WO2012168358A1 - Compound for organic electronic device - Google Patents
Compound for organic electronic device Download PDFInfo
- Publication number
- WO2012168358A1 WO2012168358A1 PCT/EP2012/060794 EP2012060794W WO2012168358A1 WO 2012168358 A1 WO2012168358 A1 WO 2012168358A1 EP 2012060794 W EP2012060794 W EP 2012060794W WO 2012168358 A1 WO2012168358 A1 WO 2012168358A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- layer
- electron transport
- transport layer
- electronic device
- organic electronic
- Prior art date
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- 150000001875 compounds Chemical class 0.000 title claims description 47
- 239000000463 material Substances 0.000 claims abstract description 43
- 229920000642 polymer Polymers 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 239000004065 semiconductor Substances 0.000 claims description 7
- 230000000903 blocking effect Effects 0.000 claims description 6
- 238000010521 absorption reaction Methods 0.000 claims description 5
- 125000006755 (C2-C20) alkyl group Chemical group 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 125000001072 heteroaryl group Chemical group 0.000 claims 1
- CPRRHERYRRXBRZ-SRVKXCTJSA-N methyl n-[(2s)-1-[[(2s)-1-hydroxy-3-[(3s)-2-oxopyrrolidin-3-yl]propan-2-yl]amino]-4-methyl-1-oxopentan-2-yl]carbamate Chemical group COC(=O)N[C@@H](CC(C)C)C(=O)N[C@H](CO)C[C@@H]1CCNC1=O CPRRHERYRRXBRZ-SRVKXCTJSA-N 0.000 claims 1
- LVWCAUSDMRMCQL-UHFFFAOYSA-N methanediimine;naphthalene Chemical compound N=C=N.C1=CC=CC2=CC=CC=C21 LVWCAUSDMRMCQL-UHFFFAOYSA-N 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 128
- 239000002800 charge carrier Substances 0.000 description 20
- 239000002019 doping agent Substances 0.000 description 19
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 19
- 238000003786 synthesis reaction Methods 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 13
- 239000000758 substrate Substances 0.000 description 11
- 230000005525 hole transport Effects 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 230000037230 mobility Effects 0.000 description 9
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical class C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 7
- 238000004770 highest occupied molecular orbital Methods 0.000 description 7
- 239000007924 injection Substances 0.000 description 7
- 238000002347 injection Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 6
- 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 6
- 238000013086 organic photovoltaic Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 4
- 229910003472 fullerene Inorganic materials 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000011358 absorbing material Substances 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- -1 anthracyl Chemical group 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 150000003384 small molecules Chemical group 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- ICSNLGPSRYBMBD-UHFFFAOYSA-N 2-aminopyridine Chemical compound NC1=CC=CC=N1 ICSNLGPSRYBMBD-UHFFFAOYSA-N 0.000 description 2
- 125000004204 2-methoxyphenyl group Chemical group [H]C1=C([H])C(*)=C(OC([H])([H])[H])C([H])=C1[H] 0.000 description 2
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 125000001207 fluorophenyl group Chemical group 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- 125000005062 perfluorophenyl group Chemical group FC1=C(C(=C(C(=C1F)F)F)F)* 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 125000006850 spacer group Chemical group 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 229930192474 thiophene Natural products 0.000 description 2
- MLCJWRIUYXIWNU-OWOJBTEDSA-N (e)-ethene-1,2-diamine Chemical compound N\C=C\N MLCJWRIUYXIWNU-OWOJBTEDSA-N 0.000 description 1
- XEVRIPWWMAOEIB-UPHRSURJSA-N (z)-1,2-difluoroethene-1,2-diamine Chemical compound N\C(F)=C(/N)F XEVRIPWWMAOEIB-UPHRSURJSA-N 0.000 description 1
- TXVWTOBHDDIASC-YPKPFQOOSA-N (z)-1,2-diphenylethene-1,2-diamine Chemical compound C=1C=CC=CC=1C(/N)=C(/N)C1=CC=CC=C1 TXVWTOBHDDIASC-YPKPFQOOSA-N 0.000 description 1
- WXIWEJTUJWKFHH-QXMHVHEDSA-N (z)-1,2-dipyridin-2-ylethene-1,2-diamine Chemical compound C=1C=CC=NC=1C(/N)=C(/N)C1=CC=CC=N1 WXIWEJTUJWKFHH-QXMHVHEDSA-N 0.000 description 1
- KXQHPHAPUSFYBS-KTKRTIGZSA-N (z)-1,2-dithiophen-2-ylethene-1,2-diamine Chemical compound C=1C=CSC=1C(/N)=C(/N)C1=CC=CS1 KXQHPHAPUSFYBS-KTKRTIGZSA-N 0.000 description 1
- DPZSNGJNFHWQDC-ARJAWSKDSA-N (z)-2,3-diaminobut-2-enedinitrile Chemical compound N#CC(/N)=C(/N)C#N DPZSNGJNFHWQDC-ARJAWSKDSA-N 0.000 description 1
- JWHXMVCSSSOAHL-UHFFFAOYSA-N 1,1,2,2,3,3,3-heptafluoropropan-1-amine Chemical compound NC(F)(F)C(F)(F)C(F)(F)F JWHXMVCSSSOAHL-UHFFFAOYSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 1
- PNZCANAYAIUNJO-UHFFFAOYSA-N 1h-benzimidazole;naphthalene Chemical compound C1=CC=C2NC=NC2=C1.C1=CC=C2NC=NC2=C1.C1=CC=CC2=CC=CC=C21 PNZCANAYAIUNJO-UHFFFAOYSA-N 0.000 description 1
- DRGAZIDRYFYHIJ-UHFFFAOYSA-N 2,2':6',2''-terpyridine Chemical compound N1=CC=CC=C1C1=CC=CC(C=2N=CC=CC=2)=N1 DRGAZIDRYFYHIJ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 125000004207 3-methoxyphenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(OC([H])([H])[H])=C1[H] 0.000 description 1
- QYWMIVHGOHYDBS-UHFFFAOYSA-N 4,5-bis(1-phenylbenzimidazol-2-yl)benzene-1,2-diamine Chemical compound N=1C2=CC=CC=C2N(C=2C=CC=CC=2)C=1C=1C=C(N)C(N)=CC=1C1=NC2=CC=CC=C2N1C1=CC=CC=C1 QYWMIVHGOHYDBS-UHFFFAOYSA-N 0.000 description 1
- UOTZJBMBHUUZJK-UHFFFAOYSA-N 4,5-bis(trifluoromethyl)benzene-1,2-diamine Chemical compound NC1=CC(C(F)(F)F)=C(C(F)(F)F)C=C1N UOTZJBMBHUUZJK-UHFFFAOYSA-N 0.000 description 1
- PCKAZQYWUDIFQM-UHFFFAOYSA-N 4,5-diaminobenzene-1,2-dicarbonitrile Chemical compound NC1=CC(C#N)=C(C#N)C=C1N PCKAZQYWUDIFQM-UHFFFAOYSA-N 0.000 description 1
- PPWRHKISAQTCCG-UHFFFAOYSA-N 4,5-difluorobenzene-1,2-diamine Chemical compound NC1=CC(F)=C(F)C=C1N PPWRHKISAQTCCG-UHFFFAOYSA-N 0.000 description 1
- RJPUFNQEEXLNHN-UHFFFAOYSA-N 5,6-bis(trifluoromethyl)pyrazine-2,3-diamine Chemical compound NC1=NC(C(F)(F)F)=C(C(F)(F)F)N=C1N RJPUFNQEEXLNHN-UHFFFAOYSA-N 0.000 description 1
- FTHBTDDIVWLRLP-UHFFFAOYSA-N 5,6-diaminopyrazine-2,3-dicarbonitrile Chemical compound NC1=NC(C#N)=C(C#N)N=C1N FTHBTDDIVWLRLP-UHFFFAOYSA-N 0.000 description 1
- MZIVWMWWIDLUAP-UHFFFAOYSA-N 5,6-difluoropyrazine-2,3-diamine Chemical compound NC1=NC(F)=C(F)N=C1N MZIVWMWWIDLUAP-UHFFFAOYSA-N 0.000 description 1
- XRGHVHLFLNZIJL-UHFFFAOYSA-N 5,6-dinitropyrazine-2,3-diamine Chemical compound NC1=NC([N+]([O-])=O)=C([N+]([O-])=O)N=C1N XRGHVHLFLNZIJL-UHFFFAOYSA-N 0.000 description 1
- AUWMGTWDEMNTHS-UHFFFAOYSA-N 5,6-diphenylpyrazine-2,3-diamine Chemical compound C=1C=CC=CC=1C=1N=C(N)C(N)=NC=1C1=CC=CC=C1 AUWMGTWDEMNTHS-UHFFFAOYSA-N 0.000 description 1
- KHIYQGLZPMKGGF-UHFFFAOYSA-N 6,7-dimethylquinoxaline-2,3-diamine Chemical compound NC1=C(N)N=C2C=C(C)C(C)=CC2=N1 KHIYQGLZPMKGGF-UHFFFAOYSA-N 0.000 description 1
- SAKWMMOWGNCYFV-UHFFFAOYSA-N 7-chlorophenazine-2,3-diamine Chemical compound C1=C(Cl)C=C2N=C(C=C(C(N)=C3)N)C3=NC2=C1 SAKWMMOWGNCYFV-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 208000033962 Fontaine progeroid syndrome Diseases 0.000 description 1
- OAZWDJGLIYNYMU-UHFFFAOYSA-N Leucocrystal Violet Chemical compound C1=CC(N(C)C)=CC=C1C(C=1C=CC(=CC=1)N(C)C)C1=CC=C(N(C)C)C=C1 OAZWDJGLIYNYMU-UHFFFAOYSA-N 0.000 description 1
- UUIQMZJEGPQKFD-UHFFFAOYSA-N Methyl butyrate Chemical compound CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- DPKHZNPWBDQZCN-UHFFFAOYSA-N acridine orange free base Chemical compound C1=CC(N(C)C)=CC2=NC3=CC(N(C)C)=CC=C3C=C21 DPKHZNPWBDQZCN-UHFFFAOYSA-N 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 1
- 125000005605 benzo group Chemical group 0.000 description 1
- DZBUGLKDJFMEHC-UHFFFAOYSA-N benzoquinolinylidene Natural products C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- YMEPVPIIHONYLV-UHFFFAOYSA-N bisbenzimidazo[2,1-b:1',2'-j]benzo[lmn][3,8]phenanthroline-6,9-dione Chemical compound C1=CC=C2N(C(C3=CC=C4C(N5C6=CC=CC=C6N=C5C=5C=CC6=C3C4=5)=O)=O)C6=NC2=C1 YMEPVPIIHONYLV-UHFFFAOYSA-N 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000003306 harvesting Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- UVNXNSUKKOLFBM-UHFFFAOYSA-N imidazo[2,1-b][1,3,4]thiadiazole Chemical compound N1=CSC2=NC=CN21 UVNXNSUKKOLFBM-UHFFFAOYSA-N 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- DGBWPZSGHAXYGK-UHFFFAOYSA-N perinone Chemical compound C12=NC3=CC=CC=C3N2C(=O)C2=CC=C3C4=C2C1=CC=C4C(=O)N1C2=CC=CC=C2N=C13 DGBWPZSGHAXYGK-UHFFFAOYSA-N 0.000 description 1
- VZPGINJWPPHRLS-UHFFFAOYSA-N phenazine-2,3-diamine Chemical compound C1=CC=C2N=C(C=C(C(N)=C3)N)C3=NC2=C1 VZPGINJWPPHRLS-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920000078 poly(4-vinyltriphenylamine) Polymers 0.000 description 1
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 1
- CAFSXVAFGILCCI-UHFFFAOYSA-N pyrazine-2,3-diamine Chemical compound NC1=NC=CN=C1N CAFSXVAFGILCCI-UHFFFAOYSA-N 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- CXZRDVVUVDYSCQ-UHFFFAOYSA-M pyronin B Chemical compound [Cl-].C1=CC(=[N+](CC)CC)C=C2OC3=CC(N(CC)CC)=CC=C3C=C21 CXZRDVVUVDYSCQ-UHFFFAOYSA-M 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- LUDZVVVPVCUUBP-UHFFFAOYSA-N quinoxaline-2,3-diamine Chemical compound C1=CC=C2N=C(N)C(N)=NC2=C1 LUDZVVVPVCUUBP-UHFFFAOYSA-N 0.000 description 1
- RWPKRIMDOGTZCW-UHFFFAOYSA-N quinoxaline-6,7-diamine Chemical compound C1=CN=C2C=C(N)C(N)=CC2=N1 RWPKRIMDOGTZCW-UHFFFAOYSA-N 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 125000006413 ring segment Chemical group 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- JIIYLLUYRFRKMG-UHFFFAOYSA-N tetrathianaphthacene Chemical compound C1=CC=CC2=C3SSC(C4=CC=CC=C44)=C3C3=C4SSC3=C21 JIIYLLUYRFRKMG-UHFFFAOYSA-N 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- GLQWRXYOTXRDNH-UHFFFAOYSA-N thiophen-2-amine Chemical compound NC1=CC=CS1 GLQWRXYOTXRDNH-UHFFFAOYSA-N 0.000 description 1
- 238000005891 transamination reaction Methods 0.000 description 1
- 238000012546 transfer Methods 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
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
- H10K85/624—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing six or more rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/12—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains three hetero rings
- C07D471/16—Peri-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed systems contains four or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
- C09B57/08—Naphthalimide dyes; Phthalimide dyes
-
- 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
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- H10K85/621—Aromatic anhydride or imide compounds, e.g. perylene tetra-carboxylic dianhydride or perylene tetracarboxylic di-imide
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
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- Y02E10/549—Organic PV cells
Definitions
- This invention is related to new compounds, organic electronic devices using the same and especially to organic photovoltaic (OPV) devices, also known as organic solar cells.
- OCV organic photovoltaic
- the solar light is one of the most attractive forms of renewable energy, because it is available in relatively large power density, and it is easily convertible into other forms of energy such as electrical, thermal, etc.
- Organic solar cells are attracting considerable interest from research and industry; they offer a big promise for the efficient and large scale conversion of light into electricity.
- the production of organic solar cells is less material demanding than the production of inorganic crystalline solar cells.
- the production also consumes considerably less energy than the production of any other inorganic solar cell.
- OPV devices have the most different devices architectures. Typically they comprise at least one organic semiconducting layer between two electrodes. That organic layer can be a blend of a donor and an acceptor such as P3HT (poly3-hexyl-tiophene) and PCBM (phenyl Cn Butyric Acid Methyl Ester).
- P3HT poly3-hexyl-tiophene
- PCBM phenyl Cn Butyric Acid Methyl Ester
- tandem or multi-unit stacks are known (Ameri et al, Energy & Env. Science, 2009. 2: p. 347). From those, the multi-layer devices can be easier optimized since different layers can comprise different materials which are suitable for different functions.
- Typical functional layers are transport layers, optically active layers, injection layers, etc.
- Optically active materials are materials with a high absorption coefficient, for at least a certain wavelength range of the solar spectra, which materials convert absorbed photons into excitons which excitons contribute to the photocurrent.
- the optically active materials are typically used in a donor-acceptor heterojunction, where at least one of the donor or acceptor is the light absorbing material.
- the interface of the donor-acceptor heterojunction is responsible for separating the generated excitons into charge carriers.
- the heterojunction can be a bulk- heterojunction (a blend), or a flat (also called planar) heterojunction, additional layers can also be provided (Hong et al, J. Appl. Phys., 2009. 106: p. 064511).
- the materials in the heterojunction must have high charge carrier mobilities and high exciton diffusion lengths.
- the excitons have to be separated at the heterointerface and the charge carriers have to leave the optically active region before any recombination takes place.
- organic materials are suitable to be used in the heterojunction. For instance, currently, there are no known materials which can compete with the fullerenes and their derivatives (e.g. C60, C70, PCBM, and so on) as acceptor in OPV devices.
- Transport materials are required to be transparent, at least in the wavelengths wherein the device is active, and have good semiconducting properties. Those semiconducting properties are intrinsic, such as energy levels or mobility, or extrinsic such as charge carrier density.
- the charge carrier density can be extrinsically influenced, for instance, by doping the material with an electrical dopant.
- the new materials can also be employed in OLEDs, and in OTFTs.
- the material is preferentially used in at least one of: an optically active layer and an electron transport layer, more preferentially at least in an electron transport layer.
- an organic electronic device especially an organic solar cell, comprising at least one compound according to the following formula (I):
- Rl is C5-20-aryl; C5-20-heteroaryl, C2-C20-alkyl, C2-C20-perfluoroalkyl;
- each X is independently selected from C, N, O and S;
- each R is independently selected from C5-20-aryl, C5-20-heteroaryl, N0 2 , CN, H, F, CF3, C2-C20-alkyl and C2-20-perfiuoroalkyl;
- n 0, 1, 2 or 3.
- C 5 -C 2 o-aryl is preferably selected from: phenyl, naphthyl, anthracyl, perfluorophenyl, fluorophenyl.
- C5-C 2 o-heteroaryl is preferably selected from pyridyl, thienyl, oxazolyl, imidazolyl, benzimidazolyl.
- aryl means an aromatic group containing only carbon in the aromatic ring or rings. An aryl group may contain 1 to 3 separate, fused, or pendant rings and from 5 to 20 ring atoms, without heteroatoms as ring members. Examples of aryl groups include, but are not limited to, phenyl, naphthyl, including 1 -naphthyl and 2-naphthyl, perfluorophenyl, fluorophenyl, and bi-phenyl.
- a compound according to formula (I) is preferentially used in an electron transport layer in a solar cell.
- the compound is the main component of the electron transport layer.
- Preferentially at least one electron transport layer comprising the compound according to formula (I) is doped with an electrical dopant.
- the compound according to formula (I) is used in an exciton blocking layer as its main component.
- the exciton blocking layer is preferentially also an electron transport layer.
- the layer has a low enough LUMO to transport electrons between the acceptor and the cathode, and at the same time, it has a high HOMO-LUMO gap to block the excitons confining them into the optically active region, which means that the HOMO-LUMO gap is larger than the HOMO-LUMO gap of any immediately (in contact) adjacent material from the optically active region.
- This layer is preferentially electrically undoped.
- the compound according to formula (I) is used as a main component of an exciton-and-hole-blocking-layer.
- the exciton-and-hole-blocking-layer has a low enough HOMO to block holes from an adjacent layers (mainly from the donor molecule of the bulk-heterojunction), and at the same time, it has a high HOMO-LUMO gap to block the excitons out of its layer confining them into the optically active region, which means that the HOMO-LUMO gap is larger than the HOMO- LUMO gap of any immediately (in contact) adjacent material from the optically active region.
- This layer is preferentially electrically undoped.
- the compound according to formula (I) is an acceptor in a donor-acceptor heterojunction.
- the compound also harvest light which light is converted into charge and contributes to the photocurrent, preferentially, the contribution of the photocurrent at OV is due to absorption of photons in the range of 350-800 nm, more preferably in the range of 350-500 nm. Preferentially the contribution is greater than 5%.
- the compound according to formula (I) is used as main component of an exciton-blocking and electron- transporting layer.
- the exciton-blocking-and-electron-transporting-layer has low enough LUMO to accept the electron from a donor molecule in an adjacent layer, and at the same time, it has a high HOMO-LUMO gap to block the excitons out of its layer confining them into the optically active region, which means that the HOMO-LUMO gap is larger than the HOMO-LUMO gap of any immediately (in contact) adjacent material from the optically active region.
- This layer is preferentially electrically undoped.
- the compound according to formula (I) is preferentially used as main component of a layer in combination with an adjacent layer, wherein the modulus(absolute value) of the difference of the LUMO of the layer and the adjacent layer is smaller 0.4 eV, more preferentially smaller than 0.2 eV (0.2 eV is about the width of the density of states of one material).
- the adjacent layer comprises as its main component a fullerene chosen from C 5 8, C 6 o, C70, or a soluble derivative of it (e.g. PC 60 BM).
- an organic solar cell comprises a compound according to the Formula (I), in a layer adjacent to the donor-acceptor heterojunction, in an undoped form.
- the organic solar cell comprises an additional doped layer comprising a compound according to the Formula (I) between the layer adjacent to the donor-acceptor heterojunction and the cathode.
- the solar cell is a polymer solar cell, comprising at least one semiconducting polymer in the at least one donor-acceptor heterojunction and comprising the compound according to formula (I) in at least one electron transport layer. Preferentially at least one electron transport layer is n-doped.
- the organic solar cell comprises a pi, ni, or pin structure, comprising a first p, i, or n layer each.
- p denotes a p-doped hole transport layer
- n denotes a n-doped electron transport layer
- i is an intrinsic photoactive layer.
- the transport layers have a greater HOMO-LUMO gap than the photoactive layer.
- n-dopants which can be employed are: tetrathianaphthacene, [Ru(terpy)2]°; rhodamine B; pyronin B chloride; acridine orange base; leuco crystal violet; 2,2'-diisopropyl-l, ,3,3'-tetramethyl-2,2',3,3',4,4',5,5',6,6',7,7'- dodecahydro-lH, l'H-2,2-bibenzo[d]imidazole; 4,4', 5,5' - tetracyclohexyl - 1, ⁇ ,2,2',3,3' - hexamethyl - 2,2', 3,3' - tetrahydro- lH,l'FI-2,2'-bisimidazole; 2,2'-diisopropyl - 4,4', 5,5' - tetrakis
- Fig. 1 is a simple diagram representing the stack of layers which forms a solar cell.
- Fig. 2 is a simple diagram representing the layers of a solar cell comprising an ETL.
- an organic solar cell comprises at least a substrate (10), an anode (1 1), at least one organic optically active layer (12), and a cathode (13).
- the stack of layers can also be inverted, wherein layer (11) would be the cathode, and layer (12) would be the anode.
- the substrate (10) is a transparent substrate, such as a glass, or polymeric plate or web;
- the anode (11) is a transparent conducting oxide, such as ITO, FTO, A1ZO; and the cathode (13) comprises aluminum or an aluminum alloy.
- the at least one organic optically active layer (12) comprises a blend of a thiophene containing polymer and a compound according to formula (I).
- the at least one organic optically active layer (12) comprises a blend of a donor polymer, preferentially a thiophene containing polymer, and an acceptor, preferentially a fullerene or a soluble fullerene derivative; in this embodiment a layer containing the compound according to Formula (I) is formed between the at least one organic optically active layer (12) and the cathode (13).
- the layer structure is inverted.
- the transparent conducting oxide can be replaced by another transparent conducting material, for example a thin metal layer, carbon nanotubes, conducting polymer, or metal nano wires.
- the anode (11) is not transparent and mainly comprises Aluminum or an Aluminum alloy.
- the substrate (10) is not necessarily transparent.
- the cathode (13) comprises a transparent conducting oxide layer or a thin (thickness ⁇ 30 nm) transparent metal layer.
- the substrate (10), the anode (11), and the cathode (13) are transparent.
- the overall device is semi-transparent, because it does not have 100% absorption of the incident light for any wavelength in the visible range of wavelengths.
- multiple stacked devices are also provided in this invention.
- at least one additional organic optically active layer is formed between the at least one organic optically active layer (12) and the cathode (13).
- Additional organic or inorganic layers may be used to provide a suitable electronic connection and optical optimization of the layer position.
- at lest parts of these functions are provide by layers comprising a compound according to the formula (I).
- surface treatment of the electrodes, buffer layers, and/or injection layers can be used to provide efficient charge carrier injection/extraction.
- Examples of surface treatments are acid, or plasma treatment of the electrode's surface.
- Example of injection layers are thin inorganic insulating layers (e.g. LiF) and thin electrical dopant layers.
- Fig.2 shows a stack of layers representing an organic solar cell comprising at least: a substrate (20), an anode (21), at least one optically active layer (22), an organic electron transport layer (ETL) (23), and a cathode (24).
- the stack of layers can also be inverted.
- the ETL is formed between cathode and optically active layer.
- the organic electron transport layer comprises as its main component a compound according to the Formula (I). Preferentially this compound according to the Formula (I) is doped with an electrical dopant.
- the ETL (23) can have any thickness, its thickness is preferably smaller than 40 nm in the case that there is no additional optically active layer between the at least one optically active layer (22) and the cathode (24).
- All embodiments as described in connection to fig. 1 can also be applied here, in connection to fig. 2. All figures are simple representations of the layered structure of a solar cell. Some device features are not shown such as electrical connections, encapsulation, optical structures which are external to the electrodes, etc. At least one of the electrodes (anode and cathode) is transparent in the wavelength range in which the device is active. In another embodiment the at least one optically active layer (22) is a donor-acceptor bulk heterojunction (blend of donor-acceptor). The donor is preferentially formed by a strong absorbing compound comprising a pyrrole or a thiophene group.
- the acceptor is preferentially a C 5 8, C 6 o, or C70 fullerene or a soluble fullerene derivative.
- the ETL (23) comprises a compound according to the formula (I) as its main component.
- the ETL (23) is preferentially doped with an n-dopant. Or organic n-dopants are highly preferred due to their easier handling in production.
- the at least one optically active layer (22) is a donor-acceptor bulk heterojunction (blend of a donor with an acceptor).
- the donor is preferentially formed by a strong absorbing compound comprising a pyrrole or a thiophene group.
- the acceptor is a compound according to Formula (I).
- all organic layers are constituted from small molecules.
- these small molecules can be deposited by VTE (Vacuum Thermal evaporation).
- At least one organic semiconducting layer comprises a polymer and at least one additional semiconducting layer comprises a compound according to Formula (I).
- Another aspect of the invention is a layer comprising a compound of Formula (I) and an n- dopant.
- the invented compounds have a special advantage of forming very stable n-doped layers with a relatively high conductivity.
- the conductivity can be measured by the so-called 2-point or 4-point-method.
- contacts of a conductive material such as gold or indium-tin-oxide
- the thin film to be examined is applied onto the substrate, so that the contacts are covered by the thin film.
- the current is measured. From the geometry of the contacts and the thickness of the sample the resistance and therefore the conductivity of the thin film material can be determined.
- the four point or two point method give the same conductivity values for doped layers since the doped layers grant a good ohmic contact, otherwise the contact resistance has to be deducted from the 2-point method.
- the temperature stability can also be measured with that method with the addition that the (undoped or doped) layer is heated stepwise, and after a waiting period the conductivity is measured.
- the maximum temperature which can be applied to the layer without loosing the desired semiconducting properties, is then the temperature just before the conductivity breaks down.
- a doped layer can be heated on the substrate with two electrodes, as disclosed above, in steps of 1°C, wherein after each step there is a waiting period of 10 seconds. Then the conductivity is measured.
- the conductivity changes with temperature and breaks down abruptly at a particular temperature.
- the temperature stability is therefore the temperature up to which the conductivity does not break down abruptly.
- the measurement is performed in vacuum or inert gas.
- HOMO highest occupied molecular orbital energy level
- LUMO lowest unoccupied molecular orbital energy level
- R1-NH2 can be, for example: Aniline, 2-aminopyridine, 2-aminothiophene, 1,1,2,2,3,3,3- heptafluoropropan- 1 -amine, propan- 1 -amine
- the structure can be, for example: 2,3-diaminobut-2-enedinitrile, 1 ,2-ethenediamine, (Z)- 1 ,2-difluoroethene- 1 ,2-diamine, (Z)- 1 ,2-diphenylethene- 1 ,2-diamine, (Z)- 1 ,2-di(pyridin- 2-yl)ethene- 1 ,2-diamine, (Z)- 1 ,2-di(thiophen-2-yl)ethene- 1 ,2-diamine.
- R is different than N02.
- the compounds R1-NH2 can be selected from those already disclosed above.
- the structure - N x R can be, for example: 4,5-diaminophthalonitrile, 5,6- diaminopyrazine-2,3-dicarbonitrile, benzene- 1,2-diamine, 5,6-dinitropyrazine-2,3-diamine, 5,6-difluoropyrazine-2,3-diamine, 4, 5-difluorobenzene- 1,2-diamine, 4,5- bis(trifluoromethyl)benzene- 1,2-diamine, 5,6-bis(trifluoromethyl)pyrazine-2,3-diamine, 5,6- diphenylpyrazine-2,3-diamine, [ 1 , :2', 1 "-terphenyl]-4',5'-diamine, 4, 5-bis(l -phenyl- 1H- benzo[d]imidazol-2-yl)benzene- 1,2-diamine, 5, 6-bis(l -phenyl- lH
- Preferred compounds are:
- the compounds R1-NH2 can be selected from those already disclosed above.
- the structure - N X X R can f or example: 6,7-diaminoquinoxaline, 2,3- phenazinediamine, 2,3-diamino-7-chlorophenazine, 6,7-Dimethyl-2,3-Quinoxalinediamine, 2,3-Quinoxalinediamine,
- NTCDA NTCDA (12g, 44,7 mmol) was heated at 150°C, under stirring, in 315 mL dry DMF. Aniline (700mg, 7,54 mmol) in solution in DMF (135mL) is then added within 20min. The mixture is stirred at 150°C for an additional 6,5 hours before let cooled down overnight. The obtained precipitate (NTCDA) is then filtered to remove the excess NTCDA. The filtrate is reduced to a l/3 rd , cooled down (fridge, 30 min), so that another fraction of NTCDA precipitates. The mixture is then filtered to separate the remaining NTCDA from the product.
- the filtrate is concentrated until almost dry and stirred 3 times with 200mL Water in an ultrasonic bath.
- the product is finally filtered and washed with 50mL water and dried in a vacuum oven overnight.
- the obtained product is then dissolved in chloroform and filtered over celite. The solvents were evaporated and the material was used as such into the second step.
- Second step Synthesis of 9,10-difluoro-2-phenylbenzo[lmn]benzo[4,5]imidazo[2,l- b][3,8]phenanthroline-l,3,6(2H)-trione (2). All manipulations were carried out in air, without any further purification of commercial solvents/chemicals.
- ETMs The conductivity at room temperature is 1,06- 10 S/cm and the stability temperature is 153 °C for a layer doped with Tetrakis(l,3,4,6,7,8-Hexahydro-2H-pyrimido[l,2- a]pyrimidinato)ditungsten (II).
- the conductivity at room temperature is 1,2- 10 S/cm and the stability temperature is 141 °C for a layer doped with 4,4',5,5'-tetracyclohexyl-l, ,2,2',3,3'- hexamethyl-2,2',3,3'-tetrahydro-lH, H-2,2'-biimidazole.
- inverted solar cell refers to a device with a layer structure in which the cathode is closer to the substrate than the anode.
- the cathode is formed on the substrate, following the deposition of the organic and other layers, which are followed by the deposition of the cathode.
- ETL - electron transport layer is a layer which is used in a device stack in such a way that the main charge carriers are electrons. Typically, this layer comprises an electron transport material (ETM). Hole blocking layers, exciton blocking layers between the cathode and its closest donor-acceptor heterojunction are also electron transport layers. Electron injection layers could also be electron transport layers, if they are semiconductors comprising an ETM.
- ETM electron transport material
- ETM - electron transport material is a semiconducting material which is stable towards reduction and has a high mobility for electrons.
- the electron mobility is typically higher than the hole mobility.
- HTL - hole transport layer is a layer which is used in a device stack in such a way that the main charge carriers are electrons.
- this layer comprises a hole transport material (HTM).
- HTM - hole transport material is a semiconducting material which is stable towards oxidation and has a high mobility for holes. In a HTM, the hole mobility is typically higher than the electron mobility.
- FHJ - Flat heterojunction is a donor-acceptor heterojunction in which the donor and acceptor materials are in separate layers. Preferentially the donor and acceptor materials are in adjacent layers providing a hetero-interface. Alternatively, other layers can be placed in between, to assist the light absorption and/or charge carrier separation.
- BHJ - Bulk heterojunction is a mixed layer comprising a donor, an acceptor, and an absorbing material. Typically at least one of the donor and acceptor materials are also the absorbing material.
- the donor-acceptor heterointerface is necessary for the separation of the excitons formed by photoabsorbtion into charge carriers.
- a bulk heterojunction can be graded, or also comprise additional layers.
- a bulk donor-acceptor heterojunction can also be a hybrid junction, comprising a mixed layer and at least one layer comprising: the acceptor but no donor material, or the donor but no acceptor material. Such a heterojunction can also be a graded bulk heterojunction.
- Acceptor - Acceptor in this invention, is a compound used in an optically active layer of a solar cell to assist the excitonic separation into charge carriers, accepting the electron.
- acceptor must not be confused with an electrical p-dopant which is a very strong acceptor capable of doping a hole transport layer.
- Donor - Donor in this invention, is a compound used in an optically active layer of a solar cell to assist the excitonic separation into charge carriers, donating an electron (accepting a hole).
- the term donor must not be confused with an electrical n-dopant which is a very strong donor capable of doping an electron transport layer.
- Electrical dopant - Electrical dopant is a dopant which is capable to, when added to a semiconductor, increase its charge carrier density, consequently increasing its conductivity.
- the increase in charge carrier density is due to a charge transfer between the LUMO and HOMO of the at least two components of the dopant-semiconductor system.
- the term electrically doped refers to a layer or material which is doped by an electrical dopant, as defined above.
- n-dopant - electrical dopant capable of increasing the density of negative charge carriers in an electron transport material or electron transport layer.
- the negative charge carriers are provided on the effective conduction band of the electron transport layer (typically the LUMO of the electron transport material).
- p-dopant - electrical dopant capable of increasing the density of positive charge carriers in a hole transport material or hole transport layer.
- the positive charge carriers are provided on the effective valence band of the hole transport layer (typically the HOMO of the hole transport material).
- Transparency those transport layers, which do not contribute to the photocurrent generation, are required to be transparent to avoid any efficiency loss due to undesired absorption.
- a high transparency is required in the range of wavelengths in which the solar cell is active.
- a high transparency preferentially means an extinction coefficient (k) smaller than 1 , more preferably smaller than 0.1.
- LUMO Lowest unoccupied molecular orbital.
- Intrinsic layer - a layer which is not doped with dopants which increases the charge carrier density in the layer.
- the layer in the dark, and no temperature gradient, or electrical field is applied to it.
Abstract
The present invention relates to new naphthalene carbodiimide (NTCDI) derivatives, and organic electronic device using the same and especially to an organic solar cell. The new NTCDI derivatives are used as acceptor, electron transport material, and doped electron transport materials.
Description
Compound for organic electronic device
Technical Field
This invention is related to new compounds, organic electronic devices using the same and especially to organic photovoltaic (OPV) devices, also known as organic solar cells.
The solar light is one of the most attractive forms of renewable energy, because it is available in relatively large power density, and it is easily convertible into other forms of energy such as electrical, thermal, etc.
Organic solar cells are attracting considerable interest from research and industry; they offer a big promise for the efficient and large scale conversion of light into electricity. The production of organic solar cells is less material demanding than the production of inorganic crystalline solar cells. The production also consumes considerably less energy than the production of any other inorganic solar cell.
Efficiency of organic solar cells has been improving steadily. In 2008 a certified power conversion efficiency value of 5% was reached, and in 2010 the psychological barrier of 8% was broken, aligning the efficiency of the organic solar cells to typical values of amorphous Si devices.
Background art
OPV devices have the most different devices architectures. Typically they comprise at least one organic semiconducting layer between two electrodes. That organic layer can be a blend of a donor and an acceptor such as P3HT (poly3-hexyl-tiophene) and PCBM (phenyl Cn Butyric Acid Methyl Ester). Such simple device structures only achieve reasonably efficiencies if interfacial injection layers are used to facilitate charge carrier injection/extraction (Liao et al., Appl. Phys. Lett., 2008. 92: p. 173303). Other organic solar cells have multi-layer structures, sometimes even hybrid polymer and small molecule structures. Also tandem or multi-unit stacks are known (Ameri et al, Energy & Env. Science,
2009. 2: p. 347). From those, the multi-layer devices can be easier optimized since different layers can comprise different materials which are suitable for different functions. Typical functional layers are transport layers, optically active layers, injection layers, etc. Optically active materials are materials with a high absorption coefficient, for at least a certain wavelength range of the solar spectra, which materials convert absorbed photons into excitons which excitons contribute to the photocurrent. The optically active materials are typically used in a donor-acceptor heterojunction, where at least one of the donor or acceptor is the light absorbing material. The interface of the donor-acceptor heterojunction is responsible for separating the generated excitons into charge carriers. The heterojunction can be a bulk- heterojunction (a blend), or a flat (also called planar) heterojunction, additional layers can also be provided (Hong et al, J. Appl. Phys., 2009. 106: p. 064511).
The loss by recombination must be minimized for high efficiency OPV devices. Therefore, the materials in the heterojunction must have high charge carrier mobilities and high exciton diffusion lengths. The excitons have to be separated at the heterointerface and the charge carriers have to leave the optically active region before any recombination takes place. For those reasons, only few organic materials are suitable to be used in the heterojunction. For instance, currently, there are no known materials which can compete with the fullerenes and their derivatives (e.g. C60, C70, PCBM, and so on) as acceptor in OPV devices.
Transport materials are required to be transparent, at least in the wavelengths wherein the device is active, and have good semiconducting properties. Those semiconducting properties are intrinsic, such as energy levels or mobility, or extrinsic such as charge carrier density. The charge carrier density can be extrinsically influenced, for instance, by doping the material with an electrical dopant.
Although in steady development, the choice of materials for OPV is still very limited, especially for optically active materials and for electron transport materials. Some highly efficient device structures employ TiO as electron transport and optical spacer with the disadvantage of being difficult to deposit (Simon et al, Int. J. of Mat. & Prod. Tech., 2009. 34: p. 469). Other devices use Fullerene C60 as ETL which is not transparent enough for functioning as an optical spacer. Other materials such as NTCDA, although transparent and
with good semiconducting properties, are not morphologically stable and crystallize even at room temperature.
The new materials can also be employed in OLEDs, and in OTFTs.
Almost no organic electron transport material is available with suitable semiconducting, chemical, and thermal properties.
Technical Problem
It is the objective of the present invention to provide a new organic semiconductor material for use in organic electronic devices, preferably organic solar cells. The material is preferentially used in at least one of: an optically active layer and an electron transport layer, more preferentially at least in an electron transport layer.
Solution of the problem
The object is achieved by compounds and organic electronic devices according independent claims 1 and 11. Preferred embodiments are disclosed in the sub-claims.
This object is especially achieved by an organic electronic device, especially an organic solar cell, comprising at least one compound according to the following formula (I):
Formula (I)
wherein
Rl is C5-20-aryl; C5-20-heteroaryl, C2-C20-alkyl, C2-C20-perfluoroalkyl;
each X is independently selected from C, N, O and S;
each R is independently selected from C5-20-aryl, C5-20-heteroaryl, N02, CN, H, F, CF3, C2-C20-alkyl and C2-20-perfiuoroalkyl;
m = 0, 1, 2 or 3.
C5-C2o-aryl is preferably selected from: phenyl, naphthyl, anthracyl, perfluorophenyl, fluorophenyl.
C5-C2o-heteroaryl is preferably selected from pyridyl, thienyl, oxazolyl, imidazolyl, benzimidazolyl. The term "aryl" means an aromatic group containing only carbon in the aromatic ring or rings. An aryl group may contain 1 to 3 separate, fused, or pendant rings and from 5 to 20 ring atoms, without heteroatoms as ring members. Examples of aryl groups include, but are not limited to, phenyl, naphthyl, including 1 -naphthyl and 2-naphthyl, perfluorophenyl, fluorophenyl, and bi-phenyl.
Advantages of the compounds
A compound according to formula (I) is preferentially used in an electron transport layer in a solar cell. The compound is the main component of the electron transport layer. Preferentially at least one electron transport layer comprising the compound according to formula (I) is doped with an electrical dopant.
In an alternative embodiment, or in addition, the compound according to formula (I) is used in an exciton blocking layer as its main component. The exciton blocking layer is preferentially also an electron transport layer. The layer has a low enough LUMO to transport electrons between the acceptor and the cathode, and at the same time, it has a high HOMO-LUMO gap to block the excitons confining them into the optically active region, which means that the HOMO-LUMO gap is larger than the HOMO-LUMO gap of any immediately (in contact)
adjacent material from the optically active region. This layer is preferentially electrically undoped.
In another alternative embodiment, or in addition, the compound according to formula (I) is used as a main component of an exciton-and-hole-blocking-layer. In this embodiment, the exciton-and-hole-blocking-layer has a low enough HOMO to block holes from an adjacent layers (mainly from the donor molecule of the bulk-heterojunction), and at the same time, it has a high HOMO-LUMO gap to block the excitons out of its layer confining them into the optically active region, which means that the HOMO-LUMO gap is larger than the HOMO- LUMO gap of any immediately (in contact) adjacent material from the optically active region.. This layer is preferentially electrically undoped.
In an alternative embodiment, or in addition, the compound according to formula (I) is an acceptor in a donor-acceptor heterojunction. In an aspect of this embodiment, the compound also harvest light which light is converted into charge and contributes to the photocurrent, preferentially, the contribution of the photocurrent at OV is due to absorption of photons in the range of 350-800 nm, more preferably in the range of 350-500 nm. Preferentially the contribution is greater than 5%. In an alternative embodiment, or in addition to the use as an acceptor, the compound according to formula (I) is used as main component of an exciton-blocking and electron- transporting layer. In this embodiment, the exciton-blocking-and-electron-transporting-layer has low enough LUMO to accept the electron from a donor molecule in an adjacent layer, and at the same time, it has a high HOMO-LUMO gap to block the excitons out of its layer confining them into the optically active region, which means that the HOMO-LUMO gap is larger than the HOMO-LUMO gap of any immediately (in contact) adjacent material from the optically active region. This layer is preferentially electrically undoped.
The compound according to formula (I) is preferentially used as main component of a layer in combination with an adjacent layer, wherein the modulus(absolute value) of the difference of the LUMO of the layer and the adjacent layer is smaller 0.4 eV, more preferentially smaller than 0.2 eV (0.2 eV is about the width of the density of states of one material).
Preferentially the adjacent layer comprises as its main component a fullerene chosen from C58, C6o, C70, or a soluble derivative of it (e.g. PC60BM).
In another aspect of the invention, an organic solar cell comprises a compound according to the Formula (I), in a layer adjacent to the donor-acceptor heterojunction, in an undoped form. In addition, the organic solar cell comprises an additional doped layer comprising a compound according to the Formula (I) between the layer adjacent to the donor-acceptor heterojunction and the cathode. In another aspect of the invention, the solar cell is a polymer solar cell, comprising at least one semiconducting polymer in the at least one donor-acceptor heterojunction and comprising the compound according to formula (I) in at least one electron transport layer. Preferentially at least one electron transport layer is n-doped. In a preferred aspect of the invention, the organic solar cell comprises a pi, ni, or pin structure, comprising a first p, i, or n layer each. Here, p denotes a p-doped hole transport layer, n denotes a n-doped electron transport layer, and i is an intrinsic photoactive layer. The transport layers have a greater HOMO-LUMO gap than the photoactive layer. For all aspects of the invention, exemplary n-dopants which can be employed are: tetrathianaphthacene, [Ru(terpy)2]°; rhodamine B; pyronin B chloride; acridine orange base; leuco crystal violet; 2,2'-diisopropyl-l, ,3,3'-tetramethyl-2,2',3,3',4,4',5,5',6,6',7,7'- dodecahydro-lH, l'H-2,2-bibenzo[d]imidazole; 4,4', 5,5' - tetracyclohexyl - 1,Γ,2,2',3,3' - hexamethyl - 2,2', 3,3' - tetrahydro- lH,l'FI-2,2'-bisimidazole; 2,2'-diisopropyl - 4,4', 5,5' - tetrakis(4-methoxyphenyl) - l,r,3,3'-tetramethyl-2,2',3,3'-tetrahydro-lH,l'H-2,2'- bisimidazole; 2-isopropyl-l,3-dimethyl - 2,3,6,7 - tetrahydro-lH-5,8-dioxa-l,3-diaza- cyclopenta[b]-naphthene; bis-[l,3-dimethyl-2-isopropyl-l,2-dihydro - benzimidazolyl-(2)]; tetrakis (1,3,4,6,7,8 - hexahydro - 2H - pyrimido [1,2-a] pyrimidinato) ditungsten(II); 2,2' - diisopropyl - 4,5 - bis(2-methoxyphenyl) - 4',5' - bis(4-methoxyphenyl) - 1,1', 3,3' - tetramethyl-2,2',3,3'-tetrahydro-lH,l'FI-2,2'-bisimidazole; 2,2'-diisopropyl-4,5-bis(2- methoxyphenyl) - 4',5' - bis(3-methoxyphenyl) - 1,1', 3,3' - tetramethyl - 2,2', 3,3' - tetrahydro - 1H, ΓΗ - 2,2' - bisimidazole (see for example, patent publications US 2005/0040390, US 2009/0212280, and US 2007/0252140).
Brief description of the drawings
Fig. 1 is a simple diagram representing the stack of layers which forms a solar cell.
Fig. 2 is a simple diagram representing the layers of a solar cell comprising an ETL.
Devices
According to Fig. 1 , an organic solar cell comprises at least a substrate (10), an anode (1 1), at least one organic optically active layer (12), and a cathode (13). The stack of layers can also be inverted, wherein layer (11) would be the cathode, and layer (12) would be the anode. Normally the layers do not overlap 100% so that extensions of the layers used for the electrodes are used for electrical connections, but other configurations are possible. In one embodiment, the substrate (10) is a transparent substrate, such as a glass, or polymeric plate or web; the anode (11) is a transparent conducting oxide, such as ITO, FTO, A1ZO; and the cathode (13) comprises aluminum or an aluminum alloy. In one embodiment the at least one organic optically active layer (12) comprises a blend of a thiophene containing polymer and a compound according to formula (I). Alternatively the at least one organic optically active layer (12) comprises a blend of a donor polymer, preferentially a thiophene containing polymer, and an acceptor, preferentially a fullerene or a soluble fullerene derivative; in this embodiment a layer containing the compound according to Formula (I) is formed between the at least one organic optically active layer (12) and the cathode (13). Optionally the layer structure is inverted. The transparent conducting oxide can be replaced by another transparent conducting material, for example a thin metal layer, carbon nanotubes, conducting polymer, or metal nano wires.
In one embodiment the anode (11) is not transparent and mainly comprises Aluminum or an Aluminum alloy. The substrate (10) is not necessarily transparent. The cathode (13) comprises a transparent conducting oxide layer or a thin (thickness < 30 nm) transparent metal layer.
Still in connection to Fig.1, in another embodiment, the substrate (10), the anode (11), and the cathode (13) are transparent. In this embodiment, the overall device is semi-transparent,
because it does not have 100% absorption of the incident light for any wavelength in the visible range of wavelengths.
Note that multiple stacked devices (e.g. tandem devices) are also provided in this invention. In such devices at least one additional organic optically active layer is formed between the at least one organic optically active layer (12) and the cathode (13). Additional organic or inorganic layers may be used to provide a suitable electronic connection and optical optimization of the layer position. Preferentially, at lest parts of these functions are provide by layers comprising a compound according to the formula (I).
Still in connection to Fig.1, surface treatment of the electrodes, buffer layers, and/or injection layers can be used to provide efficient charge carrier injection/extraction. Examples of surface treatments are acid, or plasma treatment of the electrode's surface. Example of injection layers are thin inorganic insulating layers (e.g. LiF) and thin electrical dopant layers.
Fig.2 shows a stack of layers representing an organic solar cell comprising at least: a substrate (20), an anode (21), at least one optically active layer (22), an organic electron transport layer (ETL) (23), and a cathode (24). The stack of layers can also be inverted. The ETL is formed between cathode and optically active layer.
In one embodiment, the organic electron transport layer comprises as its main component a compound according to the Formula (I). Preferentially this compound according to the Formula (I) is doped with an electrical dopant. The ETL (23) can have any thickness, its thickness is preferably smaller than 40 nm in the case that there is no additional optically active layer between the at least one optically active layer (22) and the cathode (24).
All embodiments as described in connection to fig. 1 can also be applied here, in connection to fig. 2. All figures are simple representations of the layered structure of a solar cell. Some device features are not shown such as electrical connections, encapsulation, optical structures which are external to the electrodes, etc. At least one of the electrodes (anode and cathode) is transparent in the wavelength range in which the device is active.
In another embodiment the at least one optically active layer (22) is a donor-acceptor bulk heterojunction (blend of donor-acceptor). The donor is preferentially formed by a strong absorbing compound comprising a pyrrole or a thiophene group. The acceptor is preferentially a C58, C6o, or C70 fullerene or a soluble fullerene derivative. The ETL (23) comprises a compound according to the formula (I) as its main component. The ETL (23) is preferentially doped with an n-dopant. Or organic n-dopants are highly preferred due to their easier handling in production.
In another embodiment, the at least one optically active layer (22) is a donor-acceptor bulk heterojunction (blend of a donor with an acceptor). The donor is preferentially formed by a strong absorbing compound comprising a pyrrole or a thiophene group. The acceptor is a compound according to Formula (I).
In one aspect of the invention, all organic layers are constituted from small molecules. Preferentially, these small molecules can be deposited by VTE (Vacuum Thermal evaporation).
In another aspect of the invention, at least one organic semiconducting layer comprises a polymer and at least one additional semiconducting layer comprises a compound according to Formula (I).
Another aspect of the invention is a layer comprising a compound of Formula (I) and an n- dopant. The invented compounds have a special advantage of forming very stable n-doped layers with a relatively high conductivity.
The conductivity can be measured by the so-called 2-point or 4-point-method. Here, contacts of a conductive material, such as gold or indium-tin-oxide, are disposed on a substrate. Then, the thin film to be examined is applied onto the substrate, so that the contacts are covered by the thin film. After applying a voltage to the contacts the current is measured. From the geometry of the contacts and the thickness of the sample the resistance and therefore the conductivity of the thin film material can be determined. The four point or two point method give the same conductivity values for doped layers since the doped layers grant a good ohmic contact, otherwise the contact resistance has to be deducted from the 2-point method.
The temperature stability can also be measured with that method with the addition that the (undoped or doped) layer is heated stepwise, and after a waiting period the conductivity is measured. The maximum temperature, which can be applied to the layer without loosing the desired semiconducting properties, is then the temperature just before the conductivity breaks down. For example, a doped layer can be heated on the substrate with two electrodes, as disclosed above, in steps of 1°C, wherein after each step there is a waiting period of 10 seconds. Then the conductivity is measured. The conductivity changes with temperature and breaks down abruptly at a particular temperature. The temperature stability is therefore the temperature up to which the conductivity does not break down abruptly. The measurement is performed in vacuum or inert gas.
The properties of the many different used materials can be described by the position of their highest occupied molecular orbital energy level (HOMO, synonym of ionization potential), and the lowest unoccupied molecular orbital energy level (LUMO, synonym of electron affinity).
Preferred compounds and their synthesis will be described below.
Synthesis - General
The following schema describes the general synthesis for the compounds according to the invention.
Further information on syntheses can be found in the following literature:
- W. Herbst, K. Hunger: Industrial Organic Pigments, Production, Properties, Applications, Third, completely revised edition, p.473-487, Wiley-VCH, Weinheim 1995.
- Babel et al. (2003). "High Electron Mobility in Ladder Polymer Field-Effect Transistors. " Journal of the American Chemical Society 125(45), p. 13656-13657.
- Erten and Icli (2008). "Bilayer heterojunction solar cell based on naphthalene bis- benzimidazole. " Inorganica Chimica Acta 361(3), p. 595-600.
- Feast et al. (1999). "Poly(4-vinyltriphenylamine). Synthesis and application as a hole transport layer in light- emitting diodes. " Polymer Bulletin (Berlin) 42(2), p. 167-174.
- Langhals and Jaschke (2006). "Naphthalene amidine imide dyes by transamination of naphthalene bisimides. " Chemistry— A European Journal 12(10), p. 2815-2824.
- Mizuguchi, J. (2004). "Crystal Structure and Electronic Characterization of trans- and cis- Perinone Pigments. " Journal of Physical Chemistry B 108(26), p. 8926-8930.
- Tamuly et al. (2006). "Fluorescence quenching and enhancement by H-bonding interactions in some nitrogen containing fluorophores. " Supramolecular Chemistry 18(8), p. 605-613.
- Young et al. (2009). "Comparative PCET Study of a Donor- Acceptor Pair Linked
- by Ionized and Nonionized Asymmetric Hydrogen-Bonded Interfaces " J. Am. Chem. Soc.
131, p. 7678-7684. Compounds with m=0
Modifying the general synthesis to the form below enables the synthesis of the compounds ith m=0:
R1-NH2 can be, for example: Aniline, 2-aminopyridine, 2-aminothiophene, 1,1,2,2,3,3,3- heptafluoropropan- 1 -amine, propan- 1 -amine
The structure
can be, for example: 2,3-diaminobut-2-enedinitrile, 1 ,2-ethenediamine, (Z)- 1 ,2-difluoroethene- 1 ,2-diamine, (Z)- 1 ,2-diphenylethene- 1 ,2-diamine, (Z)- 1 ,2-di(pyridin- 2-yl)ethene- 1 ,2-diamine, (Z)- 1 ,2-di(thiophen-2-yl)ethene- 1 ,2-diamine.
For m=0, it is preferably that R is different than N02.
(27) (28)
Compounds with m=l
Modifying the general synthesis to the form below enables the synthesis of the compounds
The compounds R1-NH2 can be selected from those already disclosed above.
The structure -N x R can be, for example: 4,5-diaminophthalonitrile, 5,6- diaminopyrazine-2,3-dicarbonitrile, benzene- 1,2-diamine, 5,6-dinitropyrazine-2,3-diamine, 5,6-difluoropyrazine-2,3-diamine, 4, 5-difluorobenzene- 1,2-diamine, 4,5- bis(trifluoromethyl)benzene- 1,2-diamine, 5,6-bis(trifluoromethyl)pyrazine-2,3-diamine, 5,6- diphenylpyrazine-2,3-diamine, [ 1 , :2', 1 "-terphenyl]-4',5'-diamine, 4, 5-bis(l -phenyl- 1H- benzo[d]imidazol-2-yl)benzene- 1,2-diamine, 5, 6-bis(l -phenyl- lH-benzo[d]imidazo 1-2- yl)pyrazine-2,3-diamine,
Modifying the general synthesis to the form below enables the synthesis of the compounds with m=2:
The compounds R1-NH2 can be selected from those already disclosed above.
H2N^X^X^R
The structure -N X X R can for example: 6,7-diaminoquinoxaline, 2,3- phenazinediamine, 2,3-diamino-7-chlorophenazine, 6,7-Dimethyl-2,3-Quinoxalinediamine, 2,3-Quinoxalinediamine,
(112) (113)
Synthesis of compound (55)
First step: Synthesis of 7-phenyl-lH-isochromeno[6,5,4-defJisoquinoline-l,3,6,8(7H)- tetraone(l). All manipulations were carried out in air, without any further purification of commercial solvents/chemicals.
Chemical Formula: C14H406 Chemical Formula: C6H7N Chemical Formula: C20H9NO5
Molecular Weight: 268, 178 Molecular Weight: 93, 126 Molecular Weight: 343,29 NTCDA (12g, 44,7 mmol) was heated at 150°C, under stirring, in 315 mL dry DMF. Aniline (700mg, 7,54 mmol) in solution in DMF (135mL) is then added within 20min. The mixture is stirred at 150°C for an additional 6,5 hours before let cooled down overnight. The obtained precipitate (NTCDA) is then filtered to remove the excess NTCDA. The filtrate is reduced to a l/3rd, cooled down (fridge, 30 min), so that another fraction of NTCDA precipitates. The mixture is then filtered to separate the remaining NTCDA from the product. The filtrate is concentrated until almost dry and stirred 3 times with 200mL Water in an ultrasonic bath. The product is finally filtered and washed with 50mL water and dried in a vacuum oven overnight.
The obtained product is then dissolved in chloroform and filtered over celite. The solvents were evaporated and the material was used as such into the second step.
Yield: 2,9g, GCMS purity: 92%
Second step: Synthesis of 9,10-difluoro-2-phenylbenzo[lmn]benzo[4,5]imidazo[2,l- b][3,8]phenanthroline-l,3,6(2H)-trione (2). All manipulations were carried out in air, without any further purification of commercial solvents/chemicals.
Chemical Formula: C2oHgN05 Chemical Formula: C6H6F2N2 Chemical Formula: C26H1 1 F2N303 Molecular Weight: 343,289 Molecular Weight: 144,122 Molecular Weight: 451 ,38
Scheme 2: Synthetic pathway step 2
In a 500mL flask were added (1) (5,18g, 15mmol), 4,5-difluorobenzene-l,2-diamine (2,7 lg, 18,8mmol) and 300mL acetic acid. The mixture is stirred 22 hours at 135°C, during which time a precipitate appears. The reaction medium is cooled down to room temperature and filtered using a Glass fritt (por 4). The precipitate is washed 6 times with 50mL water and twice with 15mL ethanol. The obtained red material is stirred in 50mL chloroform for one hour before being filtered and washed twice with 20mL chloroform. The obtained powder is dried overnight in a vacuum oven (40°C) and dried over an oil pump for 6 hours at room temperature.
Yield: red powder, 6,6g (97,5%). HPLC purity after sublimation: 97%
Conductivity tests
Compound (55) has a very high conductivity in a doped form, if compared to other organic
_3
ETMs. The conductivity at room temperature is 1,06- 10 S/cm and the stability temperature is 153 °C for a layer doped with Tetrakis(l,3,4,6,7,8-Hexahydro-2H-pyrimido[l,2- a]pyrimidinato)ditungsten (II). The conductivity at room temperature is 1,2- 10 S/cm and the stability temperature is 141 °C for a layer doped with 4,4',5,5'-tetracyclohexyl-l, ,2,2',3,3'- hexamethyl-2,2',3,3'-tetrahydro-lH, H-2,2'-biimidazole.
Nomenclature Inverted - The term inverted solar cell, or inverted structure, refers to a device with a layer structure in which the cathode is closer to the substrate than the anode. In the method of production of an inverted device, the cathode is formed on the substrate, following the deposition of the organic and other layers, which are followed by the deposition of the cathode.
ETL - electron transport layer, is a layer which is used in a device stack in such a way that the main charge carriers are electrons. Typically, this layer comprises an electron transport material (ETM). Hole blocking layers, exciton blocking layers between the cathode and its closest donor-acceptor heterojunction are also electron transport layers. Electron injection layers could also be electron transport layers, if they are semiconductors comprising an ETM.
ETM - electron transport material is a semiconducting material which is stable towards reduction and has a high mobility for electrons. In an ETM, the electron mobility is typically higher than the hole mobility.
HTL - hole transport layer, is a layer which is used in a device stack in such a way that the main charge carriers are electrons. Typically this layer comprises a hole transport material (HTM). HTM - hole transport material is a semiconducting material which is stable towards oxidation and has a high mobility for holes. In a HTM, the hole mobility is typically higher than the electron mobility.
FHJ - Flat heterojunction, is a donor-acceptor heterojunction in which the donor and acceptor materials are in separate layers. Preferentially the donor and acceptor materials are in adjacent layers providing a hetero-interface. Alternatively, other layers can be placed in between, to assist the light absorption and/or charge carrier separation.
BHJ - Bulk heterojunction, is a mixed layer comprising a donor, an acceptor, and an absorbing material. Typically at least one of the donor and acceptor materials are also the absorbing material. The donor-acceptor heterointerface is necessary for the separation of the excitons formed by photoabsorbtion into charge carriers. A bulk heterojunction can be graded, or also comprise additional layers. A bulk donor-acceptor heterojunction can also be a hybrid junction, comprising a mixed layer and at least one layer comprising: the acceptor but no donor material, or the donor but no acceptor material. Such a heterojunction can also be a graded bulk heterojunction.
Acceptor - Acceptor, in this invention, is a compound used in an optically active layer of a solar cell to assist the excitonic separation into charge carriers, accepting the electron. The term acceptor must not be confused with an electrical p-dopant which is a very strong acceptor capable of doping a hole transport layer.
Donor - Donor, in this invention, is a compound used in an optically active layer of a solar cell to assist the excitonic separation into charge carriers, donating an electron (accepting a hole). The term donor must not be confused with an electrical n-dopant which is a very strong donor capable of doping an electron transport layer.
Electrical dopant - Electrical dopant is a dopant which is capable to, when added to a semiconductor, increase its charge carrier density, consequently increasing its conductivity. The increase in charge carrier density is due to a charge transfer between the LUMO and HOMO of the at least two components of the dopant-semiconductor system. The term electrically doped refers to a layer or material which is doped by an electrical dopant, as defined above. n-dopant - electrical dopant capable of increasing the density of negative charge carriers in an electron transport material or electron transport layer. The negative charge carriers are
provided on the effective conduction band of the electron transport layer (typically the LUMO of the electron transport material). p-dopant - electrical dopant capable of increasing the density of positive charge carriers in a hole transport material or hole transport layer. The positive charge carriers are provided on the effective valence band of the hole transport layer (typically the HOMO of the hole transport material).
Transparency - those transport layers, which do not contribute to the photocurrent generation, are required to be transparent to avoid any efficiency loss due to undesired absorption. A high transparency is required in the range of wavelengths in which the solar cell is active. A high transparency preferentially means an extinction coefficient (k) smaller than 1 , more preferably smaller than 0.1. LUMO - Lowest unoccupied molecular orbital.
HOMO - Highest occupied molecular orbital.
Intrinsic layer - a layer which is not doped with dopants which increases the charge carrier density in the layer. Here it is considerred that the layer in the dark, and no temperature gradient, or electrical field is applied to it.
The features disclosed in the foregoing description, in the claims and in the accompanying drawings may both separately and in any combination be material for realizing the invention in diverse forms thereof.
Claims
Claims
Oganic electronic device, preferentially an solar cell, comprising at least one compound according to the following formula (I):
Formula (I)
wherein
Rl is C5-20-aryl; C5-20-heteroaryl, C2-C20-alkyl, or C2-C20-perfhioroalkyl;
each X is independently selected from C, N, O and S;
each R is independently selected from C5-20-aryl, C5-20-heteroaryl, N02, CN, H, F, CF3, C2-C20-alkyl, C2-20-perfiuoroalkyl;
m = 0, 1, 2 or 3.
Organic electronic device according to claim 1 , comprising at least one first electron transport layer, which electron transport layer comprises a material according to formula (I) of claim 1.
Organic electronic device according to claim 2, wherein the first electron transport layer is doped.
Organic electronic device according to claim 2 or 3, comprising an additional electron transport layer wherein the first electron transport layer is doped and the additional electron transport layer is undoped, and wherein the additional electron transport layer
is adjacent to a donor-acceptor heterojunction and the first electron transport layer is in between the additional electron layer and a cathode.
5. Organic electronic device according to claim 4, wherein the additional electron
transport layer is at least one of hole blocking and exciton blocking layer.
6. Organic electronic device according to any of the previous claims 4-, wherein a donor- acceptor heterojunction comprises a material according to formula (I) of claim 1 , preferentially as acceptor.
7. Organic electronic device according to claim 6, wherein at least 5 % of the
photocurrent at 0V is due to absorption of photons in the range of 300-500 nm.
8. Organic electronic device according to claims 6 or 7, wherein the donor-acceptor heterojunction is a bulk-heterojunction.
9. Organic electronic device according to claim 1, comprising at least one semiconductor polymer layer and one electron transport layer, which electron transport layer comprises a material according to Formula (I) of claim 1.
10. Organic electronic device according to claim 9, wherein the electron transport layer is n-doped.
Compounds according to the following formula (I)
Formula (I)
wherein
Rl is aryl;
each X is independently selected from C and N;
each R is independently selected from aryl, heteroaryl, N02, CN and H; m = 0, 1, 2 or 3.
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EP2718978B1 (en) | 2018-05-16 |
US20140174537A1 (en) | 2014-06-26 |
JP2014520394A (en) | 2014-08-21 |
US9142781B2 (en) | 2015-09-22 |
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