WO2014100961A1 - Use of compounds of the perylene type as acceptors in photovoltaics - Google Patents
Use of compounds of the perylene type as acceptors in photovoltaics Download PDFInfo
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- WO2014100961A1 WO2014100961A1 PCT/CN2012/087349 CN2012087349W WO2014100961A1 WO 2014100961 A1 WO2014100961 A1 WO 2014100961A1 CN 2012087349 W CN2012087349 W CN 2012087349W WO 2014100961 A1 WO2014100961 A1 WO 2014100961A1
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 81
- 239000000370 acceptor Substances 0.000 title description 7
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 title description 5
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 title description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 40
- 239000000758 substrate Substances 0.000 claims abstract description 37
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 15
- 230000000694 effects Effects 0.000 claims abstract description 14
- 229910003827 NRaRb Inorganic materials 0.000 claims abstract description 13
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 11
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 4
- 150000002367 halogens Chemical class 0.000 claims abstract description 4
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 claims abstract description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 2
- 150000002894 organic compounds Chemical class 0.000 claims description 43
- 125000000217 alkyl group Chemical group 0.000 claims description 26
- 229920001088 polycarbazole Polymers 0.000 claims description 14
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 13
- 125000001072 heteroaryl group Chemical group 0.000 claims description 12
- UJOBWOGCFQCDNV-UHFFFAOYSA-N Carbazole Natural products C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims description 9
- 229920000123 polythiophene Polymers 0.000 claims description 8
- 125000000041 C6-C10 aryl group Chemical group 0.000 claims description 4
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000006539 C12 alkyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 1
- -1 poly(3-hexylthiophene) Polymers 0.000 description 23
- 125000003118 aryl group Chemical group 0.000 description 21
- 239000004065 semiconductor Substances 0.000 description 16
- 239000010410 layer Substances 0.000 description 14
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- 125000004093 cyano group Chemical group *C#N 0.000 description 9
- 238000000151 deposition Methods 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 125000003545 alkoxy group Chemical group 0.000 description 6
- 238000009833 condensation Methods 0.000 description 6
- 230000005494 condensation Effects 0.000 description 6
- 230000008021 deposition Effects 0.000 description 6
- 125000005843 halogen group Chemical group 0.000 description 6
- 150000002430 hydrocarbons Chemical group 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 5
- 125000002102 aryl alkyloxo group Chemical group 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 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 5
- 229920000301 poly(3-hexylthiophene-2,5-diyl) polymer Polymers 0.000 description 5
- 239000007858 starting material Substances 0.000 description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 4
- 125000004414 alkyl thio group Chemical group 0.000 description 4
- 125000004104 aryloxy group Chemical group 0.000 description 4
- 125000004181 carboxyalkyl group Chemical group 0.000 description 4
- 125000005842 heteroatom Chemical group 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 125000003282 alkyl amino group Chemical group 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 230000005670 electromagnetic radiation Effects 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000003818 flash chromatography Methods 0.000 description 3
- 238000004770 highest occupied molecular orbital Methods 0.000 description 3
- 229910003437 indium oxide Inorganic materials 0.000 description 3
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 3
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000004528 spin coating Methods 0.000 description 3
- 229910052717 sulfur Chemical group 0.000 description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 0 *c1cc(-c(cc2)c(c(-c3ccc4C(N5*)=O)cc(*)c6C(N7*)=O)c6c2C7=O)c3c4c1C5=O Chemical compound *c1cc(-c(cc2)c(c(-c3ccc4C(N5*)=O)cc(*)c6C(N7*)=O)c6c2C7=O)c3c4c1C5=O 0.000 description 2
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229940126062 Compound A Drugs 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 125000000304 alkynyl group Chemical group 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 125000005678 ethenylene group Chemical group [H]C([*:1])=C([H])[*:2] 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000001786 isothiazolyl group Chemical group 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 125000003373 pyrazinyl group Chemical group 0.000 description 2
- 125000002098 pyridazinyl group Chemical group 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 125000004306 triazinyl group Chemical group 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 125000004514 1,2,4-thiadiazolyl group Chemical group 0.000 description 1
- 125000004530 1,2,4-triazinyl group Chemical group N1=NC(=NC=C1)* 0.000 description 1
- 125000004520 1,3,4-thiadiazolyl group Chemical group 0.000 description 1
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- 125000005916 2-methylpentyl group Chemical group 0.000 description 1
- QFFUHNKLCPAKII-UHFFFAOYSA-N COc1ccc(CN(C(c(ccc(-c(c2c3c(C(N4Cc(cc5)ccc5O)=O)ccc2-2)cc(Br)c3C4=O)c3c-2c2)c3c3c2Br)=O)C3=O)cc1 Chemical compound COc1ccc(CN(C(c(ccc(-c(c2c3c(C(N4Cc(cc5)ccc5O)=O)ccc2-2)cc(Br)c3C4=O)c3c-2c2)c3c3c2Br)=O)C3=O)cc1 QFFUHNKLCPAKII-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229920000144 PEDOT:PSS Polymers 0.000 description 1
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- MCEWYIDBDVPMES-UHFFFAOYSA-N [60]pcbm Chemical compound C123C(C4=C5C6=C7C8=C9C%10=C%11C%12=C%13C%14=C%15C%16=C%17C%18=C(C=%19C=%20C%18=C%18C%16=C%13C%13=C%11C9=C9C7=C(C=%20C9=C%13%18)C(C7=%19)=C96)C6=C%11C%17=C%15C%13=C%15C%14=C%12C%12=C%10C%10=C85)=C9C7=C6C2=C%11C%13=C2C%15=C%12C%10=C4C23C1(CCCC(=O)OC)C1=CC=CC=C1 MCEWYIDBDVPMES-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000007080 aromatic substitution reaction Methods 0.000 description 1
- 125000003609 aryl vinyl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000005334 azaindolyl group Chemical group N1N=C(C2=CC=CC=C12)* 0.000 description 1
- 125000004601 benzofurazanyl group Chemical group N1=C2C(=NO1)C(=CC=C2)* 0.000 description 1
- 125000001164 benzothiazolyl group Chemical group S1C(=NC2=C1C=CC=C2)* 0.000 description 1
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 125000000259 cinnolinyl group Chemical group N1=NC(=CC2=CC=CC=C12)* 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 229920000547 conjugated polymer Polymers 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 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 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000003838 furazanyl group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000000592 heterocycloalkyl group Chemical group 0.000 description 1
- UTCSSFWDNNEEBH-UHFFFAOYSA-N imidazo[1,2-a]pyridine Chemical compound C1=CC=CC2=NC=CN21 UTCSSFWDNNEEBH-UHFFFAOYSA-N 0.000 description 1
- 125000005945 imidazopyridyl group Chemical group 0.000 description 1
- 125000001041 indolyl group Chemical group 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000002183 isoquinolinyl group Chemical group C1(=NC=CC2=CC=CC=C12)* 0.000 description 1
- 125000005956 isoquinolyl group Chemical group 0.000 description 1
- 125000000842 isoxazolyl group Chemical group 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000004593 naphthyridinyl group Chemical group N1=C(C=CC2=CC=CN=C12)* 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 125000001715 oxadiazolyl group Chemical group 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 239000001301 oxygen Chemical group 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000004592 phthalazinyl group Chemical group C1(=NN=CC2=CC=CC=C12)* 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 125000000561 purinyl group Chemical group N1=C(N=C2N=CNC2=C1)* 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 125000006085 pyrrolopyridyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 125000002294 quinazolinyl group Chemical group N1=C(N=CC2=CC=CC=C12)* 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 239000011593 sulfur Chemical group 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 125000003831 tetrazolyl group Chemical group 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 125000004588 thienopyridyl group Chemical group S1C(=CC2=C1C=CC=N2)* 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Classifications
-
- 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
- C07D471/02—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 two hetero rings
- C07D471/06—Peri-condensed systems
-
- 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
- H10K85/621—Aromatic anhydride or imide compounds, e.g. perylene tetra-carboxylic dianhydride or perylene tetracarboxylic di-imide
-
- 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
- H10K30/20—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising organic-organic junctions, e.g. donor-acceptor junctions
-
- 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
- H10K30/50—Photovoltaic [PV] devices
-
- 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 present invention relates to the field of photovoltaic devices, so-called third generation devices, which apply semi-conductors of an organic nature.
- third generation devices which apply semi-conductors of an organic nature.
- the photovoltaic effect is ensured by the joint application of two distinct organic compounds used in a combination, i.e.:
- first organic compound having a semi-conductor nature of type P ⁇ electron donor which is generally a compound, preferably a polymer having electrons engaged in ⁇ bonds, advantageously delocalized bonds, and which is most often a conjugated polymer;
- organic semi-conducting compounds of type N are generally ful!erenes (C 60 ), such as for example methyl[6,6]-phenyl-C 61 -butyrate, so-called PC 6 BM
- organic semi-conducting compounds of type P electron donor
- polythiophenes such as for example poly(3-hexylthiophene), so-called P3HT
- polycarbazoles such as for example poly[[9-(1-octylnonyl)-9H-carbazo!e-2,7-diyl]- 2,5-thiophenediyl-2,1 ,3-benzothiadiazole-4,7-diyl-2,5-thiophenediyl], so-called PCDTBT), or further poly(arylene vinylene).
- P/N mixtures of the P3HT/PCBM type have for example been described in US 2008/315187 or US 2009/032808.
- An object of the present invention is to increase the variety of the semi-conducting organic compounds of type N (acceptor) and to provide a novel type of photovoltaic substrate.
- Another object of the invention is to provide a semi-conducting organic compound of type N having a greater photovoltaic effect than that of semi-conducting organic compounds of type N, known up to now, when it is used in combination with a semi-conducting organic compound of type P.
- the present invention proposes the use of a compound of the perylene type as a semi-conducting organic compound of type N, in combination with a semi-conducting organic compound of type P within a photovoltaic substrate.
- R and R' represent, independently of each other, a hydrogen atom or a C C36 hydrocarbon group non-conjugated with the nitrogen atom to which it is bound, and
- R-R-i , R 2 , R 3 , R 4 , R'i , R'2, '3 and R' 4 represent, independently of each others, a group selected from the group consisting of -R a , -NR a R b , - OR a , -CN, -C0 2 R a , -N0 2l -CH(CN) 2 and halogen, wherein R a and R b represent independently a hydrogen atom or a C C 2 alkyl group, as a semi-conducting compound of type N in a photovoltaic substrate, wherein said photovoltaic substrate comprises said compound of formula (I) and a semi-conducting compound of type P, providing, in combination with each other, a photovoltaic effect.
- the compounds of formula (I) are also called perylene-type compounds.
- Perylene-type compounds are known as dyes, notably because of their fluorescent properties.
- the two nitrogen atoms of the perylene aromatic radical are generally substituted with aromatic groups, typically of the phenyl type, which participate to the delocalization of the ⁇ electrons of the aromatic core (see for example US 2005/251930).
- the compounds according to the invention for which the nitrogen atoms are not substituted with aromatic groups, but on the contrary with a hydrogen atom or a non-conjugated group with said nitrogen atom, have a semi-conducting nature of type N particularly suitable for an application in photovoltaics.
- a donor nature (semi-conductor of type P) or acceptor nature (semi-conductor of type N) of a semi-conducting compound is relative and depends on the nature of the compound with which it is in combination within the photovoltaic substrate.
- a compound including attractor groups is generally of the acceptor nature (type N) and conversely, a compound including donor groups is generally of a donor nature (type P).
- R and/or R' represent a hydrocarbon group
- « non-conjugated » is meant that said hydrocarbon group bound to the nitrogen atom is not involved in the delocalization of the ⁇ electrons of the aromatic core of formula:
- said hydrocarbon group is for example bound to the nitrogen atom via a sp 3 carbon, typically via a -CH 2 - linker.
- an « alkyl » group represents a saturated hydrocarbon monovalent group with a linear or branched chain, comprising from 1 to 36 carbon atoms, preferably from 1 to 24, more preferably from 1 to 12, and most preferably from 1 to 5 carbon atoms.
- a linear or branched chain comprising from 1 to 36 carbon atoms, preferably from 1 to 24, more preferably from 1 to 12, and most preferably from 1 to 5 carbon atoms.
- alkyl radicals When they are branched or substituted with one or several alkyl radicals, mention may notably be made of isopropyl, tert-butyl, 2-ethylhexyl, 2-methylbutyl, 2-methyl pentyl, 1 -methylpentyl and 3- methylheptyl radicals.
- an « alkyl » group may be substituted with an aryl or heteroaryl group.
- aryl » designates a mono- or bi-cyclic aromatic hydrocarbon system comprising from 6 to 10, preferably 6 or 10 carbon atoms.
- aryl groups mention may be made of phenyl or naphthyl groups more particularly substituted with an alkoxy group.
- heteroaryl » designates an aromatic system comprising one to four heteroatoms selected from nitrogen, oxygen or sulfur, which is mono- or bi-cyclic, comprising from 1 to 10 and preferably from 5 to 10 carbon atoms.
- heteroaryl groups mention may be made of pyrazinyl, thienyl, oxazolyl, furazanyl, pyrrolyl, 1 ,2,4-thiadiazolyl, naphthyridinyl, pyridazinyl, quinoxalinyl, phthalazinyl, imidazo[1 ,2-a]pyridine, imidazo[2,1-b]thiazolyl, cinnolinyl, triazinyl, benzofurazanyl, azaindolyl, benzimidazoiyl, benzothienyl, thienopyridyl, thienopyrimidinyl, pyrrolopyridyl, imidazopyridyl, benzoazaindole, 1 ,2,4-triazinyl, benzothiazolyl, furany!, imidazoly!, indolyl, triazolyl, tetrazolyl
- the « alkyl » groups, « aryl » groups and « heteroaryl » groups may also be substituted with an amino, hydroxy, thio, halogeno, alkyl, alkoxy, alkylthio, alkylamino, aryloxy, arylalkoxy, cyano, trifluoromethyl, carboxy, carboxyalkyl or cycloalkyl group.
- the « alkoxy » groups according to the present invention are groups of formula -O-alkyl, the alkyl group being as defined earlier.
- the term « alkylthio » designates an -S-alkyl group, the alkyl group being as defined above.
- a!kylamino » designates a -NH-alkyl group, the alkyl group being as defined above.
- halogen atoms more particularly, mention will be made of fluorine, chlorine, bromine and iodine atoms, preferably bromine and iodine atoms.
- aryloxy » designates a -O-aryl group, the aryl group being as defined above.
- arylalkoxy » designates an aryl-alkoxy- group, the aryl and alkoxy group being as defined above.
- carboxyalkyl » designates a HOOC-alkyl- group, the alkyl group being as defined above.
- carboxylalkyl groups mention may notably be made of carboxymethyl or carboxyethyl groups.
- cycloaikyl designates a non-aromatic saturated or partly unsaturated mono-, bi- or tri-cyclic hydrocarbon group, comprising from 3 to 20 carbon atoms and preferably from 3 to 10 carbon atoms, such as notably cyclopropyl, cyclopentyl, cyclohexyl or adamantyl, as well as the corresponding rings containing one or several unsaturations.
- cycloaikyl » also encompasses « heterocycloalkyl » groups designating non-aromatic, saturated or partly unsaturated mono- or bicyclic systems of 3 to 8 carbon atoms, comprising one or several heteroatoms selected from N, O and S.
- a « cycloaikyl » « aryl » or « heteroaryl » group may also be substituted with at least one substituent chosen in particular from an amino, hydroxyl, thio, halogeno, alkyl, alkoxy, alkylthio, alkylamino, aryloxy, arylalkoxy, cyano, trifluoromethyl, carboxy or carboxyalkyl group.
- R' When and/or R' do not represent a hydrogen atom, they may represent an optionally substituted, alkenyl group.
- the « alkenyl » groups represent hydrocarbon groups with a straight or linear chain, and comprise one or several ethylenic unsaturations, which are not conjugated with the nitrogen atoms of the compounds of formula (I).
- R and/or R' do not represent a hydrogen atom, they may represent an optionally substituted, alkynyl group.
- the « alkynyl » groups represent hydrocarbon groups with a straight or linear chain, and comprise one or several acetylenic unsaturations, which are not conjugated with the nitrogen atoms of the compounds of formula (I).
- R' ⁇ R' 2 , R' 3 and R' 4 represent, independently of each other, a group selected from the group consisting of -H, -Br, -NR a R b and -CN, wherein R a and R b represent independently H or a C C 6 alkyl group.
- At least one group among R-i , R 2 , R3, R 4 , R'i , R'2, '3 and R' is different from a hydrogen atom.
- R , R'i , R'2, '3 and R' 4 are different from a hydrogen atom, the others six groups being a hydrogen atom.
- the present invention also relates to the use as defined above of a compound of formula (II):
- Formula (II) corresponds to formula (I) wherein each of R 2 , R 3 , R 4 , R' 2 , R'3 and R' 4 represents a hydrogen atom, and wherein Ri and R are identical.
- Ri and R'i are different from a hydrogen atom.
- R'i, R'2, '3 and R' 4 represents a hydrogen atom.
- the present invention also relates to the use as defined above of a compound of formula (III):
- Formula (III) corresponds to formula (I) wherein each of R,, R 2 , R 3 , R 4 , R'-,, R' 2l R' 3 and R' 4 represents a hydrogen atom.
- R and R' represent a hydrogen atom.
- At least one of R and R' is different from a hydrogen atom.
- R and R' are different from a hydrogen atom.
- R and R' are different from each other.
- R and R' are identical.
- R and/or R' do not represent a hydrogen atom, they may represent a C C 36 alkyl group, preferably a C 1 -C 12 alkyl group, optionally substituted.
- R and/or R' do not represent a hydrogen atom, they may represent an alkyl group, substituted with an aryl group. These are referred to as an « arylalkyl » or « aralkyl » group.
- R and R' represent, independently of each other, a group of formula -Alk-Ar wherein:
- radical -A!k- is a C-
- -Ar is an optionally substituted C 6 -C 10 aryl group or an optionally substituted
- R and R' are identical.
- an « alkylene » radical represents a divalent radical of the alkyl type, optionally substituted.
- the alkylene radical -Alk- may be substituted with any substituent defined above as a substituent of an alkyl group.
- the alkylene radical -Alk- is not substituted.
- the alkylene radical -Alk- represents a non-branched linear alkylene chain comprising from 1 to 10 carbon atoms.
- the alkylene radical -Alk- is selected from methylene (-CH 2 -), ethylene (-C 2 H 4 -), propylene (-C 3 H 6 -) and butylene (-C 4 H 8 -) radicals.
- the alkylene radical -Alk- is selected from methylene (-CH 2 -) and ethylene (-C2H 4 -) radicals.
- the alkylene radical -Alk- is a methylene radical -CH 2 -.
- -Ar is a phenyl group, optionally substituted.
- -Ar is a CTC 0 heteroaryl group comprising one to four heteroatoms, selected from N, S and O.
- an « aryi » group and a « heteroaryl » group may be substituted with at least one substituent chosen in particular from an amino, hydroxy, thio, halogeno, alkyl, alkoxy, alkylthio, alkylamino, aryloxy, arylalkoxy, cyano, trifluoromethyl, carboxy, carboxyalkyi or cycloalkyi group; said groups being as defined above.
- - radical -Alk- is -CH 2 - or -C 2 H 4 -
- - -Ar is an optionally substituted phenyl group.
- -Ar is a phenyl group substituted by a -OR a group, wherein R a is a C C 12 aikyl group.
- the -OR a group may be in the para, meta or ortho position, preferably in the para position of the phenyl group.
- R and R' are identical and represent: a group of formula
- R and/or R' do not represent a hydrogen atom, they may represent an alkyl group, linear or branched.
- R and R' represent, independently of each other, a linear or branched C2-C24 alkyl group of formula -Alk', preferably a C 12 - C24 alkyl group, in particular a C 2 o-C 24 alkyl group, said alkyl group being preferably branched.
- -Alk' is a group of formula
- the present invention also relates to the use of a compound selected from the following compounds:
- the organic compound of type P in combination with the organic compound of type N is selected so as to adjust the energy of the LUMO of the semi-conducting organic compound of type P according to the energy of the HOMO of the semi-conducting organic compound of type N, and vice versa.
- the semi-conducting organic compound of type P is selected from polythiophenes, polycarbazoles and poly(arylene vinylene).
- polythiophene an organic compound, preferably a polymer, comprising several thiophene units generally following each other, and typically bound together with the carbon atoms 2 and 5 of the thiophene units.
- the thiophene units may be alternated with other units, such as alkyl, aryl or heteroaryi units.
- a polythiophene may comprise any type of substitution on the thiophene units and the optional other units which make it up.
- poly(3-hexylthiophene) As a polythiophene, mention may be made of poly(3-hexylthiophene), so-called
- polycarbazole an organic compound, preferably a polymer, comprising a sequence of several carbazole units, generally following each other or else alternated with other units, such as alky, aryl or heteroaryi units.
- a polycarbazole may comprise any type of substitution on the thiophene units and the optional other units which make it up.
- poly ⁇ ary!ene vinylene an organic compound, preferably a polymer, comprising a sequence of several aryl and vinyl units.
- a poly(arylene vinylene) comprises several aryl vinyl units.
- the semi-conducting organic compound of type P is a polycarbazole.
- polycarbazole As a polycarbazole, mention may be made of poly[[9-(1-octylnonyl)-9H-carbazole- 2,7-diyl]-2,5-thiophenediyl-2,1 ,3-benzothiadiazole-4,7-diyl-2,5-thiophenediyl], so-called PCDTBT.
- the present invention also relates to a photovoltaic substrate comprising, in combination:
- a semi-conducting organic compound of type P capable of providing, in combination with said compound of formula (I), a photovoltaic effect.
- the semi-conducting organic compound of type P is selected from polythiophenes, polycarbazoles and poly(ary!ene vinylene), and is preferably a polycarbazole.
- the semi-conducting organic compound of type P is a polycarbazole.
- the semi-conducting compound of type P is a polycarbazole and the semi-conducting organic compound of type N is a compound of formula (I), (II) or (III) as defined above.
- the present invention also relates to a photovoltaic substrate comprising, in combination:
- a semi-conducting organic compound of type P able to provide, in combination with said compound of formula (I), a photovoltaic effect.
- the present invention also relates to a photovoltaic substrate comprising, in combination:
- R and R' represent, independently of each other, a linear or branched C 2 -C 2 4 alkyl group of formula -Alk', preferably a C 12 -C 24 alkyl group, in particular a C 20 -C 24 alkyl group, said alkyl group being preferably branched, and
- the present invention also relates to a compound of formula (I):
- R, R', R ⁇ R 2 , R 3 , R 4 , R , R' 2 , R'3 and R' 4 are as defined above,
- R 1 ; R 2 , R3, R 4 , R'i , R' 2 , R'3 and R' 4 represent, independently of each others, a group selected from the group consisting of -H, -Br, -NR a R b and -CN, wherein R a and R b represent independently H or a C-
- R and R' are different from a hydrogen atom, a methyl group, a -CH 2 CH2-C 6 H5 group and a -CH2-C 6 H 4 OCH 3 group.
- the present invention also relates to a compound of formula (I) wherein two groups among R-i , R 2 , R3, R 4 , R'i , R' 2 , R'3 and R' 4 are different from a hydrogen atom, the others six groups being a hydrogen atom.
- the present invention also relates to a compound of formula (II):
- R'i are identical and as defined above,
- Ri and R are different from a hydrogen atom.
- the present invention also relates to the use as defined above of a compound of formula (11-1 ):
- the present invention also relates to the use as defined above of a compound of formula (11-2):
- Hal is preferably bromine or iodine.
- the present invention also relates to the use as defined above of a compound of formula (11-3):
- R and R' are as defined above.
- the present invention also relates to the use as defined above of a compound of formula (11-4):
- R and R' are as defined above, and wherein R a and R b represent independently a hydrogen atom or a C ⁇ -C ⁇ alkyl group.
- R a and R b are preferably identical and most preferably represent a C,-C 6 alkyl group.
- the present invention also relates to a compound of formula (III):
- the present invention also relates to a compound of formula (I), (II) or (I II), wherein each of R 2 , R3, R4, R'i , R'2, R'3 and R' 4 represents a hydrogen atom.
- the present invention also relates to a compound of formula (I), (II) or (III), wherein:
- R and R' are identical and represent a group of -Alk-Ar wherein:
- radical -Alk- is a C ⁇ -C ⁇ alkylene radical, preferably a C C 4 alkylene radical, and
- - -Ar is an optionally substituted C 6 -C 10 aryl group or an optionally substituted C1-C10 heteroaryl group
- R are identical and represent a group selected from the group consisting of -H, -Br, -NR a Rb and -CN, wherein R a and R b independently represent a C Ce alkyl group.
- the present invention also relates to a compound of formula (I), (II) or (III), wherein:
- radical -Alk- is a C r C 4 alkylene radical
- - -Ar is a phenyl group substituted by a -OR a group, wherein R a is a C 6 -C 12 alkyl group
- R'3 and R' 4 are identical and represent a hydrogen atom.
- the present invention also relates to a compound of formula (I) or (II), wherein:
- radical -Alk- is a C C 4 alkylene radical
- - -Ar is a phenyl group substituted by a -OR a group, wherein R a is a CTC 12 alkyl group, and
- Ri and R are identical and represent a group selected from the group consisting of -Br, -NR a R b and -CN, wherein R a and R b independently represent a C ⁇ Ce alkyl group.
- the present invention also relates to a compound of formula (I), (II) or (III), wherein:
- R and R' are identical and represent a linear or branched C 2 -C 24 alkyl group of formula -Alk', preferably a Ci 2 -C 24 alkyl group, more preferably a C20-C24 alkyl group, said alkyl group being preferably branched, and
- Ri and R are identical and represent a group selected from the group consisting of -H, -Br, -NR a R b and -CN, wherein R a and R b independently represent a Ci-C 6 alkyl group.
- the compounds of the invention are for example prepared from starting material 3,4,9, 10-perylenetetracarboxylic dianhydride (notably available from TCI and Merck):
- the compounds of formula (li) are prepared according to the following general procedure, starting from 3,4,9, 10-perylenetetracarboxylic dianhydride as starting material, comprising:
- step of functionalisation of the aromatic core of said starting material by grafting groups R-i and R onto said core, and a step of condensation with primary amines R 0 -NH 2 and R' 0 -NH 2 wherein R 0 and R' 0 correspond either to R and R' or to precursors of said groups, in a solvent such as tetrahydrofuran.
- the step of functionalisation is for example carried out in two steps: a first step of grafting two halogen atoms onto the aromatic core at the R and R'i positions, and a second step of grafting suitable groups R ⁇ and R'-, by aromatic substitution.
- the step of condensation is typically carried out by refluxing for about 10 hours, then the solvent is partially evaporated and a portion of methanol is added to precipitate the product of condensation.
- R 0 and R' 0 are advantageously identical too.
- R 0 and/or R' 0 correspond to R and/or R' under a protected form for example.
- the compounds of formula (III) are prepared according to the following general procedure, starting from 3,4,9, 10-perylenetetracarboxylic dianhydride as starting material, comprising a step of condensation with primary amines R 0 -NH 2 and R'o-NH 2 wherein R 0 and R' 0 are as above described.
- the photovoltaic effect of the photovoltaic substrates according to the invention is obtained by placing both organic semi-conductors between two electrodes (anode and cathode) in the form of a substrate comprising both of these semi-conductors in combination (this substrate being in direct contact with both electrodes, or optionally connected to at least one of the electrodes via an additional coating, for example a charge-collecting coating); and by irradiating the thereby produced photovoltaic cell with adequate electromagnetic radiation, typically with light from the solar spectrum.
- one of the electrodes is generally transparent to the electromagnetic radiation used: in a way known per se, a transparent ITO (indium oxide doped with tin) anode may notably be used.
- Obtaining a substrate comprising both semi-conducting organic compounds (P and N) in combination between the electrodes may be achieved by successive depositions of semi-conductors of type P and N. Such depositions may be carried out by using the vacuum evaporation deposition technique known to one skilled in the art, or else by depositing a solution comprising a semi-conducting organic compound of type P or N in a solvent and by then evaporating said solvent, or else by spin-coating (see Blouin et al. Adv. Mater. 2007, 19, 2295-2300).
- Such a substrate may also be obtained by depositing a solution comprising both semi-conducting organic compounds of type P and N in a suitable solvent, and then by evaporating this solvent, for example by following and/or adapting the conditions described in application WO 2011/036421.
- the electrons of the inorganic semi-conductor type P are excited, typically according to a so-called ⁇ - ⁇ * transition mechanism (passage from the highest occupied molecular orbital (HOMO) to the lowest unoccupied molecular orbital (LUMO)), this leads to an effect similar to the injection of an electron from the valence band into the conduction band in an inorganic semi-conductor, which leads to the creation of an exciton (an electron/hole pair).
- HOMO highest occupied molecular orbital
- LUMO unoccupied molecular orbital
- the thereby created exciton may be disassociated at the P/N interface and the excited electron created during irradiation may be conveyed by the semi-conductor of type N towards the cathode, the hole as for it being lead to the anode via the semi-conductor of type P. Accumulation of the electrons at the cathode and of the holes at the anode generates an electric voltage at the origin of the electric current generated by the photovoltaic cell.
- Photovoltaic devices comprising a photovoltaic substrate including an organic layer with a semi-conducting nature, a support and electrodes were prepared according to the conditions hereafter.
- Example 1 preparation of novel semi-conducting compounds of type N
- Step 1
- a glass support (a plate of 15 mm x 15 mm x 0.7 mm) coated with a conducting layer of indium oxide doped with tin (ITO) as an anode (a commercial support provided with an ITO (indium oxide doped with tin) layer with a thickness of 100 nm) is cleaned beforehand in an acetone bath with ultrasound for 10 minutes, followed by an ethanoi bath with ultrasound for 10 minutes, followed by an isopropanoi bath boiling for 10 minutes.
- ITO indium oxide doped with tin
- the thereby cleaned glass support/ITO is then dried with compressed air, and then placed in an UV/ozone oven during 10 minutes at room temperature.
- PEDOT :PSS poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) is then deposited, which is a charge collecting layer) with a thickness of 50 nm, by spin coating and then by heating into a low pressure oven at 120°C for 15 minutes until the water is removed.
- a photovoltaic substrate is deposited by deposition of a thin layer of semi-conducting organic compound of type P (donor), followed by the deposition of a thin layer of semi-conducting organic compound of type N (donor).
- the deposition of the thin layer of semi-conducting organic compound of type P is achieved by spin-coating from 10 mg/mL solution of PCDTBT into ortho-dichlorobenzene: 60 sec at 1000 RPM to get 50 nm-thick layers, and 60 sec at 1500 RPM to get 20nm-thick layers.
- the deposition of the thin layer of semi-conducting organic compound of type N is achieved by evaporation in vacuo, in a vacuum chamber at 1.10-6 bar with evaporation rate at 1 angstrom/min for the 5 first nanometers and then 5 angstrom/min (20 nm and 50 nm total).
- a thin layer of aluminium (thickness of about 80 nm) is then deposited as a cathode on the thereby produced substrate, by evaporation in vacuo.
- PCDTBT/C 6 Q substrates were prepared, comprising the following thin layers, respectively:
- PCDTBT type P
- C 60 type N
- PCDTBT type P
- C 60 type N
- PCDTBT type P
- C 60 type N
- PCDTBT type P
- C 60 type N
- the following substrates were prepared, comprising the following thin layers, respectively:
- PCDTBT type P
- A type N
- PCDTBT type P
- A type N
- PCDTBT type P
- A type N
- PCDTBT type P
- A type N
- the compound A according to the invention used as semi-conducting organic compound of type N, is commercially available (Rhodia, pigment black 32).
- the photovoltaic substrate PCDTBT/A according to the invention comprising the compound A as a semi-conducting compound of type N, has better photovoltaic characteristics than the reference photovoltaic substrate PCDTBT/C 6 o.
Abstract
The present invention relates to the use of a compound of formula (I) wherein: - R and R' represent, independently of each other, a hydrogen atom or a C1-C36 hydrocarbon group non-conjugated with the nitrogen atom to which it is bound, and - R1, R2, R3, R4, R'1, R'2, R'3 and R'4 represent, independently of each others, a group selected from the group consisting of -Ra, -NRaRb, - ORa, -CN, -C02Ra, -NO2, -CH(CN)2 and halogen, wherein Ra and Rb represent independently a hydrogen atom or a C1-C12 alkyl group, as a semi-conducting compound of type N in a photovoltaic substrate, wherein said photovoltaic substrate comprises said compound of formula (I) and a semi-conducting compound of type P, providing, in combination with each other, a photovoltaic effect.
Description
USE OF COMPOUNDS OF THE PERYLENE TYPE AS ACCEPTORS IN
PHOTOVOLTAICS
The present invention relates to the field of photovoltaic devices, so-called third generation devices, which apply semi-conductors of an organic nature. In photovoltaic devices applying organic semi-conductors, the photovoltaic effect is ensured by the joint application of two distinct organic compounds used in a combination, i.e.:
- a first organic compound having a semi-conductor nature of type P {electron donor), which is generally a compound, preferably a polymer having electrons engaged in π bonds, advantageously delocalized bonds, and which is most often a conjugated polymer; and
- a second organic compound, which is immiscible with the first compound under the conditions of use of the photovoltaic device and having a semi-conducting nature of type N (electron acceptor). Photovoltaic devices applying organic semi-conductors are potentially promising.
Indeed, taking into account the application of organic compounds as a replacement for inorganic semi-conductors, they provide the advantage of being more flexible mechanically, and therefore less fragile, than the first and second generation systems. Moreover, they are more lightweight and are further easier to make and prove to be less expensive.
However, to this day, the types of organic semi-conducting compounds used in photovoltaic devices are limited, which is an obstacle to their actual use in the production of electricity of photovoltaic origin. Consequently, many efforts are made to diversify the types of organic semi-conducting compounds used. Presently, organic semi-conducting compounds of type N (electron acceptor) used are generally ful!erenes (C60), such as for example methyl[6,6]-phenyl-C61-butyrate, so-called PC6 BM, while organic semi-conducting compounds of type P (electron donor) generally used are polythiophenes (such as for example poly(3-hexylthiophene), so-called P3HT), polycarbazoles (such as for example poly[[9-(1-octylnonyl)-9H-carbazo!e-2,7-diyl]- 2,5-thiophenediyl-2,1 ,3-benzothiadiazole-4,7-diyl-2,5-thiophenediyl], so-called PCDTBT), or further poly(arylene vinylene).
P/N mixtures of the P3HT/PCBM type have for example been described in US 2008/315187 or US 2009/032808. Semi-conducting poly(arylene vinylene) compounds of type P have for example been described in WO 94/29883.
Nevertheless, semi-conducting organic compounds of type N adapted to photovoltaic application are relatively few.
An object of the present invention is to increase the variety of the semi-conducting organic compounds of type N (acceptor) and to provide a novel type of photovoltaic substrate.
Another object of the invention is to provide a semi-conducting organic compound of type N having a greater photovoltaic effect than that of semi-conducting organic compounds of type N, known up to now, when it is used in combination with a semi-conducting organic compound of type P.
For this purpose, the present invention proposes the use of a compound of the perylene type as a semi-conducting organic compound of type N, in combination with a semi-conducting organic compound of type P within a photovoltaic substrate.
More specifically, the present invention relates to the use of a compound of formula (I):
wherein:
R and R' represent, independently of each other, a hydrogen atom or a C C36 hydrocarbon group non-conjugated with the nitrogen atom to which it is bound, and
- R-i , R2, R3, R4, R'i , R'2, '3 and R'4 represent, independently of each others, a group selected from the group consisting of -Ra, -NRaRb, - ORa, -CN, -C02Ra, -N02l -CH(CN)2 and halogen, wherein Ra and Rb represent independently a hydrogen atom or a C C 2 alkyl group,
as a semi-conducting compound of type N in a photovoltaic substrate, wherein said photovoltaic substrate comprises said compound of formula (I) and a semi-conducting compound of type P, providing, in combination with each other, a photovoltaic effect. The compounds of formula (I) are also called perylene-type compounds.
Perylene-type compounds are known as dyes, notably because of their fluorescent properties. In these compounds, the two nitrogen atoms of the perylene aromatic radical are generally substituted with aromatic groups, typically of the phenyl type, which participate to the delocalization of the π electrons of the aromatic core (see for example US 2005/251930).
Those compounds are thermally and chemically stable and are difficultly oxidized. Surprisingly, the compounds according to the invention, for which the nitrogen atoms are not substituted with aromatic groups, but on the contrary with a hydrogen atom or a non-conjugated group with said nitrogen atom, have a semi-conducting nature of type N particularly suitable for an application in photovoltaics.
Within the scope of the present invention, by « in combination » is meant that the semi-conducting compound of type N and the semi-conducting organic compound of type P are positioned in contact with each other in the photovoltaic substrate, in a way capable of providing a photovoltaic effect when said substrate is irradiated with adequate electromagnetic radiation.
Within the scope of the present invention, the notion of a donor nature (semi-conductor of type P) or acceptor nature (semi-conductor of type N) of a semi-conducting compound is relative and depends on the nature of the compound with which it is in combination within the photovoltaic substrate. A compound including attractor groups is generally of the acceptor nature (type N) and conversely, a compound including donor groups is generally of a donor nature (type P).
Within the scope of the present invention, when R and/or R' represent a hydrocarbon group, by « non-conjugated » is meant that said hydrocarbon group bound to the nitrogen atom is not involved in the delocalization of the π electrons of the aromatic core of formula:
According to the present invention, an « alkyl » group represents a saturated hydrocarbon monovalent group with a linear or branched chain, comprising from 1 to 36 carbon atoms, preferably from 1 to 24, more preferably from 1 to 12, and most preferably from 1 to 5 carbon atoms. When they are linear, mention may notably be made of methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl and decyl groups. When they are branched or substituted with one or several alkyl radicals, mention may notably be made of isopropyl, tert-butyl, 2-ethylhexyl, 2-methylbutyl, 2-methyl pentyl, 1 -methylpentyl and 3- methylheptyl radicals.
According to the present invention an « alkyl » group may be substituted with an aryl or heteroaryl group.
The term « aryl » designates a mono- or bi-cyclic aromatic hydrocarbon system comprising from 6 to 10, preferably 6 or 10 carbon atoms. Among aryl groups, mention may be made of phenyl or naphthyl groups more particularly substituted with an alkoxy group.
When the aryl group comprises at least one heteroatom, this is referred to as a « heteroaryl » radical. Thus, the term « heteroaryl » designates an aromatic system comprising one to four heteroatoms selected from nitrogen, oxygen or sulfur, which is mono- or bi-cyclic, comprising from 1 to 10 and preferably from 5 to 10 carbon atoms. Among heteroaryl groups, mention may be made of pyrazinyl, thienyl, oxazolyl, furazanyl, pyrrolyl, 1 ,2,4-thiadiazolyl, naphthyridinyl, pyridazinyl, quinoxalinyl, phthalazinyl, imidazo[1 ,2-a]pyridine, imidazo[2,1-b]thiazolyl, cinnolinyl, triazinyl, benzofurazanyl, azaindolyl, benzimidazoiyl, benzothienyl, thienopyridyl, thienopyrimidinyl, pyrrolopyridyl, imidazopyridyl, benzoazaindole, 1 ,2,4-triazinyl, benzothiazolyl, furany!, imidazoly!, indolyl, triazolyl, tetrazolyl, tndolizinyl, isoxazolyl, isoquinolinyl, isothiazolyl, oxadiazolyl, pyrazinyl, pyridazinyl, pyrazolyl, pyridyl, pyrimidinyl, purinyl, quinazolinyl, quinolinyl, isoquinolyl, 1 ,3,4-thiadiazolyl, thiazolyl, triazinyl, isothiazolyl, carbazolyl, as well as the corresponding groups from their condensation or from condensation with the phenyl ring.
According to the present invention, the « alkyl » groups, « aryl » groups and « heteroaryl » groups may also be substituted with an amino, hydroxy, thio, halogeno, alkyl, alkoxy, alkylthio, alkylamino, aryloxy, arylalkoxy, cyano, trifluoromethyl, carboxy, carboxyalkyl or cycloalkyl group.
The « alkoxy » groups according to the present invention are groups of formula -O-alkyl, the alkyl group being as defined earlier.
The term « alkylthio » designates an -S-alkyl group, the alkyl group being as defined above.
The term « a!kylamino » designates a -NH-alkyl group, the alkyl group being as defined above.
Among halogen atoms, more particularly, mention will be made of fluorine, chlorine, bromine and iodine atoms, preferably bromine and iodine atoms.
The term « aryloxy » designates a -O-aryl group, the aryl group being as defined above.
The tern « arylalkoxy » designates an aryl-alkoxy- group, the aryl and alkoxy group being as defined above.
The term « carboxyalkyl » designates a HOOC-alkyl- group, the alkyl group being as defined above. As an example of carboxylalkyl groups, mention may notably be made of carboxymethyl or carboxyethyl groups.
The term « cycloaikyl » designates a non-aromatic saturated or partly unsaturated mono-, bi- or tri-cyclic hydrocarbon group, comprising from 3 to 20 carbon atoms and preferably from 3 to 10 carbon atoms, such as notably cyclopropyl, cyclopentyl, cyclohexyl or adamantyl, as well as the corresponding rings containing one or several unsaturations.
Thus, within the scope of the present invention the term « cycloaikyl » also encompasses « heterocycloalkyl » groups designating non-aromatic, saturated or partly unsaturated mono- or bicyclic systems of 3 to 8 carbon atoms, comprising one or several heteroatoms selected from N, O and S.
According to the present invention, a « cycloaikyl », « aryl » or « heteroaryl » group may also be substituted with at least one substituent chosen in particular from an amino, hydroxyl, thio, halogeno, alkyl, alkoxy, alkylthio, alkylamino, aryloxy, arylalkoxy, cyano, trifluoromethyl, carboxy or carboxyalkyl group.
When and/or R' do not represent a hydrogen atom, they may represent an optionally substituted, alkenyl group.
The « alkenyl » groups represent hydrocarbon groups with a straight or linear chain, and comprise one or several ethylenic unsaturations, which are not conjugated with the nitrogen atoms of the compounds of formula (I).
When R and/or R' do not represent a hydrogen atom, they may represent an optionally substituted, alkynyl group.
The « alkynyl » groups represent hydrocarbon groups with a straight or linear chain, and comprise one or several acetylenic unsaturations, which are not conjugated with the nitrogen atoms of the compounds of formula (I).
According to one embodiment of the invention, in formula (I), R-,, R2, R3, R4| R'^ R'2, R'3 and R'4 represent, independently of each other, a group selected from the group consisting of -H, -Br, -NRaRb and -CN, wherein Ra and Rb represent independently H or a C C6 alkyl group.
According to one embodiment of the invention, in formula (I), at least one group among R-i , R2, R3, R4, R'i , R'2, '3 and R' is different from a hydrogen atom.
According to one embodiment of the invention, in formula (I), two groups among R^ R2, R3. R , R'i , R'2, '3 and R'4 are different from a hydrogen atom, the others six groups being a hydrogen atom.
The present invention also relates to the use as defined above of a compound of formula (II):
wherein:
- R and R' are as defined above,
- Ri and R'i are identical and as defined above.
Formula (II) corresponds to formula (I) wherein each of R2, R3, R4, R'2, R'3 and R'4 represents a hydrogen atom, and wherein Ri and R are identical.
According to one embodiment of the invention, in formula (II), Ri and R'i are different from a hydrogen atom.
According to one embodiment of the invention, in formula (I), each of R^ R2, R3, R4,
R'i, R'2, '3 and R'4 represents a hydrogen atom.
The present invention also relates to the use as defined above of a compound of formula (III):
According to one embodiment of the invention, in formula (I), (II) or (III), R and R' represent a hydrogen atom.
According to another embodiment of the invention, in formula (I), (II) or (111), at least one of R and R' is different from a hydrogen atom.
According to another embodiment of the invention, in formula (I), (II) or (III), R and R' are different from a hydrogen atom.
According to another embodiment of the invention, in formula (I), (II) or (III), R and R' are different from each other.
According to another embodiment of the invention, in formula (I), (II) or (III), R and R' are identical.
When R and/or R' do not represent a hydrogen atom, they may represent a C C36 alkyl group, preferably a C1-C12 alkyl group, optionally substituted.
When R and/or R' do not represent a hydrogen atom, they may represent an alkyl group, substituted with an aryl group. These are referred to as an « arylalkyl » or « aralkyl » group.
According to one embodiment of the invention, R and R' represent, independently of each other, a group of formula -Alk-Ar wherein:
radical -A!k- is a C-|-C 2 alkylene radical, preferably in C1-C4, and
-Ar is an optionally substituted C6-C10 aryl group or an optionally substituted
C1-C10 heteroaryl group.
According to one embodiment, R and R' are identical.
According to the present invention, an « alkylene » radical represents a divalent radical of the alkyl type, optionally substituted.
The alkylene radical -Alk- may be substituted with any substituent defined above as a substituent of an alkyl group.
Preferably, the alkylene radical -Alk- is not substituted.
Preferably the alkylene radical -Alk- represents a non-branched linear alkylene chain comprising from 1 to 10 carbon atoms.
According to one embodiment of the invention, the alkylene radical -Alk- is selected from methylene (-CH2-), ethylene (-C2H4-), propylene (-C3H6-) and butylene (-C4H8-) radicals.
Preferably, the alkylene radical -Alk- is selected from methylene (-CH2-) and ethylene (-C2H4-) radicals.
Preferably, the alkylene radical -Alk- is a methylene radical -CH2-.
According to one embodiment of the invention, -Ar is a phenyl group, optionally substituted.
According to one embodiment of the invention, -Ar is a CTC 0 heteroaryl group comprising one to four heteroatoms, selected from N, S and O.
According to the present invention, an « aryi » group and a « heteroaryl » group may be substituted with at least one substituent chosen in particular from an amino, hydroxy, thio, halogeno, alkyl, alkoxy, alkylthio, alkylamino, aryloxy, arylalkoxy, cyano, trifluoromethyl, carboxy, carboxyalkyi or cycloalkyi group; said groups being as defined above.
According to one embodiment of the invention:
- radical -Alk- is -CH2- or -C2H4-, and
- -Ar is an optionally substituted phenyl group.
According to one embodiment of the invention, -Ar is a phenyl group substituted by a -ORa group, wherein Ra is a C C12 aikyl group.
The -ORa group may be in the para, meta or ortho position, preferably in the para position of the phenyl group.
According to one embodiment of the invention, R and R' are identical and represent: a group of formula
- a group of formula
When R and/or R' do not represent a hydrogen atom, they may represent an alkyl group, linear or branched.
According to one embodiment of the invention, R and R' represent, independently of each other, a linear or branched C2-C24 alkyl group of formula -Alk', preferably a C12- C24 alkyl group, in particular a C2o-C24 alkyl group, said alkyl group being preferably branched.
According to one embodiment of the invention, -Alk' is a group of formula
The present invention also relates to the use of a compound selected from the following compounds:
According to one embodiment, the semi-conducting organic compound of type P is selected from polythiophenes, polycarbazoles and poly(arylene vinylene).
Within the scope of the present invention, by « polythiophene » is meant an organic compound, preferably a polymer, comprising several thiophene units generally following each other, and typically bound together with the carbon atoms 2 and 5 of the thiophene units. Alternatively, the thiophene units may be alternated with other units, such as alkyl, aryl or heteroaryi units. A polythiophene may comprise any type of substitution on the thiophene units and the optional other units which make it up.
As a polythiophene, mention may be made of poly(3-hexylthiophene), so-called
P3HT.
Within the scope of the present invention, by « polycarbazole » is meant an organic compound, preferably a polymer, comprising a sequence of several carbazole units, generally following each other or else alternated with other units, such as alky, aryl or heteroaryi units. A polycarbazole may comprise any type of substitution on the thiophene units and the optional other units which make it up.
Within the scope of the present invention, by « poly{ary!ene vinylene) » is meant an organic compound, preferably a polymer, comprising a sequence of several aryl and vinyl units. Preferably a poly(arylene vinylene) comprises several aryl vinyl units.
According to one embodiment of the invention, the semi-conducting organic compound of type P is a polycarbazole.
As a polycarbazole, mention may be made of poly[[9-(1-octylnonyl)-9H-carbazole- 2,7-diyl]-2,5-thiophenediyl-2,1 ,3-benzothiadiazole-4,7-diyl-2,5-thiophenediyl], so-called PCDTBT.
The present invention also relates to a photovoltaic substrate comprising, in combination:
- a semi-conducting organic compound of type N of formula (I) as defined in any one of claims 1 to 10, and
a semi-conducting organic compound of type P capable of providing, in combination with said compound of formula (I), a photovoltaic effect.
According to one embodiment of the invention, the semi-conducting organic compound of type P is selected from polythiophenes, polycarbazoles and poly(ary!ene vinylene), and is preferably a polycarbazole.
According to one embodiment of the invention, the semi-conducting organic compound of type P is a polycarbazole.
According to one embodiment of the invention, the semi-conducting compound of type P is a polycarbazole and the semi-conducting organic compound of type N is a compound of formula (I), (II) or (III) as defined above.
The present invention also relates to a photovoltaic substrate comprising, in combination:
a semi-conducting organic compound of type N of formula (I) wherein R and R' represent, independently of each other, a group of formula -Alk-Ar as defined above, and
a semi-conducting organic compound of type P able to provide, in combination with said compound of formula (I), a photovoltaic effect.
The present invention also relates to a photovoltaic substrate comprising, in combination:
- a semi-conducting organic compound of type N of formula (I) wherein R and R' represent, independently of each other, a linear or branched C2-C24 alkyl group of formula -Alk', preferably a C12-C24 alkyl group, in particular a C20-C24 alkyl group, said alkyl group being preferably branched, and
- a semi-conducting organic compound of type P able to provide, in combination with said compound of formula (I), a photovoltaic effect.
The present invention also relates to a compound of formula (I):
wherein R, R', R^ R2, R3, R4, R , R'2, R'3 and R'4 are as defined above,
provided that said compound is not a compound having one of the following of formulae:
According to one embodiment of the invention, in formula (I), R1 ; R2, R3, R4, R'i , R'2, R'3 and R'4 represent, independently of each others, a group selected from the group consisting of -H, -Br, -NRaRb and -CN, wherein Ra and Rb represent independently H or a C-|-C6 alkyl group.
According to one embodiment of the invention, in formula (I), R and R' are different from a hydrogen atom, a methyl group, a -CH2CH2-C6H5 group and a -CH2-C6H4OCH3 group.
The present invention also relates to a compound of formula (I) wherein two groups among R-i , R2, R3, R4, R'i , R'2, R'3 and R'4 are different from a hydrogen atom, the others six groups being a hydrogen atom.
The present invention also relates to a compound of formula (II):
wherein:
- R and R' are as defined above,
and R'i are identical and as defined above,
provided that said compound is not a compound having one of the following of formulae:
According to one embodiment of the invention, in formula (II), Ri and R are different from a hydrogen atom.
The present invention also relates to the use as defined above of a compound of formula (11-1 ):
wherein:
- R and R' are as defined above,
- RT and R1! are identical and different from a hydrogen atom.
The present invention also relates to the use as defined above of a compound of formula (11-2):
wherein R and R' are as defined above and wherein Hal represents a halogen atom. In formula (11-2), Hal is preferably bromine or iodine.
The present invention also relates to the use as defined above of a compound of formula (11-3):
wherein R and R' are as defined above.
The present invention also relates to the use as defined above of a compound of formula (11-4):
wherein R and R' are as defined above, and wherein Ra and Rb represent independently a hydrogen atom or a C^-C^ alkyl group.
In formula (11-4), Ra and Rb are preferably identical and most preferably represent a C,-C6 alkyl group.
The present invention also relates to a compound of formula (III):
The present invention also relates to a compound of formula (I), (II) or (I II), wherein each of R2, R3, R4, R'i , R'2, R'3 and R'4 represents a hydrogen atom.
The present invention also relates to a compound of formula (I), (II) or (III), wherein:
R and R' are identical and represent a group of -Alk-Ar wherein:
radical -Alk- is a C^-C^ alkylene radical, preferably a C C4 alkylene radical, and
- -Ar is an optionally substituted C6-C10 aryl group or an optionally substituted C1-C10 heteroaryl group, and
and R are identical and represent a group selected from the group consisting of -H, -Br, -NRaRb and -CN, wherein Ra and Rb independently represent a C Ce alkyl group.
The present invention also relates to a compound of formula (I), (II) or (III), wherein:
- radical -Alk- is a CrC4 alkylene radical,
- -Ar is a phenyl group substituted by a -ORa group, wherein Ra is a C6-C12 alkyl group, and
Ri, R2, R3, R4, R'i, R'2. R'3 and R'4 are identical and represent a hydrogen atom.
The present invention also relates to a compound of formula (I) or (II), wherein:
- radical -Alk- is a C C4 alkylene radical,
- -Ar is a phenyl group substituted by a -ORa group, wherein Ra is a CTC12 alkyl group, and
Ri and R are identical and represent a group selected from the group consisting of -Br, -NRaRb and -CN, wherein Ra and Rb independently represent a C^Ce alkyl group.
The present invention also relates to a compound of formula (I), (II) or (III), wherein:
R and R' are identical and represent a linear or branched C2-C24 alkyl group of formula -Alk', preferably a Ci2-C24 alkyl group, more preferably a C20-C24 alkyl group, said alkyl group being preferably branched, and
Ri and R are identical and represent a group selected from the group consisting of -H, -Br, -NRaRb and -CN, wherein Ra and Rb independently represent a Ci-C6 alkyl group.
The compounds of formula (I) are synthesized from commercially available precursors, according to general procedures well described in the literature.
The compounds of the invention are for example prepared from starting material 3,4,9, 10-perylenetetracarboxylic dianhydride (notably available from TCI and Merck):
For example, the compounds of formula (li) are prepared according to the following general procedure, starting from 3,4,9, 10-perylenetetracarboxylic dianhydride as starting material, comprising:
- a step of functionalisation of the aromatic core of said starting material by grafting groups R-i and R onto said core, and
a step of condensation with primary amines R0-NH2 and R'0-NH2 wherein R0 and R'0 correspond either to R and R' or to precursors of said groups, in a solvent such as tetrahydrofuran. The step of functionalisation is for example carried out in two steps: a first step of grafting two halogen atoms onto the aromatic core at the R and R'i positions, and a second step of grafting suitable groups R^ and R'-, by aromatic substitution.
The step of condensation is typically carried out by refluxing for about 10 hours, then the solvent is partially evaporated and a portion of methanol is added to precipitate the product of condensation.
When R and R' are identical, R0 and R'0 are advantageously identical too.
By "precursors of R and/or R'", it is meant that R0 and/or R'0 correspond to R and/or R' under a protected form for example.
When R = R' = R0 = R'o, the step of condensation reaction is generally carried out by simple addition of two equivalents of amine R~NH2 to the starting material.
For example, the compounds of formula (III) are prepared according to the following general procedure, starting from 3,4,9, 10-perylenetetracarboxylic dianhydride as starting material, comprising a step of condensation with primary amines R0-NH2 and R'o-NH2 wherein R0 and R'0 are as above described.
The photovoltaic effect of the photovoltaic substrates according to the invention is obtained by placing both organic semi-conductors between two electrodes (anode and cathode) in the form of a substrate comprising both of these semi-conductors in combination (this substrate being in direct contact with both electrodes, or optionally connected to at least one of the electrodes via an additional coating, for example a charge-collecting coating); and by irradiating the thereby produced photovoltaic cell with adequate electromagnetic radiation, typically with light from the solar spectrum. To do this, one of the electrodes is generally transparent to the electromagnetic radiation used: in a way known per se, a transparent ITO (indium oxide doped with tin) anode may notably be used.
Obtaining a substrate comprising both semi-conducting organic compounds (P and N) in combination between the electrodes may be achieved by successive depositions of semi-conductors of type P and N. Such depositions may be carried out by using the
vacuum evaporation deposition technique known to one skilled in the art, or else by depositing a solution comprising a semi-conducting organic compound of type P or N in a solvent and by then evaporating said solvent, or else by spin-coating (see Blouin et al. Adv. Mater. 2007, 19, 2295-2300). Such a substrate may also be obtained by depositing a solution comprising both semi-conducting organic compounds of type P and N in a suitable solvent, and then by evaporating this solvent, for example by following and/or adapting the conditions described in application WO 2011/036421.
Under the effect of the irradiation, the electrons of the inorganic semi-conductor type P are excited, typically according to a so-called π-π* transition mechanism (passage from the highest occupied molecular orbital (HOMO) to the lowest unoccupied molecular orbital (LUMO)), this leads to an effect similar to the injection of an electron from the valence band into the conduction band in an inorganic semi-conductor, which leads to the creation of an exciton (an electron/hole pair). Because of the presence of the organic semi-conductor of type N in contact with the semi-conductor of type P, the thereby created exciton may be disassociated at the P/N interface and the excited electron created during irradiation may be conveyed by the semi-conductor of type N towards the cathode, the hole as for it being lead to the anode via the semi-conductor of type P. Accumulation of the electrons at the cathode and of the holes at the anode generates an electric voltage at the origin of the electric current generated by the photovoltaic cell.
EXAMPLES
Photovoltaic devices comprising a photovoltaic substrate including an organic layer with a semi-conducting nature, a support and electrodes were prepared according to the conditions hereafter.
Example 1 : preparation of novel semi-conducting compounds of type N
Compounds of formula (II) according to the present invention were prepared.
Step 1 :
Under nitrogen atmosphere, 0.05 mol of 3,4,9, 10-perylenetetracarboxylic dianhydride TCI), 0.1 mole of NaBr and 50ml of oleum were charged into a 100ml of round-bottomed flask, heated to 140°C and stirred for 12 hrs, then cooled to room temperature and poured onto crashed ice (500g), diluted with water (500ml), then filtered, washed with water, then dried to afford crude product as greenish yellow solid (yield:*! 00%).
Under nitrogen atmosphere, said product, 0.05 mol of hkN-Ph-OMe and 50ml of acetic acid were charged in a 100ml of round-bottomed flask, heated to 116-118°C and stirred for 24h. The mixture was then cooled to room temperature, the solvent was evaporated and the crude was purified on silica gel flash chromatography (ethyl acetate/hexane 50/50 V/V) to yield a brown solid (yield 55%).
Step 2a:
Under nitrogen atmosphere, 0.01 mol of the solid obtained in step 1, 0.1 mol of
Zn(CN)2 and 30ml of dry THF were charged in a 100ml of round-bottomed flask, refluxed
for 48h. The mixture was then cooled to room temperature, the solvent was evaporated and the crude was purified on silica gel flash chromatography (ethyl acetate/hexane 80/20 V/V) to yield a brown solid (yield 36%).
Step 2b:
Under nitrogen atmosphere, 0.1 mol of the solid obtained in step 1 , 0.5 mol of HN(Et)2 and 10ml of dry THF were charged in a 50ml of round-bottomed flask, refluxed for 16h. The mixture was then cooled to room temperature, the solvent was evaporated and the crude was purified on silica gel flash chromatography (ethyl acetate/hexane 50/50 V/V) to yield a brown solid (yield 44%).
Example 2: preparation of a photovoltaic substrate General procedure
A glass support (a plate of 15 mm x 15 mm x 0.7 mm) coated with a conducting layer of indium oxide doped with tin (ITO) as an anode (a commercial support provided with an ITO (indium oxide doped with tin) layer with a thickness of 100 nm) is cleaned beforehand in an acetone bath with ultrasound for 10 minutes, followed by an ethanoi bath with ultrasound for 10 minutes, followed by an isopropanoi bath boiling for 10 minutes.
The thereby cleaned glass support/ITO is then dried with compressed air, and then placed in an UV/ozone oven during 10 minutes at room temperature.
On the thereby treated support, a layer of PEDOT :PSS (poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) is then deposited, which is a charge collecting layer) with a thickness of 50 nm, by spin coating and then by heating into a low pressure oven at 120°C for 15 minutes until the water is removed.
On the thereby prepared support, a photovoltaic substrate is deposited by deposition of a thin layer of semi-conducting organic compound of type P (donor), followed by the deposition of a thin layer of semi-conducting organic compound of type N (donor).
The deposition of the thin layer of semi-conducting organic compound of type P is achieved by spin-coating from 10 mg/mL solution of PCDTBT into ortho-dichlorobenzene: 60 sec at 1000 RPM to get 50 nm-thick layers, and 60 sec at 1500 RPM to get 20nm-thick layers.
The deposition of the thin layer of semi-conducting organic compound of type N is achieved by evaporation in vacuo, in a vacuum chamber at 1.10-6 bar with evaporation rate at 1 angstrom/min for the 5 first nanometers and then 5 angstrom/min (20 nm and 50 nm total).
A thin layer of aluminium (thickness of about 80 nm) is then deposited as a cathode on the thereby produced substrate, by evaporation in vacuo.
Comparative substrates
As a reference photovoltaic substrate, PCDTBT/C6Q substrates were prepared, comprising the following thin layers, respectively:
- 20 nm of PCDTBT (type P) and 20 nm of C60 (type N);
- 20 nm of PCDTBT (type P) and 50 nm of C60 (type N);
- 50 nm of PCDTBT (type P) and 20 nm of C60 (type N); or
- 50 nm of PCDTBT (type P) and 50 nm of C60 (type N).
Substrates according to the invention
As a photovoltaic substrate according to the invention, the following substrates were prepared, comprising the following thin layers, respectively:
- 20 nm of PCDTBT (type P) and 20 nm of A (type N);
- 20 nm of PCDTBT (type P) and 50 nm of A (type N);
- 50 nm of PCDTBT (type P) and 20 nm of A (type N); or
- 50 nm of PCDTBT (type P) and 50 nm of A (type N).
The compound A according to the invention, used as semi-conducting organic compound of type N, is commercially available (Rhodia, pigment black 32).
For each type of substrate (PCDTBT/C60 and PCDTBT/A), the measurements of the photovoltaic characteristics corresponding to the best combinations of thicknesses of P and N layers are indicated in the following table:
The photovoltaic substrate PCDTBT/A according to the invention, comprising the compound A as a semi-conducting compound of type N, has better photovoltaic characteristics than the reference photovoltaic substrate PCDTBT/C6o.
Claims
WHAT IS CLAIMED IS :
1. The use of a compound of formula (I) :
wherein:
R and R' represent, independently of each other, a hydrogen atom or a Ci-C36 hydrocarbon group non-conjugated with the nitrogen atom to which it is bound, and
- R1 f R2, R3, R , R'i , R'2, R'3 and R'4 represent, independently of each others, a group selected from the group consisting of -Ra, -NRaRb, - ORa, -CN, -C02Ra, -NO2, -CH(CN)2 and halogen, wherein Ra and Rb represent independently a hydrogen atom or a C1-C12 alkyl group, as a semi-conducting compound of type N in a photovoltaic substrate, wherein said photovoltaic substrate comprises said compound of formula (I) and a semi-conducting compound of type P, providing, in combination with each other, a photovoltaic effect.
2. The use according to claim 1 , wherein R p R2, R3, R4, R'i , R'2, R'3 and R'4 represent, independently of each other, a group selected from the group consisting of -H, -Br, -NRaRb and -CN, wherein Ra and R represent independently H or a Ci-C6 alkyl group.
3. The use according to any one of claims 1 or 2, wherein at least one group among Ri , R2. 3> R4, R'i , R'2, R'3 and R'4 is different from a hydrogen atom.
4. The use according to any one of claims 1 to 3, wherein two groups among Ri , R2, R3, R4, R'-ι , R'2, R'3 and R'4 are different from a hydrogen atom, the others six groups being a hydrogen atom.
5. The use according to claim 1 or claim 2, wherein each of R-, , R2, R3, R4, R'i , R'2l R'3 and R'4 represents a hydrogen atom.
6. The use according to any one of claims 1 to 5, wherein R and R' represent, independently of each other, a group of formula -Alk-Ar wherein:
- radical -Alk- is a C1-C12 alkylene radical, preferably in C1-C4, and
- -Ar is an optionally substituted C6-C10 aryl group or an optionally substituted Ci-C10 heteroaryl group.
7. The use according to claim 6, wherein:
- radical -Alk- is -CH2- or -C2H4-, and
- -Ar is an optionally substituted phenyl group.
8. The use according to any one of claims 6 or 7, wherein -Ar is a phenyl group substituted by a -ORa group, wherein Ra is a C C 2 alky! group.
9. The use according to any one of claims 1 to 8 wherein R and R' are identical and re resent a group of formula
group of formula
10. The use according to any one of claims 1 to 5, wherein R and R' represent, independently of each other, a linear or branched C2-C24 alkyl group of formula -Alk', preferably a C12-C24 alkyl group, in particular a C20-C24 alkyl group, said alkyl group being preferably branched.
11. The use according to claim 0, wherein -Alk' is a group of formula
12. The use according to any one of claims 1 to 11 , wherein the semi-conducting organic compound of type P is selected from polythiophenes, polycarbazoles and poly(arylene vinylene).
13. The use according to claim 12, wherein the semi-conducting organic compound of type P is a polycarbazole.
14. A photovoltaic substrate comprising, in combination:
- a semi-conducting organic compound of type N of formula (I) as defined in any one of claims 1 to 10, and
- a semi-conducting organic compound of type P capable of providing, in combination with said compound of formula (I), a photovoltaic effect.
15. The substrate according to claim 14, wherein the semi-conducting organic compound of type P is selected from polythiophenes, polycarbazoles and poly(arylene vinylene), and is preferably a polycarbazole.
16. Compound of formula
- R and R' represent, independently of each other, a hydrogen atom or a Ci-C3B hydrocarbon group non-conjugated with the nitrogen atom to which it is bound, and
- Ri, F¾2, F¾3, R4, R'i, R'2, R*3 and R'4 represent, independently of each other, a group selected from the group consisting of -Ra, -NRaRb, - ORa, -CN, -C02Ra, -NO2, -CH(CN)2 and halogen, wherein Ra and Rb represent independently H or a C C12 alkyl group,
provided that said compound is not a compound having one of the following of formulae:
17. Compound according to claim 16, wherein two groups among R,, R2, R3, R4l 'i, R'2, R! 3 and R'4 are different from a hydrogen atom, the others six groups being a hydrogen atom.
18. Compound according to claim 16, wherein each of Ri, R2, R3, R4, R'i, R'2, R'3 and R' represents a hydrogen atom.
19. Compound according to claim 16, wherein:
R and R' are identical and represent a group of -A!k-Ar wherein:
radical -Alk- is a C C12 alkylene radical, preferably a CrC4 alkylene radical, and
- -Ar is an optionally substituted C6-C10 aryl group or an optionally substituted CrCi0 heteroaryl group, and
- RT and R are identical and represent a group selected from the group consisting of -H, -Br, -NRaRb and -CN, wherein Ra and Rb independently represent a C-i-C6 alkyl group.
20. Compound according to claim 19, wherein:
- radical -Alk- is a CrC4 alkylene radical,
- -Ar is a phenyl group substituted by a -ORa group, wherein Ra is a C6-C12 alkyl group, and
- R-,, R2, R3, R4, R' R'2, R'3 and R'4 are identical and represent a hydrogen atom.
21. Compound according to claim 19, wherein:
- radical -Alk- is a C C alkylene radical,
- -Ar is a phenyl group substituted by a -OR0 group, wherein Ra is a CrCi2 alkyl group, and
- R and R'i are identical and represent a group selected from the group consisting of -Br, -NRaRb and -CN, wherein Ra and Rb independently represent a C C6 alkyl group.
Compound according to claim 6, wherein
- R and R' are identical and represent a linear or branched C2-C24 alkyi group of formula -Alk', preferably a C1z-C24 alkyi group, more preferably a C20-C24 alkyi group, said alkyi group being preferably branched, and
- Ri and R'i are identical and represent a group selected from the group consisting of -H, -Br, -NRaRb and -CN, wherein Ra and Rb independently represent a CrC6 alkyi group.
23. Compound according to claim 22, wherein each of R^ R2, R3, 4. R'i , R'2. R'3 and R'4 represents a hydrogen atom.
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