WO2012058209A1 - Organic electronic devices, including organic photovoltaic devices, polymers, and monomers - Google Patents
Organic electronic devices, including organic photovoltaic devices, polymers, and monomers Download PDFInfo
- Publication number
- WO2012058209A1 WO2012058209A1 PCT/US2011/057662 US2011057662W WO2012058209A1 WO 2012058209 A1 WO2012058209 A1 WO 2012058209A1 US 2011057662 W US2011057662 W US 2011057662W WO 2012058209 A1 WO2012058209 A1 WO 2012058209A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- polymer
- group
- oligomer
- same group
- monomer
- Prior art date
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 169
- 239000000178 monomer Substances 0.000 title claims abstract description 43
- 238000013086 organic photovoltaic Methods 0.000 title abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 66
- 239000000463 material Substances 0.000 claims abstract description 53
- 230000003381 solubilizing effect Effects 0.000 claims abstract description 22
- 239000001257 hydrogen Substances 0.000 claims abstract description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002904 solvent Substances 0.000 claims description 78
- 239000000370 acceptor Substances 0.000 claims description 73
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 30
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 30
- 239000000654 additive Substances 0.000 claims description 25
- 150000001875 compounds Chemical class 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 25
- 239000000758 substrate Substances 0.000 claims description 25
- 238000006116 polymerization reaction Methods 0.000 claims description 23
- -1 thieno[3,2-b]thiophene compound Chemical class 0.000 claims description 21
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 18
- 125000003118 aryl group Chemical group 0.000 claims description 12
- 230000000996 additive effect Effects 0.000 claims description 11
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 229930192474 thiophene Natural products 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 8
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 claims description 7
- 150000007942 carboxylates Chemical class 0.000 claims description 7
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims description 6
- FKLJPTJMIBLJAV-UHFFFAOYSA-N Compound IV Chemical compound O1N=C(C)C=C1CCCCCCCOC1=CC=C(C=2OCCN=2)C=C1 FKLJPTJMIBLJAV-UHFFFAOYSA-N 0.000 claims description 6
- 229940117389 dichlorobenzene Drugs 0.000 claims description 6
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 claims description 6
- 230000005525 hole transport Effects 0.000 claims description 6
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims description 5
- 125000000524 functional group Chemical group 0.000 claims description 5
- 229920000123 polythiophene Polymers 0.000 claims description 4
- VJYJJHQEVLEOFL-UHFFFAOYSA-N thieno[3,2-b]thiophene Chemical group S1C=CC2=C1C=CS2 VJYJJHQEVLEOFL-UHFFFAOYSA-N 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 238000007363 ring formation reaction Methods 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 230000000269 nucleophilic effect Effects 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- HTSGKJQDMSTCGS-UHFFFAOYSA-N 1,4-bis(4-chlorophenyl)-2-(4-methylphenyl)sulfonylbutane-1,4-dione Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C(C(=O)C=1C=CC(Cl)=CC=1)CC(=O)C1=CC=C(Cl)C=C1 HTSGKJQDMSTCGS-UHFFFAOYSA-N 0.000 claims 2
- 238000010521 absorption reaction Methods 0.000 abstract description 11
- 239000010410 layer Substances 0.000 description 68
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 42
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 38
- 239000000243 solution Substances 0.000 description 34
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 30
- 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 29
- 238000006243 chemical reaction Methods 0.000 description 29
- 230000015572 biosynthetic process Effects 0.000 description 26
- 238000003786 synthesis reaction Methods 0.000 description 25
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 22
- 239000000976 ink Substances 0.000 description 22
- 229910052786 argon Inorganic materials 0.000 description 21
- 229910003472 fullerene Inorganic materials 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- 238000007792 addition Methods 0.000 description 16
- 0 CCCCC(CC)Cc1cc2c(cc(*)[s]3)c3c3[s]c(*)cc3c2cc1CC(CC)CCCC Chemical compound CCCCC(CC)Cc1cc2c(cc(*)[s]3)c3c3[s]c(*)cc3c2cc1CC(CC)CCCC 0.000 description 14
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 13
- 239000010408 film Substances 0.000 description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 229920001577 copolymer Polymers 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 229920000547 conjugated polymer Polymers 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 230000003993 interaction Effects 0.000 description 8
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 7
- 238000005481 NMR spectroscopy Methods 0.000 description 7
- 238000004440 column chromatography Methods 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 7
- 239000012074 organic phase Substances 0.000 description 7
- 239000002244 precipitate Substances 0.000 description 7
- 229910052720 vanadium Inorganic materials 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 101000609219 Homo sapiens Polyadenylate-binding protein 4 Proteins 0.000 description 6
- 102100039424 Polyadenylate-binding protein 4 Human genes 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 238000000137 annealing Methods 0.000 description 6
- 239000008346 aqueous phase Substances 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- 238000000151 deposition Methods 0.000 description 6
- 238000009472 formulation Methods 0.000 description 6
- 238000004770 highest occupied molecular orbital Methods 0.000 description 6
- 235000019341 magnesium sulphate Nutrition 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 229920005604 random copolymer Polymers 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000013638 trimer Substances 0.000 description 6
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 description 5
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 5
- 239000011229 interlayer Substances 0.000 description 5
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 238000010129 solution processing Methods 0.000 description 5
- 230000003595 spectral effect Effects 0.000 description 5
- UKHQRARQNZOXRL-UHFFFAOYSA-N trimethyltin Chemical compound C[SnH](C)C UKHQRARQNZOXRL-UHFFFAOYSA-N 0.000 description 5
- DRSHXJFUUPIBHX-UHFFFAOYSA-N COc1ccc(cc1)N1N=CC2C=NC(Nc3cc(OC)c(OC)c(OCCCN4CCN(C)CC4)c3)=NC12 Chemical compound COc1ccc(cc1)N1N=CC2C=NC(Nc3cc(OC)c(OC)c(OCCCN4CCN(C)CC4)c3)=NC12 DRSHXJFUUPIBHX-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 239000000539 dimer Substances 0.000 description 4
- 230000005684 electric field Effects 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 125000000623 heterocyclic group Chemical group 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000004528 spin coating Methods 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- 150000003577 thiophenes Chemical class 0.000 description 4
- 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 4
- QENGPZGAWFQWCZ-UHFFFAOYSA-N 3-Methylthiophene Chemical compound CC=1C=CSC=1 QENGPZGAWFQWCZ-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- MCEWYIDBDVPMES-UHFFFAOYSA-N [60]pcbm Chemical group 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 3
- ZQRGREQWCRSUCI-UHFFFAOYSA-N [S].C=1C=CSC=1 Chemical compound [S].C=1C=CSC=1 ZQRGREQWCRSUCI-UHFFFAOYSA-N 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 125000002877 alkyl aryl group Chemical group 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 229910021417 amorphous silicon Inorganic materials 0.000 description 3
- 229920001400 block copolymer Polymers 0.000 description 3
- 230000000903 blocking effect Effects 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
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- KWTSZCJMWHGPOS-UHFFFAOYSA-M chloro(trimethyl)stannane Chemical compound C[Sn](C)(C)Cl KWTSZCJMWHGPOS-UHFFFAOYSA-M 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- 238000006880 cross-coupling reaction Methods 0.000 description 3
- 238000003618 dip coating Methods 0.000 description 3
- 230000005281 excited state Effects 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000003306 harvesting Methods 0.000 description 3
- 238000007641 inkjet printing Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000013082 photovoltaic technology Methods 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 125000006239 protecting group Chemical group 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 125000000547 substituted alkyl group Chemical group 0.000 description 3
- 238000010345 tape casting Methods 0.000 description 3
- PWYVVBKROXXHEB-UHFFFAOYSA-M trimethyl-[3-(1-methyl-2,3,4,5-tetraphenylsilol-1-yl)propyl]azanium;iodide Chemical compound [I-].C[N+](C)(C)CCC[Si]1(C)C(C=2C=CC=CC=2)=C(C=2C=CC=CC=2)C(C=2C=CC=CC=2)=C1C1=CC=CC=C1 PWYVVBKROXXHEB-UHFFFAOYSA-M 0.000 description 3
- VMKOFRJSULQZRM-UHFFFAOYSA-N 1-bromooctane Chemical compound CCCCCCCCBr VMKOFRJSULQZRM-UHFFFAOYSA-N 0.000 description 2
- JLQRWIOOEWJODY-UHFFFAOYSA-N 3,6-bis(9-thiophen-3-ylheptadecan-9-yl)thieno[3,2-b]thiophene Chemical compound C=1SC=2C(C(CCCCCCCC)(CCCCCCCC)C3=CSC=C3)=CSC=2C=1C(CCCCCCCC)(CCCCCCCC)C=1C=CSC=1 JLQRWIOOEWJODY-UHFFFAOYSA-N 0.000 description 2
- KACAIFATVKQONW-UHFFFAOYSA-N 3,6-bis(thiophen-3-ylmethyl)thieno[3,2-b]thiophene Chemical compound C=1SC=2C(CC3=CSC=C3)=CSC=2C=1CC=1C=CSC=1 KACAIFATVKQONW-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 101000935612 Gloydius halys Bradykinin-potentiating peptide 1 Proteins 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- 238000000944 Soxhlet extraction Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000005644 Wolff-Kishner reduction reaction Methods 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- LUBAVLJLKZRSIB-UHFFFAOYSA-N [6-[hydroxy(thiophen-3-yl)methyl]thieno[3,2-b]thiophen-3-yl]-thiophen-3-ylmethanol Chemical compound C=1SC=2C(C(O)C3=CSC=C3)=CSC=2C=1C(O)C=1C=CSC=1 LUBAVLJLKZRSIB-UHFFFAOYSA-N 0.000 description 2
- 229920005603 alternating copolymer Polymers 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- RVADFRWLUMBNPB-UHFFFAOYSA-N bis[4-(2-ethylhexyl)phenyl]methanol Chemical compound C1=CC(CC(CC)CCCC)=CC=C1C(O)C1=CC=C(CC(CC)CCCC)C=C1 RVADFRWLUMBNPB-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001722 carbon compounds Chemical class 0.000 description 2
- 230000003750 conditioning effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 229960004132 diethyl ether Drugs 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000019439 ethyl acetate Nutrition 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000007306 functionalization reaction Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- ADKGOXMEPLSPNN-UHFFFAOYSA-N methyl 2-bromothiophene-3-carboxylate Chemical compound COC(=O)C=1C=CSC=1Br ADKGOXMEPLSPNN-UHFFFAOYSA-N 0.000 description 2
- 238000005442 molecular electronic Methods 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- LEHBURLTIWGHEM-UHFFFAOYSA-N pyridinium chlorochromate Chemical compound [O-][Cr](Cl)(=O)=O.C1=CC=[NH+]C=C1 LEHBURLTIWGHEM-UHFFFAOYSA-N 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 239000012312 sodium hydride Substances 0.000 description 2
- 229910000104 sodium hydride Inorganic materials 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000009718 spray deposition Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- DKLWRIQKXIBVIS-UHFFFAOYSA-N 1,1-diiodooctane Chemical compound CCCCCCCC(I)I DKLWRIQKXIBVIS-UHFFFAOYSA-N 0.000 description 1
- 238000007115 1,4-cycloaddition reaction Methods 0.000 description 1
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-UHFFFAOYSA-N 0.000 description 1
- XLINASZRJNZCAK-UHFFFAOYSA-N 1-bromo-4-(2-ethylhexyl)benzene Chemical compound CCCCC(CC)CC1=CC=C(Br)C=C1 XLINASZRJNZCAK-UHFFFAOYSA-N 0.000 description 1
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 1
- QZVHYFUVMQIGGM-UHFFFAOYSA-N 2-Hexylthiophene Chemical compound CCCCCCC1=CC=CS1 QZVHYFUVMQIGGM-UHFFFAOYSA-N 0.000 description 1
- NOYVOSGVFSEKPR-UHFFFAOYSA-N 2-Pentylthiophene Chemical compound CCCCCC1=CC=CS1 NOYVOSGVFSEKPR-UHFFFAOYSA-N 0.000 description 1
- MNDZHERKKXUTOE-UHFFFAOYSA-N 2-butylthiophene Chemical compound CCCCC1=CC=CS1 MNDZHERKKXUTOE-UHFFFAOYSA-N 0.000 description 1
- GOTHKCARNFTUSW-UHFFFAOYSA-N 2-decylthiophene Chemical compound CCCCCCCCCCC1=CC=CS1 GOTHKCARNFTUSW-UHFFFAOYSA-N 0.000 description 1
- JCCCMAAJYSNBPR-UHFFFAOYSA-N 2-ethylthiophene Chemical compound CCC1=CC=CS1 JCCCMAAJYSNBPR-UHFFFAOYSA-N 0.000 description 1
- FGGZOCMVJAJPMH-UHFFFAOYSA-N 2-heptylthiophene Chemical compound CCCCCCCC1=CC=CS1 FGGZOCMVJAJPMH-UHFFFAOYSA-N 0.000 description 1
- XQQBUAPQHNYYRS-UHFFFAOYSA-N 2-methylthiophene Chemical compound CC1=CC=CS1 XQQBUAPQHNYYRS-UHFFFAOYSA-N 0.000 description 1
- QOSKQHAWPOHNBS-UHFFFAOYSA-N 2-nonylthiophene Chemical compound CCCCCCCCCC1=CC=CS1 QOSKQHAWPOHNBS-UHFFFAOYSA-N 0.000 description 1
- GIFWAJGKWIDXMY-UHFFFAOYSA-N 2-octylthiophene Chemical compound CCCCCCCCC1=CC=CS1 GIFWAJGKWIDXMY-UHFFFAOYSA-N 0.000 description 1
- BTXIJTYYMLCUHI-UHFFFAOYSA-N 2-propylthiophene Chemical compound CCCC1=CC=CS1 BTXIJTYYMLCUHI-UHFFFAOYSA-N 0.000 description 1
- RBIGKSZIQCTIJF-UHFFFAOYSA-N 3-formylthiophene Chemical compound O=CC=1C=CSC=1 RBIGKSZIQCTIJF-UHFFFAOYSA-N 0.000 description 1
- JEDHEMYZURJGRQ-UHFFFAOYSA-N 3-hexylthiophene Chemical compound CCCCCCC=1C=CSC=1 JEDHEMYZURJGRQ-UHFFFAOYSA-N 0.000 description 1
- DHDHJYNTEFLIHY-UHFFFAOYSA-N 4,7-diphenyl-1,10-phenanthroline Chemical compound C1=CC=CC=C1C1=CC=NC2=C1C=CC1=C(C=3C=CC=CC=3)C=CN=C21 DHDHJYNTEFLIHY-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- PFTBPJBETIOCDQ-UHFFFAOYSA-N Bc([s]c(-c([s]c(Br)c1C(N2CC(CC)CCCC)=O)c1C2=O)c1C(N2CC(CC)CCCC)=O)c1C2=O Chemical compound Bc([s]c(-c([s]c(Br)c1C(N2CC(CC)CCCC)=O)c1C2=O)c1C(N2CC(CC)CCCC)=O)c1C2=O PFTBPJBETIOCDQ-UHFFFAOYSA-N 0.000 description 1
- 125000003860 C1-C20 alkoxy group Chemical group 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical class [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 238000005577 Kumada cross-coupling reaction Methods 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 238000006411 Negishi coupling reaction Methods 0.000 description 1
- 229910005855 NiOx Inorganic materials 0.000 description 1
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- 238000006619 Stille reaction Methods 0.000 description 1
- 238000006069 Suzuki reaction reaction Methods 0.000 description 1
- AVRWEULSKHQETA-UHFFFAOYSA-N Thiophene-2 Chemical compound S1C=2CCCCCC=2C(C(=O)OC)=C1NC(=O)C1=C(F)C(F)=C(F)C(F)=C1F AVRWEULSKHQETA-UHFFFAOYSA-N 0.000 description 1
- 229910003087 TiOx Inorganic materials 0.000 description 1
- 229910007667 ZnOx Inorganic materials 0.000 description 1
- SUDCTTBCJZWMSF-UHFFFAOYSA-N [6-(thiophene-3-carbonyl)thieno[3,2-b]thiophen-3-yl]-thiophen-3-ylmethanone Chemical compound C=1SC=2C(C(=O)C3=CSC=C3)=CSC=2C=1C(=O)C=1C=CSC=1 SUDCTTBCJZWMSF-UHFFFAOYSA-N 0.000 description 1
- XOCUXOWLYLLJLV-UHFFFAOYSA-N [O].[S] Chemical compound [O].[S] XOCUXOWLYLLJLV-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 125000005083 alkoxyalkoxy group Chemical group 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 230000008033 biological extinction Effects 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
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000009918 complex formation Effects 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 238000006352 cycloaddition reaction Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000001212 derivatisation Methods 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 235000021158 dinner Nutrition 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 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
- 238000001035 drying Methods 0.000 description 1
- 239000012039 electrophile Substances 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 230000008863 intramolecular interaction Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- CCZVEWRRAVASGL-UHFFFAOYSA-N lithium;2-methanidylpropane Chemical compound [Li+].CC(C)[CH2-] CCZVEWRRAVASGL-UHFFFAOYSA-N 0.000 description 1
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 1
- 230000004807 localization Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- UQAWQZIWDBGHDW-UHFFFAOYSA-N methyl 2-[5-(3-methoxycarbonylthiophen-2-yl)thieno[3,2-b]thiophen-2-yl]thiophene-3-carboxylate Chemical compound C1=CSC(C=2SC=3C=C(SC=3C=2)C2=C(C=CS2)C(=O)OC)=C1C(=O)OC UQAWQZIWDBGHDW-UHFFFAOYSA-N 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 238000004776 molecular orbital Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000005935 nucleophilic addition reaction Methods 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
- 239000011146 organic particle Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 125000001979 organolithium group Chemical group 0.000 description 1
- 238000005535 overpotential deposition Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000006223 plastic coating Substances 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000002577 pseudohalo group Chemical group 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000007342 radical addition reaction Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 125000005415 substituted alkoxy group Chemical group 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 description 1
- CRUIOQJBPNKOJG-UHFFFAOYSA-N thieno[3,2-e][1]benzothiole Chemical compound C1=C2SC=CC2=C2C=CSC2=C1 CRUIOQJBPNKOJG-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- QTWBEVAYYDZLQL-UHFFFAOYSA-N thiophene-3-carbonyl chloride Chemical compound ClC(=O)C=1C=CSC=1 QTWBEVAYYDZLQL-UHFFFAOYSA-N 0.000 description 1
- YNVOMSDITJMNET-UHFFFAOYSA-M thiophene-3-carboxylate Chemical compound [O-]C(=O)C=1C=CSC=1 YNVOMSDITJMNET-UHFFFAOYSA-M 0.000 description 1
- HLLICFJUWSZHRJ-UHFFFAOYSA-N tioxidazole Chemical compound CCCOC1=CC=C2N=C(NC(=O)OC)SC2=C1 HLLICFJUWSZHRJ-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- HDZULVYGCRXVNQ-UHFFFAOYSA-N trimethyl-(5-trimethylstannylthieno[3,2-b]thiophen-2-yl)stannane Chemical compound S1C([Sn](C)(C)C)=CC2=C1C=C([Sn](C)(C)C)S2 HDZULVYGCRXVNQ-UHFFFAOYSA-N 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
- C07D487/04—Ortho-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
- C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
- C07D495/04—Ortho-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
- C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
- C07D495/06—Peri-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
- C07D495/22—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains four or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
- C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
- C07F7/0816—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring said ring comprising Si as a ring atom
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B69/00—Dyes not provided for by a single group of this subclass
- C09B69/008—Dyes containing a substituent, which contains a silicium atom
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B69/00—Dyes not provided for by a single group of this subclass
- C09B69/10—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
- C09B69/109—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds containing other specific dyes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/52—Electrically conductive inks
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D165/00—Coating compositions based on macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Coating compositions based on derivatives of such polymers
-
- 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
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
- H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/12—Copolymers
- C08G2261/124—Copolymers alternating
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/18—Definition of the polymer structure conjugated
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/22—Molecular weight
- C08G2261/226—Oligomers, i.e. up to 10 repeat units
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/22—Molecular weight
- C08G2261/228—Polymers, i.e. more than 10 repeat units
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
- C08G2261/3243—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing one or more sulfur atoms as the only heteroatom, e.g. benzothiophene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/33—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
- C08G2261/334—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing heteroatoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/34—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain
- C08G2261/344—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain containing heteroatoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/36—Oligomers, i.e. comprising up to 10 repeat units
- C08G2261/364—Oligomers, i.e. comprising up to 10 repeat units containing hetero atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/40—Polymerisation processes
- C08G2261/41—Organometallic coupling reactions
- C08G2261/414—Stille reactions
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/50—Physical properties
- C08G2261/51—Charge transport
- C08G2261/512—Hole transport
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/90—Applications
- C08G2261/91—Photovoltaic applications
-
- 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
- H10K30/30—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
-
- 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
-
- 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
- H10K85/10—Organic polymers or oligomers
- H10K85/151—Copolymers
-
- 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
- H10K85/30—Coordination compounds
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/656—Aromatic compounds comprising a hetero atom comprising two or more different heteroatoms per ring
-
- 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
- ORGANIC ELECTRONIC DEVICES INCLUDING ORGANIC PHOTOVOLTAIC DEVICES
- active layers can comprise a combination of p-type material and n-type material.
- the p-type material can be a conjugated polymer.
- the polymer ideally should satisfy a variety of chemico-physical properties, such as solubility, processability, good film formation, proper absorption properties, proper HOMO/LUMO (molecular orbitals and energy levels), bandgap, charge carrier mobility, and other properties.
- chemico-physical properties such as solubility, processability, good film formation, proper absorption properties, proper HOMO/LUMO (molecular orbitals and energy levels), bandgap, charge carrier mobility, and other properties.
- Embodiments provided herein include, for example, compositions, devices, and methods of making and using the same.
- Compositions include, for example, monomer, oligomer, and polymer compositions, as well as ink formulations.
- Compositions also can include those prepared by particular processes.
- Devices include organic electronic devices including photovoltaic and/or solar cell devices including modules and devices which comprise a plurality of photovoltaic and/or solar cell devices.
- Coated substrates can be prepared, wherein the substrate is rigid or flexible.
- an oligomer or polymer comprising:
- RI, R2, R3, and R4 are independently hydrogen or solubilizing groups.
- Ri, R 2 , R3, and R4 are the same group. In one embodiment, Ri, R2, R3, and R4 are the same group and comprise an aromatic group. In one embodiment, Ri, R 2 , R3, and R4 are the same group and comprise an arylalkyi group. In one embodiment, Ri, R 2 , R3, and R are the same group and are a Ci - C 25 group. In one embodiment, the polymer is present having a molecular weight of at least 10,000 number average molecular weight. In one embodiment, the oligomer or polymer is a donor-acceptor oligomer or polymer. In one
- the oligomer or polymer is a donor-acceptor polymer, and has at least two types of donors, or at least two types of acceptors.
- the oligomer or polymer is soluble in chloroform, chlorobenzene, dichlorobenzene, or trichlorobenzene.
- polymer is present and has a molecular weight of at least 10,000 number average molecular weight and is soluble in chloroform, chlorobenzene, dichlorobenzene, or trichlorobenzene.
- Ri, R 2 , R 3 , and R4 are, optionally, the same group and are a Ci - C 25 group.
- a monomer is also provided to provide the repeat unit in (I), wherein the monomer can comprise a structure (II):
- end terminal rings are adapted for polymerization, and wherein Ri, R 2 , R3, and R4 an embodiment as described herein.
- Ri, R 2 , R3, and R4 are the same group. In one embodiment, Ri, R 2 , R3, and R4 are the same group and comprise an aromatic group. In one embodiment, Ri, R 2 , R3, and R4 are the same group and comprise an arylalkyl group. In one embodiment, Ri, R 2 , R 3 , and R ⁇ are the same group and are a d - C 2 5 group.
- the monomer is functionalized with electrophilic groups for polymerization. In one embodiment, the monomer is functionalized with nucleophilic groups for polymerization. In one embodiment, the monomer is functionalized with groups comprising metal, such as for example tin, for polymerization.
- the monomer is functionalized for cross coupling polymerization, including palladium cross coupling polymerization. In one embodiment, the monomer is functionalized for Ullman, Yamamoto, or Suzuki polymerization. In one embodiment, the terminal thiophene rings are functionalized for polymerization.
- the monomer can be used with one or more other comonomers to form polymers comprising (I).
- RI, R2, R3, and R4 are independently hydrogen or solubilizing groups; and at least one solvent.
- Ri, R 2 , R3, and R4 are the same group.
- Ri, R 2 , R3, and R4 are the same group and comprise an aromatic group. In one embodiment, Ri, R 2 , R 3 , and R ⁇ are the same group and comprise an arylalkyi group. In one embodiment, i, R 2 , R3, and R ⁇ are the same group and are a Ci - C25 group.
- the oligomer or polymer is a polymer having a molecular weight of at least 10,000 number average molecular weight. In one embodiment, the oligomer or polymer is a donor-acceptor oligomer or polymer. In one embodiment, the oligomer or polymer is a donor-acceptor polymer, and has at least two types of donors, or at least two types of acceptors.
- the solvent comprises at least two solvents, optionally halogenated solvents, and the ink composition further comprises at least one additive. In one embodiment, the solvent comprises a mixture comprising at least orthodichlorobenzene and
- Ri, R 2 , R 3 , and R4 are independently hydrogen or solubilizing groups.
- Ri, R 2 , R3, and R ⁇ are the same group. In one embodiment, Ri, R 2 , R3, and R ⁇ are the same group and comprise an aromatic group. In one embodiment, Ri, R 2 , R 3 , and R4 are the same group and comprise an arylalkyi group. In one embodiment, Ri, R 2 , R3, and R4 are the same group and are a Ci - C 2 5 group.
- the polymer has a molecular weight of at least 10,000 number average molecular weight. In one embodiment, the polymer is a donor-acceptor polymer. In one embodiment, the polymer is a donor-acceptor polymer, and has at least two types of donors, or at least two types of acceptors. In one embodiment, the device comprises at least one polythiophene a hole transport layer. In one embodiment, the active layer further comprises at least one n-type material.
- Another embodiment provides a coated substrate comprising at least one substrate and at least one coating, wherein the coating comprises at least one polymer comprising:
- R 2 , R 3 , and R4 are independently hydrogen or solubilizing groups.
- Ri, R 2 , R 3 , and R are the same group. In one embodiment, R ⁇ R 2 , R 3 , and R4 are the same group and comprise an aromatic group. In one embodiment, Ri, R 2 , R 3 , and R 4 are the same group and comprise an arylalkyl group. In one embodiment, Rj, R 2 , R 3 , and R ⁇ are the same group and are a Ci - C 2 5 group.
- the polymer has a molecular weight of at least 10,000 number average molecular weight. In one embodiment, the polymer is a donor-acceptor polymer. In one embodiment, the polymer is a donor-acceptor polymer, and has at least two types of donors, or at least two types of acceptors. In one embodiment, the substrate is a flexible substrate. In one embodiment, the substrate comprises a hole transporting layer next to the coating.
- Another embodiment provides a method comprising: functionalize at least one thieno[3,2-b]thiophene compound with two reactive functional groups, one reactive group on each thiophene ring to provide a compound I; provide at least one thiophene compound comprising a leaving group at the 2-position and a carboxylate at the 3-position to provide a compound II; react compound I and compound II to produce compound III which is a compound comprising a central thieno[3,2- •bjthiophene moiety linked to opposing thiophene rings; react compound III so that carboxylate groups are converted to hydroxyl groups to provide compound IV; react compound IV in a ring closure reaction to provide at least one compound
- R groups in (II) can be Rl, R2, R3, or R4 as in (I).
- Another embodiment provides a method comprising: providing a monomer comprising a moiety represented by:
- Ri, R 2 , R3, and R4 are independently hydrogen or solubilizing groups; and polymerizing the monomer.
- At least one advantage for at least one embodiment is ability to make high mobility polymers.
- At least one additional advantage for at least one embodiment is to have relatively high efficiency photovoltaic devices.
- At least one additional advantage is ability to solubilize the polymers via four side groups R1-R4.
- At least one additional advantage for at least one embodiment is to have polymers with bathochromic absorption profiles and sharp band edges.
- At least one additional advantage is ability to control the HOMO to a desired level (e.g., weaker donor) so good matching can occur between donor(s) and acceptor(s).
- a desired level e.g., weaker donor
- Figure 1 illustrates external quantum efficiency (eqe) data for several polymers.
- Figure 2 illustrates reverse bias data for several polymers.
- FIG. 3 illustrates external quantum efficiency (eqe) data for several polymers.
- one first excluded embodiment is: a device comprising: at least one cathode; at least one anode; at least one photovoltaic active layer disposed between the cathode and anode and comprising at least one p-type material and at least one n-type material, wherein the p-type material comprises at least one polymer comprising a backbone moiety:
- polymer comprises:
- Rl, R2, R3, and R4 are independently hydrogen or solubilizing groups.
- one second excluded embodiment is: a monomer, oligomer, or polymer comprising:
- Rl, R2, R3, and R4 are independently hydrogen or solubilizing groups.
- one third excluded embodiment is: a composition comprising at least one donor-acceptor polymer comprising:
- e polymer further comprises
- RI, R2, R3, and R4 are independently hydrogen or solubilizing groups.
- a fourth excluded embodiment is: an ink composition comprising at least one oligomer, or polymer comprising:
- RI, R2, R3, and R4 are independently hydrogen or solubilizing groups.
- Low band gap materials are known in the art. See, for example, Blouin et al., Accounts of Chemical Research, 1110-1119, September 2008, 41, 9.
- Polymer solar cells are known in the art. See, for example, Chen et al., Advanced Materials, 2009, 21, 1-16; Hoppe, Adv. Polym. So ' ., 2008, 214, 1-86;
- Organic semiconductors including arylamines and TPD are known in the art.
- compositions comprising at least one conjugated copolymer, wherein the copolymer backbone comprises at least one donor moiety and at least one acceptor moiety, and wherein the copolymer has at least two high extinction coefficient chromophores thereby covering the high photon flux portion of the solar spectrum which is from about 400-1000 nm and centered at about 750-800 nm. Broad absorption is desired including up to the near-infrared region. Vibronic structure can be detected.
- the side groups can be adapted to be solubilizing groups as described further herein.
- An oligomer can have a number of repeat units of six or less.
- Ri, R2, R3, and R4 are independently hydrogen or solubilizing groups.
- oligomers and polymers which comprise (I) are sufficiently soluble so that inks can be formed and solution processing can be achieved.
- Solubility can be examined in organic or aqueous solvents.
- Organic solvents can be, for example, halogenated and non-halogenated solvents.
- the solvent can be a single solvent or a mixture of solvents.
- An example of halogenated solvent is ortho-dichlorobenzene, and this solvent can be used to measure solubility. Solubility can be measured at 25°C.
- Solubility can be, for example, at least 1 mg/mL, or at least 20 mg/mL.
- solubility can be adapted to provide good bulk heterojunction (BHJ) layer morphology.
- Higher molecular weight may be preferred to modulate solubility, and molecular weight can be used with other formulation strategies including additives to modulate solubility and/or BHJ formation.
- polymers can be both soluble and also functionally dispersible in a solvent so that solution processing can be achieved, whether or not a true solution is formed.
- the R groups in (I) can be adapted to facilitate or provide solubility.
- the R groups can also be adapted to provide desired electronic properties.
- the R groups can be also adapted to provide steric and molecular stacking properties.
- the atom in the R groups bonding to the polymer chain can be, for example, carbon.
- the R groups can be optionally substituted alkyl, optionally substituted linear alkyl, optionally substituted branched alkyl, optionally substituted aryl, optionally substituted alkylaryl, optionally substituted arylalkyl, optionally substituted alkoxy, or optionally substituted aryloxy.
- the R group can have, for example, 3-30 carbons, or 4-25 carbons, or 5-15 carbons. Examples include butyl, octyl and dodecyl, as well as ethylhexyl. Different R groups can be used in the same polymer as needed.
- the R group can be chiral.
- the R group can be functionalized or substituted as desired. Examples of substituents include amino, carboxylic acid, ester, halogen (including fluoro and chloro), pseudohalogen (e.g., cyano), and other functional groups known in the art.
- the R groups can comprise a heteroatom, such as oxygen or nitrogen in the carbon chain (e.g., ether or amino linkages, respectively).
- the R group can comprise C1-C20 alkoxy, or C1-C20 alkyleneoxy, for example.
- the R group can be an oligoether, such as, for example, alkoxyalkoxy or alkoxyalkoxyalkoxy, such as, for example, methoxyethoxyethoxy.
- the polymer comprising structure (I) can be free of protecting groups, and in particular the R groups can be free of protecting groups.
- the R groups can be adapted to modulate or tune the LUMO, including provide a decreasing or increasing LUMO, or provide better solid state packing, or provide improved charge transport, and/or provide environmental stability.
- the R group can be halogenated including comprise a group comprising chlorine or fluorine.
- the R group can be, for example, perfluorinated.
- the R group can be, for example, a perfluoroalkyl group such as, for example, -C3F7.
- the R group can be, for example, a perfluoroarylgroup, such as, for example, -C6F5.
- halogenated substituent groups to modulate LUMO and solid state packing see, for example, Schmidt et al., J. Am. Chem. Soc, 2009, 131, 6215-6228.
- a particular oligomer or polymer could comprise two or more different structures (I).
- Polymer comprising (I) can be a random copolymer or a regular alternating copolymer. Polymer comprising (I) can comprise multiple repeat moieties.
- Moieties in the polymer chain can provide for carbon-carbon bonding with conjugation, and, in addition, can provide charge transport.
- Polymer side groups can provide electron withdrawing or electron accepting character, and the strength of this can be varied, e.g., weak or strong, or from weak to strong. Push-pull electronic effects can be produced. Electron donating side groups can be also used as appropriate.
- Polymer side groups can be protected or deprotected.
- BOC butyloxycarbonyl
- an embodiment comprises the polymer being totally free of protecting groups.
- Block copolymers can be prepared. Either all blocks can be embodiments as described herein, or only a subset of block(s) can be embodiments described herein.
- a block copolymer could comprise both a conjugated polymer block and a non-conjugated polymer block, or both a donor-acceptor block, and a non- donor-acceptor block.
- block copolymers can be prepared comprising blocks of different donors and acceptors, e.g., (Dl-Al)-b-(Dl-A2), and the like.
- the polymer comprises a number average molecular weight, Mn, of at least 6,000 g/mol, or of at least 7,500 g/mol, or at least 10,000. In another embodiment, the polymer comprises a number average molecular weight, Mn, of at least 20,000, or at least 30,000, or at least 40,000, or at least 50,000.
- Ri, R 2 , R 3 , and R4 can be, independently, Ci-C 25 optionally substituted alkyl, aryl, alkylaryl, or arylalkyl.
- examples include phenyl, wherein the phenyl is optionally further substituted at the 4 position with, for example, an alkyl group such as, for example, a branched group such as, for example, ethylhexyl.
- the R groups in (I) are the same.
- a monomer is also provided to provide this repeat unit (I).
- the monomer can comprise, for example, structure (II) which can be adapted to have two or more n through the terminal rings:
- the R groups shown in (II) can be as described for the R groups in structure
- the oligomer or polymer comprise one or more of the repeat unit (I).
- the oligomer or polymer can comprise a donor-acceptor structure.
- Structure (I) can be a donor.
- the polymer can comprise one or more donors, including (I), and/or one or more acceptors.
- the polymer can comprise only two donors and acceptors, or only three donors and acceptors, or at least two or at least three donors and acceptors.
- the R groups can be selected to provide a higher amount of symmetry.
- Particular examples of polymers include:
- polymer structures including donor acceptor polymers, comprising (I) are shown in the Appendix A.
- the side groups in the polymers of Appendix A can be tailored for solubility, stacking and morphology, and electronic interactions.
- monomers, oligomers, and polymers can be prepared with comprise a silole moiety represented by (III):
- Ri, R 2/ R3, and R4 are independently hydrogen or solubilizing groups.
- R ⁇ R 2 , R3, and R4 can be, independently, C C 2 5 optionally substituted alkyl, aryl, alkylaryl, or arylalkyl.
- Examples include phenyl, wherein the phenyl is optionally further substituted at the 4 position with, for example, an alkyl group such as, for example, a branched group such as, for example, ethylhexyl.
- the R groups in (I) are the same.
- the silole structure can be also shown as in (IIIB) where the linkages into the polymer chain are not shown at the end:
- the terminal thiophene rings can be adapted to include functionalities for polymerization.
- the structure can be:
- Appendix B illustrates an exemplary listing of donor structures which can be used.
- the structures shown in Appendix B can be used in monomers, dimers, trimers, oligomers, and polymers.
- the side group can be varied and is not limited by side groups shown structure in Appendix B.
- the side groups in the donor structures of Appendix B can be tailored for solubility, stacking and
- the representation of -R or R- means a linkage site for a reactive group, or a linkage site for linking into another moiety like a dimer, trimer, oligomer, or polymer. Illustration of two of these sites means the moiety can be bivalently linked to another moiety including a polymer chain.
- acceptors or acceptor moieties, can be used.
- Examples include but are not limited to those shown in Appendix C.
- the structures shown in Appendix C can be used in monomers, dimers, trimers, oligomers, and polymers.
- the side group can be varied and is not limited by shown structure in Appendix C.
- the side groups in the structures of Appendix C can be tailored for solubility, stacking and morphology, and electronic interactions.
- the representation of -R or R- means a linkage site for a reactive group, or a linkage site for, after reaction, linking into another moiety like a dimer, trimer, oligomer, or polymer. Two of these sites means the moiety can be bivalently linked to another moiety including a polymer chain.
- Acceptors are particularly important if they have one or more carbonyl groups which can interact with a thiophene ring in (I).
- an acceptor is the diketopyrroleopyrrole-based acceptor moiety. See, for example, Zhou et al., Chemistry of Materials, 2009, “Synthesis and Photovoltaic Properties of Diketopyrrolopyrrole-Based Donor-Acceptor Complexes.”
- more than one donor can be used: e.g., Dl, D2, D3, and the like.
- more than one acceptor can be used: e.g., Al, A2, A3, and the like.
- Polymers can comprise Dl-Al moieties, D2-A2 moieties, D3-A3 moieties, and the like, as well as their intermixed moieties, such as, for example, D1-A2, and the like.
- Use of more than one donor or acceptor can provide broader and/or stronger absorption bands and/or vibronic structures.
- Spacer moieties can be used as desired.
- the acceptors, Al, A2, or both can comprise the acceptors listed in Appendix
- the donors can be selected from the structure (I) and those listed in
- Chart I can be extended to further include additional donors, e.g., D3, D4, D5, and the like, or additional acceptors, e.g., A3, A4, A5, or the like.
- the molar ratio of donor and acceptor can be one, less than one, or more than one. In calculating this ratio, there can be a single donor and/or a single acceptor, or there can be more than one donor and/or more than one acceptor. In other words, the polymer does not need to comprise equal molar amounts of donor and acceptor.
- the polymer can comprise more donor than acceptor, or more acceptor than donor. Chart I shows examples of this. For example, the ratio can be 2:1.
- the ratio of different donors and acceptors within the polymer does not need to comprise equal molar amounts, e.g., the total ratio of donor and acceptor moieties in the polymer can be one where donor comprises a sum of different ratios of Dl and D2, and the like, and/or acceptor comprises a sum of different ratios of Al, A2, and the like.
- the ratio of the molar amounts of Dl and D2 does not have to be one
- the ratio of the molar amounts of Al and A2 does not have to be one.
- copolymer microstructures can be prepared as known to those skilled in the polymer chemistry arts. For example, random copolymer structures can be produced. Mixed monomer polymerization can be carried out. Non-random copolymer structures can be produced.
- Synthetic approaches include, for example, Kumada, Suzuki, Negishi or Stille couplings for polymerization. See, for example (a) Cross-Coupling Reactions: A Practical Guide, Ed. Miyaura, 2002; (b) Handbook of Organopalladium Chemistry for Organic Synthesis, Ed. Negishi, 2002; (c) Kuwano et al., J. Org. Chem., 2002, 67, 6479-6486; (d) Yu et al. J. Am. Chem. Soc.
- One embodiment provides for preparing high purity intermediates, such as trimers.
- Polymer properties can be adapted to provide the good photovoltaic properties and to follow the design rules noted herein.
- Lambda max can be, for example, greater than 600 nm.
- Absorption edge can be extended into the red region.
- the absorption edge can comprise a sharp edge.
- Absorption spectra are important parameters for the polymers, particularly for photovoltaic applications. It is known to record absorption spectra, including UV-Vis absorption spectra, for conjugated polymers. See, for example, Brown et al., Phys. Rev. B, 67, 064203 (2003) (describing spectra for different kinds of polythiophenes).
- a variety of intramolecular non-covalent interactions can be used to provide increased rigidity and/or planarity to the polymer chain and its chromophores, although various embodiments described herein are not necessarily limited by theory.
- Increased rigidity can be used to increase the likelihood for a well behaved excited state and lead to good excitonic diffusion distances and minimization of energy loss pathways from excited state (e.g., charge trapping, polaronic quenching, excited state deactivation, or even localization).
- Absorption profiling can be used to examine such features.
- Donor-Acceptor polymers comprising diketo types of structures, such as dioxypyrrolo-functionality, can provide intramolecular interactions as a "design rule" for the synthesis of new materials for application in organic electronics, such as OPVs, achieving unexpected performances.
- the thiophene ring can be part of an isolated thiophene moiety or a fused ring thiophene moiety such as the thiophene found in (I) or in benzodithiophene.
- Monomers and polymerizations for monomers comprising (I) or (II) can be carried out including the embodiments shown in the working examples.
- one embodiment provides a method comprising:
- a first step functionalize at least one thieno[3,2-b]thiophene compound with two reactive functional groups, one reactive group on each thiophene ring to provide a compound I.
- reactive functional groups can be, for example, trimethyltin.
- step (b) In another step, provide at least one thiophene compound comprising a leaving group at the 2-position and a carboxylate at the 3-position to provide a compound II.
- Example 2 in the working examples provides an example of this step.
- a carboxylic acid moiety can be converted to a carboxylate moiety.
- compound III which is a compound comprising a central thieno[3,2-b]thiophene moiety linked to opposing thiophene rings.
- Example 3 in the working examples provides an example of this step.
- Example 5 in the working examples provides an example of this step.
- step (f) optionally, in a subsequent step, functionalize compound V to have two polymerization groups and provide compound VI.
- Example 6 in the working examples provides an example of this step.
- the optional functionalization step to provide compound VI is carried out.
- the materials, monomers, dinners, trimers, oligomers, polymers, and copolymers described herein in Part I, the working examples, and claims, can be used in organic electronic devices including, for example, OLEDs, OPVs including as OPV active layer, transistors, OFETs, batteries, and printed electronics generally, as well as sensors.
- OLEDs organic light-emitting diode
- OPVs including as OPV active layer
- transistors, OFETs transistors
- batteries and printed electronics generally, as well as sensors.
- the methods described in Part II can be adapted for the particular compounds and polymers being used.
- photovoltaic cells are known in the art. See, for example, Sun and Sariciftci, Organic Photovoltaics, Mechanisms, Materials, and Devices, 2005.
- the photovoltaic cell can comprise an active layer comprising a composition comprising at least one p-type material and at least one n-type material.
- One can engineer HOMO, LUMO, and band gaps for the p- and n-type materials for good performance.
- the morphology of the active layer can be adapted to provide good performance.
- a nanoscale morphology can be prepared.
- An example is a bulk heterojunction.
- Bilayers can be made as described in, for example, Ayzner et al., J. Phys. Chem. C, 2009, 113, 20050-20060 (e.g., describing all solution-processed bilayers in solar cells).
- the photovoltaic device can comprise at least one cathode, at least one anode, and at least one photovoltaic active layer disposed between the cathode and anode.
- the active layer can comprise a p-type material and an n-type material.
- the polymers described herein, which can be a p-type material can be combined with n-type materials or acceptor moieties, such as, for example, fullerenes and fullerene derivatives.
- An example of a fullerene derivative is PCBM.
- Fullerenes can be also derivatized, as described in, for example, PCT Patent Publication WO 2008/018931 filed May 2, 2007 and US Patent Publication
- Polymer solar cells including polymer fullerene solar cells, are described in, for example, Hoppe et al., Adv. Polym. Sci. (2008), 214: 1-86; Zhu et al., "Design Rules for Efficient Organic Solar Cells," Chapter 13, 195-222 in High-Efficient Low- Cost Photovoltaics, Springer, 2009.
- OLED devices are known in the art including white OLEDs, or WOLEDs. See, for example, Li and Meng, Organic Light Emitting Materials and Devices, CRC Taylor, 2006 and US Patent Publication 2006/0078761 published April 13, 2006.
- the devices can comprise, for example, multi-layer structures including, for example, an anode, including a transparent conductor, such as a transparent conductive oxide (TCO) on glass or PET or PEN; a hole injection layer; an electroluminescent layer, such as a polymer layer; a conditioning layer, such as LiF, and a cathode, such as for example Ca, Al, or Ba.
- TCO transparent conductive oxide
- OLED patents include for example US Patent Nos. 4,356,429 and 4,539,507 (Kodak). Conducting polymers which emit light are described in for example US Patent Nos. 5,247,190 and 5,401,827
- printed electronics are generally known in the art. See, for example, Printed Organic and Molecular Electronics, Ed. D. Gamota et al., 2004.
- Chapters 1 and 2 describe organic semiconductors
- Chapter 3 describes manufacturing platforms for printing circuits
- Chapter 4 describes electrical behavior of transistors and circuits
- Chapter 5 describes applications
- Chapter 6 describes molecular electronics. See also Pope et al., Electronic Processes in Organic Crystals and Polymers, 1999.
- the materials, polymers, and copolymers can be put into solution or dispersion form, including ink formulations, for further processing, adapting to the particular application at hand including electronic devices and organic electronic devices, such as, for example, OLED, solar cells and active layers of solar cells.
- electronic devices and organic electronic devices such as, for example, OLED, solar cells and active layers of solar cells.
- Ink compositions used for forming, for example, the active layer of an organic photovoltaic device can be made by dissolving p-type and n-type materials in a solvent system, optionally containing other additives.
- the solvents and conjugated polymer inks can be formulated or adapted for use in a particular application, such as a solar cell that may include additional additives, such as electron acceptors.
- the additive(s) and solvents can be adapted to provide good dispersability of the n- and p-type materials, solubility of the n- and p-type materials, and stability of the ink formulation.
- solvents can be used which provide good solubility or dispersability for fullerenes or fullerene derivative n-type compounds.
- Solvents can be adapted to be environmentally friendly in view of regulations, and can be, for example, halogen free.
- additives can be included in the ink that can improve the final film morphology or other properties.
- solvent additives disclosed in US Patent Publication entitled "Processing Additives for Fabricating Organic Photovoltaic Cells" 2009/0108255 to Bazan etal., published on April 30, 2009 can be included.
- Solvent(s) and solvent additive(s) can be removed from the ink compositions, and films can be formed. Solid films can be formed that either comprise solvent(s) and solvent additive(s), are substantially free of solvent(s) and solvent additive(s), or are free of solvent(s) and solvent additive(s).
- the amount of remaining solvent can be less than about 5% by weight, or less than about 1% by weight, or less than about 0.1% by weight.
- the amount of remaining solvent additive can be less than about 5% by weight, or less than about 1% by weight, or less than about 0.1% by weight.
- the p-type and n-type polymers of the active layer can be dissolved in the solvent to form an ink, and then allowed to dry.
- Suitable coating methods are known. These include roll-to-roll coating, screen printing, spin casting, spin coating, doctor blading, dip coating, spray coating, or ink jet printing, and other known coating and printing methods.
- Ink components known in the art can be used including, for example, solvents and n-type materials.
- the amounts of the components can be adapted to improve performance.
- the active layer composition in, for example, a solar cell may include an n- type component or electron acceptor, or an electron acceptor moiety. These can be materials with a strong electron affinity and good electron accepting character.
- the n-type component should provide fast transfer; good stability, and good
- the n-type material is desirably soluble in, dispersible in, or otherwise miscible with the solvents in order to provide for solution processing.
- the n-type component may take the form of particles, including microparticles and nanoparticles, inorganic particles, organic particles, and/or semiconductor particles.
- the active layer can comprise an n-type material comprising at least one fullerene structure.
- Fullerenes are known in the art. Fullerenes can be described as spheroidal carbon compounds.
- the fullerene surface can present [6,6] bonding and [6,5] bonding as known in the art.
- the fullerene can have a surface comprising six-membered and five-membered rings. Fullerenes can be for example C60, C70, or C84, and additional carbon atoms can be added via derivative groups. See for example Hirsch, A.; Brettreich, M., Fullerenes: Chemistry and Reactions, Wiley-VCH Verlag, Weinheim, 2005, which is hereby incorporated by reference including teachings for fullerene nomenclature and synthesis,
- the active layer can comprise at least one n-type material, wherein the n-type material comprises at least one derivatized fullerene or fullerene derivative.
- the derivative compound can be, for example, an adduct.
- fullerenes comprising, from 1 to 84, or 1 to 70, or 1 to 60, from 1 to 20, from 1 to 18, from one to ten, or from one to six, or from one to five, or from one to three substituents each covalently bonded to, for example, one or two carbons in the spheroidal carbon compounds.
- the derivatized fullerene can comprise a fullerene covalently bonded by [4+2] cycloaddition to at least one derivative moiety, R.
- An example of an n-type material is PCBM.
- n-type materials are described in, for example, International Patent Publication No. WO/2008/018931 published on February 14, 2008 and US Patent Publication 2008/0319207 published December 25, 2008, both to Laird, etal. See also, for example, for n-type small molecules and/or polymers for use in OPVs: a) Shin, et al. Chem. Mater. 2007, 19, 1892-1894; b) Hoppe, et al. Adv Polym Sci. 2008, 214, 1; c) Panagiotis, et al. Adv. Funct. Mater. 2008, 18, 1; d) Frechet, J. M. J. et al. Chem. Mater. 2009, 21, 1775. SOLVENT
- the solvents can be halogenated or non-halogenated.
- the solvents useful for the presently claimed inventions can include, for example, halogenated benzenes, alkyl benzenes, halogenated methane, and thiophenes derivatives, and the like. More specifically, solvent can be for example chlorobenzene, dichlorobenzene, trichlorobenzene, xylenes, toluene, chloroform, 3-methylthiophene, 3- propylthiphene, 3-hexylthiophene, and mixtures thereof. At least two solvents can be used.
- the solvent system can include at least two solvents, at least one first solvent and at least one second solvent (e.g., a solvent additive), which are different from each other. They can be organic solvents. Particularly useful solvent systems can be used as described in co-pending US patent application entitled “Solvent System for Conjugated Polymers,” published as 2008/0299293, to Sheina et al., and copending US patent application entitled “Improved Solvent System,” serial no.
- Solvent additives can be used, wherein a relatively small addition of a component (e.g., 1-6 wt% or 1-3 wt%) can have a large impact on performance.
- a primary or first solvent can be used in conjunction with a solvent additive.
- Solvent additives can be volatile and can be removed upon solvent removal. Or solvent additives can be less volatile and stay in the film upon solvent removal.
- a solvent additive can comprise at least one heterocyclic ring.
- the heterocyclic ring can be, for example, at least one thiophene ring.
- the second solvent can be for example an alkylthiophene.
- the heterocyclic ring is not a nitrogen-containing ring. Or it can be a nitrogen containing ring.
- the second solvent is or is not a pyridine, pyrazine, pyrimidine, or a pyrrolidinone.
- the heterocyclic ring includes at least one S atom and at least one O atom.
- suitable solvent additives include, but are not limited to, thiophene derivatives (i.e., substituted thiophenes).
- thiophene derivatives i.e., substituted thiophenes.
- the benzene and/or thiophene ring may be substituted or unsubstituted in different positions on the ring.
- the thiophene derivatives do not contain halogen atoms.
- Alkylthiophenes and combinations thereof may be used as the second solvent.
- the alkyl group can be, for example, CI, C2, C3, C4, and the like up to and including C8, C12, C16, and C20.
- the alkyl group can be linear or branched.
- Specific examples of suitable alkylthiophenes include methylthiophene, ethylthiophene, propylthiophene, butylthiophene, pentylthiophene, hexylthiophene, heptylthiophene, octylthiophene, nonylthiophene, and decylthiophene. Fluorinated solvents and additives can be used.
- Devices can be made comprising one or more layers comprising the polymers described herein and one or more electrodes, including anode and cathode. Layers can be built up on a substrate. See, for example, Chen et al., Advanced Materials, 2009, 21, 1-16.
- Devices using the presently claimed inventions can be made using for example ⁇ as an anode material on a substrate.
- Other anode materials can include, for example, metals, such as Au, carbon nanotubes, single or multiwalled, and other transparent conducting oxides.
- the resistivity of the anode can be maintained below, for example, 15 ⁇ /sq or less, 25 or less, 50 or less, or 100 or less, or 200 or less, or 250 or less.
- the substrate can be rigid or flexible and can be, for example, glass, plastics (PTFE, polysiloxanes, thermoplastics, PET, PEN and the like), metals (Al, Au, Ag), metal foils, metal oxides, (TiOx, ZnOx, NiOx, and the like) and semiconductors, such as Si.
- the ⁇ on the substrate can be cleaned using techniques known in the art prior to device layer deposition.
- a variety of layers can be included between the anode and the active layer of a solar cell or the emissive layer of an OLED. These layers are generally referred to as hole transport layer (HTL), hole injection layers (HIL), hole collection (HCL), electron blocking layers (EBL) and/or interlayers.
- hole transport layers Various kinds of hole transport layers, hole injection layers, hole collection layers, and/or hole extraction layers can be used.
- hole transport layers of various kinds are described in the following references: 1) US Patent No.
- Hole transport layers can be added using, for example, spin casting, ink jetting, doctor blading, spray casting, dip coating, vapor depositing, or any other known deposition method.
- the HTLs can be formed as films from, for example, PEDOT, PEDOT/PSS or TBD, or NPB, or PLEXCORE® OC inks (Plextronics, Pittsburgh, PA).
- the thickness of the HTL or HIL layer can be, for example, from about a monolayer to about 10 nm or to about 300 nm thick, or from 30 nm to 60 nm, 60 nm to 100 nm, or 100 nm to 200 nm.
- the film then can be optionally dried and/or solvent and/or temperature treated and/or annealed at 110 to 200°C for 1 min to an hour, optionally in an inert atmosphere.
- Active layer thickness can be, for example, about 50 nm to about 250 nm, including for an OPV device.
- the active layer can be formulated from a mixture of n-type and p-type materials.
- the n- and p-type materials can be mixed in a ratio of, for example, from about 0.1 to 4.0 (p-type) to about 1 (n-type) based on a weight, or from about 1.1 to about 3.0 (p-type) to about 1 (n-type) or from about 1.1 to about 1.5 (p-type) to about 1 (n-type).
- the amount of each type of material or the ratio between the two types of components can be varied for the particular application.
- the active layer can be then deposited by spin casting, ink jetting, doctor blading, spray casting, dip coating, vapor depositing, or any other known deposition method, on top of the HTL or HIL film.
- the film is then optionally thermally annealed at, for example, about 40 to about 250°C, or from about 150 to 180°C, for about 10 min to an hour in an inert atmosphere.
- Solvent annealing can be also carried out as needed. Solvent annealing can be carried out at, for example, ambient temperature (for low boiling solvents).
- the film can be also optionally dried in solvent saturated and/or inert and/or vacuum atmosphere.
- the active layer can be also annealed with use of an electric field ("electric field annealing"). For example, a device can be cycled in an electric field which can in some instances improve performance.
- Internal heating may also contribute to electric field annealing.
- a cathode layer can be added to the device, generally using, for example, thermal evaporation of one or more metals. Also, solution processing can be used. For example, a 1 to 15 nm Ca layer is thermally evaporated onto the active layer through a shadow mask, followed by deposition of a 10 to 300 nm Al layer.
- a variety of layers can be included between the cathode and the active layer of a solar cell or the emissive layer of an OLED. These layers are generally referred to as electron transport layers (ETL), electron injection layers (EIL), hole blocking layers (HBL) and/or interlayers.
- ETL electron transport layers
- EIL electron injection layers
- HBL hole blocking layers
- interlayers interlayers
- an optional interlayer may be included between the active layer and the cathode, and/or between the HTL or HIL and the active layer.
- This interlayer can be, for example, from 0.5 nm to about 100 nm, or from about 1 to 3 nm, thick.
- the interlayer can comprise an electron conditioning, a hole blocking, or an extraction material, such as LiF, BCP, metal oxides, bathocuprine, fullerenes or fullerene derivatives, such as C60, C70, C84 and other fullerenes and fullerene derivatives discussed herein.
- Electron transport layers can be used in, for example, solar cell devices. See, for example, US patent application no. 61/116,963 filed November 21, 2008.
- Interfacial modification layers can be used as described in, for example, PCT/US2009/006236 filed November 20, 2009 (Plextronics, Inc.).
- the interfacial modification layer can comprise, for example, an organic semiconductor which is doped by, for example, a metal (e.g., BPhen:Yb).
- the interfacial modification layer can be prepared by vacuum deposition methods. It can have a thickness of, for example, 3 nm to 25 nm, or 5 nm to 15 nm.
- An Al layer can be disposed on top.
- the devices can be then encapsulated using a glass cover slip sealed with a curable glue, or in other epoxy or plastic coatings. Cavity glass with a
- getter/desiccant may also be used.
- the active layer can comprise additional ingredients including, for example, surfactants, dispersants, oxygen and water scavengers.
- the active layer can comprise multiple layers or be multi-layered.
- the active layer composition can be formed from an ink comprising a mixture as a film.
- Films and devices can be annealed before use and testing. Thermal/electrical annealing and solvent annealing can be carried out.
- Inverted solar cells can be made. See, for example, Chen et al. Advanced Materials, 2009, 21, 1-16. Tandem solar cells can be made.
- Known solar cell parameters can be measured including for example Jsc (mA/cm 2 ) and Voc (V) and fill factor (FF) and power conversion efficiency (%, PCE) by methods known in the art. See for example Hoppe article cited above and references cited therein.
- Oriel Solar Simulators can be used to determine PV properties including, for example, FF, Jsc, Voc, and efficiencies.
- the simulator can be calibrated by methods known in the art including, for example, calibration with a KG5-Si reference cell.
- External quantum efficiency (EQE) can be measured.
- Power conversion efficiency can be, for example, at least about 1%, or at least about 2%, or at least about 3%, or at least about 4%, or at least about 5%, or at least about 6%, or at least about 7%, or at least about 8%, or higher.
- Fill factor which can be expressed as a number between 0 and 1, or a percentage between 0 and 100%, can be, for example, at least about 0.4 (40%), or at least about 0.5 (50%), or at least about 0.6, or at least about 0.7, or at least about 0.8, or at least about 0.9 or higher.
- Open circuit voltage (Voc) in V can be, for example, at least about 0.3, or at least about 0.4, or at least about 0.5, or at least about 0.6 V, or at least about 0.7 V, or at least about 0.8 V, or at least about 0.9 V, or at least about 1.0 V, or at least about 1.1 V, or at least about 1.2 V, or at least about 1.3 V, or higher.
- Short circuit current can be, for example, at least about 0.5, or at least about 0.6, or at least about 0.7, or at least about 0.8, or at least about 0.9, or at least about 1.0, or at least about 2.0, or at least about 3.0, or at least about 4.0, or at least about 5.0, or at least about 10.0, or higher (mA/cm 2 ).
- EH energy harvesting
- Photovoltaic technology whereby an EH device harnesses ambient light, typically fluorescent office lighting, for energy storage or direct use for a wide variety of low power applications.
- a typical office environment can have light levels of about 1000 LUX, or about 0.5% (0.5 mW/cm 2) of the incident radiant energy of 1 sun. This represents the total amount of energy that can be harvested in these environments and high efficiency photovoltaic technology, suited to these light levels are important for leveraging novel applications and can be a replacement for coin- cell batteries (or equivalent).
- Typical outdoor solar technology such as mc-Si c-Si, have low performance at indoor lighting levels due to a high amount of Voltage loss.
- Organic PV and a-Si are well suited to low light levels and OPV can be a more cost effective solution vs. a-Si and thus can be used in EH technology.
- Polymers can be designed to exhibit a 'flat' response with decreasing light levels and represent a novel high-performance technology of indoor EH applications.
- Typical device stacks for EH applications are very similar to their outdoor solar analogs and a typical configuration is ITO/ZnO/conjugated
- Devices can be tested at 1000 LUX and one can determine the power density at this standard luminance level.
- one can measure devices at a variety of light intensities to understand how device parameters change with changes in ambient light level.
- One can also measure leakage current at reverse bias to help understand the diode quality as poor diode quality can result in lower performance at lower and lower light levels.
- organic photodetection is an application of PV technology where a circuit can be controlled by the presence or absence of radiant energy impinging on the said circuit, which contains a photosensitive device.
- OPD organic photodetection
- the use of organic photodetectors offers an advantage of cost and integration that may not be possible with incumbent technology, namely a-Si.
- OPD devices can be fabricated very similarly to a solar OPV device and a typical configuration is: ITO/HTL/conjugated polymer: Fullerene n-type/Cathode, where the cathode can be Ca/AI, or organic small molecule, doped with a metal, or organic material and capped with a metal such as Aluminum.
- OLED devices operate in quadrant II, OPVs in quadrant IV and OPDs in quadrant III.
- Parameter #1 is proportional to the quantum efficiency of the device and devices which are most efficient at generating current with the input radiant energy are best.
- device design is necessary to reduce the leakage current (or noise floor) and the photoactive layer materials should have as low a carrier density in the off state as possible, ie not doped. Materials described herein can offer high quantum efficiency, low doping due to deep HOMO, and air processibility that is amenable to rapid OPD device development.
- thieno[3,2-b]thiophene (7.5 g, 54 mmol) was dissolved in tetrahydrofuran (1 L). After the solution was cooled to -78°C using an isopropanol/dry ice bath, i-BuLi (100 ml_, 170 mmol) was transferred by cannula to the addition funnel. The organolithium reagent was then added dropwise. After completion of the addition, the mixture was stirred for 20 min at -78°C then warmed up with an isopropanol bath at room temperature for 30 minutes during which a yellow precipitate formed.
- Thiophene-2-bromo-3-carboxylic acid (10 g, 45 mmol) was placed in a dry 3- neck round bottom flask equipped with an argon inlet and a water condenser. Dry methanol (100 mL) was added to the flask along with a catalytic amount of cc.
- the starting compound (530 mg, 0.49 mmol) was dissolved in THF (150 mL) in a dry schlenk flask. The solution was cooled to -78°C and ter-butyllithium (0.87 mL of 1.7 M solution, 1.5 mmol) was added dropwise via syringe. After completion of the addition, the mixture was stirred 60 min at -78°C the 15 minutes at room temperature (using IPA bath at RT) during which the solution turned from orange to dark brown-orange. The solution was cooled back at -78°C, and trimethyltin chloride (2 mL of 1M solution in THF, 2 mmol) was added dropwise.
- the mixture is warmed to room temperature following completion of the addition and stirred at that temperature for 30 minutes then was poured into ice-cold water.
- the aqueous phase was further extracted with hexane.
- the combined organic phase were combined and washed with cold water then dried with magnesium sulfate. After filtration, the solvent was evaporated under vacuum to yield an orange solid.
- the product was purified by precipitation of a chloroform solution into methanol followed by filtration (540 mg, 78%).
- Example 7 Synthesis of Donor-Acceptor random copolymer based on 5,5,10,10- tetrakis(4-(2-ethylhexyl)phenyl)-3,5,8,10-tetrahydro-cyclopenta[l,2--3 ⁇ 45,4-
- the V oc for this material was 0.72 V. See Table I.
- HOMO level (AC2, eV) was 5.15.
- HOMO level for BPP-1 was 5.31 eV.
- Example 8 Synthesis of Donor-Acceptor random copolymer based on 5,5,10,10- tetrakis(4-(2-ethylhexyl)phenyl)-3,5,8,10-tetrahydro-cyclopenta[l,2-/7:5,4- Tjdithiophene[2 , ,l , :4,5]thieno[2,3-o]thiophene and 5,5'-bis(2-ethylhexyl)-4 ,4' [l ⁇ '-bithienoCS ⁇ -cJpyrrolel ⁇ G ⁇ 'CS ⁇ S' ⁇ -tetraone
- the reaction flask was removed from the glove box and 10 mL of deoxygenated chlorobenzene were added via syringe. The mixture was evacuated and refilled with argon five times. The reaction flask was immersed into a 110°C oil bath and left stirring under an argon stream for 2 days. After cooling to room temperature, 40 ml_ of methanol were added to the reaction mixture. The polymer was collected via filtration and purified by consecutive Soxhlet extractions in sequence with methanol, MTBE, hexane, and chloroform. The chloroform solution was passed through celite to remove catalyst residuals, and solvent was removed under vacuum to yield polymer.
- HIL A is an HIL ink formulation comprising 96.860 parts water; 2.826 parts
- the flask was removed from a glove box, connected to a vac/argon line, and the side arm was flushed with five vacuum-argon cycles, after which the flask was open to argon.
- the flask was purged five times with argon, and immersed into a preheated to 110°C flask for 48 hours. After cooling, methanol was added to precipitate the polymer.
- the polymer was filtered through Soxhiet thimble and Soxhiet extraction was performed in sequence with methanol, MTBE, hexane and chloroform.
- Figure 1 compares the polymer of Example 8 with a competitive polymer APP-1 which does not comprise structure (I).
- PV2000 materials are available from Plextronics, Inc. (Pittsburgh, PA).
- the flask is evacuated and backfilled with nitrogen 3 times.
- Dry CH2CI2 is added to the flask via cannula.
- the solution is bubbled with nitrogen for 15 minutes.
- the solution is then cooled to 5 °C and BF 3 -Et 2 0 (1.1 eq.) is added.
- DDQ (leq.) is added in increments over 30 minutes.
- the reaction is monitored by TLC and more DDQ is added if reaction is not complete.
- 61 e.g., diketobenzene analogues
Abstract
Materials for organic electronic devices including organic photovoltaic devices. An oligomer or polymer comprising: wherein R1, R2, R3, and R4 are independently hydrogen or solubilizing groups. Monomers and ink compositions can be also prepared. The materials can be used in an OPV active layer and show excellent absorption properties with bathochromic shift.
Description
ORGANIC ELECTRONIC DEVICES, INCLUDING ORGANIC PHOTOVOLTAIC DEVICES,
POLYMERS, AND MONOMERS
RELATED APPLICATIONS
This application claims priority to US provisional application serial no.
61/407,419 filed October 27, 2010, which is hereby incorporated by reference in its entirety.
INTRODUCTION
A need exists to provide better electronic and photonic devices including better solar cells or photovoltaic devices. If some aspects of the devices are based on organic materials, including organic polymers, cost reduction can be achieved.
In particular, a need exists to provide better active layers for organic photovoltaic devices. These active layers can comprise a combination of p-type material and n-type material. The p-type material can be a conjugated polymer. The polymer ideally should satisfy a variety of chemico-physical properties, such as solubility, processability, good film formation, proper absorption properties, proper HOMO/LUMO (molecular orbitals and energy levels), bandgap, charge carrier mobility, and other properties. However, achievement of combinations of properties can be difficult, and gaining one property may result in the sacrifice of another.
For a review of organic photovoltaic technology, see, for example, Sun and Saraciftci (Eds.), Organic Photovoltaics, Mechanisms, Materials, and Devices, CRC, 2005.
SUMMARY
Embodiments provided herein include, for example, compositions, devices, and methods of making and using the same. Compositions include, for example, monomer, oligomer, and polymer compositions, as well as ink formulations.
Compositions also can include those prepared by particular processes. Devices include organic electronic devices including photovoltaic and/or solar cell devices including modules and devices which comprise a plurality of photovoltaic and/or solar cell devices. Coated substrates can be prepared, wherein the substrate is rigid or flexible.
an oligomer or polymer comprising:
wherein RI, R2, R3, and R4 are independently hydrogen or solubilizing groups.
In one embodiment, Ri, R2, R3, and R4 are the same group. In one embodiment, Ri, R2, R3, and R4 are the same group and comprise an aromatic group. In one embodiment, Ri, R2, R3, and R4 are the same group and comprise an arylalkyi group. In one embodiment, Ri, R2, R3, and R are the same group and are a Ci - C25 group. In one embodiment, the polymer is present having a molecular weight of at least 10,000 number average molecular weight. In one embodiment, the oligomer or polymer is a donor-acceptor oligomer or polymer. In one
embodiment, the oligomer or polymer is a donor-acceptor polymer, and has at least two types of donors, or at least two types of acceptors. In one embodiment, the oligomer or polymer is soluble in chloroform, chlorobenzene, dichlorobenzene, or trichlorobenzene. In one embodiment, polymer is present and has a molecular weight of at least 10,000 number average molecular weight and is soluble in chloroform, chlorobenzene, dichlorobenzene, or trichlorobenzene.
Another embodiment provides at least one oligomer or polymer comprising at
wherein Ri, R2, R3, and R4 are, optionally, the same group and are a Ci - C25 group.
A monomer is also provided to provide the repeat unit in (I), wherein the monomer can comprise a structure (II):
wherein the end terminal rings are adapted for polymerization, and wherein Ri, R2, R3, and R4 an embodiment as described herein.
For example, in one embodiment, Ri, R2, R3, and R4 are the same group. In one embodiment, Ri, R2, R3, and R4 are the same group and comprise an aromatic group. In one embodiment, Ri, R2, R3, and R4 are the same group and comprise an arylalkyl group. In one embodiment, Ri, R2, R3, and R^ are the same group and are a d - C25 group. In one embodiment, the monomer is functionalized with electrophilic groups for polymerization. In one embodiment, the monomer is functionalized with nucleophilic groups for polymerization. In one embodiment, the monomer is functionalized with groups comprising metal, such as for example tin, for polymerization. In one embodiment, the monomer is functionalized for cross coupling polymerization, including palladium cross coupling polymerization. In one embodiment, the monomer is functionalized for Ullman, Yamamoto, or Suzuki polymerization. In one embodiment, the terminal thiophene rings are functionalized for polymerization. The monomer can be used with one or more other comonomers to form polymers comprising (I).
Another embodiment provides an ink composition comprising at least one
wherein RI, R2, R3, and R4 are independently hydrogen or solubilizing groups; and at least one solvent.
In one embodiment, Ri, R2, R3, and R4 are the same group. In one
embodiment, Ri, R2, R3, and R4 are the same group and comprise an aromatic group. In one embodiment, Ri, R2, R3, and R^ are the same group and comprise an arylalkyi group. In one embodiment, i, R2, R3, and R^ are the same group and are a Ci - C25 group. In one embodiment, the oligomer or polymer is a polymer having a molecular weight of at least 10,000 number average molecular weight. In one embodiment, the oligomer or polymer is a donor-acceptor oligomer or polymer. In one embodiment, the oligomer or polymer is a donor-acceptor polymer, and has at least two types of donors, or at least two types of acceptors. In one embodiment, the solvent comprises at least two solvents, optionally halogenated solvents, and the ink composition further comprises at least one additive. In one embodiment, the solvent comprises a mixture comprising at least orthodichlorobenzene and
trichlorobenzene.
Another embodiment provides an OPV device comprising at least one OPV active layer comprising at least one polymer comprising:
wherein Ri, R2, R3, and R4 are independently hydrogen or solubilizing groups.
In one embodiment, Ri, R2, R3, and R^ are the same group. In one embodiment, Ri, R2, R3, and R^ are the same group and comprise an aromatic group. In one embodiment, Ri, R2, R3, and R4 are the same group and comprise an arylalkyi group. In one embodiment, Ri, R2, R3, and R4 are the same group and are a Ci - C25 group. In one embodiment, the polymer has a molecular weight of at least 10,000 number average molecular weight. In one embodiment, the polymer is a donor-acceptor polymer. In one embodiment, the polymer is a donor-acceptor polymer, and has at least two types of donors, or at least two types of acceptors. In one embodiment, the device comprises at least one polythiophene a hole transport
layer. In one embodiment, the active layer further comprises at least one n-type material.
Another embodiment provides a coated substrate comprising at least one substrate and at least one coating, wherein the coating comprises at least one polymer comprising:
wherein i, R2, R3, and R4 are independently hydrogen or solubilizing groups.
In one embodiment, Ri, R2, R3, and R are the same group. In one embodiment, R^ R2, R3, and R4 are the same group and comprise an aromatic group. In one embodiment, Ri, R2, R3, and R4 are the same group and comprise an arylalkyl group. In one embodiment, Rj, R2, R3, and R^ are the same group and are a Ci - C25 group. In one embodiment, the polymer has a molecular weight of at least 10,000 number average molecular weight. In one embodiment, the polymer is a donor-acceptor polymer. In one embodiment, the polymer is a donor-acceptor polymer, and has at least two types of donors, or at least two types of acceptors. In one embodiment, the substrate is a flexible substrate. In one embodiment, the substrate comprises a hole transporting layer next to the coating.
Another embodiment provides a method comprising: functionalize at least one thieno[3,2-b]thiophene compound with two reactive functional groups, one reactive group on each thiophene ring to provide a compound I; provide at least one thiophene compound comprising a leaving group at the 2-position and a carboxylate at the 3-position to provide a compound II; react compound I and compound II to produce compound III which is a compound comprising a central thieno[3,2- •bjthiophene moiety linked to opposing thiophene rings; react compound III so that carboxylate groups are converted to hydroxyl groups to provide compound IV; react compound IV in a ring closure reaction to provide at least one compound
represented by (II) which is compound V:
optionally, functionalize compound V to have two polymerization groups and provide compound VI. In one embodiment, the optional functionalization step to provide compound VI is carried out. The R groups in (II) can be Rl, R2, R3, or R4 as in (I).
Another embodiment provides a method comprising: providing a monomer comprising a moiety represented by:
wherein Ri, R2, R3, and R4 are independently hydrogen or solubilizing groups; and polymerizing the monomer.
Another embodiment provides a composition comprising at least one donor- acceptor polymer comprising:
wherein Ri, R2, R3, and R4 are independently hydrogen or solubilizing groups.
At least one advantage for at least one embodiment is ability to make high mobility polymers.
At least one additional advantage for at least one embodiment is to have relatively high efficiency photovoltaic devices.
At least one additional advantage is ability to solubilize the polymers via four side groups R1-R4.
At least one additional advantage for at least one embodiment is to have polymers with bathochromic absorption profiles and sharp band edges.
At least one additional advantage is ability to control the HOMO to a desired level (e.g., weaker donor) so good matching can occur between donor(s) and acceptor(s).
BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 illustrates external quantum efficiency (eqe) data for several polymers.
Figure 2 illustrates reverse bias data for several polymers.
Figure 3 illustrates external quantum efficiency (eqe) data for several polymers.
DETAILED DESCRIPTION
INTRODUCTION
All references cited herein are incorporated by reference in their entirety.
Priority US regular application serial no. 12/874,163 filed September 1, 2010 is hereby incorporated by reference in its entirety. Embodiments described therein can be excluded from the claim scope, in particular embodiments describing compositions and devices based on the following moiety:
For example, one first excluded embodiment is: a device comprising: at least one cathode; at least one anode; at least one photovoltaic active layer disposed between the cathode and anode and comprising at least one p-type material and at
least one n-type material, wherein the p-type material comprises at least one polymer comprising a backbone moiety:
wherein the polymer comprises:
wherein Rl, R2, R3, and R4 are independently hydrogen or solubilizing groups.
In addition, one second excluded embodiment is: a monomer, oligomer, or polymer comprising:
wherein Rl, R2, R3, and R4 are independently hydrogen or solubilizing groups.
In addition, one third excluded embodiment is: a composition comprising at least one donor-acceptor polymer comprising:
wherein RI, R2, R3, and R4 are independently hydrogen or solubilizing groups.
In addition, a fourth excluded embodiment is: an ink composition comprising at least one oligomer, or polymer comprising:
wherein RI, R2, R3, and R4 are independently hydrogen or solubilizing groups.
US regular application serial no. 12/874,137 filed September 1, 2010 is hereby incorporated by reference in its entirety.
US regular application serial no. 12/828,121 filed June 30, 2010 is hereby incorporated by reference in its entirety.
US regular application serial no. 12/371,556 filed February 13, 2009 is hereby incorporated by reference in its entirety.
PCT applications serial nos. PCT/US2010/037802 and PCT/US2010/037805, each filed June 8, 2010, are hereby incorporated by reference in their entireties.
Low band gap materials are known in the art. See, for example, Blouin et al., Accounts of Chemical Research, 1110-1119, September 2008, 41, 9.
Polymer solar cells are known in the art. See, for example, Chen et al., Advanced Materials, 2009, 21, 1-16; Hoppe, Adv. Polym. So'., 2008, 214, 1-86;
Gunes et al., Chem. Rev., 2007, 107, 1324-1338. See also, for example, organic photovoltaic technologies described in, for example, a series of articles in Accounts of Chemical Research, 42, 11, November 2009, including Zhu et al. (1779-1787); Bredas et al. (1691-1699); Chen et al. (1709-1718); Heremans et al. (1740-1747);
Nelson et al. (1768-1778); Peet et al. (1700-1708); Potscavage et al. (1758-1767); Roncali (1719-1730).
Organic semiconductors including arylamines and TPD are known in the art.
See, for example, Walzer et al., Chem. Rev., 2007, 107, 1233-1271.
One exemplary embodiment provides compositions comprising at least one conjugated copolymer, wherein the copolymer backbone comprises at least one donor moiety and at least one acceptor moiety, and wherein the copolymer has at least two high extinction coefficient chromophores thereby covering the high photon flux portion of the solar spectrum which is from about 400-1000 nm and centered at about 750-800 nm. Broad absorption is desired including up to the near-infrared region. Vibronic structure can be detected.
For all structures shown herein, for monomers, oligomers, and polymers, the side groups can be adapted to be solubilizing groups as described further herein.
An oligomer can have a number of repeat units of six or less.
PART ONE: POLYMERS. OLIGOMERS. MONOMERS
One embodiment provides an oligomer or polymer comprising:
wherein Ri, R2, R3, and R4 are independently hydrogen or solubilizing groups.
An important aspect of oligomers and polymers which comprise (I) is that they are sufficiently soluble so that inks can be formed and solution processing can be achieved. Solubility can be examined in organic or aqueous solvents. One skilled in the art can adapt the R group and other parts of the polymer chain and side groups, as well as molecular weight, to generate sufficient solubility. Organic solvents can be, for example, halogenated and non-halogenated solvents. The solvent can be a single solvent or a mixture of solvents. An example of halogenated solvent is ortho-dichlorobenzene, and this solvent can be used to measure solubility. Solubility can be measured at 25°C. Solubility can be, for example, at least 1
mg/mL, or at least 20 mg/mL. In some embodiments, solubility can be adapted to provide good bulk heterojunction (BHJ) layer morphology. Higher molecular weight may be preferred to modulate solubility, and molecular weight can be used with other formulation strategies including additives to modulate solubility and/or BHJ formation. In addition, polymers can be both soluble and also functionally dispersible in a solvent so that solution processing can be achieved, whether or not a true solution is formed.
The R groups in (I) can be adapted to facilitate or provide solubility. The R groups can also be adapted to provide desired electronic properties. The R groups can be also adapted to provide steric and molecular stacking properties.
The atom in the R groups bonding to the polymer chain can be, for example, carbon.
For example, the R groups can be optionally substituted alkyl, optionally substituted linear alkyl, optionally substituted branched alkyl, optionally substituted aryl, optionally substituted alkylaryl, optionally substituted arylalkyl, optionally substituted alkoxy, or optionally substituted aryloxy. The R group can have, for example, 3-30 carbons, or 4-25 carbons, or 5-15 carbons. Examples include butyl, octyl and dodecyl, as well as ethylhexyl. Different R groups can be used in the same polymer as needed. The R group can be chiral. The R group can be functionalized or substituted as desired. Examples of substituents include amino, carboxylic acid, ester, halogen (including fluoro and chloro), pseudohalogen (e.g., cyano), and other functional groups known in the art.
The R groups can comprise a heteroatom, such as oxygen or nitrogen in the carbon chain (e.g., ether or amino linkages, respectively). The R group can comprise C1-C20 alkoxy, or C1-C20 alkyleneoxy, for example. The R group can be an oligoether, such as, for example, alkoxyalkoxy or alkoxyalkoxyalkoxy, such as, for example, methoxyethoxyethoxy.
The polymer comprising structure (I) can be free of protecting groups, and in particular the R groups can be free of protecting groups.
The R groups can be adapted to modulate or tune the LUMO, including provide a decreasing or increasing LUMO, or provide better solid state packing, or provide improved charge transport, and/or provide environmental stability. For
example, the R group can be halogenated including comprise a group comprising chlorine or fluorine. The R group can be, for example, perfluorinated. The R group can be, for example, a perfluoroalkyl group such as, for example, -C3F7. The R group can be, for example, a perfluoroarylgroup, such as, for example, -C6F5. For use of halogenated substituent groups to modulate LUMO and solid state packing, see, for example, Schmidt et al., J. Am. Chem. Soc, 2009, 131, 6215-6228.
A particular oligomer or polymer could comprise two or more different structures (I).
Polymer comprising (I) can be a random copolymer or a regular alternating copolymer. Polymer comprising (I) can comprise multiple repeat moieties.
Moieties in the polymer chain can provide for carbon-carbon bonding with conjugation, and, in addition, can provide charge transport.
Polymer side groups can provide electron withdrawing or electron accepting character, and the strength of this can be varied, e.g., weak or strong, or from weak to strong. Push-pull electronic effects can be produced. Electron donating side groups can be also used as appropriate.
Polymer side groups can be protected or deprotected. For example, butyloxycarbonyl (BOC) can be used to protect amino side groups. However, an embodiment comprises the polymer being totally free of protecting groups.
Block copolymers can be prepared. Either all blocks can be embodiments as described herein, or only a subset of block(s) can be embodiments described herein. For example, a block copolymer could comprise both a conjugated polymer block and a non-conjugated polymer block, or both a donor-acceptor block, and a non- donor-acceptor block. Also, block copolymers can be prepared comprising blocks of different donors and acceptors, e.g., (Dl-Al)-b-(Dl-A2), and the like.
In one embodiment, the polymer comprises a number average molecular weight, Mn, of at least 6,000 g/mol, or of at least 7,500 g/mol, or at least 10,000. In another embodiment, the polymer comprises a number average molecular weight, Mn, of at least 20,000, or at least 30,000, or at least 40,000, or at least 50,000.
In particularly preferred examples, Ri, R2, R3, and R4 can be, independently, Ci-C25 optionally substituted alkyl, aryl, alkylaryl, or arylalkyl. Examples include phenyl, wherein the phenyl is optionally further substituted at the 4 position with, for
example, an alkyl group such as, for example, a branched group such as, for example, ethylhexyl. In one embodiment, the R groups in (I) are the same.
A monomer is also provided to provide this repeat unit (I). The monomer can comprise, for example, structure (II) which can be adapted to have two or more n through the terminal rings:
The R groups shown in (II) can be as described for the R groups in structure
(I).
The oligomer or polymer comprise one or more of the repeat unit (I).
The oligomer or polymer can comprise a donor-acceptor structure. Structure (I) can be a donor. The polymer can comprise one or more donors, including (I), and/or one or more acceptors. The polymer can comprise only two donors and acceptors, or only three donors and acceptors, or at least two or at least three donors and acceptors. The R groups can be selected to provide a higher amount of symmetry.
Particular examples of polymers include:
Other examples of polymer structures, including donor acceptor polymers, comprising (I) are shown in the Appendix A. The side groups in the polymers of Appendix A can be tailored for solubility, stacking and morphology, and electronic interactions.
SILOLE
In addition, monomers, oligomers, and polymers can be prepared with comprise a silole moiety represented by (III):
wherein Ri, R2/ R3, and R4 are independently hydrogen or solubilizing groups. For example, R^ R2, R3, and R4 can be, independently, C C25 optionally substituted alkyl, aryl, alkylaryl, or arylalkyl. Examples include phenyl, wherein the phenyl is optionally further substituted at the 4 position with, for example, an alkyl group such as, for example, a branched group such as, for example, ethylhexyl. In one embodiment, the R groups in (I) are the same.
The silole structure can be also shown as in (IIIB) where the linkages into the polymer chain are not shown at the end:
The terminal thiophene rings can be adapted to include functionalities for polymerization.
More generally, the structure can be:
where X is C or Si for example.
DONORS AND OTHER ACCEPTORS
In addition to structure (I), a variety of donors, or donor moieties, are known in the art. Appendix B illustrates an exemplary listing of donor structures which can be used. The structures shown in Appendix B can be used in monomers, dimers, trimers, oligomers, and polymers. The side group can be varied and is not limited by side groups shown structure in Appendix B. For example, the side groups in the donor structures of Appendix B can be tailored for solubility, stacking and
morphology, and electronic interactions. In Appendix B, the representation of -R or
R- means a linkage site for a reactive group, or a linkage site for linking into another moiety like a dimer, trimer, oligomer, or polymer. Illustration of two of these sites means the moiety can be bivalently linked to another moiety including a polymer chain.
In addition, a variety of acceptors, or acceptor moieties, can be used.
Examples include but are not limited to those shown in Appendix C. The structures shown in Appendix C can be used in monomers, dimers, trimers, oligomers, and polymers. The side group can be varied and is not limited by shown structure in Appendix C. For example, the side groups in the structures of Appendix C can be tailored for solubility, stacking and morphology, and electronic interactions. In Appendix C, the representation of -R or R- means a linkage site for a reactive group, or a linkage site for, after reaction, linking into another moiety like a dimer, trimer, oligomer, or polymer. Two of these sites means the moiety can be bivalently linked to another moiety including a polymer chain.
Acceptors are particularly important if they have one or more carbonyl groups which can interact with a thiophene ring in (I).
An example of an acceptor is the diketopyrroleopyrrole-based acceptor moiety. See, for example, Zhou et al., Chemistry of Materials, 2009, "Synthesis and Photovoltaic Properties of Diketopyrrolopyrrole-Based Donor-Acceptor Complexes."
For a single polymer, more than one donor can be used: e.g., Dl, D2, D3, and the like. In addition, for a single polymer, more than one acceptor can be used: e.g., Al, A2, A3, and the like.
Polymers can comprise Dl-Al moieties, D2-A2 moieties, D3-A3 moieties, and the like, as well as their intermixed moieties, such as, for example, D1-A2, and the like.
Use of more than one donor or acceptor can provide broader and/or stronger absorption bands and/or vibronic structures.
Spacer moieties can be used as desired.
EMBODIMENTS FOR COPOLYMER ARCHITECTURE BASED ON Dl, D2, Al, AND A2 The following chart shows different, exemplary embodiments for copolymer architecture with different donors, Dl and D2 donors, and different acceptors, Al
and A2 acceptors. The Chart I shows examples which are different from the -[D-A]- alternating formula seen in the prior art.
-|m— ina— ^j-
Chart l
The acceptors, Al, A2, or both can comprise the acceptors listed in Appendix
C.
The donors can be selected from the structure (I) and those listed in
Appendix B, for example.
The structures shown in Chart I can be extended to further include additional donors, e.g., D3, D4, D5, and the like, or additional acceptors, e.g., A3, A4, A5, or the like.
RATIO OF DONOR AND ACCEPTOR
The molar ratio of donor and acceptor can be one, less than one, or more than one. In calculating this ratio, there can be a single donor and/or a single acceptor, or there can be more than one donor and/or more than one acceptor. In other words, the polymer does not need to comprise equal molar amounts of donor and acceptor. The polymer can comprise more donor than acceptor, or more acceptor than donor. Chart I shows examples of this. For example, the ratio can be 2:1. Also, the ratio of different donors and acceptors within the polymer does not need to comprise equal molar amounts, e.g., the total ratio of donor and acceptor
moieties in the polymer can be one where donor comprises a sum of different ratios of Dl and D2, and the like, and/or acceptor comprises a sum of different ratios of Al, A2, and the like. In other words, the ratio of the molar amounts of Dl and D2 does not have to be one, and the ratio of the molar amounts of Al and A2 does not have to be one.
RANDOM OR ALTERNA NG COPOLYMERS
Different copolymer microstructures can be prepared as known to those skilled in the polymer chemistry arts. For example, random copolymer structures can be produced. Mixed monomer polymerization can be carried out. Non-random copolymer structures can be produced.
For the random copolymer embodiment, one can use an appropriate synthetic sequence to obtain good materials. Synthetic approaches include, for example, Kumada, Suzuki, Negishi or Stille couplings for polymerization. See, for example (a) Cross-Coupling Reactions: A Practical Guide, Ed. Miyaura, 2002; (b) Handbook of Organopalladium Chemistry for Organic Synthesis, Ed. Negishi, 2002; (c) Kuwano et al., J. Org. Chem., 2002, 67, 6479-6486; (d) Yu et al. J. Am. Chem. Soc. 2009, 131, 56; (e) Hou et al., Macromolecules, 2008 , 41 (16), 6012-6018; (f) Blouin et al., J. Am. Chem. Soc. 2008 130 (2), 732-742; (g) Swager et al. Adv. Mater. 2001, 13, 1775; (h) Koeckelberghs et al. Macromolecules. 2007, 40, 4173; (i) High- Efficient-Low-Cost Photovoltaics, Springer Verlag Berlin Heidelberg, 2009, Eds:
Petrova-Kock, V.; Goetzberger, A., 195-222. Also, Ullman and Yamamoto coupling or polymerization can be used.
One embodiment provides for preparing high purity intermediates, such as trimers.
Regular alternating copolymer structures can be produced. Chart I shows examples of this.
POLYMER PROPERTCES/CHROMOPHORE/ABSORPTION SPECTRA
Polymer properties can be adapted to provide the good photovoltaic properties and to follow the design rules noted herein.
Lambda max can be, for example, greater than 600 nm.
Absorption edge can be extended into the red region. The absorption edge can comprise a sharp edge.
Absorption spectra are important parameters for the polymers, particularly for photovoltaic applications. It is known to record absorption spectra, including UV-Vis absorption spectra, for conjugated polymers. See, for example, Brown et al., Phys. Rev. B, 67, 064203 (2003) (describing spectra for different kinds of polythiophenes).
INTRAMOLECULAR NON-COVALENT INTERACTIONS INCLUDING CARBONYL
INTERACTION WITH THIOPHENE SULFUR
A variety of intramolecular non-covalent interactions, such as electrostatic, coulombic, hydrogen bonding or chelates can be used to provide increased rigidity and/or planarity to the polymer chain and its chromophores, although various embodiments described herein are not necessarily limited by theory. Increased rigidity can be used to increase the likelihood for a well behaved excited state and lead to good excitonic diffusion distances and minimization of energy loss pathways from excited state (e.g., charge trapping, polaronic quenching, excited state deactivation, or even localization). Absorption profiling can be used to examine such features.
In particular, while various embodiments described herein are not necessarily limited by theory, it is believed that for at least some embodiments, when a thiophene ring such as the terminal thiophene rings in (I) is covalently linked to a moiety which has appropriately spaced carbonyl groups, the carbonyl groups can interact with thiophene sulfur. The carbonyl oxygen is negatively charged compared to the thiophene sulfur which is relatively positively charged. This can provide planarization and/or increase rigidity in the backbone and improve performance. The interactions can be measured by methods known in the art including, for example, x-ray or NOE (Nuclear Overhauser Effect). See, for example, Pomerantz et al., Synthetic Metals, 2003, 135-136, 257-258; Pomerantz et al., Tetrahedron Letters, 2003, 44(8), 1563-1565; and Pomerantz et al., Tetrahedron Letters, 40, 1999, 3317-3320. Also, for sulfur-oxygen interactions, see, for example, Turbiez et al., Chem.-Eur. J. 2005, 11, 3742-3752.; and Apperloo et al., J. L. Chem.-Eur. J. 2002, 8, 2384-2396.
Donor-Acceptor polymers comprising diketo types of structures, such as dioxypyrrolo-functionality, can provide intramolecular interactions as a "design rule" for the synthesis of new materials for application in organic electronics, such as OPVs, achieving unexpected performances.
The thiophene ring can be part of an isolated thiophene moiety or a fused ring thiophene moiety such as the thiophene found in (I) or in benzodithiophene.
Other embodiment relate to methods of making the monomers, oligomers, and polymers.
Monomers and polymerizations for monomers comprising (I) or (II) can be carried out including the embodiments shown in the working examples.
For example, one embodiment provides a method comprising:
(a) In a first step, functionalize at least one thieno[3,2-b]thiophene compound with two reactive functional groups, one reactive group on each thiophene ring to provide a compound I. Example 1 in the working examples provides an example of this step. For example, reactive functional groups can be, for example, trimethyltin.
(b) In another step, provide at least one thiophene compound comprising a leaving group at the 2-position and a carboxylate at the 3-position to provide a compound II. Example 2 in the working examples provides an example of this step. A carboxylic acid moiety can be converted to a carboxylate moiety.
(c) In another step, react compound I and compound II to produce
compound III which is a compound comprising a central thieno[3,2-b]thiophene moiety linked to opposing thiophene rings. Example 3 in the working examples provides an example of this step.
(d) In another step, react compound III so that carboxylate groups are converted to hydroxyl groups to provide compound IV. Example 4 in the working examples provides an example of this step.
(e) In another step, react compound IV in a ring closure reaction to provide at least one compound represented by (II) which is compound V:
Example 5 in the working examples provides an example of this step.
(f) Optionally, in a subsequent step, functionalize compound V to have two polymerization groups and provide compound VI. Example 6 in the working examples provides an example of this step. In one embodiment, the optional functionalization step to provide compound VI is carried out.
PART II: USES. INKS. AND DEVICES
The materials, monomers, dinners, trimers, oligomers, polymers, and copolymers described herein in Part I, the working examples, and claims, can be used in organic electronic devices including, for example, OLEDs, OPVs including as OPV active layer, transistors, OFETs, batteries, and printed electronics generally, as well as sensors. The methods described in Part II can be adapted for the particular compounds and polymers being used.
For example, photovoltaic cells (solar cells) are known in the art. See, for example, Sun and Sariciftci, Organic Photovoltaics, Mechanisms, Materials, and Devices, 2005. The photovoltaic cell can comprise an active layer comprising a composition comprising at least one p-type material and at least one n-type material. One can engineer HOMO, LUMO, and band gaps for the p- and n-type materials for good performance. The morphology of the active layer can be adapted to provide good performance. For example, a nanoscale morphology can be prepared. An example is a bulk heterojunction. Bilayers can be made as described in, for example, Ayzner et al., J. Phys. Chem. C, 2009, 113, 20050-20060 (e.g., describing all solution-processed bilayers in solar cells).
The photovoltaic device can comprise at least one cathode, at least one anode, and at least one photovoltaic active layer disposed between the cathode and anode. The active layer can comprise a p-type material and an n-type material.
In an OPV active layer, the polymers described herein, which can be a p-type material, can be combined with n-type materials or acceptor moieties, such as, for example, fullerenes and fullerene derivatives. An example of a fullerene derivative is PCBM. Fullerenes can be also derivatized, as described in, for example, PCT Patent Publication WO 2008/018931 filed May 2, 2007 and US Patent Publication
2008/0319207 published December 25, 2008, both to Laird, etal. (Plextronics, Inc.). Other types of n-type materials known in the art can be used. If desired, larger area photovoltaics can be fabricated. See, for example, Bundgaard et al., Solar Energy Materials and Solar Cells, 2007, 91, 1019-1025.
Polymer solar cells, including polymer fullerene solar cells, are described in, for example, Hoppe et al., Adv. Polym. Sci. (2008), 214: 1-86; Zhu et al., "Design Rules for Efficient Organic Solar Cells," Chapter 13, 195-222 in High-Efficient Low- Cost Photovoltaics, Springer, 2009.
OLED devices are known in the art including white OLEDs, or WOLEDs. See, for example, Li and Meng, Organic Light Emitting Materials and Devices, CRC Taylor, 2006 and US Patent Publication 2006/0078761 published April 13, 2006. The devices can comprise, for example, multi-layer structures including, for example, an anode, including a transparent conductor, such as a transparent conductive oxide (TCO) on glass or PET or PEN; a hole injection layer; an electroluminescent layer, such as a polymer layer; a conditioning layer, such as LiF, and a cathode, such as for example Ca, Al, or Ba.
Methods known in the art can be used to fabricate organic electronic devices including for example OLED devices. Methods known in the art can be used to measure brightness, efficiency, and lifetimes. OLED patents include for example US Patent Nos. 4,356,429 and 4,539,507 (Kodak). Conducting polymers which emit light are described in for example US Patent Nos. 5,247,190 and 5,401,827
(Cambridge Display Technologies). See also Kraft et al., "Electroluminescent Conjugated Polymers - Seeing Polymers in a New Light," Angew. Chem. Int. Ed., 1998, 37, 402-428, including device architecture, physical principles, solution processing, multilayering, blends, and materials synthesis and formulation, which is hereby incorporated by reference in its entirety.
In addition, printed electronics are generally known in the art. See, for
example, Printed Organic and Molecular Electronics, Ed. D. Gamota et al., 2004. For example, Chapters 1 and 2 describe organic semiconductors, Chapter 3 describes manufacturing platforms for printing circuits, Chapter 4 describes electrical behavior of transistors and circuits, Chapter 5 describes applications, and Chapter 6 describes molecular electronics. See also Pope et al., Electronic Processes in Organic Crystals and Polymers, 1999.
SOLUTIONS AND INK FORMULATIONS
The materials, polymers, and copolymers can be put into solution or dispersion form, including ink formulations, for further processing, adapting to the particular application at hand including electronic devices and organic electronic devices, such as, for example, OLED, solar cells and active layers of solar cells.
Lower cost electronic devices can be enabled because polymers, such as those described herein, can be processed into inks which can then be handled in the same manner as inks in conventional printing processes. Ink compositions used for forming, for example, the active layer of an organic photovoltaic device can be made by dissolving p-type and n-type materials in a solvent system, optionally containing other additives.
The solvents and conjugated polymer inks can be formulated or adapted for use in a particular application, such as a solar cell that may include additional additives, such as electron acceptors. The additive(s) and solvents can be adapted to provide good dispersability of the n- and p-type materials, solubility of the n- and p-type materials, and stability of the ink formulation. For example, solvents can be used which provide good solubility or dispersability for fullerenes or fullerene derivative n-type compounds. Solvents can be adapted to be environmentally friendly in view of regulations, and can be, for example, halogen free. In other embodiments additives can be included in the ink that can improve the final film morphology or other properties. For example, solvent additives disclosed in US Patent Publication entitled "Processing Additives for Fabricating Organic Photovoltaic Cells" 2009/0108255 to Bazan etal., published on April 30, 2009 can be included.
Solvent(s) and solvent additive(s) can be removed from the ink compositions, and films can be formed. Solid films can be formed that either comprise solvent(s)
and solvent additive(s), are substantially free of solvent(s) and solvent additive(s), or are free of solvent(s) and solvent additive(s). For example, the amount of remaining solvent can be less than about 5% by weight, or less than about 1% by weight, or less than about 0.1% by weight. For example, the amount of remaining solvent additive can be less than about 5% by weight, or less than about 1% by weight, or less than about 0.1% by weight.
Conventional methods can be used to cast polymer materials from the compositions to provide solid forms, including thin film forms and printed forms. For example, the p-type and n-type polymers of the active layer can be dissolved in the solvent to form an ink, and then allowed to dry. Suitable coating methods are known. These include roll-to-roll coating, screen printing, spin casting, spin coating, doctor blading, dip coating, spray coating, or ink jet printing, and other known coating and printing methods.
INK COMPONENTS
Ink components known in the art can be used including, for example, solvents and n-type materials. The amounts of the components can be adapted to improve performance.
N-TYPE MATERIALS
The active layer composition in, for example, a solar cell may include an n- type component or electron acceptor, or an electron acceptor moiety. These can be materials with a strong electron affinity and good electron accepting character. The n-type component should provide fast transfer; good stability, and good
processability. The n-type material is desirably soluble in, dispersible in, or otherwise miscible with the solvents in order to provide for solution processing. The n-type component may take the form of particles, including microparticles and nanoparticles, inorganic particles, organic particles, and/or semiconductor particles.
For example, the active layer can comprise an n-type material comprising at least one fullerene structure. Fullerenes are known in the art. Fullerenes can be described as spheroidal carbon compounds. For example, the fullerene surface can present [6,6] bonding and [6,5] bonding as known in the art. The fullerene can
have a surface comprising six-membered and five-membered rings. Fullerenes can be for example C60, C70, or C84, and additional carbon atoms can be added via derivative groups. See for example Hirsch, A.; Brettreich, M., Fullerenes: Chemistry and Reactions, Wiley-VCH Verlag, Weinheim, 2005, which is hereby incorporated by reference including teachings for fullerene nomenclature and synthesis,
derivatization, reduction reactions (Chapter 2), nucleophilic additions (Chapter 3), cycloadditions (Chapter 4), hydrogenation (Chapter 5), radical additions (Chapter 6), transition metal complex formation (Chapter 7), oxidation and reactions with electrophiles (Chapter 8), halogenation (Chapter 9), regiochemistry (Chapter 10), cluster modification (Chapter 11), heterofullerenes (Chapter 12), and higher fullerenes (Chapter 13). Methods described herein can be used to synthesize fullerene derivatives and adducts.
In particular, the active layer can comprise at least one n-type material, wherein the n-type material comprises at least one derivatized fullerene or fullerene derivative. The derivative compound can be, for example, an adduct. The terms "derivatized fullerene," "fullerene derivative" as used herein, can be used
interchangeably and can be, for example, fullerenes comprising, from 1 to 84, or 1 to 70, or 1 to 60, from 1 to 20, from 1 to 18, from one to ten, or from one to six, or from one to five, or from one to three substituents each covalently bonded to, for example, one or two carbons in the spheroidal carbon compounds. The derivatized fullerene can comprise a fullerene covalently bonded by [4+2] cycloaddition to at least one derivative moiety, R.
An example of an n-type material is PCBM.
Examples of n-type materials are described in, for example, International Patent Publication No. WO/2008/018931 published on February 14, 2008 and US Patent Publication 2008/0319207 published December 25, 2008, both to Laird, etal. See also, for example, for n-type small molecules and/or polymers for use in OPVs: a) Shin, et al. Chem. Mater. 2007, 19, 1892-1894; b) Hoppe, et al. Adv Polym Sci. 2008, 214, 1; c) Panagiotis, et al. Adv. Funct. Mater. 2008, 18, 1; d) Frechet, J. M. J. et al. Chem. Mater. 2009, 21, 1775.
SOLVENT
The solvents can be halogenated or non-halogenated. The solvents useful for the presently claimed inventions can include, for example, halogenated benzenes, alkyl benzenes, halogenated methane, and thiophenes derivatives, and the like. More specifically, solvent can be for example chlorobenzene, dichlorobenzene, trichlorobenzene, xylenes, toluene, chloroform, 3-methylthiophene, 3- propylthiphene, 3-hexylthiophene, and mixtures thereof. At least two solvents can be used.
The solvent system can include at least two solvents, at least one first solvent and at least one second solvent (e.g., a solvent additive), which are different from each other. They can be organic solvents. Particularly useful solvent systems can be used as described in co-pending US patent application entitled "Solvent System for Conjugated Polymers," published as 2008/0299293, to Sheina et al., and copending US patent application entitled "Improved Solvent System," serial no.
12/541,500 filed August 14, 2009, which are hereby incorporated by reference in their entirety.
SOLVENT ADDITIVES
Solvent additives can be used, wherein a relatively small addition of a component (e.g., 1-6 wt% or 1-3 wt%) can have a large impact on performance. For example, a primary or first solvent can be used in conjunction with a solvent additive. Solvent additives can be volatile and can be removed upon solvent removal. Or solvent additives can be less volatile and stay in the film upon solvent removal.
Different examples exist for solvent additives. For example, a solvent additive can comprise at least one heterocyclic ring. The heterocyclic ring can be, for example, at least one thiophene ring. The second solvent can be for example an alkylthiophene. In some instances the heterocyclic ring is not a nitrogen-containing ring. Or it can be a nitrogen containing ring. Thus, in some embodiments the second solvent is or is not a pyridine, pyrazine, pyrimidine, or a pyrrolidinone. In some embodiments, the heterocyclic ring includes at least one S atom and at least one O atom. Examples of suitable solvent additives include, but are not limited to,
thiophene derivatives (i.e., substituted thiophenes). The benzene and/or thiophene ring may be substituted or unsubstituted in different positions on the ring. However, in some instances the thiophene derivatives do not contain halogen atoms.
Alkylthiophenes and combinations thereof may be used as the second solvent. The alkyl group can be, for example, CI, C2, C3, C4, and the like up to and including C8, C12, C16, and C20. The alkyl group can be linear or branched. Specific examples of suitable alkylthiophenes include methylthiophene, ethylthiophene, propylthiophene, butylthiophene, pentylthiophene, hexylthiophene, heptylthiophene, octylthiophene, nonylthiophene, and decylthiophene. Fluorinated solvents and additives can be used.
Other examples of solvent systems can be used as described in the
aforementioned co-pending US patent applications, in US Patent Publication entitled "Processing Additives for Fabricating Organic Photovoltaic Cells"2009/0108255 to Bazan eta/., published on April 30, 2009 or in Peet, et al., "Efficiency enhancement in low-bandgap polymer solar cells by processing with alkane dithiols," Nat. Mater., 2007, 6, 497-500.
DEVICE PREPARATION
Devices can be made comprising one or more layers comprising the polymers described herein and one or more electrodes, including anode and cathode. Layers can be built up on a substrate. See, for example, Chen et al., Advanced Materials, 2009, 21, 1-16.
Devices using the presently claimed inventions can be made using for example ΠΌ as an anode material on a substrate. Other anode materials can include, for example, metals, such as Au, carbon nanotubes, single or multiwalled, and other transparent conducting oxides. The resistivity of the anode can be maintained below, for example, 15 Ω/sq or less, 25 or less, 50 or less, or 100 or less, or 200 or less, or 250 or less. The substrate can be rigid or flexible and can be, for example, glass, plastics (PTFE, polysiloxanes, thermoplastics, PET, PEN and the like), metals (Al, Au, Ag), metal foils, metal oxides, (TiOx, ZnOx, NiOx, and the like) and semiconductors, such as Si. The ΓΓΟ on the substrate can be cleaned using techniques known in the art prior to device layer deposition.
A variety of layers can be included between the anode and the active layer of a solar cell or the emissive layer of an OLED. These layers are generally referred to as hole transport layer (HTL), hole injection layers (HIL), hole collection (HCL), electron blocking layers (EBL) and/or interlayers.
Various kinds of hole transport layers, hole injection layers, hole collection layers, and/or hole extraction layers can be used. For example, hole transport layers of various kinds are described in the following references: 1) US Patent No.
7,569,159, issued August, 4, 2009 to Hammond et al.; US Serial No 11/826,394, filed July 13, 2007, published 10/9/2008 as 2008/0248313; US Serial No 12/422,159, filed April 9, 2009; US Serial No 61/108,851, filed October 27, 2008; and US Serial No 61/115,877, filed November 18, 2008.
Hole transport layers (HTL) can be added using, for example, spin casting, ink jetting, doctor blading, spray casting, dip coating, vapor depositing, or any other known deposition method.
The HTLs can be formed as films from, for example, PEDOT, PEDOT/PSS or TBD, or NPB, or PLEXCORE® OC inks (Plextronics, Pittsburgh, PA).
The thickness of the HTL or HIL layer can be, for example, from about a monolayer to about 10 nm or to about 300 nm thick, or from 30 nm to 60 nm, 60 nm to 100 nm, or 100 nm to 200 nm. The film then can be optionally dried and/or solvent and/or temperature treated and/or annealed at 110 to 200°C for 1 min to an hour, optionally in an inert atmosphere.
Active layer thickness can be, for example, about 50 nm to about 250 nm, including for an OPV device.
The active layer can be formulated from a mixture of n-type and p-type materials. The n- and p-type materials can be mixed in a ratio of, for example, from about 0.1 to 4.0 (p-type) to about 1 (n-type) based on a weight, or from about 1.1 to about 3.0 (p-type) to about 1 (n-type) or from about 1.1 to about 1.5 (p-type) to about 1 (n-type). The amount of each type of material or the ratio between the two types of components can be varied for the particular application.
The active layer can be then deposited by spin casting, ink jetting, doctor blading, spray casting, dip coating, vapor depositing, or any other known deposition method, on top of the HTL or HIL film. The film is then optionally thermally annealed
at, for example, about 40 to about 250°C, or from about 150 to 180°C, for about 10 min to an hour in an inert atmosphere. Solvent annealing can be also carried out as needed. Solvent annealing can be carried out at, for example, ambient temperature (for low boiling solvents). The film can be also optionally dried in solvent saturated and/or inert and/or vacuum atmosphere. The active layer can be also annealed with use of an electric field ("electric field annealing"). For example, a device can be cycled in an electric field which can in some instances improve performance.
Internal heating may also contribute to electric field annealing.
A cathode layer can be added to the device, generally using, for example, thermal evaporation of one or more metals. Also, solution processing can be used. For example, a 1 to 15 nm Ca layer is thermally evaporated onto the active layer through a shadow mask, followed by deposition of a 10 to 300 nm Al layer.
A variety of layers can be included between the cathode and the active layer of a solar cell or the emissive layer of an OLED. These layers are generally referred to as electron transport layers (ETL), electron injection layers (EIL), hole blocking layers (HBL) and/or interlayers.
In some embodiments, an optional interlayer may be included between the active layer and the cathode, and/or between the HTL or HIL and the active layer. This interlayer can be, for example, from 0.5 nm to about 100 nm, or from about 1 to 3 nm, thick. The interlayer can comprise an electron conditioning, a hole blocking, or an extraction material, such as LiF, BCP, metal oxides, bathocuprine, fullerenes or fullerene derivatives, such as C60, C70, C84 and other fullerenes and fullerene derivatives discussed herein.
Electron transport layers can be used in, for example, solar cell devices. See, for example, US patent application no. 61/116,963 filed November 21, 2008.
Interfacial modification layers can be used as described in, for example, PCT/US2009/006236 filed November 20, 2009 (Plextronics, Inc.). The interfacial modification layer can comprise, for example, an organic semiconductor which is doped by, for example, a metal (e.g., BPhen:Yb). The interfacial modification layer can be prepared by vacuum deposition methods. It can have a thickness of, for example, 3 nm to 25 nm, or 5 nm to 15 nm. An Al layer can be disposed on top.
The devices can be then encapsulated using a glass cover slip sealed with a curable glue, or in other epoxy or plastic coatings. Cavity glass with a
getter/desiccant may also be used.
In addition, the active layer can comprise additional ingredients including, for example, surfactants, dispersants, oxygen and water scavengers.
The active layer can comprise multiple layers or be multi-layered.
The active layer composition can be formed from an ink comprising a mixture as a film.
Films and devices can be annealed before use and testing. Thermal/electrical annealing and solvent annealing can be carried out.
Inverted solar cells can be made. See, for example, Chen et al. Advanced Materials, 2009, 21, 1-16. Tandem solar cells can be made.
DEVICE TESTING
Known solar cell parameters can be measured including for example Jsc (mA/cm2) and Voc (V) and fill factor (FF) and power conversion efficiency (%, PCE) by methods known in the art. See for example Hoppe article cited above and references cited therein.
Oriel Solar Simulators can be used to determine PV properties including, for example, FF, Jsc, Voc, and efficiencies. The simulator can be calibrated by methods known in the art including, for example, calibration with a KG5-Si reference cell. External quantum efficiency (EQE) can be measured.
Other properties for the inks, films, and devices can be measured by methods known in the art.
Power conversion efficiency (PCE) can be, for example, at least about 1%, or at least about 2%, or at least about 3%, or at least about 4%, or at least about 5%, or at least about 6%, or at least about 7%, or at least about 8%, or higher.
Fill factor, which can be expressed as a number between 0 and 1, or a percentage between 0 and 100%, can be, for example, at least about 0.4 (40%), or at least about 0.5 (50%), or at least about 0.6, or at least about 0.7, or at least about 0.8, or at least about 0.9 or higher.
Open circuit voltage (Voc) in V can be, for example, at least about 0.3, or at least about 0.4, or at least about 0.5, or at least about 0.6 V, or at least about 0.7 V, or at least about 0.8 V, or at least about 0.9 V, or at least about 1.0 V, or at least about 1.1 V, or at least about 1.2 V, or at least about 1.3 V, or higher.
Short circuit current (Jsc) can be, for example, at least about 0.5, or at least about 0.6, or at least about 0.7, or at least about 0.8, or at least about 0.9, or at least about 1.0, or at least about 2.0, or at least about 3.0, or at least about 4.0, or at least about 5.0, or at least about 10.0, or higher (mA/cm2).
ENERGY HARVESTING
In addition, devices and applications can be made and carried out in energy harvesting (EH). Energy harvesting is an indoor application of photovoltaic technology, whereby an EH device harnesses ambient light, typically fluorescent office lighting, for energy storage or direct use for a wide variety of low power applications. For example, a typical office environment can have light levels of about 1000 LUX, or about 0.5% (0.5 mW/cm 2) of the incident radiant energy of 1 sun. This represents the total amount of energy that can be harvested in these environments and high efficiency photovoltaic technology, suited to these light levels are important for leveraging novel applications and can be a replacement for coin- cell batteries (or equivalent). Typical outdoor solar technology, such as mc-Si c-Si, have low performance at indoor lighting levels due to a high amount of Voltage loss. Organic PV and a-Si are well suited to low light levels and OPV can be a more cost effective solution vs. a-Si and thus can be used in EH technology.
Polymers can be designed to exhibit a 'flat' response with decreasing light levels and represent a novel high-performance technology of indoor EH applications. Typical device stacks for EH applications are very similar to their outdoor solar analogs and a typical configuration is ITO/ZnO/conjugated
polymer: PCBM[C60]/HTL/Ag.
Devices can be tested at 1000 LUX and one can determine the power density at this standard luminance level. In addition, one can measure devices at a variety of light intensities to understand how device parameters change with changes in ambient light level. One can also measure leakage current at reverse bias to help
understand the diode quality as poor diode quality can result in lower performance at lower and lower light levels.
PHOTODETECTION
In addition, organic photodetection (OPD) is an application of PV technology where a circuit can be controlled by the presence or absence of radiant energy impinging on the said circuit, which contains a photosensitive device. The use of organic photodetectors offers an advantage of cost and integration that may not be possible with incumbent technology, namely a-Si.
OPD devices can be fabricated very similarly to a solar OPV device and a typical configuration is: ITO/HTL/conjugated polymer: Fullerene n-type/Cathode, where the cathode can be Ca/AI, or organic small molecule, doped with a metal, or organic material and capped with a metal such as Aluminum.
There are four quadrants of a current voltage plot which are defined by positive and negative current and voltage (I = +c/-v, II = +c/+v (OLED), III = -c/-v (OPD), IV = -C/+V (OPV)). OLED devices operate in quadrant II, OPVs in quadrant IV and OPDs in quadrant III.
For OPD the product of current and voltages are always positive thus this is a device which requires power input. The input power is provided to the OPD circuit and when the OPV cell is exposed to light, a massive gain (several decades, up to > 10A4) in current can occur. This provides a 'gate' which allows the circuit to differentiate between light (on) and dark (off) states, thus allowing for
photodetection.
For OPD technology, key parameters include 1) current density (expressed as mA/cm 2 and higher is better) at a negative voltage (at typically -1 or -2 V) and 2) the noise floor in the dark state, typically expressed as a current density (nA/cm 2) and the lower the better. Parameter #1 is proportional to the quantum efficiency of the device and devices which are most efficient at generating current with the input radiant energy are best. For #2, device design is necessary to reduce the leakage current (or noise floor) and the photoactive layer materials should have as low a carrier density in the off state as possible, ie not doped.
Materials described herein can offer high quantum efficiency, low doping due to deep HOMO, and air processibility that is amenable to rapid OPD device development.
PART HI. WORKING EXAMPLES
METHOD 1:
In a 3-neck round bottom flask equipped with an argon inlet and an addition funnel, thieno[3,2-b]thiophene (7.5 g, 54 mmol) was dissolved in tetrahydrofuran (1 L). After the solution was cooled to -78°C using an isopropanol/dry ice bath, i-BuLi (100 ml_, 170 mmol) was transferred by cannula to the addition funnel. The organolithium reagent was then added dropwise. After completion of the addition, the mixture was stirred for 20 min at -78°C then warmed up with an isopropanol bath at room temperature for 30 minutes during which a yellow precipitate formed. The solution was cooled back at -78°C, and after cannula transfer to the addition funnel, trimethyltin chloride (200 mL of 1 M solution in THF, 200 mmol) was added dropwise. During addition of trimethyltin chloride, the precipitate disappeared and the solution turned light brown. After warming to room temperature the solution was stirred for 30 minutes then was poured into ice-cold water. The aqueous phase was further extracted with hexane. The combined organic phases were washed with cold water then dried with magnesium sulfate. After filtration, the solvent is evaporated under vacuum to yield a grey-brown solid. The product was purified by precipitation of a chloroform solution into methanol followed by filtration (13.2 g,
53%).
Spectral data: *H NMR (CDCI3, 300 MHz): δ„0.41 (s, 18H), 7.26 (s, 2H).
13C (CDC , 75 MHz): δ 7.99, 126.29, 141.4, 147.62.
Thiophene-2-bromo-3-carboxylic acid (10 g, 45 mmol) was placed in a dry 3- neck round bottom flask equipped with an argon inlet and a water condenser. Dry methanol (100 mL) was added to the flask along with a catalytic amount of cc.
sulfuric acid (1 mL). The reaction completion was determined by NMR analysis. When complete, the reaction was cooled to room temperature. The methanol was evaporated and the resulting product was purified via column chromatography, using a 100% hexane to 60% hexane/ 40% ethyl acetate gradient to yield a slightly yellow clear oil (9 g, 91%).
Spectral data: *H NMR (CDCI3 300 MHz): δ„3.89 (s, 3H), 7.23 (d, 5.76), 7.36 (d,
5.78Hz).
"C NMR (CDCI3, 75 MHz): δ 52.13, 120.15, 126.09, 129.48, 131.07, 162.61.
Example 3. Synthesis of dimethyl 2,2'-(thieno[3,2-_¾thiophene-2,5- diyl)bis(thiophene-3-carboxylate)
In a glove box, 2,5-bis(trimethylstannyl)thieno[3,2-b]thiophene (2.67 g, 5.7 mmol), methyl 2-bromothiophene-3-carboxylate (2.5 g, 11.31 mmol), Pd2dba3 (131 mg, 0.14 mmol) and P(o-tolyl)3 (174 mg, 0.57 mmol) were charged in a Schlenk flask. The flask was connected to an argon/vacuum line and its side arm was purged 5 times before the flask was open to argon. Toluene (100 mL, purged overnight with argon) was added and the mixture was purged five times with vacuum argon cycles. The flask was placed in a preheated bath at 110 °C and the mixture was stirred overnight. Over time a yellow-green precipitate formed. After cooling, the precipitate was filtered and washed with hexane. NMR analysis
indicated product was pure (2 g, 42%) and as a result it was used without further purification.
Spectral data: *H NMR (CDCI3 300 MHz): δ„3.85 (s, 6H), 7.25 (d, 2H, 5.46Hz), 7.51 (d, 2H, 5.39 Hz).
13C (CDC , 75 MHz): 552.11, 121.47, 124.77, 128.07, 130.88, 147.69, 163.69.
Example 4. Synthesis of (2,2'-(thieno[3,2-b]thiophene-2,5-diyl)bis(thiophene-3,2- diyl))bis(bis(4-(2-ethylhexyl)phenyl)methanol)
A flame-dried 3-neck round bottom flask equipped with an argon inlet, a water condenser and an addition funnel, was charged with magnesium (0.81 g, 33 mmol) and anhydrous THF (30 mL) that was added via deoxygenated syringe. A few crystals of iodine were added to initiate reaction, and 4-(2-ethylhexyl)- phenylbromide (7.5 g, 27.9 mmol) was added dropwise. The solution was refluxed for a few hours, until GC analysis of an aliquot showed no starting material remained. After cooling, dimethyl 2,2'-(thieno[3,2-b]thiophene-2,5- diyl)bis(thiophene-3-carboxylate) (2.0 g, 4.8 mmol) was added in one portion. And the solution was refluxed and its progress was monitored by TLC. Upon reaction completion, the reaction was cooled and poured in 1M HCI solution. The aqueous phase was extracted with MTBE. The combined organic phases were washed with water then dried with anhydrous magnesium sulfate. After filtration the solvent was removed under vacuum, and the final product, a dark orange viscous oil, was obtained after silica column chromatography using 100% hexane to 100% CHCI3 gradient (2.6 g, 48%).
Example 5. Synthesis of 5,5,10,10-tetrakis(4-(2-ethylhexyl)phenyl)-3,5,8,10- tet'rahydro-cyclopenta[l, 2-/7:5,4- Z/]dithiophene[2',l':4,5]thieno[2,3-o]thiophene
(2,2,-(Thieno[3,2-b]thiophene-2/5-diyl)bis(thiophene-3,2-diyl))bis(bis(4-(2- ethylhexyl)phenyl)methanol) (2.1 g, 1.78 mmol) was charged in a schlenk flask under argon atmosphere. Toluene (200 mL, bubbled overnight with argon) was added along with Amberlyst 15 (1 g). The flask was purged with vacuum-argon cycles 5 times then placed in a preheated bath at 110°C. The reaction was monitored by TLC using hexane as eluent. When the reaction was completed, it was cooled to room temperature, and immediately filtered through silica plug to yield the product as a yellow-orange solid (1.1 g, 57%). Spectral data: H NMR (CDCI3, 300 MHz): δ„ 0.72-0.96 (t, 24H, 7.39 Hz) 1.12-1.35 (m, 32H), 1.43-1.6 (m, 4H), 2.46 (d, 8H, 6.9 Hz), 7.03 (d, 8H, 8.21 Hz), 7.07 (d, 2H, 4.86 Hz), 7.13 (d, 8H, 7.95 Hz), 7.15 (d, 2H, ~3.9Hz).
13C (CDC , 75 MHz): 510.94, 14.34, 23.2, 25.62, 29.01, 32.49, 39.9, 41.01, 62.11, 123.54, 125.36, 127.83, 129.48, 135.15, 137.31, 140.82, 148.68, 157.24.
Example 6. Synthesis of (5,5,10,10-tetrakis(4-(2-ethylhexyl)phenyl)-3,5,8,10- tetrahydro-cyclopenta[l,2-Z7:5,4-- ]dithiophene[2,, :4,5]thieno[2,3-i7]thiophene-2,7- diyl)bis(trimethylstannane)
The starting compound (530 mg, 0.49 mmol) was dissolved in THF (150 mL) in a dry schlenk flask. The solution was cooled to -78°C and ter-butyllithium (0.87 mL of 1.7 M solution, 1.5 mmol) was added dropwise via syringe. After completion of the addition, the mixture was stirred 60 min at -78°C the 15 minutes at room temperature (using IPA bath at RT) during which the solution turned from orange to dark brown-orange. The solution was cooled back at -78°C, and trimethyltin chloride (2 mL of 1M solution in THF, 2 mmol) was added dropwise. The mixture is warmed to room temperature following completion of the addition and stirred at that temperature for 30 minutes then was poured into ice-cold water. The aqueous phase was further extracted with hexane. The combined organic phase were combined and washed with cold water then dried with magnesium sulfate. After filtration, the solvent was evaporated under vacuum to yield an orange solid. The product was purified by precipitation of a chloroform solution into methanol followed by filtration (540 mg, 78%).
Spectral data: ^ IMMR (CDCI3, 300 MHZ) 5//0.36 (s, 18H), 0.83 (t, 12H, 6.04 Hz), 0.84 (t, 12H, 7.21Hz), 1.13-1.34 (m, 32H), 1.46-1.59 (m, 4H), 2.46 (d, 8H, 6.86Hz), 7.03 (d, 8H, 8.18Hz), 7.07 (s, 2H), 7.13 (d, 8H, 8.36 Hz).
Example 7. Synthesis of Donor-Acceptor random copolymer based on 5,5,10,10- tetrakis(4-(2-ethylhexyl)phenyl)-3,5,8,10-tetrahydro-cyclopenta[l,2--¾5,4-
/y]dithiophene[2',l':4,5]thieno[2,3-o]thiophene
In a glove box, l,3-dibromo-5-(2-ethylhexyl)-4 thieno[3,4-<:]pyrrole-4,6(5 )- dione (43.78 mg, 0.10 mmol), (5,5,10,10-tetrakis(4-(2-ethylhexyl)
tetrahydro-cyclopenta[l,2-ft5,4-_y]dithiophene[2^
diyl)bis(trimethylstannane) (224 mg, 0.159 mmol), 4,7- dibromobenzo[c][l,2,5]thiadiazole (16.38 mg, 0.056 mmol), Pd2dba3 (3.64 mg, 0.004 mmol), P(o-tolyl)3 (4.84. mg, 0.016 mmol) were charged in a 100 ml Schlenk flask. After connecting the flask to vac/argon line, the side arm was flushed with 5 vacuum-argon cycles and the flask was opened to argon. Toluene (10 ml_), degassed with argon overnight, was added. The flask was purged five times through vacuum-argon cycles then placed in a preheated flask at 110°C for 48 hours. After cooling, methanol was added to precipitate the polymer. The polymer was filtered through Soxhlet thimble and Soxhlet extraction was performed with methanol, MTBE, hexane and chloroform (100 mg). Molecular weight was determined by GPC
in chlorobenzene (1 mL/min at 80°C) vs. polystyrene standards: Mn= 28,100, 7^=47,800, PDI= 1.7.
In a solar cell device, the Voc for this material was 0.72 V. See Table I.
HOMO level (AC2, eV) was 5.15. In contrast, HOMO level for BPP-1 was 5.31 eV.
Example 8. Synthesis of Donor-Acceptor random copolymer based on 5,5,10,10- tetrakis(4-(2-ethylhexyl)phenyl)-3,5,8,10-tetrahydro-cyclopenta[l,2-/7:5,4- Tjdithiophene[2,,l,:4,5]thieno[2,3-o]thiophene and 5,5'-bis(2-ethylhexyl)-4 ,4' [l^'-bithienoCS^-cJpyrrolel^^ G^'CS^S' ^-tetraone
In a glove box, (5,5,10,10-tetrakis(4-(2-ethylhexyl)phenyl)-3,5,8,10- tetrahydro-cyclopenta[l,2- ¾5,4-/y]dithiophene[2',l':4,5]thieno[2 3-o]thiophene-2 7- diyl)bis(trimethylstannane) (0.40 mmol), l-bromo-3-[3-bromo-5-(2-ethylhexyl)-4,6- dioxo-thieno[3,4-c]pyrrol-l-yl]-5-(2-ethylhexyl)thieno[3,4-<:]pyrrole-4,6-dione (0.40 mmol), tris(dibenzylideneacetone)dipalladium(0) (9.2 mg, 0.010 mmol) and tris(o- tolyl)phosphine (12 mg, 0.040 mmol) were charged into a flame dried 50 ml_ Schlenk flask. The reaction flask was removed from the glove box and 10 mL of deoxygenated chlorobenzene were added via syringe. The mixture was evacuated
and refilled with argon five times. The reaction flask was immersed into a 110°C oil bath and left stirring under an argon stream for 2 days. After cooling to room temperature, 40 ml_ of methanol were added to the reaction mixture. The polymer was collected via filtration and purified by consecutive Soxhlet extractions in sequence with methanol, MTBE, hexane, and chloroform. The chloroform solution was passed through celite to remove catalyst residuals, and solvent was removed under vacuum to yield polymer. The polymer was re-dissolved in a small amount of chloroform, re-precipitated in the mixture of IPA, water and methanol, isolated via centrifuge and dried (200 mg). Molecular weight was determined by GPC in chlorobenzene (1 mL/min at 80°C) vs. polystyrene standards: A n=31,500,
PDI=2.9. The polymer was called BPP-1, and solar cell preparation and testing performance is shown in Table I.
Example 9. Device Testing
Inks and devices were prepared according Table I, and the devices were tested and the results are shown in Table I.
Table I. Photovoltaic Performance of single layer OPVs based on Donor-Acceptor polymers comprising dioxypyrrolo-functionality
DBT - dibromotoluene
^DCBiDIO - dichlorobenzene:diiodooctane (97:3%); TCB - trichlorobenzene
2GB - glove box (N2); Sol - solvent atmosphere (CHCI3) for 15 minutes
Note: HIL A is an HIL ink formulation comprising 96.860 parts water; 2.826 parts
Nafion (sulfonated perfluorinated copolymer); and 0.314 parts sulfonated
polythiophene as described in PCT publication WO 2008/073149.
Comparative Example A
US Serial Nos. 12/828,121 filed June 30, 2010 and 12/874,163 filed
September 1, 2010 describe synthesis and structures relevant to APP-1.
Polymerization methods are described herein.
Example. Synthesis of poly(3-(5,6-bis(2-ethylhexyl)naphtho[2, l-fr.3,4-b ]dithiophen- 2-yl)-^5,5'-bis(2-ethylhexyl)-4 ¾4, [l,l,-bithieno[3,4-c]pyrrole]-4,4,,6,6'(5 /,5, 70- tetraone)
In a glove box, 3,3,-dibromo-5,5,-bis(2-ethylhexyl)-4r,4, [l,l'-bithieno[3,4- clpyrrolel^^'^^ S ^S' j-tetraone (304 mg, 0.44 mmol), (5,6-bis(2- ethylhexyl)naphtho[2,l-b:3,4-b']dithiophene-2,9-diyl)bis(trimethylstannane) (350 mg, 0.44 mmol), Pd2dba3 (10 mg, 0.011 mmol), P(otolyl)3 (13 mg, 0.044 mmol) were charged in a 100 ml_ schlenk flask. The flask was removed from a glove box, connected to a vac/argon line, and the side arm was flushed with five vacuum-argon cycles, after which the flask was open to argon. Anhydrous toluene (20 mL), degassed with argon overnight, was added via a deoxygenated syringe. The flask was purged five times with argon, and immersed into a preheated to 110°C flask for 48 hours. After cooling, methanol was added to precipitate the polymer. The polymer was filtered through Soxhiet thimble and Soxhiet extraction was performed in sequence with methanol, MTBE, hexane and chloroform. The final polymer was isolated as a chloroform insoluble fraction (270 mg, 65%). Molecular weight was determined by GPC in chlorobenzene (1 mL/min at 80°C) vs. polystyrene standards:
/%=23,700, / = 168,300, PDI= 7.1. The polymer was labeled APP-1, and solar cell preparation and testing performance is shown in Table I.
EXAMPLE 10. Testing of Polymer Properties
Figure 1 (EQE data) compares the polymer of Example 8 with a competitive polymer APP-1 which does not comprise structure (I).
Both polymers display absorption and EQE with very sharp onset. However, in the case of the Example 8 polymer, the absorption is pushed all the way to 780 nm, from about 700 nm compared to APP-1. The band edge is almost 0.2 eV bathochromically shifted and at an optimal location for maximum light absorption.
Both materials showed high efficiency (3.56% for APP-1 and 2.83% for Example 8, see Table I). However, reverse bias measurement indicated a much higher reverse bias current for Example 8 compared to APP-1, reflective of its optimized absorption. See Figure 2.
Additional EQE data are provided in Figure 3. PV2000 materials are available from Plextronics, Inc. (Pittsburgh, PA).
SYNTHESIS METHOD 2:
In a 3 neck round bottom flask equipped with an addition funnel, a water condenser and a nitrogen inlet, thieno[3,2-b]thiophene was dissolved in a mixture of acetic acid and chloroform. For safety, the top of the water condenser was vented into an Erlenmeyer containing a 5M NaOH solution so as to quench HBr gas. Bromine was added carefully. After 1 hour stirring, more bromine was added to the reaction and the mixture was stirred for another hour. An aliquot was tested by gas
chromatography, indicating the reaction was not complete. As a result, more bromine was added. The reaction was then refluxed overnight, and a large amount of solids precipitated. A sample analyzed by gas chromatography indicated reaction
completion. The mixture was then allowed to cool back to room temperature. The precipitate was filtered, washed with water and methanol. The solids were then dried under vacuum. GC-MS showed a single peak, [M+] = 455.0.
In a 3-neck flask equipped with a water condenser, tetrabromothienothiophene (20g, 44mmol), zinc powder (5.74g, 88mmol) were added to a mixture of acetic acid (500 ml.) and toluene (200ml_). A few drops of 1M hydrochloric acid were also added for activation of zinc surface. The mixture was refluxed until gas
chromatography indicated a complete reaction. After cooling to room temperature, the solution was concentrated down and the resulting precipitate was filtered through Buchner funnel.
Example 12: Synthesis of thieno[3,2-b]thiophene-3,6-diylbis(thiophen-3-ylmethanol)
In a flame-dried schlenk flask under argon atmosphere, 3,3'-dibromothienothiophene was dissolved in diethylether. The solution was cooled down to -90°C (MeOH+liq. N2 bath), and n-butyllithium was added dropwise. After 30 minutes stirring at - 90°C, a solution of thiophene-3-carboxaldehyde in diethyl ether was added dropwise at -80°C. The mixture was then allowed to slowly warm up back to room
temperature. A solution of 1M HCI was added to quench any reactive lithiated species. The aqueous phase was extracted with MTBE three times. The combined organic layers were washed with water three times, then dried with magnesium sulfate. After evaporation, the resulting solid was purified by column
chromatography (100% CHCI3 to 20% EtOAc/CHC ).
Example 13. Prophetic example: Synthesis of thieno[3,2-b]thiophene-3,6- diylbis(thiophen-3-ylmethanone)
To a solution of thieno[3,2-b]thiophene-3,6-diylbis(thiophen-3-ylmethanol) in dichloromethane at 0°C was added pyridinium chlorochromate. The mixture was allowed to warm up at room temperature and stirred for 4 hours. The mixture was then filtered through celite. The solvent was evaporated and the resulting product was purified by column chromatography.
Example 14: Synthesis of 3,6-bis(thiophen-3-ylmethyl)thieno[3,2-b]thiophene
This conversion can be accomplished using the Huang-Minion modification of the Wolff-Kishner reaction, as described in Vogel's textbook of Organic Chemistry (? Edition) page 820.
Prophetic example 15: Synthesis of 3,6-bis(9-(thiophen-3-yl)heptadecan-9- yl)thieno[3,2-b]thiophene
To a suspension of sodium hydride in THF is added a THF solution of 3,6- bis(thiophen-3-ylmethyl)thieno[3,2-b]thiophene. Octyl bromide is then added and the mixture is refluxed until reaction completion, as determined by TLC. The reaction is then poured into cold water, extracted with MTBE and combined organic phases are washed with water. After drying the organic phase with magnesium
sulfate and filtering through Buchner the solvent is evaporated. The resulting product can be purified by column chromatography.
Prophetic example 16:
oct oct
A dry 500mL 3-neck flask, flushed with dry nitrogen, is charged with of 3,6-bis(9- (thiophen-3-yl)heptadecan-9-yl)thieno[3,2-b]thiophene (1 eq.). The flask is evacuated and backfilled with nitrogen 3 times. Dry CH2CI2 is added to the flask via cannula. The solution is bubbled with nitrogen for 15 minutes. The solution is then cooled to 5 °C and BF3-Et20 (1.1 eq.) is added. DDQ (leq.) is added in increments over 30 minutes. The reaction is monitored by TLC and more DDQ is added if reaction is not complete. At 15 minutes after DDQ addition, add another 0.1 g of DDQ followed by another 0.1 g addition at 18 minutes after first DDQ addition. At 30 minutes after initial DDQ addition, 0.3 mL of BF3-Et20 is added followed by another 1 mL of BF3-Et20 at 40 minutes. At 1 hour after initial DDQ addition is complete, no starting material was noticed by TLC and the reaction is quenched by the addition Zn powder and stirring of the reaction for 2 hours. The mixture is diluted with 200 mL of methanol and stirred for another hour. The mixture is diluted with water and extracted with chloroform. The organic fractions are dried over MgS04 and then concentrated. The product is purified by column chromatography.
Method 3:
,5-
To a solution of the diester in THF, a 1M solution of lithium hydroxide is added. The mixture is refluxed overnight. After cooling to room temperature, THF was evaporated under vacuum. The aqueous phase was acidified with 5M HCI solution until PH=1. The formed precipitate is filtered and dried.
Prophetic example 18: Synthesis of 2,2'-(thieno[3,2-b]thiophene-2,5- diyl)bis(thiophene-3-carbonyl chloride)
To a suspension of diacid in dry toluene are added two equivalents of thionyl chloride. The mixture was refluxed for one hour. Toluene and excess thionyl chloride are removed under vacuum. The resulting product is used without further purification.
Prophetic example 19: Synthesis of BP3 diketone precursor
To a suspension of aluminum chloride in dry dichloromethane at 0°C is added a solution of diacyl chloride in dry dichloromethane. The mixture is stirred for one hour at room temperature. The mixture is then poured onto ice. The aqueous phase is further extracted with dichloromethane. The combined organic phases are washed with water, then dried with magnesium sulfate and filtered through Buchner funnel. After evaporation the product is purified by column chromatography.
Prophetic example: Synthesis of BP non alkylated precursor
This conversion can be accomplished using the well-known Huang-Minion
modification of the Wolff-Kishner reaction, as described in Vogel's textbook of Organic Chemistry (5th Edition) page 820.
oct oct
To a suspension of sodium hydride in THF is added a THF solution of starting material. Octyl bromide is then added and the mixture is refluxed until reaction completion, as determined by TLC. The reaction is then poured into cold water, extracted with MTBE. The combined organic phases are washed with water then dried with magnesium sulfate. After filtration through Buchner funnel the solvent is evaporated. The resulting product can be purified by column chromatography or recrystallization.
Also, forming part of the application written description:
APPENDIX A - LISTING OF POLYMERS
APPENDIX B - LISTING OF DONORS
APPENDIX C - LISTING OF ACCEPTORS
APPENDIX A.
51
52
53
54
55
APPENDIX B
APPENDIX C.
Claims
1. An oligomer or polymer comprising:
wherein Ri, R2, R3, and R4 are independently hydrogen or solubilizing groups.
2. The oligomer or polymer of claim 1, wherein Ri, R2, R3, and R4 are the same group.
3. The oligomer or polymer of claim 1, wherein Ri, R2, R3, and R4 are the same group and comprise an aromatic group.
4. The oligomer or polymer of claim 1, wherein Ri, R2, R3, and R4 are the same group and comprise an arylalkyl group.
5. The oligomer or polymer of claim 1, wherein Ri, R2, R3, and R4 are the same group and are a Ci - C25 group.
6. The oligomer or polymer of claim 1, wherein it is as polymer having a molecular weight of at least 10,000 number average molecular weight.
7. The oligomer or polymer of claim 1, wherein the oligomer or polymer is a donor- acceptor oligomer or polymer.
8. The oligomer or polymer of claim 1, wherein the oligomer or polymer is a donor- acceptor polymer, and has at least two types of donors, or at least two types of acceptors.
9. The oligomer or polymer of claim 1, wherein the oligomer or polymer is soluble in chloroform, chlorobenzene, dichlorobenzene, or trichlorobenzene.
10. The oligomer or polymer of claim 1, wherein the oligomer or polymer has a molecular weight of at least 10,000 number average molecular weight and is soluble in chloroform, chlorobenzene, dichlorobenzene, or trichlorobenzene.
11. A monomer comprising a moiety represented by:
wherein Ri, R2, R3, and R4 are independently hydrogen or solubilizing groups.
12. The monomer of claim 11, wherein Ri, R2, R3, and R4 are the same group.
13. The monomer of claim 11, wherein Ri, R2, R3, and R4 are the same group and comprise an aromatic group.
14. The monomer of claim 11, wherein Ri, R2, R3, and R4 are the same group and comprise an arylalkyl group.
15. The monomer of claim 11, wherein Ri, R2, R3, and R4 are the same group and are a Ci - C25 group.
16. The monomer of claim 11, wherein the monomer is functionalized with electrophilic groups for polymerization.
17. The monomer of claim 11, wherein the monomer is functionalized with nucleophilic groups for polymerization.
18. The monomer of claim 11, wherein the monomer is functionalized with groups comprising metal, optionally tin, for polymerization.
19. The monomer of claim 11, wherein the monomer is functionalized for Ullman, Yamamoto, or Suzuki polymerization.
20. The monomer of claim 11, wherein the terminal thiophene rings are
functionalized for polymerization.
21. An ink composition comprising at least one oligomer or polymer comprising:
wherein Ri, R2, R3, and R4 are independently hydrogen or solubilizing groups; and at least one solvent for the oligomer or polymer.
22. The ink composition of claim 21, wherein the Ri, R2, R3, and R4 are the same group.
23. The ink composition of claim 21, wherein Ri, R2, R3, and R4 are the same group and comprise an aromatic group.
24. The ink composition of claim 21, wherein Ri, R2, R3, and R4 are the same group and comprise an arylalkyl group.
25. The ink composition of claim 21, wherein Ri, R2, R3, and R4 are the same group and are a Ci - C25 group.
26. The ink composition of claim 21, wherein the oligomer or polymer is a polymer having a molecular weight of at least 10,000 number average molecular weight.
27. The ink composition of claim 21, wherein the oligomer or polymer is a donor- acceptor oligomer or polymer.
28. The ink composition of claim 21, wherein the oligomer or polymer is a donor- acceptor polymer, and has at least two types of donors, or at least two types of acceptors.
29. The ink composition of claim 21, wherein the solvent comprises at least two solvents, and the ink composition further comprises at least one additive.
30. The ink composition of claim 21, wherein the solvent comprises a mixture comprising at least orthodichlorobenzene and trichlorobenzene.
31. A OPV device comprising at least one OPV active layer comprising at least one polymer comprising:
wherein Ri, R2, R3, and R4 are independently hydrogen or solubilizing groups.
32. The device of claim 31, wherein the Ri, R2, R3, and R4 are the same group.
33. The device of claim 31, wherein Ri, R2, R3, and R4 are the same group and comprise an aromatic group.
34. The device of claim 31, wherein Ri, R2, R3, and R4 are the same group and comprise an arylalkyl group.
35. The device of claim 31, wherein Ri, R2, R3, and R4 are the same group and are a Ci - C25 group.
36. The device of claim 31, wherein the polymer has a molecular weight of at least 10,000 number average molecular weight.
37. The device of claim 31, wherein the polymer is a donor-acceptor polymer.
38. The device of claim 31, wherein the polymer is a donor-acceptor polymer, and has at least two types of donors, or at least two types of acceptors.
39. The device of claim 31, wherein the device comprises at least one
polythiophene a hole transport layer.
40. The device of claim 31, wherein the active layer further comprises at least one n-type material.
41. A coated substrate comprising at least one substrate and at least one coating, wherein the coating comprises at least one polymer comprising:
wherein Ri, R2, R3, and R4 are independently hydrogen or solubilizing groups.
42. The coated substrate of claim 41, wherein the Ri, R2, R3, and R4 are the same group.
43. The coated substrate of claim 41, wherein Ri, R2, R3, and R4 are the same group and comprise an aromatic group.
44. The coated substrate of claim 41, wherein Ri, R2, R3, and R4 are the same group and comprise an arylalkyl group.
45. The coated substrate of claim 41, wherein Ri, R2, R3, and R4 are the same group and are a Ci - C25 group.
46. The coated substrate of claim 41, wherein the polymer has a molecular weight of at least 10,000 number average molecular weight.
47. The coated substrate of claim 41, wherein the polymer is a donor-acceptor polymer.
48. The coated substrate of claim 41, wherein the polymer is a donor-acceptor polymer, and has at least two types of donors, or at least two types of acceptors.
49. The coated substrate of claim 41, wherein the substrate is a flexible substrate.
50. The coated substrate of claim 41, wherein the substrate comprises a hole transporting layer next to the coating.
51. A method comprising:
functionalize at least one thieno[3,2-b]thiophene compound with two reactive functional groups, one reactive group on each thiophene ring to provide a compound I;
provide at least one thiophene compound comprising a leaving group at the 2-position and a carboxylate at the 3-position to provide a compound II;
react compound I and compound II to produce compound III which is a compound comprising a central thieno[3,2-b]thiophene moiety linked to opposing thiophene rings;
react compound III so that carboxylate groups are converted to hydroxyl groups to provide compound IV; react compound IV in a ring closure reaction to provide at least one
h is compound V:
optionally, functionalize compound V to have two polymerization groups and provide compound VI.
52. A method comprising: providing a monomer comprising a moiety represented by:
wherein Ri, R2, R3, and R4 are independently hydrogen or solubilizing groups; and polymerizing the monomer.
53. The method of claim 52, wherein the polymerization is carried out with an acceptor moiety to form a donor-acceptor polymer.
54. A com osition comprising at least one donor-acceptor polymer comprising:
wherein Ri, R2, R3, and R4 are independently hydrogen or solubilizing groups.
55. An oligomer or polymer comprising at least one repeat unit comprising:
wherein Ri, R2, R3, and R4 are the same group and are a Ci - C25 group.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP11782286.6A EP2632968A1 (en) | 2010-10-27 | 2011-10-25 | Organic electronic devices, including organic photovoltaic devices, polymers, and monomers |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US40741910P | 2010-10-27 | 2010-10-27 | |
US61/407,419 | 2010-10-27 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2012058209A1 true WO2012058209A1 (en) | 2012-05-03 |
Family
ID=44947205
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2011/057662 WO2012058209A1 (en) | 2010-10-27 | 2011-10-25 | Organic electronic devices, including organic photovoltaic devices, polymers, and monomers |
Country Status (3)
Country | Link |
---|---|
US (1) | US9062152B2 (en) |
EP (1) | EP2632968A1 (en) |
WO (1) | WO2012058209A1 (en) |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2013056355A1 (en) * | 2011-10-20 | 2013-04-25 | UNIVERSITé LAVAL | Preparation of high molecular weight polymers 8y direct arylation and heteroarylation |
WO2014005667A1 (en) * | 2012-07-02 | 2014-01-09 | Merck Patent Gmbh | Conjugated polymers |
WO2015058827A1 (en) * | 2013-10-22 | 2015-04-30 | Merck Patent Gmbh | Conjugated polymers |
WO2015078551A1 (en) | 2013-11-28 | 2015-06-04 | Merck Patent Gmbh | Novel polycyclic polymer comprising thiophene units, a method of producing and uses of such polymer |
EP2824128A4 (en) * | 2012-12-10 | 2015-11-11 | Lg Chemical Ltd | Copolymer and organic solar cell using same |
CN106188090A (en) * | 2016-07-05 | 2016-12-07 | 北京大学深圳研究生院 | A kind of stereochemical structure organic semiconducting materials and method for preparing monomer |
US9796811B2 (en) | 2013-08-23 | 2017-10-24 | Sumitomo Chemical Company, Limited | Polymer compound and organic semiconductor device using the same |
US10239886B2 (en) | 2014-07-23 | 2019-03-26 | Sumitomo Chemical Company, Limited | Polymer compound and organic semiconductor device using the same |
WO2019137354A1 (en) * | 2018-01-10 | 2019-07-18 | The Hong Kong University Of Science And Technology | Thiophene-based fused aromatic systems |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2857429A4 (en) | 2012-05-31 | 2015-04-22 | Mitsubishi Chem Corp | Copolymer, organic semiconductor material, organic electrical device, and solar cell module |
JP6366728B2 (en) | 2014-02-28 | 2018-08-01 | コーニング インコーポレイテッド | Diketopyrrolopyrrole semiconductor material, preparation method thereof and use thereof |
US10875957B2 (en) * | 2015-11-11 | 2020-12-29 | The Regents Of The University Of California | Fluorine substitution influence on benzo[2,1,3]thiodiazole based polymers for field-effect transistor applications |
EP3523835B1 (en) | 2016-10-05 | 2022-11-16 | Raynergy Tek Inc. | Organic photodetector |
EP3406675A1 (en) | 2017-05-22 | 2018-11-28 | InnovationLab GmbH | Electronic and optoelectronic devices having anisotropic properties and method for their production |
CN111059512A (en) * | 2019-12-24 | 2020-04-24 | 上海晶合光电科技有限公司 | Automobile tail lamp based on OLED and preparation method thereof |
Citations (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4356429A (en) | 1980-07-17 | 1982-10-26 | Eastman Kodak Company | Organic electroluminescent cell |
US4539507A (en) | 1983-03-25 | 1985-09-03 | Eastman Kodak Company | Organic electroluminescent devices having improved power conversion efficiencies |
US5247190A (en) | 1989-04-20 | 1993-09-21 | Cambridge Research And Innovation Limited | Electroluminescent devices |
US5401827A (en) | 1990-08-24 | 1995-03-28 | Cambridge Display Technology Limited | Semiconductive copolymers for use in luminescent devices |
US20060078761A1 (en) | 2004-09-24 | 2006-04-13 | Plextronics, Inc. | Heteroatomic regioregular poly (3-substitutedthiophenes) in electroluminescent devices |
WO2008018931A2 (en) | 2006-06-13 | 2008-02-14 | Plextronics, Inc. | Organic photovoltaic devices comprising fullerenes and derivatives thereof |
US20080248313A1 (en) | 2006-07-21 | 2008-10-09 | Plextronics, Inc. | Sulfonation of conducting polymers and OLED, photovoltaic, and ESD devices |
US20080299293A1 (en) | 2007-05-02 | 2008-12-04 | Plextronics, Inc. | Solvent system for conjugated polymers |
US20090108255A1 (en) | 2007-10-31 | 2009-04-30 | Guillermo Bazan | Processing Additives for Fabricating Organic Photovoltaic Cells |
US7569159B2 (en) | 2005-02-10 | 2009-08-04 | Plextronics, Inc. | Hole injection/transport layer compositions and devices |
WO2011028827A2 (en) * | 2009-09-04 | 2011-03-10 | Plextronics, Inc. | Organic electronic devices and polymers, including photovoltaic cells and diketone-based polymers |
US10885108B2 (en) | 2012-12-04 | 2021-01-05 | Sonos, Inc. | Media content search based on metadata |
US11587708B2 (en) | 2019-10-02 | 2023-02-21 | Imec Vzw | Magnetic device with a hybrid free layer stack |
US11696308B2 (en) | 2011-03-23 | 2023-07-04 | Sun Patent Trust | Resource assignment for single and multiple cluster transmission |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8273599B2 (en) * | 2006-12-01 | 2012-09-25 | The Regents Of The University Of California | Enhancing performance characteristics of organic semiconducting films by improved solution processing |
US7754847B2 (en) * | 2007-12-27 | 2010-07-13 | Industrial Technology Research Institute | Soluble polythiophene derivatives |
JP2009302470A (en) * | 2008-06-17 | 2009-12-24 | Mitsui Chemicals Inc | Organic transistor |
PT2501698T (en) * | 2009-11-18 | 2018-07-23 | Nat Res Council Canada | Fluorinated monomers, oligomers and polymers for use in organic electronic devices |
-
2011
- 2011-10-25 US US13/281,023 patent/US9062152B2/en not_active Expired - Fee Related
- 2011-10-25 EP EP11782286.6A patent/EP2632968A1/en not_active Withdrawn
- 2011-10-25 WO PCT/US2011/057662 patent/WO2012058209A1/en active Application Filing
Patent Citations (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4356429A (en) | 1980-07-17 | 1982-10-26 | Eastman Kodak Company | Organic electroluminescent cell |
US4539507A (en) | 1983-03-25 | 1985-09-03 | Eastman Kodak Company | Organic electroluminescent devices having improved power conversion efficiencies |
US5247190A (en) | 1989-04-20 | 1993-09-21 | Cambridge Research And Innovation Limited | Electroluminescent devices |
US5401827A (en) | 1990-08-24 | 1995-03-28 | Cambridge Display Technology Limited | Semiconductive copolymers for use in luminescent devices |
US20060078761A1 (en) | 2004-09-24 | 2006-04-13 | Plextronics, Inc. | Heteroatomic regioregular poly (3-substitutedthiophenes) in electroluminescent devices |
US7569159B2 (en) | 2005-02-10 | 2009-08-04 | Plextronics, Inc. | Hole injection/transport layer compositions and devices |
US20080319207A1 (en) | 2006-06-13 | 2008-12-25 | Plextronics, Inc. | Organic photovoltaic devices comprising fullerenes and derivatives thereof |
WO2008018931A2 (en) | 2006-06-13 | 2008-02-14 | Plextronics, Inc. | Organic photovoltaic devices comprising fullerenes and derivatives thereof |
US20080248313A1 (en) | 2006-07-21 | 2008-10-09 | Plextronics, Inc. | Sulfonation of conducting polymers and OLED, photovoltaic, and ESD devices |
US20080299293A1 (en) | 2007-05-02 | 2008-12-04 | Plextronics, Inc. | Solvent system for conjugated polymers |
US20090108255A1 (en) | 2007-10-31 | 2009-04-30 | Guillermo Bazan | Processing Additives for Fabricating Organic Photovoltaic Cells |
WO2011028827A2 (en) * | 2009-09-04 | 2011-03-10 | Plextronics, Inc. | Organic electronic devices and polymers, including photovoltaic cells and diketone-based polymers |
US11696308B2 (en) | 2011-03-23 | 2023-07-04 | Sun Patent Trust | Resource assignment for single and multiple cluster transmission |
US10885108B2 (en) | 2012-12-04 | 2021-01-05 | Sonos, Inc. | Media content search based on metadata |
US11587708B2 (en) | 2019-10-02 | 2023-02-21 | Imec Vzw | Magnetic device with a hybrid free layer stack |
Non-Patent Citations (49)
Title |
---|
A.I VOGEL ET AL.: "Vogel's textbook of Organic Chemistry(5th Edition)", pages: 820 |
ACCOUNTS OF CHEMICAL RESEARCH, vol. 42, no. 11, November 2009 (2009-11-01) |
APPERLOO ET AL., J. L. CHEM.-EUR. J., vol. 8, 2002, pages 2384 - 2396 |
AYZNER ET AL., J, PHYS. CHEM. C, vol. 113, 2009, pages 20050 - 20060 |
BLOUIN ET AL., ACCOUNTS OF CHEMICAL RESEARCH, vol. 41, no. 9, September 2008 (2008-09-01), pages 1110 - 1119 |
BLOUIN ET AL., J. AM. CHEM. SOC., vol. 130, no. 2, 2008, pages 732 - 742 |
BREDAS ET AL., ACCOUNTS OF CHEMICAL RESEARCH, pages 1691 - 1699 |
BROWN ET AL., PHYS. REV., vol. 8, no. 67, 2003, pages 064203 |
BUNDGAARD ET AL., SOLAR ENERGY MATERIALS AND SOLAR CELLS, vol. 91, 2007, pages 1019 - 1025 |
CHEN ET AL., ACCOUNTS OF CHEMICAL RESEARCH, pages 1709 - 1718 |
CHEN ET AL., ADVANCED MATERIALS, vol. 21, 2009, pages 1 - 16 |
D. GAMOTA ET AL.: "Printed Organic and Molecular Electronia", 2004 |
FRECHET, J. M. J. ET AL., CHEM. MATER., vol. 21, 2009, pages 1775 |
GUNES ET AL., CHEM. REV., vol. 107, 2007, pages 1324 - 1338 |
HEREMANS ET AL., ACCOUNTS OF CHEMICAL RESEARCH, pages 1740 - 1747 |
HIRSCH, A., BRETTREICH, M.: "ullerenes; Chemistry and Reactions", 2005, WILEY-VCH VERLAG |
HOPPE ET AL., ADV POLYM SCI, vol. 214, 2008, pages 1 |
HOPPE ET AL., ADV. POLYM. SCI, vol. 214, 2008, pages 1 - 86 |
HOPPE, ADV. POLYM. SCI., vol. 214, 2008, pages 1 - 86 |
HOU ET AL., MACROMOLECULES, vol. 41, no. 16, 2008, pages 6012 - 6018 |
KOECKELBERGHS ET AL., MACROMOLECULES., vol. 40, 2007, pages 4173 |
KRAFT ET AL.: "Electroluminescent Conjugated Polymers - Seeing Polymers in a New Light", ANGEW. CHEM. INT ED, vol. 37, 1998, pages 402 - 428, XP000879607, DOI: doi:10.1002/(SICI)1521-3773(19980302)37:4<402::AID-ANIE402>3.0.CO;2-9 |
KUWANO ET AL., J. ORG. CHEM., vol. 67, 2002, pages 6479 - 6486 |
LI, MENG: "Organic Light Emitting Materials and Devices", 2006, CRC TAYLOR |
MIYAURA,: "Cross-Coupling Reactions: A Practical Guide", 2002 |
NEGISHI,: "Handbook of Organopalladium Chemistry for Organic Synthesis", 2002 |
NELSON ET AL., ACCOUNTS OF CHEMICAL RESEARCH, pages 1768 - 1778 |
PANAGIOTIS ET AL., ADV. FUNCT. MATER., vol. 18, 2008, pages 1 |
PEET ET AL., ACCOUNTS OF CHEMICAL RESEARCH, pages 1700 - 1708 |
PEET ET AL.: "Efficiency enhancement in low-bandgap polymer solar cells by processing with alkane dithiols", NAT. MATER, vol. 6, 2007, pages 497 - 500, XP002515637, DOI: doi:10.1038/NMAT1928 |
PETROVA-KOCK, V.; GOETZBERGER, A.: "High-Efficient-Low-Cost Photovoltaics", 2009, SPRINGER VERLAG, pages: 195 - 222 |
POMERANTZ ET AL., SYNTHETIC METALS, 2003, pages 135 - 136,257-258 |
POMERANTZ ET AL., TETRAHEDRON LETTERS, vol. 40, 1999, pages 3317 - 3320 |
POMERANTZ ET AL., TETRAHEDRON LETTERS, vol. 44, no. 8, 2003, pages 1563 - 1565 |
POPE ET AL., ELECTRONIC PROCESSES IN ORGANIC CRYSTALS AND POLYMERS, 1999 |
POTSCAVAGE ET AL., ACCOUNTS OF CHEMICAL RESEARCH, pages 1758 - 1767 |
RONCALI, ACCOUNTS OF CHEMICAL RESEARCH, pages 1719 - 1730 |
SCHMIDT ET AL., AM. CHEM. SOC., vol. 131, 2009, pages 6215 - 6228 |
See also references of EP2632968A1 |
SHIN ET AL., CHEM. MATER., vol. 19, 2007, pages 1892 - 1894 |
SUN AND SARACIFTCI: "Organic Photovoltaics, Mechanisms, Materials, and Devices", 2005, CRC |
SUN, SARICIFTCI, ORGANIC PHOTOVOLTAICS, MECHANISMS, MATERIALS, AND DEVICES, 2005 |
SWAGER ET AL., ADV. MATER., vol. 13, 2001, pages 1775 |
TURBIEZ ET AL., CHEM.-EUR. J., vol. 11, 2005, pages 3742 - 3752 |
WALZER, CHEM. REV., vol. 107, 2007, pages 1233 - 1271 |
YU ET AL., J. AM. CHEM. SOC., vol. 131, 2009, pages 56 |
ZHOU ET AL.: "Synthesis and Photovoltaic Properties of Diketopyrrolopyrrole-Based Donor-Acceptor Complexes", CHEMISTRY OF MATERIALS, 2009 |
ZHU ET AL., ACCOUNTS OF CHEMICAL RESEARCH, pages 1779 - 1787 |
ZHU ET AL.: "High-Efficient Low-Cost Photovoltaics", 2009, SPRINGER, article "Design Rules for Efficient Organic Solar Cells", pages: 195 - 222 |
Cited By (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10584203B2 (en) | 2011-10-20 | 2020-03-10 | Universite Laval | Preparation of high molecular weight polymers by direct arylation and heteroarylation |
WO2013056355A1 (en) * | 2011-10-20 | 2013-04-25 | UNIVERSITé LAVAL | Preparation of high molecular weight polymers 8y direct arylation and heteroarylation |
US9505876B2 (en) | 2011-10-20 | 2016-11-29 | Universite Laval | Preparation of high molecular weight polymers by direct arylation and heteroarylation |
WO2014005667A1 (en) * | 2012-07-02 | 2014-01-09 | Merck Patent Gmbh | Conjugated polymers |
CN104395372A (en) * | 2012-07-02 | 2015-03-04 | 默克专利股份有限公司 | Conjugated polymers |
KR20150036247A (en) * | 2012-07-02 | 2015-04-07 | 메르크 파텐트 게엠베하 | Conjugated polymers |
KR102128635B1 (en) | 2012-07-02 | 2020-06-30 | 메르크 파텐트 게엠베하 | Conjugated polymers |
US9695190B2 (en) | 2012-07-02 | 2017-07-04 | Merck Patent Gmbh | Conjugated polymers |
US9666804B2 (en) | 2012-12-10 | 2017-05-30 | Lg Chem, Ltd. | Copolymer and organic solar cell using same |
EP2824128A4 (en) * | 2012-12-10 | 2015-11-11 | Lg Chemical Ltd | Copolymer and organic solar cell using same |
US9796811B2 (en) | 2013-08-23 | 2017-10-24 | Sumitomo Chemical Company, Limited | Polymer compound and organic semiconductor device using the same |
CN105658761A (en) * | 2013-10-22 | 2016-06-08 | 默克专利股份有限公司 | Conjugated polymers |
US9806263B2 (en) | 2013-10-22 | 2017-10-31 | Merck Patent Gmbh | Conjugated polymers |
WO2015058827A1 (en) * | 2013-10-22 | 2015-04-30 | Merck Patent Gmbh | Conjugated polymers |
US10134994B2 (en) | 2013-11-28 | 2018-11-20 | Merck Patent Gmbh | Polycyclic polymer comprising thiophene units, a method of producing and uses of such polymer |
WO2015078551A1 (en) | 2013-11-28 | 2015-06-04 | Merck Patent Gmbh | Novel polycyclic polymer comprising thiophene units, a method of producing and uses of such polymer |
US10239886B2 (en) | 2014-07-23 | 2019-03-26 | Sumitomo Chemical Company, Limited | Polymer compound and organic semiconductor device using the same |
CN106188090A (en) * | 2016-07-05 | 2016-12-07 | 北京大学深圳研究生院 | A kind of stereochemical structure organic semiconducting materials and method for preparing monomer |
WO2019137354A1 (en) * | 2018-01-10 | 2019-07-18 | The Hong Kong University Of Science And Technology | Thiophene-based fused aromatic systems |
Also Published As
Publication number | Publication date |
---|---|
US20120283377A1 (en) | 2012-11-08 |
US9062152B2 (en) | 2015-06-23 |
EP2632968A1 (en) | 2013-09-04 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US9062152B2 (en) | Organic electronic devices, including organic photovoltaic devices, polymers, and monomers | |
US8691931B2 (en) | Organic electronic devices and polymers, including photovoltaic cells and diketone-based and diketopyrrolopyrrole-based polymers | |
US9376529B2 (en) | Fluoro monomers, oligomers, and polymers for inks and organic electronic devices | |
US10026899B2 (en) | Active materials for electro-optic devices and electro-optic devices | |
EP2507287A1 (en) | Novel photoactive polymers | |
WO2011002927A2 (en) | Novel compositions, methods and polymers | |
KR101853395B1 (en) | Electron donating polymer and solar cell including the same | |
Patil et al. | Synthesis and photovoltaic properties of narrow band gap copolymers of dithieno [3, 2-b: 2′, 3′-d] thiophene and diketopyrrolopyrrole | |
Murali et al. | Narrow band gap conjugated polymer for improving the photovoltaic performance of P3HT: PCBM ternary blend bulk heterojunction solar cells | |
WO2008143838A1 (en) | Aryl-substituted conjugated polymers | |
WO2012132733A1 (en) | Organic semiconductor polymer, composition for organic semiconductor material, and photovoltaic cell | |
Qiu et al. | Two new medium bandgap asymmetric copolymers based on thieno [2, 3-f] benzofuran for efficient organic solar cells | |
Qi et al. | Enhanced photovoltaic performance of polymer solar cells through design of a fused dithienosilolodithiophene structure with an enlarged π-conjugated system | |
Li et al. | A new narrow bandgap polymer as donor material for high performance non-fullerene polymer solar cells | |
Heo et al. | Regioregular polymers containing benzodithiophene and thienothiophene segments with different electron donating side chains for high-performance polymer solar cells | |
Wang et al. | Synthesis and optoelectronic property manipulation of conjugated polymer photovoltaic materials based on benzo [d]-dithieno [3, 2-b; 2′, 3′-f] azepine | |
Lee et al. | Difluorobenzothiadiazole based two-dimensional conjugated polymers with triphenylamine substituted moieties as pendants for bulk heterojunction solar cells | |
Ha et al. | Low-band gap copolymers based on diketopyrrolopyrrole and dibenzosilole and their application in organic photovoltaics | |
Liu et al. | Synthesis and property characterization of two novel side-chain isoindigo copolymers for polymer solar cells. | |
정의혁 | Design and Synthesis of Isoindigo-Based Conjugated Polymers for High Performance Polymer Solar Cells | |
김주현 | Synthesis and photovoltaic properties of π-conjugated polymers based on benzimidazole, arylene imide and benzooxadiazole for polymer solar cells |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 11782286 Country of ref document: EP Kind code of ref document: A1 |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2011782286 Country of ref document: EP |