CN116178716B - Polyisonimide and preparation method and application thereof - Google Patents
Polyisonimide and preparation method and application thereof Download PDFInfo
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- CN116178716B CN116178716B CN202310487165.5A CN202310487165A CN116178716B CN 116178716 B CN116178716 B CN 116178716B CN 202310487165 A CN202310487165 A CN 202310487165A CN 116178716 B CN116178716 B CN 116178716B
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- polyisoimide
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- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 229920001721 polyimide Polymers 0.000 claims abstract description 56
- 239000004642 Polyimide Substances 0.000 claims abstract description 55
- 239000000203 mixture Substances 0.000 claims abstract description 46
- 239000011248 coating agent Substances 0.000 claims abstract description 25
- 238000000576 coating method Methods 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 239000000178 monomer Substances 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 125000003118 aryl group Chemical group 0.000 claims description 13
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 239000012024 dehydrating agents Substances 0.000 claims description 8
- 239000007888 film coating Substances 0.000 claims description 8
- 238000009501 film coating Methods 0.000 claims description 8
- 150000004984 aromatic diamines Chemical class 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- -1 siloxane diamine Chemical class 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 4
- 239000003431 cross linking reagent Substances 0.000 claims description 4
- 239000003999 initiator Substances 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- 230000014759 maintenance of location Effects 0.000 abstract description 16
- 239000007787 solid Substances 0.000 abstract description 14
- 238000004528 spin coating Methods 0.000 abstract description 9
- 238000004090 dissolution Methods 0.000 abstract description 6
- 238000013007 heat curing Methods 0.000 abstract description 4
- 238000009835 boiling Methods 0.000 abstract description 3
- 239000011347 resin Substances 0.000 description 62
- 229920005989 resin Polymers 0.000 description 62
- 239000000243 solution Substances 0.000 description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 20
- 230000000694 effects Effects 0.000 description 20
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 19
- 239000002244 precipitate Substances 0.000 description 16
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 14
- 238000012360 testing method Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 238000001723 curing Methods 0.000 description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 10
- 229920002120 photoresistant polymer Polymers 0.000 description 10
- 238000004108 freeze drying Methods 0.000 description 9
- 239000012299 nitrogen atmosphere Substances 0.000 description 9
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 238000010907 mechanical stirring Methods 0.000 description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 7
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 7
- 239000000706 filtrate Substances 0.000 description 6
- 229920005575 poly(amic acid) Polymers 0.000 description 6
- QAEDZJGFFMLHHQ-UHFFFAOYSA-N trifluoroacetic anhydride Chemical compound FC(F)(F)C(=O)OC(=O)C(F)(F)F QAEDZJGFFMLHHQ-UHFFFAOYSA-N 0.000 description 6
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 5
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 5
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 5
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 5
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 238000001029 thermal curing Methods 0.000 description 4
- UVUCUHVQYAPMEU-UHFFFAOYSA-N 3-[2-(3-aminophenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]aniline Chemical compound NC1=CC=CC(C(C=2C=C(N)C=CC=2)(C(F)(F)F)C(F)(F)F)=C1 UVUCUHVQYAPMEU-UHFFFAOYSA-N 0.000 description 3
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- HCLJOFJIQIJXHS-UHFFFAOYSA-N 2-[2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOCCOC(=O)C=C HCLJOFJIQIJXHS-UHFFFAOYSA-N 0.000 description 2
- LTHJXDSHSVNJKG-UHFFFAOYSA-N 2-[2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOCCOC(=O)C(C)=C LTHJXDSHSVNJKG-UHFFFAOYSA-N 0.000 description 2
- MSTZGVRUOMBULC-UHFFFAOYSA-N 2-amino-4-[2-(3-amino-4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]phenol Chemical compound C1=C(O)C(N)=CC(C(C=2C=C(N)C(O)=CC=2)(C(F)(F)F)C(F)(F)F)=C1 MSTZGVRUOMBULC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 1
- RDLGTRBJUAWSAF-UHFFFAOYSA-N 1-(6-hydroxy-6-methylcyclohexa-2,4-dien-1-yl)propan-2-one Chemical compound CC(=O)CC1C=CC=CC1(C)O RDLGTRBJUAWSAF-UHFFFAOYSA-N 0.000 description 1
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- BEKFRNOZJSYWKZ-UHFFFAOYSA-N 4-[2-(4-aminophenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]aniline Chemical compound C1=CC(N)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(N)C=C1 BEKFRNOZJSYWKZ-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- RIFGWPKJUGCATF-UHFFFAOYSA-N ethyl chloroformate Chemical compound CCOC(Cl)=O RIFGWPKJUGCATF-UHFFFAOYSA-N 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001843 polymethylhydrosiloxane Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000000233 ultraviolet lithography Methods 0.000 description 1
Classifications
-
- 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
- C08G73/1075—Partially aromatic polyimides
- C08G73/1082—Partially aromatic polyimides wholly aromatic 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
- C08G73/1003—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
-
- 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
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
-
- 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
- C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
- C08G73/106—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing silicon
-
- 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
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Materials For Photolithography (AREA)
- Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention discloses a polyisoimide, a preparation method and application thereofAccording to the polyisoimide disclosed by the invention, the structural formula is shown as a formula I, the dissolution solid content of the polyisoimide in a polar high-boiling point solvent is higher than 60%, negative photosensitive polyimide compositions with different viscosities can be prepared according to different solid contents, the thickness range of a coating after spin coating is 0.5-100 mu m, the coating can realize negative patterns with the depth-to-width ratio of more than 2.5 and the minimum line width of 10-20 mu m after the steps of developing and heat curing processes, and the film retention rate of the negative patterns is higher than 85%.
Description
Technical Field
The invention relates to the technical field of materials, in particular to a polyisoimide and a preparation method and application thereof.
Background
UV-LIGA ultraviolet lithography is a lithography process applied to manufacturing sensor components of a micro motor system, and the application scene is to prepare precise parts with the size ranging from 0.1 mu m to 100 mu m. One of the biggest features in this process is that its special photoresist has a high aspect ratio (ratio of photoresist thickness to minimum line width of photoresist pattern), also called thick film photoresist. The larger the aspect ratio, the more stereoscopic the pattern structure is, and the more difficult the process is. In particular, for photoresists with pattern film thickness application requirements above 20 μm, the viscosity range is an important criterion for achieving a spin-on film thickness range thereof. Generally, the viscosity is proportional to the film thickness after photoresist spin coating, i.e., increasing the upper limit of photoresist viscosity is one idea of designing thick film photoresist.
In the field of photosensitive polyimide material application, negative photosensitive polyimide (which is difficult to dissolve after exposure and cross-linked) and positive photosensitive polyimide (which is accelerated to dissolve after exposure) can be classified according to different photoreaction characteristics of different photosensitive groups. Photosensitive polyimide precursor resins are typically dissolved and formulated into negative or positive photosensitive polyimide compositions, which are widely used in the photoresist field. There are two key factors in preparing photosensitive polyimide compositions: (1) the structure of a polyimide precursor; (2) selecting auxiliary agents such as a photocrosslinking agent, a solvent and the like.
Polyimide precursors can be classified into polyamic acids, polyamic acid salts, polyamic acid esters, and polyisoimides. When the polyimide is thermally cured, the polyamic acid, polyamic acid salt and polyamic acid ester are converted into polyimide from the molecular chain structure, small molecules of side chains are inevitably dropped, so that the thermal mass loss is larger, the film retention rate of the coating after the development and post-baking steps is smaller, the polyisoimide is polyimide isomer, small molecules are not dropped when the polyimide is converted into polyimide, and the film retention rate is larger after the development and post-baking steps. In thick film processes, the thermal mass loss is excessive, which results in a smaller film retention rate due to the increased film thickness requirements, and the effect is more pronounced.
However, conventional aromatic polyisoimides have limited solubility in high boiling polar organic solvents and are extremely prone to gel formation during dissolution or preparation, resulting in failure to perform subsequent processing. In order to avoid the above gel problem, the technical scheme in the related art is as follows: (1) controlling the solid content to be below 15%; (2) increasing the proportion of the end-capping agent to reduce the molecular weight of the polymer. However, the solution to the problem of the polyisoimide gel described above has significant drawbacks, especially for the preparation of thick film coatings. If the solid content is lower than 15%, the viscosity is too small, and the conventional spin coating process is difficult to prepare a coating with the thickness of more than 20 um; if the proportion of the end-capping agent is increased, the polymer molecular weight is reduced to increase the solubility, and too low a molecular weight can affect the film retention rate, thermal stability, etc. of the coating after thermal curing. The design of a photosensitive polyimide type photoresist with high solubility, large viscosity range, large spin-coating film thickness range, higher molecular weight and excellent comprehensive coating performance is a challenge for solving the problems.
Disclosure of Invention
The present invention aims to solve at least one of the above technical problems in the prior art. Therefore, the invention aims to provide a polyisoimide which can be dissolved in a polar high-boiling-point solvent to have a solid content higher than 60%, and a negative photosensitive polyimide composition prepared according to different solid contents can be used for preparing a coating with a thickness ranging from 0.5 mu m to 100 mu m. After the coating is subjected to the steps of development and thermal curing, the film retention rate is higher than 85%, and patterns with depth-to-width ratios higher than 2.5 and minimum line widths in the range of 10 um-20 mu m can be realized.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
in a first aspect of the present invention, a polyisoimide is provided, which has a structural formula as shown in formula I:
，
wherein n is x ：n y Is (1.5-4): 1, mn ranges from 20000 to 65000; preferably n x ：n y Is (1.5-3): 1, mn ranges from 20000 to 50000;
Ar 1 Included、/>、、/>、any one of (3);
Ar 2 Included、/>、、/>any one of (3);
Ar 3 Includedin the formula a, n=0 to 20, preferably n=0 to 10; r is R 1 、R 2 Each independently selected fromAt least one of (2);
r comprisesAny one of the following.
In a second aspect of the present invention, a method for preparing the polyisoimide is provided, comprising the following steps:
and (3) under an inert atmosphere, polymerizing an aromatic dianhydride monomer, an aromatic diamine monomer and a siloxane diamine monomer to obtain the polyisoimide.
In some embodiments of the invention, the method for preparing the polyisoimide comprises the following steps: under inert atmosphere, an aromatic dianhydride monomer (containing Ar 1 ) Dissolving in organic solvent, adding end capping agent, reacting, and adding aromatic diamine monomer (containing Ar 2 ) After the reaction, a siloxane diamine monomer (containing Ar) 3 ) And (3) reacting, namely dripping a dehydrating agent for reacting to obtain the polyisoimide.
In some embodiments of the present invention, the reaction temperature of the aromatic dianhydride monomer and the capping agent is 45 ℃ to 55 ℃ for 2h to 5h.
In some embodiments of the invention, the reaction temperature of the aromatic diamine monomer is 0-50 ℃ and the reaction time is 4-6 hours; the reaction temperature is preferably 10-35 ℃.
In some embodiments of the invention, the reaction temperature of adding siloxane diamine monomer is 0-50 ℃ and the reaction time is 10-12 hours; the reaction temperature is preferably 10-35 ℃.
In some embodiments of the invention, the time of dripping the dehydrating agent is 0.5 h-2 h.
In some embodiments of the invention, the reaction time of dropwise adding the dehydrating agent is 10-12 h.
In some embodiments of the present invention, the method for preparing the polyisoimide further comprises a purification treatment step, wherein the purification treatment step comprises filtering a product obtained after the reaction of dripping the dehydrating agent to obtain a filtrate, dripping the filtrate into a mixture of water and ethanol to precipitate out a precipitate, and drying the precipitate.
In some embodiments of the invention, the molar ratio of the aromatic dianhydride monomer to the aromatic diamine monomer is 1:0.6 to 0.8.
In some embodiments of the invention, the molar ratio of the aromatic dianhydride monomer to the siloxane diamine monomer is 1:0.2 to 0.4.
In some embodiments of the invention, the molar ratio of the aromatic dianhydride monomer to the capping agent is 1:0.025 to 0.05.
In some embodiments of the invention, the molar ratio of the aromatic dianhydride monomer to the dehydrating agent is 1: 1-3.
In some embodiments of the invention, the organic solvent comprises at least one of N, N-dimethylacetamide, N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, tetrahydrofuran.
In some embodiments of the invention, the dehydrating agent comprises any of dicyclohexylcarbodiimide, trifluoroacetic anhydride/triethylamine, ethyl chloroformate/triethylamine.
In a third aspect of the present invention, a negative photosensitive polyimide composition is provided, comprising the polyisoimide.
In some embodiments of the invention, the negative photosensitive polyimide composition comprises 30-50 wt% of the polyisoimide, 3-15 wt% of the photo-crosslinking agent and 40-60 wt% of the solvent.
In some embodiments of the invention, the negative photosensitive polyimide composition comprises 30-50 wt% of the polyisoimide, 3-15 wt% of the photo-crosslinking agent, 40-60 wt% of the solvent and 1-10 wt% of the initiator.
In some embodiments of the invention, the negative photosensitive polyimide composition comprises 40-50 wt% of the polyisoimide, 5-10 wt% of the photo-crosslinking agent, 40-50 wt% of the solvent and 1-5 wt% of the initiator.
In some embodiments of the invention, the photocrosslinking agent comprises at least one of hydroxyethyl methacrylate, hydroxyethyl acrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, ethylene glycol diacrylate, tetraethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate.
In some embodiments of the invention, the initiator comprises at least one of 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl phenyl acetone, diphenyl (2, 4, 6-trimethylbenzoyl) phosphine oxide.
In a fourth aspect of the present invention, there is provided a method for manufacturing a negative photosensitive polyisoimide pattern, comprising the steps of:
s1: coating the negative photosensitive polyimide composition on a substrate, baking for the first time, exposing a mask, and baking for the second time to obtain a dry film coating;
s2: and (3) developing, cleaning and curing the dry film coating of the S1 to obtain the negative photosensitive polyimide pattern.
In some embodiments of the present invention, the method for manufacturing a negative photosensitive polyisoimide pattern includes the steps of:
s1: spin-coating the negative photosensitive polyimide composition on a substrate, pre-baking at 80-100 ℃ for 90-400 s, exposing by using an i-line light source through a mask, wherein the exposure is 120-500 mJ/cm 2 Then carrying out post-baking at 120-150 ℃ for 90 s-300s, obtaining a dry film coating;
s2: and (3) developing and cleaning the dry film coating of the S1, heating to 320-350 ℃ from 100-120 ℃ at a rate of 80-100 ℃ per hour, and curing for 2-3 hours to obtain the negative photosensitive polyimide pattern.
In some embodiments of the invention, the substrate material includes any one of quartz, wafer, and copper.
In some embodiments of the present invention, the thickness of the negative photosensitive polyimide pattern is 0.05 μm to 100 μm; preferably 20-60 mu m.
According to a fifth aspect of the present invention, there is provided the use of the negative photosensitive polyimide composition in an integrated circuit.
The beneficial effects of the invention are as follows:
1. the synthesized polyisoimide resin with the main chain containing siloxane has higher molecular weight and excellent solubility in polar high-boiling point organic solvents, and the dissolution solid content can reach more than 60 percent without gel.
2. The negative photosensitive polyimide composition prepared from the polyimide resin with the main chain containing siloxane synthesized by the invention has a larger viscosity range, particularly, the negative photosensitive polyimide composition with the viscosity of more than 10000 mPa.s can be prepared, meanwhile, the film retention rate after heat curing is higher, after spin coating, development and baking processes, a coating with the thickness ranging from submicron to tens of microns can be prepared, and patterns with the minimum line width of 10-20 microns can be realized on the premise that the depth-to-width ratio is more than 2.5.
Drawings
FIG. 1 is a FTIR spectrum of a polyisoimide resin I in example 1 of the present invention.
FIG. 2 is a thermogravimetric analysis of the polyisoimide resin I according to example 1 of the present invention.
FIG. 3 is a confocal microscope image of the negative photosensitive polyimide pattern prepared in effect example 1 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The starting materials, reagents or apparatus used in the examples and comparative examples were either commercially available from conventional sources or may be obtained by prior art methods unless specifically indicated. Unless otherwise indicated, assays or testing methods are routine in the art.
Example 1
The embodiment prepares the polyisoimide resin, which comprises the following specific processes:
(1) Dissolving 10mmol of hexafluorodianhydride in 50g of N, N-dimethylacetamide under a nitrogen atmosphere at 25 ℃, adding 0.5mmol of hydroxyethyl methacrylate after mechanical stirring and dissolving, reacting for 2 hours at 50 ℃, adding 6mmol of 4,4' -diaminodiphenyl ether after cooling to 25 ℃ for reacting for 4 hours to 6 hours, and then adding 4mmol of 1, 3-bis (3-aminopropyl) -1, 3-tetramethyldisiloxane) Reacting for 10-12 h. (2) And slowly dropwise adding a mixed solution of 20mmol dicyclohexylcarbodiimide and 10g of N, N-dimethylacetamide into the solution within 2 hours, and then reacting for 10-12 hours. (3) And filtering the turbid solution to obtain a clear solution, dripping the clear solution into a mixture of water and ethanol to precipitate, and freeze-drying to constant weight of the resin to obtain the polyisoimide resin I.
The structural formula of the polyisoimide resin I is
Wherein n is x ：n y =1.5: 1, number average molecular weight mn=20000.
Example 2
The embodiment prepares the polyisoimide resin, which comprises the following specific processes:
(1) Dissolving 10mmol of pyromellitic anhydride in 55g of N, N-dimethylformamide under a nitrogen atmosphere at 25 ℃, adding 0.25mmol of hydroxyethyl acrylate after mechanical stirring and dissolving, reacting for 2 hours at 50 ℃, adding 6mmol of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane after cooling to 25 ℃ for reacting for 4 hours to 6 hours, and then adding 4mmol of alpha, omega-bis (3-aminopropyl) poly 1, 3-methylhydrogen siloxane) Reacting for 10-12 h. (2) And slowly dropwise adding a mixed solution of 20mmol dicyclohexylcarbodiimide and 10g of N, N-dimethylformamide into the solution within 2 hours, and then reacting for 10-12 hours. (3) Filtering the turbid solution to obtain a clear solution, dripping the clear solution into a mixture of water and ethanol to precipitate, and freeze-drying to constant weight of the resin to obtain the polyisoimide resin II.
The structural formula of the polyisoimide resin II is as follows:
2
wherein n is x ：n y =1.5: 1, number average molecular weight mn=50000.
Example 3
The embodiment prepares the polyisoimide resin, which comprises the following specific processes:
(1) 10mmol of 3,3', 4' -benzophenone tetracarboxylic dianhydride is dissolved in 50g N-methylpyrrolidone under nitrogen atmosphere at 25 ℃, 0.25mmol of pentaerythritol triacrylate is added after mechanical stirring and dissolution, reaction is carried out for 2 hours at 50 ℃, 7.5mmol of 2, 2-bis (4-aminophenyl) hexafluoropropane is added after the temperature is reduced to 25 ℃ for reaction for 4 hours to 6 hours, and then 2.5mmol of alpha, omega-bis (3-aminopropyl) poly 1, 3-methylvinylsiloxane is added) Reacting for 10-12 h. (2) And slowly dropwise adding a mixed solution of 20mmol dicyclohexylcarbodiimide and 10g N-methylpyrrolidone into the solution within 2 hours, and then reacting for 10-12 hours. (3) And (3) carrying out suction filtration on the turbid solution to obtain a clarified solution, dripping the clarified solution into a mixture of water and ethanol to precipitate, and freeze-drying to constant weight of the resin to obtain the polyisoimide resin III.
The structural formula of the polyisoimide resin III is as follows:
wherein n is x ：n y =3: 1, number average molecular weight mn=65000.
Example 4
The embodiment prepares the polyisoimide resin, which comprises the following specific processes:
(1) Dissolving 10mmol of hexafluorodianhydride in 65g of dimethyl sulfoxide under a nitrogen atmosphere at 25 ℃, adding 0.5mmol of hydroxyethyl methacrylate after mechanical stirring and dissolving, reacting for 2 hours at 50 ℃, adding 8mmol of 2, 2-bis (3-aminophenyl) hexafluoropropane after the temperature is reduced to 25 ℃ for reacting for 4 hours to 6 hours, and then adding 2mmol of alpha, omega-bis (3-aminopropyl) poly (1, 3-diphenylsiloxane)) Reacting for 10-12 h. (2) 21mmol of trifluoroacetic anhydride and 5mmol of triethylamine are slowly added dropwise to the solution in sequence in an ice-water bath for 30min, and then the reaction is carried out for 10-12 h. (3) And (3) dropwise adding the solution into a mixture of water and ethanol to separate out a precipitate, filtering the precipitate to obtain a precipitate, repeating the purification steps on the precipitate until the pH value of the filtrate is 7, and freeze-drying the filtrate until the weight of the precipitate is constant to obtain the polyisoimide resin IV.
The structural formula of the polyisoimide resin IV is as follows:
wherein n is x ：n y =4: 1, number average molecular weight mn=50000.
Comparative example 1
The comparative example prepared a polyisoimide resin, which was prepared by the following steps:
(1) Dissolving 5mmol of hexafluorodianhydride in 25g of N, N-dimethylacetamide under a nitrogen atmosphere at 25 ℃, adding 0.25mmol of hydroxyethyl acrylate after mechanical stirring and dissolving, reacting for 10-12 h at 50 ℃, adding 5mmol of 4,4' -diaminodiphenyl ether after cooling to 25 ℃, and slowly dropwise adding a mixed solution of 10mmol of dicyclohexylcarbodiimide and 7g of N, N-dimethylacetamide in 2h, and reacting for 10-12 h. (3) And (3) carrying out suction filtration on the turbid solution to obtain a clarified solution, dripping the clarified solution into a mixture of water and ethanol to precipitate, and freeze-drying to constant weight of the resin to obtain the polyisoimide resin V.
The structural formula of the polyisoimide resin V is as follows:
its number average molecular weight mn=22000.
Comparative example 2
The comparative example prepared a polyisoimide resin, which was prepared by the following steps:
(1) 5mmol of pyromellitic anhydride is dissolved in 25g of N, N-dimethylformamide under the nitrogen atmosphere at the temperature of 25 ℃, 0.125mmol of hydroxyethyl acrylate is added after the pyromellitic anhydride is mechanically stirred and dissolved, the reaction is carried out for 2 hours at the temperature of 50 ℃, and 5mmol of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane is added after the reaction is cooled to the temperature of 25 ℃ for 4 hours to 6 hours. (2) And slowly dropwise adding a mixed solution of 10mmol dicyclohexylcarbodiimide and 13g of N, N-dimethylformamide into the solution within 2h, and then reacting for 10-12 h. (3) Filtering the turbid solution to obtain a clear solution, dripping the clear solution into a mixture of water and ethanol to separate out a precipitate, and freeze-drying the precipitate until the weight of the resin is constant to obtain the polyisoimide resin VI.
The structural formula of the polyisoimide resin VI is as follows:
its number average molecular weight mn=40000.
Comparative example 3
The comparative example prepared a polyisoimide resin, which was prepared by the following steps:
(1) Under the nitrogen atmosphere at 25 ℃, 5mmol of 3,3', 4' -benzophenone tetracarboxylic dianhydride is dissolved in 25g N-methylpyrrolidone, 0.125mmol of pentaerythritol triacrylate is added after mechanical stirring and dissolution, the reaction is carried out for 2 hours at 50 ℃, and 5mmol of 2, 2-bis (3-aminophenyl) hexafluoropropane is added after the reaction is cooled to 25 ℃ for 10 to 12 hours. (2) And slowly dropwise adding a mixed solution of 10mmol dicyclohexylcarbodiimide and 5g N-methylpyrrolidone into the solution within 2 hours, and then reacting for 10-12 hours. (3) Filtering the turbid solution to obtain a clear solution, dripping the clear solution into a mixture of water and ethanol to separate out a precipitate, and freeze-drying the precipitate until the weight of the resin is constant to obtain the polyisoimide resin VII.
The structural formula of the polyisoimide resin VII is:
its number average molecular weight mn=45000.
Comparative example 4
The comparative example prepared a polyisoimide resin, which was prepared by the following steps:
(1) 5mmol of hexafluorodianhydride is dissolved in 33g of dimethyl sulfoxide under the nitrogen atmosphere at 25 ℃, 0.25mmol of hydroxyethyl methacrylate is added after mechanical stirring and dissolution, the mixture is reacted for 2 hours at 50 ℃, and 5mmol of 2, 2-bis (3-aminophenyl) hexafluoropropane is added after the temperature is reduced to 25 ℃ for 10 hours to 12 hours. (2) And slowly dropwise adding 11mmol of trifluoroacetic anhydride and 0.25mmol of triethylamine into the solution in an ice-water bath for 30min, and then reacting for 10-12 h. (3) And (3) dropwise adding the solution into a mixture of water and ethanol to separate out a precipitate, filtering the precipitate to obtain a precipitate, repeating the purification steps on the precipitate until the pH value of the filtrate is 7, and freeze-drying the filtrate until the weight of the precipitate is constant to obtain the polyisoimide resin VIII.
The structural formula of the polyisoimide resin VIII is as follows:
its number average molecular weight mn=25000.
Comparative example 5
The comparative example prepared a polyisoimide resin, which was prepared by the following steps:
(1) Dissolving 5mmol of hexafluorodianhydride in 25g of N, N-dimethylacetamide under a nitrogen atmosphere at a temperature of 25 ℃, adding 2mmol of hydroxyethyl acrylate after mechanical stirring and dissolving, reacting for 10-12 hours at a temperature of 50 ℃, adding 5mmol of 4,4' -diaminodiphenyl ether after cooling to the temperature of 25 ℃, slowly dropwise adding a mixed solution of 10mmol of dicyclohexylcarbodiimide and 7g of N, N-dimethylacetamide into the solution within 2 hours, and reacting for 10-12 hours. (3) Filtering the turbid solution to obtain a clear solution, dripping the clear solution into a mixture of water and ethanol to precipitate, and freeze-drying to constant weight of the resin to obtain the polyisoimide resin IX.
The structural formula of the polyisoimide resin IX is as follows:
its number average molecular weight mn=3000.
Test example 1
The above resins I, II, III, IV, V, VI, VII, VIII, IX were subjected to solubility tests, and the resins were gradually added to a quantitative solvent in a stepwise manner, and the solids content was recorded when the presence of gel in the solution was observed. The results are shown in Table 1.
Effect example 1
The resin I prepared in example 1 was used to prepare a negative photosensitive polyimide pattern, comprising the following steps:
(1) 2.5g of resin I, 0.4g of hydroxyethyl methacrylate and 0.15g of 1-hydroxycyclohexyl phenyl ketone are dissolved in 2.45g of N, N-dimethylacetamide and uniformly mixed to prepare a negative photosensitive polyimide composition I (the solid content of the resin in the composition is 45 percent), and the viscosity is 12000 mPa.s;
(2) Spin-coating negative photosensitive polyimide composition I on wafer at 1000rpm to form coating, pre-baking at 80deg.C for 300s, exposing with a mask plate under i-line light source at exposure of 400 mJ/cm 2 Then, carrying out 200s postbaking at 120 ℃, developing by adopting N, N-dimethylacetamide, and then, cleaning by using deionized water to obtain a negative photosensitive polyimide pattern;
(3) The negative photosensitive polyimide coating is placed in an oven, and is heated to 320 ℃ from 120 ℃ at a rate of 100 ℃/h to be cured for 2 hours, so as to obtain the polyimide pattern.
Through testing, the film retention rate after curing is 88%, the thickness of the coating after curing is 30 mu m, a negative pattern with the minimum line width of 10 mu m can be formed, and the depth-to-width ratio is 2.5.
The film retention rate testing method comprises the following steps: coating thickness was measured using a Dektak XT 8 inch stepmeter from Bruker, germany. Recording the thickness of the spin-coated and pre-baked dry film coating as the original film thickness, then performing i-line exposure under a mask plate, developing with DMAC, cleaning with deionized water, heating to 320 ℃ from 120 ℃ at a speed of 100 ℃/h on a glue baking machine for curing for 2 hours, and recording the thickness of the coating as the remained film thickness. Film retention = film retention/original film thickness 100%.
The depth-to-width ratio testing method comprises the following steps: the pattern coating thickness after thermal curing was measured using a Dektak XT 8 inch stepmeter from Bruker, germany, and the pattern minimum linewidth was measured using a laser confocal microscope. Aspect ratio = pattern coating thickness/pattern linewidth.
Effect example 2
The resin II prepared in example 2 is used for preparing a negative photosensitive polyimide pattern, and the specific steps are as follows:
(1) 2.5g of resin II, 0.4g of ethylene glycol diacrylate and 0.15g of 2-hydroxy-2-methyl propiophenone are dissolved in 2.45g of N, N-dimethylformamide and uniformly mixed to prepare a negative photosensitive polyimide composition II (the solid content of the resin in the composition is 45 percent), and the viscosity is 17000 mPa.s;
steps (2) and (3) are the same as those of effect example 1, except that N, N-dimethylformamide is used instead of N, N-dimethylacetamide in step (2).
Through testing, the film retention rate after curing is 88%, the thickness of the coating after curing is 60 mu m, a negative pattern with the minimum line width of 20 mu m can be formed, and the depth-to-width ratio is 3.
Effect example 3
The negative photosensitive polyimide pattern was prepared by taking the resin III prepared in example 3, and the specific steps were as follows:
(1) 2.5g of resin III, 0.4g of pentaerythritol triacrylate and 0.15g of diphenyl (2, 4, 6-trimethylbenzoyl) phosphine oxide are taken and dissolved in 2.45-g N-methylpyrrolidone, and the mixture is uniformly mixed to prepare a negative photosensitive polyimide composition III (the solid content of the resin in the composition is 45 percent), and the viscosity is 15000 mPa.s;
steps (2) and (3) are the same as in effect example 1, except that N-methylpyrrolidone is used in place of N, N-dimethylacetamide in step (2).
Through testing, the film retention rate after curing is 87%, the thickness of the coating after curing is 50 mu m, a negative pattern with the minimum line width of 20 mu m can be formed, and the depth-to-width ratio is 3.
Effect example 4
The resin IV prepared in example 4 is used for preparing a negative photosensitive polyimide pattern, and the specific steps are as follows:
(1) 2.5g of resin IV, 0.4g of pentaerythritol triacrylate and 0.15g of 1-hydroxycyclohexyl phenyl ketone are taken and dissolved in 2.45g of dimethyl sulfoxide, and the mixture is uniformly mixed to prepare a negative photosensitive polyimide composition IV (the solid content of the resin in the composition is 45 percent), and the viscosity is 16000 mPa.s;
the steps (2) and (3) are the same as those of effect example 1, except that dimethyl sulfoxide is used in place of N, N-dimethylacetamide in step (2).
Through testing, the film retention rate after curing is 85%, the thickness of the coating after curing is 60 mu m, a negative pattern with the minimum line width of 20 mu m can be formed, and the depth-to-width ratio is 3.
Effect example 5
The resin V prepared in comparative example 1 was used to prepare a negative photosensitive polyimide pattern, comprising the following steps:
(1) 1.25g of resin V, 0.2g of pentaerythritol triacrylate and 0.075g of 1-hydroxycyclohexyl phenyl ketone are dissolved in 5.9g of N, N-dimethylacetamide, and the mixture is uniformly mixed to prepare a negative photosensitive polyimide composition V (the solid content of the resin in the composition is 17 percent), and the viscosity is 300 mPa.s;
the steps (2) and (3) are the same as those of effect example 1.
Through testing, the film retention rate after curing is 85%, the thickness of the coating after curing is 1 mu m, a negative pattern with the minimum line width of 20 mu m can be formed, and the depth-to-width ratio is 0.05.
Effect example 6
The resin IX prepared in comparative example 5 was used to prepare a negative photosensitive polyimide pattern, comprising the following steps:
(1) 2.5g of resin IX, 0.4g of pentaerythritol triacrylate and 0.15g of 1-hydroxycyclohexyl phenyl ketone are dissolved in 2.45g of N, N-dimethylacetamide and uniformly mixed to prepare a negative photosensitive polyimide composition VI (the solid content of the resin in the composition is 45 percent), and the viscosity is 8000 mPa.s;
the steps (2) and (3) are the same as those of effect example 1.
After testing, the coating disintegrates after heat curing, and cannot form a film.
According to the test results of effect examples 1-6, the viscosity of the negative photosensitive polyimide composition prepared in effect examples 1-4 is more than 10000 mPa.s, the spin coating thickness reaches 30-60 um, the pattern with the minimum line width of 10-20 um is realized, the depth-to-width ratio reaches 2.5-3, and the film retention rate is higher than 85%. The photosensitive polyimide prepared in effect example 5 has the viscosity of only 300 mPas, the spin coating thickness of 1um, the development of a pattern with the minimum line width of 20um is realized, and the depth-to-width ratio is only 0.05. In effect example 6, since the molecular weight was too small, when the coating thickness demand was increased, the coating was broken after completion of the heat curing step, and film formation was impossible.
Test example 2
The negative photosensitive polyimide pattern of the polyisoimide resin I of example 1 and effect example 1 was also tested in this test example.
The infrared spectrum of the polyisoimide resin I in example 1 is shown in FIG. 1.
A thermogravimetric analysis of the polyisoimide resin I according to example 1 is shown in FIG. 2.
A laser confocal microscope image of the negative photosensitive polyimide pattern prepared in effect example 1 is shown in FIG. 3.
As can be seen from FIGS. 1 to 2, in FIG. 1, 1800cm -1 The characteristic absorption peak of the polyisoimide ring in the resin of example 1 is 1000-630 cm -1 The broad peak at this point is the characteristic absorption peak of Si-O-Si groups, 750cm -1 、845cm -1 At which is the characteristic absorption of Si-Me groupsPeaks, which demonstrate the synthesis of the polymer.
The mass loss of the polyisoimide during thermal curing was analyzed in fig. 2, with a heat loss rate of 1.5% at 320 ℃ with lower thermal mass loss compared to other precursors.
Fig. 3 photographs the negative photosensitive polyimide pattern prepared in effect example 1 under a laser confocal microscope, and at a film thickness of 30 μm, the line width of the negative pattern and the gap between the patterns are both 10 μm, and the aspect ratio is 3.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (9)
1. The structural formula of the polyisoimide is shown as formula I:
，
wherein n is x ：n y Is (1.5-4): 1, mn ranges from 20000 to 65000;
Ar 1 Included、/>、/>、、/>any one of (3);
Ar 2 Included、/>、、/>any one of (3);
Ar 3 Includedin the formula a, n=0 to 20; r is R 1 、R 2 Each independently selected from->At least one of (2);
r comprisesAny one of (3);
the preparation method of the polyisoimide comprises the following steps: under inert atmosphere, the aromatic dianhydride monomer is dissolved in an organic solvent, a capping agent is added for reaction, then an aromatic diamine monomer is added for reaction, a siloxane diamine monomer is added for reaction, and a dehydrating agent is dripped for reaction, so that the polyisoimide is prepared.
2. A process for the preparation of the polyisoimide according to claim 1, characterized in that: the method comprises the following steps:
under inert atmosphere, the aromatic dianhydride monomer is dissolved in an organic solvent, a capping agent is added for reaction, then an aromatic diamine monomer is added for reaction, a siloxane diamine monomer is added for reaction, and a dehydrating agent is dripped for reaction, so that the polyisoimide is prepared.
3. The method for producing a polyisoimide according to claim 2, wherein: the molar ratio of the aromatic dianhydride monomer to the aromatic diamine monomer is 1:0.6 to 0.8.
4. The method for producing a polyisoimide according to claim 2, wherein: the molar ratio of the aromatic dianhydride monomer to the siloxane diamine monomer is 1:0.2 to 0.4.
5. The method for producing a polyisoimide according to claim 2, wherein: the molar ratio of the aromatic dianhydride monomer to the end-capping agent is 1:0.025 to 0.05.
6. A negative photosensitive polyimide composition characterized in that: comprising the polyisoimide according to claim 1.
7. The negative photosensitive polyimide composition according to claim 6, wherein: the composition comprises 30-50 wt% of the polyisoimide, 3-15 wt% of the photo-crosslinking agent, 40-60 wt% of the solvent and 1-10 wt% of the initiator.
8. A method for manufacturing a negative photosensitive polyisoimide pattern, which is characterized in that: the method comprises the following steps:
s1: coating the negative photosensitive polyimide composition according to claim 7 on a substrate, performing a first baking, exposing the mask, and performing a second baking to obtain a dry film coating;
s2: and (3) developing, cleaning and curing the dry film coating of the S1 to obtain the negative photosensitive polyimide pattern.
9. Use of the polyisoimide according to claim 1 or the negative photosensitive polyimide composition according to claim 7 in integrated circuits.
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| CN116178716A (en) | 2023-05-30 |
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