NL2008810C2 - Electroluminescent composition. - Google Patents
Electroluminescent composition. Download PDFInfo
- Publication number
- NL2008810C2 NL2008810C2 NL2008810A NL2008810A NL2008810C2 NL 2008810 C2 NL2008810 C2 NL 2008810C2 NL 2008810 A NL2008810 A NL 2008810A NL 2008810 A NL2008810 A NL 2008810A NL 2008810 C2 NL2008810 C2 NL 2008810C2
- Authority
- NL
- Netherlands
- Prior art keywords
- organic
- luminescent
- group
- metal
- electroluminescent composition
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims description 58
- 125000005647 linker group Chemical group 0.000 claims description 47
- 150000001875 compounds Chemical class 0.000 claims description 42
- 239000000891 luminescent agent Substances 0.000 claims description 37
- 125000000524 functional group Chemical group 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 22
- -1 nitrogen-containing carboxylates Chemical class 0.000 claims description 21
- 229910052751 metal Inorganic materials 0.000 claims description 20
- 239000002184 metal Substances 0.000 claims description 20
- 125000002524 organometallic group Chemical group 0.000 claims description 16
- 239000011159 matrix material Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- 239000011148 porous material Substances 0.000 claims description 11
- 229920001940 conductive polymer Polymers 0.000 claims description 10
- 230000005693 optoelectronics Effects 0.000 claims description 10
- 125000000623 heterocyclic group Chemical group 0.000 claims description 9
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 8
- 125000003277 amino group Chemical group 0.000 claims description 7
- 150000002902 organometallic compounds Chemical class 0.000 claims description 7
- 229910052733 gallium Inorganic materials 0.000 claims description 6
- 229910052738 indium Inorganic materials 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 6
- 125000004104 aryloxy group Chemical group 0.000 claims description 5
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 5
- 229910052693 Europium Inorganic materials 0.000 claims description 4
- 229910052771 Terbium Inorganic materials 0.000 claims description 4
- 150000007942 carboxylates Chemical class 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical class C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 4
- 238000000295 emission spectrum Methods 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 150000002910 rare earth metals Chemical class 0.000 claims description 4
- 229910052706 scandium Inorganic materials 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- 229910052691 Erbium Inorganic materials 0.000 claims description 3
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 3
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 3
- 125000002252 acyl group Chemical group 0.000 claims description 3
- 125000004442 acylamino group Chemical group 0.000 claims description 3
- 125000004423 acyloxy group Chemical group 0.000 claims description 3
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 125000004466 alkoxycarbonylamino group Chemical group 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000004414 alkyl thio group Chemical group 0.000 claims description 3
- 125000000304 alkynyl group Chemical group 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 125000004397 aminosulfonyl group Chemical group NS(=O)(=O)* 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 125000005161 aryl oxy carbonyl group Chemical group 0.000 claims description 3
- 125000005110 aryl thio group Chemical group 0.000 claims description 3
- 239000011244 liquid electrolyte Substances 0.000 claims description 3
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 claims description 3
- 150000003003 phosphines Chemical class 0.000 claims description 3
- 229920000767 polyaniline Polymers 0.000 claims description 3
- 229920000123 polythiophene Polymers 0.000 claims description 3
- 125000006296 sulfonyl amino group Chemical group [H]N(*)S(*)(=O)=O 0.000 claims description 3
- 125000004149 thio group Chemical group *S* 0.000 claims description 3
- 229910052695 Americium Inorganic materials 0.000 claims description 2
- 241000195493 Cryptophyta Species 0.000 claims description 2
- 229910052685 Curium Inorganic materials 0.000 claims description 2
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 2
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 2
- 229910052689 Holmium Inorganic materials 0.000 claims description 2
- 229910052766 Lawrencium Inorganic materials 0.000 claims description 2
- 229910052764 Mendelevium Inorganic materials 0.000 claims description 2
- 229910052781 Neptunium Inorganic materials 0.000 claims description 2
- 229910052778 Plutonium Inorganic materials 0.000 claims description 2
- 229910052774 Proactinium Inorganic materials 0.000 claims description 2
- 229910052772 Samarium Inorganic materials 0.000 claims description 2
- 229910052776 Thorium Inorganic materials 0.000 claims description 2
- 229910052775 Thulium Inorganic materials 0.000 claims description 2
- 229910052770 Uranium Inorganic materials 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 125000005067 haloformyl group Chemical group 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 150000002460 imidazoles Chemical class 0.000 claims description 2
- 150000002466 imines Chemical class 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 claims description 2
- 238000007146 photocatalysis Methods 0.000 claims description 2
- 229920001088 polycarbazole Polymers 0.000 claims description 2
- 229920000128 polypyrrole Polymers 0.000 claims description 2
- 150000004032 porphyrins Chemical class 0.000 claims description 2
- 150000003222 pyridines Chemical class 0.000 claims description 2
- 125000004076 pyridyl group Chemical group 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 150000003852 triazoles Chemical class 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 claims 2
- 229910002651 NO3 Inorganic materials 0.000 claims 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 1
- 229930002875 chlorophyll Natural products 0.000 claims 1
- 235000019804 chlorophyll Nutrition 0.000 claims 1
- ATNHDLDRLWWWCB-AENOIHSZSA-M chlorophyll a Chemical compound C1([C@@H](C(=O)OC)C(=O)C2=C3C)=C2N2C3=CC(C(CC)=C3C)=[N+]4C3=CC3=C(C=C)C(C)=C5N3[Mg-2]42[N+]2=C1[C@@H](CCC(=O)OC\C=C(/C)CCC[C@H](C)CCC[C@H](C)CCCC(C)C)[C@H](C)C2=C5 ATNHDLDRLWWWCB-AENOIHSZSA-M 0.000 claims 1
- 235000015165 citric acid Nutrition 0.000 claims 1
- 150000002311 glutaric acids Chemical class 0.000 claims 1
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 150000002531 isophthalic acids Chemical class 0.000 claims 1
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- 150000002913 oxalic acids Chemical class 0.000 claims 1
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- 150000003022 phthalic acids Chemical class 0.000 claims 1
- 235000011044 succinic acid Nutrition 0.000 claims 1
- 150000003444 succinic acids Chemical class 0.000 claims 1
- 150000003504 terephthalic acids Chemical class 0.000 claims 1
- MDDUHVRJJAFRAU-YZNNVMRBSA-N tert-butyl-[(1r,3s,5z)-3-[tert-butyl(dimethyl)silyl]oxy-5-(2-diphenylphosphorylethylidene)-4-methylidenecyclohexyl]oxy-dimethylsilane Chemical group C1[C@@H](O[Si](C)(C)C(C)(C)C)C[C@H](O[Si](C)(C)C(C)(C)C)C(=C)\C1=C/CP(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 MDDUHVRJJAFRAU-YZNNVMRBSA-N 0.000 claims 1
- 150000003639 trimesic acids Chemical class 0.000 claims 1
- 239000012621 metal-organic framework Substances 0.000 description 73
- 239000013206 MIL-53 Substances 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 9
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 8
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 8
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000004411 aluminium Substances 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 238000005401 electroluminescence Methods 0.000 description 5
- 230000004044 response Effects 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000012552 review Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 239000002019 doping agent Substances 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 239000000990 laser dye Substances 0.000 description 3
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- 150000003384 small molecules Chemical class 0.000 description 3
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- 239000004593 Epoxy Substances 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- 239000013177 MIL-101 Substances 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
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- 239000000654 additive Substances 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 2
- 125000005162 aryl oxy carbonyl amino group Chemical group 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 2
- VSSSHNJONFTXHS-UHFFFAOYSA-N coumarin 153 Chemical compound C12=C3CCCN2CCCC1=CC1=C3OC(=O)C=C1C(F)(F)F VSSSHNJONFTXHS-UHFFFAOYSA-N 0.000 description 2
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- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 2
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- 229920000553 poly(phenylenevinylene) Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000012990 sonochemical synthesis Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- YFPJFKYCVYXDJK-UHFFFAOYSA-N Diphenylphosphine oxide Chemical compound C=1C=CC=CC=1[P+](=O)C1=CC=CC=C1 YFPJFKYCVYXDJK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 241001082241 Lythrum hyssopifolia Species 0.000 description 1
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- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
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- 150000001266 acyl halides Chemical class 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000000231 atomic layer deposition Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 229910052799 carbon Inorganic materials 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
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- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
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- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
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- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
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- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
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- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical class PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical class [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
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- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 229920002098 polyfluorene Polymers 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
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- 238000004729 solvothermal method Methods 0.000 description 1
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- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
-
- 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
- H05B33/145—Arrangements of the electroluminescent material
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Electroluminescent Light Sources (AREA)
Description
P97834NL00
Title: Electroluminescent composition
The invention is directed to an electroluminescent composition, to a method for preparing said electroluminescent composition, to an optoelectronic device comprising said electroluminescent composition, and to uses of said optoelectronic device.
5 The invention relates to electroluminescent devices and, more in particular, electroluminescent materials for use in such devices. Light emitting diode technology forms a major opportunity for advanced materials development impacting a large number of technology based applications.
These, for example, include flat panel displays which offer significant 10 advantages over liquid crystal displays including much lower power requirements, improved definition, broader viewing angles and faster response times. The technology for light emitting diodes offers the potential for lower cost lighting sources compared to incandescent lighting as well as fluorescent lighting applications. Inorganic based light emitting diodes are already 15 replacing some of these conventional applications including traffic lighting as well as flashlights offering equal or improved lighting at much lower power requirements.
Small molecule organic light emitting diodes are being commercialised to replace liquid crystal displays based on lower power 20 requirements, faster response times, better definition and also easier fabrication.
Another area receiving considerable interest involves polymeric light emitting diodes where polymeric light emitting materials can be utilised for flexible organic light emitting diodes. A significant advantage of polymeric 25 materials concerns the fabrication possibilities. Flexible organic light emitting diodes offer the potential for inkjet printing of flat panel displays on flexible substrates such as indium-tin oxide coated polymeric films (e.g. poly(ethylene terephthalate), oriented polypropylene or polycarbonate). Roll-to-roll printing processes could also be utilised for flexible organic light emitting diodes. The 2 potential for flexible organic light emitting diodes is considered to be quite large offering unique flat or contoured display panels. The development of polymeric light emitting diodes has focused on polymeric materials which exhibit electroluminescence. These materials are generally conjugated 5 polymers, such as poly(phenylene vinylene), polyfluorenes, polyphenylenes, polythiophenes and combinations of such structures.
Furthermore, a large number of low molecular weight compounds exists which exhibit fluorescence and electroluminescence. Some of these materials are commonly referred to as laser dyes. Many of these compounds 10 offer very high fluorescence and electroluminescence. However, the properties desired for light emitting diode applications are generally only observed in solution or at low levels of doping in electro-optical or electro-active polymers. In the solid state, these materials can crystallise and lack the mechanical integrity to be utilised in polymeric light emitting diodes or small molecule 15 organic light emitting diodes. Additionally (and more importantly), their excellent fluorescence and electroluminescence properties is lost with crystallisation. These problems have been well documented in various reviews on the subjects of materials for light emitting diodes.
Some attempts have been made to combine different components in 20 order to profit from the advantages of each component. For example, light-emitting devices have been proposed wherein a polymer matrix hosts an emitter guest material, such as an emitting dye or emitting polymer. Another example of the combination of different components is the use of organic/inorganic hybrid materials, such as hybrid nanocrystal polymer light 25 emitting diodes, such as described e.g. by Colvin et al. (Nature 1994, 370, 354-357).
Metal organic frameworks typically comprise an organic compound nature coordinated to at least one metal ion. Such metal-organic frameworks are described for example, in US-A-5 648 508 or EP-A-0 790 253. More 30 recently, several reviews have been published on the topic. Cui et al. (Chem.
3
Rev. 2012, 112, 1126-1162) published a review article concerning luminescent functional metal-organic frameworks. These materials are said to be very promising as multifunctional luminescent materials, such as for applications in light-emitting and display devices. In the outlook, this review article 5 mentions that it is theoretically feasible to incorporate nanoscale electroluminescence metal-organic frameworks between two conductors, e.g. for organic light emitting devices. However, it is mentioned that the realisation of such important functionality first requires the realisation of electroluminescent metal-organic frameworks.
10 Hence, there remains a need in the art for further electroluminescent materials, and improvements thereof, which are useful for being applied in optoelectronic applications, and in particular in light emitting diodes.
An objective of the invention is to address this need in the art and 15 provide an electroluminescent composition, such as for use in light emitting diodes.
A further objective of the invention is to provide an optoelectronic device comprising said electroluminescent composition.
The inventors found that an advantageous electroluminescent 20 composition metal-organic-framework can be prepared by combining an electroluminescent functionalised , metal-organic-framework with a matrix material as the continuous phase.
Accordingly, in a first aspect the invention is directed to an electroluminescent composition comprising a blend one or more luminescent 25 metal-organic frameworks and a matrix material as the continuous phase, wherein said one or more luminescent metal-organic frameworks comprise inorganic connectors linked by linkers, wherein said framework further comprises one or more luminescent agents, wherein 4 i) at least a part of said linkers are luminescent linkers which comprise one or more organometallic luminescent moieties and/or organic luminescent moieties as luminescent agents; ii) one or more organometallic luminescent compounds and/or organic 5 luminescent compounds reside as luminescent agents in pores of the framework; and/or iii) one or more organometallic luminescent compounds, inorganic luminescent compounds, organic luminescent compounds, and/or organic-inorganic luminescent compounds are grafted to metal vacancies of the metal-organic 10 framework.
In accordance with the invention a luminescent agent is combined with a support (viz. the metal-organic framework). These components can either be chemically combined, the luminescent agent can reside within pores of the framework as a guest molecule, and/or the luminescent agent can be 15 grafted to metal vacancies of the framework.
The term “metal-organic framework” as used in this application is meant to refer to a one, two, or three-dimensional polymer including both organic and metal or metal oxide structural units, where at least one of the metal units is bonded to at least one bi-, tri- or poly-dentate organic unit.
20 The term “inorganic connectors” as used in this application is meant to refer to the metal or metal oxide structural units of the metal-organic framework.
The term “linkers” as used in this application is meant to refer to the organic structural units of the metal-organic framework. Although the term 25 refers to the organic structural units, the term is meant to also cover modified linkers which may contain inorganic moieties.
The term “luminescent agent” as used in this application is meant to refer to a compound or moiety which is capable of emitting light. The luminescence may refer to fluorescence or phosphorescence or both.
5
The term “functional group” as used in this application is meant to refer to its usual and ordinary meaning in organic chemistry, namely an interconnected group of atoms that is responsible for a characteristic chemical reaction of the molecule to which the group is bonded. The functional group 5 may comprise a leaving group.
The metal-organic framework in the composition of the invention can comprise a variety of inorganic connectors that are well-known in the art. Typically, the inorganic connectors will comprise one or more selected from Al, Zn, Cu, Cr, In, Ga, Fe, Sc, Ti, V, Co, Ni, La, Ce, Pr, Nb, Pm, Sm, Eu, Gd, Tb, 10 Dy, Ho, Er, Tm, Yb, Lu, Ac, Th, Pa, U, Np, Pu, Am, Cm, Bk, Cf, Es, Fm, Md,
No and Lr. Preferably, the inorganic connectors can comprise one or more selected from Al, Ga, In, Fe, Cr and Sc. More preferably, the inorganic connectors are selected from Al, In, and Ga. Usually, the metal-organic framework is made up of a single type of inorganic connector, but optionally 15 more than one type of inorganic connector can be used. In an embodiment, at least part of the inorganic connectors in the metal-organic framework comprise rare earth elements. By using rare earth materials in inorganic connectors it is possible e.g. to tune the emission wavelength of the electroluminescent composition of the invention.
20 Also a variety of linkers can be used. Suitable linkers include porphyrins derivatives, perylene derivatives, carboxylates, including nitrogen-containing carboxylates, such as pyridine-like moieties with one nitrogen atom (pyridines), two nitrogen atoms (imidazoles, bipyridines), or more nitrogen atoms, such as three nitrogen atoms (triazoles).
25 Nitrogen-containing carboxylates may be used in combination with dicarboxylates or tricarboxylates. Suitable carboxylates include those selected from the group consisting of oxalic acid, malonic acid, succinic acid, glutaric acid, phthalic acid, isophthalic acid, terephthalic acid, citric acid, trimesic acid. In an embodiment, the linker is a phthalic acid, such as isophthalic acid, 30 terephthalic acid or a mixture thereof.
6
Particularly, suitable metal-organic frameworks which may be used for the invention include metal-organic frameworks comprising aluminium, such as aluminium carboxylates. Specific examples thereof include MIL-53, MIL-69, MIL-88, MIL-96, MIL-100, MIL-101, and MIL-110. Note that in this 5 terminology, MIL-n means Materials of the Lavoisier Institute (Materiaux de 1’Institut Lavoisier, MIL, in French). Particularly preferred metal-organic frameworks include MIL-53, MIL-69, MIL-88, and MIL-101.
The metal-organic framework can be flexible or rigid. From a practical point of view it is preferred that the metal-organic framework used in 10 accordance with the invention is flexible.
In an embodiment, the metal-organic framework is a porous metal-organic framework. In case the initial (non-luminescent) metal-organic framework is porous, the resulting luminescent metal-organic framework does not necessarily have to be porous.
15 The luminescent agents in the metal-organic framework may be either chemically bound to the linker as luminescent moieties, may reside in the pores of the metal-organic framework as luminescent molecules, and/or can be chemically bound to the metal vacancies (open metal sites) of the framework. Combinations of these options are also possible. It is preferred that 20 the luminescent agents are chemically bound to the linkers or to the metal vacancies so as to prevent diffusion of the luminescent agents out of the metal-organic framework. Furthermore, by chemically binding luminescent agents to the linkers it is has shown possible to prepare metal-organic frameworks having a higher content of luminescent agents.
25 In an embodiment, the luminescent agents are chemically bound to the linkers. For example, the metal-organic framework can comprise luminescent linkers that are the reaction product of i) an organic linker provided with a functional group; and ii) one or more organometallic luminescent compounds and/or organic 30 luminescent compounds.
7
The preparation of such luminescent agents can be done by using various functional groups. For instance, the linker can be modified with one or more functional groups selected from the group consisting of an amine, a nitro group, an imine, a pyridyl or derivative thereof, a haloformyl, a haloalkyl, a 5 halogen (including acyl halides, such as acid chlorides), and the like.
Preferably, the linker is not modified with more than one functional group. Good results have been achieved by modifying the linker with an amine functional group. However, other functional groups maybe used as well.
The functional group can be used to couple the one or more 10 organometallic luminescent compounds and/or organic luminescent compounds to the linked so as to produce a luminescent linker. Suitably, the functional group can comprise a leaving group, which may be replaced with the organometallic luminescent compound and/or organic luminescent compound.
Examples of possible organometallic luminescent compounds that 15 can be used are well-known to the person skilled in the art. Some examples include lanthanides, Ag, Au, ferrocenes, and the like. In an embodiment, the organometallic luminescent compounds comprise a rare earth element, such as one or more lanthanides.
Examples of possible organic, inorganic or organic-inorganic 20 luminescent compounds that may be used are also well-known to the person skilled in the art. Some examples include phosphors and organic laser dyes. In an embodiment, the organic luminescent compounds comprise a phosphorus atom, preferably in the form of a phosphine or phosphinate.
It is preferred that the organometallic luminescent compound and/or 25 organic luminescent compound is a phosphorous containing compound.
Examples of such compounds include phosphines (such as phenyl phosphines), phosphine oxides.
In accordance with this embodiment of the invention (where the luminescent agents are chemically bound to the linkers) it is preferred that 30 50 % or more of the linkers in the metal-organic framework are functionalised 8 with the luminescent agent, preferably 60 % or more of the linkers, such as 70 % or more of the linkers. For example, 70-90 % of the linkers can be functionalised with the luminescent agent, such as 70-80 % of the linkers. In an embodiment, essentially all of the linkers in the metal-organic framework 5 have been functionalised with the luminescent agent.
In a special embodiment of the invention, the organic linker provided with a functional group is an amino group functionalised phthalic acid, such as an amino group functionalised isophthalic acid or an amino group functionalised terephthalic acid. The inventors found that such an amino 10 group functionalised phthalic acid can be readily reacted with a suitable luminescent compound. Examples of resulting luminescent linkers include the linkers of general formula (I) and (II) below.
O
R' P—R" O
II
O (I)
In general formula (I), R can be hydrogen, an alkyl group, an alkenyl group, an 15 alkynyl group, an aryl group, an amino group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, an acylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonylamino group, a sulfamoyl group, a carbamoyl group, an alkylthio group, an arylthio 20 group, a heterocyclic thio group or a heterocyclic group. R can be the same as R” and can be a phenyl ring which may optionally be substituted.
O
9
R'-P—R" O
II
0
O*' ''O
xS^s^N^x6 y?\ hx5 X3 X4 (II)
In general formula (II), R can be hydrogen, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an amino group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an acyl group, an alkoxycarbonyl group, an 5 aryloxycarbonyl group, an acyloxy group, an acylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonylamino group, a sulfamoyl group, a carbamoyl group, an alkylthio group, an arylthio group, a heterocyclic thio group or a heterocyclic group. R’ can be the same as R” and can be a phenyl ring which may optionally be substituted. M’ is a metal 10 atom, preferably a rare earth metal element, such as selected from the group consisting of yttrium, cerium, praseodymium, neodymium, europium, terbium, erbium and ytterbium. More preferably M’ is europium or terbium. X^X6 in general formula (II) can each independently be halogen atoms, such as fluorine, chlorine, or bromine. Preferably, X^X6 are the same.
15 In a further embodiment, which may optionally be combined with the previous embodiment (where the luminescent agents are chemically bound to the linkers), the luminescent agents reside as luminescent agents in pores of the framework. The luminescent agents can, for example, be adsorbed to the inner surface of the metal-organic framework. Luminescent agents can be 20 intercalated after preparation of the metal-organic framework via known methods including vapour deposition and/or adsorption and/or post-synthetic 10 functionalisation. However, it is also possible to prepare the metal-organic framework in the presence of luminescent agents which will then be incorporated (encapsulated) in the porous structure of the metal-organic framework.
5 Advantageously, the size restrictions imposed by the metal-organic framework prevent (or at least reduce) the formation of crystals of the luminescent agent. Accordingly, luminescent quenching by crystal formation is significantly reduced and relatively high luminescence quantum yields are maintained. Additionally, without wishing to be bound by theory, the inventors 10 believe that the close proximity of the luminescent agents may lead to charge/electron hopping mechanisms to occur.
In accordance with this embodiment of the invention it is preferred that the metal-organic framework is loaded with the luminescent agent to an extent of at least 0.8 electroluminiscence units per organic linker in the metal-15 organic-framework.
An advantage of this embodiment of the invention, wherein guest luminescent agents reside in the host porous structure of the framework, is that also luminescent agents can be used that lack a reactive group. Hence, this embodiment broadens the range of possible luminescent agents to be used. 20 The person skilled in the art will be able to determine, depending on his needs, which embodiment suits the intended application best.
In yet a further embodiment, which may optionally be combined with both previous embodiments (where the luminescent agents are chemically bound to the linkers and where the luminescent agents reside as luminescent 25 agents in pores of the framework), the luminescent agents are organometallic compounds that are grafted to metal vacancies of the metal-organic framework. This embodiment requires a metal-organic framework that comprises inorganic connectors with one or more metal vacancies (free coordination sites at a metal atom). These metal vacancies can then be 30 occupied by organometallic luminescent compounds, inorganic luminescent 11 compounds, organic luminescent compounds, and/or organic-inorganic luminescent compounds.
As mentioned before, various metal-organic frameworks can be used in accordance with the invention. In an advantageous embodiment, the 5 metal-organic framework to be used has a one-dimensional porous structure (at least prior to functionalisation). The luminescent agents present in such a one-dimensional porous metal-organic framework are highly ordered. The metal organic framework host can give rise to second-harmonic generation (also known as frequency doubling). In accordance with this phenomenon, a 10 material is capable of generating photons with twice the frequency (half the wavelength) of incident photons. In another embodiment, the metal-organic framework has a two-dimensional porous structure or a three-dimensional porous structure (at least prior to functionalisation).
The electroluminescent composition of the invention further 15 comprises a matrix material as the continuous phase. This material embeds the metal-organic framework particles. Preferably, the matrix material is a transparent material or is at least partially transparent. Depending on the intended application, the matrix material can comprise one or more selected from the group consisting of a polymer (such as an electrically conductive 20 polymer or an electrically non-conductive polymer), an amalgamate paste, and a liquid electrolyte.
Preferably, the matrix material comprises one or more electrically conductive polymers. Many different electrically conductive polymers are known in the art. Some examples include polythiophenes, polyanilines, 25 polycarbazoles, polypyrroles, and substituted derivatives thereof. As specific examples can be mentioned poly(3-butylthiophene-2,5-diyl (optionally with a phosphor based dopant), poly(thiophene-2,5-diyl) which may optionally be bromine terminated, poly(3,4-ethylenedioxythiophene)-polystyrenesulphonate), poly(p-phenylene vinylene), polyaniline doped with BF3, polyphenylene 30 sulphide, conductive nylon, polyester urethane, and polyether urethane.
12
Also non-conductive polymers can be used in accordance with the present invention. Some examples thereof include epoxy resin without hardener and nafion. Non-conductive polymers can yield electroluminescent composition at small areas. For example, a small scale device can be designed 5 using point electrodes, which each are in direct contact with luminescent metal-organic framework crystals. A schematic example of such a small scale device is shown in figure 1, wherein 11 is an active light emitting phase comprising luminescent metal-organic framework, 12 is a non-conductive polymer, 13 is a protective layer and 14 are point electrodes.
10 In an embodiment, the matrix material comprises a polymer that is doped with a dopant with the purpose of changing the electrically conductive properties of the matrix.
The blend of matrix material and luminescent metal-organic frameworks suitably comprises 2-70 vol.% of the metal-organic framework, 15 based on total volume of the blend, such as in the range of 4-40 vol.%, preferably in the range of 5-30 vol.%, or in the range of 5-25 vol.%.
In an embodiment, the blend comprises two or more luminescent metal-organic frameworks, wherein each of said luminescent metal-organic frameworks has a different or overlapping emission spectrum. By selecting 20 different emission spectra, the overall emission spectrum of the electroluminescent composition of the invention can be tuned to the specific needs of the user. Hence, the invention advantageously provides the user with a high degree of freedom for tuning the emission wavelength of the electroluminescent composition.
25 The composition of the invention may optionally comprise further
components such as conventional additives including dopants, electron transport media (such as solid or liquid electrolytes). Further, laser dyes may be included as optional additives for changing or tuning the wavelength of the emitted light (e.g. Coumarin 540A (also known as 2,3,6,7-tetrahydro-30 9-(trifhioromethyl)-li7,5iT,lliT-[l]benzopyrano[6,7,8-ij]quinolizin-ll-one, CAS
13
No. 53518-18-6) for a yellow output). The dye laser can be physically separate from the light emitting device.
In a further aspect, the invention is directed to a for preparing the electroluminescent composition of the invention, the method comprising 5 i) preparing a metal-organic framework using an organic linker with a functional group; ii) reacting said functional group with one or more organometallic luminescent compounds and/or organic luminescent compounds; and thereafter 10 iii) blending said metal-organic framework with a matrix material, wherein step i) is performed before step ii) or wherein step ii) is performed before step i).
The preparation of metal-organic frameworks is well-known in the art and has been reported in various prior art documents (e.g. Rowsell et al., 15 Microporous and Mesoporous Materials 2004, 73, 3-14). Typically, the synthesis of metal-organic frameworks involves heating a mixture containing inorganic salts and organic linkers in specific types of solvents (DMF is the mostly used solvent) at a specific temperature (such as in the range for 60-120 °C) for several hours to 2 days. Recently, some alternative syntheses of 20 metal-organic frameworks have been disclosed, including mechanochemical grinding, and electrochemical, and sonochemical and microwave-assisted synthesis. In mechanochemical grinding, a mixture of organic linkers and metal salts is ground together in a mechanical ball mill to yield the metal-organic framework. The advantage of this method is that no organic 25 solvents are required. In electrochemical synthesis the metal element is provided by one of the electrodes and no salt residues are occluded in the metal-organic framework. In general lower temperatures are required than in solvothermal synthesis, and continuous production is feasible. Sonochemical synthesis has the advantage of leading to homogeneous nucleation and short 30 crystallisation time. Microwave-assisted synthesis makes use of microwaves to 14 produce nanosized crystals. Microwave synthesis allows instant synthesis of high-quality metal-organic frameworks of high-quality within a minute
Providing an organic linker compound with a functional group is well known in the art of organic chemistry. Moreover, it is possible to prepare 5 the functionalised metal-organic framework by using an organic linker starting material that already has a functional group.
Normally, step i) of the method of the invention involves a conventional metal-organic framework synthesis using an organic linker that already comprises a functional group. Alternatively, the functional group could 10 be introduced after having prepared the metal-organic framework. However, this is not preferred.
In step ii) of the method of the invention, the functional group is reacted with one or more organometallic luminescent compounds and/or organic luminescent compounds. Step i) can be performed before step ii), but it 15 is also possible to perform step ii) before step i).
In a further step, the metal-organic framework is blended with a matrix material. This blending may involve using of a solvent.
An alternative method for preparing the electroluminescent composition of the invention comprises 20 i) preparing a metal-organic framework using an organic linker; ii) adsorbing one or more organometallic luminescent compounds and/or organic luminescent compounds at the internal surface of the metal organic framework; and thereafter iii) blending said metal-organic framework with a matrix material, 25 wherein step i) is performed before step ii) or wherein step ii) is performed before step i).
In accordance with this alternative method, the luminescent agents are not chemically bound to the metal-organic framework, but are adsorbed to the surface of the framework structure, preferably to internal pores of the 30 framework structure. Adsorption can, for instance, be performed from the gas 15 phase, or from solution. Step i) can be performed before step ii), but it also possible to perform step ii) before step i).
Electroluminescent compositions wherein the organometallic luminescent compounds are grafted to metal vacancies in the metal-organic 5 framework can be prepared, e.g. by impregnation (dry impregnation also known as incipient wetness or pore volume impregnation, i.e. using an amount of solution equal to the pore volume also, or wet impregnation, i.e. using an excess of solution volume), or by following chemical vapour deposition or atomic layer deposition methodologies.
10 In a further aspect, the invention is directed to an optoelectronic device comprising the electroluminescent composition of the invention.
In a particularly, preferred embodiment the optoelectronic device is a light emitting diode, such as an organic light emitting diode. Typically, such light emitting diode comprises the electroluminescent composition of the 15 invention in electrical contact with a first electrode and a second electrode.
Any conventional electrode materials can be used, such as aluminium electrodes. The first and second electrode may suitably be applied on one side of the electroluminescent composition. Alternatively, it is possible to sandwich the electroluminescent composition between two electrodes, but then at least 20 one of the electrodes should be transparent. Transparent conductive oxides (such as tin-doped indium oxide, also known as ITO) can then be suitably used as transparent electrode materials.
The layer of the electroluminescent composition in the light emitting diode can be in the range of 5-100 pm, such as in the range of 10-80 pm or in 25 the range of 20-50 pm.
Optionally, the device of the invention can comprise additional layers, such as hole injection/transfer layers and/or electron injection/transfer layers.
Advantageously, the invention allows the provision of a light 30 emitting diode device what is based on abundant elements which are not (or 16 hardly) harmful for the environment, or poisonous. Therefore in an embodiment, the device essentially consists of elements selected from the group consisting of hydrogen, oxygen, carbon, aluminium, and phosphorus.
In accordance with a simple preparation method, a light emitting 5 diode according to the invention can be prepared by a very simple procedure, wherein the electroluminescent composition is applied in wet form (typically as a paste).
An example of this simple procedure is schematically shown in figure 2A. As shown in this figure, two separate electrodes may be provided (a), 10 such as by cutting a sheet of a suitable electrode material (such as aluminium) in two pieces. The two electrodes may then both be attached on a non-conductive support, such as a non-conductive epoxy support (b). The support with the electrodes can be secured on the work surface (c), for example by using chemically inert tape (such as Scotch tape obtainable from 3M). It is 15 advisable that an antistatic agent (such as antistatic foam cleanser) is applied to the work surface prior to use. Then, the electroluminescent composition of the invention can be applied onto the electrodes such that the composition at least bridges the first electrode with the second electrode (d). Typically, a paste of the electroluminescent composition in a solvent is spread over the electrodes 20 using a doctor blade technique. Excess composition and excess epoxy support may be removed, together with the optionally applied chemically inert tape . The resulting device may be dried to remove solvent. Further, the resulting device may be provided with suitable contacts (e). Optionally, the light emitting diode device can be provided with conventional transparent 25 protection coatings. Suitably, the device can be sealed (e.g. by lamination) for optimal protection against environmental influences.
Figure 2B shows a schematic design of a sandwich electrode assembly which may be obtained in accordance with the present invention. Figure 2C shows a schematic design of a single layer electrode assembly which 30 may be obtained in accordance with the present invention. In figures 2B and 17 2C, 21 is a light emitting layer, 22 is a protective bilayer, 23 is an electrode assembly, 24 is an anode, and 25 is an electrode contact.
In yet a further aspect, the invention is directed to various uses of the optoelectronic device of the invention. These uses include growing of algae 5 and other chlorophylic containing species, solar cells, illumination panels, photocatalysis, and lighting of greenhouses.
The invention will now be further demonstrated by means of the following examples, which are not intended to limit the scope of the invention in any manner.
10
Examples
Amino MIL-53 (Al) was used as an appropriate MOF for the introduction of diphenyl phosphine oxide, that was chemically anchored at the 15 amines to the terephthalic acid found in the MOF.
The post functionalisation of the amino MIL-53 (Al) changed many aspects of the metal-organic framework structure. From high quality X-ray diffraction (XRD) patterns it was observed that the metal-organic framework lattices were permanently expanded to accommodate the organo-phosphines 20 that were introduced. More significant, electronic changes occur through this functionalisation, causing a remarkable shift and enhancement of light emission, brought about by visible light illumination. Figure 3 illustrates the response of phosphinated amino MIL-53 (Al) to an excitation of 400 nm (violet), as compared to a non-functionalised amino MIL-53 (Al). The emitted 25 light colour of the phosphinated amino MIL-53 (Al) is a light blue with maximum emission at a wavelength of 466 nm, while the non-functionalised amino MIL-53 (Al) has significantly lower emission intensity with a maximum emission at a wavelength of 616 nm.
It was found that a very similar, if not identical, emission response 30 can be observed by applying a sufficient potential difference to the phosphine 18 oxide functionalised amino MIL-53 (Al). This potential can take the form of both alternating and direct current (AC/DC). Thus far, operating conditions of 0.93-18 V DC and 30-260 V AC were explored. Figure 4 illustrates the emission response of a device fabricated on the basis of the functionalised 5 metal-organic framework. In figure 4A the light emission driven by photo-excitation is compared to light emitted under the influence of an electrical potential (emission wavelength at 9 V versus excitation at 375 nm). In figure 4B the light emission driven by direct current (DC) is compared to the light emission driven by alternate current (AC) (emission wavelength at 10 9 V DC versus 260 V AC, ~ 60 Hz). No significant differences can be observed up to 500 nm, after which the relative intensity of the AC excited sample seems to fluctuate (only slightly). It should be noted that the line thickness of DC has been increased to show overlay of the two graphs clearly.
A light emitting diode device was constructed from a single thin 15 layer (0.0384 mm) of phosphine amino MIL-53 (Al) and poly(thiophene-2,5-diyl) (CAS No. 25233-34-5) paste, prepared by mixing the two components in chloroform in a weight ratio of 1:4. This paste adheres to aluminium when dried on aluminium foil, which is pre-cut to make a small separation between the two electrodes that are placed on the same side of the 20 dried film. The resulting product is sealed by lamination. It was found that the device lifetime is increased if during the first operation the voltage is built up slowly to desired long term operating voltage. Also, during the lifetime that voltage is not to be exceeded.
Applying DC voltage above 0.8 V over the electrodes resulted in 25 light emission of a fairly well defined wavelength. The emission intensity increased with voltage to a certain maximum of 18 V when exposed to non-inert atmospheres.
Applying AC voltage also resulted in the same light emission, but at higher voltages, starting at about 10 V. Up to 260 V and 600 V have been 30 tested while exposed to a non-inert atmosphere.
19
The emission of the light was quite homogeneous over the whole surface. No dark area was seen at the separation line between the two electrode surfaces
Figure 5 shows a photograph of the device when switched off (5A), 5 i.e. when no voltage is applied, and of the same device when a voltage is applied and the device is emitting (5B).
Device efficiency was determined using an Ulbricht integrating sphere to count the photon emission rate and using the wavelength distribution, the emitted energy relative to the electrical energy input (current 10 times voltage) amounted to at least 0.89 (or 89 %).
Claims (20)
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| WO2011133999A1 (en) * | 2010-04-30 | 2011-11-03 | Commonwealth Scientific And Industrial Research Organisation | Crystallisation facilitators for the synthesis of metal organic frameworks |
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