KR101397085B1 - White polymer containing quinacridone or quinoxaline derivative and electroluminescence device - Google Patents
White polymer containing quinacridone or quinoxaline derivative and electroluminescence device Download PDFInfo
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- KR101397085B1 KR101397085B1 KR1020110012822A KR20110012822A KR101397085B1 KR 101397085 B1 KR101397085 B1 KR 101397085B1 KR 1020110012822 A KR1020110012822 A KR 1020110012822A KR 20110012822 A KR20110012822 A KR 20110012822A KR 101397085 B1 KR101397085 B1 KR 101397085B1
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- organic electroluminescent
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- 229920000642 polymer Polymers 0.000 title claims abstract description 54
- 238000005401 electroluminescence Methods 0.000 title claims description 6
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 title abstract description 13
- 125000001567 quinoxalinyl group Chemical class N1=C(C=NC2=CC=CC=C12)* 0.000 title 1
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical compound N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000463 material Substances 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 15
- -1 Pyrolle Chemical compound 0.000 claims description 14
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 12
- 229920000144 PEDOT:PSS Polymers 0.000 claims description 7
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- 238000004528 spin coating Methods 0.000 claims description 6
- 229930192474 thiophene Natural products 0.000 claims description 6
- 229910016036 BaF 2 Inorganic materials 0.000 claims description 3
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 3
- OYLGJCQECKOTOL-UHFFFAOYSA-L barium fluoride Chemical compound [F-].[F-].[Ba+2] OYLGJCQECKOTOL-UHFFFAOYSA-L 0.000 claims description 3
- 229910001632 barium fluoride Inorganic materials 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- 150000004866 oxadiazoles Chemical class 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- 238000000151 deposition Methods 0.000 claims 1
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 abstract description 10
- 150000001875 compounds Chemical class 0.000 description 27
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 18
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 12
- 239000000243 solution Substances 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 8
- 238000004020 luminiscence type Methods 0.000 description 7
- CYKLQIOPIMZZBZ-UHFFFAOYSA-N 2,7-dibromo-9,9-dioctylfluorene Chemical compound C1=C(Br)C=C2C(CCCCCCCC)(CCCCCCCC)C3=CC(Br)=CC=C3C2=C1 CYKLQIOPIMZZBZ-UHFFFAOYSA-N 0.000 description 6
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 6
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229940126062 Compound A Drugs 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000005191 phase separation Methods 0.000 description 3
- 235000011181 potassium carbonates Nutrition 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- CRGSMSNUTNRNQM-UHFFFAOYSA-N 2-(4-tert-butylphenyl)-1,3,4-oxadiazole Chemical compound C1=CC(C(C)(C)C)=CC=C1C1=NN=CO1 CRGSMSNUTNRNQM-UHFFFAOYSA-N 0.000 description 2
- MRWWWZLJWNIEEJ-UHFFFAOYSA-N 4,4,5,5-tetramethyl-2-propan-2-yloxy-1,3,2-dioxaborolane Chemical compound CC(C)OB1OC(C)(C)C(C)(C)O1 MRWWWZLJWNIEEJ-UHFFFAOYSA-N 0.000 description 2
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 2
- 238000006069 Suzuki reaction reaction Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000001194 electroluminescence spectrum Methods 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 238000005424 photoluminescence Methods 0.000 description 2
- 238000000103 photoluminescence spectrum Methods 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 235000015320 potassium carbonate Nutrition 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000013557 residual solvent Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- FNQJDLTXOVEEFB-UHFFFAOYSA-N 1,2,3-benzothiadiazole Chemical compound C1=CC=C2SN=NC2=C1 FNQJDLTXOVEEFB-UHFFFAOYSA-N 0.000 description 1
- MNDIARAMWBIKFW-UHFFFAOYSA-N 1-bromohexane Chemical compound CCCCCCBr MNDIARAMWBIKFW-UHFFFAOYSA-N 0.000 description 1
- OJMAUBALNSWGDC-UHFFFAOYSA-N 2,7-dibromo-9,9-bis(6-bromohexyl)fluorene Chemical compound C1=C(Br)C=C2C(CCCCCCBr)(CCCCCCBr)C3=CC(Br)=CC=C3C2=C1 OJMAUBALNSWGDC-UHFFFAOYSA-N 0.000 description 1
- ZILMKVHUHRYQAV-UHFFFAOYSA-N 2,9-dibromo-5,12-dihexylquinolino[2,3-b]acridine-7,14-dione Chemical compound CCCCCCN1C2=CC=C(Br)C=C2C(=O)C2=C1C=C1C(=O)C3=CC(Br)=CC=C3N(CCCCCC)C1=C2 ZILMKVHUHRYQAV-UHFFFAOYSA-N 0.000 description 1
- RICKKZXCGCSLIU-UHFFFAOYSA-N 2-[2-[carboxymethyl-[[3-hydroxy-5-(hydroxymethyl)-2-methylpyridin-4-yl]methyl]amino]ethyl-[[3-hydroxy-5-(hydroxymethyl)-2-methylpyridin-4-yl]methyl]amino]acetic acid Chemical compound CC1=NC=C(CO)C(CN(CCN(CC(O)=O)CC=2C(=C(C)N=CC=2CO)O)CC(O)=O)=C1O RICKKZXCGCSLIU-UHFFFAOYSA-N 0.000 description 1
- FAHIZHKRQQNPLC-UHFFFAOYSA-N 2-[9,9-dioctyl-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)fluoren-2-yl]-4,4,5,5-tetramethyl-1,3,2-dioxaborolane Chemical compound C1=C2C(CCCCCCCC)(CCCCCCCC)C3=CC(B4OC(C)(C)C(C)(C)O4)=CC=C3C2=CC=C1B1OC(C)(C)C(C)(C)O1 FAHIZHKRQQNPLC-UHFFFAOYSA-N 0.000 description 1
- YGEABBRWEQAISX-UHFFFAOYSA-N 5,12-dihexylquinolino[2,3-b]acridine-7,14-dione Chemical compound CCCCCCN1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3N(CCCCCC)C1=C2 YGEABBRWEQAISX-UHFFFAOYSA-N 0.000 description 1
- YIDNZGJPZBNZNE-UHFFFAOYSA-N 5,8-bis(5-bromothiophen-2-yl)-2,3-bis(4-hexoxyphenyl)quinoxaline Chemical compound BrC1=CC=C(S1)C1=C2N=C(C(=NC2=C(C=C1)C=1SC(=CC1)Br)C1=CC=C(C=C1)OCCCCCC)C1=CC=C(C=C1)OCCCCCC YIDNZGJPZBNZNE-UHFFFAOYSA-N 0.000 description 1
- 239000005964 Acibenzolar-S-methyl Substances 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- SPYOEJSFMNENPM-UHFFFAOYSA-N O=C(C1=CC=CC=C1NC1=C2)C1=CC(NC1=C3C(C4=CC=CS4)=CC=C1)=C2C3=O Chemical compound O=C(C1=CC=CC=C1NC1=C2)C1=CC(NC1=C3C(C4=CC=CS4)=CC=C1)=C2C3=O SPYOEJSFMNENPM-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- ARQRPTNYUOLOGH-UHFFFAOYSA-N chcl3 chloroform Chemical compound ClC(Cl)Cl.ClC(Cl)Cl ARQRPTNYUOLOGH-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- JNGZXGGOCLZBFB-IVCQMTBJSA-N compound E Chemical compound N([C@@H](C)C(=O)N[C@@H]1C(N(C)C2=CC=CC=C2C(C=2C=CC=CC=2)=N1)=O)C(=O)CC1=CC(F)=CC(F)=C1 JNGZXGGOCLZBFB-IVCQMTBJSA-N 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 1
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- ZGWZWRHJHVTXEL-UHFFFAOYSA-N trimethyl(thiophen-2-yl)stannane Chemical compound C[Sn](C)(C)C1=CC=CS1 ZGWZWRHJHVTXEL-UHFFFAOYSA-N 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
- C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
- C07D241/38—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems with only hydrogen or carbon atoms directly attached to the ring nitrogen atoms
- C07D241/40—Benzopyrazines
- C07D241/42—Benzopyrazines with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
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- 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
- H10K85/115—Polyfluorene; Derivatives thereof
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- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/02—Ortho- or ortho- and peri-condensed systems
- C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
- C07C2603/22—Ortho- or ortho- and peri-condensed systems containing three rings containing only six-membered rings
- C07C2603/24—Anthracenes; Hydrogenated anthracenes
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/14—Macromolecular compounds
- C09K2211/1408—Carbocyclic compounds
- C09K2211/1416—Condensed systems
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/14—Macromolecular compounds
- C09K2211/1441—Heterocyclic
- C09K2211/1475—Heterocyclic containing nitrogen and oxygen as heteroatoms
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- 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
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
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- Electroluminescent Light Sources (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
본 발명은 퀴나크리돈 또는 퀴녹살린을 함유하는 유기 전계발광고분자 및 이를 이용한 유기 전기발광소자에 관한 것으로, 더욱 상세하게는 분자간 상호작용을 최소화할 수 있는 치환체를 포함하며, 플로렌, 카바졸, 안트라센 및 그 유도체를 각각 주쇄로 하고, 상기 주쇄에 퀴나크리돈 또는 퀴녹살린을 함유하는 구조를 갖는 유기 전계발광고분자 및 이를 이용한 유기 전기발광소자에 관한 것이다.The present invention relates to an organic electroluminescent polymer containing quinacridone or quinoxaline and an organic electroluminescent device using the electroluminescent polymer. More particularly, the present invention relates to an organic electroluminescent polymer comprising quinacridone or quinoxaline, An organic electroluminescent polymer having an anthracene and a derivative thereof as main chains and having a main chain containing quinacridone or quinoxaline, and an organic electroluminescent device using the same.
Description
본 발명은 퀴나크리돈 또는 퀴녹살린을 함유하는 유기 전계발광고분자 및 이를 이용한 유기 전기발광소자에 관한 것으로, 더욱 상세하게는 분자간 상호작용을 최소화할 수 있는 치환체를 포함하며, 플로렌, 카바졸, 안트라센 및 그 유도체를 각각 주쇄로 하고, 상기 주쇄에 퀴나크리돈 또는 퀴녹살린을 함유하는 구조를 갖는 유기 전계발광고분자 및 이를 이용한 유기 전기발광소자에 관한 것이다.The present invention relates to an organic electroluminescent polymer containing quinacridone or quinoxaline and an organic electroluminescent device using the electroluminescent polymer. More particularly, the present invention relates to an organic electroluminescent polymer comprising quinacridone or quinoxaline, An organic electroluminescent polymer having an anthracene and a derivative thereof as main chains and having a main chain containing quinacridone or quinoxaline, and an organic electroluminescent device using the same.
최근 수년 동안 디스플레이에 대한 연구가 활발히 진행되어 왔으며, 그 중 가장 주목받고 있는 분야가 고분자 발광 소자(Polymer light-emitting diode, PLED)이다. PLED는 기존의 LCD나 CRT에 비해서 자체 발광 소자이기 때문에 백라이트(backlight)가 필요하지 않으며, 광시야각이 우수하고, 초경량 초박형이며, 소비전력이 낮고, 대조비 등이 우수한 특징이 있다.In recent years, research on displays has been actively conducted, and the most noteworthy field is polymer light-emitting diodes (PLEDs). Since PLED is a self-luminous device as compared to conventional LCD or CRT, it does not require a backlight, has excellent optical viewing angle, is ultra light and thin, has low power consumption, and has excellent contrast ratio.
또한, 응답속도가 빠르고 높은 해상도를 가지기 때문에 동영상 재생이 우수하며, 기질(substrate)로 플라스틱을 사용하여 구부릴 수 있는 장점을 갖고 있고, 제작 공정 측면에서 살펴보면, 고분자는 진공 증착 공정이 필요 없어 제작 공정이 간단하며, 대량 생산 및 대면적 생산에 용이한 점을 가지고 있다.In addition, since it has a high response speed and a high resolution, it is excellent in moving picture reproduction and has advantages of being able to bend using plastic as a substrate. From the viewpoint of the manufacturing process, a polymer does not need a vacuum deposition process, And is easy to mass-produce and large-area production.
이러한, 고분자 백색 발광 소자를 구현하기 위해서는 주쇄에 결합 된 각각의 분자들이 전압 인가에 따라 청색, 녹색, 적색이 혼합되어 백색광을 구현하는 단일형 고분자 및 청색, 녹색, 적색을 발광하는 고분자 물질을 각각 혼합하는 방법 또는 디바이스제작 시 각 층마다 다른 색을 발광하는 고분자를 적층하여 구현하는 방법이 있다. 이들 중 상 분리 현상이 일어나서 효율 및 색감의 안정성의 구현에 문제가 없는 단일형 고분자가 큰 장점을 갖는다. In order to realize such a polymeric white light emitting device, each of the molecules bonded to the main chain is mixed with blue, green, and red according to a voltage applied to form a single polymer that emits white light, and a polymer material emitting blue, green, Or a method of stacking a polymer layer emitting light of different colors for each layer at the time of manufacturing a device. Among them, a single-type polymer has a great advantage in that phase separation phenomenon occurs and there is no problem in realizing efficiency and color stability.
결국, 본 발명은 청색 발광 물질을 주쇄로 배열하고 소량의 황색 발광 물질을 함유함으로써 청색 발광 물질에서 황색 발광 물질로의 효과적인 에너지 전이를 발생시켜 전 가시광 영역에서 스펙트럼이 나타나 백색발광특성을 나타내는 유기 전계발광고분자를 제공하는데 그 주된 목적이 있다.As a result, the blue light emitting material is arranged in the main chain and contains a small amount of yellow light emitting material, thereby generating effective energy transfer from the blue light emitting material to the yellow light emitting material, There is a main purpose in providing a light emitting polymer.
또한, 본 발명은 상기 전계발광고분자를 발광재료로 사용하여 고효율, 장수명의 유기 전기발광소자를 제공하는데 다른 목적이 있다. Another object of the present invention is to provide a highly efficient, long-life organic electroluminescent device using the electroluminescent polymer as a light emitting material.
상기 목적을 달성하기 위해, 본 발명은 백색 발광을 구현할 수 있는 재료로서 청색 발광물질을 주쇄로 하여 소량의 황색 발광물질을 공중합한 유기 전계발광고분자 및 이를 이용한 전기발광소자를 제공한다.In order to achieve the above object, the present invention provides an organic electroluminescent polymer in which a small amount of a yellow light emitting material is copolymerized with a blue light emitting material as a main chain, which can realize white light emission, and an electroluminescent device using the same.
본 발명에 있어서, 청색 발광 재료로 사용될 수 있는 물질은 플로렌(flourene), 카바졸(carbazole), 안트라센(anthracene) 및 그 유도체 등이 있으며, 황색 발광 재료로 사용될 수 있는 물질은 퀴나크리돈(quinacridone), 퀴녹살린(quinoxaline), 벤조사이아디아졸(benzothiadiazole)등이 있으며, 바람직하게는 퀴나크리돈 또는 퀴녹살린이다.In the present invention, substances which can be used as a blue light emitting material include flourenes, carbazole, anthracene and its derivatives, and substances which can be used as a yellow light emitting material include quinacridone quinacridone, quinoxaline, benzothiadiazole and the like, preferably quinacridone or quinoxaline.
상기와 같은 본 발명에 따르면, 청색 발광 물질을 주쇄로 하고 소량의 황색 발광 물질을 첨가하여 공중합함으로써 청색 발광 물질에서 황색 발광 물질로의 효과적인 에너지 전이를 발생시켜 전 가시광 영역에서 스펙트럼이 나타나 최종적으로 백색발광특성을 나타내는 유기 전계발광고분자를 제공하는 효과가 있다.According to the present invention, effective energy transfer from a blue light emitting material to a yellow light emitting material is generated by using a blue light emitting material as a main chain and a small amount of a yellow light emitting material is added and copolymerized to form a spectrum in an entire visible light region, There is an effect of providing an organic electroluminescence polymer exhibiting luminescence characteristics.
본 발명에 따른 유기 전기발광소자는 안정된 백색발광을 보이며, 그 발광효율이 우수하므로, 평판 및 플라스틱 디스플레이용 소자로 유용하게 이용될 수 있다.The organic electroluminescent device according to the present invention exhibits stable white light emission and is excellent in luminous efficiency, so that it can be effectively used as a device for flat panel displays and plastic displays.
도 1은 본 발명에 따른 화학식 1로 표시되는 화합물의 1H-NMR 스펙트럼이다.
도 2는 본 발명에 따른 화학식 1로 표시되는 화합물의 열중량 분석(Thermogravimetric analysis; TGA) 그래프이다.
도 3은 본 발명에 따른 화학식 1로 표시되는 화합물의 UV 흡수 스펙트럼이다.
도 4는 본 발명에 따른 화학식 1로 표시되는 화합물의 PL(Photoluminescence) 스펙트럼이다.
도 5는 본 발명에 따른 화학식 1로 표시되는 화합물의 전기화학적 특성을 평가한 CV(cyclicvoltammetry) 그래프 및 화합물들의 밴드다이어그램이다.
도 6는 본 발명에 따른 화학식 1로 표시되는 화합물의 전기발광특성을 측정하기 위해 제작한 유기 전기발광소자의 구조를 보여주는 단면도이다.
도 7은 본 발명의 일실시예에 따라 제조된 화학식 1로 표시되는 화합물의 전기발광(Electroluminescence) 스펙트럼이다.
도 8은 본 발명의 일실시예에 따라 제조된 화학식 1로 표시되는 화합물의 색좌표 그래프이다.
도 9는 본 발명의 일실시예에 따라 제조된 화학식 1로 표시되는 화합물의 휘도-전압 그래프이다.
도 10은 본 발명에 따른 화학식 2로 표시되는 화합물의 1H-NMR 스펙트럼이다.
도 11은 본 발명에 따른 화학식 2로 표시되는 화합물의 UV 흡수 스펙트럼이다.
도 12는 본 발명에 따른 화학식 2로 표시되는 화합물의 PL(Photoluminescence) 스펙트럼이다.
도 13은 본 발명에 따른 화학식 2로 표시되는 화합물의 전기화학적 특성을 평가한 CV(cyclicvoltammetry) 그래프이다.
도 14는 본 발명의 일실시예에 따라 제조된 화학식 2로 표시되는 화합물의 전기발광(Electroluminescence) 스펙트럼이다.
도 15는 본 발명의 일실시예에 따라 제조된 화학식 2로 표시되는 화합물의 색좌표 그래프이다.
도 16은 본 발명의 일실시예에 따라 제조된 화학식 2로 표시되는 화합물의 휘도-전압 그래프이다.1 is a 1 H-NMR spectrum of a compound represented by the formula (1) according to the present invention.
2 is a thermogravimetric analysis (TGA) graph of the compound represented by
3 is a UV absorption spectrum of the compound represented by the formula (1) according to the present invention.
4 is a PL (Photoluminescence) spectrum of the compound represented by Formula 1 according to the present invention.
FIG. 5 is a cyclic voltammetry (CV) graph and a band diagram of compounds that evaluate the electrochemical properties of the compound represented by Formula 1 according to the present invention.
6 is a cross-sectional view illustrating the structure of an organic electroluminescent device manufactured to measure electroluminescence characteristics of the compound represented by Formula 1 according to the present invention.
7 is an electroluminescence spectrum of a compound represented by the formula (1) prepared according to an embodiment of the present invention.
FIG. 8 is a color coordinate graph of a compound represented by Chemical Formula 1, prepared according to an embodiment of the present invention. FIG.
FIG. 9 is a graph of a luminance-voltage of a compound represented by Chemical Formula 1, prepared according to an embodiment of the present invention.
10 is a 1 H-NMR spectrum of the compound represented by the formula (2) according to the present invention.
11 is a UV absorption spectrum of a compound represented by the general formula (2) according to the present invention.
12 is a PL (Photoluminescence) spectrum of the compound represented by Formula 2 according to the present invention.
13 is a cyclic voltammetry (CV) graph for evaluating the electrochemical characteristics of the compound represented by
14 is an electroluminescence spectrum of a compound represented by the general formula (2) prepared according to an embodiment of the present invention.
15 is a chromaticity diagram graph of the compound of
16 is a graph of a luminance-voltage of a compound represented by the formula (2) prepared according to an embodiment of the present invention.
이하, 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
본 발명은 백색 발광 재료로서 청색 발광 물질과 소량의 황색 발광 물질을 공중합한 하기 화학식 1로 표시되는 유기 전계발광고분자를 제공한다.The present invention provides an organic electroluminescent polymer represented by the following formula (1) wherein a blue light emitting material and a small amount of a yellow light emitting material are copolymerized as a white light emitting material.
구체적으로, 본 발명은 청색 발광 물질인 플로렌, 카바졸, 안트라세 및 그 유도체, 바람직하게는 플로렌을 주쇄로 하여 소량의 황색 발광 물질인 퀴나크리돈을 첨가하여 공중합한 하기 화학식 1의 유기 전계발광고분자 [poly(fluorene-co-quinacridone)]을 제공한다. Specifically, the present invention relates to an organic electroluminescent device comprising a blue light emitting material selected from the group consisting of fluorene, carbazole, anthracene and derivatives thereof, preferably fluorene as a main chain, quinacridone as a main chain, And provides an electroluminescent polymer (poly (fluorene-co-quinacridone)].
본 발명에 있어서, 상기 식의 R은 독립적으로 수소원자; 탄소수 1 내지 25의 알킬기이거나 옥사디아졸(oxadiazole) 유도체를 포함하며, Ar은 벤젠(bezene)및 나프탈렌(naphtalene), 싸이오펜(thiophene), 싸이아졸(thiazole), 퓨즈드 싸이오펜(fused thiophene), 피롤(pyrolle), 피리딘(pyridine)을 포함한다. l과 m은 각각 모노머의 몰 비로써 1~100의 정수이며, N은 1~100,000의 정수인 것이 바람직하다.In the present invention, R in the above formula independently represents a hydrogen atom; Ar is an alkyl group having 1 to 25 carbon atoms or an oxadiazole derivative and Ar is selected from the group consisting of benzene and naphtalene, thiophene, thiazole, fused thiophene, Pyrolle, and pyridine. 1 and m are each an integer of 1 to 100 in terms of the molar ratio of the monomers, and N is preferably an integer of 1 to 100,000.
또한, 본 발명은 플로렌을 주쇄로 하여 퀴나크리돈을 첨가하여 상기 화학식 1의 구조를 갖는 유기 전계발광고분자를 제조하는 방법을 제공한다.The present invention also provides a method for preparing an organic electroluminescent polymer having the structure of Formula 1 by adding quinacridone with fluorene as a main chain.
본 발명의 유기 전계발광고분자는 하기의 반응식 1의 과정으로 제조될 수 있다.The organic electroluminescent polymer of the present invention can be prepared by the
[반응식 1][Reaction Scheme 1]
구체적으로, 본 발명에 따른 고분자는 스즈끼 커플링(suzuki coupling)을 이용하여 제조할 수 있다. 이 때, 용매로는 자일렌(xylene), 톨루엔(toluene), 디메틸포름아미드(DMF)등을 사용할 수 있으며, 1내지 5몰 K2CO3와 테트라키스(트리페닐포스핀)팔라듐(tetrakistriphenylphosphinepalladium)을 0.5~10몰%를 사용하며, 알리큐오트336((Aliquot336)와 테트라뷰틸 암모니윰 브로마이드(tetrabutylammonium bromide)를 사용하여 중합체를 얻을 수 있다.Specifically, the polymer according to the present invention can be prepared by using a Suzuki coupling. In this case, xylene, toluene, dimethylformamide (DMF) and the like can be used as the solvent, and 1 to 5 mol K 2 CO 3 and tetrakis (triphenylphosphine) palladium (Aliquot 336) and tetrabutylammonium bromide can be used to obtain a polymer.
상세하게는 톨루엔(Toluene)에 9,9-디옥틸-2,7-디브로모플루오렌(9,9-dioctyl-2,7-dibromofluorene), 2,2'-(9,9-dioctyl-9H-fluorene -2,7-diyl)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane) 및 2,9-bis(5-bromothiophen-2-yl)-5,12-dihexylquinolino[2,3-b]acridine-7,14(5H,12H)-dione을 넣고 교반 후, 테트라키스(트리페닐포스핀)팔라듐(tetrakistriphenylphosphinepalladium)을 0.5~10몰%을 넣고 10분간 교반 한다. 또한, 탄산칼륨(K2CO3)용액을 다른 2구 플라스크에 넣어 진공으로 산소제거하고 질소로 충진 한 후 플라스크에 넣고 알리큐오트 336을 1~2방울 떨어뜨려 72시간(85℃) 교반한다. 이후 브로모벤젠(bromobenzene)을 1~2방울 떨어뜨리고 12시간 반응한다. TLC확인 후 반응이 종결되면 HCl로 담금질 시킨다. 클로로포름으로 추출 및 증류수로 씻은 후 수분제거 하고 컬럼 정제한다.More specifically, in toluene, 9,9-dioctyl-2,7-dibromofluorene, 2,2 '- (9,9-dioctyl- 9H-fluorene-2,7-diyl bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolane) and 2,9-bis (5-bromothiophen- dihexylquinolino [2,3-b] acridine-7,14 (5H, 12H) -dione is added and stirred, 0.5-10 mol% of tetrakis (triphenylphosphine) palladium is added and stirred for 10 minutes. Further, the potassium carbonate (K 2 CO 3 ) solution is put into another two-necked flask, and oxygen is removed by vacuum, filled with nitrogen, put into a flask, and 1 or 2 drops of Aliquot 336 is added and stirred for 72 hours . After dropping 1-2 drops of bromobenzene, react for 12 hours. After the TLC is confirmed, the reaction is quenched with HCl. Extract with chloroform and wash with distilled water, remove water and purify the column.
본 발명에서는 상기와 같이 전계발광고분자를 제조하는 방법을 설명하였으나, 고분자 화합물을 제조방법은 특별히 한정시킬 필요는 없으며, 상기 화학식 1을 만족하는 고분자 화합물을 제조하는 어떠한 방법도 무방하다.In the present invention, the method of preparing the electroluminescent polymer as described above has been described. However, the method of preparing the polymer compound is not particularly limited, and any method of producing the polymer compound satisfying the formula (1) may be used.
본 발명에서 제조된 화학식 1의 유기 전계발광고분자는 5wt% loss가 약 420℃인 높은 열적안정성을 나타내었으며(도 2참조), PL 스펙트럼에 나타나듯이 용액 상에서는 청색 발광, 필름 상에서는 청색발광과 황색 발광의 피크를 확인할 수 있다(도 4참조). 이는 파이-파이 적층에 인한 것으로 전기발광 특성에서 백색 발광의 가능성을 보였다. As shown in the PL spectrum, the organic electroluminescent polymer of Formula 1 produced by the present invention exhibited a high thermal stability with a 5 wt% loss of about 420 ° C. (see FIG. 2), and the blue light emission in the solution phase, (See Fig. 4). This is due to the pie-pile lamination and showed the possibility of white luminescence in electroluminescent properties.
또한, 본 발명은 상기 고분자를 발광 재료로서 채용한 고효율, 장수명의 유기전기발광소자를 제공한다. The present invention also provides a high-efficiency, long-life organic electroluminescent device employing the polymer as a light emitting material.
본 발명에 따른 유기 전계발광소자는 ITO 위에 PEDOT:PSS를 스핀 코팅하여 열처리 한 후 상기의 전기발광고분자를 스핀 코팅하여 열처리한 다음 불화바륨(BaF2)과 바륨(Ba), 알루미늄(Al)을 각각 진공 증착하여 디바이스를 제조하는 것을 특징으로 하며, 이 때 제조된 디바이스는 6~7V에서 백색발광을 나타낸다.
The organic electroluminescent device according to the present invention can be produced by spin coating PEDOT: PSS on ITO, heat-treating the electroluminescent polymer by spin coating, and then heat-treating the electroluminescent polymer. Then, barium fluoride (BaF 2 ), barium (Ba) And each of them is vacuum-deposited to manufacture a device, wherein the device produced exhibits white light emission at 6 to 7V.
또한, 본 발명은 백색 발광 재료로서 청색 발광 물질과 소량의 황색 발광 물질을 공중합한 하기 화학식 2로 표시되는 유기 전계발광고분자를 제공한다.The present invention also provides an organic electroluminescent polymer represented by the following formula (2), which is a white light emitting material and is a copolymer of a blue light emitting material and a small amount of a yellow light emitting material.
구체적으로, 본 발명은 청색 발광 물질인 플로렌, 카바졸, 안트라세 및 그 유도체, 바람직하게는 플로렌을 주쇄로 하여 소량의 황색 발광 물질인 퀴녹살린을 첨가하여 공중합한 하기 화학식 2의 유기 전계발광고분자 [poly(fluorene-co-quinoxaline)]를 제공한다. Specifically, the present invention relates to an organic electroluminescent device comprising fluorene, carbazole, anthracene and derivatives thereof, which are blue luminescent materials, preferably fluorene as a main chain and quinoxaline as a main chain, Thereby providing a poly (fluorene-co-quinoxaline).
본 발명에 있어서, 상기 식의 R은 독립적으로 수소원자;탄소수 1 내지 25의 알킬기이거나 옥사디아졸(oxadiazole) 유도체를 포함하며, Ar은 벤젠(bezene)및 나프탈렌(naphtalene), 싸이오펜(thiophene), 싸이아졸(thiazole), 퓨즈드 싸이오펜(fused thiophene), 피롤(pyrolle), 피리딘(pyridine)을 포함한다. l과 m은 각각 모노머의 몰 비로써 1~100의 정수이며, N은 1~100,000의 정수인 것이 바람직하다.In the present invention, R in the above formula is independently a hydrogen atom, an alkyl group having 1 to 25 carbon atoms or an oxadiazole derivative, Ar is benzene, naphtalene, thiophene, Thiazole, fused thiophene, pyrolle, pyridine, and the like. 1 and m are each an integer of 1 to 100 in terms of the molar ratio of the monomers, and N is preferably an integer of 1 to 100,000.
또한, 본 발명은 플로렌을 주쇄로 하여 퀴녹살린을 첨가하여 상기 화학식 2의 구조를 갖는 유기 전계발광고분자를 제조하는 방법을 제공한다.The present invention also provides a method for preparing an organic electroluminescent polymer having the structure of Formula 2 by adding quinoxaline with fluorene as a main chain.
본 발명의 유기 전계발광고분자는 하기의 반응식 2의 과정으로 제조될 수 있다.The organic electroluminescent polymer of the present invention can be prepared by the process of the following reaction formula (2).
[반응식 2][Reaction Scheme 2]
구체적으로, 본 발명에 따른 고분자는 스즈끼 커플링(suzuki coupling)을 이용하여 제조할 수 있다. 이 때, 용매로는 자일렌(xylene), 톨루엔(toluene), 디메틸포름아미드(DMF)등을 사용할 수 있으며, 1내지 5몰 K2CO3와 테트라키스(트리페닐포스핀)팔라듐(tetrakistriphenylphosphinepalladium)을 0.5~10몰%를 사용하며, 알리큐오트336((Aliquot336)와 테트라뷰틸 암모니윰 브로마이드(tetrabutylammonium bromide)를 사용하여 중합체를 얻을 수 있다.Specifically, the polymer according to the present invention can be prepared by using a Suzuki coupling. In this case, xylene, toluene, dimethylformamide (DMF) and the like can be used as the solvent, and 1 to 5 mol K 2 CO 3 and tetrakis (triphenylphosphine) palladium (Aliquot 336) and tetrabutylammonium bromide can be used to obtain a polymer.
상세하게는 톨루엔(Toluene)에 9,9-디옥틸-2,7-디브로모플루오렌(9,9-dioctyl-2,7-dibromofluorene), 5,8-bis(5-bromothiophen-2-yl)-2,3-bis(4-(hexyloxy)phenyl)quinoxaline, 5,5'-(4,4'-(6,6'-(2,7-dibromo-9H-fluorene-9,9-diyl)bis(hexane-6,1-diyl))bis(oxy)bis(4,1-phenylene))bis(2-(4-tert-butylphenyl)-1,3,4-oxadiazole) 및 2,2'-(9,9-dioctyl-9H-fluorene-2,7-diyl)bis(4,4,5,5- tetramethyl-1,3,2-dioxaborolane)을 넣고 교반 후, 테트라키스(트리페닐포스핀)팔라듐(tetrakistriphenylphosphinepalladium)을 0.5~10몰%을 넣고 10분간 교반 한다. 또한, 탄산칼륨(K2CO3)용액을 다른 2구 플라스크에 넣어 진공으로 산소제거하고 질소로 충진 한 후 플라스크에 넣고 알리큐오트 336을 1~2방울 떨어뜨려 72시간(85℃) 교반한다. 이후 브로모벤젠(bromobenzene)을 1~2방울 떨어뜨리고 12시간 반응한다. TLC확인 후 반응이 종결되면 HCl로 담금질 시킨다. 클로로포름으로 추출 및 증류수로 씻은 후 수분제거 하고 컬럼 정제한다.Specifically, a method of adding 9,9-dioctyl-2,7-dibromofluorene, 5,8-bis (5-bromothiophen-2- 5, 5 '- (4,4' - (6,6 '- (2,7-dibromo-9H-fluorene-9,9- bis (4,1-phenylene)) bis (2- (4-tert-butylphenyl) -1,3,4-oxadiazole) and 2,2 (9,4-dioctyl-9H-fluorene-2,7-diyl) bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolane) 0.5 to 10 mol% of palladium (tetrakistriphenylphosphinepalladium) is added and stirred for 10 minutes. Further, the potassium carbonate (K 2 CO 3 ) solution is put into another two-necked flask, and oxygen is removed by vacuum, filled with nitrogen, put into a flask, and 1 or 2 drops of Aliquot 336 is added and stirred for 72 hours . After dropping 1-2 drops of bromobenzene, react for 12 hours. After the TLC is confirmed, the reaction is quenched with HCl. Extract with chloroform and wash with distilled water, remove water and purify the column.
본 발명에서는 상기와 같이 전계발광고분자를 제조하는 방법을 설명하였으나, 고분자 화합물을 제조방법은 특별히 한정시킬 필요는 없으며, 상기 화학식 2를 만족하는 고분자 화합물을 제조하는 어떠한 방법도 무방하다.In the present invention, the method of producing the electroluminescent polymer as described above has been described. However, the method of preparing the polymer compound is not particularly limited, and any method of producing the polymer compound satisfying the
본 발명에서 제조된 화학식 2의 유기 전계발광고분자는 도3에 PL 스펙트럼에 나타나듯이 용액 상에서는 청색 발광을 나타냈고 필름 상에서는 청색발광과 황색 발광의 피크를 나타냈다. 이는 파이-파이 적층에 인한 것으로 Electroluminescence 특성에서 백색 발광의 가능성을 보였다. As shown in FIG. 3, the organic electroluminescent polymer of
또한, 본 발명은 상기 전계발광고분자를 발광 재료로서 채용한 고효율, 장수명의 유기전계발광소자를 제공한다. 유기전계 발광소자의 제조방법으로는 ITO위에 PEDOT:PSS를 스핀 코팅하여 열처리 한 후 본 발명에서 얻어진 고분자를 스핀 코팅하여 열처리 하였으며, 이후 바륨 플루오라이드(BaF2)와 바륨(Ba), 알루미늄(Al)을 각각 진공 증착하여 디바이스를 제조하였다. 제조된 디바이스는 6~7V에서 백색발광을 나타내었다.
The present invention also provides a highly efficient, long-life organic electroluminescent device employing the electroluminescent polymer as a light emitting material. As a manufacturing method of the organic electroluminescent device, PEDOT: PSS was spin-coated on ITO and heat-treated. Then, the polymer obtained in the present invention was spin-coated and heat-treated. Then, barium fluoride (BaF 2 ), barium (Ba) ) Were respectively vacuum-deposited to manufacture devices. The fabricated device showed white luminescence at 6 to 7V.
이하, 실시예를 통하여 본 발명을 더욱 상세히 설명하고자 한다. 이들 실시예는 오로지 본 발명을 예시하기 위한 것으로서, 본 발명의 범위가 이들 실시예에 의해 제한되는 것으로 해석되지는 않는 것은 당업계에서 통상의 지식을 가진 자에게 있어서 자명할 것이다.
Hereinafter, the present invention will be described in more detail with reference to Examples. It is to be understood by those skilled in the art that these examples are for illustrative purposes only and that the scope of the present invention is not construed as being limited by these examples.
실시예Example 1. 유기 전기발광소자의 제조 (1) 1. Preparation of Organic Electroluminescent Device (1)
퀴나크리돈(Quinacridone, Aldrich사) 5g과 포타슘하이드록사이드(Potassium hydroxide, Aldrich사) 22g을 디메틸설폭사이드(DMSO) 50㎖에 녹이고, 1-브로모헥세인(1-bromohexane, Aldrich사) 26g을 서서히 첨가하였다. 이후 반응 혼합물은 상온에서 24시간 동안 교반하였다. 반응이 종결되면 물로 씻어준 후 컬럼을 통해 정제하여 화합물 A(5,12-dihexylquinolino[2,3-b]acridine-7,14(5H,12H)-dione) 5.5g을 얻었다. 5 g of quinacridone (Aldrich) and 22 g of potassium hydroxide (Aldrich) were dissolved in 50 ml of dimethylsulfoxide (DMSO), and 26 g of 1-bromohexane (Aldrich) Lt; / RTI > The reaction mixture was then stirred at room temperature for 24 hours. After the reaction was completed, the reaction mixture was washed with water and then purified through a column to obtain 5.5 g of Compound A (5,12-dihexylquinolino [2,3-b] acridine-7,14 (5H, 12H) -dione).
상기 얻어진 화합물 A 2g과 소듐아세테이트(sodium acetate, Aldrich사) 0.8g을 아세트산 용액에 녹여 100도로 가열한 다음, 브로민(bromine; Br2, Aldrich사) 1.5g을 아세트산에 녹인 용액을 천천히 넣어주었다. 이 후 1시간정도 교반 후 소듐바이설페이트(sodium bisulfate; NaHSO3, 삼천사)로 씻어주고 에틸아세테이트(Ethyl acetate, 삼천사)로 재결정 정제하여 화합물 B(2,9-dibromo-5,12-dihexylquinolino[2,3-b]acridine-7,14(5H,12H)-dione) 2.4g을 얻었다. 2 g of the obtained compound A and 0.8 g of sodium acetate (Aldrich) were dissolved in acetic acid solution and heated to 100 DEG C. Then, a solution in which 1.5 g of bromine (Br2, Aldrich) was dissolved in acetic acid was slowly added. After stirring for about 1 hour, the mixture was washed with sodium bisulfate (NaHSO3) and recrystallized with ethyl acetate (triethylsilane) to obtain 2,9-dibromo-5,12-dihexylquinolino [ 2,3-b] acridine-7,14 (5H, 12H) -dione.
상기 얻어진 화합물 B 1g과 트리메틸싸이오펜2일스테네인(Trimethyl(thiophen-2-yl)stannane, Aldrich사) 2g을 디엠에프(DMF, Aldrich사) 20ml에 녹이고, 비스트리페닐포스핀팔라디윰(Ⅱ)디클로라이드 (Bis(triphenylphosphine)palladium(Ⅱ)dichlororide, Aldrich사)를 넣어 130도에서 가열하여 16시간 교반 하였다. 이 후 온도를 상온으로 내린 후 헥세인(hexane, 삼천사)으로 씻어 주고 컬럼 정제하여 화합물 C (5,12-dihexyl-2,9-di(thiophen-2-yl)quinolino[2,3-b]acridine-7,14(5H,12H)-dione) 0.23g을 얻었다. 2 g of the compound B obtained above and 2 g of trimethyl (thiophen-2-yl) stannane (Aldrich) were dissolved in 20 ml of DMF (Aldrich) to obtain bistriphenylphosphine palladium (Triphenylphosphine) palladium (II) dichloride, Aldrich) was added, and the mixture was heated at 130 ° C and stirred for 16 hours. After the temperature was lowered to room temperature, the solution was washed with hexane and subjected to column purification to obtain the compound C (5,12-dihexyl-2,9-di) thiophen-2-yl quinolino [2,3-b ] acridine-7,14 (5H, 12H) -dione).
상기 얻어진 화합물 C 0.23g과 클로로포름(Chloroform, Aldrich사) 10ml와 아세트산 10ml에 녹이고 브로모썩신이미드(N-bromosuccinimide, Aldrich사) 0.14g을 천천히 넣어 주었다. 이 후 상온에서 24시간 정도 교반 후 물로 씻어주고 클로로포름(chloroform, 삼천사)로 재결정 정제하여 화합물 D(2,9-bis(5-bromothiophen-2-yl)-5,12-dihexylquinolino[2,3-b]acridine-7,14(5H,12H)-dione) 0.22g을 얻었다. 0.23 g of the compound C obtained above was dissolved in 10 ml of chloroform (Chloroform, Aldrich) and 10 ml of acetic acid, and 0.14 g of N-bromosuccinimide (Aldrich) was slowly added thereto. After stirring for 24 hours at room temperature, the mixture was washed with water and recrystallized with chloroform (chloroform) to obtain compound D (2,9-bis (5-bromothiophen-2-yl) -5,12-dihexylquinolino -b] acridine-7,14 (5H, 12H) -dione).
한편, 9,9-디옥틸-2,7-디브로모플루오렌(9,9-dioctyl-2,7-dibromofluorene, Aldrich사) 5g을 건조된 THF 30㎖에 녹이고, -78℃로 온도를 낮춘 후 2.2당량의 노르말뷰틸리튬(n-BuLi, Aldrich사)을 서서히 첨가하였다. 반응 혼합물은 2시간 동안 -78℃에서 교반한 다음, 2-아이소프로폭시-4,4,5,5-테트라메틸-1,3,2-디옥사보로레인(2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, Aldrich사)을 첨가하고, 2시간 동안 -78℃에서 교반 후 서서히 상온으로 온도를 높이면서 24시간 동안 교반하였다. 반응이 종결되면 클로로포름으로 유기물을 추출하고, 물로 씻은 후 헥산으로 재결정하여 혼합물 E (2,2'-(9,9-dioctyl-9H-fluorene-2,7-diyl)bis(4,4,5,5- tetramethyl-1,3,2-dioxaborolane))를 3.5g 얻었다.On the other hand, 5 g of 9,9-dioctyl-2,7-dibromofluorene (Aldrich) was dissolved in 30 ml of dried THF, and the solution was cooled to -78 ° C After lowering, 2.2 equivalents of n-butyllithium (n-BuLi, Aldrich) was slowly added. The reaction mixture was stirred at -78 < 0 > C for 2 hours and then treated with 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2-Isopropoxy- 5,5-tetramethyl-1,3,2-dioxaborolane, Aldrich) was added, and the mixture was stirred at -78 ° C for 2 hours, and then slowly stirred at room temperature for 24 hours. After the reaction was completed, the organic material was extracted with chloroform, washed with water and recrystallized with hexane to obtain a mixture E (2,2 '- (9,9-dioctyl-9H-fluorene-2,7-diyl) bis , 5-tetramethyl-1,3,2-dioxaborolane)).
상기에서 얻어진 화합물 D 0.00024g, 화합물 E 0.35g, 9,9-디옥틸-2,7-디브로모플루오렌(9,9-dioctyl-2,7-dibromofluorene, Aldrich사) 0.27g을 톨루엔 20㎖에 녹이고 테트라키스(트리페닐포스핀)팔라듐(tetrakistriphenylphosphinepalladium(0), Aldrich사) 0.015g을 첨가하여 10분간 교반한 후, 2몰 포타슘카보네이트(K2CO3, Aldrich사) 수용액 10㎖와 알리큐오트336(Aliquot336, Aldrich사)을 1방울 넣어 90℃에서 48시간 동안 교반하였다. 마지막으로 브로모벤젠(Bromo benzene)을 0.5㎖ 첨가하여 12시간 교반한 다음 정제하여 화학식 1의 유기 전계발광고분자를 0.30g을 얻었다.0.00024 g of the compound D obtained above, 0.35 g of the compound E and 0.27 g of 9,9-dioctyl-2,7-dibromofluorene (Aldrich) were dissolved in
합성한 고분자를 이용하여 다음과 같은 조건으로 소자를 제작하였다. PEDOT:PSS는 0.45㎛ PTFE 실린지 필터를 이용하여 filtering하였으며, shaker에서 교반하여 PEDOT과 PSS가 상분리 되는것을 막았다. AedotronTMC는 5㎛ PTFE 실린지 필터를 이용하여 filtering하였으며, 역시 shaker에서 교반하여 PEDOT-PEG와 ClO4-의 고른 분산을 도왔다. Polymer는 chlorobenzene에 0.5wt%의 농도로 용해시켜 24시간 교반해 주었으며, 5㎛ PTFE 실린지 필터를 이용하여 filtering 하였다. 준비된 substrate와 시료들을 glove box로 이송하였으며, 여러 조건으로 spin coating 하였다. Spin coating 후 PEDOT:PSS는 110℃에서 20분, AedotronTMC는 140℃에서 20분, polymer는 90℃에서 1시간동안 열처리하여 잔류용매를 제거하였으며, 발광면을 제외한 전극부분의 고분자들을 지워주었다. EIL과 전극물질을 증착하기 위하여의 열증착기(thermal evaporator)의 고진공 챔버(1×10-6 torr 이하)로 이송하였으며, 모두 BaF2(0.1Å/s, 2nm)/Ba(0.2Å/s, 2nm)/Al(5Å/s, 200nm)순으로 전극을 형성하였다. 제조된 소자는 도7,8에 나타나듯이 6~7V에서 백색발광을 나타내었다.
The device was fabricated using the synthesized polymer under the following conditions. PEDOT: PSS was filtered using a 0.45 μm PTFE syringe filter and stirred in a shaker to prevent phase separation of PEDOT and PSS. AedotronTMC was filtered using a 5 μm PTFE syringe filter and agitated in a shaker again to facilitate even dispersion of PEDOT-PEG and ClO4-. The polymer was dissolved in chlorobenzene at a concentration of 0.5 wt% and stirred for 24 hours. The polymer was filtered using a 5 μm PTFE syringe filter. The prepared substrates and samples were transferred to a glove box and spin - coated under various conditions. After spin coating, PEDOT: PSS was annealed at 110 ° C for 20 minutes, AedotronTMC at 140 ° C for 20 minutes, and polymer at 90 ° C for 1 hour to remove the residual solvent. (0.1 Å / s, 2 nm) / Ba (0.2 Å / s, 2 nm / s) in order to deposit the EIL and the electrode material in a high vacuum chamber (under 1 × 10 -6 torr) of a thermal evaporator. ) / Al (5 A / s, 200 nm). As shown in FIGS. 7 and 8, the manufactured device showed white light emission at 6 to 7V.
실시예Example 2. 유기 전기발광소자의 제조 (2) 2. Preparation of Organic Electroluminescent Device (2)
상기 화합물A(5,8-bis(5-bromothiophen-2-yl)-2,3-bis(4-(hexyloxy)phenyl)quinoxaline)는 문헌(Journal of materials and chemistry, 2009, 19, 4938-4945)을 참조하여 합성하였다. The compound A (5,8-bis (5-bromothiophen-2-yl) -2,3-bis (4- (hexyloxy) phenyl) quinoxaline was prepared according to the method described in Journal of materials and chemistry, 2009, 19, 4938-4945 ).
또한, 상기 화합물B(2,7-dibromo-9,9-bis(6-bromohexyl)-9H-fluorene)는 문헌(Organic electronics, 2007, 8, 773-783)을 참조하여 합성하였다.Further, the compound B (2,7-dibromo-9,9-bis (6-bromohexyl) -9H-fluorene) was synthesized with reference to Organic electronics, 2007, 8, 773-783.
상기 얻어진 화합물 B 5.0g, 4-(5-(4-터트뷰틸페닐)옥사디아졸2-일)페놀(4-(5-(4-tert-butylphenyl)-1,3,4-oxadiazol-2-yl)phenol) 5.0g, 포타슘카포네이트(Potassium carbonate, Aldrich사) 3.2g을 디메틸포름아미드(Dimethylformamide, Aldrich사) 80ml에 녹여 90도로 가열한 24시간 정도 교반 하였다. 이 후 물로 씻어주고 컬럼 정제하여 화합물 C(5,5'-(4,4'-(6,6'-(2,7-dibromo-9H-fluorene-9,9-diyl)bis(hexane-6,1-diyl))bis(oxy)bis(4,1-phenylene))bis(2-(4-tert-butylphenyl)-1,3,4-oxadiazole)) 6.7g을 얻었다. The obtained compound B (5.0 g), 4- (5- (4-tert-butylphenyl) oxadiazol-2-yl) -yl) phenol and 3.2 g of potassium carbonate (Aldrich) were dissolved in 80 ml of dimethylformamide (Aldrich), and the mixture was stirred at about 90 ° C. for about 24 hours. After washing with water and column purification, the compound C (5,5 '- (4,4'- (6,6' - (2,7- dibromo-9H-fluorene-9,9-diyl) bis Bis (4,1-phenylene)) bis (2- (4-tert-butylphenyl) -1,3,4-oxadiazole).
한편, 9,9-디옥틸-2,7-디브로모플루오렌(9,9-dioctyl-2,7-dibromofluorene, Aldrich사) 5g을 건조된 THF 30㎖에 녹이고, -78℃로 온도를 낮춘 후 2.2당량의 노르말뷰틸리튬(n-BuLi, Aldrich사)을 서서히 첨가하였다. 반응 혼합물은 2시간 동안 -78℃에서 교반한 다음, 2-아이소프로폭시-4,4,5,5-테트라메틸-1,3,2-디옥사보로레인(2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, Aldrich사)을 첨가하고, 2시간 동안 -78℃에서 교반 후 서서히 상온으로 온도를 높이면서 24시간 동안 교반하였다. 반응이 종결되면 클로로포름으로 유기물을 추출하고, 물로 씻은 후 헥산으로 재결정하여 혼합물 D (2,2'-(9,9-dioctyl-9H-fluorene-2,7-diyl)bis(4,4,5,5- tetramethyl-1,3,2-dioxaborolane))를 3.5g 얻었다.On the other hand, 5 g of 9,9-dioctyl-2,7-dibromofluorene (Aldrich) was dissolved in 30 ml of dried THF, and the solution was cooled to -78 ° C After lowering, 2.2 equivalents of n-butyllithium (n-BuLi, Aldrich) was slowly added. The reaction mixture was stirred at -78 < 0 > C for 2 hours and then treated with 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2-Isopropoxy- 5,5-tetramethyl-1,3,2-dioxaborolane, Aldrich) was added, and the mixture was stirred at -78 ° C for 2 hours, and then slowly stirred at room temperature for 24 hours. After the reaction was completed, the organic material was extracted with chloroform, washed with water and then recrystallized with hexane to obtain a mixture D (2,2 '- (9,9-dioctyl-9H-fluorene-2,7-diyl) bis , 5-tetramethyl-1,3,2-dioxaborolane)).
상기에서 얻어진 화합물 A 0.0002g, 화합물 C 0.08g, 화합물 D 0.17g, 9,9-디옥틸-2,7-디브로모플루오렌(9,9-dioctyl-2,7-dibromofluorene, Aldrich사) 0.0.09g을 톨루엔 15㎖에 녹이고 테트라키스(트리페닐포스핀)팔라듐 (tetrakistriphenylphosphinepalladium(0), Aldrich사) 0.008g을 첨가하여 10분간 교반한 후, 2몰 포타슘카보네이트(K2CO3, Aldrich사) 수용액 10㎖와 알리큐오트336(Aliquot336, Aldrich사)을 1방울 넣어 90℃에서 48시간 동안 교반하였다. 마지막으로 브로모벤젠(Bromo benzene)을 0.5㎖ 첨가하여 12시간 교반한 다음 정제하여 화학식 2의 유기 전기발광고분자를 0.12g을 얻었다. 0.0002 g of the compound A obtained above, 0.08 g of the compound C, 0.17 g of the compound D, 9,9-dioctyl-2,7-dibromofluorene (Aldrich) 0.008 g of tetrakistriphenylphosphinepalladium (0), Aldrich) was added to the solution, and the mixture was stirred for 10 minutes. 10 ml of an aqueous solution of 2 mol potassium carbonate (K2CO3, Aldrich) Ml and Aliquot 336 (Aliquot 336, Aldrich) were added dropwise at 90 占 폚 for 48 hours. Finally, 0.5 ml of bromo benzene was added, and the mixture was stirred for 12 hours and then purified to obtain 0.12 g of the organic electroluminescent polymer represented by the formula (2).
합성한 고분자를 이용하여 다음과 같은 조건으로 소자를 제작하였다. PEDOT:PSS는 0.45㎛ PTFE 실린지 필터를 이용하여 filtering하였으며, shaker에서 교반하여 PEDOT과 PSS가 상분리 되는것을 막았다. AedotronTMC는 5㎛ PTFE 실린지 필터를 이용하여 filtering하였으며, 역시 shaker에서 교반하여 PEDOT-PEG와 ClO4-의 고른 분산을 도왔다. Polymer는 chlorobenzene에 0.5wt%의 농도로 용해시켜 24시간 교반해 주었으며, 5㎛ PTFE 실린지 필터를 이용하여 filtering 하였다. 준비된 substrate와 시료들을 glove box로 이송하였으며, 여러 조건으로 spin coating 하였다. Spin coating 후 PEDOT:PSS는 110℃에서 20분, AedotronTMC는 140℃에서 20분, polymer는 90℃에서 1시간동안 열처리하여 잔류용매를 제거하였으며, 발광면을 제외한 전극부분의 고분자들을 지워주었다. EIL과 전극물질을 증착하기 위하여의 열증착기(thermal evaporator)의 고진공 챔버(1×10-6 torr 이하)로 이송하였으며, 모두 BaF2(0.1Å/s, 2nm)/Ba(0.2Å/s, 2nm)/Al(5Å/s, 200nm)순으로 전극을 형성하였다. 제조된 소자는 도14,15에 나타나듯이 6~7V에서 백색발광을 나타내었다.
The device was fabricated using the synthesized polymer under the following conditions. PEDOT: PSS was filtered using a 0.45 μm PTFE syringe filter and stirred in a shaker to prevent phase separation of PEDOT and PSS. AedotronTMC was filtered using a 5 μm PTFE syringe filter and agitated in a shaker again to facilitate even dispersion of PEDOT-PEG and ClO4-. The polymer was dissolved in chlorobenzene at a concentration of 0.5 wt% and stirred for 24 hours. The polymer was filtered using a 5 μm PTFE syringe filter. The prepared substrates and samples were transferred to a glove box and spin - coated under various conditions. After spin coating, PEDOT: PSS was annealed at 110 ° C for 20 minutes, AedotronTMC at 140 ° C for 20 minutes, and polymer at 90 ° C for 1 hour to remove the residual solvent. (0.1 Å / s, 2 nm) / Ba (0.2 Å / s, 2 nm / s) in order to deposit the EIL and the electrode material in a high vacuum chamber (under 1 × 10 -6 torr) of a thermal evaporator. ) / Al (5 A / s, 200 nm). As shown in FIGS. 14 and 15, the manufactured device showed white light emission at 6 to 7 V. FIG.
이상, 본 발명의 내용의 특정한 부분을 상세히 기술하였는바, 당업계의 통상의 지식을 가진 자에게 있어서, 이러한 구체적인 기술은 단지 바람직한 실시양태일 뿐이며, 이에 의해 본 발명의 범위가 제한되는 것이 아닌 점은 명백할 것이다. 따라서, 본 발명의 실질적인 범위는 첨부된 청구항들과 그것들의 등가물에 의해 의하여 정의된다고 할 것이다. Having described specific portions of the present invention in detail, those skilled in the art will appreciate that these specific descriptions are only for the preferred embodiment and that the scope of the present invention is not limited thereby. It will be obvious. Accordingly, the actual scope of the present invention will be defined by the appended claims and their equivalents.
Claims (12)
[화학식 2]
단, 상기에서 R은 독립적으로 수소원자; 탄소수 1 내지 25의 알킬기이거나 옥사디아졸(oxadiazole) 유도체를 포함하며, Ar은 벤젠(bezene)및 나프탈렌(naphtalene), 싸이오펜(thiophene), 싸이아졸(thiazole), 퓨즈드 싸이오펜(fused thiophene), 피롤(pyrolle), 피리딘(pyridine)으로 이루어진 군으로부터 선택되며, l과 m은 각각 모노머의 몰 비로써 1~100의 정수이며, n은 1~100,000의 정수이다.
Quinoxaline, and having a structure represented by the following formula (2).
(2)
Provided that R is independently a hydrogen atom; Ar is an alkyl group having from 1 to 25 carbon atoms or an oxadiazole derivative and Ar is selected from the group consisting of benzene and naphtalene, thiophene, thiazole, fused thiophene, Pyrolle, pyridine, and 1 and m are each an integer of 1 to 100, and n is an integer of 1 to 100,000 in terms of the molar ratio of the respective monomers.
An organic electroluminescence device employing the organic electroluminescence polymer of claim 7 as a light emitting material.
상기 소자는 ITO 위에 PEDOT:PSS를 스핀 코팅하여 열처리 한 후 상기의 전기발광고분자를 스핀 코팅하여 열처리한 다음 바륨 플루오라이드(BaF2)와 바륨(Ba), 알루미늄(Al)을 각각 진공 증착하여 디바이스를 제조하는 것을 특징으로 하는 유기 전기발광소자.
11. The method of claim 10,
The device was prepared by spin-coating PEDOT: PSS on ITO and then heat-treating the electroluminescent polymer by spin coating and then vacuum-depositing barium fluoride (BaF 2 ), barium Ba and aluminum (Al) And an organic electroluminescent device.
상기 소자는 6~7V에서 백색발광을 나타내는 것을 특징으로 하는 유기 전기발광소자.11. The method of claim 10,
Wherein the device exhibits white light emission at 6 to 7V.
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| KR102267797B1 (en) | 2020-02-24 | 2021-06-22 | 한국교통대학교 산학협력단 | Indenocabazole based copolymer for organic electroluminescent device and organic electroluminescent device comprising the same |
-
2011
- 2011-02-14 KR KR1020110012822A patent/KR101397085B1/en active IP Right Grant
Non-Patent Citations (1)
| Title |
|---|
| Jun Liu et al. Novel White Electroluminescent Single Polymer Derived from Fluorene and Quinacridone, Macromolecules, 2008, 41, 1162-1167. * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102267797B1 (en) | 2020-02-24 | 2021-06-22 | 한국교통대학교 산학협력단 | Indenocabazole based copolymer for organic electroluminescent device and organic electroluminescent device comprising the same |
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|---|---|
| KR20120092903A (en) | 2012-08-22 |
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