TWI412528B - 發光材料 - Google Patents
發光材料 Download PDFInfo
- Publication number
- TWI412528B TWI412528B TW097118735A TW97118735A TWI412528B TW I412528 B TWI412528 B TW I412528B TW 097118735 A TW097118735 A TW 097118735A TW 97118735 A TW97118735 A TW 97118735A TW I412528 B TWI412528 B TW I412528B
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- TW
- Taiwan
- Prior art keywords
- group
- complex
- same
- aromatic
- alkyl
- Prior art date
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- 239000000463 material Substances 0.000 title claims abstract description 60
- 125000003118 aryl group Chemical group 0.000 claims description 28
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 125000001424 substituent group Chemical group 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 125000001072 heteroaryl group Chemical group 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 239000002019 doping agent Substances 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid group Chemical group C(C1=CC=CC=C1)(=O)O WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 125000004663 dialkyl amino group Chemical group 0.000 claims description 5
- 125000002950 monocyclic group Chemical group 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 125000003367 polycyclic group Chemical group 0.000 claims description 4
- 229910052711 selenium Inorganic materials 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 150000001450 anions Chemical class 0.000 claims description 2
- 125000003107 substituted aryl group Chemical group 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 150000001924 cycloalkanes Chemical class 0.000 claims 1
- 239000003446 ligand Substances 0.000 abstract description 41
- 229910052751 metal Inorganic materials 0.000 abstract description 18
- 239000002184 metal Substances 0.000 abstract description 18
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 6
- 230000007935 neutral effect Effects 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 3
- 229910052723 transition metal Inorganic materials 0.000 abstract description 3
- 150000003624 transition metals Chemical class 0.000 abstract description 3
- 239000013522 chelant Substances 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 48
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 18
- 238000004020 luminiscence type Methods 0.000 description 15
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- 230000000903 blocking effect Effects 0.000 description 8
- 238000005401 electroluminescence Methods 0.000 description 8
- HRGDZIGMBDGFTC-UHFFFAOYSA-N platinum(2+) Chemical compound [Pt+2] HRGDZIGMBDGFTC-UHFFFAOYSA-N 0.000 description 8
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 description 7
- CYQABZPFRAEXPO-UHFFFAOYSA-N 4-[2-(2,5-dimethoxyphenyl)ethenyl]-2-phenylpyridine Chemical compound COC1=CC=C(OC)C(C=CC=2C=C(N=CC=2)C=2C=CC=CC=2)=C1 CYQABZPFRAEXPO-UHFFFAOYSA-N 0.000 description 7
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 7
- 229910052741 iridium Inorganic materials 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 230000005525 hole transport Effects 0.000 description 6
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- OQLZINXFSUDMHM-UHFFFAOYSA-N Acetamidine Chemical compound CC(N)=N OQLZINXFSUDMHM-UHFFFAOYSA-N 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 5
- 239000011368 organic material Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000003086 colorant Substances 0.000 description 4
- 150000004696 coordination complex Chemical class 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- -1 lanthanide metals Chemical class 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 4
- VFUDMQLBKNMONU-UHFFFAOYSA-N 9-[4-(4-carbazol-9-ylphenyl)phenyl]carbazole Chemical group C12=CC=CC=C2C2=CC=CC=C2N1C1=CC=C(C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=C1 VFUDMQLBKNMONU-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000003490 calendering Methods 0.000 description 3
- 239000002800 charge carrier Substances 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 230000005281 excited state Effects 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- IBHBKWKFFTZAHE-UHFFFAOYSA-N n-[4-[4-(n-naphthalen-1-ylanilino)phenyl]phenyl]-n-phenylnaphthalen-1-amine Chemical compound C1=CC=CC=C1N(C=1C2=CC=CC=C2C=CC=1)C1=CC=C(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C3=CC=CC=C3C=CC=2)C=C1 IBHBKWKFFTZAHE-UHFFFAOYSA-N 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- BPEVHDGLPIIAGH-UHFFFAOYSA-N ruthenium(3+) Chemical compound [Ru+3] BPEVHDGLPIIAGH-UHFFFAOYSA-N 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 230000005283 ground state Effects 0.000 description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 2
- MILUBEOXRNEUHS-UHFFFAOYSA-N iridium(3+) Chemical compound [Ir+3] MILUBEOXRNEUHS-UHFFFAOYSA-N 0.000 description 2
- 238000001465 metallisation Methods 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 125000006574 non-aromatic ring group Chemical group 0.000 description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical compound N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 229910000104 sodium hydride Inorganic materials 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 150000003852 triazoles Chemical class 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- DIIIISSCIXVANO-UHFFFAOYSA-N 1,2-Dimethylhydrazine Chemical compound CNNC DIIIISSCIXVANO-UHFFFAOYSA-N 0.000 description 1
- QLWOUBCORTYSPP-UHFFFAOYSA-N 1h-imidazol-1-ium;hydroxide Chemical compound O.C1=CNC=N1 QLWOUBCORTYSPP-UHFFFAOYSA-N 0.000 description 1
- AFUKNJHPZAVHGQ-UHFFFAOYSA-N 2,5-dimethoxy-Benzaldehyde Chemical compound COC1=CC=C(OC)C(C=O)=C1 AFUKNJHPZAVHGQ-UHFFFAOYSA-N 0.000 description 1
- STTGYIUESPWXOW-UHFFFAOYSA-N 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline Chemical compound C=12C=CC3=C(C=4C=CC=CC=4)C=C(C)N=C3C2=NC(C)=CC=1C1=CC=CC=C1 STTGYIUESPWXOW-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- LGEZMLUMGCVEDF-UHFFFAOYSA-N 2-[4-(4-chlorophenyl)pyridin-2-yl]-6-phenylpyridine Chemical compound C1=CC(Cl)=CC=C1C1=CC=NC(C=2N=C(C=CC=2)C=2C=CC=CC=2)=C1 LGEZMLUMGCVEDF-UHFFFAOYSA-N 0.000 description 1
- 150000005759 2-chloropyridine Chemical class 0.000 description 1
- 229940093475 2-ethoxyethanol Drugs 0.000 description 1
- FFNTVKOXGNGMLE-UHFFFAOYSA-N 2-phenylpyridine platinum(2+) Chemical compound [Pt+2].C1=CC=CC=C1C1=CC=CC=N1 FFNTVKOXGNGMLE-UHFFFAOYSA-N 0.000 description 1
- IDGNCJDSNCVWBZ-UHFFFAOYSA-N 4-(4-methylphenyl)-2-phenyl-6-pyridin-2-ylpyridine Chemical compound C1=CC(C)=CC=C1C1=CC(C=2C=CC=CC=2)=NC(C=2N=CC=CC=2)=C1 IDGNCJDSNCVWBZ-UHFFFAOYSA-N 0.000 description 1
- NFBZJFQUHWHNBZ-UHFFFAOYSA-N 4-[2-(6-phenylpyridin-2-yl)pyridin-4-yl]phenol Chemical group C1=CC(O)=CC=C1C1=CC=NC(C=2N=C(C=CC=2)C=2C=CC=CC=2)=C1 NFBZJFQUHWHNBZ-UHFFFAOYSA-N 0.000 description 1
- 150000005761 4-chloropyridine Chemical class 0.000 description 1
- AFGKZCKOSMXRRY-UHFFFAOYSA-N 4-methyl-2-phenylpyridine;hydrochloride Chemical compound Cl.CC1=CC=NC(C=2C=CC=CC=2)=C1 AFGKZCKOSMXRRY-UHFFFAOYSA-N 0.000 description 1
- TXNLQUKVUJITMX-UHFFFAOYSA-N 4-tert-butyl-2-(4-tert-butylpyridin-2-yl)pyridine Chemical compound CC(C)(C)C1=CC=NC(C=2N=CC=C(C=2)C(C)(C)C)=C1 TXNLQUKVUJITMX-UHFFFAOYSA-N 0.000 description 1
- 235000000621 Bidens tripartita Nutrition 0.000 description 1
- 240000004082 Bidens tripartita Species 0.000 description 1
- 239000003341 Bronsted base Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 239000012327 Ruthenium complex Substances 0.000 description 1
- 241001351225 Sergey Species 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 238000006069 Suzuki reaction reaction Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 125000005210 alkyl ammonium group Chemical group 0.000 description 1
- IUFDZNVMARBLOJ-UHFFFAOYSA-K aluminum;quinoline-2-carboxylate Chemical compound [Al+3].C1=CC=CC2=NC(C(=O)[O-])=CC=C21.C1=CC=CC2=NC(C(=O)[O-])=CC=C21.C1=CC=CC2=NC(C(=O)[O-])=CC=C21 IUFDZNVMARBLOJ-UHFFFAOYSA-K 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000001543 aryl boronic acids Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 1
- 208000006637 fused teeth Diseases 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- WCKWXPBDKSOVOK-UHFFFAOYSA-H hexachlororuthenium Chemical compound Cl[Ru](Cl)(Cl)(Cl)(Cl)Cl WCKWXPBDKSOVOK-UHFFFAOYSA-H 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- KNVVMNKJHCIPRV-UHFFFAOYSA-M lithium;3-hydroxyquinoline-2-carboxylate Chemical compound [Li+].C1=CC=C2N=C(C([O-])=O)C(O)=CC2=C1 KNVVMNKJHCIPRV-UHFFFAOYSA-M 0.000 description 1
- 238000001748 luminescence spectrum Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical compound C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 description 1
- 150000004866 oxadiazoles Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000003880 polar aprotic solvent Substances 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000005258 radioactive decay Effects 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical compound [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 description 1
- 125000005259 triarylamine group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0033—Iridium compounds
-
- 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
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/12—Light sources with substantially two-dimensional radiating surfaces
- H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
- H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
-
- 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
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
-
- 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
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
-
- 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
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2101/00—Properties of the organic materials covered by group H10K85/00
- H10K2101/10—Triplet emission
-
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Description
本發明關於一種發光材料,該材料的用途和一種能夠將電能轉換為光的發光裝置。
今日,各種顯示裝置正在積極地研究並發展,特別是建基於來自有機材料的電致發光(electroluminescence)(EL)者。
相較於光致發光(即,從活性材料由於光的吸收和經激發狀態的放射衰變引起的鬆弛所導致之發光),電致發光(EL)係指對基質施加電場所導致的無熱光產生。於後者的情況中,係藉由在外部電路的存在下將射入有機半導體中的相反符號之電荷載體(電子和電洞)的再結合而達成激發。
有機發光二極體(OLED)的簡單雛型,即一單層OLED,典型地係由活性有機材料薄膜所組成,其係夾置於兩電極之間,其中一個電極需要為半透明者以觀察到來自於有機層的發光。通常,使用經銦錫氧化物(ITO)塗覆的玻璃基板作為陽極。
若施加外部電壓到該兩個電極,則陽極的電荷載體(即,電洞)和陰極的電子會在超過所用有機材料之特定底限電壓時注入有機層內。在電場存在下,電荷載體會移動通過活性層並於彼等到達相反電荷的電極處之時非放射地
放電。不過,若電洞和電子於漂過有機層時彼此相遇,則形成單重(反對稱)和三重(對稱)激發態(所謂的激子(exciton))。光因此從分子激發態(或激子)的衰變而於有機材料中產生。對於在一OLED中由電激發形成的每三個三重態激子,僅產生一個對稱態(單重態)激子。
許多有機材料會展現來自單重態激子的螢光(即,來自對稱允許程序(symmetry-allowed process)的發光)。由於此程序係於相同對稱性的狀態之間發生,因此其可為非常有效率者。相反的,若激子的對稱性與基態不同,則激子的放射性鬆弛不被允許,且發光會減緩並無效率。由於基態通常為反對稱性者,所以來自三重態的衰變會破壞對稱性。因此,該程序不被允許且EL的效率非常低。如此一來,包含於三重態中的能量會大部份浪費掉。
來自對稱不允許程序的發光係稱為燐光。特性上,燐光可於激發之後由於低躍遷機率所致,而持續達數秒,這不同於源自快速衰變的螢光。
不過,僅有少數種材料被鑑定出顯示來自三重態的有效率室溫燐光。
燐光材料的成功利用對於有機電致發光裝置會有巨大的希望。例如,利用燐光材料的一項優點為所有激子(於EL中由電洞和電子的結合所形成者),其於燐光裝置中係(部份)以三重態為基礎者,可參與能量轉移和發光。此可經由燐光發光本身達成或經由使用用於改善螢光程序效率之燐光材料來達成。
於每一情況中,重要的是發光材料提供集中於接近所選光譜區(該等區係對應於三原色(紅,綠和藍)之一)之相對狹窄譜帶內之電致發光。這使得它們可在OLED中用作著色層。
作為用以改善發光裝置的性質之手段,已有報導一種利用來自正金屬化銥錯合物的發光之發綠光裝置。(Ir(ppy)3:tris-ortho-metalated complex of iridium(III)with 2-phenylpyridine(ppy).Appl.phys.Lett..1999,vol.75,p.4.)。
因此,US 2005214576(SERGEY LAMANSKY ET AL.)29/09/2005揭露一種發燐光性有機金屬化合物,其可用於有機發光裝置的製造,其舉例之化合物如下:鉑(II)(2-苯基吡啶-N,C2’
)(乙醯丙酮)[Pt(ppy)(acac)];鉑(II)(2-(對-甲苯基)吡啶-N,C2’
)(乙醯丙酮)[Pt(tpy)(acac)];鉑(II)(7,8-苯并喹啉-N,C3’
)(乙醯丙酮)[Pt(bzq)(acac)];鉑(II)(2-苯甲基吡啶-N,C2’
)(乙醯丙酮)[Pt(bzpy)(ocac)];鉑(II)(2-(2’-噻吩基)吡啶-N,C3’
)(乙醯丙酮)[Pt(thpy)(acac)];鉑(II)(2-(2’-(4’,5’-苯并噻吩基)吡啶-N,C3’
)(乙醯丙酮)[Pt(btp)(acac)];鉑(II)(2-(4’,6’-二氟苯基)吡啶-N,C2’
)(乙醯
丙酮)[Pt(4,6-F2
ppy)(acac)];鉑(II)(2-(4’,5’-二氟苯基)吡啶-N,C2’
)(乙醯丙酮)[Pt(4,5-F2
ppy)(acac)];和鉑(II)(2-(4’,5’-二氟苯基)吡啶-N,C2’
)(2-甲基吡啶)[Pt(4,5-F2
ppy)(pico)]。
WO 2005/117159(CDT OXFORD LIMITED)8/12/2005揭露一種由式I表的用於發光之金屬錯合物,其係如下所示:M-L其中M為一金屬,L為一配位基且L包含Ar(即經取代或未經取代的雜芳基環),其含至少一個磷原子。這建議了L較佳為一雙牙配位基例如聯吡啶基(bipyridyl)。
WO 2005/117160(CDT OXFORD LIMITED)8/12/2001揭露一種可用於發光裝置的帶電金屬錯合物。該帶電金屬錯合物可為螢光性或燐光性,其含金屬M和配位基L。合適的金屬M包括鑭系金屬,d-封阻金屬(d-block metal)和形成螢光性錯合物的金屬。再者,配位基L可為單牙,雙牙或三牙者。
SPROUSE,S.,等人的Photophysical effects of metal-carbon σ bonds in ortho-metalated complexes of Ir(III)and Rh(III).J.Am.Chem.Soc..1984,vol.106,p.6647-6653.揭露[M(L)2
Cl]2
型的經氯橋接二聚物,其中L為2-苯基吡啶(ppy)或苯并[h]喹啉(bzq)且M為Rh(III)
或Ir(III)。上述參考資料教示正金屬化配位基展現出相較於2,2’-聯吡啶(bpy)和1,10-啡啉(phen)的Rh(III)和Ir(III)錯合物顯著較高的光譜效應及較低能量電荷轉移躍遷。
SLINKER,Jason D.,等人的Efficient yellow electroluminescence from a single layer of a cyclometalated iridium complex.J.Am.Chem.Soc.2004,vol.126,p.2763-2767.揭露一種帶電銥錯合物[Ir(ppy)2
-(dtb-bpy)]+
(PF6
)-
,及其作為多功能環金屬化配位基的用途。該帶電銥錯合物含有三個配位基,其中二個環金屬化配位基(ppy:2-苯基吡啶)係經選擇來配位銥金屬中心以進一步增加配位基場***能量。再者,第三個配位基,4,4’-二第三丁基-2,2’-二吡啶基(dtb-bpy),確保氧化還原的可逆性,減少自我淬滅和增強裝置特性。
LEPELTIER,Marc,等人的Synthesis,structure and photophysical and electrochemical properties of cyclometallated iridium(III)complexes with phenylated bipyridine ligands.Eur.J.Inorg.Chem..2005,p.110-117.揭露一系列的陽離子性dimino銥(III)錯合物,[Ir(ppy-N,C)2
(L-N,N)](PF6
)(Hppy=2-苯基吡啶,L=4,4’-tBu2
dpbpy,4,4’-Me2
dpbpy,4,4’-Me2
pbpy,4,4’-Me2
bpy),及彼等的光物理和電化學性質。
SLINKER,Jason D.,等人的Green electroluminescence from an ionic iridium complex.Appl.
phys.Lett..2005,vol.86,p.173506.揭露來自離子銥錯合物的綠螢光,[Ir(F-mppy)2
(dtb-ppy)]+
(PF6)-
,其中F-mppy為2-(4’-氟苯基)-5-甲基吡啶且dtb-bpy為4,4’-二第三丁基-2,2’-聯吡啶。
EVANS,Rachel C.,等人的Coordination complexes exhibiting room temperature phosphorescence:Evaluation of their suitability as triplet emitters in organic light emitting diodes.Coordination Chemistry review.2006,vol.150,p,2093-2126.揭露數種含有環金屬化配位基的銥(III)錯合物例如4-(4’-氯苯基)-6’-苯基-2,2’-聯吡啶(clpby),4’-(4-羧基苯基)-6’-苯基-2,2’-聯吡啶(cpbpy),4,4’-二丁基-2-2’-聯吡啶(dbbpy),4-(4-羥基苯基)-6’-苯基-2,2’-聯吡啶(hpbpy)或4’-(4-甲苯基)-6’-苯基-2,2’-聯吡啶及其衍生物。
不過,由於上述先前技藝的發光材料不能顯示多種純色,亦即,彼等的發光譜帶,通常受限在綠色者,並非集中於靠近所選光譜區(此對應於三原色(紅,綠和藍)之一),因此彼等可用為OLED活性化合物的範圍狹窄。因此有需要開發出能夠發出具有其他顏色的光,尤其是在紅色區內的光的發光材料。
具有良好色座標的有效且長壽紅光發射物係目前公認為在有機電致發光裝置領域中所欠缺者。
因此本發明的目的為提供一種包含具有輔助配位基的正金屬化錯合物之發光材料,如下所述。
本發明的另一項目的為該發光材料的用途和一種包括該發光材料的有機發光裝置。
如上所述,本發明的目的為提供一種發光材料,其包含下式(I)之錯合物:
其中:M表一原子序至少40,較佳為第8至第12族的過渡金屬,更佳為Ir或Pt,且最佳為Ir;E1
表芳環或雜芳環,隨意地與另外的芳族部份或非芳族環縮合,其中該環隨意地具有一或更多個取代基,且隨意地與包括E2
的環形成一縮合結構,且其中該環係經由使用sp2
混成碳與金屬M配位;E2
表含N芳環,隨意地與另外的芳族部份或非芳族環縮合,其中該環隨意地具有一或更多個取代基,且隨意地與包括E1
的環形成一縮合結構,且其中該環係經由使
用sp2
混成氮與金屬M配位;R’於每一出現處為相同或不同者且係選自-H,-F,-Cl,-Br,-NO2
,-CN,直鏈或支鏈C1-20
烷基,C3-20
環狀烷基,直鏈或支鏈C1-20
烷氧基,C1-20
二烷基胺基,C4-14
芳基,C4-14
雜芳基(其可經一或更多非芳族基團所取代),其中複數個取代基R’可在相同環上或在兩不同環上集合地形成一額外的單-或多-環狀環系統(隨意為芳族者);X1
,X2
,X3
,X4
,X5
和X6
於每一出現處為相同或不同者且係獨立地選自氫,烷基,芳基,雜芳基和烷基,彼等分別可經至少一個取代基所取代;A-
為一抗衡陰離子;且n1
、n2
、m1
和m2
於每一出現處為相同或不同者且表從0至4的整數,其中n1
+m1
=4且n2
+m2
=4,其先決條件為n1
和n2
不可同時為0。
如於上面式(I)中所載明者,該二個鉗合單陰離子配位基係透過碳和氮原子與金屬結合,並包括E1
和E2
部份。此類配位基通常稱為正金屬化配位基(C^N配位基)。
該透過兩個氮原子結合至金屬的鉗合性雙牙聯吡啶配位基通常稱為輔助配位基(N^N配位基)。
令人訝異的是,已發現當中性鉗合配位基(N^N)(也稱為輔助配位基)包含帶有共軛乙烯式不飽和取代基的2,2’-聯吡啶從而擁有足夠的電子接受性之時,該配位基會
有利地參與發光程序。亦即,此類配位基會顯著地將發光偏移向較低能量(紅-移)並實質地改善錯合物[C^N]2
M[N^N]在紅光區內的發光效率。
再者,透過載有共軛乙烯式不飽和取代基的鉗合配位基(N^N),可獲得包含式(I)之[C^N]2
M[N^N]錯合物的高度燐光性發光材料,其具有介於650奈米與750奈米間的最大發光,因此對應於紅色發光。
較佳為,本發明發光材料包含下式(II)之錯合物:
其中:X1
,X2
,X3
,X4
,X5
,X6
,R’,n1
,n2
,m1
,m2,和A-
具有與上述定義相同的意義;X係選自由-CH=CH-,-CR=CH-,-CR=CR-,N-H,N-R1
,O,S和Se所組成的群組,其中X較佳為選自-CH=CH-,-CR=CH-或S;Y係選自由-CH=CH-,-CR=CH-,-CR=CR-,N-H,N-R1
,O,S和Se所組成的群組,其中Y較佳為選自
-CH=CH-,-CR=CH-或S;R於每一出現處為相同或不同者且為-F,-Cl,-Br,-NO2
,-CN,直鏈或支鏈C1-20
烷基,C3-20
環狀烷基,直鏈或支鏈C1-20
烷氧基,C1-20
二烷基胺基,乙烯基(其可為一或更多芳基或非芳族基團所取代),C4-14
芳基,C4-14
雜芳基(其可為一或更多非芳族基團所取代),其中複數個取代基R可於相同環上或於兩不同的環上集合地形成一額外的單-或多-環狀環系統(隨意為芳族者);a為從0至4的整數;且b為從0至4的整數。
更佳為,本發明發光材料包括下式(IIA)之錯合物:
其中:X1
,X2
,X3
,X4
,X5
,X6
,X,Y,R,R’,n1
,n2
,m1
,m2
,a和A-
具有與上述定義相同的意義;
X7
,X8
和X9
於每一出現處為相同或不同者且係獨立地選自氫,烷基,芳基,雜芳基和烷基,它們分別可經至少一個取代基所取代;R”於每一出現處為相同或不同者且表-F,-Cl,-Br,-NO2
,-CN,直鏈或支鏈C1-20
烷基,C3-20
環狀烷基,直鏈或支鏈C1-20
烷氧基,C1-20
二烷基胺基,C4-14
芳基或C4-14
雜芳基(其可為一或更多非芳族基團所取代),其中複數個取代基R”可於相同環上或於兩不同的環上集合地形成一額外的單-或多-環狀環系統(隨意為芳族者);b為從0至3的整數;且w為從1至4的整數。
在本發明的錯合物中,較佳者為其中X1
,X2
,X3
,X4
,X5
,和X6
為各自獨立地選自氫和未取代或經取代芳基者。
更佳者為其中:X1
、X2
和X3
中有二者為氫且另一者為苯甲酸基;X4
、X5
和X6
中有二者為氫且另一者為苯甲酸基;或X7
、X8
和X9
中有二者為氫且另一者為苯甲酸基。
顯示於下的式(III)錯合物可產生優良結果:
其中A-
具有與上述定義相同的意義。
包含2-苯基-N-吡啶(ppy)正金屬化配位基和作為輔助配位基的帶有共軛乙烯式不飽和取代基之雙牙聯吡啶(bpy)的式(III)錯合物,由於在紅光區具有高色純度的發光而特別有利於本發明。
式(I)錯合物(亦即包含二個正金屬化配位基(C^N配位基)和一個中性雙牙聯吡啶配位基(N^N)的金屬錯合物)的合成可由任何已知方法達成。適用於製備式(I)錯合物的合成方法之細節係詳細地揭露於下列文獻中:“Inorg.Chem.”,No.30,pg.1685(1991);“Inorg.Chem.”,No.27,pg.3464(1988);“Inorg.Chem.”,No.33,pg.545(1994);“Inorg.Chem.Acta”,No.181,pg.245(1991),“J.Organomet.Chem.”,No.35,pg.293(1987);和“J.Am.Chem.Soc.”,No.107,pg.1431(1985)。
大體上,根據本發明第一具體實例,式(I)錯合物可根據下列反應流程所製備:
該正金屬化配位基的酸形式(H-C^N)和輔助配位基的酸形式(N^N)可於商業上取得或可經由使用熟知的有機合成反應途徑容易地合成。
尤其是,正金屬化配位基(H-C^N)可經由將經取代吡啶化合物與對應的芳基硼酸Suzuki偶合而以良好到優良的產率所製備,如於Olivier Lohse,et al.(The Palladium Catalyzed Suzuki Coupling of 2-and 4-chloropyridines.Syn.Lett..1999,No.1,pgs.15-18.)及US 6670645(DU PONT DE NEMOURS)30/12/2003中所述者。
經特別調適用於製備氟化正金屬化配位基(H-C^N)的合成方法,係載於JP2003113164 A(MITSUBISHI MATERIALS CORP)18/04/2003和JP2003113163 A(MITSUBISHI MATERIALS CORP)18/04/2003之中。
若過渡金屬為銥,可使用三鹵化銥(III)化合物例如IrCl3
.H2
O,六鹵化銥(III)化合物例如M°3
IrX°6
,其中X°為鹵素(較佳為Cl)且M°為鹼金屬(較佳為K),及六鹵化銥(IV)化合物諸如M°2
IrX°6
,其中X°為鹵素(較佳為Cl)且M°為鹼金屬(較佳為K)(“Ir鹵化先質
”),作為起始物質來合成式(I)錯合物。
[C^N]2
Ir(μ-X°)2
Ir[C^N]2
錯合物(化合物VI,其中M=Ir)(其中X°為鹵素(較佳為Cl)),可從該Ir鹵化先質和適當的正金屬化配位基藉由使用文獻中已揭示的程序來製備(S.Sprouse,K.A.King,P.J.Spellane,R.J.Watts,J.Am.Chem.Soc.,1984,106,6647-6653;M.E.Thompson et al.,Inorg.Chem.,2001,40(7),1704;M.E.Thompson et al.,J.Am.Chem.SOC.,2001,123(18),4304-4312)。
較佳為,反應係經由使用過量的中性形式正金屬化配位基(H-C^N)來實施。再者,高沸點溶劑係較佳者。
術語“高沸點溶劑”係表具有至少80℃,較佳地至少85℃,更佳地至少90℃的沸點之溶劑。合適的溶劑為,例如,甲氧基乙醇,乙氧基乙醇,甘油,二甲基甲醯胺(DMF),N-甲基吡咯烷酮(NMP),二甲亞碸(DMSO)及類似者。該溶劑可以其本身使用或以與水的混合物使用。
隨意地,反應可在合適的布忍斯特鹼諸如金屬碳酸鹽(尤其是碳酸鉀(K2
CO3
));金屬氫化物(尤其是氫化鈉(NaH));金屬乙氧化物或金屬甲氧化物(尤其是NaOCH3
,NaOC2
H5
);烷基銨氫氧化物(尤其是氫氧化四甲銨);或咪唑鎓(imidazolium)氫氧化物的存在下進行。
以合適配位基(N^N)對金屬原子所進行之親核性取
代,係為形成相應的([C^N]2
Ir[N^N])+
A-
(式I,其中Me=Ir),其較佳為經由於合適溶劑中令化學計量的配位基N^N與橋接中間體(VI)粗略接觸來進行。
極性非質子溶劑對於此等反應而言通常係較佳者。一種產生特別良好結果的溶劑為二氯甲烷(CH2
Cl2
)。
本發明也有關發光材料於有機發光裝置(OLED)的發光層內之用途。
再者,本發明也有關發光材料用作在主體層中的摻雜劑,因而在有機發光裝置中作為發光層的用途。
若發光材料係作為摻雜劑用於主體層中,其通常以相對於主體和摻雜劑的總重量為至少1重量%,較佳為至少3重量%,且更佳為至少5重量%的量使用。再者,其通常以最多25重量%,較佳為最多20重量%,且更佳為最多15重量%的量使用。
本發明也有關一種包括發光層(EML)的有機發光裝置(OLED),其中該發光層包括上述發光材料。該OLED可隨意地包含一主體材料(於其中該發光材料較佳係以摻雜劑形式存在),其中該主體材料係經調適成在跨該裝置結構施加電壓時發光。
OLED通常包括:一玻璃基板;一通常為透明的陽極例如銦錫氧化物(ITO)陽極;一電洞傳輸層(HTL);一發光層(EML);
一電子傳輸層(ETL);一通常為金屬的陰極例如Al層。
對於電洞傳導發光層,在該發光層與電子傳輸層之間,可具有激子阻斷層,尤其是電洞阻斷層(HBL)。對於電子傳導發光層,可在發光層和電洞傳輸層之間具有激子阻斷層,尤其是電子阻斷層(EBL)。該發光層可等於該電洞傳輸層(於此情況中激子阻斷層係接近陽極或在陽極處)或等於電子傳輸層(於此情況中激子阻斷層係接近陰極或在陰極處)。
發光層可用其中含有客體形式的發光材料的主體材料來形成。或者,該發光層可基本上由該發光材料本身所構成。於前者的情況中,主體材料可為選自經取代三-芳基胺類的群組中之電洞傳輸材料。較佳為,該發光層係用其中含有發光材料作為客體之主體材料所形成。該主體材料可為選自由羥基喹啉金屬quinoxolate(例如羥基喹啉鋁(aluminium quinolate)(Alq3
),羥基喹啉鋰(Liq)),二唑和***所組成的群組中之電子傳輸材料。主體材料的一個例子為4,4’-N,N’-二咔唑-聯苯[“CBP”],其係以下式為特徵:
隨意地,該發光層也可含有極化分子,其係作為摻雜劑存在於該主體材料中並具有偶極矩而在作為摻雜劑的該發光材料發光時通常會影響所發光的波長。
電子傳輸材料所形成的層係用來將電子傳輸到包含發光材料和隨意的主體材料之發光層內。該電子傳輸材料可為選自羥基喹啉金屬(例如Alq3
,Liq),二唑和***所組成的群組中之電子傳輸基質。電子傳輸材料的一個例子為下式的三-(8-羥基喹啉)鋁[“Alq3
”]:
電洞傳輸材料所形成的層係用來將電洞傳輸到包含發光材料和隨意的主體材料之發光層內。電洞傳輸材料的一個例子為4,4’-雙[N-(1-萘基)-N-苯胺基]聯苯[“α-NPD”]。
使用激子阻斷層(“障壁層”)將激子拘束在發光層(“發光區”)內係極佳者。對於電洞傳輸主體,可將該阻斷層放置於發光層與電子傳輸層之間。一種用為此障壁層的材料之例子為2,9-二甲基-4,7-二苯基-1,10-啡啉(也稱為bathocuproine或“BCP”),其具有下式:
OLED較佳為具有多層結構(如於圖1中所示者),其中:1係玻璃基板;2係一ITO層;3係一包括α
-NPD的HTL層;4係一包括作為主體材料的CBP和作為摻雜劑的發光材料之EML,該發光材料的量相對於主體和摻雜劑的總重為約8%;5係一包括BCP的HBL;6係一包括Alq3
的ETL;且7係一Al層陰極。
2-苯基-4-(2,5-二甲氧基苯乙烯基)吡啶之合成
a)t-BuOK,DMF,rt
於2-苯基-4-甲基吡啶鹽酸鹽(1克,4.9毫莫耳)和2,5-二甲氧基苯甲醛(1.2克,7.3毫莫耳)在無水DMF(40毫升)中的混合物中添加固體t-BuOK(2克,18毫莫耳)。將所得混合物於80℃氮氣下攪拌整夜。在將DMF蒸發之後,對其添加Et2
O並將沉澱物過濾並以水清洗。將固體經由管柱層析術(SiO2
,CH2
Cl2
/MeOH,99/1)純化而得0.6克(39%)呈黃色固體的所欲化合物。
[(2-苯基-4-(2,5-二甲氧基苯乙烯基)吡啶)2
IrCl]2
之合成
b)IrCl3
.H2
O,EtOCH2
CH2
OH/H2
O,△。
將1當量的IrCl3
.3H2
O和2.5當量的2-苯基-4-(2,5-二甲氧基苯乙烯基)吡啶於2-乙氧基乙醇和水(3/1,v/v)的混合物中及110℃氮氣下加熱整夜。在冷卻至室溫之後,過濾出所得沉澱物,依次用甲醇(而後Et2
O)
清洗且最後乾燥而得所欲二聚物。由於此化合物的溶解度低,其1
H-NMR係以其[C^N]2
Ir(Cl)(DMSO)衍生物在DMSO-d6
中記錄。
1
H-NMR(DMSO-d6
,298K,200MHz,δ ppm)3.80(s,12H),3.88(s,12H),5.85(d,J=7Hz,1H),6.31(d,J=7Hz,1H),6.70-7.90(m,42H),8.26(s,1H),8.32(s,1H),9.45(d,J=7Hz,1H),9.75(d,J=7Hz,1H)。
[(2-苯基-4-(2,5-二甲氧基苯乙烯基)吡啶)2
Ir(4,4’-二羧酸2,2’-聯吡啶)][比較用錯合物(VII)]之合成
將[(2-苯基-4-(2,5-二甲氧基苯乙烯基)吡啶)2
IrCl]2
(122毫克,0.071毫莫耳),4,4’-二羧酸2,2’-聯吡啶(40毫克,0.164毫莫耳)和氫氧化四丁基銨30水合物(261毫克,0.326毫莫耳)於CH2
Cl2
(100毫升)中及氬氣下迴流6小時。將所得橘色溶液濃縮為5毫升且經由乙醇的緩慢擴散予以結晶化。過濾出淡黃色沉澱物,以Et2
O清洗之並經空氣乾燥而得50毫克的所欲錯合物(產
率:33%)。
[(2-苯基-4-(2,5-二甲氧基苯乙烯基)吡啶)2
Ir(4,4’-二羧酸苯乙烯基)-2,2’-聯吡啶)][錯合物(III)]之合成
將[(2-苯基-4-(2,5-二甲氧基苯乙烯基)吡啶)2
IrCl]2
(83毫克,0.048毫莫耳),(4,4’-對二羧酸苯乙烯基)-2,2’-聯吡啶(44毫克,0.095毫莫耳)和氫氧化四丁基銨30水合物(194毫克,0.242毫莫耳)於DMF(30毫升)中及氬氣下迴流8小時。將所得溶液蒸發至乾燥且將所得固體以甲醇再結晶化而得100毫克的所欲錯合物(產率:80%)。
錯合物(III)的發光光譜顯示其於710奈米附近的最大值(對應於紅色發光),具有大幅超過參考錯合物(VII)的發光強度且相對於參考錯合物(VII)有約20奈米的紅-移,因此能夠獲得純紅色發光。
1‧‧‧玻璃基板
2‧‧‧ITO層
3‧‧‧包含α
-NPD的HTL層
4‧‧‧EML
5‧‧‧包含BCP的HBL
6‧‧‧包含Alq3
的ETL
7‧‧‧Al層陰極
圖1顯示一OLED的多層結構。
Claims (13)
- 一種下式(II)的錯合物:
- 根據申請專利範圍第1項之錯合物,其中X係選自-CH=CH-,-CR=CH-或S。
- 根據申請專利範圍第1或2項之錯合物,其中Y係選自-CH=CH-,-CR=CH-或S。
- 根據申請專利範圍第1項之錯合物,其係以下式(IIA)所表示:
- 根據申請專利範圍第1項之錯合物,其中X1 、X2 和X3 中有兩者為氫且另一者為苯甲酸基。
- 根據申請專利範圍第1項之錯合物,其中X4 、X5 和X6 中有兩者為氫且另一者為苯甲酸基。
- 根據申請專利範圍第4至6項中任一項之錯合物,其中X7 、X8 和X9 中有兩者為氫且另一者為苯甲酸基。
- 根據申請專利範圍第1項之錯合物,其係以式(III)所表示:
- 一種發光材料,其包含根據申請專利範圍第1至8項中任一項之錯合物。
- 一種根據申請專利範圍第9項之發光材料用於有機發光裝置的發光層中之用途。
- 一種根據申請專利範圍第9項之發光材料用作主體層中之摻雜劑而於有機發光裝置中作為發光層的用途。
- 一種包括發光層(EML)的有機發光裝置(OLED),其特徵在於該發光層包含申請專利範圍第9項之發光材料,及隨意之主體材料。
- 一種包括根據申請專利範圍第12項之有機發光裝置之顯示裝置。
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