Bio-derived organic solvents

Abstract

This disclosure relates to a method and system for purifying bio-derived organic solvents. The purified bio-derived organic solvents can be used in multi-step semiconductor manufacturing processes.

Description

[Technical Field]

[0001] Cross-reference of related applications This application claims priority to U.S. Provisional Patent Application No. 63 / 472,011, filed on 9 June 2023, the contents of which are incorporated herein by reference.

[0002] This disclosure relates to bio-derived organic solvents, as well as systems and methods for the purification and / or use of such solvents. [Background technology]

[0003] The requirements for dielectric materials for semiconductor packaging applications are constantly evolving. Trends in electronics packaging continue to move towards faster processing speeds, increasing complexity, and higher packaging densities, while maintaining high levels of reliability. As electronics packaging technology advances and chips become smaller, the demand for innovative, high-performance, and environmentally friendly solvents is growing. The development and awareness of sustainable solvents is a field of interest in both research and the chemical industry, given the significant impact solvents can have on pollution, energy use, air quality, and climate change. To make semiconductor manufacturing safer and more sustainable, it is desirable to use bio-based solvents that are safer, more efficient, and more environmentally friendly than those currently in use. [Overview of the Initiative] [Problems that the invention aims to solve]

[0004] This disclosure is based on the unexpected discovery that certain purified bio-derived organic solvents can be used in dielectric film-forming compositions for forming dielectric films having relatively low film shrinkage rates, relatively low dielectric constants and / or dielectric loss tangents, and relatively high glass transition temperatures (Tg) (e.g., Tg higher than the reflow temperature of solder paste (e.g., 260°C)). [Means for solving the problem]

[0005] In one embodiment, the present disclosure is characterized by a method for purifying a bio-derived organic solvent, the method comprising: (1) an ion exchange filter comprising a housing and an ion exchange filter comprising at least one first ion exchange filter and at least one second ion exchange filter located in the housing, wherein at least one first ion exchange filter and at least one second ion exchange filter are both negatively charged ion exchange filters and are connected in series, and at least one first ion exchange filter is different from at least one second ion exchange filter, the ion exchange filter unit (1) passing a bio-derived organic solvent through; (2) passing the bio-derived organic solvent through at least one column containing an adsorbent to remove water from the bio-derived organic solvent; and (3) distilling the bio-derived organic solvent in a distillation column to obtain a purified bio-derived organic solvent, wherein the bio-derived organic solvent is obtained from a biological raw material, the purified bio-derived organic solvent contains an amount of acid components (e.g., organic acids and / or inorganic acids) by mass of about 0.1 ppb to about 1000 ppm, and the purified bio-derived organic solvent contains an amount of water by mass of about 0.1 ppb to about 1000 ppm.

[0006] In another aspect, the disclosure features a method for purifying a bio-derived organic solvent, the method comprising: (1) passing the bio-derived organic solvent through at least one column containing an adsorbent to remove water from the bio-derived organic solvent; and (2) an ion exchange filter comprising a housing and at least one first ion exchange filter and at least one second ion exchange filter located within the housing, wherein at least one first ion exchange filter and at least one second ion exchange filter are both negatively charged ion exchange filters and are connected in series, and at least one (3) passing the bio-derived organic solvent through an ion exchange filter unit, wherein the first ion exchange filter is different from at least one second ion exchange filter; and (4) distilling the bio-derived organic solvent in a distillation column to obtain a purified bio-derived organic solvent, wherein the bio-derived organic solvent is obtained from a biological raw material, the purified bio-derived organic solvent contains an amount of acid components (e.g., organic acids and / or inorganic acids) by mass of about 0.1 ppb to about 1000 ppm, and the purified bio-derived organic solvent contains an amount of water by mass of about 0.1 ppb to about 1000 ppm.

[0007] In another aspect, the present disclosure features purified bio-derived organic solvents produced from the purification methods described herein.

[0008] In another embodiment, the disclosure features a purified bio-derived organic solvent, the bio-derived organic solvent obtained from a biological raw material, the bio-derived organic solvent containing an acid component in an amount of about 0.1 ppb to about 1000 ppm by mass, and the bio-derived organic solvent containing water in an amount of about 0.1 ppb to about 1000 ppm by mass.

[0009] In another embodiment, the present disclosure features a method for producing a polymer, the method comprising forming a polymer comprising a polyimide precursor polymer, a polybenzoxazole precursor polymer, or a fully imidized polyimide polymer in a solvent system comprising at least one first organic solvent and optionally at least one second organic solvent, wherein the at least one first organic solvent comprises a purified bio-derived organic solvent as described herein, the bio-derived organic solvent being an aprotic polar solvent selected from the group consisting of lactones, ketones, ethers, alkyl aromatic compounds, and alkyl alicyclic compounds, and the at least one second organic solvent comprising a carbonyl moiety.

[0010] In another embodiment, the present disclosure features a photosensitive composition comprising (1) at least one resin selected from the group consisting of epoxy resins, novolac resins, polyamide resins, polybenzoxazole precursor polymers, polyimide precursor polymers, and fully imidized polyimide polymers; and (2) a solvent system comprising at least one first organic solvent and optionally at least one second organic solvent, wherein the at least one first organic solvent comprises a purified bio-derived organic solvent as described herein, the bio-derived organic solvent being a solvent selected from the group consisting of lactones, ketones, ethers, alcohols, alkyl aromatic compounds, and alkyl alicyclic compounds, and the at least one second organic solvent comprising a carbonyl group.

[0011] In another aspect, this disclosure is: a) At least one dielectric polymer comprising an epoxy resin, a novolac resin, a polyamide resin, a polybenzoxazole precursor polymer, a polyimide precursor polymer, or a fully imidized polyimide polymer in a solvent system comprising at least one first organic solvent and optionally at least one second organic solvent, wherein the at least one first organic solvent comprises a purified bio-derived organic solvent as described herein, the bio-derived organic solvent being a solvent selected from the group consisting of lactones, ketones, ethers, alcohols, alkyl aromatic compounds, and alkyl alicyclic compounds, and the at least one second organic solvent is at least one dielectric polymer comprising a carbonyl moiety; b) At least one solubility switching compound (SSC); c) At least one catalyst capable of inducing a polymerization reaction; d) Optionally, at least one inorganic filler; and e) Optionally, at least one metal-containing (meth)acrylate compound, The present invention is characterized by a dielectric film forming composition containing [a specific compound].

[0012] In another aspect, this disclosure is: a) At least one cyanate ester compound containing at least two cyanate groups; b) At least one dielectric polymer comprising epoxy resin, novolac resin, polyamide polymer, polybenzoxazole precursor polymer, polyimide precursor polymer, or fully imidized polyimide polymer; and c) At least one purified bio-derived organic solvent as described herein, The present invention is characterized by a dielectric film forming composition containing [a specific compound].

[0013] In another embodiment, the present disclosure features a dry film comprising a carrier substrate and a dielectric film supported on the carrier substrate, wherein the film is manufactured from a dielectric film-forming composition described herein.

[0014] In another aspect, the present disclosure features a patterning method comprising: (a) disposing a photosensitive composition described herein on a substrate to form a film; (b) exposing the film to radiation, heat, or a combination thereof; and (c) developing the exposed film using an organic developer to form a pattern on the substrate, wherein the organic developer comprises a purified bio-derived organic solvent described herein.

[0015] In another aspect, the present disclosure a) depositing a dielectric film-forming composition described herein on a substrate to form a dielectric film; b) exposing the dielectric film to radiation or heat or a combination of radiation and heat; c) developing the exposed film using an organic developer to form a patterned dielectric film having openings, wherein the organic developer comprises a purified bio-derived organic solvent described herein.

[0016] In another aspect, the present disclosure features processes for depositing a metal layer. These processes include: a) depositing a dielectric film-forming composition described herein on a substrate to form a dielectric film; b) exposing the dielectric film to radiation or heat or a combination of radiation and heat; c) patterning the dielectric film to form a patterned dielectric film having openings; d) optionally, depositing a seed layer on the patterned dielectric film; and e) depositing a metal layer in at least one opening in the patterned dielectric film. including.

[0017] In another aspect, the present disclosure features processes for forming a dielectric film on a substrate. These processes include: a) Providing a substrate comprising a conductive metal wire structure (which may contain copper) forming a network of lines and interconnects on the substrate; b) Depositing a dielectric film-forming composition described herein on the substrate to form a dielectric film; and c) Exposing the dielectric film to radiation or heat or a combination of radiation and heat, is included.

[0018] In yet another aspect, the present disclosure features a three-dimensional object manufactured by the process described herein. In some embodiments, the object comprises at least two or three stacks of dielectric films.

Mode for Carrying Out the Invention

[0019] In the present disclosure, "ppm" means "parts per million (10 -6 )", "ppb" means "parts per billion (10 -9 )", and "ppt" means "parts per trillion (10 -12 )". As defined herein, unless otherwise specified, it should be understood that all percentages expressed are weight percentages based on the total weight of the composition. The term "solvent" referred to herein means, unless otherwise specified, a single solvent or a combination of two or more (e.g., 3 or 4) solvents.

[0020] Bio-derived organic solvent Generally, the present disclosure relates to a purified bio-derived organic solvent. As used herein, "bio-derived organic solvent" means an organic solvent derived from or obtained from biological raw materials (e.g., biologically renewable materials). Examples of suitable biological raw materials include lignocellulosic biomass, sugarcane, corn, vegetable oil, waste oil, or citrus waste. In some embodiments, the bio-derived organic solvent may include a polar solvent (e.g., an aprotic polar solvent or a protic polar solvent).

[0021] Examples of suitable bio-derived organic solvents include lactones (e.g., C3~C10 lactones), ketones (e.g., C3-C 10 linear or cyclic ketones), ethers (e.g., C3-C 10 ethers), alkyl aromatic compounds (e.g., monocyclic and polycyclic aromatic hydrocarbons substituted with one or more C1-C 10 alkyl groups), alcohols (e.g., C1-C 10 alcohols), or alkyl alicyclic compounds (e.g., optionally containing one or more carbon-carbon double bonds and substituted with one or more C1-C 10 alkyl groups, monocyclic and polycyclic aliphatic hydrocarbons). Examples of bio-derived lactones include γ-valerolactone, which can be derived from corn and sugarcane. Examples of bio-derived ketones include acetone, which can be derived from corn and sugarcane. Examples of bio-derived ethers include 2-methyltetrahydrofuran, which can be derived from lignocellulosic biomass. Examples of bio-derived alcohols include glycerol, which can be derived from vegetable oils. Examples of bio-derived alkyl alicyclic compounds include limonene (e.g., d-limonene) and pinene (e.g., α-pinene), which can be derived from waste oil or citrus waste. Examples of bio-derived alkyl alicyclic compounds include cymene (e.g., p-cymene), which can be derived from waste oil or citrus waste.

[0022] It should be noted that there is an inaccuracy in the original text where "シレン" is translated as "acetone" in the English translation. "シレン" is "acetaldehyde", not "acetone". The above translation has been corrected according to the correct meaning.γ-Valerolactone (GVL) is a bio-derived solvent. GVL is a C5 (valero-)cyclic ester with five atoms (four carbon atoms and one oxygen atom) in the ring (γ-lactone). GVL is a stable, colorless liquid under standard conditions with a sweet, grassy odor, making it suitable for the manufacture of perfumes and food additives. Several routes exist for producing GVL. For example, hydrogenation of levulinic acid (LA) derived from biological systems can produce the unstable intermediate γ-hydroxyvaleric acid, which undergoes intramolecular esterification, spontaneously losing water molecules to produce GVL. Alternatively, dehydration of LA derived from biological systems can form angelicalactone, and subsequent hydrogenation can produce GVL. Therefore, unpurified bio-derived GVL may contain impurities such as formic acid, acetic acid, sulfuric acid, water, unconverted levulinic acid (LA), methyltetrahydrofuran (MTHF), and 1,4-pentanediol, which may be undesirable for electronics applications.

[0023] In some embodiments, γ-valerolactone can be produced from levulinic acid derived from biological systems via catalytic hydrogenation using a non-acidic heterogeneous hydrogenation catalyst containing a metal hydride supported on a solid catalyst support. These and other methods for producing γ-valerolactone are described, for example, in U.S. Patent Application Publication No. 2010 / 0217038, U.S. Patents No. 6,946,563; No. 6,617,464; No. 8,975,421; and No. 9,376,411, which are incorporated herein by reference.

[0024] Dihydrolevoglucocenone (Syrene) is a polar solvent that can be derived from cellulose in a simple two-step process. See, for example, Sherwood et al., Chemical Communications. 2014; 50(68): 9650-9652. Sirene has shown great promise as a bipolar aprotic solvent for use in the methods described herein. The polarity of dihydrolevoglucocenone is similar to that of NMP, DMF, and sulfolane.

[0025] water content In some embodiments, the bio-derived organic solvents described herein may be substantially water-free or contain relatively small amounts of water. In some embodiments, the water content in the bio-derived organic solvents of this disclosure is between about 0.1 ppb or more by mass (e.g., about 1 ppb or more, about 10 ppb or more, about 50 ppb or more, about 100 ppb or more, about 1 ppm or more, about 10 ppm or more, or about 100 ppm or more) and about 1000 ppm or less (e.g., about 500 ppm or less, about 200 ppm or less, about 100 ppm or less, or about 50 ppm or less). In some embodiments, the amount of water in the solvent used for polymerization to form polyimide polymers may be extremely important, as the amount of water in the solvent during the polymerization process can affect the molecular weight of the resulting polymer. Although not bound by theory, it is believed that when a bio-derived organic solvent is used in a coating formulation and the water content is 10 ppm or more by mass, the adhesion of the film to substrates such as Si, SiOx, SiN, and Cu can be improved by partial hydrolysis of the siloxane compound used as an adhesion promoter. In addition, although not bound by theory, it is believed that the corrosion resistance of the bio-derived organic solvent can be sufficient when the water content is 100 ppm or less by mass. In some embodiments, the bio-derived organic solvent described herein may not contain water. The water content in the bio-derived organic solvent can be measured using the Karl Fischer moisture metering method (coulometric titration) as the measurement principle.

[0026] Trace metal components In some embodiments, the bio-derived organic solvents of this disclosure may be substantially free of metallic components, or may contain relatively small amounts of certain metallic components. The metallic components may include at least one metallic element selected from the group consisting of Na, K, Ca, Fe, Cu, Mg, Mn, Co, Al, Cr, Ni, Ti, Ag, and Zn. In some embodiments, the metallic components may be in the form of ions, complex compounds, metallic salts, alloys, etc. In some embodiments, the metallic components may be in the form of particles. In some embodiments, the metallic components may be present in the raw materials used in the production of the bio-derived organic solvent, or may be intentionally added to the bio-derived organic solvent during or after its production.

[0027] In some embodiments, reducing the amount of trace metals in the bio-derived organic solvents described herein may be important to optimize performance when the solvent is used as a casting solvent in which a higher amount of metal may act as a corrosive agent to the device. In some embodiments, the content of individual metal components in the bio-derived organic solvents of this disclosure is about 10 ppt or more by mass (e.g., about 100 ppt or more, about 500 ppt or more, about 1 ppb or more, or about 10 ppb or more) to about 500 ppb or less (e.g., about 200 ppb or less, about 100 ppb or less, about 50 ppb or less, about 20 ppb or less, about 10 ppb or less, about 1 ppb or less, or about 100 ppt or less).

[0028] When used herein, if a bio-derived organic solvent described herein contains two or more metal components, the content of metal components refers to the total content of the two or more metal components in the solvent. In some embodiments, the total content of all metal components in the bio-derived organic solvent described herein is between approximately 50 ppt or more by mass (e.g., approximately 100 ppt or more, approximately 1 ppb or more, approximately 5 ppb or more, or approximately 10 ppb or more) and approximately 500 ppb or less (e.g., approximately 200 ppb or less, approximately 100 ppb or less, approximately 50 ppb or less, approximately 10 ppb or less, or approximately 1 ppb or less). The content of metal components in the bio-derived organic solvent described herein can be measured using inductively coupled plasma mass spectrometry (ICP-MS). Measurement of the content of metal components by ICP-MS can be performed using, for example, an instrument such as the NexION350 available from PerkinElmer, Inc. (Walthan, MA).

[0029] While not bound by theory, it is believed that if the content of metal components is within the above range, the occurrence of defects in semiconductor devices can be suppressed. In some embodiments, the bio-derived organic solvents described herein may not contain metal components.

[0030] Trace acid component In some embodiments, the bio-derived organic solvents described herein may be substantially free of acidic components such as organic acids (e.g., formic acid, acetic acid, or unconverted levulinic acid) or inorganic acids (e.g., sulfuric acid), or may contain relatively small amounts of acidic components. In some embodiments, the acidic components may be present in amounts of about 1000 ppm or less by mass (e.g., about 500 ppm or less, about 200 ppm or less, about 100 ppm or less, about 50 ppm or less, about 10 ppm or less, about 5 ppm or less, about 1 ppm or less, about 500 ppb or less, about 100 ppb or less, about 50 ppb or less, about 10 ppb or less, about 5 ppb or less, or about 1 ppb or less) and about 0.1 ppb or more (e.g., about 0.5 ppb or more, about 1 ppb or more, about 5 ppb or more, or about 10 ppb or more) relative to the bio-derived organic solvents described herein.

[0031] Purification process of bio-derived organic solvents In some embodiments, the present disclosure features a method for purifying a bio-derived organic solvent. The method may include: (1) passing the bio-derived organic solvent through an ion exchange filter unit; (2) passing the bio-derived organic solvent through at least one column containing an adsorbent to remove water from the bio-derived organic solvent; and (3) distilling the bio-derived organic solvent in a distillation column to obtain a purified bio-derived organic solvent.

[0032] In general, the three steps described above may be carried out in any order. For example, the three steps described above may be carried out in the order listed in the previous paragraph. As another example, the purification process may be carried out in the following order: passing the bio-derived organic solvent through at least one column containing an adsorbent, distilling the bio-derived organic solvent, and passing the bio-derived organic solvent through an ion exchange filter. As yet another example, the purification process may be carried out in the following order: passing the bio-derived organic solvent through at least one column containing an adsorbent, passing the bio-derived organic solvent through an ion exchange filter, and distilling the bio-derived organic solvent.

[0033] In some embodiments, the purification process described herein may use at least one (e.g., two or three) columns (e.g., dehydration columns) containing an adsorbent to remove water or certain other impurities from a bio-derived organic solvent. In some embodiments, the adsorbent in such a column may be a molecular sieve (e.g., zeolite 3A, zeolite 4A, or zeolite 5A), silica gel, activated alumina, activated carbon, or an ion exchange resin. In some embodiments, if one column containing an adsorbent is not sufficient to reduce the water content in the bio-derived organic solvent to a desired level (e.g., about 1000 ppm or less), two or more such columns may be used. In such embodiments, these columns may be in fluid communication with each other and connected in series.

[0034] In some embodiments, the purification process described herein may use at least one (e.g., two or three) ion exchange filter units to remove metal impurities from bio-derived organic solvents. In some embodiments, the ion exchange filter unit may include a housing and at least one (e.g., two, three, four, or five) first ion exchange filters and at least one (e.g., two, three, four, or five) second ion exchange filters located within the housing. In some embodiments, at least one first ion exchange filter and at least one second ion exchange filter are both negatively charged ion exchange filters or cation exchange filters (i.e., including one or more filtration media containing negatively charged ion exchange resins) and are connected in series. If there are two or more first ion exchange filters, the multiple first ion exchange filters may be connected in parallel to improve flow rate and productivity. If there are two or more second ion exchange filters, the multiple second ion exchange filters may be connected in parallel to improve flow rate and productivity.

[0035] Generally, at least one first ion exchange filter is different from at least one second ion exchange filter (e.g., contains a different filter medium). In some embodiments, at least one first ion exchange filter can remove mainly heavy metals (e.g., Fe, Ni, Cr, Zn, or Cu), while at least one second ion exchange filter can remove mainly alkali metals or alkaline earth metals (e.g., K, Na, or Ca). In some embodiments, the first ion exchange filter may be capable of removing about 90% by weight or more (e.g., about 92% by weight or about 95% by weight or more) of one or more heavy metals and / or about 10% by weight or less (e.g., about 8% by weight or about 5% by weight or less) of one or more alkali metals or alkaline earth metals from a bio-derived organic solvent. In some embodiments, the second ion exchange filter may be capable of removing about 70% by weight or more (e.g., about 75% by weight or more, about 80% by weight or more, about 85% by weight or more, or about 90% by weight or more) of one or more alkali metals or alkaline earth metals, and / or about 30% by weight or less (e.g., about 25% by weight or less, about 20% by weight or less, about 15% by weight or less, or about 10% by weight or less) of one or more heavy metals from a bio-derived organic solvent.

[0036] In some embodiments, it is preferable that at least one second ion exchange filter is placed downstream of at least one first ion exchange filter. Although not theoretically bound, in such embodiments, heavy metals in the organic solvent can be removed first, which is thought to facilitate the removal of alkali metals or alkaline earth metals, as residual heavy metals in the organic solvent may hinder the removal of alkali metals or alkaline earth metals by at least one second ion exchange filter. In some embodiments, the order of at least one first and second ion exchange filter may be reversed.

[0037] In some embodiments, at least one first or second ion exchange filter may include one or more negatively charged ion exchange resin membranes as a filtration medium for removing positively charged particles and / or cationic metal ions from organic solvents. The negatively charged ion exchange resin membranes used in this disclosure are not particularly limited, and filters may be used that include an ion exchange resin in which suitable ion exchange groups are immobilized on the resin membrane. Examples of such ion exchange resin membranes include strongly acidic cation exchange resins having chemically modified cation exchange groups (such as sulfonic acid groups or sulfonate groups) on the resin membrane. Examples of suitable resin membranes include membranes containing cellulose, diatomaceous earth, polyamides (e.g., nylon), polyolefins (e.g., polyethylene (e.g., high-density polyethylene or ultra-high molecular weight polyethylene), polypropylene, or polystyrene), resins having imide groups, resins having amide and imide groups, fluoropolymers (e.g., polytetrafluoroethylene or perfluoroalkoxyalkane polymers), or copolymers or combinations thereof. In some embodiments, the ion exchange resin membrane may be a membrane having an integrated structure of a particle removal membrane and an ion exchange resin membrane. A polyalkylene (e.g., PE, PP, or PTFE) membrane having chemically modified cation exchange groups (e.g., sulfonate groups) on the membrane is preferred. The filter having the cation exchange resin membrane used in this disclosure may be a commercially available filter having metal ion removal functionality. Examples of such commercially available cation exchange filters include the IonKleen filter available from Pall Corporation (Port Washington, NY) and the Protego Plus filter available from Entegris (Billerica, MA). These filters can be selected based on ion exchange efficiency and have an estimated pore size in the range of about 100 nm to about 500 nm.

[0038] Examples of the shape of the membrane material in at least one first or second ion exchange filter include pleated type, flat membrane type, hollow fiber type, and porous body, as described in Japanese Patent Application Publication No. 2003-112060, etc. In some embodiments, if the ion exchange membrane is porous, it is also possible to remove at least a portion of the fine particles in bio-derived organic solvents.

[0039] In some embodiments, at least one first ion exchange filter may contain a filter medium comprising polyethylene having sulfonate groups, polytetrafluoroethylene having sulfonate groups, or copolymers thereof, which can primarily remove heavy metals (e.g., Fe, Ni, Cr, Zn, or Cu). A commercially available example of such a filter is the IonKleen filter (e.g., IonKleen SL filter) manufactured by Pall Corporation (Port Washington, NY). In some embodiments, the ion exchange filter unit described herein may include two or three such first ion exchange filters connected in parallel to improve productivity.

[0040] In some embodiments, at least one second ion exchange filter may contain a filter medium comprising polyethylene having sulfonate groups, polytetrafluoroethylene having sulfonate groups, or copolymers thereof, which can primarily remove alkali metals or alkaline earth metals (e.g., K, Na, or Ca). Examples of commercially available filters of this type include the Protego Plus filters (such as the Protego Plus IPA filter) and the Protego AT 5nm / Ionex combo filter, available from Entegris (Billerica, MA). In some embodiments, the ion exchange filter unit described herein may include two or three such second ion exchange filters connected in parallel to improve productivity.

[0041] While not bound by theory, it is believed that including two different types of ion exchange filters in the ion exchange filter unit described herein can significantly reduce the amount of metal impurities in the purified organic solvent compared to a system using only one type of ion exchange filter (e.g., to approximately 200 ppt or less in total).

[0042] In some embodiments, the purification process described herein may use at least one (e.g., two or three) distillation columns to purify the bio-derived organic solvent. Generally, such distillation columns may be any suitable distillation columns known in the art and can be used to purify the bio-derived organic solvent by distillation to remove most organic and metallic impurities and particulate matter.

[0043] In some embodiments, the purification process described herein may use at least one (e.g., two or three) additional filter units (i.e., located upstream or downstream of the ion exchange filter units described above) to purify bio-derived organic solvents. In some embodiments, each additional filter unit may include a filter housing and one or more filters within the filter housing. The additional filter units may differ in function or properties and may provide different purification treatments. In some embodiments, each additional filter unit may be independently selected from the group consisting of particle removal filters, ion exchange filters, and ion absorption filters.

[0044] In some embodiments, the untreated or unpurified bio-derived organic solvent may have a purity of about 99% or less (e.g., about 98% or less, about 97% or less, about 96% or less, or about 95% or less). In some embodiments, the treated or purified bio-derived organic solvent obtained from the methods described herein may have a purity of about 99.5% or more (e.g., about 99.9% or more, about 99.95% or more, about 99.99% or more, about 99.995% or more, about 99.999% or more, about 99.9995% or more, about 99.9999% or more, or 100%). Where used herein, “purity” means the weight percentage of the solvent in the total weight of the liquid. The content of the organic solvent in the liquid can be measured using a gas chromatography-mass spectrometer (GC-MS) (e.g., a thermal desorption (TD) GC-MS).

[0045] Other methods for purifying organic solvents are described, for example, in U.S. Patent Applications No. 202103008; No. 2021060526; No. 2021220754; and No. 2021300851, which are incorporated herein by reference.

[0046] Polymerization process In some embodiments, the disclosure features a method (e.g., polymerization method) for forming polymers using bio-derived organic solvents as described herein. In some embodiments, the method may involve forming a polymer comprising a polyimide (PI) precursor polymer, a polybenzoxazole (PBO) precursor polymer, or a fully imidized polyimide in a solvent system containing at least one first organic solvent and optionally at least one second organic solvent. In some embodiments, the at least one first organic solvent may include one or more bio-derived organic solvents as described herein (e.g., aprotic polar solvents). In some embodiments, the at least one second organic solvent may include a solvent containing a carbonyl group (e.g., a non-aqueous solvent).

[0047] Examples of second organic solvents suitable for the polymerization methods described herein include, but are not limited to, 1-butylpyrrolidine-2-one (e.g., Tamisolve NxG), N-methyl-2-pyrrolidone (NMP), N-ethyl-2-pyrrolidone (NEP), 1,3-dimethyl-2-imidazolidinone (DMI), γ-butyrolactone (GBL), δ-valerolactone (δ-VL), ε-caprolactone (ε-CL), 3-dimethyl-2-imidazolidinone, 3-methoxy-N,N-dimethylpropanamide, 3-methoxy-N,N-dibutylpropanamide, cyclohexanone (CH), cyclopentanone (CP), isophorone (IP), propylene carbonate (PC), and ethylene carbonate (EC).

[0048] In some embodiments, a mixed solvent system containing at least one bio-derived organic solvent and at least one second organic solvent may be used in the production of polyimide precursor polymers, polybenzoxazole precursor polymers, or fully imidized polyimide polymers. In some embodiments, such a solvent system can prevent changes in liquid properties such as viscosity caused by the absorption of water by the polymer formed during the reaction. The polyimide precursors, polybenzoxazole precursors, or fully imidized polyimide polymers thus formed may have excellent film-forming properties (coating properties) and storage stability. In some embodiments, even when such compositions (e.g., coating liquids) are stirred while exposed to an air atmosphere, such as in a roll-type coating apparatus, an increase in the viscosity of the composition can be avoided, and uniform film formation can be achieved.

[0049] photosensitive composition In some embodiments, the present disclosure features a photosensitive composition comprising at least one resin, at least one first organic solvent as described herein (e.g., at least one bio-derived organic solvent), and optionally at least one second organic solvent as described herein. As used herein, the terms “resin” and “polymer” are interchangeable.

[0050] In some embodiments, the resin suitable for the photosensitive composition described herein may include at least one (e.g., two, three, or four) dielectric polymers, including epoxy resins, novolac resins, polyamide resins, polybenzoxazole precursor polymers, polyimide precursor polymers, or fully imidized polyimide polymers. The photosensitive composition described herein may be a composition that is radiation-sensitive to chemical rays or similar light rays. In some embodiments, the dielectric polymer is a fully imidized polyimide polymer. The fully imidized polyimide polymers referred to herein are imidized to at least about 90% (e.g., at least about 95%, at least about 98%, at least about 99%, or about 100%).

[0051] In some embodiments, the weight-average molecular weight of the fully imidized polymer is about 20,000 daltons or more (e.g., about 25,000 daltons or more, about 30,000 daltons or more, about 35,000 daltons or more, about 40,000 daltons or more, about 45,000 daltons or more, about 50,000 daltons or more, or about 55,000 daltons or more) and / or about 100,000 daltons or less (e.g., about 95,000 daltons or less, about 90,000 daltons or less, about 85,000 daltons or less, about 80,000 daltons or less, about 75,000 daltons or less, about 70,000 daltons or less, about 65,000 daltons or less, or about 60,000 daltons or less).

[0052] In some embodiments, at least one (e.g., two, three, or four) fully imidized polyimide polymers are produced by the reaction of at least one diamine with at least one tetracarboxylic dianhydride. In some embodiments, the resulting polymers are soluble in the bio-derived organic solvents of this disclosure and facilitate the formation of dielectric films having a planarized surface (e.g., the difference between the highest and lowest points on the upper surface of the dielectric film is less than about 2 microns). Examples of fully imidized polyimide polymers are known in the art and are described, for example, in U.S. Patent Application Publication 2019 / 0077913, the entire contents of which are incorporated herein by reference.

[0053] Methods for synthesizing end-capped and end-capped PI precursor polymers are known to those skilled in the art. Examples of such methods and PI precursor polymers are, for example, U.S. Patents 2,731,447, 3,435,002, 3,856,752, 3,983,092, 4,026,876, 4,040,831, 4,579,809, 4,629,777, 4,656,116, 4,960,860, 4,985,529, and 5,006,61 This is disclosed in U.S. Patent Applications No. 1, No. 5,122,436, No. 5,252,534, No. 5,4789,15, No. 5,773,559, No. 5,783,656, No. 5,969,055, No. 9617386, and in U.S. Patent Publications No. 2004 / 0265731, No. 2004 / 0235992, and No. 2007 / 0083016, the entire contents of which are incorporated herein by reference.

[0054] Methods for synthesizing polybenzoxazole precursor polymers are known to those skilled in the art. Such methods and examples of PBO precursor polymers are disclosed, for example, in U.S. Patents 6,143,467, 7,195,849, 7,129,011, and 9,519,216, the entire contents of which are incorporated herein by reference.

[0055] Methods for synthesizing polyimide precursor polymers (e.g., polyamic acid ester polymers) are also known to those skilled in the art. Examples of such methods and PI precursor polymers are disclosed, for example, in U.S. Patents 4,040,831, 4,548,891, 5,834,581, and 6,511,789, the entire contents of which are incorporated herein by reference.

[0056] Examples of suitable epoxy resins used as dielectric film materials are known to those skilled in the art. Such examples are disclosed, for example, in U.S. Patent No. 4,882,245 and U.S. Patent Application Publication No. 2006 / 0257785, the entire contents of which are incorporated herein by reference.

[0057] Examples of suitable novolac resins used as dielectric film materials are known to those skilled in the art. Examples of such resins are disclosed in U.S. Patents No. 5,413,894, No. 5,306,594, and No. 4,959,292, the entire contents of which are incorporated herein by reference.

[0058] In some embodiments, the photosensitive composition described herein may be a dielectric film-forming composition, and the resin described herein may be a dielectric polymer. In some embodiments, the dielectric film-forming composition described herein may comprise at least one (e.g., two, three, or four) cyanate ester compounds. In some embodiments, the cyanate ester compound may comprise at least two cyanate groups. Not limited to theory, it is considered that the cyanate ester compound can be thermally cyclized and / or crosslinked (e.g., with or without a catalyst) to form an interpenetrating network structure with the dielectric polymer. Furthermore, not limited to theory, it is considered that including a cyanate ester compound in the dielectric film-forming composition described herein can reduce the dielectric constant (K) and / or dielectric loss tangent (DF) of the film formed from the composition. Examples of suitable cyanate ester compounds are, for example, described in U.S. Patent Application Publication 2022 / 0127459, the entire content of which is incorporated herein by reference.

[0059] In some embodiments, the amount of at least one cyanate ester compound is about 0.1% by weight or more (e.g., about 0.5% by weight or more, about 1.0% by weight or more, about 2.0% by weight or more, or about 2.5% by weight or more) and / or about 10% by weight or less (e.g., about 5% by weight or less, about 7% by weight or less, or about 9% by weight or less) based on the total weight of the photosensitive composition described herein (e.g., dielectric film-forming composition).

[0060] In some embodiments, the dielectric film-forming compositions described herein may comprise at least one (e.g., two, three, or four) dielectric polymers selected from the group consisting of polybenzoxazole precursor polymers, polyimide precursor polymers, and fully imidized polyimide polymers, such as those described herein. In some embodiments, the dielectric polymer is a fully imidized polyimide polymer. A preferred fully imidized polyimide polymer is one in which no polymerizable moieties are bonded to the polymer. While not theoretically bound, it is believed that including the above polymers in the dielectric film-forming compositions described herein can increase the glass transition temperature, decrease the thermal shrinkage rate, and improve the mechanical properties of the film formed by the composition.

[0061] In some embodiments, the amount of the resin or dielectric polymer is about 2% by weight or more (e.g., about 5% by weight or more, about 10% by weight or more, about 15% by weight or more, or about 20% by weight or more) and / or about 55% by weight or less (e.g., about 50% by weight or less, about 45% by weight or less, about 40% by weight or less, about 35% by weight or less, about 30% by weight or less, or about 25% by weight or less) based on the total weight of the photosensitive composition described herein (e.g., dielectric film-forming composition).

[0062] In some embodiments, the dielectric film-forming compositions described herein may further comprise a solvent system containing at least one first organic solvent and optionally at least one second organic solvent. In some embodiments, the first organic solvent may be a purified bio-derived organic solvent as described herein (e.g., an aprotic polar solvent selected from the group consisting of lactones, ketones, ethers, alkyl aromatics, and alkyl alicyclic solvents). In some embodiments, the second organic solvent is preferably a solvent containing a carbonyl group. In some embodiments, the bio-derived organic solvent used in the dielectric film-forming composition is γ-valerolactone, sylen, or 2-methyltetrahydrofuran.

[0063] Examples of second organic solvents suitable for the dielectric film-forming compositions described herein include, but are not limited to, alkylene carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate, and glycerin carbonate; lactones such as γ-butyrolactone, ε-caprolactone, γ-caprolactone, and γ-valerolactone; cycloketones such as cyclopentanone and cyclohexanone; linear ketones such as methyl ethyl ketone (MEK) and methyl isobutyl ketone (MIBK); esters such as n-butyl acetate; and lactic acid. Examples include ester alcohols such as tyl alcohol; ether alcohols such as tetrahydrofurfuryl alcohol; glycol esters such as propylene glycol methyl ether acetate; glycol ethers such as propylene glycol methyl ether (PGME); cyclic ethers such as tetrahydrofuran (THF); and pyrrolidones such as N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, or N-butyl-2-pyrrolidone or TamiSolve® NxG; and dialkyl sulfoxides such as dimethyl sulfoxide.

[0064] In some embodiments, the total amount of the solvent (e.g., the first and second organic solvents) is about 20% by weight or more (e.g., about 25% by weight or more, about 30% by weight or more, about 35% by weight or more, about 40% by weight or more, about 45% by weight or more, about 50% by weight or more, about 55% by weight or more, about 60% by weight or more, or about 65% by weight or more) and / or about 98% by weight or less (e.g., about 95% by weight or less, about 90% by weight or less, about 85% by weight or less, about 80% by weight or less, about 75% by weight or less, about 70% by weight or less, or about 60% by weight or less) based on the total weight of the photosensitive composition (e.g., dielectric film-forming composition) described herein.

[0065] In some embodiments, the dielectric film-forming compositions of the present disclosure may optionally contain at least one (e.g., two, three, or four) catalysts (e.g., initiators). In some embodiments, depending on the type of catalyst used, the catalyst can cyclize and / or crosslink cyanate esters, or induce crosslinking or polymerization reactions, when exposed to heat (e.g., thermal initiators) and / or a radiation source (e.g., photoinitiators such as free radical initiators).

[0066] In some embodiments, the dielectric film-forming compositions described herein may optionally include at least one (e.g., two, three, or four) cyanate curing catalysts to accelerate the curing of the cyanate ester compound (e.g., to form interpenetrating network structures) and / or to lower the curing temperature of the dielectric film. The cyanate curing catalysts may be included in either a photosensitive dielectric film-forming composition or a non-photosensitive dielectric film-forming composition.

[0067] In some embodiments, the cyanate curing catalyst may be selected from the group consisting of metal carboxylate salts and metal acetylacetonate salts. The metal of the metal carboxylate salt and metal acetylacetonate salt may be selected from the group consisting of zinc, copper, manganese, cobalt, iron, nickel, aluminum, titanium, zirconium, and mixtures thereof. Examples of cyanate curing catalysts include metal salts such as zirconyl dimethacrylate, zinc octanoate, zinc naphthenate, cobalt naphthenate, copper naphthenate, and iron acetylacetone; phenolic compounds such as octylphenol and nonylphenol; alcohols such as 1-butanol and 2-ethylhexanol; 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, and 2-phenyl-4,5-dihydroxymethyl Examples of catalysts include imidazole and imidazole compounds such as 2-phenyl-4-methyl-5-hydroxymethylimidazole; amine compounds such as dicyandiamide, benzyldimethylamine, and 4-methyl-N,N-dimethylbenzylamine; phosphorus compounds such as phosphine compounds and phosphonium compounds; epoxy-imidazole adducts; and peroxides such as benzoyl peroxide, p-chlorobenzoyl peroxide, di-t-butyl peroxide, diisopropyl peroxycarbonate, and di-2-ethylhexyl peroxycarbonate. These catalysts are commercially available. Examples of commercially available catalysts include Amicure PN-23 (trademark, manufactured by Ajinomoto Fine-Techno Co., Inc.), Novacure HX-3721 (trademark, manufactured by Asahi Kasei Corporation), and Fujicure FX-1000 (trademark, manufactured by Fuji Kasei Kogyo Co., Ltd.). One or more combinations of these catalysts may be used in the compositions described herein. Other examples of such catalysts are described, for example, in U.S. Patent Application Publication No. 2018 / 0105488 and U.S. Patent No. 9,822,226, which are incorporated herein by reference.

[0068] In some embodiments (e.g., in the case of a photosensitive composition), the dielectric film-forming composition described herein may optionally contain at least one (e.g., two, three, or four) photoinitiators to promote the crosslinking reaction of a crosslinking agent (e.g., a reactive functional compound described herein) or the crosslinking reaction between a crosslinking agent and a dielectric polymer (e.g., if it contains crosslinkable groups). Specific examples of photoinitiators, though not limited to these, include 1,8-octanedione, 1,8-bis[9-(2-ethylhexyl)-6-nitro-9H-carbazole-3-yl]-1,8-bis(O-acetyloxime), 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone (BASF Irgacure 184), a blend of 1-hydroxycyclohexyl phenyl ketone and benzophenone (BASF Irgacure 500), 2,4,4-trimethylpentylphosphine oxide (BASF Irgacure 1800, 1850, and 1700), 2,2-dimethoxyl-2-acetophenone (BASF Irgacure 651), and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (BASF Irgacure 819), 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (BASF Irgacure 907), (2,4,6-trimethylbenzoyl)diphenylphosphine oxide (BASF Lucerin TPO), 2-(benzoyloxyimino)-1-[4-(phenylthio)phenyl]-1-octanone (BASF Irgacure OXE-01), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethanone, 1-(O-acetyloxime) (BASF Irgacure OXE-2), ethoxy(2,4,6-trimethylbenzoyl)phenylphosphine oxide (BASF Lucerin TPO-L), blend of phosphine oxide, hydroxyketone and benzophenone derivative (Arkema ESACURE KTO46), 2-hydroxy-2-methyl-1-phenylpropan-1-one (Darocur 1173, manufactured by Merck), NCI-831 (ADEKA Corp.)Examples include NCI-930 (ADEKA Corp.), N-1919 (ADEKA Corp.), benzophenone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, benzodimethyl ketal, 1,1,1-trichloroacetophenone, diethoxyacetophenone, m-chloroacetophenone, propiophenone, anthraquinone, and dibenzosverone.

[0069] In some embodiments, a photosensitizer may be used in the dielectric film-forming composition, and the photosensitizer can absorb light in the wavelength range of 193 to 405 nm. Examples of photosensitizers, but are not limited to, include 9-methylanthracene, anthracenemethanol, acenaphthylene, thioxanthone, methyl-2-naphthylketone, 4-acetylbiphenyl, and 1,2-benzofluorene.

[0070] Specific examples of thermal initiators, though not limited to these, include benzoyl peroxide, cyclohexanone peroxide, lauroyl peroxide, tert-amyl peroxybenzoate, tert-butyl hydroperoxide, di(tert-butyl) peroxide, dicumyl peroxide, cumene hydroperoxide, succinate peroxide, di(n-propyl) peroxydicarbonate, 2,2-azobis(isobutyronitrile), 2,2-azobis(2,4-dimethylvaleronitrile), dimethyl-2,2-azobisisobutyrate, 4,4-azobis(4-cyanopentanoic acid), azobiscyclohexanecarbonitrate, and 2,2-azobis(2-methylbutyronitrile).

[0071] In some embodiments, the amount of the catalyst is about 0.2% by weight or more (e.g., about 0.5% by weight or more, about 0.8% by weight or more, about 1.0% by weight or more, or about 1.5% by weight or more) and / or about 3.0% by weight or less (e.g., about 2.8% by weight or less, about 2.6% by weight or less, about 2.3% by weight or less, or about 2.0% by weight or less) based on the total weight of the photosensitive composition described herein (e.g., dielectric film forming composition).

[0072] In some embodiments, the dielectric film-forming compositions described herein may optionally include at least one (e.g., two, three, or four) reactive-sensitive compounds. In some embodiments, the reactive functional compound may include at least two functional groups (e.g., (meth)acrylate groups, alkenyl groups, or alkynyl groups). In some embodiments, the functional groups on the reactive functional compound may react with other molecules of the reactive functional compound or with a dielectric polymer (e.g., if it includes crosslinking groups). While not theoretically bound, it is conceivable that reactive functional compounds can be used as crosslinking agents in photosensitive compositions for forming negative-type photosensitive films.

[0073] In some embodiments, the reactive functional compound is a compound containing at least two (meth)acrylate groups. As used herein, the term "(meth)acrylate" includes both acrylate and methacrylate.Examples of such compounds, though not limited to them, include 1,3-butylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, and cyclohexane Dimethanol di(meth)acrylate, polyethylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, diurethane di(meth)acrylate, 1,4-phenylenedi(meth)acrylate, 2,2-bis[4-(2-hydroxy-3-methacryloxypropoxy)phenyl]propane, bis(2-hydroxyethyl)-isocyanurate di(meth)acrylate, neopentyl glycol di(meth)acrylate, tricycline Rodecane dimethanol di(meth)acrylate, propoxylated (3)glycerol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta- / hexa-(meth)acrylate, isocyanurate tri(meth)acrylate, ethoxylated glycerin tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, etoxy Examples include sylated pentaerythritol tetra(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, 1,2,4-butanetriol tri(meth)acrylate, diglycerol tri(meth)acrylate, trimethylolpropane ethoxylate tri(meth)acrylate, trimethylolpropane polyethoxylate tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, and tris(2-hydroxyethyl) isocyanurate triacrylate. Preferred reactive functional compounds are unsubstituted / substituted linear, branched, or cyclic C1-C. 10These are alkyl di(meth)acrylates or unsubstituted / substituted aromatic group di(meth)acrylates. The reactive functional compounds may be used alone or in combination of two or more in the dielectric film-forming compositions described herein.

[0074] In some embodiments, the amount of at least one reactive functional compound is about 1% by weight or more (e.g., about 2% by weight or more, about 3% by weight or more, about 4% by weight or more, or about 5% by weight or more) and / or about 25% by weight or less (e.g., about 20% by weight or less, about 15% by weight or less, about 10% by weight or less, or about 8% by weight or less) based on the total weight of the photosensitive composition described herein (e.g., dielectric film-forming composition).

[0075] In some embodiments, the dielectric film-forming composition may optionally contain at least one mono(meth)acrylate-containing compound. In some embodiments, the compound containing at least one mono(meth)acrylate is bornyl acrylate, isobornyl acrylate, dicyclopentenyloxyethyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl methacrylate, dicyclopentenyl methacrylate, bicyclo[2.2.2]octa-5-en-2-yl acrylate, 2-[(bicyclo[2.2.2]octa-5-en-2-yl)oxy]ethyl acrylate, 3a,4,5,6,7,7a-hexahydro-1H-4,7-ethanoinden-6-yl acrylate, 2-[(3a,4,5,6,7,7a-hexahydro-1H-4,7-ethanoinden-6-yl)oxy]ethyl acrylate, tricyclo[5,2,1,0 2,6 ]decyl acrylate and tetracyclo[4,4,0,1 2,5 ,1 7,10The compound is selected from the group consisting of dodecanyl acrylates. Although not bound by theory, it is believed that including at least one mono(meth)acrylate-containing compound can enhance the mechanical properties of the film formed by the dielectric film-forming compositions described herein (e.g., by forming a polymer and / or by reacting (or crosslinking) with reactive functional compounds).

[0076] In some embodiments, the dielectric film-forming composition optionally includes one or more (e.g., two, three, or four) inorganic fillers, adhesion promoters, surfactants, copper passivators, plasticizers, antioxidants, dyes, and / or colorants, and other optional components. Examples of such components are, for example, described in U.S. Patent Application Publication No. 2022 / 0127459, the entire content of which is incorporated herein by reference.

[0077] In some embodiments, a dielectric film can be produced from a dielectric film-forming composition of the present disclosure by a process comprising: (a) coating a substrate (e.g., a semiconductor substrate) with a dielectric film-forming composition described herein to form a dielectric film; and (b) optionally firing at a high temperature (e.g., about 50°C to about 150°C) for a period of time (e.g., about 20 seconds to about 600 seconds).

[0078] Coating methods for manufacturing dielectric films include, but are not limited to, (1) spin coating, (2) spray coating, (3) roll coating, (4) rod coating, (5) rotational coating, (6) slit coating, (7) compression coating, (8) curtain coating, (9) die coating, (10) wire bar coating, (11) knife coating, and (12) dry film lamination. In coating methods (1) to (11), the dielectric film-forming composition is typically provided in the form of a solution. Those skilled in the art will select the appropriate type and concentration of solvent based on the type of coating.

[0079] The substrate may have a circular, square, or rectangular shape, such as a wafer or panel of various dimensions. Suitable substrates include epoxy molded compound (EMC), silicon, glass, copper, stainless steel, copper-clad laminate (CCL), aluminum, silicon oxide, and silicon nitride. The substrate may also be flexible, such as polyimide, PEEK, polycarbonate, and polyester films. The substrate may have surface-mounted or embedded chips, dyes, or packages. The substrate may be sputtered or pre-coated with a combination of a seed layer and a passivation layer. In some embodiments, the substrate described herein may be a semiconductor substrate. As used herein, a semiconductor substrate is a substrate (e.g., a silicon or copper substrate or wafer) that will become part of a final electronic device.

[0080] The thickness of the dielectric film in this disclosure is not particularly limited. In some embodiments, the dielectric film has a thickness of about 1 micron or more (e.g., about 2 microns or more, about 3 microns or more, about 4 microns or more, about 5 microns or more, about 6 microns or more, about 8 microns or more, about 10 microns or more, about 15 microns or more, about 20 microns or more, or about 25 microns or more) and / or about 100 microns or less (e.g., about 90 microns or less, about 80 microns or less, about 70 microns or less, about 60 microns or less, about 50 microns or less, about 40 microns or less, or about 30 microns or less). In some embodiments, the thickness of the dielectric film is less than about 5 microns (e.g., less than about 4.5 microns, less than about 4.0 microns, less than about 3.5 microns, less than about 3.0 microns, less than about 2.5 microns, or less than 2.0 microns).

[0081] In some embodiments, when the dielectric composition is photosensitive, the process for manufacturing a patterned photosensitive dielectric film includes converting the photosensitive dielectric film into a patterned dielectric film by a lithography process. In such cases, the conversion may include exposing the photosensitive dielectric film to high-energy radiation (such as electron beams, ultraviolet rays, and X-rays) using a patterned mask.

[0082] After exposure, the dielectric film may be heat-treated at a temperature of approximately 50°C or higher (e.g., approximately 55°C or higher, approximately 60°C or higher, or approximately 65°C or higher) to approximately 100°C or lower (e.g., approximately 95°C or lower, or approximately 90°C or lower, approximately 85°C or lower, approximately 80°C or lower, approximately 75°C or lower, or approximately 70°C or lower) for approximately 60 seconds or higher (e.g., approximately 65 seconds or higher or approximately 70 seconds or higher) to approximately 240 seconds or lower (e.g., approximately 180 seconds or lower, approximately 120 seconds or lower, or approximately 90 seconds or lower). The heat treatment is usually carried out using a hot plate or oven.

[0083] After exposure and heat treatment, the dielectric film can be developed using a developer to remove unexposed areas and form openings or relief images on the substrate. Development can be performed, for example, by immersion or spraying. After development, micropores and fine lines can be created in the dielectric film on the laminated substrate.

[0084] In some embodiments, the dielectric film may be developed using an organic developer. Examples of such developers include, but are not limited to, the purified bio-derived organic solvents described herein, such as γ-valerolactone, sylen, and 2-methyltetrahydrofuran. Other solvents include, but are not limited to, γ-butyrolactone (GBL), dimethyl sulfoxide (DMSO), N,N-diethylacetamide, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), 2-heptanone, cyclopentanone (CP), cyclohexanone, n-butyl acetate (nBA), propylene glycol methyl ether acetate (PGMEA), propylene glycol methyl ether (PGME), ethyl lactate (EL), propyl lactate, 3-methyl-3-methoxybutanol, tetralin, isophorone, ethylene glycol monobutyl ether, and diethylene glycol Examples include chol monoethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, triethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, diethyl malonate, ethylene glycol, 1,4:3,6-dianhydrosorbitol, isosorbide dimethyl ether, 1,4:3,6-dianhydrosorbitol 2,5-diethyl ether (2,5-diethyl isosorbide), and mixtures thereof. Preferred developers include γ-valerolactone, silene, 2-methyltetrahydrofuran, γ-butyrolactone (GBL), cyclopentanone (CP), cyclohexanone, ethyl lactate (EL), n-butyl acetate (nBA), and dimethyl sulfoxide (DMSO). More preferred developers are γ-valerolactone, sylen, 2-methyltetrahydrofuran, γ-butyrolactone (GBL), cyclopentanone (CP), and cyclohexanone. These developers can be used alone or in combination of two or more to optimize the composition and image quality in the lithography process.

[0085] In some embodiments, the dielectric film may be developed using an aqueous developer. When the developer is an aqueous solution, it preferably contains one or more aqueous bases. Suitable bases include, but are not limited to, inorganic alkalis (e.g., potassium hydroxide, sodium hydroxide), primary amines (e.g., ethylamine, n-propylamine), secondary amines (e.g., diethylamine, di-n-propylamine), tertiary amines (e.g., triethylamine), alcohol amines (e.g., triethanolamine), quaternary ammonium hydroxides (e.g., tetramethylammonium hydroxide or tetraethylammonium hydroxide), and mixtures thereof. The concentration of the base used varies, for example, depending on the base solubility of the polymer used. The most preferred aqueous developer contains tetramethylammonium hydroxide (TMAH). A suitable concentration of TMAH is in the range of about 1% to about 5%.

[0086] In some embodiments, after development with an organic developer, an optional rinse may be performed using an organic rinse solvent to remove residue. Specific examples of organic rinse solvents, but are not limited to, alcohols such as isopropyl alcohol, methyl isobutylcarbinol (MIBC), propylene glycol monomethyl ether (PGME), and amyl alcohol; esters such as n-butyl acetate (nBA), ethyl lactate (EL), and propylene glycol monomethyl ether acetate (PGMEA); ketones such as methyl ethyl ketone, and mixtures thereof.

[0087] In some embodiments, an optional firing process (e.g., post-development firing) may be performed after the developing process or an optional rinsing process at a temperature within the range of approximately 120°C or higher (e.g., approximately 130°C or higher, approximately 140°C or higher, approximately 150°C or higher, approximately 160°C or higher, approximately 170°C or higher, or approximately 180°C or higher) to approximately 250°C or lower (e.g., approximately 240°C or lower, approximately 230°C or lower, approximately 220°C or lower, approximately 210°C or lower, approximately 200°C or lower, or approximately 190°C or lower). The firing time is approximately 5 minutes or more (e.g., approximately 10 minutes or more, approximately 20 minutes or more, approximately 30 minutes or more, approximately 40 minutes or more, approximately 50 minutes or more, or approximately 60 minutes or more) and / or approximately 5 hours or less (e.g., approximately 4 hours or less, approximately 3 hours or less, approximately 2 hours or less, or approximately 1.5 hours or less). This firing process allows for the removal of residual solvent from the remaining dielectric film and can also crosslink the remaining dielectric film. Post-development firing may be carried out in air, or preferably under a nitrogen blanket, and may be carried out by any suitable heating means.

[0088] In some embodiments, the patterned dielectric film includes at least one element having a feature size of about 10 microns or less (e.g., about 9 microns or less, about 8 microns or less, about 7 microns or less, about 6 microns or less, about 5 microns or less, about 4 microns or less, about 3 microns or less, about 2 microns or less, or about 1 micron or less). One important aspect of the present disclosure is that dielectric films produced from the dielectric film-forming compositions described herein can be produced by a laser ablation process to produce patterned films having a feature size of about 3 microns or less (e.g., 2 microns or less or 1 micron or less).

[0089] In some embodiments, the aspect ratio (height-to-width ratio) of the features (e.g., minimum features) of the patterned dielectric film of the Disclosure is approximately 1 / 3 or greater (e.g., approximately 1 / 2 or greater, approximately 1 / 1 or greater, approximately 2 / 1 or greater, approximately 3 / 1 or greater, approximately 4 / 1 or greater, or approximately 5 / 1 or greater).

[0090] In some embodiments (e.g., when the dielectric film-forming composition is non-photosensitive), the process for producing a patterned dielectric film includes converting the dielectric film into a patterned dielectric film by a laser ablation method. Direct laser ablation processes using an excimer laser beam are generally dry, one-step material removal processes for forming apertures (or patterns) in a dielectric film. In some embodiments, the laser wavelength is 351 nm or less (e.g., 351 nm, 308 nm, 248 nm, or 193 nm). Examples of suitable laser ablation processes include, but are not limited to, the processes described in U.S. Patents 7,598,167, 6,667,551, and 6,114,240, the contents of which are incorporated herein by reference.

[0091] In embodiments where the dielectric film-forming composition is non-photosensitive, the composition can be used to form the lower layer of a two-layer photoresist. In such embodiments, the upper layer of the two-layer photoresist may be a photosensitive layer that can be patterned by exposure to high-energy radiation. The pattern of the upper layer can be transferred to the lower dielectric layer (e.g., by etching). The upper layer can then be removed (e.g., by using a wet chemical etching method) to form the patterned dielectric film.

[0092] In some embodiments, the Disclosure features a process for depositing a metal layer (e.g., for creating an embedded copper trace structure), comprising: (a) forming a patterned dielectric film having openings; and d) depositing a metal layer (e.g., an electrically conductive metal layer) on at least one opening in the patterned dielectric film. For example, the process may include: (a) depositing the dielectric film-forming composition of the Disclosure onto a substrate (e.g., a semiconductor substrate) to form a dielectric film; (b) exposing the dielectric film to a radiation source, heat, or a combination thereof (e.g., through a mask); (c) patterning the dielectric film to form a patterned dielectric film having openings; and (d) depositing a metal layer (e.g., an electrically conductive metal layer) on at least one opening in the patterned dielectric film. In some embodiments, steps (a) to (d) may be repeated one or more times (e.g., two, three, or four times).

[0093] In some embodiments, the disclosure features a process for depositing a metal layer (e.g., an electrically conductive copper layer for creating an embedded copper trace structure) on a semiconductor substrate. In some embodiments, to achieve this, a conformal seed layer is first deposited on the patterned dielectric film (e.g., outside the openings of the film). The seed layer may include a barrier layer and a metal seed layer (e.g., a copper seed layer). In some embodiments, the barrier layer is manufactured using a material that can prevent the diffusion of an electrically conductive metal (e.g., copper) through the dielectric layer. Suitable materials that may be used for the barrier layer include, but are not limited to, tantalum (Ta), titanium (Ti), tantalum nitride (TiN), tungsten nitride (WN), and Ta / TaN. A suitable method for forming the barrier layer is sputtering (e.g., PVD or physical vapor deposition). Sputtering deposition has several advantages as a metal deposition technique because it allows for the deposition of many conductive materials at high deposition rates with good uniformity and low total cost of ownership. Conventional sputtering fill yields relatively poor results for deeper and narrower (higher aspect ratio) features. The fill efficiency of sputtering deposition has been improved by collimating the sputtering flux. Typically, this is achieved by inserting a collimator plate with an array of hexagonal cells between the target and the substrate.

[0094] The next step in the process described above is the deposition of a metal seed. To improve the deposition of the metal layer (e.g., copper layer) formed in the subsequent step, a thin seed layer of metal (e.g., an electrically conductive metal such as copper) may be formed on top of the barrier layer.

[0095] The next step in the process is to deposit an electrically conductive metal layer (e.g., a copper layer) on a metal seeding layer at the openings in the patterned dielectric film, the metal layer being thick enough to fill the openings in the patterned dielectric film. The metal layer for filling the openings in the patterned dielectric film can be deposited by plating (such as electroless or electrolytic plating), sputtering, plasma deposition (PVD), and chemical deposition (CVD). Electrochemical copper deposition is generally the preferred method for applying copper because it is more economical than other deposition methods and can fill interconnect features with copper without defects. The copper deposition method should generally meet the stringent requirements of the semiconductor industry. For example, the copper deposit should be uniform and able to fill small interconnect features of the device, e.g., openings of 100 nm or less, without defects. This technology is described, for example, in U.S. Patent No. 5,891,804 (Havemann et al.), No. 6,399,486 (Tsai et al.), and No. 7,303,992 (Paneccasio et al.), the contents of which are incorporated herein by reference.

[0096] In some embodiments, the process of depositing an electrically conductive metal layer further includes removing the overburden of the electrically conductive metal or removing a seed layer (e.g., a barrier layer and a metal seed layer). In some embodiments, the overburden of the electrically conductive metal (e.g., a copper layer) is about 3 microns or less (e.g., about 2.8 microns or less, about 2.6 microns or less, about 2.4 microns or less, about 2.2 microns or less, about 2.0 microns or less, or about 1.8 microns or less) and about 0.4 microns or more (e.g., about 0.6 microns or more, about 0.8 microns or more, about 1.0 micron or more, about 1.2 microns or more, about 1.4 microns or more, or about 1.6 microns or more). Examples of copper etching agents for removing the overburden of copper include aqueous solutions containing cupric chloride and hydrochloric acid, or aqueous mixtures of ferric nitrate and hydrochloric acid. Other suitable copper etching agents include, but are not limited to, the copper etching agents described in U.S. Patents Nos. 4,784,785, 3,361,674, 3,816,306, 5,524,780, 5,650,249, 5,431,776, and 5,248,398, the content of which is incorporated herein by reference, and U.S. Patent Application Publication No. 2017175274.

[0097] Some embodiments describe a process for surrounding a metal-structured substrate, which includes a wire structure of a conductive metal (e.g., copper) forming a network of lines and interconnections, with a dielectric film of the present disclosure. The process is: a) A step of providing a substrate including a conductive metal wire structure that forms a network of lines and interconnections on the substrate; b) A step of depositing the dielectric film-forming composition of the present disclosure onto a substrate to form a dielectric film (e.g., surrounding conductive metal lines and interconnections); and c) Exposing the dielectric film to a radiation source, heat, or a combination of radiation and heat (with or without a mask), It may include.

[0098] The above process may be repeated multiple times (e.g., two, three, or four times) to form a complex multi-layered three-dimensional object.

[0099] In some embodiments, the present disclosure features a method for producing a dry film structure. The method is: a) Coating a carrier substrate (e.g., a substrate comprising at least one polymer or plastic film) with a dielectric film-forming composition described herein. b) Drying the coated dielectric film-forming composition to form a dry film; and c) Optionally, apply a protective layer to the dry film. It may include.

[0100] In some embodiments, the carrier substrate is a single or multi-layer polymer or plastic film, which may comprise one or more polymers (e.g., polyethylene terephthalate). In some embodiments, the carrier substrate has excellent optical transparency and is substantially transparent to chemical radiation used to form a relief pattern on the polymer layer. The thickness of the carrier substrate is preferably in the range of about 10 μm or more (e.g., about 15 μm or more, about 20 μm or more, about 30 μm or more, about 40 μm or more, about 50 μm or more, or about 60 μm or more) to about 150 μm or less (e.g., about 140 μm or less, about 120 μm or less, about 100 μm or less, about 90 μm or less, about 80 μm or less, or about 70 μm or less).

[0101] In some embodiments, the protective layer may be a single or multiple layer and may comprise one or more types of polymers (e.g., polyethylene or polypropylene). Examples of carrier substrates and protective layers are described, for example, in U.S. Patent Application Publication No. 2016 / 0313642, the contents of which are incorporated herein by reference.

[0102] In some embodiments, the dielectric film of the dry film can be peeled from the carrier layer as a self-supporting dielectric film. A self-supporting dielectric film is a film that can maintain physical integrity without using any supporting layers such as a carrier layer. In some embodiments, the self-supporting dielectric film is neither crosslinked nor cured and may contain the components of the dielectric film forming composition described above, excluding the solvent.

[0103] In some embodiments, the dielectric loss tangent or dielectric loss tangent of a film produced from the dielectric film-forming composition of the present disclosure, measured at 10 GHz, 15 GHz, and / or 35 GHz, is in the range of about 0.001 or more (e.g., about 0.002 or more, about 0.003 or more, about 0.004 or more, about 0.005 or more, about 0.01 or more, or about 0.05 or more) to about 0.1 or less (e.g., about 0.08 or less, about 0.06 or less, about 0.05 or less, about 0.04 or less, about 0.02 or less, about 0.01 or less, about 0.008 or less, about 0.006 or less, or about 0.005 or less).

[0104] In some embodiments, a dry film dielectric film can be laminated onto a substrate (e.g., a semiconductor substrate such as a wafer) using a vacuum laminator at approximately 50°C to 140°C after pre-lamination of the dry film dielectric film using a planar compression method or a hot roll compression method. When hot roll lamination is used, the dry film structure may be placed in a hot roll laminator, an optional protective layer may be peeled off from the dielectric film / carrier substrate, and the dielectric film may be contacted and laminated to the substrate by heat and pressure using rollers to form an article containing the substrate, dielectric film, and carrier substrate. Subsequently, the dielectric film may be exposed to a radiation source or heat (e.g., through the carrier substrate) to form a crosslinked photosensitive dielectric film. In some embodiments, the carrier substrate may be removed before the dielectric film is exposed to a radiation source or heat.

[0105] Some embodiments of this disclosure describe a process for fabricating a planar dielectric film on a substrate having a copper pattern. In some embodiments, the process includes depositing a dielectric film-forming composition on a substrate having a copper pattern to form a dielectric film. In some embodiments, the process is: a. A step of providing a dielectric film forming composition, and b. A step of forming a dielectric film by depositing a dielectric film-forming composition on a substrate having a copper pattern, wherein the difference between the highest and lowest points on the upper surface of the dielectric film is less than approximately 2 microns (e.g., less than 1.5 microns, less than 1 micron, or less than 0.5 microns), Includes.

[0106] In some embodiments, the Disclosure features articles comprising at least one patterned dielectric film formed by processes described herein. Examples of such articles include semiconductor substrates, flexible films for electronics, wire isolations, wire coatings, wire enamels, and inked substrates. In some embodiments, the Disclosure features semiconductor devices comprising one or more of these articles. Examples of semiconductor devices that can be manufactured from such articles include integrated circuits, light-emitting diodes, solar cells, and transistors.

[0107] All publications cited herein (e.g., patents, patent application publications, and articles) are incorporated herein by reference in their entirety.

[0108] This disclosure is illustrated in more detail by the following examples, which are illustrative and should not be construed as limiting the scope of this disclosure.

[0109] Purification Example 1: Purification of GVL Table 1 below contains data compiled for γ-valerolactone (GVL) from Sigma-Aldrich. [Table 1]

[0110] Processing of purified bio-derived solvents In the manufacturing process of the Examples and Comparative Examples, the following bio-derived organic solvents are prepared: GVL, cymene, and siren. For each of the bio-derived organic solvents, a high-purity grade organic solvent with a purity of 99% by mass or higher is used as a raw material for the production of the purified bio-derived organic solvent, and in addition, the raw material is pre-purified by distillation, ion exchange, filtration, etc. Using the raw materials thus obtained, each bio-derived organic solvent is purified by the following steps: (1) an ion exchange treatment step in which the organic solvent is subjected to ion exchange treatment, (2) a dehydration treatment step in which the organic solvent after the first ion exchange treatment is subjected to dehydration treatment, and (3) a distillation treatment step in which the organic solvent after dehydration treatment is subjected to distillation treatment.

[0111] Overview of trace metal detection Inductively coupled plasma mass spectrometry (ICP-MS) will be used to test the total trace metal concentrations in purified bio-derived organic solvent samples. Each sample will be tested for the presence of 36 different metal species using a method developed by Fujifilm. Detection limits vary depending on the metal, but typical detection limits are in the range of 0.00010 to 100.0 ppb.

[0112] Overview of trace moisture and organic impurity measurement Trace amounts of water and organic impurities in purified bio-derived solvent samples are measured using thermal desorption-gas chromatography / mass spectrometry (TD-GC / MS). A small amount of liquid sample is injected into a thermal desorption tube containing an adsorbent and placed in a thermal desorption apparatus. The sample is heated and then injected into a GC / MS unit, where the sample mixture is separated into its components, which are then identified by mass.

[0113] Overview of particle count measurement The number of particles in purified bio-derived solvent samples is measured using RION KS 18F.

[0114] Photosensitive composition example 1: Preparation of a photosensitive composition containing a PBO precursor (PBO-1) The photosensitive composition is prepared with 28.48 g of PBO precursor polymer (I): [ka] The composition was prepared using 46.10 g of bio-derived γ-butyrolactone, 0.87 g of γ-ureidopropyltrimethoxysilane, 0.70 g of diphenylsilanediol, and 3.85 g of structure (II) PAC. This composition was easily filtered using a 0.2 μm filter. [ka]

[0115] Comparative photosensitive composition example 1 A photosensitive composition was prepared using 28.48 g of PBO precursor polymer (I), 46.10 g of γ-butyrolactone, 0.87 g of γ-ureidopropyltrimethoxysilane, 0.70 g of diphenylsilanediol, and 3.85 g of PAC of structure (II). Filtration of this composition using a 0.2 μm filter was slow. A pre-filter was required before using the 0.2 μm filter to filter this composition.

[0116] Synthesis Example 1: Preparation of Polymer FCP-1 [ka] Solid 4,4'-(hexafluoroisopropylidene)bis(phthalic anhydride) (6FDA) (2.370 kg, 5.33 mol) was added at 25°C to a solution of 1-(4-aminophenyl)-1,3,3-trimethylindan-5-amine (also known as 4,4'-[1,4-phenylene-bis(1-methylethylidene)]bisaniline (DAPI)) (1.465 kg, 5.51 mol) in NMP (9.86 kg). The temperature of the reaction mixture was raised to 40°C and the mixture was reacted for 6 hours. Next, acetic anhydride (1.125 kg) and pyridine (0.219 kg) were added, and the temperature of the reaction mixture was raised to 100°C and the mixture was reacted for 12 hours.

[0117] The reaction mixture described above was cooled to room temperature and transferred to a large container equipped with a mechanical stirrer. The reaction solution was diluted with ethyl acetate and washed with water for 1 hour. After stopping the stirring, the mixture was allowed to stand without disturbing it. Once phase separation occurred, the aqueous phase was removed. The organic phase was diluted with a combination of ethyl acetate and acetone and washed twice with water. The amounts of organic solvents (ethyl acetate and acetone) and water used in all washing solutions are shown in Table 2. [Table 2]

[0118] Cyclopentanone (10 kg) was added to the washed organic phase, and the solution was concentrated by vacuum distillation to obtain polymer solution FCP-1. The solids content of the final polymer was 29.19%, and the weight-average molecular weight (Mw) measured by GPC was 54,000 daltons.

[0119] Synthesis Example 2: Preparation of fully cyclized polyimide (1) The following is an example of the preparation of a polyimide (PI) polymer using one type of diamine and one type of dianhydride, where the isolation solvent (i.e., lactone) was different from the purification solvent (i.e., ketone and ester).

[0120] Solid 4,4'-oxydiphthalic anhydride (ODPA, 664.5 g) was added at 25°C to a solution of 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl (TFMB, 722.1 g) in NMP (3296 g). The dianhydride was rinsed into the solution with an additional NMP (1346 g). The reaction temperature was raised to 40°C and the mixture was reacted for 3 hours. Next, acetic anhydride (507.2 g) and pyridine (98.3 g) were added, the reaction temperature was raised to 100°C, and the mixture was reacted for 12 hours.

[0121] The reaction mixture was cooled to room temperature, and a portion (899 g) was transferred to a 5 L container equipped with a mechanical stirrer. The reaction solution was diluted with a combination of cyclopentanone and n-butyl acetate and washed with water for 1 hour. Stirring was stopped, and the mixture was allowed to stand without disturbing it. Once phase separation occurred, the aqueous phase was removed. The organic phase was diluted with cyclopentanone and washed three more times with water. The amounts of purified solvent (i.e., cyclopentanone and n-butyl acetate) and water used in all washing solutions are shown in Table 3. [Table 3]

[0122] The washed organic phase was concentrated by vacuum distillation. γ-valerolactone (605 g) was added as an isolation solvent, and vacuum distillation was continued. The final polymer solution had a concentration of 24.99% by weight.

[0123] Synthesis Example 2: Preparation of fully cyclized polyimide (2) Solid ODPA (14.73 g) was added to a solution of TFMB (16.01 g) in a 1:1 bio-derived γ-valerolactone:siren (73.18 g) at 25°C. The dianhydride was rinsed into the solution with another 1:1 bio-derived γ-valerolactone:siren (29.75 g). The reaction temperature was raised to 40°C and the mixture was reacted for 3 hours. Next, acetic anhydride (11.32 g) and pyridine (2.21 g) were added, the reaction temperature was raised to 100°C, and the mixture was reacted for 12 hours.

[0124] Synthesis Example 3: Preparation of fully cyclized polyimide (3) A mixture of solid ODPA (94.78 g) and 2,2-[bis(3,4-dicarboxyphenyl)]hexafluoropropane dianhydride (6FDA) (45.25 g) was added to a solution of TFMB (135.5 g) in NMP (819 g) at 25°C. The dianhydride was rinsed into the solution with an additional 100 g of NMP. The reaction temperature was raised to 40°C and the mixture was reacted for 3 hours. Next, acetic anhydride (94.25 g) and pyridine (18.27 g) were added, the reaction temperature was raised to 100°C, and the mixture was reacted for 12 hours.

[0125] Photosensitive composition example 2: Preparation of photosensitive composition PSC-1 A photosensitive dielectric film-forming composition was prepared using 36.65 parts of a polyamic acid ester prepared from 4,4'-oxydiphthalic anhydride (ODPA), 4,4'-diaminophenyl ether (ODA), and 2-hydroxyethyl methacrylate (Durimide 733), 5.5 parts of 3,6,9-trioxaundekamethylenedimethacrylate, 0.73 parts of 3-(triethoxysilyl)propyl succinic anhydride, 0.88 parts of 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzoyl oxime) (OXE01 from BASF), 0.073 parts of monomethyl etherhydroquinone, 0.060 parts of tetrazole (5% solution in GBL / DMSO), 22.2 parts of dimethyl sulfoxide, and 88.8 parts of bio-derived γ-valerolactone (GVL) commercially available from Sigma-Aldrich. After stirring with a mechanical stirrer for 24 hours, the solution was filtered using a 0.2 micron filter (Ultradyne, Meissner Corporation, catalog number CLTM0.2-552).

[0126] Photosensitive composition example 3: Preparation of photosensitive composition PSC-2 The photosensitive dielectric film-forming composition (PSC-2) is prepared using 100 parts of a 29.19% solution of a polyimide polymer (FCP-1) having a weight-average molecular weight of 54,000 daltons in cyclopentanone, 2.76 parts of cyclopentanone, 41.5 parts of commercially available bio-derived γ-valerolactone (GVL) from Sigma-Aldrich as mentioned in Purification Example 1, 1.75 parts of a 0.5 wt% solution of PolyFox 6320 (a surfactant available from OMNOVA Solutions) in cyclopentanone, 1.46 parts of methacryloxypropyltrimethoxysilane (adhesion promoter), and 2-(O-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione (Irgacure The solution was prepared using 0.88 parts of OXE-1 (available from BASF, photoinitiator), 0.06 parts of monomethyl etherhydroquinone (antioxidant), 10.95 parts of tetraethylene glycol diacrylate (reactive functional compound), 3.65 parts of pentaerythritol triacrylate (reactive functional compound), 2.92 parts of 2,2-bis(4-cyanatophenyl)propane (cyanate ester), and 0.15 parts of 5-methylbenzotriazole (copper corrosion inhibitor). After stirring with a mechanical stirrer for 24 hours, the solution was filtered using a 0.2 micron filter (Ultradyne from Meissner Corporation, catalog no. CLTM0.2-552).

[0127] The aforementioned solution is subjected to trace metal analysis. All trace metals are below 500 ppb, which meets the requirements for employing such a solution for semiconductor packaging applications.

[0128] Dry film example 1 The photosensitive dielectric film-forming composition consists of 1345.24 g of a 31.69% solution of polyimide polymer (FCP-1) having a weight-average molecular weight of 57000 in cyclopentanone, 1021.91 g of bio-derived γ-valerolactone (GVL) prepared in Purification Example 1, 102.31 g of a 0.5 wt% solution of PolyFox 6320 in cyclopentanone, 21.31 g of methacryloxypropyltrimethoxysilane, 34.11 g of a 50% solution of XU-378 (bisphenol M cyanate ester available from Huntsman) in cyclopentanone, and Irgacure Prepare the solution using 12.79 g of OXE-1, 0.43 g of monomethyl etherhydroquinone, 138.55 g of tetraethylene glycol diacrylate, 53.39 g of pentaerythritol triacrylate, 21.32 g of ethylene glycol dicyclopentenyl ether acrylate, 4.26 g of dicumyl peroxide, and 0.426 g of 5-methylbenzotriazole. After stirring with a mechanical stirrer for 24 hours, filter the solution using a 0.2 micron filter (Ultradyne from Meissner Corporation, catalog number CLTM0.2-552).

[0129] This photosensitive dielectric film-forming composition was applied to a polyethylene terephthalate (PET) film (TCH21, manufactured by DuPont Teijin Films USA) used as a carrier substrate, having a width of 16.2 inches and a thickness of 36 microns, using a slot die coater at a line speed of approximately 2 feet / min (61 cm / min) with a clearance of 60 microns, and dried at 194°F to obtain a photosensitive polymer layer with a thickness of approximately 12.0 microns. A biaxially oriented polypropylene film (BOPP, manufactured by Impex Global, Houston, TX), having a width of 16 inches and a thickness of 30 microns, was roll-compressed onto this polymer layer to function as a protective layer. The carrier substrate, photosensitive polymer layer, and protective layer together formed a dry film (i.e., DF-1).

[0130] Example: Formation of a three-dimensional object The photosensitive dielectric film-forming composition prepared in Dry Film Example 1 is converted into a film deposited on various substrates used in microelectronics and packaging applications. Approximately 5 g of the solution is spin-coated at a spin speed of approximately 2000 rpm to deposit the film on a 100 mm silicon wafer. The film is dried on a hot plate at 105°C for 3 minutes. A clear, transparent film of 12 microns is obtained. The film thickness uniformity across the entire 100 mm substrate is within 0.5 microns. The total number of particle defects in the film is less than 500 particles / cm². The film quality in terms of transparency, defect count, and uniformity meets the requirements for employing such a solution for semiconductor packaging applications.

[0131] The above tests are repeated on aluminum, copper, and silicon nitride. All films obtained in this way meet the requirements for employing such solutions for semiconductor packaging applications.

[0132] Other embodiments are described in the claims.

Claims

1. A method for purifying bio-derived organic solvents: (1) Passing the bio-derived organic solvent through an ion exchange filter unit comprising a housing and an ion exchange filter containing at least one first ion exchange filter and at least one second ion exchange filter, wherein both the at least one first ion exchange filter and the at least one second ion exchange filter are negatively charged ion exchange filters and are connected in series, and the at least one first ion exchange filter is different from the at least one second ion exchange filter; (2) Passing the bio-derived organic solvent through at least one column containing an adsorbent to remove water from the bio-derived organic solvent; and (3) Distill the bio-derived organic solvent using a distillation column to obtain a purified bio-derived organic solvent. A method comprising: the bio-derived organic solvent being obtained from a biological raw material; the purified bio-derived organic solvent containing an acid component in an amount of about 0.1 ppb to about 1000 ppm by mass; and the purified bio-derived organic solvent containing water in an amount of about 0.1 ppb to about 1000 ppm by mass.

2. The method according to claim 1, wherein the bio-derived organic solvent comprises a lactone, a ketone, an ether, an alkyl aromatic compound, an alcohol, or an alkyl alicyclic compound.

3. The method according to claim 2, wherein the bio-derived organic solvent comprises γ-valerolactone, sylen, 2-methyltetrahydrofuran, glycerol, pinene, limonene, or cymene.

4. The method according to claim 2, wherein the lactone is γ-valerolactone.

5. The method according to claim 2, wherein the ketone is siren.

6. The method according to claim 2, wherein the ether is 2-methyltetrahydrofuran.

7. The method according to any one of claims 1 to 6, wherein the biological raw material is selected from the group consisting of lignocellulosic biomass, sugarcane, corn, vegetable oil, waste oil, or citrus waste.

8. The method according to any one of claims 1 to 7, wherein the purified bio-derived organic solvent contains a metal component in an amount of about 10 ppt to about 500 ppb by mass.

9. The method according to any one of claims 1 to 8, wherein the purified bio-derived organic solvent contains a total amount of metal components in an amount of about 50 ppt to about 500 ppb.

10. The method according to any one of claims 1 to 9, wherein the bio-derived organic solvent is a lactone or an ether, and the purified bio-derived organic solvent contains an acid component in an amount of about 0.1 ppb to about 100 ppb by mass.

11. The method according to any one of claims 1 to 10, wherein the bio-derived organic solvent contains water in an amount of about 10 ppb to about 100 ppm by mass.

12. A purified bio-derived organic solvent produced by the method according to any one of claims 1 to 11.

13. A purified bio-derived organic solvent, The bio-derived organic solvent is obtained from a biological raw material; The bio-derived organic solvent contains an acidic component in an amount of about 0.1 ppb to about 1000 ppm by mass; and The aforementioned bio-derived organic solvent contains water in an amount of approximately 0.1 ppb to approximately 1000 ppm by mass. Purified bio-derived organic solvent.

14. The organic solvent according to claim 12 or claim 13, comprising a lactone, ketone, ether, alkyl aromatic compound, alcohol, or alkyl alicyclic compound.

15. The organic solvent according to claim 14, comprising γ-valerolactone, sylen, 2-methyltetrahydrofuran, glycerol, pinene, limonene, or cymene.

16. A method for producing a polymer, comprising forming a polymer containing a polyimide precursor polymer, a polybenzoxazole precursor polymer, or a fully imidized polyimide polymer in a solvent system containing at least one first organic solvent and optionally at least one second organic solvent, The method wherein the at least one first organic solvent comprises a purified bio-derived organic solvent according to any one of claims 12 to 15, wherein the bio-derived organic solvent is an aprotic polar solvent selected from the group consisting of lactones, ketones, ethers, alkyl aromatic compounds, and alkyl alicyclic compounds, and the at least one second organic solvent comprises a carbonyl group.

17. A resin selected from the group consisting of epoxy resins, novolac resins, polyamide resins, polybenzoxazole precursor polymers, polyimide precursor polymers, and fully imidized polyimide polymers; A solvent system comprising at least one first organic solvent and optionally at least one second organic solvent, A photosensitive composition comprising, wherein the at least one first organic solvent comprises a purified bio-derived organic solvent according to any one of claims 12 to 15, the bio-derived organic solvent being a solvent selected from the group consisting of lactones, ketones, ethers, alkyl aromatic compounds, and alkyl alicyclic compounds, and the at least one second organic solvent comprising a carbonyl group.

18. The composition according to claim 17, further comprising at least one cyanate ester compound containing at least two cyanate groups.

19. The composition according to claim 17 or claim 18, further comprising at least one reactive functional compound.

20. The composition according to claim 19, wherein the at least one reactive functional compound is a di(meth)acrylate-containing crosslinking agent in an amount of about 5% to about 50% by weight relative to the resin.

21. (a) Placing a photosensitive composition on a substrate to form a film; (b) Exposing the film to radiation, heat, or a combination thereof; and (c) Develop the exposed film using an organic developer to form a pattern on the substrate. A pattern forming method comprising, wherein the organic developer comprises a purified bio-derived organic solvent according to any one of claims 12 to 15.

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