CN114106295A - Cross-linkable polymer, preparation method and application thereof - Google Patents
Cross-linkable polymer, preparation method and application thereof Download PDFInfo
- Publication number
- CN114106295A CN114106295A CN202011601382.5A CN202011601382A CN114106295A CN 114106295 A CN114106295 A CN 114106295A CN 202011601382 A CN202011601382 A CN 202011601382A CN 114106295 A CN114106295 A CN 114106295A
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- CN
- China
- Prior art keywords
- crosslinkable polymer
- electron transport
- substituted
- cycloalkyl
- ring atoms
- Prior art date
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- 229920000642 polymer Polymers 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 39
- 125000000217 alkyl group Chemical group 0.000 claims description 49
- 125000003118 aryl group Chemical group 0.000 claims description 36
- 125000006413 ring segment Chemical group 0.000 claims description 36
- 150000001875 compounds Chemical class 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 15
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 14
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 5
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 2
- 150000003839 salts Chemical class 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract description 13
- 238000004132 cross linking Methods 0.000 abstract description 11
- 239000002346 layers by function Substances 0.000 abstract description 9
- 239000006227 byproduct Substances 0.000 abstract description 3
- -1 -NRR' Chemical group 0.000 description 70
- 239000010410 layer Substances 0.000 description 70
- 239000000243 solution Substances 0.000 description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 16
- 239000000758 substrate Substances 0.000 description 16
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- 238000002347 injection Methods 0.000 description 13
- 239000007924 injection Substances 0.000 description 13
- 239000011259 mixed solution Substances 0.000 description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 125000000623 heterocyclic group Chemical group 0.000 description 9
- 125000001072 heteroaryl group Chemical group 0.000 description 8
- 230000005525 hole transport Effects 0.000 description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 8
- 150000003457 sulfones Chemical group 0.000 description 8
- UMIVXZPTRXBADB-UHFFFAOYSA-N benzocyclobutene Chemical group C1=CC=C2CCC2=C1 UMIVXZPTRXBADB-UHFFFAOYSA-N 0.000 description 7
- 230000005540 biological transmission Effects 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 7
- 150000003254 radicals Chemical class 0.000 description 7
- 125000001424 substituent group Chemical group 0.000 description 7
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 7
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 7
- IIOSDXGZLBPOHD-UHFFFAOYSA-N tris(2-methoxyphenyl)phosphane Chemical compound COC1=CC=CC=C1P(C=1C(=CC=CC=1)OC)C1=CC=CC=C1OC IIOSDXGZLBPOHD-UHFFFAOYSA-N 0.000 description 7
- 239000011787 zinc oxide Substances 0.000 description 7
- KXFYXFVWCIUKDR-UHFFFAOYSA-N 3-(4-tert-butylphenyl)-4-ethyl-1h-1,2,4-triazole-5-thione Chemical compound N1C(=S)N(CC)C(C=2C=CC(=CC=2)C(C)(C)C)=N1 KXFYXFVWCIUKDR-UHFFFAOYSA-N 0.000 description 6
- 150000001642 boronic acid derivatives Chemical class 0.000 description 6
- 229950004394 ditiocarb Drugs 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 230000001376 precipitating effect Effects 0.000 description 6
- 238000000746 purification Methods 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000009210 therapy by ultrasound Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 125000004429 atom Chemical group 0.000 description 5
- 230000000903 blocking effect Effects 0.000 description 5
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- 238000004528 spin coating Methods 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 238000007738 vacuum evaporation Methods 0.000 description 4
- ZOKIJILZFXPFTO-UHFFFAOYSA-N 4-methyl-n-[4-[1-[4-(4-methyl-n-(4-methylphenyl)anilino)phenyl]cyclohexyl]phenyl]-n-(4-methylphenyl)aniline Chemical compound C1=CC(C)=CC=C1N(C=1C=CC(=CC=1)C1(CCCCC1)C=1C=CC(=CC=1)N(C=1C=CC(C)=CC=1)C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 ZOKIJILZFXPFTO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- DKHNGUNXLDCATP-UHFFFAOYSA-N dipyrazino[2,3-f:2',3'-h]quinoxaline-2,3,6,7,10,11-hexacarbonitrile Chemical compound C12=NC(C#N)=C(C#N)N=C2C2=NC(C#N)=C(C#N)N=C2C2=C1N=C(C#N)C(C#N)=N2 DKHNGUNXLDCATP-UHFFFAOYSA-N 0.000 description 3
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthene Chemical compound C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 238000003848 UV Light-Curing Methods 0.000 description 2
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000001246 bromo group Chemical group Br* 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000002207 thermal evaporation Methods 0.000 description 2
- 229930192474 thiophene Natural products 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 125000006545 (C1-C9) alkyl group Chemical group 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- CSNIZNHTOVFARY-UHFFFAOYSA-N 1,2-benzothiazole Chemical class C1=CC=C2C=NSC2=C1 CSNIZNHTOVFARY-UHFFFAOYSA-N 0.000 description 1
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical class C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 1
- AVRPFRMDMNDIDH-UHFFFAOYSA-N 1h-quinazolin-2-one Chemical class C1=CC=CC2=NC(O)=NC=C21 AVRPFRMDMNDIDH-UHFFFAOYSA-N 0.000 description 1
- 125000003229 2-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000005917 3-methylpentyl group Chemical group 0.000 description 1
- 125000004920 4-methyl-2-pentyl group Chemical group CC(CC(C)*)C 0.000 description 1
- SNFCXVRWFNAHQX-UHFFFAOYSA-N 9,9'-spirobi[fluorene] Chemical compound C12=CC=CC=C2C2=CC=CC=C2C21C1=CC=CC=C1C1=CC=CC=C21 SNFCXVRWFNAHQX-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical class N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- FMMWHPNWAFZXNH-UHFFFAOYSA-N Benz[a]pyrene Chemical compound C1=C2C3=CC=CC=C3C=C(C=C3)C2=C2C3=CC=CC2=C1 FMMWHPNWAFZXNH-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 1
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 241000288906 Primates Species 0.000 description 1
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- XBDYBAVJXHJMNQ-UHFFFAOYSA-N Tetrahydroanthracene Natural products C1=CC=C2C=C(CCCC3)C3=CC2=C1 XBDYBAVJXHJMNQ-UHFFFAOYSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- SLGBZMMZGDRARJ-UHFFFAOYSA-N Triphenylene Natural products C1=CC=C2C3=CC=CC=C3C3=CC=CC=C3C2=C1 SLGBZMMZGDRARJ-UHFFFAOYSA-N 0.000 description 1
- CWRYPZZKDGJXCA-UHFFFAOYSA-N acenaphthene Chemical compound C1=CC(CC2)=C3C2=CC=CC3=C1 CWRYPZZKDGJXCA-UHFFFAOYSA-N 0.000 description 1
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229940111121 antirheumatic drug quinolines Drugs 0.000 description 1
- 125000005161 aryl oxy carbonyl group Chemical group 0.000 description 1
- 229910001632 barium fluoride Inorganic materials 0.000 description 1
- 125000003785 benzimidazolyl group Chemical class N1=C(NC2=C1C=CC=C2)* 0.000 description 1
- 150000008316 benzisoxazoles Chemical class 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 1
- 150000001716 carbazoles Chemical class 0.000 description 1
- 150000001717 carbocyclic compounds Chemical class 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 150000001907 coumarones Chemical class 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000006165 cyclic alkyl group Chemical group 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000001987 diarylethers Chemical class 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- RMBPEFMHABBEKP-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2C3=C[CH]C=CC3=CC2=C1 RMBPEFMHABBEKP-UHFFFAOYSA-N 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 125000005067 haloformyl group Chemical group 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 238000004770 highest occupied molecular orbital Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 150000002475 indoles Chemical class 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- VINBVOMNIBDIPH-UHFFFAOYSA-N isocyanoimino(oxo)methane Chemical compound O=C=N[N+]#[C-] VINBVOMNIBDIPH-UHFFFAOYSA-N 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002537 isoquinolines Chemical class 0.000 description 1
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- 239000003446 ligand Substances 0.000 description 1
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
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- 239000002052 molecular layer Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000006574 non-aromatic ring group Chemical group 0.000 description 1
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 1
- 229940078552 o-xylene Drugs 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical compound C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 150000005053 phenanthridines Chemical class 0.000 description 1
- LFSXCDWNBUNEEM-UHFFFAOYSA-N phthalazine Chemical class C1=NN=CC2=CC=CC=C21 LFSXCDWNBUNEEM-UHFFFAOYSA-N 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 150000003230 pyrimidines Chemical class 0.000 description 1
- MHOZZUICEDXVGD-UHFFFAOYSA-N pyrrolo[2,3-d]imidazole Chemical class C1=NC2=CC=NC2=N1 MHOZZUICEDXVGD-UHFFFAOYSA-N 0.000 description 1
- RQGPLDBZHMVWCH-UHFFFAOYSA-N pyrrolo[3,2-b]pyrrole Chemical class C1=NC2=CC=NC2=C1 RQGPLDBZHMVWCH-UHFFFAOYSA-N 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 150000003246 quinazolines Chemical class 0.000 description 1
- 150000003248 quinolines Chemical class 0.000 description 1
- 150000003252 quinoxalines Chemical class 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- IFLREYGFSNHWGE-UHFFFAOYSA-N tetracene Chemical compound C1=CC=CC2=CC3=CC4=CC=CC=C4C=C3C=C21 IFLREYGFSNHWGE-UHFFFAOYSA-N 0.000 description 1
- 150000003536 tetrazoles Chemical class 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 150000003577 thiophenes Chemical class 0.000 description 1
- 125000005259 triarylamine group Chemical group 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 125000005580 triphenylene group Chemical group 0.000 description 1
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Abstract
The invention discloses a cross-linkable polymer, a preparation method thereof and an electron transport material. The cross-linkable polymer has a structure shown as a general formula (I). The polymer can be dissolved in a solvent before crosslinking, and the polymer formed after crosslinking is not easily dissolved in a conventional solvent, so that the crosslinked functional layer is not easily dissolved or mixed with the next functional layer, and the performance of a device is prevented from being influenced. In addition, the cross-linkable polymer has good thermal stability at room temperature, excellent electron transport performance and higher triplet state energy level, can realize cross-linking at high temperature without generating any by-product, and has great potential in soluble and liquefied OLED devices.
Description
Technical Field
The invention relates to the technical field of organic electroluminescence, in particular to a cross-linkable polymer, a preparation method thereof and an electron transport material.
Background
The solution processing for preparing the OLED device is a low-cost processing method, can be used for preparing large-area OLED display panels, and is currently interesting to many manufacturers. OLED devices are built up from a carrier injection layer, a carrier transport layer, and a light emitting layer. On the one hand, if the conventional solution processing method is used, mixing between functional layers is likely to be caused, so that the performance of the device is reduced, and how to realize solution processing of multiple functional layers without affecting the performance of the device is a problem to be solved urgently. On the other hand, most of the electron transport layer materials on the market are based on vacuum evaporation type materials, and the electron transport layer materials suitable for solution processing type are few. Therefore, there remains a significant challenge to the development of fully solution processed OLED devices.
The design of the solubilized electron transport layer material is divided into two concepts: one type is a micromolecule type electron transport layer material, the structure of the micromolecule type electron transport layer material is re-modified and designed to be capable of being processed in a dissolving mode, however, the micromolecule type electron transport layer material is easily dissolved by a solvent of a next functional layer in the solution processing process, and because the common organic micromolecule material has good solubility in the common organic solvent, the solvent used in the next layer is difficult to ensure not to dissolve the material deposited in the previous layer, and the solvent selection range is narrow. The other type is a polymer type electron transport layer material, and because the design idea is different from that of a small molecule electron transport layer material and the synthesis difficulty is large, the reports based on the type of material are few at present.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention aims to provide a crosslinkable polymer, which can be dissolved in a solvent before crosslinking, and the polymer formed after crosslinking is not easily dissolved by a conventional solvent, so that the crosslinked functional layer and the next functional layer are not easily dissolved or mixed with each other, thereby avoiding affecting the performance of the device. In addition, the cross-linkable polymer has good thermal stability at room temperature, excellent electron transport performance and higher triplet state energy level, can realize cross-linking at high temperature without generating any by-product, and has great potential in soluble and liquefied OLED devices.
The crosslinkable polymer has a structure as shown in formula (1):
R1each independently selected from C1-C25 linear alkyl, C3-C25 branched alkyl or C3-C25 cycloalkyl;
R2each independently selected from C1-C25 linear alkyl, C3-C25 branched alkyl or C3-C25 cycloalkyl;
L1selected from single bond, substituted or unsubstituted aromatic group with 5-20 ring atoms;
L2selected from single bond, substituted or unsubstituted aromatic group with 5-20 ring atoms;
a represents an integer of 1 to 4;
b represents an integer of 1 to 3;
m and n both represent the number of structural units, m: n is 1:99-99: 1.
The invention also provides a preparation method of the crosslinkable polymer.
The preparation method of the crosslinkable polymer comprises the following steps:
polymerizing a compound with a structure shown in formula A, a compound with a structure shown in formula B and a compound with a structure shown in formula C;
wherein:
R1each independently selected from C1-C25 linear alkyl, C3-C25 branched alkyl or C3-C25 cycloalkyl;
R2each independently selected from C1-C25 linear alkyl, C3-C25 branched alkyl or C3-C25 cycloalkyl;
L1selected from single bond, substituted or unsubstituted aromatic group with 5-20 ring atoms;
L2selected from single bond, substituted or unsubstituted aromatic group with 5-20 ring atoms;
a represents an integer of 1 to 4;
b represents an integer of 1 to 3;
X0represents halogen.
The invention further relates to an electron transport material, which comprises the crosslinkable polymer as described above, or comprises the crosslinkable polymer prepared by the preparation method.
The invention further relates to a light-emitting diode comprising an electron transport layer, wherein the material of the electron transport layer comprises the crosslinkable polymer as described above, or comprises the crosslinkable polymer prepared by the preparation method as described above, or comprises the electron transport material as described above.
Has the advantages that:
the cross-linkable polymer disclosed by the invention consists of a main chain structural unit, an electron transmission structural unit and a cross-linkable structural unit. The main chain structural unit is a phenyl structural unit with a side chain and both stability and solubility, the electron transmission structural unit is a sulfone structural unit, and the structural unit has good electron transmission performance and good heat-resistant stability; the crosslinkable structural unit is a derivative based on a benzocyclobutene structure, the structure has good stability at room temperature, but can be subjected to ring-opening crosslinking at high temperature, the crosslinkable polymer can be dissolved in a solvent before crosslinking, and the polymer formed after crosslinking is not easily dissolved by a conventional solvent, so that the polymer has good solvent resistance. In addition, the polymer constructed based on the three structural units has good thermal stability at room temperature, keeps the excellent electron-withdrawing capability of the sulfone structural unit, has good electron transmission performance, has a high triplet state energy level, and can effectively block quenching of excitons. In addition, the compounds have great potential in soluble and liquefiable OLED devices due to the fact that crosslinking can be achieved at high temperature and no by-products are generated.
Drawings
Fig. 1 is a schematic structural diagram of an organic light emitting diode device.
Detailed Description
The invention provides a cross-linkable polymer, a preparation method thereof and an electron transport material. In order to make the objects, technical solutions and effects of the present invention clearer and clearer, the present invention is described in further detail below. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In the present invention, "substituted" means that a hydrogen atom in a substituent is substituted by a substituent.
In the present invention, when the same substituent is present in multiple times, it may be independently selected from different groups. As shown in the general formula, the compound contains a plurality of R1Then R is1Can be independently selected from different groups.
In the present invention, "substituted or unsubstituted" means that the defined group may or may not be substituted. When a defined group is substituted, it is understood to be optionally substituted with art-acceptable groups including, but not limited to: c1-30Alkyl, heterocyclyl containing 3 to 20 ring atoms, aryl containing 5 to 20 ring atoms, heteroaryl containing 5 to 20 ring atoms, silyl, carbonyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, haloformyl, formyl, -NRR', cyano, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxy, trifluoromethyl, nitro or halogen, and the above groups may be further substituted with art-acceptable substituents; it is understood that R and R 'in-NRR' are each independently substituted with art-acceptable groups including, but not limited to, H, C1-6An alkyl group, a cycloalkyl group having 3 to 8 ring atoms, a heterocyclic group having 3 to 8 ring atoms, an aryl group having 5 to 20 ring atoms or a heteroaryl group having 5 to 10 ring atoms; said C is1-6Alkyl, cycloalkyl containing 3 to 8 ring atoms, heterocyclyl containing 3 to 8 ring atoms, aryl containing 5 to 20 ring atoms or heteroaryl containing 5 to 10 ring atoms are optionally further substituted by one or more of the following: c1-6Alkyl, cycloalkyl having 3 to 8 ring atoms, heterocyclyl having 3 to 8 ring atoms, halogen, hydroxy, nitro or amino.
In the present invention, the "number of ring atoms" represents the number of atoms among atoms constituting the ring itself of a structural compound (for example, a monocyclic compound, a condensed ring compound, a crosslinked compound, a carbocyclic compound, and a heterocyclic compound) in which atoms are bonded in a ring shape. When the ring is substituted with a substituent, the atoms contained in the substituent are not included in the ring-forming atoms. The "number of ring atoms" described below is the same unless otherwise specified. For example, the number of ring atoms of the benzene ring is 6, the number of ring atoms of the naphthalene ring is 10, and the number of ring atoms of the thienyl group is 5.
In the present invention, "alkyl" may mean a linear, branched and/or cyclic alkyl group. The carbon number of the alkyl group may be 1 to 50, 1 to 30, 1 to 20, 1 to 10, or 1 to 6. Phrases containing the term, e.g., "C1-9Alkyl "refers to an alkyl group containing 1 to 9 carbon atoms, which may be independently at each occurrence C1Alkyl radical, C2Alkyl radical, C3Alkyl radical, C4Alkyl radical, C5Alkyl radical, C6Alkyl radical, C7Alkyl radical, C8Alkyl or C9An alkyl group. Non-limiting examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, 2-ethylbutyl, 3-dimethylbutyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, 1-methylpentyl, 3-methylpentyl, 2-ethylpentyl, 4-methyl-2-pentyl, n-hexyl, 1-methylhexyl, 2-ethylhexyl, 2-butylhexyl, cyclohexyl, 4-methylcyclohexyl, 4-tert-butylcyclohexyl, n-heptyl, 1-methylheptyl, 2-dimethylheptyl, 2-ethylheptyl, 2-butylheptyl, n-octyl, tert-octyl, 2-ethyloctyl, 2-butyloctyl, 2-hexyloctyl, tert-butyl, 2-isobutyl, 2-ethylbutyl, 3-dimethylbutyl, 2-methylhexyl, 2-ethylhexyl, 2-butylhexyl, cyclohexyl, 4-butylcyclohexyl, 2-butylheptyl, 2-methylheptyl, 2-ethylheptyl, 2-ethyloctyl, 2-tert-butylhexyl, 2-butylhexyl, or a, 3, 7-dimethyloctyl, cyclooctyl, n-nonyl, n-decyl, adamantyl, 2-ethyldecyl, 2-butyldecyl, 2-hexyldecyl, 2-octyldecyl, n-undecyl, n-dodecyl, 2-ethyldodecyl, 2-butyldodecyl, 2-hexyldodecyl, 2-octyldodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, 2-ethylhexadecyl, 2-butylhexadecyl, 2-hexylhexadecyl, 2-octylhexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl, 2-ethyleicosyl, 2-butyleicosyl, 2-hexyleicosyl, 2-octyleicosyl, N-heneicosyl, n-docosyl, n-tricosyl, n-tetracosyl, n-eicosanylPentaalkyl, n-hexacosanyl, n-heptacosanyl, n-octacosanyl, n-nonacosanyl, n-triacontanyl, adamantane and the like.
An aromatic group refers to a hydrocarbon group containing at least one aromatic ring. Heteroaryl refers to an aromatic hydrocarbon group containing at least one heteroatom. The heteroatoms are preferably selected from Si, N, P, O, S and/or Ge, particularly preferably from Si, N, P, O and/or S. By fused ring aromatic group is meant that the rings of the aromatic group may have two or more rings in which two carbon atoms are shared by two adjacent rings, i.e., fused rings. The fused heterocyclic aromatic group means a fused ring aromatic hydrocarbon group containing at least one hetero atom. For the purposes of the present invention, aromatic or heteroaromatic radicals include not only aromatic ring systems but also non-aromatic ring systems. Thus, for example, systems such as pyridine, thiophene, pyrrole, pyrazole, triazole, imidazole, oxazole, oxadiazole, thiazole, tetrazole, pyrazine, pyridazine, pyrimidine, triazine, carbene, and the like, are also considered aromatic or heterocyclic aromatic groups for the purposes of this invention. For the purposes of the present invention, fused-ring aromatic or fused-heterocyclic aromatic ring systems include not only systems of aromatic or heteroaromatic groups, but also systems in which a plurality of aromatic or heterocyclic aromatic groups may also be interrupted by short non-aromatic units (< 10% of non-H atoms, preferably less than 5% of non-H atoms, such as C, N or O atoms). Thus, for example, systems such as 9, 9' -spirobifluorene, 9, 9-diarylfluorene, triarylamines, diaryl ethers, etc., are also considered fused aromatic ring systems for the purposes of this invention.
In a certain preferred embodiment, the aromatic group is selected from: benzene, naphthalene, anthracene, fluoranthene, phenanthrene, triphenylene, perylene, tetracene, pyrene, benzopyrene, acenaphthene, fluorene, and derivatives thereof; the heteroaromatic group is selected from the group consisting of triazines, pyridines, pyrimidines, imidazoles, furans, thiophenes, benzofurans, benzothiophenes, indoles, carbazoles, pyrroloimidazoles, pyrrolopyrroles, thienopyrroles, thienothiophenes, furopyrroles, furofurans, thienofurans, benzisoxazoles, benzisothiazoles, benzimidazoles, quinolines, isoquinolines, phthalazines, quinoxalines, phenanthridines, primates, quinazolines, quinazolinones, and derivatives thereof.
"amino" refers to a derivative of ammonia having the formula-N (X)2Wherein each "X" is independently H, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocyclyl, or the like. Non-limiting types of amine groups include-NH2-N (alkyl)2NH (alkyl), -N (cycloalkyl)2NH (cycloalkyl), -N (heterocyclyl)2NH (heterocyclyl), -N (aryl)2NH (aryl), -N (alkyl) (heterocyclyl), -N (cycloalkyl) (heterocyclyl), -N (aryl) (heteroaryl), -N (alkyl) (heteroaryl), and the like.
In the present invention, "+" attached to a single bond represents a connection or a fusion site;
in the present invention, when the attachment site is not specified in the group, it means that an optional attachment site in the group is used as the attachment site;
in the present invention, when a fused site is not specified in a group, it means that an optionally fused site in the group is a fused site, and preferably two or more sites in the ortho-position in the group are fused sites;
a crosslinkable polymer having a structure according to formula (I):
wherein:
R1each independently selected from C1-C25 linear alkyl, C3-C25 branched alkyl or C3-C25 cycloalkyl;
R2each independently selected from C1-C25 linear alkyl, C3-C25 branched alkyl or C3-C25 cycloalkyl;
L1selected from single bond, substituted or unsubstituted aromatic group with 5-20 ring atoms;
L2selected from single bond, substituted or unsubstituted aromatic group with 5-20 ring atoms;
a represents an integer of 1 to 4;
b represents an integer of 1 to 3;
m and n both represent the number of structural units, m: n is 1:99-99: 1.
It will be appreciated that the ratio of m/n varies, the molecular structure varies and the properties vary. The number of defined building blocks can be calibrated by measuring their molecular weight.
In a preferred embodiment, the crosslinkable polymer has a structure represented by the general formula (II):
preferably, L1Selected from single bonds and substituted or unsubstituted aromatic groups with 5-10 ring atoms. More preferably, L1Selected from single bonds or phenyl.
Preferably, L2Selected from single bonds and substituted or unsubstituted aromatic groups with 5-10 ring atoms. More preferably, L2Selected from single bonds or phenyl.
In a preferred embodiment, the crosslinkable polymer has a structure represented by the general formula (II-1) or the general formula (II-2):
in some preferred embodiments, R1Are respectively and independently selected from C5-C15 linear alkyl, C5-C15 branched alkyl and C5-C15 cycloalkyl.
Further preferably, R2Are respectively and independently selected from C5-C15 linear alkyl, C5-C15 branched alkyl or C5-C15 cycloalkyl.
The structure of the crosslinkable polymer of the present invention includes, but is not limited to:
wherein-C6H13and-C8H17All represent straight chain alkyl groups.
m is 6 and n is 1, and the numbers of the structural units are not 6 and 1, but 6 parts and 1 part. Similarly, m is 11 and n is 2, and the numbers of structural units are not 11 and 2, but 11 parts and 2 parts.
The preparation method of the crosslinkable polymer comprises the following steps:
polymerizing a compound with a structure shown in formula A, a compound with a structure shown in formula B and a compound with a structure shown in formula C;
wherein:
R1each independently selected from C1-C25 linear alkyl, C3-C25 branched alkyl or C3-C25 cycloalkyl;
R2each independently selected from C1-C25 linear alkyl, C3-C25 branched alkyl or C3-C25 cycloalkyl;
L1selected from single bond, substituted or unsubstituted aromatic group with 5-20 ring atoms;
L2selected from single bond, substituted or unsubstituted aromatic group with 5-20 ring atoms;
a represents an integer of 1 to 4;
b represents an integer of 1 to 3;
X0represents halogen.
Preferably, the compound having the structure of formula a has a structure as shown in general formula (a-1):
preferably, the compound having the structure of formula B has a structure represented by the general formula (B-1):
preferably, L1Selected from single bonds and substituted or unsubstituted aromatic groups with 5-10 ring atoms. More preferably, L1Selected from single bonds or phenyl.
Preferably, L2Selected from single bonds and substituted or unsubstituted aromatic groups with 5-10 ring atoms. More preferably, L2Selected from single bonds or phenyl.
In a preferred embodiment, the compound having the structure of formula C has a structure represented by the general formula (C-1) or (C-2):
in some preferred embodiments, R1Are respectively and independently selected from C5-C15 linear alkyl, C5-C15 branched alkyl or C5-C15 cycloalkyl.
In some preferred embodiments, R2Are respectively and independently selected from C5-C15 linear alkyl, C5-C15 branched alkyl or C5-C15 cycloalkyl.
An electron transport material comprises the crosslinkable polymer or the crosslinkable polymer prepared by the preparation method.
In one embodiment, the electron transport layer is prepared by printing or coating. In one embodiment, the light emitting diode of the present invention is selected from solution type light emitting diodes, and all functional layers thereof are prepared by printing or coating.
In the above-mentioned light emitting device, especially an OLED, it comprises a substrate, an anode, at least one light emitting layer, and a cathode.
The substrate may be opaque or transparent. A transparent substrate may be used to fabricate a transparent light emitting device. See, for example, Bulovic et al Nature 1996,380, p29, and Gu et al, appl.Phys.Lett.1996,68, p 2606. The substrate may be rigid or flexible. The substrate may be plastic, metal, semiconductor wafer or glass. Preferably, the substrate has a smooth surface. A substrate free of surface defects is a particularly desirable choice. In a preferred embodiment, the substrate is flexible, and may be selected from polymeric films or plastics having a glass transition temperature Tg of 150 deg.C or greater, preferably greater than 200 deg.C, more preferably greater than 250 deg.C, and most preferably greater than 300 deg.C. Examples of suitable flexible substrates are poly (ethylene terephthalate) (PET) and polyethylene glycol (2, 6-naphthalene) (PEN).
The anode may comprise a conductive metal or metal oxide, or a conductive polymer. The anode can easily inject holes into a Hole Injection Layer (HIL) or a Hole Transport Layer (HTL) or an emission layer. In one embodiment, the absolute value of the difference between the work function of the anode and the HOMO level or valence band level of the emitter in the light emitting layer or the p-type semiconductor material acting as a HIL or HTL or Electron Blocking Layer (EBL) is less than 0.5eV, preferably less than 0.3eV, most preferably less than 0.2 eV. Examples of anode materials include, but are not limited to: al, Cu, Au, Ag, Mg, Fe, Co, Ni, Mn, Pd, Pt, ITO, aluminum-doped zinc oxide (AZO), and the like. Other suitable anode materials are known and can be readily selected for use by one of ordinary skill in the art. The anode material may be deposited using any suitable technique, such as a suitable physical vapor deposition method including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like. In certain embodiments, the anode is pattern structured. Patterned ITO conductive substrates are commercially available and can be used to prepare devices according to the present invention.
The cathode may comprise a conductive metal or metal oxide. The cathode can easily inject electrons into the EIL or ETL or directly into the light emitting layer (EML). In one embodiment, the absolute value of the difference between the work function of the cathode and the LUMO level or conduction band level of the emitter in the light-emitting layer or of the n-type semiconductor material as Electron Injection Layer (EIL) or Electron Transport Layer (ETL) or Hole Blocking Layer (HBL) is less than 0.5eV, preferably less than 0.3eV, most preferably less than 0.2 eV. In principle, all materials which can be used as cathodes in OLEDs are possible as cathode materials for the devices according to the invention. Examples of cathode materials include, but are not limited to: al, Au, Ag, Ca, Ba, Mg, LiF/Al, MgAg alloy, BaF2Al, Cu, Fe, Co, Ni, Mn, Pd, Pt, ITO, etc. The cathode material may be deposited using any suitable technique, such as a suitable physical vapor deposition method, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like.
The OLED may also comprise further functional layers, such as a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), an Electron Blocking Layer (EBL), an Electron Injection Layer (EIL), an Electron Transport Layer (ETL), a Hole Blocking Layer (HBL).
The invention also relates to the use of the light emitting diode according to the invention in various electronic devices, including, but not limited to, display devices, lighting devices, light sources, sensors, etc.
The present invention also relates to electronic devices including, but not limited to, display devices, lighting devices, light sources, sensors, etc., incorporating light emitting diodes according to the present invention.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
In the following examples, the substituents are not specifically defined, but all represent a linear structure, i.e., -C6H13and-C8H17All represent straight chain alkyl groups.
In the following examples, toluene is the solvent; palladium acetate is a catalyst; tris (2-methoxyphenyl) phosphine is a catalyst ligand; tetraethyl ammonium hydroxide is alkali and plays a role in promoting reaction; phenylboronic acid is the molecule that ultimately serves as the polymer end-cap, the concept of which is that unreacted bromine groups in the polymer react with the phenylboronic acid, leaving no bromine in the polymer chain. Because the presence of bromine atoms will quench the luminescence to some extent.
1. Synthesis of Compounds
EXAMPLE 1 Compound P1 and method for its preparation
4.2mmol of borate derivative with side chain phenyl are added into a 100mL two-mouth bottle in sequence
3.6mmol of sulfone derivative
0.6mmol of benzocyclobutene derivative
26.5. mu. mol of tris (2-methoxyphenyl) phosphine, 5. mu. mol of palladium acetate Pd (OAc)2Then, vacuumizing and nitrogen exchanging operation is carried out, repeating for 3 times, then adding 20 wt% tetraethylammonium hydroxide solution by using an injector, then adding 60mL toluene solvent, and refluxing for 6h at 110 ℃ under the nitrogen atmosphere; then 4mmol of phenylboronic acid is added into the mixed solution, and the reaction is continued for 12 hours. After the reaction is finished, adding a sodium diethyldithiocarbamate solution into the mixed solution, and stirring for 2 hours at 85 ℃; then, washing the oil phase for multiple times, and separating and purifying by using a chromatographic column; precipitating in methanol after purification, filtering and drying. P1 polymer was obtained. The molecular weight was measured by GPC, and Mn was 54000 and Mw was 120000.
The synthetic route of this example is as follows:
EXAMPLE 2 Compound P2 and its preparation
4.2mmol of borate derivative with side chain phenyl are added into a 100mL two-mouth bottle in sequence
3.56mmol of sulfone derivative
0.64mmol of benzocyclobutene derivative
26.5. mu. mol of tris (2-methoxyphenyl) phosphine, 5. mu. mol of palladium acetate Pd (OAc)2Then, the operation of evacuating and changing nitrogen gas is carried out, the operation is repeated for 3 times, and then 20 wt% tetraethylammonium hydroxide solution is added by a syringe, and thenAdding 60mL of toluene solvent, and refluxing for 6h at 110 ℃ under the nitrogen atmosphere; then 4mmol of phenylboronic acid is added into the mixed solution, and the reaction is continued for 12 hours. After the reaction is finished, adding a sodium diethyldithiocarbamate solution into the mixed solution, and stirring for 2 hours at 85 ℃; then, washing the oil phase for multiple times, and separating and purifying by using a chromatographic column; precipitating in methanol after purification, filtering and drying. P2 polymer was obtained. The molecular weight was measured by GPC, and Mn was 62000 and Mw was 130000.
The synthetic route of this example is as follows:
EXAMPLE 3 Compound P3 and method for its preparation
4.2mmol of borate derivative with side chain phenyl are added into a 100mL two-mouth bottle in sequence
3.6mmol of sulfone derivative
0.6mmol of benzocyclobutene derivative
26.5. mu. mol of tris (2-methoxyphenyl) phosphine, 5. mu. mol of palladium acetate Pd (OAc)2Then, vacuumizing and nitrogen exchanging operation is carried out, repeating for 3 times, then adding 20 wt% tetraethylammonium hydroxide solution by using an injector, then adding 60mL toluene solvent, and refluxing for 6h at 110 ℃ under the nitrogen atmosphere; then 4mmol of phenylboronic acid is added into the mixed solution, and the reaction is continued for 12 hours. After the reaction is finished, adding a sodium diethyldithiocarbamate solution into the mixed solution, and stirring for 2 hours at 85 ℃; then, washing the oil phase for multiple times, and separating and purifying by using a chromatographic column; precipitating in methanol after purification, filtering and drying. P3 polymer was obtained. The molecular weight was measured by GPC, and Mn was 60000 and Mw was 133000.
The synthetic route of this example is as follows:
EXAMPLE 4 Compound P4 and its preparation
4.2mmol of borate derivative with side chain phenyl are added into a 100mL two-mouth bottle in sequence
3.56mmol of sulfone derivative
0.64mmol of benzocyclobutene derivative
26.5. mu. mol of tris (2-methoxyphenyl) phosphine, 5. mu. mol of palladium acetate Pd (OAc)2Then, vacuumizing and nitrogen exchanging operation is carried out, repeating for 3 times, then adding 20 wt% tetraethylammonium hydroxide solution by using an injector, then adding 60mL toluene solvent, and refluxing for 6h at 110 ℃ under the nitrogen atmosphere; then 4mmol of phenylboronic acid is added into the mixed solution, and the reaction is continued for 12 hours. After the reaction is finished, adding a sodium diethyldithiocarbamate solution into the mixed solution, and stirring for 2 hours at 85 ℃; then, washing the oil phase for multiple times, and separating and purifying by using a chromatographic column; precipitating in methanol after purification, filtering and drying. P4 polymer was obtained. The molecular weight was measured by GPC, and Mn was 65000 and Mw was 136000.
The synthetic route of this example is as follows:
EXAMPLE 5 Compound P5 and method for its preparation
4.2mmol of borate derivative with side chain phenyl are added into a 100mL two-mouth bottle in sequence
3.56mmol of sulfone derivative
0.64mmol of benzocyclobutene derivative
26.5. mu. mol of tris (2-methoxyphenyl) phosphine, 5. mu. mol of palladium acetate Pd (OAc)2Then, vacuumizing and nitrogen exchanging operation is carried out, repeating for 3 times, then adding 20 wt% tetraethylammonium hydroxide solution by using an injector, then adding 60mL toluene solvent, and refluxing for 6h at 110 ℃ under the nitrogen atmosphere; then 4mmol of phenylboronic acid is added into the mixed solution, and the reaction is continued for 12 hours. After the reaction is finished, adding a sodium diethyldithiocarbamate solution into the mixed solution, and stirring for 2 hours at 85 ℃; then, washing the oil phase for multiple times, and separating and purifying by using a chromatographic column; precipitating in methanol after purification, filtering and drying. P5 polymer was obtained. The molecular weight was measured by GPC, and Mn was 58000 and Mw was 174000.
The synthetic route of this example is as follows:
EXAMPLE 6 Compound P6 and method for its preparation
4.2mmol of borate derivative with side chain phenyl are added into a 100mL two-mouth bottle in sequence
3.56mmol of sulfone derivative
0.64mmol of benzocyclobutene derivative
26.5. mu. mol of tris (2-methoxyphenyl) phosphine, 5. mu. mol of palladium acetate Pd (OAc)2Then vacuum-pumping nitrogen-changing operation is carried out, and the operation is repeatedRepeating the steps for 3 times, then adding 20 wt% tetraethylammonium hydroxide solution by using an injector, then adding 60mL toluene solvent, and refluxing for 6h at 110 ℃ under the nitrogen atmosphere; then 4mmol of phenylboronic acid is added into the mixed solution, and the reaction is continued for 12 hours. After the reaction is finished, adding a sodium diethyldithiocarbamate solution into the mixed solution, and stirring for 2 hours at 85 ℃; then, washing the oil phase for multiple times, and separating and purifying by using a chromatographic column; precipitating in methanol after purification, filtering and drying. P6 polymer was obtained. The molecular weight was measured by GPC, and Mn was 68000 and Mw was 153000.
The synthetic route of this example is as follows:
2. organic light-emitting diode component and preparation thereof
The structure of the organic light-emitting diode component is as follows: a first electrode, an electron injection layer formed on the first electrode, an electron transport layer formed on the electron injection layer, a light emitting layer formed on the electron transport layer, a hole transport layer formed on the light emitting layer, a hole injection layer formed on the hole transport layer, a second electrode on the hole injection layer, and the electron transport layer includes the crosslinkable polymer as described above, as shown in fig. 1.
Example (c): ITO/ZnO (35nm)/P1(20nm)/mCP Ir (ppy)2acac,7w％(30nm)/TAPC(30nm)/NPB(10nm)/HAT-CN(10nm)/Al(120nm)。
Wherein ZnO is used as an electron injection layer, a cross-linkable polymer P1 is used as an electron transport layer, mCP is used as a main material, Ir (ppy)2acac is used as a guest material, TAPC is used as a hole transport layer material and an electron blocking layer material, NPB is used as a hole transport layer material, HAT-CN is used as a hole injection layer material, and Ag is used as an anode.
The preparation method comprises the following steps:
firstly, the ITO substrate is cleaned according to the following sequence: 5% KOH solution is subjected to ultrasonic treatment for 15min, pure water is subjected to ultrasonic treatment for 15min, isopropanol is subjected to ultrasonic treatment for 15min, and the mixture is dried in an oven for 1 h; the substrate was then transferred to a UV-ozon apparatus for surface treatment for 15min and immediately transferred to a glove box after treatment. And (3) spin-coating a layer of ZnO nanoparticles on a clean ITO substrate, and then baking for 15min at the temperature of 120 ℃. Dissolving a cross-linkable polymer by using a solvent (such as o-xylene) to be used as an electron transport layer material, spin-coating the electron transport layer material on a ZnO nano layer, baking at 120 ℃ for 10min to remove residual solvent after the electron transport layer material is spin-coated, and then carrying out ring-opening cross-linking on the polymer at 200 ℃ for 30-60 min; spin coating with luminescent layer ink; and evaporating the upper hole transport layer, the hole injection layer and the cathode in a vacuum evaporation mode. And finally, carrying out UV curing packaging, and heating and baking for 20min to prepare the device. Denoted as "T1 device".
Referring to the above method, P2-P6 are respectively used to replace P1 and used as electron transport layer material to prepare organic light emitting diode devices, which are respectively referred to as "T2 device", "T3 device", … … "T6 device".
Contrast device and preparation method thereof
The structure of the comparison device is as follows: ITO/ZnO (35nm)/TPBi (20nm)/mCP Ir (ppy)2acac,7w％(30nm)/TAPC(30nm)/NPB(10nm)/HAT-CN(10nm)/Al(120nm)。
Firstly, the ITO substrate is cleaned according to the following sequence: 5% KOH solution is subjected to ultrasonic treatment for 15min, pure water is subjected to ultrasonic treatment for 15min, isopropanol is subjected to ultrasonic treatment for 15min, and the mixture is dried in an oven for 1 h; the substrate was then transferred to a UV-ozon apparatus for surface treatment for 15min and immediately transferred to a glove box after treatment. And (3) spin-coating a layer of ZnO nanoparticles on a clean ITO substrate, and then baking for 15min at the temperature of 120 ℃. Evaporating an electron transport layer material TPBi in a vacuum evaporation mode, wherein the thickness is 20nm, and the evaporation rate is 0.1 nm/s; after spin coating the ink of the light-emitting layer, the hole transport layer, the hole injection layer and the cathode are evaporated by vacuum evaporation. Finally, packaging through UV curing, and heating and baking for 20min to obtain a device, which is recorded as a contrast device.
The material structure involved is as follows:
and (3) performance testing:
the prepared devices were tested for their luminescence properties by an IV-L test system using an F-star CS2000A instrument, the device properties are shown in table 1:
TABLE 1
It can be seen that, with the crosslinkable polymer of the present invention as an electron transport layer material, an electron transport layer can be produced by a solution process, and when a light-emitting layer is continuously produced by a solution process on the electron transport layer, the crosslinked polymer is insoluble in a solvent of the light-emitting layer. The T1 device performance is comparable to that of the traditional electron transport layer formed by evaporation, and the T2 device performance can even exceed that of the traditional device. Meanwhile, the cross-linkable polymer disclosed by the invention is high in electron transmission capacity, capable of effectively promoting electron transmission, good in thermal stability, suitable for constructing a thermal cross-linkable electron transmission layer material and suitable for obtaining an OLED device with a large area and low cost through solution film forming.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (11)
1. A crosslinkable polymer characterized by: having the structure of formula (I):
wherein:
R1each independently selected from C1-C25 linear alkyl, C3-C25 branched alkyl or C3-C25 cycloalkyl;
R2each independently selected from C1-C25 linear alkyl, C3-C25 branched alkyl or C3-C25 cycloalkyl;
L1selected from single bond, substituted or unsubstituted aromatic group with 5-20 ring atoms;
L2selected from single bond, substituted or unsubstituted aromatic group with 5-20 ring atoms;
a represents an integer of 1 to 4;
b represents an integer of 1 to 3;
m and n both represent the number of structural units, m: n is 1:99-99: 1.
2. The crosslinkable polymer of claim 1, wherein: the crosslinkable polymer has a structure as shown in formula (II):
3. the crosslinkable polymer of claim 2, wherein: l is1Selected from single bonds and substituted or unsubstituted aromatic groups with 5-10 ring atoms.
4. The crosslinkable polymer of claim 3, wherein: l is2Selected from single bond, and substituted or unsubstituted ring atom number of 5-10, or a pharmaceutically acceptable salt thereof.
5. The crosslinkable polymer of claim 4, wherein: the crosslinkable polymer has a structure represented by the general formula (II-1) or the general formula (II-2):
6. the crosslinkable polymer according to any one of claims 1 to 5, characterized in that: r1Are respectively and independently selected from C5-C15 linear alkyl, C5-C15 branched alkyl and C5-C15 cycloalkyl.
7. The crosslinkable polymer according to any one of claims 1 to 5, characterized in that: r2Are respectively and independently selected from C5-C15 linear alkyl, C5-C15 branched alkyl or C5-C15 cycloalkyl.
8. A process for preparing a crosslinkable polymer, characterized by: the method comprises the following steps:
polymerizing a compound with a structure shown in formula A, a compound with a structure shown in formula B and a compound with a structure shown in formula C;
wherein:
R1each independently selected from C1-C25 linear alkyl, C3-C25 branched alkyl or C3-C25 cycloalkyl;
R2each independently selected from the group consisting of C1-C25 linear alkyl, C3-C25 branched alkyl, and C3-C25A cycloalkyl group;
L1selected from single bond, substituted or unsubstituted aromatic group with 5-20 ring atoms;
L2selected from single bond, substituted or unsubstituted aromatic group with 5-20 ring atoms;
a represents an integer of 1 to 4;
b represents an integer of 1 to 3;
X0represents halogen.
9. The process for preparing a crosslinkable polymer according to claim 8, wherein: the compound with the structure of the formula C has the structure shown as a general formula (C-1) or (C-2):
10. an electron transport material, comprising: comprising a crosslinkable polymer according to any one of claims 1 to 7 or a crosslinkable polymer prepared by a process according to claim 8 or 9.
11. A light-emitting diode comprising an electron transport layer, wherein the material of the electron transport layer comprises the crosslinkable polymer according to any one of claims 1 to 7, or comprises the crosslinkable polymer prepared by the preparation method according to claim 8 or 9, or comprises the electron transport material according to claim 10.
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