Bio-based solvents for negative development

Abstract

Non-aqueous bio-based organic solvents for lithographic processes are described, as well as methods of making and using such solvents. More specifically, the present disclosure contemplates non-aqueous developers and rinse compositions synthesized from biological or renewable sources, and also contemplates using such bio-based developers and utilizing the bio-based rinse agent for negative type development patterning methods to produce high resolution negative type images.

Description

[0001] Priority claim

[0002] This patent application claims the benefit of priority to U.S. application serial number 63 / 426,285, filed on November 17, 2022, which is incorporated herein by reference in its entirety. Technical Field

[0003] The technical field of the present disclosure includes bio-based compositions for negative tone development and methods of using such bio-based compositions. More particularly, the present disclosure contemplates non-aqueous developers and rinse compositions synthesized from biological or renewable sources, and also contemplates negative tone patterning methods employing such bio-based developers using photoresists and / or utilizing the bio-based rinse agents to produce high resolution negative tone images. Background Art

[0004] Achieving advanced lithography beyond the 14nm node requires patterning materials and processes with ultimate performance to cope with inherently contrast-limited exposure tools. The reduction of imaging wavelengths from the long-standing 193nm ArF lithography (DUV) to the anticipated 13.5nm Extreme Ultraviolet Lithography (EUV) will increase the resolution capabilities of the final optical systems used by the semiconductor industry and is expected to extend Moore's Law to the 10nm node and beyond.

[0005] The optical resolving power of ArF and EUV scanners can only be realized as material patterns formed on semiconductor substrates if the spatial resolution of the imaging material is commensurate with the quality of the delivered spatial image. At the same time, the imaging layer is required to have acceptable sensitivity to the imaging wavelength and provide low line-width roughness (LWR), good adhesion to the underlying substrate, and large post apply bake (PAB) and post exposure bake (PEB) ranges. Chemically amplified resists have become a workhorse in the lithography industry due to their ability to meet the above requirements in a suitable manner at multiple technology nodes.

[0006] Chemically-amplified (CA) resists are incorporated into the photolithography process by two different types of development. Positive resist imaging and development is a process in which, after the PEB step, the exposed areas of the photoresist are removed by an aqueous alkaline developer (tetraalkylammonium hydroxide (TMAH)), while the unexposed areas remain insoluble. This is called positive-tone development (PTD) and is described in detail in 4 J. Photopolym Sci. Technol. 299 (1991).

[0007] Alternatively, negative resists work in the opposite way. When exposed to UV light, negative resists become cross-linked / polymerized and more difficult to dissolve in the developer. Therefore, the negative resist remains on the exposed surface of the substrate, and the developer solution removes only the unexposed areas. Therefore, the mask for negative photoresist contains a reverse or photographic "negative" of the pattern to be transferred. A method for reversing the type of chemically amplified resists that were originally designed to be developed in a positive tone with an aqueous alkaline developer is to use an organic developer that removes the unexposed portion of the resist film, while the exposed area remains unaffected. This process is called negative-tone development (NTD), and has been widely used in the field of 193nm double patterning using a bright field mask, particularly in the case of small feature openings such as contact holes and groove patterning. As used herein, NTD refers to the use of an organic solvent as a developer to produce a negative image.

[0008] However, there are many challenges regarding the industrial application of NTD. Due to toxicological issues, environmental issues, and especially flammability issues, the number of organic solvents that are compatible with practical industrial-scale semiconductor manufacturing is limited. Common solvents used in the track process 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.

[0009] Although the solvents currently used in the NTD process are commercially viable, they are still not ideal and pose additional problems for the semiconductor industry. These solvents are all made from petrochemical-derived raw materials. Due to the environmental costs associated with petrochemical-derived solvents and their contribution to greenhouse gas emissions due to their high petroleum-derived carbon content, the integrated circuit industry is particularly interested in finding alternatives to these products. In addition, petrochemicals take hundreds of thousands of years to form naturally, making petrochemical-derived products non-renewable, meaning that they cannot be re-manufactured, re-grown, or regenerated at a rate comparable to their consumption.

[0010] Therefore, there is an unmet need for solvents derived from renewable resources that share similar properties with petroleum-derived solvents that can be used to make developed traces. In addition, due to the large investment costs associated with semiconductor development and manufacturing, it would also be advantageous if solvents derived from renewable resources could be processed by existing solvent manufacturing facilities. Summary of the invention

[0011] The present disclosure includes compositions, methods, and products that address the aforementioned needs and provide environmental improvements, such as lower greenhouse gas emissions, to gum development based processes through the synthesis of bio-based organic solvents and the utilization of such solvents.

[0012] A first aspect of the present disclosure includes a composition comprising an 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 at least 0.1 dpm / gC (decays per gram of carbon per minute); wherein the organic developer comprises each of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn at a metal element concentration of 5 ppb or less. In some embodiments, the first aspect further comprises 1 ppb or less of an alkane or olefin having a carbon number of 22 or less, and Zn; and 3 wt% or less of bio-based n-butanol.

[0013] In some embodiments of the first aspect, the organic developer comprises one or more of: 0.5 ppb or less of an alkane or olefin having a carbon number of 22 or less; 3 ppb or less of each of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn; 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.

[0014] In some embodiments of the first aspect, the organic developer comprises one or more of: 0.3 ppb or less of an alkane or olefin having a carbon number of 22 or less; 1 ppb or less of each of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn in a metal element concentration; and a total of 1 wt % or less of other bio-based solvents.

[0015] 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 nonionic fluorine-based or silicon-based surfactant.

[0016] A second aspect of the present disclosure includes a pattern forming method comprising: a) providing a semiconductor substrate; b) forming a resist film, comprising coating the semiconductor substrate with a resist composition having a solubility, wherein the solubility of the resist composition in an organic developer decreases when irradiated with actinic rays or radiation; c) exposing the resist film to actinic rays or electromagnetic radiation; and d) developing the resist film with an 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 at least 0.1 dpm / gC (disintegrations per gram of carbon per minute) of decay.

[0017] In some embodiments of the second aspect, after the resist film is exposed to actinic or electromagnetic radiation, the solubility of the resist composition in the organic developer is determined according to the ratio m sv / m su Described as 25 or less, where m sv is the amount of resist composition m dissolved per unit mass su The mass of organic developer solvent required.

[0018] The second aspect may also include forming an integrated circuit on the semiconductor substrate. In some embodiments, the transistor density of the integrated circuit is 3×10 7 Transistors / mm 2 .

[0019] In some embodiments of the second aspect, the organic developer comprises 5 ppb or less of each of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni and Zn in a metal element concentration. In some embodiments, the second aspect further comprises 1 ppb or less of an alkane or olefin having a carbon number of 22 or less and 3 wt % or less of bio-based n-butanol.

[0020] In some embodiments of the second aspect, the organic developer comprises one or more of: 0.5 ppb or less of an alkane or olefin having a carbon number of 22 or less; 3 ppb or less of each of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn; 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.

[0021] In some embodiments of the second aspect, the organic developer comprises one or more of: 0.3 ppb or less of an alkane or olefin having a carbon number of 22 or less; 2 ppb or less of each of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn at a metal element concentration of 2 ppb or less; and a total of 1 wt % or less of other bio-based solvents.

[0022] 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.

[0023] In some embodiments of the second aspect, the organic developer further comprises 0.001 wt % to 5 wt % of a surfactant. In some embodiments, the surfactant comprises an ionic or nonionic fluorine-based or silicon-based surfactant.

[0024] In some embodiments of the second aspect, the method further comprises a step of rinsing the semiconductor substrate with a rinse solution after the developing step, wherein the rinse solution comprises at least one bio-based organic solvent, and each of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni and Zn at a metal element concentration of 5 ppb or less, and the at least one bio-based organic solvent comprises carbon-14 (C-14) in an amount sufficient to produce at least 0.1 dpm / gC (decays per gram of carbon per minute). In some embodiments of the second aspect, the bio-based organic solvent is selected from one or more of the following: hydrocarbon-based solvents, ketone-based solvents, ester-based solvents, alcohol-based solvents, amide-based solvents, ether-based solvents, and combinations thereof. In some embodiments of the second aspect, the bio-based organic solvent of the rinse solution is selected from one or more of the following: 1-hexanol, methyl isobutyl carbinol, 2-hexanol, 1-heptanol, 2-heptanol, and combinations thereof.

[0025] A third aspect of the present disclosure includes a rinse composition comprising: at least 25 wt% of a bio-based organic rinse solvent selected from a hydrocarbon-based solvent, a ketone-based solvent, an ester-based solvent, an alcohol-based solvent, an amide-based solvent, an ether-based solvent, and combinations thereof, wherein the bio-based rinse organic solvent comprises carbon-14 in an amount sufficient to produce at least 0.1 dpm / gC (decays per gram of carbon per minute); and wherein the rinse composition comprises each of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn at a metal element concentration of 5 ppb or less. In some embodiments, the bio-based organic rinse solvent is selected from one or more of the following: 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 olefin having a carbon number of 22 or less, or 3 wt% or less of bio-based n-butanol. In some embodiments, the organic developer comprises at least 90% by weight of one or more of: bio-based 1-hexanol, bio-based methyl isobutyl carbinol, bio-based 2-hexanol, bio-based 1-heptanol, and bio-based 2-heptanol. In some embodiments, the organic developer comprises at least 95% by weight of one or more of: bio-based 1-hexanol, bio-based methyl isobutyl carbinol, bio-based 2-hexanol, bio-based 1-heptanol, and bio-based 2-heptanol.

[0026] In some embodiments of the fourth aspect, the rinse composition comprises one or more of: 0.5 ppb or less of alkanes or olefins having a carbon number of 22 or less; 3 ppb or less of each of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni and Zn at a metal element concentration of 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.

[0027] In some embodiments of the fourth aspect, the rinse composition comprises one or more of: 0.3 ppb or less of alkanes or olefins having a carbon number of 22 or less; 2 ppb or less of each of the metal element concentrations of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn; and a total of 1 wt % or less of other bio-based solvents.

[0028] According to another aspect of the present disclosure, an electronic device formed by the method described herein is provided. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] The present disclosure will be described with reference to the following drawings, in which like reference numerals represent like features, and in which:

[0030] Figures 1A to 1E An exemplary process flow for forming a pattern according to the present disclosure is shown.

[0031] With reference to the drawings in general, it will be understood that the illustrations are for the purpose of describing particular embodiments and are not intended to limit the present disclosure or the appended claims. The drawings are not necessarily drawn to scale, and certain features and certain views of the drawings may be shown exaggerated in scale or schematically for the sake of clarity and conciseness. DETAILED DESCRIPTION

[0032] The following description sets forth exemplary embodiments of the present technology. However, it should be appreciated that such description is not intended as a limitation on the scope of the present disclosure, but rather is provided as a description of exemplary embodiments.

[0033] Unless otherwise defined, all technical terms and scientific terms used herein have the same meanings as those generally understood by those of ordinary skill in the art. As used herein, unless otherwise indicated, the following terms have the following meanings. Any methods, devices and materials similar or equivalent to those described herein can be used in the practice of the compositions and methods described herein. The following definitions are provided to facilitate understanding of certain terms frequently used herein and are not intended to limit the scope of the present disclosure. All references mentioned herein are incorporated by reference in their entirety.

[0034] The term "comprising" and variations thereof, such as "containing" and "including" should be interpreted as having an open, inclusive meaning, i.e., like "including, but not limited to". The term "consisting essentially of" is interpreted to mean that the composition / method (a) must include the listed ingredients / steps and (b) is open to unlisted ingredients / steps that do not significantly affect the basic and novel properties of the composition / method. The term "consisting of" is closed and does not include any element, step, or ingredient that is not specifically mentioned after the phrase. In addition, unless the context clearly indicates otherwise, the singular forms "a", "an", and "the / said" include plural referents. Thus, reference to an "embodiment" includes a plurality of such embodiments.

[0035] In some embodiments, there are many possible alternatives to choose from. In such cases, the term "at least one of [A], [B], and [C]" or "one or more of [A], [B], and [C]" is used to mean "any one of [A], [B], [C] or any possible combination of [A], [B], and [C]", such as [A] and [B] or [A], [B], and [C]. Where "[A] or [B]" is used, it should be interpreted as "any one or both", and should not be interpreted as an alternative - for example, "[A] or [B]" is equivalent to "a combination of [A] or [B] or [A] and [B]". For clarity, the disclosure may include "and combinations thereof" to further illustrate that where alternatives are listed, the list also includes combinations thereof.

[0036] It should be noted that the terms "substantially" and "approximately" can be used herein to represent the inherent uncertainty that can be attributed to any quantitative comparison, value, measurement or other representation. These terms are also used herein to represent that the quantitative representation can be different from the referenced degree without causing the basic function of the subject in question to change. For example, the "about" value or parameter mentioned herein includes (and describes) embodiments involving the value or parameter itself. In certain embodiments, the term "about" includes the indicated amount ± 10%. In other embodiments, the term "about" includes the indicated amount ± 5%. In certain other embodiments, the term "about" includes the indicated amount ± 1%. In addition, the term "about X" includes a description of "X".

[0037] Terms like "ring," "circular ring," "cyclic," "alicyclic" and the like 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 ring types, or combinations thereof, including monocyclic, bicyclic, tricyclic and similar conventional designations.

[0038] "Alkyl" includes linear alkyl and branched alkyl. "Substituted alkyl" or "optionally substituted alkyl" refers to an alkyl substituent, which may include, for example, a linear alkyl or branched alkyl having 1 to 4 optional substituents selected from, for example, hydroxyl (—OH), halogen, amino (—NH2 or —NR2), nitro (—NO2), acyl (—C(═O)R), alkylsulfonyl (—S(═O)2R), alkoxy (—OR), (C 3-10)cycloalkyl and similar substituents, wherein R is a hydrocarbyl, aryl, het or similar moiety, such as a monovalent alkyl or divalent alkylene group having 1 to about 10 carbon atoms. For example, the hydroxy-substituted alkyl group can be a 2-hydroxy-substituted propylene group of the formula —CH2—CH(OH)—CH2—, the alkoxy-substituted alkyl group can be a 2-methoxy-substituted ethyl group of the formula —CH2—CH2—O—CH3, or the amino-substituted alkyl group can be a 1-dialkylamino-substituted ethyl group of the formula —CH(NR2)—CH3.

[0039] "Alkanes" include unsubstituted linear, cyclic and branched saturated alkanes.

[0040] "Olefin" includes unsubstituted linear, cyclic and branched saturated olefins having at least one carbon-carbon double bond.

[0041] "Cycloalkyl" includes cyclic alkyl groups. "Substituted cycloalkyl" or "optionally substituted cycloalkyl" refers to cycloalkyl substituents having 1 to 4 optional substituents selected from, for example, alkyl, alkenyl, alkynyl, hydroxy (—OH), halogen, amino (—NH2 or —NR2), nitro (—NO2), acyl (—C(═O)R), alkylsulfonyl (—S(═O)2R), alkoxy (—OR) and the like.

[0042] "Alkoxy" includes an alkyl group bonded to the base structure through an oxygen atom, -OR a , where R a Optionally substituted linear alkyl groups or branched alkyl groups as described above may be included.

[0043] "Alkoxycarbonyl" includes an alkyl group bonded to the base structure through an oxygen and a carbonyl group adjacent to the oxygen, -OC(=O)--R b , where R b Optionally substituted linear alkyl groups or branched alkyl groups as described above may be included.

[0044] "Carboxyl" means a moiety consisting of carbon bonded to both an oxygen and a hydroxyl group, -C(=O)-0-H.

[0045] "Hydroxyl" means the -O-H chemical moiety.

[0046] "Aryl" includes monovalent or divalent phenyl groups or ortho-fused bicyclic carbocyclic groups having about nine to twenty ring atoms, wherein at least one ring is aromatic. Aryl (Ar) may include substituted aryl groups, such as phenyl groups having 1 to 5 substituents (e.g., alkyl, alkoxy, halogen, and the like).

[0047] "Het" includes a four (4), five (5), six (6) or seven (7) membered saturated or unsaturated heterocyclic ring having 1, 2, 3 or 4 heteroatoms selected from oxygen, sulfur, sulfinyl, sulfonyl, selenium, tellurium and nitrogen, which ring is optionally fused to a benzene ring. Het also includes "heteroaryl" which includes radicals attached through the ring carbons of a monocyclic aromatic ring containing five or six ring atoms consisting of carbon and 1, 2, 3 or 4 heteroatoms, each heteroatom selected from non-peroxide oxygen, sulfur and N (X), wherein X is absent or is H, O, (C 1-4 )alkyl, phenyl or benzyl; and radicals of ortho-fused bicyclic heterocycles of about eight to ten ring atoms derived therefrom, in particular benzo derivatives or radicals derived therefrom by fusing thereto a propylene, trimethylene or tetramethylene diradical.

[0048] Alkyl, alkoxy, and the like include both straight chain and branched groups; however, reference to an individual group such as "propyl" includes only the straight chain group, branched chain isomers such as "isopropyl" being specifically mentioned.

[0049] The carbon atom content of various hydrocarbon-containing (i.e., hydrocarbyl) moieties may alternatively be indicated by prefixes indicating the lower and upper numbers of carbon atoms in the moiety, i.e., the prefix C i-j represents a moiety having an integer number "i" to an integer number "j" of carbon atoms (inclusive). Thus, for example, (C1-C8)alkyl or C 1-8 Alkyl refers to an alkyl group of one to eight carbon atoms (inclusive), as well as a hydrocarbyloxy group such as (C1-C8)alkoxy or C 1-8 Alkoxy refers to an alkoxy group (—OR) of an alkyl group having one to eight carbon atoms (inclusive). 1-8 The alkyl group may be, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, 3-pentyl, hexyl, heptyl or octyl; (C 3-12 ) The cycloalkyl group may be cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, including bicyclic, tricyclic or polycyclic substituents and the like.

[0050] As used herein, the specific "C x-y For example (C 10-20 ) alkyl may be used to limit this group and includes all intermediate chain lengths and values. C 1-8 The alkoxy group may be, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, pentyloxy, 3-pentyloxy, hexyloxy, 1-methylhexyloxy, heptyloxy, octyloxy, and the like.

[0051] The present disclosure provides new bio-based compounds for lithography and other patterning processes, as well as methods for synthesizing such compounds and methods for using such compounds in lithography processes. The term "bio-based" as used in this application means that it contains some components derived from at least one bio-based material. For example, a "bio-based n-butyl acetate" solvent ("NBA") would be a NBA derived in part or in whole from at least one bio-based material. As used herein, "bio-based materials" refers to organic materials in which carbon comes from non-fossil biological sources. Examples of bio-based materials include, but are not limited to, sugar, starch, corn, natural fibers, sugar cane, beets, citrus fruits, woody plants, cellulose products, lignocellulosic products, hemicellulose, potatoes, vegetable oils, other polysaccharides such as pectin, chitin, fructan and pullulan, and combinations thereof. According to a specific embodiment, at least one bio-based material is selected from corn, sugar cane, beets, potatoes, starch, citrus fruits, woody plants, cellulose lignin, vegetable oils, natural fibers, oil-containing wood raw materials, and combinations thereof.

[0052] As used herein, fossil biomass sources or fossil fuels include hydrocarbon-containing materials that form naturally in the earth's crust from the remains of dead plants and animals, such as coal, crude oil, and natural gas, and refined or synthetic materials derived therefrom. The key difference between fossil biomass sources and bio-based materials is that fossil biomass sources are derived from buried dead organisms that have undergone anaerobic decomposition over millions of years into high-carbon fossil fuels.

[0053] Carbon-14 is a radioactive isotope of carbon that is formed in the troposphere and upper stratosphere by thermal neutrons absorbed by nitrogen atoms. When cosmic rays enter the atmosphere, they undergo various transformations, including the production of neutrons. The produced neutrons (1n) participate in the following np reactions:

[0054] 14 / 7N+neutron→14 / 6C+proton

[0055] After being created in the upper atmosphere, carbon-14 atoms react rapidly to form most (about 93%) 14 CO (carbon monoxide), which is then oxidized at a slower rate to form 14 CO2 (radioactive carbon dioxide). The gas mixes rapidly and is evenly distributed throughout the atmosphere (mixing time scales are on the order of weeks), and is incorporated into biological organisms.

[0056] Carbon-14 (C-14) has a half-life of about 5,700 years, making it useful as a detector for determining the origin of carbon in synthetic materials. The relatively short half-life of C-14 means that it can be found in bio-based materials, but not in fossil biological sources. A compound sample that is a bio-based compound will have a measurable amount of C-14 incorporated into the compound. A compound sample prepared from petroleum-based materials will have essentially no C-14, or will have negligible to undetectable levels of C-14. Therefore, the key distinguishing factor of the new bio-based solvents described herein is that they contain C-14 in a detectable amount, which allows them to be distinguished from traditional fossil-based solvents.

[0057] The detection of C-14 presence in the compositions described herein can be carried out based on techniques known in the art. Without limitation, examples of methods for determining the presence and composition levels of C-14 include the use of accelerator mass spectrometry (AMS), liquid scintillation counting (LSC) or beta-ionization techniques (BI). In some embodiments, liquid scintillation is used as a standard method for measuring C-14 levels. The carbon percentage can be compared with the total carbon in the product or as a percentage of a function of the total mass of the product. Specific examples of standards for measuring C-14 in commercial products are:

[0058] a. ASTM D6866, Standard Test Methods for Determining the Biobased Content of Solid, Liquid, and Gaseous Samples Using Radiocarbon Analysis, first published in 2004 and last updated as ASTM D6866-22 in March 2022 (incorporated herein by reference), ASTM D686 was developed in the United States as a standardized analytical method for determining the biobased content of solid, liquid, and gaseous samples using radiocarbon dating. It is a method for certifying the biobased content of commercial products. The working standard for radiocarbon dating for industrial use was completed in 2004 and is now referenced by U.S. federal law (7 CFR Part 2902).

[0059] b. CEN / TS16640:2014, Bio-based products-Determination of the bio-based carbon content of productsusing the radiocarbon method is a European standard that provides technical specifications for determining the bio-based carbon content in products based on 14C content measurement. It specifies three test methods for determining 14C content (from which the bio-based carbon content is calculated): A) Liquid Scintillation Counter (LSC); B) β-ionization (BI); and C) Accelerator Mass Spectrometry (AMS). The bio-based carbon content is expressed as a fraction of the sample mass, a fraction of the total carbon content, or a fraction of the total organic carbon content. This calculation method is applicable to any product containing organic carbon, including biocomposites.

[0060] c.CSN EN 16785-1 – Biobased products – Biobased content – ​​Part 1: Determination of biobased content using radiocarbon analysis and elemental analysis.

[0061] The bio-based solvents described herein have a non-zero or detectable amount of C- 14. Examples of quantitatively measured levels of C- 14 in a composition include:

[0062] a. at least 0.01 dpm / gC (disintegrations per gram of carbon per minute), 0.1 dpm / gC, 0.5 dpm / gC, 1.0 dpm / gC, 1.5 dpm / gC, 2 dpm / gC, 3 dpm / gC, 4 dpm / gC, 5 dpm / gC, 6 dpm / gC, 7 dpm / gC, 8 dpm / gC, 9 dpm / gC, 10 dpm / gC, 11 dpm / gC, 12 dpm / gC, 13 dpm / gC, or 14 dpm / gC of radioactive decay of carbon-14 (C-14). In some embodiments, the compositions described herein measure 0.1 dpm / gC to 14 dpm / gC, 0.1 dpm / gC to 13 dpm / gC, 0.1 dpm / gC to 12 dpm / gC, 0.1 dpm / gC to 11 dpm / gC, 0.1 dpm / gC to 10 dpm / gC, 0.1 dpm / gC to 8 dpm / gC, 0.1 dpm / gC to 6 dpm / gC, 0.1 dpm / gC to 4 dpm / gC, 0.1 dpm / gC to 2dpm / gC, 0.1dpm / gC to 0.5dpm / gC, 0.5dpm / gC to 14dpm / gC, 0.5dpm / gC to 13dpm / gC, 0.5dpm / gC to 12dpm / gC, 0.5dpm / gC to 11dpm / gC, 0.5dpm / gC to 10dpm / gC, 0.5dpm / gC to 8dpm / gC, 0.5dpm / gC to 6dpm / gC, 0.5dpm / gC to 4dpm / gC, 0.5dpm / gC to 2dpm / gC, 1dpm / gC to 14dpm / gC, 1dpm / gC to 13dpm / gC, 1dpm / gC to 12dpm / gC, 1dpm / gC to 11dpm / gC, 1dpm / gC to 10dpm / gC, 1dpm / gC to 8dpm / gC, 1dpm / gC to 6dpm / gC, 1dpm / gC to 4dpm / gC, 1dpm / gC to 2dpm / gC, 2dpm / gC to 14dpm / gC, 2dpm / gC to 13dpm / gC, 2dpm / gC to 12dpm / gC, 2dpm / gC to 11dpm / gC, 2dpm / gC to 10dpm / gC, 2dpm / gC to 8dpm / gC, 2dpm / gC to 6dpm / gC, 2dpm / gC to 4dpm / gC, 4dpm / gC to 14dpm / gC, 4dpm / gC to 13dpm / gC, 4dpm / gC to 12dpm / gC, 4dpm / gC to 11dpm / gC, 4dpm / gC to 10dpm / gC, 4dpm / gC to 8dpm / gC, 4dpm / gC to 6dpm / gC, 6dpm / gC to 14dpm / gC, 6dpm / gC to 13dpm / gC, 6dpm / gC to 12dpm / gC, 6dpm / gC to 11dpm / gC, 6dpm / gC to 10dpm / gC, 6dpm / gC to 8dpm / gC, 8dpm / gC to 14dpm / gC, 8dpm / gC to 13dpm / gC, 8dpm / gC to 12dpm / gC, 8dpm / gC to 11dpm / gC, 8d dpm / gC to 10 dpm / gC, 10 dpm / gC to 14 dpm / gC, 10 dpm / gC to 13 dpm / gC, 10 dpm / gC to 12 dpm / gC, 10 dpm / gC to 11 dpm / gC, 11 dpm / gC to 14 dpm / gC, 11 dpm / gC to 13 dpm / gC, 11 dpm / gC to 12 dpm / gC, 12 dpm / gC to 14 dpm / gC, 12 dpm / gC to 13 dpm / gC, or 13 dpm / gC to 14 dpm / gC.

[0063] b. Measure the compound in the sample 14 C and 12 C ratio. Biobased compounds will contain greater than zero 14 C / 12 In some embodiments, the biobased compound will have a C ratio greater than or equal to 1×10 -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 of 14 C / 12 C ratio. In some embodiments, the biobased compound will have a C ratio of 7.5×10 -13 to 1.5×10 -12 , 1.2×10 -12 to 1.5×10 -12 , 1.3×10 -12 to 1.5×10 -12 , 1.4×10 -12 to 1.5×10 -12 , or 1.45×10 -12 to 1.5×10 -12 of 14 C / 12 C ratio.

[0064] c. In some embodiments, the bio-based solvents described herein contain greater than 25 Bq, 50 Bq, 75 Bq, 100 Bq, 150 Bq, 175 Bq, 200 Bq, or 225 Bq of C-14 per kilogram (kg) of total carbon.

[0065] In some embodiments, there may be practical or economic reasons for using a solvent mixture or solvent combination in which at least some of the solvents are bio-based. In some embodiments, the bio-based solvents comprise greater than 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 60%, 70%, 80%, 90%, 95%, 98%, 99%, 99.5%, or 99.9% by weight of the total solvent mixture. In some embodiments, the bio-based solvent comprises 5% to 99%, 10% to 99%, 20% to 99%, 30% to 99%, 40% to 99%, 50% to 99%, 60% to 99%, 70% to 99%, 80% to 99%, 90% to 99%, 5% to 90%, 10% to 90 ... % to 90 wt%, 30 wt% to 90 wt%, 40 wt% to 90 wt%, 50 wt% to 90 wt%, 60 wt% to 90 wt%, 70 wt% to 90 wt%, 80 wt% to 90 wt%, 5 wt% to 80 wt%, 10 wt% to 80 wt%, 20 wt% to 80 wt%, 30 wt% to 80 wt%, 40 wt% to 80 wt%, 50 wt% to 80 wt%, 60 wt% to 80 wt%, 70 wt% to 90 wt%, % to 80 wt%, 5 wt% to 70 wt%, 10 wt% to 70 wt%, 20 wt% to 70 wt%, 30 wt% to 70 wt%, 40 wt% to 70 wt%, 50 wt% to 70 wt%, 60 wt% to 70 wt%, 5 wt% to 60 wt%, 10 wt% to 60 wt%, 20 wt% to 60 wt%, 30 wt% to 60 wt%, 40 wt% to 60 wt%, 50 wt% to 60 wt%, 5 wt% to 50 %, 10 wt % to 50 wt %, 20 wt % to 50 wt %, 30 wt % to 50 wt %, 40 wt % to 50 wt %, 5 wt % to 40 wt %, 10 wt % to 40 wt %, 20 wt % to 40 wt %, 30 wt % to 40 wt %, 5 wt % to 30 wt %, 10 wt % to 30 wt %, 20 wt % to 30 wt %, 5 wt % to 20 wt %, 10 wt % to 20 wt %, or 5 wt % to 10 wt %.

[0066] 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, where at least some of the solvents are biobased, the biobased content of the solvent can be approximated by several methods. For example, measuring the specific activity of the mixture in dpm / gC and applying the following equation can provide an estimate of the biobased content:

[0067] Weight % biobased = 100*(specific activity of mixture) / (specific activity of 100% biobased)

[0068] Since the global stock of natural C-14 is approximately 75 tons, the specific activity is >13.56 dpm / gC. The expected specific activity of bio-based materials can be approximated from this value using the following equation:

[0069] Specific activity of the material X = (weight fraction of carbon in the material) * 13.56dpm / gC

[0070] For example, the carbon content of NBA is 0.621, so the expected specific activity of pure bio-based NBA is 8.4 dpm / gC. Therefore, a mixture containing greater than 50 wt% bio-based NBA is expected to have a specific activity of about 4.2 dpm / gC.

[0071] Bio-based negative developer

[0072] As part of a semiconductor patterning process, a bio-based negative developer is a bio-based organic solvent that dissolves a resist film that has been exposed to actinic or electromagnetic radiation. In a specific embodiment, the present disclosure relates to the use of n-butyl acetate (NBA) (also known as butyl acetate, acetic acid n-butyl ester, butyl ethanoate, or butile) as a bio-based negative developer. Traditionally, NBA is derived from fossil fuels. It is highly desirable to find bio-based alternatives that will meet the needs of the integrated circuit community while also providing environmentally friendly, sustainable, and renewable solvents. However, as described herein, the development of bio-based solvents presents unique, undefined challenges that need to be overcome to make bio-based solvent substitution feasible in the semiconductor field. The processes used to synthesize bio-based solvents—such as fermentation—result in multiple side reactions, thereby producing additional solvents such as isobutyl alcohol and isobutyl acetate, acetone, butanol, and ethanol (ABE) that are difficult to separate, as well as water and acetic acid, butyric acid, and higher alcohols and impurities such as metals and particulate matter.

[0073] In order to meet the stringent requirements of the semiconductor industry, bio-based NBA negative developers need to have high to ultra-high purity. It is critical that the surface of the semiconductor wafer is not contaminated by any metal impurities present in NBA. In fact, micro-contamination accounts for more than 50% of yield losses in IC manufacturing. Therefore, it is a natural requirement to minimize the metal impurity content of the materials used in these processes. The solvent must be purified to an extremely low level of metal content. The metal element concentration can be measured according to inductively coupled plasma mass spectrometry (e.g., an inductively coupled plasma mass spectrometer Agilent 7500cs (ICP-MS device) manufactured by Agilent Technologies, Inc.). The bio-based NBA negative developer should contain each of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni and Zn at a metal element concentration of 5 parts per billion (ppb) or less. In some embodiments, the metal element concentration of each of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn is 5 ppb, 4 ppb, 3 ppb, 2 ppb, 1 ppb, 0.5 ppb, 0.1 ppb, 0.05 ppb, 0.01 ppb, 0.005 ppb, or 0.001 ppb or less. In some embodiments, the metal element concentration of each of Na and Ca is 0.75 ppb or less, the metal element concentration of each of Al, K, Fe, Mg, and Zn is 0.25 ppb or less, and the metal element concentration of each of Cu, Mn, Li, Cr, and Ni is 0.1 ppb or less. In some embodiments, the bio-based developer comprises each of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn at a metal element concentration of 0.001 ppb to 1 ppb.

[0074] Organic compounds or impurities may also create contamination issues during semiconductor manufacturing. In addition to minimizing the amount of impurities in the solvent, it is also necessary to reduce or eliminate organic impurities. In particular, relatively low molecular weight organic compounds pose a significant challenge to semiconductor processing because they can be difficult to remove by filtration techniques, thereby forming particle contamination, especially for fine patterns (e.g., 30 nm nodes or less). In some embodiments, the bio-based NBA negative developer contains 5 ppb or less of an alkane or olefin (“C 1-22 In some embodiments, the bio-based NBA negative developer comprises 5 ppb, 4 ppb, 4 ppb, 2 ppb, 1 ppb, 0.5 ppb, 0.1 ppb, 0.05 ppb, or 0.01 ppb or less of C 1-22 In some embodiments, C 1-22The concentration of alkanes / olefins is 0.001 ppb to 1 ppb. 1-22 The alkane / olefin content can be measured according to a gas chromatograph mass spectrometer (for example, GCMS-QP2010 (gas chromatograph mass spectrometer) manufactured by Shimadzu Corporation) connected to a pyrolysis apparatus (for example, PY2020D manufactured by Frontier Lab).

[0075] As a result of the synthesis technology used, additional organic solvents may be present in small amounts. In some embodiments, it is necessary to reduce or remove these impurities or intermediates. Such compounds include, but are not limited to, bio-based n-butanol, n-hexadecane, isopropanol, and ethyl acetate. In some embodiments, the bio-based NBA negative developer comprises 3%, 2%, 1%, 0.5%, 0.1%, 0.05%, 0.01%, or 0.001% or less of bio-based n-butanol. In some embodiments, the bio-based NBA negative developer comprises 3%, 2%, 1%, 0.5%, 0.1%, or 0.5% or less of one or more of bio-based n-butanol, n-hexadecane, isopropanol, and ethyl acetate. In some embodiments, the bio-based NBA negative developer comprises 3%, 2%, 1%, 0.5%, 0.1%, 0.05%, 0.01%, or 0.001% or less of total other (non-NBA) bio-based solvents.

[0076] In addition to metals and low molecular weight organics, general particle contamination including nano to micron-sized particles originating from various other sources also leads to device defects that negatively affect yields. Therefore, as described above, it is crucial to remove any trace particles from bio-based solvents. Specifically, depending on the purification method, the number of particles with a particle size of 0.15 μm or more contained in the solvent can be, for example, 20 particles / mL or less, 10 particles / mL or less, or 5 particles / mL or less. Particle counts are measured by liquid particle counting techniques and by wafer measurement. For example, after a specified amount of solvent is deposited on a substrate and spun out at a specified number of revolutions, the wet particle amount is further dried at a specified number of revolutions, and then the number of defects on the substrate is determined by, for example, a KLA Surfscan SP7 unpatterned wafer inspection system.

[0077] The bio-based negative developer may further include additional components such as a surfactant and a stabilizer. The surfactant is not particularly limited, but for example, an ionic or nonionic fluorine-based and / or silicon-based surfactant and the like may be used. Examples of fluorine-based and / or silicon-based surfactants include surfactants described in Japanese Patent Application Laid-Open 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, and nonionic surfactants are 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 is generally 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.

[0078] The bio-based negative developer may further include a nitrogen-containing enhancer compound, which, when included in the developer, interacts with the polar groups generated in the resist film due to the acid, thereby further increasing the insolubility of the exposed area in the organic solvent. For example, the nitrogen-containing enhancer compound reacts with the polar group to form a salt or an ionic bond. Considering, for example, the storage stability of the developer, the nitrogen-containing enhancer compound may be preferably added to the organic developer immediately before the pattern forming method of the present invention is performed. The enhancer compound has the following structure:

[0079]

[0080] Where R 1 , R 2 and R 3 each independently represents a hydrogen atom, a hydroxyl group, a formyl group, an alkoxy group, an alkoxycarbonyl group, an optionally substituted C 1-30 Alkyl, optionally substituted C 3-30 cycloalkyl or aryl, or a group formed by two or more of these groups, and R 1 , R 2 and R 3 The two of them may be bonded to form a ring structure together with the nitrogen atom bonded thereto.

[0081] In embodiments where an enhancer compound is present, the amount of enhancer 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.

[0082] Bio-based rinse solution

[0083] The bio-based rinse solution comprises a bio-based material that improves the quality of the patterned photoresist. The bio-based rinse solution may be derived in part or in whole from at least one bio-based material. The bio-based rinse solution may comprise 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 solvents, or in some embodiments may comprise an alcohol-based solvent in combination with an ester-based solvent.

[0084] As in the case of negative developer, bio-based rinsing solution needs to have high to ultra-high purity. It is crucial that the semiconductor wafer surface is not contaminated by any metal impurities present in NBA. Therefore, it is a matter of course to minimize the metal impurity content of the materials used in these processes. The solvent must be purified to an extremely low level of metal content. The metal element concentration can be measured according to inductively coupled plasma mass spectrometry (for example, an inductively coupled plasma mass spectrometer Agilent 7500cs (ICP-MS device) manufactured by Agilent Technologies, Inc.). The bio-based rinsing solution should contain each of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni and Zn with a metal element concentration of 5ppb or less. In some embodiments, the metal element concentration of each of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn is 5 ppb, 4 ppb, 3 ppb, 2 ppb, 1 ppb, 0.5 ppb, 0.1 ppb, 0.05 ppb, 0.01 ppb, 0.005 ppb, or 0.001 ppb or less. In some embodiments, the metal element concentration of each of Na and Ca is 0.75 ppb or less, the metal element concentration of each of Al, K, Fe, Mg, and Zn is 0.25 ppb or less, and the metal element concentration of each of Cu, Mn, Li, Cr, and Ni is 0.1 ppb or less. In some embodiments, the bio-based rinse solution comprises each of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn at a metal element concentration of 0.001 ppb to 1 ppb.

[0085] Organic compounds or impurities may also create contamination issues during semiconductor manufacturing. In addition to minimizing the amount of impurities in the solvent, it is also necessary to reduce or eliminate organic impurities. In particular, relatively low molecular weight organic compounds pose a significant challenge to semiconductor processing because they can be difficult to remove by filtration techniques, thereby forming particle contamination, especially for fine patterns (e.g., 30 nm nodes or less). In some embodiments, the bio-based NBA negative developer contains 5 ppb or less of an alkane or olefin (“C 1-22 In some embodiments, the bio-based NBA negative developer comprises 5 ppb, 4 ppb, 4 ppb, 2 ppb, 1 ppb, 0.5 ppb, 0.1 ppb, 0.05 ppb, or 0.01 ppb or less of C 1-22 In some embodiments, C 1-22 The concentration of alkanes / olefins is 0.001 ppb to 1 ppb. 1-22 The alkane / olefin content can be measured according to a gas chromatography mass spectrometer (eg, GCMS-QP2010 (gas chromatograph mass spectrometer) manufactured by Shimadzu Corporation) connected to a pyrolysis apparatus (eg, PY2020D manufactured by Frontier Lab).

[0086] As a result of the synthesis techniques used, additional organic solvents may be present in small amounts. In some embodiments, it is desirable to reduce or remove these impurities or intermediates. In some embodiments, the bio-based rinse solution comprises 3%, 2%, 1%, 0.5%, 0.1%, 0.05%, 0.01%, or 0.001% or less of total other bio-based solvents.

[0087] In addition to metals and low molecular weight organics, general particle contamination including nanometer to micron-sized particles derived from various other sources also causes device defects that negatively affect output. Therefore, as mentioned above, it is crucial to remove any trace particles from bio-based solvents. Specifically, according to the purification method, the particle size contained in the solvent is that the number of particles of 0.15 μm or larger can be, for example, 20 particles / mL or less, 10 particles / mL or less or even 5 particles / mL or less. Particle count is measured by liquid particle counting technology and by wafer measurement. For example, after a specified amount of solvent is deposited on a substrate and spun out with a specified number of revolutions, the wet particle amount is further dried under a specified number of revolutions, and then the number of defects on the substrate is determined by, for example, a KLASurfscan SP7 unpatterned wafer detection system.

[0088] The bio-based rinse solution can be characterized by its Hansen Solubility Parameter. In some embodiments, the bio-based solvent herein should have a solubility of about 14.5 MPa. 0.5 Up to 17MPa 0.5 The dispersion parameter, polar parameter and hydrogen bond parameter sum is about 14 MPa 0.5 Up to 20MPa 0.5 In some embodiments, the dispersion parameter value of the selected solvent is about 15 MPa. 0.5 Up to 16MPa 0.5 , or for example 15.4MPa 0.5 Up to 15.9MPa 0.5 ; and the sum of the polarity parameter and the hydrogen bond parameter is 15MPa 0.5 About 19MPa 0.5 , more preferably 15.5MPa 0.5 Up to 18.5MPa 0.5 .

[0089] In the present disclosure, a ketone-based rinsing solution means a solvent having a ketone group in the molecule, an ester-based solvent means a solvent having an ester group in the molecule, an alcohol-based solvent means a solvent having an alcohol hydroxyl group in the molecule, an amide-based solvent means a solvent having an amide group in the molecule, and an ether-based solvent means a solvent having an ether bond in the molecule. Some of these solvents have a plurality of the above-mentioned functional groups in one molecule, and in this case, the solvent belongs to all solvent types corresponding to the functional groups contained in the solvent. For example, in the above classification, diethylene glycol monomethyl ether belongs to both alcohol-based solvents and ether-based solvents. A hydrocarbon-based solvent means a hydrocarbon solvent having no substituent.

[0090] 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, methylethylketone, methylisobutylketone, 4-methyl-2-pentanone, acetylacetone, acetonylacetone, ionone, diacetone alcohol, acetylcarbinol, acetophenone, methylnaphthylketone, isophorone, propylene carbonate, γ-butyrolactone, γ-valerolactone, and dihydrolevoglucose ketone. Among ketone-based solvents, 2-heptanone is most preferred.

[0091] Examples of ester-based rinse solutions include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, methoxyethyl acetate, ethoxyethyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, -Propyloxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, 4-methyl-4-methoxypentyl acetate, propylene glycol diacetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate Ester, 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, propyl-3-methoxypropionate. As for the solvent represented by formula (1), alkyl acetate is still more preferred, and butyl acetate is most preferred.

[0092] As for the ester-based rinsing solution, a solvent represented by formula (1) described later or a solvent represented by formula (2) described later is preferred, a solvent represented by formula (1) is more preferred, an alkyl acetate is still more preferred, and butyl acetate is most preferred.

[0093] Examples of alcohol-based rinsing solutions include alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, isobutanol, n-hexylmethylisobutylcarbinol, ethanol, n-heptanol, n-octanol, n-decanol, and 3-methoxy-1-butanol; glycol-based solvents such as ethylene glycol, diethylene glycol, and triethylene glycol; and hydroxyl-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 them, glycol ether-based solvents are preferred.

[0094] In addition to the above hydroxyl-containing glycol ether-based solvents, examples of the ether-based rinsing solution include hydroxyl-free glycol ether-based solvents such as propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol dimethyl ether, and diethylene glycol diethyl ether; alkane; tetrahydrofuran; anisole; perfluoro-2-butyltetrahydrofuran; and 1,4-difluoro Preference is given to using solvents based on glycol ethers.

[0095] Examples of hydrocarbon-based rinsing 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, xylene, diethylbenzene, ethyltoluene, trimethylbenzene, ethylxylene, and dipropylbenzene. Among them, aromatic hydrocarbon-based solvents are preferred.

[0096] In some embodiments, the bio-based rinse solution mainly contains monohydric alcohols having carbon numbers of 6 to 8. Monohydric alcohols having carbon numbers of 6 to 8 include linear, branched or cyclic monohydric alcohols, and specific examples of monohydric alcohols that can be used 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, of which 1-hexanol, methyl isobutyl carbinol, 2-hexanol, 1-heptanol and 2-heptanol are preferred, and methyl isobutyl carbinol is most preferred.

[0097] A plurality of these solvents may be mixed, or the solvent may be mixed with a solvent other than the above-mentioned solvents or water and used.

[0098] Bio-based solvents for solubilizing photoresists

[0099] In some embodiments, the bio-based solvents described herein can be used as or incorporated into the formulation of photoresist compositions. Photoresist compositions typically include solvents for dissolving the components of the composition and facilitating its coating on a substrate. Due to toxicological issues, environmental issues, and especially flammability issues, the number of organic solvents that are compatible with practical industrial-scale semiconductor manufacturing is limited.

[0100] The photoresist composition of the present disclosure comprises: (A) a polymer matrix whose solubility in an alkaline developer increases and whose solubility in an organic solvent decreases under the action of an acid; (B) a compound capable of generating an acid when irradiated with actinic rays or radiation (sometimes referred to as a "photoacid generator"); (C) a bio-based solvent that can be used to dissolve the various components of the photoresist composition, which contains at least 0.1 dpm / gC (decays per gram of carbon per minute) of carbon-14 (C-14), and optionally, one or more of the following: (D) a basic compound, (E) a surfactant, (F) a photodecomposable quencher, and (G) other additives.

[0101] In another embodiment, the photoresist composition includes a class of radiation-based resists based on metal oxide chemicals (metal oxygen / hydroxyl compositions), which use radiation-sensitive ligands to control the stability and processability of the resist. Typically, when developed with an organic solvent, these resist compositions act as negative photoresists. Related resist compounds are discussed in U.S. Patent No. 8,703,386B2, incorporated herein by reference. It has been demonstrated that organometallic photoresists such as organotin oxide hydroxides have excellent properties as photoresists for photolithography photopatterning. Suitable organometallic photoresists include organotin materials, such as U.S. Patent No. 9,310,684B2, disclosed U.S. Patent Application No. 2016 / 0116839A1 and U.S. Patent No. 10,228,618B2, all of which are incorporated herein by reference. Other organometallic patterning compositions based on various metals are described in published U.S. Patent Application 2002 / 0076495 and U.S. Patent No. 9,372,402B2, both of which are incorporated herein by reference. Resists containing metal oxide particles with organic coatings are described in published U.S. Patent Application 2015 / 0234272A1, incorporated herein by reference. Applicants have developed organotin patterning materials that have been developed to a high degree, and some of these are described in exemplary compositions.

[0102] Typical solvents used in photoresist compositions include n-butyl acetate (NBA), 2-heptanone, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), methyl hydroxyisobutyrate (HBM) and cyclohexanone (CHO). Based on the total weight of the photoresist composition, the total solvent content in the photoresist composition is generally 70 wt % to 99 wt %. The present disclosure contemplates NBA used alone or as part of a mixture of one or more solvents. The percentage of NBA includes the percentages listed herein for the mixture, such as 5 wt % to 99 wt %.

[0103] As in the case of negative developer and rinse agent, bio-based photoresist solvent needs to have high to ultra-high purity. The solvent must be purified to a very low level of metal content. The metal element concentration can be measured according to inductively coupled plasma mass spectrometry (e.g., an inductively coupled plasma mass spectrometer Agilent 7500cs (ICP-MS device) manufactured by Agilent Technologies, Inc.). The bio-based rinse solution should contain 5 parts per million (ppb) or less of each of the metal element concentrations of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn. In some embodiments, the metal element concentration of each of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn is 5 ppb, 4 ppb, 3 ppb, 2 ppb, 1 ppb, 0.5 ppb, 0.1 ppb, 0.05 ppb, 0.01 ppb, 0.005 ppb, or 0.001 ppb or less. In some embodiments, the metal element concentration of each of Na and Ca is 0.75 ppb or less, the metal element concentration of each of Al, K, Fe, Mg, and Zn is 0.25 ppb or less, and the metal element concentration of each of Cu, Mn, Li, Cr, and Ni is 0.1 ppb or less. In some embodiments, the bio-based rinse solution comprises each of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn at a metal element concentration of 0.001 ppb to 1 ppb.

[0104] As previously mentioned, organic compounds or impurities may also create contamination issues during semiconductor manufacturing. In addition to minimizing the amount of impurities in the solvent, it is also necessary to reduce or eliminate organic impurities. In particular, relatively low molecular weight organic compounds pose a significant challenge to semiconductor processing because they can be difficult to remove by filtration techniques, thereby forming particle contamination, especially in fine patterns (e.g., 30 nm nodes or less). In some embodiments, the bio-based rinse solution contains 5 ppb or less of alkanes or alkenes (“C 1-22 In some embodiments, the bio-based rinse solution comprises 5 ppb, 4 ppb, 4 ppb, 2 ppb, 1 ppb, 0.5 ppb, 0.1 ppb, 0.05 ppb, or 0.01 ppb or less of C 1-22 In some embodiments, C 1-22 The concentration of alkanes / olefins is 0.001 ppb to 1 ppb. 1-22The alkane / olefin content can be measured according to a gas chromatography mass spectrometer (eg, GCMS-QP2010 (gas chromatograph mass spectrometer) manufactured by Shimadzu Corporation) connected to a pyrolysis apparatus (eg, PY2020D manufactured by Frontier Lab).

[0105] As a result of the synthesis techniques used, additional organic solvents may be present in small amounts. In some embodiments, it is desirable to reduce or remove these impurities or intermediates. In some embodiments, the bio-based rinse solution comprises 3%, 2%, 1%, 0.5%, 0.1%, 0.05%, 0.01%, or 0.001% or less of total other bio-based solvents.

[0106] In addition to metals and low molecular weight organics, general particle contamination including nanometer to micron-sized particles derived from various other sources also causes device defects that negatively affect output. Therefore, as mentioned above, it is crucial to remove any trace particles from bio-based solvents. Specifically, according to the purification method, the particle size contained in the solvent is that the number of particles of 0.15 μm or larger can be, for example, 20 particles / mL or less, 10 particles / mL or less or even 5 particles / mL or less. Particle count is measured by liquid particle counting technology and by wafer measurement. For example, after a specified amount of solvent is deposited on a substrate and spun out with a specified number of revolutions, the wet particle amount is further dried under a specified number of revolutions, and then the number of defects on the substrate is determined by, for example, a KLASurfscan SP7 unpatterned wafer detection system.

[0107] Bio-based solvents can be characterized by their Hansen solubility parameters. Bio-based solvents herein should have a solubility parameter of about 14.5 MPa. 0.5 Up to 17MPa 0.5 The dispersion parameter, polar parameter and hydrogen bond parameter sum is about 14 MPa 0.5 Up to 20MPa 0.5 More specifically, the solvent is selected to have a dispersion parameter value of about 15 MPa. 0.5 Up to 16MPa 0.5 , or for example 15.4MPa 0.5 Up to 15.9MPa 0.5 ; and the sum of the polarity parameter and the hydrogen bond parameter is 15MPa 0.5 About 19MPa 0.5 , more preferably 15.5MPa 0.5 Up to 18.5MPa 0.5 .

[0108] Resin binder of the present invention is preferably a binder or alkali-insoluble binder with poor alkali solubility, which comprises one or more blocked (shielded) alkali solubilizing groups (acid-sensitive groups). Blocking some or all of the functionality in the alkali solubilizing groups is acid-sensitive. The presence of acid catalyzes the blocking removal (deblocking) of the alkali solubilizing groups, and makes the polymer become alkali-soluble. Suitable alkali solubilizing groups include but are not limited to carboxylic acids, sulfonic acids, phenols, acidic alcohols, hydroxyimide, hydroxymethylimide and silanol. Suitable acidic hydroxyl, carboxyl and sulfonamide are further described in U.S. Patent Application 2006 / 0110677.

[0109] Photoactive compounds that are capable of generating strong acids when exposed to a high energy radiation source are generally referred to as photoacid generators or PAGs. Any suitable photoacid generator may be used in the photosensitive compositions of the present invention. One skilled in the art will be able to select a suitable PAG based on factors such as acidity, catalytic activity, volatility, diffusivity, and solubility. Suitable types of PAGs that generate sulfonic acids include, but are not limited to, sulfonium salts or iodonium salts. The photoacid generator compounds are disclosed in, for example, 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 tris(perfluoroalkylsulfonyl)methides, tris(perfluoroalkylsulfonyl)imides and those that produce perfluoroalkylsulfonic acids.

[0110] Additional examples of suitable photoacid generators for use in the present invention include, but are not limited to, triphenylsulfonium perfluorooctane sulfonate, triphenylsulfonium perfluorobutane sulfonate, methylphenyldiphenylsulfonium perfluorooctane sulfonate, 4-n-butoxyphenyldiphenylsulfonium perfluorobutane sulfonate, 2,4,6-trimethylphenyldiphenylsulfonium perfluorobutane sulfonate, 2,4,6-trimethylphenyldiphenylsulfonium benzene sulfonate, 2,4,6-trimethylphenyldiphenylsulfonium 2,4,6-triisopropylbenzene sulfonate, phenylthiophenyldiphenylsulfonium 4-dodecylbenzene sulfonic acid, tri(tert-butylphenyl)sulfonium perfluorooctane sulfonate, tri(tert-butylphenyl)sulfonium perfluorobutane sulfonate, tri(tert-butylphenyl)sulfonium 2,4,6-triisopropylbenzene sulfonate, tri(tert-butylphenyl)sulfonium benzene sulfonate, and phenylthiophenyldiphenylsulfonium perfluorooctane sulfonate.

[0111] Suitable iodine for use in the present invention Examples of salts include, but are not limited to, diphenyl iodide Perfluorobutane sulfonate, bis(tert-butylphenyl) iodide Perfluorobutane sulfonate, bis(tert-butylphenyl) iodide Perfluorooctane sulfonate, diphenyl iodide Perfluorooctane sulfonate, bis(tert-butylphenyl) iodide Benzenesulfonate, bis(tert-butylphenyl)iodide 2,4,6-Triisopropylbenzenesulfonate, and diphenyl iodide 4-Methoxybenzenesulfonate.

[0112] Examples of tris(perfluoroalkylsulfonyl)methides and tris(perfluoroalkylsulfonyl)imide PAGs suitable for use in the present invention can be found in U.S. Patent Nos. 5,554,664 and 6,306,555, each of which is incorporated herein in its entirety. Additional examples of this type of PAG can be found in SPIE Conference Proceedings, Vol. 4690, pp. 817 to 828 (2002). Suitable methides 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.

[0113] Further examples of suitable photoacid generators for use in the present invention are 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-cyclohexylcarbonyl diazomethane, 2-methyl-2-(p-toluenesulfonyl)propiophenone, 2-methanesulfonyl-2-methyl-(4-methylthiopropiophenone, 2,4-methyl-2-(p-toluenesulfonyl)pentan-3-one, 1-diazo-1-methylsulfonyl-4-phenyl-2-butanone, 2-(cyclohexylcarbonyl-2-(p-toluenesulfonyl)propane, 1-cyclohexylsulfonyl-1-cyclohexylcarbonyldiazomethane, 1-diazo-1-cyclohexylsulfonyl Acyl-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 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.

[0114] More preferred PAGs are triarylsulfonium perfluoroalkylsulfonates and triarylsulfonium tris(perfluoroalkylsulfonyl)methides. Most preferred PAGs are triphenylsulfonium perfluorooctanesulfonate (TPS-PFOS), triphenylsulfonium perfluorobutanesulfonate (TPS-Nonaflate), methylphenyldiphenylsulfonium perfluorooctanesulfonate (TDPS-PFOS), tri(tert-butylphenyl)sulfonium perfluorobutanesulfonate (TTBPS-Nonaflate), triphenylsulfonium tris(trifluoromethylsulfonyl)methide (TPS-C1) and methylphenyldiphenylsulfonium tris(perfluoroethylsulfonyl)methide.

[0115] The total photoacid generator content of the photosensitive composition is about 0.05 weight % to about 20 weight % of the total solid content. The preferred range is about 1 weight % to about 15 weight %. The photoacid generator can be used alone or in combination with one or more photoacid generators. The percentage of each PAG in the photoacid generator mixture is about 10 weight % to about 90 weight % of the total photoacid generator mixture. The preferred photoacid generator mixture comprises about 2 or 3 photoacid generators. Such a mixture can be of the same kind or different kinds. The example of the preferred mixture includes sulfonium salt and bissulfonyldiazomethane compound, sulfonium salt and iminosulfonate and two kinds of sulfonium salts.

[0116] Base additives can also be added to the photosensitive composition as quenchers to act as diffusion control agents. One purpose of the base additive is to remove protons present in the photosensitive composition before being irradiated by actinic radiation. The base prevents attack and cleavage of acid-labile groups by undesirable acids, thereby improving the performance and stability of the photosensitive composition. In addition, the base can act as a diffusion control agent to prevent the photogenerated acid from migrating too far after exposure and reducing the resolution. The percentage of base in the photosensitive composition should be significantly lower than the photoacid generator, otherwise the photosensitivity becomes too low. When present, the preferred range of the base compound is from about 3% by weight to about 50% by weight of the photoacid generator compound. Suitable examples of base additives include, but are not limited to, cyclopropylamine, cyclobutylamine, cyclopentylamine, dicyclopentylamine, dicyclopentylmethylamine, dicyclopentylethylamine, cyclohexylamine, dimethylcyclohexylamine, dicyclohexylmethylamine, dicyclohexylethylamine, dicyclohexylbutylamine, cyclohexyltert-butylamine, cycloheptylamine, cyclooctylamine, 1-adamantanamine, 1-dimethylaminoadamantane, 1-diethylaminoadamantane, 2-adamantanamine, 2-dimethylaminoadamantane, 2-aminonorbornene, and 3-noradamantanamine, 2-methylaminoadamantane, 2-methylaminoadamantane, 2-methylaminoadamantane, 2-aminonorbornene ...methylaminoadamantane, 2-methylaminoadamantane, 2-methylaminoadamantane, 2-methylaminoadamantane, imidazole, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, triisopropylamine, trioctylamine, trilaurylamine, 4-dimethylaminopyridine, 4,4'-diaminodiphenyl ether, 2,4,5-triphenylimidazole, 1,4-diazabicyclo[4.3.0]non-5-ene and 1,5-diazabicyclo[4.3.0]non-5-ene, and 1,8-diazabicyclo[5.4.0]undec-7-ene, guanidine, 1,1-dimethylguanidine, 1,1,3,3-tetramethylguanidine, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-dimethylaminopyridine, 4-dimethylaminopyrimidine, 2-diethylaminopyridine, 2-(aminomethyl)pyridine, 2-amino-3-methylpyridine, 2-amino-4-methylpyridine, 2-amino-5-methylpyridine, 2-amino-6-methylpyridine, 3-aminoethylpyridine, 4-aminoethylpyridine, 3-aminopyrrolidine, piperazine, N-(2-aminoethyl)piperazine, N-(2-aminoethyl)piperidine, 4-amino-2,2, 6,6-tetramethylpiperidine, 4-piperidinopiperidine, 2-iminopiperidine, 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 base additives are trilaurylamine, 2,4,5-triphenylimidazole, 1,5-diazobicyclo[4.3.0]non-5-ene and 1,8-diazobicyclo[5.4.0]undec-7-ene.

[0117] Production of bio-based solvents

[0118] Bio-based solvents can be derived from bio-based materials, including sugars, starches, corn, natural fibers, sugar cane, beets, citrus fruits, woody plants, cellulosic products, lignocellulosic products, hemicelluloses, potatoes, vegetable oils, other polysaccharides such as pectin, chitin, fructan and pullulan, and combinations thereof. According to a specific embodiment, at least one bio-based material is selected from corn, sugar cane, beets, potatoes, starch, citrus fruits, woody plants, cellulose lignin, vegetable oils, natural fibers, oil-containing wood raw materials, and combinations thereof.

[0119] The production of homogeneous chemicals using bio-based materials involves processes that are significantly different from fossil fuel feedstocks. Crude oil feedstocks have low functionality, which makes them suitable for use as solvents or fuels directly after primary processing (e.g., cracking and isomerization). Functional groups such as C=O and OH are added to crude oil-derived feedstocks to produce bulk chemicals and specialty chemicals. Here, special attention is paid to ensuring selective addition of functional groups without over-functionalizing the substrate. In contrast, biomass-derived feedstocks such as cellulose and hemicellulose contain too much functionality to be used directly as fuels or bulk chemicals, so selective strategies for separation and defunctionalization are required.

[0120] The three conversion technologies for carbohydrates and cellulose include bioconversion (enzymatic fermentation), catalytic conversion (dehydration, rehydration, hydrogenation, hydrolysis, aldol condensation, hydrogenolysis, oxidation, etc.), and thermochemical and thermocatalytic conversion. Although the production of first-generation biofuels (bioethanol and biobutanol) has been recognized, the process relies on starch and sugar feeds, which compete with the food chain. The hydrolysis of cellulose feedstocks to fermentable sugars has been implemented as an alternative to bioalcohols as fuels to avoid food sources as raw materials. However, slow reaction rates, high costs and sensitivity of enzymes, and energy-intensive subsequent distillation and drying steps remain challenges to achieving cost-effectiveness in these processes. Thermocatalytic conversion provides an alternative to enzymatic fermentation for converting biomass (such as wood, bagasse or corn stover) into aromatic compounds. For example, a process for producing gases using zeolite-based catalysts and then converting these gases into benzene, xylene and toluene (bio-BTX) has been developed. Thermochemical processes such as gasification, pyrolysis, roasting and liquefaction require intense heating at elevated temperatures, thus bringing energy efficiency issues. In addition, the selectivity of bio-oil produced by pyrolysis is extremely poor, so expensive additional upgrading and separation steps are inevitably required. Finally, the catalytic conversion of cellulosic biomass and cellulose-derived intermediates into fuels, fuel additives and chemicals can be used. Various types of catalysts have shown potential in this field, such as precious metal catalyst systems for various key reaction steps such as hydrolysis, dehydration, hydrodeoxygenation (hydrodeoxygenation, HDO), hydrogenation and oxidation, thereby producing value-added products from cellulosic biomass. Examples of catalytically derived compounds include 5-hydroxymethylfurfural, furfural and acetic acid. However, high catalyst costs and catalyst poisoning continue to cause problems for these processes.

[0121] The latest progress of gene editing has the possibility of opening the field of bio-based solvent production. Clustered regularly spaced short palindromic repeats (clustered regularly interspaced short palindromic repeat, CRISPR) and CRISPR-related (Cas) systems are RNA-guided immune systems in bacteria and archaea, which have been engineered into efficient genome editing tools, which have been implemented in a wide range of organisms such as bacteria, yeast, plants, mammalian cells and human cells. In addition to single gene knock-in or knock-out, multiple genome editing and transcriptional regulation, including inhibition and activation, have also been successfully reported.

[0122] Clostridia is a bacterium that has been long studied for biobutanol production through its acetone-butanol-ethanol (ABE) fermentation pathway. Although great efforts have been invested in the metabolic engineering of solvent-producing Clostridia strains for increasing biobutanol production, only very limited success has been achieved. This is because, on the one hand, there are several inherent by-products in ABE fermentation that are difficult to eliminate, including fatty acids, acetone and ethanol; on the other hand, ABE fermentation for butanol production undergoes a biphasic process and is subject to complex metabolic regulation. Recent efforts have focused on improving the ABE fermentation pathway of Clostridia to reduce undesirable by-products while increasing the total yield of butanol. One method for achieving these improvements involves the use of a CRISPR-Cas9 system.

[0123] In one approach, as described in U.S. Pat. No. 11,142,751 B2, incorporated herein by reference, the endogenous CRISPR-Cas system of C. tyrobutyricum was used to successfully engineer C. tyrobutyricum to increase butanol production. By introducing the adhE2 gene and inactivating the native cat1 gene, the resulting mutant produced a record high of 26.2 g / L butanol in batch fermentation.

[0124] In addition, the production of biobased butyl acetate from glucose by microbial fermentation has been demonstrated by the following bacteria: Clostridium acetobutylicum NJ4, which produces butanol, when supplemented with exogenous acetic acid; Actinobacillus succinogenes 130z (ΔpflA), which produces acetate / ester, when exogenous butanol is added; and a microbial co-culture system of Clostridium acetobutylicum NJ4 and Actinobacillus succinogenes 130z (ΔpflA) when exogenous precursors are eliminated (14Biotechnol.Biofuels 203(2021)).

[0125] Alternatively, bio-based butyl acetate has also been produced by utilizing a solventogenic Clostridium for co-production of acyl-CoA, acids, and alcohols as precursors in combination with systems metabolic engineering, resulting in a strain that can produce 20.3 g / L butyl acetate (12 Nat. Commun. 4368 (2021)). Bio-based acetates such as n-butyl acetate can also be prepared from the corresponding bio-based ethanol, n-butanol by direct Fischer esterification and transesterification reactions with bio-based acetic acid or acetate.

[0126] These fermentation processes produce the desired butyl acetate and a mixture of significant levels of intermediates and impurities. For example, in the DOE Bioenergy Technologies Office (BETO) 2021 project peer review, Yi Wang, entitled "Bioproduction and Evaluation of Renewable Butyl Acetate as a Desirable Bioblendstock for Diesel Fuel" submitted on March 16, 2021, disclosed the following composition in the production of butyl acetate:

[0127] Chemicals NBA n-Butanol n-Hexadecane Isopropyl alcohol Ethyl acetate unknown Mass fraction (%) 94.3 3.8 0.4 0.134 0.118 1.248

[0128] The two-step bio-based process described in U.S. Patent Publication No. 2014 / 0329275 can convert glucose into methyl isobutyl ketone (MIBK), diisobutyl ketone (DIBK), or methyl isoamyl ketone (MIAK). The process utilizes a modified microorganism that converts glucose into isovaleric acid and isocaproate. These intermediate chemicals can then be converted to the corresponding ketones. These ketones can then be reduced to the corresponding alcohols, methyl isobutyl carbinol (MIBC), diisobutyl carbinol (DIBC), or methyl isoamyl carbinol (MIAC).

[0129] U.S. Patent 8,298,798 describes a metabolically modified microorganism for producing biofuels from bio-based feedstocks such as glucose, including higher alcohols, including C5 to C8 alcohols. The method is capable of producing 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 alcohol 5-methyl-1-heptanol.

[0130] Bio-based 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). As described in 1 Chemistry Select 6396 (2016), bio-based heptanol can be prepared by catalytic hydrocracking-hydrogenation of castor oil fatty acid methyl esters.

[0131] Process steps and additional synthetic methods not specifically described herein may also be found in references such as Oklu et al., Bio-Solvents: Synthesis, Industrial Production and Applications, in Solvents,IonicLiquidsandSolventEffects The synthesis and industrial production of biosolvents were reviewed in IntechOpen, London (2019).

[0132] Purification of bio-based solvents

[0133] As previously mentioned, solvents used in semiconductor manufacturing processes must generally have high to ultra-high purity. It is critical that the surface of the semiconductor wafer is not contaminated by any metal impurities present in the solvent, as metals inhibit the function of the semiconductor components. In fact, micro-contamination accounts for more than 50% of yield losses in IC manufacturing. Therefore, it is a natural requirement to minimize the metal impurity content of the materials used in these processes. Solvents must be purified to extremely low levels of metal content, for example, several parts per billion (ppb) to several parts per trillion (ppt) for each metal such as sodium, iron, etc.

[0134] Organic compounds or impurities may also cause pollution problems in the semiconductor manufacturing process. In addition to minimizing the amount of impurities in the solvent, it is also necessary to reduce or eliminate organic impurities. In particular, relatively low molecular weight organic compounds have brought major challenges to semiconductor processes because they may be difficult to remove by filtering techniques, thereby forming particle contamination, especially fine patterns (e.g., 30nm nodes or less). The possible way to introduce these organic impurities is through impure or unpurified solvents, or through containers or pipelines used in transportation or semiconductor formation processes. Therefore, it is necessary to think a lot about how to purify solvents and how to store solvents and the materials that solvents contact, to avoid the increase of impurities during storage or transportation, the denaturation of components, the quantitative change of composition, the increase of impure metal elements, or the quality reduction caused by the deterioration of photosensitive components caused by light.

[0135] In addition to metals and low molecular weight organics, general particle contamination including nanometer to micron-sized particles originating from various other sources also leads to device defects that negatively affect yields. Therefore, as mentioned above, it is crucial to remove any trace particles from bio-based solvents. Although the number of particles on the semiconductor surface would ideally be zero, the number of sources makes this almost impossible. The process for monitoring and detecting particle contamination is described in ISO 14644-1:2015 and ISO 21501-4, which are incorporated herein by reference.

[0136] Although not limited to the description herein, purification of bio-based solvents generally uses one or more of distillation, physical or chemical adsorption filtration or ion exchange membranes. Ultimately, one or more processes are used in such a way as to obtain the necessary purity and level of metals and low molecular weight organics as disclosed herein.

[0137] The distillation process can be used to purify bio-based solvents. Depending on the composition of the primary product from the process used, a multiphase distillation can be used, including a first distillation device for removing low-boiling impurities, a second distillation device for removing high-boiling impurities, and a third distillation device for removing trace water. The distillation device is selected from a multi-stage, packed distillation tower or a spiral rotating belt distillation tower. The rotating belt distillation tower is particularly useful for separating compounds and removing trace water to produce electronic grade purity solvents. A spiral stirring column made of metal or Teflon is provided inside the rotating belt distillation tower, and the spiral stirring column rotates at a high speed to maximize the contact area of ​​the vapor component evaporated in the tower and the liquid component condensed in the tower, so that high separation and purification efficiency can be obtained through fast and effective gas-liquid equilibrium. By changing the rotation speed of the spiral stirring column in the rotating belt distillation tower, the separation efficiency can be appropriately adjusted. The resulting high separation and purification efficiency makes it possible to remove trace water and easily separate and purify various components with similar boiling points into electronic grade purity.

[0138] If necessary, a metal removal step is adopted, which generally includes contacting the bio-based solvent with an acidic cation exchange resin. Various metals such as alkali metals, alkaline earth metals and transition metals, such as sodium, potassium, calcium, iron, nickel, etc., can be removed by a metal removal step. Commercially available strong acid cation exchange resins can be used in the present invention. Among them, the cation exchange resin of sulfonated styrene-divinylbenzene crosslinked polymer is preferred. There are two types of strong acid cation exchange resins, one is a porous type made of porous resin, and the other is a gel type made of non-porous resin. Suitable acid exchange resins can be obtained from Rohm and Haas, such as AMBERLYST 15 acidic ion exchange resins. These AMBERLYST resins generally contain up to 80,000 ppb to 200,000 ppb of sodium and iron. Before being used in the method of the present invention, the ion exchange resin should be treated with water and then treated with a mineral acid solution to reduce the metal ion level. It is important that the ion exchange resin is rinsed with a solvent that is the same as or at least compatible with the solvent to be purified. The procedures in this step can be similar to those disclosed in U.S. Pat. No. 5,284,930 and U.S. Pat. No. 5,288,850. Generally, the cation exchange process is carried out at any temperature, pressure and flow rate that achieves the desired end result. Liquid purifiers such as PURASOL and PROTEGO purifiers can be used to remove metal impurities.

[0139] A microfilter can be provided before and after the ion exchange resin treatment to remove the insoluble impurities contained in the solvent or the fine particles that may flow out from the ion exchange resin by filtering. A filter device with a filter medium having a pore size of 0.05 μm or less is generally used, and the solvent is circulated in the filter device, whereby the filter medium is passed through twice or more. Liquid filters based on various membranes and media can be used, such as the MICROGARD series filters from Entegris. In some embodiments, the microfilter comprises a polytetrafluoroethylene filter material. Such a method enables the effective removal of insoluble foreign matter, particles and metallic impurities with high polarity in the solvent. Specifically, according to the purification method, the number of particles with a particle size of 0.15 μm or more contained in the solvent can be, for example, 20 particles / mL or less, 10 particles / mL or less, or even 5 particles / mL or less. Particle counts are measured by liquid particle counting technology and by wafer measurement. For example, after depositing a specified amount of solvent on a substrate and spinning it off at a specified number of revolutions, the wet particle amount is further dried at a specified number of revolutions and then the number of defects on the substrate is determined by, for example, a KLASurfscan SP7 unpatterned wafer inspection system.

[0140] In addition to the above method for purifying the solvent, an additional step may include storing or treating the solvent in a material containing a perfluororesin, wherein the perfluororesin includes polytetrafluoroethylene resin (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer resin (FEP), ethylene tetrafluoroethylene copolymer resin (ETFE), ethylene chlorotrifluoroethylene copolymer resin (ECTFE), polyvinylidene resin (PVDF), polychlorotrifluoroethylene copolymer resin (PCTFE) or polyvinyl fluoride resin (PVF) can be exemplified. Such materials can reduce the amount of low molecular weight organic matter, metal impurities and other particles in the solvent.

[0141] In addition, according to the purification method, the amount of the metal element concentration of each of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni and Zn is preferably 5 ppb or less, and more preferably 3 ppb or less. Most preferably, there is no any one of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni and Zn. However, if there is any one of these metal elements, the minimum concentration of the existing metal element is generally 0.001 ppb or greater. The metal element concentration of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni and Zn can be measured according to inductively coupled plasma mass spectrometry (e.g., by Agilent Technologies, Inc. manufactured inductively coupled plasma mass spectrometer Agilent 7500cs (ICP-MS equipment)).

[0142] Patterning method

[0143] The photolithography pattern forming system utilizes the phenomenon that the solubility of the resist film in the developer changes by a chemical reaction initiated by light irradiation, and the resist that makes the light-irradiated part dissolve in the developer is called a positive system, and the resist that makes the non-light-irradiated part dissolve in the developer is called a negative system. The positive resist utilizes a chemical reaction such as polarity conversion to enhance the solubility in the developer, while the negative resist utilizes bond formation between molecules, such as a cross-linking reaction or a polymerization reaction.

[0144] Since the advent of resists for KrF excimer lasers (248 nm), an imaging method known as chemical amplification has been used to compensate for the reduction in sensitivity caused by light absorption. Positive chemical amplification is an imaging method in which an acid generator in the exposed area decomposes, and the generated acid is used as a reaction catalyst in baking after exposure (FEB: post-exposure baking). The resulting catalyst then converts alkali-insoluble groups into alkali-soluble groups, and the exposed area is removed by alkaline development (also known as positive tone development (PTD). In other words, a positive resist composition is a resin composition capable of forming a film whose solubility in an alkaline developer increases and whose solubility in a developer containing an organic solvent decreases due to a chemical reaction initiated by exposure to radiation.

[0145] Alternatively, chemically amplified resists that were originally designed to be developed in a positive tone with an aqueous alkaline developer can instead be developed with a negative tone development (NTD) using an organic developer that causes the unexposed portions of the resist film to be removed while leaving the exposed areas unaffected. The resist contrast of 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, a bio-based organic developer comprising an organic solvent can be used as a negative developer.

[0146] Regarding material-related parameters, controlling various physical values ​​(e.g., solubility parameters) related to the solubility of the positive resist composition in the developer and the organic solvent is effective for adjusting the performance. Specific examples thereof for the positive resist composition include the average molecular weight of the polymer species, molecular weight dispersity, monomer composition ratio, polarity of the monomers, monomer sequence, addition of polymer blends and low-molecular additives, and addition of surfactants.

[0147] In the pattern forming method of the present disclosure, the steps of forming a film on a substrate by using a resin composition whose solubility in a positive developer increases and whose solubility in a negative developer decreases when irradiated with actinic rays or radiation, the step of exposing the film, the step of heating (baking, also referred to as PEB (post-exposure baking)) the film, and the step of achieving development of the film can be performed by generally known methods.

[0148] In addition, specific examples of process-related parameters include film formation temperature and time, post-heating temperature and time after exposure, temperature during development, development time, nozzle system of development equipment (puddle method, dynamic spraying, etc.), and rinsing method after development.

[0149] Reference will now be made to an exemplary process flow showing a pattern forming method according to the present disclosure. Figures 1A to 1E Non-limiting examples of methods according to the present disclosure are described. Although the illustrated process flow describes a patterning method in which a single resist mask is used to transfer a photoresist pattern to an underlying substrate, the method can be used in other lithography processes, for example, in double patterning processes such as lithography-lithography-etch (LLE), lithography-etch-lithography-etch (LELE), or self-aligned double patterning (SADP), as an ion implantation mask, or in any other lithography process in which such photoresist pattern manipulation would be beneficial.

[0150] Figure 1A A substrate 100, which may include multiple layers and features, is depicted in cross section. The substrate may include materials such as semiconductors (e.g., silicon) or compound semiconductors (e.g., III to V or II to VI), glass, quartz, ceramics, copper, etc. Typically, the substrate is a semiconductor wafer, such as a single crystal silicon or a compound semiconductor wafer, and may have one or more layers and patterned features formed on the surface. One or more layers 102 to be patterned may be disposed above the substrate 100. Optionally, for example, when it is desired to form grooves in the substrate material, the underlying base substrate material itself may be patterned. In the case where the base substrate material itself is patterned, the pattern is considered to be formed in the layer of the substrate.

[0151] The layers may include, for example, one or more conductive layers, such as layers of aluminum, copper, molybdenum, tantalum, titanium, tungsten, alloys of such metals, nitrides of such metals, or silicides of such metals, doped with amorphous silicon or doped with polycrystalline silicon; one or more dielectric layers, such as layers of silicon oxide, silicon nitride, silicon oxynitride, or metal oxide; semiconductor layers, such as single crystal silicon; and combinations thereof. The layers to be etched may be formed by various techniques, such as chemical vapor deposition (CVD) such as plasma enhanced CVD (PECVD), low pressure CVD (LPCVD) or epitaxial growth, physical vapor deposition (PVD) such as 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 specific device.

[0152] Depending on the specific layer to be etched, the film thickness, and the photolithographic material and process to be used, it may be desirable to provide a hard mask layer 103 above the layer 102 and / or a bottom anti-reflective coating (BARC) 104 on which a photoresist layer 106 is to be coated. For example, for very thin resist layers, it may be desirable to use a hard mask layer when the layer to be etched requires a considerable etching depth, and / or when a specific etchant has poor resist selectivity. In the case of using a hard mask layer, the resist pattern to be formed may be transferred to the hard mask layer 103, which in turn may be used as a mask for etching the lower layer 102. Suitable hard mask materials and formation methods 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 include a single layer or a plurality of layers of different materials. The hard mask layer may be formed, for example, by CVD, PVD or spin coating techniques.

[0153] Bottom anti-reflective coatings may be desirable in cases where the substrate and / or underlying layers would otherwise reflect a significant amount of incident radiation during photoresist exposure, such that the quality of the pattern formed would be adversely affected. Such coatings can improve depth of focus, exposure latitude, line width uniformity, and CD control. Anti-reflective coatings are typically used when the resist is exposed to deep ultraviolet radiation (300nm or less) such as KrF (248nm), ArF (193nm), or EUV (13.5nm) radiation. Anti-reflective coatings may include a single layer or a plurality of different layers. Suitable anti-reflective materials and methods of formation are known in the art. Anti-reflective materials are commercially available, for example, available from DuPont (Wilmington, USA) as AR TM Those sold under a trademark, such as AR TM 3ARTM 40A and AR TM 124 anti-reflection material, DUV-30 series and DUV-40 series produced by Brewer Science, Inc., and ARC series (e.g., ARC29A) produced by Nissan Chemical Industries, Ltd. In addition, inorganic anti-reflection films can also be used as anti-reflection films. For example, anti-reflection films such as titanium, titanium dioxide, titanium nitride, chromium oxide, carbon, and amorphous silicon can be used.

[0154] A photoresist layer 106 formed of a chemically amplified photosensitive composition is disposed on the substrate above the antireflective layer (if any). The chemically amplified photosensitive composition generally comprises: (a) a matrix polymer having an acid-labile group whose solubility in an alkaline developer increases and whose solubility in an organic solvent decreases under the action of an acid; (b) a compound capable of generating an acid when irradiated with actinic rays or radiation, generally referred to as a photoacid generator; (c) a solvent that can be used to dissolve the components of the photoresist composition; and (d) optional other additives, wherein the other additives include at least one of the following: a resin having at least any one of a fluorine atom or a silicon atom, a basic compound, a surfactant, a carboxylic acid Dyes, plasticizers, photosensitizers, light absorbers, alkali-soluble resins, dissolution inhibitors and compounds for accelerating dissolution in developers.

[0155] A photoresist layer is disposed on the substrate above the antireflective layer 104 (if present). The photoresist composition can be applied to the substrate by spin coating, dip coating, roller coating or other conventional coating techniques. Among them, spin coating is typical. For spin coating, the solid content of the coating solution can be adjusted based on the specific coating equipment used, the viscosity of the solution, the speed of the coating tool and the amount of time allowed for spinning to provide the desired film thickness. The typical thickness of the photoresist layer 106 is about 1000 Å. to

[0156] Next, the photoresist layer 106 is typically soft-baked to minimize the solvent content in the layer, thereby forming a tack-free coating and improving the adhesion of the layer to the substrate. The soft bake can be performed on a hot plate or in an oven, with a hot plate being typical. The soft bake temperature and time will depend, for example, on the specific material and thickness of the photoresist. A typical soft bake is performed at a temperature of about 90° C. to 150° C. for a time of about 30 seconds to 90 seconds.

[0157] Next, the photoresist layer 106 is exposed to the activating radiation 108 passing through the photomask 110 to produce a solubility difference between the exposed area and the unexposed area. The exposure of the photoresist composition mentioned herein to the radiation activated to the composition indicates that the radiation can form a latent image in the photoresist composition. By activating radiation, the photomask has an optically transparent area and an optically opaque area corresponding to the exposed resist layer area and the unexposed resist layer area respectively. The exposure device used in the present disclosure is not limited in terms of light source wavelength, but for example, KrF excimer laser wavelength (248nm), ArF excimer laser wavelength (193nm), F2 excimer laser wavelength (157nm) and EUV light (13.5nm) can be applied. In the step of performing the exposure of the present disclosure, an immersion exposure method can be applied. The immersion exposure method is a technology for enhancing resolution, and according to the technology, exposure is performed by filling a high refractive index liquid (hereinafter sometimes referred to as "immersion liquid (immersion liquid)") between the projection lens and the sample. The exposure energy is generally about 10 mJ / cm 2 Up to 80mJ / cm 2 .

[0158] After the photoresist layer 106 is exposed, a post-exposure bake (PEB) is typically performed. PEB can be performed, for example, on a hot plate or in an oven. The conditions for PEB will depend, for example, on the specific photoresist composition and layer thickness. PEB is typically performed at a temperature of about 80° C. to 150° C. for a time of about 30 seconds to 90 seconds. A latent image defined by the boundaries between the polarity switching regions and the unswitched regions (corresponding to the exposed regions and the unexposed regions, respectively) is thereby formed.

[0159] The photoresist layer 106 is then developed using a bio-based developer to remove the unexposed areas of the layer, leaving a layer such as Figure 1B An exposure area of ​​a resist pattern 106′ having a plurality of features is shown. The features are not limited and may include, for example, a plurality of lines, columns and / or contact hole patterns, which allow such patterns to be formed in the underlying layer to be patterned. Regarding the negative development method, for example, a method of immersing a substrate in a bath filled with a developer for a fixed time (immersion method), a method of lifting the developer onto the surface of the substrate by the action of surface tension and keeping it stationary for a fixed time to perform development (puddle method), a method of spraying the developer onto the surface of the substrate (spraying method), and a method of continuously spraying the developer on a substrate rotating at a constant speed while scanning the developer spray nozzle at a constant rate (dynamic spray method) can be applied.

[0160] After the step of performing negative development with a bio-based developer, a step of stopping development by replacing with another solvent may be implemented. After the step of performing negative development, a step of washing the resist film with a rinsing solution containing a bio-based organic solvent is preferably provided. The cleaning treatment method is not particularly limited, but for example, a method of continuously spraying a rinsing solution on a substrate rotating at a constant speed (spin coating method), a method of immersing a substrate in a bath filled with a rinsing solution for a fixed time (immersion method), and a method of spraying a rinsing solution on the substrate surface (spraying method) can be applied.

[0161] In addition, the treatment of removing the bio-based developer or bio-based rinsing solution adhering to the pattern by using a supercritical fluid can be performed after the development or rinsing treatment. In addition, after development, rinsing or treatment with a supercritical fluid, a heat treatment can be performed to remove the solvent remaining in the pattern. The heating temperature is not particularly limited as long as a good resist pattern is obtained. In some embodiments, the heating temperature is about 40°C to 160°C. The heat treatment can be performed multiple times.

[0162] Using the resist pattern 106 as an etching mask, the BARC layer 104 is selectively etched to form a BARC pattern 104', exposing the underlying hard mask layer 103. Figure 1C Next, the hard mask layer is selectively etched using the resist pattern as an etching mask again, thereby producing a patterned BARC and hard mask layer 103 ′, as shown in FIG. Figure 1D As shown. Suitable etching techniques and chemicals for etching the BARC layer and the hard mask layer are known in the art and will depend, for example, on the specific materials of these layers. A dry etching process such as reactive ion etching is typical. Next, the resist pattern 106 and the patterned BARC layer 104′ are removed from the substrate using known techniques such as oxygen plasma ashing. Using the hard mask pattern 103′ as an etching mask, one or more layers 102 are then selectively etched. Suitable etching techniques and chemicals 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′ can then be removed from the substrate surface using known techniques, such as a dry etching process such as reactive ion etching or wet stripping. The resulting structure is as shown. Figure 1E The pattern of etched features 102' is shown. In an alternative exemplary method, it may be desirable to pattern layer 102 directly using photoresist pattern 106 without using hard mask layer 103. Whether direct patterning using a resist pattern can be used will depend on factors such as the materials involved, resist selectivity, resist pattern thickness, and pattern size.

[0163] Exemplary embodiments described herein include:

[0164] 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 comprises carbon-14 in an amount sufficient to produce at least 0.1 dpm / gC (disintegrations per gram of carbon per minute); and wherein the organic developer comprises each of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni and Zn at a metal element concentration of 5 ppb or less.

[0165] Embodiment 2: The composition according to embodiment 1, wherein the organic developer further comprises 1 ppb or less of an alkane or alkene having a carbon number of 22 or less; or 3 wt% or less of bio-based n-butanol.

[0166] Embodiment 3: A composition according to Embodiment 1 or Embodiment 2, wherein the organic developer comprises each of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni and Zn at a metal element concentration of 3 ppb or less; and optionally, one or both of the following: 0.5 ppb or less of alkanes or olefins having a carbon number of 22 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.

[0167] Embodiment 4: A composition according to any one of Embodiments 1 to 3, wherein the organic developer comprises each of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni and Zn at a metal element concentration of 1 ppb or less; and optionally, one or both of the following: 0.3 ppb or less of alkanes or olefins having a carbon number of 22 or less; and a total of 1 wt % or less of other bio-based solvents.

[0168] Embodiment 5: The composition of any one of Embodiments 1 to 4, wherein the organic developer comprises at least 90 wt% bio-based n-butyl acetate.

[0169] Embodiment 6: The composition of any one of Embodiments 1 to 4, wherein the organic developer comprises at least 95 wt% bio-based n-butyl acetate.

[0170] 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.

[0171] Embodiment 8: The composition of Embodiment 7, wherein the surfactant comprises an ionic or nonionic fluorine-based or silicon-based surfactant.

[0172] Embodiment 9: A composition according to any one of Embodiments 1 to 8, wherein the organic developer comprises at least 95 wt% of bio-based n-butyl acetate; 0 wt% to 2 wt% of an ionic or non-ionic fluorine-based or silicon-based surfactant; 1 ppb or less of an alkane or olefin having a carbon number of 22 or less; 1 ppb or less of a metal element concentration of each of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni and Zn; and a total of 1 wt% or less of other bio-based solvents.

[0173] Embodiment 10: The composition according to any one of Embodiments 1 to 9, wherein the organic developer further comprises 0.1 wt % to 10 wt % of a nitrogen-containing compound having the following structure:

[0174]

[0175] Where R 1 , R 2 and R 3 each independently represents a hydrogen atom, a hydroxyl group, a formyl group, an alkoxy group, an alkoxycarbonyl group, an optionally substituted C 1-30 Alkyl, optionally substituted C 3-30 cycloalkyl or aryl, or a group formed by two or more of these groups, and R 1 , R 2 and R 3 The two of them may be bonded to form a ring structure together with the nitrogen atom bonded thereto.

[0176] Embodiment 11: The composition of any one of Embodiments 1 to 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.

[0177] Embodiment 12: The composition of Embodiment 11, wherein the biobased n-butyl acetate comprises carbon-14 in an amount sufficient to produce a decay of at least 6.0 dpm / gC.

[0178] Embodiment 13: The composition of Embodiment 11, wherein the biobased n-butyl acetate comprises carbon-14 in an amount sufficient to produce a decay of at least 9.0 dpm / gC.

[0179] Embodiment 14: The composition of Embodiment 11, wherein the biobased n-butyl acetate comprises carbon-14 in an amount sufficient to produce a decay of at least 12.0 dpm / gC.

[0180] Embodiment 15: A pattern forming method, comprising: providing a semiconductor substrate; forming a resist film, comprising coating the semiconductor substrate with a resist composition having a certain solubility, wherein the solubility of the resist composition in an organic developer decreases when irradiated with actinic rays or radiation; exposing the resist film to actinic rays or electromagnetic radiation; and developing the resist film with the organic developer, wherein the organic developer comprises at least 25 weight percent of bio-based n-butyl acetate, wherein the bio-based n-butyl acetate comprises an amount of carbon-14 sufficient to produce a decay of at least 0.1 dpm / gC.

[0181] Embodiment 16: The method according to Embodiment 15, wherein after the resist film is exposed to actinic rays or electromagnetic radiation, the solubility of the resist composition in the organic developer is in the ratio m sv / m su Described as 25 or less, where m sv is the amount of resist composition m dissolved per unit mass su The mass of solvent required for the organic developer.

[0182] Embodiment 17: The method according to Embodiment 15 or Embodiment 16 also includes forming an integrated circuit on the semiconductor substrate.

[0183] Embodiment 18: The method of embodiment 17, wherein the transistor density of the integrated circuit is 3×10 7 Transistors / mm 2 .

[0184] Embodiment 19: A method according to any one of Embodiments 15 to 18, wherein the organic developer comprises one or more of the following: 1 ppb or less of alkanes or olefins having a carbon number of 22 or less; 5 ppb or less of a metal element concentration of each of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni and Zn; and 3 wt % or less of bio-based n-butanol.

[0185] Embodiment 20: A method according to any one of embodiments 15 to 19, wherein the organic developer comprises one or more of the following: 0.5 ppb or less of alkanes or olefins having a carbon number of 22 or less; 3 ppb or less of each of the metal element concentrations of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni and Zn; 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.

[0186] Embodiment 21: A method according to any one of Embodiments 15 to 21, wherein the organic developer comprises one or more of the following: 0.3 ppb or less of alkanes or olefins having a carbon number of 22 or less; 2 ppb or less of a metal element concentration of each of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni and Zn; and a total of 1 wt % or less of other bio-based solvents.

[0187] Embodiment 22: The method of any one of Embodiments 15 to 21, wherein the organic developer comprises at least 90 wt% bio-based n-butyl acetate.

[0188] Embodiment 23: The method of any one of Embodiments 15 to 22, wherein the organic developer comprises at least 95% by weight of bio-based n-butyl acetate.

[0189] Embodiment 24: The method according to any one of Embodiments 15 to 23, wherein the organic developer further comprises 0.001 wt % to 5 wt % of a surfactant.

[0190] Embodiment 25: A method according to Embodiment 24, wherein the surfactant comprises an ionic or non-ionic fluorine-based or silicon-based surfactant.

[0191] Embodiment 26: The method according to any one of Embodiments 15 to 25, wherein the organic developer further comprises 0.1 wt % to 10 wt % of a nitrogen-containing compound having the following structure:

[0192]

[0193] Where R 1 , R 2 and R 3 each independently represents a hydrogen atom, a hydroxyl group, a formyl group, an alkoxy group, an alkoxycarbonyl group, an optionally substituted C 1-30 Alkyl, optionally substituted C 3-30 cycloalkyl or aryl, or a group formed by two or more of these groups, and R 1 , R 2 and R 3 The two of them may be bonded to form a ring structure together with the nitrogen atom bonded thereto.

[0194] Embodiment 27: The method of any one of Embodiments 15 to 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.

[0195] Embodiment 28: The method of Embodiment 27, wherein the biobased n-butyl acetate comprises carbon-14 in an amount sufficient to produce a decay of at least 6.0 dpm / gC.

[0196] Embodiment 29: The method of Embodiment 27, wherein the biobased n-butyl acetate comprises carbon-14 in an amount sufficient to produce a decay of at least 9.0 dpm / gC.

[0197] Embodiment 30: The method of Embodiment 27, wherein the biobased n-butyl acetate comprises carbon-14 in an amount sufficient to produce a decay of at least 12.0 dpm / gC.

[0198] Embodiment 31: The method according to any one of Embodiments 15 to 30, further comprising a step of rinsing the semiconductor substrate with a rinsing solution after the developing step.

[0199] Embodiment 32: A method according to Embodiment 31, wherein the rinse solution comprises at least one bio-based organic solvent, and each of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni and Zn at a metal element concentration of 5 ppb or less, and the at least one bio-based organic solvent comprises an amount of carbon-14 (C-14) sufficient to produce a decay of at least 0.1 dpm / gC.

[0200] Embodiment 33: A method according to embodiment 31 or embodiment 32, wherein the at least one bio-based organic solvent is selected from one or more of the following: hydrocarbon-based solvents, ketone-based solvents, ester-based solvents, alcohol-based solvents, amide-based solvents, ether-based solvents, and combinations thereof.

[0201] Embodiment 34: The method of any one of Embodiments 31 to 33, wherein the at least one bio-based organic solvent is selected from 1-hexanol, methyl isobutyl carbinol, 2-hexanol, 1-heptanol, 2-heptanol, and combinations thereof.

[0202] 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.

[0203] Embodiment 36: The method of Embodiment 35, 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.

[0204] Embodiment 37: The method of Embodiment 35, 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.

[0205] Embodiment 38: The method of Embodiment 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.

[0206] Embodiment 39: A rinse composition comprising: at least 25 wt% of at least one bio-based organic rinse solvent, the at least one bio-based organic rinse solvent being selected from one or more of the following: hydrocarbon-based solvents, ketone-based solvents, ester-based solvents, alcohol-based solvents, amide-based solvents, ether-based solvents, and combinations thereof; wherein the bio-based organic rinse solvent comprises carbon-14 in an amount sufficient to produce at least 0.1 dpm / gC (disintegrations per gram of carbon per minute) of decay; and wherein the rinse composition comprises each of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni and Zn at a metal element concentration of 5 ppb or less.

[0207] Embodiment 40: The rinse composition of Embodiment 39, wherein the rinse composition further comprises 1 ppb or less of an alkane or alkene having a carbon number of 22 or less; or 3 wt% or less of bio-based methyl isobutyl ketone.

[0208] Embodiment 41: A rinse composition according to Embodiment 39 or Embodiment 40, wherein the rinse composition comprises each of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni and Zn at a metal element concentration of 3 ppb or less; and optionally, one or both of the following: 0.5 ppb or less of alkanes or olefins having a carbon number of 22 or less; 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.

[0209] Embodiment 42: A rinse composition according to any one of Embodiments 39 to 41, wherein the rinse composition comprises each of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni and Zn at a metal element concentration of 2 ppb or less; and optionally, one or both of the following: 0.3 ppb or less of alkanes or olefins having a carbon number of 22 or less; and a total of 1 wt% or less of other bio-based solvents.

[0210] 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 one or more of the following: 1-hexanol, methyl isobutyl carbinol, 2-hexanol, 1-heptanol, 2-heptanol, methyl isoamyl carbinol, diisobutyl carbinol, and combinations thereof.

[0211] Embodiment 44: A rinse composition according to any one of Embodiments 39 to 43, wherein the at least one bio-based organic solvent is at least 90 weight percent of one or more of the following: bio-based 1-hexanol, bio-based methyl isobutyl carbinol, bio-based 2-hexanol, bio-based 1-heptanol, bio-based 2-heptanol, bio-based methyl isoamyl carbinol, and bio-based diisobutyl carbinol.

[0212] Embodiment 45: A rinse composition according to any one of Embodiments 39 to 44, wherein the at least one bio-based organic solvent is at least 95 weight percent of one or more of the following: bio-based 1-hexanol, bio-based methyl isobutyl carbinol, bio-based 2-hexanol, bio-based 1-heptanol, bio-based 2-heptanol, bio-based methyl isoamyl carbinol, and bio-based diisobutyl carbinol.

[0213] Embodiment 46: The composition of any one of Embodiments 39 to 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.

[0214] 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.

[0215] 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.

[0216] 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.

[0217] Embodiment 50: A photoresist composition comprising: a polymer binder, or a mixture of polymer binders, which becomes alkaline soluble by the action of an acid to remove protective acid-sensitive groups on the polymer binder; at least one photoacid generator (PAG) which decomposes when exposed to a high energy source and generates a photoacid strong enough to remove protective acid-sensitive groups on the polymer binder; at least one bio-based organic solvent; and optionally, at least one base as a quencher; and wherein the bio-based organic solvent comprises 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; and wherein the organic solvent comprises each of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni and Zn at a metal element concentration of 5 ppb or less.

[0218] Embodiment 51: The composition of Embodiment 50, wherein the bio-based organic solvent further comprises 1 ppm or less of alkanes or alkenes having a carbon number of 22 or less; or 3 wt% or less of bio-based n-butanol.

[0219] Embodiment 52: A composition according to embodiment 50 or embodiment 51, wherein the bio-based organic solvent comprises a metal element concentration of 3 ppm or less of each of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni and Zn; and optionally, one or both of the following: 0.5 ppm or less of alkanes or alkenes having a carbon number of 22 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.

[0220] Embodiment 53: A composition according to any one of Embodiments 50 to 53, wherein the bio-based organic solvent comprises a metal element concentration of 2 ppm or less of each of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni and Zn; and optionally, one or both of the following: 0.3 ppm or less of alkanes or alkenes having a carbon number of 22 or less; and a total of 1 wt% or less of other bio-based solvents.

[0221] Embodiment 54: The composition of any one of Embodiments 50 to 54, wherein the bio-based organic solvent comprises at least 90 wt% bio-based n-butyl acetate.

[0222] Embodiment 55: The composition of any one of Embodiments 50 to 55, wherein the bio-based organic solvent comprises at least 95% by weight bio-based n-butyl acetate.

[0223] 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.

[0224] Embodiment 57: A composition according to Embodiment 56, wherein the surfactant comprises an ionic or non-ionic fluorine-based or silicon-based surfactant.

[0225] Embodiment 58: A composition according to any one of Embodiments 50 to 57, wherein the bio-based organic solvent comprises at least 95 wt% bio-based n-butyl acetate; 0.3 ppm or less of alkanes or alkenes having a carbon number of 22 or less; 2 ppm or less of each of the metal element concentrations of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni and Zn; and a total of 1 wt% or less of other bio-based solvents.

[0226] Example

[0227] Example 1. Formation of the bio-based developer n-butyl acetate (NBA).

[0228] Bio-based NBA is produced by fermentation of glucose or glycerol in a bioreactor as described in 12 Nat. Commun. 4368 (2021). The fermentation is carried out in a two-phase system in a slurry bottle, where 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 hexadecane is removed and distilled to separate the purified NBA. Metals are removed by treatment with ion exchange beads and / or through a purifier, and particles are removed by passing the solvent through a PTFE filter with a pore size of 0.05 μm. Additional purification steps are performed to reduce the content of low molecular weight organic compounds and metal concentrations. The final bio-based NBA negative developer contains: 1 ppb or less of alkanes or olefins having a carbon number of 22 or less, as measured by a gas chromatography mass spectrometer GCMS-QP2010 manufactured by Shimadzu Corporation connected to a pyrolysis device PY2020D manufactured by Frontier Lab; 5 ppb or less of each of the metal element concentrations of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni and Zn, as measured by an inductively coupled plasma mass spectrometer Agilent 7500cs (ICP-MS equipment) manufactured by Agilent Technologies, Inc.; and 3 wt % or less of bio-based n-butanol, as measured by a liquid scintillation counter method (LSC).

[0229] Example 2. Formation of the bio-based developer n-butyl acetate (NBA).

[0230] Biobased NBA was produced by fermentation of FadM homologues from Providencia sneebia in a bioreactor, such as 61 MetabolicEngineering 335-343 (2020). The product was purified as described in Example 1 above. The final product was separated and analyzed. The analysis showed that the bio-based NBA developer contained 0.5 ppb or less of an alkane or olefin having a carbon number of 22 or less; 1 ppb or less of each of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni and Zn in a metal element concentration; and 0.1 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.

[0231] Example 3. Formation of Bio-based Methyl Isobutyl Carbinol

[0232] The two-step bio-based process described in U.S. Patent Publication No. 2014 / 0329275 converts glucose into methyl isobutyl ketone (MIBK). The process utilizes modified microorganisms to convert glucose into isovaleric acid and isocaproate, which are then converted into the corresponding ketones. The ketone is then reduced to the corresponding alcohol, methyl isobutyl carbinol (MIBC). The resulting MIBC is processed to the desired purity by distillation, removal of metals using ion exchange or purifiers to produce 3 ppb or less metal element concentrations of each of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn, and PTFE filtration to remove particles (via, for example, KLA 20 particles / mL or less as determined by SP7 unpatterned wafer inspection system).

[0233] Example 4. Formation of Bio-based Hexanol

[0234] According to the method described in 10 Front. Bioeng. Biotechnol., art. 850370 (2022), bio-based hexanol is produced by fermentation of syngas using Clostridium monoxide-eating P7. The resulting hexanol is treated to the desired purity by distillation, removal of metals using ion exchange or purifiers, and filtration to remove particles.

[0235] Example 5. Formation of bio-based heptanol

[0236] Bio-based 1-heptanol is derived from a renewable castor oil source supplied by Arkema. The heptanol is processed to the desired purity (97 wt%) by distillation, metal removal using ion exchange or purifiers to produce 1 ppb or less metal element concentrations of each of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni and Zn, and PTFE filtration to remove particulates (via, for example, KLA 20 particles / mL or less as determined by SP7 unpatterned wafer inspection system).

[0237] Example 5. Identification of Developers and Rinsers as Bio-based

[0238] The following samples were measured in a blind test mode to determine the presence of C-14 content by liquid scintillation counting. The results are shown in Table 2. As shown in Table 2, samples derived entirely from petroleum (Comparative Example A and Comparative Example B) contain negligible amounts of C-14 measured according to dpm / gC, indicating that approximately zero percent of the samples are made from bio-based materials. In contrast, samples containing materials known to be derived from bio-based materials show higher levels of C-14 measured according to dpm / gC.

[0239] Table 2

[0240] ID Sample description (dpm / gC) Comparative Example A NBA (derived entirely from oil) <0.01 Example 1 Bio-based NBA 13.5±0.1 Comparative Example B MIBC (completely derived from petroleum) <0.01 Example 3 Bio-based MIBC 13.2±0.2 Example 4 Bio-based 1-hexanol 13.4±0.1 Example 5 Bio-based 1-Heptanol 13.3±0.2

[0241] Example 6. Photolithography process for NTD patterning, development and rinsing

[0242] In Tokyo Electron Ltd.(TEL)CLEAN TRACK TM AR for Act 8 coating equipment TM 3-600 organic bottom anti-reflective coating (BARC) material (DuPont) was used to coat 200 mm silicon wafers and baked at 205 °C for 60 seconds until The thickness of the UV coating is TM 217G-0.25 polyhydroxystyrene-based photoresist (DuPont) was coated over the BARC layer and the wafer was soft-baked at 130°C for 60 seconds to The coated wafers were exposed to KrF (248 nm) radiation on a Canon FPA-5000ES4 DUV scanner with NA = 0.68, conventional illumination (σ, 0.75) using a duplex mask with a 140 nm dense (1:1 line spacing) groove pattern. TMThe wafer was post-exposure baked at 125°C for 60 seconds on an Act 8 coating tool, developed with bio-based n-butyl acetate for 45 seconds, rinsed with bio-based methyl isobutyl carbinol, and spin-dried. The resist pattern was then examined using a scanning electron microscope, which showed the expected line-space pattern.

[0243] EPIC TM 3013ArF photoresist (Rohm and Haas Electronic Materials LLC) spin-coated on an organic bottom anti-reflective coating (BARC AR TM 124 23nm / AR TM 26N 77nm (Rohm and Haas Electronic Materials LLC)) and soft-baked at 110°C for 60 seconds until The thickness of OPTICOAT TM OC2000 top coating material (Rohm and Haas Electronic Materials LLC) was coated on the resist to form an immersion top coating. The coated wafer was exposed with an ASML ArF 1900i immersion scanner (where NA = 1.35, dipole 35Y illumination (0.9 / 0.635σ), plus x polarization) and post-exposure baked (PEB) at 100°C for 60 seconds. The CLEAN TRACK TM The coated wafers were developed on the coating apparatus with bio-based n-butyl acetate from Example 1 for 45 seconds, rinsed with bio-based methyl isobutyl carbinol from Example 3, and spin dried.

[0244] Example 7. Photolithography process for NTD patterning, development and rinsing

[0245] The procedure of Example 6 was repeated with the following modifications: the coated wafers were developed with bio-based n-butyl acetate from Example 1 for 45 seconds, rinsed with bio-based 1-hexanol from Example 4, and cleaned on a Tokyo Electron Ltd. (TEL) CLEAN TRACK TM Spin dry on coating equipment.

[0246] Example 8. Photolithography process for NTD patterning, development and rinsing

[0247] The procedure of Example 6 was repeated with the following modifications: the coated wafers were developed with bio-based n-butyl acetate from Example 1 for 45 seconds, rinsed with bio-based 1-heptanol from Example 4, and cleaned on a Tokyo Electron Ltd. (TEL) CLEAN TRACK TM Spin dry on coating tool.

Claims

1. A composition comprising: a) an 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 at least 0.1 dpm / gC (disintegrations per minute per gram of carbon); and b) wherein the organic developer contains each of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni and Zn at a metal element concentration of 5 ppb or less.

2. The composition according to claim 1, wherein the organic developer further comprises: i) 1 ppb or less of alkanes or alkenes having a carbon number of 22 or less; or ii) 3 wt% or less bio-based n-butanol.

3. The composition according to claim 1, wherein the organic developer comprises each of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni and Zn at a metal element concentration of 3 ppb or less; and optionally, one or both of the following: i) 0.5 ppb or less of alkanes or olefins having a carbon number of 22 or less; and ii) 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.

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

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

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

7. The composition according to 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 nonionic fluorine-based or silicon-based surfactant.

9. The composition of claim 1, wherein the organic developer comprises: a) at least 95% by weight of bio-based n-butyl acetate; b) 0 to 2 wt% of an ionic or nonionic fluorine-based or silicon-based surfactant; c) 1 ppb or less of alkanes or alkenes having a carbon number of 22 or less; d) each of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn at a metal element concentration of 1 ppb or less; and e) 1 wt % or less of other bio-based solvents.

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

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

12. The composition of claim 10, wherein the biobased n-butyl acetate comprises carbon-14 in an amount sufficient to produce a decay of at least 9.0 dpm / gC.

13. The composition of claim 10, wherein the biobased n-butyl acetate comprises carbon-14 in an amount sufficient to produce a decay of at least 12.0 dpm / gC.

14. A method for forming a pattern, include: a) providing a semiconductor substrate; b) forming a resist film, comprising coating the semiconductor substrate with a resist composition having a solubility, wherein the solubility of the resist composition in an organic developer decreases upon irradiation with actinic rays or radiation; c) exposing the resist film to actinic rays or electromagnetic radiation; as well as d) developing the resist film with the organic developer, the organic developer comprising at least 25 wt% of 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.

15. The method according to claim 14, wherein after exposing the resist film to actinic rays or electromagnetic radiation, the solubility of the resist composition in the organic developer is adjusted according to the ratio m sv / m su Described as 25 or less, where m sv is the amount of resist composition m dissolved per unit mass su The mass of solvent required for the organic developer. The method of claim 14 , further comprising forming an integrated circuit on the semiconductor substrate.

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

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

19. The method according to any one of claims 14 to 16, wherein the organic developer comprises one or more of: a) 0.5 ppb or less of alkanes or alkenes having a carbon number of 22 or less; b) 3 ppb or less of each of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn; and c) 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.

20. The method according to any one of claims 14 to 16, wherein the organic developer comprises one or more of: a) 0.3 ppb or less of alkanes or alkenes having a carbon number of 22 or less; b) 2 ppb or less of each of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn; and c) 1 wt % or less of other bio-based solvents.

21. A method according to any one of claims 14 to 16, wherein the organic developer comprises at least 90% by weight bio-based n-butyl acetate.

22. A method according to any one of claims 14 to 16, wherein the organic developer comprises at least 95% by weight bio-based n-butyl acetate.

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

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

25. The method of any one of claims 14 to 16, wherein the biobased n-butyl acetate comprises carbon-14 in an amount sufficient to produce at least 3.0 dpm / gC of decay.

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

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

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

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

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

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

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. 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. 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. 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. 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 one or more of the following: a hydrocarbon-based solvent, a ketone-based solvent, an ester-based solvent, an alcohol-based solvent, an amide-based solvent, an ether-based solvent, and combinations thereof; b) wherein the bio-based organic rinse solvent comprises carbon-14 in an amount sufficient to produce at least 0.1 dpm / gC of decay; and c) wherein the rinse composition comprises each of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni and Zn at a metal element concentration of 5 ppb or less.

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

39. The rinse composition of claim 37, wherein the rinse composition comprises each of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni and Zn at a metal element concentration of 3 ppb or less; and optionally, one or both of the following: i) 0.5 ppb or less of alkanes or olefins having a carbon number of 22 or less; and ii) 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.

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

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

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

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

44. The composition of any one of claims 37 to 40, wherein the biobased n-butyl acetate comprises carbon-14 in an amount sufficient to produce at least 3.0 dpm / gC of decay.

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

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

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

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