3-methoxypropionate, ethyl methoxyacetate, ethyl ethoxyacetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3- methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, 2-ethoxybutyl acetate, 4- ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3- methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, or 4-methyl-4-methoxypentyl acetate.62) The solvent of claim 50, wherein the solvent comprises a solvent represented by Formula (3).63) The solvent of claim 62, wherein the solvent comprises a bio-based methyl 4-methoxy valerate, bio-based ethyl 4-ethoxy valerate, or bio-based ethyl 3-ethoxypropionate.64) The solvent of claim 63, wherein the solvent comprises 50 wt% or more of a bio-based methyl4-methoxy valerate, bio-based ethyl 4-ethoxy valerate, or bio-based ethyl 3- ethoxypropionate.65) The solvent of claim 63, wherein the solvent comprises 70 wt% or more of a bio-based methyl 4-methoxy valerate, bio-based ethyl 4-ethoxy valerate, or bio-based ethyl 3- ethoxypropionate.66) A composition or method as substantially shown, described or embodiment in the application.

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