BIO-based compositions for photoresists and patterning

Abstract

Compositions for use in novel lithographic pattern forming processes based on metal oxide chemistry are described, along with methods of using such. The disclosure further contemplates bio-based solvents for use in metal oxide lithographic processes as pre-wet solvents, edge removal solvents and in resist 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 / 600,332, 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] Conventional photoresists are based on organic polymeric species. 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. Recently, a new class of radiation-based resists has emerged with great potential for patterning. These resists are based on metal oxide chemistry (metal oxo / hydroxo compositions), which uses radiation sensitive ligands to control stability and processability of the resists. These metal oxide based resists are particularly useful when patterned with extreme ultraviolet (EUV) radiation.[5] Photoresist compositions also 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 in photoresist compositions is typically 70 to 99 wt % based on total weight of the photoresist composition.[6] 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 greenhouseemissions 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.[7] 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[8] 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.[9] A first aspect comprises a photoresist composition comprising 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); and a metal polynuclear oxo / hydroxo cation with organic ligands having metal carbon bonds and / or with metal carboxylate bonds at a concentration from about 0.01M to about 1.4M, wherein the metal polynuclear oxo / hydroxo cation with organic ligands forms an oxo-hydroxo network, wherein the oxo-hydroxo network has both M-O— H linkages and M-O-M linkages.

[0010] 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.

[0011] In some embodiments of the first aspect, the bio-based organic solvent comprises a bio-based propylene glycol monomethyl ether, bio-based 2-heptanone, bio-based cyclohexanone, bio-based methyl ethyl ketone, bio-based methyl isobutyl carbinol, 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.

[0012] In some embodiments of the first aspect, the bio-based organic solvent comprises propylene glycol monomethyl ether, a bio-based 2-heptanone, a bio-based cyclohexanone, a bio-based methyl ethyl ketone, or a bio-based methyl isobutyl carbinol. In some embodiments, the bio-based organic solvent comprises 50 wt% or more, or alternatively, 70 wt% or more, of propylene glycol monomethyl ether, a bio-based 2-heptanone, a bio-based cyclohexanone, a bio-based methyl ethyl ketone, or a bio-based methyl isobutyl carbinol.

[0013] 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.

[0014] 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 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. 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.

[0015] 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.

[0016] 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

[0017] 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 coated substrate by coating the semiconductor substrate with a photoresist composition comprising a metal polynuclear oxo / hydroxo cation with organic ligands having metal carbon bonds and / or with metal carboxylate bonds and a bio-based organic solvent, wherein the coated substrate comprises a coating having an average thickness from about 5 nm to about 200 nm and that comprises a metal oxo- hydroxo network with organic ligands with metal carbon bonds and / or with metal carboxylate bonds and free of peroxide ligands; 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; irradiating a coated substrate along aselected pattern to form an irradiated structure with a region of irradiated coating and a region with un-irradiated coating; heating the irradiated structure at a temperature from about 45° C. to about 250° C. for 0.1 minutes to about 30 minutes to form an annealed irradiated structure; and selectively developing the annealed irradiated structure to remove a substantial portion of the irradiated coating or of the un-irradiated coating to form a patterned substrate, wherein the metal oxo-hydroxo network comprises both M-O— H linkages and M-O-M linkages.

[0018] In a first embodiment of the second aspect comprises a photoresist composition characterized by the composition of any embodiment of the first aspect.

[0019] 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, methyl isobutyl carbinol, 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. 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 prewet 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 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.

[0020] 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 comprises propylene glycol monomethyl ether, cyclohexanone, methyl isobutyl carbinol, methyl ethyl ketone, butyl acetate, ethyl lactate, gammabutyrolactone, 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 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.

[0021] A third aspect comprises a solvent comprising a bio-based propylene glycol monomethyl ether, a bio-based 2-heptanone, cyclohexanone, a bio-based methyl ethyl ketone, a bio-based methyl isobutyl carbinol, 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.

[0022] In some embodiments of the third aspect, the solvent comprises a bio-based propylene glycol monomethyl ether, a bio-based 2-heptanone, cyclohexanone, a bio-based methyl ethyl ketone, or a bio-based methyl isobutyl carbinol. 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 2-heptanone, cyclohexanone, a bio-based methyl ethyl ketone, or a bio-based methyl isobutyl carbinol.

[0023] In some embodiments of the third aspect, the solvent comprises a bio-based propylene glycol monomethyl ether, a bio-based 2-heptanone, cyclohexanone, a bio-based methyl ethyl ketone, or a bio-based methyl isobutyl carbinol. 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 propylene glycol monomethyl ether, a bio-based 2-heptanone, cyclohexanone, a biobased methyl ethyl ketone, or a bio-based methyl isobutyl carbinol.

[0024] 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.

[0025] 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, 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.

[0026] 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.

[0027] 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 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.

[0028] A fourth aspect comprises any composition or method as substantially shown, described, or embodied in the application.DETAILED DESCRIPTION OF THE DISCLOSURE

[0029] 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.

[0030] 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 below terms 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.

[0031] 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.

[0032] 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.

[0033] 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."

[0034] "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.

[0035] "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 alkylhaving from 1 to 4 optional substituents selected from, for example, hydroxyl (—OH), halogen, amino (— NH2 or — NR2), nitro (— NO2), acyl (— C(=O)R), alkylsulfonyl (— S(=O)2R), 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 — CH2— CH(OH)— CH2— , an alkoxy substituted alkyl, can be a 2-methoxy substituted ethyl of the formula — CH2— CH2— O— CH3, an amino substituted alkyl, or can be a 1-dialkylamino substituted ethyl of the formula — CH(NR2)— CH3.

[0036] "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(=0)2R), alkoxy (—OR), and like substituents .

[0037] "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.

[0038] "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.

[0039] "Carboxyl" means a moiety composed of carbon bonded to both an oxygen and a hydroxyl group, -C(=O)-O-H.

[0040] "Hydroxyl" mean an -O-H chemical moiety.

[0041] "Cyano" means a -CEN chemical moiety.

[0042] "Halogen" or "halo" includes fluoro (-F), chloro (-CI), bromo (-Br), or iodo (-1) moieties.

[0043] "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.

[0044] "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-4)alkyl, 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.

[0045] 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.

[0046] 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 themoiety, 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-galkyl 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; (Cg-ujcycloalkyl can be cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, including bicyclic, tricyclic, or multi-cyclic substituents, and like substituents.

[0047] A specific "hydrocarbyl" can be, for example, (Ci0-2o)hydrocarbyl, including all intermediate chain lengths and values, and (Cg-izjcyclohydrocarbyl including all intermediate values and ring sizes.

[0048] 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.

[0049] 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).

[0050] 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.

[0051] 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.

[0052] 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.

[0053] 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 form14CO2, 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.

[0054] 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.

[0055] 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.

[0056] 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.

[0057] 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 0.25xl012to 1.2xl012.

[0058] 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 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.

[0059] 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.

[0060] 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)

[0061] 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

[0062] An aspect of the present disclosure relates to photoresist compositions that contain a metalorganic or metal-based resist on metal oxide chemistry and a bio-based solvent which can be used for dissolving respective components of the photoresist composition that comprises at least 0.1 dpm / gC of carbon-14 (C-14).(A) Metalorganic or Metal-Based Resists

[0063] The photoresist composition includes a class of radiation-based resists based on metal oxide chemistry (metal oxo / hydroxo compositions), which uses radiation sensitive ligands to control stability and processability of the resists. In general, these resist compositions function as negative tone photoresists when developed with organic solvents. Related resist compounds are discussed in U.S. Pat. No. 8,703,386B2, herein incorporated by reference. As used herein, the metal polynuclear oxo / hydroxo cation may comprise Cu, Al, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Zn, Y, Zr, Nb, Mo, In, Sn, Sb, Hf, Ta, W, Ir, Pt, La, Ce, Pr, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu or a combination thereof.

[0064] Organometallic photoresists such as organotin oxide hydroxides have been shown to possess excellent properties as photoresists for use in lithographic photopatterning. Suitable organometallic photoresists include organotin materials as described in U.S. Pat. No. 9,310,684B2, published U.S. patent application 2016 / 0116839A1, and U.S. Pat. No. 10,228, all of which are incorporated herein by reference. Other organometallic patterning compositions based on various metals are described in published U.S. patent application 2002 / 0076495 and U.S. Pat. No. 9,372,402B2, both of which are incorporated herein by reference. Resists with metal oxide particles having organic coatings are described in published U.S. patent application 2015 / 0234272A1, incorporated herein by reference. Applicant has developed organometallic, such as organotin, patterning materials that have been progressed to a high degree, and some of these are the exemplified compositions.

[0065] Suitable organotin materials are generally based on the chemistry of radiation sensitive patterning compositions represented by the formula RzSnO(2-(Z / 2)-(x / 2))(OH)xwhere 0<z<2 and 0<(z+x)<4, in which R is a hydrocarbyl group with 1-31 carbon atoms or blends thereof with distinct R groups, which can be written as RN, for N distinct compositions. In a coating layer, the compositions can be integrated into a common oxo / hydroxo network. In particular, branched alkyl ligands can be desirable for some patterning compositions where the compound can be represented as R1R2R3CSn(NR')3, where R3and R2are independently an alkyl group with 1-10 carbon atoms, and R3is hydrogen or an alkyl group with 1-10 carbon atoms. As noted below, this representation of alkyl ligand R is similarly applicable to the other embodiments generally with R1R2R3CSn(X)3, with X corresponding to the trialkoxide or triamide moieties. In some embodiments R1and R2can form a cyclic alkyl moiety, and R3may also join the other groups in a cyclic moiety. Suitable branched alkyl ligands can be, for example, isopropyl (R3and R2are methyl and R3is hydrogen), tert-butyl (R1, R2and R3are methyl), tert-amyl (R1and R2are methyl and R3is — CH2CH3), sec-butyl (R1is methyl, R2is — CH2CH3, and R3is hydrogen), neopentyl (R1and R2are hydrogen, and R3is — C(CH3)3), cyclohexyl, cyclopentyl, cyclobutyl, and cyclopropyl. Examples of suitable cyclic groups include, for example, 1-adamantyl (— C(CH2)3(CH)3(CH2)3 or tricyclo(3.3.1.13,7) decane bonded to the metal at a tertiary carbon) and 2- adamantyl (— CH(CH)2(CH2)4(CH)2(CH2) or tricyclo(3.3.1.13,7) decane bonded to the metal at a secondary carbon). In other embodiments hydrocarbyl groups may include aryl or alkenyl groups, for example, benzyl or allyl, or alkynyl groups. In other embodiments the hydrocarbyl ligand R may include any group consisting solely of C and H and containing 1-31 carbon atoms. In summary, some examples of suitable alkyl groups bonded to tin include, for example, linear or branched alkyl (i-Pr ((CHshCH— ), t-Bu ((CHsJsC— ), Me (CH3— ), n-Bu (CH3CH2CH2CH2— )), cyclo-alkyl (cyclo-propyl, cyclo-butyl, cyclopentyl), olefinic (alkenyl, aryl, allylic), or alkynyl groups, or combinations thereof. In further embodiments suitable R groups may include hydrocarbyl groups substituted with hetero-atomfunctional groups including cyano, thio, silyl, ether, keto, ester, or halogenated groups or combinations thereof.

[0066] Precursor compositions to the form organotin oxo / hydroxyl coating compositions that integrate into a common oxo / hydroxo network can comprise one or more soluble organotin oxo / hydroxo compounds, or corresponding compounds with hydrolyzable ligands that form oxo and / or hydroxo ligands upon hydrolysis. For precursor compositions with a plurality of compounds, the compounds can have distinct organic ligands with metal-carbon bonds and the same or distinct hyrolyzable ligands. Thus, precursor compositions to form the radiation sensitive coatings can comprise solutions of one or more compounds represented by RnSnX4.nwhere n=l or 2, in which R is a hydrocarbyl group with 1-31 carbon atoms, such as described above, and X is a ligand with a hydrolysable M-X bond, and mixtures thereof. Suitable hydrolysable ligands can include, for example, alkynides RCEC, alkoxides RO“, carboxylates RCOO“, halides, dialkylamides or combinations thereof. In particular, organotin trialkoxide compositions can be represented by the formula RSn(OR°)3, where the R° group can be one of the same moieties described above for R. In some embodiments, the aforementioned organotin precursor compositions can further comprise compositions represented by MX4and / or MO((m / 2)-i / 2)(OH)i where 0<z<2, 0<(z+w)<4, m=formal valence of Mm+, 0<l<m, and M=M' or Sn, where M' is a non-tin metal of groups 2-16 of the periodic table, such as Cu, Al, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Zn, Y, Zr, Nb, Mo, In, Sb, Hf, Ta, W, Ir, Pt, La, Ce, Pr, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu or a combination thereof. In general, organotin photoresists exhibit both high resolution and high etch resistances that enable the formation of small features and patterns. In situ hydrolysis during the coating process or after a coating step can be used to hydrolyze the hydrolyzable M-X bonds to form an oxo / hydroxo network in the coating prior to patterning. The precursor compounds can also form clusters in solution with appropriate ligand rearrangement, in which at least some of the hydrolyzable ligands may be replaced with oxo bridges or hydroxyl groups, such as with three tin atoms, as described in published U.S. patent applications 2019 / 0053001 and 2019 / 0308998, both of which are incorporated herein by reference. The precursor compositions preferably have a concentration of metal species from 0.01 M to about 1.4 M.(B) Bio-Based Solvent

[0067] 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.

[0068] 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; 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 oneor 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^alkane / 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 C1-22 alkane / alkene. In some embodiments, the concentration of Cl-22 alkane / alkene is from 0.001-1 ppm. The content of C1-22 alkane / 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° Cto less than 250° C and the ignition point of the solvent used at the negative development is preferably 200° C or more.

[0069] 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.

[0070] 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.

[0071] 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 alcohol, methyl isobutyl carbinol, 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, propyleneglycol monobutyl ether and propylene glycol monophenyl ether. Among these, a methyl isobutyl carbinol and propylene glycol monomethyl ether being most preferred.

[0072] 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.

[0073] 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.

[0074] In some embodiments, the bio-based solvent comprises a solvent represented by formula (1):In 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.

[0075] 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.

[0076] 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.

[0077] 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 solventsrepresented 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.

[0078] 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 preferably 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.

[0079] 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.

[0080] 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 byformula (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.

[0081] 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.

[0082] 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.

[0083] 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% Ci-C4lactate ester and about 10-70 wt% Cj-Cgaliphatic alcohol as described in US Patent 7,754,104.

[0084] 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.(C) Optional Other Additives

[0085] The resist composition of the present disclosure may further contain, for example, an actinic or contrast dye, an anti-striation agent, a surfactant, 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.

[0086] 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.

[0087] 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.

[0088] 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

[0089] 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.

[0090] 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 and specialty 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.

[0091] 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.

[0092] 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 hydrolysing 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.

[0093] 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 microbial biorefineries 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.

[0094] 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.

[0095] 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.

[0096] 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)).

[0097] 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.

[0098] 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:

[0099] 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).

[0100] 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.

[0101] 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)).

[0102] 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).

[0103] 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).

[0104] 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.

[0105] 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).

[0106] 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.

[0107] 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).

[0108] 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 into glucose 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.

[0109] 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

[0110] 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.

[0111] 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.

[0112] 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 nearly impossible. Processes for monitoring and detecting particle contamination are described in ISO 14644-1:2015 and ISO 21501-4, herein incorporated by reference.

[0113] 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.

[0114] 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 distillationtowers 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.

[0115] 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.

[0116] 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.

[0117] 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 resincomprises 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.

[0118] 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

[0119] Formation of photosensitive metal oxide coatings can be achieved through various means known by those of ordinary skill in the art, such as spin coating. For solution deposition of precursors, for tin based resists described above, tin concentrations generally can be in the range of about 1 mM to about 1 M, in further embodiments from about 2 mM to about 750 mM, and in other embodiments from about 5 mM to about 500 mM by amount of tin. In some embodiments photosensitive organotin coatings can be formed via vapor deposition techniques, such as atomic layer deposition (ALD) or chemical vapor deposition (CVD) techniques, as described in Meyers et al., U.S. Pat. No. 10,228,618B2 entitled "Organotin Oxide Hydroxide Patterning Compositions, Precursors, and Patterning", and Smith et al. U.S. Pat. No. 9,996,004B2, entitled "EUV Photopatterning of Vapor-Deposited Metal Oxide- Containing Hardmasks", respectively, and both of which incorporated herein by reference

[0120] In some embodiments, prior to coating the photosensitive metal oxide composition on the substrate, a "pre-wet solvent" can be applied to the substrate, which encourages a more even distribution of the 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. 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.

[0121] 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. More preferably, the pre-wet solvent comprises propylene glycol monomethyl ether, cyclohexanone, methyl ethyl ketone, butyl acetate, ethyl lactate, gamma-butyrolactone, gamma-valerolactone, hydroxyisobutyrate methylester, propylene glycol monomethyl ether acetate, methyl 4-methoxy valerate, ethyl 4-ethoxy valerate, or ethyl 3-ethoxypropionate, or a combination thereof.

[0122] The thickness of the coating generally can be a function of the precursor solution concentration, viscosity, and the spin speed. For other coating processes such as vapor deposition, the thickness can generally also be adjusted through the selection of the coating parameters. In some embodiments, it can be desirable to use a thin coating to facilitate formation of small and highly resolved features. In some embodiments, the coating materials can have an average dry thickness prior to development of no more than about 1 micron, in further embodiments no more than about 250 nanometers (nm), in additional embodiments from about 1 nm to about 50 nm, in other embodiments from about 1 nm to about 40 nm and in some embodiments from about 1 nm to about 25 nm. The ranges of post development coating thickness for the exposed regions generally fall within the same ranges as presented above with the realization that development may remove a relatively small amount of exposed material. A person of ordinary skill in the art will recognize that additional ranges of solution concentrations and thicknesses within the explicit ranges above are contemplated and are within the present disclosure. The thickness can be evaluated using non-contact methods of x-ray reflectivity and / or ellipsometry based on the optical properties of the film.

[0123] After deposition and formation of an organotin coating, an edge bead removal (EBR) rinse step generally is used. EBR processing typically occurs prior to any thermal processing or baking following deposition of the photoresist and involves rinsing the peripheral edge of a wafer or substrate with a solvent to remove the photoresist in selected regions. An EBR and backside rinse involves applying the edge bead rinse solution to the edge as well as the back of the wafer, as described in Waller et al. U.S. Pat. No. 10,627,719, entitled "Methods of Reducing Metal Residue in Edge Bead Region from Metal-Containing Resists", incorporated herein by reference.

[0124] 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. 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.

[0125] A soft bake, or a post-apply bake (PAB) is typically performed prior to radiation exposure to hydrolyze the hydrolysable bonds in the precursor compositions, and / or further drive off solvent, and promote densification of the coating material. In some embodiments, the PAB can be performed at temperatures from about 25° C. to about 250° C., in additional embodiments from about 50° C. to about 200° C. and in further embodiments from about 80° C. to about 150° C. The post exposure heating can generally be performed for at least about 0.1 minute, in further embodiments from about 0.5 minutes to about 30 minutes and in additional embodiments from about 0.75 minutes to about 10 minutes. A person of ordinary skill in the art will recognize that additional ranges of PEB temperatures and times within the explicit ranges above are contemplated and are within the present disclosure. The coated material generally comprises a polymeric metal oxo-hydroxo network based on the binding oxo-hydroxo ligands to the metals in which the metals also have some alkyl ligands, or a molecular solid comprised of polynuclear metal oxo-hydroxo species with alkyl ligands.

[0126] Generally, organotin photoresist coatings can be patterned using radiation. Suitable radiation sources include extreme ultraviolet (EUV), ultraviolet (UV), or electron beam (EB) radiation. For fabrication of semiconductor devices, EUV radiation is generally preferable due to its higher resolution compared to UV radiation, and its higher throughput compared to EB-based processing. Radiation can generally be directed to the substrate material through a mask or a radiation beam can be controllably scanned across the substrate to form a latent image within the resist coating.

[0127] Following International Standard ISO 21348 (2007) incorporated herein by reference, ultraviolet light extends between wavelengths of greater than or equal 100 nm and less than 400 nm. A krypton fluoride laser can be used as a source for 248 nm ultraviolet light. The ultraviolet range can be subdivided in several ways under accepted Standards, such as extreme ultraviolet (EUV) from greater than or equal 10 nm to less than 121 nm and far ultraviolet (FUV) from greater than or equal to 122 nm to less than 200 nm. A 193 nm line from an argon fluoride laser can be used as a radiation source in the FUV. EUV light has been used for lithography at 13.5 nm, and this light is generated from a Xe or Sn plasma source excited using high energy lasers or discharge pulses. Commercial sources of EUV photons include scanners fabricated by ASML Holding N.V. Netherlands. Soft x-rays can be defined from greater than or equal 0.1 nm to less than 10 nm. The light is directed through a mask to form a latent image in the radiation sensitive coating with exposed regions and un-exposed regions.

[0128] The amount of electromagnetic radiation can be characterized by a fluence or dose which is obtained by the integrated radiative flux over the exposure time. In some embodiments, suitable radiation fluences can be from about 1 mJ / cm2to about 200 mJ / cm2, in further embodiments from about 2 mJ / cm2to about 150 mJ / cm2and in further embodiments from about 3 mJ / cm2to about 100 mJ / cm2. In an embodiment, the EUV radiation can be done at a dose of less than or equal to about 150 mJ / cm2or with an electron beam at a dose equivalent to or not exceeding about 2 mC / cm2at 30 kV. A person of ordinary skill in the art will recognize that additional ranges of radiation fluences within the explicit ranges above are contemplated and are within the present disclosure.

[0129] With electron beam lithography, the electron beam generally induces secondary electrons which generally modify the irradiated material. The resolution can be a function at least in part of the range of the secondary electrons in the material in which a higher resolution is generally believed to result from a shorter range of the secondary electrons. Based on high resolution achievable with electron lithography using the organometallic coating materials described herein, the range of the secondary electrons in the organometallic material is limited. Electron beams can be characterized by the energy of the beam, and suitable energies can range from about 5 eV to about 200 keV and in further embodiments from about 7.5 eV to about 100 keV. Proximity-corrected beam doses at 30 keV can range from about 0.1 microcoulombs per centimeter squared (pC / cm2) to about 5 millicoulombs per centimeter squared (mC / cm2), in further embodiments from about 0.5 pC / cm2to about 1 mC / cm2and in other embodiments from about 1 pC / cm2to about 100 pC / cm2. A person of ordinary skill in the art can compute corresponding doses at other beam energies based on the teachings herein and will recognize that additional ranges of electron beam properties within the explicit ranges above are contemplated and are within the present disclosure.

[0130] Following exposure to radiation and the formation of a latent image, a subsequent postexposure bake (PEB) is typically performed. In some embodiments, the PEB can be performed at temperatures from about 45° C. to about 250° C., in additional embodiments from about 50° C. toabout 190° C. and in further embodiments from about 60° C. to about 175° C. The post exposure heating can generally be performed for at least about 0.1 minute, in further embodiments from about 0.5 minutes to about 30 minutes and in additional embodiments from about 0.75 minutes to about 10 minutes. A person of ordinary skill in the art will recognize that additional ranges of PEB temperatures and times within the explicit ranges above are contemplated and are within the present disclosure. The PEB can be designed to further consolidate the exposed regions without decomposing the un-exposed regions into a metal oxide.

[0131] Owing to their compositions comprising both metal oxide and organic ligands, it has been shown that both positive tone and negative tone patterning can be achieved in an organotin oxide hydroxide system. For example, when an aqueous acid or base solution, for example comprising tetraalkyl ammonium hydroxide, is used as a developer then positive tone patterning can be realized wherein the exposed material is dissolved away and the unexposed material remains. In contrast, when an organic solvent is used as a developer then negative tone patterning is realized wherein the unexposed material is dissolved away and the exposed material remains.

[0132] Suitable developers for a positive tone 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 a negative tone 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 NTD developer solvent can also be bio-based.

[0133] In particular, suitable base solvents for the developer include, for example, aromatic compounds (e.g., benzene, xylenes, toluene), esters (e.g., propylene glycol monomethyl ether acetate, ethyl acetate, ethyl lactate, n-butyl acetate, butyrolactone), ketones (e.g., methyl ethyl ketone, acetone, 2-butanone, cyclohexanone, 2-heptanone, 2-octanone), ethers (e.g., tetrahydrofuran, dioxane, anisole), 4-methyl-2-pentanol (and other weakly polar alcohols), blends thereof, and the like. For embodiments with a blend of solvents, the developer generally comprises at least about 55 volume percent base solvent, in further embodiments from about 60 vol % to about 99.75 vol %, in additional embodiments from about 65 vol % to about 99.5 vol %, in additional embodiments from about 70 vol % to about 99.25 vol %, and in other embodiments form about 75 vol % to about 99 vol % base solvent, which can involve one or more solvent compounds with the selected solubility parameters. A person of ordinary skill in the art will recognize that additional ranges of base solvent concentrations within the explicit ranges above are contemplated and are within the present disclosure. Volume percent values are calculated based on the solvent volumes prior to blending. Volume percent values can be converted to weight percent values according to the densities, if desired.

[0134] In some embodiments, one or more highly polar additional solvent, referred to as a polar solvent, can be added to the solvent blend to form improved developers. In some embodiments, the developer can have from 0.25 vol % to about 45 vol % polar solvent, in further embodiments from about 0.4 vol % to about 30 vol %, in additional embodiments from about 0.5 vol % to about 25 vol %,and in other embodiments form about 0.75 vol % to about 22 vol % polar solvent. Suitable polar solvents include, for example, water, acetone, polar monohydroxyl alcohols (such as methanol, ethanol, propanol, isobutanol, pentanol, and mixtures thereof), polyhydroxyl compounds (such as ethylene glycol, propylene glycol, glycerol), pyrrolidones (such as 2-pyrrolidone, l-ethyl-2- pyrrolidone, N-methyl-2-pyrrolidone), glycol ethers (such as ethylene glycol monomethyl ether), carboxylic acids (such as formic acid, acetic acid oxalic acid, 2-ethylhexanoic acid), diols (e.g., 1,2- hexanediol, 1,2-propanediol, 1,3-propanediol), and mixtures thereof.

[0135] In addition to the primary developer solvent compositions, the developer can comprise additional compositions to facilitate the development process. Suitable additives include, for example, dissolved salts with cations selected from the group consisting of ammonium, d-block metal cations (hafnium, zirconium, lanthanum, or the like), f-block metal cations (cerium, lutetium or the like), p- block metal cations (aluminum, tin, or the like), alkali metals (lithium, sodium, potassium or the like), and combinations thereof, and with anions selected from the group consisting of fluoride, chloride, bromide, iodide, nitrate, sulfate, phosphate, silicate, borate, peroxide, butoxide, formate, ethylenediamine-tetraacetic acid (EDTA), tungstate, molybdate, or the like and combinations thereof. A surfactant can be added to lower surface tension to facilitate application of the developer. Suitable surfactants can include, for example, ionic surfactants (such as alkyl ether sulfates, benzyl sulfonates, and phosphate esters, and the like) and non-ionic surfactants (such as ethoxylated and alkoxylated fatty acids, ethoxylated amines, ethoxylated alcohol, alkyl and nonyl-phenol ethoxylates, and the like). Other suitable optional additives include, for example, phase transfer agents (such as tetraalkyl ammonium salts, polyethylene glycols, and crown ethers). If the optional additives are present, the developer can comprise no more than about 5 weight percent additive, in further embodiments no more than about 2.5 weight percent additive, and in additional embodiments no more than about 1 weight percent additive. A person of ordinary skill in the art will recognize that additional ranges of additive concentrations within the explicit ranges above are contemplated and are within the present disclosure. The additives can be selected to improve contrast, sensitivity and line width roughness. The additives in the developer can also inhibit formation and precipitation of metal oxide particles.

[0136] 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.

[0137] The developer can be applied to the patterned coating material using any reasonable approach. For example, the developer can be sprayed onto the patterned coating material, or the structure can be dipped or otherwise immersed in the developer. Also, spin coating can be used. For automated processing, a puddle method can be used involving the pouring of the developer onto the coating material in a stationary format. If desired spin rinsing and / or drying can be used to complete the development process. After the image is developed, the coating material is disposed on the substrate as a pattern.

[0138] Development can be performed using any reasonable process approach, such as spray coating, puddle dipping and the like. For commercial production, development generally is adapted for the process equipment provided. The development can be performed for about 2 seconds to about 30 minutes, in further embodiments from about 3 seconds to about 15 minutes, in other embodimentsfrom about 4 seconds to about 10 minutes, and in additional embodiments from about 5 seconds to about 5 minutes. A person of ordinary skill in the art will recognize that additional ranges within the explicit ranges above are contemplated and are within the present disclosure.

[0139] Based on the design of the coating material, there can be a large contrast of material properties between the irradiated regions that have condensed coating material and the un-irradiated regions of the coating material with substantially intact photosensitive ligands, such as organic and / or carboxylate ligands. This high contrast in material properties further facilitates the formation of high- resolution lines with smooth edges in the pattern following development as described in the examples.

[0140] After completion of the development step including any optional rinses, the coating materials can be heat treated to further condense the material and to further dehydrate, densify, or remove residual developer from the material. This heat treatment can be particularly desirable for embodiments in which the oxide coating material is incorporated into the ultimate device, although it may be desirable to perform the heat treatment for some embodiments in which the coating material is used as a resist and ultimately removed if the stabilization of the coating material is desirable to facilitate further patterning. In particular, the bake of the patterned coating material can be performed under conditions in which the patterned coating material exhibits desired levels of etch selectivity. In some embodiments, the patterned coating material can be heated to a temperature from about 100° C to about 600° C, in further embodiments from about 175° C to about 500° C and in additional embodiments from about 200° C to about 400° C. The heating can be performed for at least about 1 minute, in other embodiment for about 2 minutes to about 1 hour, in further embodiments from about 2.5 minutes to about 25 minutes. The heating may be performed in air, vacuum, or an inert gas ambient, such as Ar or Nj. A person of ordinary skill in the art will recognize that additional ranges of temperatures and time for the heat treatment within the explicit ranges above are contemplated and are within the present disclosure. Likewise, non-thermal treatments, including blanket UV exposure, or exposure to an oxidizing plasma such as O2 may also be employed for similar purposes.

[0141] In some embodiments it may be beneficial to perform an additional rinse process immediately following the development process. The rinse process may generally comprise contacting the developed material with an additional composition comprising a solvent or a solvent and an additive. As shown in the examples, a rinse step with solvent alone tends to result in greater numbers of defects. A rinse step though with the improved development compositions described above with an additive can result in a decrease of defects and / or greater uniformity of process results. In some embodiments, the rinse composition can be one of the same compositions as described above for developers. For example, the rinse composition can comprise a solvent chosen from a ketone, an ester, an ether, or a mixture thereof, and the additive can comprise a carboxylic acid, a monohydroxyl alcohol, a polyol, such as a diol, a pyrrolidone, a lactone, or mixtures thereof. Specifically, for example, the rinse composition can comprise a mixture of 2-heptanone and 1,2-hexanediol. The rinse solvent can also be bio-based. In general, the rinse process can be similar to the development process except that the development step results in significant coating removal, while the rinse step generally does not involve a large removal of material. The rinse process can be performed for about 1 seconds to about 20 minutes, in further embodiments from about 2 seconds to about 12 minutes and in additional embodiments from about 4 seconds to about 6 minutes. A person of ordinary skill in theart will recognize that additional ranges within the explicit ranges above are contemplated and are within the present disclosure.

[0142] After patterning, the patterned material can be used for further processing such as deposition of material into gaps in the patterned material, and / or etching to remove substrate material between gaps in the patterned material. Then, the patterned resist material can be removed following further processing with a suitable etchant composition, such as a dilute base or BCU plasma. The processing is frequently repeated to form stacks of patterned layers to form functional components.

[0143] 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. Preparation of Organotin Coated Resins and Evaluation of Patterning Performance

[0144] Photoresist precursor coating solutions are prepared using a method similar to that described in published U.S. patent application 2019 / 0391486 to Jiang et al. A mixture comprising 20 mol % MeSn(OlAmyl)3 and 80 mol %lBuSn(OlAmyl)3(where OtAmyl=2-methylbutan-2-oxide) is prepared under an inert atmosphere and subsequently dissolved in bio-based 4-methyl-2-pentanol in which the H2O concentration had been pre-adjusted to ~300 ppm. The final Sn concentration of the precursor coating solution is 0.05 M. The photoresist precursor coating solution has an amount of carbon-14 sufficient to produce a decay greater than 1 dpm / gC.

[0145] The precursor solution described above is used to coat organotin oxide hydroxide photoresist films using a TEL CLEAN TRACK LITHIUS Pro Z coater / developer. Silicon wafers (300-mm diameter) are coated with a 10 nm spin-on-glass (SOG) underlayer (ISX328, JSR) and baked in air at 220° C for 1 minute prior to photoresist coating. A solvent pre-wet step using a bio-based PGME / PGMEA mixture was used to improve photoresist coat uniformity. The PGME / PGMEA mixture has an amount of carbon-14 sufficient to produce a decay greater than 1 dpm / gC. Resist precursor coating solutions are then spin-coated on underlayer-coated substrates in air at 1400 rpm. An edge-bead rinse (EBR) and back-side rinse process is conducted using the same bio-based PGME / PGMEA mixture. The coated wafers are then subjected to a post-apply bake (PAB) on a hotplate in air for 1 min at 100° C. Following PAB, resist-coated substrates are exposed to extreme ultraviolet radiation using an ASML NXE:3300B scanner at a numerical aperture of 0.33 with dipole 90x illumination. A pattern of equal vertical 16- nm lines and spaces (16p32) is projected on the coated wafer at a fixed focus, and the wafer stepped after each exposure to create an approximately annular array of fields about the center of the wafer with varied exposure doses. The exposed resist films and substrates are then returned to the coater / developer track and subjected to a hotplate PEB for 1 min in air at a specified temperature. Following PEB, the exposed films are then developed using set puddle development recipe with bio-based 2-heptanone developer composition for 15 seconds, then dynamically rinsed an additional 10 seconds with a bio-based 2-heptanone rinse solution to form a negative tone image, i.e., unexposed portions of the coating were removed. A final 1-min hotplate bake at 150° C. in air was performed after development.

Claims

We claim:

1. A photoresist composition comprising: a) a bio-based organic solvent, i) 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); and b) a metal polynuclear oxo / hydroxo cation with organic ligands having metal carbon bonds and / or with metal carboxylate bonds at a concentration from about 0.01M to about 1.4M, i) wherein the metal polynuclear oxo / hydroxo cation with organic ligands forms an oxo-hydroxo network, wherein the oxo-hydroxo network has both M-O— H linkages and M-O-M linkages.

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, bio-based 2-heptanone, bio-based cyclohexanone, bio-based methyl ethyl ketone, bio-based methyl isobutyl carbinol, 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.

7. The composition of claim 6, wherein the bio-based organic solvent comprises a bio-based propylene glycol monomethyl ether, a bio-based 2-heptanone, a bio-based cyclohexanone, a bio-based methyl ethyl ketone, or a bio-based methyl isobutyl carbinol.

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 2-heptanone, a bio-based cyclohexanone, a bio-based methyl ethyl ketone, or a bio-based methyl isobutyl carbinol.

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 2-heptanone, a bio-based cyclohexanone, a bio-based methyl ethyl ketone, or a bio-based methyl isobutyl carbinol.

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 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.

13. 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.

14. The composition of claim 6, wherein the bio-based organic solvent comprises a solvent represented by Formula (2).

15. The composition of claim 14, 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.

16. The composition of claim 15, 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.

17. The composition of claim 15, 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 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 6, wherein the bio-based organic solvent comprises a solvent represented by Formula (3).

19. The composition of claim 18, 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.

20. The composition of claim 19, 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.

21. 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.

22. The composition of claim 1, wherein the metal comprises a tin ion, antimony ion, indium ion or a combination thereof and wherein the organic ligand forms a metal carbon bond and wherein the ligand forming the metal carbon bond comprises an alkyl ligand, alkenyl ligand, aryl ligand, or a combination thereof, each ligand containing 1 to 16 carbon atoms and / or organic ligands form a metal-carboxyl bond and wherein the metal-carboxyl bond is formed by an alkyl carboxylate ligand, alkenyl carboxylate ligand, aryl carboxylate ligand or a combination thereof, each ligand having 1 to 16 carbon atoms.

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 coated substrate by coating the semiconductor substrate with a photoresist composition comprising a metal polynuclear oxo / hydroxo cation with organic ligands having metal carbon bonds and / or with metal carboxylate bonds and a bio-based organic solvent, wherein the coated substrate comprises a coating having an average thickness from about 5 nm to about 200 nm and that comprises a metal oxo-hydroxo network with organic ligands with metal carbon bonds and / or with metal carboxylate bonds and free of peroxide ligands; d) optionally, performing an edge bead removal process wherein a peripheral portion of the photoresist coating 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 an edge of the substrate, is contacted with an edge bead removal solvent; e) irradiating the coated substrate along a selected pattern to form an irradiated structure with a region of irradiated coating and a region with un-irradiated coating; f) heating the irradiated structure at a temperature from about 45° C. to about 250° C. for 0.1 minutes to about 30 minutes to form an annealed irradiated structure; and g) selectively developing the annealed irradiated structure to remove a substantial portion of the irradiated coating or of the un-irradiated coating to form a patterned substrate, wherein the metal oxo-hydroxo network comprises both M-O— H linkages and M-O-M linkages.

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, methyl isobutyl carbinol, 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 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.

44. The pattern forming method of claim 41, wherein the bio-based edge bead removal solvent comprises propylene glycol monomethyl ether, cyclohexanone, methyl isobutyl carbinol, 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 or claim 44, 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 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.

50. The composition of claim 1, wherein the metal polynuclear oxo / hydroxo cation comprises Cu, Al, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Zn, Y, Zr, Nb, Mo, In, Sn, Sb, Hf, Ta, W, Ir, Pt, La, Ce, Pr, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu or a combination thereof.

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