ITMI20112452A1 - COPOLYMER CONJUGATE STATISTIC PHOTOACTIVE INCLUDING CARBAZOLIC UNITS - Google Patents
COPOLYMER CONJUGATE STATISTIC PHOTOACTIVE INCLUDING CARBAZOLIC UNITS Download PDFInfo
- Publication number
- ITMI20112452A1 ITMI20112452A1 IT002452A ITMI20112452A ITMI20112452A1 IT MI20112452 A1 ITMI20112452 A1 IT MI20112452A1 IT 002452 A IT002452 A IT 002452A IT MI20112452 A ITMI20112452 A IT MI20112452A IT MI20112452 A1 ITMI20112452 A1 IT MI20112452A1
- Authority
- IT
- Italy
- Prior art keywords
- photoactive
- groups
- copolymer
- statistical
- photovoltaic
- Prior art date
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- 229920001577 copolymer Polymers 0.000 title claims description 40
- -1 unsaturated Chemical group 0.000 claims description 29
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims description 20
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 238000010276 construction Methods 0.000 claims description 11
- 125000003545 alkoxy group Chemical group 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 5
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical group [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 5
- 229910052711 selenium Inorganic materials 0.000 claims description 5
- 125000003367 polycyclic group Chemical group 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Chemical group 0.000 claims description 4
- 125000004434 sulfur atom Chemical group 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Chemical group 0.000 claims description 3
- 239000011669 selenium Chemical group 0.000 claims description 3
- 239000011593 sulfur Chemical group 0.000 claims description 3
- 125000005842 heteroatom Chemical group 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 125000005346 substituted cycloalkyl group Chemical group 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 description 34
- 238000013086 organic photovoltaic Methods 0.000 description 13
- 238000000034 method Methods 0.000 description 11
- 239000002904 solvent Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical class C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 230000003287 optical effect Effects 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 6
- 239000010408 film Substances 0.000 description 6
- 229910052731 fluorine Inorganic materials 0.000 description 6
- 239000011737 fluorine Substances 0.000 description 6
- 230000005855 radiation Effects 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 230000000875 corresponding effect Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 125000000753 cycloalkyl group Chemical group 0.000 description 4
- 125000005843 halogen group Chemical group 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000004528 spin coating Methods 0.000 description 4
- 229930192474 thiophene Natural products 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 3
- 238000003306 harvesting Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 3
- 239000011368 organic material Substances 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 230000006798 recombination Effects 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 2
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- 239000005964 Acibenzolar-S-methyl Substances 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 229920000144 PEDOT:PSS Polymers 0.000 description 2
- 229910002666 PdCl2 Inorganic materials 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 238000006619 Stille reaction Methods 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 230000002596 correlated effect Effects 0.000 description 2
- 229910021419 crystalline silicon Inorganic materials 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 229940117389 dichlorobenzene Drugs 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- RHZWSUVWRRXEJF-UHFFFAOYSA-N indium tin Chemical compound [In].[Sn] RHZWSUVWRRXEJF-UHFFFAOYSA-N 0.000 description 2
- 238000007641 inkjet printing Methods 0.000 description 2
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 229920000301 poly(3-hexylthiophene-2,5-diyl) polymer Polymers 0.000 description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 description 2
- 239000011736 potassium bicarbonate Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical compound N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- 238000001392 ultraviolet--visible--near infrared spectroscopy Methods 0.000 description 2
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 description 1
- FNQJDLTXOVEEFB-UHFFFAOYSA-N 1,2,3-benzothiadiazole Chemical group C1=CC=C2SN=NC2=C1 FNQJDLTXOVEEFB-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- PDQRQJVPEFGVRK-UHFFFAOYSA-N 2,1,3-benzothiadiazole Chemical compound C1=CC=CC2=NSN=C21 PDQRQJVPEFGVRK-UHFFFAOYSA-N 0.000 description 1
- XQJNXCHDODCAJF-UHFFFAOYSA-N 2-bromo-3-hexylthiophene Chemical compound CCCCCCC=1C=CSC=1Br XQJNXCHDODCAJF-UHFFFAOYSA-N 0.000 description 1
- FEOWHLLJXAECMU-UHFFFAOYSA-N 4,7-dibromo-2,1,3-benzothiadiazole Chemical compound BrC1=CC=C(Br)C2=NSN=C12 FEOWHLLJXAECMU-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 125000003860 C1-C20 alkoxy group Chemical group 0.000 description 1
- 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 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 230000010748 Photoabsorption Effects 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 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
- 238000002835 absorbance Methods 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 229940107816 ammonium iodide Drugs 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 125000002837 carbocyclic group Chemical group 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 125000000068 chlorophenyl group Chemical group 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 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
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl 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 description 1
- 238000009510 drug design Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 125000001207 fluorophenyl group Chemical group 0.000 description 1
- 239000003574 free electron Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 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 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000004464 hydroxyphenyl group Chemical group 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000002960 margaryl 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])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
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 125000006501 nitrophenyl group Chemical group 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
- 239000012074 organic phase Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000004351 phenylcyclohexyl group Chemical group C1(=CC=CC=C1)C1(CCCCC1)* 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 229920001062 poly(2,7-carbazoles) Polymers 0.000 description 1
- 229920001088 polycarbazole Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920002098 polyfluorene Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 230000008521 reorganization Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000000126 substance Substances 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
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 description 1
- VJYJJHQEVLEOFL-UHFFFAOYSA-N thieno[3,2-b]thiophene Chemical compound S1C=CC2=C1C=CS2 VJYJJHQEVLEOFL-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000000411 transmission spectrum Methods 0.000 description 1
- COIOYMYWGDAQPM-UHFFFAOYSA-N tris(2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P(C=1C(=CC=CC=1)C)C1=CC=CC=C1C COIOYMYWGDAQPM-UHFFFAOYSA-N 0.000 description 1
- WXAZIUYTQHYBFW-UHFFFAOYSA-N tris(4-methylphenyl)phosphane Chemical compound C1=CC(C)=CC=C1P(C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 WXAZIUYTQHYBFW-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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Description
“COPOLIMERO CONIUGATO STATISTICO FOTOATTIVO COMPRENDENTE UNITA’ CARBAZOLICHE” "PHOTOACTIVE STATISTICAL CONJUGATE COPOLYMER INCLUDING CARBAZOLIC UNITS"
La presente invenzione riguarda un copolimero coniugato statistico fotoattivo. Più in particolare, la presente invenzione riguarda un copolimero coniugato statistico fotoattivo comprendente unità carbazoliche. The present invention relates to a photoactive statistical conjugate copolymer. More particularly, the present invention relates to a photoactive statistical conjugated copolymer comprising carbazole units.
La presente invenzione riguarda altresì l’utilizzo di detto copolimero coniugato statistico fotoattivo comprendente unità carbazoliche nella costruzione di dispositivi fotovoltaici quali, ad esempio, celle fotovoltaiche, moduli fotovoltaici, celle solari, moduli solari, sia su supporto rigido, sia su supporto flessibile. The present invention also relates to the use of said photoactive statistical conjugated copolymer comprising carbazole units in the construction of photovoltaic devices such as, for example, photovoltaic cells, photovoltaic modules, solar cells, solar modules, both on rigid and flexible supports.
I dispositivi fotovoltaici sono dispositivi in grado di convertire l’energia di una radiazione luminosa in energia elettrica. Attualmente, la maggior parte dei dispositivi fotovoltaici utilizzabili per applicazioni pratiche, sfrutta le proprietà chimico-fisiche di materiali fotoattivi di tipo inorganico, in particolare il silicio cristallino ad elevata purezza. A causa degli elevati costi di produzione del silicio la ricerca scientifica, tuttavia, sta da tempo orientando i propri sforzi verso lo sviluppo di materiali alternativi di tipo organico aventi struttura coniugata, oligomerica o polimerica, allo scopo di ottenere dispositivi fotovoltaici organici quali, ad esempio, le celle fotovoltaiche organiche. Infatti, a differenza del silicio cristallino ad elevata purezza, detti materiali di tipo organico sono caratterizzati da una relativa facilità di sintesi, un basso costo di produzione, un peso ridotto dei relativi dispositivi fotovoltaici organici, oltre a permettere il riciclo di detti materiali di tipo organico al termine del ciclo di vita del dispositivo fotovoltaico organico in cui sono utilizzati. Photovoltaic devices are devices capable of converting the energy of a light radiation into electrical energy. Currently, most photovoltaic devices that can be used for practical applications exploit the chemical-physical properties of photoactive inorganic materials, in particular high purity crystalline silicon. Due to the high production costs of silicon, however, scientific research has for some time been orienting its efforts towards the development of alternative organic materials having a conjugate, oligomeric or polymeric structure, in order to obtain organic photovoltaic devices such as, for example , organic photovoltaic cells. In fact, unlike high purity crystalline silicon, said organic materials are characterized by a relative ease of synthesis, a low production cost, a reduced weight of the related organic photovoltaic devices, as well as allowing the recycling of said materials of the type organic at the end of the life cycle of the organic photovoltaic device in which they are used.
I vantaggi sopra riportati rendono l’utilizzo di detti materiali di tipo organico energicamente ed economicamente appetibile nonostante eventuali inferiori efficienze (η) dei dispositivi fotovoltaici organici così ottenuti rispetto ai dispositivi fotovoltaici inorganici. The above advantages make the use of said organic materials energetically and economically attractive despite any lower efficiencies (η) of the organic photovoltaic devices thus obtained compared to inorganic photovoltaic devices.
Il funzionamento dei dispositivi fotovoltaici organici quali, ad esempio, le celle fotovoltaiche organiche, si basa sull’impiego combinato di un composto accettore di elettroni e di un composto donatore di elettroni. Allo stato della tecnica, i composti accettori di elettroni maggiormente impiegati nei dispositivi fotovoltaici organici sono i derivati fullerenici, in particolare il PC61BM (6,6-fenil-C61-metil estere butirrico) o il PC71BM (6,6-fenil-C71-metil estere butirrico), i quali hanno portato alle maggiori efficienze quando miscelati con composti donatori di elettroni scelti tra pohmeri π-coniugati quali, ad esempio, politiofeni (η > 5%), policarbazoli (η > 6%), derivati del poli(tienotiofene)-benzoditiofene (PTB) (η > 8%). The operation of organic photovoltaic devices such as, for example, organic photovoltaic cells, is based on the combined use of an electron acceptor compound and an electron donor compound. In the state of the art, the electron accepting compounds most used in organic photovoltaic devices are fullerene derivatives, in particular PC61BM (6,6-phenyl-C61-methyl butyric ester) or PC71BM (6,6-phenyl-C71- methyl butyric ester), which led to the greatest efficiencies when mixed with electron donor compounds selected from π-conjugated pohmmers such as, for example, polythiophenes (η> 5%), polycarbazoles (η> 6%), derivatives of poly ( thienotyophene) -benzodithiophene (PTB) (η> 8%).
Il processo elementare di conversione della luce in corrente elettrica in una cella fotovoltaica organica avviene attraverso i seguenti stadi: The elementary process of converting light into electric current in an organic photovoltaic cell takes place through the following stages:
1. assorbimento di un fotone da parte del composto donatore di elettroni con formazione di un eccitone, ossia una coppia di trasportatori di carica “elettronelacuna elettronica (o buca)”; 1. absorption of a photon by the electron donor compound with the formation of an exciton, that is a pair of charge transporters "electron the electronic hole (or hole)";
2. diffusione dell’eccitone in una regione del composto donatore di elettroni fino all’ interfaccia con il composto accettore di elettroni; 2. diffusion of the exciton in a region of the electron donor compound up to the interface with the electron acceptor compound;
3. dissociazione dell’eccitone nei due trasportatori di carica: elettrone (-) nella fase accettrice (i.e. nel composto accettore di elettroni) e lacuna elettronica (o buca) (+)] nella fase donatrice (i.e. nel composto donatore di elettroni); 3. dissociation of the exciton in the two charge transporters: electron (-) in the accepting phase (i.e. in the electron acceptor compound) and electronic hole (or hole) (+)] in the donor phase (i.e. in the electron donor compound);
4. trasporto delle cariche così formate al catodo (elettrone attraverso il composto accettore di elettroni) e all’anodo [lacuna elettronica (o buca) attraverso il composto donatore di elettroni], con generazione di una corrente elettrica nel circuito della cella fotovoltaica organica. 4. transport of the charges thus formed to the cathode (electron through the electron acceptor compound) and to the anode [electronic hole (or hole) through the electron donor compound], with the generation of an electric current in the organic photovoltaic cell circuit.
Il processo di fotoassorbimento con formazione dell’eccitone e successiva cessione dell’elettrone al composto accettore di elettroni comporta l’eccitazione di un elettrone dall’HOMO (“Highest Occupied Molecular Orbitai”) al LUMO (“Lowest Unoccupied Molecular Orbitai”) del composto donatore di elettroni e, successivamente, il passaggio da questo al LUMO del composto accettore di elettroni. The photoabsorption process with the formation of the exciton and subsequent transfer of the electron to the electron acceptor compound involves the excitation of an electron from the HOMO ("Highest Occupied Molecular Orbitai") to the LUMO ("Lowest Unoccupied Molecular Orbitai") of the compound electron donor and, subsequently, the transition from this to the LUMO of the electron acceptor compound.
Poiché l’efficienza di una cella fotovoltaica organica dipende dal numero di elettroni liberi che si generano per dissociazione degli eccitoni a loro volta direttamente correlabili al numero di fotoni assorbiti, una delle caratteristiche strutturali dei composti donatori di elettroni che più influisce su tale efficienza è la differenza di energia esistente tra gli orbitali HOMO e LUMO del composto donatore di elettroni, ovvero il cosiddetto “band-gap”. Da tale differenza dipende, in particolare, il valore massimo della lunghezza d’onda al quale il composto donatore di elettroni è in grado di raccogliere e di convertire efficacemente fotoni in energia elettrica, ovvero il cosiddetto processo di “light harvesting” o di “photon harvesting”. Al fine di ottenere correnti elettriche accettabili, il “band-gap”, cioè la differenza di energia tra HOMO e LUMO del composto donatore, se da un lato non deve essere troppo elevata per poter permettere l’assorbimento del maggior numero di fotoni, dall’altro non deve essere troppo bassa perché potrebbe diminuire la tensione agli elettrodi del dispositivo. Since the efficiency of an organic photovoltaic cell depends on the number of free electrons that are generated by dissociation of the excitons, which in turn are directly correlated to the number of absorbed photons, one of the structural characteristics of electron donor compounds that most affects this efficiency is the energy difference existing between the HOMO and LUMO orbitals of the electron donor compound, or the so-called “band-gap”. In particular, the maximum value of the wavelength at which the electron donor compound is able to collect and efficiently convert photons into electrical energy, or the so-called "light harvesting" or "photon" process, depends on this difference. harvesting ". In order to obtain acceptable electric currents, the "band-gap", that is the difference in energy between HOMO and LUMO of the donor compound, if on the one hand it must not be too high to allow the absorption of the greatest number of photons, from 'other must not be too low because it could decrease the voltage at the electrodes of the device.
Per migliorare la resa del processo di “light harvesting” e, conseguentemente, l’efficienza dei dispositivi fotovoltaici, è quindi fondamentale individuare nuovi composti donatori in grado di catturare e convertire le lunghezze d’onda della radiazione solare avente più bassa energia, ossia composti donatori di elettroni caratterizzati da valori di “band-gap” relativamente bassi, i.e da valori di “band-gap” inferiori o uguali a 2 eV. To improve the yield of the "light harvesting" process and, consequently, the efficiency of photovoltaic devices, it is therefore essential to identify new donor compounds capable of capturing and converting the wavelengths of solar radiation with lower energy, that is compounds electron donors characterized by relatively low "band-gap" values, i. and by "band-gap" values lower than or equal to 2 eV.
Nel modo più semplice di operare, le celle fotovoltaiche organiche sono fabbricate introducendo tra due elettrodi, usualmente costituiti da ossido di indiostagno (ΓΓΟ) (anodo) e alluminio (Al) (catodo), uno strato sottile (circa 100 nanometri) di una miscela del composto accettore di elettroni e del composto donatore di elettroni (architettura nota come “bulk heterojunction”). Generalmente, allo scopo di realizzare uno strato di questo tipo, viene preparata una soluzione dei due composti e, successivamente, viene creato un film fotoattivo sull’anodo [ossido di indio-stagno (ITO)] a partire da detta soluzione, ricorrendo ad opportune tecniche di deposizione quali, ad esempio, lo "spin-coating", lo "spray-coating", l’"ink-jet printing", e simili. Infine, sul film essiccato, viene depositato il controelettrodo [i.e. il catodo di alluminio (Al)]. Opzionalmente, tra gli elettrodi ed il film fotoattivo, possono essere introdotti altri strati addizionali in grado di svolgere funzioni specifiche di natura elettrica, ottica, o meccanica. In the simplest way of operating, organic photovoltaic cells are manufactured by introducing a thin layer (about 100 nanometers) of a mixture between two electrodes, usually consisting of indiotain oxide (ΓΓΟ) (anode) and aluminum (Al) (cathode) of the electron acceptor compound and of the electron donor compound (architecture known as “bulk heterojunction”). Generally, in order to create a layer of this type, a solution of the two compounds is prepared and, subsequently, a photoactive film is created on the anode [indium-tin oxide (ITO)] starting from said solution, resorting to suitable deposition techniques such as, for example, "spin-coating", "spray-coating", "ink-jet printing", and the like. Finally, on the dried film, the counter electrode is deposited [i.e. the aluminum cathode (Al)]. Optionally, between the electrodes and the photoactive film, other additional layers capable of performing specific functions of an electrical, optical or mechanical nature can be introduced.
Generalmente, allo scopo di favorire il raggiungimento dell’anodo [ossido di indio-stagno (ΓΓΟ)] da parte delle lacune elettroniche (o buche) e di bloccare al contempo il trasporto degli elettroni, così migliorando la raccolta delle cariche da parte dell’elettrodo ed inibendo i fenomeni di ricombinazione, viene depositato, prima di creare il film fotoattivo a partire dalla miscela del composto accettore e del composto donatore come sopra descritto, un film a partire da una sospensione acquosa di PEDOT:PSS [poli(3,4-etilenediossitiofene)polistirene sulfonato], ricorrendo ad opportune tecniche di deposizione quali, ad esempio, lo "spin-coating", lo "spray-coating", l’"ink-jet printing", e simili. Generally, in order to favor the reaching of the anode [indium-tin oxide (ΓΓΟ)] by the electron holes (or holes) and at the same time block the transport of electrons, thus improving the collection of charges by the electrode and inhibiting the recombination phenomena, before creating the photoactive film starting from the mixture of the acceptor compound and the donor compound as described above, a film starting from an aqueous suspension of PEDOT: PSS [poly (3,4 -ethylenedioxythiophene) polystyrene sulfonate], resorting to suitable deposition techniques such as, for example, "spin-coating", "spray-coating", "ink-jet printing", and the like.
Il composto donatore di elettroni più comunemente utilizzato nella realizzazione di celle fotovoltaiche organiche è il poli(3-esiltiofene) (P3HT) regioregolare. Questo polimero presenta delle caratteristiche elettroniche ed ottiche ottimali (buoni valori degli orbitali HOMO e LUMO, buon coefficiente di assorbimento), una buona solubilità nei solventi che vengono impiegati per fabbricare le celle fotovoltaiche ed una discreta mobilità delle lacune elettroniche. The electron donor compound most commonly used in the construction of organic photovoltaic cells is the regioregular poly (3-hexylthiophene) (P3HT). This polymer has excellent electronic and optical characteristics (good values of the HOMO and LUMO orbitals, good absorption coefficient), a good solubility in the solvents that are used to manufacture the photovoltaic cells and a fair mobility of the electronic gaps.
Altri esempi di polimeri che possono essere vantaggiosamente utilizzati come composti donatori di elettroni sono polimeri comprendenti unità carbazoliche e/o benzotiadiazoliche quali, ad esempio, il polimero PCDTBT {poli[N-9”-eptadecanil-2.7-carbazolo-alt-5,5-(4’,7’-di-2-tienil-2’,r,3’-benzotia-diazolo] }, il polimero PCPDTBT {poli[2,6-(4,4-bis-(2-etilesil)-4//-ciclopenta[2,l-b;3,4-b’]-ditiofene)-alt-4.7-(2,l,3-benzotiadiazolo)]}. Other examples of polymers which can be advantageously used as electron donor compounds are polymers comprising carbazole and / or benzothiadiazole units such as, for example, the PCDTBT polymer {poly [N-9 "-heptadecanil-2.7-carbazole-alt-5,5 - (4 ', 7'-di-2-thienyl-2', r, 3'-benzothia-diazole]}, the PCPDTBT polymer {poly [2,6- (4,4-bis- (2-ethylhexyl) -4 // - cyclopenta [2,1-b; 3,4-b '] - dithiophene) -alt-4.7- (2, 1,3-benzothiadiazole)]}.
Ad esempio, Bluoin N. e altri, nell’articolo “Toward a Rational Design of Poly(2,7-Carbazole) Derivatives for Solar Cells”, Journal of American Chemical Society (2008), Voi. 130, pag. 732-742, descrive varie strutture polimeriche alternate contenenti unità carbazoliche particolarmente utili nella costruzione di dispositivi fotovoltaici, in particolare celle solari. Il polimero PCDTBT {poli[N-9”-eptadecanil-2,7-carbazolo-alt-5,5-(4’,7’-di-2-tienil-2’,r,3’-benzotiadiazolo]} è detto essere in grado di dare i migliori risultati quando applicato nella costruzione di celle solari. For example, Bluoin N. and others, in the article "Toward a Rational Design of Poly (2,7-Carbazole) Derivatives for Solar Cells", Journal of the American Chemical Society (2008), Vol. 130, p. 732-742, discloses various alternating polymeric structures containing carbazole units particularly useful in the construction of photovoltaic devices, in particular solar cells. The PCDTBT polymer {poly [N-9 "-heptadecanyl-2,7-carbazole-alt-5,5- (4 ', 7'-di-2-thienyl-2', r, 3'-benzothiadiazole]} is said to be able to give the best results when applied in the construction of solar cells.
Liu R. e altri, nell’ articolo “Novel red emitting polymers based on 2,7-carbazole and thiophene derivatives”, Chinese Journal of Polymer Science (2008), Voi 26, No. 2, pag. 231-240, descrive diversi copolimeri coniugati derivati da 9etilesil-2,7-carbazolo (Cz) e 4,7-di(4-esiltiene-2-il)-2,l,3-benzotiadiazolo (DHTBT) che vengono sintetizzati tramite la reazione di policondensazione di Suzuki. I suddetti copolimeri sono detti essere particolarmente utili se impiegati in diodi polimeri ad emissione di luce (“Polymer Light Emitting Diodes” - PLEDs). Il suddetto articolo non fa alcuna menzione dell’uso dei copolimeri ivi descritti nel settore dei dispositivi fotovoltaici. Liu R. and others, in the article "Novel red emitting polymers based on 2,7-carbazole and thiophene derivatives", Chinese Journal of Polymer Science (2008), Vol 26, No. 2, p. 231-240, describes several conjugated copolymers derived from 9ethylhexyl-2,7-carbazole (Cz) and 4,7-di (4-hexyl-2-yl) -2, 1,3-benzothiadiazole (DHTBT) which are synthesized by the Suzuki polycondensation reaction. The aforementioned copolymers are said to be particularly useful when used in “Polymer Light Emitting Diodes” - PLEDs. The aforementioned article makes no mention of the use of the copolymers described therein in the field of photovoltaic devices.
E’ noto che nella individuazione di materiali elettroluminescenti per la fabbricazione di diodi ad emissione di luce (LEDs) non sono richieste molecole caratterizzate da valori di “band-gap” tendenzialmente ridotti al di sotto di una certa soglia, al contrario di quanto accade nel caso dei dispositivi fotovoltaici. Infatti, i diodi ad emissione di luce (LEDs) devono essere in grado di emettere radiazioni luminose di varie lunghezze d’onda, inclusa la luce bianca. Tali lunghezze d’onda vengono generate da composti che possiedono un ampio spettro di valori di “bandgap”, ed ognuno di essi viene ottimizzato per una specifica lunghezza d’onda. Diversamente, nel caso dei dispositivi fotovoltaici, è necessario individuare composti aventi valori di “band-gap” relativamente bassi, allo scopo di intercettare la parte di spettro a maggiore intensità della radiazione solare. Inoltre, mentre un composto adatto per diodi ad emissione di luce (LEDs) deve possedere proprietà adatte per l’instaurarsi di processi efficienti di ricombinazione della coppia “elettrone-lacuna elettronica (o buca)” in modo da ottenere una ottimale conversione di elettroni in fotoni, nei composti adatti per dispositivi fotovoltaici devono sussistere le condizioni esattamente opposte, dato che la ricombinazione della “lacuna elettronica (o buca)” e dell’elettrone appena generati entrerebbe in competizione con la loro separazione e il trasporto agli elettrodi, con una conseguente diminuzione inaccettabile dell’ efficienza di generazione di potenza elettrica. It is known that in the identification of electroluminescent materials for the manufacture of light emitting diodes (LEDs), molecules characterized by "band-gap" values tend to be reduced below a certain threshold are not required, contrary to what happens in case of photovoltaic devices. In fact, light emitting diodes (LEDs) must be able to emit light radiation of various wavelengths, including white light. These wavelengths are generated by compounds that have a wide spectrum of "bandgap" values, and each of them is optimized for a specific wavelength. Otherwise, in the case of photovoltaic devices, it is necessary to identify compounds with relatively low "band-gap" values, in order to intercept the part of the spectrum with the greatest intensity of solar radiation. Furthermore, while a compound suitable for light emitting diodes (LEDs) must possess suitable properties for the establishment of efficient recombination processes of the "electron-electron hole (or hole)" pair in order to obtain an optimal conversion of electrons into photons, in compounds suitable for photovoltaic devices the exact opposite conditions must exist, since the recombination of the "electronic hole (or hole)" and the electron just generated would compete with their separation and transport to the electrodes, with a consequent unacceptable decrease in electrical power generation efficiency.
Un chiaro esempio di quanto sopra riportato è rappresentato dal polifluorene che è un materiale largamente utilizzato nei diodi ad emissione luminosa ma totalmente inadatto nella costruzione di dispositivi fotovoltaici. A clear example of the above is represented by polyfluorene which is a material widely used in light emitting diodes but totally unsuitable in the construction of photovoltaic devices.
Lo studio di nuovi copolimeri in grado di essere utilizzati nella costruzione di dispositivi fotovoltaici, in particolare, di celle fotovoltaiche, è tuttora di grande interesse. The study of new copolymers capable of being used in the construction of photovoltaic devices, in particular, of photovoltaic cells, is still of great interest.
La Richiedente si è quindi posta il problema di trovare copolimeri in grado di essere utilizzati nella costruzione di dispositivi fotovoltaici aventi buoni valori di HOMO e LUMO e valori di “band-gap” relativamente bassi, i.e. valori di “band-gap” inferiori o uguali a 2 eV. The Applicant therefore posed the problem of finding copolymers capable of being used in the construction of photovoltaic devices having good HOMO and LUMO values and relatively low "band-gap" values, i.e. band-gap values lower than or equal to 2 eV.
La Richiedente ha ora trovato copolimeri coniugati statistici fotoattivi comprendenti unità carbazoliche, detti copolimeri aventi valori di “band-gap” relativamente bassi, i.e. valori di “band-gap” inferiori o uguali a 2 eV, che possono essere vantaggiosamente utilizzati nella costruzione di dispositivi fotovoltaici quali, ad esempio, celle fotovoltaiche, moduli fotovoltaici, celle solari, moduli solari, sia su supporto rigido, sia su supporto flessibile. Inoltre, detti copolimeri coniugati statistici comprendenti unità carbazoliche possono essere ottenuti tramite un procedimento di preparazione semplice che richiede minori passaggi sintetici, con conseguenti minori tempi e costi di produzione. The Applicant has now found photoactive statistical conjugated copolymers comprising carbazole units, said copolymers having relatively low "band-gap" values, i.e. "band-gap" values lower than or equal to 2 eV, which can be advantageously used in the construction of photovoltaic devices such as, for example, photovoltaic cells, photovoltaic modules, solar cells, solar modules, both on rigid support and on flexible support . Furthermore, said statistical conjugated copolymers comprising carbazole units can be obtained by means of a simple preparation process which requires fewer synthetic steps, with consequent lower production times and costs.
Costituisce pertanto oggetto della presente invenzione un copolimero coniugato statistico fotoattivo comprendente unità carbazoliche avente formula generale (I): Therefore, the object of the present invention is a photoactive statistical conjugated copolymer comprising carbazole units having general formula (I):
in cui: in which:
Y e W, uguali o diversi tra loro, rappresentano un atomo di zolfo, un atomo di ossigeno, un atomo di selenio; un gruppo NRI2in cui R12rappresenta un atomo di idrogeno, oppure è scelto tra gruppi alchilici Ci-C32, preferibilmente C2-C2o, lineari o ramificati; Y and W, the same or different from each other, represent a sulfur atom, an oxygen atom, a selenium atom; an NRI2 group in which R12 represents a hydrogen atom, or is selected from C1-C32 alkyl groups, preferably C2-C2o, linear or branched;
Ri rappresenta un atomo di idrogeno; oppure è scelto tra: gruppi alchilici Ci-C32, preferibilmente C2-C2o, lineari o ramificati, gruppi alcossilici Ci-C32, preferibilmente C2-C2o, lineari o ramificati, opzionalmente sostituiti, gruppi ardici opzionalmente sostituiti; Ri represents a hydrogen atom; or it is selected from: C1-C32 alkyl groups, preferably C2-C2o, linear or branched, C1-C32 alkoxyl groups, preferably C2-C2o, linear or branched, optionally substituted, optionally substituted ardic groups;
R2, R3, R4, R5, R6, R7, R8, R9, RIOe RII, uguali o diversi tra loro, rappresentano un atomo di idrogeno; oppure sono scelti tra: gruppi alchilici Ci-C32, preferibilmente C2-C20, lineari o ramificati, gruppi cicloalchilici opzionalmente sostituiti, gruppi ardici opzionalmente sostituiti, gruppi alcossilici Ci-C32, preferibilmente C2-C20, lineari o ramificati, opzionalmente sostituiti; R2, R3, R4, R5, R6, R7, R8, R9, RIO and RII, the same or different from each other, represent a hydrogen atom; or they are selected from: C1-C32 alkyl groups, preferably C2-C20, linear or branched, optionally substituted cycloalkyl groups, optionally substituted ardic groups, C1-C32 alkoxyl groups, preferably C2-C20, linear or branched, optionally substituted;
oppure R3e R4, R5 e R6, R8e R9, Rio e Rn, possono essere eventualmente legati tra loro così da formare, insieme agli atomi di carbonio a cui sono legati, un ciclo o un sistema policiclico contenente da 3 a 14 atomi di carbonio, saturo, insaturo, o aromatico, eventualmente contenente uno o più eternatomi quali ossigeno, zolfo, azoto, silicio, fosforo, selenio; or R3e R4, R5 and R6, R8e R9, Rio and Rn, can optionally be bonded together so as to form, together with the carbon atoms to which they are bonded, a cycle or a polycyclic system containing from 3 to 14 carbon atoms, saturated, unsaturated, or aromatic, possibly containing one or more eternatoms such as oxygen, sulfur, nitrogen, silicon, phosphorus, selenium;
n è un numero compreso tra 0,05 e 0,95, preferibilmente compreso tra 0,25 e 0,75. n is a number comprised between 0.05 and 0.95, preferably comprised between 0.25 and 0.75.
Allo scopo della presente descrizione e delle rivendicazioni che seguono, le definizioni degli intervalli numerici comprendono sempre gli estremi a meno di diversa specificazione. For the purpose of the present description and of the following claims, the definitions of the numerical ranges always include the extremes unless otherwise specified.
In accordo con una forma di attuazione particolarmente preferita della presente invenzione, in detta formula generale (I): In accordance with a particularly preferred embodiment of the present invention, in said general formula (I):
Y e W rappresentano un atomo di zolfo; Y and W represent a sulfur atom;
Ri rappresenta un gruppo alchilico Ci-C32, preferibilmente un iso-eptadecile; R2, R3, R4, R5, R6, R7, R8, R9, RIOe Rii, rappresentano un atomo di idrogeno; - n è un numero compreso tra 0,25 e 0,75. R1 represents a C 1 -C32 alkyl group, preferably an iso-heptadecyl; R2, R3, R4, R5, R6, R7, R8, R9, RIO and Rii, represent a hydrogen atom; - n is a number between 0.25 and 0.75.
Con il termine “gruppi alchilici Ci-C32” si intendono gruppi alchilici aventi da 1 a 32 atomi di carbonio, lineari o ramificati. Esempi specifici di gruppi alchilici Ci-C32sono: metile, etile, n-propile, iso-propile, n-butile, iso-butile, t-butile, pentile, etil-esile, esile, eptile, ottile, nonile, eptadecile, iso-eptadecile, decile, dodecile, isododecile. The term "C-C32 alkyl groups" refers to alkyl groups having from 1 to 32 carbon atoms, linear or branched. Specific examples of C-C32 alkyl groups are: methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, t-butyl, pentyl, ethyl-hexyl, hexyl, heptyl, octyl, nonyl, heptadecyl, iso -heptadecyl, decyl, dodecyl, isododecyl.
Con il termine “gruppi alcossilici Ci-C32” si intendono gruppi alcossilici aventi da 1 a 32 atomi di carbonio, lineari o ramificati. Detti gruppi alcossilici possono essere opzionalmente sostituiti con uno o più gruppi, uguali o diversi tra loro, scelti tra: atomi di alogeno quali, ad esempio, fluoro, cloro, preferibilmente fluoro; gruppi idrossilici; gruppi alchilici Ci-C20; gruppi alcossilici Ci-C20; gruppi ciano; gruppi ammino; gruppi nitro. Esempi specifici di gruppi alcossilici Ci-C20sono: metossile, etossile, fluoroetossile, n-propossile, iso-propossile, n-butossile, n-fluoro-butossile, iso-butossile, t-butossile, pentossile, esilossile, eptilossile, ottilossile, nonilossile, decilossile, dodecilossile. The term "C-C32 alkoxy groups" refers to alkoxy groups having from 1 to 32 carbon atoms, linear or branched. Said alkoxy groups can optionally be substituted with one or more groups, the same or different from each other, selected from: halogen atoms such as, for example, fluorine, chlorine, preferably fluorine; hydroxyl groups; C1-C20 alkyl groups; C1-C20 alkoxy groups; cyan groups; amino groups; nitro groups. Specific examples of C-C20 alkoxy groups are: methoxy, ethoxy, fluoroethoxy, n-propoxy, iso-propoxy, n-butoxy, n-fluoro-butoxy, iso-butoxy, t-butoxy, pentoxyl, hexyloxy, heptyloxy, octyloxy, nonyloxy , decyloxyl, dodecyloxyl.
Con il termine “gruppi cicloalchilici” si intendono gruppi cicloalchilici aventi da 3 a 10 atomi di carbonio. Detti gruppi cicloalchilici possono essere opzionalmente sostituiti con uno o più gruppi, uguali o diversi tra loro, scelti tra: atomi di alogeno quali, ad esempio, fluoro, cloro, preferibilmente fluoro; gruppi idrossilici; gruppi alchilici Ci-C2o; gruppi alcossilici Ci-C2o; gruppi ciano; gruppi animino; gruppi nitro; gruppi ardici. Esempi specifici di gruppi cicloalchilici sono: ciclopropile, 1,4-diossino, 2,2-difluorociclopropile, ciclobutile, ciclopentile, cicloesile, metilcicloesile, metossicicloesile, fluorocicloesile, fenilcicloesile. The term "cycloalkyl groups" refers to cycloalkyl groups having from 3 to 10 carbon atoms. Said cycloalkyl groups can optionally be substituted with one or more groups, the same or different from each other, selected from: halogen atoms such as, for example, fluorine, chlorine, preferably fluorine; hydroxyl groups; C 1-C2o alkyl groups; C1-C2o alkoxy groups; cyan groups; animino groups; nitro groups; ardic groups. Specific examples of cycloalkyl groups are: cyclopropyl, 1,4-dioxino, 2,2-difluorocyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, methoxycyclohexyl, fluorocyclohexyl, phenylcyclohexyl.
Con il termine “gruppi ardici” si intendono gruppi carbociclici aromatici. Detti gruppi ardici possono essere opzionalmente sostituiti con uno o più gruppi, uguali o diversi tra loro, scelti tra: atomi di alogeno quali, ad esempio, fluoro, cloro, preferibilmente fluoro; gruppi idrossilici; gruppi alchilici Ci-C2o; gruppi alcossilici Ci-C2o; gruppi ciano; gruppi ammino; gruppi nitro; gruppi ardici. Esempi specifici di gruppi ardici sono: fenile, metilfenile, trimetilfenile, metossifenile, idrossifenile, fenilossifenile, fluorofenile, pentafluorofenile, clorofenile, nitrofenile, dimetilamminofenile, naftile, fenilnaftile, fenantrene, antracene. The term "ardic groups" refers to aromatic carbocyclic groups. Said ardic groups can optionally be replaced with one or more groups, the same or different from each other, selected from: halogen atoms such as, for example, fluorine, chlorine, preferably fluorine; hydroxyl groups; C 1-C2o alkyl groups; C1-C2o alkoxy groups; cyan groups; amino groups; nitro groups; ardic groups. Specific examples of ardic groups are: phenyl, methylphenyl, trimethylphenyl, methoxyphenyl, hydroxyphenyl, phenyloxyphenyl, fluorophenyl, pentafluorophenyl, chlorophenyl, nitrophenyl, dimethylaminophenyl, naphthyl, phenylnaphthyl, phenanthrene, anthracene.
Con il termine “ciclo o sistema policiclico” si intende un sistema contenente uno o più anelli contenente/i da 3 a 14 atomi di carbonio, eventualmente contenente eteroatomi scelti tra azoto, ossigeno, zolfo, silicio, selenio, fosforo. Esempi specifici di ciclo o sistema policiclico sono: tieno[3,2-b]tiofene, tiadiazolo, benzotiofene, chinossalina, piridina. The term "cycle or polycyclic system" means a system containing one or more rings containing / s from 3 to 14 carbon atoms, possibly containing heteroatoms selected from nitrogen, oxygen, sulfur, silicon, selenium, phosphorus. Specific examples of a cycle or polycyclic system are: thieno [3,2-b] thiophene, thiadiazole, benzothiophene, quinoxaline, pyridine.
In accordo con una forma di attuazione preferita della presente invenzione, detto copolimero coniugato statistico fotoattivo comprendente unità carbazoliche avente formula generale (I) può avere un peso molecolare medio ponderale (Mw) compreso tra 2000 Dalton e 150000 Dalton, preferibilmente compreso tra 8000 Dalton e 70000 Dalton. Detto peso molecolare medio ponderale (Mw) può essere determinato come sotto riportato. In accordance with a preferred embodiment of the present invention, said photoactive statistical conjugated copolymer comprising carbazole units having general formula (I) can have a weight average molecular weight (Mw) between 2000 Dalton and 150000 Dalton, preferably between 8000 Dalton and 70000 Dalton. Said weight average molecular weight (Mw) can be determined as reported below.
Detto copolimero coniugato statistico fotoattivo comprendente unità carbazoliche avente formula generale (I) è caratterizzato da un valore di “band-gap” inferiore o uguale a 2 eV e, pertanto, può essere vantaggiosamente utilizzato come composto donatore di elettroni, in dispositivi fotovoltaici, in particolare per sfruttare la radiazione solare a bassa energia, quindi a più elevata lunghezza d’onda. Said photoactive statistical conjugate copolymer comprising carbazole units having general formula (I) is characterized by a "band-gap" value lower than or equal to 2 eV and, therefore, can be advantageously used as an electron donor compound, in photovoltaic devices, in particularly to exploit the low energy solar radiation, therefore with a higher wavelength.
Il copolimero coniugato statistico fotoattivo comprendente unità carbazoliche avente formula generale (I) può essere sintetizzato tramite procedimenti noti nell’ arte. The photoactive statistical conjugate copolymer comprising carbazole units having general formula (I) can be synthesized by methods known in the art.
Ad esempio, detto copolimero coniugato statistico fotoattivo comprendente unità carbazoliche avente formula generale (I) può essere sintetizzato secondo il seguente Schema 1: For example, said photoactive statistical conjugate copolymer comprising carbazole units having general formula (I) can be synthesized according to the following Scheme 1:
Schema 1 Scheme 1
in cui R’ rappresenta un gruppo alchilico Ci-C32, preferibilmente C2-C2o, lineare o ramificato, W, Y, Ri, R2, R3, R4, R5, R^, R7, R8, R9, RIO, RI Ied n, hanno gli stessi significati sopra descritti, X rappresenta un atomo di alogeno scelto tra cloro, bromo, iodio, preferibilmente bromo. wherein R 'represents a C-C32 alkyl group, preferably C2-C2o, linear or branched, W, Y, Ri, R2, R3, R4, R5, R ^, R7, R8, R9, RIO, RI Ied n, have the same meanings described above, X represents a halogen atom selected from chlorine, bromine, iodine, preferably bromine.
La reazione riportata nello Schema 1 è nota come reazione di Stille che è generalmente catalizzata da PdCl2(PPh3)2ital quale o preparato in situ a partire da PdCl2e trifenilfosfina; oppure da palladio-tetrakistrifenilfosfina [Pd(PPh3)3]; oppure da Pd(OAc)2ed altre fosfine quali, ad esempio, tri-orto-tolilfosfina o tris-para-tolil fosfina. The reaction reported in Scheme 1 is known as the Stille reaction which is generally catalyzed by PdCl2 (PPh3) 2ital such as or prepared in situ starting from PdCl2 and triphenylphosphine; or from palladium-tetrakistriphenylphosphine [Pd (PPh3) 3]; or from Pd (OAc) 2 and other phosphines such as, for example, tri-ortho-tolylphosphine or tris-para-tolyl phosphine.
Detta reazione di Stille può essere condotta in solventi scelti, ad esempio, tra: eteri (ad esempio, 1,2-dimetossietano, 1,4-diossano, tetraidrofurano); idrocarburi (toluene, xilene); solventi aprotici dipolari (Ν,Ν-dimetilformammide, N-metilpirrolidone, dimetilsolfossido). Generalmente, le temperature di reazione sono comprese tra 50°C e 160°C. Said Stille reaction can be carried out in solvents selected, for example, from: ethers (for example, 1,2-dimethoxyethane, 1,4-dioxane, tetrahydrofuran); hydrocarbons (toluene, xylene); dipolar aprotic solvents (Ν, Ν-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide). Generally, the reaction temperatures are between 50 ° C and 160 ° C.
Generalmente, a detta reazione può essere aggiunta una base quale, ad esempio, soluzione acquosa satura di bicarbonato di sodio o di bicarbonato di potassio, oppure una soluzione acquosa satura di carbonato di sodio o di carbonato di potassio. Generally, a base such as, for example, a saturated aqueous solution of sodium bicarbonate or potassium bicarbonate, or a saturated aqueous solution of sodium carbonate or potassium carbonate can be added to said reaction.
Generalmente, al termine della suddetta reazione può essere aggiunta una piccola quantità di 2-alogeno-3-alchiltiofene e/o di 2-(trialchilstannil)tiofene allo scopo di ottenere il cosiddetto “capping” del copolimero. Generally, at the end of the aforesaid reaction a small quantity of 2-halogen-3-alkylthiophene and / or 2- (trialkylstannil) thiophene can be added in order to obtain the so-called “capping” of the copolymer.
Generalmente, al termine delle suddetta reazione, il solvente può essere allontanato per distillazione ed il prodotto grezzo ottenuto può essere disciolto nella quantità mininima di un opportuno solvente quale, ad esempio, clorobenzene, cloroformio, e precipitato in un opportuno solvente quale, ad esempio, metanolo. Generally, at the end of the aforementioned reaction, the solvent can be removed by distillation and the raw product obtained can be dissolved in the minimum quantity of a suitable solvent such as, for example, chlorobenzene, chloroform, and precipitated in a suitable solvent such as, for example, methanol.
Allo scopo di migliorare il trasferimento della suddetta base dalla fase acquosa alla fase organica, può essere aggiunto un alogenuro di ammonio quaternario quale, ad esempio, fluoruro, cloruro, bromuro, ioduro di ammonio quaternario, preferibilmente cloruro di ammonio quaternario. In order to improve the transfer of the aforementioned base from the aqueous phase to the organic phase, a quaternary ammonium halide can be added such as, for example, fluoride, chloride, bromide, quaternary ammonium iodide, preferably quaternary ammonium chloride.
Il di(trialchilstannil)eterociclo avente formula generale (Π), il 2,7-dialogenocarbazolo avente formula generale (IH) ed il 4,7-dialogeno-2,l,3-benzoeterodiazolo avente formula generale (IV), sono facilmente reperibili in commercio. The di (trialkylstannil) heterocycle having general formula (Π), 2,7-dihalogenocarbazole having general formula (1H) and 4,7-dihalogen-2, 1,3-benzoeterodiazole having general formula (IV), are readily available on the market.
Ulteriori dettagli relativi al procedimento di sintesi del copolimero coniugato statistico fotoattivo avente formula generale (I), sono sotto riportati negli esempi che seguono. Further details relating to the synthesis process of the photoactive statistical conjugated copolymer having general formula (I), are reported below in the following examples.
Detto copolimero coniugato statistico fotoattivo comprendente unità carbazoliche avente formula generale (I) può essere utilizzato nella costruzione di dispositivi fotovoltaici quali, ad esempio, celle fotovoltaiche, moduli fotovoltaici, celle solari, moduli solari, sia su supporto rigido, sia su supporto flessibile. Said photoactive statistical conjugate copolymer comprising carbazole units having general formula (I) can be used in the construction of photovoltaic devices such as, for example, photovoltaic cells, photovoltaic modules, solar cells, solar modules, both on rigid and flexible supports.
E’ quindi un ulteriore oggetto della presente invenzione l’uso di detto copolimero coniugato statistico fotoattivo comprendente unità carbazoliche avente formula generale (I) nella costruzione di dispositivi fotovoltaici quali, ad esempio, celle fotovoltaiche, moduli fotovoltaici, celle solari, moduli solari, sia su supporto rigido, sia su supporto flessibile. A further object of the present invention is therefore the use of said photoactive statistical conjugate copolymer comprising carbazole units having general formula (I) in the construction of photovoltaic devices such as, for example, photovoltaic cells, photovoltaic modules, solar cells, solar modules, both on rigid support, both on flexible support.
Come detto sopra, grazie al valore di “band-gap” relativamente basso (i.e. un valore di “band-gap” inferiore o uguale a 2 eV), detto copolimero coniugato statistico fotoattivo comprendente unità carbazoliche avente formula generale (I) è in grado di raccogliere e di convertire efficacemente in energia elettrica anche radiazioni solari a bassa energia, quindi a più elevata lunghezza d’onda. As mentioned above, thanks to the relatively low "band-gap" value (i.e. a "band-gap" value lower than or equal to 2 eV), said photoactive statistical conjugate copolymer comprising carbazole units having general formula (I) is able to collect and efficiently convert even low-energy solar radiation, therefore at a higher wavelength, into electricity.
E’ quindi un ulteriore oggetto della presente invenzione, un dispositivo fotovoltaico che può essere scelto, ad esempio, tra celle fotovoltaiche, moduli fotovoltaici, celle solari, moduli solari, sia su supporto rigido, sia su supporto flessibile, comprendente almeno un copolimero coniugato statistico fotoattivo comprendente unità carbazoliche avente formula generale (I) sopra descritto. A further object of the present invention is therefore a photovoltaic device which can be chosen, for example, among photovoltaic cells, photovoltaic modules, solar cells, solar modules, both on a rigid support and on a flexible support, comprising at least one statistical conjugated copolymer photoactive comprising carbazole units having general formula (I) described above.
Allo scopo di meglio comprendere la presente invenzione e per mettere in pratica la stessa, di seguito si riportano alcuni esempi illustrativi e non limitativi della stessa. In order to better understand the present invention and to put it into practice, some illustrative and non-limiting examples thereof are reported below.
Caratterizzazione dei copolimeri ottenuti Characterization of the obtained copolymers
Determinazione del peso molecolare Determination of the molecular weight
II peso molecolare dei copolimeri ottenuti operando in accordo con i successivi esempi, è stato determinato mediante “Gel Permeation Chromatography” (GPC) su strumento WATERS 150C, utilizzando colonne HT5432, con eluente triclorobenzene, a 80°C. The molecular weight of the copolymers obtained by operating in accordance with the following examples, was determined by "Gel Permeation Chromatography" (GPC) on a WATERS 150C instrument, using HT5432 columns, with trichlorobenzene eluent, at 80 ° C.
Sono riportati il peso molecolare medio ponderale (Mw) e l’indice di pobdispersità (“Polydispersion Index” - PDI), corrispondente al rapporto Mw/Mn (Mn = peso molecolare medio numerico). The weight average molecular weight (Mw) and the pobdispersity index ("Polydispersion Index" - PDI), corresponding to the Mw / Mn ratio (Mn = number average molecular weight) are reported.
Determinazione del “band-gap” ottico Determination of the optical "band-gap"
I copolimeri ottenuti operando in accordo con i successivi esempi, sono stati caratterizzati mediante spettroscopia UV-Vis-NIR per determinare l’entità energetica del “band-gap” ottico su film sottile secondo la seguente procedura. The copolymers obtained by operating in accordance with the following examples, were characterized by UV-Vis-NIR spectroscopy to determine the energy entity of the optical "band-gap" on thin film according to the following procedure.
II copolimero ottenuto è stato disciolto in toluene, cloroformio, clorobenzene, diclorobenzene, triclorobenzene, o altro solvente idoneo, ottenendo una soluzione avente una concentrazione pari a circa 10 mg/ml, che è stata deposta, per “spincoating”, su un vetrino in quarzo Suprasil. Il film sottile così ottenuto, è stato analizzato in trasmissione mediante uno spettrofotometro UV-Vis-NIR a doppio raggio e doppio monocromatore Perkin Elmer λ 950, nell’intervallo 200 nm - 850 nm, con banda passante di 2 nm, velocità di scansione di 220 nm/min e step di 1 nm, utilizzando come riferimento un identico vetrino in quarzo Suprasil, tal quale, come riferimento. The copolymer obtained was dissolved in toluene, chloroform, chlorobenzene, dichlorobenzene, trichlorobenzene, or other suitable solvent, obtaining a solution having a concentration of about 10 mg / ml, which was deposited, by "spincoating", on a glass slide. Suprasil quartz. The thin film thus obtained was analyzed in transmission by means of a double beam UV-Vis-NIR spectrophotometer and double monochromator Perkin Elmer λ 950, in the range 200 nm - 850 nm, with a bandwidth of 2 nm, scanning speed of 220 nm / min and 1 nm step, using as reference an identical Suprasil quartz slide, as it is, as a reference.
Dagli spettri in trasmissione è stato stimato il “band-gap” ottico misurando l’edge di assorbimento corrispondente alla transizione dalla banda di valenza (VB) a quella di conduzione (CB). Per la determinazione delPedge, è stato fatto ricorso all’ intersezione con l’asse delle ascisse della retta tangente alla banda di assorbimento nel punto di flesso. The optical "band-gap" was estimated from the transmission spectra by measuring the absorption edge corresponding to the transition from the valence band (VB) to the conduction band (CB). For the determination of the Edge, the intersection with the abscissa axis of the tangent line to the absorption band at the inflection point was used.
Il punto di flesso (λρ, yi ) è stato determinato in base alle coordinate del minimo dello spettro in derivata prima, indicate con λ'π^ ed y’mm-L’equazione della retta tangente allo spettro UV-Vis nel punto di flesso (λρ, yi ) è la seguente: The inflection point (λρ, yi) was determined on the basis of the coordinates of the minimum of the spectrum in first derivative, denoted by λ'π ^ and y'mm-The equation of the tangent line to the UV-Vis spectrum at the inflection point (λρ, yi) is the following:
Infine, dalla condizione di intersezione con l’asse delle ascisse ψ = 0, è stato ricavato: Finally, from the condition of intersection with the abscissa axis ψ = 0, it was obtained:
Pertanto, misurando le coordinate del minimo dello spettro in derivata prima ed il corrispondente valore di assorbanza yFdallo spettro UV-Vis, per sostituzione è stato ricavato direttamente AEDGE-L’energia corrispondente è: Therefore, by measuring the coordinates of the minimum of the spectrum in first derivative and the corresponding absorbance value yF from the UV-Vis spectrum, AEDGE was obtained directly by substitution-The corresponding energy is:
in cui: in which:
os os
sia: is:
Ricordando, infine, che 1 J = 6,24x1018 eV, si ha: Finally, remembering that 1 J = 6.24x1018 eV, we have:
Determinazione di HOMO e LUMO Determination of HOMO and LUMO
La determinazione dei valori di HOMO e LUMO dei copolimeri ottenuti operando in accordo con i successivi esempi, è stata effettuata mediante la tecnica della voltammetria ciclica (CV). Con tale tecnica è possibile misurare i valori dei potenziali di formazione del radicai catione e del radicai anione del campione in esame. Questi valori, inseriti in una apposita equazione, permettono di ottenere i valori di HOMO e LUMO del copolimero in oggetto. La differenza tra HOMO e LUMO dà il valore del “band-gap” elettrochimico. The determination of the HOMO and LUMO values of the copolymers obtained by operating in accordance with the following examples, was carried out by means of the cyclic voltammetry (CV) technique. With this technique it is possible to measure the values of the formation potentials of the root cation and the root anion of the sample under examination. These values, inserted in a specific equation, allow to obtain the HOMO and LUMO values of the copolymer in question. The difference between HOMO and LUMO gives the value of the electrochemical "band-gap".
I valori del “band-gap” elettrochimico sono generalmente più alti rispetto ai valori del “band-gap” ottico poiché durante l’esecuzione della voltammetria ciclica (CV), il composto neutro viene caricato e subisce una riorganizzazione conformazionale, con innalzamento del “gap” energetico, mentre la misura ottica non porta alla formazione di specie cariche. The values of the electrochemical "band-gap" are generally higher than the values of the optical "band-gap" since during the execution of the cyclic voltammetry (CV), the neutral compound is loaded and undergoes a conformational reorganization, with an increase of the " energy gap ", while the optical measurement does not lead to the formation of charged species.
Le misure della voltammetria ciclica (CV) sono state eseguite con un potenziostato Autolab PGSTAT12 (con software GPES Ecochemie) in una cella a tre elettrodi. Nelle misure effettuate sono stati utilizzati come elettrodo di riferimento un elettrodo ad Ag/AgCl, come controelettrodo un filo di platino e come elettrodo di lavoro un elettrodo di grafite vetrosa. Il campione da analizzare è stato sciolto in un opportuno solvente e, successivamente, è stato deposto, con un capillare tarato, sull’elettrodo di lavoro, in modo da formare un film. Gli elettrodi sono stati immersi in una soluzione elettrolitica 0,1 M di tetrabutilammonio tetrafluroborato 95% in acetonitrile. Il campione è stato successivamente sottoposto ad un potenziale ciclico a forma di onda triangolare. Contemporaneamente, in funzione della differenza di potenziale applicata, è stata monitorata la corrente, che segnala il verificarsi di reazioni di ossidazione o di riduzione delle specie presenti. The cyclic voltammetry (CV) measurements were performed with an Autolab PGSTAT12 potentiostat (with GPES Ecochemie software) in a three-electrode cell. In the measurements carried out, an Ag / AgCl electrode was used as a reference electrode, a platinum wire as a counter electrode and a glassy graphite electrode as a working electrode. The sample to be analyzed was dissolved in a suitable solvent and, subsequently, was deposited, with a calibrated capillary, on the working electrode, so as to form a film. The electrodes were immersed in a 0.1 M electrolytic solution of 95% tetraflurobate tetrabutylammonium in acetonitrile. The sample was subsequently subjected to a cyclic potential in the shape of a triangular wave. At the same time, according to the applied potential difference, the current was monitored, which signals the occurrence of oxidation or reduction reactions of the species present.
Il processo di ossidazione corrisponde alla rimozione di un elettrone dall’HOMO, mentre il ciclo di riduzione corrisponde all’introduzione di un elettrone nel LUMO. I potenziali di formazione del radicai catione e del radicai anione sono stati ricavati dal valore dell’onset di picco (Eonset), che è determinato da molecole e/o segmenti di catena con livelli HOMO-LUMO più vicini ai margini delle bande. I potenziali elettrochimici a quelli relativi ai livelli elettronici sono correlabili se entrambi riferiti al vuoto. A questo scopo, è stato preso come riferimento il potenziale del ferrocene nel vuoto, noto in letteratura e pari a -4,8 eV. La coppia redox intersolvenziale ferrocene/ferrocinio (Fc/Fc<+>) è stata scelta perché dotata di un potenziale di ossido-riduzione indipendente dal solvente di lavoro. The oxidation process corresponds to the removal of an electron from HOMO, while the reduction cycle corresponds to the introduction of an electron into the LUMO. The potential for the formation of the root cation and the root anion were derived from the value of the peak onset (Eonset), which is determined by molecules and / or chain segments with HOMO-LUMO levels closest to the edges of the bands. The electrochemical potentials to those relating to the electronic levels can be correlated if both refer to the vacuum. For this purpose, the potential of ferrocene in vacuum, known in literature and equal to -4.8 eV, was taken as a reference. The inter-solvent redox ferrocene / ferrocinium pair (Fc / Fc <+>) was chosen because it has an oxidation-reduction potential independent of the working solvent.
La formula generale per calcolare le energie dei livelli HOMO-LUMO è quindi data dalla seguente equazione: The general formula for calculating the energies of the HOMO-LUMO levels is therefore given by the following equation:
copolimero)] copolymer)]
in cui: in which:
E = HOMO o LUMO a seconda del valore di Eonsetinserito; E = HOMO or LUMO depending on the Eonset value inserted;
EI/2Ag/Agci = potenziale di mezz’onda del picco corrispondente alla coppia redox ferrocene/ferrocinio misurata nelle stesse condizioni di analisi del campione e con la stessa tema di elettrodi utilizzati per il campione; EonsetAg/Agci = potenziale di onset misurato per il copolimero in zona anodica quando si vuole calcolare ΓΗΟΜΟ e in zona catodica quando si vuole calcolare il LUMO. EI / 2Ag / Agci = half-wave potential of the peak corresponding to the redox ferrocene / ferrocinium couple measured under the same analysis conditions as the sample and with the same theme of electrodes used for the sample; EonsetAg / Agci = onset potential measured for the copolymer in the anodic zone when we want to calculate ΓΗΟΜΟ and in the cathode zone when we want to calculate the LUMO.
ESEMPIO 1 EXAMPLE 1
Sintesi del composto avente formula (la) Synthesis of the compound having formula (la)
In un pallone a due colli da 25 mi, munito di agitatore magnetico e refrigerante a ricadere, sono stati introdotti, sotto atmosfera di azoto, i seguenti componenti : - 830,8 mg (2,03 mmol) di di(trimetilstannil)tiofene (SunaTech Ine.); The following components were introduced, under a nitrogen atmosphere, into a 25 ml double-necked flask, equipped with a magnetic stirrer and reflux refrigerant: - 830.8 mg (2.03 mmol) of di (trimethylstannil) thiophene ( SunaTech Ine.);
571.5 mg (1,015 mmol) di 2,7-dibromo-N-isoeptadecil-carbazolo (SunaTech Ine.); 571.5 mg (1.015 mmol) of 2,7-dibromo-N-isoheptadecyl-carbazole (SunaTech Ine.);
298,15 mg (1,015 mmoli) di 4,7-dibromo-2,l,3-benzotiadiazolo (Sigma-Aldrich); 298.15 mg (1.015 mmol) of 4,7-dibromo-2,1,3-benzothiadiazole (Sigma-Aldrich);
- 2,5 mi di n-propanolo (Carlo Erba); - 2.5 ml of n-propanol (Carlo Erba);
2.5 mi di una soluzione acquosa 4 M di bicarbonato di potassio (K2C03) (Carlo Erba); 2.5 ml of a 4 M aqueous solution of potassium bicarbonate (K2C03) (Carlo Erba);
4 mi di toluene (Carlo Erba) (distillato su NaH in atmosfera inerte); 4 ml of toluene (Carlo Erba) (distilled on NaH in an inert atmosphere);
5 gocce di (metil tri-alchil ammonio cloruro) [Aliquat<®>336 (Cognis)]. 5 drops of (methyl tri-alkyl ammonium chloride) [Aliquat <®> 336 (Cognis)].
La miscela di reazione ottenuta, è stata scaldata a 70°C, per 15 minuti, e successivamente sono stati aggiunti 17,5 mg (0,015 mmol ) di palladiotetrakistrifenilfosfina [Pd(PPh ) ] (Sigma-Aldrich): la miscela di reazione ottenuta è stata scaldata a riflusso, per 40 ore, ottenendosi una soluzione. Successivamente, sono stati aggiunti 50 mg di 2-bromo-3-esiltiofene (Sigma-Aldrich). Dopo altre 4 ore alla temperatura di riflusso, è stato aggiunto 1 mi di 2-(tributilstannil)tiofene (Sigma-Aldrich): il tutto è stato lasciato 4 ore alla temperatura di riflusso e 12 ore a temperatura ambiente (25 °C). The reaction mixture obtained was heated to 70 ° C, for 15 minutes, and 17.5 mg (0.015 mmol) of palladiotetrakistrifenilfosfina [Pd (PPh)] (Sigma-Aldrich) were then added: the reaction mixture obtained was heated under reflux for 40 hours, obtaining a solution. Subsequently, 50 mg of 2-bromo-3-hexylthiophene (Sigma-Aldrich) was added. After a further 4 hours at the reflux temperature, 1 ml of 2- (tributylstannil) thiophene (Sigma-Aldrich) was added: the whole was left for 4 hours at the reflux temperature and 12 hours at room temperature (25 ° C).
Il solvente è stato allontanato per distillazione ed il prodotto solido ottenuto è stato ridisciolto in 10 mi di clorobenzene (Sigma-Aldrich) e successivamente precipitato in 200 mi di metanolo (Carlo Erba). Il precipitato ottenuto è stato filtrato, lavato con metanolo e acqua e lasciato essiccare ottenendosi 690 mg di una polvere verde scuro. The solvent was removed by distillation and the solid product obtained was redissolved in 10 ml of chlorobenzene (Sigma-Aldrich) and subsequently precipitated in 200 ml of methanol (Carlo Erba). The precipitate obtained was filtered, washed with methanol and water and left to dry to obtain 690 mg of a dark green powder.
Il “band-gap” ottico, misurato su film sottile, operando come sopra descritto, dopo aver sciolto la polvere ottenuta in diclorobenzene (Sigma-Aldrich), ed aver deposto la soluzione ottenuta avente una concentrazione pari a circa 10 mg/ml su un vetrino in quarzo Suprasil per “spin coating”, è pari a 1,72 eV. The optical "band-gap", measured on a thin film, operating as described above, after having dissolved the powder obtained in dichlorobenzene (Sigma-Aldrich), and having deposited the obtained solution having a concentration equal to about 10 mg / ml on a Suprasil quartz slide for "spin coating", is equal to 1.72 eV.
Sono stati altresì determinati sia il peso molecolare (solo della frazione di copolimero solubile nelle condizioni operative), sia HOMO e LUMO, operando come sopra descritto, ottenendosi i seguenti valori: Both the molecular weight (only of the fraction of soluble copolymer under operating conditions), and HOMO and LUMO were also determined, operating as described above, obtaining the following values:
peso molecolare medio ponderale (Mw) = 9000 Dalton; weight average molecular weight (Mw) = 9000 Dalton;
peso molecolare medio numerico (Mn) = 6000 Dalton; number average molecular weight (Mn) = 6000 Dalton;
indice di polidispersità (PDI) = 1,6; HOMO = -5,16 eV; polydispersity index (PDI) = 1.6; HOMO = -5.16 eV;
LUMO = -3,28 eV. LUMO = -3.28 eV.
Claims (6)
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| WO2010046114A2 (en) * | 2008-10-22 | 2010-04-29 | Eni S.P.A. | π-CONJUGATED LOW-BAND-GAP COPOLYMERS CONTAINING BENZOTRIAZOLE UNITS |
| WO2010117158A2 (en) * | 2009-04-08 | 2010-10-14 | 한국화학연구원 | Conductive polymer containing carbazole, and organic photovoltaic device using same |
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| WO2010046114A2 (en) * | 2008-10-22 | 2010-04-29 | Eni S.P.A. | π-CONJUGATED LOW-BAND-GAP COPOLYMERS CONTAINING BENZOTRIAZOLE UNITS |
| WO2010117158A2 (en) * | 2009-04-08 | 2010-10-14 | 한국화학연구원 | Conductive polymer containing carbazole, and organic photovoltaic device using same |
| US20120018715A1 (en) * | 2009-04-08 | 2012-01-26 | Korea Research Institute Of Chemical Technology | Conductive polymer containing carbazole, and organic photovoltaic device using same |
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