Metal Complex, Semiconductor Layer Comprising a Metal Complex and Organic Electronic Device

Abstract

The present invention relates to a metal complex, a semiconductor layer comprising the metal complex and an organic electronic device comprising at least one metal complex thereof.

Claims

1.-23. (canceled)

24. A metal complex of formula (I) ##STR00146## wherein M is a metal ion; n is the valency of M and selected from 1 to 4; L has formula (II) ##STR00147## R.sup.1 and R.sup.2 are independently selected from substituted or unsubstituted C.sub.1 to C.sub.12 alkyl, substituted or unsubstituted C.sub.6 to C.sub.19 aryl, substituted or unsubstituted C.sub.2 to C.sub.20 heteroaryl, or substituted or unsubstituted 6-membered heteroaryl; R.sup.3 is selected from substituted or unsubstituted C.sub.1 to C.sub.12 alkyl, substituted or unsubstituted C.sub.6 to C.sub.19 aryl, substituted or unsubstituted C.sub.2 to C.sub.20 heteroaryl, substituted or unsubstituted 6-membered heteroaryl, or CN; wherein at least one of the substituents of the substituted C.sub.1 to C.sub.12 alkyl, substituted C.sub.6 to C.sub.19 aryl, substituted C.sub.2 to C.sub.20 heteroaryl, or substituted 6-membered heteroaryl are independently selected from halogen, Cl, F, CN, partially or perfluorinated C.sub.1 to C.sub.8 alkyl, partially or perfluorinated C.sub.1 to C.sub.8 alkoxy; wherein at least one of R.sup.1, R.sup.2 and R.sup.3 or the group of R.sup.1, R.sup.2 and R.sup.3 comprises at least three atoms selected from the group consisting of halogen, Cl, F or N; wherein AL is an ancillary ligand which coordinates to the metal M; m is an integer selected from 0 to 2.

25. The metal complex of formula (I) according to claim 24, wherein M is a metal ion; wherein M is a metal ion selected from Li(I), K(I), Rb(I), Cs(I), Ag(I), Cu(II), Zn(II), Pd(II), Ir(III), Al(III), Sc(III), Mn(III), Ru(III), In(III), Y(III), Eu(III), Fe(III), V(IV), Zr(IV), Hf(IV) and Ce(IV); n is the valency of M and selected from 1 to 4; L has formula (II) ##STR00148## R.sup.1 and R.sup.2 are independently selected from substituted or unsubstituted C.sub.1 to C.sub.12 alkyl, substituted or unsubstituted C.sub.6 to C.sub.19 aryl, substituted or unsubstituted C.sub.2 to C.sub.20 heteroaryl, or substituted or unsubstituted 6-membered heteroaryl; R.sup.3 is selected from substituted or unsubstituted C.sub.1 to C.sub.12 alkyl, substituted or unsubstituted C.sub.6 to C.sub.19 aryl, substituted or unsubstituted C.sub.2 to C.sub.20 heteroaryl, substituted or unsubstituted 6-membered heteroaryl, or CN; wherein at least one of the substituents of the substituted C.sub.1 to C.sub.12 alkyl, substituted C.sub.6 to C.sub.19 aryl, substituted C.sub.2 to C.sub.20 heteroaryl, or substituted 6-membered heteroaryl are independently selected from halogen, Cl, F, CN, partially or perfluorinated C.sub.1 to C.sub.8 alkyl, partially or perfluorinated C.sub.1 to C.sub.8 alkoxy; wherein at least one of R.sup.1, R.sup.2 and R.sup.3 or the group of R.sup.1, R.sup.2 and R.sup.3 comprises at least three atoms selected from the group consisting of halogen, Cl, F or N; wherein AL is an ancillary ligand which coordinates to the metal M; m is an integer selected from 0 to 2.

26. The metal complex of formula (I) according to claim 24, wherein at least one of R.sup.1, R.sup.2 and R.sup.3 or the group of R.sup.1, R.sup.2 and R.sup.3 comprises at least three atoms selected from the group consisting of halogen, Cl, F or N.

27. The metal complex of formula (I) according to claim 24, wherein the group of R.sup.1, R.sup.2 and R.sup.3 comprises at least three atoms selected from the group consisting of halogen, Cl, F or N.

28. The metal complex of formula (I) according to claim 24, wherein R.sup.1 and R.sup.2 are independently selected from substituted or unsubstituted C.sub.1 to C.sub.12 alkyl, substituted or unsubstituted C.sub.6 to C.sub.19 aryl, substituted or unsubstituted C.sub.2 to C.sub.20 heteroaryl that comprises at least one substituted or unsubstituted 6-membered heteroaryl; R.sup.3 is selected from partially or perfluorinated C.sub.1 to C.sub.4 alkyl or CN.

29. The metal complex of formula (I) according to claim 24, wherein the group consisting of R.sup.1, R.sup.2 and R.sup.3 are selected from the group comprising at least two moieties selected from CF.sub.3 or CN.

30. The metal complex of formula (I) according to claim 24, wherein the group consisting of R.sup.1, R.sup.2 and R.sup.3, wherein at least one moiety is selected from CF.sub.3, CN and one substituted or unsubstituted 6-membered heteroaryl.

31. The metal complex of formula (I) according to claim 24, wherein at least one of the group consisting of R.sup.1, R.sup.2 and R.sup.3 is selected from CN, CH.sub.3, CF.sub.3, C.sub.2F.sub.5, C.sub.3F.sub.7 or C.sub.4F.sub.9.

32. The metal complex of formula (I) according to claim 24, wherein the metal complex of formula (I) is selected from the group comprising at least one CF.sub.3 group, at least two CF.sub.3 groups, at least three CF.sub.3 groups, at least four CF.sub.3 groups, at least two CF.sub.3 groups and at least one C.sub.2F.sub.5.

33. The metal complex of formula (I) according to claim 24, wherein at least one of the group consisting of R.sup.1, R.sup.2 and R.sup.3 is selected from the group comprising a substituted or unsubstituted C.sub.6 to C.sub.19 aryl, a substituted C.sub.2 to C.sub.20 heteroaryl group comprising at least 6 ring-forming atoms, or is selected from the following Formulae D1 to D71: ##STR00149## ##STR00150## ##STR00151## ##STR00152## ##STR00153## ##STR00154## ##STR00155## wherein the * denotes the binding position.

34. The metal complex of formula (I) according to claim 24, wherein M is a metal ion selected from an alkali, alkaline earth, transition, rare earth metal or group III to V metal, Li(I), K(I), Rb(I), Cs(I), Ag(I), Cu(II), Zn(II), Pd(II), Ir(III), Al(III), Sc(III), Mn(III), Ru(III), In(III), Y(III), Eu(III), Fe(III), V(IV), Zr(IV), Hf(IV) and Ce(IV); wherein the number in brackets denotes the oxidation state.

35. The metal complex of formula (I) according to claim 24, wherein the Ligand L is selected from the group comprising the following Formulae E1 to E212: ##STR00156## ##STR00157## ##STR00158## ##STR00159## ##STR00160## ##STR00161## ##STR00162## ##STR00163## ##STR00164## ##STR00165## ##STR00166## ##STR00167## ##STR00168## ##STR00169## ##STR00170## ##STR00171## ##STR00172## ##STR00173## ##STR00174## ##STR00175## ##STR00176## ##STR00177## ##STR00178## ##STR00179## ##STR00180## ##STR00181## ##STR00182## ##STR00183## ##STR00184##

36. The metal complex of formula (I) according to claim 24, wherein AL 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, or a compound according to Formula (III); ##STR00185## wherein R.sup.6 and R.sup.7 are independently selected from 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, or at least one R.sup.6 and R.sup.7 are bridged and form a 5 to 20 member ring, or the two R.sup.6 and/or the two R.sup.7 are bridged and form a 5 to 40 member ring or form a 5 to 40 member ring comprising an unsubstituted or C.sub.1 to C.sub.12 substituted phenanthroline.

37. The metal complex of formula (I) according to claim 24, wherein n is selected 2 or 3.

38. The metal complex of formula (I) according to claim 24, wherein m is an integer selected from 0 or 1.

39. The metal complex of formula (I) of Formula (I) according to claim 24, wherein at least one R.sup.1 or R.sup.3, or R.sup.1 and R.sup.3 are selected from a substituted C.sub.2 to C.sub.20 heteroaryl group comprising at least 6 ring-forming atoms, wherein the C.sub.2 to C.sub.20 heteroaryl group comprising at least 6 ring-forming atoms is selected from pyridyl, pyrimidinyl, pyrazinyl, triazinyl.

40. The metal complex of formula (I) according to claim 24: ##STR00186## wherein M is a metal ion selected from a main group metal or transition metal, Cu, Fe, Mn, Al, Hf, Zr; n is the valency of M and selected from 2 or 3; L has formula (II); ##STR00187## R.sup.1 and R.sup.2 are independently selected from substituted or unsubstituted C.sub.1 to C.sub.12 alkyl, substituted or unsubstituted C.sub.6 to C.sub.19 aryl, substituted or unsubstituted C.sub.2 to C.sub.20 heteroaryl, or substituted or unsubstituted 6-membered heteroaryl; R.sup.3 is selected from substituted or unsubstituted C.sub.1 to C.sub.12 alkyl, substituted or unsubstituted C.sub.6 to C.sub.19 aryl, substituted or unsubstituted C.sub.2 to C.sub.20 heteroaryl, substituted or unsubstituted 6-membered heteroaryl, or CN; wherein at least one of the substituents of the substituted C.sub.1 to C.sub.12 alkyl, substituted C.sub.6 to C.sub.19 aryl, substituted C.sub.2 to C.sub.20 heteroaryl, or substituted 6-membered heteroaryl are independently selected from halogen, Cl, F, CN, partially or perfluorinated C.sub.1 to C.sub.8 alkyl, partially or perfluorinated C.sub.1 to C.sub.8 alkoxy; wherein at least one of R.sup.1, R.sup.2 and R.sup.3 or the group of R.sup.1, R.sup.2 and R.sup.3 comprises at least three atoms selected from the group consisting of halogen, Cl, F or N; wherein the group consisting of R.sup.1, R.sup.2 and R.sup.3 comprises in addition: at least two moieties selected from CF.sub.3 or CN; or at least one moiety selected from CF.sub.3 or CN and one substituted or unsubstituted 6-membered heteroaryl; or R.sup.3 is CN; AL is an ancillary ligand which coordinates to the metal M; m is an integer selected from 0 to 2.

41. The metal complex of formula (I) according to claim 24: ##STR00188## wherein M is a Ce ion; n is the valency of M and is 4; L has formula (II) ##STR00189## R.sup.1 and R.sup.2 are independently selected from substituted or unsubstituted C.sub.1 to C.sub.12 alkyl, substituted or unsubstituted C.sub.6 to C.sub.19 aryl, substituted or unsubstituted C.sub.2 to C.sub.20 heteroaryl, or substituted or unsubstituted 6-membered heteroaryl; R.sup.3 is selected from substituted or unsubstituted C.sub.1 to C.sub.12 alkyl, substituted or unsubstituted C.sub.6 to C.sub.19 aryl, substituted or unsubstituted C.sub.2 to C.sub.20 heteroaryl, substituted or unsubstituted 6-membered heteroaryl, or CN; wherein at least one of the substituents of the substituted C.sub.1 to C.sub.12 alkyl, substituted C.sub.6 to C.sub.19 aryl, substituted C.sub.2 to C.sub.20 heteroaryl, or substituted 6-membered heteroaryl are independently selected from halogen, Cl, F, CN, partially or perfluorinated C.sub.1 to C.sub.8 alkyl, partially or perfluorinated C.sub.1 to C.sub.8 alkoxy; wherein at least one of R.sup.1, R.sup.2 and R.sup.3 or the group of R.sup.1, R.sup.2 and R.sup.3 comprise at least three atoms selected from the group consisting of halogen, Cl, F or N; AL is an ancillary ligand which coordinates to the metal M; m is an integer selected from 0 to 2.

42. The metal complex of formula (I) according to claim 24: ##STR00190## wherein M is a metal ion; n is the valency of M and selected from 1 to 4; L has formula (II) ##STR00191## R.sup.1 and R.sup.2 are independently selected from substituted or unsubstituted C.sub.1 to C.sub.12 alkyl, substituted or unsubstituted C.sub.6 to C.sub.19 aryl, substituted or unsubstituted C.sub.2 to C.sub.20 heteroaryl that comprises at least one substituted or unsubstituted 6-membered heteroaryl; R.sup.3 is selected from partially or perfluorinated C.sub.1 to C.sub.4 alkyl or CN; wherein at least one of the substituents of the substituted C.sub.1 to C.sub.12 alkyl, substituted C.sub.6 to C.sub.19 aryl, substituted C.sub.2 to C.sub.20 heteroaryl, or substituted 6-membered heteroaryl are independently selected from halogen, Cl, F, CN, partially or perfluorinated C.sub.1 to C.sub.8 alkyl, partially or perfluorinated C.sub.1 to C.sub.8 alkoxy; wherein AL is an ancillary ligand which coordinates to the metal M; m is an integer selected from 0 to 2.

43. The metal complex of formula (I) according to claim 24: ##STR00192## wherein M is a metal ion; n is the valency of M and selected from 1 to 4; L has formula (II) ##STR00193## R.sup.1 and R.sup.2 are independently selected from substituted or unsubstituted C.sub.1 to C.sub.12 alkyl, substituted or unsubstituted C.sub.6 to C.sub.19 aryl, substituted or unsubstituted C.sub.2 to C.sub.20 heteroaryl, substituted or unsubstituted 6-membered heteroaryl; R.sup.3 is selected from substituted or unsubstituted C.sub.1 to C.sub.12 alkyl, substituted or unsubstituted C.sub.6 to C.sub.19 aryl, substituted or unsubstituted C.sub.2 to C.sub.20 heteroaryl, substituted or unsubstituted 6-membered heteroaryl, or CN wherein at least one of the substituents of the substituted C.sub.1 to C.sub.12 alkyl, substituted C.sub.6 to C.sub.19 aryl, substituted C.sub.2 to C.sub.20 heteroaryl, or substituted 6-membered heteroaryl are independently selected from halogen, Cl, F, CN, partially or perfluorinated C.sub.1 to C.sub.8 alkyl, partially or perfluorinated C.sub.1 to C.sub.8 alkoxy; wherein at least one of R.sup.1, R.sup.2 and R.sup.3 or the group of R.sup.1, R.sup.2 and R.sup.3 comprises a substituted or unsubstituted C.sub.2 to C.sub.20 heteroaryl that comprises at least one 6 membered heteroaryl ring; wherein AL is an ancillary ligand which coordinates to the metal M; m is an integer selected from 0 to 2.

44. A semiconductor material comprising at least one metal complex of Formula (I) according to any of the preceding claim 1.

45. A semiconductor material according to claim 44, wherein the semiconductor material comprises in addition at least one covalent matrix compound.

46. An organic electronic device comprising a first electrode layer, a second electrode layer, at least one photoactive layer and a semiconductor layer, wherein the semiconductor layer is arranged between the first electrode layer and the at least one photoactive layer, the semiconductor layer comprises a metal complex of formula (I) ##STR00194## wherein M is a metal ion; n is the valency of M and selected from 1 to 4; L has formula (II) ##STR00195## R.sup.1 and R.sup.2 are independently selected from substituted or unsubstituted C.sub.1 to C.sub.12 alkyl, substituted or unsubstituted C.sub.6 to C.sub.19 aryl, substituted or unsubstituted C.sub.2 to C.sub.20 heteroaryl, or substituted or unsubstituted 6-membered heteroaryl; R.sup.3 is selected from substituted or unsubstituted C.sub.1 to C.sub.12 alkyl, substituted or unsubstituted C.sub.6 to C.sub.19 aryl, substituted or unsubstituted C.sub.2 to C.sub.20 heteroaryl, substituted or unsubstituted 6-membered heteroaryl, or CN; wherein at least one of the substituents of the substituted C.sub.1 to C.sub.12 alkyl, substituted C.sub.6 to C.sub.19 aryl, substituted C.sub.2 to C.sub.20 heteroaryl, or substituted 6-membered heteroaryl are independently selected from halogen, Cl, F, CN, partially or perfluorinated C.sub.1 to C.sub.8 alkyl, partially or perfluorinated C.sub.1 to C.sub.8 alkoxy; wherein at least one of R.sup.1, R.sup.2 and R.sup.3 or the group of R.sup.1, R.sup.2 and R.sup.3 comprises at least three atoms selected from the group consisting of halogen, Cl, F or N; AL is an ancillary ligand which coordinates to the metal M; m is an integer selected from 0 to 2.

47. The organic electronic device according to claim 46, wherein the semiconductor layer comprises a metal complex of formula (I) according to claim 1.

48. The organic electronic device according to claim 47, wherein the organic electronic device is selected from the group comprising a light emitting device, a thin film transistor, a battery, a display device, a photovoltaic device, a part of a display device or a part of a lighting device.

49. An organic electronic device comprising a metal complex of formula (I) according to claim 24, wherein the organic electronic device is a light emitting device, thin film transistor, a battery, a display device, a photovoltaic device, a part of a display device or a part of a lighting device.

Description

DESCRIPTION OF THE DRAWINGS

[0464] 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.

[0465] 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.

[0466] FIG. 1 is a schematic sectional view of an organic electronic device, according to an exemplary embodiment of the present invention;

[0467] FIG. 2 is a schematic sectional view of an organic light-emitting diode (OLED), according to an exemplary embodiment of the present invention;

[0468] FIG. 3 is a schematic sectional view of an organic light-emitting diode (OLED), according to an exemplary embodiment of the present invention.

[0469] FIG. 4 is a schematic sectional view of an organic light-emitting diode (OLED), according to an exemplary embodiment of the present invention;

[0470] FIG. 5 is a schematic sectional view of an organic light-emitting diode (OLED), according to an exemplary embodiment of the present invention.

[0471] FIG. 6 is a schematic sectional view of an organic light-emitting diode (OLED), according to an exemplary embodiment of the present invention.

[0472] FIG. 1 is a schematic sectional view of an organic electronic device 101, according to an exemplary embodiment of the present invention. The organic electronic device 101 includes a substrate (110), an anode layer (120), a hole injection layer comprising a metal complex according to formula (I) (130), a photoactive layer (PAL) (151) and a cathode layer (190).

[0473] FIG. 2 is a schematic sectional view of an organic light-emitting diode (OLED) 100, according to an exemplary embodiment of the present invention. The OLED 100 includes a substrate (110), an anode layer (120), a hole injection layer comprising a metal complex according to formula (I) (130), an emission layer (EML) (150) and a cathode layer (190).

[0474] FIG. 3 is a schematic sectional view of an organic light-emitting diode (OLED) 100, according to an exemplary embodiment of the present invention. The OLED 100 includes a substrate (110), an anode layer (120), a hole injection layer comprising a metal complex according to formula (I) (130), a hole transport layer (HTL) (140), an emission layer (EML) (150), an electron transport layer (ETL) (160) and a cathode layer (190).

[0475] FIG. 4 is a schematic sectional view of an organic light-emitting diode (OLED) 100, according to an exemplary embodiment of the present invention. The OLED 100 includes a substrate (110), an anode layer (120), a hole injection layer comprising a metal complex according to formula (I) (130), a hole transport layer (HTL) (140), an electron blocking layer (EBL) (145), an emission layer (EML) (150), a hole blocking layer (HBL) (155), an electron transport layer (ETL) (160), an optional electron injection layer (EIL) (180), and a cathode layer (190).

[0476] FIG. 5 is a schematic sectional view of an organic light-emitting diode (OLED) 100, according to an exemplary embodiment of the present invention. The OLED 100 includes a substrate (110), an anode layer (120) that comprises a first anode sub-layer (121) and a second anode sub-layer (122), a hole injection layer comprising a metal complex according to formula (I) (130), a hole transport layer (HTL) (140), an electron blocking layer (EBL) (145), an emission layer (EML) (150), a hole blocking layer (EBL) (155), an electron transport layer (ETL) (160) and a cathode layer (190).

[0477] FIG. 6 is a schematic sectional view of an organic light-emitting diode (OLED) 100, according to an exemplary embodiment of the present invention. The OLED 100 includes a substrate (110), an anode layer (120) that comprises a first anode sub-layer (121), a second anode sub-layer (122) and a third anode sub-layer (123), a hole injection layer comprising a metal complex according to formula (I) (130), a hole transport layer (HTL) (140), an electron blocking layer (EBL) (145), an emission layer (EML) (150), a hole blocking layer (EBL) (155), an electron transport layer (ETL) (160) and a cathode layer (190). The layers are disposed exactly in the order as mentioned before.

[0478] In the description above the method of manufacture an organic electronic device 101 of the present invention is for example started with a substrate (110) onto which an anode layer (120) is formed, on the anode layer (120), a hole injection layer comprising a metal complex according to formula (I) (130), a photoactive layer (151) and a cathode electrode 190 are formed, exactly in that order or exactly the other way around.

[0479] In the description above the method of manufacture an OLED of the present invention is started with a substrate (110) onto which an anode layer (120) is formed, on the anode layer (120), a hole injection layer comprising a metal complex according to formula (I) (130), optional a hole transport layer (140), optional an electron blocking layer (145), an emission layer (150), optional a hole blocking layer (155), optional an electron transport layer (160), optional an electron injection layer (180), and a cathode electrode 190 are formed, exactly in that order or exactly the other way around.

[0480] The semiconductor layer comprising a metal complex according to formula (I) (130) can be a hole injection layer.

[0481] While not shown in FIG. 1, FIG. 2, FIG. 3, FIG. 4, FIG. 5 and FIG. 6, a capping layer and/or a sealing layer may further be formed on the cathode electrodes 190, in order to seal the OLEDs 100. In addition, various other modifications may be applied thereto.

[0482] Hereinafter, one or more exemplary embodiments of the present invention will be described in detail with, reference to the following examples. However, these examples are not intended to limit the purpose and scope of the one or more exemplary embodiments of the present invention.

General Method for Preparation of the Ink Formulation

[0483] To prepare the ink formulation, the compounds were weighed into vials. Then, the solvent was added. The mixture was stirred for 10 min. The inks were transferred to inert atmosphere. An aliquot of benzonitrile solutions was added to the anisole solution to obtain a solution with a ratio of 5:1 of anisole to benzonitrile solution. The resulting solution was stirred again for at least 10 min at room temperature. The resulting ink formulation had a solid content of 4 wt.-%.

Dipole Moment

[0484] The dipole moment |{right arrow over ()}| of a molecule containing N atoms is given by:

[00001] $\begin{matrix} \overset{.fwdarw.}{} = {.Math.}_{i}^{N} q_{i} \overset{.fwdarw.}{r_{.Math.}} \\ .Math. \overset{.fwdarw.}{} .Math. = \sqrt{_{x}^{2} +_{y}^{2} +_{z}^{2}} \end{matrix}$

where q.sub.i and {right arrow over (r)}.sub.i are the partial charge and position of atom i in the molecule.

[0485] The dipole moment is determined by density functional theory (DFT) method.

[0486] The geometries of the molecular structures are optimized using the GGA functional BP86 with the Def2-SVP basis set with inclusion of solvent effects via conductor-like polarizable continuum model (CPCM) and as solvent acetonitrile (CPCM(Acetonitrile)) as implemented in the program package ORCA V5.0.3 (Max Planck Institute fuer Kohlenforschung, Kaiser Wilhelm Platz 1, 45470, Muelheim/Ruhr, Germany) and WEASEL 1.9.2 (FAccTs GmbH, Rolandstrasse 67, 50677 Koln, Germany). If more than one conformation is viable, the conformation with the lowest total energy is selected to determine the bond lengths of the molecules. The structures of all the molecules were optimized without symmetry or internal coordinate constrains and were verified as true minima by the absence of negative eigenvalues in the harmonic vibrational frequency analysis. [0487] I. Geometry optimization using BP86 functional with def2-SVP basis set and SDD ECPs for elements starting with atomic number 21. [0488] II. Frequency calculation using BP86 functional with def2-SVP basis set, and SDD ECPs for elements starting with atomic number 21. [0489] III. Single Point DFT calculation using (Gaussian)-B3LYP functional with ZORA-def2-TZVP basis set and auxiliary basis SARC/J.

[0490] For the calculations it has been considered for Cu(II) charge 0 and multiplicity 2, for Fe(III) charge 0 and multiplicity 6 (high-spin); temperature is 298.15 K and pressure is 1.0 atm. For all the calculations solvent effects have been included via conductor-like polarizable continuum model (CPCM) with solvent acetonitrile [0491] Programs: WEASEL (Version 1.9.2) and ORCA (5.0.3-f.1), for visualization: Chemcraft.

Calculated HOMO and LUMO of the Metal Complex of Formula (I)

[0492] The HOMO and LUMO are calculated with the program package ORCA V5.0.3 (Max Planck Institute fuer Kohlenforschung, Kaiser Wilhelm Platz 1, 45470, Muelheim/Ruhr, Germany) and WEASEL 1.9.2 (FAccTs GmbH, Rolandstrasse 67, 50677 Koln, Germany). The optimized geometries and the HOMO and LUMO energy levels of the molecular structures are determined by applying the hybrid functional (Gaussian)-B3LYP with a ZORA-Def2-TZVP basis set with inclusion of solvent effects via conductor-like polarizable continuum model (CPCM) and as solvent acetonitrile. If more than one conformation is viable, the conformation with the lowest total energy is selected. The structures of all the molecules were optimized without symmetry or internal constrains and were verified as true minima by the absence of negative eigenvalues in the harmonic vibrational frequency analysis.

[0493] LUMO References: see Table 1

Experimental Data

Synthesis Examples

[0494] Compounds of formula (I) may be prepared by known methods or as described below.

Synthesis of Tris((3-methyl-1-phenyl-4-(2,2,2-trifluoroacetyl)-1H-pyrazol-5-yl)oxy)iron (MC7)

##STR00140##

[0495] To a mixture of 12.8 g (47.4 mmol) Ligand and 3.98 g (47.4 mmol) NaHCO.sub.3 in 120 ml methanol was added in portions a solution of 2.56 g (15.8 mmol) of FeCl3 in 15 ml of water at ice-bath-temperature. The mixture was allowed to stir overnight, then the suspension was filtered and the product washed with little water-methanol. Drying resulted in 12.4 g (91%) of the desired product.

Synthesis of Bis((3-methyl-1-phenyl-4-(2,2,2-trifluoroacetyl)-1H-pyrazol-5-yl)oxy)copper (MC6)

##STR00141##

[0496] To a solution of 2.5 g (9.25 mmol) of ligand in 50 ml of Ethanol was added 0.92 g (4.63 mmol) of copper (II) acetate and the mixture was stirred overnight. The resulting green suspension was filtered off and the solid was dried in vacuum to obtain 2.3 g (83%) light green-yellowish powder.

Synthesis of Tetrakis((3-methyl-1-phenyl-4-(2,2,2-trifluoroacetyl)-1H-pyrazol-5-yl)oxy)cerium (MC9)

##STR00142##

[0497] 3.76 g (13.92 mmol) of ligand and 1.07 g ammonium acetate (13.92 mmol) were dissolved in 50 ml acetic acid. 2.86 g (5.22 mmol) cerium ammonium nitrate were dissolved in 30 ml water and added drop wise to the ligand. After 30 min the resulting precipitate was filtered off and dried overnight at 100 C. in vacuum to obtain 2.63 g (62%) black solid.

Synthesis of 1-(1-(3,5-bis(trifluoromethyl)phenyl)-5-hydroxy-3-methyl-1H-pyrazol-4-yl)-2,2,2-trifluoroethan-1-one

Step 1. 1-(3,5-bis(trifluoromethyl)phenyl)-3-methyl-1H-pyrazol-5-ol

##STR00143##

[0498] 4.0 g (16.38 mmol) 3,5-bis(trifluoromethyl)phenyl hydrazine were dissolved in 60 ml ethanol and a solution of 1.9 g (16.38 mmol) methyl acetoacetate was added dropwise. The reactions for heated to reflux for 4 h. After removing the solvent, the residue was distilled from bulb to bulb in vacuum. The residue was further purified by flash chromatography using ethyl acetate/hexane and sublimation to obtain 2.33 g (46%) slightly yellow, crystalline solid.

Step 2. 1-(1-(3,5-bis(trifluoromethyl)phenyl)-5-hydroxy-3-methyl-1H-pyrazol-4-yl)-2,2,2-trifluoroethan-1-one

##STR00144##

[0499] 1.38 g (14.38 mmol) sodium tert-butylate and 1.1 g (8.63 mmol) trifluoroaceticacid methyl ester were dissolved in 10 ml dry diethyl ether and cooled with an ice bath. A solution of 2.23 g (7.19 mmol) 1-(3,5-bis(trifluoromethyl)phenyl)-3-methyl-1H-pyrazol-5-ol in 15 ml diethyl ether was added dropwise. The mixture was stirred at room temperature overnight. After drying with magnesium sulfate the solvent was removed and the crude product sublimed to obtain 2.1 g (72%) slightly reddish solid.

Synthesis of Bis((1-(3,5-bis(trifluoromethyl)phenyl)-3-methyl-4-(2,2,2-trifluoroacetyl)-1H-pyrazol-5-yl)oxy)copper (MC56)

##STR00145##

[0500] 2.0 g (4.92 mmol) ligand was dissolved in 20 ml ethanol and 0.49 g (2.46 mmol) copper (II) acetate were added. The mixture was stirred overnight at room temperature, cooled with an ice bath and the precipitate was filtered off, washed with ethanol and dried at 70 C. in vacuum to obtain 1.95 g (910%) bright green powder.

[0501] Further compounds according to invention may be prepared by the methods described above or by methods known in the art.

[0502] Further compounds according to invention may be prepared by the methods described above or by methods known in the art.

General Procedure for Fabrication of OLEDs

General Procedure for Fabrication of Organic Electronic Devices Comprising a Semiconductor Laver Comprising a Metal Complex and a Matrix Compound Wherein the Semiconductor Layer is Deposited in Vacuum

[0503] For inventive examples 1-1 to 1-26 and comparative example 1-1 in Table 3 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.

[0504] Then, the metal complex and the matrix compound 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 3. The formulae of the metal complexes can be seen in Table 1.

[0505] Then, the matrix compound was vacuum deposited on the HIL, to form a HTL having a thickness of 123 nm. The compound of formula (II) in the HTL is selected the same as the matrix compound in the HIL. The matrix compound can be seen in Table 3.

[0506] 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.

[0507] 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.

[0508] 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.

[0509] 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.

[0510] 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.

[0511] Then, K1 was deposited on the cathode layer to form a capping layer with a thickness of 75 nm.

[0512] 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.

[0513] 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.

[0514] 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.

[0515] 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.

[0516] Lifetime LT of the device is measured at ambient conditions (20 C.) and 30 mA/cm.sup.2, using a Keithley 2400 source meter, and recorded in hours.

[0517] 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.

[0518] To determine the voltage stability over time U(100 h)(1 h), a current density of at 30 mA/cm.sup.2 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. A low value for U(100 h)(1 h) denotes a low increase in operating voltage over time and thereby improved voltage stability.

[0519] Conductivity is determined by transmission line method. Voltage between 5 and +5V in steps of 0.5V is applied on a transmission line covered with a homogeneous layer of studied material having a uniform thickness. The current is measured using a Keithley SM2635 source measure unit. Conductivity is calculated using known geometry of the transmission line and thickness of the deposited layer.

General Method for Preparation of the Ink Formulation

[0520] To prepare the ink formulation, the compounds were weighed into vials. Then, the solvent was added. The mixture was stirred for 10 min. The inks were transferred to inert atmosphere. An aliquot of benzonitrile solutions was added to the anisole solution to obtain a solution with a ratio of 5:1 of anisole to benzonitrile solution. The resulting solution was stirred again for at least 10 min at room temperature. The resulting ink formulation had a solid content of 4 wt.-%.

Ink Formulation for Inventive Example 2-1

[0521] The ink formulation for example 2-3 has the following composition: 4 wt.-% K1 in anisole benzonitrile (5:1). To prepare the ink, solution of 166 mg K1 in 3.3 ml anisole were prepared as described above. 0.7 ml benzonitrile was added to the anisole solution and stirred as described above.

Ink Formulation for Inventive Example 2-1

[0522] The ink formulation for example 2-1 has the following composition: 4 wt.-% MC-9:K1 in anisole:benzonitrile (5:1). To prepare the ink, solutions of 12.6 mg (1 mol. %, 1.78 wt. %) MC9 in 3 ml benzonitrile and 163 mg K1 in 3.3 ml anisole were prepared as described above. 0.7 ml benzonitrile solution was added to the anisole solution and stirred as described above.

Ink Formulation for Inventive Example 2-3

[0523] The ink formulation for example 2-2 has the following composition: 4 wt.-% MC-2:K1 in anisole:benzonitrile (5:1). To prepare the ink, solutions of 24 mg (1 mol. %, 5.25 wt. %) MC9 in 2 ml benzonitrile and 158 mg K1 in 3.3 ml anisole were prepared as described above. 0.7 ml benzonitrile solution was added to the anisole solution and stirred as described above.

General Procedure for Fabrication of Electronic Devices Comprising a Semiconductor Laver Comprising a Metal Complex and a Matrix Compound Wherein the Semiconductor Layer is Deposited from Solution

[0524] For conductivity devices, see Examples 2-1, 2-2 and 2-3 in Table 4, a 152/cm.sup.2 glass substrate with 90 nm ITO (available from Corning Co.) with the dimensions 150 mm150 mm0.7 mm was ultrasonically washed with isopropyl alcohol for 5 minutes and then with pure water for 5 minutes and dried at elevated temperature.

[0525] To form the organic layer, the substrate is placed on a spin-coater with ITO side facing upwards and fixed with vacuum. 4 ml of ink formulation is applied with a syringe with filter (PTFE0.2 m) on the substrate. Spin-coating parameter are 650 rpm (3 sec ramp-up from zero to maximum speed) for 30 sec. The resulting film is dried at 60 C. for 1 minute on a hotplate. Next step is the cleaning of the substrate around the active area (to ensure a good encapsulation before measurement). An additional bake-out at 100 C. for 10 minutes on a hotplate is done. The composition of the organic layer can be seen in Table 4. The formulae of the metal complexes can be seen in Table 1.

[0526] Then, the substrate is transferred to another inert glovebox for encapsulation.

[0527] Then, Biphenyl-4-yl(9,9-diphenyl-9H-fluoren-2-yl)-[4-(9-phenyl-9H-carbazol-3-yl) phenyl]-amine was vacuum deposited on the HIL, to form a first HTL having a thickness of 89 nm.

Technical Effect of the Invention

[0528] In Table 1 are shown the calculated LUMO in electron volt of metal complexes of formula (I). Where more than one spin state is viable, the spin state is stated in brackets. As can be seen in Table 1, the LUMO energy are within the range suitable for organic electronic devices.

[0529] Also in Table 1 are shown calculated LUMO in electron volt of comparative metal complexes CC1 to CC5. The same method was used as for metal complexes of formula (I).

[0530] As can be seen in Table 1, the LUMO energies of known acetyl pyrazolonate compounds CC1-CC3 are closer to vacuum level than LUMO energies of the inventive acetylpyrazolonate compounds.

[0531] Without being bound by theory, a LUMO energies further away from vacuum level is beneficial for improved performance of organic electronic devices.

[0532] In Table 2 are shown data for top emission organic electronic devices fabricated by co-deposition from vacuum of metal complex and matrix compound.

[0533] In comparative example 1-1, a metal complex known in the art is tested at 10 wt.-00.

[0534] As can be seen in Table 2, in comparative example 1-1 the operating voltage is 3.75 V, the external quantum efficiency EQE is 14.5% and the voltage stability over time is 1.988 V.

[0535] In inventive example 1-1, the semiconductor layer comprises a compound of formula (I) MC6. MC6 is a metal complex of formula (I). As can be seen in Table 2, the operating voltage is improved to 3.71 V, cd/A efficiency is 6.5 cd/A, the EQE is 14.4% and operating voltage stability over time is improved to 0.184 V.

[0536] In inventive examples 1-2, the semiconductor layer comprises 15 vol.-% MC6. As can be seen in Table 2, the operating voltage, cd/A efficiency, EQE, and voltage stability over time are further improved.

[0537] In inventive examples 1-3 to 1-5, the semiconductor layer comprises metal complex of formula (I) MC7. As can be seen in Table 2, the operating voltage, cd/A efficiency, EQE, lifetime and/or operating voltage stability over time are improved over comparative example 1-1.

[0538] In inventive examples 1-6 to 1-17 and 1-22 to 1-26, the semiconductor layer comprises metal complexes of formula (I) and various matrix compounds, wherein the HOMO of the matrix compound is further away from vacuum level compared to comparative example 1 and inventive examples 1-1 to 1-5. As can be seen in Table 2, the operating voltage, cd/A efficiency, EQE, lifetime and/or operating voltage stability over time are improved over comparative example 1-1.

[0539] Improvements in performance of inventive organic electronic devices can be observed also in comparison with another prior art metal complex CC5 used as a p-dopant in comparative examples 1-2 to 1-8.

[0540] In inventive examples 1-18 to 1-21, the semiconductor layer consists of metal complex of formula (I). As can be seen in Table 2, the operating voltage, cd/A efficiency, EQE, lifetime and/or operating voltage stability over time are improved over comparative examples 1-1 to 1-8.

[0541] In Table 3 are shown data for organic electronic conductivity devices fabricated by co-deposition from solution of compound of formula (I) and a matrix compound.

[0542] As can be seen in Table 3, a significant conductivity increase of the materials doped with inventive compound MC9 in comparison with undoped matrix compound is obtained.

[0543] A low operating voltage, high efficiency, high lifetime and/or improved operating voltage stability over time are important for the performance and long-term stability of organic electronic devices.

TABLE-US-00002 TABLE 2 Performance of an organic electroluminescent device comprising a semiconductor layer comprising a metal complex of formula 1 Percentage Percentage metal HOMO matrix Vrise complex in level of compound in Semiconductor Voltage Ceff at EQE at LT97 at (1-100 h) semiconductor matrix semiconductor layer at 10 10 10 30 at 30 Metal layer Matrix compound layer thickness mA/cm.sup.2 mA/cm.sup.2 mA/cm.sup.2 mA/cm.sup.2 mA/cm.sup.2 complex [wt.-%] compound [eV] [wt.-%] [nm] [V] [cd/A] [%] [h] [V] Comparative CC4 10 K1 5.04 90 10 3.75 6.5 14.5 136 1.988 example 1-1 Comparative CC5 10 K1 5.04 90 10 3.76 6.5 14.5 117 0.634 example 1-2 Comparative CC5 10 K16 5.14 90 10 3.93 6.8 14.7 31 1.204 example 1-3 Comparative CC5 20 K16 5.14 80 10 3.78 7.0 15.2 43 1.487 example 1-4 Comparative CC5 30 K16 5.14 70 10 3.78 6.8 15.0 24 2.175 example 1-5 Comparative CC5 10 K2 5.19 90 10 4.43 6.2 13.8 11 2.152 example 1-6 Comparative CC5 20 K2 5.19 80 10 4.14 5.7 12.9 8 2.815 example 1-7 Comparative CC5 30 K2 5.19 70 10 3.91 5.9 13.1 8 3.300 example 1-8 Inventive MC6 10 K1 5.04 90 10 3.71 6.5 14.4 103 0.184 example 1-1 Inventive MC6 15 K1 5.04 85 10 3.70 6.6 14.6 89 0.075 example 1-2 Inventive MC7 5 K1 5.04 95 10 3.73 6.5 14.3 110 0.406 example 1-3 Inventive MC7 10 K1 5.04 90 10 3.69 6.5 14.5 90 0.072 example 1-4 Inventive MC7 20 K1 5.04 80 10 3.69 6.5 14.4 91 0.051 example 1-5 Inventive MC6 10 K16 5.14 90 10 3.68 7.1 16.1 77 0.186 example 1-6 Inventive MC6 15 K16 5.14 85 10 3.68 7.2 16.0 76 0.093 example 1-7 Inventive MC6 20 K16 5.14 20 10 3.67 7.2 16.0 75 0.080 example 1-8 Inventive MC7 10 K16 5.14 90 10 3.69 7.3 15.6 78 0.265 example 1-9 Inventive MC7 20 K16 5.14 80 10 3.67 7.2 15.6 75 0.101 example 1-10 Inventive MC7 30 K16 5.14 70 10 3.67 7.3 15.6 71 0.118 example 1-11 Inventive MC56 10 K16 5.14 90 10 3.69 7.5 16.7 75 0.291 example 1-12 Inventive MC6 10 K2 5.19 90 10 3.66 7.1 15.3 187 0.704 example 1-13 Inventive MC6 15 K2 5.19 85 10 3.62 7.1 15.5 115 0.077 example 1-14 Inventive MC7 5 K2 5.19 95 10 3.64 7.0 15.4 121 0.089 example 1-15 Inventive MC7 10 K2 5.19 90 10 3.61 7.0 15.4 118 0.035 example 1-16 Inventive MC7 15 K2 5.19 85 10 3.62 7.0 15.4 121 0.029 example 1-17 Inventive MC6 100 n.a. .sup.1) n.a. n.a. 3 3.71 6.3 14.5 87 0.048 example 1-18 Inventive MC6 100 n.a. n.a. n.a. 5 3.73 6.2 14.7 89 0.012 example 1-19 Inventive MC7 100 n.a. n.a. n.a. 2 3.71 6.6 14.6 79 0.047 example 1-20 Inventive MC7 100 n.a. n.a. n.a. 3 3.71 6.4 14.5 81 0.062 example 1-21 Inventive MC57 6 K16 5.14 94 10 3.72 7.1 15.2 92 0.071 example 1-22 Inventive MC59 4 K16 5.14 96 10 3.90 6.6 14.2 72 0.426 example 1-23 Inventive MC29 8 K16 5.14 92 10 3.88 7.0 14.8 59 0.497 example 1-24 Inventive MC58 12 K16 5.14 88 10 3.74 6.8 14.8 95 0.158 example 1-25 Inventive MC60 4 K16 5.14 96 10 3.74 6.8 14.7 100 0.063 example 1-26 .sup.1) n.a. = not applicable

TABLE-US-00003 TABLE 3 Conductivity of p-doped materials prepared via deposition from solution Percentage metal Percentage matrix complex in compound in Current Metal semiconductor Matrix semiconductor (5 V, 40 m) Conductivity complex layer [wt.-%] compound layer [wt.-%] [A] [S/cm] Comparative example 2-1 none 0 K1 100% 9e6 5.8e11 Inventive example 2-2 MC9 1.78 K1 98.22 0.39 2.58e6 Inventive example 2-2 MC9 5.25 K1 94.75 1.41 9.1e6
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.

Metal Complex, Semiconductor Layer Comprising a Metal Complex and Organic Electronic Device

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C07F3/003

CHEMISTRY; METALLURGY

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H10K85/331

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H10K2101/30

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H10K50/17

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H10K30/86

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C07F15/025

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H10K85/351

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H10K30/60

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C07F1/08

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H10K85/341

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C07F3/00

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C07F1/08

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C07F15/02

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H10K30/86

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H10K85/30

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Abstract

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