CN118307750A - Polycyclic phosphoric acid polymer material and preparation method and application thereof - Google Patents
Polycyclic phosphoric acid polymer material and preparation method and application thereof Download PDFInfo
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- CN118307750A CN118307750A CN202410415938.3A CN202410415938A CN118307750A CN 118307750 A CN118307750 A CN 118307750A CN 202410415938 A CN202410415938 A CN 202410415938A CN 118307750 A CN118307750 A CN 118307750A
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- Prior art keywords
- polycyclic
- phosphoric acid
- acid polymer
- polymer material
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 title claims abstract description 142
- 125000003367 polycyclic group Chemical group 0.000 title claims abstract description 84
- 229910000147 aluminium phosphate Inorganic materials 0.000 title claims abstract description 71
- 239000002861 polymer material Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 78
- 238000000034 method Methods 0.000 claims abstract description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 30
- 229910019142 PO4 Inorganic materials 0.000 claims description 26
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 25
- 239000010452 phosphate Substances 0.000 claims description 25
- 125000003118 aryl group Chemical group 0.000 claims description 18
- 238000006116 polymerization reaction Methods 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 12
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 9
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 8
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims description 8
- 125000001424 substituent group Chemical group 0.000 claims description 8
- 229910052731 fluorine Inorganic materials 0.000 claims description 7
- 229910052740 iodine Inorganic materials 0.000 claims description 7
- 125000005129 aryl carbonyl group Chemical group 0.000 claims description 6
- 125000005199 aryl carbonyloxy group Chemical group 0.000 claims description 6
- 125000005161 aryl oxy carbonyl group Chemical group 0.000 claims description 6
- 125000004104 aryloxy group Chemical group 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 6
- 125000001072 heteroaryl group Chemical group 0.000 claims description 6
- 125000005223 heteroarylcarbonyl group Chemical group 0.000 claims description 6
- 125000005204 heteroarylcarbonyloxy group Chemical group 0.000 claims description 6
- 125000005553 heteroaryloxy group Chemical group 0.000 claims description 6
- 125000005226 heteroaryloxycarbonyl group Chemical group 0.000 claims description 6
- 238000006460 hydrolysis reaction Methods 0.000 claims description 6
- 229920000137 polyphosphoric acid Polymers 0.000 claims description 6
- 230000007062 hydrolysis Effects 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 4
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 4
- 125000004122 cyclic group Chemical group 0.000 claims description 4
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 claims description 4
- 230000005669 field effect Effects 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 125000006413 ring segment Chemical group 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 claims description 2
- 150000003577 thiophenes Chemical class 0.000 claims description 2
- 230000005693 optoelectronics Effects 0.000 claims 1
- 230000005855 radiation Effects 0.000 claims 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 abstract description 84
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 54
- 239000000463 material Substances 0.000 abstract description 24
- 229920000642 polymer Polymers 0.000 abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 12
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 abstract description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 6
- 239000011248 coating agent Substances 0.000 abstract description 5
- 238000000576 coating method Methods 0.000 abstract description 5
- 238000009792 diffusion process Methods 0.000 abstract description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 abstract description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 abstract description 4
- 230000002349 favourable effect Effects 0.000 abstract description 4
- 238000003618 dip coating Methods 0.000 abstract description 2
- 239000012046 mixed solvent Substances 0.000 abstract description 2
- 238000004528 spin coating Methods 0.000 abstract description 2
- 238000005507 spraying Methods 0.000 abstract description 2
- 238000010345 tape casting Methods 0.000 abstract description 2
- 230000003993 interaction Effects 0.000 abstract 1
- 238000010189 synthetic method Methods 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 59
- -1 small molecule polycyclic phosphoric acids Chemical class 0.000 description 54
- 235000011007 phosphoric acid Nutrition 0.000 description 52
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 30
- 239000004912 1,5-cyclooctadiene Substances 0.000 description 22
- IYYIVELXUANFED-UHFFFAOYSA-N bromo(trimethyl)silane Chemical compound C[Si](C)(C)Br IYYIVELXUANFED-UHFFFAOYSA-N 0.000 description 22
- 238000003756 stirring Methods 0.000 description 22
- 235000021317 phosphate Nutrition 0.000 description 21
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 21
- 150000003384 small molecules Chemical class 0.000 description 21
- 239000000243 solution Substances 0.000 description 21
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 18
- 238000001914 filtration Methods 0.000 description 18
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- 229920000388 Polyphosphate Polymers 0.000 description 15
- 239000000203 mixture Substances 0.000 description 15
- 239000001205 polyphosphate Substances 0.000 description 15
- 235000011176 polyphosphates Nutrition 0.000 description 15
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 14
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 14
- 238000001816 cooling Methods 0.000 description 13
- 239000010410 layer Substances 0.000 description 13
- 239000012074 organic phase Substances 0.000 description 13
- 239000012467 final product Substances 0.000 description 12
- 230000005525 hole transport Effects 0.000 description 12
- 239000000843 powder Substances 0.000 description 12
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 10
- 238000012512 characterization method Methods 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- LFULEKSKNZEWOE-UHFFFAOYSA-N propanil Chemical compound CCC(=O)NC1=CC=C(Cl)C(Cl)=C1 LFULEKSKNZEWOE-UHFFFAOYSA-N 0.000 description 9
- 239000000758 substrate Substances 0.000 description 8
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 7
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 6
- 238000004821 distillation Methods 0.000 description 6
- VVVPGLRKXQSQSZ-UHFFFAOYSA-N indolo[3,2-c]carbazole Chemical compound C1=CC=CC2=NC3=C4C5=CC=CC=C5N=C4C=CC3=C21 VVVPGLRKXQSQSZ-UHFFFAOYSA-N 0.000 description 6
- 229960005544 indolocarbazole Drugs 0.000 description 6
- QTERVOZQCNPERI-UHFFFAOYSA-N 1h-indole;phosphoric acid Chemical compound OP(O)(O)=O.C1=CC=C2NC=CC2=C1 QTERVOZQCNPERI-UHFFFAOYSA-N 0.000 description 5
- 238000000137 annealing Methods 0.000 description 5
- 239000005457 ice water Substances 0.000 description 5
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 5
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 5
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 229920002959 polymer blend Polymers 0.000 description 4
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 4
- YMNBGNNSBURRAD-UHFFFAOYSA-N 4-bromobutyl diethyl phosphate Chemical compound CCOP(=O)(OCC)OCCCCBr YMNBGNNSBURRAD-UHFFFAOYSA-N 0.000 description 3
- QJTQKPNNQVLHHO-UHFFFAOYSA-N 9h-carbazole;1h-indole Chemical compound C1=CC=C2NC=CC2=C1.C1=CC=C2C3=CC=CC=C3NC2=C1 QJTQKPNNQVLHHO-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 3
- 239000007983 Tris buffer Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000007790 scraping Methods 0.000 description 3
- 229930192474 thiophene Natural products 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- ULTHEAFYOOPTTB-UHFFFAOYSA-N 1,4-dibromobutane Chemical compound BrCCCCBr ULTHEAFYOOPTTB-UHFFFAOYSA-N 0.000 description 2
- MCBADHLJNYYFMZ-UHFFFAOYSA-N 2,8-dibromoindolo[3,2-b]carbazole Chemical compound C12=CC(Br)=CC=C2N=C2C1=CC1=NC3=CC=C(Br)C=C3C1=C2 MCBADHLJNYYFMZ-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229920001167 Poly(triaryl amine) Polymers 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- XZCBYXUKPMELOQ-UHFFFAOYSA-N n,n-bis(4-bromophenyl)-2,4,6-trimethylaniline Chemical compound CC1=CC(C)=CC(C)=C1N(C=1C=CC(Br)=CC=1)C1=CC=C(Br)C=C1 XZCBYXUKPMELOQ-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- QNMMYUBZGLXCCK-UHFFFAOYSA-N pyrrolo[3,2-a]carbazole Chemical compound N1=C2C=CC=CC2=C2C1=C1C=CN=C1C=C2 QNMMYUBZGLXCCK-UHFFFAOYSA-N 0.000 description 2
- 238000010129 solution processing Methods 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
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- RGGOWBBBHWTTRE-UHFFFAOYSA-N (4-bromophenyl)hydrazine;hydron;chloride Chemical compound Cl.NNC1=CC=C(Br)C=C1 RGGOWBBBHWTTRE-UHFFFAOYSA-N 0.000 description 1
- UKOMUVPFRFPHDS-UHFFFAOYSA-N 1,4,2-dioxazine Chemical compound O1C=CON=C1 UKOMUVPFRFPHDS-UHFFFAOYSA-N 0.000 description 1
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- WGTASENVNYJZBK-UHFFFAOYSA-N 3,4,5-trimethoxyamphetamine Chemical compound COC1=CC(CC(C)N)=CC(OC)=C1OC WGTASENVNYJZBK-UHFFFAOYSA-N 0.000 description 1
- LORUWPJEPLSPNN-UHFFFAOYSA-N 3,8-dibromo-11,12-dihydroindolo[2,3-a]carbazole Chemical compound C12=CC(Br)=CC=C2NC2=C1C=CC1=C2NC2=CC=C(Br)C=C21 LORUWPJEPLSPNN-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 229940122361 Bisphosphonate Drugs 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- HTASKTWYLDXXPU-UHFFFAOYSA-N CCCCC(CC)COc1c2sc3ccsc3c2c(OCC(CC)CCCC)c2sc3ccsc3c12 Chemical compound CCCCC(CC)COc1c2sc3ccsc3c2c(OCC(CC)CCCC)c2sc3ccsc3c12 HTASKTWYLDXXPU-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
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- 238000009825 accumulation Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000004663 bisphosphonates Chemical class 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Chemical group 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- DCZFGQYXRKMVFG-UHFFFAOYSA-N cyclohexane-1,4-dione Chemical compound O=C1CCC(=O)CC1 DCZFGQYXRKMVFG-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
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- 239000011737 fluorine Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 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
- 150000004820 halides Chemical class 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- GLBITHOZXJPRGL-UHFFFAOYSA-N methyl 3-(bromoamino)benzoate Chemical compound BrNC=1C=CC=C(C(=O)OC)C=1 GLBITHOZXJPRGL-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- BAVYZALUXZFZLV-UHFFFAOYSA-N mono-methylamine Natural products NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 1
- 229920000301 poly(3-hexylthiophene-2,5-diyl) polymer Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
The invention discloses a polycyclic phosphoric acid polymer material, a preparation method and application thereof, and belongs to the field of new energy material preparation. The polycyclic phosphoric acid polymer material provided by the invention has excellent stability, and the problems of poor compactness, easy diffusion and the like of the traditional small phosphoric acid molecules can be effectively solved by the favorable film forming property and the interaction between macromolecular chains, so that a stable photoelectric device based on the polycyclic phosphoric acid polymer is realized. The synthetic method of the polycyclic phosphoric acid polymer is simple and quick, the reaction condition is mild, the obtained polycyclic phosphoric acid polymer material is dissolved in single or mixed solvents such as toluene, chlorobenzene, chloroform, dichloromethane, methanol, ethanol, isopropanol and the like, and the polycyclic phosphoric acid polymer material is processed into a film through processes such as spin coating, knife coating, slit coating, dip coating, spray coating and the like, so that the photoelectric device based on the polycyclic phosphoric acid polymer material is prepared. The invention has important scientific significance and extremely high industrial value.
Description
Technical Field
The invention belongs to the field of preparation of new energy materials, and particularly relates to a polycyclic phosphoric acid polymer material, and a preparation method and application thereof.
Background
The small-molecule polycyclic phosphoric acid is a hole transport material developed in recent years, has the advantage of solution processing, can form a monomolecular layer on a conductive substrate (ITO and FTO), has better wettability on the small-molecule polycyclic phosphoric acid compared with PTAA type polytrianiline hole transport layer materials, is favorable for large-area coating of the perovskite film, realizes efficient hole transport in trans-perovskite photovoltaics, and is now becoming a common hole transport material for trans-structure perovskite solar cells. Although small-molecule polycyclic phosphoric acid has excellent hole transport properties, it has problems in compactness and stability. The small-molecule polycyclic phosphoric acid needs to form a compact and uniform monolayer on the conductive substrate to realize efficient hole transmission, but in the actual solution processing process, the small-molecule polycyclic phosphoric acid locally forms a multi-molecule layer to increase the hole extraction resistance. Diffusion of small molecule polycyclic phosphoric acids into the perovskite active layer also occurs under photothermal conditions. In addition, on some rough conductive substrates, such as FTO, small-molecule polycyclic phosphoric acid cannot completely cover the whole conductive substrate, so that the perovskite film is in direct contact with the conductive substrate, on one hand, local electric leakage is caused, on the other hand, the conductive substrate can induce decomposition of perovskite, and attenuation (Science 2020,370,1300-1309;Nature 2023,Nature https://doi.org/10.1038/s41586-41023-05992-y;Joule 2020,4,850-864;Nature Energy 2023,https://doi.org/10.1038/s41560-41023-01227-41566). of a perovskite solar cell is caused, so that the development of a novel hole transport layer material for solving the problems existing in the current small-molecule polycyclic phosphoric acid is an important step for improving the stability of a trans-perovskite photovoltaic device and promoting the industrialization process of the trans-perovskite photovoltaic device.
Disclosure of Invention
The first technical problem to be solved by the present invention is to provide a polycyclic phosphoric acid for preparing a polycyclic phosphoric acid polymer material, which is a repeating unit of the material, against the above problems existing in the prior art. The second technical problem to be solved by the invention is to provide a polycyclic phosphoric acid polymer material which has the characteristics of good film forming property, excellent stability, difficult diffusion and the like. The third technical problem to be solved by the invention is to provide a preparation method of the polycyclic phosphoric acid polymer material, which is simple and convenient, and the prepared polycyclic phosphoric acid polymer material is stable. The fourth technical problem to be solved by the invention is to provide an application of the polycyclic phosphoric acid polymer material in preparing a photoelectric device structure, which solves the problems of high hole resistance, poor coverage, diffusion and the like of small-molecule polycyclic phosphoric acid applied to a conductive substrate.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
A polycyclic phosphoric acid of the formula:
Wherein the benzene ring on the polycyclic phosphoric acid unit contains or does not contain substituent groups; the substituent is selected from: halogen groups, cyano groups, alkyl groups, aromatic groups, and cyclic groups; the values of m 1、m2 and m 3 are 1-40, and the values of m can be 1,2,3, 5, 10, 15 and 20, or the parameter ranges formed by any integers in the ranges.
Further, the halogen group is F, cl, br or I; the alkyl is (C1-C40) straight chain alkyl, (C3-C40) branched alkyl or (C3-C40) cycloalkyl; the aromatic group is one or more of aryl, heteroaryl, aryloxy, heteroaryloxy, arylcarbonyl, heteroarylcarbonyl, arylcarbonyloxy, heteroarylcarbonyloxy, aryloxycarbonyl and heteroaryloxycarbonyl; the merging group is used for merging benzene rings into macrocyclic naphthalene or anthracene.
A polycyclic phosphoric acid polymer material obtained by polycyclic phosphoric acid polymerization has the following structural general formula:
wherein, the polymerization site of the poly-polycyclic phosphoric acid is at any position on the benzene ring, and the value range of n is 2-10000000;
In the polycyclophosphoric acid structure of the invention, the film forming property of the coating after coating can be effectively improved as long as the small-molecule polycyclophosphoric acid can be polymerized to a certain degree and the molecular weight is improved, the number of the repeating units in the polymeric material can be 2 to 10000000, preferably the number of the repeating units is more than 5, 8, 10, 15, 20, 25, 30, 50, 80, 100, 200, 500, 1000, 2000, 5000 and the like, and the parameter ranges formed by any integers in the range can also be adopted.
The poly-polycyclic phosphoric acid adopted in the invention is polymerized by the small-molecule polycyclic phosphoric acid, the number of the rings is more than 3, the small-molecule polycyclic phosphoric acid can adopt the structure disclosed in the prior art, the molecular weight is improved after the polymerization, the purpose of the invention can be realized by the small-molecule polycyclic phosphoric acid with certain hole transmission property, and the invention can also be modified by some substituents for adjusting and improving the performance.
R 1、R2、R3 and R 4 are selected from: h, halogen, cyano, alkyl, aromatic, and cyclic groups.
Further, the halogen group is F, cl, br or I;
the alkyl is (C1-C40) straight chain alkyl, (C3-C40) branched alkyl or (C3-C40) cycloalkyl;
In said alkyl, one or more non-adjacent C atoms are optionally replaced by-O-, -S-, -C (O) -, -C (O-) -O-, -O-C (O) -, -OC (O) -O-, -CR 0＝CR00 -, or-c≡c-, wherein R 0 and R 00 are independently straight chain alkyl, branched chain alkyl or cycloalkyl;
wherein one or more H atoms in said alkyl group are optionally replaced by F, cl, br, I or CN;
The aromatic group is one or more of aryl, heteroaryl, aryloxy, heteroaryloxy, arylcarbonyl, heteroarylcarbonyl, arylcarbonyloxy, heteroarylcarbonyloxy, aryloxycarbonyl and heteroaryloxycarbonyl, and has 4 to 30 ring atoms;
the merging group is used for merging benzene rings into macrocyclic naphthalene or anthracene.
The invention provides a polycycle phosphate material with or without substituent groups, which is obtained by polymerizing small molecule polycycle phosphate and hydrolyzing ester groups, wherein the polymerization site is any position on benzene rings; alternatively, the polycyclophosphate may be hydrolyzed to polycyclophosphoric acid by copolymerizing the polycyclic phosphate by adding the corresponding halogenated compound during the polycondensation reaction, followed by adding the halosilane and the alcohol compound.
The preparation method of the polycyclic phosphoric acid polymer material comprises the following specific steps:
1) Grafting phosphate functional groups on the reaction sites of N of the polycyclic phosphoric acid to obtain polycyclic phosphate molecules, and then adding halogenated compounds to carry out halogenated substitution to obtain halogenated polycyclic phosphate;
Or, grafting phosphate functional groups on the reaction sites of N of the halogenated polycyclic molecules to obtain halogenated polycyclic phosphate; wherein, the mass ratio of the polycyclic phosphate to the halogenated compound is 1:0.01 to 1000;
2) Adding or not adding other halogenated compounds into the halogenated polycyclic phosphate prepared in the step 1), adding a solvent and a catalyst to perform polymerization reaction, wherein the reaction time is below 72h, and the reaction temperature is below 300 ℃;
3) After the polymerization reaction in the step 2) is completed, halosilane and alcohols are added for hydrolysis, and the polycyclic phosphoric acid polymer material is obtained.
Further, in step 2), the other halogenated compound is a halogenated aromatic hydrocarbon or a halogenated thiophene with or without a substituent;
further, the aromatic group of the halogenated aromatic hydrocarbon is one or more of aryl, heteroaryl, aryloxy, heteroaryloxy, arylcarbonyl, heteroarylcarbonyl, arylcarbonyloxy, heteroarylcarbonyloxy, aryloxycarbonyl and heteroaryloxycarbonyl.
Further, the yield of the hydrolysis reaction is 1% to 100%.
Further, the catalyst is selected from a nickel-based catalyst or a palladium catalyst.
Self-polymerization of halogenated polycyclic phosphates without addition of halogenated compounds;
When other halogenated compounds are added, the halogenated polycyclic phosphate is randomly copolymerized or alternately copolymerized with other halogenated compounds.
In one embodiment, the polybenzazole phosphate is obtained by catalytic polymerization of dibromoindolocarbazole phosphate as a raw material; stirring and reacting polybenzazole phosphate and trimethyl bromosilane in a solvent, and then adding excessive methanol for hydrolysis to obtain a polybenzazole phosphate material; the reaction equation is as follows:
Wherein n has a value ranging from 2 to 10000000, m has a value ranging from 1 to 40, R is a (C1-C40) straight-chain alkyl group, a (C3-C40) branched-chain alkyl group or a (C3-C40) cycloalkyl group.
In one embodiment, the polybenzazole indole phosphate is obtained by catalytic polymerization of dibromoindole phosphate as a raw material; stirring and reacting polybenzazole indole phosphate and trimethyl bromosilane in a solvent, and then adding excessive methanol for hydrolysis to obtain a polybenzazole indole phosphate material; the reaction equation is as follows:
Wherein n has a value ranging from 2 to 10000000, m has a value ranging from 1 to 40, R is a (C1-C40) straight-chain alkyl group, a (C3-C40) branched-chain alkyl group or a (C3-C40) cycloalkyl group.
In one embodiment, the polybenzazole indole phosphate copolymer is obtained by taking dibromoindole indole phosphate and aromatic groups as raw materials and carrying out catalytic reaction; stirring and reacting the polybenzazole indole phosphate copolymer and trimethyl bromosilane in a solvent, and then adding excessive methanol for hydrolysis to obtain a polybenzazole indole phosphate copolymer polymer; the reaction equation is as follows:
wherein n is in the range of 2 to 10000000, m is in the range of 1 to 40, R is (C1-C40) straight-chain alkyl, (C3-C40) branched-chain alkyl or (C3-C40) cycloalkyl, and Ar is an aromatic group.
Further, the polycyclic phosphoric acid polymer material is applied to the preparation of the photoelectric device structure.
Further, the photoelectric device structure is a solar cell, a field effect transistor, a photoelectric detector, a ray detector and a light emitting diode.
Further, the solar cell has the following structure:
the polycyclic phosphoric acid polymer material is used as a hole transport layer material or an electron blocking material in an organic solar cell or a perovskite solar cell or an organic light-emitting diode or a perovskite light-emitting diode, or is subjected to interface modification based on the original hole transport layer.
The perovskite light absorbing layer comprises a metal perovskite halide having the chemical formula ABX 3, wherein a includes, but is not limited to, methylamine ions, formamidine ions, cesium, rubidium, potassium, sodium, ammonium ions, ethylamine, propylamine, butylamine, aniline, benzylamine, phenethylamine, or a combination thereof; b includes lead, tin, cadmium, germanium, zinc, nickel, or a combination thereof. X is fluorine, chlorine, bromine, iodine anions or a combination of the above.
Specifically, the solar cell electrode contains one or more of gold, silver, copper, aluminum, carbon and chromium. The hole transport layer comprises PTAA, spiro-OMeTAD, PEDOT: PSS, niO, moO 3,V2O5, poly-TPD, EH44, P3HT, or combinations thereof. The electron transport layer comprises C 60,BCP,TiO2,SnO2,PCBM,ICBA,ZnO,ZrAcac,LiF,TPBi,PFN,Nb2O5 or a combination of the above materials.
Specifically, the perovskite solar cell has a photoelectric conversion efficiency of 1% to 35%. The organic solar cell has a photoelectric conversion efficiency of 1% to 25%.
The beneficial effects are that: compared with the prior art, the invention has the advantages that:
(1) The polycyclic phosphoric acid polymer material prepared by the invention has excellent stability and film forming property, and the problems of poor compactness, easy diffusion and the like of the traditional micromolecular polycyclic phosphoric acid can be effectively solved by the mutual high polymer chains, so that a stable photoelectric device based on the polycyclic phosphoric acid polymer is realized.
(2) The method for preparing the polycyclic phosphoric acid polymer material is simple and convenient, and the reaction condition is mild. The obtained polycyclic phosphoric acid polymer material is dissolved in single or mixed solvents such as toluene, chlorobenzene, chloroform, dichloromethane, methanol, ethanol, isopropanol and the like, and is processed into a film through processes such as spin coating, knife coating, slit coating, dip coating, spray coating and the like, so that photoelectric devices based on polycyclic phosphoric acid sense and insight materials are prepared, wherein the photoelectric devices comprise perovskite solar cells, organic solar cells, field effect transistors, light emitting diodes, photoelectric detectors, ray detectors and the like.
(3) According to the invention, the molecular weight is improved after the polymerization of the micromolecular polycyclic phosphoric acid, so that the film forming property of the polycyclic phosphoric acid polymer material on the surface of the conductive substrate can be effectively improved, and a stable hole transport layer with proper thickness can be formed.
Drawings
FIG. 1 is a graph of current-voltage for a perovskite solar cell based on DCPA and P-DCPA according to the present invention;
FIG. 2 is a graph of perovskite solar current-voltage curves for D4CPA and P-D4CPA of the present invention.
Detailed Description
The present invention will be further described with reference to specific embodiments for the purpose of making the objects, technical solutions and advantages of the present invention more apparent.
Example 1
The preparation procedure for P-DCPA was as follows:
1) 3.98g of 4-bromophenylhydrazine hydrochloride and 1.46g of sodium acetate were dissolved in 40mL of ethanol, 20mL of a 0.05g/mL ethanol solution of 1,4 cyclohexanedione was added, and the mixture was stirred at 30℃for 30 minutes, followed by cooling to 0℃and filtration, washing with cold water, to give 3.4g of 1,4-bis (2- (4-bromophenyl) hydrazineylidene) cyclohexane (1, 4-bis (2- (4-bromophenyl) hydrazinomethylene) cyclohexane) having the following structural formula:
2) 3.4g of 1,4-bis (2- (4-bromophenyl) hydrazineylidene) cyclohexane is dissolved in a mixed solution of 85mL of acetic acid and 21mL of concentrated sulfuric acid, the mixture is reacted for 5min at 0 ℃, then the temperature is raised to 30 ℃ for 1h, the temperature is raised to 65 ℃ for 1h, the mixture is cooled to room temperature, ice water is added, filtration is carried out, water and ethanol are respectively washed for 3 times to neutrality, and 1.35g of 2,8-dibromoindolo (3, 2-b) carbazole (2, 8-dibromoindole (3, 2-b) carbazole) is obtained, and the structural formula is shown as follows:
1H NMR(400MHz,DMSO-d6)δ11.29(s,2H),8.47(d,J＝2.0Hz,2H),8.22(s,2H),7.50(dd,J＝8.6,2.0Hz,2H),7.42(d,J＝8.6Hz,2H).
3) 500mg of 2,8-dibromoindolo (3, 2-b) carbazole (2, 8-dibromoindole (3, 2-b) carbazole) was dissolved in 5mL of DMSO, 106.2mg of NaH was slowly added, the reaction was performed at room temperature for 30min, 0.48mL of diethyl 4-bromobutylphosphate was slowly dropped, the reaction was performed for 30min, the temperature was raised to 60 ℃ for 20h, the reaction solution was cooled to room temperature, 25mL of ice water was added, the reaction solution was acidified to pH=2 with 1M hydrochloric acid, and extracted with ethyl acetate to obtain 559mg tetraethyl((2,8-dibromoindolo[3,2-b]carbazole-5,11-diyl)bis(butane-4,1-diyl))bis(phos phonate)( tetraethyl ((2, 8-dibromoindole [3,2-b ] carbazole-5, 11-diyl) bis (butane-4, 1-diyl)) bis (phosphate)) as shown in the following structural formula:
1H NMR(400MHz,Chloroform-d)δ8.30(d,J＝1.9Hz,2H),7.93(s,2H),7.56(dd,J＝8.7,1.9Hz,2H),7.28(d,J＝8.6Hz,2H),4.38(t,J＝7.1Hz,4H),4.09–3.97(m,8H),2.04(p,J＝7.1Hz,4H),1.74(d,J＝3.5Hz,4H),1.26(q,J＝6.9Hz,16H).
4) 172mg of Ni (COD) 2, 97.9mg of bipyridine and 81 mu L of COD were dissolved in 2mL of DMF, activated at 80 ℃ for 30min, 500mg tetraethyl((2,8-dibromoindolo[3,2-b]carbazole-5,11-diyl)bis(butane-4,1-diyl))bis(phosphonate)( tetraethyl ((2, 8-dibromoindolo [3,2-b ] carbazole-5, 11-diyl) bis (butane-4, 1-diyl)) bis (phosphate)) was dissolved in 4mL of DMF, activated catalyst (activated Ni (COD) 2, bipyridine, COD and DMF) was added, reacted at 80 ℃ for 12h, cooled to room temperature, 1M hydrochloric acid 2mL was added, stirred for 10min, extracted with dichloromethane, and the organic phase was taken to give 295mg of polybenzocarbazole phosphate of the formula:
5) 50mg of polybenzazole phosphate is dissolved in 10mL of dichloromethane, 100 mu L of trimethyl bromosilane is added for reaction at normal temperature for 12 hours, excessive methanol is added, diethyl ether is added for precipitation after stirring for 4 hours, 38mg of polybenzazole phosphate (P-DCPA) is obtained after filtration, and the structural formula is determined to be shown as follows by characterization:
Example 2
The preparation of P-D4CPA was as follows:
1) 1.39g of NaH was dissolved in 100mL of anhydrous tetrahydrofuran, 4g of methyl 5-bromoaminobenzoate was added in portions, and the reaction solution was gradually warmed to 60℃and stirred for 12 hours. Cooling to room temperature, slowly pouring into 0.1M hydrochloric acid, filtering to collect precipitate, washing with deionized water, and drying at 50deg.C to obtain 2g of 2,8-dibromodibenzo [ b, f ] [1,5] diazocine-6,12 (5H, 11H) -dione (2, 8-dibromodibenzo [ b, f ] [1,5] diazocyclohexane-6, 12 (5H, 11H) -dione) with the following structural formula:
1H NMR(400MHz,DMSO-d6,ppm):10.37(s,1H),7.57(dd,J＝8.5,2.4Hz,1H),7.51(d,J＝2.3Hz,1H),7.06(d,J＝8.5Hz,1H).13C NMR(101MHz,DMSO,ppm):167.81,135.63,134.33,134.00,131.10,128.49,120.36.
2) 3g of 2,8-dibromodibenzo [ b, f ] [1,5] diazocine-6,12 (5H, 11H) -dione are dissolved in 50mL of chloroform, 6g of phosphorus pentachloride are added in portions, the reaction solution is gradually heated to 50 ℃, stirred for 4 hours, cooled to room temperature, and the reaction solution is distilled off under reduced pressure. The resulting solid was dissolved in 200mL of tetrahydrofuran, 5.94g of zinc powder was added, followed by 13.5mL of trifluoroacetic acid, stirring at room temperature for 12 hours, adding a saturated ammonium chloride solution to quench the reaction, extracting the reaction solution with ethyl acetate, collecting the organic phase, distilling under reduced pressure, purifying by column to obtain 1.2g of 3,8-dibromo-5,10-dihydroindolo [3,2-b ] indole (3, 8-dibromo-5, 10-indoline [3,2-b ] indole) having the following structural formula:
1H NMR(400MHz,DMSO-d6,ppm):11.38(s,1H),7.92(d,J＝2.0Hz,1H),7.50(d,J＝8.7Hz,1H),7.31(dd,J＝8.7,2.0Hz,1H).13C NMR(101MHz,DMSO,ppm):139.51,125.89,124.74,120.45,116.17,114.68,110.59.
3) 3g of 3,8-dibromo, 10-dihydroindolo [3,2-b ] indole are dissolved in 20mL of 1, 4-dibromobutane, 1.07g of tetrabutylammonium bromide is added, followed by 12.4mL of 50% potassium hydroxide, and stirred at 60℃for 12 hours. After cooling to room temperature, concentrating under reduced pressure, filtering to obtain a product, purifying the product by a column to obtain 3.6g of 3,8-dibromo-5,10-bis (4-bromobutyl) -5,10-dihydroindolo [3,2-b ] indole (3, 8-dibromo-5,10-bis (4-bromobutyl) -5, 10-indoline [3,2-b ] indole) with the following structural formula:
1H NMR(400MHz,Chloroform-d,ppm):7.91(d,J＝2.0Hz,1H),7.40(dd,J＝8.8,1.9Hz,1H),7.32(d,J＝8.9Hz,1H),4.48(t,J＝6.8Hz,2H),3.36(t,J＝6.4Hz,2H),2.18–2.08(m,2H),1.94–1.85(m,2H).13C NMR(101MHz,CDCl3)δ139.29,125.59,125.11,120.26,115.58,111.51,111.21,77.34,77.02,76.70,44.57,32.98,29.95,28.79.
4) 4g of 3,8-dibromo, 10-bis (4-bromobutyl) -5,10-dihydroindolo [3,2-b ] indole are dissolved in 20mL of triethyl phosphite, heated and stirred at 140 ℃ for 12h, the triethyl phosphite is removed by distillation under reduced pressure, and the mixture is purified by a column to obtain 3.9g of tetraethyl ((3, 8-dibromoindole [3,2-b ] indole-5, 10-diyl) bis-butane-4, 1-diyl) bisphosphonate (tetraethylene ((3, 8-dibromoindolo [3,2-b ] indole-5, 10-diyl) bis (but ane-4, 1-diyl)) bis (phosphonate) with the following structural formula:
1H NMR(400MHz,Chloroform-d,ppm):7.88(d,J＝1.8Hz,1H),7.38(dd,J＝8.8,1.9Hz,1H),7.31(d,J＝8.9Hz,1H),4.43(t,J＝6.9Hz,2H),4.01(tt,J＝8.1,6.3Hz,4H),2.09–2.00(m,2H),1.77–1.62(m,4H),1.24(t,J＝7.1Hz,6H).13CNMR(101MHz,CDCl3,ppm):139.32,125.62,125.00,120.18,115.57,111.38,111.22,61.53,44.95,26.12,24.71,20.33,16.38.
5) 0.176g Ni (Cod) 2, 0.1g bipyridine and 0.082mL 1, 5-cyclooctadiene were dissolved in 5mL DM F and heated and stirred at 80deg.C for half an hour; 0.5g of tetraethylene ((3, 8-dibromoindolo [3,2-b ] indole-5, 10-diyl) bis (butane-4, 1-diyl)) bis (phosphonate) was dissolved in 10mL of DMF, slowly added dropwise to the reaction system, and stirring was continued at 80℃for 24 hours. Cooling to room temperature after the reaction is finished, slowly dropwise adding dilute hydrochloric acid under the stirring condition, extracting an organic phase by using dichloromethane, spin-drying, and obtaining a final product which is gray polybenzazole indole phosphate powder, wherein the structural formula is as follows:
6) 0.12g of polybenzazole indole phosphate is dissolved in 20mL of dichloromethane, 1.5mL of 0.1g/mL of trimethyl bromosilane is added dropwise, the mixture is stirred at room temperature for 24h, and after the reaction is finished, excessive methanol is added dropwise to the reaction system for reaction to remove excessive trimethyl bromosilane. The concentrated solution was distilled under reduced pressure, precipitated in diethyl ether, and washed by filtration with diethyl ether, the final product was indole polyphosphate powder (P-D4 CPA), having a number average molecular weight of about 79267, a weight average molecular weight of about 95248, and the structural formula was determined by characterization as follows:
example 3
The preparation method of the polyphosphoric acid indolocarbazole comprises the following steps:
1) 500mg of 3,8-dibromo-11,12-dihydroindolo [2,3-a ] carbazole (3, 8-dibromo-11, 12-indoline [2,3-a ] carbazole) is dissolved in 5mL of DMSO, 106.2mg of NaH is slowly added for reaction at room temperature for 30min, 0.48mL of diethyl 4-bromobutyl phosphate is slowly added dropwise, the reaction temperature is raised to 60 ℃ for reaction for 20h after 30min, after cooling to room temperature, 25mL of ice water is added into the reaction solution, the reaction solution is acidified to pH=2 by 1M hydrochloric acid and extracted by ethyl acetate to obtain 559mg tetraethyl((3,8-dibromoindolo[2,3-a]carbazole-11,12-diyl)bis(butane-4,1-diyl))bis(phosphonate)( tetraethyl ((3, 8-dibromoindole [2,3-a ] carbazole-11, 12-diyl) bis (butane-4, 1-diyl)) bis (phosphonate) with the following structural formula:
2) 172mg of Ni (COD) 2, 97.9mg of bipyridine and 81 mu L of COD are dissolved in 2mL of DMF, activated for 30min at 80 ℃, 500mg tetraethyl((3,8-dibromoindolo[2,3-a]carbazole-11,12-diyl)bis(butane-4,1-diyl))bis(phosphonate)( tetraethyl ((3, 8-dibromoindole [2,3-a ] carbazole-11, 12-diyl) bis (butane-4, 1-diyl)) bis (phosphonate)) are dissolved in 4mL of DMF, the activated catalyst is added, the reaction is carried out for 12h at 80 ℃, cooled to room temperature, 1M hydrochloric acid 2mL is added, stirred for 10min, extracted with dichloromethane, and an organic phase is taken to obtain 295mg of diethyl polyphosphate indole carbazole with the following structural formula:
3) 50mg of diethyl indolocarbazole polyphosphate is dissolved in 10mL of dichloromethane, 100 mu L of trimethyl bromosilane is added for reaction at normal temperature for 12h, excessive methanol is added, diethyl ether is added for precipitation after stirring for 4h, 38mg of indolocarbazole polyphosphate is obtained after filtration, and the structural formula is determined by characterization as follows:
Example 4
The preparation method of the polyphosphoric acid indolocarbazole comprises the following steps:
1) 500mg of 3,9-dibromo, 12-dihydroindolo [3,2-a ] carbazole (3, 9-dibromo-5, 12-indoline [3,2-a ] carbazole) is dissolved in 5mL of DMSO, 106.2mg of NaH is slowly added for reaction at room temperature for 30min, 0.48mL of diethyl 4-bromobutyl phosphate is slowly added dropwise, the reaction temperature is raised to 60 ℃ for reaction for 20h after 30min, after cooling to room temperature, 25mL of ice water is added into the reaction solution, the reaction solution is acidified to pH=2 by 1M hydrochloric acid and extracted by ethyl acetate to obtain 559mg tetraethyl((3,9-dibromoindolo[3,2-a]carbazole-5,12-diyl)bis(butane-4,1-diyl))bis(phosphonate)( tetraethyl ((3, 9-dibromoindole [3,2-a ] carbazole-5, 12-diyl) bis (butane-4, 1-diyl)) bis (phosphonate) with the following structural formula:
2) 172mg of Ni (COD) 2, 97.9mg of bipyridine and 81 mu L of COD are dissolved in 2mL of DMF, activated for 30min at 80 ℃, 500mg tetraethyl((3,9-dibromoindolo[3,2-a]carbazole-5,12-diyl)bis(butane-4,1-diyl))bis(phosphonate)( tetraethyl ((3, 9-dibromoindole [3,2-a ] carbazole-5, 12-diyl) bis (butane-4, 1-diyl)) bis (phosphonate)) are dissolved in 4mL of DMF, the activated catalyst is added, the reaction is carried out for 12h at 80 ℃, cooled to room temperature, 1M hydrochloric acid 2mL is added, stirred for 10min, extracted with dichloromethane, and an organic phase is taken to obtain 295mg of diethyl polyphosphate indole carbazole with the following structural formula:
3) 50mg of diethyl indolocarbazole polyphosphate is dissolved in 10mL of dichloromethane, 100 mu L of trimethyl bromosilane is added for reaction at normal temperature for 12h, excessive methanol is added, diethyl ether is added for precipitation after stirring for 4h, 38mg of indolocarbazole polyphosphate is obtained after filtration, and the structural formula is determined by characterization as follows:
Example 5
The preparation method of the polyphosphoric acid indolocarbazole comprises the following steps:
1) 500mg of 2,10-dibromo, 7-dihydroindolo [2,3-b ] carbazole (2, 10-dibromo-5, 7-indoline [2,3-b ] carbazole) is dissolved in 5mL of DMSO, 106.2mg of NaH is slowly added for reaction at room temperature for 30min, 0.48mL of diethyl 4-bromobutyl phosphate is slowly added dropwise, the reaction temperature is raised to 60 ℃ for reaction for 20h after 30min, after cooling to room temperature, 25mL of ice water is added into the reaction solution, the reaction solution is acidified to pH=2 by 1M hydrochloric acid and extracted by ethyl acetate to obtain 559mg tetraethyl((2,10-dibromoindolo[2,3-b]carbazole-5,7-diyl)bis(butane-4,1-diyl))bis(phosphonate)( tetraethyl ((2, 10-dibromoindole [2,3-b ] carbazole-5, 7-diyl) bis (butane-4, 1-diyl)) bis (phosphonate) with the following structural formula:
2) 172mg of Ni (COD) 2, 97.9mg of bipyridine and 81 mu L of COD are dissolved in 2mL of DMF, activated for 30min at 80 ℃, 500mg tetraethyl((2,10-dibromoindolo[2,3-b]carbazole-5,7-diyl)bis(butane-4,1-diyl))bis(phosphonate)( tetraethyl ((2, 10-dibromoindole [2,3-b ] carbazole-5, 7-diyl) bis (butane-4, 1-diyl)) bis (phosphonate)) are dissolved in 4mL of DMF, the activated catalyst is added, the reaction is carried out for 12h at 80 ℃, cooled to room temperature, 1M hydrochloric acid 2mL is added, stirred for 10min, extracted with dichloromethane, and an organic phase is taken to obtain 295mg of diethyl polyphosphate indole carbazole with the following structural formula:
3) 50mg of diethyl indolocarbazole polyphosphate is dissolved in 10mL of dichloromethane, 100 mu L of trimethyl bromosilane is added for reaction at normal temperature for 12h, excessive methanol is added, diethyl ether is added for precipitation after stirring for 4h, 38mg of indolocarbazole polyphosphate is obtained after filtration, and the structural formula is determined by characterization as follows:
Example 6
The preparation steps of the polypyrrolocarbazole are as follows:
1) 4g of 3,8-dibromo, 10-dihydroindolo [3,2-b ] indole are dissolved in 20mL of 1, 4-dibromobutane, 1.07g of tetrabutylammonium bromide is added, followed by 12.4mL of 50% potassium hydroxide, and stirred at 60℃for 12 hours. After cooling to room temperature, concentrating under reduced pressure, filtering to obtain a product, purifying the product by a column to obtain 3.6g of 2,11-dibromo-5,8,14-tris (4-bromobutyl) -8,14-dihydro-5H-pyrrolo [3,2-b:4,5-b '] dicarb azole (2, 11-dibromo-5,8,14-tris (4-bromobutyl) -8,14-dihydro-5H-pyrrolo [3,2-b:4,5-b' ] dicarbazole), wherein the structural formula is as follows:
2) 4g of 2,11-dibromo, 8,14-tris (4-bromobutyl) -8,14-dihydro-5H-pyrrolo [3,2-b:4,5-b '] dicarbazole are dissolved in 20mL of triethyl phosphite, heated and stirred at 140℃for 12 hours, the triethyl phosphite is removed by distillation under reduced pressure, and the mixture is purified by a column to give 3.9g of tetraethyl ((2, 11-dibromo-14- (4- (diethoxyphosphoryl) butyl) -5H-pyrrolo [3,2-b:4,5-b' ] dicarbazole-5, 8 (14H) -diyl) bis (butane-4, 1-diyl)) bis (phosphonate )(tetraethyl((2,11-dibromo-14-(4-(diethoxyphosphoryl)butyl)-5H-pyrrolo[3,2-b:4,5-b']dicarbazole-5,8(14H)-diyl)bis(butane-4,1-diyl))bis(phosphonate)),) having the following structural formula:
3) 0.176g of Ni (Cod) 2, 0.1g of bipyridine and 0.082mL of 1, 5-cyclooctadiene were dissolved in 5mL of DMF, heated and stirred at 80℃for half an hour, 0.7g tetraethyl((2,11-dibromo-14-(4-(diethoxyphosphoryl)butyl)-5H-pyrrolo[3,2-b:4,5-b']dicarbazole-5,8(14H)-diyl)bis(butane-4,1-diyl))bis(phosphonate) was dissolved in 15mL of LDMF, slowly added dropwise to the reaction system, and stirring was continued at 80℃for 24 hours. Cooling to room temperature after the reaction is finished, slowly dropwise adding dilute hydrochloric acid under the stirring condition, extracting an organic phase by using dichloromethane, spin-drying, and obtaining a final product which is gray polyphosphate pyrrolocarbazole powder, wherein the structural formula is as follows:
4) 0.12g of polyphosphate pyrrolocarbazole is dissolved in 20mL of dichloromethane, 2.25mL of 0.1g/mL of trimethylbromosilane is added dropwise, the mixture is stirred at room temperature for 24h, and after the reaction is finished, excessive methanol is added dropwise to the reaction system for reaction to remove excessive trimethylbromosilane. The solution was concentrated by distillation under reduced pressure, precipitated in diethyl ether and washed by filtration with diethyl ether, the final product being a powder of polypyrrolocarbazole, which, by characterization, was determined to have the following structural formula:
example 7
The preparation method of the polypyrrolocarbazole-triphenylamine polyphosphate comprises the following steps:
1) 0.25g of Ni (Cod) 2, 0.14g of bipyridine and 0.117mL of 1, 5-cyclooctadiene were dissolved in 5mL of DMF, heated and stirred at 80℃for half an hour, 0.5g tetraethyl((2,11-dibromo-14-(4-(diethoxyphosphoryl)butyl)-5H-pyrrolo[3,2-b:4,5-b']dicarbazole-5,8(14H)-diyl)bis(butane-4,1-diyl))bis(phosphonate) and 0.2g of N, N-bis (4-bromophenyl) -2,4,6-TRIMETHYLANIL INE were dissolved in 15mL of DMF, slowly added dropwise to the reaction system, and stirring was continued at 80℃for 24 hours. Cooling to room temperature after the reaction is finished, slowly dropwise adding dilute hydrochloric acid under the stirring condition, extracting an organic phase by using dichloromethane, spin-drying, and obtaining a final product which is gray polyphosphate pyrrolocarbazole-triphenylamine powder, wherein the structural formula is as follows:
2) 0.12g of polyphosphate pyrrolocarbazole-triphenylamine is dissolved in 20mL of dichloromethane, 1.73mL of 0.1g/mL trimethyl bromosilane is added dropwise, the mixture is stirred at room temperature for 24h, and after the reaction is finished, excessive methanol is added dropwise to the reaction system for reaction to remove excessive trimethyl bromosilane. The concentrated solution was distilled under reduced pressure, precipitated in diethyl ether and washed by filtration with diethyl ether, the final product being a powder of polypyrrolocarbazole-triphenylamine, which, by characterization, was determined to have the following structural formula:
example 8
The preparation method of the indolocarbazole phosphate and thiophene mixed polymer comprises the following steps:
1) 172mg of Ni (COD) 2, 97.9mg of bipyridine and 81 mu L of COD are dissolved in 2mL of DMF, activated for 30min at 80 ℃, 250mg tetraethyl((2,8-dibromoindolo[3,2-b]carbazole-5,11-diyl)bis(butane-4,1-diyl))bis(phosphonate)( tetraethyl ((2, 8-dibromoindolo [3,2-b ] carbazole-5, 11-diyl) bis (butane-4, 1-diyl)) bis (phosphate)) and 76mg of 2,5-dibromothiophene (2, 5-dibromothiophene)) are dissolved in 4mL of DMF, added to the activated catalyst, reacted for 12h at 80 ℃, cooled to room temperature, added with 1M of hydrochloric acid 2mL, stirred for 10min, extracted with dichloromethane, and an organic phase is taken to obtain 195mg of diethyl indolocarbazole phosphate and thiophene mixed polymer with the following structural formula:
2) 50mg of the mixture is dissolved in 10mL of dichloromethane, 889 mu L of trimethyl bromosilane is added for reaction at normal temperature for 12h, excessive methanol is added, diethyl ether is added for precipitation after stirring for 4h, 36mg of indolocarbazole phosphate and thiophene mixed polymer is obtained after filtration, and the structural formula of the mixture is determined by characterization as follows:
example 9
1) 172Mg of Ni (COD) 2, 97.9mg of bipyridine and 81. Mu.L of COD are dissolved in 2mL of DMF, activated for 30min at 80 ℃, 250mg tetraethyl((2,8-dibromoindolo[3,2-b]carbazole-5,11-diyl)bis(butane-4,1-diyl))bis(phosphonate)( tetraethyl ((2, 8-dibromoindolo [3,2-b ] carbazole-5, 11-diyl) bis (butane-4, 1-diyl)) bis (phosphate)) and 94mg of 5,7-dibromo-2,3dihydrothien o[3,4-b ] [1,4] dioxane (5, 7-dibromo-2, 3-dihydrothiophene [3,4-b ] [1,4] dithiophene) are dissolved in 4mL of DMF, added to the activated catalyst, reacted for 12h at 80 ℃, cooled to room temperature, added with 1M hydrochloric acid for 2mL, stirred for 10min, extracted with dichloromethane to obtain 195mg of a mixed polymer with the following structural formula:
2) 50mg of the polymer blend was dissolved in 10mL of methylene chloride, 823. Mu.L of trimethylbromosilane was added, the mixture was reacted at room temperature for 12 hours, excess methanol was added, the mixture was stirred for 4 hours, diethyl ether was added for precipitation, and 36mg of the polymer blend was obtained by filtration, and the following structural formula was confirmed by characterization:
Example 10
1) 172Mg of Ni (COD) 2, 97.9mg of bipyridine and 81. Mu.L of COD were dissolved in 2mL of DMF, activated at 80℃for 30min, 250mg tetraethyl((2,8-dibromoindolo[3,2-b]carbazole-5,11-diyl)bis(butane-4,1-diyl))bis(phosphonate)( tetraethyl ((2, 8-dibromoindolo [3,2-b ] carbazole-5, 11-diyl) bis (butane-4, 1-diyl)) bis (phosphate)) and 109mg of 6,8-dibromo-3,3-dimethyl-3, 4-dihydro-2H-ieno [3,4-b ] [1,4] dioxazine (6, 8-dibromo-3,3-dimethyl-3, 4-dihydro-2H-thiophene [3,4-b ] [1,4] dithiophene ether) were dissolved in 4mL of DMF, added to the activated catalyst, reacted at 80℃for 12H, cooled to room temperature, added with 1M hydrochloric acid for 2mL, stirred for 10min, extracted with dichloromethane, and the organic phase was extracted to give 205mg of a mixed polymer having the following structure:
2) 50mg of the polymer blend was dissolved in 10mL of methylene chloride, 661. Mu.L of trimethylbromosilane was added, the reaction was carried out at room temperature for 12 hours, excess methanol was added, stirring was carried out for 4 hours, diethyl ether was added for precipitation, and 38mg of the polymer blend was obtained by filtration, and by characterization, the structural formula was determined as follows:
Example 11
1) 0.176G of Ni (Cod) 2, 0.1g of bipyridine, and 0.082mL of 1, 5-cyclooctadiene were dissolved in 5mL of DMF, heated and stirred at 80℃for half an hour, 0.350g of tetraethylene ((3, 8-dibromoind olo [3,2-b ] indole-5, 10-diyl) bis (butane-4, 1-diyl)) bis (phosphonate) and 0.250g of N, N-bis (4-bromophenyl) -2,4, 6-TRIMETHYLANILINE) were dissolved in 15mL of DMF, slowly added dropwise to the reaction system, and stirring was continued at 80℃for 24 hours. Cooling to room temperature after the reaction is finished, slowly dropwise adding dilute hydrochloric acid under the stirring condition, extracting an organic phase by using dichloromethane, and spin-drying to obtain a final product which is gray powder, wherein the structural formula is as follows:
2) The product, 0.12g, was dissolved in 20mL of methylene chloride, 2.25mL of 0.1g/mL of trimethylbromosilane was added dropwise, and the mixture was stirred at room temperature for 24 hours, and after the reaction was completed, excess methanol was added dropwise to the reaction system to remove excess trimethylbromosilane. The solution was concentrated by distillation under reduced pressure, precipitated in diethyl ether and washed by filtration with diethyl ether, the final product being a tan powder, which was characterized by the following formula:
Example 12
1) 0.25G of Ni (Cod) 2, 0.14g of bipyridine, and 0.117mL of 1, 5-cyclooctadiene were dissolved in 5mL of DMF, heated and stirred at 80℃for half an hour, 0.3g of tetraethylene ((3, 8-dibromoindolo [3,2-b ] indole-5, 10-diyl) bis (butane-4, 1-diyl)) bis (phosphonate) and 0.2g of 2,6-dibromobenz o [1,2-b:4,5-b' ] dithiophene were dissolved in 15mL of DMF, slowly added dropwise to the reaction system, and stirring was continued at 80℃for 24 hours. Cooling to room temperature after the reaction is finished, slowly dropwise adding dilute hydrochloric acid under the stirring condition, extracting an organic phase by using dichloromethane, and spin-drying to obtain a final product which is gray powder, wherein the structural formula is as follows:
2) 0.12g of the above product was dissolved in 20mL of methylene chloride, 1.73mL of 0.1g/mL of trimethylbromosilane was added dropwise, and the mixture was stirred at room temperature for 24 hours, and after the reaction was completed, excess methanol was added dropwise to the reaction system to remove excess trimethylbromosilane. The solution was concentrated by distillation under reduced pressure, precipitated in diethyl ether and washed by filtration with diethyl ether, the final product being a tan powder, which was characterized by the following formula:
example 13
1) 0.25G of Ni (Cod) 2, 0.14g of bipyridine, and 0.117mL of 1, 5-cyclooctadiene were dissolved in 5mL of DMF, heated and stirred at 80℃for half an hour, 0.3g of tetraethylene ((3, 8-dibromoindolo [3,2-b ] indole-5, 10-diyl) bis (butane-4, 1-diyl)) bis (phosphonate) and 0.2g of 1,4-dibromobenze ne were dissolved in 15mL of DMF, slowly dropped into the reaction system, and stirring was continued at 80℃for 24 hours. Cooling to room temperature after the reaction is finished, slowly dropwise adding dilute hydrochloric acid under the stirring condition, extracting an organic phase by using dichloromethane, and spin-drying to obtain a final product which is gray powder, wherein the structural formula is as follows:
2) 0.12g of the product was dissolved in 20mL of methylene chloride, 1.73mL of 0.1g/mL of trimethylbromosilane was added dropwise, and the mixture was stirred at room temperature for 24 hours, and after the reaction was completed, excess methanol was added dropwise to the reaction system to remove excess trimethylbromosilane. The solution was concentrated by distillation under reduced pressure, precipitated in diethyl ether and washed by filtration with diethyl ether, the final product being a tan powder, which was characterized by the following formula:
Example 14
1. Perovskite solar energy production
The ITO conductive glass is placed in an ultraviolet ozone cleaner for 15min, then small-molecule polycyclic phosphoric acid (DCPA) or poly-polycyclic phosphoric acid (P-DCPA) is coated on the ITO conductive glass in a scraping way, and annealing treatment is carried out at 100 ℃. Then, a MA 0.7FA0.3PbI3 perovskite polycrystalline film is scraped, and 25nm C 60, 5nm BCP and 100nm copper electrodes are evaporated on the surface of the film after thermal annealing so as to prepare the perovskite solar cell. Wherein P-DCPA was prepared from the polycyclophosphoric acid polymer prepared in example 1; the structure of DCPA is as follows:
2. Perovskite solar cell efficiency test
And placing the prepared perovskite solar cell under a 3A-level solar simulator, wherein the solar intensity of the simulator is 100mW/cm 2, scanning a current-voltage curve of the perovskite solar cell and recording, taking the maximum value of the product of the current and the voltage in the current-voltage curve as the maximum output power of the perovskite solar cell, and obtaining the photoelectric conversion efficiency of the perovskite solar cell by dividing the unit area maximum output power of the perovskite solar cell by the solar energy spectral intensity. The results are shown in FIG. 1 and Table 1.
Table 1 DCPA and P-DCPA device Performance comparison perovskite solar cell device parameters
| Hole transport layer | Voc(V) | Jsc(mA·cm-2) | FF(％) | PCE(％) |
| DCPA | 1.107 | 25.01 | 79.4 | 22.00 |
| P-DCPA | 1.163 | 25.84 | 80.2 | 24.10 |
Fig. 1 is a current-voltage curve of a perovskite solar cell based on DCPA and P-DCPA according to the present invention, and table 1 is a comparison between DCPA and P-DCPA device performance and perovskite solar cell device parameters, and as can be seen from fig. 1 and table 1, small-molecule polycyclic phosphoric acid (DCPA) and poly-polycyclic phosphoric acid polymer (P-DCPA) are coated on ITO conductive glass, the coverage of the small-molecule polycyclic phosphoric acid on ITO is poor, local multilayer stacking is present, and the resistance is large. In contrast, the poly-P-DCPA has good coverage rate and film forming property on ITO, has small resistance, and is favorable for extracting holes. Therefore, the poly-polycyclic phosphoric acid (P-DCPA) material realizes better photovoltaic performance relative to a small molecule (DCPA) material, and the prepared perovskite solar cell has 1-35% of photoelectric conversion efficiency.
Example 15
1. Perovskite solar energy production
The ITO conductive glass is placed in an ultraviolet ozone cleaner for 15min, then small-molecule polycyclic phosphoric acid (D4 CPA) or poly-polycyclic phosphoric acid (P-D4 CPA) is coated on the ITO conductive glass, and annealing treatment is carried out at 100 ℃. Then, a MA 0.7FA0.3PbI3 perovskite polycrystalline film is scraped, and 25nm C 60, 5nm BCP and 100nm copper electrodes are evaporated on the surface of the film after thermal annealing so as to prepare the perovskite solar cell. Wherein, the P-D4CPA uses the poly-polycyclic phosphoric acid macromolecule prepared in the example 2; the structure of D4CPA is as follows:
2. Perovskite solar cell efficiency test
And placing the prepared perovskite solar cell under a 3A-level solar simulator, wherein the solar intensity of the simulator is 100mW/cm 2, scanning a current-voltage curve of the perovskite solar cell and recording, taking the maximum value of the product of the current and the voltage in the current-voltage curve as the maximum output power of the perovskite solar cell, and obtaining the photoelectric conversion efficiency of the perovskite solar cell by dividing the unit area maximum output power of the perovskite solar cell by the solar energy spectral intensity. The results are shown in FIG. 2 and Table 2.
Table 2D 4CPA versus P-D4CPA device performance comparison perovskite solar cell device parameters
| Hole transport layer | Voc(V) | Jsc(mA·cm-2) | FF(％) | PCE(％) |
| D4CPA | 1.152 | 25.06 | 76.6 | 22.11 |
| P-D4CPA | 1.176 | 25.82 | 81.3 | 24.69 |
FIG. 2 is a graph of perovskite solar current-voltage curves for D4CPA and P-D4CPA according to the present invention; table 2 shows that the performance of the D4CPA and P-D4CPA devices is compared with the parameters of perovskite solar cell devices, and as can be seen from FIGS. 2 and 2, the small-molecule polycyclic phosphoric acid (D4 CPA) and the poly-polycyclic phosphoric acid polymer (P-D4 CPA) are coated on the ITO conductive glass by scraping, the coverage of the small-molecule polycyclic phosphoric acid on the ITO is poor, the partial multilayer accumulation exists, and the resistance is large. In contrast, the poly-P-D4 CPA has good coverage rate and film forming property on ITO, has small resistance, and is favorable for extracting holes. Therefore, the poly-polycyclic phosphoric acid (P-D4 CPA) material achieves better photovoltaic performance than the small molecule (D4 CPA) material, and the perovskite solar cell has a photoelectric conversion efficiency of 1% to 35%.
Example 16
The method for preparing perovskite solar cells using the materials obtained in examples 3 to 13 was as follows:
The ITO conductive glass was placed in an ultraviolet ozone cleaner for 15min, and then 1mg/mL of the polymer materials prepared in examples 3 to 13 were knife coated thereon. Then scraping MA 0.7FA0.3PbI3 perovskite polycrystalline film, evaporating 25nmC 60, 5nmBCP and 100nm copper electrode on the surface of the film after thermal annealing, thereby completing the preparation of the perovskite solar cell. The perovskite solar cell was tested for efficiency using the same solar cell test method as in examples 14 and 15 above, and the results of the solar cell performance parameters obtained are shown in table 3.
TABLE 3 preparation of perovskite solar cell device parameters from the materials obtained in examples 3-13
| Voc(V) | Jsc(mA·cm-2) | FF(％) | PCE(％) | |
| Example 3 | 1.12 | 24.5 | 0.83 | 22.8 |
| Example 4 | 1.14 | 25.1 | 0.82 | 23.5 |
| Example 5 | 1.17 | 24.8 | 0.84 | 24.4 |
| Example 6 | 1.16 | 25.2 | 0.83 | 24.3 |
| Example 7 | 1.15 | 25.3 | 0.84 | 24.4 |
| Example 8 | 1.18 | 25.1 | 0.84 | 24.9 |
| Example 9 | 1.17 | 25.5 | 0.83 | 24.8 |
| Example 10 | 1.13 | 25.3 | 0.83 | 23.7 |
| Example 11 | 1.18 | 25.6 | 0.84 | 25.4 |
| Example 12 | 1.15 | 25.7 | 0.82 | 24.2 |
| Example 13 | 1.19 | 25.7 | 0.84 | 25.7 |
Table 3 shows parameters of perovskite solar cell devices prepared from the materials obtained in examples 3 to 13, and it is clear from the table that the control of open-circuit voltage, short-circuit current, filling factor and final efficiency of the perovskite solar cell can be achieved by controlling the structure of poly-polycyclic phosphoric acid. In addition, the material prepared by the copolymerization strategy realizes better photoelectric conversion efficiency than the self-polymerization material.
Claims (10)
1. A polycyclic phosphoric acid characterized by the following structural formula:
Wherein the benzene ring contains or does not contain substituent groups; the substituent is selected from: halogen groups, cyano groups, alkyl groups, aromatic groups, and cyclic groups; the value ranges of m 1、m2 and m 3 are 1-40.
2. The polycyclic phosphoric acid according to claim 1, wherein the halogen group is F, cl, br or I; the alkyl is (C1-C40) straight chain alkyl, (C3-C40) branched alkyl or (C3-C40) cycloalkyl; the aromatic group is one or more of aryl, heteroaryl, aryloxy, heteroaryloxy, arylcarbonyl, heteroarylcarbonyl, arylcarbonyloxy, heteroarylcarbonyloxy, aryloxycarbonyl and heteroaryloxycarbonyl; the merging group is used for merging benzene rings into macrocyclic naphthalene or anthracene.
3. A polyphosphoric acid polymer material obtained by polymerizing a polyphosphoric acid according to claim 1, characterized by a general structural formula as follows:
wherein, the polymerization site of the poly-polycyclic phosphoric acid is at any position on the benzene ring, and the value range of n is 2-10000000; r 1、R2、R3 and R 4 are selected from: h, halogen, cyano, alkyl, aromatic, and cyclic groups.
4. A polycyclic phosphoric acid polymer material according to claim 3, characterized in that the halogen groups are F, cl, br or I; the alkyl is (C1-C40) straight chain alkyl, (C3-C40) branched alkyl or (C3-C40) cycloalkyl; in said alkyl, one or more non-adjacent C atoms are optionally replaced by-O-, -S-, -C (O) -, -C (O-) -O-, -O-C (O) -, -OC (O) -O-, -CR 0＝CR00 -, or-c≡c-, wherein R 0 and R 00 are independently straight chain alkyl, branched chain alkyl or cycloalkyl; wherein one or more H atoms in said alkyl group are optionally replaced by F, cl, br, I or CN; the aromatic group is one or more of aryl, heteroaryl, aryloxy, heteroaryloxy, arylcarbonyl, heteroarylcarbonyl, arylcarbonyloxy, heteroarylcarbonyloxy, aryloxycarbonyl and heteroaryloxycarbonyl, and has 4 to 30 ring atoms; the merging group is used for merging benzene rings into macrocyclic naphthalene or anthracene.
5. The method for preparing the polycyclic phosphoric acid polymer material according to claim 3 or 4, comprising the specific steps of:
1) Grafting phosphate functional groups on the reaction sites of N of the polycyclic phosphoric acid to obtain polycyclic phosphate molecules, and then adding halogenated compounds to carry out halogenated substitution to obtain halogenated polycyclic phosphate;
Or, grafting phosphate functional groups on the reaction sites of N of the halogenated polycyclic molecules to obtain halogenated polycyclic phosphate; wherein, the mass ratio of the polycyclic phosphate to the halogenated compound is 1:0.01 to 1000;
2) Adding or not adding other halogenated compounds into the halogenated polycyclic phosphate prepared in the step 1), adding a solvent and a catalyst to perform polymerization reaction, wherein the reaction time is below 72h, and the reaction temperature is below 300 ℃;
3) After the polymerization reaction in the step 2) is completed, halosilane and alcohols are added for hydrolysis, and the polycyclic phosphoric acid polymer material is obtained.
6. The method for producing a polycyclic phosphoric acid polymer material according to claim 5, wherein the other halogenated compound in step 2) is a halogenated aromatic hydrocarbon or a halogenated thiophene with or without a substituent.
7. The method for preparing a polyphosphoric acid polymer material according to claim 6, wherein the aromatic group of the halogenated aromatic hydrocarbon is one or more of an aryl group, a heteroaryl group, an aryloxy group, a heteroaryloxy group, an arylcarbonyl group, a heteroarylcarbonyl group, an arylcarbonyloxy group, a heteroarylcarbonyloxy group, an aryloxycarbonyl group, and a heteroaryloxycarbonyl group.
8. Use of the polycyclic phosphoric acid polymer material of claim 3 or 4 in the preparation of an optoelectronic device structure.
9. The use of the polycyclic phosphoric acid polymer material according to claim 8 for the preparation of a photovoltaic device structure, wherein the photovoltaic device structure is a solar cell, a field effect transistor, a photodetector, a radiation detector, and a light emitting diode.
10. The use of the polycyclic phosphoric acid polymer material according to claim 9 for the preparation of photovoltaic device structures, characterized in that the solar cell structure is as follows:
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