CN104662687A - 用作有机电子器件的n型掺杂剂的氧化磷的盐 - Google Patents
用作有机电子器件的n型掺杂剂的氧化磷的盐 Download PDFInfo
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- CN104662687A CN104662687A CN201380050032.6A CN201380050032A CN104662687A CN 104662687 A CN104662687 A CN 104662687A CN 201380050032 A CN201380050032 A CN 201380050032A CN 104662687 A CN104662687 A CN 104662687A
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- Prior art keywords
- ester
- phosphate
- organic
- salt
- phosphonate
- Prior art date
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- 239000002019 doping agent Substances 0.000 title claims abstract description 31
- 150000003839 salts Chemical class 0.000 title claims description 33
- 229910001392 phosphorus oxide Inorganic materials 0.000 title 1
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical class O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 title 1
- -1 phosphorus oxo compound Chemical class 0.000 claims abstract description 97
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 12
- 239000011574 phosphorus Substances 0.000 claims abstract description 12
- 239000000758 substrate Substances 0.000 claims abstract description 10
- 239000002585 base Substances 0.000 claims description 66
- 150000001875 compounds Chemical class 0.000 claims description 45
- 238000000034 method Methods 0.000 claims description 24
- 229910019142 PO4 Inorganic materials 0.000 claims description 23
- 239000010452 phosphate Substances 0.000 claims description 23
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 19
- 150000002148 esters Chemical class 0.000 claims description 16
- 125000001072 heteroaryl group Chemical group 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 15
- 238000000859 sublimation Methods 0.000 claims description 13
- 230000008022 sublimation Effects 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 125000003118 aryl group Chemical group 0.000 claims description 11
- 150000001340 alkali metals Chemical class 0.000 claims description 10
- 150000001768 cations Chemical class 0.000 claims description 10
- 238000001704 evaporation Methods 0.000 claims description 10
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- DJFBJKSMACBYBD-UHFFFAOYSA-N phosphane;hydrate Chemical compound O.P DJFBJKSMACBYBD-UHFFFAOYSA-N 0.000 claims description 9
- 229910052783 alkali metal Inorganic materials 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 229910052792 caesium Inorganic materials 0.000 claims description 7
- 230000008020 evaporation Effects 0.000 claims description 7
- 125000004415 heterocyclylalkyl group Chemical group 0.000 claims description 7
- 229940122361 Bisphosphonate Drugs 0.000 claims description 6
- 150000004663 bisphosphonates Chemical class 0.000 claims description 6
- 150000004780 naphthols Chemical class 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- RRTJOAHJZQVSSE-UHFFFAOYSA-N 1,3,2-dioxaphosphepine Chemical compound C=1C=COPOC=1 RRTJOAHJZQVSSE-UHFFFAOYSA-N 0.000 claims description 5
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 5
- 125000002769 thiazolinyl group Chemical group 0.000 claims description 5
- 125000000304 alkynyl group Chemical group 0.000 claims description 4
- 239000004305 biphenyl Substances 0.000 claims description 4
- 150000002168 ethanoic acid esters Chemical class 0.000 claims description 4
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 claims description 4
- 125000000262 haloalkenyl group Chemical group 0.000 claims description 4
- 125000001188 haloalkyl group Chemical group 0.000 claims description 4
- 125000000232 haloalkynyl group Chemical group 0.000 claims description 4
- 125000005216 haloheteroaryl group Chemical group 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 229910052701 rubidium Inorganic materials 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- XCXJLWLQQPJVDR-UHFFFAOYSA-N 3-(azepan-2-yl)quinoline Chemical compound C1CCCCNC1C1=CN=C(C=CC=C2)C2=C1 XCXJLWLQQPJVDR-UHFFFAOYSA-N 0.000 claims description 3
- OINNEUNVOZHBOX-XBQSVVNOSA-N Geranylgeranyl diphosphate Natural products [P@](=O)(OP(=O)(O)O)(OC/C=C(\CC/C=C(\CC/C=C(\CC/C=C(\C)/C)/C)/C)/C)O OINNEUNVOZHBOX-XBQSVVNOSA-N 0.000 claims description 3
- 239000005562 Glyphosate Substances 0.000 claims description 3
- 229940097068 glyphosate Drugs 0.000 claims description 3
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 3
- IMOOIRRVPMIBOL-UHFFFAOYSA-N (6-benzoylnaphthalen-2-yl) dihydrogen phosphate Chemical compound C1=CC2=CC(OP(O)(=O)O)=CC=C2C=C1C(=O)C1=CC=CC=C1 IMOOIRRVPMIBOL-UHFFFAOYSA-N 0.000 claims description 2
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 2
- CDAISMWEOUEBRE-LKPKBOIGSA-N 1D-chiro-inositol Chemical compound O[C@H]1[C@@H](O)[C@H](O)[C@H](O)[C@@H](O)[C@@H]1O CDAISMWEOUEBRE-LKPKBOIGSA-N 0.000 claims description 2
- HHHBEVPEYINXHC-UHFFFAOYSA-N 3-butyl-1-methyl-1,2-dihydroimidazol-1-ium;dibutyl phosphate Chemical compound CCCCN1C[NH+](C)C=C1.CCCCOP([O-])(=O)OCCCC HHHBEVPEYINXHC-UHFFFAOYSA-N 0.000 claims description 2
- 125000006201 3-phenylpropyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- LHJBSGRDQKMZAX-UHFFFAOYSA-N 4-chloroheptan-4-ylphosphonic acid Chemical compound CCCC(Cl)(CCC)P(O)(O)=O LHJBSGRDQKMZAX-UHFFFAOYSA-N 0.000 claims description 2
- XKUIRNKUINBHGH-UHFFFAOYSA-N C1=CC=CC=CC1.O1POC=CC=C1 Chemical compound C1=CC=CC=CC1.O1POC=CC=C1 XKUIRNKUINBHGH-UHFFFAOYSA-N 0.000 claims description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 2
- DWPBDZDXURNBJP-UHFFFAOYSA-N P(=O)(O)(O)O.[N+](=O)([O-])C1=CC=C(C=C1)C(C1=CC=CC=C1)=O Chemical compound P(=O)(O)(O)O.[N+](=O)([O-])C1=CC=C(C=C1)C(C1=CC=CC=C1)=O DWPBDZDXURNBJP-UHFFFAOYSA-N 0.000 claims description 2
- 102000004160 Phosphoric Monoester Hydrolases Human genes 0.000 claims description 2
- 108090000608 Phosphoric Monoester Hydrolases Proteins 0.000 claims description 2
- FFQKYPRQEYGKAF-UHFFFAOYSA-N carbamoyl phosphate Chemical compound NC(=O)OP(O)(O)=O FFQKYPRQEYGKAF-UHFFFAOYSA-N 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- ASMQGLCHMVWBQR-UHFFFAOYSA-M diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-M 0.000 claims description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 239000011630 iodine Substances 0.000 claims description 2
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 claims description 2
- LFGREXWGYUGZLY-UHFFFAOYSA-N phosphoryl Chemical group [P]=O LFGREXWGYUGZLY-UHFFFAOYSA-N 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 150000003297 rubidium Chemical class 0.000 claims description 2
- 238000004528 spin coating Methods 0.000 claims description 2
- 125000004646 sulfenyl group Chemical group S(*)* 0.000 claims description 2
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- YACKEPLHDIMKIO-UHFFFAOYSA-L methylphosphonate(2-) Chemical compound CP([O-])([O-])=O YACKEPLHDIMKIO-UHFFFAOYSA-L 0.000 claims 2
- BEMGCKJKWZLIMQ-UHFFFAOYSA-N P(ONCC1=CC=C(C=C1)Cl)(OC)=O Chemical compound P(ONCC1=CC=C(C=C1)Cl)(OC)=O BEMGCKJKWZLIMQ-UHFFFAOYSA-N 0.000 claims 1
- CHVJITGCYZJHLR-UHFFFAOYSA-N cyclohepta-1,3,5-triene Chemical compound C1C=CC=CC=C1 CHVJITGCYZJHLR-UHFFFAOYSA-N 0.000 claims 1
- 239000010410 layer Substances 0.000 description 59
- 150000001450 anions Chemical class 0.000 description 17
- 125000002091 cationic group Chemical group 0.000 description 11
- 230000008569 process Effects 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 7
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 125000001424 substituent group Chemical group 0.000 description 7
- JMBIWKJKSNHIIC-UHFFFAOYSA-N 1,3,6,10-tetrazacyclododecane Chemical compound C1CNCCNCNCCNC1 JMBIWKJKSNHIIC-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 6
- 239000002800 charge carrier Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000006872 improvement Effects 0.000 description 5
- 125000000962 organic group Chemical group 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- STTGYIUESPWXOW-UHFFFAOYSA-N 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline Chemical compound C=12C=CC3=C(C=4C=CC=CC=4)C=C(C)N=C3C2=NC(C)=CC=1C1=CC=CC=C1 STTGYIUESPWXOW-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 238000001212 derivatisation Methods 0.000 description 4
- 125000000623 heterocyclic group Chemical group 0.000 description 4
- 125000006588 heterocycloalkylene group Chemical group 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052711 selenium Inorganic materials 0.000 description 4
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical group [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 3
- 229910000024 caesium carbonate Inorganic materials 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 150000003949 imides Chemical class 0.000 description 3
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 238000005240 physical vapour deposition Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 150000003217 pyrazoles Chemical class 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 229930192474 thiophene Natural products 0.000 description 3
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 2
- NZZAEWPIVSDHGF-UHFFFAOYSA-N 2-oxidodioxaphosphinan-2-ium Chemical compound [O-][O+]1OCCCP1 NZZAEWPIVSDHGF-UHFFFAOYSA-N 0.000 description 2
- DHDHJYNTEFLIHY-UHFFFAOYSA-N 4,7-diphenyl-1,10-phenanthroline Chemical compound C1=CC=CC=C1C1=CC=NC2=C1C=CC1=C(C=3C=CC=CC=3)C=CN=C21 DHDHJYNTEFLIHY-UHFFFAOYSA-N 0.000 description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- ASMQGLCHMVWBQR-UHFFFAOYSA-N Diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)(O)OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-N 0.000 description 2
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 2
- KVIYXIWBXOQZDN-UHFFFAOYSA-N [3-(phenylcarbamoyl)naphthalen-2-yl] dihydrogen phosphate Chemical compound OP(O)(=O)OC1=CC2=CC=CC=C2C=C1C(=O)NC1=CC=CC=C1 KVIYXIWBXOQZDN-UHFFFAOYSA-N 0.000 description 2
- DZBUGLKDJFMEHC-UHFFFAOYSA-N acridine Chemical compound C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 239000004411 aluminium Substances 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
- ZSIQJIWKELUFRJ-UHFFFAOYSA-N azepane Chemical compound C1CCCNCC1 ZSIQJIWKELUFRJ-UHFFFAOYSA-N 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 230000005669 field effect Effects 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 2
- 229910052747 lanthanoid Inorganic materials 0.000 description 2
- 150000002602 lanthanoids Chemical class 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- YACKEPLHDIMKIO-UHFFFAOYSA-N methylphosphonic acid Chemical compound CP(O)(O)=O YACKEPLHDIMKIO-UHFFFAOYSA-N 0.000 description 2
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- YCOZIPAWZNQLMR-UHFFFAOYSA-N pentadecane Chemical compound CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 description 2
- 150000003009 phosphonic acids Chemical class 0.000 description 2
- CLYVDMAATCIVBF-UHFFFAOYSA-N pigment red 224 Chemical compound C=12C3=CC=C(C(OC4=O)=O)C2=C4C=CC=1C1=CC=C2C(=O)OC(=O)C4=CC=C3C1=C42 CLYVDMAATCIVBF-UHFFFAOYSA-N 0.000 description 2
- 125000005936 piperidyl group Chemical group 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical compound N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 description 2
- 150000003967 siloles Chemical group 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 2
- RAOIDOHSFRTOEL-UHFFFAOYSA-N tetrahydrothiophene Chemical compound C1CCSC1 RAOIDOHSFRTOEL-UHFFFAOYSA-N 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- VOROEQBFPPIACJ-SCSAIBSYSA-N (2r)-2-amino-5-phosphonopentanoic acid Chemical compound OC(=O)[C@H](N)CCCP(O)(O)=O VOROEQBFPPIACJ-SCSAIBSYSA-N 0.000 description 1
- 125000006552 (C3-C8) cycloalkyl group Chemical group 0.000 description 1
- AGQAQYPGJDBIQR-UHFFFAOYSA-N (S)-TRIP Chemical compound CC(C)C1=CC(C(C)C)=CC(C(C)C)=C1C1=CC2=CC=CC=C2C2=C1OP(O)(=O)OC1=C(C=3C(=CC(=CC=3C(C)C)C(C)C)C(C)C)C=C(C=CC=C3)C3=C21 AGQAQYPGJDBIQR-UHFFFAOYSA-N 0.000 description 1
- GDAXJBDYNVDMDF-UHFFFAOYSA-N 1,2,4-benzotriazine Chemical compound N1=NC=NC2=CC=CC=C21 GDAXJBDYNVDMDF-UHFFFAOYSA-N 0.000 description 1
- OSZBUZFYUHNYDC-UHFFFAOYSA-N 1,2,4-triazine Chemical compound C1=CN=NC=N1.C1=CN=NC=N1 OSZBUZFYUHNYDC-UHFFFAOYSA-N 0.000 description 1
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 description 1
- 125000004958 1,4-naphthylene group Chemical group 0.000 description 1
- YKMUHKQSUBZERU-UHFFFAOYSA-N 1-[chloromethyl(propoxy)phosphoryl]oxypropane Chemical compound CCCOP(=O)(CCl)OCCC YKMUHKQSUBZERU-UHFFFAOYSA-N 0.000 description 1
- IWEOGHGFCXMKFM-UHFFFAOYSA-N 1-[ethoxy(methoxymethyl)phosphoryl]oxyethane Chemical compound CCOP(=O)(COC)OCC IWEOGHGFCXMKFM-UHFFFAOYSA-N 0.000 description 1
- WMZCREDANYEXRT-UHFFFAOYSA-N 1-[phenyl(pyren-1-yl)phosphoryl]pyrene Chemical compound C=1C=C(C2=C34)C=CC3=CC=CC4=CC=C2C=1P(C=1C2=CC=C3C=CC=C4C=CC(C2=C43)=CC=1)(=O)C1=CC=CC=C1 WMZCREDANYEXRT-UHFFFAOYSA-N 0.000 description 1
- DHABJYRHJWDIDN-UHFFFAOYSA-N 1-hydroxybutylphosphonic acid Chemical compound CCCC(O)P(O)(O)=O DHABJYRHJWDIDN-UHFFFAOYSA-N 0.000 description 1
- XNCMQRWVMWLODV-UHFFFAOYSA-N 1-phenylbenzimidazole Chemical class C1=NC2=CC=CC=C2N1C1=CC=CC=C1 XNCMQRWVMWLODV-UHFFFAOYSA-N 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 1
- DDOQBQRIEWHWBT-UHFFFAOYSA-N 2-azaniumyl-4-phosphonobutanoate Chemical compound OC(=O)C(N)CCP(O)(O)=O DDOQBQRIEWHWBT-UHFFFAOYSA-N 0.000 description 1
- UXGVMFHEKMGWMA-UHFFFAOYSA-N 2-benzofuran Chemical compound C1=CC=CC2=COC=C21 UXGVMFHEKMGWMA-UHFFFAOYSA-N 0.000 description 1
- LYTMVABTDYMBQK-UHFFFAOYSA-N 2-benzothiophene Chemical compound C1=CC=CC2=CSC=C21 LYTMVABTDYMBQK-UHFFFAOYSA-N 0.000 description 1
- OINNEUNVOZHBOX-QIRCYJPOSA-K 2-trans,6-trans,10-trans-geranylgeranyl diphosphate(3-) Chemical compound CC(C)=CCC\C(C)=C\CC\C(C)=C\CC\C(C)=C\COP([O-])(=O)OP([O-])([O-])=O OINNEUNVOZHBOX-QIRCYJPOSA-K 0.000 description 1
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- FPQQVYWYBKEPPE-UHFFFAOYSA-N N1=CN=CC2=C1N=CC=C2.N2=CN=CC1=CC=CN=C21 Chemical compound N1=CN=CC2=C1N=CC=C2.N2=CN=CC1=CC=CN=C21 FPQQVYWYBKEPPE-UHFFFAOYSA-N 0.000 description 1
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- OEURRDRFVZBFAC-UHFFFAOYSA-N O1POC(=CC=C1)O Chemical compound O1POC(=CC=C1)O OEURRDRFVZBFAC-UHFFFAOYSA-N 0.000 description 1
- XLWACYJIFXXOOK-UHFFFAOYSA-N OP(=O)(OC(C)C)CCCCCC(=O)OC Chemical compound OP(=O)(OC(C)C)CCCCCC(=O)OC XLWACYJIFXXOOK-UHFFFAOYSA-N 0.000 description 1
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- IOMLBTHPCVDRHM-UHFFFAOYSA-N [3-[(2,4-dimethylphenyl)carbamoyl]naphthalen-2-yl] dihydrogen phosphate Chemical compound CC1=CC(C)=CC=C1NC(=O)C1=CC2=CC=CC=C2C=C1OP(O)(O)=O IOMLBTHPCVDRHM-UHFFFAOYSA-N 0.000 description 1
- HNAHQHKURIZAPU-UHFFFAOYSA-N [4-(2-methylbutan-2-yl)phenyl] dihydrogen phosphate Chemical compound CCC(C)(C)C1=CC=C(OP(O)(O)=O)C=C1 HNAHQHKURIZAPU-UHFFFAOYSA-N 0.000 description 1
- MGONUNJWACERJR-UHFFFAOYSA-L [Cs+].[Cs+].[O-]P([O-])(=O)OC1=CC=CC=C1 Chemical compound [Cs+].[Cs+].[O-]P([O-])(=O)OC1=CC=CC=C1 MGONUNJWACERJR-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 1
- GPTRBFOMEQPFNJ-UHFFFAOYSA-N ac1n4cwb Chemical compound O1CCOP(O)(=O)OCCOC2=CC=CC=C2OCCOP(O)(=O)OCCOC2=CC=CC=C21 GPTRBFOMEQPFNJ-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000001118 alkylidene group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- RFRXIWQYSOIBDI-UHFFFAOYSA-N benzarone Chemical compound CCC=1OC2=CC=CC=C2C=1C(=O)C1=CC=C(O)C=C1 RFRXIWQYSOIBDI-UHFFFAOYSA-N 0.000 description 1
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 1
- MHSVUSZEHNVFKW-UHFFFAOYSA-N bis-4-nitrophenyl phosphate Chemical compound C=1C=C([N+]([O-])=O)C=CC=1OP(=O)(O)OC1=CC=C([N+]([O-])=O)C=C1 MHSVUSZEHNVFKW-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002872 contrast media Substances 0.000 description 1
- KXNNUYCXODNFBD-UHFFFAOYSA-N cyclohexylazanium;(4-nitrophenyl) phosphate Chemical compound NC1CCCCC1.NC1CCCCC1.OP(O)(=O)OC1=CC=C([N+]([O-])=O)C=C1 KXNNUYCXODNFBD-UHFFFAOYSA-N 0.000 description 1
- DZQISOJKASMITI-UHFFFAOYSA-N decyl-dioxido-oxo-$l^{5}-phosphane;hydron Chemical compound CCCCCCCCCCP(O)(O)=O DZQISOJKASMITI-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- TUHZSMCNIUXAIJ-UHFFFAOYSA-L dilithium;carbamoyl phosphate Chemical compound [Li+].[Li+].NC(=O)OP([O-])([O-])=O TUHZSMCNIUXAIJ-UHFFFAOYSA-L 0.000 description 1
- GOMCKELMLXHYHH-UHFFFAOYSA-L dipotassium;phthalate Chemical compound [K+].[K+].[O-]C(=O)C1=CC=CC=C1C([O-])=O GOMCKELMLXHYHH-UHFFFAOYSA-L 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000011532 electronic conductor Substances 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000005549 heteroarylene group Chemical group 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 150000002475 indoles Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000000904 isoindolyl group Chemical group C=1(NC=C2C=CC=CC12)* 0.000 description 1
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 1
- 125000005956 isoquinolyl group Chemical group 0.000 description 1
- ZLTPDFXIESTBQG-UHFFFAOYSA-N isothiazole Chemical compound C=1C=NSC=1 ZLTPDFXIESTBQG-UHFFFAOYSA-N 0.000 description 1
- CTAPFRYPJLPFDF-UHFFFAOYSA-N isoxazole Chemical compound C=1C=NOC=1 CTAPFRYPJLPFDF-UHFFFAOYSA-N 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- FQHFBFXXYOQXMN-UHFFFAOYSA-M lithium;quinolin-8-olate Chemical compound [Li+].C1=CN=C2C([O-])=CC=CC2=C1 FQHFBFXXYOQXMN-UHFFFAOYSA-M 0.000 description 1
- BDQOCXQVIFQJRK-UHFFFAOYSA-N macmillan tipsy catalyst Chemical compound O1P(O)(=O)OC(C(=CC2=CC=CC=C22)[Si](C=3C=CC=CC=3)(C=3C=CC=CC=3)C=3C=CC=CC=3)=C2C(C2=CC=CC=C2C=2)=C1C=2[Si](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 BDQOCXQVIFQJRK-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- LENFGSWREFCVDP-UHFFFAOYSA-N methyl-[4-(trifluoromethyl)phenoxy]phosphinic acid Chemical compound CP(=O)(O)OC1=CC=C(C=C1)C(F)(F)F LENFGSWREFCVDP-UHFFFAOYSA-N 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
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- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000002757 morpholinyl group Chemical group 0.000 description 1
- YTVNOVQHSGMMOV-UHFFFAOYSA-N naphthalenetetracarboxylic dianhydride Chemical compound C1=CC(C(=O)OC2=O)=C3C2=CC=C2C(=O)OC(=O)C1=C32 YTVNOVQHSGMMOV-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 150000003013 phosphoric acid derivatives 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
- DFOLZSTWYAQVDC-UHFFFAOYSA-N phthalic acid;potassium Chemical compound [K].[K].OC(=O)C1=CC=CC=C1C(O)=O DFOLZSTWYAQVDC-UHFFFAOYSA-N 0.000 description 1
- 125000004193 piperazinyl group Chemical group 0.000 description 1
- 150000003053 piperidines Chemical class 0.000 description 1
- 125000003386 piperidinyl group Chemical group 0.000 description 1
- QVLTXCYWHPZMCA-UHFFFAOYSA-N po4-po4 Chemical compound OP(O)(O)=O.OP(O)(O)=O QVLTXCYWHPZMCA-UHFFFAOYSA-N 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- CPNGPNLZQNNVQM-UHFFFAOYSA-N pteridine Chemical compound N1=CN=CC2=NC=CN=C21 CPNGPNLZQNNVQM-UHFFFAOYSA-N 0.000 description 1
- 125000004309 pyranyl group Chemical class O1C(C=CC=C1)* 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 125000002098 pyridazinyl group Chemical group 0.000 description 1
- LOEIREHXGIGRTN-UHFFFAOYSA-N pyrido[3,2-d]pyrimidine Chemical compound N1=CN=CC2=C1C=CC=N2.N2=CN=CC1=C2C=CC=N1 LOEIREHXGIGRTN-UHFFFAOYSA-N 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 150000003235 pyrrolidines Chemical class 0.000 description 1
- 125000000719 pyrrolidinyl group Chemical group 0.000 description 1
- 125000001422 pyrrolinyl group Chemical group 0.000 description 1
- JWVCLYRUEFBMGU-UHFFFAOYSA-N quinazoline Chemical compound N1=CN=CC2=CC=CC=C21 JWVCLYRUEFBMGU-UHFFFAOYSA-N 0.000 description 1
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 1
- 125000005493 quinolyl group Chemical group 0.000 description 1
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000005958 tetrahydrothienyl group Chemical group 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
- RFDGVZHLJCKEPT-UHFFFAOYSA-N tris(2,4,6-trimethyl-3-pyridin-3-ylphenyl)borane Chemical compound CC1=C(B(C=2C(=C(C=3C=NC=CC=3)C(C)=CC=2C)C)C=2C(=C(C=3C=NC=CC=3)C(C)=CC=2C)C)C(C)=CC(C)=C1C1=CC=CN=C1 RFDGVZHLJCKEPT-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及一种有机电子元件,其包括基底、第一电极、第二电极以及设置在第一和第二电极之间的至少一个电子传导层,其特征在于,所述电子传导层包含磷氧化合物的盐类型衍生物作为n型掺杂剂。
Description
技术领域
本发明涉及一种有机电子元件,其包括基底、第一电极、第二电极以及设置在第一和第二电极之间的至少一个电子传导层,其特征在于,所述电子传导层包括磷氧化合物(phosphorus oxo compound)的盐类型衍生物作为n型掺杂剂(n-dopant)。所述层序列(layer sequence)可被嵌入复杂的部件,例如OLED中。
背景技术
一般通过掺杂外来物质来提高有机层的导电性这样的事实是充分公知的。如果被用作掺杂剂的化合物相对于有机基体表现出合适的HOMO/LUMO(最高占据的分子轨道/最低未占分子轨道),那么就可将电子从掺杂剂转移到基体中,从而导致相应的电荷载流子密度的增加并且有机的导电层的导电性一般也因此而增高。这种机制一般形成设置的一个基本原则并被用来优化有机电子元件。
按照其功能,上述有机元件(organic components)可被划分成具有以下能力的组:
-将光转换成电流,例如具有如图1所示的示意性结构的有机太阳能电池,
-由电流产生光,例如具有如图2所示的示意性结构的有机发光二极管,以及
-控制电流,例如具有如图3所示的示意性结构的有机场效应晶体管。
所有元件类别的共同因素是,元件的质量基本由所使用的有机层的电荷载流子密度和迁移率决定。
基本上有两种不同的方法被使用在有机电子器件中以增加导电性。第一,可通过在阴极和电子传导层之间插入中间层来提高电荷载流子迁移率(charge carrier mobility)。第二,使用具有不同强度的供体的导电性有机基体材料的n型掺杂是第二个选项。
对于前一种方法通常使用由LiF、CsF或(在近期的文献中)碳酸铯组成的薄的盐层,其降低了电子的逸出功(work function)。例如,Huang,Jinsong等人在Adv.Funct.Mater.2007,00,1-8中、Wu,Chih-I等人在APPLIEDPHYSICS LETTERS 88,152104(2006)中以及Xiong,Tao等人在APPLIEDPHYSICS LETTERS 92,263305(2008)中描述了碳酸铯的特性和效果。这些中间层显著改善了电子传输,但是这些改进对于高效的元件来说是不充分的。
相对地,对于电子传导层的掺杂来说,通常情况是,使用具有HOMO(最高占据的分子轨道)高于基体材料的LUMO(最低未占分子轨道)的物质。其为将电子从掺杂剂传送至基体材料的先决条件,因此是其传导性提高的先决条件。此外,进一步优选引入其价电子具有非常低的逸出功或电离能的物质。这也可以促进掺杂剂的电子的释放并且增加层的导电性。
文献列举了含碱金属和碱土金属或镧系元素作为阳离子的成功的掺杂剂。例如,Meng-Huan Ho等人描述了邻苯二甲酸二钾盐(dipotassium phthalate)的使用(Applied Physics Letters 93,083505,2008)。其它的由例如Schmid等人(Organic Electronic Conference;Sept.24-26,2007,Frankfurt,Germany)和Meng-Huan Hoa等人(Applied Physics Letters 91,233507;2007)推行的方法,关注使用碳酸铯来在OLED中掺杂电子导体。后者发现,通过铯盐的掺杂来实现的基体层的导电性的改进本质上是所发射的盐的阴离子的作用。此外,已表明阴离子对这样的化合物的可蒸发性(evaporability)施加了相对较小的影响。该蒸发的温度显然是化合物加工性能(processibility)的重要参数,并且由于能量因素,高的蒸发温度在过程中是不利的。
在使用磷酸铯作为掺杂剂的情况下高的蒸发温度也是不利的,例如在WO 2011 039323 A2中就对其进行了描述。尽管通过掺杂这种盐可以获得非常好的有机层的n-电导性,但是由于掺杂剂的盐类型的性质需要要使用高的升华温度,这使得掺杂步骤在工艺技术方面非常困难。
因此,本发明的目的是提供一种有机电子元件,其相比于现有技术具有改进的特性,并且可以以简单且廉价的方式来制造。此外,其生产路径也被披露。
本发明的目的是通过独立权利要求1的特征来实现的。本发明优选的实施方式在从属权利要求反映。
发明内容
因此,本发明提供一种有机电子元件,其包括基底、第一电极、第二电极以及设置在第一和第二电极之间的至少一个电子传导层,其特征在于,所述电子传导层包括通式1所示的磷氧化合物(phosphorus oxo compound)的盐类型衍生物作为n型掺杂剂,
其中,X、Y大于0且小于或等于3;n、m为整数并且大于或等于1且小于或等于3;M=金属,以及R1=O、S、Se、O-R、S-R、Se-R,R2=R、O-R、S-R、Se-R,并且R选自:取代和未取代的烷基、长链烷基、环烷基、卤代烷基、芳基、亚芳基、卤代芳基、杂芳基、亚杂芳基、亚杂环烷基(heterocycloalkylene)、杂环烷基、卤代杂芳基、烯基、卤代烯基、炔基、卤代炔基、酮芳基(ketoaryl)、卤代酮芳基、酮杂芳基、酮烷基、卤代酮烷基、酮烯基、卤代酮烯基。令人惊奇的是,已发现包括下述电子传导层作为组件的有机电子元件具有改善的电子性能并且可以以更简单且更便宜的方式蒸发(evaporated),所述电子传导层包含式1的磷氧化合物的盐类型衍生物作为n型掺杂剂。特别地,磷氧化合物的盐类型衍生物用作n型掺杂剂使得电子传导层的导电性显著增加。此外,相比于现有技术中已知的掺杂剂,本发明的磷氧化物的盐类型衍生物(salt-type phosphorus oxo derivatives)的使用实现了这些化合物的升华温度的降低,这对制备的总的能量需求以及所获得的层的均匀性产生了积极影响。
不受理论的约束,盐类型的磷氧化合物的衍生化导致了掺杂剂的升华温度的降低。所述衍生化增加了磷氧化合物的分子量,并因此原则上有助于蒸发温度的提高。然而,由于盐类化合物的蒸发,阴离子和阳离子之间的离子相互作用很可能被有机取代基的空间阻位效应削弱,以至于阴离子和阳离子之间的离子相互作用相比于未衍生化的化合物有整体上的减少。因此,阴离子和阳离子的分离能被降低。其结果是,衍生化的化合物可更易于蒸发,尽管其分子量较高。
本发明的掺杂剂的衍生化可以正式的术语通过磷酸盐中一个或两个氧原子的取代来描述。所得的磷氧化合物形成了盐类化合物的阴离子并可携带一价或二价负电荷n。
阴离子和阳离子的化学计量系数X,Y不必是整数,并且可以大于0且小于或等于3。阴离子或阳离子的非整数化学计量系数意味着一个阴离子或一个阳离子被配合至多个其它抗衡离子。一般的情况是,化学计量系数和阴离子电荷的乘积等于该化学计量系数和阳离子电荷的乘积。阴离子和阳离子的电荷系数n和m仅可假设为正的整数值。之后,认为阴离子的电荷是电荷系数n的负值,并且阳离子的电荷是电荷系数m的正值。
所述阴离子包含两个取代基R1和R2,其中R1选自O、S、Se、O-R、S-R、Se-R。相对地,所述取代基R选自:取代和未取代的烷基、长链烷基、环烷基、卤代烷基、芳基、亚芳基、卤代芳基、杂芳基、亚杂芳基、亚杂环烷基(heterocycloalkylene)、杂环烷基、卤代杂芳基、烯基、卤代烯基、炔基、卤代炔基、酮芳基、卤代酮芳基、酮杂芳基、酮烷基、卤代酮烷基、酮烯基、卤代酮烯基。通过这样的定义,R1可以代表键合至磷的唯一的一个氧、硫或硒原子或者代表其它更复杂的有机化合物,其中氧、硫或硒原子额外地携带(bear)上述特定的有机基团中的一种。
相对地,根据本发明取代基R2被定义为R、O-R、S-R、Se-R,其中R选自:取代和未取代的烷基、长链烷基、环烷基、卤代烷基、芳基、亚芳基、卤代芳基、杂芳基、亚杂芳基(heteroarylene)、亚杂环烷基(heterocycloalkylene)、杂环烷基、卤代杂芳基、烯基、卤代烯基、炔基、卤代炔基、酮芳基、卤代酮芳基、酮杂芳基、酮烷基、卤代酮烷基、酮烯基、卤代酮烯基。相应地,R2可以是与磷直接键结的有机基团R,或者通过氧、硫或硒原子与磷键结的有机基团R。
R1和R2均可被独立地选择,并且本发明不包括其中R1=R2=氧的化合物。
在说明书和权利要求中,要求保护并描述了一般的基团,例如烷基、烷氧基、芳基等。除非另有说明,优选使用一般在本发明的上下文中所描述的基团中的下列基团:
烷基:直链和支链的Cl-C8-烷基,
长链烷基:直链和支链的C5-C20烷基,
烯基:C2-C6-烯基,
环烷基:C3-C8-环烷基,
亚烷基:选自:亚甲基、1,1-亚乙基(1,1-ethylene)、1,2-亚乙基(1,2-ethylene)、1,1-亚丙基(1,1-propylidene)、1,2-亚丙基(1,2-propylene)、1,3-亚丙基(1,3-propylene)、2,2-亚丙基(2,2-propylidene)、丁-2-醇-1,4-二基、丙-2-醇-1,3-二基、1,4-亚丁基(1,4-butylene)、环己烷-1,1-二基、环己烷-1,2-二基、环己烷-1,3-二基、环己烷-1,4-二基、环戊烷-1,1-二基、环戊烷-1,2-二基和环戊烷-1,3-二基,
芳基:选自分子量低于300Da的芳族基团。
亚芳基:选自:1,2-亚苯基、1,3-亚苯基、1,4-亚苯基、1,2-亚萘基(1,2-naphthylene)、1,3-亚萘基(1,3-naphthalenylene)、1,4-亚萘基(1,4-naphthylene)、2,3-亚萘基(2,3-naphthylene)、1-羟基-2,3-亚苯基、1-羟基-2,4-亚苯基、1-羟基-2,5-亚苯基和1-羟基-2,6-亚苯基,
杂芳基:选自:吡啶基、嘧啶基、吡嗪基、三唑基、哒嗪基、1,3,5-三嗪基、喹啉基(quinoninyl)、异喹啉基(isoquinoninyl)、喹喔啉基、咪唑基、吡唑基、苯并咪唑基、噻唑基、噁唑烷基、吡咯基、噻吩基、咔唑基、吲哚基和异吲哚基,其中所述杂芳基可通过所选的杂芳基的环中的任意原子与所述化合物键结,
亚杂芳基:选自:吡啶二基(pyridinediyl)、喹啉二基(quinolinediyl)、吡唑二基(pyrazodiyl)、吡唑二基(pyrazolediyl)、三唑二基(triazolediyl)、吡嗪二基(pyrazinediyl)、噻吩二基(thiophenediyl)和咪唑二基(imidazolediyl),其中所述亚杂芳基经由所选的杂芳基的环中的任意所需的原子在化合物中作为桥,特别优选的是:吡啶-2,3-二基;吡啶-2,4-二基;吡啶-2,5-二基;吡啶-2,6-二基;吡啶-3,4-二基;吡啶-3,5-二基;喹啉-2,3-二基;喹啉-2,4-二基;喹啉-2,8-二基;异喹啉-1,3-二基;异喹啉-1,4-二基;吡唑-1,3-二基;吡唑-3,5-二基;三唑-3,5-二基;三唑-1,3-二基;吡嗪-2,5-二基;以及咪唑-2,4-二基、噻吩-2,5-二基、噻吩-3,5-二基;选自以下的C1-C6-杂环烷基:哌啶基(piperidinyl)、哌啶(piperidine)、1,4-哌嗪(1,4-piperazine)、四氢噻吩(tetrahydrothiophene)、四氢呋喃、1,4,7-三氮杂环壬烷(1,4,7-triazacyclononane)、1,4,8,11-四氮杂环十四烷(1,4,8,11-tetraazacyclotetradecane)、1,4,7,10,13-五氮杂环十五烷(1,4,7,10,13-pentaazacyclopentadecane)、1,4-二氮杂-7-硫杂环壬烷(1,4-diaza-7-oxacyclononane)、1,4-二氮杂-7-氧杂环壬烷(1,4-diaza-7-oxacyclononane)、1,4,7,10-四氮杂环十二烷(1,4,7,10-tetraazacyclododecane)、1,4-二噁烷、1,4,7-三硫杂环壬烷(1,4,7-trithiacyclononane)、吡咯烷(pyrrolidine)和四氢吡喃(tetrahydropyran),其中所述杂芳基可通过所选的杂芳基的环中的任意原子与C1-C6-烷基键结,
亚杂环烷基(heterocycloalkylene):选自:哌啶-1,2-亚基(piperidin-1,2-ylene)、哌啶-2,6-亚基(piperidin-2,6-ylene)、哌啶-4,4-亚基(piperidin-4,4-ylidene)、1,4-哌嗪-1,4-亚基(1,4-piperazin-1,4-ylene)、1,4-哌嗪-2,3-亚基(1,4-piperazin-2,3-ylene)、1,4-哌嗪-2,5-亚基(1,4-piperazin-2,5-ylene)、1,4-哌嗪-2,6-亚基(1,4-piperazin-2,6-ylene)、1,4-哌嗪-1,2-亚基(1,4-piperazin-1,2-ylene)、1,4-哌嗪-1,3-亚基(1,4-piperazin-1,3-ylene)、1,4-哌嗪-1,4-亚基(1,4-piperazin-1,4-ylene)、四氢噻吩-2,5-亚基(tetrahydrothiophen-2,5-ylene)、四氢噻吩-3,4-亚基(tetrahydrothiophen-3,4-ylene)、四氢噻吩-2,3-亚基(tetrahydrothiophen-2,3-ylene)、四氢呋喃-2,5-亚基(tetrahydrofuran-2,5-ylene)、四氢呋喃-3,4-亚基(tetrahydrofuran-3,4-ylene)、四氢呋喃-2,3-亚基(tetrahydrofuran-2,3-ylene)、吡咯烷-2,5-亚基(pyrrolidin-2,5-ylene)、吡咯烷-3,4-亚基(pyrrolidin-3,4-ylene)、吡咯烷-2,3-亚基(pyrrolidin-2,3-ylene)、吡咯烷-1,2-亚基(pyrrolidin-1,2-ylene)、吡咯烷-1,3-亚基(pyrrolidin-1,3-ylene)、吡咯烷-2,2-亚基(pyrrolidin-2,2-ylidene)、1,4,7-三氮杂环壬烷-1,4-亚基(1,4,7-triazacyclonon-1,4-ylene)、1,4,7-三氮杂环壬烷-2,3-亚基(1,4,7-triaza-cyclonon-2,3-ylene)、1,4,7-三氮杂环壬烷-2,9-亚基(1,4,7-triazacyclonon-2,9-ylene)、1,4,7-三氮杂环壬烷-3,8--亚基(1,4,7-triazacyclonon-3,8-ylene)、1,4,7-三氮杂环壬烷-2,2-亚基(1,4,7-triazacyclonon-2,2-ylidene)、1,4,8,11-四氮杂环十四烷-1,4-亚基(1,4,8,11-tetraazacyclotetradec-1,4-ylene)、1,4,8,11-四氮杂环十四烷-1,8-亚基(1,4,8,11-tetraaza-cyclotetradec-1,8-ylene)、1,4,8,11-四氮杂环十四烷-2,3-亚基(1,4,8,ll-tetraazacyclotetradec-2,3-ylene)、1,4,8,11-四氮杂环十四烷-2,5-亚基(1,4,8,ll-tetraazacyclotetradec-2,5-ylene)、1,4,8,11-四氮杂环十四烷-1,2-亚基(1,4,8,11-tetraazacyclotetradec-1,2-ylene)、1,4,8,11-四氮杂环十四烷-2,2-亚基(1,4,8,11-tetraazacyclo-tetradec-2,2-ylidene)、1,4,7,10-四氮杂环十二烷-1,4-亚基(1,4,7,10-tetraazacyclododec-1,4-ylene)、1,4,7,10-四氮杂环十二烷-1,7-亚基(1,4,7,10-tetraazacyclododec-1,7-ylene)、1,4,7,10-四氮杂环十二烷-1,2-亚基(1,4,7,10-tetraaza-cyclododec-1,2-ylene)、1,4,7,10-四氮杂环十二烷-2,3-亚基(1,4,7,10-tetraazacyclododec-2,3-ylene)、1,4,7,10-四氮杂环十二烷-2,2-亚基(1,4,7,10-tetraazacyclododec-2,2-ylidene)、1,4,7,10,13-五氮杂环十五烷-1,4-亚基(1,4,7,10,13-pentaaza-cyclopentadec-1,4-ylene)、1,4,7,10,13-五氮杂环十五烷-1,7-亚基(1,4,7,10,13-pentaazacyclopentadec-1,7-ylene)、1,4,7,10,13-五氮杂环十五烷-2,3-亚基(1,4,7,10,13-pentaazacyclopentadec-2,3-ylene)、1,4,7,10,13-五氮杂环十五烷-1,2-亚基(1,4,7,10,13-pentaazacyclopentadec-1,2-ylene)、1,4,7,10,13-五氮杂环十五烷-2,2-亚基(1,4,7,10,13-pentaazacyclopentadec-2,2-ylidene)、1,4-二氮杂-7-硫杂环壬烷-1,4-亚基(1,4-diaza-7-thiacyclonon-1,4-ylene)、1,4-二氮杂-7-硫杂环壬烷-1,2-亚基(1,4-diaza-7-thiacyclonon-1,2-ylene)、1,4-二氮杂-7-硫杂环壬烷-2,3-亚基(1,4-diaza-7-thiacyclonon-2,3-ylene)、1,4-二氮杂-7-硫杂环壬烷-6,8-亚基(1,4-diaza-7-thiacyclonon-6,8-ylene)、1,4-二氮杂-7-硫杂环壬烷-2,2-亚基(1,4-diaza-7-thiacyclonon-2,2-ylidene)、1,4-二氮杂-7-氧杂环壬烷-1,4-亚基(1,4-diaza-7-oxacyclonon-1,4-ylene)、1,4-二氮杂-7-氧杂环壬烷-1,2-亚基(1,4-diaza-7-oxacyclonon-1,2-ylene)、1,4-二氮杂-7-氧杂环壬烷-2,3-亚基(1,4-diaza-7-oxa-cyclonon-2,3-ylene)、1,4-二氮杂-7-氧杂环壬烷-6,8-亚基(1,4-diaza-7-oxacyclonon-6,8-ylene)、1,4-二氮杂-7-氧杂环壬烷-2,2-亚基(1,4-diaza-7-oxacyclonon-2,2-ylidene)、1,4-二噁烷-2,3-亚基(1,4-dioxan-2,3-ylene)、1,4-二噁烷-2,6-亚基(1,4-dioxan-2,6-ylene)、1,4-二噁烷-2,2-亚基(1,4-dioxan-2,2-ylidene)、四氢吡喃-2,3-亚基(tetrahydropyran-2,3-ylene)、四氢吡喃-2,6-亚基(tetrahydropyran-2,6-ylene)、四氢吡喃-2,5-亚基(tetrahydropyran-2,5-ylene)、四氢吡喃-2,2-亚基(tetrahydropyran-2,2-ylidene)、1,4,7-三硫杂环壬烷-2,3-亚基(1,4,7-trithiacyclonon-2,3-ylene)、1,4,7-三硫杂环壬烷-2,9-亚基(1,4,7-trithia-cyclonon-2,9-ylene)、和1,4,7-三硫杂环壬烷-2,2-亚基(1,4,7-trithiacyclonon-2,2-ylidene),
杂环烷基:选自:吡咯啉基、吡咯烷基、吗啉基、哌啶基、哌嗪基、六亚甲基亚胺基(hexamethylene imine)、1,4-哌嗪基、四氢噻吩基、四氢呋喃基、1,4,7-三氮杂环-壬基、1,4,8,11-四氮杂环十四烷基、1,4,7,10,13-五氮杂环十五烷基、1,4-二氮杂-7-硫杂环壬基、1,4-二氮杂-7-氧杂环壬基、1,4,7,10-四氮杂环十二烷基、1,4-二噁烷基、1,4,7-三硫杂环壬基、四氢吡喃基和噁唑烷基,其中所述杂环烷基可通过所选的杂环烷基的环上的任意原子与化合物键结。
取代基R可在其基础结构中任意能够键结的位置处额外具有经取代的或未经取代的杂环。所述取代基可优选地选自经取代的和未经取代的杂环,例如,呋喃、噻吩、吡咯、噁唑、噻唑、咪唑、异噁唑、异噻唑、吡唑、吡啶、吡嗪、嘧啶、1,3,6-三嗪(1,3,6-triazine)、吡喃鎓、α-吡喃酮、γ-吡喃酮、苯并呋喃、苯并噻吩、吲哚、2H-异吲哚、苯并噻唑、2-苯并噻吩、1H-苯并咪唑、1H-苯并三唑、1,3-苯并噁唑、2-苯并呋喃、7H-嘌呤、喹啉、异喹啉、喹唑啉、喹喔啉、酞嗪、1,2,4-苯并三嗪(1,2,4-benzotriazine)、吡啶并[2,3-d]嘧啶(pyrido[2,3-d]pyrimidine)、吡啶并[3,2-d]嘧啶(pyrido[3,2-d]pyrimidine)、蝶啶、吖啶、吩嗪、苯并[g]蝶啶(benzo[g]pteridine)、9H-咔唑、和联吡啶,以及它们的衍生物。以庞大(bulky)的取代基对取代基R的进一步取代可导致盐类化合物的升华温度的进一步降低。此外,额外的取代基会影响HOMO/LUMO的位置。
本发明的电子传导层可包括电子传输材料、电子受体和有机电子供体化合物。
现有技术已知的是,电子传输材料担负电子并进一步输送它们,优选的材料可选自:2,2',2"-(1,3,5-苯三基)三(1-苯基-1H-苯并咪唑)、2-(4-联苯基)-5-(4-叔丁基苯基)-1,3-4-噁二唑、2,9-二甲基-4,7-二苯基-1,10-菲咯啉(BCP)、8-羟基喹啉锂(8-hydroxy-quinolinolatolithium)、4-(萘-1-基)-3,5-二苯基-4H-1-1,2,4-三唑、1,3-双[2-(2,2'-联吡啶-6-基)-1,3,4-噁二唑-5-基]苯、4,7-二苯基-1,10-菲咯啉(BPhen)、3-(4-联苯基)-4-苯基-5-叔丁基苯基-1,2,4-三唑、双(2-甲基-8-喹啉)-4-(苯基苯酚)铝(bis(2-methyl-8-quinolinolate)-4-(phenylphenolato)aluminum)、6,6'-双[5-(联苯-4-基)-1,3,4-噁二唑-2-基]-2,2'-联吡啶、2-苯基-9,10-二(萘吡啶-2-基)蒽、2,7-双[2-(2,2'-联吡啶-6-基)-1,3,4-噁二唑-5-基]-9,9-二甲基芴、1,3-双[2-(4-叔丁基苯基)-1,3,4-噁二唑-5-基]苯、2-(萘-2-基)-4,7-二苯基-1,10-菲咯啉、2,9-二(萘-2-基)-4,7-二苯基-1,10-菲咯啉、三(2,4,6-三甲基-3-(吡啶-3-基)苯基)硼烷(tris(2,4,6-trimethyl-3-(pyridin-3-yl)-phenyl)borane)、1-甲基2-(4-(萘-2-基)苯基)-1H-咪唑并[4,5-f][1,10]菲咯啉(1-methyl-2-(4-(naphthalen-2-yl)phenyl)-1H-imidazo[4,5-f][1,10]phenanthroline)、苯基二芘基氧化膦(phenyl-dipyrenylphosphine oxide)、萘四甲酸二酐(naphthalenetetracarboxylic dianhydride)或其酰亚胺(imides)、苝四甲酸二酐(perylenetetracarboxylic dianhydride)或其酰亚胺、基于噻咯类的材料,其具有硅杂环戊二烯单元(silacyclopentadiene unit)或另外的杂环,如EP 2092041B1所述。
本发明的盐类型衍生物由一个或多个阴离子和阳离子组成,其中所述阴离子可衍生自磷酸(phosphoric acid)或膦酸(phosphonic acid),所述磷酸或膦酸中一个或两个氧基团已被有机基团改性。
金属阳离子M可选自包括碱金属、碱土金属、主族金属、过渡族金属、镧系金属和过渡金属的组。特别优选的是来自于上述组的形成盐类型化合物中的稳定的、带单价正电荷的阳离子的金属。
额外更优选的是,所述金属来自于元素周期表中的第一主族,即碱金属。碱金属的组包括元素Li、Na、K、Rb和Cs。由于它们在基体材料中的溶解性以及盐类型化合物的易蒸发性,碱金属是用于形成n型掺杂剂的特定选择。
在一项特别的实施方式中,特别优选R基团通过氧原子键结至磷。
在一项特别的实施方式中,特别优选取代基R1和R2各自携带有机基团并且各自通过氧原子键结至磷。
在本发明的一项特别的实施方式中,所述有机电子元件可包含选自磷酸酯(phosphoric esters)和/或膦酸酯(phosphonic esters)的磷氧化合物的盐类型衍生物。所述磷氧化合物的酯可对应于通式2:
或通式3:
其中Z=O、S、Se。
磷酸酯(通式2)或膦酸酯(通式3)形式的磷氧化合物的酯是特别优选的,因为,首先阳离子的HOMO/LUMO的分布特别好地匹配于在现有技术所指定的电子传输材料。其次,这些化合物的空间属性可特别有利地促进盐类型化合物的升华温度的降低。因此,可获得升华温度特别低的特别有效的掺杂剂。
在本发明的一项特别的实施方式中,磷氧化合物的盐类型衍生物的阳离子可选自包括铯和/或铷的重碱金属组。这样的选择是特别有利的,因为相比于碱金属中轻量级的代表,重碱金属在基体材料中的溶解性更好。这会导致与本发明的阴离子关连的层内的特别均匀的分布。此外,碱金属的重量级代表可使得化合物因金属阳离子的尺寸而具有特别优异的可蒸发性。
在本发明的一项特别的实施方式中,有机电子元件可为磷氧化合物的盐类型衍生物,其分子量大于或等于70g/mol且小于或等于1000g/mol,并且升华温度大于或等于120℃且小于或等于1200℃。不受理论的束缚,这样的分子量范围使得取代基具有足够的尺寸,以便破坏盐类型化合物的对称性,从而获得较低的升华温度。用这种方法可降低阴离子和阳离子间的库仑相互作用力。相对地,较大的分子量会是不利的,因为盐类型化合物的升华温度会作为质量增加的函数不成比例地增加。在处理的过程中,额外发现,升华温度大于或等于120℃且小于或等于1200℃的化合物可以从气相中以特别均匀的方式被沉积。这意味着可获得特别均匀的层。可以由经验公式很容易地计算出化合物的分子量并且由现有技术中已知的方法来确定升华温度。
在本发明的另一方面,有机电子元件可包含选自环状的磷酸酯(phosphoric esters)和/或膦酸酯(phosphonic esters)的磷氧化合物的盐类型衍生物。环状的磷酸酯或膦酸酯可以是特别有利的,因为相对刚性的环状结构在空间上是庞大的,从而可实现衍生物的升华温度的特别大程度的降低。
在本发明的另一项实施方式中,有机电子元件在电子传导层中可包含层厚浓度大于或等于0.01%且小于或等于50%的磷氧化合物的盐类型衍生物。这里的层厚浓度描述了盐类型衍生物的体积在整个电子传导层中所占的比例。例如,可基于层中阳离子的分布计算所述比例,可例如通过能量色散X射线结构分析法(EDX)或AAS(原子吸收光谱)来确定所述阳离子的分布。在所述掺杂剂形成电荷转移络合物(charge transfer complexes)的情况下,可通过测量UV吸收来确定层厚浓度。
通过添加盐类型掺杂剂可改善电子传导层的特性。掺杂剂能够释放电子至所述层,并由此促进了层的导电性的提高。已发现,令人惊讶的是,掺杂剂高于和低于上述特定范围会导致导电性变差。不受理论的束缚,较低的掺杂剂浓度导致电子注入导电层不足,而较高的掺杂剂浓度会导致该层内电子传输组分的不足。两种情况下,电子传导层的导电性均是不足的。
在本发明的另一方面,磷氧盐(phosphorus oxo salt)的衍生物可以是选自以下的化合物的铯盐或铷盐:
6,7,11,12,19,20,24,25-八氢二苯并[G,R]-[1,3,6,9,12,14,17,20,2,13]-八氧杂二磷杂环二十二烷-9,22-二醇9,22-二氧化物(6,7,11,12,19,20,24,25-octahydrodibenzo[G,R]-[1,3,6,9,12,14,17,20,2,13]-octaoxadiphosphacyclodocosine-9,22-diol 9,22-dioxide)、(4R)-22-羟基-5,5-二甲基-4-苯基-1,3,2-二氧杂磷杂环己烷2-氧化物((4R)-22-hydroxy-5,5-dimethyl-4-phenyl-1,3,2-dioxaphosphorinan 2-oxide)、8,9-二苯基二菲并[4,3-d:3,4-f][1,3,2]二氧杂磷杂环庚三烯-18-醇18-氧化物(8,9-diphenyldiphenanthro[4,3-d:3,4-f][1,3,2]dioxaphosphepin-18-ol 18-oxide)、2,6-双(三苯基甲硅烷基)二萘并[2,1-d:1,2-f][1,3,2]二氧杂磷杂环庚三烯-4-醇4-氧化物(2,6-bis(triphenylsilyl)dinaphtho[2,1-d:1,2-f][1,3,2]dioxaphosphe-pin-4-ol4-oxide)、1-丁基-3-甲基咪唑鎓二丁基磷酸盐(1-butyl-3-methylimidazoliumdibutylphosphates)以及相应的二(C1-C10)烷基衍生物、磷酸二苯酯(diphenylhydrogenphosphate)、双(4-硝基苯基)磷酸酯(bis(4-nitrophenyl)hydrogenphosphate)、2-萘基4-[(E)-苯基二氮烯基]苯基磷酸酯(2-naphthyl4-[(E)-phenyldiazenyl]phenylhydrogenphosphate)、二萘并[2,1-d:1,2-f][1,3,2]二氧杂磷杂环庚三烯-4-醇4-氧化物(dinaphtho[2,1-d:1,2-f][1,3,2]dioxaphosphepin-4-ol 4-oxide)、(R)-3,3'-双[3,5-双(三氟甲基)苯基]-1,1'-联萘-2,2'-二基磷酸酯((R)-3,3'-bis[3,5-bis(trifluoromethyl)phenyl]-1,1'-binaphthyl-2,2'-diylhydrogenphosphate)、(S)-3,3'-双(2,4,6-三异丙基-苯基)-1,1'-联萘-2,2'-二基磷酸酯((S)-3,3'-bis(2,4,6-triisopropyl-phenyl)-1,1'-binaphthyl-2,2'-diylhydrogenphosphate)、18-羟基-8,9-二苯基二菲并[4,3-d:3',4'-f][1,3,2]-二氧杂磷杂环庚三烯18-氧化物(18-hydroxy-8,9-diphenyldiphenanthro[4,3-d:3',4'-f][1,3,2]-dioxa-phosphepin18-oxide)、(llbR)-4-羟基-2,6-双(三苯基甲硅烷基)-二萘并[2,1-d:1',2'f]-1,3,2-二氧杂磷杂环庚三烯4-氧化物((llbR)-4-hydroxy-2,6-bis(triphenylsilyl)-dinaphtho-[2,1-d:1',2'f]-1,3,2-dioxaphosphepin 4-oxide)、(R)-(-)-3,3'-双(三苯基甲硅烷基)-1,1'-联萘-2,2'-二基磷酸酯((R)-(-)-3,3'-bis(triphenylsilyl)-1,1'-binaphthyl-2,2'-diyl hydrogenphosphate)、氨甲酰磷酸锂(lithium carbamoylphosphate)、D-肌醇1-单磷酸酯(D-myo-inositol1-monophosphate)、6-苯甲酰基-2-萘基磷酸酯(6-benzoyl-2-naphthylphosphate)、磷酸4-硝基苯基酯二(环己铵)盐(4-nitrophenyl phosphatebis(cyclohexylammonium)salt)、萘酚AS磷酸酯(Naphthol AS phosphate)、萘酚AS-MX磷酸酯(Naphthol AS-MX phosphate)、4-(叔戊基)苯基磷酸酯(4-(tert-pentyl)phenyl phosphate)、香叶基香叶基焦磷酸酯(geranylgeranylpyrophosphate)、萘酚AS磷酸酯(Naphthol AS phosphate)、甲基膦酸酯(methylphosphonate)、三氯甲基膦酸酯(trichloromethyl phosphonate)、庚烷-1,7-二基二膦酸酯(heptane-1,7-diyl diphosphonate)、(庚硫基)甲基膦酸酯((heptylsulfanyl)methyl phosphonate)、1-羟基丁基膦酸酯(1-hydroxybutylphosphonate)、2-苯乙基膦酸酯(2-phenylethyl phosphonate)、丁基氢三氯甲基膦酸酯(butylhydrogentrichloromethyl phosphonate)、4-甲氧基苯基膦酸酯(4-methoxyphenyl phosphonate)、3-苯基丙基膦酸酯(3-phenylpropylphosphonate)、二甲基烯丙基膦酸酯(dimethylallyl phosphonate)、1-氨基戊烷-1,1-二基二膦酸酯(1-aminopentane-1,1-diyl diphosphonate)、4-碘苄基膦酸酯(4-iodobenzyl phosphonate)、((2-氰基乙基)-膦酰基甲基氨基)-乙酸酯(((2-cyanoethyl)-phosphonomethylamino)-acetate)、4-乙氧基苯基膦酸酯(4-ethoxyphenyl phosphonate)、(+-)-2-氨基-4-膦酰基丁酸酯((+-)-2-amino-4-phosphonobutanate)、草甘膦3-13C[(膦酰基甲基)氨基]乙酸酯(glyphosate 3-13C[(phosphonomethyl)amino]-acetate)、氨基(苯基)甲基膦酸酯(amino(phenyl)methyl phosphonate)、3-(羧甲基膦酰基甲基氨基)丙酸酯(3-(carboxymethyl-phosphonomethylamino)propionate)、D-(-)-2-氨基-5-膦酰基戊酸酯(D-(-)-2-amino-5-phosphono-pentanate)、2-氨基-7-膦酰基庚酸酯(2-amino-7-phosphonoheptanate)、四甲基2-氧代丙烷-1,3-二基二膦酸酯(tetramethyl 2-oxopropane-1,3-diyl diphosphonate)、2-甲氧苄基膦酸酯(2-methoxybenzyl phosphonate)、四乙基亚甲基二膦酸酯(tetraethylmethylenediphosphonate)、二乙基甲氧基甲基膦酸酯(diethylmethoxymethyl-phosphonate)、6-[羟基(异丙氧基)磷酰基]-己酸甲酯(methyl6-[hydroxy(isopropoxy)phosphoryl]-hexanoate)、((2-氰基乙基)(羟基甲氧基磷酰基甲基)-氨基)乙酸酯(((2-cyanoethyl)(hydroxymethoxyphosphorylmethyl)-amino)acetate)、二丙基氯甲基膦酸酯(dipropylchloromethylphosphonate)、氨基[4-(三氟甲基)苯基]甲基膦酸酯(dipropylchloromethylphosphonateamino[4-(trifluoromethyl)phenyl]methylphosphonate)、[(4-氯苄基)-氨基]甲基膦酸酯([(4-chlorobenzyl)-amino]methylphosphonate)。
所列出的化合物形成磷酸(phosphoric)盐和膦酸(phosphonic)盐的部分基团,且凭借其立体结构及其价态特性,可导致电子传导层的材料和掺杂剂的阴离子之间有利的HOMO/LUMO的组合。这可有助于提高掺杂剂的电子注入,从而导致电子传导层较高的导电性。
此外,根据本发明,上面所列举的磷氧化合物的组中的阳离子可选自钠、钾、铯或铷。
此外,根据本发明,为制造有机电子元件的方法,包括以下步骤:
a)提供具有第一电极的基底载体,
b)将包含磷氧盐的衍生物和有机基体材料的至少一个电子传导层施加至第一电极,以及
c)施加与所述电子传导层导电性接触的第二电极,
其中通过溶剂或蒸发过程来实现步骤b)中所述电子传导层的施加。
在一项特别的实施方式中,可利用本发明的方法将中间层施加至有机电子元件的阴极。
更优选地,在方法步骤b)中,通过气相沉积,更优选物理气相沉积(PVD)来制造电子传导区域。在该步骤中,掺杂剂可优选与电子传导层一起沉积。通过所述过程,获得了特别均质且均匀的层。可优选通过将电子传导层的组分和掺杂剂从无水溶剂沉积至基底的方式来进行步骤b)的溶剂法过程。
本发明进一步提供制造有机电子元件的方法,其中磷氧盐在施加前具有大于或等于0重量%且小于或等于0.25重量%的水含量。更优选的是,磷氧盐在施加前水含量为0重量%。水含量为0重量%的磷氧盐也包括含低于检测极限的痕量水的磷氧盐。本领域技术人员可通过已知的标准方法来确定水含量。在这方面值得一提的是,根据Karl Fischer来进行水分测定。
在本发明的另一构成中,在制造有机电子元件的方法中,在步骤b)中可通过旋涂、缝涂、印刷或刮涂来施加电子传导层。可以以特别优选的方式用这些方法来可重现地生产具有高空间分辨率的均匀层。具体地说,在湿法过程中,能够借助于本发明化合物的改善的溶解度获得非常均匀的层。
在本发明的另一构成中,可将有机电子元件设置在有机太阳能电池、有机晶体管、发光有机元件,有机发光二极管和/或有机发光电化学电池中。
附图说明
有机电子元件的结构将通过附图在下文被详述。附图示出了:
图1示出了有机发光二极管(10)的结构的示意图。该发光二极管由玻璃层(1)、氧化铟锡(ITO)层(2)、空穴注入层(3)、空穴传输层(HTL)(4)、发射层(EML)(5)、空穴阻挡层(HBL)(6)、电子传输层(ETL)(7)、电子注入层(8)和阴极层(9)形成;
图2示出了将光(21)转换成电流的具有PIN结构(20)的有机太阳能电池的结构的示意图。所述太阳能电池由氧化铟锡层(22)、p掺杂层(23)、吸收层(24)、n掺杂层(25)和金属层(26)组成;
图3示出了有机场效应晶体管(30)的可能的横截面的示意图。施加在基底(31)上的是栅电极(32)、栅极电介质(33)、源极和漏极接触(34+35)和有机半导体(36)。阴影区域表示接触掺杂是有利的地方。
实施例
I)对比材料的制备
通过热蒸发在ITO(氧化铟锡=铟掺杂的氧化锡)(indium tin oxide=indium-doped tin oxide)电极上沉积200nm厚的电子传导层BCP(2,9-二甲基-4,7-二苯基-1,10-菲咯啉)(2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline)。所使用的反电极为150纳米厚的铝层。
II.包含磷酸衍生物的有机导电层的制备
在三个其它的实验中,相对于BCP(2,9-二甲基-4,7-二苯基-1,10-菲咯啉)的蒸发速率以2重量%、5重量%和10重量%的浓度通过掺杂引入苯基磷酸二铯(dicesium phenyl phosphate)。
在物理表征的过程中,对于经掺杂的有机元件的电流-电压特性来说,所得的结果是,经掺杂的层的电流密度远高于相同电压条件下的对比基底的电流密度。这种效果几乎与掺杂强度成比例,至少在较低浓度的范围内。由此获得的结论是,增加的电流密度导致电荷载流子密度和/或迁移率的增加。
III.包含膦酸衍生物的有机导电层的制备
在另外三个实验中,相对于BCP(2,9-二甲基-4,7-二苯基-1,10-菲咯啉)的蒸发速率以2重量%、5重量%和10重量%的浓度通过掺杂引入癸基膦酸二铯(dicesium decyl phosphonate)。
在物理表征的过程中,对于经掺杂的有机元件的电流-电压特性来说,所得的结果是,经掺杂的层的电流密度远高于相同电压条件下的对比基底的电流密度。这种效果几乎与掺杂强度成比例。由此获得的结论是,增加的电流密度导致电荷载流子密度和/或迁移率的增加。
尽管通过优选的实施方式已对本发明进行了详述和说明,但是本发明不受所公开的实施例的限制,并且本领域技术人员在不离开本发明的保护范围的情况下可作出由其衍生的其它变化。
Claims (11)
1.一种有机电子元件,其包括基底、第一电极、第二电极以及设置在第一和第二电极之间的至少一个电子传导层,其特征在于,所述电子传导层包含通式1的磷氧化合物的盐类型衍生物作为n型掺杂剂,
其中,X、Y大于0且小于或等于3;n、m为整数并且大于或等于1且小于或等于3;M=金属,以及R1=O、S、Se、O-R、S-R、Se-R,R2=R、O-R、S-R、Se-R,并且R选自:取代和未取代的烷基、长链烷基、环烷基、卤代烷基、芳基、亚芳基、卤代芳基、杂芳基、亚杂芳基、亚杂环烷基、杂环烷基、卤代杂芳基、烯基、卤代烯基、炔基、卤代炔基、酮芳基、卤代酮芳基、酮杂芳基、酮烷基、卤代酮烷基、酮烯基、卤代酮烯基。
2.权利要求1所述的有机电子元件,其中所述磷氧化合物的盐类型衍生物选自磷酸酯和/或膦酸酯。
3.前述权利要求中任一项所述的有机电子元件,其中所述磷氧化合物的盐类型衍生物的阳离子选自包括铯和/或铷的重碱金属。
4.前述权利要求中任一项所述的有机电子元件,其中所述磷氧化合物的盐类型衍生物的分子量大于或等于70g/mol且小于或等于1000g/mol,并且升华温度大于或等于120℃且小于或等于1200℃。
5.前述权利要求中任一项所述的有机电子元件,其中所述磷氧化合物的盐类型衍生物选自环状磷酸酯和/或膦酸酯。
6.前述权利要求中任一项所述的有机电子元件,其中所述磷氧化合物的盐类型衍生物以大于或等于0.01%且小于或等于50%的层厚浓度存在于所述电子传导层中。
7.前述权利要求中任一项所述的有机电子元件,其中所述磷氧盐的衍生物为化合物的铯盐或铷盐,所述化合物选自包括以下的化合物:
6,7,11,12,19,20,24,25-八氢二苯并[g,r]-[1,3,6,9,12,14,17,20,2,13]-八氧杂二磷杂环二十二烷-9,22-二醇9,22-二氧化物、(4R)-22-羟基-5,5-二甲基-4-苯基-1,3,2-二氧杂磷杂环己烷2-氧化物、8,9-二苯基二菲并[4,3-d:3,4-f][1,3,2]二氧杂磷杂环庚三烯-18-醇18-氧化物、2,6-双(三苯基甲硅烷基)二萘并[2,1-d:1,2-f][1,3,2]二氧杂磷杂环庚三烯-4-醇4-氧化物、1-丁基-3-甲基咪唑鎓二丁基磷酸盐以及相应的二(C1-C10)烷基衍生物、磷酸二苯酯、双(4-硝基苯基)磷酸酯、2-萘基4-[(E)-苯基二氮烯基]苯基磷酸酯、二萘并[2,1-d:1,2-f][1,3,2]二氧杂磷杂环庚三烯-4-醇4-氧化物、(R)-3,3'-双[3,5-双(三氟甲基)苯基]-1,1'-联萘-2,2'-二基磷酸酯、(S)-3,3'-双(2,4,6-三异丙基-苯基)-1,1'-联萘-2,2'-二基磷酸酯、18-羟基-8,9-二苯基二菲并[4,3-d:3',4'-f][1,3,2]-二氧杂磷杂环庚三烯18-氧化物、(llbR)-4-羟基-2,6-双(三苯基甲硅烷基)-二萘并[2,1-d:1',2'f]-1,3,2-二氧杂磷杂环庚三烯4-氧化物、(R)-(-)-3,3'-双(三苯基甲硅烷基)-1,1'-联萘-2,2'-二基磷酸酯、氨甲酰磷酸锂、D-肌醇1-单磷酸酯、6-苯甲酰基-2-萘基磷酸酯、磷酸4-硝基苯基酯二(环己铵)盐、萘酚AS磷酸酯、萘酚AS-MX磷酸酯、4-(叔戊基)苯基磷酸酯、香叶基香叶基焦磷酸酯、萘酚AS磷酸酯、甲基膦酸酯、三氯甲基膦酸酯、庚烷-1,7-二基二膦酸酯、(庚硫基)甲基膦酸酯、1-羟基丁基膦酸酯、2-苯乙基膦酸酯、丁基氢三氯甲基膦酸酯、4-甲氧基苯基膦酸酯、3-苯基丙基膦酸酯、二甲基烯丙基膦酸酯、1-氨基戊烷-1,1-二基二膦酸酯、4-碘苄基膦酸酯、((2-氰基乙基)-膦酰基甲基氨基)-乙酸酯、4-乙氧基苯基膦酸酯、(+-)-2-氨基-4-膦酰基丁酸酯、草甘膦3-13C[(膦酰基甲基)氨基]乙酸酯、氨基(苯基)甲基膦酸酯、3-(羧甲基膦酰基甲基氨基)丙酸酯、D-(-)-2-氨基-5-膦酰基戊酸酯、2-氨基-7-膦酰基庚酸酯、四甲基2-氧代丙烷-1,3-二基二膦酸酯、2-甲氧苄基膦酸酯、四乙基亚甲基二膦酸酯、二乙基甲氧基甲基膦酸酯、6-[羟基(异丙氧基)磷酰基]-己酸甲酯、((2-氰基乙基)(羟基甲氧基磷酰基甲基)-氨基)乙酸酯、二丙基氯甲基膦酸酯、氨基[4-(三氟甲基)苯基]甲基膦酸酯、[(4-氯苄基)-氨基]甲基膦酸酯。
8.一种制造权利要求1-7中任一项所述的有机电子元件的方法,其具有以下方法步骤:
提供具有第一电极的基底载体,
将包含磷氧盐的衍生物和有机基体材料的至少一个电子传导层施加至第一电极,以及
施加与所述电子传导层导电性接触的第二电极,
其中通过溶剂法或蒸发的方法来实现步骤b)中所述电子传导层的施加。
9.权利要求8所述的制造有机电子元件的方法,其中所述磷氧盐在施加前具有大于或等于0重量%且小于或等于0.25重量%的水含量。
10.权利要求8或9所述的制造有机电子元件的方法,其中在步骤b)中通过旋涂、缝涂、印刷或刮涂来施加所述电子传导层。
11.权利要求1-7中任一项所述的有机电子元件,其中所述有机电子元件被设置在有机太阳能电池、有机晶体管、发光有机元件,有机发光二极管和/或有机发光电化学电池中。
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DE102012217574.1 | 2012-09-27 | ||
DE102012217574.1A DE102012217574A1 (de) | 2012-09-27 | 2012-09-27 | Phosphoroxo-Salze als n-Dotierstoffe für die organische Elektronik |
PCT/EP2013/068826 WO2014048753A1 (de) | 2012-09-27 | 2013-09-11 | Phosphoroxo-salze als n-dotierstoffe für die organische elektronik |
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US (1) | US9806266B2 (zh) |
EP (1) | EP2885825B1 (zh) |
KR (1) | KR101891386B1 (zh) |
CN (1) | CN104662687B (zh) |
DE (1) | DE102012217574A1 (zh) |
WO (1) | WO2014048753A1 (zh) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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TWI642678B (zh) * | 2013-12-23 | 2018-12-01 | 諾瓦發光二極體有限公司 | 含磷雜環庚三烯基質化合物半導體材料 |
CN111900255A (zh) * | 2015-06-23 | 2020-11-06 | 诺瓦尔德股份有限公司 | 包含极性基质、金属掺杂剂和银阴极的有机发光器件 |
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DE102012217574A1 (de) | 2012-09-27 | 2014-03-27 | Siemens Aktiengesellschaft | Phosphoroxo-Salze als n-Dotierstoffe für die organische Elektronik |
DE102015210388A1 (de) | 2015-06-05 | 2016-12-08 | Siemens Aktiengesellschaft | Organische Heterozyklische Alkalimetallsalze als n-Dotierstoffe in der Organischen Elektronik |
DE102016208298A1 (de) | 2016-05-13 | 2017-11-16 | Siemens Aktiengesellschaft | Organische elektronenleitende Schicht mit n-Dotierstoff |
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- 2013-09-11 EP EP13765322.6A patent/EP2885825B1/de not_active Not-in-force
- 2013-09-11 WO PCT/EP2013/068826 patent/WO2014048753A1/de active Application Filing
- 2013-09-11 KR KR1020157010345A patent/KR101891386B1/ko active IP Right Grant
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TWI642678B (zh) * | 2013-12-23 | 2018-12-01 | 諾瓦發光二極體有限公司 | 含磷雜環庚三烯基質化合物半導體材料 |
CN111900255A (zh) * | 2015-06-23 | 2020-11-06 | 诺瓦尔德股份有限公司 | 包含极性基质、金属掺杂剂和银阴极的有机发光器件 |
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Also Published As
Publication number | Publication date |
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CN104662687B (zh) | 2019-06-14 |
DE102012217574A1 (de) | 2014-03-27 |
EP2885825B1 (de) | 2016-07-06 |
US9806266B2 (en) | 2017-10-31 |
KR101891386B1 (ko) | 2018-08-24 |
US20150255719A1 (en) | 2015-09-10 |
KR20150059780A (ko) | 2015-06-02 |
WO2014048753A1 (de) | 2014-04-03 |
EP2885825A1 (de) | 2015-06-24 |
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