EP2837046A1 - Organic electronic components having organic superdonors having at least two coupled carbene groups and use thereof as an n-type dopants - Google Patents
Organic electronic components having organic superdonors having at least two coupled carbene groups and use thereof as an n-type dopantsInfo
- Publication number
- EP2837046A1 EP2837046A1 EP13717462.9A EP13717462A EP2837046A1 EP 2837046 A1 EP2837046 A1 EP 2837046A1 EP 13717462 A EP13717462 A EP 13717462A EP 2837046 A1 EP2837046 A1 EP 2837046A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- organic
- dopant
- carbene
- electron
- groups
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000002019 doping agent Substances 0.000 title claims abstract description 66
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical group [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 title claims description 56
- 150000001875 compounds Chemical class 0.000 claims description 47
- 239000000463 material Substances 0.000 claims description 23
- 125000004122 cyclic group Chemical group 0.000 claims description 18
- 102100039648 Lactadherin Human genes 0.000 claims description 17
- 101710191666 Lactadherin Proteins 0.000 claims description 17
- 125000005842 heteroatom Chemical group 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 230000005284 excitation Effects 0.000 claims description 8
- 239000003446 ligand Substances 0.000 claims description 8
- 239000010410 layer Substances 0.000 description 76
- 239000000370 acceptor Substances 0.000 description 17
- 239000000126 substance Substances 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 14
- -1 heterocyclic radicals Chemical class 0.000 description 13
- 238000003786 synthesis reaction Methods 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000002347 injection Methods 0.000 description 10
- 239000007924 injection Substances 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 9
- 238000001704 evaporation Methods 0.000 description 8
- 230000008020 evaporation Effects 0.000 description 8
- 125000001424 substituent group Chemical group 0.000 description 8
- 239000002585 base Substances 0.000 description 7
- 239000011159 matrix material Substances 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 108010078791 Carrier Proteins Proteins 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 230000006870 function Effects 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical compound [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000005684 electric field Effects 0.000 description 4
- 230000005669 field effect Effects 0.000 description 4
- 125000000623 heterocyclic group Chemical group 0.000 description 4
- 238000004770 highest occupied molecular orbital Methods 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 150000005839 radical cations Chemical group 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 101100046790 Mus musculus Trappc2 gene Proteins 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 238000013459 approach Methods 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 239000002800 charge carrier Substances 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000000539 dimer Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 230000027756 respiratory electron transport chain Effects 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 2
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 2
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- DPOPAJRDYZGTIR-UHFFFAOYSA-N Tetrazine Chemical compound C1=CN=NN=N1 DPOPAJRDYZGTIR-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001412 amines Chemical group 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
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000005899 aromatization reaction Methods 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 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
- 230000001419 dependent effect Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000003574 free electron Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000003949 imides Chemical class 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 230000005693 optoelectronics Effects 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000000103 photoluminescence spectrum Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 150000005838 radical anions Chemical class 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 238000000859 sublimation Methods 0.000 description 2
- 230000008022 sublimation Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- FHCPAXDKURNIOZ-UHFFFAOYSA-N tetrathiafulvalene Chemical compound S1C=CSC1=C1SC=CS1 FHCPAXDKURNIOZ-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- NDQXKKFRNOPRDW-UHFFFAOYSA-N 1,1,1-triethoxyethane Chemical compound CCOC(C)(OCC)OCC NDQXKKFRNOPRDW-UHFFFAOYSA-N 0.000 description 1
- HTJMXYRLEDBSLT-UHFFFAOYSA-N 1,2,4,5-tetrazine Chemical compound C1=NN=CN=N1 HTJMXYRLEDBSLT-UHFFFAOYSA-N 0.000 description 1
- GDAXJBDYNVDMDF-UHFFFAOYSA-N 1,2,4-benzotriazine Chemical class N1=NC=NC2=CC=CC=C21 GDAXJBDYNVDMDF-UHFFFAOYSA-N 0.000 description 1
- FYADHXFMURLYQI-UHFFFAOYSA-N 1,2,4-triazine Chemical compound C1=CN=NC=N1 FYADHXFMURLYQI-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
- AAAXMNYUNVCMCJ-UHFFFAOYSA-N 1,3-diiodopropane Chemical compound ICCCI AAAXMNYUNVCMCJ-UHFFFAOYSA-N 0.000 description 1
- QBPPRVHXOZRESW-UHFFFAOYSA-N 1,4,7,10-tetraazacyclododecane Chemical compound C1CNCCNCCNCCN1 QBPPRVHXOZRESW-UHFFFAOYSA-N 0.000 description 1
- ZQBYWDDCENHNPA-UHFFFAOYSA-N 1,4-dihydro-1,2,3,5-tetrazine Chemical compound C1N=CNN=N1 ZQBYWDDCENHNPA-UHFFFAOYSA-N 0.000 description 1
- WZZBNLYBHUDSHF-DHLKQENFSA-N 1-[(3s,4s)-4-[8-(2-chloro-4-pyrimidin-2-yloxyphenyl)-7-fluoro-2-methylimidazo[4,5-c]quinolin-1-yl]-3-fluoropiperidin-1-yl]-2-hydroxyethanone Chemical compound CC1=NC2=CN=C3C=C(F)C(C=4C(=CC(OC=5N=CC=CN=5)=CC=4)Cl)=CC3=C2N1[C@H]1CCN(C(=O)CO)C[C@@H]1F WZZBNLYBHUDSHF-DHLKQENFSA-N 0.000 description 1
- WMZCREDANYEXRT-UHFFFAOYSA-N 1-[phenyl(pyren-1-yl)phosphoryl]pyrene Chemical class 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
- XNCMQRWVMWLODV-UHFFFAOYSA-N 1-phenylbenzimidazole Chemical class C1=NC2=CC=CC=C2N1C1=CC=CC=C1 XNCMQRWVMWLODV-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- 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 1
- GTPNJFWMUYHPEP-UHFFFAOYSA-N 2-(4-phenylphenyl)-5-[6-[6-[5-(4-phenylphenyl)-1,3,4-oxadiazol-2-yl]pyridin-2-yl]pyridin-2-yl]-1,3,4-oxadiazole Chemical group C1=CC=CC=C1C1=CC=C(C=2OC(=NN=2)C=2N=C(C=CC=2)C=2N=C(C=CC=2)C=2OC(=NN=2)C=2C=CC(=CC=2)C=2C=CC=CC=2)C=C1 GTPNJFWMUYHPEP-UHFFFAOYSA-N 0.000 description 1
- FQJQNLKWTRGIEB-UHFFFAOYSA-N 2-(4-tert-butylphenyl)-5-[3-[5-(4-tert-butylphenyl)-1,3,4-oxadiazol-2-yl]phenyl]-1,3,4-oxadiazole Chemical compound C1=CC(C(C)(C)C)=CC=C1C1=NN=C(C=2C=C(C=CC=2)C=2OC(=NN=2)C=2C=CC(=CC=2)C(C)(C)C)O1 FQJQNLKWTRGIEB-UHFFFAOYSA-N 0.000 description 1
- NBYLBWHHTUWMER-UHFFFAOYSA-N 2-Methylquinolin-8-ol Chemical class C1=CC=C(O)C2=NC(C)=CC=C21 NBYLBWHHTUWMER-UHFFFAOYSA-N 0.000 description 1
- IXHWGNYCZPISET-UHFFFAOYSA-N 2-[4-(dicyanomethylidene)-2,3,5,6-tetrafluorocyclohexa-2,5-dien-1-ylidene]propanedinitrile Chemical compound FC1=C(F)C(=C(C#N)C#N)C(F)=C(F)C1=C(C#N)C#N IXHWGNYCZPISET-UHFFFAOYSA-N 0.000 description 1
- RYTUDCZDAVNDOI-UHFFFAOYSA-N 2-[9,9-dimethyl-7-[5-(6-pyridin-2-ylpyridin-2-yl)-1,3,4-oxadiazol-2-yl]fluoren-2-yl]-5-(6-pyridin-2-ylpyridin-2-yl)-1,3,4-oxadiazole Chemical compound C1=C2C(C)(C)C3=CC(C=4OC(=NN=4)C=4N=C(C=CC=4)C=4N=CC=CC=4)=CC=C3C2=CC=C1C(O1)=NN=C1C(N=1)=CC=CC=1C1=CC=CC=N1 RYTUDCZDAVNDOI-UHFFFAOYSA-N 0.000 description 1
- TVTJUIAKQFIXCE-HUKYDQBMSA-N 2-amino-9-[(2R,3S,4S,5R)-4-fluoro-3-hydroxy-5-(hydroxymethyl)oxolan-2-yl]-7-prop-2-ynyl-1H-purine-6,8-dione Chemical compound NC=1NC(C=2N(C(N(C=2N=1)[C@@H]1O[C@@H]([C@H]([C@H]1O)F)CO)=O)CC#C)=O TVTJUIAKQFIXCE-HUKYDQBMSA-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
- VHMICKWLTGFITH-UHFFFAOYSA-N 2H-isoindole Chemical compound C1=CC=CC2=CNC=C21 VHMICKWLTGFITH-UHFFFAOYSA-N 0.000 description 1
- ZPSJGADGUYYRKE-UHFFFAOYSA-N 2H-pyran-2-one Chemical compound O=C1C=CC=CO1 ZPSJGADGUYYRKE-UHFFFAOYSA-N 0.000 description 1
- MCSXGCZMEPXKIW-UHFFFAOYSA-N 3-hydroxy-4-[(4-methyl-2-nitrophenyl)diazenyl]-N-(3-nitrophenyl)naphthalene-2-carboxamide Chemical compound Cc1ccc(N=Nc2c(O)c(cc3ccccc23)C(=O)Nc2cccc(c2)[N+]([O-])=O)c(c1)[N+]([O-])=O MCSXGCZMEPXKIW-UHFFFAOYSA-N 0.000 description 1
- BSVILDUORGWESI-UHFFFAOYSA-N 3-methyl-2-(4-naphthalen-2-ylphenyl)imidazo[4,5-f][1,10]phenanthroline Chemical class C1=CC=CC2=CC(C3=CC=C(C=C3)C=3N(C4=C(C5=CC=CN=C5C5=NC=CC=C54)N=3)C)=CC=C21 BSVILDUORGWESI-UHFFFAOYSA-N 0.000 description 1
- 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 1
- AOQKGYRILLEVJV-UHFFFAOYSA-N 4-naphthalen-1-yl-3,5-diphenyl-1,2,4-triazole Chemical class C1=CC=CC=C1C(N1C=2C3=CC=CC=C3C=CC=2)=NN=C1C1=CC=CC=C1 AOQKGYRILLEVJV-UHFFFAOYSA-N 0.000 description 1
- KDCGOANMDULRCW-UHFFFAOYSA-N 7H-purine Chemical compound N1=CNC2=NC=NC2=C1 KDCGOANMDULRCW-UHFFFAOYSA-N 0.000 description 1
- RFVBBELSDAVRHM-UHFFFAOYSA-N 9,10-dinaphthalen-2-yl-2-phenylanthracene Chemical class C1=CC=CC=C1C1=CC=C(C(C=2C=C3C=CC=CC3=CC=2)=C2C(C=CC=C2)=C2C=3C=C4C=CC=CC4=CC=3)C2=C1 RFVBBELSDAVRHM-UHFFFAOYSA-N 0.000 description 1
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical class C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 101000679575 Homo sapiens Trafficking protein particle complex subunit 2 Proteins 0.000 description 1
- 238000005481 NMR spectroscopy Methods 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
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- CVQUWLDCFXOXEN-UHFFFAOYSA-N Pyran-4-one Chemical compound O=C1C=COC=C1 CVQUWLDCFXOXEN-UHFFFAOYSA-N 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
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 102100022613 Trafficking protein particle complex subunit 2 Human genes 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- LJOOWESTVASNOG-UFJKPHDISA-N [(1s,3r,4ar,7s,8s,8as)-3-hydroxy-8-[2-[(4r)-4-hydroxy-6-oxooxan-2-yl]ethyl]-7-methyl-1,2,3,4,4a,7,8,8a-octahydronaphthalen-1-yl] (2s)-2-methylbutanoate Chemical compound C([C@H]1[C@@H](C)C=C[C@H]2C[C@@H](O)C[C@@H]([C@H]12)OC(=O)[C@@H](C)CC)CC1C[C@@H](O)CC(=O)O1 LJOOWESTVASNOG-UFJKPHDISA-N 0.000 description 1
- 150000001251 acridines Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000008901 benefit Effects 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
- 150000001555 benzenes Chemical class 0.000 description 1
- BTZVACANDIHKJX-UHFFFAOYSA-N benzo[g]pteridine Chemical class N1=CN=CC2=NC3=CC=CC=C3N=C21 BTZVACANDIHKJX-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000010504 bond cleavage reaction Methods 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- YMBYDCYFUDVJSS-UHFFFAOYSA-N carbon monoxide;cyclopentane;iron Chemical compound [Fe].[O+]#[C-].[O+]#[C-].[CH]1[CH][CH][CH][CH]1 YMBYDCYFUDVJSS-UHFFFAOYSA-N 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229940125851 compound 27 Drugs 0.000 description 1
- 229940127204 compound 29 Drugs 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 125000006841 cyclic skeleton Chemical group 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 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 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 210000003608 fece Anatomy 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000002390 heteroarenes Chemical class 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 1
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229940079865 intestinal antiinfectives imidazole derivative Drugs 0.000 description 1
- CTAPFRYPJLPFDF-UHFFFAOYSA-N isoxazole Chemical compound C=1C=NOC=1 CTAPFRYPJLPFDF-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 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
- 238000004020 luminiscence type Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 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
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 238000013086 organic photovoltaic Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 150000002988 phenazines Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000000628 photoluminescence spectroscopy Methods 0.000 description 1
- LFSXCDWNBUNEEM-UHFFFAOYSA-N phthalazine Chemical class C1=NN=CC2=CC=CC=C21 LFSXCDWNBUNEEM-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 150000003195 pteridines Chemical class 0.000 description 1
- 125000004309 pyranyl group Chemical group O1C(C=CC=C1)* 0.000 description 1
- LYKXFSYCKWNWEZ-UHFFFAOYSA-N pyrazino[2,3-f][1,10]phenanthroline-2,3-dicarbonitrile Chemical compound N1=CC=CC2=C(N=C(C(C#N)=N3)C#N)C3=C(C=CC=N3)C3=C21 LYKXFSYCKWNWEZ-UHFFFAOYSA-N 0.000 description 1
- 159000000018 pyrido[2,3-d]pyrimidines Chemical class 0.000 description 1
- 159000000017 pyrido[3,2-d]pyrimidines Chemical class 0.000 description 1
- WVIICGIFSIBFOG-UHFFFAOYSA-N pyrylium Chemical compound C1=CC=[O+]C=C1 WVIICGIFSIBFOG-UHFFFAOYSA-N 0.000 description 1
- 150000003246 quinazolines Chemical class 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 150000003252 quinoxalines Chemical class 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001055 reflectance spectroscopy Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 229940065287 selenium compound Drugs 0.000 description 1
- 150000003343 selenium compounds Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000004819 silanols Chemical class 0.000 description 1
- 150000003967 siloles Chemical group 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- YNJQKNVVBBIPBA-UHFFFAOYSA-M tetrabutylazanium;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.CCCC[N+](CCCC)(CCCC)CCCC YNJQKNVVBBIPBA-UHFFFAOYSA-M 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- RFDGVZHLJCKEPT-UHFFFAOYSA-N tris(2,4,6-trimethyl-3-pyridin-3-ylphenyl)borane Chemical class 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
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/611—Charge transfer complexes
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
- H10K50/16—Electron transporting layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/653—Aromatic compounds comprising a hetero atom comprising only oxygen as heteroatom
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having a potential-jump barrier or a surface barrier
- H10K10/40—Organic transistors
- H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
- H10K10/462—Insulated gate field-effect transistors [IGFETs]
- H10K10/484—Insulated gate field-effect transistors [IGFETs] characterised by the channel regions
- H10K10/488—Insulated gate field-effect transistors [IGFETs] characterised by the channel regions the channel region comprising a layer of composite material having interpenetrating or embedded materials, e.g. a mixture of donor and acceptor moieties, that form a bulk heterojunction
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
- H10K50/16—Electron transporting layers
- H10K50/165—Electron transporting layers comprising dopants
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Definitions
- the invention relates to a novel material for n-doping of electron transport layers, the use of these compounds for the construction of organic electronic Bauelemen- te, transistors, organic light-emitting diodes, light-emitting electrochemical cells, organic solar cells, photodiodes and electronic components enthal ⁇ tend these compounds.
- Organic electrical components consist at least partially stabilized, organic materials or compounds, which may have in addition to the well known insulating properties and electrically conductive or semiconductive characteristics. The quality and functionality of organic electrical components such as organic solar cells, transistors, light-emitting components and photodiodes depends essentially on the design of the components used.
- Organic electrical components typically have transport layers with p (hole) or n (electron) conductivity, the efficiency of the layers for many
- Components is highly influenced by the achievable conductivity.
- the electron mobility and the number of moving / free charge carriers thereby determine generally the transport-conductivity and thus also the injection and / or transport ⁇ properties of the layers.
- the efficiency of organic solar cells increases when the least possible voltage drops across the transport layers with p or n conductivity.
- the clock Kon ⁇ resistors which effectively measured mobility of the semiconductor is a function of the clock Kon ⁇ resistors. If these contact resistances are minimized, higher switching frequencies can generally be realized in the circuit. be siert.
- Equally significant impact has the Ausgestal ⁇ processing of the transport layers in bi-polar transistor devices, as described for example in detail in DE102010041331.
- the luminescence, efficiency and service life depend strongly on the exciton density of the light-emitting layer and is limited, inter alia, by this.
- an improvement in the properties of electron transport layers can be achieved by doping the matrix material.
- the doping is significantly more difficult than in the p-doping since doping substances whose HOMO (Highest Occupied Molecular Orbital) is higher than the LUMO (Lowest Unoccupied Molecular Orbital) of the electron transporter must be found. Only in this way an effective electric ⁇ nenschreibtrag can take place from the dopant to the electron transporter. In general, this is due to materials with extremely low work functions or ionization energies reached (alkali and alkaline earth metals, as well as the Lanthanoi- the).
- tetrathiafulvalenes have been described as doping substances in combination with strong electron acceptors from the class of the tetracyanoquinodimethanes as the first charge transfer salts which have metallic conductivity (Ferraris, J. et al., J. Am. Chem. Soc. 1973 , 95, 948; Coleman, LB, et al., Solid State Municipal. 1973, 12, 1125.).
- WO 2007 107306 A1 describes the use of heterocyclic radicals or diradicals whose dimers, oligomers,
- EP 1837926 AI EP
- 1837926 Bl, US 2007 0252140-A1, EP 1837927 Al, WO 2007 107306 are also heterocyclic radicals or diradicals, their dimers, oligomers, polymers, dispiro compounds and poly ⁇ cyclen and rials their use as organic semi-conductive Mate ⁇ and electronic and optoelectronic devices disclosed ,
- US 2008 029 7035 A1 describes the use of donor carbene intermediates for improving electron injection and electron transport in organic electronic components such as organic light-emitting diodes (OLEDs), organic field-effect transistors (OFETs) and organic photovoltaic components, in particular organic solar cells .
- donor carbene intermediates are disclosed for injection purposes in electron transport layers, it is characteristic of the classes of compounds presented that they have (several) amine substituents on the donor carbene body, which after the donation of an electron to the electron transport layer stabilize the dopant as a quinoidal system. This can be exemplified by the reaction mechanism of a connec ⁇ tion
- the object of the present invention is to eliminate the disadvantages occurring in the prior art and to provide an organic electronic device with an organic electron donor compound or an electron donor compound, which is used for doping electron transport ⁇ layers and the effectiveness organic increased electrical components.
- the electron donor compound consists of at least two carbene groups Qi and Q 2 (generally Q x ), which are coupled to each other via a bridge (B).
- the bridge (B) consists of at least one double bond.
- a single bond is not inventive as these Bin ⁇ dung dissociated in case of electronic excitation.
- the bridge (B) but also quinoid ring systems with and without heteroatom included. Two quinoid ring systems are shown below by way of example, which may also be part of more complex inventory ⁇ , fused-systems.
- the lone pair of electrons of the carbon is over the
- the bis-carbene is made up of two individual carbene groups.
- the bridge (B) in the product in this case consists of the double bond between the two carbene groups.
- the substance class having a double bond in the bridge referred to as bis-carbene compound having the above Darge ⁇ presented structure, as this is purely formal composed of two carbenes. Since the bis-carbenes no Carbene properties, they are hereinafter referred to as "super-electron donors" (SED), as well as in modern literature, since they are capable of acting as reducing ⁇ onsmittel.As super-donor substances be - which have a quinoidal structure in their neutral form, and which become completely or partially aromatic by electron donation.
- systems for the doping of electron transport layers consist of two quinoid units which are linked to one another via a double bond or to a bridge analogous thereto.
- Such a system is in equilibrium with its diradical without the need to break the binding framework of the molecule as indicated in the prior art.
- the biscarbene can donate an electron.
- the result is a radical cation.
- the driving force for the reac ⁇ tion is the re-flavoring of the radical cation. Since formally "only" electrons are transferred and no bonds broken, this process is reversible, meaning that the equilibrium between the donor, the radical cation, and the (radical) acceptor anion sets in.
- the radical anions are the most unstable species in the system, they can In the organic component, the functionality can be set as follows:
- the donor strength of the organic electron donor compound should be adapted so that only a few radicals are on the acceptor in the quiescent state of the device. This can extend the service life of the component.
- Electron transport materials are weak electron acceptors.
- a general example of an electron acceptor is, for example, BPhen (4,7-di (phenyl) -1,10-phenanthroline).
- the electron acceptors take up, at least temporarily, an electron of the biscarbene.
- the driving force for the release of the electron is the re-aromatization of the electron-donating cyclic organic
- Electron donor connection It creates a radical cation. The reaction is reversible, since in the electron donor compound no binding scaffolds are cleaved. There is only a partial charge exchange.
- a bis-carbene comprises 2 analogue 6-membered ring systems and another example verdeut ⁇ light electron transfer of an analog 5-membered ring system.
- Both bis-carbene compounds are capable of reversibly releasing an electron to an organic electron transporter (in this case exemplified by BPhen).
- the respective radical anion / cation pair are formed.
- the present invention provides an organic electronic device comprising at least two electrodes and an organic electron transport layer comprising one or ⁇ ganischen n-dopants available, which is characterized in that the n-dopant at least two via a bridge (B) connected contains cyclic carbene groups (Q x ), which do not dissociate upon electronic excitation of the compound and aromatized at least one carbene base body and the carbene groups are not directly connected to each other via a Me ⁇ tall ligands.
- organic electronic component and polymer electronic components are understood here as organic light emitting diodes, organic Solarzel ⁇ len, light-emitting electrochemical cells, photo diodes and organic field effect transistors.
- the organic electron-donor compound is from constructed or may contain at least two verbun via a covalent bridge ⁇ dene carbene groups.
- the combination of two carbene groups forms a so-called bis-carbene.
- Carbene groups are understood to mean electrically neutral, unstable electron deficient compounds which have a divalent carbon atom with an electron septum at one point of their skeleton. Carbenes thus formally have a free electron pair on a carbon, which is not involved in a covalent bond.
- the carbene groups may consist of cyclic hydrocarbons. More preferably, the carbenes may consist of cyclic hydrocarbons which are partially unsaturated and allow for resonance stabilization of the free carbene electron pair.
- This Resonanzsta ⁇ bilmaschine can additionally also free, ie non bonding electron pairs of heteroatoms (eg oxygen, sulfur, selenium or tellurium, nitrogen, phosphorus or arsenic, etc.) take place, which can be incorporated within the cyclic skeleton of the carbene groups. Preference is given to the incorporation of nitrogen as a heteroatom.
- the carbene groups can have a quinoid structure.
- a quinone is a benzene derivative in which the substituents are replaced by double-bond oxygen, thus eliminating the aromaticity of the ring on two carbon atoms
- the chemical compound, i. Coupling of the two carbene groups may preferably lead to an organic electron donor compound which is electrically neutral in its entirety and preferably has a quinoid structure. Since within this bis-carbene structure the carbene groups no longer possess any carbene properties, this type of compound is also referred to in modern literature as the "super-electron donor" (SED).
- SED super-electron donor
- the SEDs can have substituted or unsubstituted homocycles or hetero cycles at each bondable site of the main body.
- the substituents may preferably be selected from substituted and unsubstituted heterocycles, such as, for example, furan, thiophene, pyrrole, oxazole, thiazole, imidazole, isoxazole, isothazole, pyrazole, pyridine, pyrazine, pyrimidine, 1,3,6-triazine, pyrylium, alpha- Pyrone, gamma-pyrone, benzofuran, benzothiophene, indole 2H-isoindole, benzothiazole, 2-benzothiophene, 1H-benzimidazole, ⁇ -benzotriazole, 1, 3-benzoxazole, 2-benzofuran, 7H-purine, quinoline, iso-quinoline , Quinazolines, quinoxalines, phthal
- alkyl radicals may generally contain ether groups (ethoxy, methoxy, etc.), ester, amide, amines, carbonate groups, etc., or else halogens, in particular CN and F.
- ether groups ethoxy, methoxy, etc.
- ester ethoxy, methoxy, etc.
- amide ethoxy, etc.
- amines ethoxy, etc.
- carbonate groups e.g., benzyl
- F halogens
- substituent R is not limited to saturated systems, but may also include substituted or unsubstituted aromatics such as phenyl, diphenyl, naphthyl, phenanthryl or benzyl, etc. All substituents R of the compound main body can be chosen independently of one another.
- the SEDs can generally act as a reducing agent.
- the compound In the case of electronic stimulation e.g. by light, thermal radiation or the application of a voltage or by self-activation, the compound is capable of donating an electron while retaining its binding skeleton to an acceptor. The compound can then form a resonance-stabilized cation. It can commonly form salts with electron acceptors.
- the electron transport layers may include electron transport materials, electron acceptors, and organic electron donor compounds.
- 2, 2 ', 2 "- (1,3,5-triethylene triyl) tris (1-phenyl-1H-benzimidazoles), 2- (4-electron) can be preferably selected as electron transporting materials for the absorption of electrons.
- Electron acceptors for the purposes of the present invention 2,3,5, 6-tetrafluoro-7, 7,8, 8-tetracyano-quinodimethane, pyrazino [2, 3-f] [1, 10] phenanthroline-2, 3-dicarbonitrile and Dipyrazino [2,3-f: 2 ', 3'-h] quinoxaline-2, 3, 6, 7, 10, 11-hexacarbonitrile.
- the organic electron donor compounds may be applied to a layer together with an electron acceptor (s).
- the compounds can be processed both in the gas phase, as well as the liquid phase.
- both the dopant and the matrix material are vaporized together, preferably from different sources in a high vacuum, and deposited as a layer.
- the finished layer is obtained by evaporation of the solvent. It can be adjusted by the different mass ratios of organic electron donor compound to the electron acceptor any doping ratios.
- the two carbenes are not directly connected or bridged via a metal ligand.
- this does not exclude that one or both carbene groups may have a metal Li ⁇ ligands within their binding scaffold.
- the organic electron donor compounds according to the invention may contain, by way of example but not limitation, ferrocenyl, cyclopentadienyl dicarbonyl iron or phthalocyanines and porphyrins.
- the organic electronic component is characterized in that the carbene groups of the organic n-dopant are directly connected to one another by a double bond.
- the binding skeleton of the organic electron donor compound is not cleaved. That is, the two carbenes are still connected by a single bond in the electronically excited state and the molecule does not dissociate.
- compounds of the following type are considered to be particularly inventive:
- the organic electronic component is characterized in that the bridge (B) of the n-dopant contains at least one quinoid ring system.
- the quinoid ring systems can either be based purely on carbon or contain heteroatoms.
- the bridging quinoid units may be part of complex fused systems.
- the number of quinoid units in the bridge can be between 0 and 20 units. If there is no quinoid unit between the carbene groups, then the two carbenes are bound together directly by a double bond.
- a further particular embodiment of the invention constitutes the organic electronic device characterized labeled in ⁇ characterized in that at least one of the carbene groups of the organic ⁇ rule n-type dopant includes a 5- or 6-ring, which min- has at least 1 heteroatom.
- a cyclic carbene compound of the invention in the following diagram is shown which consists of a 5-membered ring and contain other compounds, which ei ⁇ NEN cyclic 5-ring.
- the structure with the letter (A) designates a fused aromatic Sys tem ⁇ (compound 27 + 28 + 29).
- the 5-ring of the organic n-dopant can be connected to the second carbene group by an additional bridge (dashed line Verbindun ⁇ gen 28 + 29).
- the carbene group can be connected via two additional compounds of the ring system with the other carbene group (compound 29).
- Y denotes either O, S or N-R, the derivatives N-R being particularly preferred according to the invention.
- the substituents R mentioned in the above example can be selected to be equivalent to the substituents already listed of the bondable sites of the main body.
- organic electronic device of the organic n-type dopant is characterized labeled in ⁇ characterized in that the carbene groups from the same 5-rings are sawn, which have at least 1 heteroatom in the skeleton. Excluded from this class, however, are the Tetrathialfulvalene and their derivatives.
- the organic n-dopant is thereby in that at least one of the carbene groups contains a 6-membered ring. Examples of these special execution ⁇ forms are given in the following drawing:
- the first two structural formulas show a cyclic carbene group derived from a heteroaromatic compound.
- the heteroatom Y stands at not conjugated with a double bond position.
- the Z - positions (Z i to Z 4 ) denote atoms, which by a
- Double bond bound and as C-H, C-D, C-R (the definition is equivalent to the definition of R of the substituted 5-rings) or N can be executed.
- positions Z ⁇ there is the possibility that neighboring Zs (Z ⁇ and Z ⁇ + i) may be assembled into higher-annealed systems (naphthalene, anthracene, etc., or their hetero analogues).
- the dashed arcs indicate those positions where bridging to other carbene groups is possible.
- the bridge is located on the non-aromatic atom or, secondly, on one of the Z-formed CRs or, thirdly, on a combination of the different Z-positions (i and i, ii and ii, i and ii .).
- both carbene groups can be of identical construction and each contain at least one 5- or 6-membered ring.
- the bis-carbene would then be mirror-symmetrical in this particular case.
- the organic n-dopant is characterized in that at least one of the carbene groups contains a tetrazine iodide.
- the Tetrazinodihetarene were synthesized in 1986 by Eichenberger and Balli (Eichenberger, T. and Balli H., Helv. Chim Acta 1986, 69, 1521-1530.).
- This class of compounds is formally constituted by an s-tetrazine at the oxidation state of a 1,4-dihydro-1,2,3,5-tetrazine and fused heterocyclic ring systems such as e.g. Pyridine, quinoline and isoquinoline.
- planar nitrogen atoms on the bridgehead of the tetrazine ring participate in the ⁇ system with two electrons, thus leading to an overcompensation of the acceptor character of the pyridine-type nitrogen atoms.
- This substance class can also be classified as a "Weitz type" donor.
- the organic n-type dopant may be ge ⁇ is characterized in that it contains or consists of a bis-pyran a bis-pyran.
- the synthesis of bis-pyrans was elaborated by A. Kanitz, among others.
- the disclosure content of patent application WO2007 / 028738 may be added here.
- the organic electronic device of the organic n-type dopant is characterized in that it comprises a 2.2 ⁇ , 6.6 ⁇ - contains tetraphenyl-4, 4 ⁇ -dipyran or from a 2.2 ⁇ , 6 , 6 ⁇ - tetraphenyl-4, 4 ⁇ -dipyran.
- a further preferred embodiment of the organic electronic component is characterized in that the carbene groups of the organic n-dopant are additionally connected to one another via at least one second bridge.
- Some non-limiting examples of multiple bridged super donors are given above (for example, compounds 1, 3, 5, 6, 7, 9, 15).
- principle additional bridging possibilities for 5- or 6-atom cyclic compounds are given above (for example compound fertilize 28, 29 or compounds 32, 33).
- Organic electron transport also According to the invention ⁇ layers containing an organic n-dopant, characterized in that the n-dopant at least two via a bridge (B) connected, cyclic carbene groups (QX), which do not dissociate upon electronic excitation of the connection and at least one carbene base body is aromatized and the carbene groups are not connected directly to one another via a metal ligand.
- the individual or combinations of the properties and configurations of the n-dopants of the electron transport layers according to the invention correspond to those which are described above in the context of the description of the n-dopants of the organic electronic components according to the invention.
- an organic electron transport layer an n-dopant, characterized in that the n-dopant at least two via a bridge (B) connected, cyclic carbene groups (QX), which do not dissociate in electronic ⁇ shear excitation of the connection and at least one carbene-flavored base body case and the Car ⁇ ben-groups are not directly connected together via a metal ligand.
- a bridge B
- QX cyclic carbene groups
- the organically electronic components according to the invention can be used for the production of polymer-electronic components.
- the synthesis of the GBP is two-tiered.
- Sed1 The synthesis of Sed1 occurs in two stages according to a modi fied ⁇ provision JA Murphy, J. Garnier, SR Park, F. Schoenebeck, S. Zhou, A.. Turner, Org. Lett. 2008, 10, 1227.
- IC-1) Preparation of Organic Electrically Conductive Layers Containing GBP On an ITO (indium-tin-oxide) electrode, a 200 nm thick layer of the electron conductor BCP (2, 9-dimethyl-4, 7 -diphenyl-1,10-phenanthroline).
- the counterelectrode used is a 150 nm thick aluminum layer.
- the GBP produced under I.A. is doped in concentrations of 2%, 5%, 15% and 25% relative to the rate of evaporation of the BCP.
- Prefabricated ITO glass substrates are treated for 10 minutes using an oxygen plasma and quickly transferred into egg ⁇ NEN evaporator, which is filled glove box within an argon will be ⁇ having a water content less than 2 ppm.
- the thermal evaporation is carried out at a base pressure klei ⁇ ner than 2xl0 ⁇ 6 mbar, which evaporation step is maintained during the entire Bedamp-.
- the electron conductor and the dopant are simultaneously heated to a temperature just below their evaporation point on ⁇ . Then, the dopant is further heated while ⁇ until a constant vaporization rate is achieved.
- the same procedure is followed with the electron conductor and with constant evaporation rates on both sides, the slide of the evaporator is opened.
- the rate of electron transport is estimated at 1 ⁇ / s and the set Dotandenrate is selected in dependence on the concentration tandemich Verdampfungsra ⁇ te of the electron transport material and the desired Do-.
- both sources are cooled down to below 40 ° C after evaporation.
- the counter electrode is by means of thermal vapor deposition ist ⁇ eliminated and consists of a stack of a 10 nm thick calcium and a 150 nm thick aluminum layer.
- the deposition is started at a rate of 0.5A / s by opening the gate and then slowly increasing the deposition rate to 5A / s.
- the electrodes thus produced are subjected to a physical characterization.
- GBP doping concentrations in the range between 5 and 15%.
- the horizontal areas of the characteristic curves do not represent a current limit of the component, but are due to the safety-related current limits for the component. In general, the smaller the voltage at which the component reaches the maximum current density, the better the Dotieref ⁇ fect.
- the symmetrical behavior of the current-voltage characteristic shows for the undoped BCP layer and the layers with the different GBP doping concentrations that the electron injection is independent of the work function of the metal electrodes and works equally well for aluminum and ITO electrodes. This is a desirable property for good dopants.
- the conductivities as a function of the different GBP doping concentrations are illustrated once again in FIG. The course found does not correspond to the results of the IV characteristics.
- the conductivity is small for the conductivity substrate with undoped GCP layer and increases with higher GBP doping concentration.
- the measured conductivities, even at the highest measured GBP doping concentrations, are not in the range that would be expected from a good dopant (1E-5 to 1E-3 S / m).
- the absorption spectra (see FIG. 3) of the layers with different GBP doping concentrations show that the absorption increases strongly with increasing GBP doping concentrations in the visible range of 400-700 nm. This increase is particularly evident in the blue-green range of 400-550 nm, which means that the layer has a distinctly red effect on the human eye.
- the increase in absorption with increasing GBP doping concentration may be due, on the one hand, to the formation of charge-transfer complexes and, on the other hand, to the reddish base color of the GBP.
- the quartz glass sheets produced in II.C were examined by photoluminescence spectroscopy. The results are shown in FIG.
- the comparison of PL-spectra of pure BCP layers with GBP-doped BCP layers shows that the emission maximum shifts from 396 nm to 383 nm.
- a marked second peak is formed for the GPB-doped layers at 480-540 nm, which becomes more pronounced as the GBP doping concentration increases.
- the shift of the emission maximum on the formation of charge-transfer complexes is Komple ⁇ Without being bound by theory returned, while the second peak is attributable to the GBP.
- the high emission can affect organic photodetectors and solar cells in particular posi ⁇ tively.
- the quartz glass sheets produced in II.C were examined by reflection spectroscopy.
- the results of Reflection spectra are shown in FIG. Comparing the reflection spectra of pure BCP layers with GBP-doped BCP layers reveals a GBP concentration-dependent decrease in blue-green wavelength reflection (420-550nm), whereas red-reflectance is GBP concentration-independent. From a purely optical point of view, this is also evident in the layers, whose hue is becoming darker and redder with increasing GBP concentration for the human eye.
- the measurement data are obtained on components manufactured according to IC-2.
- Layer can be determined depending on the dopant concentration, a higher output current, both positive and negative voltage curve relative to the ITO electrode.
- the good effectiveness of the dopant can be derived for both dopant concentrations also from the symmetrical course of the current density / voltage curve.
- the layer with the 10% doping shows a slightly better course than the layer with the 5% dopant content due to the higher current densities achieved.
- FIG. 9 shows the current / voltage characteristics of components with a pure Alq3-, an Alq3-doped with 5% SED1 and a Component having a Alq3- doped with 5% Sed1 and a zusharm ⁇ union 15 nm thick SEDL-layer which was to cathode and doped electron transport layer till ⁇ eliminated between the calcium.
- the individual doped layers differ only insignificantly in their current / voltage curves.
- FIG 10 shows the current / voltage characteristics of a 4mm 2 large component with a 200 nm thick ETM-036 layer (ETM 036 is an electron transporting material of Fa. Merck OLED Mate ⁇ rials GmbH respectively Merck KGaA) with and without Sed1 as Do ⁇ tanden.
- ETM 036 is an electron transporting material of Fa. Merck OLED Mate ⁇ rials GmbH respectively Merck KGaA
- Sed1 Do ⁇ tanden
- FIG. 12 shows the current / voltage characteristics of a 4 mm 2 large component with a 200 nm thick TMM-004 layer (TMM-004 is a triplet host and an electron transport material from Merck OLED Materials GmbH or Merck KGaA) with and without SED1 as dopants.
- TMM-004 is a triplet host and an electron transport material from Merck OLED Materials GmbH or Merck KGaA
- SED1 as dopants.
- a higher output current can be detected for the layer doped with 5% SED1, both in the case of a positive and a negative voltage curve relative to the ITO electrode.
- FIG. 14 shows the absorption properties of a ⁇ ETM-03- and one with 5% Sed1 doped ETM-03 layer. Both layers show an absorption maximum around 354 nm, with a lower absolute absorption of the doped ETM-03 layer. The decrease in absorption correlates with the concentration of ETM-03, which suggests that the absorption at these wavelengths is mainly determined by the electron transport material.
Abstract
The invention relates to an organic electron transport layer n-dopant, the use of said n-dopant to construct organic electronic components, transistors, organic light-emitting diodes, light-emitting electrochemical cells, organic solar cells, photodiodes, and electronic components containing said n-dopant.
Description
Beschreibung description
Organisch elektronische Bauelemente mit organischen Super¬ donoren mit mindestens zwei gekoppelten Carben-Gruppen und deren Verwendung als n-Dotierstoffe Organic electronic components with organic super ¬ donors with at least two coupled carbene groups and their use as n-dopants
Die Erfindung betrifft ein neuartiges Material zur n-Do- tierung von Elektronentransportschichten, die Verwendung dieser Verbindungen zum Bau organisch elektronischer Bauelemen- te, Transistoren, organischer lichtemittierender Dioden, lichtemittierender elektrochemischer Zellen, organischer Solarzellen, Photodioden und elektronische Bauelemente enthal¬ tend diese Verbindungen. Organisch elektrische Bauelemente bestehen, zumindest teil¬ weise, aus organischen Materialien oder Verbindungen, die neben den altbekannten Isolatoreigenschaften auch elektrisch leitende oder halbleitende Charakteristiken aufweisen können. Die Qualität und Funktionalität organisch elektrischer Bau- elemente wie z.B. organischer Solarzellen, Transistoren, lichtemittierender Bauteile und Photodioden hängt dabei im Wesentlichen von der Ausgestaltung der verwendeten Bauelemente ab. Organisch elektrische Bauelemente weisen in der Regel Transportschichten mit p- (Loch) oder n- (Elektronen) Leit- fähigkeit auf, wobei die Effizienz der Schichten für vieleThe invention relates to a novel material for n-doping of electron transport layers, the use of these compounds for the construction of organic electronic Bauelemen- te, transistors, organic light-emitting diodes, light-emitting electrochemical cells, organic solar cells, photodiodes and electronic components enthal ¬ tend these compounds. Organic electrical components consist at least partially stabilized, organic materials or compounds, which may have in addition to the well known insulating properties and electrically conductive or semiconductive characteristics. The quality and functionality of organic electrical components such as organic solar cells, transistors, light-emitting components and photodiodes depends essentially on the design of the components used. Organic electrical components typically have transport layers with p (hole) or n (electron) conductivity, the efficiency of the layers for many
Bauelemente im hohen Maße von der erreichbaren Leitfähigkeit geprägt ist. Components is highly influenced by the achievable conductivity.
Die Elektronenmobilität und die Zahl der beweglichen/freien Ladungsträger bestimmen dabei allgemein die Transport-Leitfähigkeit und damit auch die Injektions- und/oder Transport¬ eigenschaften der Schichten. So steigt z.B. die Effizienz organischer Solarzellen an, wenn möglichst wenig Spannung über die Transportschichten mit p- beziehungsweise n-Leitfähigkeit abfällt. Im Falle von Feldeffektransistoren ist die effektiv gemessene Mobilität des Halbleiters eine Funktion der Kon¬ taktwiderstände. Werden diese Kontaktwiderstände minimiert so können im Schaltkreis generell höhere Schaltfrequenzen reali-
siert werden. Ebenso wesentlichen Einfluss hat die Ausgestal¬ tung der Transportschichten in bi-polaren Transistorbauteilen, wie sie zum Beispiel detailliert in der DE102010041331 beschrieben werden. Für organische Leuchtdioden hingegen hängt die Lumineszenz, Effizienz und Lebensdauer stark von der Exzitonendichte der lichtemittierenden Schicht ab und wird unter anderem auch durch diese limitiert. The electron mobility and the number of moving / free charge carriers thereby determine generally the transport-conductivity and thus also the injection and / or transport ¬ properties of the layers. For example, the efficiency of organic solar cells increases when the least possible voltage drops across the transport layers with p or n conductivity. In the case of field effect transistors which effectively measured mobility of the semiconductor is a function of the clock Kon ¬ resistors. If these contact resistances are minimized, higher switching frequencies can generally be realized in the circuit. be siert. Equally significant impact has the Ausgestal ¬ processing of the transport layers in bi-polar transistor devices, as described for example in detail in DE102010041331. For organic light-emitting diodes, on the other hand, the luminescence, efficiency and service life depend strongly on the exciton density of the light-emitting layer and is limited, inter alia, by this.
Zur Erhöhung der Effizienz der Transport-Leitfähigkeit und der Injektionseigenschaften lassen sich generell zwei unterschiedliche Wege beschreiten. To increase the efficiency of transport conductivity and injection properties, two different approaches can generally be taken.
Zum einen kann man durch Einführung einer dünnen Salzschicht (0,5-3 nm Dicke) aus z.B. LiF oder CsF zwischen der Kathode und der Elektronentransportschicht eine erhöhte Injektion von Elektronen in die Emitterschicht erreichen. In der neueren Literatur (Huang, Jinsong et al . , Adv. Funct . Mater. 2007, 00, 1-8.; Wu, Chih-I et al . , APPLIED PHYSICS LETTERS 88, 152104 (2006); Xiong, Tao et al . , APPLIED PHYSICS LETTERS 92, 263305 (2008)) wird dazu auch Cäsiumcarbonat als Substanz zur Herstellung dieser Zwischenschicht vorgeschlagen (Briere, T. R. et al., Journal of Applied Physics, 48, 3547 (1977); Li, Yang et al . , APPLIED PHYSICS LETTERS 90, 012119 (2007)). Der Elektrontransport wird dadurch signifikant verbessert, für sehr hocheffiziente organische Leuchtdioden ist diese Verbesserung jedoch unzureichend. On the one hand, by introducing a thin salt layer (0.5-3 nm thickness) of e.g. LiF or CsF between the cathode and the electron transport layer achieve increased injection of electrons into the emitter layer. In recent literature (Huang, Jinsong et al., Adv. Funct. Mater., 2007, 00, 1-8, Wu, Chih-I et al., APPLIED PHYSICS LETTERS 88, 152104 (2006); Xiong, Tao et al al., APPLIED PHYSICS LETTERS 92, 263305 (2008)), cesium carbonate is also proposed as a substance for making this intermediate layer (Briere, TR et al., Journal of Applied Physics, 48, 3547 (1977); Li, Yang et al. , APPLIED PHYSICS LETTERS 90, 012119 (2007)). The electron transport is thereby significantly improved, but for very high efficiency organic light-emitting diodes this improvement is insufficient.
Zum anderen kann durch die Dotierung des Matrixmaterials eine Verbesserung der Eigenschaften von Elektronentransportschich- ten erreicht werden. Die Dotierung ist jedoch im Falle der n- Dotierung von Elektronentransportern deutlich schwieriger als in der p-Dotierung, da Dotierungs-Substanzen gefunden werden müssen deren HOMO (Highest Occupied Molecular Orbital) höher liegt als das LUMO (Lowest Unoccupied Molecular Orbital) des Elektronentransporters. Nur so kann ein effektiver Elektro¬ nenübertrag vom Dotierungsmittel zum Elektronentransporter stattfinden. Im Allgemeinen wird dies durch Materialien mit extrem niedrigen Austrittsarbeiten bzw. Ionisierungsenergien
erreicht (Alkali- und Erdalkalimetalle, sowie den Lanthanoi- den) . On the other hand, an improvement in the properties of electron transport layers can be achieved by doping the matrix material. However, in the case of n-doping of electron transporters, the doping is significantly more difficult than in the p-doping since doping substances whose HOMO (Highest Occupied Molecular Orbital) is higher than the LUMO (Lowest Unoccupied Molecular Orbital) of the electron transporter must be found. Only in this way an effective electric ¬ nenübertrag can take place from the dopant to the electron transporter. In general, this is due to materials with extremely low work functions or ionization energies reached (alkali and alkaline earth metals, as well as the Lanthanoi- the).
Zur speziellen p-Dotierung werden in der Patent-Literatur or- ganische Substanzen aufgeführt, welche die Lochleitung elek¬ tronischer Bauelemente verbessern sollen. So beschreibt z.B. die WO 2006/081780 AI organische chinoide, mesomere Verbin¬ dungen zur Dotierung organisch halbleitenden Matrixmaterials. Desweiteren werden in der WO 2008/138580 AI spezielle Imi- dazolderivate angeführt, welche als p-Dotand zur Dotierung eines organischen halbleitenden Matrixmaterials Einsatz finden. Einen anderen Ansatz zur Herstellung organischer elektronischer, lumineszierender Bauelemente verfolgt hingegen die EP 1950817 AI, welche als Akzeptormaterial spezielle Qui- noid-Verbindungen vorschlägt. Allen Offenbarungen gemein, ist der Einsatz dieser Substanzen zur Verbesserung der Lochleitung, d.h. zur p-Dotierung organischer elektrischer Schichten . Auf der Suche nach geeigneten Substanzen zur direkten n-Do- tierung von Elektronentransportschichten wurden unterschiedliche Ansätze verfolgt. So wurden z.B. Tetrathiafulvalene als Dotierungssubstanzen in Verbindung mit starken Elektronenakzeptoren aus der Klasse der Tetracyanoquinodimethane als ers- te Charge-Transfer-Salze beschrieben, welche eine metallische Leitfähigkeit aufwiesen (Ferraris, J. et al . , J. Am. Chem. Soc. 1973, 95, 948; Coleman, L. B., et al . , Solid State Com- mun . 1973, 12, 1125.). Die Donorstärke der Tetrathiafulvalene ist aber für „normale" organische Halbleiter nicht ausrei- chend und daher scheinen die Tetrathiafulvalene und ihre ho¬ mologen Selenverbindungen als Dotierungsmaterial nicht geeig¬ net. Diese Substanzklasse ist aus diesem Grund auch nicht be¬ vorzugt im Sinne der vorliegenden Erfindung. In einer ganzen Reihe von Dokumenten aus der Patentliteratur werden zudem Dotierungs-Substanzen vorgeschlagen, welche über Lichteinstrahlung aktiviert werden. So beschreibt die For special p-doping in the patent literature or- ganic substances are listed, which should improve the hole conduction elec ¬ tronic components. For example, WO 2006/081780 AI organic quinoid, mesomeric Verbin ¬ applications for doping organic semiconducting matrix material. Furthermore, WO 2008/138580 A1 mentions specific imidazole derivatives which are used as p-dopant for doping an organic semiconductive matrix material. However, another approach for the production of organic electronic, luminescent components is pursued by EP 1950817 A1, which proposes special quinone compounds as the acceptor material. Common to all disclosures is the use of these substances for improving the hole conduction, ie for the p-doping of organic electrical layers. In the search for suitable substances for the direct n-doping of electron transport layers different approaches were pursued. Thus, for example, tetrathiafulvalenes have been described as doping substances in combination with strong electron acceptors from the class of the tetracyanoquinodimethanes as the first charge transfer salts which have metallic conductivity (Ferraris, J. et al., J. Am. Chem. Soc. 1973 , 95, 948; Coleman, LB, et al., Solid State Municipal. 1973, 12, 1125.). But the donor strength of Tetrathiafulvalene is for "normal" organic semiconductors is not sufficient and therefore the Tetrathiafulvalene and their ho ¬ homologues selenium compounds as doping material seem Not to be used ¬ net. This substance class is for this reason not be ¬ vorzugt the purposes of the present invention In a whole series of documents from the patent literature doping substances are also proposed, which are activated by light irradiation
DE 10 2007 014 048 AI eine Mischung aus zumindest einem Mat-
rixmaterial und zumindest einem Dotierungsmaterial zur Her¬ stellung einer Schicht aus einem dotierten organischen Material, wobei das Dotierungsmaterial eine nicht aktive Dotan- denvorstufe ist, und ausgewählt ist aus Dimeren, Oligomeren, Polymeren, Dispiro-Verbindungen oder Polyzyklen eines Dotan- den in dem das Dotierungsmaterial durch Beaufschlagung von Aktivierungsenergie aufgespalten wird. DE 10 2007 014 048 AI a mixture of at least one mat rixmaterial and at least one dopant material for the manufacture ¬ position a layer of a doped organic material in which the dopant material is a non-active Dotan- denvorstufe, and is selected from dimers, oligomers, polymers, dispiro compounds and polycycles a Dotan- the in which the Doping material is split by applying activation energy.
Die WO 2007 107306 AI beschreibt die Verwendung heterocycli- scher Radikale oder Diradikale, deren Dimeren, Oligomeren,WO 2007 107306 A1 describes the use of heterocyclic radicals or diradicals whose dimers, oligomers,
Polymeren, Dispiroverbindungen und Polycyclen als Dotand zur Dotierung eines organischen halbleitenden Matrixmaterials, als Blockerschicht, als Ladungsinj ektionsschicht , als Elek¬ trodenmaterial, als Speichermaterial oder als Halbleiter- schicht selbst in elektronischen oder opto-elektronischen Bauelementen . Polymers, dispiro compounds and polycycles as a dopant for doping an organic semiconducting matrix material, as a blocking layer, as a charge injection layer, as Elek ¬ trodenmaterial, as a memory material or as a semiconductor layer itself in electronic or opto-electronic devices.
In weiteren Anmeldungen wie z.B. der EP 1837926 AI, EP In other applications, e.g. EP 1837926 AI, EP
1837926 Bl, US 2007 0252140-A1, EP 1837927 AI, WO 2007 107306 werden zudem heterocyclische Radikale oder Diradikale, deren Dimere, Oligomere, Polymere, Dispiroverbindungen und Poly¬ cyclen und deren Verwendung als organische halbleitende Mate¬ rialien sowie elektronische und optoelektronische Bauelemente offenbart . 1837926 Bl, US 2007 0252140-A1, EP 1837927 Al, WO 2007 107306 are also heterocyclic radicals or diradicals, their dimers, oligomers, polymers, dispiro compounds and poly ¬ cyclen and rials their use as organic semi-conductive Mate ¬ and electronic and optoelectronic devices disclosed ,
Weitere Ausgestaltungen dieses Konzeptes und dieser Verbindungsklasse finden sich in der US 2011 0108772 AI, Further embodiments of this concept and this class of compounds can be found in US 2011 0108772 AI,
WO 2007 107356 AI, US 2010 0233844 AI und der EP 2008 318 AI. Allen diesen Anmeldungen ist gemein, dass durch Bindungsspaltung in der Dotierungs-Substanz ein Radikal erzeugt wird, welches sich dann durch Abgabe eines Elektrons an die Elek- tronentransportschicht stabilisiert. Treibende Kraft ist die Re-Aromatisierung des Systems, indem sich das freie Elektro- nenpaar des Sauerstoffs im Pyranring bzw. des Stickstoffs am Imidazol an der Konjugation beteiligt und sich dadurch ein aromatisches 6n-Elektronensystem bildet. Durch die Bindungs¬ trennung entstehen dabei zwei unabhängige, räumlich getrennte
Einheiten, die unter normalen Umständen nicht mehr rekombinieren. Entscheidender Nachteil dieser vorgestellten Verbindungsklasse ist also, dass mit der Bindungsspaltung das Mole¬ kül dissoziiert und sich die beiden Molekülhälften irreversi- bei räumlich voneinander trennen. Durch den Dissoziationspro- zess kann die Lebensdauer des Bauelements begrenzt werden. WO 2007 107356 AI, US 2010 0233844 AI and EP 2008 318 AI. All these applications have in common that bond cleavage in the doping substance generates a radical which then stabilizes upon release of an electron to the electron transport layer. The driving force is the re-aromatization of the system, in which the free electron pair of the oxygen in the pyran ring and the nitrogen on the imidazole participate in the conjugation, thereby forming an aromatic 6n-electron system. By binding ¬ separation thereby creating two independent, physically separate Units that do not recombine under normal circumstances. Major disadvantage of this class of compounds presented is therefore that with the cleavage of the bond Mole ¬ kül dissociated and the two halves of the molecule irreversibly at spatially separate. The dissociation process can limit the life of the device.
Die US 2008 029 7035 AI hingegen beschreibt die Verwendung von Donor Carben-Intermediaten zu Verbesserung der Elektro- neninjektion und dem Elektronentransport in organisch elektronischen Komponenten wie organischen lichtemittierenden Dioden (OLEDs) , organischen Feldeffekttransistoren (OFETs) und organischen Photovoltaik-Komponenten, insbesondere organischen Solarzellen. In dieser Anmeldung werden zwar Donor Car- ben-Intermediate zu Injektionszwecken in Elektronentransport- schichten offenbart, charakteristisch für die vorgestellten Verbindungsklassen ist jedoch, dass diese (mehrere) Amin- substituenten am Donor-Carbenkörper aufweisen, welche nach der Abgabe eines Elektrons an die Elektronentransportschicht den Dotanden als chinoides System stabilisieren. Exemplarisch lässt sich dies durch den Reaktionsmechanismus einer Verbin¬ dung In contrast, US 2008 029 7035 A1 describes the use of donor carbene intermediates for improving electron injection and electron transport in organic electronic components such as organic light-emitting diodes (OLEDs), organic field-effect transistors (OFETs) and organic photovoltaic components, in particular organic solar cells , In this application, although donor carbene intermediates are disclosed for injection purposes in electron transport layers, it is characteristic of the classes of compounds presented that they have (several) amine substituents on the donor carbene body, which after the donation of an electron to the electron transport layer stabilize the dopant as a quinoidal system. This can be exemplified by the reaction mechanism of a connec ¬ tion
zeigen, wobei nach der Elektronenabgabe geladene n-Dotanden mit einer chinoiden Dotandenstruktur resultieren. Eine aroma- tische Stabilisierung der Dotanden nach Elektronenabgabe lässt sich nicht feststellen. show, wherein after the electron donation charged n-dopants with a quinoid dopant structure result. Aromatic stabilization of the dopants after electron donation can not be determined.
Die Aufgabe der vorliegenden Erfindung ist die im Stand der Technik auftretenden Nachteile auszuräumen und ein organisch elektronisches Bauelement mit einer organischen Elektronen- donor-Verbindung bzw. eine Elektronendonor-Verbindung bereitzustellen, welche zur Dotierung von Elektronen-Transport¬ schichten Verwendung findet und die Effektivität organisch elektrischer Bauelemente erhöht. The object of the present invention is to eliminate the disadvantages occurring in the prior art and to provide an organic electronic device with an organic electron donor compound or an electron donor compound, which is used for doping electron transport ¬ layers and the effectiveness organic increased electrical components.
Gelöst wird die Aufgabe durch den Einsatz von Substanzen, welche prinzipiell der unten dargestellten Struktur genügen. The problem is solved by the use of substances, which in principle satisfy the structure shown below.
Die Elektronendonor-Verbindung besteht aus mindestens zwei Carben-Gruppen Qi und Q2 (im allgemeinen Qx) , welche über eine Brücke (B) miteinander gekoppelt sind. Im einfachsten Fall besteht die Brücke (B) aus mindestens einer Doppelbindung. The electron donor compound consists of at least two carbene groups Qi and Q 2 (generally Q x ), which are coupled to each other via a bridge (B). In the simplest case, the bridge (B) consists of at least one double bond.
Eine Einfachbindung ist nicht erfindungsgemäß, da diese Bin¬ dung im Falle einer elektronischen Anregung dissoziiert. Desweiteren kann die Brücke (B) aber auch chinoide Ringsysteme
mit und ohne Heteroatom enthalten. Beispielhaft sind unten zwei chinoide Ringsysteme dargestellt, welche auch Bestand¬ teil komplexerer, annelierter Systeme sein können. A single bond is not inventive as these Bin ¬ dung dissociated in case of electronic excitation. Furthermore, the bridge (B) but also quinoid ring systems with and without heteroatom included. Two quinoid ring systems are shown below by way of example, which may also be part of more complex inventory ¬, fused-systems.
Das Heteroatom Z entspricht in diesem Fall 0, S, N-R und die Anzahl n der möglichen chinoiden Einheiten innerhalb der Brücke liegt zwischen n = 0 - 20. The heteroatom Z in this case corresponds to 0, S, N-R and the number n of possible quinoid units within the bridge is between n = 0-20.
Ein Beispiel für Substanzen gemäß der oben genannten Schemata und einer Doppelbindung als Brücke (B) lässt sich wie folgt darstellen: An example of substances according to the above schemes and a double bond as bridge (B) can be represented as follows:
Das freie Elektronenpaar des Kohlenstoffs wird über den The lone pair of electrons of the carbon is over the
Strich in den Edukten symbolisiert. Das Bis-Carben ist aus zwei einzelnen Carben-Gruppen aufgebaut. Die Brücke (B) im Produkt besteht in diesem Fall aus der Doppelbindung zwischen den beiden Carben-Gruppen. In der Literatur wird die Substanzklasse mit der oben darge¬ stellten Struktur mit einer Doppelbindung in der Brücke als Bis-Carben-Verbindung bezeichnet, da diese rein formal aus zwei Carbenen zusammengesetzt ist. Da die Bis-Carbene keine
Carben-Eigenschaften mehr aufweisen, werden sie im Folgenden, wie auch in der modernen Literatur, als „Super-Elektron-Donoren" (SED) bezeichnet, da sie befähigt sind, als Redukti¬ onsmittel zu wirken. Als Super-Donor werden Substanzen be- zeichnet, die in ihrer neutralen Form eine chinoide Struktur besitzen. Durch Elektronenabgabe werden die SED ganz oder teilweise aromatisch. Stroke symbolized in the educts. The bis-carbene is made up of two individual carbene groups. The bridge (B) in the product in this case consists of the double bond between the two carbene groups. In the literature, the substance class having a double bond in the bridge referred to as bis-carbene compound having the above Darge ¬ presented structure, as this is purely formal composed of two carbenes. Since the bis-carbenes no Carbene properties, they are hereinafter referred to as "super-electron donors" (SED), as well as in modern literature, since they are capable of acting as reducing ¬ onsmittel.As super-donor substances be - which have a quinoidal structure in their neutral form, and which become completely or partially aromatic by electron donation.
Erfindungsgemäß werden Systeme für die Dotierung von Elektro- nentransportschichten beansprucht, die aus zwei chinoiden Einheiten bestehen, die über eine Doppelbindung bzw. dazu analoge Brücke miteinander verknüpft sind. Ein derartiges System steht mit seinem Diradikal im Gleichgewicht ohne das dazu das Bindungsgerüst des Moleküls wie im Stand der Technik aufgezeigt gebrochen werden muss. Ist nun ein Elektronen- Akzeptor zugegen, kann das Bis-Carben ein Elektron abgeben. Es entsteht eine Radikal-Kation. Die Triebkraft für die Reak¬ tion ist die Re-Aromatisierung des Radikal-Kations. Da formal „nur" Elektronen übertragen und keine Bindungen gebrochen werden, ist dieser Prozess reversibel. Das heißt es stellt sich ein Gleichgewicht zwischen Donor, Radikalkation und (Radikal-) Akzeptor-Anion ein. Da die Radikalanionen die instabilste Spezies des Systems darstellen, kann im organischen Bauelement die Funktionalität folgendermaßen eingestellt wer- den: According to the invention, systems for the doping of electron transport layers are claimed, which consist of two quinoid units which are linked to one another via a double bond or to a bridge analogous thereto. Such a system is in equilibrium with its diradical without the need to break the binding framework of the molecule as indicated in the prior art. If an electron acceptor is present, the biscarbene can donate an electron. The result is a radical cation. The driving force for the reac ¬ tion is the re-flavoring of the radical cation. Since formally "only" electrons are transferred and no bonds broken, this process is reversible, meaning that the equilibrium between the donor, the radical cation, and the (radical) acceptor anion sets in. As the radical anions are the most unstable species in the system, they can In the organic component, the functionality can be set as follows:
a. Um den Akzeptor möglichst wenig zu belasten, sollte die Donorstärke der organischen Elektronendonor-Verbindung so an- gepasst sein, dass im Ruhezustandes des Bauelements sich nur wenige Radikale auf dem Akzeptor befinden. Dies kann die Le- bensdauer des Bauteils verlängern. a. In order to charge the acceptor as little as possible, the donor strength of the organic electron donor compound should be adapted so that only a few radicals are on the acceptor in the quiescent state of the device. This can extend the service life of the component.
b. Im Betrieb des Bauteils wird ein elektrisches Feld ange¬ legt, welche Elektronen aus dem Elektronentransporter zieht. In diesem Fall wird die organische Elektronendonor-Verbindung zusätzlich aktiviert. Es erfolgt ein Elektronenübergang vom Donor zum Akzeptor, welches die Gesamtelektronendichte und damit die Leitfähigkeit der Transportschicht erhöht.
Im SED besteht ein Gleichgewicht zwischen der Doppelbindungs¬ struktur und dem Diradikal. Dazu muss der SED nicht erst, wie im Stand der Technik beschrieben, durch Licht angeregt werden. Elektronentransportmaterialien sind schwache Elektrone- nakzeptoren. Ein allgemeines Beispiel für einen Elektronenakzeptor ist zum Beispiel BPhen (4, 7-di (phenyl) -1, 10- phenanthroline) . Die Elektronenakzeptoren nehmen zumindest zeitweise ein Elektron des Bis-Carbens auf. Treibende Kraft für die Abgabe des Elektrons ist hierbei die Re-Aromati- sierung der Elektronen abgebenden cyclischen organischenb. In operation of the device, an electric field is likely ¬ which draws electrons from the electron transporter. In this case, the organic electron donor compound is additionally activated. There is an electron transfer from the donor to the acceptor, which increases the total electron density and thus the conductivity of the transport layer. In the SED there is a balance between the double bond ¬ structure and the diradical. For this purpose, the SED does not first have to be excited by light, as described in the prior art. Electron transport materials are weak electron acceptors. A general example of an electron acceptor is, for example, BPhen (4,7-di (phenyl) -1,10-phenanthroline). The electron acceptors take up, at least temporarily, an electron of the biscarbene. The driving force for the release of the electron is the re-aromatization of the electron-donating cyclic organic
Elektronendonor-Verbindung . Es entsteht ein Radikalkation. Die Reaktion ist reversibel, da in der Elektronendonor-Verbindung keine Bindungsgerüste gespalten werden. Es findet nur ein partieller Ladungsaustausch statt. Electron donor connection. It creates a radical cation. The reaction is reversible, since in the electron donor compound no binding scaffolds are cleaved. There is only a partial charge exchange.
Beispielhaft ist unten der Elektronentransfer zweier Bis- Carben-Verbindungen dargestellt. Ein Bis-Carben besteht aus 2 analogen 6-Ringsystemen und ein weiteres Beispiel verdeut¬ licht den Elektronentransfer eines analogen 5-Ringsystems . Beide Bis-Carben-Verbindungen sind in der Lage reversibel, ein Elektron an einen organischen Elektronentransporter (in diesem Fall beispielhaft BPhen) abzugeben. Es bilden sich das jeweilige radikalische Anion/Kationpaar .
As an example, the electron transfer of two bis-carbene compounds is shown below. A bis-carbene comprises 2 analogue 6-membered ring systems and another example verdeut ¬ light electron transfer of an analog 5-membered ring system. Both bis-carbene compounds are capable of reversibly releasing an electron to an organic electron transporter (in this case exemplified by BPhen). The respective radical anion / cation pair are formed.
System wobei X = O oder N-R System where X = O or NR
Allgemein enthält ein Artikel von Wang et al . eine Zusammenfassung der elektrochemischen Eigenschaften über eine Doppel bindung verbrückter Carben-Gruppen ("Design of new neutral or ganic super-electron donors : a theoretical study", Wang, H.J et al., J. Phys. Org. Chem. 2010, 23, 75 - 83).
Generally, an article by Wang et al. a summary of the electrochemical properties of a double bond bridged carbene groups ("Design of new neutral or ganic super-electron donors: a theoretical study", Wang, HJ et al., J. Phys. Org. Chem. 2010, 23, 75 - 83).
Detaillierte Beschreibung der Erfindung Detailed description of the invention
Mit der vorliegenden Erfindung wird ein organisch elektronisches Bauelement umfassend mindestens zwei Elektroden und ei- ne organische Elektronentransportschicht enthaltend einen or¬ ganischen n-Dotanden zur Verfügung gestellt, welches dadurch gekennzeichnet ist, dass der n-Dotand mindestens zwei über eine Brücke (B) verbundene, cyclische Carben-Gruppen (Qx) enthält, welche bei elektronischer Anregung der Verbindung nicht dissoziieren und mindestens ein Carben-Grundkörper dabei aromatisiert und die Carben-Gruppen nicht über eine Me¬ tall-Liganden direkt miteinander verbunden sind. The present invention provides an organic electronic device is provided comprising at least two electrodes and an organic electron transport layer comprising one or ¬ ganischen n-dopants available, which is characterized in that the n-dopant at least two via a bridge (B) connected contains cyclic carbene groups (Q x ), which do not dissociate upon electronic excitation of the compound and aromatized at least one carbene base body and the carbene groups are not directly connected to each other via a Me ¬ tall ligands.
Unter den Begriff des organisch elektronisches Bauelementes werden auch polymerelektronische Bauelemente verstanden, hier beispielsweise organische Leuchtdioden, organische Solarzel¬ len, lichtemittierende elektrochemische Zellen, Photodioden und organische Feldeffekttransistoren. Die organische Elektronendonor-Verbindung ist aufgebaut aus oder kann mindestens zwei über eine kovalente Brücke verbun¬ dene Carben-Gruppen enthalten. Durch die Verbindung zweier Carben-Gruppen bildet sich ein sogenanntes Bis-Carben. Unter Carben-Gruppen sind elektrisch neutrale, instabile Elektro- nenmangelverbindungen zu verstehen, welche an einer Stelle ihres Gerüstes ein zweiwertiges Kohlenstoffatom mit einem Elektronensextett aufweisen. Carbene weisen also formal an einem Kohlenstoff ein freies Elektronenpaar auf, welches nicht an einer kovalenten Bindung beteiligt ist. Under the concept of organic electronic component and polymer electronic components are understood here as organic light emitting diodes, organic Solarzel ¬ len, light-emitting electrochemical cells, photo diodes and organic field effect transistors. The organic electron-donor compound is from constructed or may contain at least two verbun via a covalent bridge ¬ dene carbene groups. The combination of two carbene groups forms a so-called bis-carbene. Carbene groups are understood to mean electrically neutral, unstable electron deficient compounds which have a divalent carbon atom with an electron septum at one point of their skeleton. Carbenes thus formally have a free electron pair on a carbon, which is not involved in a covalent bond.
Verbinden sich zwei Carben-Einheiten direkt miteinander entsteht zwischen den beiden Carben-Gruppen eine Doppelbindung. Bevorzugter weise können die Carben-Gruppen aus cyclischen Kohlenwasserstoffen bestehen. Noch bevorzugter können die Carbene aus cyclischen Kohlenwasserstoffen bestehen, welche partiell ungesättigt sind und eine Resonanzstabilisierung des freien Carben-Elektronenpaars ermöglichen. Diese Resonanzsta¬ bilisierung kann zusätzlich auch über freie, d.h. nicht-
bindende Elektronenpaare von Heteroatomen (z.B. Sauerstoff, Schwefel, Selen oder Tellur, Stickstoff, Phosphor oder Arsen etc.) erfolgen, welche innerhalb des cyclischen Gerüstes der Carben-Gruppen eingebaut sein können. Bevorzugt ist der Ein- bau von Stickstoff als Heteroatom. Am bevorzugtesten ist, dass die Carben-Gruppen eine chinoide Struktur aufweisen können . If two carbene units connect directly with each other, a double bond is formed between the two carbene groups. Preferably, the carbene groups may consist of cyclic hydrocarbons. More preferably, the carbenes may consist of cyclic hydrocarbons which are partially unsaturated and allow for resonance stabilization of the free carbene electron pair. This Resonanzsta ¬ bilisierung can additionally also free, ie non bonding electron pairs of heteroatoms (eg oxygen, sulfur, selenium or tellurium, nitrogen, phosphorus or arsenic, etc.) take place, which can be incorporated within the cyclic skeleton of the carbene groups. Preference is given to the incorporation of nitrogen as a heteroatom. Most preferred is that the carbene groups can have a quinoid structure.
Ein Molekül besitzt eine „chinoide Struktur", wenn dessen chemischer Aufbau ein Strukturelement des Chinons enthält. Chinone sind Benzolderivate, in denen unter Aufhebung der Aromatizität des Ringes an zwei Kohlenstoffatomen die Substi- tuenten durch doppelbindigen Sauerstoff ersetzt sind. Unter chinoiden Verbindungen im Sinne dieser Erfindung werden auch Verbindungen erfasst, in denen eine oder beide Carbonyl- Gruppen durch =NH, =NOH, =N2 oder =CH2 ersetzt wurden. A quinone is a benzene derivative in which the substituents are replaced by double-bond oxygen, thus eliminating the aromaticity of the ring on two carbon atoms The invention also covers compounds in which one or both carbonyl groups have been replaced by = NH, = NOH, = N 2 or = CH 2.
Die chemische Verbindung, d.h. Kopplung der beiden Carben- Gruppen kann bevorzugter weise zu einer organischen Elek- tronendonor-Verbindung führen, welche in seiner Gesamtheit elektrisch neutral ist und bevorzugt eine chinoide Struktur aufweist. Da innerhalb dieser Bis-Carben-Struktur die Carben- Gruppen keine Carben-Eigenschaften mehr besitzen, wird diese Art von Verbindungen in der modernen Literatur auch als „Su- per-Elektron-Donor" (SED) bezeichnet. The chemical compound, i. Coupling of the two carbene groups may preferably lead to an organic electron donor compound which is electrically neutral in its entirety and preferably has a quinoid structure. Since within this bis-carbene structure the carbene groups no longer possess any carbene properties, this type of compound is also referred to in modern literature as the "super-electron donor" (SED).
Die SED können an jeder bindungsfähigen Stelle des Grundkörpers substituierte oder unsubstituierte Homozyklen oder Hete- rozyklen aufweisen. Vorzugsweise können die Substituenten aus substituierten und unsubstituierter Heterocyclen wie z.B. Fu- ran, Thiophen, Pyrrol, Oxazol, Thiazol, Imidazol, Isoxazol, Isothazol, Pyrazol, Pyridin, Pyrazin, Pyrimidin, 1,3,6 Tria- zin, Pyrylium, alpha-Pyrone, gamma-Pyrone, Benzofuran, Ben- zothiophen, Indol 2H-Isoindol, Benzothiazol, 2-benzothiophene, lH-benzimidazole, ΙΗ-benzotriazole, 1, 3.benzoxazole, 2- benzofuran, 7H-purine, Chinolin, Iso-Chinolin, Quinazoline, Quinoxaline, phthalazine, 1 , 2 , 4-benzotriazine, Pyrido[2,3- d] pyrimidine, Pyrido [3, 2-d] pyrimidine, pteridine, acridine,
phenazine, benzo [g] pteridine, 9H-carbazole und Bipyridin und deren Derivate ausgewählt werden. The SEDs can have substituted or unsubstituted homocycles or hetero cycles at each bondable site of the main body. The substituents may preferably be selected from substituted and unsubstituted heterocycles, such as, for example, furan, thiophene, pyrrole, oxazole, thiazole, imidazole, isoxazole, isothazole, pyrazole, pyridine, pyrazine, pyrimidine, 1,3,6-triazine, pyrylium, alpha- Pyrone, gamma-pyrone, benzofuran, benzothiophene, indole 2H-isoindole, benzothiazole, 2-benzothiophene, 1H-benzimidazole, ΙΗ-benzotriazole, 1, 3-benzoxazole, 2-benzofuran, 7H-purine, quinoline, iso-quinoline , Quinazolines, quinoxalines, phthalazines, 1, 2, 4-benzotriazines, pyrido [2,3-d] pyrimidines, pyrido [3, 2-d] pyrimidines, pteridines, acridines, phenazines, benzo [g] pteridines, 9H-carbazoles and bipyridine and derivatives thereof.
Beispielhaft kommen als Homozyklen zur Substitution der bin- dungsfähigen Stellen des Grundkörpers Methyl-, Ethyl- verallgemeinert unverzweigte, verzweigte, kondensierte (Decahydro- naphthyl-) , ringförmige (Cyclohexyl- ) oder ganz oder teilwei¬ se substituierte Alkylreste (Cl - C20) in Frage. Die Alkyl- reste können allgemein Ethergruppen (Ethoxy-, Methoxy-, usw.), Ester-, Amid-, Amine, Carbonatgruppen etc. oder auch Halogene, insbesondere CN und F enthalten. Im Sinne der Er¬ findung sind auch substituierte oder unsubstituierte alipha¬ tische Ringe bzw. Ringsysteme, wie Cyclohexyl geeignet. Ins¬ besondere können diese Substituenten verbrückend wirken. Der Substituent R ist nicht auf gesättigte Systeme beschränkt, sondern kann auch substituierte bzw. unsubstituierte Aromaten wie Phenyl, Diphenyl, Naphthyl, Phenanthryl bzw. Benzyl etc. beinhalten . Alle Substituenten R des Verbindungs-Grundkörpers können un¬ abhängig voneinander gewählt werden. Exemplary suitable as Homo cycles for the substitution of the binding sites capable of the base body methyl, ethyl generalized straight, branched, condensed (decahydro-naphthyl), annular (cyclohexyl) or wholly or teilwei ¬ se substituted alkyl (Cl - C20) in Question. The alkyl radicals may generally contain ether groups (ethoxy, methoxy, etc.), ester, amide, amines, carbonate groups, etc., or else halogens, in particular CN and F. For the purposes of the invention It ¬ also substituted or unsubstituted alipha ¬ diagram rings or ring systems such as cyclohexyl are suitable. Ins ¬ special these substituents may have a bridging effect. The substituent R is not limited to saturated systems, but may also include substituted or unsubstituted aromatics such as phenyl, diphenyl, naphthyl, phenanthryl or benzyl, etc. All substituents R of the compound main body can be chosen independently of one another.
Die SEDs können ganz allgemein als Reduktionsmittel wirken. Im Falle einer elektronischen Anregung z.B. durch Licht, thermische Strahlung oder das Anlegen einer Spannung oder durch Selbstaktivierung ist die Verbindung in der Lage ein Elektron unter Beibehaltung ihres Bindungsgerüstes an einen Akzeptor abzugeben. Die Verbindung kann daraufhin ein resonanzstabilisiertes Kation bilden. Mit Elektronenakzeptoren kann sie gemeinhin Salze bilden. The SEDs can generally act as a reducing agent. In the case of electronic stimulation e.g. by light, thermal radiation or the application of a voltage or by self-activation, the compound is capable of donating an electron while retaining its binding skeleton to an acceptor. The compound can then form a resonance-stabilized cation. It can commonly form salts with electron acceptors.
Die Elektronentransportschichten können Elektronentransport- materialien, Elektronenakzeptoren und organische Elektronen- donor-Verbindungen enthalten. The electron transport layers may include electron transport materials, electron acceptors, and organic electron donor compounds.
Als Elektronentransportmaterialien zur Aufnahme von Elektronen können bevorzugt ausgewählt werden 2, 2 ',2" -(1,3,5- Benzinetriyl ) -tris ( 1-phenyl-l-H-benzimidazole) , 2- (4-
Biphenylyl) -5- (4-tert-butylphenyl) -1, 3, 4-oxadiazole; 2, 9- Dimethyl-4, 7-diphenyl-l, 10-phenanthroline (BCP) , 8- Hydroxyquinolinolato-lithium; 4- (Naphthalen-l-yl) -3, 5- diphenyl-4H-l , 2,4-triazole; l,3-Bis[2-(2,2'-bipyridine-6-yl)- 1,3, 4-oxadiazo-5-yl ] benzene; 4, 7-Diphenyl-l , 10-phenanthroline (BPhen) ; 3- (4-Biphenylyl) -4-phenyl-5-tert-butylphenyl-l , 2, 4- triazole ;Bis (2-methyl-8-quinolinolate) -4-2, 2 ', 2 "- (1,3,5-triethylene triyl) tris (1-phenyl-1H-benzimidazoles), 2- (4-electron) can be preferably selected as electron transporting materials for the absorption of electrons. Biphenylyl) -5- (4-tert-butylphenyl) -1, 3, 4-oxadiazoles; 2, 9-dimethyl-4,7-diphenyl-l, 10-phenanthroline (BCP), 8-hydroxyquinolinolato-lithium; 4- (naphthalen-1-yl) -3, 5-diphenyl-4H-1, 2,4-triazoles; l, 3-bis [2- (2,2'-bipyridine-6-yl) -1,3,4-oxadiazo-5-yl] benzene; 4,7-diphenyl-l, 10-phenanthroline (BPhen); 3- (4-biphenylyl) -4-phenyl-5-tert-butylphenyl-1,2,2,4-triazoles; bis (2-methyl-8-quinolinolates) -4-
(phenylphenolato) aluminium; 6, 6 ' -Bis [5- (biphenyl-4-yl) -1,3,4- oxadiazo-2-yl ] -2,2' -bipyridyl ; 2-phenyl-9, 10 -di (naphthalen-2- yl ) -anthracene ; 2, 7-Bis [2- (2, 2 ' -bipyridine- 6-yl ) -1, 3, 4- oxadiazo-5-yl ] -9, 9-dimethylfluorene ; 1, 3-Bis [2- (4-tert- butylphenyl) -1,3, 4-oxadiazo-5-yl ] benzene; 2- (naphthalen-2- yl) -4, 7-diphenyl-l, 10-phenanthroline; 2, 9-Bis (naphthalen-2- yl) -4, 7-diphenyl-l, 10-phenanthroline; Tris (2,4, 6-trimethyl-3- (pyridin-3-yl ) phenyl ) borane ; l-methyl-2- (4- (naphthalen-2- yl) phenyl) -lH-imidazo [4, 5-f ] [ 1 , 10 ] phenanthroline ; Phenyl- dipyrenylphosphine oxide; Naphtahlintetracarbonsäuredian- hydrid bzw. dessen Imide; Perylentetracarbonsäuredianhydrid bzw. dessen Imide; Materialien basierend auf Silolen mit ei- ner Silacyclopentadieneinheit oder weitere Heterozyklen wie in der EP 2 092 041 Bl beschrieben. (phenylphenolato) aluminum; 6, 6 '- bis [5- (biphenyl-4-yl) -1,3,4-oxadiazol-2-yl] -2,2'-bipyridyl; 2-phenyl-9,10-di (naphthalen-2-yl) -anthracenes; 2, 7-bis [2- (2,2'-bipyridine-6-yl) -1, 3, 4-oxadiazol-5-yl] -9,9-dimethylfluorene; 1, 3-bis [2- (4-tert-butylphenyl) -1,3,4-oxadiazo-5-yl] benzene; 2- (naphthalen-2-yl) -4,7-diphenyl-l, 10-phenanthrolines; 2,9-bis (naphthalen-2-yl) -4,7-diphenyl-l, 10-phenanthrolines; Tris (2,4,6-trimethyl-3- (pyridin-3-yl) phenyl) boranes; 1-methyl-2- (4- (naphthalen-2-yl) phenyl) -1H-imidazo [4, 5-f] [1, 10] phenanthrolines; Phenyldipyrenylphosphine oxides; Naphthalenetetracarboxylic dianhydride or its imides; Perylenetetracarboxylic dianhydride or its imides; Materials based on silanols with a silacyclopentadiene unit or further heterocycles as described in EP 2 092 041 Bl.
Elektronenakzeptoren im Sinne der vorliegenden Erfindung können 2,3,5, 6-tetrafluoro-7 , 7,8, 8-tetracyano-quinodimethane, Pyrazino [2, 3-f ] [ 1 , 10 ] phenanthroline-2 , 3-dicarbonitrile und Dipyrazino [2, 3-f: 2 ' , 3 ' -h] quinoxaline-2, 3, 6, 7, 10, 11- hexacarbonitrile sein. Electron acceptors for the purposes of the present invention, 2,3,5, 6-tetrafluoro-7, 7,8, 8-tetracyano-quinodimethane, pyrazino [2, 3-f] [1, 10] phenanthroline-2, 3-dicarbonitrile and Dipyrazino [2,3-f: 2 ', 3'-h] quinoxaline-2, 3, 6, 7, 10, 11-hexacarbonitrile.
Zu Dotierungszwecken können die organischen Elektronendonor- Verbindungen zusammen mit einem Elektronenakzeptor bzw. den Elektronentransportmaterialien auf eine Schicht aufgebracht werden. Dabei können die Verbindungen sowohl in der Gasphase, als auch der Flüssigphase verarbeitet werden. Bei der Gaspha- senabscheidung werden sowohl Dotierstoff als auch Matrixmate- rial gemeinsam, bevorzugt aus unterschiedlichen Quellen im Hochvakuum verdampft und als Schicht abgeschieden. Bei der Verarbeitung aus der Flüssigphase werden der organische For doping purposes, the organic electron donor compounds may be applied to a layer together with an electron acceptor (s). The compounds can be processed both in the gas phase, as well as the liquid phase. In the gas phase separation, both the dopant and the matrix material are vaporized together, preferably from different sources in a high vacuum, and deposited as a layer. During processing from the liquid phase of the organic
Elektronendonor und das Matrixmaterial in einem Lösungsmittel
gelöst und mittels Drucktechniken, Spincoating, Rakeln, Slot- coating etc. abgeschieden. Die fertige Schicht wird durch Verdampfen des Lösungsmittels erhalten. Dabei lassen sich durch die unterschiedlichen Massenverhältnisse von organi- scher Elektronendonor-Verbindung zum Elektronenakzeptor beliebige Dotierungsverhältnisse einstellen. Electron donor and the matrix material in a solvent dissolved and deposited by means of printing techniques, spin coating, knife coating, slot coating, etc. The finished layer is obtained by evaporation of the solvent. It can be adjusted by the different mass ratios of organic electron donor compound to the electron acceptor any doping ratios.
Erfindungsgemäß sind die beiden Carbene nicht über einen Me¬ tall-Liganden direkt miteinander verbunden oder verbrückt. Dies schließt aber nicht aus, dass eine oder beide Carben- Gruppen innerhalb ihres Bindungsgerüstes einen Metall-Li¬ ganden aufweisen können. Als metallhaltige Substituenten können die erfindungsgemäßen organischen Elektronendonor-Verbin- dungen beispielhaft, aber nicht einschränkend Ferrocenyl, Cyclopentadienyl-dicarbonyleisen oder Phthalocyanine und Porphyrine enthalten. According to the invention, the two carbenes are not directly connected or bridged via a metal ligand. However, this does not exclude that one or both carbene groups may have a metal Li ¬ ligands within their binding scaffold. As metal-containing substituents, the organic electron donor compounds according to the invention may contain, by way of example but not limitation, ferrocenyl, cyclopentadienyl dicarbonyl iron or phthalocyanines and porphyrins.
In einer besonderen Ausführungsform ist das organisch elektronische Bauelement dadurch gekennzeichnet, dass die Carben- Gruppen des organischen n-Dotanden durch eine Doppelbindung direkt miteinander verbunden sind. Besonders erfindungsgemäß wird im Falle einer elektronischen Anregung das Bindungsgerüst der organischen Elektronendonor-Verbindung nicht gespalten. Das heißt die beiden Carbene sind im elektronisch ange- regten Zustand immer noch über eine Einfachbindung miteinander verbunden und das Molekül dissoziiert nicht. Zur n-Do- tierung elektrischer Transportschichten gelten Verbindungen folgenden Typs als besonders erfindungsgemäß: In a particular embodiment, the organic electronic component is characterized in that the carbene groups of the organic n-dopant are directly connected to one another by a double bond. Particularly according to the invention, in the case of electronic excitation, the binding skeleton of the organic electron donor compound is not cleaved. That is, the two carbenes are still connected by a single bond in the electronically excited state and the molecule does not dissociate. For the n-doping of electrical transport layers, compounds of the following type are considered to be particularly inventive:
22 23 24 22 23 24
Die oben dargestellten Verbindungen zeigen beispielhaft und nicht einschränkend Grundverbindungen organischer Elek- tronendonor-Verbindung mit einer Doppelbindung als Brücke The compounds shown above are illustrative and not limiting of basic organic electron donor compound compounds having a double bond as a bridge
(B) . Die in diesen Verbindungen aufgeführten Variablen bedeuten m = 2 - 4, n = 2 - 4 ; Ri, R2, R3, R4 = Wasserstoff oder Methyl oder COMe oder CC^Et . Anstelle der Wasserstoffatome können beliebige organische oder metallorganische Substituen- ten angebracht sein. Besonders bevorzugt im Sinne der Erfin¬ dung sind diejenigen Varianten, die anstelle der Wasserstoffe (H) Reste (R) wie oben zur Substitution des Grundkörpers der SEDs aufgeführt aufweisen. Besonders bevorzug sind zudem die Verbindungen mit Stickstoff als Heteroatom im Grundgerüst der Verbindung. (B). The variables listed in these compounds mean m = 2 - 4, n = 2 - 4; Ri, R2, R3, R4 = hydrogen or methyl or COMe or CC ^ Et. Instead of the hydrogen atoms, any organic or organometallic substituents may be attached. Particularly preferred according to the invention are the those variants which have in place of the hydrogens (H) radicals (R) as listed above for the substitution of the base body of the SEDs. Particularly preferred are also the compounds with nitrogen as the heteroatom in the backbone of the compound.
In einer besonderen Ausführungsform der Erfindung ist das organisch elektronische Bauelement dadurch gekennzeichnet, dass die Brücke (B) des n-Dotanden mindestens ein chinoides Ring- System enthält. Die chinoiden Ringsysteme können entweder rein auf Kohlenstoff basieren oder Heteroatome enthalten. Zu¬ dem können die verbrückenden chinoiden Einheiten Bestandteil komplexer annellierter Systeme sein. Die Anzahl der in der Brücke enthaltenen chinoiden Einheiten kann zwischen 0 und 20 Einheiten liegen. Liegt keine chinoide Einheit zwischen den Carben-Gruppen vor, so sind die beiden Carbene zwangsläufig über eine Doppelbindung direkt miteinander verbunden. In a particular embodiment of the invention, the organic electronic component is characterized in that the bridge (B) of the n-dopant contains at least one quinoid ring system. The quinoid ring systems can either be based purely on carbon or contain heteroatoms. In addition , the bridging quinoid units may be part of complex fused systems. The number of quinoid units in the bridge can be between 0 and 20 units. If there is no quinoid unit between the carbene groups, then the two carbenes are bound together directly by a double bond.
Eine weitere, besondere Ausführungsform der Erfindung bein- haltet das organisch elektronische Bauelement dadurch gekenn¬ zeichnet, dass wenigstens eine der Carben-Gruppen des organi¬ schen n-Dotanden einen 5- oder 6-Ring enthält, welcher min-
destens 1 Heteroatom aufweist. Neben den oben aufgeführten Bis-Carben-Verbindungen ist in folgender Zeichnung eine erfindungsgemäße cyclische Carbenverbindung dargestellt, welche aus einem 5-Ring besteht und weitere Verbindungen, welche ei¬ nen cyclischen 5-Ring enthalten. Die Struktur mit dem Buchstaben (A) bezeichnet dabei ein anneliertes aromatisches Sys¬ tem (Verbindung 27 + 28 + 29) . Leg A further particular embodiment of the invention constitutes the organic electronic device characterized labeled in ¬ characterized in that at least one of the carbene groups of the organic ¬ rule n-type dopant includes a 5- or 6-ring, which min- has at least 1 heteroatom. Apart from the above bis-carbene compounds, a cyclic carbene compound of the invention in the following diagram is shown which consists of a 5-membered ring and contain other compounds, which ei ¬ NEN cyclic 5-ring. The structure with the letter (A) designates a fused aromatic Sys tem ¬ (compound 27 + 28 + 29).
In einer weiteren Ausführungsform des organisch elektronischen Bauelements kann der 5-Ring des organischen n-Dotanden durch eine zusätzliche Brücke (gestrichelte Linie Verbindun¬ gen 28 + 29) mit der zweiten Carben-Gruppe verbunden sein. Desweiteren kann in einer besonderen Ausführungsform die Carben-Gruppe über zwei zusätzliche Verbindungen des Ringsystems mit der anderen Carben-Gruppe verbunden sein (Verbindung 29) . In a further embodiment of the organically electronic component, the 5-ring of the organic n-dopant can be connected to the second carbene group by an additional bridge (dashed line Verbindun ¬ gen 28 + 29). Furthermore, in a particular embodiment, the carbene group can be connected via two additional compounds of the ring system with the other carbene group (compound 29).
Im obigen Beispiel bezeichnet Y entweder 0, S bzw. N-R, wobei die Derivate N-R erfindungsgemäß besonders bevorzugt sind. In the above example, Y denotes either O, S or N-R, the derivatives N-R being particularly preferred according to the invention.
Die im obigen Beispiel genannten Substituenten R können äquivalent zu den schon aufgeführten Substituenten der bindungs- fähigen Stellen des Grundkörpers gewählt werden. The substituents R mentioned in the above example can be selected to be equivalent to the substituents already listed of the bondable sites of the main body.
In einer besonderen Ausführungsform des organisch elektronischen Bauelements ist der organische n-Dotand dadurch gekenn¬ zeichnet, dass die Carben-Gruppen aus gleichen 5-Ringen be- stehen, welche in ihrem Grundgerüst mindestens 1 Heteroatom aufweisen. Von dieser Substanzklasse ausgeschlossen sind allerdings die Tetrathialfulvalene und deren Derivate. In a particular embodiment of the organic electronic device of the organic n-type dopant is characterized labeled in ¬ characterized in that the carbene groups from the same 5-rings are sawn, which have at least 1 heteroatom in the skeleton. Excluded from this class, however, are the Tetrathialfulvalene and their derivatives.
In weiteren besonderen Ausführungsformen des organisch elek- tronischen Bauelements ist der organische n-Dotand dadurch
gekennzeichnet, dass wenigstens eine der Carben-Gruppen einen 6-Ring enthält. Beispiele für diese besonderen Ausführungs¬ formen sind in nachfolgender Zeichnung angegeben: In further particular embodiments of the organic electronic component, the organic n-dopant is thereby in that at least one of the carbene groups contains a 6-membered ring. Examples of these special execution ¬ forms are given in the following drawing:
Die ersten beiden Strukturformeln (Verbindung 30 + 30a) zeigen eine cyclische Carben-Gruppe, welche sich aus einem Hete- roaromaten ableitet. Das Heteroatom Y steht dabei an nicht mit einer Doppelbindung konjugierten Position. Die mit Z - Positionen ( Z i bis Z 4 ) bezeichnen Atome, welche durch eineThe first two structural formulas (compound 30 + 30a) show a cyclic carbene group derived from a heteroaromatic compound. The heteroatom Y stands at not conjugated with a double bond position. The Z - positions (Z i to Z 4 ) denote atoms, which by a
Doppelbindung gebunden und als C-H, C-D, C-R (die Definition ist äquivalent der Definition von R der substituierten 5- Ringe) oder N ausgeführt sein können. Für die Positionen Z± besteht die Möglichkeit, dass sich benachbarte Z (Z± und Z±+i) zu höher annelierten Systemen zusammensetzen können (Naphthalin, Anthracen etc., bzw. deren Heteroanalogen) . Double bond bound and as C-H, C-D, C-R (the definition is equivalent to the definition of R of the substituted 5-rings) or N can be executed. For the positions Z ± there is the possibility that neighboring Zs (Z ± and Z ± + i) may be assembled into higher-annealed systems (naphthalene, anthracene, etc., or their hetero analogues).
Die gestrichelten Bögen deuten diejenigen Positionen an, an denen eine Verbrückung zu anderen Carben-Gruppen möglich ist. Für die Verbrückung zu anderen Carben-Gruppen lassen sich prinzipiell drei Möglichkeiten unterscheiden. In der ersten Möglichkeit befindet sich die Brücke am nicht-aromatischen Atom oder zweitens an einem der aus Z-gebildeten C-R oder drittens aus einer Kombination der unterschiedlichen Z - Positionen (i. und i., ii. und ii., i. und ii.) .
In einer weiteren, bevorzugten Ausführungsform können beide Carben-Gruppen gleich aufgebaut sein und jeweils mindestens einen 5- oder 6-Ring enthalten. Je nach Ausgestaltung der Brückeneinheit wäre das Bis-Carben in diesem besonderen Fall dann spiegel-symmetrisch . The dashed arcs indicate those positions where bridging to other carbene groups is possible. In principle, three possibilities can be distinguished for the bridging to other carbene groups. In the first possibility, the bridge is located on the non-aromatic atom or, secondly, on one of the Z-formed CRs or, thirdly, on a combination of the different Z-positions (i and i, ii and ii, i and ii .). In a further, preferred embodiment, both carbene groups can be of identical construction and each contain at least one 5- or 6-membered ring. Depending on the configuration of the bridge unit, the bis-carbene would then be mirror-symmetrical in this particular case.
In einer besonderen Ausführungsform des organisch elektronischen Bauelements ist der organische n-Dotand dadurch gekenn- zeichnet, dass wenigstens eine der Carben-Gruppen ein Tetra- zinodihetaren enthält. Die Tetrazinodihetarene wurden 1986 durch Eichenberger und Balli synthetisiert (Eichenberger, T. und Balli H., Helv. Chim Acta 1986, 69,1521 -1530.). Diese Substanzklasse besteht formal aus einem s-Tetrazin auf der Oxidationsstufe eines 1, 4-Dihydro-l, 2, 4, 5-tetrazins und ankondensierten heterocyclischen Ringsystemen wie z.B. Pyridin, Chinolin und Isochinolin. Die planaren Stickstoffatome am Brückenkopf des Tetrazinrings beteiligen sich mit jeweils zwei Elektronen am π-System und führen so zu einer Überkom- pensation des Akzeptorcharakters der pyridinartigen Stickstoffatome. Diese Substanzklasse lässt sich auch als „Weitz- Typ"-Donor einordnen. In a particular embodiment of the organically electronic component, the organic n-dopant is characterized in that at least one of the carbene groups contains a tetrazine iodide. The Tetrazinodihetarene were synthesized in 1986 by Eichenberger and Balli (Eichenberger, T. and Balli H., Helv. Chim Acta 1986, 69, 1521-1530.). This class of compounds is formally constituted by an s-tetrazine at the oxidation state of a 1,4-dihydro-1,2,3,5-tetrazine and fused heterocyclic ring systems such as e.g. Pyridine, quinoline and isoquinoline. The planar nitrogen atoms on the bridgehead of the tetrazine ring participate in the π system with two electrons, thus leading to an overcompensation of the acceptor character of the pyridine-type nitrogen atoms. This substance class can also be classified as a "Weitz type" donor.
In einer weiteren Ausführungsform des organisch elektroni- sehen Bauelements kann der organische n-Dotand dadurch ge¬ kennzeichnet sein, dass sie ein Bis-Pyran enthält oder aus einem Bis-Pyran besteht. Die Synthese der Bis-Pyrane wurde u.a. von A. Kanitz ausgearbeitet. Als Beispiel zur Synthese der Bis-Pyrane sei hier der Offenbarungsgehalt der Patentan- meidung WO2007/028738 hinzugefügt. In another embodiment of the organic electronic device see the organic n-type dopant may be ge ¬ is characterized in that it contains or consists of a bis-pyran a bis-pyran. The synthesis of bis-pyrans was elaborated by A. Kanitz, among others. As an example of the synthesis of bis-pyrans, the disclosure content of patent application WO2007 / 028738 may be added here.
In noch einer weiteren erfindungsgemäßen Ausführungsform des organisch elektronischen Bauelements ist der organische n- Dotand dadurch gekennzeichnet, dass sie ein 2,2λ,6,6λ- Tetraphenyl-4 , 4 λ -dipyran enthält oder aus einem 2,2λ,6,6λ- Tetraphenyl-4 , 4 λ -dipyran besteht .
Eine weitere bevorzugte Ausführungsform des organisch elektronischen Bauelements ist dadurch gekennzeichnet, dass die Carben-Gruppen des organischen n-Dotanden zusätzlich über mindestens eine zweite Brücke miteinander verbunden sind. Einige, nicht limitierende Beispiele für mehrfach verbrückte Super-Donoren sind oben angegeben (zum Beispiel die Verbindungen 1, 3, 5, 6, 7, 9, 15) . Desweiteren sind prinzipielle zusätzliche Verbrückungsmöglichkeiten bei 5- oder 6-atomigen cyclischen Verbindungen oben angegeben (zum Beispiel Verbin- düngen 28, 29 oder Verbindungen 32, 33) . In yet another embodiment of the invention the organic electronic device of the organic n-type dopant is characterized in that it comprises a 2.2 λ, 6.6 λ - contains tetraphenyl-4, 4 λ -dipyran or from a 2.2 λ, 6 , 6 λ - tetraphenyl-4, 4 λ -dipyran. A further preferred embodiment of the organic electronic component is characterized in that the carbene groups of the organic n-dopant are additionally connected to one another via at least one second bridge. Some non-limiting examples of multiple bridged super donors are given above (for example, compounds 1, 3, 5, 6, 7, 9, 15). Furthermore, principle additional bridging possibilities for 5- or 6-atom cyclic compounds are given above (for example compound fertilize 28, 29 or compounds 32, 33).
Erfindungsgemäß sind zudem organische Elektronentransport¬ schichten enthaltend einen organischen n-Dotanden, dadurch gekennzeichnet, dass der n-Dotand mindestens zwei über eine Brücke (B) verbundene, cyclische Carben-Gruppen (QX) enthält, welche bei elektronischer Anregung der Verbindung nicht dissoziieren und mindestens ein Carben-Grundkörper dabei aromatisiert und die Carben-Gruppen nicht über einen Metall- Liganden direkt miteinander verbunden sind. Insbesondere sei dabei explizit offenbart, das einzelne oder Kombinationen der Eigenschaften und Ausgestaltungen der n-Dotanden der erfindungsgemäßen Elektronentransportschichten denjenigen entsprechen, welche weiter oben im Rahmen der Beschreibung der n- Dotanden der erfindungsgemäßen organisch elektronischen Bau- elemente beschrieben sind. Organic electron transport also According to the invention ¬ layers containing an organic n-dopant, characterized in that the n-dopant at least two via a bridge (B) connected, cyclic carbene groups (QX), which do not dissociate upon electronic excitation of the connection and at least one carbene base body is aromatized and the carbene groups are not connected directly to one another via a metal ligand. In particular, it is explicitly disclosed here that the individual or combinations of the properties and configurations of the n-dopants of the electron transport layers according to the invention correspond to those which are described above in the context of the description of the n-dopants of the organic electronic components according to the invention.
Desweiteren erfindungsgemäß ist ein organischer Elektronen- transportschicht n-Dotand, gekennzeichnet dadurch, dass der n-Dotand mindestens zwei über eine Brücke (B) verbundene, cyclische Carben-Gruppen (QX) enthält, welche bei elektroni¬ scher Anregung der Verbindung nicht dissoziieren und mindestens ein Carben-Grundkörper dabei aromatisiert und die Car¬ ben-Gruppen nicht über einen Metall-Liganden direkt miteinander verbunden sind. Insbesondere sei dabei explizit offen- bart, dass einzelne oder Kombinationen der Eigenschaften und Ausgestaltungen der organischen Elektronentransportschicht n- Dotanden denjenigen entsprechen, welche weiter oben im Rahmen
der Beschreibung der n-Dotanden der erfindungsgemäßen organisch elektronischen Bauelemente beschrieben sind. Furthermore, according to the invention is an organic electron transport layer an n-dopant, characterized in that the n-dopant at least two via a bridge (B) connected, cyclic carbene groups (QX), which do not dissociate in electronic ¬ shear excitation of the connection and at least one carbene-flavored base body case and the Car ¬ ben-groups are not directly connected together via a metal ligand. In particular, it should be explicitly disclosed here that individual or combinations of the properties and configurations of the organic electron transport layer correspond to n-dopants which are above in the context the description of the n-dopants of the organic electronic components according to the invention are described.
Desweiteren lassen sich die erfindungsgemäßen organisch elektronischen Bauelemente zur Herstellung von polymerelektronischen Bauelementen verwenden. Darunter fallen alle Verarbeitungstechnologien zur Herstellung organischer Leuchtdioden, organischer Solarzellen, lichtemittierender elektrochemischer Zellen, Photodioden und organischer Feldeffekttran- sistoren.
Furthermore, the organically electronic components according to the invention can be used for the production of polymer-electronic components. This includes all processing technologies for the production of organic light emitting diodes, organic solar cells, light emitting electrochemical cells, photodiodes and organic field effect transistors.
Beispiele Examples
I . Synthese I. synthesis
I.A) Zweistufige Synthese von 2 , 2 ' , 6 , 6 ' -Tetraphenyl-4 , 4 ' - dipyran (GBP) I.A) Two-Step Synthesis of 2, 2 ', 6, 6' -Tetraphenyl-4,4'-dipyran (GBP)
Die Synthese des GBPs erfolgt zweistufig. The synthesis of the GBP is two-tiered.
I.A-1) Synthese von Diphenylpyrrylium-perchlorat I.A-1) Synthesis of diphenylpyrrylium perchlorate
30 g Acetophenon (0,25 mol) werden in 250 g Ethylorthoacetat (1,68 mol) gelöst und zum Sieden gebracht. Daraufhin werden 18 g 70%iger Perchlorsäure (0,13 mol) langsam zu der Lösung getropft. Die Temperatur wird auf 80 °C reduziert und die Re¬ aktion über Nacht fortgeführt. Der entstandene Niederschlag wird nach dem Abkühlen abgesaugt und mit Ether gewaschen. Man erhält Diphenylpyrrylium-Perchlorat mit einem Schmelzpunkt von 222 °C nach folgendem Reaktionsschema als Reaktionspro¬ dukt . 30 g of acetophenone (0.25 mol) are dissolved in 250 g of ethyl orthoacetate (1.68 mol) and brought to a boil. Then, 18 g of 70% perchloric acid (0.13 mol) are slowly added dropwise to the solution. The temperature is reduced to 80 ° C and the re ¬ action continued overnight. The resulting precipitate is filtered off with suction after cooling and washed with ether. This gives diphenylpyrrylium perchlorate having a melting point of 222 ° C according to the following reaction scheme as Reaktionspro ¬ product.
I.A-2) Synthese von 2 , 2 ', 6 , 6 ' -Tetraphenyl-4 , 4 ' -dipyran I.A-2) Synthesis of 2, 2 ', 6, 6'-tetraphenyl-4,4'-dipyran
0,2 mol Diphenylpyrrylium-Perchlorat werden in Pyridin und 0,01 mol Triphenylphosphin 3 h unter Rückfluss erhitzt. Der entstandene Niederschlag wird nach Abkühlen abgesaugt und mit Ether gewaschen. Man erhält 2 , 2 ' , 6, 6 ' -Tetraphenyl-4 , 4 ' - dipyran (GBP, Gamma-Bi-Pyran) nach folgendem Reaktionsschema als Reaktionsprodukt:
0.2 mol of diphenylpyrrylium perchlorate are refluxed in pyridine and 0.01 mol of triphenylphosphine for 3 h. The resulting precipitate is filtered off with suction after cooling and washed with ether. 2, 2 ', 6, 6'-tetraphenyl-4,4'-dipyran (GBP, gamma-bi-pyran) are obtained as reaction product according to the following reaction scheme:
I.B) Zweistufige Synthese von Ν,Ν, ' , ' -Tetramethyl-7 , 8- dihydro-6H-dipyrido [1 ,2-a;2 ' , 1 ' -c] [1 , 4] diazepin-2 , 12-diamin (SED1) IB) Two-Step Synthesis of Ν, Ν, ',' -Tetramethyl-7,8-dihydro-6H-dipyrido [1, 2-a; 2 ', 1'-c] [1, 4] diazepine-2, 12- diamine (SED1)
Die Synthese von SED1 erfolgt in zwei Stufen nach einer modi¬ fizierten Vorschrift nach J. A. Murphy, J. Garnier, S. R. Park, F. Schoenebeck, S. Zhou, A. . Turner, Org. Lett. 2008, 10, 1227. The synthesis of Sed1 occurs in two stages according to a modi fied ¬ provision JA Murphy, J. Garnier, SR Park, F. Schoenebeck, S. Zhou, A.. Turner, Org. Lett. 2008, 10, 1227.
I.B-1) Synthese von 1 , 3-bis (N,N-dimethyl-4-aminopyridinium) propan diiodid I.B-1) Synthesis of 1,3-bis (N, N-dimethyl-4-aminopyridinium) propane diiodide
Eine Lösung von 4,58 g (37,5 mmol) 4-dimethylaminopyridin und 4,44 g (15 mmol) 1 , 3-diiodopropan werden in 100 ml Aceto- nitril in einer Inertgasatmosphäre unter Rückfluss über Nacht gerührt. Nach Abkühlen wird der feste Rückstand abgefiltert.
Zu der Acetonitril-Lösung werden 20 ml Diethylether gegeben, wobei mehr Feststoff ausfällt. Der feste Rückstand wird drei¬ mal mit 30 ml Diethlyether gewaschen und unter Vakuum getrocknet. Man erhält 1 , 3-bis (N, N-dimethyl-4-aminopyridinium) - propan diiodid als weißes Pulver mp 280 - 285 °C (dec. ) ; [Found: (ESI+) (MI)+ 413.1194. C17H26I2 4 requires M-I, 413.1197]; / x (KBr) /cm"1 3005, 1651, 1574, 1540, 1404, 1204, 1185, 1129, 1067, 1036, 829, 805; 1H-NMR (400 MHz, DMSO-d6) ; 2.36 (2H, quintet, J = 7.2 Hz, CH2) , 3.20 (12H, s, CH3) , 4.27 (4H, t, J = 7.2 Hz, NCH2), 7.05 (4H, d, J = 7.7 Hz, ArH) , 8.30 (4H, d, J = 7.7 Hz, ArH); 13C NMR (100 MHz, DMSO-d6) ; 31.0 (CH2), 39.8 (4 CH3) , 53.6 (2 CH2) , 107.8 (2 CH) , 141.8 (2 CH) , 155.8 (2 C) ; m/z (ESI+) 413 [(M-I)+, 4%], 143 (100), 96 (10) . A solution of 4.58 g (37.5 mmol) of 4-dimethylaminopyridine and 4.44 g (15 mmol) of 1, 3-diiodopropane are stirred in 100 ml of acetonitrile in an inert gas atmosphere under reflux overnight. After cooling, the solid residue is filtered off. 20 ml of diethyl ether are added to the acetonitrile solution, with more solid precipitating out. The solid residue is washed three times with 30 ml ¬ Diethlyether and dried under vacuum. 1,3-bis (N, N-dimethyl-4-aminopyridinium) -propane diiodide is obtained as white powder mp 280-285 ° C. (dec.); [Found: (ESI + ) (MI) + 413.1194. C 17 H 2 6 I 2 4 requires MI, 413.1197]; / x (KBr) / cm -1 3005, 1651, 1574, 1540, 1404, 1204, 1185, 1129, 1067, 1036, 829, 805, 1 H-NMR (400 MHz, DMSO-d6), 2.36 (2H, quintet, J = 7.2 Hz, CH 2 ), 3.20 (12H, s, CH 3 ), 4.27 (4H, t, J = 7.2 Hz, NCH 2 ), 7.05 (4H, d, J = 7.7 Hz, ArH), 8.30 (4H, d, J = 7.7 Hz, ArH); 13 C NMR (100 MHz, DMSO-d6); 31.0 (CH 2 ), 39.8 (4 CH 3 ), 53.6 (2 CH 2 ), 107.8 (2 CH ), 141.8 (2 CH), 155.8 (2 C), m / z (ESI + ) 413 [(MI) + , 4%], 143 (100), 96 (10).
I.B-2) Synthese von Ν,Ν, ' , ' -Tetramethyl-7 , 8-dihydro-6H- dipyrido [1 ,2-a;2 ' , 1 ' -c] [1 , 4] diazepin-2 , 12-diamin (SED1) IB-2) Synthesis of Ν, Ν, ',' -Tetramethyl-7,8-dihydro-6H-dipyrido [1, 2-a; 2 ', 1'-c] [1, 4] diazepine-2, 12 diamine (SED1)
Eine Mischung aus 5,4 g (10 mmol) 1 , 3-bis (N, N-dimethyl-4- aminopyridinium) propan diiodid und 1,45 g (60 mmol) NaH (in Pulverform erhalten aus einer 60%igen Dispersion in Mineralöl durch Waschen mit Cyclohexan und anschließender Trocknung im Vakuum) wird unter Argon-Schutzgasatmosphäre in einen 100 ml Dreihalskolben gegeben, welcher mit einer Ammoniakzufuhr und einem Trockeneiskühler ausgerüstet ist. Der Kolben wird auf -80°C abgekühlt und der Trockeneiskühler wird mit Flüssig¬ stickstoff gefüllt. Unter Rühren wird 70 ml Ammoniak in den Kolben kondensiert. Es bildet sich eine gelbe Lösung, welche für weitere 90 Minuten bei -30 °C unter Rückfluss gerührt wird. Die Farbe der Lösung ändert sich dabei von Gelb nach Rot. Man lässt die Lösung auf Raumtemperatur erwärmen und dampft das überschüssige Ammoniak ab. Der tiefrote Feststoff wird mit trockenem Ether extrahiert, aufkonzentriert und im
Vakuum getrocknet. Das schwarze Produkt wird im Vakuum bei 105-110°C sublimiert. Aufgrund der Tatsache, dass das Materi¬ al vor dem Sublimieren aufschmilzt werden nur 220 mg subli- miertes Material erhalten. Eine Ausbeuteverbesserung lässt sich dadurch erreichen, dass das Restmaterial aus der Vakuumdestille gekratzt und einer weiteren Sublimation unterworfen wird . A mixture of 5.4 g (10 mmol) of 1,3-bis (N, N-dimethyl-4-aminopyridinium) propane diiodide and 1.45 g (60 mmol) of NaH (in powder form obtained from a 60% dispersion in Mineral oil by washing with cyclohexane and subsequent drying in vacuo) under argon inert gas atmosphere in a 100 ml three-necked flask equipped with an ammonia feed and a dry ice condenser. The flask is cooled to -80 ° C and the dry ice is filled with liquid ¬ nitrogen. With stirring, 70 ml of ammonia is condensed in the flask. It forms a yellow solution which is stirred for a further 90 minutes at -30 ° C under reflux. The color of the solution changes from yellow to red. The solution is allowed to warm to room temperature and the excess ammonia is evaporated off. The deep red solid is extracted with dry ether, concentrated and concentrated Vacuum dried. The black product is sublimed in vacuo at 105-110 ° C. Due to the fact that the Materi ¬ al, 220 mg melted before the sublimation obtained sublimed-optimized material. A yield improvement can be achieved by scraping the residual material from the vacuum still and subjecting it to further sublimation.
I.C) Herstellung organisch elektrisch leitfähiger Schichten I.C) Preparation of Organic Electrically Conductive Layers
I.C-1) Herstellung organisch elektrisch leitfähiger Schichten enthaltend GBP Auf einer ITO- ( Indium-Tin-Oxide = Indium-dotiertes Zinnoxid) Elektrode wird durch thermisches Verdampfen eine 200 nm dicke Schicht des Elektronenleiters BCP (2 , 9-Dimethyl-4 , 7-diphenyl- 1, 10-phenanthroline) abgeschieden. Als Gegenelektrode wird eine 150 nm dicke Aluminiumschicht verwendet. IC-1) Preparation of Organic Electrically Conductive Layers Containing GBP On an ITO (indium-tin-oxide) electrode, a 200 nm thick layer of the electron conductor BCP (2, 9-dimethyl-4, 7 -diphenyl-1,10-phenanthroline). The counterelectrode used is a 150 nm thick aluminum layer.
In vier weiteren Experimenten wird das unter I.A) hergestellte GBP in Konzentrationen von 2%, 5%, 15% und 25% relativ zur Verdampfungsrate des BCP eindotiert. In four further experiments, the GBP produced under I.A.) is doped in concentrations of 2%, 5%, 15% and 25% relative to the rate of evaporation of the BCP.
I.C-2) Herstellung organisch elektrisch leitfähiger Schichten enthaltend SED1 I.C-2) Preparation of organic electrically conductive layers containing SED1
Vorgefertigte ITO-Glassubstrate werden für 10 Minuten mittels eines Sauerstoffplasmas behandelt und schnellstmöglich in ei¬ nen Evaporator überführt, welcher sich innerhalb einer Argon gefüllten Glovebox mit einem Wassergehalt kleiner 2 ppm be¬ findet . Das thermische Verdampfen erfolgt bei einem Basisdruck klei¬ ner als 2xl0~6 mbar, welcher während des gesamten Bedamp- fungsschrittes beibehalten wird.
Der Elektronenleiter und der Dotand werden gleichzeitig auf eine Temperatur kurz unterhalb ihres Verdampfungspunktes auf¬ geheizt. Anschließend wird der Dotand solange weiter aufge¬ heizt, bis eine konstante Verdampfungsrate erzielt ist. Eben- so verfährt man mit dem Elektronenleiter und bei beidseitig konstanten Evaporationsraten wird der Schieber des Evapora- tors geöffnet. Prefabricated ITO glass substrates are treated for 10 minutes using an oxygen plasma and quickly transferred into egg ¬ NEN evaporator, which is filled glove box within an argon will be ¬ having a water content less than 2 ppm. The thermal evaporation is carried out at a base pressure klei ¬ ner than 2xl0 ~ 6 mbar, which evaporation step is maintained during the entire Bedamp-. The electron conductor and the dopant are simultaneously heated to a temperature just below their evaporation point on ¬ . Then, the dopant is further heated while ¬ until a constant vaporization rate is achieved. The same procedure is followed with the electron conductor and with constant evaporation rates on both sides, the slide of the evaporator is opened.
Die Rate des Elektronentransports wird auf 1 Ä/s eingestellt und die Dotandenrate wird in Abhängigkeit der Verdampfungsra¬ te des Elektronentransportmaterials und der gewünschten Do- tandenkonzentration gewählt. The rate of electron transport is estimated at 1 Å / s and the set Dotandenrate is selected in dependence on the concentration tandemich Verdampfungsra ¬ te of the electron transport material and the desired Do-.
Vor dem Aufbringen der Gegenelektrode werden nach erfolgter Bedampfung beide Quellen auf unter 40 °C herabgekühlt. Before applying the counter electrode both sources are cooled down to below 40 ° C after evaporation.
Die Gegenelektrode wird mittels thermischen Bedampfens abge¬ schieden und besteht aus einem Stapel aus einer 10 nm dicken Calcium- und einer 150 nm dicken Aluminiumschicht. The counter electrode is by means of thermal vapor deposition abge ¬ eliminated and consists of a stack of a 10 nm thick calcium and a 150 nm thick aluminum layer.
Die Abscheidung wird bei einer Abscheiderate von 0,5 Ä/s durch Öffnen des Schiebers gestartet und anschließend wird die Abscheiderate langsam auf 5 Ä/s erhöht. Die so hergestellten Elektroden werden einer physikalischen Charakterisierung unterzogen. The deposition is started at a rate of 0.5A / s by opening the gate and then slowly increasing the deposition rate to 5A / s. The electrodes thus produced are subjected to a physical characterization.
II) Physikalische Charakterisierung der GBP-Dotanden ILA Strom-Spannung-Kennlinien II) Physical characterization of GBP dopants ILA current-voltage characteristics
An 4 mm2 großen Bauelementen der in Schritt I.C-1 hergestellten Elektroden wurden Strom-Spannungs-Kennlinien aufgenommen. Die Kennlinien der einzelnen Verbindungen sind in Fig. 1 dargestellt. Der Anteil des GBP betrug dabei 2, 5, 15 und 25% relativ zur Verdampfungsrate des BCPs . Current-voltage characteristics were recorded on 4 mm 2 devices of the electrodes prepared in step IC-1. The characteristics of the individual compounds are shown in Fig. 1. The share of the GBP was 2, 5, 15 and 25% relative to the evaporation rate of the BCP.
Für alle GBP-Dotierungskonzentrationen kann gezeigt werden, dass die Dotierung einen konzentrationsabhängigen Effekt auf
die IV-Kennlinie hat. In einer GBP-Dotierungskonzentration von 2% zeigt sich nur eine leichte Erhöhung der Stromdichte, wohingegen GBP-Dotierungskonzentrationen von 5 und 10 ~6 einen deutlichen Anstieg der Stromdichten im Vergleich zum Refe- renzbauteil aufweisen. Eine GBP-Dotierungskonzentration von 25% ist dann wiederum zu hoch um zu einer effektiven Stromdichte zu führen, in diesem Fall liegt die Stromdichte unter¬ halb der Stromdichten der Elektroden mit GBP-Dotierungskonzentrationen von 5 und 10%. For all GBP doping concentrations, it can be shown that the doping has a concentration-dependent effect has the IV characteristic. At a GBP doping concentration of 2%, there is only a slight increase in current density, whereas GBP doping concentrations of 5 and 10 -6 show a significant increase in current densities compared to the reference component. A GBP-doping concentration of 25% is then again too high to result in an effective current density, in this case, the current density is below ¬ half the current density of the electrodes with GBP-doping concentrations of 5 and 10%.
Hinreichend starke Dotierungseffekte erreicht man in diesem Fall beispielhaft mit GBP-Dotierungskonzentrationen im Bereich zwischen 5 und 15%. Sufficiently strong doping effects are achieved in this case by way of example with GBP doping concentrations in the range between 5 and 15%.
Die waagerechten Bereiche der Kennlinien stellen keine Strom- begrenzung des Bauteils dar, sondern sind durch die sicherheitsbedingten Stromgrenzen für das Bauteil bedingt. Allgemein gilt, je kleiner die Spannung bei der das Bauteil die maximale Stromdichte erreicht, desto besser ist der Dotieref¬ fekt. The horizontal areas of the characteristic curves do not represent a current limit of the component, but are due to the safety-related current limits for the component. In general, the smaller the voltage at which the component reaches the maximum current density, the better the Dotieref ¬ fect.
Das symmetrische Verhalten der Strom-Spannungskennlinie zeigt für die nicht dotierte BCP-Schicht und die Schichten mit den unterschiedlichen GBP-Dotierungskonzentrationen, dass die Elektroneninjektion unabhängig von der Austrittsarbeit der Metallelektroden ist und für Aluminium- sowie ITO-Elektroden gleich gut funktioniert. Dies ist für gute Dotierstoffe eine wünschenswerte Eigenschaft. The symmetrical behavior of the current-voltage characteristic shows for the undoped BCP layer and the layers with the different GBP doping concentrations that the electron injection is independent of the work function of the metal electrodes and works equally well for aluminum and ITO electrodes. This is a desirable property for good dopants.
II.B Leitfähigkeitsmessungen II.B Conductivity measurements
Mit den in I.C-1 gewählten GBP-Dotierungskonzentrationen von 2, 5, 15 und 25% bezogen auf GCP wurden Leitfähigkeitssub¬ strate beschichtet. Für diesen Substrattyp ist es nicht er¬ forderlich eine Gegenelektrode aus Aluminium aufzubringen. Zudem wurden, um auszuschließen das die Leitfähigkeit eine Funktion der Bauteilfläche und -dicke ist, insgesamt 9 unter¬ schiedlich dimensionierte Bauteile erzeugt.
Für die so erzeugten Bauelemente wurde eine Schichtleitfähigkeit bestimmt, welche für die unterschiedlichen Dotierstoff¬ konzentrationen, folgende spezifische Werte aufweist: Related with the selected in IC-1 GBP-doping concentrations of 2, 5, 15 and 25% to GCP Leitfähigkeitssub ¬ strate were coated. For this type of substrate, it is not him ¬ conducive apply a counter electrode made of aluminum. Moreover, the conductivity was to exclude the function of a component surface and is a total thickness 9 generated ¬ differently dimensioned components. For the thus produced components a layer conductivity was determined, which has for the different dopant concentrations ¬, the following specific values:
Tabelle 1: Elektrische Leitfähigkeiten unterschiedlicher GBP- Dotierungskonzentrationen Table 1: Electrical conductivities of different GBP doping concentrations
Die Leitfähigkeiten als Funktion der unterschiedlichen GBP- Dotierungskonzentrationen sind noch einmal in Fig. 2 verdeut- licht. Der gefundene Verlauf entspricht nicht den Ergebnissen der IV-Kennlinien . Die Leitfähigkeit ist für das Leitfähigkeitssubstrat mit nicht dotierter GCP-Schicht klein und steigt mit höherer GBP-Dotierungskonzentration an. Die gemessenen Leitfähigkeiten liegen auch bei den höchsten vermesse- nen GBP-Dotierungskonzentrationen nicht in Größenordnungen die man von einem guten Dotierstoff erwarten würde (1E-5 bis 1E-3 S/m) . The conductivities as a function of the different GBP doping concentrations are illustrated once again in FIG. The course found does not correspond to the results of the IV characteristics. The conductivity is small for the conductivity substrate with undoped GCP layer and increases with higher GBP doping concentration. The measured conductivities, even at the highest measured GBP doping concentrations, are not in the range that would be expected from a good dopant (1E-5 to 1E-3 S / m).
Zusammen mit den IV-Kennlinien aus II.A lässt sich schließen, dass die mit GBP dotierten Schichten zwar eine gute Ladungs¬ trägerinjektion und Stromtragfähigkeit aufweisen, die Leitfä¬ higkeit bei sehr niedrigen Feldern aber nur gering verbessert wird. Bei dem erfindungsgemäß eingesetzten Dotierstoffen handelt sich also um eine Substanzklasse, welche die Ladungsträ- gerinjektion verbessern können. Together with the I-V characteristics of II.A suggests that, although the doped with GBP layers have a good charge carrier injection ¬ and current carrying capacity, the ability Leitfä ¬ but is only slightly improved at very low fields. The dopants used according to the invention are therefore a class of substances which can improve charge carrier injection.
Ohne durch die dargestellten Leitfähigkeitswerte gebunden zu sein, kann nicht ausgeschlossen werden, dass mit höherer GBP- Dotierungskonzentration Schichten mit noch höherer Leitfähig- keit hergestellt werden können. Without being bound by the illustrated conductivity values, it can not be ruled out that layers with even higher conductivity can be produced with higher GBP doping concentration.
II . C Absorptionsspektra
Zur Bestimmung der Emissions- und Reflexionsspektra unter¬ schiedlichen Dotierungs-Zusammensetzungen wurden Schichten mit unterschiedlichen GBP-Dotierungskonzentrationen analog zuII. C absorption spectra To determine the emission and Reflexionsspektra under ¬ different union doping compositions layers were analogous to having different doping concentrations GBP-
I. C-1 auf Quarzglasscheiben abgeschieden. Diese Proben sind ohne elektrische Kontakte ausgeführt und dienen nur zur Mes¬ sung der optischen Schichteigenschaften. I. C-1 deposited on quartz glass panes. These samples are designed without electrical contacts and serve only for measurement of the optical layer properties.
Die Absorptionsspektren (siehe Fig. 3) der Schichten mit unterschiedlichen GBP-Dotierungskonzentrationen zeigen, dass sich die Absorption mit steigenden GBP- Dotierungskonzentrationen im sichtbaren Bereich von 400-700 nm stark erhöht. Diese Erhöhung wird besonders im blau-grünen Bereich von 400-550 nm deutlich, was dazu führt, dass die Schicht deutlich rot auf das menschliche Auge wirkt. Ohne durch die Theorie gebunden zu sein liegt die Erhöhung der Absorption mit steigender GBP-Dotierungskonzentration einerseits möglicherweise an der Ausbildung von Charge-Transfer- Komplexen und andererseits an der rötlichen Grundfarbe des GBPs . The absorption spectra (see FIG. 3) of the layers with different GBP doping concentrations show that the absorption increases strongly with increasing GBP doping concentrations in the visible range of 400-700 nm. This increase is particularly evident in the blue-green range of 400-550 nm, which means that the layer has a distinctly red effect on the human eye. Without being bound by theory, the increase in absorption with increasing GBP doping concentration may be due, on the one hand, to the formation of charge-transfer complexes and, on the other hand, to the reddish base color of the GBP.
II. D Photolumineszenz-Spektra (PL-Spektra) II. D Photoluminescence Spectra (PL-Spektra)
Die in II.C hergestellten Quarzglasscheiben wurden mittels der Photolumineszenz-Spektroskopie untersucht. Die Ergebnisse sind in Fig. 4 dargestellt. Der Vergleich der PL-Spektra rei- ner BCP-Schichten mit GBP-dotierten BCP-Schichten zeigt, dass sich das Emissionsmaximum von 396 nm auf 383 nm verschiebt. Außerdem bildet sich für die mit GPB-dotierten Schichten bei 480-540 nm ein deutlicher zweiter Peak aus, welcher mit steigender GBP-Dotierungskonzentration ausgeprägter wird. Ohne durch die Theorie gebunden zu sein wird die Verschiebung des Emissionsmaximums auf die Bildung von Charge-Transfer Komple¬ xen zurückgeführt, während der zweite Peak auf das GBP zurück zu führen ist. Die hohe Emission kann sich insbesondere posi¬ tiv für organische Photodetektoren und Solarzellen auswirken. The quartz glass sheets produced in II.C were examined by photoluminescence spectroscopy. The results are shown in FIG. The comparison of PL-spectra of pure BCP layers with GBP-doped BCP layers shows that the emission maximum shifts from 396 nm to 383 nm. In addition, a marked second peak is formed for the GPB-doped layers at 480-540 nm, which becomes more pronounced as the GBP doping concentration increases. The shift of the emission maximum on the formation of charge-transfer complexes is Komple ¬ Without being bound by theory returned, while the second peak is attributable to the GBP. The high emission can affect organic photodetectors and solar cells in particular posi ¬ tively.
II.E Reflexions-Spektra II.E reflection spectra
Die in II.C hergestellten Quarzglasscheiben wurden mittels der Reflexions-Spektroskopie untersucht. Die Ergebnisse der
Reflexions-Spektren sind in Fig. 5 dargestellt. Der Vergleich der Reflexionsspektra reiner BCP-Schichten mit GBP-dotierten BCP-Schichten zeigt eine GBP-konzentrationsabhängige Abnahme der Reflexion im blau-grünen Wellenlängenbereich (420-550nm) , wohingegen die Reflexion im roten Bereich GBP- konzentrationsunabhängig ist. Rein optisch zeigt sich das auch an den Schichten, deren Farbton für das menschliche Auge mit steigender GBP-Konzentration immer dunkler und roter wird . The quartz glass sheets produced in II.C were examined by reflection spectroscopy. The results of Reflection spectra are shown in FIG. Comparing the reflection spectra of pure BCP layers with GBP-doped BCP layers reveals a GBP concentration-dependent decrease in blue-green wavelength reflection (420-550nm), whereas red-reflectance is GBP concentration-independent. From a purely optical point of view, this is also evident in the layers, whose hue is becoming darker and redder with increasing GBP concentration for the human eye.
II.F Cyclovoltametrie (CV) Messung II.F cyclic voltammetry (CV) measurement
0,8±0,1 mg GBP wurden in 986,7±0,1 mg Dimethylformamid gelöst und mit 67,2±0,1 mg Tetrabutylammoniumtriflat als Leitsalz versetzt. Alle Komponenten waren vollständig gelöst. Drei Platindrähte dienten als Arbeits-, Gegen- und Referenzelekt¬ rode. Eine Strom-Spannungskennlinie wurde zwischen -3 V und 1 V bezogen auf die Referenzelektrode aufgenommen. Ferrocen diente als Referenz zur Eichung der Spannungsachse. Der Onset der ersten Ein-Elektronenoxidation wurde zu +0,05 V gegen Normalwasserstoffelektrode (-4,45 eV vs . Vakuumlevel). Der Onset der entsprechenden Reduktion wurde zu +0,22 V gegen Normalwasserstoffelektrode (-4,62 eV vs . Vakuumlevel) be¬ stimmt. Der Durchschnittswert ergibt eine HOMO-Lage von 0.8 ± 0.1 mg GBP was dissolved in 986.7 ± 0.1 mg dimethylformamide and treated with 67.2 ± 0.1 mg tetrabutylammonium triflate as the conducting salt. All components were completely solved. Three platinum wires were used as working, counter and Referenzelekt ¬ rode. A current-voltage characteristic was recorded between -3 V and 1 V with respect to the reference electrode. Ferrocene served as a reference for calibrating the stress axis. The onset of the first one-electron oxidation became +0.05 V versus normal hydrogen electrode (-4.45 eV vs. vacuum level). The onset of the corresponding reduction was to +0.22 V versus the normal hydrogen electrode (-4.62 eV vs. Vacuum level) ¬ be true. The average results in a HOMO location of
-4,53 eV. -4.53 eV.
Dies zeigt beispielhaft das Potential dieser Verbindungsklas¬ se auf. Obwohl das HOMO relativ tief liegt ist trotzdem eine Verbesserung der Leitfähigkeit, insbesondere der Injektion, beobachtbar . This example demonstrates the potential of this compound Klas ¬ se. Although the HOMO is relatively low, nevertheless an improvement in the conductivity, in particular the injection, is observable.
III) Physikalische Charakterisierung der SEDl-Dotanden III) Physical characterization of the SEDI dopants
III.A Strom-Spannung-Kennlinien mit SED1 als Dotanden III.A current-voltage characteristics with SED1 as dopants
Es werden Messergebnisse des Dotanden SED1 mit unterschiedl chen Elektronentransportmaterialien und unterschiedlichen
Schichtaufbauten vorgestellt. Die Messdaten werden an Bauteilen erhalten, welche nach I.C-2 hergestellt wurden. Measurement results of the dopant SED1 with different electron transport materials and different Layered structures presented. The measurement data are obtained on components manufactured according to IC-2.
III.A-1 Strom-Spannung-Kennlinien Alq3 mit SEDl III.A-1 Current-voltage characteristics Alq3 with SED1
Es werden 3 Proben eines 4 mm2 großen Bauteils mit Alq3, ei¬ nem Elektronentransportmaterial der Fa Sensient Imaging Tech¬ nology GmbH, hergestellt. Für die Blindprobe wird eine 200 nm dicke Alq3-Schicht , wie schon zuvor beschrieben, mittelsThere are three samples of 4 mm 2 component with Alq3, egg ¬ nem electron transport material from the company Sensient Imaging Tech ¬ nology GmbH produced. For the blank, a 200 nm thick Alq3 layer, as previously described, means
Dampfphasenabscheidung auf einer ITO-Elektrode abgeschieden. Zusätzlich werden zwei weitere Proben, jeweils mit 5% und 10% SEDl bezogen auf die Verdampfungsrate des Alq3 mit eindo¬ tiert. Die Strom-Spannungs-Kennlinien dieser Versuche sind in Figur 7 dargestellt. Im Vergleich zu einer reinen Alq3-Deposited vapor deposition on an ITO electrode. In addition, two other samples, both with 5% and 10% SEDL be related to the evaporation rate of Alq3 with eindo ¬ advantage. The current-voltage characteristics of these experiments are shown in FIG. Compared to a pure Alq3
Schicht lässt sich in Abhängigkeit der Dotandenkonzentration ein höherer Ausgangsstrom feststellen, dies sowohl bei positivem wie auch negativem Spannungsverlauf bezogen auf die ITO-Elektrode. Die gute Effektivität des Dotanden lässt sich für beide Dotanden-Konzentrationen auch aus dem symmetrischen Verlauf der Stromdichte/Spannungskurve ableiten. Layer can be determined depending on the dopant concentration, a higher output current, both positive and negative voltage curve relative to the ITO electrode. The good effectiveness of the dopant can be derived for both dopant concentrations also from the symmetrical course of the current density / voltage curve.
Der Anstieg des Stromes bei niedrigen Spannungswerten (schwa¬ chem elektrischen Feld, siehe Figur 8) zeigt ein Ohmsches Verhalten, welches sowohl für eine gute Dotierung des Halbleiters als auch für eine gute Dotierung der Grenzfläche Ka¬ thode/organische Phase spricht. The rise of the current at low voltage values (schwa ¬ chem electric field, see Figure 8) showing an ohmic behavior that speaks both a good doping of the semiconductor as well as a good doping the interface Ka ¬ Thode / organic phase.
Insgesamt zeigt die Schicht mit der 10% Dotierung aufgrund der höheren erreichten Stromdichten einen etwas besseren Verlauf als die Schicht mit dem 5%igen Dotandengehalt . Overall, the layer with the 10% doping shows a slightly better course than the layer with the 5% dopant content due to the higher current densities achieved.
III.A-2 Strom-Spannung-Kennlinien Alq3 mit SEDl mit/ohne SEDl Zwischenschicht III.A-2 Current-voltage characteristics Alq3 with SEDl with / without SEDl interlayer
Figur 9 zeigt die Strom/Spannungsverläufe von Bauteilen mit einer reinen Alq3-, einer Alq3- dotiert mit 5% SEDl und einem
Bauteil mit einer Alq3- dotiert mit 5% SED1 und einer zusätz¬ lichen 15 nm dicken SEDl-Schicht , welche zwischen der Calci- um-Kathode und dotierten Elektronentransportschicht abge¬ schieden wurde. Die einzelnen dotierten Schichten unterschei- den sich in ihren Strom/Spannungsverläufen nur unwesentlich. Dies bedeutet, dass die reine SEDl-Schicht „unsichtbar" und der Strom eine reine Funktion des Dotanden ist. Der Kurvenverlauf zeigt, dass SED1 Elektronen aus der Calcium-Kathode injiziert werden. Dieses wiederum ist ein Indiz für die guten elektronenabgebenden Eigenschaften des SED1 innerhalb eines elektronischen Bauteils und für die guten dotierenden Eigenschaften des SED1 für Elektronentransportmaterialien im Allgemeinen . FIG. 9 shows the current / voltage characteristics of components with a pure Alq3-, an Alq3-doped with 5% SED1 and a Component having a Alq3- doped with 5% Sed1 and a zusätz ¬ union 15 nm thick SEDL-layer which was to cathode and doped electron transport layer abge ¬ eliminated between the calcium. The individual doped layers differ only insignificantly in their current / voltage curves. This means that the pure SEDl layer is "invisible" and the current is a pure function of the dopant, and the curve shows that SED1 injects electrons from the calcium cathode, which in turn indicates the good electron-donating properties of the SED1 of an electronic device and for the good doping properties of the SED1 for electron transport materials in general.
III.A-3 Strom-Spannung-Kennlinien ETM-036 mit SED1 III.A-3 Current-voltage characteristics ETM-036 with SED1
Figur 10 zeigt die Strom/Spannungskennlinien eines 4mm2 großen Bauteils mit einer 200 nm dicken ETM-036 Schicht (ETM-036 ist ein Elektronentransportmaterial der Fa. Merck OLED Mate¬ rials GmbH respektive Merck KGaA) mit und ohne SED1 als Do¬ tanden. Im Vergleich zu einer reinen ETM-036-Schicht lässt sich für die mit 5% SED1 dotierte Schicht ein höherer Aus¬ gangsstrom feststellen, dies sowohl bei positivem wie auch negativem Spannungsverlauf bezogen auf die ITO-Elektrode Figure 10 shows the current / voltage characteristics of a 4mm 2 large component with a 200 nm thick ETM-036 layer (ETM 036 is an electron transporting material of Fa. Merck OLED Mate ¬ rials GmbH respectively Merck KGaA) with and without Sed1 as Do ¬ tanden. Compared to a pure ETM-036 layer can be for the 5% Sed1 doped layer, a higher output current from ¬ determine this based both positive as well as negative voltage profile on the ITO electrode
Der Anstieg des Stromes bei niedrigen Spannungswerten (schwa¬ chem elektrischen Feld, siehe Figur 11) zeigt ein Ohmsches Verhalten, welches sowohl für eine gute Dotierung des Halb- leiters als auch für eine gute Dotierung der Grenzfläche Ka¬ thode/organische Phase spricht.
III.A-4 Strom-Spannung-Kennlinien TMM-004 mit SED1 The rise of the current at low voltage values (schwa ¬ chem electric field, see Figure 11) shows an ohmic behavior that speaks both a good doping of the semi-conductor as well as a good doping the interface Ka ¬ Thode / organic phase. III.A-4 current-voltage characteristics TMM-004 with SED1
Figur 12 zeigt die Strom/Spannungskennlinien eines 4mm2 gro- ßen Bauteils mit einer 200 nm dicken TMM-004 Schicht (TMM-004 ist ein Triplet-host und ein Elektronentransportmaterial der Fa. Merck OLED Materials GmbH respektive Merck KGaA) mit und ohne SED1 als Dotanden. Im Vergleich zu einer reinen TMM-004- Schicht lässt sich für die mit 5% SED1 dotierte Schicht ein höherer Ausgangsstrom feststellen, dies sowohl bei positivem wie auch negativem Spannungsverlauf bezogen auf die ITO- Elektrode . FIG. 12 shows the current / voltage characteristics of a 4 mm 2 large component with a 200 nm thick TMM-004 layer (TMM-004 is a triplet host and an electron transport material from Merck OLED Materials GmbH or Merck KGaA) with and without SED1 as dopants. Compared to a pure TMM-004 layer, a higher output current can be detected for the layer doped with 5% SED1, both in the case of a positive and a negative voltage curve relative to the ITO electrode.
Der Anstieg des Stromes bei niedrigen Spannungswerten (schwa- ehern elektrischen Feld, siehe Figur 13) zeigt ein Ohmsches Verhalten, welches sowohl für eine gute Dotierung des Halbleiters als auch für eine gute Dotierung der Grenzfläche Ka¬ thode/organische Phase spricht. The rise of the current at low voltage values (weak ehern electric field, see Figure 13) shows an ohmic behavior that speaks both a good doping of the semiconductor as well as a good doping the interface Ka ¬ Thode / organic phase.
III.B Absorptionsspektren SED1 III.B Absorption Spectra SED1
Unter denselben Versuchsbedingungen und demselben Schichtaufbau wie in Beispiel III.A-3 geschildert wird ein Quarzglas als Substrat beschichtet. Der Aufbau weist keine elektrischen Kontaktschichten auf und wurde nur zur Bestimmung der optischen Eigenschaften gewählt. Figur 14 zeigt die Absorptions¬ eigenschaften einer ETM-03- und einer mit 5% SED1 dotierten ETM-03-Schicht . Beide Schichten zeigen ein Absorptionsmaximum um 354 nm, mit einer geringeren absoluten Absorption der dotierten ETM-03-Schicht . Die Abnahme der Absorption korreliert mit der Konzentration an ETM-03, welches dafür spricht, dass die Absorption bei diesen Wellenlängen hauptsächlich durch das Elektronentransportmaterial bestimmt wird. Under the same experimental conditions and the same layer structure as described in Example III.A-3, a quartz glass is coated as a substrate. The structure has no electrical contact layers and was chosen only to determine the optical properties. Figure 14 shows the absorption properties of a ¬ ETM-03- and one with 5% Sed1 doped ETM-03 layer. Both layers show an absorption maximum around 354 nm, with a lower absolute absorption of the doped ETM-03 layer. The decrease in absorption correlates with the concentration of ETM-03, which suggests that the absorption at these wavelengths is mainly determined by the electron transport material.
In einem höheren Wellenlängenbereich ab ca. 535 nm zeigt sich eine höhere Absorption der SED1 dotierten Schicht. Dies kann auf die Bildung schwacher Charge-Transfer Komplexe zwischen
dem Dotanden und dem Elektronentransporter hindeuten. Dies wiederum ist ein sehr starkes Indiz für einen Dotiereffekt. Somit ergibt sich eine gute Übereinstimmung der optischen mit den elektrischen Messungen.
In a higher wavelength range from about 535 nm shows a higher absorption of the SED1 doped layer. This can be due to the formation of weak charge transfer complexes between indicate the dopant and the electron transporter. This in turn is a very strong indication of a doping effect. This results in a good agreement between the optical and the electrical measurements.
Claims
1. Organisch elektronisches Bauelement umfassend mindestens zwei Elektroden und eine organische Elektronentransport- schicht enthaltend einen organischen n-Dotanden, dadurch gekennzeichnet, dass der n-Dotand mindestens zwei über eine Brücke (B) verbundene, cyclische Carben-Gruppen (QX) enthält, welche bei elektronischer Anregung der Verbindung nicht dissoziieren und mindestens ein Carben- Grundkörper dabei aromatisiert und die Carben-Gruppen nicht über einen Metall-Liganden direkt miteinander verbunden sind. 1. An organic electronic component comprising at least two electrodes and an organic electron transport layer containing an organic n-dopant, characterized in that the n-dopant at least two connected via a bridge (B), cyclic carbene groups (QX) containing do not dissociate on electronic excitation of the compound and aromatized at least one carbene body and the carbene groups are not directly connected to each other via a metal ligand.
2. Organisch elektronisches Bauelement nach Anspruch 1, dadurch gekennzeichnet, dass die Carben-Gruppen des or¬ ganischen n-Dotanden durch eine Doppelbindung direkt miteinander verbunden sind. 2. Organic electronic component according to claim 1, characterized in that the carbene groups of or ¬ ganic n-dopant are directly connected to each other by a double bond.
3. Organisch elektronisches Bauelement nach Anspruch 1, da¬ durch gekennzeichnet, dass die Brücke (B) des organi¬ schen n-Dotanden mindestens ein chinoides Ringsystem enthält . 3. Organic electronic component according to claim 1, since ¬ characterized by that the bridge (B) contains the organic ¬ rule n-dopant at least one quinoid ring system.
4. Organisch elektronisches Bauelement nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass wenigstens eine der Carben-Gruppen des organischen n-Dotanden einen 5- oder 6-Ring enthält, welcher mindestens 1 Heteroatom aufweist . 4. Organic electronic component according to one of claims 1 to 3, characterized in that at least one of the carbene groups of the organic n-dopant contains a 5- or 6-membered ring which has at least 1 heteroatom.
5. Organisch elektronisches Bauelement nach einem der An¬ sprüche 1 bis 4, dadurch gekennzeichnet, dass beide Car¬ ben-Gruppen des organischen n-Dotanden gleich aufgebaut sind und jeweils mindestens einen 5- oder 6-Ring enthal¬ ten . 5. Organic electronic component according to any one of claims ¬ 1 to 4, characterized in that both Car ¬ ben groups of the organic n-dopant are the same structure and in each case at least one 5- or 6-ring contained enthal ¬ th.
6. Organisch elektronisches Bauelement nach einem der An¬ sprüche 1 - 5, dadurch gekennzeichnet, dass wenigstens eine der Carben-Gruppen des organischen n-Dotanden ein Tetrazinodihetaren enthält. 6. Organic electronic component according to one of claims ¬ 1-5, characterized in that at least one of the carbene groups of the organic n-dopant contains a tetrazinodihetene.
Organisch elektronisches Bauelement nach einem der An¬ sprüche 1 - 6, dadurch gekennzeichnet, dass der organi¬ sche n-Dotand ein Bis-Pyran enthält. Organic electronic component according to ¬ claims 1-6, characterized in that the organic ¬ specific n-dopant bis-pyran contains a.
Organisch elektronisches Bauelement nach einem der An¬ sprüche 1 - 7, dadurch gekennzeichnet, dass der organi¬ sche n-Dotand 2 , 2 λ , 6, 6 λ -Tetraphenyl-4 , 4 λ -dipyran enthält . Organic electronic component according to ¬ claims 1-7, characterized in that the organic ¬ specific n-dopant 2, 2 λ, 6, 6 λ -Tetraphenyl-4, 4 λ -dipyran contains.
Organisch elektronisches Bauelement nach einem der An¬ sprüche 1 - 5, dadurch gekennzeichnet, dass der organi¬ sche n-Dotand N, , ' , ' -Tetramethyl-7 , 8 -dihydro- 6H- dipyrido [ 1 , 2-a; 2 ' , 1 ' -c] [ 1 , 4 ] diazepin-2 , 12-diamin (SED1) enthält . Organic electronic component according to ¬ claims 1-5, characterized in that the organic ¬ specific n-dopant N,, ',' -tetramethyl-7, 8 -dihydro- 6 H -dipyrido [1, 2-a; 2 ', 1'-c] [1, 4] diazepine-2, 12-diamine (SED1).
Organische Elektronentransportschicht enthaltend einen organischen n-Dotanden, dadurch gekennzeichnet, dass der n-Dotand mindestens zwei über eine Brücke (B) verbunde¬ ne, cyclische Carben-Gruppen (QX) enthält, welche bei elektronischer Anregung der Verbindung nicht dissoziieren und mindestens ein Carben-Grundkörper dabei aromati¬ siert und die Carben-Gruppen nicht über einen Metall- Liganden direkt miteinander verbunden sind.. Organic electron transport layer containing an organic n-dopant, characterized in that the n-dopant at least two connected via a bridge (B) ¬ ne, cyclic carbene groups (QX), which do not dissociate upon electronic excitation of the compound and at least one carbene base material while aromati ¬ Siert and the carbene groups are not directly connected to each other via a metal ligand ..
Organischer Elektronentransportschicht n-Dotand, gekenn¬ zeichnet dadurch, dass der n-Dotand mindestens zwei über eine Brücke (B) verbundene, cyclische Carben-Gruppen (QX) enthält, welche bei elektronischer Anregung der Verbindung nicht dissoziieren und mindestens ein Carben- Grundkörper dabei aromatisiert und die Carben-Gruppen nicht über einen Metall-Liganden direkt miteinander verbunden sind. Organic electron transport layer n-dopant, marked ¬ distinguished by the fact that the n-dopant at least two connected via a bridge (B), cyclic carbene groups (QX), which do not dissociate upon electronic excitation of the compound and at least one carbene body here aromatized and the carbene groups are not directly connected to each other via a metal ligand.
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PCT/EP2013/057293 WO2013153025A1 (en) | 2012-04-12 | 2013-04-08 | Organic electronic components having organic superdonors having at least two coupled carbene groups and use thereof as an n-type dopants |
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US6645579B1 (en) * | 1999-11-29 | 2003-11-11 | Canon Kabushiki Kaisha | Liquid crystal device |
JP4717198B2 (en) * | 1999-11-29 | 2011-07-06 | キヤノン株式会社 | Organic electroluminescence device |
US7364804B2 (en) * | 2003-08-29 | 2008-04-29 | Semiconductor Energy Laboratory Co., Ltd. | Pyran derivative, method for manufacturing the same, and light-emitting element containing the pyran derivative |
US7405129B2 (en) * | 2004-11-18 | 2008-07-29 | International Business Machines Corporation | Device comprising doped nano-component and method of forming the device |
WO2006081780A1 (en) | 2005-02-04 | 2006-08-10 | Novaled Ag | Dopants for organic semiconductors |
WO2007028738A1 (en) | 2005-09-05 | 2007-03-15 | Siemens Aktiengesellschaft | Novel materials for n-type doping of the electron transporting layers in organic electronic devices |
JPWO2007058172A1 (en) | 2005-11-17 | 2009-04-30 | 出光興産株式会社 | Organic electroluminescence device |
DE502006000749D1 (en) | 2006-03-21 | 2008-06-19 | Novaled Ag | Heterocyclic radical or diradical, their dimers, oligomers, polymers, dispiro compounds and polycycles, their use, organic semiconducting material and electronic component |
DE102007014048B4 (en) | 2006-03-21 | 2013-02-21 | Novaled Ag | Mixture of matrix material and doping material, and method for producing a layer of doped organic material |
EP1837927A1 (en) | 2006-03-22 | 2007-09-26 | Novaled AG | Use of heterocyclic radicals for doping of organic semiconductors |
DE102006053644A1 (en) | 2006-11-14 | 2008-06-12 | Siemens Ag | Novel highly conductive organic carrier transport material |
EP1990847B1 (en) | 2007-05-10 | 2018-06-20 | Novaled GmbH | Use of quinoid bisimidazoles and their derivatives as dopant for doping an organic semi-conductor matrix material |
DE102009057212B4 (en) * | 2009-12-01 | 2017-04-06 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Suppression of partial short circuit causes in electrical components based on organic materials |
DE102010041331A1 (en) | 2010-09-24 | 2012-03-29 | Siemens Aktiengesellschaft | Charge carrier modulation for color and brightness tuning in organic light-emitting diodes |
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2012
- 2012-04-12 DE DE102012205945A patent/DE102012205945A1/en not_active Ceased
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2013
- 2013-04-08 KR KR1020147028177A patent/KR20150001747A/en not_active Application Discontinuation
- 2013-04-08 EP EP13717462.9A patent/EP2837046A1/en not_active Withdrawn
- 2013-04-08 JP JP2015504919A patent/JP2015519731A/en active Pending
- 2013-04-08 US US14/391,920 patent/US20150060804A1/en not_active Abandoned
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- 2013-04-08 WO PCT/EP2013/057293 patent/WO2013153025A1/en active Application Filing
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HUA-JING WANG ET AL: "Design of new neutral organic super-electron donors: a theoretical study", JOURNAL OF PHYSICAL ORGANIC CHEMISTRY., vol. 23, 21 August 2009 (2009-08-21), GB, pages 75 - 83, XP055290174, ISSN: 0894-3230, DOI: 10.1002/poc.1590 * |
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US20150060804A1 (en) | 2015-03-05 |
KR20150001747A (en) | 2015-01-06 |
DE102012205945A1 (en) | 2013-10-17 |
JP2015519731A (en) | 2015-07-09 |
CN104285311A (en) | 2015-01-14 |
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