KR101794723B1 - Polymer compound and electronic device comprising same - Google Patents
Polymer compound and electronic device comprising same Download PDFInfo
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- KR101794723B1 KR101794723B1 KR1020150131904A KR20150131904A KR101794723B1 KR 101794723 B1 KR101794723 B1 KR 101794723B1 KR 1020150131904 A KR1020150131904 A KR 1020150131904A KR 20150131904 A KR20150131904 A KR 20150131904A KR 101794723 B1 KR101794723 B1 KR 101794723B1
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- 229920000642 polymer Polymers 0.000 title claims abstract description 81
- 150000001875 compounds Chemical class 0.000 title claims abstract description 73
- 125000000217 alkyl group Chemical group 0.000 claims description 74
- 239000000463 material Substances 0.000 claims description 28
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 24
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 20
- 125000000732 arylene group Chemical group 0.000 claims description 19
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical group [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 18
- 229910052711 selenium Inorganic materials 0.000 claims description 18
- 229910052717 sulfur Inorganic materials 0.000 claims description 18
- 125000004434 sulfur atom Chemical group 0.000 claims description 18
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 239000000178 monomer Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 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 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 9
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound 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 claims description 8
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 8
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 125000001153 fluoro group Chemical group F* 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 101150024701 PPH3 gene Proteins 0.000 claims description 3
- 125000004653 anthracenylene group Chemical group 0.000 claims description 3
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 claims description 3
- PIMYDFDXAUVLON-UHFFFAOYSA-M chloro(triethyl)stannane Chemical compound CC[Sn](Cl)(CC)CC PIMYDFDXAUVLON-UHFFFAOYSA-M 0.000 claims description 3
- 229910003472 fullerene Inorganic materials 0.000 claims description 3
- 125000004957 naphthylene group Chemical group 0.000 claims description 3
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 125000005548 pyrenylene group Chemical group 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 230000031700 light absorption Effects 0.000 abstract description 7
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 125000003118 aryl group Chemical group 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- MCEWYIDBDVPMES-UHFFFAOYSA-N [60]pcbm Chemical compound C123C(C4=C5C6=C7C8=C9C%10=C%11C%12=C%13C%14=C%15C%16=C%17C%18=C(C=%19C=%20C%18=C%18C%16=C%13C%13=C%11C9=C9C7=C(C=%20C9=C%13%18)C(C7=%19)=C96)C6=C%11C%17=C%15C%13=C%15C%14=C%12C%12=C%10C%10=C85)=C9C7=C6C2=C%11C%13=C2C%15=C%12C%10=C4C23C1(CCCC(=O)OC)C1=CC=CC=C1 MCEWYIDBDVPMES-UHFFFAOYSA-N 0.000 description 10
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- 229920000301 poly(3-hexylthiophene-2,5-diyl) polymer Polymers 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
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- 125000001424 substituent group Chemical group 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- -1 phenylmercaptoethylmethane ester Chemical class 0.000 description 3
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 description 2
- 229920000144 PEDOT:PSS Polymers 0.000 description 2
- 238000000944 Soxhlet extraction Methods 0.000 description 2
- NPNMHHNXCILFEF-UHFFFAOYSA-N [F].[Sn]=O Chemical compound [F].[Sn]=O NPNMHHNXCILFEF-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 125000005605 benzo group Chemical group 0.000 description 2
- 239000000872 buffer Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 230000014509 gene expression Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- LYRCQNDYYRPFMF-UHFFFAOYSA-N trimethyltin Chemical compound C[Sn](C)C LYRCQNDYYRPFMF-UHFFFAOYSA-N 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 1
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- KZDTZHQLABJVLE-UHFFFAOYSA-N 1,8-diiodooctane Chemical compound ICCCCCCCCI KZDTZHQLABJVLE-UHFFFAOYSA-N 0.000 description 1
- MVPPADPHJFYWMZ-RALIUCGRSA-N 1-chloro-2,3,4,5,6-pentadeuteriobenzene Chemical compound [2H]C1=C([2H])C([2H])=C(Cl)C([2H])=C1[2H] MVPPADPHJFYWMZ-RALIUCGRSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
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- WZGZUMHXFWEKPM-UHFFFAOYSA-N BrC1=C(C=C(S1)C1=CC=C(C2=NSN=C21)C=2SC(=C(C2)CC(CCCC)CC)Br)CC(CCCC)CC.FC2=C(C=1C(=NSN1)C(=C2F)C=2SC(=C(C2)CC(CCCC)CC)Br)C=2SC(=C(C2)CC(CCCC)CC)Br Chemical compound BrC1=C(C=C(S1)C1=CC=C(C2=NSN=C21)C=2SC(=C(C2)CC(CCCC)CC)Br)CC(CCCC)CC.FC2=C(C=1C(=NSN1)C(=C2F)C=2SC(=C(C2)CC(CCCC)CC)Br)C=2SC(=C(C2)CC(CCCC)CC)Br WZGZUMHXFWEKPM-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical group [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-UHFFFAOYSA-N Hydrogen atom Chemical class [H] YZCKVEUIGOORGS-UHFFFAOYSA-N 0.000 description 1
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 1
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
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- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
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- 229910052805 deuterium Inorganic materials 0.000 description 1
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Natural products CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 1
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- 238000000605 extraction Methods 0.000 description 1
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- 239000002803 fossil fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 125000005553 heteroaryloxy group Chemical group 0.000 description 1
- 125000000592 heterocycloalkyl group Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
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- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- PTMHPRAIXMAOOB-UHFFFAOYSA-N phosphoric acid amide group Chemical group P(N)(O)(O)=O PTMHPRAIXMAOOB-UHFFFAOYSA-N 0.000 description 1
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- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
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- UKTDFYOZPFNQOQ-UHFFFAOYSA-N tributyl(thiophen-2-yl)stannane Chemical compound CCCC[Sn](CCCC)(CCCC)C1=CC=CS1 UKTDFYOZPFNQOQ-UHFFFAOYSA-N 0.000 description 1
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- 238000010792 warming Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- 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
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- 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
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/32—Polythiazoles; Polythiadiazoles
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- H01L51/424—
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- 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
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- 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
- C08G2261/3246—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing nitrogen and sulfur as heteroatoms
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- 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
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L2031/0344—Organic materials
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Abstract
The present invention relates to a polymer compound represented by the following structural formula (1). The polymer compound of the present invention can lower the HOMO energy level by introducing an alkoxy-phenyl group into the side chain and extend the conjugation in two dimensions. Also, by applying such a polymer compound, crystallinity of the polymer crystal is improved due to high regularity of side chains and high planarity of the polymer compound, so that the light absorption efficiency and the photoelectric conversion efficiency of the organic solar cell can be improved.
[Structural formula 1]
Description
TECHNICAL FIELD The present invention relates to a polymer compound and an electronic device including the polymer compound, and more particularly, to a polymer compound having an HOMO energy level lowered by introducing an alkoxy-phenyl group into a side chain and extending a two-dimensional conjugation, and an electronic device containing the same.
Concerns about depletion of fossil fuels, warming due to their abuse, safety concerns with climate change and nuclear energy have raised the need for photovoltaic power generation, which is sustainable energy, higher than ever. The average energy delivered by the sun to the Earth on average is 105 TW, a fraction of which is well above the 20 TW expected to be required by the entire 2020 region.
Of course, not all energy from the sun can be exploited, but because of its relatively sub-regional characteristics and inherent eco-friendliness, photovoltaics has always been regarded as one of the most attractive renewable energy sources.
Organic semiconductors constituting organic solar cells can be implemented at a relatively low temperature and process relative to other semiconductor technologies, which is advantageous in that they can be compatible with low-cost glass or various plastic substrates, which can be a problem in high temperature processing. In particular, when a plastic substrate is used, roll-to-roll and printing processes can be applied. In this case, it is expected to realize an ultra-low-cost solar cell technology by realizing high production per unit time. The efficiency of the organic solar cell has been steadily developed since Kodak's Tang realized about 1% of the efficiency using the multilayer thin film of the low-molecular semiconductor layer using the vacuum deposition in the middle of 1980's. In particular, research on organic solar cells has increased rapidly since 2000, and polymer solar cells capable of introducing a photoactive layer by a solution process introduced a bulk heterojunction concept with PCBM in the early 2000s By using P3HT as a photoactive layer, efficiency of 4-6% can be generally obtained, and this result is an attempt to develop a new material and device structure attracting attention from academia and industry Have started in earnest since 2005.
Polymer solar cell efficiency In addition, the efficiency of solar cells using new polymers other than PPV and P3HT, which had not reached 1-2% by 2005, is expected to increase 9.1% Respectively. In addition, recent theoretical predictions that the energy conversion efficiency of 10% or more based on the single layer structure is possible by well controlling the energy level and the photoelectric property of the organic semiconductor brightens the practical use of the organic thin film solar cell, .
As a method of improving the photoelectric conversion efficiency, a bulk heterojunction type solar cell in which an electron acceptor material (n-type organic semiconductor) and an electron donor material (p-type organic semiconductor) are mixed to increase the bonding surface contributing to photoelectric conversion It has been developed. Among them, poly (3-hexylthiophene) (P3HT) is used as an electron donor material (p-type organic semiconductor) and phenylmercaptoethylmethane ester (PCBM) Organic solar cells are reported.
However, poly (3-hexylthiophene) (P3HT), which is an electron donor material mainly used at present, is relatively low in light absorption efficiency due to its relatively small absorption wavelength band. In addition, due to the high occupied molecular orbital (HOMO) energy level, there is a problem that the open circuit voltage is low and the photoelectric conversion efficiency of the organic solar battery is limited.
An object of the present invention is to provide a polymer compound having an HOMO energy level lowered by introducing an alkoxy-arylene group as a side chain and extending the conjugation two-dimensionally.
Another object of the present invention is to provide an organic solar cell having improved light absorption efficiency and photoelectric conversion efficiency by improving crystallinity of a polymer crystal due to high regularity of side chains and high planarity of a polymer compound by applying such a polymer compound I have to.
According to an aspect of the present invention,
A polymer compound represented by the following
[Structural formula 1]
In
Ar 1 and Ar 2 are the same or different from each other, Ar 1 and Ar 2 are each independently a substituted or unsubstituted C6 to C30 arylene group,
X 1 and X 2 are the same or different from each other, and X 1 and X 2 are each independently an oxygen atom, a sulfur atom, or a selenium atom,
R 1 and R 2 are the same or different from each other, and R 1 and R 2 are each independently a straight chain alkyl group of
R 3 and R 4 are the same or different from each other, and R 3 and R 4 are each independently a hydrogen atom or a halogen atom,
Q 1 and Q 2 are the same or different, and Q 1 and Q 2 are each independently
R 5 to R 9 are the same or different from each other, and R 5 to R 9 are each independently a straight-chain alkyl group of C6 to C30,
n is a repetition number of repeating units,
The number average molecular weight (Mn) is 3,000 to 500,000.
Ar 1 and Ar 2 are the same or different from each other, and Ar 1 and Ar 2 are each independently any one selected from a phenylene group, a biphenylene group, a naphthylene group, an anthrylene group and a pyrenylene group.
X 1 and X 2 may be an oxygen atom.
R 1 and R 2 are the same or different from each other, R 1 and R 2 are each independently a
R 3 and R 4 may be the same or different from each other, and R 3 and R 4 may each independently be a fluorine atom or a chlorine atom.
According to another aspect of the present invention,
There is provided a process for producing a polymer compound by polymerizing a monomer represented by the following structural formula 2 and a monomer represented by the following structural formula 3 to produce a polymer represented by the following
[Structural formula 1]
In
Ar 1 and Ar 2 are the same or different from each other, Ar 1 and Ar 2 are each independently a substituted or unsubstituted C6 to C30 arylene group,
X 1 and X 2 are the same or different from each other, and X 1 and X 2 are each independently an oxygen atom, a sulfur atom, or a selenium atom,
R 1 and R 2 are the same or different from each other, and R 1 and R 2 are each independently a straight chain alkyl group of
R 3 and R 4 are the same or different from each other, and R 3 and R 4 are each independently a hydrogen atom or a halogen atom,
Q 1 and Q 2 are the same or different, and Q 1 and Q 2 are each independently
R 5 to R 9 are the same or different from each other, and R 5 to R 9 are each independently a straight-chain alkyl group of C6 to C30,
n is a repetition number of repeating units,
The number average molecular weight (Mn) is 3,000 to 500,000.
[Structural formula 2]
In formula 2,
Ar 1 and Ar 2 are the same or different from each other, Ar 1 and Ar 2 are each independently a substituted or unsubstituted C6 to C30 arylene group,
X 1 and X 2 are the same or different from each other, and X 1 and X 2 are each independently an oxygen atom, a sulfur atom, or a selenium atom,
R 1 and R 2 are the same or different from each other, and R 1 and R 2 are each independently a straight chain alkyl group of
[Structural Formula 3]
In Structure 3,
R 3 and R 4 are the same or different from each other, and R 3 and R 4 are each independently a hydrogen atom or a halogen atom,
Q 1 and Q 2 are the same or different, and Q 1 and Q 2 are each independently
R 5 to R 9 are the same as or different from each other, and R 5 to R 9 are each independently a straight-chain alkyl group of C6 to C30, or a crushed alkyl group.
(A) preparing a mixture by mixing a monomer represented by the formula 2, a monomer represented by the formula 3, and a catalyst; And (b) adding an organic solvent to the mixture to perform a polymerization reaction to prepare the polymer compound represented by the structural formula (1).
Wherein the catalyst is selected from the group consisting of tetrakis (triphenylphosphine) palladium (0), Pd (PPH3) 4 and tris (dibenzylideneacetone) dipalladium (0) (0)).
The organic solvent may include at least one selected from toluene, dimethylformamide (DMF), and chlorobenzene.
(A'-1) reacting a compound represented by the following formula (1) and a compound represented by the following formula (2) to prepare a compound represented by the following formula (3); And (a'-2) reacting the compound represented by Formula 3 with n-butyllithium and triethyltin chloride to prepare a compound represented by Formula 2, As shown in FIG.
[Chemical Formula 1]
(2)
R-X-Ar-Br
In formula (2)
Ar is a substituted or unsubstituted C6 to C30 arylene group,
X is an oxygen atom, a sulfur atom, or a selenium atom,
R is a straight chain alkyl group of C10 to C30, or a crushed alkyl group.
(3)
In formula (3)
Ar is independently a substituted or unsubstituted C6 to C30 arylene group,
Each X is independently an oxygen atom, a sulfur atom, or a selenium atom,
Each R is independently a straight chain alkyl group of C10 to C30, or a crushed alkyl group.
According to another aspect of the present invention,
An electronic device comprising the polymer compound is provided.
The electronic device may be an organic solar cell.
Wherein the organic solar cell comprises:
A first electrode; A photoactive layer formed on the first electrode; And a second electrode formed on the light absorbing layer, wherein the photoactive layer may include a polymer compound represented by the following structural formula (1).
[Structural formula 1]
In
Ar 1 and Ar 2 are the same or different from each other, Ar 1 and Ar 2 are each independently a substituted or unsubstituted C6 to C30 arylene group,
X 1 and X 2 are the same or different from each other, and X 1 and X 2 are each independently an oxygen atom, a sulfur atom, or a selenium atom,
R 1 and R 2 are the same or different from each other, and R 1 and R 2 are each independently a straight chain alkyl group of
R 3 and R 4 are the same or different from each other, and R 3 and R 4 are each independently a hydrogen atom or a halogen atom,
Q 1 and Q 2 are the same or different, and Q 1 and Q 2 are each independently
R 5 to R 9 are the same or different from each other, and R 5 to R 9 are each independently a straight-chain alkyl group of C6 to C30,
n is a repetition number of repeating units,
The number average molecular weight (Mn) is 3,000 to 500,000.
The photoactive layer may comprise an electron donor material and an electron acceptor material.
The mass ratio of the electron donor material and the electron donor material may be 1: 0.5 to 1: 3.
The electron donor may include the polymer compound represented by the structural formula (1).
The electron acceptor material may include at least one selected from fullerene and fullerene derivatives.
Wherein the fullerene derivative is selected from the group consisting of phenyl-C71-butyric acid methyl ester, PC61BM ([6,6] -phenyl-C61-butyric acid methyl ester), bisPCBM (bisadduct of phenyl C61-butyric acid methyl ester), trisPCBM of phenyl C61-butyric acid methyl ester).
The first electrode may include at least one selected from fluorine tin oxide (FTO), indium tin oxide (ITO), ZnO-Ga 2 O 3 , ZnO-Al 2 O 3 , tin oxide and zinc oxide .
The second electrode may include at least one selected from Ag, Au, Pt, Ni, Cu, In, Ru, Pd, Rh, Ir, Os, and a conductive polymer.
The first electrode may further include a substrate on the side opposite to the side in contact with the light absorbing layer.
The substrate may comprise a glass substrate, a conductive transparent substrate or a plastic substrate.
The polymer compound of the present invention can lower the HOMO energy level and extend the two-dimensional conjugation by introducing an alkoxy-arylene group to the side chain.
Also, by applying such a polymer compound, crystallinity of the polymer crystal is improved due to high regularity of side chains and high planarity of the polymer compound, thereby improving the light absorption efficiency and photoelectric conversion efficiency of the organic solar cell.
Fig. 1 shows the results of UV-Vis spectroscopy of the polymer prepared according to Example 1 and Comparative Example 1. Fig.
Fig. 2 shows the measurement results of the light absorption coefficient of the polymer prepared according to Example 1 and Comparative Example 1. Fig.
FIG. 3 shows the results of measurement of crystallinity and intermolecular packing of the polymer prepared according to Example 1 and Comparative Example 1. FIG.
4 shows the results of measurement of the device characteristics of the organic solar cell produced according to the
Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art can easily carry out the present invention.
However, the following description does not limit the present invention to specific embodiments. In the following description of the present invention, detailed description of related arts will be omitted if it is determined that the gist of the present invention may be blurred .
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The singular expressions include plural expressions unless the context clearly dictates otherwise. In the present application, the terms "comprises ", or" having ", and the like, specify that the presence of stated features, integers, steps, operations, elements, or combinations thereof, But do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, or combinations thereof.
Furthermore, terms including an ordinal number such as first, second, etc. to be used below can be used to describe various elements, but the constituent elements are not limited by the terms. The terms are used only for the purpose of distinguishing one component from another. For example, without departing from the scope of the present invention, the first component may be referred to as a second component, and similarly, the second component may also be referred to as a first component.
Also, when an element is referred to as being "formed" or "laminated" on another element, it may be directly attached or laminated to the front surface or one surface of the other element, It will be appreciated that other components may be present in the < / RTI >
The term "substituted" as used herein means that at least one hydrogen atom is replaced by a substituent selected from the group consisting of deuterium, C1 to C30 alkyl groups, C3 to C30 cycloalkyl groups, C2 to C30 heterocycloalkyl groups, C1 to C30 halogenated alkyl groups, C6 to C30 aryl groups, C1 to C30 heteroaryl groups, C1 to C30 alkoxy groups, C2 to C30 alkenyl groups, C2 to C30 alkynyl group, C6 to C30 aryloxy group, a silyloxy (-OSiH 3), -OSiR 1 H 2 (R 1 is a C1 to C30 alkyl groups or C6 to C30 aryl group), -OSiR 1 R 2 H ( R 1 and R 2 are each independently a C1 to C30 alkyl or C6 to C30 aryl group), -OSiR 1 R 2 R 3 , (R 1, R 2, and R 3 each independently represent a C1 to C30 alkyl group or a C6 to C30 aryl group), a C1 to C30 acyl group, a C2 to C30 acyloxy group, a C2 to C30 heteroaryloxy group, a C1 to C30 sulfonyl group, a C1 to C30 alkylthiol group , A C6 to C30 arylthiol group, a C1 to C30 heterocyclothiol group, a C1 to C30 phosphoric acid amide group, a silyl group (- SiH 3), -SiR 1 H 2 (R 1 is a C1 to C30 alkyl or C6 to C30 aryl group), -SiR 1 R 2 H ( R 1 and R 2 are each independently a C1 to C30 alkyl or C6 to C30 aryl group), -SiR 1 R 2 R 3 , (R 1, R 2, and R 3 are each independently a C1 to C30 alkyl or C6 to C30 aryl group), an amine group -NRR '(here, R and R' Are each independently a substituent selected from the group consisting of a hydrogen atom, a C1 to C30 alkyl group, and a C6 to C30 aryl group), a carboxyl group, a halogen group, a cyano group, a nitro group, an azo group and a hydroxy group Substituted by a substituent.
Preferably a C1 to C30 straight-chain alkyl group, or a branched alkyl group, more preferably a C1 to C10 straight-chain alkyl group, or a branched alkyl group.
The carbon number range of the alkyl group or aryl group in the above "substituted or unsubstituted C1 to C30 alkyl group" or "substituted or unsubstituted C6 to C30 aryl group" Quot; means the total number of carbon atoms constituting the alkyl moiety or the aryl moiety when it is considered to be " substituted ". For example, a phenyl group substituted with a butyl group at the para position means an aryl group having 6 carbon atoms substituted with a butyl group having 4 carbon atoms.
As used herein, "hydrogen" means monohydrogen, double hydrogen, or tritium, unless otherwise defined.
As used herein, unless otherwise defined, the term "alkyl group" means an aliphatic hydrocarbon group.
The alkyl group may be a "saturated alkyl group" which does not contain any double or triple bonds.
The alkyl group may be an "unsaturated alkyl group" comprising at least one double bond or triple bond.
The alkyl group may be a C1 to C50 alkyl group. More specifically, the alkyl group may be a C1 to C20 alkyl group, a C1 to C10 alkyl group or a C1 to C6 alkyl group.
For example, the C1 to C4 alkyl groups may have 1 to 4 carbon atoms in the alkyl chain, i.e., the alkyl chain may be optionally substituted with one or more substituents selected from the group consisting of methyl, ethyl, propyl, iso-propyl, n-butyl, Indicating that they are selected from the group.
Specific examples of the alkyl group include a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, ethenyl group, Butyl group, cyclopentyl group, cyclohexyl group, and the like.
Hereinafter, the polymer compound of the present invention will be described in detail. However, it should be understood that the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.
The polymer compound of the present invention can be represented by the following
[Structural formula 1]
In
Ar 1 and Ar 2 are the same or different from each other, Ar 1 and Ar 2 are each independently a substituted or unsubstituted C6 to C30 arylene group,
X 1 and X 2 are the same or different from each other, and X 1 and X 2 are each independently an oxygen atom, a sulfur atom, or a selenium atom,
R 1 and R 2 are the same or different from each other, and R 1 and R 2 are each independently a straight chain alkyl group of
R 3 and R 4 are the same or different from each other, and R 3 and R 4 are each independently a hydrogen atom or a halogen atom,
Q 1 and Q 2 are the same or different, and Q 1 and Q 2 are each independently
R 5 to R 9 are the same or different from each other, and R 5 to R 9 are each independently a straight-chain alkyl group of C6 to C30,
n is a repetition number of repeating units,
The number average molecular weight (Mn) is 3,000 to 500,000.
Ar 1 and Ar 2 are the same or different from each other, and Ar 1 and Ar 2 each independently represent a phenylene group, a biphenylene group, a naphthylene group, an anthrylene group, a pyrenylene group or the like, have. However, the scope of the present invention is not limited thereto, and all of the arylene groups having a symmetric structure can be applied.
In the case of the thienylene group used conventionally, it is not preferable because there is no symmetry and the regioregularity of the polymer compound may be decreased and intermolecular packing may be reduced.
X 1 and X 2 may preferably be an oxygen atom.
R 1 and R 2 may preferably be a
R 5 to R 9 may preferably be straight or branched alkyl groups of C6 to C20.
R 3 and R 4 may preferably be a fluorine atom, or a chlorine atom.
Hereinafter, a method for producing the polymer compound of the present invention will be described.
The method for producing a polymer compound of the present invention comprises polymerizing a monomer represented by the following structural formula 2 and a monomer represented by the following structural formula 3 to prepare a polymer compound represented by the following
[Structural formula 2]
In formula 2,
Ar 1 and Ar 2 are the same or different from each other, Ar 1 and Ar 2 are each independently a substituted or unsubstituted C6 to C30 arylene group,
X 1 and X 2 are the same or different from each other, and X 1 and X 2 are each independently an oxygen atom, a sulfur atom, or a selenium atom,
R 1 and R 2 are the same or different from each other, and R 1 and R 2 are each independently a straight chain alkyl group of
[Structural Formula 3]
In Structure 3,
R 3 and R 4 are the same or different from each other, and R 3 and R 4 are each independently a hydrogen atom or a halogen atom,
Q 1 and Q 2 are the same or different, and Q 1 and Q 2 are each independently
R 5 to R 9 are the same as or different from each other, and R 5 to R 9 are each independently a straight-chain alkyl group of C6 to C30, or a crushed alkyl group.
[Structural formula 1]
In
Ar 1 and Ar 2 are the same or different from each other, Ar 1 and Ar 2 are each independently a substituted or unsubstituted C6 to C30 arylene group,
X 1 and X 2 are the same or different from each other, and X 1 and X 2 are each independently an oxygen atom, a sulfur atom, or a selenium atom,
R 1 and R 2 are the same or different from each other, and R 1 and R 2 are each independently a straight chain alkyl group of
R 3 and R 4 are the same or different from each other, and R 3 and R 4 are each independently a hydrogen atom or a halogen atom,
Q 1 and Q 2 are the same or different, and Q 1 and Q 2 are each independently
R 5 to R 9 are the same or different from each other, and R 5 to R 9 are each independently a straight-chain alkyl group of C6 to C30,
n is a repetition number of repeating units,
The number average molecular weight (Mn) is 3,000 to 500,000.
More specifically, first, the monomer represented by the formula 2, the monomer represented by the formula 3, and the catalyst are mixed to prepare a mixture (step (a)).
The catalyst may be selected from the group consisting of tetrakis (triphenylphosphine) palladium (0), Pd (PPH3) 4, tris (dibenzylideneacetone) dipalladium (0) (0)), but preferably tetrakis (triphenylphosphine) palladium (0) or tris (dibenzylideneacetone) dipalladium (0).
Next, an organic solvent is added to the mixture to perform a polymerization reaction to prepare a polymer compound represented by the structural formula 1 (step (b)).
The organic solvent may include toluene, dimethylformamide (DMF), chlorobenzene, and the like, but may be a mixed solution of toluene and dimethylformamide.
First, a compound represented by the following formula (1) and a compound represented by the following formula (2) are polymerized to prepare a compound represented by the following formula (3 ') (step (a'-1)).
[Chemical Formula 1]
(2)
R-X-Ar-Br
In formula (2)
Ar is a substituted or unsubstituted C6 to C30 arylene group,
X is an oxygen atom, a sulfur atom, or a selenium atom,
R is a straight chain alkyl group of C10 to C30, or a crushed alkyl group.
(3)
In formula (3)
Ar is independently a substituted or unsubstituted C6 to C30 arylene group,
Each X is independently an oxygen atom, a sulfur atom, or a selenium atom,
Each R is independently a straight chain alkyl group of C10 to C30, or a crushed alkyl group.
Next, the compound represented by Formula 2 can be prepared by reacting the compound represented by Formula 3 with n-butyllithium and triethyltin chloride (Step (a'- 2)).
Hereinafter, an organic solar cell of an electronic device of the present invention will be described as an example.
The organic solar battery of the present invention may include a first electrode, a photoactive layer formed on the first electrode, and a second electrode formed on the light absorbing layer. At this time, the photoactive layer may include a polymer compound represented by the following structural formula (1).
[Structural formula 1]
In
Ar 1 and Ar 2 are the same or different from each other, Ar 1 and Ar 2 are each independently a substituted or unsubstituted C6 to C30 arylene group,
X 1 and X 2 are the same or different from each other, and X 1 and X 2 are each independently an oxygen atom, a sulfur atom, or a selenium atom,
R 1 and R 2 are the same or different from each other, and R 1 and R 2 are each independently a straight chain alkyl group of
R 3 and R 4 are the same or different from each other, and R 3 and R 4 are each independently a hydrogen atom or a halogen atom,
Q 1 and Q 2 are the same or different, and Q 1 and Q 2 are each independently
R 5 to R 9 are the same or different from each other, and R 5 to R 9 are each independently a straight-chain alkyl group of C6 to C30,
n is a repetition number of repeating units,
The number average molecular weight (Mn) is 3,000 to 500,000.
The photoactive layer may comprise an electron donor material and an electron acceptor material.
The mass ratio of the electron donor material and the electron donor material may be 1: 0.5 to 1: 3, preferably 1: 0.7 to 1: 2, more preferably 1: 0.9 to 1: 1.5.
The electron donor material may include the polymer compound represented by the structural formula (1). The polymer compound increases the regularity of alignment, increases intermolecular packing and planarity, and increases mobility and device characteristics when applied to an organic solar cell.
The electron acceptor material may be fullerene or a fullerene derivative.
The fullerene derivative may be selected from the group consisting of PC71BM (phenyl-C71-butyric acid methyl ester), PC61BM ([6,6] -phenyl-C61-butyric acid methyl ester), bisPCBM (bisadduct of phenyl C61-butyric acid methyl ester), trisPCBM of phenyl C61-butyric acid methyl ester), but it is preferably PC71BM.
The first electrode may be made of fluorine tin oxide (FTO), indium tin oxide (ITO), ZnO-Ga 2 O 3 , ZnO-Al 2 O 3 , tin oxide, zinc oxide, .
The second electrode may include Ag, Au, Pt, Ni, Cu, In, Ru, Pd, Rh, Ir, Os, C,
The first electrode may further include a substrate on the side opposite to the side in contact with the light absorbing layer, and the substrate may be a glass substrate, a conductive transparent substrate, or a plastic substrate.
[Example]
Hereinafter, preferred embodiments of the present invention will be described. However, this is for illustrative purposes only, and thus the scope of the present invention is not limited thereto.
Example One: PBDT2FBT - Ph Produce
(Trimethyltin) -4,8-bis (4-ethylhexyloxy-1-phenyl) -benzo [1,2- b: 4,5-b '] - dithiophene , 4-ethylhexyloxy-1-phenyl) -benzo [1,2-b: 4,5-b '] - dithiophene (0.311 g, 0.3 mmol) and 5,6-difluoro-4,7-bis (5-bromo-4- (2-ethylhexyl) -2-thienyl) -2,1,3-benzothiadiazole -4,7-bis (5-bromo-4- (2-ethylhexyl) -2-thienyl) -2,1,3-benzothiadiazole (0.216 g, 0.3 mmol) and a ligand for catalysis (Tris (dibenzylideneacetone) dipalladium (0)) (8.2 mg, 0.009 mmol) was added to a solution of 4- And placed in a three-necked round-bottomed flask full of gas.
Next, 9 ml of degassed toluene and 1 ml of DMF were added to the three-neck round bottom flask. Thereafter, the above three-necked round bottom flask was refluxed at 110 ° C for 8 hours to carry out the polymerization reaction.
Then, 0.2 ml of 2- (tributylstannyl) thiophene, which is an end capping agent, was added to the above three-necked round bottom flask, and the mixture was refluxed for 1 hour and 30 minutes, 0.2 ml of another end-capping agent, 2-bromothiophene was added, and the mixture was refluxed for 1 hour and 30 minutes.
The reaction solution was poured into 250 mL of methanol and precipitated. The precipitated polymer was separated by Soxhlet extraction in the order of methanol, acetone, hexane, chloroform, chlorobenzene and dichlorobenzene. (Molecular weight: Mn = 13.6 kDa, PDI = 2.02) was prepared by pouring the polymer compound dissolved in dichlorobenzene into methanol, precipitating the precipitate, filtering and vacuum- drying the polymer compound (PBDT2FBT-
1H NMR (400MHz, Chlorobenzene-d 5): δ 8.59-8.49 (br, 2H), 8.13-8.10 (br, 4H), 8.10-8.03 (br, 2H), 7.55-7.50 (br, 4H), 4.38- 4.31 (br, 4H), 3.28-3.11 (br, 4H), 2.23-1.71 (br, 48H), 1.41-1.13
Comparative Example One: PBDT2FBT - Th Produce
(Trimethyltin) -4,8-bis (5- (2-butyloctyloxy) thiophen-2-yl) benzo [1,2-b; 4,5 -b '] trimethyltin-4,8-bis (5- (2-butyloctyloxy) thiophene-2-yl) benzo [1,2- dithiophene (0.315 g, 0.3 mmol) was used as a starting material, and the polymer dissolved in chlorobenzene was omitted by extraction with dichloro benzene in the Soxhlet extraction method and poured into methanol to precipitate Polymer compound (PBDT2FBT-Th) (Molecular weight: Mn = 15.4 kDa, PDI = 1.67)
device Example 1: Manufacture of organic solar cell
Glass substrates coated with indium tin oxide (ITO) were washed with detergent, distilled water, acetone, and isopropyl alcohol and UV ozonized. PEDOT: PSS (poly (3,4-ethylenedioxythiophene) -poly (styrene sulfonate)) was spin-coated on the substrate and heated in an oven at 120 ° C to form a buffer layer.
Then, 10 mg of the electron donor PBDT2FBT-Ph prepared according to Example 1 was dissolved in 1 ml of chlorobenzene or dichlorobenzene (O-DCB) at 120 DEG C, and the solution temperature was maintained at 90 DEG C or higher. The solution in which PBDT2FBT-Ph was dissolved was spin-coated on the PEDOT: PSS buffer layer under a nitrogen atmosphere to form a layer of electron-spinning material.
Next, PC 71 BM was dissolved in chlorobenzene or dichlorobenzene at room temperature, and then the solution temperature was maintained at 90 캜 or higher. A solution in which PCBM was dissolved was spin-coated on the electron donor layer under a nitrogen atmosphere to form a layer of electron acceptor material. The weight ratio of PBDT2FBT-Ph to PC 71 BM was 1: 1.2. Finally, a gold electrode was deposited on the electron acceptor material layer in a vacuum chamber to produce an organic solar cell.
device Example 2: Manufacture of organic solar cell DIO adding)
An organic solar cell was prepared in the same manner as in Example 1 except that 1.5% of DIO (1,8-diiodooctane) was added to the solution in which PCBM was dissolved.
device Comparative Example 1: Manufacture of organic solar cell
An organic solar cell was prepared in the same manner as in Example 1 except that PBDT2FBT-Th prepared in Comparative Example 1 was used instead of PBDT2FBT-Ph prepared in Example 1 as an electron donor material layer.
device Comparative Example 2: Manufacture of organic solar cell DIO adding)
Except that PBDT2FBT-Th prepared according to Comparative Example 1 was used as the electron donor material layer instead of PBDT2FBT-Ph prepared according to Example 1, and 1.5 V% of DIO was added to the PCBM-dissolved solution. An organic solar cell was prepared in the same manner as in Example 1.
[Test Example]
Test Example 1: UV-Vis spectrum measurement
Polymeric compounds prepared according to Example 1 (PBDT2FBT-Ph) and Comparative Example 1 (PBDT2FBT-Th) were dissolved in chlorobenzene or dichlorobenzene (O-DCB) at 120 DEG C for UV-Vis spectrum measurement, The solution of the polymer compound was spin-coated on a glass substrate under a nitrogen atmosphere and dried to prepare a polymer compound film. The UV-Vis spectrum of the polymer solution and film was measured and shown in FIG.
In the case of film of a high molecular compound prepared according to Example 1, λ 1] Referring to the onset cases of the film of the polymer compound produced according to 723nm, Comparative example 1 λ onset appeared to 730nm. As a result of calculating the band gap by each value, the polymer compound prepared according to Example 1 was 1.70 eV, and the polymer compound prepared according to Comparative Example 1 was 1.72 eV.
Therefore, it was found that the band gap of the polymer prepared according to Example 1 was smaller than that of the polymer prepared according to Comparative Example 1.
Test Example 2: Measurement of light absorption coefficient
The absorption coefficient of the polymer compound prepared according to Example 1 (PBDT2FBT-Ph) and Comparative Example 1 (PBDT2FBT-Th) was measured and shown in FIG.
2, the light absorption coefficient of the polymer compound prepared according to Example 1 was higher than that of the polymer compound prepared according to Comparative Example 1.
Thus, it was found that the polymer compound prepared according to Example 1 was more efficiently absorbed by light than the polymer compound prepared according to Comparative Example 1. This is because the introduction of phenyl, which is not a thienyl group, into the side chain increases the regioregularity of the polymer prepared according to Example 1 and increases the intermolecular packing .
Test Example 3: Determination of crystallinity and intermolecular packing
The crystallinity and intermolecular packing of the polymer prepared according to Example 1 (PBDT2FBT-Ph) and Comparative Example 1 (PBDT2FBT-Th) were measured and shown in FIG.
3 (a) shows the measurement result (homo polymer) of the film of the polymer compound prepared according to Example 1 (PBDT2FBT-Ph) used in Test Example 1 and Comparative Example 1 (PBDT2FBT-Th) The blend film obtained by spin-coating a solution of PCBM dissolved in a polymer film on a nitrogen atmosphere is shown in FIG. 3 (b).
3 (a), a polymer compound prepared according to Example 1 (PBDT2FBT-Ph) in the case of a polymer compound film (Homo polymer) was compared with a polymer compound prepared according to Comparative Example 1 (PBDT2FBT-Th) The peak related to crystallinity was high.
Thus, it was found that the polymeric compound prepared according to Example 1 had a higher crystallinity than that of the polymer compound prepared according to Comparative Example 1.
Referring to FIG. 3 (b), in the case of the blend film (Blend), both the polymer compound prepared according to Example 1 (PBDT2FBT-Ph) and the polymer compound prepared according to Example 2 (PBDT2FBT-Th) The peaks related to the crystallinity in the homo polymer were reduced.
Therefore, it is considered that both the polymer compound prepared according to Example 1 and the polymer compound prepared according to Comparative Example 1 are well mixed with PCBM.
Test Example 4: Measurement of device characteristics
The device characteristics of the organic solar cell manufactured according to the device example 1 and the device comparative example 1 were measured and shown in FIG. 4. The photovoltaic parameters were measured and are shown in Table 1 below.
(V)
(mA / cm 2 )
(%)
(%)
(PBDT2FBT-Th)
PBDT2FBT-Th (DIO)
(PBDT2FBT-Ph)
PBDT2FBT-Ph (DIO)
Referring to FIG. 4 and Table 1, it can be seen that the current density of the organic solar cell manufactured according to Embodiment 2 is the lowest. In addition, the external quantum efficiency (EQE) of the organic solar cell manufactured according to Example 1 was relatively higher than that of the organic solar cell produced according to Comparative Example 1 of the device. PCE (power conversion efficiency) value of the organic solar cell element according to Comparative Example 2 is 3.04%, the open-circuit voltage (V OC, open-circuit voltage) value is 0.82V, the short circuit current density (J SC, short circuit current density ) Value was 8.61 mA / cm 2 , and the fill factor (FF) was 42.6%. On the other hand, the organic solar cell manufactured according to Embodiment 2 showed a PCE value of 6.02%, a V OC value of 0.81 V, a J SC value of 14.48 mA / cm 2 , and an FF value of 51.4%. In addition, all of the photovoltaic parameters of the organic solar cell produced according to the Device Example 2 were found to be superior to those of the organic solar cell prepared according to Example 1.
Therefore, it was found that the organic photovoltaic cell manufactured according to the device example 2 had the best photovoltaic parameters except the open-circuit voltage. It was also found that the performance of the organic solar cell is improved by adding DIO in the production of the organic solar battery.
The scope of the present invention is defined by the appended claims rather than the detailed description and all changes or modifications derived from the meaning and scope of the claims and their equivalents are to be construed as being included within the scope of the present invention do.
Claims (17)
[Structural formula 1]
In formula 1,
Ar 1 and Ar 2 are the same or different from each other, Ar 1 and Ar 2 are each independently a substituted or unsubstituted C6 to C30 arylene group,
X 1 and X 2 are the same or different from each other, and X 1 and X 2 are each independently an oxygen atom, a sulfur atom, or a selenium atom,
R 1 and R 2 are the same or different from each other, and R 1 and R 2 are each independently a straight chain alkyl group of C 10 to C 30,
R 3 and R 4 are fluorine atoms,
Q 1 and Q 2 are the same or different, and Q 1 and Q 2 are each independently
R 5 to R 9 are the same or different from each other, and R 5 to R 9 are each independently a straight-chain alkyl group of C6 to C30,
n is a repetition number of repeating units,
The number average molecular weight (Mn) is 3,000 to 500,000.
Ar 1 and Ar 2 are the same or different from each other, and Ar 1 and Ar 2 are each independently any one selected from a phenylene group, a biphenylene group, a naphthylene group, an anthrylene group and a pyrenylene group.
X < 1 > and X < 2 > are oxygen atoms.
R 1 and R 2 are the same or different from each other, R 1 and R 2 are each independently a C 10 to C 20 branched alkyl group,
R 5 to R 9 are the same as or different from each other, and each of R 5 to R 9 is independently a C6 to C20 branched alkyl group.
[Structural formula 1]
In formula 1,
Ar 1 and Ar 2 are the same or different from each other, Ar 1 and Ar 2 are each independently a substituted or unsubstituted C6 to C30 arylene group,
X 1 and X 2 are the same or different from each other, and X 1 and X 2 are each independently an oxygen atom, a sulfur atom, or a selenium atom,
R 1 and R 2 are the same or different from each other, and R 1 and R 2 are each independently a straight chain alkyl group of C 10 to C 30,
R 3 and R 4 are fluorine atoms,
Q 1 and Q 2 are the same or different, and Q 1 and Q 2 are each independently
R 5 to R 9 are the same or different from each other, and R 5 to R 9 are each independently a straight-chain alkyl group of C6 to C30,
n is a repetition number of repeating units,
The number average molecular weight (Mn) is 3,000 to 500,000.
[Structural formula 2]
In formula 2,
Ar 1 and Ar 2 are the same or different from each other, Ar 1 and Ar 2 are each independently a substituted or unsubstituted C6 to C30 arylene group,
X 1 and X 2 are the same or different from each other, and X 1 and X 2 are each independently an oxygen atom, a sulfur atom, or a selenium atom,
R 1 and R 2 are the same or different from each other, and R 1 and R 2 are each independently a straight chain alkyl group of C 10 to C 30, or a crushed alkyl group.
[Structural Formula 3]
In Structure 3,
R 3 and R 4 are fluorine atoms,
Q 1 and Q 2 are the same or different, and Q 1 and Q 2 are each independently
R 5 to R 9 are the same as or different from each other, and R 5 to R 9 are each independently a straight-chain alkyl group of C6 to C30, or a crushed alkyl group.
The method for producing the above-
(a) mixing a monomer represented by the formula 2, a monomer represented by the formula 3, and a catalyst to prepare a mixture; And
(b) adding an organic solvent to the mixture and performing a polymerization reaction to prepare a polymer compound represented by Formula 1;
Wherein the polymer is a polymer.
Wherein the catalyst is selected from the group consisting of tetrakis (triphenylphosphine) palladium (0), Pd (PPH3) 4 and tris (dibenzylideneacetone) dipalladium (0) (0)). ≪ / RTI >
Wherein the organic solvent comprises at least one selected from the group consisting of toluene, dimethylformamide (DMF), and chlorobenzene.
Prior to step (a)
(a'-1) reacting a compound represented by the following formula (1) and a compound represented by the following formula (2) to prepare a compound represented by the following formula (3); And
(a'-2) reacting a compound represented by Formula 3 with n-butyllithium and triethyltin chloride to prepare a compound represented by Formula 2;
Wherein the method further comprises the steps of:
[Chemical Formula 1]
(2)
RX-Ar-Br
In formula (2)
Ar is a substituted or unsubstituted C6 to C30 arylene group,
X is an oxygen atom, a sulfur atom, or a selenium atom,
R is a straight chain alkyl group of C10 to C30, or a crushed alkyl group.
(3)
In formula (3)
Ar is independently a substituted or unsubstituted C6 to C30 arylene group,
Each X is independently an oxygen atom, a sulfur atom, or a selenium atom,
Each R is independently a straight chain alkyl group of C10 to C30, or a crushed alkyl group.
Wherein the electronic device is an organic solar cell.
Wherein the organic solar cell comprises:
A first electrode;
A photoactive layer formed on the first electrode; And
And a second electrode formed on the photoactive layer,
Wherein the photoactive layer comprises a polymeric compound represented by the following structural formula (1).
[Structural formula 1]
In formula 1,
Ar 1 and Ar 2 are the same or different from each other, Ar 1 and Ar 2 are each independently a substituted or unsubstituted C6 to C30 arylene group,
X 1 and X 2 are the same or different from each other, and X 1 and X 2 are each independently an oxygen atom, a sulfur atom, or a selenium atom,
R 1 and R 2 are the same or different from each other, and R 1 and R 2 are each independently a straight chain alkyl group of C 10 to C 30,
R 3 and R 4 are fluorine atoms,
Q 1 and Q 2 are the same or different, and Q 1 and Q 2 are each independently
R 5 to R 9 are the same or different from each other, and R 5 to R 9 are each independently a straight-chain alkyl group of C6 to C30,
n is a repetition number of repeating units,
The number average molecular weight (Mn) is 3,000 to 500,000.
Wherein the photoactive layer comprises an electron donor material and an electron acceptor material.
Wherein the mass ratio of the electron donor material to the electron acceptor material is 1: 0.5 to 1: 3.
Wherein the electron donor material comprises a polymeric compound represented by the structural formula (1).
Wherein the electron-accepting material comprises at least one selected from fullerene and fullerene derivatives.
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