WO2025207687A2 - Générateurs de photobase cyclique pour la formation de polyimide - Google Patents

Générateurs de photobase cyclique pour la formation de polyimide

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Publication number
WO2025207687A2
WO2025207687A2 PCT/US2025/021415 US2025021415W WO2025207687A2 WO 2025207687 A2 WO2025207687 A2 WO 2025207687A2 US 2025021415 W US2025021415 W US 2025021415W WO 2025207687 A2 WO2025207687 A2 WO 2025207687A2
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WO
WIPO (PCT)
Prior art keywords
mmol
compound
pbg2
solution
added
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/US2025/021415
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English (en)
Other versions
WO2025207687A3 (fr
Inventor
Raghunath R. DASARI
Xinliang DING
Shijun Zheng
Tissa Sajoto
Cheng-Kang Mai
Kota Nishino
Kumpei OTSUKA
Peng Wang
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.)
Nitto Denko Corp
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Nitto Denko Corp
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Publication date
Application filed by Nitto Denko Corp filed Critical Nitto Denko Corp
Publication of WO2025207687A2 publication Critical patent/WO2025207687A2/fr
Publication of WO2025207687A3 publication Critical patent/WO2025207687A3/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B51/00—Nitro or nitroso dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B57/00—Other synthetic dyes of known constitution
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0387—Polyamides or polyimides

Definitions

  • the present disclosure relates to photobase generators which may be used for polyimide formation.
  • Photobase Generators typically include three parts: a chromophore, responsible for light absorption and thus transforming the energy of photons into chemical energy, a latent base, which is the moiety that releases the actual base upon application of light, and a linker that connects the base with the chromophore. PBGs release amine bases upon light irradiation and are being explored in the areas of photoinitiated polymerization, photoinduced crosslinking of polymers, photo-patterning, adhesives, and lithography. However, photobase generators are less developed than photoacid generators. PBGs are based on both non-ionic and ionic types.
  • Typical PBG linkers include carbamates, O- acyloximes, ammonium salts, sulfonamides, formamides, nifedipines, and o- aminoketones.
  • O-acyloximes require water to release the base so they may not be ideal in polymeric substrates that are sensitive to water.
  • carbamate linker based PBGs are efficient and synthetically versatile.
  • Photosensitive polyimides may be attractive for microelectronics because they can be patterned by direct exposure and developed without a photoresist. PSPIs may find applications in various electronic, electro-optic, waveguide, and nonlinear optical materials.
  • a photosensitive polyimide system typically includes a polyimide precursor and a photobase generator as an accelerator to form a polyimide by a photoreaction.
  • a polyimide precursor with an aromatic ring as a basic skeleton typically has a broad absorption band in the ultraviolet (UV) region of wavelengths below 400 nm. Therefore, when ultraviolet light is applied, the photochemical reaction may not proceed effectively in the exposed area because the absorption of light is predominantly by the polyimide precursor, which results in low sensitivity and deterioration of the pattern shape.
  • UV ultraviolet
  • UV responsive catalysts require high photon energy, often achieve reduced curing depths, and may also cause irreversible damage to UV-sensitive materials.
  • existing photobase generators also show high thermal residue, and low photolytic base release efficiency, which are undesirable for improving efficiency of a photosensitive polyimide-based electronic device.
  • Ra is hydrogen, a Ci-Ce alkyl (cyclopropyl or a trihalomethyl group ; and R 4 is a C 3 -C 8 alkyl and Rs is a C 3 -C 8 alkyl or R 4 and Rs are connected together to form a nitrogen containing ring provided that when R 4 and Rs are connected together to form the nitrogen containing ring Ra is hydrogen, a C 3 -C 8 alkyl, or a trihalomethyl group.
  • n is 1 or 2 and X and Y are connected together to form one of the following rings : ,
  • R1 is In some embodiments, R 2 is In some embodiments, In some embodiments,
  • R 4 and Rs are connected together and the nitrogen containing ring is one of
  • a method for making a polyimide includes providing a photobase generator compound as described herein and a polyimide precursor dispersion in a dispersant; covering a substrate with the PBG compound and polyimide precursor; applying visible light to the PBG compound and polyimide precursor on the substrate; and heating the substrate to accomplish at least one of removing the dispersant from the covering and curing the covered substrate.
  • the method may further include masking portions of the covered substrate to selectively apply visible light to unmasked portions of the substrate.
  • a method for measuring the base release efficiency of a photobase generator compound includes dissolving a photobase generator as described herein in acetonitrile; measuring the pH of a solution including the compound dissolved in the acetonitrile; exposing the solution to visible light; and measuring the pH of the solution following exposure to visible light.
  • a photobase generator compound described herein may exhibit excellent absorption in the visible spectral region, low thermal residue upon heating up to 450 °C and/or base moiety separation.
  • a method for manufacturing polyimide films using a photobase generator compound described herein is provided.
  • FIG. 1 is a graphical illustration of polyimidization efficiency.
  • FIG. 2 is graphical illustration of absorption spectra of different photobase generator compounds.
  • the present disclosure relates to photobase generator compounds and their use(s) in generating reactive precursors for polyimide generation.
  • the photobase generator compounds disclosed herein may be used for formation of a polyimide under light irradiation conditions, which in turn may be useful for fabrication of efficient microelectronic devices.
  • the photobase generator may absorb light in the visible region, for example from about 380 nm to about 440 nm, exhibit high photobase release activity, and/or may have a very low thermal residue upon heating above 400 °C.
  • the photobase generator compounds described herein may absorb light energy of first wavelength and on heterolytic cleavage, form an aci-nitro intermediate and carbamate that contains a base moiety.
  • the carbamate and carbon dioxide can be further cleaved to provide a desired base compound.
  • the cleaved base compound(s) may act as a catalyst(s) for formation of polyimide from a polyimide precursor.
  • moiety refers to a specific segment or functional group of a molecule. Chemical moieties are often recognized as chemical entities embedded in or appended to a molecule.
  • benzodioxole refers to a chemical moiety with the following structure:
  • benzoimidazole refers to a chemical moiety with the following structure:
  • benzodioxine refers to a chemical moiety with the following structure:
  • benzooxazine refers to a chemical moiety with the following structure:
  • n 0, 1 , or 2
  • X is C, O or N
  • Y is N or O
  • X and Y are optionally connected together to form a ring when n is 1 or 2
  • R1 is a hydrogen, nitro, phenyl, substituted phenyl, alkynyl, substituted alkynyl or methoxy
  • R2 is hydrogen, phenyl, substituted phenyl, alkynyl, substituted alkynyl, cyano ) or methoxy
  • R 3 is hydrogen, a C 1 -C 6 alkyl (e.g., methyl, cyclopropyl, cyclopentyl, or cyclohexyl), or a trihalomethyl group such as CF 3
  • R 4 is a C 3 -C 8 alkyl and Rs is a C 3 -C 8 alkyl or wherein R 4 and Rs are connected together to form a nitrogen containing ring provided that when R 4 and Rs are
  • the reaction flask was evacuated and refilled with Argon twice and cyclohexanecarbonitrile (5.45 mL, 45.78 mmol).
  • 1:3 (v/v) trifluoroacetic acid (11.5 mL) and water (34.5 mL) were added, and the reaction mixture was heated at 60 °C for 90 minutes.
  • the reaction mixture was dropped slowly into saturated sodium bicarbonate (NaHCOa) (100 mL), and the organic product was extracted into CH2CI2, washed with NaCI solution, and dried over Na 2 SO 4 After drying, the crude product was purified by flash chromatography (silica gel, 50-60% CH2CI2 in hexanes) to afford the product.
  • Cyclohexyl(6-nitrobenzo[d][1,3]dioxol-5-yl)methanone (PBG2-8.2): A 250 mL 3-neck RBF was charged with benzo[d][1,3]dioxol-5-yl(cyclohexyl)methanone, PBG2-8.1, (5.50 g, 23.70 mmol), and nitromethane (42 mL). At room temperature (RT), nitric acid (15 mL, 70%) was added dropwise via an addition funnel over 20 min, and the reaction mixture was stirred for 15 h at RT.
  • the mixture was purged with Argon and was warmed up to 150 °C and kept at this temperature for 2 hours. Both TLC and LCMS showed the completion of the reaction.
  • the mixture was cooled down to room temperature and then poured into saturated sodium bicarbonate solution (180 mL). The mixture was extracted with ethyl acetate (3* 150 mL). The combined organic phase was washed with water (100 mL), and brine (100 mL) sequentially and was dried over anhydrous sodium sulfate. After filtration and concentration, the crude was purified by silica gel chromatography to provide PBG2-12.2 as a yellow solid using 0-40% ethyl acetate in Hexane as the eluants. 91% yield.
  • Compound PBG6-1.2 To a solution of compound PBG6-1.1 (0.75 g, 4.2 mmol) in 10 mL nitromethane, 5 mL of 70% nitric acid and 5 mL of 90% nitric acid were added. The solution was then stirred at room temperature for 10 min. To the solution, 50 mL water was added, and a precipitate formed. After filtration, the solid was washed with water, dried in air, then redissolved in dichloromethane (DCM), loaded on silica gel, and purified by flash chromatography using eluents of DCM/ethyl acetate (0% to 5% ethyl acetate). The 2 nd peak was collected as the desired product.
  • DCM dichloromethane
  • N,N-dihexylamine (0.67 mL, 2.9 mmol) was added, and it was then stirred at room temperature overnight.
  • the solution was washed with a 20% NaCI solution (50 mL), then a 5% NaHCO3 solution (50 mL x 2). It was loaded on silica gel, and purified by flash chromatography using eluents of hexanes/DCM (0% to 10% DCM to DCM with 3% EA). The 2 nd main peak was collected as the desired product. Removal of solvents gave a pale-yellow solid (0.70 g, in 75% yield).
  • TGA measurements were taken from 25 °C to 450 °C under nitrogen with a flow rate of 25 ml/min using a method with a ramp rate of 10 °C/min by TA instrument TGA550.
  • the TGA data of the o-nitro heteroaryl-based PBGs are presented in Table 1.
  • a selected PBG e.g., PBG2-2, PBG2-8, and or PBG2-7
  • a polyimide precursor e.g., a polyamidic acid such as PAA-55 and/or PAA-56 identified above
  • Thinky 2000 rpm for 3 min, added more mixing time as needed until all fully dissolved.
  • the mixed solution was spin-coated on Steel Use Stainless (SUS) 304 substrates taped on a rigid glass plate
  • SUS304 is a Japanese JIS Standard and one of the most frequently used stainless steels, comprising 18% Cr and 8% Ni.
  • the substrates were then baked at 120 °C for 10 min to remove N-methyl-2-pyrrolidone (NMP) solvent. Thereafter, 600 mJ/cm 2 of mercury lamp was then exposed on the sample with a mask (using Dymax UV curing conveyor). Afterwards, the post-exposure baking was conducted at 185 °C for 5 min.
  • NMP N-methyl-2-pyrrolidone
  • FT-IR Thermo Nicolet i860
  • the imidization contrast ratio is the ratio of imidization rate% of exposed area to the imidization rate% of the unexposed area. See Figure 1.
  • PBG2-2, PBG2-8 and PBG2-7 showed good imidization contrast ratio of 1.50, 1.62, and 1.33, respectively, as shown in Figure 1.
  • PBG3-1, PBG2-2, PBG3-2, PBG6-1, and PBG5-2 are graphically illustrated in FIG. 2.
  • Absorbance spectra of the PBGs were measured in N- methylpyrrolidone (NMP) solvent ( ⁇ 0.001 mmol/ml concentration) using Shimadzu UV3600 spectrometer.
  • NMP N- methylpyrrolidone
  • This disclosure may sometimes illustrate different components contained within, or connected with, other different components. Such depicted architectures are merely examples, and many other architectures can be implemented to achieve the same or similar functionality.
  • any disjunctive word and/or phrase presenting two or more alternative terms should be understood to contemplate the possibilities of including one of those terms, either of the terms, or both terms.
  • the phrase “A or B” will be understood to include the possibilities of A” or “B” or “A and B”.
  • the phrase “A and/or B” will be understood to include the possibilities of A” or “B” or “A and B”.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente divulgation concerne des générateurs de photobase qui comprennent une fraction hétérocyclique, une fraction absorbant la lumière visible et un complexe lieur. L'application de lumière visible au générateur de photobase peut produire une entité de base pour la fabrication de polyimide.
PCT/US2025/021415 2024-03-26 2025-03-25 Générateurs de photobase cyclique pour la formation de polyimide Pending WO2025207687A2 (fr)

Applications Claiming Priority (2)

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US202463570228P 2024-03-26 2024-03-26
US63/570,228 2024-03-26

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WO2025207687A2 true WO2025207687A2 (fr) 2025-10-02
WO2025207687A3 WO2025207687A3 (fr) 2025-10-30

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2182106T3 (es) * 1996-07-26 2003-03-01 Vantico Ag Mezclas curables a base de resinas epoxi.
JP2006189591A (ja) * 2005-01-05 2006-07-20 Tokyo Institute Of Technology 感光性樹脂組成物、レリーフパターンの製造方法及び半導体装置
JP5333452B2 (ja) * 2008-10-02 2013-11-06 大日本印刷株式会社 感光性樹脂組成物、およびこれを用いた物品、及びネガ型パターン形成方法
JP2024029569A (ja) * 2022-08-22 2024-03-06 株式会社ニコン 感光性表面処理剤、積層体、パターン形成用基板、トランジスタ、パターン形成方法及びトランジスタの製造方法

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