Bio-based solvent for negative tone development

Abstract

Non-aqueous bio-based organic solvents for use in lithography processes are described, along with methods for making and using such solvents. More specifically, the present disclosure contemplates non-aqueous developer and rinse compositions synthesized from biological or renewable sources, and further contemplates employing such bio-based developers to produce high-resolution negative-tone images using photoresists and utilizing the bio-based rinse agents for negative-tone development patterning processes.

Description

[Technical Field]

[0001] Priority claims This patent application claims priority to U.S. Application No. 63 / 426,285, filed November 17, 2022, which is incorporated by reference in its entirety into this application.

[0002] The field of the present disclosure includes bio-based compositions for negative tone development and methods of using such bio-based compositions. More specifically, the present disclosure contemplates non-aqueous developer and rinse compositions synthesized from biological or renewable sources, and further contemplates employing such bio-based developers to create high-resolution negative tone images using photoresists and / or utilizing the bio-based rinse agents for negative tone development patterning processes. [Background technology]

[0003] The realization of advanced lithography technologies beyond the 14nm node requires the implementation of patterning materials and processes with ultimate performance to address inherently contrast-limited exposure tools. The reduction in imaging wavelength from the long-standing 193nm ArF lithography (DUV) to the anticipated 13.5nm extreme ultraviolet lithography (EUV) is expected to improve the resolution of the ultimate optical systems used in the semiconductor industry, enabling the extension of Moore's Law to the 10nm node and beyond.

[0004] The optical resolution of ArF and EUV scanners can only be realized in the material patterns formed on semiconductor substrates if the spatial resolution of the imaging material is commensurate with the quality of the aerial image provided. At the same time, the imaging layer must have acceptable sensitivity to the imaging wavelength, low linewidth roughness (LWR), good adhesion to the underlying substrate, and a large post-apply bake (PAB) and post-exposure bake (PEB) tolerance. Chemically amplified resists have become the workhorses of the lithography industry because they can adequately meet these requirements across multiple technology nodes.

[0005] Chemically amplified (CA) resists are incorporated into the lithography process through two different types of development. Positive resist imaging and development is a process in which the exposed areas of the photoresist are removed after the PEB step by an aqueous basic developer (tetraalkylammonium hydroxide (TMAH)), leaving the unexposed areas insoluble. This is called positive tone development (PTD) and is described in detail in 4 J. Photopolymer Sci. Technol. 299 (1991).

[0006] Instead, negative resists exhibit the opposite behavior. When exposed to UV light, they crosslink / polymerize, becoming less soluble in the developer. Therefore, the negative resist remains on the exposed substrate surface, while the developer removes only the unexposed portions. Thus, the mask used with negative photoresist contains the inverse, or photographic "negative," of the pattern to be transferred. One method for reversing the tone of a chemically amplified resist designed for positive development with an aqueous developer is to use an organic developer to remove the unexposed portions of the resist film, leaving the exposed portions unaffected. This process, known as negative tone development (NTD), has found widespread application in the field of 193-nm double patterning using bright-field masks, particularly for small recess openings such as contact hole and trench patterning. As used herein, NTD refers to the use of organic solvents as developers to produce negative-tone images.

[0007] However, the industrial application of NTDs faces many challenges. Due to toxicological, environmental, and especially flammability issues, the number of organic solvents compatible with practical industrial-scale semiconductor manufacturing is limited. Common solvents used in trace processes include n-butyl acetate (NBA), 2-heptanone, propylene glycol methyl ether acetate (PGMEA), propylene glycol methyl ether (PGME), methyl isobutyl carbinol (MIBC), and ethyl lactate.

[0008] While commercially viable, the solvents currently used in NTD processes are still less than ideal, creating further problems for the semiconductor industry. All of these solvents are produced from petrochemical-derived feedstocks. The integrated circuit industry is particularly interested in finding alternatives to petroleum-derived solvents because of the environmental costs associated with these products, as well as their contribution to greenhouse gas emissions due to the high carbon content of petroleum. Furthermore, because petrochemicals take hundreds of thousands of years to form naturally, they are non-renewable; that is, they cannot be remanufactured, re-cultivated, or regenerated at a rate comparable to their consumption.

[0009] Therefore, there is an unmet need for solvents that are derived from renewable resources and have properties similar to petroleum-derived solvents that can be used in the manufacturing process. Furthermore, because semiconductor development and manufacturing involve significant investment costs, it would be advantageous if solvents derived from renewable resources could be processed in existing solvent manufacturing facilities. Summary of the Invention [Means for solving the problem]

[0010] The present disclosure includes compositions, processes, and products that address the aforementioned needs and provide environmental improvements, such as reduced greenhouse gas emissions, to trajectory-based processes through the synthesis of bio-based organic solvents and the utilization of such solvents.

[0011] A first aspect of the present disclosure includes a composition comprising an organic developer comprising at least 25 wt% bio-based n-butyl acetate, the bio-based n-butyl acetate containing a sufficient amount of carbon-14 to produce decay of at least 0.1 dpm / gC (degradations per gram of carbon per minute), and the organic developer containing 5 ppb or less of each of the following metal elements: Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn. In some embodiments, the first aspect further comprises 1 ppb or less of an alkane or alkene having 22 or fewer carbon atoms and Zn, and 3 wt% or less of bio-based n-butanol.

[0012] In some embodiments of the first aspect, the organic developer comprises 0.5 ppb or less of an alkane or alkene having 22 or less carbon atoms, Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn, each at a metal element concentration of 3 ppb or less, and one of 1 wt % or less of bio-based n-butanol, 0.1 wt % or less of n-hexadecane, 0.1 wt % or less of isopropanol, and 0.1 wt % or less of ethyl acetate.

[0013] In some embodiments of the first aspect, the organic developer comprises one of an alkane or alkene having 22 or fewer carbon atoms at 0.3 ppb or less, metal element concentrations of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn each at 1 ppb or less, and other bio-based solvents at a total concentration of 1 wt % or less.

[0014] In some embodiments of the first aspect, the organic developer comprises at least 90 wt% bio-based n-butyl acetate. The composition of claim 1, wherein the organic developer comprises at least 95 wt% bio-based n-butyl acetate. The composition of claim 1, wherein the organic developer comprises 0.001 wt% to 5 wt% surfactant. The composition of claim 6, wherein the surfactant comprises an ionic or non-ionic fluorine-based or silicon-based surfactant.

[0015] A second aspect of the present disclosure includes a method for forming a pattern, comprising: a) providing a semiconductor substrate; b) forming a resist film comprising coating the semiconductor substrate with a resist composition having solubility in an organic developer, wherein the solubility of the resist composition in an organic developer is reduced by exposure to actinic radiation or radiation; c) exposing the resist film to actinic radiation or radiation; and d) developing the resist film with an organic developer, wherein the organic developer comprises at least 25 wt % bio-based n-butyl acetate, wherein the bio-based n-butyl acetate comprises carbon-14 in an amount to produce a decay of at least 0.1 dpm / gC (degradation per gram of carbon per minute).

[0016] In some embodiments of the second aspect, the solubility of the resist composition in an organic developer after exposing the resist film to actinic or electromagnetic radiation is m sv / m su When expressed as a ratio, it is 25 or less, where m sv is one unit mass m of the resist composition su is the mass of the organic developer solvent required to dissolve

[0017] The second aspect may further include forming an integrated circuit on the semiconductor substrate. In some embodiments, the integrated circuit has a 3×10 7 Transistors / mm 2 It has a transistor density of

[0018] In some embodiments of the second aspect, the organic developer contains 5 ppb or less of each of the metal elements Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn. In some embodiments, the second aspect further contains 1 ppb or less of an alkane or alkene having 22 or fewer carbon atoms and 3 wt % or less of bio-based n-butanol.

[0019] In some embodiments of the second aspect, the organic developer comprises one or more of an alkane or alkene having 22 or fewer carbon atoms at 0.5 ppb or less, a metal element concentration of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn each at 3 ppb or less, and 1 wt % or less of bio-based n-butanol, 0.1 wt % or less of n-hexadecane, 0.1 wt % or less of isopropanol, and 0.1 wt % or less of ethyl acetate.

[0020] In some embodiments of the second aspect, the organic developer comprises one or more of an alkane or alkene having 22 or fewer carbon atoms at 0.3 ppb or less, metal element concentrations of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn each at 2 ppb or less, and other bio-based solvents totaling 1 wt % or less.

[0021] In some embodiments of the second aspect, the organic developer comprises at least 90 wt% bio-based n-butyl acetate. In some embodiments, the organic developer comprises at least 95 wt% bio-based n-butyl acetate.

[0022] In some embodiments of the second aspect, the organic developer further comprises 0.001 wt % to 5 wt % of a surfactant, hi some embodiments, the surfactant comprises an ionic or non-ionic fluorine-based or silicon-based surfactant.

[0023] In some embodiments of the second aspect, the method further includes rinsing the semiconductor substrate with a rinse solution after the developing step, wherein the rinse solution includes at least one bio-based organic solvent containing carbon-14 (C-14) in an amount sufficient to produce decay of at least 0.1 dpm / gC (decays per gram of carbon per minute), and Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn, each of which has a metal element concentration of 5 ppb or less. In some embodiments of the second aspect, the bio-based organic solvent is selected from the group consisting of one or more of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, and combinations thereof. In some embodiments of the second aspect, the bio-based organic solvent of the rinse solution is selected from the group consisting of one or more of 1-hexanol, methyl isobutyl carbinol, 2-hexanol, 1-heptanol, 2-heptanol, and combinations thereof.

[0024] A third aspect of the present disclosure provides a rinse composition comprising at least 25 wt. % of a bio-based organic rinse solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, and combinations thereof, wherein the bio-based organic rinse solvent contains carbon-14 in an amount sufficient to produce decay of at least 0.1 dpm / gC (decays per gram of carbon per minute), and wherein the rinse composition contains 5 ppb or less of each of the following metal elements: Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn. In some embodiments, the bio-based organic rinse solvent is selected from the group consisting of one or more of 1-hexanol, methyl isobutyl carbinol, 2-hexanol, 1-heptanol, 2-heptanol, and combinations thereof. In some embodiments, the rinse composition further comprises 1 ppb or less of an alkane or alkene having 22 or fewer carbon atoms, or 3 wt% or less of bio-based n-butanol. In some embodiments, the organic developer comprises at least 90 wt% of bio-based one or more of 1-hexanol, methyl isobutyl carbinol, 2-hexanol, 1-heptanol, and 2-heptanol. In some embodiments, the organic developer comprises at least 95 wt% of bio-based one or more of 1-hexanol, methyl isobutyl carbinol, 2-hexanol, 1-heptanol, and 2-heptanol.

[0025] In some embodiments of the fourth aspect, the rinse composition comprises one or more of: an alkane or alkene having 22 or fewer carbon atoms at 0.5 ppb or less; metal element concentrations of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn each at 3 ppb or less; and biobased n-butanol at 1 wt. % or less, n-hexadecane at 0.1 wt. % or less, isopropanol at 0.1 wt. % or less, and ethyl acetate at 0.1 wt. % or less.

[0026] In some embodiments of the fourth aspect, the rinse composition comprises one or more of: an alkane or alkene having 22 or fewer carbon atoms at 0.3 ppb or less; metal element concentrations of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn each at 2 ppb or less; and other bio-based solvents at a total concentration of 1 wt % or less.

[0027] According to a further aspect of the present disclosure, there is provided an electronic device formed by the methods described herein.

[0028] The present disclosure will now be described with reference to the following drawings, in which like reference numerals indicate like features.

[0029] Referring generally to the drawings, it will be understood that the illustrations are for purposes of illustrating particular embodiments and are not intended to limit the scope of the disclosure or the appended claims. The drawings are not necessarily to scale, and certain features and views of the drawings may be shown in reduced scale or exaggerated in diagrammatic terms for clarity and conciseness. [Brief explanation of the drawings]

[0030] [Figure 1A] AE show exemplary process flows for forming patterns according to the present disclosure. [Figure 1B] Same as above [Figure 1C] Same as above [Figure 1D] Same as above [Figure 1E] Same as above DETAILED DESCRIPTION OF THE INVENTION

[0031] The following description sets forth exemplary embodiments of the present technology, however, it should be recognized that such description is not intended to limit the scope of the present disclosure, but is instead provided as a description of exemplary embodiments.

[0032] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. As used herein, the following terms have the following meanings unless otherwise specified. Any methods, devices, and materials similar or equivalent to those described herein may 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 intended to limit the scope of the present disclosure. All references cited herein are incorporated by reference in their entirety.

[0033] The term "comprise" and variations thereof, such as "comprises" and "comprising," are to be interpreted in an open, inclusive sense, i.e., "including, but not limited to." The term "consisting essentially of" is to be interpreted to mean that the composition / process (a) necessarily includes the recited ingredients / processes, and (b) is open to unrecited ingredients / processes that do not materially affect the basic and novel characteristics of the composition / process. The term "consisting of" is closed-ended and excludes any element, step, or ingredient not specifically recited after the phrase. Furthermore, the singular forms "a," "an," and "the" include plural references unless the context clearly dictates otherwise. Thus, reference to "the" embodiment includes such plural embodiments.

[0034] In some embodiments, there are multiple alternatives from which to choose. In such cases, the terms "at least one of [A], [B], and [C]" or "one or more of [A], [B], and [C]" are used to mean "any of [A], [B], and [C], or any possible combination of [A], [B], and [C]," such as [A] and [B], or [A], [B], and [C]." When "[A] or [B]" is used, it should be interpreted as "either or both," not as alternatives. For example, "[A] or [B]" is equivalent to "[A] or [B], or a combination of [A] and [B]." For clarity, the disclosure may include "and combinations thereof," further clarifying that when alternatives are listed, the list also includes that combination.

[0035] It should be noted that the terms "substantially" and "about" used herein may represent the inherent degree of uncertainty that may result from any quantitative comparison, value, measurement, or other representation. These terms are also used herein to represent the degree to which a quantitative representation may deviate from the stated reference without resulting in a change in the basic functionality of the subject matter at issue. For example, reference herein to "about" a value or parameter includes (and describes) embodiments directed to that value or parameter itself. In certain embodiments, the term "about" includes the stated amount ±10%. In other embodiments, the term "about" includes the stated amount ±5%. In certain other embodiments, the term "about" includes the stated amount ±1%. Furthermore, the term "about X" includes a description of "X."

[0036] The terms "ring," "cyclocyclic," "cyclic," "alicyclic," or similar terms generally refer to at least one continuous closed loop, ring, or chain of atoms, and may include, for example, saturated alicyclic, unsaturated alicyclic, aromatic, heteroaromatic (heteroaryl), and similar cyclic classifications, or combinations thereof, including monocyclic, bicyclic, tricyclic, and similar conventional designations.

[0037] "Alkyl" includes straight-chain and branched alkyls. "Substituted alkyl" or "optionally substituted alkyl" refers to alkyl substituents, such as, for example, hydroxyl (-OH), halogen, amino (-NH or -NR), nitro (-NO), acyl (-C(=O)R), alkylsulfonyl (-S(=O)R), alkoxy (-OR), C 3-10 ) cycloalkyl, and similar substituents, where R is a hydrocarbyl, aryl, heteroaromatic ring, or similar moiety, such as a monovalent alkyl or divalent alkylene having from 1 to about 10 carbon atoms. For example, a hydroxy-substituted alkyl can be 2-hydroxy-substituted propylene of the formula -CH2-CH(OH)-CH2-, an alkoxy-substituted alkyl can be 2-methoxy-substituted ethyl of the formula -CH2-CH2-O-CH3, or an amino-substituted alkyl can be 1-dialkylamino-substituted ethyl of the formula -CH(NR2)-CH3.

[0038] "Alkane" includes unsubstituted linear, cyclic and branched saturated alkanes.

[0039] "Alkene" includes unsubstituted, linear, cyclic, and branched saturated alkenes having at least one carbon-carbon double bond.

[0040] "Cycloalkyl" includes cyclic alkyl. "Substituted cycloalkyl" or "optionally substituted cycloalkyl" refers to a cycloalkyl substituent having from 1 to 4 optional substituents selected from, for example, alkyl, alkenyl, alkynyl, hydroxyl (-OH), halogen, amino (-NH or -NR), nitro (-NO), acyl (-C(=O)R), alkylsulfonyl (-S(=O)R), alkoxy (-OR), and similar substituents.

[0041] "Alkoxyl" comprises an alkyl group attached to the base structure through an oxygen atom, -ORa where R a may include straight chain or branched alkyl optionally substituted as above.

[0042] "Alkoxycarbonyl" refers to a group containing an alkyl group attached through an oxygen atom to a base structure having a carbonyl group adjacent to the oxygen atom, -OC(=O)-R b where R b may include straight chain or branched alkyl optionally substituted as above.

[0043] "Carboxyl" means a moiety containing a carbon bonded to both an oxygen and a hydroxyl group, --C(.dbd.O)--OH.

[0044] "Hydroxyl" means the chemical moiety -OH.

[0045] "Aryl" includes a monovalent or divalent phenyl radical or an ortho-fused bicyclic carbocyclic radical having about 9 to 20 ring atoms in which at least one ring is aromatic. Aryl (Ar) can include substituted aryl, such as, for example, a phenyl radical having 1 to 5 substituents, e.g., alkyl, alkoxy, halo, etc.

[0046] "Heteroaromatic ring (Het)" includes 4-, 5-, 6-, or 7-membered saturated or unsaturated heterocyclic rings having 1, 2, 3, or 4 heteroatoms selected from the group consisting of oxy, thio, sulfinyl, sulfonyl, selenium, tellurium, and nitrogen, which are optionally fused to a benzene ring. Heteroaromatic rings also include "heteroaryl," which includes carbon and oxy, thio, and N(X), each of which is a non-peroxide, where X is absent or is selected from H, O, (C 1-4) alkyl, phenyl, or benzyl) and radicals of ortho-fused bicyclic heterocycles of about 8 to 10 ring atoms derived therefrom, particularly benzo derivatives, or those derived therefrom by fusing a propylene, trimethylene, or tetramethylene diradical thereto.

[0047] Alkyl, alkoxy, etc. include both straight-chain and branched groups, although references to individual radicals such as "propyl" encompass only the straight-chain radical; branched-chain isomers such as "isopropyl" are specifically referred to.

[0048] The carbon atom content of various hydrocarbon-containing (i.e., hydrocarbyl) moieties can alternatively be indicated by prefixes specifying the lower and upper number of carbon atoms in the moiety, i.e., the prefix C i-j denotes a moiety containing carbon atoms from integer "i" to integer "j". Thus, for example, (C1-C8) alkyl or C 1-8 Alkyl refers to alkyl containing 1 to 8 carbon atoms, including (C1-C8)alkoxy or C 1-8 Hydrocarbyloxy, such as alkoxy, refers to an alkoxy radical (—OR) having an alkyl group containing from 1 to 8 carbon atoms, inclusive. 1-8 Alkyl can be, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, 3-pentyl, hexyl, heptyl, or octyl; (C 3-12 ) Cycloalkyl can be cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and includes bicyclic, tricyclic, or polycyclic substituents, and the like.

[0049] As used herein, the groups described, such as (C 10-20 ) alkyl, the specific "C x-y" may be used to qualify the group and is inclusive of all intermediate chain lengths and values. 1-8 Alkoxy can be, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, pentoxy, 3-pentoxy, hexyloxy, 1-methylhexyloxy, heptyloxy, octyloxy, and similar substituents.

[0050] The present disclosure provides novel biobased compounds for use in lithography and other patterning processes, along with methods for synthesizing such compounds and processes for using such compounds in lithography processes. As used herein, the term "biobased" refers to the inclusion of any component derived from at least one biobased material. For example, "biobased n-butyl acetate" solvent ("NBA") would be NBA derived partially or entirely from at least one biobased material. As used herein, "biobased material" refers to organic materials whose carbon is derived from non-fossil biological sources. Examples of biobased materials include, but are not limited to, sugars, starches, corn, natural fibers, sugarcane, beets, citrus fruits, woody plants, celluloses, lignocelluloses, hemicelluloses, potatoes, vegetable oils, other polysaccharides (e.g., pectin, chitin, levan, and pullulan), and combinations thereof. According to certain embodiments, the at least one bio-based material is selected from corn, sugarcane, beet, potato, starch, citrus fruit, woody plants, cellulosic lignin, vegetable oils, natural fibers, oily wood materials, and combinations thereof.

[0051] As used herein, fossil biological resources, or fossil fuels, include hydrocarbon-containing materials such as coal, crude oil, and natural gas that are naturally formed in the Earth's crust from the remains of dead plants and animals, as well as materials refined or synthesized therefrom. The primary difference between fossil biological resources and bio-based materials is that fossil biological resources are formed from buried organisms that have been anaerobically decomposed over millions of years into high-carbon fossil fuels.

[0052] Carbon-14 is a radioactive isotope of carbon that is produced in the troposphere and upper stratosphere by thermal neutrons absorbed by nitrogen atoms. When cosmic rays strike the air, the air undergoes various transformations, including the production of neutrons. The resulting neutrons (1n) participate in the following np reactions:

number

[0053] Carbon-14 (C-14) has a half-life of approximately 5,700 years, making it useful as a detector for identifying carbon sources in synthetic materials. Because of its relatively short half-life, C-14 is present in biobased materials but not in fossil biological sources. Samples of biobased compounds will have measurable amounts of C-14 incorporated into the compounds. Samples of compounds prepared from petroleum-based materials will have essentially no C-14 or negligible to undetectable levels of C-14. Thus, a key distinguishing factor for the novel biobased solvents described herein is that they contain detectable amounts of C-14 that distinguish them from conventional fossil-based solvents.

[0054] The detection of the presence of C-14 in the compositions described herein can be performed based on techniques known in the art. Non-limiting examples of methods for determining the presence and level of C-14 in a composition include the use of accelerator mass spectrometry (AMS), liquid scintillation counting (LSC), or beta ionization technology (BI). In some embodiments, liquid scintillation is used as the standard method for measuring C-14 levels. The carbon percentage can be compared to the total carbon in the product or compared to the percentage of the total mass of the product. Specific examples of standards for measuring C-14 in commercial products include: a) ASTM D6866, Standard Test Methods for Determining the Biobased Content of Solid, Liquid, and Gaseous Samples Using Radiocarbon Analysis. First published in 2004, it was updated in March 2022 as ASTM D6866-22. It is a standardized analytical method developed in the United States for measuring the biobased content of solid, liquid, and gaseous samples using radiocarbon dating. This is one way to certify the biobased content of commercially available products. The practical standard for industrial radiocarbon dating was completed in 2004 and is now cited in US Federal Law (7 CFR part 2902). b) CEN / TS 16640:2014, Bio-based products - Determination of the bio-based carbon content of products using the radiocarbon method. This European standard provides technical specifications for determining the bio-based carbon content of products based on 14C content measurements. This standard specifies three test methods for measuring 14C content to calculate bio-based carbon content: A) liquid scintillation counter (LSC), B) beta ionization (BI), and C) accelerator mass spectrometry (AMS). Bio-based carbon content is expressed as a percentage of the sample mass, a percentage of the total carbon content, or a percentage of the total organic carbon content. This calculation method is applicable to any product containing organic carbon, including biocomposites. c)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.

[0055] The bio-based solvents described herein have non-zero or detectable amounts of C-14. Examples of quantitatively measured levels of C-14 in compositions include: a) Radioactive decay of carbon-14 (C-14) 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 gram of carbon per minute). In some embodiments, the measurements of the compositions described herein are from 0.1 to 14, 0.1 to 13, 0.1 to 12, 0.1 to 11, 0.1 to 10, 0.1 to 8, 0.1 to 6, 0.1 to 4, 0.1 to 2, 0.1 to 0.5, 0.5 to 14, 0.5 to 13, 0.5 to 12, 0.5 to 11, 0.5 to 10, 0.5 to 8, 0.5 to 6, 0.5 to 4, 0.5 to 2, 1 to 14, 1 to 13, 1 to 12, 1 to 11, 1 to 10, 1 to 8, 1 to 6, 1 to 4, 1 to 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) in a sample of the compound 14 C and 12 C. Biobased compounds are greater than zero. 14 C / 12 In some embodiments, the bio-based compound comprises a 1×10 C ratio. -13 , 2.5×10 -13 , 5×10 -13 , 7.5×10 -13 , 9×10 -13 , 1×10 -12 , 1.1×10 -12 , 1.2 × 10 -12 , 1.3 × 10 -12 , 1.4×10 -12 , 1.45×10 -12 , 1.5×10 -12 The above 14 C / 12 In some embodiments, the biobased compound will have a C ratio of 7.5×10 -13 ~1.5×10 -12 , 1.2 × 10 -12 ~1.5×10-12 , 1.3 × 10 -12 ~1.5×10 -12 , 1.4×10 -12 ~1.5×10 -12 , or 1.45 × 10 -12 ~1.5×10 -12 of 14 C / 12 C ratio. c) In some embodiments, the bio-based solvents described herein contain greater than 25, 50, 75, 100, 150, 175, 200, or 225 becquerels (Bq) of C-14 per kg of total carbon.

[0056] In some embodiments, there may be practical or economic reasons to use a solvent mixture or combination of solvents in which at least a portion of the solvent is bio-based. In some embodiments, the bio-based solvent comprises more than 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 60, 70, 80, 90, 95, 98, 99, 99.5, or 99.9 wt.% of the total solvent mixture. In some embodiments, the bio-based solvent is present in an amount, by weight percent, of the total solvent mixture, between 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%.

[0057] Biobased content is determined based on the amount of biobased carbon in a material or product as a weight percentage of the total organic carbon in the material or product. In embodiments where the solvent is a mixture or combination of solvents, at least a portion of which is biobased, the biobased content of the solvent may be approximated by several methods. For example, the biobased content can be estimated by measuring the specific activity (dpm / gC) of the mixed solvent and applying the following formula: wt% biobased = 100 x (specific activity of the mixture) / (specific activity of 100% biobased) The global stock of natural C-14 is approximately 75 tonnes, resulting in a specific activity of over 13.56 dpm / gC. The expected specific activity of biobased materials can be estimated according to this value using the following formula: Specific activity of material X = (weight fraction of carbon in material) x 13.56 dpm / gC For example, the carbon content of NBA is 0.621, so the specific activity of pure biobased NBA is expected to be 8.4 dpm / gC. Therefore, a mixture containing more than 50% biobased NBA by weight is expected to have a specific activity of approximately 4.2 dpm / gC.

[0058] Bio-based negative developer Bio-based negative tone developers are bio-based organic solvents that dissolve resist films exposed to actinic or electromagnetic radiation as part of semiconductor patterning processes. In certain embodiments, the present disclosure is directed to the use of n-butyl acetate ("NBA"), also known as butyl acetate, n-butyl acetate ester, butyl ethanoate, or butile, as a bio-based negative tone developer. Traditionally, NBA has been derived from fossil fuels. There is a strong desire to find bio-based alternatives that meet the needs of the integrated circuit community while providing an environmentally friendly, sustainable, and renewable solvent. However, as discussed herein, the development of bio-based solvents presents unique and non-trivial challenges that must be overcome to make the replacement of bio-based solvents in the semiconductor space feasible. The process of synthesizing bio-based solvents, e.g., fermentation, results in multiple side reactions that produce other solvents, such as isobutanol and isobutyl acetate, as well as difficult-to-separate acetone, butanol, and ethanol (ABE), as well as water, acetic acid, butyric acid, and higher alcohols, along with impurities such as metals and particulate matter.

[0059] To meet the stringent requirements of the semiconductor industry, bio-based NBA negative developers must be highly to ultra-pure. It is crucial that semiconductor wafer surfaces are not contaminated by any metal impurities contained in NBA. In fact, more than 50% of yield losses in IC manufacturing are due to microcontamination. Therefore, it is a given that the metal impurity content of materials used in these processes must be minimized. Solvents must be purified to extremely low metal content levels. Metal element concentrations may be measured using inductively coupled plasma mass spectrometry (e.g., an Agilent 7500cs inductively coupled plasma mass spectrometer (ICP-MS) manufactured by Agilent Technologies, Inc.). The metal element concentrations of bio-based NBA negative developers should be 5 ppb or less for each of the following metal elements: Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn. In some embodiments, the metal element concentrations of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn are each 5, 4, 3, 2, 1, 0.5, 0.1, 0.05, 0.01, 0.005, or 0.001 ppb or less. In some embodiments, the metal element concentrations of Na and Ca are each 0.75 ppb or less, Al, K, Fe, Mg, and Zn are 0.25 ppb or less, and Cu, Mn, Li, Cr, and Ni are 0.1 ppb or less. In some embodiments, the bio-based developer has a metal element concentration of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn of 0.001 to 1 ppb.

[0060] Organic compounds or impurities can also cause contamination problems in semiconductor manufacturing processes. In addition to minimizing the amount of impurities in solvents, it is also necessary to reduce or remove organic impurities. In particular, relatively low molecular weight organic compounds pose significant challenges to semiconductor processes because they are difficult to remove by filtration techniques and can cause particle contamination, especially in fine patterns (e.g., 30 nm node and below). In some embodiments, the bio-based NBA negative tone developer contains 5 ppb or less of alkanes or alkenes with 22 or fewer carbon atoms ("C"). 1-22 In some embodiments, the bio-based NBA negative tone developer contains no more than 5, 4, 4, 2, 1, 0.5, 0.1, 0.05, or 0.01 ppb of C. 1-22 In some embodiments, C 1-22 The concentration of alkane / alkene is 0.001 to 1 ppb. 1-22 The alkane / alkene content may be measured according to gas chromatography mass spectrometry (e.g., GCMS-QP2010 (gas chromatography mass spectrometry) manufactured by Shimadzu Corporation) connected to a pyrolysis apparatus (e.g., PY2020D manufactured by Frontier Lab).

[0061] As a result of the synthetic techniques used, small amounts of additional organic solvents may be present. In some embodiments, it is necessary to reduce or remove these impurities or intermediates. Such compounds include, but are not limited to, biobased n-butanol, n-hexadecane, isopropanol, and ethyl acetate. In some embodiments, the biobased NBA negative developer contains no more than 3, 2, 1, 0.5, 0.1, 0.05, 0.01, or 0.001% biobased n-butanol. In some embodiments, the biobased NBA negative developer contains no more than 3, 2, 1, 0.5, 0.1, or 0.5% of one or more of biobased n-butanol, n-hexadecane, isopropanol, and ethyl acetate. In some embodiments, the biobased NBA negative developer contains no more than 3, 2, 1, 0.5, 0.1, 0.05, 0.01, or 0.001% total of other (non-NBA) biobased solvents.

[0062] In addition to metals and low-molecular-weight organics, general particulate contamination, including nano- to micro-scale particles from various sources, can also lead to yield-detrimental device defects. Therefore, as mentioned above, it is important to remove particulates from biobased solvents. Specifically, depending on the purification method, the number of particles with a diameter of 0.15 μm or larger in the solvent can be reduced to, for example, 20 particles / mL or less, 10 particles / mL or less, or 5 particles / mL or less. Particle counts are measured using liquid particle counting techniques, similar to measurements on wafers. For example, a predetermined amount of solvent is applied to a substrate, shaken off at a predetermined rotation speed, and then the wet particle amount is dried at a predetermined rotation speed. The number of defects on the substrate is then measured, for example, using a KLA Surfscan SP7 unpatterned wafer inspection system.

[0063] The bio-based negative developer may further contain additional components such as a surfactant, a stabilizer, etc. The surfactant may be, but is not limited to, an ionic or non-ionic fluorine-based surfactant and / or a silicone-based surfactant. Examples of fluorine-based and / or silicone-based surfactants include those described in Japanese Patent Application Publication Nos. S62-36663, S61-226746, S61-226745, S62-170950, S63-34540, H7-230165, H8-62834, H9-54432 and H9-5988, and U.S. Pat. Nos. 5,405,720, 5,360,692, 5,529,881, 5,296,330, 5,436,098, 5,576,143, 5,294,511 and 5,824,451, with nonionic surfactants being preferred. The nonionic surfactant is not particularly limited, but a fluorine-based surfactant or a silicon-based surfactant is more preferably used. When present, the amount of the surfactant used is usually in the range of 0.001 wt% to 5 wt%, 0.005 wt% to 2 wt%, or 0.01 wt% to 0.5 wt% based on the total amount of the developer.

[0064] When the bio-based negative developer is contained in the developer, it may further contain a nitrogen-containing sensitizer compound that interacts with polar groups generated in the resist film due to acid, further increasing the insolubility of the exposed area in organic solvents. For example, the nitrogen-containing sensitizer compound reacts with the polar groups to form a salt or an ionic bond. For example, from the viewpoint of the storage stability of the developer, the nitrogen-containing sensitizer compound may be added to the organic developer, preferably immediately before carrying out the pattern formation method of the present invention. The sensitizer compound has the following structure: [ka] (In the formula, R 1 , R 2 and R 3 are independently a hydrogen atom, a hydroxyl group, a formyl group, an alkoxy group, an alkoxycarbonyl group, an optionally substituted C1-30 Alkyl groups, optionally substituted C 3-30 represents a cycloalkyl group, an aryl group, or a group formed by two or more of these groups; R 1 , R 2 and R 3 two of them may combine to form a ring structure with the nitrogen atom to which they are attached).

[0065] In embodiments where a sensitizer compound is present, the amount of sensitizer compound ranges from 0.001 wt % to 10 wt %, 0.1 wt % to 10 wt %, or 1 wt % to 5 wt %, based on the total amount of developer.

[0066] Bio-based rinse solution The bio-based rinse solution includes a bio-based material that improves the quality of the patterned photoresist. The bio-based rinse solution may be partially or completely derived from at least one bio-based material. The bio-based rinse solution may include a hydrocarbon-based solvent, a ketone-based solvent, an ester-based solvent, an alcohol-based solvent, or an amide-based solvent, or a combination of one or more of the foregoing solvents, or in some embodiments, an alcohol-based solvent in combination with an ester-based solvent.

[0067] As with negative developers, bio-based rinse solutions must be highly to ultra-pure. It is crucial that the semiconductor wafer surface is not contaminated by any metal impurities contained in NBA. Therefore, it is naturally required to minimize the metal impurity content of materials used in these processes. Metal element concentrations may be measured using inductively coupled plasma mass spectrometry (e.g., an Agilent 7500cs ICP-MS instrument manufactured by Agilent Technologies, Inc.). Bio-based rinse solutions preferably contain 5 ppb or less of each of the following metal elements: Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn. In some embodiments, the metal element concentrations of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn are 5, 4, 3, 2, 1, 0.5, 0.1, 0.05, 0.01, 0.005, or 0.001 ppb or less. In some embodiments, the metal element concentrations of Na and Ca are each 0.75 ppb or less, Al, K, Fe, Mg, and Zn are 0.25 ppb or less, and Cu, Mn, Li, Cr, and Ni are 0.1 ppb or less. In some embodiments, the metal element concentrations of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn contained in the bio-based rinse solution are 0.001 to 1 ppb.

[0068] Organic compounds or impurities can also cause contamination problems in semiconductor manufacturing processes. In addition to minimizing the amount of impurities in solvents, it is also necessary to reduce or remove organic impurities. In particular, relatively low molecular weight organic compounds pose significant challenges to semiconductor processes because they are difficult to remove by filtration techniques and can cause particle contamination, especially in fine patterns (e.g., 30 nm node and below). In some embodiments, the bio-based NBA negative tone developer contains 5 ppb or less of alkanes or alkenes with 22 or fewer carbon atoms ("C"). 1-22In some embodiments, the bio-based NBA negative tone developer contains no more than 5, 4, 4, 2, 1, 0.5, 0.1, 0.05, or 0.01 ppb of C. 1-22 In some embodiments, C 1-22 The concentration of alkane / alkene is 0.001 to 1 ppb. 1-22 The alkane / alkene content may be measured according to gas chromatography mass spectrometry (e.g., GCMS-QP2010 (gas chromatography mass spectrometry) manufactured by Shimadzu Corporation) connected to a pyrolysis apparatus (e.g., PY2020D manufactured by Frontier Lab).

[0069] Small amounts of additional organic solvents may be present as a result of the synthetic techniques used. In some embodiments, it is necessary to reduce or remove these impurities or intermediates. In some embodiments, the bio-based rinse solution contains no more than 3, 2, 1, 0.5, 0.1, 0.05, 0.01, or 0.001% total of other bio-based solvents.

[0070] In addition to metals and low-molecular-weight organics, general particulate contamination, including nano- to micro-scale particles from various sources, also leads to yield-detrimental device defects. Therefore, as mentioned above, it is important to remove particulates from biobased solvents. Specifically, depending on the purification method, the number of particles with a diameter of 0.15 μm or larger in the solvent can be reduced to, for example, 20 particles / mL or less, 10 particles / mL or less, or even 5 particles / mL or less. Particle counts are measured using liquid particle counting techniques, similar to measurements on wafers. For example, a predetermined amount of solvent is deposited on a substrate, shaken off at a predetermined rotation speed, and then the wet particle amount is dried at a predetermined rotation speed. The number of defects on the substrate is then measured, for example, using a KLA Surfscan SP7 unpatterned wafer inspection system.

[0071] Bio-based rinse solutions may be characterized by their Hansen Solubility Parameter. In some embodiments, the bio-based solvents herein have a Hansen Solubility Parameter of about 14.5 to 17 MPa. 0.5 The sum of the polarity parameter and the hydrogen bonding parameter should be about 14-20 MPa. 0.5 In some embodiments, the solvent selected has a pressure of about 15-16 MPa. 0.5 , or for example 15.4 to 15.9 MPa 0.5 The sum of the polarity parameter and hydrogen bond parameter is 15 to about 19 MPa. 0.5 , more preferably 15.5 to 18.5 MPa 0.5 is.

[0072] In this disclosure, a ketone-based rinse solution refers to a solvent having a ketone group in the molecule, an ester-based solvent refers to a solvent having an ester group in the molecule, an alcohol-based solvent refers to a solvent having an alcoholic hydroxyl group in the molecule, an amide-based solvent refers to a solvent having an amide group in the molecule, and an ether-based solvent refers to a solvent having an ether bond in the molecule. Some of these solvents have multiple types of the above functional groups in one molecule, and in this case, the solvent falls under all solvent types corresponding to the functional groups contained in the solvent. For example, diethylene glycol monomethyl ether falls under both alcohol-based solvents and ether-based solvents in the above classification. A hydrocarbon-based solvent refers to a hydrocarbon-based solvent without a substituent.

[0073] Examples of ketone-based rinse solutions 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, propylene carbonate, γ-butyrolactone, γ-valerolactone, and dihydrolevoglucosenone. Among ketone-based solvents, 2-heptanone is the most preferred.

[0074] Examples of ester-based rinse solutions 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 monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene ...ethyl ether acetate, propylene glycol monobutyl 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 monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl 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, These include 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 benzoate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, and propyl 3-methoxypropionate.As the solvent represented by formula (1), alkyl acetate is more preferred, and butyl acetate is most preferred.

[0075] As the ester-based rinse solution, a solvent represented by formula (1) described below or a solvent represented by formula 2 described below is preferred, a solvent represented by formula (1) is more preferred, alkyl acetate is further preferred, and butyl acetate is most preferred.

[0076] Examples of alcohol-based rinse solutions include alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexylmethylisobutylcarbinol, n-heptyl alcohol, n-octyl alcohol, n-decanol, and 3-methoxy-1-butanol; glycol-based solvents such as ethylene glycol, diethylene glycol, and triethylene glycol; and hydroxyl group-containing glycol ether-based solvents such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methoxymethylbutanol, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, and propylene glycol monophenyl ether. Among these, glycol ether-based solvents are preferred.

[0077] Examples of ether-based rinse solutions include the above-mentioned hydroxyl group-containing glycol ether-based solvents, as well as hydroxyl group-free glycol ether-based solvents such as propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol dimethyl ether, and diethylene glycol diethyl ether, as well as dioxane, tetrahydrofuran, anisole, perfluoro-2-butyltetrahydrofuran, and 1,4-dioxane. Glycol ether-based solvents are preferably used.

[0078] Examples of hydrocarbon-based rinse solutions include aromatic hydrocarbon-based solvents such as toluene and xylene, aliphatic hydrocarbon-based solvents such as pentane, hexane, octane, decane, 2,2,4-trimethylpentane, 2,2,3-trimethylhexane, perfluorohexane, and perfluoroheptane, and aromatic hydrocarbon-based solvents such as toluene, xylene, ethylbenzene, propylbenzene, 1-methylpropylbenzene, 2-methylpropylbenzene, dimethylbenzene, diethylbenzene, ethylmethylbenzene, trimethylbenzene, ethyldimethylbenzene, and dipropylbenzene. Among these, aromatic hydrocarbon-based solvents are preferred.

[0079] In some embodiments, the bio-based rinse solution primarily comprises a monohydric alcohol having 6 to 8 carbon atoms. Examples of monohydric alcohols having 6 to 8 carbon atoms include linear, branched, and cyclic monohydric alcohols. Specific examples of usable monohydric alcohols include 1-hexanol, 1-heptanol, 1-octanol, 2-hexanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol, methyl isobutyl carbinol, and benzyl alcohol. 1-hexanol, methyl isobutyl carbinol, 2-hexanol, 1-heptanol, and 2-heptanol are preferred, and methyl isobutyl carbinol is most preferred.

[0080] These solvents may be used in combination, or may be used in combination with a solvent other than those mentioned above or with water.

[0081] Bio-based solvent for photoresist solubilization The bio-based solvents described herein may, in some embodiments, be used as or incorporated into formulations for photoresist compositions. Photoresist compositions generally contain a solvent to dissolve the components of the composition and facilitate coating onto a substrate. Due to toxicological, environmental, and especially flammability concerns, the number of organic solvents compatible with practical industrial-scale semiconductor manufacturing is limited.

[0082] The photoresist composition of the present disclosure comprises: (A) a polymer matrix that exhibits increased solubility in alkaline developers and decreased solubility in organic solvents upon the action of an acid; (B) a compound capable of generating an acid upon exposure to actinic or radiation (sometimes referred to as a “photoacid generator”); (C) a bio-based solvent that can be used to dissolve each component of the photoresist composition, the bio-based solvent containing at least 0.1 dpm / gC (disintegrations per gram of carbon per minute) of carbon-14 (C-14); and, optionally, one or more of (D) a basic compound, (E) a surfactant, (F) a photodegradable quencher, and (G) other additives.

[0083] In another embodiment, the photoresist composition comprises radiation-based resists based on metal oxide chemistry (metal oxo / hydroxo compositions), which use radiation-sensitive ligands to control resist stability and processability. Generally, these compositions function as negative-acting photoresists when developed with organic solvents. Related resist compounds are described in U.S. Pat. No. 8,703,386 B2, which is incorporated herein by reference. Organometallic photoresists, such as organotin oxide hydroxides, have been shown to have excellent properties as photoresists for use in lithographic photopatterning. Suitable organometallic photoresists include organotin materials such as those described in U.S. Pat. No. 9,310,684 B2, published U.S. patent application Ser. No. 2016 / 0116839 A1, and U.S. Pat. No. 10,228,618 B2, all of which are incorporated herein by reference. Other organometallic patterning compositions based on various metals are described in Published U.S. Patent Application No. 2002 / 0076495 and U.S. Patent No. 9,372,402 B2, both of which are incorporated herein by reference. Resists having organically coated metal oxide particles are described in Published U.S. Patent Application No. 2015 / 0234272 A1, which is incorporated herein by reference. Applicant has developed highly advanced organotin patterning materials, some of which are described in the exemplified compositions.

[0084] Typical solvents used in photoresist compositions include n-butyl acetate (NBA), 2-heptanone, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), hydroxyisobutyric acid methyl ester (HBM), and cyclohexanone (CHO). The total solvent content in a photoresist composition is typically 70-99 wt% based on the total weight of the photoresist composition. The present disclosure contemplates the use of NBA alone or as part of a mixture of one or more solvents. Percentages of NBA include those recited herein for mixtures of, for example, 5-99 wt%.

[0085] As with negative developers and rinse solutions, bio-based photoresist solvents must be highly to ultra-pure. Solvents must be purified to extremely low metal content levels. Metal element concentrations may be measured by inductively coupled plasma mass spectrometry (e.g., an Agilent 7500cs ICP-MS instrument manufactured by Agilent Technologies, Inc.). The metal element concentrations of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn contained in bio-based rinse solutions should be 5 ppb (parts per billion) or less. In some embodiments, the metal element concentrations of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn are 5, 4, 3, 2, 1, 0.5, 0.1, 0.05, 0.01, 0.005, or 0.001 ppb or less. In some embodiments, the metal element concentrations of Na and Ca are each 0.75 ppb or less, Al, K, Fe, Mg, and Zn are 0.25 ppb or less, and Cu, Mn, Li, Cr, and Ni are 0.1 ppb or less. In some embodiments, the metal element concentrations of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn contained in the bio-based rinse solution are 0.001 to 1 ppb.

[0086] As previously mentioned, organic compounds or impurities can also cause contamination problems in semiconductor manufacturing processes. In addition to minimizing the amount of impurities in the solvent, it is also necessary to reduce or remove organic impurities. In particular, relatively low molecular weight organic compounds pose significant challenges to semiconductor processes because they are difficult to remove by filtration techniques and can cause particle contamination, especially in fine patterns (e.g., 30 nm node and below). In some embodiments, the bio-based rinse solution contains 5 ppb or less of alkanes or alkenes with 22 carbon atoms or less ("C 1-22 In some embodiments, the biobased rinse solution contains no more than 5, 4, 4, 2, 1, 0.5, 0.1, 0.05, or 0.01 ppb of C.1-22 In some embodiments, C 1-22 The concentration of alkane / alkene is 0.001 to 1 ppb. 1-22 The alkane / alkene content may be measured according to gas chromatography mass spectrometry (e.g., GCMS-QP2010 (gas chromatography mass spectrometry) manufactured by Shimadzu Corporation) connected to a pyrolysis apparatus (e.g., PY2020D manufactured by Frontier Lab).

[0087] Small amounts of additional organic solvents may be present as a result of the synthetic techniques used. In some embodiments, it is necessary to reduce or remove these impurities or intermediates. In some embodiments, the bio-based rinse solution contains no more than 3, 2, 1, 0.5, 0.1, 0.05, 0.01, or 0.001% total of other bio-based solvents.

[0088] In addition to metals and low-molecular-weight organics, general particulate contamination, including nano- to micro-scale particles from various sources, also leads to yield-detrimental device defects. Therefore, as mentioned above, it is important to remove particulates from biobased solvents. Specifically, depending on the purification method, the number of particles with a diameter of 0.15 μm or larger in the solvent can be reduced to, for example, 20 particles / mL or less, 10 particles / mL or less, or even 5 particles / mL or less. Particle counts are measured using liquid particle counting techniques, similar to measurements on wafers. For example, a predetermined amount of solvent is deposited on a substrate, shaken off at a predetermined rotation speed, and then the wet particle amount is dried at a predetermined rotation speed. The number of defects on the substrate is then measured, for example, using a KLA Surfscan SP7 unpatterned wafer inspection system.

[0089] Bio-based solvents may be characterized by their Hansen Solubility Parameter. Bio-based solvents herein have a Hansen Solubility Parameter of about 14.5 to 17 MPa. 0.5The sum of the polarity parameter and the hydrogen bonding parameter should be about 14-20 MPa. 0.5 In some embodiments, the solvent selected has a pressure of about 15-16 MPa. 0.5 , or for example 15.4 to 15.9 MPa 0.5 The sum of the polarity parameter and hydrogen bond parameter is 15 to about 19 MPa. 0.5 , more preferably 15.5 to 18.5 MPa 0.5 is.

[0090] The resin binder of the present invention is preferably a poorly alkali-soluble or alkali-insoluble binder containing one or more blocked (hidden) alkali-solubilizing groups (acid-sensitive groups). The functionality that blocks some or all of the alkali-solubilizing groups is acid-sensitive. The presence of acid catalyzes the unblocking of the alkali-solubilizing groups, rendering the polymer alkali-soluble. Suitable alkali-solubilizing groups include, but are not limited to, carboxylic acids, sulfonic acids, phenols, acidic alcohols, hydroxyimides, hydroxymethylimides, and silanols. Suitable acidic hydroxyl groups, carboxyl groups, and sulfamide groups are further described in U.S. Patent Application Publication No. 2006 / 0110677.

[0091] Photoactive compounds capable of generating strong acids upon exposure to a high-energy radiation source are commonly referred to as photoacid generators, or PAGs. Any suitable photoacid generator may be used in the photosensitive compositions of the present invention. Those skilled in the art will be able to select an appropriate PAG based on factors such as acid value, catalytic activity, volatility, diffusibility, and solubility. Suitable PAGs that generate sulfonic acids include, but are not limited to, sulfonium or iodonium salts, oxime sulfonates, bissulfonyldiazomethanes, and nitrobenzyl sulfonate esters. Suitable photoacid generator compounds are disclosed, for example, in U.S. Patent Nos. 5,558,978, 5,468,589, 6,844,132, 6,855,476, and 6,911,297, which are incorporated herein by reference. Preferred PAGs are those that generate tris(perfluoroalkylsulfonyl)methides, tris(perfluoroalkylsulfonyl)imides, and perfluoroalkylsulfonic acids.

[0092] Further examples of photoacid generators suitable for use in the present invention include triphenylsulfonium perfluorooctane sulfonate, triphenylsulfonium perfluorobutane sulfonate, methylphenyldiphenylsulfonium perfluorooctane sulfonate, 4-n-butoxyphenyldiphenylsulfonium perfluorobutane sulfonate, 2,4,6-trimethylphenyldiphenylsulfonium perfluorobutane sulfonate, 2,4,6-trimethylphenyldiphenylsulfonium benzenesulfonate, 2,4,6-trimethylphenyldiphenylsulfonium 2,4,6-triisopropylbenzenesulfonate, phenylthiophenyldiphenylsulfonium 4-dodecylbenzenesulfonate, tris(t-butylphenyl)sulfonium perfluorooctane sulfonate, tris(t-butylphenyl)sulfonium perfluorobutane sulfonate, tris(t-butylphenyl)sulfonium These include, but are not limited to, 2,4,6-triisopropylbenzenesulfonate, tris(t-butylphenyl)sulfonium benzenesulfonate, and phenylthiophenyldiphenylsulfonium perfluorooctanesulfonate.

[0093] Examples of iodonium salts suitable for use in the present invention include, but are not limited to, diphenyliodonium perfluorobutanesulfonate, bis-(t-butylphenyl)iodonium perfluorobutanesulfonate, bis-(t-butylphenyl)iodonium perfluorooctane sulfonate, diphenyliodonium perfluorooctane sulfonate, bis-(t-butylphenyl)iodonium benzenesulfonate, bis-(t-butylphenyl)iodonium 2,4,6-triisopropylbenzenesulfonate, and diphenyliodonium 4-methoxybenzenesulfonate.

[0094] Examples of tris(perfluoroalkylsulfonyl)methide PAGs and tris(perfluoroalkylsulfonyl)imide PAGs suitable for use in the present invention are described in U.S. Patent Nos. 5,554,664 and 6,306,555, each of which is incorporated herein in its entirety. Further examples of PAGs of this type can be found in Proceedings of SPIE, Vol. 4690, pp. 817-828 (2002). Suitable methide and imide PAGs include, but are not limited to, triphenylsulfonium tris(trifluoromethylsulfonyl)methide, methylphenyldiphenylsulfonium tris(perfluoroethylsulfonyl)methide, triphenylsulfonium tris(perfluorobutylsulfonyl)methide, triphenylsulfonium bis(trifluoromethylsulfonyl)imide, triphenylsulfonium bis(perfluoroethylsulfonyl)imide, and triphenylsulfonium bis(perfluorobutylsulfonyl)imide.

[0095] Further examples of photoacid generators suitable for use in the present invention include bis(p-toluenesulfonyl)diazomethane, methylsulfonyl p-toluenesulfonyldiazomethane, 1-cyclohexylsulfonyl-1-(1,1-dimethylethylsulfonyl)diazomethane, bis(1,1-dimethylethylsulfonyl)diazomethane, bis(1-methylethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, 1-p-toluenesulfonyl-1-cyclohexylcarbonyldiazomethane, 2-methyl-2-(p-toluenesulfonyl)propiophenone, 2-methanesulfonyl-2-methyl-4-methylthiopropiophenone, 2,4-methyl-2-(p-toluenesulfonyl)pent-3-one, 1-diazo-1-methylsulfonyl-4-phenyl-2-butanone, 2-methyl-2-(p-toluenesulfonyl)propiophenone, 2-methyl-2-(p-toluenesulfonyl)pent-3-one, 2-methyl-4-phenyl-2-butanone, 2-methyl-2-(p-toluenesulfonyl)propiophen ... -(Cyclohexylcarbonyl)-2-(p-toluenesulfonyl)propane, 1-cyclohexylsulfonyl-1-cyclohexylcarbonyldiazomethane, 1-diazo-1-cyclohexylsulfonyl-3,3-dimethyl-2-butanone, 1-diazo-1-(1,1-dimethylethylsulfonyl)-3,3-dimethyl-2-butanone, 1-acetyl-1-(1-methylethylsulfonyl)diazomethane, 1-diazo-1-(p-toluenesulfonyl)-3,3-dimethyl-2-butanone, 1-diazo-1-benzenesulfonyl-3,3-dimethyl-2-butanone, 1-diazo-1-(p-toluenesulfonyl)-3-methyl-2-butanone, cyclohexyl 2-diazo-2-(p-toluenesulfonyl)acetate, tert-butyl 2-diazo-2-benzenesulfonyl acetate, isopropyl-2-diazo-2-methanesulfonyl acetate, cyclohexyl 2-diazo-2-benzenesulfonyl acetate, tert-butyl 2-diazo-2-(p-toluenesulfonyl)acetate, 2-nitrobenzyl p-toluenesulfonate, 2,6-dinitrobenzyl p-toluenesulfonate, 2,4-dinitrobenzyl p-trifluoromethylbenzenesulfonate.

[0096] More preferred PAGs are triarylsulfonium perfluoroalkylsulfonates and triarylsulfonium tris(perfluoroalkylsulfonyl)methides. Most preferred PAGs are triphenylsulfonium perfluorooctanesulfonate (TPS-PFOS), triphenylsulfonium perfluorobutanesulfonate (TPS-Nonaflate), methyldiphenylsulfonium perfluorooctanesulfonate (TDPS-PFOS), tris(t-butylphenyl)sulfonium perfluorobutanesulfonate (TTBPS-nonaflate), triphenylsulfonium tris(trifluoromethylsulfonyl)methide (TPS-C1), and methylphenyldiphenylsulfonium tris(perfluoroethylsulfonyl)methide.

[0097] The total photoacid generator content of the photosensitive composition is about 0.05 wt% to about 20 wt% based on the total solids content. A preferred range is about 1 wt% to about 15 wt%. The photoacid generator may be used alone or in combination with one or more other photoacid generators. The proportion of each PAG in the photoacid generator mixture is about 10 wt% to about 90 wt% of the total photoacid generator mixture. A preferred photoacid generator mixture contains about two or three photoacid generators. Such mixtures may be from the same or different classes. Examples of preferred mixtures include a sulfonium salt and a bissulfonyldiazomethane compound, a sulfonium salt and an imidosulfonate, and two sulfonium salts.

[0098] A basic additive may also be added to the photosensitive composition as a quencher, acting as a diffusion control agent. One purpose of the basic additive is to remove protons present in the photosensitive composition before it is irradiated with actinic radiation. The base prevents attack and cleavage of acid-labile groups by undesired acids, thereby improving the performance and stability of the photosensitive composition. Furthermore, the base acts as a diffusion control agent, preventing excessive migration of photogenerated acid after exposure, which would result in reduced resolution. The proportion of base in the photosensitive composition should be significantly lower than that of the photoacid generator, or the photosensitivity will be too low. When a base compound is present, the preferred range is about 3 wt % to about 50 wt % of the photoacid generator compound. Suitable examples of the basic additive include cyclopropylamine, cyclobutylamine, cyclopentylamine, dicyclopentylamine, dicyclopentylmethylamine, dicyclopentylethylamine, cyclohexylamine, dimethylcyclohexylamine, dicyclohexylamine, dicyclohexylmethylamine, dicyclohexylethylamine, dicyclohexylbutylamine, cyclohexyl-t-butylamine, cycloheptylamine, cyclooctylamine, 1-adamantanamine, 1-dimethylaminoadamantane, 1-diethylaminoadamantane, 2-Adamantanamine, 2-dimethylaminoadamantane, 2-aminonorbornene, and 3-noradamantanamine, 2-methylimidazole, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, triisopropylamine, triosylamine, tridodecylamine, 4-dimethylaminopyridine, 4,4'-diaminodiphenyl ether, 2,4,5-triphenylimidazole, 1,4-diazabicyclo[4.3.0]non-5-ene, 1,5-diazabicyclo[4.3.0]non-5-ene, 1,8-diazabicyclo[5.4.0]undec-7-ene, guanidine, 1,1-dimethylguanidine, 1,1,3,3-tetramethylguanidine, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-dimethylaminopyridine, 4-dimethylaminopyridine, 2-diethylaminopyridine, 2-(aminomethyl)pyridine, 2-amino-3-methylpyridine, 2-amino-4-methylpyridine, 2-amino-5-methylpyridine, 2-amino-6-methylpyridine, 3-aminoethylpyridine, 4-aminoethylpyridine, 3-aminopyrrolidine, piperazine, N-(2-aminoethyl)piperazine, N-(2-aminoethyl)piperidine, These include, but are not limited to, 4-amino-2,2,6,6-tetramethylpiperidine, 4-piperidinopiperidine, 2-iminopiperidine, 1-(2-aminoethyl)pyrrolidine, pyrazole, 3-amino-5-methylpyrazole, 5-amino-3-methyl-1-p-tolylpyrazole, pyrazine, 2-(aminomethyl)-5-methylpyrazine, pyrimidine, 2,4-diaminopyrimidine, 4,6-dihydroxypyrimidine, 2-pyrazoline, 3-pyrazoline, N-aminomorpholine, N-(2-aminoethyl)morpholine, trimethylimidazole, triphenylimidazole, and methyldiphenylimidazole. More preferred basic additives are tridodecylamine, 2,4,5-triphenylimidazole, 1,5-diazobicyclo[4.3.0]non-5-ene, and 1,8-diazobicyclo[5.4.0]undec-7-ene.

[0099] Bio-based solvent production The biobased solvent can be derived from biobased materials including sugars, starches, corn, natural fibers, sugarcane, beets, citrus fruits, woody plants, celluloses, lignocelluloses, hemicelluloses, potatoes, vegetable oils, other polysaccharides (e.g., pectin, chitin, levan, and pullulan), and combinations thereof. According to certain embodiments, the at least one biobased material is selected from corn, sugarcane, beets, potatoes, starches, citrus fruits, woody plants, cellulosic lignin, vegetable oils, natural fibers, oily wood materials, and combinations thereof.

[0100] The use of biobased feedstocks to produce homogeneous chemicals involves a dramatically different process than fossil fuel feedstocks. Crude petroleum feedstocks have low functionality, making them suitable for direct use as solvents or fuels after prior processing (e.g., cracking or isomerization). Functional groups such as C=O and OH are added to crude petroleum-derived feedstocks to produce bulk and specialty chemicals. In this case, special care is taken to selectively add the functional groups without over-functionalizing the substrate. In contrast, biomass-derived feedstocks, such as cellulose and hemicellulose, have too many functional groups for direct use as fuels or bulk chemicals, necessitating selective isolation and defunctionalization strategies.

[0101] There are three main technologies for carbohydrate and cellulose conversion: biological conversion (enzymatic fermentation), catalytic conversion (dehydration, rehydrogenation, hydrogenation, hydrolysis, aldo condensation, hydrogenolysis, oxidation, etc.), and thermochemical and thermocatalytic conversion. While the production of first-generation biofuels (bioethanol and biobutanol) is well established, this process relies on starch and sugar feedstocks, which compete with the food chain. Hydrolysis of cellulosic feedstocks to fermentable sugars has been achieved as an alternative route to bioalcohol as fuel, avoiding food sources as feedstock. However, slow reaction rates, the high cost and sensitivity of enzymes, and energy-intensive subsequent distillation and drying steps remain challenges for achieving cost-effectiveness in these processes. Thermocatalytic conversion offers an alternative to enzymatic fermentation for converting biomass (such as wood, sugarcane bagasse, or corn stover) to aromatic compounds. For example, a process has been developed that uses zeolite-based catalysts to generate gas and then convert it to benzene, xylene, and toluene (bio-BTX). Thermochemical processes such as gasification, pyrolysis, torrefaction, and liquefaction require high-temperature heating, raising energy efficiency concerns. Furthermore, the selectivity of bio-oil produced from pyrolysis is extremely low, inevitably necessitating additional, expensive upgrading and separation steps. Finally, catalytic conversion of cellulosic biomass and cellulose-derived intermediates into fuels, fuel additives, and chemicals may be employed. Several types of catalysts, such as precious metal catalyst systems used in various key reaction steps such as hydrolysis, dehydration, hydrodeoxygenation (HDO), hydrogenation, and oxidation, have shown promise in this area, resulting in value-added products from cellulosic biomass. Examples of catalyst-derived compounds include 5-hydroxymethylfurfural, furfural, and acetic acid. However, high catalyst costs and catalyst poisoning remain challenges for these processes.

[0102] Recent advances in gene editing have the potential to open up the field of bio-based solvent production. CRISPR (clustered regularly interspaced short palindromic repeats) and CRISPR-associated (Cas) systems, which are RNA-guided immune systems in bacteria and archaea, have been introduced as highly efficient genome editing tools into a wide range of organisms, including bacteria, yeast, plants, mammalian cells, and human cells. In addition to single-gene knock-in or knock-out, successful multiplex genome editing and transcriptional regulation, including repression and activation, have also been reported.

[0103] Clostridia is a species of bacteria that has been studied for many years for biobutanol production via the acetone-butanol-ethanol (ABE) fermentation pathway. Significant efforts have been made to metabolically engineer solvent-producing Clostridia strains to enhance biobutanol production, but success has been limited. This is due to the inherent byproducts of ABE fermentation, such as fatty acids, acetone, and ethanol, which are difficult to remove, and the fact that ABE fermentation for butanol production is a biphasic process and subject to complex metabolic regulation. Recent efforts have focused on modifying the ABE fermentation pathway in Clostridia to increase the overall butanol yield while reducing unwanted byproducts. One method used to achieve such modifications is the use of the CRISPR-Cas9 system.

[0104] In one process, as described in U.S. Patent No. 11,142,751 B2 and incorporated herein by reference, the endogenous CRISPR-Cas system of C. tyrobutyricum was successfully used to enhance butanol production in C. tyrobutyricum. By introducing the adhE2 gene and inactivating the native cat1 gene, the resulting mutant produced 26.2 g / L of butanol in batch fermentation, the highest production ever.

[0105] Furthermore, biobased butyl acetate production has been demonstrated using microbial fermentation of glucose by the butanol-producing bacterium Clostridium acetobutylicum NJ4 supplemented with exogenous acetic acid, microbial fermentation by the acetogenic bacterium Actinobacillus succinogenes130z(ΔpflA) supplemented with exogenous butanol, and a microbial co-culture system of C. acetobutylicum NJ4 and A. succinogenes130z(ΔpflA) with exogenous precursor removal (14 Biotechnol. Biofuels 203(2021)).

[0106] Alternatively, biobased butyl acetate has been produced by utilizing a solventogenic Clostridia pathway that co-produces acyl-CoA, acid, and alcohol precursors, combined with systematic metabolic engineering, resulting in a strain capable of producing 20.3 g / L of butyl acetate (12 Nat. Commun. 4368 (2021)). Biobased acetate esters, such as n-butyl acetate, can also be prepared from the corresponding biobased alcohol, n-butanol, by direct Fischer esterification and transesterification using biobased acetic acid or acetate esters.

[0107] These fermentation processes produce a mixture of the desired butyl acetate along with significant levels of intermediates and impurities. For example, 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," published March 16, 2021, Yi Wang discloses the following composition in butyl acetate production: [Table 1]

[0108] A two-stage biobased process described in U.S. Patent Publication No. 2014 / 0329275 can convert glucose to methyl isobutyl ketone (MIBK), diisobutyl ketone (DIBK), or methyl isoamyl ketone (MIAK). The process utilizes modified microorganisms that convert glucose to isovaleric acid and isocaproic acid. 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).

[0109] U.S. Patent No. 8,298,798 describes metabolically modified microorganisms useful for producing biofuels, including higher alcohols, including C5-C8 alcohols, from biobased feedstocks such as glucose. This method can produce C5 alcohols such as 2-methyl-1-butanol, 3-methyl-1-butanol, and 1-pentanol, C6 alcohols such as 3-methyl-1-pentanol and 1-hexanol, C7 alcohols such as 2-isopropyl-1-butanol, and C8 alcohols such as 5-methyl-1-heptanol.

[0110] Biobased alcohols such as hexanol can be produced by fermentation of syngas using Clostridium carboxidivorans P7 according to the method described in 10 Front.Bioeng.Biotechnol., art.850370 (2022). Biobased heptanol can be prepared by catalytic hydrogenolysis-hydrogenation of castor oil fatty acid methyl esters as described in 1 ChemistrySelect 6396 (2016).

[0111] Process steps and additional synthetic methods not specifically described herein may be found in further references such as Oklu, et al., Bio-Solvents: Synthesis, Industrial Production and Applications (Solvents, Ionic Liquids and Solvent Effects, IntechOpen, London (2019)), which provides an overview of the synthesis and industrial production of biosolvents.

[0112] Bio-based solvent purification As mentioned above, solvents used in semiconductor manufacturing processes typically must be highly to ultra-pure. Because metals can disrupt the functionality of semiconductor devices, it is crucial that the semiconductor wafer surface is not contaminated by any metallic impurities present in the solvent. In fact, more than 50% of yield losses in IC manufacturing are due to microcontamination. Therefore, it is a given that the metallic impurity content of materials used in these processes must be minimized. Solvents must be purified to extremely low metal content levels, ranging from a few parts per billion (ppb) to a few parts per trillion (ppt) for each metal, such as sodium or iron.

[0113] Organic compounds or impurities can also cause contamination problems in semiconductor manufacturing processes. In addition to minimizing the amount of impurities in solvents, it is also necessary to reduce or eliminate organic impurities. Relatively low-molecular-weight organic compounds, in particular, pose significant challenges to semiconductor processing because they are difficult to remove using filtration techniques and can cause particle contamination, especially in fine patterns (e.g., 30 nm node and below). These organic impurities can be introduced through impurities, unpurified solvents, or containers or tubing used in transportation or semiconductor formation steps. Therefore, considerable consideration must be given to solvent purification methods, solvent storage methods, and materials that come into contact with the solvent to avoid deterioration of quality due to impurity accumulation, component denaturation, quantitative changes in composition, increase in impurity metal elements, or degradation of photosensitive components by light during storage or transportation.

[0114] In addition to metals and low-molecular-weight organics, general particulate contamination, including nano- to micro-scale particles from a variety of other sources, also leads to yield-detrimental device defects. Therefore, as discussed above, it is important to remove particulates from bio-based solvents. Ideally, the particle count on semiconductor surfaces should be zero, but due to the large number of sources, this is nearly impossible. Processes for monitoring and detecting particulate contamination are described in ISO 14644-1:2015 and ISO 21501-4, which are incorporated herein by reference.

[0115] Although not limited to the description herein, purification of bio-based solvents typically involves one or more of distillation, physical or chemical filtration, or ion exchange membranes, ultimately using processes or steps in such a way as to obtain the required purity and levels of metals and low molecular weight organics as disclosed herein.

[0116] A distillation process may be employed to purify bio-based solvents. Depending on the composition of the primary product from the process employed, multiphase distillation may be employed, including a first distillation unit for removing low-boiling impurities, a second distillation unit for removing high-boiling impurities, and a third distillation unit for removing trace amounts of water. The distillation unit may be selected from a multi-stage, packed, or spiral rotating-zone distillation column. Rotating-zone distillation columns are particularly useful for separating compounds and removing trace amounts of water to produce solvents of electronics grade purity. A metal or Teflon spiral stirring column is installed inside the rotating-zone distillation column. The high-speed rotation of this column maximizes the contact area between the vaporized vapor component and the condensed liquid component, resulting in rapid and effective vapor-liquid equilibration, resulting in high separation and purification efficiency. The rotation speed of the spiral stirring column of the rotating-zone distillation column can be adjusted appropriately. The resulting high separation and purification efficiency allows for the removal of trace amounts of water and for the easy separation and purification of individual components with similar boiling points to electronic grade.

[0117] Optionally, a metal removal step may be employed, typically involving contacting the bio-based solvent with an acidic cation exchange resin. Various metals, including alkali metals, alkaline earth metals, and transition metals such as sodium, potassium, calcium, iron, and nickel, can be removed by the metal removal step. Commercially available strong acidic cation exchange resins can be used in the present invention. Among these, sulfonated styrene-divinylbenzene crosslinked polymer cation exchange resins are preferred. There are two types of strong acidic cation exchange resins: porous types containing porous resins and gel types containing non-porous resins. Suitable acidic exchange resins are available from Rohm and Haas Company, such as AMBERLYST 15 acidic ion exchange resin. These AMBERLYST resins typically contain 80,000 to 200,000 ppb of sodium and iron. Prior to use in the process of the present invention, the ion exchange resin must be treated with water followed by a mineral acid solution to reduce the metal ion levels. It is important to rinse the ion exchange resin with a solvent that is the same as, or at least compatible with, the solvent to be purified. The procedure for this step may be similar to that disclosed in U.S. Patent Nos. 5,284,930 and 5,288,850. Generally, the cation exchange procedure is carried out at any temperature, pressure, and flow rate that achieves the desired end result. Liquid purifiers such as PURASOL and PROTEGO may be employed to remove metal impurities.

[0118] Microfilters may be used before and after the ion exchange resin treatment to filter out insoluble impurities in the solvent or particulates that may be released from the ion exchange resin. Typically, a filter device with a filter medium with a pore size of 0.05 μm or less is used, and the solvent is circulated through the filter medium, passing it through the filter medium two or more times. Various membrane- and media-based liquid filters may be used, such as Entegris' MICROGARD series filters. In some embodiments, the microfilter contains polytetrafluoroethylene filter material. This method can efficiently remove highly polar insoluble foreign matter, particles, and metal impurities from the solvent. Specifically, depending on the purification method, the number of particles with a diameter of 0.15 μm or larger in the solvent can be reduced to, for example, 20 particles / mL or less, 10 particles / mL or less, or even 5 particles / mL or less. The particle count is measured using liquid particle counting techniques, similar to measurements on wafers. For example, a predetermined amount of solvent is applied to a substrate, shaken off at a predetermined rotation speed, and then the amount of wet particles is dried at a predetermined rotation speed, and the number of defects on the substrate is measured, for example, using a KLA Surfscan SP7 unpatterned wafer inspection system.

[0119] In addition to the above-described methods for purifying a solvent, a further step may include storing or handling the solvent in a material containing a perfluororesin, where the perfluororesin may be, for example, polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), ethylene-tetrafluoroethylene copolymer (ETFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene copolymer (PCTFE), or polyvinyl fluoride (PVF). Such materials may reduce the amount of low-molecular-weight organic matter, metal impurities, and other particles in the solvent.

[0120] Furthermore, according to the purification method of the present invention, the metal element concentrations of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn are preferably 5 ppb or less, more preferably 3 ppb or less. Most preferably, none of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, or Zn is present. However, if even one of these metal elements is present, the lower limit of the concentration of that metal element is generally 0.001 ppb or more. The metal element concentrations of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn may be measured using an inductively coupled plasma mass spectrometer (e.g., an inductively coupled plasma mass spectrometer, Agilent 7500cs (ICP-MS) manufactured by Agilent Technologies, Inc.).

[0121] Pattern Formation Method Lithography pattern formation systems utilize the phenomenon in which the solubility of a resist film in a developer changes due to a chemical reaction caused by light exposure. Resists in which the exposed areas dissolve in the developer are called positive systems, while resists in which the unexposed areas dissolve in the developer are called negative systems. Positive resists use chemical reactions such as polarity conversion to increase solubility in the developer, while negative resists use intermolecular bond formation such as crosslinking or polymerization reactions.

[0122] Since the emergence of resists for KrF excimer lasers (wavelength 248 nm), an imaging method called chemical amplification has been used to compensate for the loss of sensitivity due to light absorption. Positive chemical amplification is an imaging method in which an acid generator in the exposed area decomposes, generating an acid that serves as a reaction catalyst in post-exposure bake (FEB). The resulting catalyst then converts alkali-insoluble groups to alkali-soluble groups, and the exposed areas are removed by alkaline development. This process is also known as positive-tone development (PTD). Specifically, a positive resist composition is a resin composition that, upon exposure to radiation, initiates a chemical reaction to form a film that increases its solubility in alkaline developers and decreases its solubility in developers containing organic solvents.

[0123] Alternatively, chemically amplified resists originally designed for positive tone development with aqueous developers can instead be developed with negative tone development (NTD), which uses an organic developer that removes the unexposed portions of the resist film while leaving the exposed areas unaffected. The resist contrast in the NTD process is determined by the solubility difference between the relatively non-polar unexposed resist and the more polar resist material produced in the exposed areas of the film. In the present disclosure, bio-based organic developers containing organic solvents can be used as negative tone developers.

[0124] Regarding material-related parameters, controlling various physical values, such as solubility parameters, related to the solubility of a positive resist composition in a developer and an organic solvent is effective for adjusting performance. Specific examples of such parameters in a positive resist composition include the average molecular weight of the polymer species, the molecular weight dispersity, the monomer composition ratio, the polarity of the monomer, the monomer sequence, the polymer blend, and the addition of one or more low-molecular-weight additives and one or more surfactants.

[0125] In the pattern formation method of the present disclosure, the steps of forming a film on a substrate using a resin composition whose solubility in a positive developer increases and whose solubility in a negative developer decreases upon exposure to actinic rays or radiation, exposing the film to light, heating the film (baking, also called PEB (post-exposure bake)), and developing the film may be performed by generally known methods.

[0126] Specific examples of process-related parameters include film formation temperature and time, post-exposure heating temperature and time, development temperature, development time, nozzle type of the development device (paddle type, dynamic spray type, etc.), and post-development rinsing method.

[0127] 1A-E, which illustrate an exemplary process flow of a patterning method according to the present disclosure. While the illustrated process flow describes a patterning process in which a single resist mask is used to transfer a photoresist pattern to an underlying substrate, this method can be used in other lithography processes, such as litho-litho-etch (LLE), litho-etch-litho-etch (LELE), or double patterning processes such as self-aligned double patterning (SADP), ion implantation masks, or any other lithography process in which such photoresist pattern processing would be beneficial.

[0128] FIG. 1A shows a substrate 100 in cross section, which may include various layers and features. The substrate may include materials such as semiconductors (e.g., silicon) or compound semiconductors (e.g., III-V or II-VI), glass, quartz, ceramic, copper, etc. Typically, the substrate is a semiconductor wafer, such as a single crystal silicon or compound semiconductor wafer, and may have one or more layers and patterned features formed on its surface. One or more layers 102 to be patterned may be provided on the substrate 100. Optionally, the underlying base substrate material may itself be patterned, for example, if it is desired to form grooves in the substrate material. When the base substrate itself is patterned, the pattern is considered to be formed in a layer of the substrate.

[0129] The layers may include, for example, one or more conductive layers such as aluminum, copper, molybdenum, tantalum, titanium, tungsten, alloys, nitrides or silicides of these metals, doped amorphous silicon or doped polysilicon layers, one or more dielectric layers such as silicon oxide, silicon nitride, silicon oxynitride, or metal oxide layers, semiconductor layers such as single crystalline silicon, and combinations thereof. The layer to be etched can be formed by a variety of techniques, for example, chemical vapor deposition (CVD), e.g., plasma-enhanced CVD (PECVD), low-pressure CVD (LPCVD) or epitaxial growth, physical vapor deposition (PVD), e.g., sputtering or evaporation, or electroplating. The specific thickness of the one or more layers 102 to be etched will vary depending on the material being formed and the particular device.

[0130] Depending on the particular layer being etched, the film thickness, and the photolithography materials and processes used, it may be desirable to deposit a hard mask layer 103, onto which a photoresist layer 106 is coated, and / or a bottom antireflective coating (BARC) 104, over the layer 102. The use of a hard mask layer may be desirable, for example, for very thin resist layers, when the layer being etched requires a significant etch depth, and / or when the resist selectivity of a particular etchant is low. If a hard mask layer is used, the resulting resist pattern can be transferred to the hard mask layer 103, which can then be used as a mask for etching the underlying layer 102. Suitable hard mask materials and methods of formation are known in the art. Typical materials include, for example, tungsten, titanium, titanium nitride, titanium oxide, zirconium oxide, aluminum oxide, aluminum oxynitride, hafnium oxide, amorphous carbon, spin-on carbon (SOC), silicon oxynitride, and silicon nitride. The hard mask layer may comprise a single layer or multiple layers of different materials. The hard mask layer can be formed, for example, by CVD, PVD, or spin-coating techniques.

[0131] Bottom antireflective coatings may be desirable when the substrate and / or underlying layers reflect a significant amount of incident radiation during photoresist exposure, adversely affecting the quality of the formed pattern. Such coatings can improve depth of focus, exposure latitude, linewidth uniformity, and CD control. Antireflective coatings are typically used when the resist is exposed to deep ultraviolet (sub-300 nm) radiation, such as KrF (248 nm), ArF (193 nm), or EUV (13.5 nm). Antireflective coatings may include a single layer or multiple layers of different materials. Suitable antireflective materials and methods for their formation are known in the art. Antireflective materials are commercially available, for example, those sold under the AR™ trademark by DuPont (Wilmington, Del., USA), such as AR™3, AR™40A, and AR™124 antireflective materials, the DUV-30 series and DUV-40 series manufactured by Brewer Science, Inc., and the ARC series (e.g., ARC29A) manufactured by Nissan Chemical Industries, Ltd. Furthermore, inorganic antireflective films can also be used as antireflective films. For example, antireflective films made of titanium, titanium oxide, titanium nitride, chromium oxide, carbon, amorphous silicon, etc. may be used.

[0132] A photoresist layer 106 formed from a chemically amplified photosensitive composition is disposed on the substrate and, if present, on the antireflective layer. The chemically amplified photosensitive composition typically comprises: (a) a matrix polymer having acid-labile groups that, upon exposure to acid, become more soluble in alkaline developers and less soluble in organic solvents; (b) a compound capable of generating an acid upon exposure to actinic or radiation, commonly referred to as a photoacid generator; (c) a solvent that can be used to dissolve the components of the photoresist composition; and (d) optionally, other additives, including at least one of a resin having at least one of fluorine atoms or silicon atoms, a basic compound, a surfactant, an onium carboxylate, a dye, a plasticizer, a photosensitizer, a light absorber, an alkali-soluble resin, a dissolution inhibitor, and a compound for promoting dissolution in the developer.

[0133] The photoresist layer is disposed on the substrate, over the antireflective layer 104 (if present). The photoresist composition can be applied to the substrate by spin coating, dipping, roller coating, or other conventional coating techniques. Of these, spin coating is typical. For spin coating, the solids content of the coating solution can be adjusted to provide the desired film thickness based on the particular coating equipment used, the viscosity of the solution, the speed of the coating tool, and the time allowed for spinning. A typical thickness of the photoresist layer 106 is about 500-3000 Å.

[0134] The photoresist layer 106 is typically then low-temperature baked to minimize the solvent content in the layer, thereby forming a tack-free coating and improving adhesion of the layer to the substrate. The low-temperature bake can be performed on a hot plate or in an oven, with a hot plate being typical. The temperature and time of the low-temperature bake depend, for example, on the particular material and thickness of the photoresist. A typical low-temperature bake is performed at a temperature of about 90-150°C for a time of about 30-90 seconds.

[0135] The photoresist layer 106 is then exposed to activating radiation 108 through a photomask 110, creating a difference in solubility between the exposed and unexposed regions. Herein, irradiating a photoresist composition with activating radiation refers to the radiation forming a latent image in the photoresist composition. The photomask has optically transparent and optically opaque regions corresponding to the regions of the resist layer exposed and unexposed to activating radiation, respectively. The exposure apparatus used in this disclosure is not limited by the wavelength of the light source, but may utilize, for example, a KrF excimer laser wavelength (248 nm), an ArF excimer laser wavelength (193 nm), an F2 excimer laser wavelength (157 nm), and EUV light (13.5 nm). The exposure step of this disclosure can employ an immersion lithography method. Immersion lithography is a technique for improving resolution. According to this technique, exposure is performed by filling a high-refractive-index liquid (hereinafter sometimes referred to as "immersion liquid") between the projection lens and the sample. The exposure energy varies depending on the components of the exposure tool and the photosensitive composition, but is usually about 10 to 80 mJ / cm 2 is.

[0136] After the photoresist layer 106 is exposed, it is typically subjected to a post-exposure bake (PEB). PEB can be performed, for example, on a hot plate or in an oven. The PEB conditions depend, for example, on the specific photoresist composition and layer thickness. PEB is typically performed at a temperature of about 80-150°C for a time of about 30-90 seconds. This results in the formation of a latent image defined by the boundaries between polarity-switched and non-switched regions (corresponding to exposed and unexposed regions, respectively).

[0137] The photoresist layer 106 is then developed using a bio-based developer, removing the unexposed areas of the layer and leaving the exposed areas to form a resist pattern 106' with a plurality of features, as shown in FIG. 1B. The features are not limited and may include, for example, a plurality of lines, pillars, and / or contact hole patterns that allow for the formation of such patterns in the underlying layer. Negative-tone development methods may include, for example, immersion of the substrate in a bath filled with developer for a certain period of time (dipping method), puddling of the developer by surface tension to the surface of the substrate and allowing it to stand for a certain period of time for development, spraying of the developer onto the substrate surface (spraying method), and dynamic dispensing of the developer onto a substrate rotating at a constant speed while scanning a developer discharge nozzle at a constant speed.

[0138] After the negative development step using a bio-based developer, a step of replacing the developer with another solvent to stop development may be performed. After the negative development step, a step of washing the resist film with a rinse solution containing a bio-based organic solvent is preferably performed. The washing method is not particularly limited, but may be, for example, a method of continuously discharging a rinse solution onto a substrate rotating at a constant speed (rotary coating method), a method of immersing a substrate in a bath filled with a rinse solution for a certain period of time (immersion method), or a method of spraying a rinse solution onto the substrate surface (spray method).

[0139] After the development process or the rinse process, a process may be performed using a supercritical fluid to remove the bio-based developer or bio-based rinse solution adhering to the pattern. Furthermore, after the development process, the rinse process, or the treatment with the supercritical fluid, a heat treatment may be performed to remove the solvent remaining in the pattern. The heating temperature is not particularly limited as long as a good resist pattern can be obtained. In some embodiments, the heating temperature is about 40 to 160°C. The heat treatment may be performed multiple times.

[0140] Using the resist pattern 106 as an etch mask, the BARC layer 104 is selectively etched to form a BARC pattern 104′, exposing the underlying hard mask layer 103, as shown in FIG. 1C. The hard mask layer is then selectively etched, again using the resist pattern as an etch mask, to yield a patterned BARC layer and hard mask layer 103′, as shown in FIG. 1D. Suitable etching techniques and chemistries for etching the BARC layer and hard mask layer are known in the art and depend, for example, on the particular materials of these layers. A dry etching process, such as reactive ion etching, is typically used. The resist pattern 106 and patterned BARC layer 104′ are then removed from the substrate using known techniques, such as oxygen plasma ashing. One or more layers 102 are then selectively etched using the hard mask pattern 103′ as an etch mask. Suitable etching techniques and chemistries for etching the underlying layer 102 are known in the art. In some embodiments, a dry etching process, such as reactive ion etching, is used to etch the underlying layer 102. The patterned hard mask layer 103' may then be removed from the substrate surface using known techniques, such as, for example, a dry etching process such as reactive ion etching or wet removal. The resulting structure is a pattern of etched features 102', as shown in FIG. 1E. In an alternative exemplary method, it may be desirable to directly pattern layer 102 using a photoresist pattern 106, without using a hard mask layer 103. Whether direct patterning with a resist pattern can be employed depends on factors such as the materials involved, the selectivity of the resist, the thickness of the resist pattern, and the pattern dimensions.

[0141] Example embodiments described herein include the following:

[0142] Embodiment 1: A composition comprising: an organic developer comprising at least 25 wt. % bio-based n-butyl acetate, wherein the bio-based n-butyl acetate contains carbon-14 in an amount sufficient to produce decays of at least 0.1 dpm / gC (degradations per gram of carbon per minute), and wherein the organic developer contains 5 ppb or less of each of the following metal elements: Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn.

[0143] Embodiment 2: The composition of embodiment 1, wherein said organic developer further comprises 1 ppb or less of an alkane or alkene having 22 or fewer carbon atoms, or 3 wt. % or less of bio-based n-butanol.

[0144] Embodiment 3: The composition of embodiment 2, wherein the organic developer comprises the following metal element concentrations: Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn, each at 3 ppb or less; and optionally, 0.5 ppb or less of one or both of an alkane or alkene having 22 or fewer carbon atoms; and 1 wt. % or less of bio-based n-butanol, 0.1 wt. % or less of n-hexadecane, 0.1 wt. % or less of isopropanol, and 0.1 wt. % or less of ethyl acetate.

[0145] Embodiment 4: The composition of any one of embodiments 1-3, wherein the organic developer comprises Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn, each at a metal element concentration of 1 ppb or less, and optionally 0.3 ppb or less of one or both of an alkane or alkene having 22 or fewer carbon atoms, and 1 wt % or less of other bio-based solvents in total.

[0146] Embodiment 5: The composition of any of embodiments 1-4, wherein the organic developer comprises at least 90 wt % bio-based n-butyl acetate.

[0147] Embodiment 6: The composition of any of embodiments 1-4, wherein the organic developer comprises at least 95 wt % bio-based n-butyl acetate.

[0148] Embodiment 7: The composition of any one of embodiments 1 to 6, wherein the organic developer further comprises 0.001 wt % to 5 wt % of a surfactant.

[0149] Embodiment 8: The composition of embodiment 7, wherein the surfactant comprises an ionic or non-ionic fluorine-based or silicon-based surfactant.

[0150] Embodiment 9: The composition of any of embodiments 1 to 8, wherein the organic developer comprises at least 95 wt. % bio-based n-butyl acetate, 0-2 wt. % ionic or non-ionic fluorine-based or silicon-based surfactant, 1 ppb or less of an alkane or alkene having 22 or fewer carbon atoms, Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn, each at an elemental metal concentration of 1 ppb or less, and 1 wt. % or less of other bio-based solvents.

[0151] Embodiment 10: The composition of any one of embodiments 1-9, wherein the organic developer further comprises 0.1 wt % to 10 wt % of a nitrogen-containing compound having the following structure: [ka] (In the formula, R 1 , R 2 and R 3 are independently a hydrogen atom, a hydroxyl group, a formyl group, an alkoxy group, an alkoxycarbonyl group, an optionally substituted C 1-30 Alkyl groups, optionally substituted C 3-30 represents a cycloalkyl group, an aryl group, or a group formed by two or more of these groups; R 1 , R 2 and R 3 two of them may combine to form a ring structure with the nitrogen atom to which they are attached).

[0152] Embodiment 11: The composition of any of embodiments 1-10, wherein the biobased n-butyl acetate comprises carbon-14 in an amount sufficient to produce a decay of at least 3.0 dpm / gC.

[0153] Embodiment 12: The composition of embodiment 11, wherein said biobased n-butyl acetate comprises carbon-14 in an amount sufficient to produce a decay of at least 6.0 dpm / gC.

[0154] Embodiment 13: The composition of embodiment 11, wherein said biobased n-butyl acetate comprises carbon-14 in an amount sufficient to produce a decay of at least 9.0 dpm / gC.

[0155] Embodiment 14: The composition of embodiment 11, wherein said bio-based n-butyl acetate comprises carbon-14 in an amount sufficient to produce a decay of at least 12.0 dpm / gC.

[0156] Embodiment 15: A method of forming a pattern, comprising: providing a semiconductor substrate; forming a resist film comprising coating the semiconductor substrate with a resist composition having solubility in an organic developer, wherein the solubility of the resist composition in an organic developer is reduced by exposure to actinic or electromagnetic radiation; exposing the resist film to actinic or electromagnetic radiation; and developing the resist film with the organic developer, wherein the organic developer comprises at least 25 wt % bio-based n-butyl acetate, the bio-based n-butyl acetate comprising a sufficient amount of carbon-14 to produce a decay of at least 0.1 dpm / gC.

[0157] Embodiment 16: The resist film described above, after exposure to actinic or electromagnetic radiation, has a solubility in an organic developer of the resist composition of m sv / m su When expressed as a ratio, it is 25 or less, where m sv is one unit mass m of the resist composition su 16. The method of embodiment 15, wherein the organic developer solvent is the mass of the organic developer solvent required to dissolve

[0158] Embodiment 17: The method of embodiment 15 or embodiment 16, further comprising forming an integrated circuit on the semiconductor substrate.

[0159] Embodiment 18: The integrated circuit described above has a 3×10 7 Transistors / mm 2 18. The method of embodiment 17, having a transistor density of

[0160] Embodiment 19: The method of any one of embodiments 15 to 18, wherein the organic developer comprises one or more of: an alkane or alkene having 22 or fewer carbon atoms at 1 ppb or less; Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn, each at a metal element concentration of 5 ppb or less; and 3 wt % or less bio-based n-butanol.

[0161] Embodiment 20: The method of any one of embodiments 15 to 19, wherein the organic developer comprises one or more of the following: an alkane or alkene having 22 or fewer carbon atoms at 0.5 ppb or less; Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn, each at a metal element concentration of 3 ppb or less; and 1 wt. % or less bio-based n-butanol, 0.1 wt. % or less n-hexadecane, 0.1 wt. % or less isopropanol, and 0.1 wt. % or less ethyl acetate.

[0162] Embodiment 21: The method of any one of embodiments 15 to 21, wherein the organic developer comprises one or more of the following: an alkane or alkene having 22 or fewer carbon atoms at 0.3 ppb or less; metal element concentrations of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn, each at 2 ppb or less; and other bio-based solvents totaling 1 wt % or less.

[0163] Embodiment 22: The method of any one of embodiments 15-21, wherein the organic developer comprises at least 90 wt % bio-based n-butyl acetate.

[0164] Embodiment 23: The method of any one of embodiments 15-22, wherein the organic developer comprises at least 95 wt % bio-based n-butyl acetate.

[0165] Embodiment 24: The method of any one of embodiments 15 to 23, wherein the organic developer further comprises 0.001 wt % to 5 wt % of a surfactant.

[0166] Embodiment 25: The method of embodiment 24, wherein the surfactant comprises an ionic or non-ionic fluorine-based or silicon-based surfactant.

[0167] Embodiment 26: The method of any one of embodiments 15-25, wherein the organic developer further comprises 0.1 wt % to 10 wt % of a nitrogen-containing compound having the following structure: [ka] (In the formula, R 1 , R 2 and R 3 are independently a hydrogen atom, a hydroxyl group, a formyl group, an alkoxy group, an alkoxycarbonyl group, an optionally substituted C 1-30 Alkyl groups, optionally substituted C 3-30 represents a cycloalkyl group, an aryl group, or a group formed by two or more of these groups; R 1 , R 2 and R 3 two of them may combine to form a ring structure with the nitrogen atom to which they are attached).

[0168] Embodiment 27: The method of any one of embodiments 15-26, wherein the biobased n-butyl acetate comprises carbon-14 in an amount sufficient to produce a decay of at least 3.0 dpm / gC.

[0169] Embodiment 28: The method of embodiment 27, wherein said biobased n-butyl acetate comprises carbon-14 in an amount sufficient to produce a decay of at least 6.0 dpm / gC.

[0170] Embodiment 29: The method of embodiment 27, wherein said biobased n-butyl acetate comprises carbon-14 in an amount sufficient to produce a decay of at least 9.0 dpm / gC.

[0171] Embodiment 30: The method of embodiment 27, wherein said biobased n-butyl acetate comprises carbon-14 in an amount sufficient to produce a decay of at least 12.0 dpm / gC.

[0172] Embodiment 31: The method of any one of embodiments 15 to 30, further comprising, after said developing step, rinsing said semiconductor substrate with a rinsing solution.

[0173] Embodiment 32: The method of embodiment 31, wherein the rinse solution comprises at least one bio-based organic solvent containing carbon-14 (C-14) in an amount sufficient to produce an attenuation of at least 0.1 dpm / gC, and the following metal element concentrations of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn each at 5 ppb or less.

[0174] Embodiment 33: The method of embodiment 31 or embodiment 32, wherein the at least one bio-based organic solvent is selected from the group consisting of one or more of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, and combinations thereof.

[0175] Embodiment 34: The method of any one of embodiments 31 to 33, wherein the at least one bio-based organic solvent is selected from the group consisting of 1-hexanol, methyl isobutylcarbinol, 2-hexanol, 1-heptanol, 2-heptanol, and combinations thereof.

[0176] Embodiment 35: The method of any one of embodiments 31 to 34, wherein the at least one bio-based organic solvent comprises carbon-14 in an amount sufficient to produce a decay of at least 3.0 dpm / gC.

[0177] Embodiment 36: The method of embodiment 35, wherein said at least one bio-based organic solvent comprises carbon-14 in an amount sufficient to produce a decay of at least 6.0 dpm / gC.

[0178] Embodiment 37: The method of embodiment 35, wherein said at least one bio-based organic solvent comprises carbon-14 in an amount sufficient to produce a decay of at least 9.0 dpm / gC.

[0179] Embodiment 38: The method of embodiment 35, wherein said at least one bio-based organic solvent comprises carbon-14 in an amount sufficient to produce a decay of at least 12.0 dpm / gC.

[0180] Embodiment 39: A rinse composition comprising at least 25 wt. % of at least one bio-based organic rinse solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, and combinations thereof, wherein the bio-based organic rinse solvent contains carbon-14 in an amount sufficient to produce a decay of at least 0.1 dpm / gC (decays per gram of carbon per minute), and wherein the rinse composition contains Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn each having an elemental concentration of 5 ppb or less.

[0181] Embodiment 40: The rinse composition of embodiment 39, wherein the rinse composition further comprises 1 ppb or less of an alkane or alkene having 22 or fewer carbon atoms, or 3 wt. % or less of bio-based methyl isobutyl ketone.

[0182] Embodiment 41: A rinse composition according to embodiment 39 or embodiment 40, comprising metal element concentrations of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn each of 3 ppb or less, and optionally 0.5 ppb or less of one or both of an alkane or alkene having 22 or fewer carbon atoms, and 1 wt. % or less of bio-based methyl isobutyl ketone, 0.1 wt. % or less of n-hexadecane, 0.1 wt. % or less of diisobutyl ketone, and 0.1 wt. % or less of methyl isoamyl ketone.

[0183] Embodiment 42: A rinse composition according to any one of embodiments 39 to 41, wherein the rinse composition comprises metal element concentrations of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn, each of which is 2 ppb or less, and optionally 0.3 ppb or less of one or both of an alkane or alkene having 22 or fewer carbon atoms, and 1 wt % or less of other bio-based solvents in total.

[0184] Embodiment 43: The rinse composition of any one of embodiments 39 to 42, wherein the at least one bio-based organic solvent is selected from the group consisting of one or more of 1-hexanol, methyl isobutyl carbinol, 2-hexanol, 1-heptanol, 2-heptanol, methyl isoamyl carbinol, diisobutyl carbinol, and combinations thereof.

[0185] Embodiment 44: The rinse composition of any one of embodiments 39 to 43, wherein the at least one bio-based organic solvent is at least 90 wt. % of one or more of 1-hexanol, methyl isobutyl carbinol, 2-hexanol, 1-heptanol, 2-heptanol, methyl isoamyl carbinol, and diisobutyl carbinol.

[0186] Embodiment 45: The rinse composition of any one of embodiments 39 to 44, wherein the at least one bio-based organic solvent is at least 95 wt% of one or more of 1-hexanol, methyl isobutyl carbinol, 2-hexanol, 1-heptanol, 2-heptanol, methyl isoamyl carbinol, and diisobutyl carbinol.

[0187] Embodiment 46: The composition of any of embodiments 39-45, wherein the at least one bio-based organic solvent comprises carbon-14 in an amount sufficient to produce a decay of at least 3.0 dpm / gC.

[0188] Embodiment 47: The composition of embodiment 46, wherein the at least one bio-based organic solvent comprises carbon-14 in an amount sufficient to produce a decay of at least 6.0 dpm / gC.

[0189] Embodiment 48: The composition of embodiment 46, wherein the at least one bio-based organic solvent comprises carbon-14 in an amount sufficient to produce a decay of at least 9.0 dpm / gC.

[0190] Embodiment 49: The composition of embodiment 46, wherein the at least one bio-based organic solvent comprises carbon-14 in an amount sufficient to produce a decay of at least 12.0 dpm / gC.

[0191] Embodiment 50. A photoresist composition comprising a polymeric binder or a mixture of polymeric binders that is rendered alkali-soluble by the action of an acid that removes acid-sensitive protecting groups on the polymeric binder; at least one photoacid generator (PAG) that, upon exposure to a high energy source, decomposes to generate a photoacid strong enough to remove acid-sensitive protecting groups on the polymeric binder; at least one bio-based organic solvent; and, optionally, at least one base as a quencher, wherein the bio-based organic solvent comprises at least 25 wt. % bio-based n-butyl acetate, wherein the bio-based n-butyl acetate contains carbon-14 in an amount sufficient to produce a decay of at least 0.1 dpm / gC, and wherein the organic solvent contains Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn each at a metal elemental concentration of 5 ppb or less.

[0192] Embodiment 51: The composition of embodiment 50, wherein the bio-based organic solvent further comprises 1 ppm or less of an alkane or alkene having 22 or fewer carbon atoms, or 3 wt. % or less of bio-based n-butanol.

[0193] Embodiment 52: The composition of embodiment 50 or embodiment 51, wherein the bio-based organic solvent comprises the following metal element concentrations: Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn, each at 3 ppm or less; and optionally, 0.5 ppm or less of one or both of an alkane or alkene having 22 or fewer carbon atoms; and 1 wt. % or less of bio-based n-butanol, 0.1 wt. % or less of n-hexadecane, 0.1 wt. % or less of isopropanol, and 0.1 wt. % or less of ethyl acetate.

[0194] Embodiment 53: The composition of any of embodiments 50-53, wherein the bio-based organic solvent comprises Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn, each at a metal element concentration of 2 ppm or less, and optionally 0.3 ppm or less of one or both of an alkane or alkene having 22 or fewer carbon atoms, and 1 wt. % or less of other bio-based solvents in total.

[0195] Embodiment 54: The composition of any of embodiments 50-54, wherein the bio-based organic solvent comprises at least 90 wt% bio-based n-butyl acetate.

[0196] Embodiment 55: The composition of any of embodiments 50-55, wherein the bio-based organic solvent comprises at least 95 wt% bio-based n-butyl acetate.

[0197] Embodiment 56: The composition of any one of embodiments 50 to 56, wherein the bio-based organic solvent further comprises 0.001 wt % to 5 wt % of a surfactant.

[0198] Embodiment 57: The composition of embodiment 56, wherein the surfactant comprises an ionic or non-ionic fluorine-based or silicon-based surfactant.

[0199] Embodiment 58: The composition of any of embodiments 50-57, wherein the bio-based organic solvent comprises at least 95 wt% bio-based n-butyl acetate, 0.3 ppm or less of an alkane or alkene having 22 or fewer carbon atoms, 2 ppm or less of each of the following metal elements: Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn, and 1 wt% or less in total of other bio-based solvents. [Example]

[0200] Example 1. Preparation of a bio-based developer, n-butyl acetate (NBA) Biobased NBA is produced in a bioreactor using glucose or glycerol fermentation, as described in 12 Nat. Commun. 4368 (2021). Fermentation is performed in a serum bottle in a two-phase system, and the extractant n-hexadecane is added to the fermentation at a ratio of 1:1 (volume of extractant to volume of fermentation broth) for in situ ester extraction. The organic layer containing NBA and n-hexadecane is removed and distilled to isolate purified NBA. Metals are removed by treatment with ion exchange beads and / or passage through a purifier, and particulates are removed by passing the solvent through a PTFE filter with a pore size of 0.05 μm. Further purification steps are performed to reduce the content of low molecular weight organic compounds and metal concentrations. The final bio-based NBA negative tone developer contains 1 ppb or less of alkanes or alkenes having 22 or fewer carbon atoms as measured by gas chromatography mass spectrometry (e.g., Shimadzu Corporation's GCMS-QP2010 (gas chromatography mass spectrometer)) connected to a pyrolysis apparatus (e.g., Frontier Lab's PY2020D), metal element concentrations of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn each at 5 ppb or less as measured by inductively coupled plasma mass spectrometry (e.g., Agilent Technologies, Inc.'s inductively coupled plasma mass spectrometer Agilent 7500cs (ICP-MS apparatus)), and 3 wt % or less of bio-based n-butanol as measured by liquid scintillation counting (LSC).

[0201] Example 2. Preparation of a bio-based developer, n-butyl acetate (NBA) Biobased NBA is produced in a bioreactor using fermentation with a FadM homologue from Providencia sneebia as described in 61 Metabolic Engineering 335-343 (2020). The product is purified as described in Example 1 above. The final product is isolated and analyzed. Analysis shows that the biobased NBA developer contains 0.5 ppb or less of alkanes or alkenes with 22 carbon atoms or less, 1 ppb or less of each of the following metal elements: Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn, and 0.1 wt% or less of biobased n-butanol, 0.1 wt% or less of n-hexadecane, 0.1 wt% or less of isopropanol, and 0.1 wt% or less of ethyl acetate.

[0202] Example 3. Production of bio-based methyl isobutyl carbinol A two-stage biobased process described in U.S. Patent Publication No. 2014 / 0329275 converts glucose to methyl isobutyl ketone (MIBK). The process utilizes modified microorganisms that convert glucose to isovaleric acid and isocaproic acid, which are then converted to the corresponding ketones. The ketones are then reduced to the corresponding alcohol, methyl isobutyl carbinol (MIBC). The resulting MIBC is processed to the desired purity by distillation, metal removal using an ion exchanger or purifier to achieve elemental concentrations of 3 ppb or less each of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn, and particulate removal by PTFE filtration (e.g., 20 particles / mL or less as measured by a KLA Surfscan® SP7 unpatterned wafer inspection system).

[0203] Example 4. Production of biobased hexanol Biobased hexanol is produced by fermenting syngas using Clostridium carboxidivorans P7 according to the method described in 10 Front.Bioeng.Biotechnol., art. 850370 (2022). The resulting hexanol is processed to the desired purity by distillation, metals are removed using ion exchange or a purifier, and particles are removed by filtration.

[0204] Example 5. Production of bio-based heptanol Biobased 1-heptanol is derived from renewable castor oil supplied by Arkema. The heptanol is processed by distillation to the desired purity (97 wt%), metal removal using an ion exchanger or purifier to achieve elemental concentrations of 1 ppb or less each of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn, and PTFE filtration to remove particles (e.g., 20 particles / mL or less as measured by a KLA Surfscan® SP7 unpatterned wafer inspection system).

[0205] Example 6. Identification of Developer and Rinse Solutions as Biobased The following samples were measured in a blinded manner to determine the presence or absence of C-14 by liquid scintillation counting. The results are shown in Table 2. As shown in Table 2, the samples derived entirely from petroleum (Comparative Samples A and B) had negligible C-14 content as measured by dpm / gC, indicating that approximately 0% of the samples were made from biobased materials. In contrast, samples containing materials known to be derived from biobased materials showed elevated levels of C-14 as measured by dpm / gC. [Table 2]

[0206] Example 7. Photolithography process for NTD pattern creation, development, and rinsing A 200 mm silicon wafer is coated with AR™ 3-600 organic bottom antireflective coating (BARC) material (DuPont) and baked at 205°C for 60 seconds to a thickness of 600 Å using a Tokyo Electron Ltd. (TEL) CLEAN TRACK™ Act8 coating tool. UV™ 217G-0.25 polyhydroxystyrene-based photoresist (DuPont) is coated on top of the BARC layer, and the wafer is low-baked at 130°C for 60 seconds on the coating tool to a target thickness of 3550 Å. The coated wafer is exposed to KrF (248 nm) radiation using a dual reticle with a 140 nm high-density (1:1 line spacing) groove pattern on a Canon FPA-5000 ES4 DUV scanner with NA=0.68 and conventional illumination (σ, 0.75). The wafer was post-exposure baked at 125°C for 60 seconds, developed with bio-based n-butyl acetate for 45 seconds, rinsed with bio-based methyl isobutyl carbinol, and spin-dried using a Tokyo Electron Ltd. (TEL) CLEAN TRACK™ Act 8 coating tool. The resist pattern was then observed under a scanning electron microscope, revealing the expected line-space pattern.

[0207] EPIC™ 3013 ArF photoresist (Rohm and Haas Electronic Materials LLC) was spin-coated onto an organic bottom antireflective coating (BARC AR™ 124 23 nm / AR™ 26N 77 nm (Rohm and Haas Electronic Materials LLC)) on a 12-inch silicon wafer and low-temperature baked at 110°C for 60 seconds to a thickness of 900 Å. OPTICOAT™ OC2000 topcoat material (Rohm and Haas Electronic Materials LLC) was coated onto the resist to form an electroless topcoat layer. The coated wafer was exposed using an ASML ArF 1900i immersion scanner equipped with NA=1.35, dipole 35Y illumination (0.9 / 0.635σ), and x-polarized light, and post-exposure baked (PEB) at 100°C for 60 seconds. The coated wafer is developed for 45 seconds with the bio-based n-butyl acetate of Example 1, rinsed with the bio-based methyl isobutyl carbinol of Example 3, and spin-dried on a Tokyo Electron Ltd. (TEL) CLEAN TRACK™ coating tool.

[0208] Example 8. Photolithography steps for NTD pattern fabrication, development, and rinsing The procedure of Example 7 was repeated with the following modifications: the coated wafer was developed for 45 seconds with the bio-based n-butyl acetate of Example 1, rinsed with the bio-based 1-hexanol of Example 4, and spin-dried on a Tokyo Electron Ltd. (TEL) CLEAN TRACK™ coating tool.

[0209] Example 9. Photolithography steps for NTD pattern fabrication, development, and rinsing The procedure of Example 7 was repeated with the following modifications: the coated wafer was developed for 45 seconds in the bio-based n-butyl acetate of Example 1, rinsed in the bio-based 1-heptanol of Example 4, and spin-dried on a Tokyo Electron Ltd. (TEL) CLEAN TRACK™ coating tool.

Claims

1. a) an organic developer comprising at least 25 wt % bio-based n-butyl acetate, said bio-based n-butyl acetate containing carbon-14 in an amount sufficient to produce decay of at least 0.1 dpm / gC (destructions per gram of carbon per minute); b) the organic developer contains Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn at a concentration of 5 ppb or less; A composition comprising the organic developer.

2. The organic developer is i) 1 ppb or less of alkanes or alkenes having 22 or fewer carbon atoms, or ii) 3 wt% or less of bio-based n-butanol The composition of claim 1 further comprising:

3. the organic developer comprises Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn, each at a metal element concentration of 3 ppb or less, and optionally i) 0.5 ppb or less of alkanes or alkenes having 22 or fewer carbon atoms; and ii) ≤1 wt% bio-based n-butanol, ≤0.1 wt% n-hexadecane, ≤0.1 wt% isopropanol, and ≤0.1 wt% ethyl acetate The composition of claim 1 , comprising one or both of:

4. the organic developer comprises Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn, each at a metal element concentration of 1 ppb or less, and optionally i) 0.3 ppb or less of alkanes or alkenes having 22 or fewer carbon atoms; and ii) ≤1 wt% total of other bio-based solvents The composition of claim 1 , comprising one or both of:

5. The composition of any of claims 1 to 4, wherein the organic developer comprises at least 90 wt% bio-based n-butyl acetate.

6. The composition of any of claims 1 to 4, wherein the organic developer comprises at least 95 wt% bio-based n-butyl acetate.

7. The composition of any one of claims 1 to 4, wherein the organic developer further comprises 0.001 wt% to 5 wt% of a surfactant.

8. The composition of claim 7, wherein the surfactant comprises an ionic or non-ionic fluorine-based or silicon-based surfactant.

9. The organic developer is a) at least 95 wt% biobased n-butyl acetate; b) 0-2 wt % of an ionic or non-ionic fluorine-based or silicone-based surfactant; c) 1 ppb or less of alkanes or alkenes having 22 or fewer carbon atoms; d) Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn, each at a metal element concentration of 1 ppb or less; and e) 1 wt. % or less of other bio-based solvents in total; The composition of claim 1 comprising:

10. 5. The composition of any of claims 1-4, wherein the bio-based n-butyl acetate contains a sufficient amount of carbon-14 to produce a decay of at least 3.0 dpm / gC.

11. 11. The composition of claim 10, wherein the bio-based n-butyl acetate contains a sufficient amount of carbon-14 to produce a decay of at least 6.0 dpm / gC.

12. 11. The composition of claim 10, wherein the bio-based n-butyl acetate contains a sufficient amount of carbon-14 to produce a decay of at least 9.0 dpm / gC.

13. 11. The composition of claim 10, wherein the bio-based n-butyl acetate contains a sufficient amount of carbon-14 to produce a decay of at least 12.0 dpm / gC.

14. a) providing a semiconductor substrate; b) forming a resist film, comprising coating the semiconductor substrate with a resist composition having solubility in an organic developer, wherein the solubility of the resist composition in an organic developer decreases upon exposure to actinic rays or radiation; c) exposing the resist film to actinic or electromagnetic radiation; and d) developing the resist film with the organic developer, the organic developer comprising at least 25 wt % bio-based n-butyl acetate, wherein the bio-based n-butyl acetate comprises carbon-14 in an amount sufficient to produce a decay of at least 0.1 dpm / gC; A pattern forming method comprising:

15. After exposing the resist film to actinic or electromagnetic radiation, the solubility of the resist composition in the organic developer is ｓｖ / m ｓｕ When expressed as a ratio, it is 25 or less (where m ｓｖ is one unit mass m of the resist composition ｓｕ 15. The method of claim 14, wherein the organic developer solvent is a solvent required to dissolve the

16. The method of claim 14 further comprising forming an integrated circuit on the semiconductor substrate.

17. The integrated circuit is 3×10 ７ Transistors / mm ２ 17. The method of claim 16, wherein the transistor density is

18. The organic developer is a) 1 ppb or less of alkanes or alkenes having 22 or fewer carbon atoms; b) Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn, each at a metal element concentration of 5 ppb or less; and c) 3 wt% or less of bio-based n-butanol The method according to any one of claims 14 to 16, comprising one or more of the following:

19. The organic developer is a) 0.5 ppb or less of alkanes or alkenes having 22 or fewer carbon atoms; b) Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn, each at a metal element concentration of 3 ppb or less; and c) less than or equal to 1 wt. % biobased n-butanol, less than or equal to 0.1 wt. % n-hexadecane, less than or equal to 0.1 wt. % isopropanol, and less than or equal to 0.1 wt. % ethyl acetate; The method according to any one of claims 14 to 16, comprising one or more of the following:

20. The organic developer is a) 0.3 ppb or less of alkanes or alkenes having 22 or fewer carbon atoms; b) Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn, each at a metal element concentration of 2 ppb or less; and c) 1 wt. % or less of other bio-based solvents in total; The method according to any one of claims 14 to 16, comprising one or more of the following:

21. The method of any of claims 14 to 16, wherein the organic developer comprises at least 90 wt% bio-based n-butyl acetate.

22. The method of any of claims 14 to 16, wherein the organic developer comprises at least 95 wt% bio-based n-butyl acetate.

23. The method of any one of claims 14 to 16, wherein the organic developer further comprises 0.001 wt% to 5 wt% of a surfactant.

24. 24. The method of claim 23, wherein the surfactant comprises an ionic or non-ionic fluorine-based or silicon-based surfactant.

25. 17. The method of any of claims 14-16, wherein the bio-based n-butyl acetate contains a sufficient amount of carbon-14 to produce a decay of at least 3.0 dpm / gC.

26. 26. The method of claim 25, wherein the bio-based n-butyl acetate comprises a sufficient amount of carbon-14 to produce a decay of at least 6.0 dpm / gC.

27. 27. The method of claim 26, wherein the bio-based n-butyl acetate comprises a sufficient amount of carbon-14 to produce a decay of at least 9.0 dpm / gC.

28. 28. The method of claim 27, wherein the bio-based n-butyl acetate comprises a sufficient amount of carbon-14 to produce a decay of at least 12.0 dpm / gC.

29. 15. The method of claim 14, further comprising the step of rinsing the semiconductor substrate with a rinse solution after the developing step.

30. 30. The method of claim 29, wherein the rinse solution comprises at least one bio-based organic solvent containing carbon-14 (C-14) in an amount sufficient to produce disintegrations of at least 0.1 dpm / gC (disintegrations per gram of carbon per minute), and metal element concentrations of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn each of 5 ppb or less.

31. 31. The method of claim 30, wherein the at least one bio-based organic solvent is selected from the group consisting of one or more of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, and combinations thereof.

32. 32. The method of claim 31, wherein the at least one bio-based organic solvent is selected from the group consisting of 1-hexanol, methyl isobutyl carbinol, 2-hexanol, 1-heptanol, 2-heptanol, and combinations thereof.

33. 31. The method of claim 30, wherein the at least one bio-based organic solvent comprises carbon-14 in an amount sufficient to produce a decay of at least 3.0 dpm / gC.

34. 34. The method of claim 33, wherein the at least one bio-based organic solvent comprises carbon-14 in an amount sufficient to produce a decay of at least 6.0 dpm / gC.

35. 35. The method of claim 34, wherein the at least one bio-based organic solvent comprises carbon-14 in an amount sufficient to produce a decay of at least 9.0 dpm / gC.

36. 36. The method of claim 35, wherein the at least one bio-based organic solvent comprises carbon-14 in an amount sufficient to produce a decay of at least 12.0 dpm / gC.

37. A rinse composition comprising: a) at least 25 wt. % of a bio-based organic rinse solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, and combinations thereof; b) wherein said bio-based organic rinse solvent contains carbon-14 in an amount sufficient to produce a decay of at least 0.1 dpm / gC; and c) wherein the concentration of each of the metal elements Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn contained in the rinse composition is 5 ppb or less; The rinse composition.

38. The rinse composition comprises: i) 1 ppb or less of alkanes or alkenes having 22 or fewer carbon atoms, or ii) 3 wt% or less of bio-based methyl isobutyl ketone; 38. The rinse composition of claim 37, further comprising:

39. the rinse composition contains Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn, each at a metal element concentration of 3 ppb or less, and optionally i) 0.5 ppb or less of alkanes or alkenes having 22 or fewer carbon atoms; and ii) ≦1 wt % bio-based methyl isobutyl ketone, ≦0.1 wt % n-hexadecane, ≦0.1 wt % diisobutyl ketone, and ≦0.1 wt % methyl isoamyl ketone; 38. The rinse composition of claim 37, comprising one or both of:

40. the rinse composition contains Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn, each at a metal element concentration of 2 ppb or less, and optionally i) 0.3 ppb or less of alkanes or alkenes having 22 or fewer carbon atoms; and ii) 1 wt. % or less of other bio-based solvents in total; 38. The rinse composition of claim 37, comprising one or both of:

41. 41. The rinse composition of any of claims 37-40, wherein the bio-based organic rinse solvent is selected from the group consisting of one or more of 1-hexanol, methyl isobutyl carbinol, 2-hexanol, 1-heptanol, 2-heptanol, methyl isoamyl carbinol, diisobutyl carbinol, and combinations thereof.

42. 41. The rinse composition of any one of claims 37 to 40, wherein the rinse composition comprises at least 90 wt% of bio-based one or more of 1-hexanol, methyl isobutyl carbinol, 2-hexanol, 1-heptanol, 2-heptanol, methyl isoamyl carbinol, and diisobutyl carbinol.

43. 41. The rinse composition of any of claims 37-40, wherein the rinse composition comprises at least 95 wt% of one or more of bio-based 1-hexanol, methyl isobutyl carbinol, 2-hexanol, 1-heptanol, 2-heptanol, methyl isoamyl carbinol, and diisobutyl carbinol.

44. 41. The composition of any of claims 37-40, wherein the bio-based n-butyl acetate contains a sufficient amount of carbon-14 to produce a decay of at least 3.0 dpm / gC.

45. 45. The composition of claim 44, wherein the bio-based n-butyl acetate comprises a sufficient amount of carbon-14 to produce a decay of at least 6.0 dpm / gC.

46. 46. ​​The composition of claim 45, wherein the bio-based n-butyl acetate comprises a sufficient amount of carbon-14 to produce a decay of at least 9.0 dpm / gC.

47. 47. The composition of claim 46, wherein the bio-based n-butyl acetate comprises a sufficient amount of carbon-14 to produce a decay of at least 12.0 dpm / gC.

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