CN114479020A - Polymer semiconductor photoresist with side chain containing azide group, and preparation method and application thereof - Google Patents
Polymer semiconductor photoresist with side chain containing azide group, and preparation method and application thereof Download PDFInfo
- Publication number
- CN114479020A CN114479020A CN202210161724.9A CN202210161724A CN114479020A CN 114479020 A CN114479020 A CN 114479020A CN 202210161724 A CN202210161724 A CN 202210161724A CN 114479020 A CN114479020 A CN 114479020A
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- heteroaryl
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- 229920000642 polymer Polymers 0.000 title claims abstract description 47
- 239000004065 semiconductor Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229920002120 photoresistant polymer Polymers 0.000 title claims abstract description 10
- IVRMZWNICZWHMI-UHFFFAOYSA-N azide group Chemical group [N-]=[N+]=[N-] IVRMZWNICZWHMI-UHFFFAOYSA-N 0.000 title abstract description 10
- 125000001072 heteroaryl group Chemical group 0.000 claims abstract description 19
- 238000000059 patterning Methods 0.000 claims abstract description 18
- 125000001424 substituent group Chemical group 0.000 claims abstract description 14
- 238000005859 coupling reaction Methods 0.000 claims abstract description 11
- 125000003118 aryl group Chemical group 0.000 claims abstract description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 7
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims abstract description 7
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 7
- 239000001301 oxygen Substances 0.000 claims abstract description 7
- 239000011593 sulfur Substances 0.000 claims abstract description 7
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 7
- 229920000620 organic polymer Polymers 0.000 claims abstract description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 16
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 229920000547 conjugated polymer Polymers 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- -1 (1, 4-diphenylphosphino) butyl palladium dichloride Chemical compound 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 8
- 230000005669 field effect Effects 0.000 claims description 8
- 229910052763 palladium Inorganic materials 0.000 claims description 8
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000003446 ligand Substances 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 125000004404 heteroalkyl group Chemical group 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 5
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 claims description 4
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 4
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000010534 nucleophilic substitution reaction Methods 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 229910052711 selenium Inorganic materials 0.000 claims description 4
- 239000011669 selenium Substances 0.000 claims description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 4
- DTJVECUKADWGMO-UHFFFAOYSA-N 4-methoxybenzenesulfonyl chloride Chemical compound COC1=CC=C(S(Cl)(=O)=O)C=C1 DTJVECUKADWGMO-UHFFFAOYSA-N 0.000 claims description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical group OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 239000003431 cross linking reagent Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- 125000001544 thienyl group Chemical group 0.000 claims description 3
- 238000000944 Soxhlet extraction Methods 0.000 claims description 2
- 239000007983 Tris buffer Substances 0.000 claims description 2
- 125000004423 acyloxy group Chemical group 0.000 claims description 2
- 125000004448 alkyl carbonyl group Chemical group 0.000 claims description 2
- 125000004414 alkyl thio group Chemical group 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 239000012634 fragment Substances 0.000 claims description 2
- 125000002541 furyl group Chemical group 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 125000002883 imidazolyl group Chemical group 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- 150000002825 nitriles Chemical class 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000001725 pyrenyl group Chemical group 0.000 claims description 2
- 125000004076 pyridyl group Chemical group 0.000 claims description 2
- 125000000168 pyrrolyl group Chemical group 0.000 claims description 2
- 125000005493 quinolyl group Chemical group 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- 125000000335 thiazolyl group Chemical group 0.000 claims description 2
- SYUVAXDZVWPKSI-UHFFFAOYSA-N tributyl(phenyl)stannane Chemical compound CCCC[Sn](CCCC)(CCCC)C1=CC=CC=C1 SYUVAXDZVWPKSI-UHFFFAOYSA-N 0.000 claims description 2
- COHOGNZHAUOXPA-UHFFFAOYSA-N trimethyl(phenyl)stannane Chemical group C[Sn](C)(C)C1=CC=CC=C1 COHOGNZHAUOXPA-UHFFFAOYSA-N 0.000 claims description 2
- DLQYXUGCCKQSRJ-UHFFFAOYSA-N tris(furan-2-yl)phosphane Chemical compound C1=COC(P(C=2OC=CC=2)C=2OC=CC=2)=C1 DLQYXUGCCKQSRJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 230000005693 optoelectronics Effects 0.000 claims 1
- 239000010408 film Substances 0.000 description 17
- 239000000243 solution Substances 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- OHZAHWOAMVVGEL-UHFFFAOYSA-N 2,2'-bithiophene Chemical group C1=CSC(C=2SC=CC=2)=C1 OHZAHWOAMVVGEL-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000001459 lithography Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000010200 validation analysis Methods 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- ANCBHJKEYPZCTE-UHFFFAOYSA-N ethyl 5-carbamoyl-4-methyl-2-[(2,3,4,5,6-pentafluorobenzoyl)amino]thiophene-3-carboxylate Chemical compound CC1=C(C(N)=O)SC(NC(=O)C=2C(=C(F)C(F)=C(F)C=2F)F)=C1C(=O)OCC ANCBHJKEYPZCTE-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000004896 high resolution mass spectrometry Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000006713 insertion reaction Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- 238000002464 physical blending Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- FYNROBRQIVCIQF-UHFFFAOYSA-N pyrrolo[3,2-b]pyrrole-5,6-dione Chemical compound C1=CN=C2C(=O)C(=O)N=C21 FYNROBRQIVCIQF-UHFFFAOYSA-N 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000010129 solution processing Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- PIILXFBHQILWPS-UHFFFAOYSA-N tributyltin Chemical group CCCC[Sn](CCCC)CCCC PIILXFBHQILWPS-UHFFFAOYSA-N 0.000 description 1
- LYRCQNDYYRPFMF-UHFFFAOYSA-N trimethyltin Chemical group C[Sn](C)C LYRCQNDYYRPFMF-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
- C07D487/04—Ortho-condensed systems
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- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/124—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one nitrogen atom in the ring
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- 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
- G03F7/008—Azides
- G03F7/012—Macromolecular azides; Macromolecular additives, e.g. binders
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- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
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- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
- C08G2261/3223—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
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- C08G2261/3241—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing one or more nitrogen atoms as the only heteroatom, e.g. carbazole
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Abstract
The invention discloses an organic polymer semiconductor photoresist with side chains containing azide groups, a preparation method and application thereof, and realizes the patterning of an organic semiconductor device efficiently crosslinked by 365nm ultraviolet light. The structural formula of the semiconductor photoresist provided by the invention is shown as the following formula I, wherein Ar is selected from any one of aryl, heteroaryl, aryl containing substituent groups and heteroaryl containing substituent groups, and the bonding mode in the group is selected from at least one of single bond, double bond and triple bond; the heteroaryl is selected from any one of monocyclic heteroaryl, bicyclic heteroaryl and tricyclic heteroaryl, and the heteroatom in the heteroaryl is selected from at least one of oxygen, sulfur and seleniumSeed; the preparation method obtains the polymer through carbon-carbon coupling reaction. Efficient patterning of organic semiconductor devices is achieved.
Description
Technical Field
The invention belongs to the field of organic semiconductor materials, and particularly relates to a polymer semiconductor photoresist with side chains containing azide groups, a preparation method thereof and application thereof in organic photoelectric devices.
Background
The conjugated polymer has photoelectric properties comparable to those of the traditional inorganic semiconductor materials, has unique mechanical flexibility and has huge application prospects in the aspect of flexible electronic devices (Science,2017,355 and 59). However, the practical application of organic semiconducting polymers to flexible circuits still has many limitations, such as the inability to perform large scale patterning processes by conventional photolithographic processes, and its solubility limits the non-orthogonal solvent integration of multilayer materials. Therefore, the development of new methods for polymer semiconductor lithography processing is one of the necessary ways to realize organic flexible electronic devices.
The azide group is a photosensitive active group, can rapidly generate a nitrene intermediate with high reaction activity under the irradiation of ultraviolet light, and can perform insertion reaction with adjacent C-H bonds and release nitrogen (nat. Mat.,2010,9,152) to realize chemical crosslinking. Because the reaction ultraviolet light is controllable and has no byproduct residue, the method is widely applied to the fields of biology, chemistry and the like.
Research on patterning of organic semiconductor materials using azide groups has also received increasing attention in recent years, but most of the semiconductor lithographic patterning reported at present mainly involves physical blending of binary or multicomponent components (Nature,2018,555, 83; nat. Commun.,2020,11,1520), while the mobility of the patterned devices is low. The current semiconductor photoresist with carrier transport and patterning functions is still very lacking. The conjugated polymer integrating the functions of the semiconductor and the photoresist is expected to obtain a high-mobility patterning device, can improve the patterning precision, and has important research significance and practical value for developing organic semiconductor integrated circuits.
Disclosure of Invention
The invention aims to provide a polymer semiconductor photoresist with a side chain containing an azide group, and a preparation method and application thereof; according to the invention, azide groups are introduced into side chains of the conjugated polymer, so that the patterning of the ultraviolet-light efficient crosslinked organic semiconductor device is realized.
The structural formula of the side chain azide group-containing polymer provided by the invention is shown as the following formula I:
in the formula I, R1、R2Each independently selected from any one of C1-C50 linear or branched alkyl, C1-C50 alkoxy, C7-C50 aralkyl heteroaryl and C5-C50 heteroalkyl;
the number average molecular weight of the polymer in the formula I is 5000-500000; further more 20000-50000, such as 28 kDa.
Specifically, the R is1、R2May be 2-decyltetradecyl;
in the formula I, x is more than 0:1 and y is less than or equal to 1: 0; specifically, in the polymer, x: y is 1: 0;
ar is selected from any one of aryl, heteroaryl, aryl containing substituent and heteroaryl containing substituent, and the bonding mode of the group interior is selected from at least one of single bond, double bond and triple bond;
wherein, one of the aryl or heteroaryl (phenyl, thienyl, thiazolyl, pyridyl, quinolyl, furyl, pyrrolyl, imidazolyl, naphthyl and pyrenyl) or a combined fragment formed by connecting the above units through one or more of single bond, double bond, triple bond, oxygen, sulfur, silicon or nitrogen; the heteroatom in the heteroalkyl group is at least one of oxygen, sulfur and selenium, and the substitution number of the heteroatom is 1-10; the heteroaryl is selected from any one of monocyclic heteroaryl, bicyclic heteroaryl and tricyclic heteroaryl, and the heteroatom in the heteroaryl is selected from at least one of oxygen, sulfur and selenium; in the aryl group containing the substituent and the heteroaryl group containing the substituent, the substituent is any one of alkyl of C1-C50, alkylthio of C1-C50, alkylcarbonyl of C1-C50, acyloxy, nitrile and alkoxy of C1-C50, and the number of the substituent is an integer of 1-4.
For example, Ar can be selected from any one of the following structural formulas a-u:
in Ar, R is selected from any one of hydrogen, C1-C50 alkyl and C1-C50 alkoxy; most preferably any of thienyl, bithiophenyl and bithiophenyl.
In the present invention, in the group represented by Ar
Indicating the position of the linkage of formula I.
The invention also provides a preparation method of the polymer shown in the formula I.
The invention provides a preparation method of a polymer shown in a formula I, which comprises the following steps: carrying out carbon-carbon coupling reaction on the compound shown in the formula II, the compound shown in the formula III and the compound shown in the formula IV in an organic solvent in the presence of an inert atmosphere and a catalyst, and obtaining the polymer shown in the formula I after the carbon-carbon coupling reaction is finished;
in the formulae II, III and IV, R1、R2And Ar is the same as in formula I, and Y is a trialkyltin group or a borate group.
In the present invention, the trialkyltin group may specifically be a trimethyltin group or a tributyltin group, and the borate group may specifically be a 1,3, 2-dioxaborolan-2-yl group or a 4,4,5, 5-tetramethyl-1, 2, 3-dioxaborolan-2-yl group.
In the above preparation method, the gas of the inert atmosphere is nitrogen;
the catalyst consists of a palladium catalyst and a phosphine ligand, wherein the palladium catalyst is selected from at least one of tetrakis (triphenylphosphine) palladium, tris (tri-p-methylphenyl phosphine) palladium, tris (dibenzylideneacetone) dipalladium and bis (1, 4-diphenyl phosphine) butyl palladium dichloride, and specifically can be tris (dibenzylideneacetone) dipalladium; the phosphine ligand is selected from at least one of triphenylphosphine, o-trimethylphenylphosphine, tri (2-furyl) phosphine and 2- (di-tert-butylphosphine) biphenyl, and specifically can be o-trimethylphenylphosphine;
in the above preparation method, the molar ratio of the compound represented by the formula ii, the compound represented by the formula III, the compound represented by the formula IV, the palladium catalyst and the phosphine ligand may be 1:0 to 20: 0 to 20: 0.01-0.03: 0.03-0.12 (specifically, 1: 0: 1: 0.03: 0.12); the reaction temperature of the carbon-carbon coupling reaction can be 90-110 ℃, preferably 100 ℃, and the reaction time is 1-3 hours, preferably 3 hours;
the organic solvent is at least one selected from toluene, N-dimethylformamide and chlorobenzene.
In the above preparation method, the trialkyltin reagent (compound shown in formula IV) is selected from trimethylphenyltin and/or tributylphenyltin;
in the above preparation method, the coupling reaction further comprises the following steps: dripping the system after the coupling reaction into methanol, and filtering to obtain a solid; then sequentially extracting the solid with acetone and n-hexane, and taking the extracted solid; and finally, extracting the solid subjected to the soxhlet extraction by using chloroform to obtain a target product, dripping the chloroform dissolved with the target product into methanol, and performing suction filtration to obtain a solid, namely the polymer shown in the formula I.
The present invention also provides a compound of formula II:
in the formula II, R1Is selected from any one of C1-C50 straight chain or branched chain alkyl, C1-C50 alkoxy, C7-C50 aralkyl and C5-C50 heteroalkyl. For example R1Can be selected from linear or branched alkyl of C1-C50.
The invention also provides a preparation method of the compound shown in the formula II, which comprises the following steps:
a compound shown as a formula V and N3Carrying out nucleophilic substitution reaction on the group compound in a solvent to obtain a compound shown as a formula II;
in the formula V, A is selected from halogen atoms or p-methoxybenzenesulfonyl chloride, and can be selected from any one of F, Cl, Br, I and p-methoxybenzenesulfonyl chloride.
In the above preparation method, the compound represented by the formula V and the N3N in the radical compound3The molar ratio of the groups is 1: 2-50, preferably 1: 4; said group containing N3The radical compound may be specifically sodium azide.
The reaction temperature of the nucleophilic substitution reaction is room temperature, specifically 25 ℃, and the reaction time is 2-7 hours, specifically 4 hours;
the solvent is DMF.
The invention also provides application of the polymer shown in the formula I.
The invention provides an application of the polymer containing the azide group in at least one of the following (1) to (4): (1) an organic polymer semiconductor photoresist which can be used as a single component; (2) as a general purpose crosslinking agent to crosslink other polymer semiconductors; (3) realizing organic semiconductor patterning; (4) application in the preparation of organic photoelectric devices. The polymer includes non-conjugated polymer and conjugated polymer (such as copolymer PDPP4T, structure formula is shown as b in figure 7).
In the above application, the organic photoelectric device includes at least one of an organic field effect transistor, an organic digital circuit, an organic solar cell, an organic thermoelectric, and an organic light emitting diode.
Compared with the prior art, the invention has the following advantages:
1. the raw materials used in the synthesis are convenient and easy to obtain, and the method is easy for industrial production.
2. The polymer has excellent carrier transmission performance and dissolution characteristic, and is beneficial to solution processing of devices.
3. The polymer can realize self semiconductor patterning through a simple photoetching technology, and is easy to construct an organic semiconductor large-scale integrated circuit.
4. The polymer can be subjected to efficient crosslinking reaction with other P-type conjugated polymers.
Drawings
FIG. 1 is a process for the preparation of the compound of formula II of example 1 of the present invention;
FIG. 2 is a flow chart illustrating the preparation of the polymer of formula I of example 2 according to the present invention;
FIG. 3 shows a compound of formula II of example 1 of the present invention1H-NMR chart;
FIG. 4 shows a compound of formula II in example 1 of the present invention13C-NMR chart;
FIG. 5 shows a polymer of formula I in example 2 of the present invention1H-NMR chart;
FIG. 6 shows a polymer of formula I in example 2 of the present invention13C-NMR chart;
FIG. 7 shows PDPP4T and F4BDOPV-2T polymer structural formula;
FIG. 8 is a diagram of PDPP4T-N according to example 2 of the present invention3Polymer implementing a patterned legend;
FIG. 9 is a diagram of PDPP4T-N according to example 2 of the present invention3A polymer cross-linked field effect transistor device structure diagram;
FIG. 10 shows PDPP4T-N according to example 2 of the present invention3A representative transfer curve for a polymer cross-linked field effect transistor device;
FIG. 11 shows PDPP4T-N of example 2 of the present invention3The polymer is used as an additional component to crosslink PDPP4T polymer to realize a representative transfer curve of a field effect transistor device;
FIG. 12 is a diagram of PDPP4T-N according to example 2 of the present invention3An inverter circuit diagram prepared by polymer crosslinking and an output voltage curve.
Detailed Description
The present invention will be further illustrated with reference to the following specific examples, but the present invention is not limited to the following examples. The methods are conventional methods unless otherwise specified. The starting materials, reagents and the like can be obtained from publicly available commercial sources unless otherwise specified.
Example 1:
synthesis of Compound represented by formula II (wherein, R in formula II1Is 2-decyltetradecyl, N3With radicals at the end of the alkyl side chain)
The specific reaction step conditions are as follows:
the chemical reaction scheme is shown in figure 1. Compound 1(0.96mmol) was dissolved in 30mL DMF and compound 2NaN was added3(3.83mmol) and reacted at room temperature for 7 hours to stop the reaction. Multiple extractions with copious amounts of water and dichloromethane were carried out. The organic phase was removed by rotary evaporation and isolated on a silica gel column to give product 3(0.48mmol, yield: 49.9%); the structure validation data is as follows:1H NMR(400MHz,CDCl3) δ 8.63(d, J4.4 Hz,2H),7.22(d, J4.0 Hz,2H),3.92(d, J8.0 Hz,4H),3.25(t, J6.8 Hz,4H),1.88(m,2H),1.60-1.55(m,4H),1.30-1.21(m,76H),0.88(t, 6H); HR-MS calculated as C62H101Br2N8O2S2(M+) 1211.5850, mass spectrum peak 1211.5858.
Example 2:
synthesis of Polymer of formula I (wherein, R1And R2Is 2-octyldodecyl, N3The radical being located at R1An alkyl backbone terminus; ar is a bithiophene substituent; when x: y is 1:0, the polymer is defined as PDPP4T-N3)：
The chemical reaction scheme is shown in FIG. 2, and the product 3(0.050mmol) obtained in inventive example 1 and 5,5 '-bis (trimethylstannyl) -2,2' -dithiazoleDissolving thiophene 4(0.050mmol) in anhydrous toluene, blowing nitrogen for 10min, adding 1.48 mu mol of tris (dibenzylideneacetone) dipalladium catalyst and 5.93 mu mol of o-trimethylphenylphosphine ligand, reacting at 100 ℃ for 3 hours under the protection of nitrogen, cooling to room temperature, pouring the reaction system into 100mL of methanol, separating out a solid, and filtering. The obtained solid was passed through a Soxhlet extractor to sequentially remove the catalyst, unreacted raw materials and oligomers with methanol, n-hexane and acetone, and finally the target product was extracted with chloroform. Then the chloroform solution dissolved with the target product is poured into 200mL of methanol, solid is separated out and filtered, and the final product PDPP4T-N is obtained3The molecular weight Mn is 2.8 kDa. (56.5mg, yield 94%); the structure validation data is as follows:1H NMR(500MHz,1,1,2,2-tetrachloroethane-d2,373k):δ＝8.75(s,2H),7.24-6.98(m,7H),3.95(m,4H),3.13(t,4H),1.91(s,2H),1.48-1.18(m,70H),0.81-0.78(t,6H).13c NMR (100MHz, solid): δ 160.79,141.20,136.94,128.93,124.22,108.69,45.73,39.09,32.84,30.69,23.59,14.89 elemental analysis: calculated value is C70H104N8O2S4C, 69.03; h, 8.61; n, 9.20; s, 10.53; actual value C, 68.59; h, 8.47; n, 8.86; s,10.41.
Example 3:
the specific steps for realizing patterning based on the polymer of the formula I are as follows: PDPP4T-N prepared in example 2 of the invention3The polymer (structural formula shown in figure 5) is dissolved in chloroform solution at room temperature, wherein PDPP4T-N3The concentration of (3) is 3 mg/ml. The solution was then spin coated on a silicon wafer by a spin coater at 3000 rpm, with a film thickness of about 20 nm. The mask was then covered on the film and irradiated with a 365nm ultraviolet LED lamp at 85 milliwatts per square centimeter for 400 seconds. And then soaking the irradiated film in chloroform for 30 seconds, taking out the film, rinsing the film twice with 5 ml of isopropanol, and drying the silicon wafer by using nitrogen to realize patterning, wherein a patterned graph is shown in fig. 8.
Example 4:
PDPP4T-N based on embodiment 2 of the invention3The application of the self-patterning thin film of the polymer in the field effect transistor comprises the following specific steps: the inventionPDPP4T-N prepared in example 23The polymer was dissolved in chloroform solution at room temperature, wherein PDPP4T-N3Is 3 mg per ml. Then the solution is put on Si/SiO containing gold electrode by a spin coater2The substrate was spin coated at 3000 rpm to a film thickness of about 20 nm (device structure shown in fig. 9). The mask was then covered on the film and irradiated with a 365nm ultraviolet LED lamp at 85 milliwatts per square centimeter for 400 seconds. And then soaking the irradiated film in chloroform for 30 seconds, taking out the film, rinsing the film twice with 5 ml of isopropanol, and drying the silicon wafer by using nitrogen to realize the patterning of the field effect transistor device. The mobility of the patterned device can reach 0.78cm2V-1s-1A representative transfer curve is shown in fig. 10.
Example 5:
PDPP4T-N based on embodiment 2 of the invention3The application of the patterned P-type conjugated polymer film of the polymer in the field effect transistor comprises the following specific steps: mixing copolymer of pyrrolopyrroledione and bithiophene PDPP4T (structural formula is shown as b in figure 7, molecular weight is 5.3kDa) and PDPP4T-N3The solution was dissolved in chloroform solution at room temperature in a mass ratio of 100:5, wherein the concentration of PDPP4T was 3 mg per ml. The blended solution was then spin coated on a silicon wafer through a spin coater at 3000 rpm to a film thickness of about 20 nm. The mask was then covered on the film and illuminated with a 365nm UV LED lamp at 85 milliwatts per square centimeter for 400 seconds. And then soaking the irradiated film in chloroform for 30 seconds, taking out the film, then leaching the film twice by using 5 ml of isopropanol, and drying the silicon wafer by using nitrogen to realize patterning. The mobility of the patterned device can reach 2.74cm2V-1s-1A representative transfer curve is shown in fig. 11.
Example 5:
PDPP4T-N based on embodiment two of the invention3The application of the conjugated polymer film patterning in the inverter comprises the following specific steps: PDPP4T-N was prepared using the procedure described in example three3After patterning the polymer, spin-coating a layer F4BDOPV-2T (FIG. 7b) polymer, building a simple logic gate: inverter (fig. 1)2) The specific test condition is VddThe input voltage and the output voltage range are both 0-50V, and the test result shows that the highest gain value is 68 (figure 12), which proves that the cross-linking agent has potential application value in the aspect of organic digital circuits.
Claims (10)
1. A polymer of formula I:
in the formula I, R1、R2Each independently selected from any one of C1-C50 linear or branched alkyl, C1-C50 alkoxy, C7-C50 aralkyl heteroaryl and C5-C50 heteroalkyl;
ar is selected from any one of aryl, heteroaryl, aryl containing substituent and heteroaryl containing substituent, and the bonding mode of the group interior is selected from at least one of single bond, double bond and triple bond;
wherein the aryl or heteroaryl is selected from any one of the following: phenyl, thienyl, thiazolyl, pyridyl, quinolyl, furyl, pyrrolyl, imidazolyl, naphthyl and pyrenyl, or a combined fragment formed by connecting the above units through one or more of single bond, double bond, triple bond, oxygen, sulfur, silicon or nitrogen; the heteroatom in the heteroalkyl group is at least one of oxygen, sulfur and selenium, and the substitution number of the heteroatom is 1-10; the heteroaryl is selected from any one of monocyclic heteroaryl, bicyclic heteroaryl and tricyclic heteroaryl, and the heteroatom in the heteroaryl is selected from at least one of oxygen, sulfur and selenium; in the aryl group containing the substituent and the heteroaryl group containing the substituent, the substituent is any one of alkyl of C1-C50, alkylthio of C1-C50, alkylcarbonyl of C1-C50, acyloxy, nitrile and alkoxy of C1-C50, and the number of the substituent is an integer of 1-4;
in the formula I, x is more than 0:1 and y is less than or equal to 1: 0.
2. The polymer of claim 1, wherein: ar is selected from any one of the following structural formulas a-u:
in the structural formulas a to u, R is selected from any one of hydrogen, alkyl of C1-C50 and alkoxy of C1-C50;
in the structural formulas a to u, in the formula,
indicating the position of the linkage of formula I.
3. A process for the preparation of a polymer of formula I according to claim 1 or 2, comprising the steps of: carrying out carbon-carbon coupling reaction on the compound shown in the formula II, the compound shown in the formula III and the compound shown in the formula IV in an organic solvent in the presence of an inert atmosphere and a catalyst, and obtaining the polymer shown in the formula I after the carbon-carbon coupling reaction is finished;
in the formulae II, III and IV, R1、R2And Ar is as defined for formula I, and Y is a trialkyltin or borate group.
4. The production method according to claim 3, characterized in that:
the gas of the inert atmosphere is nitrogen;
the catalyst consists of a palladium catalyst and a phosphine ligand, wherein the palladium catalyst is selected from at least one of tetrakis (triphenylphosphine) palladium, tris (tri-p-methylphenyl phosphine) palladium, tris (dibenzylideneacetone) dipalladium and bis (1, 4-diphenylphosphino) butyl palladium dichloride; the phosphine ligand is selected from at least one of triphenylphosphine, o-trimethylphenylphosphine, tri (2-furyl) phosphine and 2- (di-tert-butylphosphine) biphenyl;
the molar ratio of the compound shown in the formula II, the compound shown in the formula III, the compound shown in the formula IV, the palladium catalyst and the phosphine ligand is 1:0 to 20: 0 to 20: 0.01-0.03: 0.03 to 0.12;
the reaction temperature of the carbon-carbon coupling reaction can be 90-110 ℃, and the reaction time is 1-3 h;
the organic solvent is at least one selected from toluene, N-dimethylformamide and chlorobenzene;
the trialkyltin reagent is selected from trimethylphenyltin and/or tributylphenyltin.
5. The production method according to claim 3 or 4, characterized in that: the coupling reaction further comprises the following steps: dripping the system after the coupling reaction into methanol, and filtering to obtain a solid; then sequentially extracting the solid with acetone and n-hexane, and taking the extracted solid; and finally, extracting the solid subjected to the soxhlet extraction by using chloroform to obtain a target product, dripping the chloroform dissolved with the target product into methanol, and performing suction filtration to obtain a solid, namely the polymer shown in the formula I.
6. A compound of formula II:
in the formula II, R1Is selected from any one of C1-C50 straight chain or branched chain alkyl, C1-C50 alkoxy, C7-C50 aralkyl and C5-C50 heteroalkyl.
7. A process for the preparation of a compound of formula ii as described in claim 6 comprising the steps of:
a compound shown as a formula V and N3Carrying out nucleophilic substitution reaction on the group compound in a solvent to obtain a compound shown as a formula II;
in the formula V, A is selected from halogen atoms or p-methoxybenzenesulfonyl chloride.
8. The method for producing according to claim 7, characterized in that: the compound shown as the formula V and the N3N in the radical compound3The molar ratio of the groups is 1: 2-50; said group containing N3The radical compound is sodium azide;
the reaction temperature of the nucleophilic substitution reaction is room temperature, and the reaction time is 2-7 h;
the solvent is DMF.
9. Use of the polymer of formula I as defined in claim 1 or 2 in at least one of the following (1) to (4):
(1) an organic polymer semiconductor photoresist which can be used as a single component; (2) as a general purpose crosslinking agent to crosslink other polymer semiconductors; (3) realizing organic semiconductor patterning; (4) application in the preparation of organic photoelectric devices.
10. Use according to claim 9, characterized in that:
the other polymers include non-conjugated polymers as well as conjugated polymers;
the organic optoelectronic device includes at least one of an organic field effect transistor, an organic digital circuit, an organic solar cell, an organic thermoelectric, an organic laser, and an organic light emitting diode.
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