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WO2025123268A1 - Deep eutectic solvent compositions for electronic applications - Google Patents

Deep eutectic solvent compositions for electronic applications Download PDF

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Publication number
WO2025123268A1
WO2025123268A1 PCT/CN2023/138692 CN2023138692W WO2025123268A1 WO 2025123268 A1 WO2025123268 A1 WO 2025123268A1 CN 2023138692 W CN2023138692 W CN 2023138692W WO 2025123268 A1 WO2025123268 A1 WO 2025123268A1
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WO
WIPO (PCT)
Prior art keywords
composition
urea
solvent
des
glycerine
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/CN2023/138692
Other languages
French (fr)
Inventor
Qinyuan GUI
Cheng Shen
Hua Ren
Jongcheol Kim
Tsukishima SHIN
Jitao CHEN
Meijia HE
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dow Chemical Korea Ltd
Dow Global Technologies LLC
Original Assignee
Dow Chemical Korea Ltd
Dow Global Technologies LLC
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Publication date
Application filed by Dow Chemical Korea Ltd, Dow Global Technologies LLC filed Critical Dow Chemical Korea Ltd
Priority to PCT/CN2023/138692 priority Critical patent/WO2025123268A1/en
Publication of WO2025123268A1 publication Critical patent/WO2025123268A1/en
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0048—Photosensitive materials characterised by the solvents or agents facilitating spreading, e.g. tensio-active agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • C08G73/1028—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous
    • C08G73/1032—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous characterised by the solvent(s) used
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/42—Stripping or agents therefor
    • G03F7/422—Stripping or agents therefor using liquids only
    • G03F7/425—Stripping or agents therefor using liquids only containing mineral alkaline compounds; containing organic basic compounds, e.g. quaternary ammonium compounds; containing heterocyclic basic compounds containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
    • C08G73/1053—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the tetracarboxylic moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain

Definitions

  • Embodiments relate to solvent compositions containing a mixture of two or more deep eutectic solvents and a glycol ether solvent for use in electronic and photolithography applications.
  • Photosensitive materials are used extensively, for example in the electronics industry in the fabrication of integrated circuits.
  • One useful class of photosensitive materials is the class of photosensitive polyimides (PSPI) .
  • PSPI photosensitive polyimides
  • Polyimides in general, are usually the reaction products of one or more dianhydride monomer with one or more diamine monomer.
  • one or more of the monomers has one or more substituent groups, such that the substituent group is capable of reacting with a photon to form a group that initiates a crosslinking reaction and/or is capable of participating in a crosslinking reaction.
  • a layer that contains a photosensitive polyimide or photoresist is present on a surface. Some portions of the layer are exposed to radiation (such as, for example, ultraviolet light) , while other portions are not. The portions exposed to radiation present different dissolving performance in developers compared with the unexposed portions.
  • the layer is then contacted with an alkaline solution, which degrades the non-crosslinked polyimide or photoresist to produce monomeric moieties; the layer is then washed with one or more solvents to dissolve the monomeric moieties; and then the layer is washed with water to remove the solvent along with the dissolved monomeric moieties.
  • Solvents suitable for dissolving photoresists or PSPI-forming monomers prioritize a number of factors, such as selecting solvents that are relatively non-volatile, have a melting point of 65°C or lower, non-halogenated, and low toxicity. While N-Methyl-2-Pyrrolidone (NMP) has been widely used to fill the role as solvent for photoresists or PSPI-forming monomers, the solvent has been identified as a threat to human reproductive health and alternatives are needed.
  • NMP N-Methyl-2-Pyrrolidone
  • embodiments disclosed herein are directed to methods that include dissolving one or more photosensitive polyimide-forming monomers with a solvent composition containing a mixture of: a deep eutectic solvent (DES) composition containing: urea, glycerine, and optionally betaine or triethanolamine; and a glycol ether according to the formula:
  • DES deep eutectic solvent
  • R1 is hydrogen or a C1 to C4 alkyl chain
  • R2 is hydrogen or methyl
  • n ranges from 1 to 4.
  • compositions consisting essentially of a DES composition containing: urea, glycerine, and optionally betaine or triethanolamine; and a glycol ether according to the formula:
  • R1 is hydrogen or a C1 to C4 alkyl chain
  • R2 is hydrogen or methyl
  • n ranges from 1 to 4
  • the solvent composition has a viscosity determined according to ASTM D445 of 80 cP or less.
  • Embodiments relate to solvent compositions containing a mixture of two or more deep eutectic solvents and a glycol ether solvent for use in electronic and photolithography applications.
  • Solvent compositions may include a DES composition and one or more glycol ether solvents to modify various properties including viscosity and solubilizing effectiveness for various highly polar materials, including PSPI-forming (co) monomers.
  • Solvent compositions may be used as a bio-friendly alternative to replace NMP for the application of electronic processing, such as dissolving monomers for PSPI synthesis, photoresist stripping, and the like.
  • Solvent compositions disclosed herein may meet the criteria for minimal toxicity, including safety in reproductive risk as outlined in the 2012 publication "Hazard Communication Standard, " published by the US Occupational Health and Safety Administration in US Federal Regulations publication 29 CFR 1910.1200.
  • Solvent compositions disclosed herein may be essentially free of halogen atoms.
  • the amount of halogen atoms present in the solvent composition may be present at a percent by weight (wt%) of less than 0.1 wt%, less than 0.01 wt%, or 0.001 wt%.
  • Solvent compositions may include mixtures containing a DES composition, one or more glycol ether solvents, and optionally one or more polyglycols.
  • the term “deep eutectic solvent” means a mixture of two or more materials that are capable of self-association, such as through hydrogen bond interactions, to form a eutectic mixture with a melting point lower than that of each individual component.
  • the DES composition may include two or more chemicals.
  • the DES composition may be a binary composition containing urea and glycerin; or a ternary composition containing betaine, urea, and glycerin, or triethanolamine, urea, and glycerine.
  • Binary DES compositions may include a mixture of urea and glycerine at a molar ratio ranging from 1 ⁇ 50 to 1 ⁇ 1, or 1 ⁇ 50 to 1 ⁇ 4.
  • the molar ratio of betaine ⁇ urea ⁇ glycerine may range from 0.11 ⁇ 0.44 ⁇ 0.44 to 0.16 ⁇ 0.33 ⁇ 0.5, or 0.28 ⁇ 0.14 ⁇ 0.57 to 0.16 ⁇ 0.33 ⁇ 0.5.
  • the molar ratio of triethanolamine ⁇ urea ⁇ glycerin may range from 0.01 ⁇ 0.03 ⁇ 0.95 to 0.95 ⁇ 0.03 ⁇ 0.01.
  • Solvent compositions may include one or more glycol ethers that are used to control viscosity and solubilization of PSPI monomers. Suitable glycol ethers may be described according to the formula:
  • Suitable glycol ethers may include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol n-propyl ether, propylene glycol t-butyl ether, propylene glycol n-butyl ether, dipropylene glycol methyl ether, dipropylene glycoln-propyl ether, dipropylene glycol t-butyl ether, dipropylene glycol n-butyl ether, tripropylene glycol n-propyl ether, tripropylene glycol t-butyl ether, tripropylene glycol n-butyl ether, tripropylene glycol n-butyl ether, tripropylene glycol n-butyl ether
  • Solvent compositions may include a mass ratio of a DES composition and one or more glycol ethers ranging from 4 ⁇ 1 to 1 ⁇ 4, 3 ⁇ 1 to 1 ⁇ 4, or 2 ⁇ 1 to 1 ⁇ 4.
  • Solvent compositions may also include one or more polyglycols such as triethylene glycol and tetraethylene glycol. Solvent compositions may include a polyglycol at a percent by weight (wt%) of 80 wt%or less, 70 wt%or less, or 60 wt%or less, such as in a range of 1.5 wt%to 60 wt%.
  • wt% percent by weight
  • Solvent compositions containing mixtures of DES compositions, glycol ethers and optional polyglycol may have a viscosity determined according to ASTM D445 of 80 cP or less, 75 cP or less, or 60 cP or less, such as in a range of 15 cP to 80 cP.
  • Solvent compositions may have suitable properties for a number of electronic manufacturing applications, such as solubilizing PSPI (co) monomers for synthesis or removal, photoresist stripping, photolithography, and the like.
  • Methods may include dissolving one or more photosensitive polyimide-forming monomers with a solvent composition comprising a mixture of: a DES composition containing urea, glycerine, and optionally betaine or triethanolamine; and a glycol ether according to the formula:
  • R1 is hydrogen or a C1 to C4 alkyl chain
  • R2 is hydrogen or methyl
  • n ranges from 1 to 4.
  • Solvent compositions disclosed herein may be capable of solubilizing PSPI-forming monomers at percent by weight (wt%) of at least 0.5 wt%.
  • PSPI monomers include dianhydrides including bisphenol-A dianhydride, oxydiphthalic anhydride such as 4, 4’-Oxydiphthalic anhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, pyromellitic dianhydride, and mixtures thereof; and diamines such as meta-phenylenediamine, para-phenylenediamine, oxydianiline, diaminodiphenylsulfone, 1, 3-bis (3-aminophenoxy) benzene, 1, 3-bis (4-aminophenoxy) benzene, 4, 4′-bis (3-aminophenoxy) biphenyl, 4, 4′-bis (4-aminophenoxy) biphenyl, bis (aminophen
  • Methods may also include photoresist stripping and photolithography processes that include providing a surface having a photoresist layer; and stripping at least a portion of the photoresist layer from the surface with the solvent mixture of the present disclosure.
  • Photoresist layers may be selected from those formed by a photosensitive polyimide layer, a phenolic resin layer, an acrylic layer or combination thereof.
  • formulation components and properties have been disclosed individually, it is envisioned that component elements may be included, excluded, or combined in any manner or subcombination utilizing any of the above concentration ranges and nested subranges therein. Further, that the recited formulation properties may be similarly achieved through various combinations of the recited components within the recited ranges.
  • CE1 is selected as NMP and CE2 is CARBITOL TM Solvent.
  • CEs and IEs they are the combination of DES and glycol ether solvent.
  • the DES is formulated by combining different ratio of betaine, urea and glycerin. The formulations are summarized in Tables 2 and 3.
  • the DES was prepared with heating and stirring methods. Specifically, the designed amount of betaine, urea, and glycerin were put into a glass beaker and heated to 80 °C with continuous stirring at 300 rpm. After 2 hours of stirring, a transparent DES was obtained. The DES composition was then cooled to room temperature. Solvent samples were prepared by combining the DES composition with the desired amount of glycol ether solvent, and left at room temperature until any generated bubbles disappeared.
  • glycol ether solvent in IE1 to IE7 improves photoresist stripping performance.
  • the higher concentration of glycol ether solvent possesses better performance to photoresist stripping, which is attributed to a reduction in viscosity and enhanced penetration and stripping performance.
  • samples containing betaine or TEA exhibit increased monomer dissolution properties. Similar results are demonstrated for glycerin. Compared with glycol ether alone, the combination of DES has a significant increase in monomer dissolving performance.
  • Viscosity measurements were conducted on a Hamilton Microlab Star (Hamilton Robotics, Inc. ) under room temperature (22 °C) .
  • This is a kind of high throughput liquid handlers with 8 independent channels that uses air displacement to aspirate and dispense fluids and differential pressure sensors to continuously monitor the pressure inside the pipet tips.
  • 1.00 gram of each solvent mixture was transferred into a glass vial and placed in 96-well plates. The samples were then sent for testing on Hamilton Microlab Star. After 20 minutes of testing, the results can be read on the screen. Viscosity testing results are shown in Tables 8 and 9.
  • inventive samples IE1 to IE7 containing DES and glycol ether solvent form a complementary system in which the DES composition functions as a high polar solvent, while the glycol ether solvent reduces the viscosity of the mixture without affecting polarity or solubilizing performance.

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
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Abstract

Methods that include dissolving one or more photosensitive polyimide-forming monomers with a solvent composition containing a mixture of: a deep eutectic solvent (DES) composition containing: urea, glycerine, and optionally betaine or triethanolamine; and a glycol ether according to the formula (I), where R1 is hydrogen or a C1 to C4 alkyl chain, R2 is hydrogen or methyl, n ranges from 1 to 4. Compositions may consist essentially of a deep eutectic solvent (DES) composition containing: urea, glycerine, and optionally betaine or triethanolamine; and a glycol ether.

Description

DEEP EUTECTIC SOLVENT COMPOSITIONS FOR ELECTRONIC APPLICATIONS Field
Embodiments relate to solvent compositions containing a mixture of two or more deep eutectic solvents and a glycol ether solvent for use in electronic and photolithography applications.
Introduction
Photosensitive materials are used extensively, for example in the electronics industry in the fabrication of integrated circuits. One useful class of photosensitive materials is the class of photosensitive polyimides (PSPI) . Polyimides, in general, are usually the reaction products of one or more dianhydride monomer with one or more diamine monomer. For the formation of photosensitive polyimides, usually one or more of the monomers has one or more substituent groups, such that the substituent group is capable of reacting with a photon to form a group that initiates a crosslinking reaction and/or is capable of participating in a crosslinking reaction.
In one common process for fabricating integrated circuits, a layer that contains a photosensitive polyimide or photoresist is present on a surface. Some portions of the layer are exposed to radiation (such as, for example, ultraviolet light) , while other portions are not. The portions exposed to radiation present different dissolving performance in developers compared with the unexposed portions. In this process, the layer is then contacted with an alkaline solution, which degrades the non-crosslinked polyimide or photoresist to produce monomeric moieties; the layer is then washed with one or more solvents to dissolve the monomeric moieties; and then the layer is washed with water to remove the solvent along with the dissolved monomeric moieties.
Solvents suitable for dissolving photoresists or PSPI-forming monomers prioritize a number of factors, such as selecting solvents that are relatively non-volatile, have a melting point of 65℃ or lower, non-halogenated, and low toxicity. While N-Methyl-2-Pyrrolidone (NMP) has been widely used to fill the role as solvent for photoresists or PSPI-forming monomers, the solvent has been identified as a threat to human reproductive health and alternatives are needed.
Summary
In one aspect, embodiments disclosed herein are directed to methods that include dissolving one or more photosensitive polyimide-forming monomers with a solvent composition containing a mixture of: a deep eutectic solvent (DES) composition containing: urea, glycerine, and optionally betaine or triethanolamine; and a glycol ether according to the formula:
where R1 is hydrogen or a C1 to C4 alkyl chain, R2 is hydrogen or methyl, n ranges from 1 to 4.
In one aspect, embodiments disclosed herein are directed to compositions consisting essentially of a DES composition containing: urea, glycerine, and optionally betaine or triethanolamine; and a glycol ether according to the formula:
where R1 is hydrogen or a C1 to C4 alkyl chain, R2 is hydrogen or methyl, n ranges from 1 to 4, and wherein the solvent composition has a viscosity determined according to ASTM D445 of 80 cP or less.
Detailed Description
Embodiments relate to solvent compositions containing a mixture of two or more deep eutectic solvents and a glycol ether solvent for use in electronic and photolithography applications. Solvent compositions may include a DES composition and one or more glycol ether solvents to modify various properties including viscosity and solubilizing effectiveness for various highly polar materials, including PSPI-forming (co) monomers. Solvent compositions may be used as a bio-friendly alternative to replace NMP for the application of electronic processing, such as dissolving monomers for PSPI synthesis, photoresist stripping, and the like.
Solvent compositions disclosed herein may meet the criteria for minimal toxicity, including safety in reproductive risk as outlined in the 2012 publication "Hazard Communication Standard, " published by the US Occupational Health and Safety Administration in US Federal Regulations publication 29 CFR 1910.1200.
Solvent compositions disclosed herein may be essentially free of halogen atoms. For example, the amount of halogen atoms present in the solvent composition may be present at a percent by weight (wt%) of less than 0.1 wt%, less than 0.01 wt%, or 0.001 wt%.
Solvent compositions may include mixtures containing a DES composition, one or more glycol ether solvents, and optionally one or more polyglycols. As used herein, the term “deep eutectic solvent” means a mixture of two or more materials that are capable of self-association,  such as through hydrogen bond interactions, to form a eutectic mixture with a melting point lower than that of each individual component.
The DES composition may include two or more chemicals. In some cases, the DES composition may be a binary composition containing urea and glycerin; or a ternary composition containing betaine, urea, and glycerin, or triethanolamine, urea, and glycerine. Binary DES compositions may include a mixture of urea and glycerine at a molar ratio ranging from 1∶50 to 1∶1, or 1∶50 to 1∶4.
Ternary compositions may include a molar ratio of betaine∶urea∶glycerine (a∶b∶c) , where a+b+c = 1, and a＜0.3, b＞0, and c＞0. For example, the molar ratio of betaine∶urea∶glycerine may range from 0.11∶0.44∶0.44 to 0.16∶0.33∶0.5, or 0.28∶0.14∶0.57 to 0.16∶0.33∶0.5. In some cases, ternary compositions may include a molar ratio of triethanolamine∶urea∶glycerine (a∶b∶c) , where a+b+c = 1, and a＜0.9, b＞0, and c＞0. For example, the molar ratio of triethanolamine∶urea∶glycerin may range from 0.01∶0.03∶0.95 to 0.95∶0.03∶0.01.
Solvent compositions may include one or more glycol ethers that are used to control viscosity and solubilization of PSPI monomers. Suitable glycol ethers may be described according to the formula:
where R1 is hydrogen or a C1 to C4 alkyl chain, R2 is hydrogen or methyl, n ranges from 1 to 4. Suitable glycol ethers may include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol n-propyl ether, propylene glycol t-butyl ether, propylene glycol n-butyl ether, dipropylene glycol methyl ether, dipropylene glycoln-propyl ether, dipropylene glycol t-butyl ether, dipropylene glycol n-butyl ether, tripropylene glycol n-propyl ether, tripropylene glycol t-butyl ether, tripropylene glycol n-butyl ether, and the like. In some cases, the glycol ether may be propylene glycol methyl ether.
Solvent compositions may include a mass ratio of a DES composition and one or more glycol ethers ranging from 4∶1 to 1∶4, 3∶1 to 1∶4, or 2∶1 to 1∶4.
Solvent compositions may also include one or more polyglycols such as triethylene glycol and tetraethylene glycol. Solvent compositions may include a polyglycol at a percent by weight  (wt%) of 80 wt%or less, 70 wt%or less, or 60 wt%or less, such as in a range of 1.5 wt%to 60 wt%.
Solvent compositions containing mixtures of DES compositions, glycol ethers and optional polyglycol may have a viscosity determined according to ASTM D445 of 80 cP or less, 75 cP or less, or 60 cP or less, such as in a range of 15 cP to 80 cP.
Solvent compositions may have suitable properties for a number of electronic manufacturing applications, such as solubilizing PSPI (co) monomers for synthesis or removal, photoresist stripping, photolithography, and the like. Methods may include dissolving one or more photosensitive polyimide-forming monomers with a solvent composition comprising a mixture of: a DES composition containing urea, glycerine, and optionally betaine or triethanolamine; and a glycol ether according to the formula:
where R1 is hydrogen or a C1 to C4 alkyl chain, R2 is hydrogen or methyl, n ranges from 1 to 4. Following dissolution of the PSPI (co) monomers, standard methods may be used to synthesize PSPI and/or prepare PSPI-functionalized surfaces.
Solvent compositions disclosed herein may be capable of solubilizing PSPI-forming monomers at percent by weight (wt%) of at least 0.5 wt%. In some cases, PSPI monomers include dianhydrides including bisphenol-A dianhydride, oxydiphthalic anhydride such as 4, 4’-Oxydiphthalic anhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, pyromellitic dianhydride, and mixtures thereof; and diamines such as meta-phenylenediamine, para-phenylenediamine, oxydianiline, diaminodiphenylsulfone, 1, 3-bis (3-aminophenoxy) benzene, 1, 3-bis (4-aminophenoxy) benzene, 4, 4′-bis (3-aminophenoxy) biphenyl, 4, 4′-bis (4-aminophenoxy) biphenyl, bis (aminophenoxy) benzophenone, and fluorinated diamines such as 2, 2’-Bis (trifluoromethyl) benzidine and 2, 2-bis [4- (-aminophenoxy) phenyl] hexafluoropropane.
Methods may also include photoresist stripping and photolithography processes that include providing a surface having a photoresist layer; and stripping at least a portion of the photoresist layer from the surface with the solvent mixture of the present disclosure. Photoresist layers may be selected from those formed by a photosensitive polyimide layer, a phenolic resin layer, an acrylic layer or combination thereof.
While formulation components and properties have been disclosed individually, it is  envisioned that component elements may be included, excluded, or combined in any manner or subcombination utilizing any of the above concentration ranges and nested subranges therein. Further, that the recited formulation properties may be similarly achieved through various combinations of the recited components within the recited ranges.
The numerical ranges disclosed herein include all values from, and including, the lower and upper value and all values in between. Unless stated to the contrary, implicit from the context, or customary in the art, all parts and percentages are based on weight and all test methods are current as of the filing date of this disclosure.
Examples
The following examples are provided to illustrate the embodiments of the invention, but are not intended to limit the scope thereof. Table 1 provides the materials used in the following examples.
Example 1: Solvent composition preparation
In this example, CE1 is selected as NMP and CE2 is CARBITOLTM Solvent. For other CEs and IEs, they are the combination of DES and glycol ether solvent. And the DES is formulated by combining different ratio of betaine, urea and glycerin. The formulations are summarized in Tables 2 and 3.


The DES was prepared with heating and stirring methods. Specifically, the designed amount of betaine, urea, and glycerin were put into a glass beaker and heated to 80 ℃ with continuous stirring at 300 rpm. After 2 hours of stirring, a transparent DES was obtained. The DES composition was then cooled to room temperature. Solvent samples were prepared by combining the DES composition with the desired amount of glycol ether solvent, and left at room temperature until any generated bubbles disappeared.
Example 2: Photoresist stripping performance
To test photoresist stripping performance evaluation, 3 mL of AZ SFP-1400 photoresist solution was applied dropwise to the surface of indium tin oxide (ITO) coated glass substrate (100 mm × 100 mm × 1 mm in size) . The substrate was spun at the rotation speed of 500 rpm for 10 s to spin-coat the photoresist solution. Then rotation speed was accelerated to 1000 rpm and maintained for 30 s to achieve 1 μm thick of photoresist film. The spin-coated photoresist was heated at 130 ℃ for 10 min under N2 atmosphere to evaporate solvent completely and cure the photoresist film. Afterwards, around 100 μL of each prepared solvents were dropped onto the  photoresist film under room temperature. The glass substrate was shaken slightly and the time for completely removing the photoresist was recorded.
Results for photoresist stripping performance are shown in Tables 4 and 5, where a stripping performance of 40 seconds or less is regarded as acceptable.

As the results show, inclusion of glycol ether solvent in IE1 to IE7 improves photoresist stripping performance. In terms of the ratio of the glycol ether solvent, the higher concentration of glycol ether solvent possesses better performance to photoresist stripping, which is attributed to a reduction in viscosity and enhanced penetration and stripping performance.
Example 3: PSPI comonomer dissolving performance
The ability of the solvent compositions to dissolve PSPI monomers was evaluated by loading 2.5 g of the sample solvent into a glass vial, followed by 0.125 g 4, 4’-Oxydiphthalic anhydride and 0.125 g 2, 2’-Bia (trifluoromethyl) benzidine. Components were then mixed until dispersed. The sample was then placed into a 65 ℃ oven for 2 h and determine the presence of a residue. Results containing a residue were denoted “R” , and no residue was indicated as “NR. ” Dissolving performance for tested samples are shown in Tables 6 and 7.

As shown, samples containing betaine or TEA exhibit increased monomer dissolution properties. Similar results are demonstrated for glycerin. Compared with glycol ether alone, the combination of DES has a significant increase in monomer dissolving performance.
Example 4: Solvent composition viscosity control
Viscosity measurements were conducted on a Hamilton Microlab Star (Hamilton Robotics, Inc. ) under room temperature (22 ℃) . This is a kind of high throughput liquid handlers with 8 independent channels that uses air displacement to aspirate and dispense fluids and differential pressure sensors to continuously monitor the pressure inside the pipet tips. Specifically, 1.00 gram of each solvent mixture was transferred into a glass vial and placed in 96-well plates. The samples were then sent for testing on Hamilton Microlab Star. After 20 minutes of testing, the results can be read on the screen. Viscosity testing results are shown in Tables 8 and 9.

As shown, inventive samples IE1 to IE7 containing DES and glycol ether solvent form a complementary system in which the DES composition functions as a high polar solvent, while the glycol ether solvent reduces the viscosity of the mixture without affecting polarity or solubilizing performance.
While the foregoing is directed to exemplary embodiments, other and further embodiments may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.

Claims (10)

  1. A method comprising:
    dissolving one or more photosensitive polyimide-forming monomers with a solvent composition comprising a mixture of:
    a deep eutectic solvent (DES) composition comprising:
    urea,
    glycerine, and
    optionally betaine or triethanolamine; and
    a glycol ether according to the formula:
    where R1 is hydrogen or a C1 to C4 alkyl chain, R2 is hydrogen or methyl, n ranges from 1 to 4.
  2. [Corrected under Rule 26, 10.01.2024]
    The method of claim 1, wherein the solvent composition has a viscosity determined according to ASTM D445 of 80 cP or less.
  3. The method of claim 1, wherein the DES composition comprises a mixture of urea and glycerine at a molar ratio ranging from 1: 50 to 1: 1.
  4. The method of claim 1, wherein the DES composition comprises one of:
    a mixture of betaine, urea, and glycerine having a molar ratio of betaine: urea: glycerine (a: b: c) , where a+b+c = 1, and a＜0.3, b＞0, and c＞0; or
    a mixture of triethanolamine, urea, and glycerin having a molar ratio of triethanolamine: urea: glycerin (a: b: c) , where a+b+c=1, and a＜0.9, b＞0, c＞0.
  5. The method of claim 1, wherein the DES composition comprises urea, glycerine, and betaine or optionally triethanolamine, and wherein the glycol ether is propylene glycol methyl ether.
  6. The method of claim 1, wherein the solvent composition is capable of solubilizing 4, 4’-Oxydiphthalic anhydride or 2, 2’-Bia (trifluoromethyl) benzidine at a percent by weight (wt%) of the solvent composition of at least 0.5 wt%.
  7. A composition consisting essentially of:
    a deep eutectic solvent (DES) composition comprising:
    urea,
    glycerine, and
    optionally betaine or triethanolamine; and
    a glycol ether according to the formula:
    where R1 is hydrogen or a C1 to C4 alkyl chain, R2 is hydrogen or methyl, n ranges from 1 to 4, and
    wherein the solvent composition has a viscosity determined according to ASTM D445 of 80 cP or less.
  8. The composition of claim 7, wherein the composition has halogen atoms at a percent by weight (wt%) of less than 0.001 wt%.
  9. The composition of claim 1, wherein the DES composition comprises urea, glycerine, and betaine, and wherein the glycol ether is propylene glycol methyl ether.
  10. A method comprising solubilizing at least one of 4, 4’-Oxydiphthalic anhydride or 2, 2’-Bia (trifluoromethyl) benzidine in the composition of claim 7.
PCT/CN2023/138692 2023-12-14 2023-12-14 Deep eutectic solvent compositions for electronic applications Pending WO2025123268A1 (en)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0532953A2 (en) * 1991-08-28 1993-03-24 Unitika Ltd. Polyimide precursor solution, process for producing the solution, and moldings and coatings obtained therefrom
WO2007047365A2 (en) * 2005-10-13 2007-04-26 Advanced Technology Materials, Inc. Metals compatible photoresist and/or sacrificial antireflective coating removal composition
JP2019203120A (en) * 2018-05-16 2019-11-28 旭化成株式会社 Polyimide precursor resin composition
US20210088903A1 (en) * 2019-01-23 2021-03-25 Microcosm Technology Co., Ltd. Photosensitive polyimide resin composition and polyimide film thereof
KR102260889B1 (en) * 2018-04-25 2021-06-04 엘티씨 주식회사 Soluble polyimides and positive photosensitive resin composition containing the same
WO2022076252A1 (en) * 2020-10-05 2022-04-14 Entegris, Inc. Microelectronic device cleaning composition
EP4105261A1 (en) * 2021-06-14 2022-12-21 Evonik Fibres GmbH New non-toxic polyimide solutions

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0532953A2 (en) * 1991-08-28 1993-03-24 Unitika Ltd. Polyimide precursor solution, process for producing the solution, and moldings and coatings obtained therefrom
WO2007047365A2 (en) * 2005-10-13 2007-04-26 Advanced Technology Materials, Inc. Metals compatible photoresist and/or sacrificial antireflective coating removal composition
KR102260889B1 (en) * 2018-04-25 2021-06-04 엘티씨 주식회사 Soluble polyimides and positive photosensitive resin composition containing the same
JP2019203120A (en) * 2018-05-16 2019-11-28 旭化成株式会社 Polyimide precursor resin composition
US20210088903A1 (en) * 2019-01-23 2021-03-25 Microcosm Technology Co., Ltd. Photosensitive polyimide resin composition and polyimide film thereof
WO2022076252A1 (en) * 2020-10-05 2022-04-14 Entegris, Inc. Microelectronic device cleaning composition
EP4105261A1 (en) * 2021-06-14 2022-12-21 Evonik Fibres GmbH New non-toxic polyimide solutions

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