Organic Electronic Device Comprising at Least One Metal Complex of Formula (I)
20240397744 ยท 2024-11-28
Inventors
Cpc classification
H10K85/6572
ELECTRICITY
H10K85/331
ELECTRICITY
H10K85/371
ELECTRICITY
H10K85/633
ELECTRICITY
H10K85/351
ELECTRICITY
H10K85/6574
ELECTRICITY
H10K85/636
ELECTRICITY
International classification
Abstract
The present invention relates to an organic electronic device comprising a substrate, an anode layer, a cathode layer, at least one first emission layer, and a hole injection layer, wherein the hole injection layer comprises a metal complex, wherein the metal complex has the formula (I): Formula (I).
##STR00001##
Claims
1.-15. (canceled)
16. An organic electronic device comprising a substrate, an anode layer, a cathode layer, at least one first emission layer, and a hole injection layer, wherein the hole injection layer comprises a metal complex, wherein the metal complex has the formula (I): ##STR00062## wherein M is a metal; L is a charge-neutral ligand, which coordinates to the metal M; n is an integer selected from 1 to 4, which corresponds to the oxidation number of M; m is an integer selected from 0 to 2; R.sup.1 and R.sup.3 are independently selected from H, D, substituted or unsubstituted C.sub.1 to C.sub.12 alkyl, substituted or unsubstituted C.sub.1 to C.sub.12 alkoxy, substituted or unsubstituted C.sub.6 to C.sub.24 aryl, and substituted or unsubstituted C.sub.2 to C.sub.24 heteroaryl group, wherein at least one substituent is selected from halogen, F, Cl, CN, substituted or unsubstituted C.sub.1 to C.sub.12 alkyl, partially or fully fluorinated C.sub.1 to C.sub.12 alkyl, substituted or unsubstituted C.sub.1 to C.sub.12 alkoxy, partially or fully fluorinated C.sub.1 to C.sub.12 alkoxy, substituted or unsubstituted C.sub.6 to C.sub.18 aryl, and substituted or unsubstituted C.sub.2 to C.sub.18 heteroaryl, wherein the substituents of the substituted or unsubstituted C.sub.1 to C.sub.12 alkyl, substituted or unsubstituted C.sub.1 to C.sub.12 alkoxy, substituted or unsubstituted C.sub.6 to C.sub.18 aryl, and substituted or unsubstituted C.sub.2 to C.sub.18 heterodaryl are selected from halogen, F, Cl, CN, C.sub.1 to C.sub.6 alkyl, CF.sub.3, OCH.sub.3, OCF.sub.3; R.sup.2 is selected from CN, C.sub.1 to C.sub.4 alkyl, partially or perfluorinated C.sub.1 to C.sub.4 alkyl, or F; the anode layer comprises a first anode sub-layer and a second anode sub-layer, wherein the first anode sub-layer comprises a first metal having a work function in the range of 4 and 6 eV, or the first anode sub-layer comprises a first metal selected from the group comprising Ag, Mg, Al, Cr, Pt, Au, Pd, Ni, Nd, Ir; the second anode sub-layer comprises a transparent conductive oxide; the hole injection layer is arranged between the first emission layer and the anode layer, the first anode sub-layer is arranged closer to the substrate, and the second anode sub-layer is arranged closer to the hole injection layer; wherein the compounds A1 to A18 are excluded from Formula (I): ##STR00063## ##STR00064## ##STR00065## ##STR00066##
17. The organic electronic device according to claim 16, wherein R.sup.2 is selected from CN, CH.sub.3, CF.sub.3, C.sub.2F.sub.5, C.sub.3F.sub.7 or F.
18. The organic electronic device according to claim 16, wherein at least one of the group comprising R.sup.1 and R.sup.3 is selected from a substituted C.sub.6 to C.sub.24 aryl or substituted C.sub.2 to C.sub.24 heteroaryl group, wherein at least one substituent or at least two substituents of the substituted C.sub.6 to C.sub.24 aryl or substituted C.sub.2 to C.sub.24 heteroaryl group is selected from CN or partially or fully fluorinated C.sub.1 to C.sub.12 alkyl, partially or fully fluorinated C.sub.1 to C.sub.4 alkyl, CN CF.sub.3, C.sub.2F.sub.5 or C.sub.3F.sub.7.
19. The organic electronic device according to claim 16, wherein at least one of the group comprising R.sup.1 and R.sup.3 are selected from a substituted C.sub.2 to C.sub.24 heteroaryl group, wherein the substituted heteroaryl group comprises at least one six-membered ring, at least 1 to 6 N atoms, a six-membered ring that comprises 1, 2 or 3 hetero atoms, or a six-membered ring that comprises 1, 2 or 3 N atoms.
20. The organic electronic device according to claim 16, wherein at least one of the group comprising R.sup.1 and R.sup.3 are selected from the following Formulas D1 to D71: ##STR00067## ##STR00068## ##STR00069## ##STR00070## ##STR00071## ##STR00072## ##STR00073## ##STR00074## ##STR00075## ##STR00076## wherein the * denotes the binding position.
21. (Ncw) The organic electronic device according to claim 16, wherein the metal complex is represented by Formula I and is selected from the following Formulas E1 to E20: ##STR00077## ##STR00078## ##STR00079## ##STR00080## ##STR00081##
22. The organic electronic device according to claim 16, wherein the metal complex is represented by Formula I and is selected from the following Formulas G1 to G8: ##STR00082## ##STR00083##
23. The organic electronic device according to claim 16, wherein the metal M is selected from alkali, alkaline earth, transition, rare earth metal, group III to V metal, Li (I), Na(I), K(I), Rb(I), Cs(I), Cu(II), Zn(II), Pd(II), Al(III), Sc(III), Mn(III), In(III), Y(III), Eu(III), Fe(III), Zr(IV), Hf(IV) or Ce(IV).
24. The organic electronic device according to claim 16, wherein L is selected from the group comprising H.sub.2O, C.sub.2 to C.sub.40 mono-or multi-dentate ethers and C.sub.2 to C.sub.40 thioethers, C.sub.2 to C.sub.40 amines, C.sub.2 to C.sub.40 phosphine, C.sub.2 to C.sub.20 alkyl nitrile or C.sub.2 to C.sub.40 aryl nitrile, a compound according to Formula (II); ##STR00084## wherein R.sup.6 and R.sup.7 are independently selected from at least one group comprising C.sub.1 to C.sub.20 alkyl, C.sub.1 to C.sub.20 heteroalkyl, C.sub.6 to C.sub.20 aryl, heteroaryl with 5 to 20 ring-forming atoms, halogenated or perhalogenated C.sub.1 to C.sub.20 alkyl, halogenated or perhalogenated C.sub.1 to C.sub.20 heteroalkyl, halogenated or perhalogenated C.sub.6 to C.sub.20 aryl, halogenated or perhalogenated heteroaryl with 5 to 20 ring-forming atoms, R.sup.6 and R.sup.7 are bridged and form a 5 to 20 member ring, two R.sup.6 are bridged and form a 5 to 40 member ring, two R.sup.7 are bridged and form a 5 to 40 member ring, two of R.sup.6 and R.sup.7 are bridged and form a 5 to 40 member ring, two R.sup.6 are bridged and form a 5 to 40 member ring comprising an unsubstituted or C.sub.1 to C.sub.12 substituted phenanthroline, two R.sup.7 are bridged and form a 5 to 40 member ring comprising an unsubstituted or C.sub.1 to C.sub.12 substituted phenanthroline, two of R.sup.6 and R.sup.7 are bridged and form a 5 to 40 member ring comprising an unsubstituted or C.sub.1 to C.sub.12 substituted phenanthroline.
25. The organic electronic device according to claim 16, wherein n is an integer selected from 1, 2 and 3, which corresponds to the oxidation number of M.
26. The organic electronic device according to claim 16, wherein m is an integer selected from 0 or 1.
27. The organic electronic device according to claims 16, wherein the first metal of the first anode sub-layer is selected from the group comprising Ag, Mg, Al, Cr, Pt, Au, Pd, Ni, Nd, Ir.
28. The organic electronic device according to claim 16, wherein the organic electronic device further comprises a hole transport layer, wherein the hole transport layer is arranged between the hole injection layer and the at least one emission layer.
29. The organic electronic device according to claim 28, wherein the hole transport layer comprises a matrix compound selected from the group of covalent matrix compound or substantially covalent matrix compound.
30. The organic electronic device according to claim 28, wherein the hole transport layer and hole injection layer comprises a matrix compound selected from the group of covalent matrix compound or substantially covalent matrix compound, wherein the matrix compound selected from the group of covalent matrix compound or substantially covalent matrix compound in the hole injection layer and hole transport layer are selected the same.
31. The organic electronic device according to claim 16, wherein the organic electronic device is a light emitting device or a display device.
Description
DESCRIPTION OF THE DRAWINGS
[0422] The aforementioned components, as well as the claimed components and the components to be used in accordance with the invention in the described embodiments, are not subject to any special exceptions with respect to their size, shape, material selection and technical concept such that the selection criteria known in the pertinent field can be applied without limitations.
[0423] Additional details, characteristics and advantages of the object of the invention are disclosed in the dependent claims and the following description of the respective figures which in an exemplary fashion show preferred embodiment according to the invention. Any embodiment does not necessarily represent the full scope of the invention, however, and reference is made therefore to the claims and herein for interpreting the scope of the invention. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are intended to provide further explanation of the present invention as claimed.
FIGS. 1 to 9
[0424]
[0425]
[0426]
[0427]
[0428]
[0429]
[0430]
[0431]
[0432]
[0433] Hereinafter, the
[0434] Herein, when a first element is referred to as being formed or disposed on or onto a second element, the first element can be disposed directly on the second element, or one or more other elements may be disposed there between. When a first element is referred to as being formed or disposed directly on or directly onto a second element, no other elements are disposed there between.
[0435]
[0436]
[0437]
[0438]
[0439]
[0440]
[0441]
[0442]
[0443]
[0444] While not shown in
[0445] Hereinafter, the embodiments are illustrated in more detail with reference to examples. However, the present disclosure is not limited to the following examples.
DETAILED DESCRIPTION
[0446] The invention is furthermore illustrated by the following examples which are illustrative only and non-binding.
Metal Complexes of Formula (I)
[0447] Metal complexes of formula (I) may be prepared by known methods or as described below.
Synthesis of 1,3-bis(3,5-bis(trifluoromethyl)phenyl)propane-1,3-dione
##STR00044##
[0448] To a suspension of NaH (2.34 g, 100 mmol) in 100 ml THF was added dropwise 1-(3,5-bis(trifluoromethyl)phenyl)ethan-1-one (10 g, 39 mmol) and methyl 3,5-bis(trifluoromethyl)benzoate (11.7 g, 43 mmol) dissolved together in 50 ml THF. The resulting mixture was refluxed for 30 h. The reaction mixture was cooled to RT and ice-cold 10% HCl (200 ml) was added during rapidly stirring. Et.sub.2O was added (250 ml) and organic phase was separated, washed with water and dried over Na.sub.2SO.sub.4, concentrated. Crude product was triturated in hexane with traces of Et.sub.2O for 3 h, filtered, washed with hexane and dried. Yield 13.4 g (69%).
Synthesis of 2-(3,5-bis(trifluoromethyl)benzoyl)-3-(3,5-bis(trifluoromethyl)phenyl)-3-oxopropanenitrile
##STR00045##
[0449] To a solution of 17.37 g (35 mmol) of 1,3-bis(3,5-bis(trifluoromethyl)phenyl)propane-1,3-dione and K.sub.2CO.sub.3 (7.26 g, 52.5 mmol) in THF-water was added p-Tolylsulfonylcyanid (9.51 g, 52.5 mmol) in one portion and the resulting mixture was stirred at RT for 3 h. The reaction mixture was cooled to 0 C., acidified with aq. 2M HCl, and extracted 2500 ml of ethyl acetate. The combined organic phases were dried over MgSO.sub.4 and concentrated. Crude product was triturated in mixture of 100 ml hexane and 10 ml ethyl acetate for 1 h. Solid precipitate was filtered and washed with hexane.
[0450] Filtrate was purified by chromatography on silica gel (DCM/Ethyl acetate/Hexane). Fractions with product were concentrated followed by acidic extraction (aq. 2M HCl/ethyl acetate). The combined organic phases were dried over MgSO.sub.4 and concentrated. Product was triturated in 20% Et.sub.2O in hexane for 2 h, solid was filtered, washed with hexane, and dried. Yield 9.52 g (52%).
Synthesis of bis(((Z)-1,3-bis(3,5-bis(trifluoromethyl)phenyl)-2-cyano-3-oxoprop-1-en-1-yl)oxy)copper (MC-1)/(G1)
##STR00046##
[0451] 2.42 g (4.64 mmol) of 2-(3,5-bis(trifluoromethyl)benzoyl)-3-(3,5-bis(trifluoromethyl)phenyl)-3-oxopropanenitrile were dissolved in 40 ml methanol and solution of 0.46g (2.32 mmol) copper(II) acetate monohydrate in 30 ml methanol and 20 ml water was added. The mixture was stirred at room temperature overnight. The precipitate was filtered off, washed with water and dried in high vacuum. 2.29 g (89%) product was obtained as a powder.
Synthesis of 2-(3,5-bis(trifluoromethyl)-[1,1-biphenyl]-4-carbonyl)-4,4,5,5,5-pentafluoro-3-oxopentanenitrile
##STR00047##
[0452] To a solution of 16.7 g (35 mmol) of 1-(3,5-bis(trifluoromethyl)-[1,1-biphenyl]-4-yl)-4,4,5,5,5-pentafluoropentane-1,3-dione and K.sub.2CO.sub.3 (7.26 g, 52.5 mmol) in THF-water was added p-Tolylsulfonylcyanid (9.51 g, 52.5 mmol) in one portion and the resulting mixture was stirred at RT for 20 h. THF was removed and 300 ml water and 300 ml DCM were added and stirred in ice/water bath for 30 min. White solid was filtered and washed with 2300 ml water and 2300 ml DCM and dried. Crude material was suspended in 100 ml DCM and 60 ml 1M HCl for 30 min, Layers were separated. Organic phase was washed with 30 ml of 1M HCl. Combined aq. phases were washed with 100 ml DCM. Combined organic phases were washed with 100 ml water, dried over MgSO.sub.4 and concentrated at 40 C. 100 ml hexane was added and stirred with 5 ml DCM in ice/water bath for 1 h. Solid was filtered, washed with cold hexane and dried. 14.27 g (yield 81%).
Synthesis of bis(((Z)-1-(3,5-bis(trifluoromethyl)-[1,1-biphenyl]-4-yl)-2-cyano-4,4,5,5,5-pentafluoro-3-oxopent-1-en-1-yl)oxy)copper (MC-2)/(G3)
##STR00048##
[0453] 5.0 g (9.94mmol) of 2-(3,5-bis(trifluoromethyl)-[1,1-biphenyl]-4-carbonyl)-4,4,5,5,5-pentafluoro-3-oxopentanenitrile were dissolved in 50 ml methanol and 0.99 g (4.97 mmol) copper(II) acetate monohydrate and 20 ml water were added. The mixture was stirred at room temperature overnight. The precipitate was filtered off, washed with water and dried in high vacuum. The crude product was crystallised from chloroform/ethyl acetate to obtain 3.60 g (68%) product as a solid.
Synthesis of N-methoxy-N-methyl-2-(trifluoromethyl)isonicotinamide
##STR00049##
[0454] The flask was charged with 2-(trifluoromethyl)isonicotinic acid (20.1 g, 100 mmol), dichloromethane (100 ml) and CDI (19.4 g, 120 mmol) was added within 10 min. RM was stirred at r.t. for 1.5 h. Then, N,O-dimethylhydroxylamine hydrochloride (14.6g, 150 mmol) was added and reaction mixture was stirred at r.t. for 17 h (overnight). Reaction was quenched with 1 M sol. of NaOH (50 mL) and extracted with dichloromethane (2100 mL). Combined organic layers were washed with water, brine and solvent was evaporated in vacuo to give an oil (20.5 g, yield 87%).
Synthesis of 1-(2-(trifluoromethyl)pyridin-4-yl)propan-1-one
##STR00050##
[0455] The flask was charged with N-methoxy-N-methyl-2-(trifluoromethyl) isonicotinamide (20.3 g, 87 mmol), evacuated and filled with Ar. THF was added and RM was cooled to 79 C. Then, EtMgBr (3M in THF, 130 mmol) was added dropwise within 15 min. The reaction mixture was stirred at 79 C. for 1 h and then 0 C. for 2 h. Upon completion, the reaction mixture was poured into sol. of NH.sub.4Cl and extracted with Et.sub.2O. Obtained red oil was purified by column chromatography (hexane-ethyl acetate) to give product as a liquid (13.2, yield 74%).
Synthesis of 2-methyl-1,3-bis(2-(trifluoromethyl)pyridin-4-yl)propane-1,3-dione
##STR00051##
[0456] The flask was charged with 1-(2-(trifluoromethyl)pyridin-4-yl)propan-1-one (10.2 g, 50 mmol), evacuated and filled with Ar. THF was added, reaction mixture was cooled to 0 C. and NaH (2.4 g, 100 mmol) was added. Reaction mixture was stirred for 30 min. and 2,2,2-trifluoroethyl trifluoroacetate (5.9 g, 30 mmol) was added dropwise within 20 min and mixture was stirred at 0 C. for 30 min. Upon completion reaction was quenched at 0 C. by diluted HCl and extracted with Et.sub.2O, combined organic layers were washed with water, brine, dried over Na.sub.2SO.sub.4 and solvent was evaporated in vacuo. The residue was purified by column chromatography (Hexane, ethyl acetate). Obtained yellow solid was triturated with 20 mL of Et.sub.2O, filtrated off and washed with cold Et.sub.2O. Colorless product was obtained 4.42 g (47%).
Synthesis of bis(((Z)-2-methyl-3-oxo-1,3-bis(2-(trifluoromethyl)pyridin-4-yl) prop-1-en-1-yl)oxy)copper (MC-3)/(G4)
##STR00052##
[0457] 2.50 g (6.64 mmol) of 2-methyl-1,3-bis(2-(trifluoromethyl)pyridin-4-yl) propane-1,3-dione were dissolved in 25 ml methanol and 0.66 g (3.32 mmol) copper(II) acetate monohydrate and 10 ml water were added. The mixture was stirred at room temperature overnight. The precipitate was filtered off, washed with water and dried in high vacuum. The crude product was stirred in 200 mL hot ethyl acetate, filtered off and dried in high vacuum to obtain 1.97 g (73%) product as a solid.
Synthesis of bis(((Z)-2-methyl-3-oxo-1,3-bis(2-(trifluoromethyl)pyridin-4-yl)prop-1-en-1-yl)oxy)copper (MC-4)/(G5)
##STR00053##
[0458] 2.98 g (7.70 mmol) of 2-methyl-1,3-bis(2-(trifluoromethyl)pyridin-4-yl)propane-1,3-dione were dissolved in 60 ml methanol and 0.65 g (7.70 mmol) sodium bicarbonate was added. 0.41 g (2.57 mmol) iron trichloride were dissolved in 2 ml water and added dropwise to the reaction. The mixture was stirred at room temperature overnight. The precipitate was filtered off, washed with water and dried in high vacuum. 0.73 g (24%) product were obtained as a solid.
Synthesis of tris(((Z)-1,3-bis(3,5-bis(trifluoromethyl)phenyl)-2-cyano-3-oxoprop-1-en-1-yl)oxy)iron (MC-5/G8)
##STR00054##
[0459] 1.63 g (3.12 mmol) of 2-(3,5-bis(trifluoromethyl)benzoyl)-3-(3,5-bis(trifluoromethyl)phenyl)-3-oxopropanenitrile were dissolved in methanol and 0.26 g (3.12 mmol) sodium bicarbonate was added. 0.17 g (1.04 mmol) iron trichloride were dissolved in water and added to the mixture under cooling. The mixture was stirred at room temperature overnight. The precipitate was filtered off, washed with water and dried under vacuum. Product was obtained as a powder (1.08 g, 64% yield).
[0460] Further compounds according to invention may be prepared by the methods described above or by methods known in the art.
TABLE-US-00001 TABLE 1a Formulae of comparative compounds CC-1 and CC-2 and compounds of Formula (I) MC-1 to MC-5 Name Formula CC-1
Compounds of Formula (II)
[0461] Compounds of formula (II) may be prepared by methods known in the art.
Matrix Compound, Compounds of Formula (III) and Compounds for Formula (IV)
[0462] Matrix compound, compounds of formula (III) and compounds of formula (IV) may be prepared by methods known in the art.
HOMO and LUMO Levels of Matrix Compounds, Compounds of Formula (III) and Compounds of Formula (IV)
[0463] The HOMO and LUMO levels of matrix compounds, compounds of formula (III) and compounds of formula (IV) are calculated with the program package TURBOMOLE V6.5 (TURBOMOLE GmbH, Litzenhardtstrasse 19, 76135 Karlsruhe, Germany). The optimized geometries and the HOMO and LUMO energy levels of the molecular structures are determined by applying the hybrid functional B3LYP with a 6-31G* basis set in the gas phase. If more than one conformation is viable, the conformation with the lowest total energy is selected.
LUMO Levels of Metal Complexes of Formula (I)
[0464] The LUMO levels of the metal complexes of formula (I) are calculated with the program package TURBOMOLE V6.5 (TURBOMOLE GmbH, Litzenhardtstrasse 19, 76135 Karlsruhe, Germany). The optimized energies of the LUMO are obtained from a geometry optimization at the TPSSh/Def2-SVP level of the theory with inclusion of solvent effects via the COSMO (COnductor-like Screening MOdel) model with a dielectric constant () set to be equal to 3. For M=Hf, the basis set Def-SV(P) was used instead. All the calculations were performed with Turbomole. If more than one conformation is viable, the conformation with the lowest total energy is selected. If more than one spin state is viable, the spin state with the lowest total energy is selected.
In Table 1b are shown LUMO levels of metal complexes of formula (I) and of comparative compound CC-2, wherein the LUMO level was calculated using above method.
TABLE-US-00002 TABLE 1b LUMO levels of comparative compound CC-2 and metal complexes of formula (I) Name LUMO (eV) CC-2 3.92 () MC-1 4.55 () MC-2 4.68 () MC-3 3.92 () MC-5 5.07 ()
[0465] As can be seen in Table 1b, the LUMO levels of metal complexes of formula (I) are in the range suitable for organic electronic devices, in particular for use in the hole injection layer.
General Procedure for Fabrication of Organic Electronic Devices Comprising a Hole Injection Layer Comprising a Metal Complex and a Substantially Covalent Matrix Compound
[0466] For inventive examples 1-1 to 1-25 and comparative examples 1-1 to 1-4 in Table 2, a glass substrate with an anode layer comprising a first anode sub-layer of 120 nm Ag, a second anode sub-layer of 8 nm ITO and a third anode sub-layer of 10 nm ITO was cut to a size of 50 mm50 mm0.7 mm, ultrasonically washed with water for 60 minutes and then with isopropanol for 20 minutes. The liquid film was removed in a nitrogen stream, followed by plasma treatment to prepare the anode layer. The plasma treatment was performed in an atmosphere comprising 97.6 vol.-% nitrogen and 2.4 vol.-% oxygen at 75 W for 30 seconds.
[0467] Then, the substantially covalent matrix compound and the metal complex were co-deposited in vacuum on the anode layer, to form a hole injection layer (HIL) having a thickness of 10 nm. The composition of the hole injection layer can be seen in Table 2. The formulae of the metal complexes can be seen in Table 1.
[0468] Then, the substantially covalent matrix compound was vacuum deposited on the HIL, to form a HTL having a thickness of 123 nm. The substantially covalent matrix compound in the HTL is selected the same as the substantially covalent matrix compound in the HIL. The substantially covalent matrix compound can be seen in Table 2.
[0469] Then N-(4-(dibenzo[b,d]furan-4-yl)phenyl)-N-(4-(9-phenyl-9H-fluoren-9-yl)phenyl)-[1,1-biphenyl]-4-amine (CAS 1824678-59-2) was vacuum deposited on the HTL, to form an electron blocking layer (EBL) having a thickness of 5 nm.
[0470] Then 97 vol.-% H09 as EML host and 3 vol.-% BD200 (Sun Fine Chemicals, Korea) as fluorescent blue emitter dopant were deposited on the EBL, to form a blue-emitting first emission layer (EML) with a thickness of 20 nm.
[0471] Then a hole blocking layer was formed with a thickness of 5 nm by depositing 2-(3-(9,9-dimethyl-9H-fluoren-2-yl)-[1,1-biphenyl]-3-yl)-4,6-diphenyl-1,3,5-triazine on the emission layer EML.
[0472] Then the electron transporting layer having a thickness of 31 nm was formed on the hole blocking layer by depositing 50 wt.-% 4-(4-(4-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)naphthalen-1-yl)-[1,1-biphenyl]-4-carbonitrile and 50 wt.-% of LiQ.
[0473] Then Ag:Mg (90:10 vol.-%) was evaporated at a rate of 0.01 to 1 /s at 10.sup.7 mbar to form a cathode layer with a thickness of 13 nm on the electron transporting layer.
[0474] Then, K1 was deposited on the cathode layer to form a capping layer with a thickness of 75 nm.
[0475] The OLED stack is protected from ambient conditions by encapsulation of the device with a glass slide. Thereby, a cavity is formed, which includes a getter material for further protection.
Comparative Example 1-5
[0476] For comparative example 1-5 in Table 2, a 15 /cm.sup.2 glass substrate with 90 nm ITO (available from Corning Co.) was cut to a size of 50 mm50 mm0.7 mm, ultrasonically washed with water for 60 minutes and then with isopropanol for 20 minutes. The liquid film was removed in a nitrogen stream, followed by plasma treatment in nitrogen atmosphere at a power of 100 W for 75 seconds to prepare the anode layer.
[0477] Then, 90 vol.-% K1 and 10 vol.-% MC-1 were co-deposited in vacuum on the anode layer, to form a hole injection layer (HIL) having a thickness of 10 nm.
[0478] Then, K1 was vacuum deposited on the HIL, to form a HTL having a thickness of 123 nm.
[0479] Then, the EBL, EML, HBL and ETL are deposited in this order on the HTL, as described for inventive example 1-1.
[0480] Then Al was evaporated at a rate of 0.01 to 1 /s at 10.sup.7 mbar to form a cathode layer with a thickness of 100 nm on the electron transporting layer.
[0481] The OLED stack is protected from ambient conditions by encapsulation of the device with a glass slide. Thereby, a cavity is formed, which includes a getter material for further protection.
Comparative example 1-6
[0482] For comparative example 1-6 in Table 2, a glass substrate was cut to a size of 50 mm50 mm0.7 mm, ultrasonically washed with water for 60 minutes and then with isopropanol for 20 minutes. The liquid film was removed in a nitrogen stream, followed by plasma treatment in nitrogen atmosphere at a power of 100 W for 75 seconds, to prepare the substrate.
[0483] Then, 100 nm Ag was deposited in vacuum on the substrate to form the anode layer.
[0484] Then, 90 vol.-% K1 and 10 vol.-% MC-1 were co-deposited in vacuum on the anode layer, to form a hole injection layer (HIL) having a thickness of 10 nm.
[0485] Then, K1 was vacuum deposited on the HIL, to form a HTL having a thickness of 123 nm.
[0486] Then, the EBL, EML, HBL and ETL, cathode layer and capping layer are deposited in this order on the HTL, as described for inventive example 1-1.
[0487] The OLED stack is protected from ambient conditions by encapsulation of the device with a glass slide. Thereby, a cavity is formed, which includes a getter material for further protection.
[0488] To assess the performance of the inventive examples compared to the prior art, the current efficiency is measured at 20 C. The current-voltage characteristic is determined using a Keithley 2635 source measure unit, by sourcing a voltage in V and measuring the current in mA flowing through the device under test. The voltage applied to the device is varied in steps of 0.1V in the range between 0V and 10V. Likewise, the luminance-voltage characteristics and CIE coordinates are determined by measuring the luminance in cd/m.sup.2 using an Instrument Systems CAS-140CT array spectrometer (calibrated by Deutsche Akkreditierungsstelle (DAkkS)) for each of the voltage values. The cd/A efficiency at 10 mA/cm.sup.2 is determined by interpolating the luminance-voltage and current-voltage characteristics, respectively.
[0489] In bottom emission devices, the emission is predominately Lambertian and quantified in percent external quantum efficiency (EQE). The light is emitted through the anode layer. To determine the efficiency EQE in % the light output of the device is measured using a calibrated photodiode at 10 mA/cm2.
[0490] In top emission devices, the emission is forward directed through the cathode layer, non-Lambertian and also highly dependent on the micro-cavity. Therefore, the efficiency EQE will be higher compared to bottom emission devices. To determine the efficiency EQE in % the light output of the device is measured using a calibrated photodiode at 10 mA/cm.sup.2.
[0491] Lifetime LT of the device is measured at ambient conditions (20 C.) and 30 mA/cm.sup.2, using a Keithley 2400 sourcemeter, and recorded in hours.
[0492] The brightness of the device is measured using a calibrated photo diode. The lifetime LT is defined as the time till the brightness of the device is reduced to 97% of its initial value.
[0493] To determine the voltage stability over time U (100 h)(1 h), a current density of at 30 mA/cm2 was applied to the device. The operating voltage was measured after 1 hour and after 100 hours, followed by calculation of the voltage stability for the time period of 1 hour to 100 hours.
TECHNICAL EFFECT OF THE INVENTION
[0494] In Table 2 are shown data for top emission organic electronic devices fabricated by co-deposition from vacuum of metal complex and substantially covalent matrix compound.
[0495] In comparative examples 1-1 to 1-4, two metal complexes known in the art are tested at two different doping concentrations.
[0496] As can be seen in Table 2, in comparative examples 1-1 to 1-4 the operating voltage is between 3.67 and 3.78 V, the external quantum efficiency EQE is between 12.9 and 13.91% and the voltage stability over time is between 0.85 and 1.28 V.
[0497] In comparative example 1-5, the anode layer consists of ITO. As can be seen in Table 2, the operating voltage is increased compared to comparative examples 1-1 to 1-4 and the efficiency is reduced. The operating voltage stability over time is reduced compared to comparative examples 1-1 to 1-4.
[0498] In comparative example 1-6, the anode layer consists of Ag. As can be seen in Table 2, the operating voltage is substantially increased compared to comparative examples 1-1 to 1-4 and the efficiency is substantially reduced. The operating voltage stability over time is substantially reduced compared to comparative examples 1-1 to 1-4.
[0499] In inventive example 1-1, the semiconductor layer comprises metal complex of formula (I) MC-1. MC-1 comprises a group R.sup.2 selected from CN. As can be seen in Table 2, the EQE is improved to 14.32% and operating voltage stability over time is improved to 0.46 V compared to comparative example 1-4. The performance in inventive example 1-1 is substantially improved compared to comparative examples 1-5 and 1-6, which do not comprise an anode layer according to invention.
[0500] In inventive examples 1-2, the semiconductor layer comprises 15 vol.-% MC-1. As can be seen in Table 2, EQE and operating voltage stability over time remain improved over comparative examples 1-1 to 1-4.
[0501] In inventive examples 1-3 to 1-25, the semiconductor layer comprises metal complex of formula (1) at a range of doping concentrations and substantially covalent matrix compounds with a range of HOMO levels. As can be seen in Table 2, EQE and operating voltage stability over time are improved over comparative examples 1-1 to 1-4.
[0502] A high efficiency and/or improved operating voltage stability over time are important for the performance and long-term stability of organic electronic devices.
TABLE-US-00003 TABLE 2 Organic electronic devices comprising a hole injection layer comprising a metal complex and a matrix compound Percentage HOMO Percentage metal level of matrix Cd/A U(100 h) complex in matrix compound in U at 10 efficiency at EQE at 10 U(1 h) at Metal semiconductor Matrix compound semiconductor mA/cm.sup.2 10 mA/cm.sup.2 mA/cm.sup.2 30 mA/cm.sup.2 Anode complex layer [vol.-%] compound [eV] layer [vol.-%] [V] [cd/A] [%] [V] Comparative ITO/Ag/ITO CC-1 5 K1 4.68 95 3.67 6.38 12.99 0.85 example 1-1 Comparative ITO/Ag/ITO CC-2 6 K1 4.68 94 3.8 7.0 13.91 1.24 example 1-2 Comparative ITO/Ag/ITO CC-1 9 K1 4.68 91 3.65 6.24 12.90 0.89 example 1-3 Comparative ITO/Ag/ITO CC-2 10 K1 4.68 90 3.78 6.92 13.81 1.28 example 1-4 Comparative ITO MC-1 10 K1 4.68 90 4.06 5.21 10.38 1.98 example 1-5 Comparative Ag MC-1 10 K1 4.68 90 >10 <3 <6 >2 example 1-6 Inventive ITO/Ag/ITO MC-1 10 K1 4.68 90 3.75 6.73 14.32 0.46 example 1-1 Inventive ITO/Ag/ITO MC-1 15 K1 4.68 85 3.73 6.70 14.36 0.47 example 1-2 Inventive ITO/Ag/ITO MC-1 18 K16 4.73 82 3.81 7.34 15.42 0.07 example 1-3 Inventive ITO/Ag/ITO MC-1 22 K16 4.73 78 3.8 7.31 15.44 0.06 example 1-4 Inventive ITO/Ag/ITO MC-1 15 K2 4.85 85 3.75 7.25 14.73 0.06 example 1-5 Inventive ITO/Ag/ITO MC-1 21 K2 4.85 79 3.74 7.23 14.72 0.03 example 1-6 Inventive ITO/Ag/ITO MC-1 25 K2 4.85 75 3.73 7.21 14.71 0.02 example 1-7 Inventive ITO/Ag/ITO MC-5 1 K16 4.73 99 3.90 7.04 15.35 0.18 example 1-8 Inventive ITO/Ag/ITO MC-5 2 K16 4.73 98 3.84 7.39 15.47 0.10 example 1-9 Inventive ITO/Ag/ITO MC-5 4 K16 4.73 96 3.82 7.48 15.41 0.06 example 1-10 Inventive ITO/Ag/ITO MC-5 6 K16 4.73 94 3.80 7.39 15.41 0.05 example 1-11 Inventive ITO/Ag/ITO MC-5 9 K16 4.73 91 3.78 7.36 15.57 0.06 example 1-12 Inventive ITO/Ag/ITO MC-5 10 K16 4.73 90 3.78 7.40 15.57 0.08 example 1-13 Inventive ITO/Ag/ITO MC-5 11 K16 4.73 89 3.79 7.26 15.59 0.05 example 1-14 Inventive ITO/Ag/ITO MC-5 14 K16 4.73 86 3.78 7.26 15.51 0.05 example 1-15 Inventive ITO/Ag/ITO MC-5 16 K16 4.73 84 3.78 7.36 15.66 0.07 example 1-16 Inventive ITO/Ag/ITO MC-5 20 K16 4.73 80 3.78 7.28 15.54 0.07 example 1-17 Inventive ITO/Ag/ITO MC-5 12 K7 4.84 88 3.81 6.85 14.01 0.15 example 1-18 Inventive ITO/Ag/ITO MC-5 14 K7 4.84 86 3.80 6.84 14.03 0.11 example 1-19 Inventive ITO/Ag/ITO MC-5 16 K7 4.84 84 3.79 6.84 14.04 0.08 example 1-20 Inventive ITO/Ag/ITO MC-5 8 K2 4.85 82 3.74 6.93 14.80 0.09 example 1-21 Inventive ITO/Ag/ITO MC-5 10 K2 4.85 90 3.73 6.90 14.85 0.16 example 1-22 Inventive ITO/Ag/ITO MC-5 12 K2 4.85 88 3.72 6.91 14.80 0.05 example 1-23 Inventive ITO/Ag/ITO MC-5 15 K2 4.85 85 3.71 6.90 14.89 0.04 example 1-24 Inventive ITO/Ag/ITO MC-5 19 K2 4.85 81 3.71 6.82 14.86 0.03 example 1-25
[0503] The particular combinations of elements and features in the above detailed embodiments are exemplary only; the interchanging and substitution of these teachings with other teachings in this and the patents/applications incorporated by reference are also expressly contemplated. As those skilled in the art will recognize, variations, modifications, and other implementations of what is described herein can occur to those of ordinary skill in the art without departing from the spirit and the scope of the invention as claimed. Accordingly, the foregoing description is by way of example only and is not intended as limiting. In the claims, the word comprising does not exclude other elements or steps, and the indefinite article a or an does not exclude a plurality. The mere fact that certain measures are recited in mutually different dependent claims does not indicate that a combination of these measured cannot be used to advantage. The invention's scope is defined in the following claims and the equivalents thereto. Furthermore, reference signs used in the description and claims do not limit the scope of the invention as claimed.