CN107698622B - Organic electronic device comprising a layer containing at least one metal-organic compound and at least one metal oxide - Google Patents

Organic electronic device comprising a layer containing at least one metal-organic compound and at least one metal oxide Download PDF

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CN107698622B
CN107698622B CN201610649460.6A CN201610649460A CN107698622B CN 107698622 B CN107698622 B CN 107698622B CN 201610649460 A CN201610649460 A CN 201610649460A CN 107698622 B CN107698622 B CN 107698622B
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CN107698622A (en
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渡部惣一
C·席尔德克内希特
G·瓦根布拉斯特
C·伦纳茨
E·弗茨
O·莫尔特
T·格博纳
K·多尔曼
N·兰格尔
田边润一
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Abstract

The present invention relates to an organic electronic device comprising a first electrode, a second electrode and a first organic layer disposed between the first electrode and the second electrode, wherein the first organic layer comprises at least one metal organic compound and at least one metal oxide. The invention further relates to an apparatus comprising the organic electronic device of the invention.

Description

Organic electronic device comprising a layer containing at least one metal-organic compound and at least one metal oxide
The present application is a divisional application of the patent application having the title "organic electronic device comprising a layer containing at least one metal organic compound and at least one metal oxide", having application No. 201180039004.5, application date 2011, 6/16.
The invention relates to an organic electronic device comprising a first electrode, a second electrode and a first organic layer disposed between the first electrode and the second electrode, wherein the first organic layer comprises at least one metal organic compound and at least one metal oxide. The invention further relates to an apparatus comprising the organic electronic device of the invention.
Organic electrons are a sub-domain of electronics and use electronic circuits comprising polymers or smaller organic compounds. The fields of use of organic electronics are the use of polymers or smaller organic compounds in organic light-emitting diodes (OLEDs), in organic solar cells (organic photovoltaic cells), and in switching elements, for example organic transistors such as organic FETs and organic TFTs.
The use of suitable novel organic materials thus allows the provision of various novel components based on organic electronics, such as displays, sensors, transistors, data memories or photovoltaic cells. This makes it possible to develop new applications that are thin, light, flexible and producible at low cost.
A preferred field of use for this application is the use of smaller organic compounds in organic light emitting diodes.
Organic Light Emitting Diodes (OLEDs) utilize the ability of a material to emit light when excited by an electrical current. OLEDs are of particular interest as alternatives to cathode ray tubes and liquid crystal displays for producing flat video display devices. Due to the very compact design and the inherently low power consumption, devices comprising OLEDs are particularly suitable for mobile applications, such as applications and lighting devices for use in wireless phones, laptops, etc.
The basic principle of the OLED operating method and suitable OLED structures (layers) are described, for example, in WO 2005/113704 and the documents cited therein.
In addition to fluorescent materials (fluorescent emitters), the light-emitting materials (emitters) used may be phosphorescent materials (phosphorescent emitters). In contrast to fluorescent emitters, which exhibit singlet emission, phosphorescent emitters are generally organometallic complexes which exhibit triplet emission (m.a. baldow et al, appl.phys. lett.1999, 75, 4-6). For quantum-mechanical reasons, up to 4 times the quantum efficiency, energy efficiency and power efficiency are possible when phosphorescent emitters are used.
Of particular interest are organic light emitting diodes with long operating life, good efficiency, high stability to thermal stress and low use and operating voltage.
In practice, to achieve the above-mentioned properties, it is necessary not only to provide suitable emitter materials, but also to balance the other components of the OLED (complementary materials) with one another in a suitable device composition. Such device compositions may, for example, comprise a special matrix material in which the actual luminophores are present in distributed form. In addition, the composition also includes a blocker material, and a hole blocker, exciton blocker, and/or electron blocker may be present in the device composition. Additionally or alternatively, the device composition may further comprise a hole injection material and/or an electron injection material and/or a charge transport material such as a hole transport material and/or an electron transport material. The choice of the above-mentioned materials to be used in combination with the actual light emitter has a significant influence on the parameters of the OLED, including efficiency and lifetime and use and operating voltage.
In particular with regard to the reduction of power consumption of devices comprising organic electronic devices, in particular Organic Light Emitting Diodes (OLEDs), is increasing. In order to reduce power consumption, it is attempted to reduce the driving voltage of the organic electronic device. In addition to reducing the drive voltage, it is also important to extend the lifetime of organic electronic devices, especially OLEDs. In the prior art, light emitting elements have been developed to overcome the above problems.
US 2006/0180812 a1 discloses a light-emitting element having a layer containing an organic material and an inorganic material, wherein the activation energy of the conductivity of the layer is 0.01eV or more and less than 0.30 eV. Suitable organic materials are organic compounds comprising an arylamine skeleton and having hole-transporting properties, such as 4,4' -bis (N- {4- [ N, N ' -bis (3-methylphenyl) amino ] phenyl } -N-phenylamino ] biphenyl (DNTPD) and N, N ' -bis (spiro-9, 9' -bifluoren-2-yl) -N, N ' -diphenylbenzidine (BSPB) suitable inorganic materials are metal oxides, in particular molybdenum oxide, vanadium oxide, ruthenium oxide and tungsten oxide US 2006/0180812 a1 mentions that the more the concentration of molybdenum oxide increases, the more the resistance decreases and when the concentration of molybdenum oxide is greater than 80 wt%, the more the resistance increases.
US 2008/0008905 a1 discloses an electrode having a pixel or a pixel portion with a light-transmitting conductive film, which contains a hole-transporting organic compound and a metal oxide showing an electron accepting property with respect to the hole-transporting organic compound. The organic compound is an aromatic amine compound, a carbazole derivative, an aromatic hydrocarbon, and a high molecular weight compound. The inorganic compound is a transition metal oxide, and thus molybdenum oxide is particularly preferable.
DE 102008051132 a1 discloses organic electronic devices with a specific layer sequence. The device comprises a charge transport layer comprising a matrix material comprising a dopant, wherein the matrix material and the dopant form a charge transport complex. In DE 102008051132 a1, suitable matrix materials for the hole transport layer are mentioned. All the materials mentioned are organic materials, in particular aromatic amino compounds. Suitable dopants are, for example, metal oxides.
US 2006/0008740 a1 discloses organic devices comprising organic compounds having charge transport capabilities. The device comprises a layer containing a charge-transporting complex having a charge-transporting complex formed when contacted by lamination or mixing with an organic hole-transporting compound and molybdenum trioxide; wherein the organic hole transporting compound is in a radical cation state in the layer containing the charge transporting complex. Suitable organic hole transport compounds are arylamine compounds.
In the above-described prior art, reduction in power consumption is achieved by using a hole transport layer comprising an organic compound, particularly an arylamine compound, and a metal oxide, particularly (in most cases) molybdenum oxide.
However, there is room for further improvement in terms of reduction in power consumption and extension of the life of organic electronic devices.
It is therefore an object of the present invention to provide organic electronic devices, in particular Organic Light Emitting Diodes (OLEDs), which exhibit a low operating voltage, a good operating life and also a good efficiency and a high stability to thermal stress.
This object is solved by an organic electronic device comprising a first electrode, a second electrode and a first organic layer disposed between the first electrode and the second electrode, wherein the first organic layer comprises at least one metal organic compound and at least one metal oxide.
The organic electronic device of the present invention having a first organic layer comprising at least one metal organic compound and at least one metal oxide exhibits excellent power efficiency, lifetime, quantum efficiency and/or low operating voltage.
Metal oxides
The first organic layer comprises at least one metal oxide, preferably one or two metal oxides, more preferably one metal oxide.
The metal oxide is preferably a transition metal oxide, more preferably an oxide of a metal belonging to group 4,5, 6, 7 or8 of the periodic table. Even more preferably, the metal oxide is selected from the group consisting of rhenium oxide, molybdenum oxide, vanadium oxide, tungsten oxide, niobium oxide, tantalum oxide, chromium oxide, and manganese oxide. The metal may be present in the oxide in each of the appropriate oxidation states. Most preferably, the metal oxide is molybdenum oxide (MoO)x) Or rhenium oxide (ReO)x) In particular MoO3Or ReO3. In particular, ReO is particularly preferred3. The inventors have found that by using ReO3An electronic device having an excellent operating life is obtained.
The metal oxide is generally used in the first organic layer in an amount of 0.1 to <10 wt%, preferably 1-8 wt%, more preferably 3-5 wt%, based on the total amount of the first organic layer (100 wt%). The inventors have found that the optimum amount of metal oxide is present. If more than the optimum amount is used, the operating life of the electronic device is high, but is significantly reduced compared to the optimum amount.
Metal organic compound
The first organic layer comprises at least one metal organic compound, preferably one or two metal organic compounds, more preferably one metal organic compound.
The term "metal organic compound" (or organometallic compound) is generally understood by the skilled person. According to the present invention, the term is to be understood as defined in Inorganic Chemistry (2 nd edition), Gary L.Miesler and Donald A.Tarr, Prentice-Hall (1998), page 422, chapter 13, paragraph 1.
Preferred metal organic compounds are metal organic compounds having hole transporting properties. In the case of OLEDs, the band gap of at least one metal-organic compound having hole-transporting properties is generally greater than the band gap of the emitter material used. In the context of the present application, "band gap" should be understood to mean the triplet energy.
Particularly preferred organometallic compounds are carbene complexes. Suitable carbene complexes are, for example, the carbene complexes described in WO 2005/019373, WO 2006/056418, WO 2005/113704, WO2007/115970, WO 2007/115981 and WO 2008/000727.
Examples of particularly preferred carbene complexes are compounds of the following formula (I):
Figure BDA0001074230950000041
wherein the symbols have the following meanings:
M1is a metal atom selected from the group consisting of Co, Rh, Ir, Nb, Pd, Pt, Fe, Ru, Os, Cr, Mo, W, Mn, Tc, Re, Cu, Ag and Au in any oxidation state possible for the corresponding metal atom;
the carbene is a carbene ligand, which may be uncharged or monoanionic and monodentate, bidentate or tridentate, wherein the carbene ligand may also be a bi-carbene or tri-carbene ligand;
l is a monoanionic or dianionic ligand, which may be monodentate or bidentate;
k is an uncharged monodentate or bidentate ligand selected from: a phosphine; phosphonates and their derivatives, arsenates and their derivatives; a phosphite salt; CO; pyridine; nitriles and with M1Conjugation to form pi complexesA diene;
n is the number of carbene ligands, wherein n is at least 1, and when n >1, the carbene ligands in the complex of formula I may be the same or different;
m is the number of ligands L, where m can be 0 or ≧ 1 and when m >1, the ligands L can be the same or different;
o is the number of ligands K, where o can be 0 or ≧ 1, and when o >1, the ligands K can be the same or different;
wherein the sum of n + m + o depends on the oxidation state and coordination number of the metal atom, and the degree of denticity of the ligands carbene, L and K, and the charge on the ligands carbene and L, with the proviso that n is at least 1.
The carbene complexes are described in WO 2005/19373.
An example of a suitable carbene complex is the facial form of iridium-tris (1, 3-diphenylbenzimidazol-2-ylidene-C, C2') (Ir (dppic) having the formula (Ia)3)：
Figure BDA0001074230950000051
Which is disclosed in WO 2005/19373.
The at least one metal-organic compound, preferably a carbene complex, is generally used in the first organic layer in an amount of >90 to 99.9% by weight, preferably 92 to 99% by weight, more preferably 95 to 97% by weight, based on the total amount of the first organic layer (which is 100% by weight).
First organic layer
The first organic layer comprises at least one metal organic compound and at least one metal oxide. Suitable amounts of the preferred metal organic compounds and preferred metal oxides and metal organic compounds and metal oxides are as described hereinbefore.
The first organic layer is preferably a hole transport layer or a hole injection layer, more preferably a hole transport layer.
The first organic layer preferably comprises:
i)0.1 to<10% by weight, preferably from 1 to 8% by weight, more preferably from 3 to 5% by weight, of a metal oxide,preferably a metal oxide selected from the group consisting of: rhenium oxide, molybdenum oxide, vanadium oxide, tungsten oxide, niobium oxide, tantalum oxide, chromium oxide and manganese oxide in each suitable oxidation state, more preferably molybdenum oxide (MoO)x) Or rhenium oxide (ReO)x) In particular MoO3Or ReO3Most preferably ReO3(ii) a And
ii) >90 to 99.9% by weight, preferably 92 to 99% by weight, more preferably 95 to 97% by weight, of a metal-organic compound, preferably a carbene complex, more preferably a carbene complex of the formula (I), most preferably a carbene complex of the formula (Ia),
wherein the total amount of metal oxide and organometallic compound is 100% by weight.
In a more preferred embodiment, the first organic layer comprises:
i)0.1 to<10 wt.%, preferably 1-8 wt.%, more preferably 3-5 wt.% ReO3(ii) a And
ii) >90 to 99.9% by weight, preferably 92 to 99% by weight, more preferably 95 to 97% by weight, of a carbene complex, preferably a carbene complex of the formula (I), more preferably a carbene complex of the formula (Ia),
wherein the total amount of metal oxide and carbene complex is 100% by weight.
The first organic layer is prepared by any method, for example, by a wet or dry process. The first organic layer can be prepared, for example, by co-evaporation of the metal organic compound and the metal oxide described above. Especially due to ReO3Evaporation is easy in vacuo, and co-evaporation mentioned earlier is the preferred method. However, the first organic layer can also be prepared in such a way that: a solution containing the above-described metal organic compound and metal alkoxide is coated and baked. As the coating method, for example, an inkjet method or a spin coating method can be used. The other organic layers of the electronic device of the invention mentioned below can be prepared in the same manner as the first organic layer.
The first organic layer typically has a thickness of 5-100nm, preferably 20-80 nm.
In another embodiment, the present invention relates to an organic layer, preferably a hole transport layer or a hole injection layer, comprising at least one metal organic compound and at least one metal oxide. Suitable organometallic compounds and metal oxides and suitable amounts are mentioned hereinbefore. Preferably, the hole transport layer or the hole injection layer is a hole transport layer or a hole injection layer in an Organic Light Emitting Diode (OLED).
In one embodiment of the present invention, the organic electronic device further comprises a second organic layer comprising at least one compound of formula (II):
Figure BDA0001074230950000071
wherein:
R1and R2Independently of one another is F, C1-C8Alkyl or may be optionally substituted by one or more C1-C8Alkyl substituted C6-C14Aryl, or
Two substituents R1And/or R2Combined to form a mixture optionally substituted by one or more C1-C8An alkyl-substituted fused benzene ring group,
a and b are each independently of the other 0, or an integer from 1 to 3,
m is an alkali metal atom or an alkaline earth metal atom,
if M is an alkali metal atom, n is 1, and if M is an alkaline earth metal atom, n is 2.
The most preferred metal complexes are
Figure BDA0001074230950000072
(Liq) which may be present as a single species or in other forms, such as LigQg, where g is an integer, such as Li6Q 6. Q represents an 8-hydroxyquinoline ligand or a derivative of 8-hydroxyquinoline.
Preferably, the second organic layer further comprises at least one compound of formula (III), (IVa) and/or (IVb):
Figure BDA0001074230950000073
wherein:
R81、R82、R83、R84、R81’、R82’、R83’and R84’Independently of one another is H, C1-C18Alkyl, C substituted by E and/or interrupted by D1-C18Alkyl radical, C6-C24Aryl, C substituted by G6-C24Aryl radical, C2-C20Heteroaryl, or C substituted by G2-C20(ii) a heteroaryl group, wherein,
q is arylene or heteroarylene, each of which may be optionally substituted with G;
d is-CO-; -COO-; -S-; -SO-; -SO2-；-O-；-NR25-；-SiR30R31-；-POR32-；-CR23＝CR24-; or-C ≡ C-; and is
E is-OR29；-SR29；-NR25R26；-COR28；-COOR27；-CONR25R26(ii) a -CN; or F; g is E, C1-C18Alkyl, C interrupted by D1-C18Alkyl radical, C1-C18Perfluoroalkyl group, C1-C18Alkoxy, or C substituted by E and/or interrupted by D1-C18Alkoxy, wherein:
R23and R24Independently of one another is H, C6-C18An aryl group; quilt C1-C18Alkyl or C1-C18Alkoxy-substituted C6-C18An aryl group; c1-C18An alkyl group; or C interrupted by-O-)1-C18An alkyl group;
R25and R26Independently of one another are C6-C18An aryl group; quilt C1-C18Alkyl or C1-C18Alkoxy-substituted C6-C18An aryl group; c1-C18An alkyl group; or C interrupted by-O-)1-C18An alkyl group; or
R25And R26Together form a 5-or 6-membered ring,
R27and R28Independently of one another are C6-C18An aryl group; quilt C1-C18Alkyl or C1-C18Alkoxy-substituted C6-C18An aryl group; c1-C18An alkyl group; or C interrupted by-O-)1-C18An alkyl group, a carboxyl group,
R29is C6-C18An aryl group; quilt C1-C18Alkyl or C1-C18Alkoxy-substituted C6-C18An aryl group; c1-C18An alkyl group; or C interrupted by-O-)1-C18An alkyl group, a carboxyl group,
R30and R31Independently of one another are C1-C18Alkyl radical, C6-C18Aryl radicals, or by C1-C18Alkyl substituted C6-C18An aryl group, a heteroaryl group,
R32is C1-C18Alkyl radical, C6-C18Aryl radicals, or by C1-C18Alkyl substituted C6-C18And (4) an aryl group. Preferred compounds of formula (III) are compounds of formula (IIIa):
Figure BDA0001074230950000081
wherein Q is:
Figure BDA0001074230950000082
R85is H or C1-C18Alkyl radical, and
R85’is H, C1-C18Alkyl or
Figure BDA0001074230950000083
Most preferred are compounds of formula (IIIaa):
Figure BDA0001074230950000091
wherein:
R89is phenanthryl, pyrenyl, triphenylenyl, 1, 10-phenanthrolinyl, triazinyl, dibenzothienyl, or pyrimidinyl, each of which may optionally be substituted by one or more C1-C18Alkyl radical, C6-C14Aryl or C2-C20A heteroaryl group is substituted by a heteroaryl group,
R90is phenanthryl, pyrenyl, triphenylenyl, 1, 10-phenanthrolinyl, triazinyl, dibenzothienyl, or pyrimidinyl, each of which may optionally be substituted by one or more C1-C18Alkyl radical, C6-C14Aryl or C2-C20A heteroaryl group is substituted by a heteroaryl group,
R91is phenanthryl, pyrenyl, triphenylenyl, 1, 10-phenanthrolinyl, triazinyl, dibenzothienyl, pyrimidinyl or dibenzofuranyl, each of which may optionally be substituted by one or more C1-C18Alkyl radical, C6-C14Aryl or C2-C20A heteroaryl group is substituted by a heteroaryl group,
R92is H, phenanthryl, pyrenyl, triphenylenyl, 1, 10-phenanthrolinyl, triazinyl, dibenzothienyl, or pyrimidinyl, each of which may optionally be substituted with one or more C1-C18Alkyl radical, C6-C14Aryl or C2-C20A heteroaryl group is substituted by a heteroaryl group,
a is a single bond, an arylene or heteroarylene group, each of which may optionally be substituted by one or more C1-C18Alkyl substitution; or-SiR87R88-, wherein R87And R88Independently of one another are C1-C18Alkyl, or may be optionally substituted by one or more C1-C18Alkyl substituted C6-C14And (4) an aryl group.
Preferred compounds of formulae (IVa) and (IVb) are:
Figure BDA0001074230950000092
Figure BDA0001074230950000101
a, R therein89、R90、R91And R92As defined above.
Most preferred are compounds of formula (IVaaa):
Figure BDA0001074230950000102
if possible, C1-C18The alkyl groups are generally linear or branched. Examples are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2-dimethylpropyl, 1,3, 3-tetramethylpentyl, n-hexyl, 1-methylhexyl, 1,3,3,5, 5-hexamethylhexyl, n-heptyl, isoheptyl, 1,3, 3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 1,3, 3-tetramethylbutyl and 2-ethylhexyl, n-nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl or octadecyl. C1-C8Alkyl is typically methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2-dimethyl-propyl, n-hexyl, n-heptyl, n-octyl, 1,3, 3-tetramethylbutyl and 2-ethylhexyl. C1-C4Alkyl is typically methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl.
Optionally substituted C6-C14Aryl is usually phenyl, 4-methylphenyl, 4-methoxyphenyl, naphthyl, especially 1-naphthyl or 2-naphthyl, biphenyl, terphenyl, pyrenyl, 2-or 9-fluorenyl, phenanthryl or anthracenyl, which may be unsubstituted or substituted.
C2-C20Heteroaryl denotes a ring or fused ring having 5 to 7 ring atomsA ring system in which nitrogen, oxygen or sulfur is a possible heteroatom, and is generally a heterocyclic group having 5 to 30 atoms and having at least 6 conjugated pi-electrons, such as thienyl, benzothienyl, dibenzothienyl, thianthrenyl, furyl, furfuryl, 2H-pyranyl, benzofuryl, isobenzofuryl, dibenzofuryl, phenoxythienyl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl, bipyridyl, triazinyl, pyrimidinyl, pyrazinyl, pyridazinyl, indolizinyl, isoindolyl, indolyl, indazolyl, purinyl, quinolizyl, quinolyl, isoquinolyl, phthalazinyl, naphthyridinyl, quinoxalyl, quinazolinyl, cinnolinyl, pteridinyl, carbazolyl, carbolinyl, benzotriazolyl, benzoquinoxalyl, and phenanthridinyl
Figure BDA0001074230950000114
Azolyl, phenanthridinyl, acridinyl, pyrimidinyl, phenanthrolinyl, phenazinyl, isothiazolyl, phenothiazinyl, isothiazinyl
Figure BDA0001074230950000115
Azolyl, furazanyl or thiophenyl
Figure BDA0001074230950000116
An oxazine group, which may be unsubstituted or substituted.
C6-C14Aryl and C2-C20Heteroaryl is preferably substituted by one or more C1-C8Alkyl substitution.
Examples of arylenes are phenylene, naphthylene, phenalene, anthrylene and phenanthrylene, which may optionally be substituted by one or more C1-C18Alkyl substitution. Preferred arylenes are 1, 3-phenylene, 3, 6-naphthylene and 4, 9-phenalene, which may optionally be substituted by one or more C1-C18Alkyl substitution.
Examples of heteroarylenes are 1,3, 4-thiadiazole-2, 5-ylidene, 1, 3-thiazole-2, 4-ylidene, 1, 3-thiazole-2, 5-ylidene, 2, 4-thienylene, 2, 5-thienylene, 1,3-
Figure BDA0001074230950000117
Azole-2, 4-ylidene, 1,3-
Figure BDA0001074230950000118
Oxazole-2, 5-subunit and 1,3,4-
Figure BDA0001074230950000119
Diazole-2, 5-ylidene, 2, 5-indenylidene, 2, 6-indenylidene, especially pyrazinylidene, pyridylidene, pyrimidinylidene and triazolylidene, which may optionally be substituted by one or more C1-C18Alkyl substitution. Preferred heteroarylenes are 2, 6-pyrazinylene, 2, 6-pyridinylene, 4, 6-pyrimidinylene and 2, 6-triazolylene, which may optionally be substituted by one or more C1-C18Alkyl substitution.
In a particularly preferred embodiment, the second organic layer comprises formula (II)
Figure BDA0001074230950000111
(Liq) compounds and formula
Figure BDA0001074230950000112
Mixtures of compounds.
In another particularly preferred embodiment, the second organic layer comprises formula (II)
Figure BDA0001074230950000113
(Liq) compounds and formula
Figure BDA0001074230950000121
Mixtures of compounds.
The organometallic complex of the formula (II) is contained in the second organic layer in an amount of 99 to 1% by weight, preferably 75 to 25% by weight, more preferably about 50% by weight, wherein the amount of compounds of the formulae (II) and (III) or (IVa) or (IVb) amounts to 100% by weight.
The synthesis of compounds of formula (III) is described in J.Kido et al, chem.Commun. (2008)5821-5823, J.Kido et al, chem.Mater.20(2008)5951-5953 and JP2008-127326, or can be carried out analogously to the methods described therein.
The synthesis of compounds of formula (VIa) and (VIb) is described in WO2006128800 or can be carried out analogously to the methods described therein.
The synthesis of the compounds of the formula (II) is described, for example, in Christoph Schmittz et al, chem. Mater.12(2000)3012-3019 and WO00/32717 or can be carried out analogously thereto.
The second organic layer is preferably an electron transport layer.
Organic electronic device
The organic electronic device of the present invention comprises a first electrode, a second electrode, and a first organic layer disposed between the first electrode and the second electrode, wherein the first organic layer comprises at least one metal organic compound and at least one metal oxide. Preferred embodiments of the first organic layer are mentioned above.
Suitable first and second electrodes are known to those skilled in the art.
The organic electronic devices according to the invention are, for example, organic solar cells (organic photovoltaic cells), switching elements such as organic transistors, for example organic Field Effect Transistors (FETs) or organic Thin Film Transistors (TFTs), Organic Light Emitting Field Effect Transistors (OLEFETs) or Organic Light Emitting Diodes (OLEDs), preferably OLEDs.
The structure of suitable organic electronic devices is known to those skilled in the art and is described below. Organic transistor
An organic transistor generally includes a semiconductor layer formed of an organic layer having a hole transporting ability and/or an electron transporting ability; a gate electrode formed of a conductive layer; and an insulating layer introduced between the semiconductor layer and the conductive layer. The source and drain are mounted on this arrangement to thereby produce a transistor element. In addition, other layers known to those skilled in the art may be present in the organic transistor. In a preferred embodiment, the organic layer having hole transport capability comprises at least one metal organic compound and at least one metal oxide. Suitable organometallic compounds and metal oxides and suitable amounts are mentioned hereinbefore.
Organic solar cell
An organic solar cell (photoelectric conversion element) generally includes an organic layer present between two plate-type electrodes arranged in parallel. The organic layer may be disposed on the comb-shaped electrode. There is no particular limitation as to the location of the organic layer, and there is no particular limitation as to the electrode material. However, when parallel plate-type electrodes are used, at least one electrode is preferably formed of a transparent electrode such as an ITO electrode or a fluorine-doped tin oxide electrode. The organic layer is formed of two sublayers, i.e., a layer having p-type semiconductor properties or hole transporting ability and a formation layer having n-type semiconductor properties or electron transporting ability. In addition, other layers known to those skilled in the art may be present in the organic solar cell. In a preferred embodiment, the layer with hole transport capability comprises at least one metal organic compound and at least one metal oxide. Suitable organometallic compounds and metal oxides and suitable amounts are mentioned hereinbefore.
Organic Light Emitting Diode (OLED)
The invention further relates to An organic light-emitting diode comprising An anode An and a cathode Ka, a light-emitting layer E arranged between the anode An and the cathode Ka, a hole-transporting layer and/or a hole-injecting layer arranged between the light-emitting layer E and the anode An, and if appropriate at least one further layer selected from the group consisting of: at least one hole/exciton blocking layer, at least one electron transport layer and at least one electron injection layer, wherein the hole transport layer and/or the hole injection layer comprise at least one metal organic compound and at least one metal oxide. Suitable organometallic compounds and metal oxides and suitable amounts are mentioned hereinbefore.
Structure of OLED of the invention
The Organic Light Emitting Diode (OLED) of the present invention therefore typically has the following structure:
an anode (An) and a cathode (Ka), and a light-emitting layer E interposed between the anode (An) and the cathode (Ka), and a hole-transporting layer and/or a hole-injecting layer interposed between the light-emitting layer E and the anode An.
In a preferred embodiment, the inventive OLED can be formed, for example, from the following layers:
1. anode
2. Hole transport layer
3. Luminescent layer
4. Hole/exciton blocking layers
5. Electron transport layer
6. Cathode electrode
Layer sequences other than the above-described structures are also possible and known to the person skilled in the art. For example, an OLED may not have all of the layers; for example, OLEDs having layers (1), (2), (3), (4) and (6) are likewise possible. In addition, the OLED may have an electron/exciton blocking layer between the hole transport layer (2) and the light-emitting layer (3). In addition, the OLED may have a hole injection layer between the hole transport layer (2) and the light emitting layer.
In addition, a plurality of the above-mentioned functions (electron/exciton blocker, hole injection, hole transport, electron injection, electron transport) can be combined in one layer and present, for example, by a single material present in the layer. For example, in one embodiment, the materials used in the hole transport layer may block both excitons and/or electrons.
Furthermore, in those described above, the individual layers of the OLED may in turn be formed from two or more layers. For example, the hole transport layer may be formed of a layer into which holes are injected from the electrode and a layer which transports the holes from the hole injection layer into the light emitting layer. The electron transport layer may also be composed of multiple layers, for example, a layer into which electrons are injected through an electrode and a layer which accepts electrons from the electron injection layer and transports them into the light emitting layer. Each of the layers is selected based on factors such as energy level, thermal resistance, and charge carrier mobility, and energy difference of the layer from the organic layer or the metal electrode. The person skilled in the art is able to select the structure of the OLED such that it optimally matches the organic compounds used according to the invention as emitter substances.
To obtain a particularly efficient OLED, for example, the HOMO (highest occupied molecular orbital) of the hole transport layer should match the work function of the anode and the LUMO (lowest unoccupied molecular orbital) of the electron transport layer should match the work function of the cathode, provided that the above-mentioned layers are present in the OLED according to the invention.
The anode (1) is an electrode that provides positive charge carriers. It may for example be formed from a material comprising a metal, a mixture of different metals, a metal alloy, a metal oxide or a mixture of different metal oxides. Alternatively, the anode may be a conductive polymer. Suitable metals include metals and alloys of the following metals: main group metals, transition metals and lanthanides, especially metals of groups Ib, IVa, Va and VIa of the periodic table of the elements, and transition metals of group VIIIa. When the anode is to be transparent, mixed metal oxides of groups IIb, IIIb and IVb of the periodic table (IUPAC version) are typically used, for example Indium Tin Oxide (ITO). The anode (1) may likewise comprise an organic material, for example polyaniline, as described, for example, in Nature, Vol. 357, p. 477-479 (1992, 11.6). At least the anode or the cathode should be at least partially transparent in order to be able to emit the light formed. The material for the anode (1) is preferably ITO.
Hole-transporting materials suitable for the OLED layer (2) according to the invention in the case of hole-transporting layers which do not comprise or in addition to at least one metal-organic compound and at least one metal oxide are disclosed, for example, in Kirk-Othmer Encyclopedia of Chemical Technology, 4 th edition, volume 18, page 837-860, 1996. Hole transporting molecules or polymers can be used as hole transporting materials. The hole-transporting molecules usually used are selected from tris [ N- (1-naphthyl) -N- (phenylamino) ] triphenylamine (1-NaphDATA), 4' -bis [ N- (1-naphthyl) -N-phenylamino ] biphenyl (. alpha. -NPD), N ' -diphenyl-N, N ' -bis (3-methylphenyl) - [1,1 ' -biphenyl ] -4, 4' -diamine (TPD), 1-bis [ (di-4-tolylamino) phenyl ] cyclohexane (TAPC), N ' -bis (4-methylphenyl) -N, N ' -bis (4-ethylphenyl) - [1,1 ' - (3,3 ' -dimethyl) biphenyl ] -4,4 '-diamine (ETPD), tetrakis (3-methylphenyl) -N, N, N', N '-2, 5-Phenylenediamine (PDA), alpha-phenyl-4-N, N-diphenylaminostyrene (TPS), p- (diethylamino) benzaldehyde Diphenylhydrazone (DEH), Triphenylamine (TPA), bis [4- (N, N-diethylamino) -2-methylphenyl) (4-methylphenyl) methane (MPMP), 1-phenyl-3- [ p- (diethylamino) styryl ] -5- [ p- (diethylamino) phenyl ] pyrazoline (PPR or DEASP), 1, 2-trans-bis (9H-carbazol-9-yl) cyclobutane (DCZB), N, N, N', n ' -tetrakis (4-methylphenyl) - (1,1 ' -biphenyl) -4, 4' -diamine (TTB), 4' -tris (N, N-diphenylamino) triphenylamine (TDTA), 4' -tris (N-carbazolyl) triphenylamine (TCTA), N ' -bis (naphthalen-2-yl) -N, N ' -bis (phenyl) benzidine (. beta. -NPB), N ' -bis (3-methylphenyl) -N, N ' -bis (phenyl) -9, 9-spirobifluorene (Spiro-TPD), N ' -bis (naphthalen-1-yl) -N, N ' -bis (phenyl) -9, 9-spirobifluorene (Spiro-NPB), N, n '-bis (3-methylphenyl) -N, N' -bis (phenyl) -9, 9-dimethylfluorene (DMFL-TPD), bis [4- (N, N-xylylamino) phenyl ] cyclohexane, N '-bis (naphthalen-1-yl) -N, N' -bis (phenyl) -9, 9-dimethylfluorene, N '-bis (naphthalen-1-yl) -N, N' -bis (phenyl) -2, 2-dimethylbenzidine, N '-bis (naphthalen-1-yl) -N, N' -bis (phenyl) benzidine, N '-bis (3-methylphenyl) -N, N' -bis (phenyl) benzidine, 2,3,5, 6-tetrafluoro-7, 7,8, 8-tetracyanoquinodimethane (F4-TCNQ), 4' -tris (N-3-methylphenyl-N-phenylamino) triphenylamine, 4' -tris (N- (2-naphthyl) -N-phenyl-amino) triphenylamine, pyrazino [2,3-F ] [1,10] phenanthroline-2, 3-dinitrile (PPDN), N, N, N ', N ' -tetrakis (4-methoxyphenyl) benzidine (MeO-TPD), 2, 7-bis [ N, N-bis (4-methoxyphenyl) amino ] -9, 9-spirobifluorene (MeO-Spiro-TPD), 2' -bis [ N, N-bis (4-methoxyphenyl) amino ] -9, 9-spirobifluorene (2,2' -MeO-Spiro-TPD), N ' -diphenyl-N, N ' -bis [4- (N, N-xylylamino) phenyl ] benzidine (NTNPB), N ' -diphenyl-N, N ' -bis [4- (N, N-diphenylamino) phenyl ] benzidine (NPNPNPB), N ' -bis (naphthalen-2-yl) -N, N ' -bistriphenyl-1, 4-diamine (. beta. -NPP), N ' -bis (3-methylphenyl) -N, N ' -bis (phenyl) -9, 9-diphenylfluorene (DPFL-TPD), N ' -bis (naphthalen-1-yl) -N, N ' -bis (phenyl) -9, 9-diphenylfluorene (DPFL-NPB), 2',7,7' -tetrakis (N, N-diphenylamino) -9,9 '-spirobifluorene (Spiro-TAD), 9-bis [4- (N, N-bis (biphenyl-4-yl) amino) phenyl ] -9H-fluorene (BPAPF), 9-bis [4- (N, N-bis (naphthalene-2-yl) amino) phenyl ] -9H-fluorene (NPAPF), 9-bis [4- (N, N-bis (naphthalene-2-yl) -N, N' -bisphenylamino) phenyl ] -9H-fluorene (NPBAPF), 2',7,7' -tetrakis [ N-naphthyl (phenyl) amino ] -9,9' -spirobifluorene (Spiro-2NPB), N, N ' -bis (phenanthren-9-yl) -N, N ' -bis (phenyl) benzidine (PAPB), 2, 7-bis [ N, N-bis (9, 9-spirobifluoren-2-yl) amino ] -9, 9-spirobifluorene (Spiro-5), 2' -bis [ N, N-bis (biphenyl-4-yl) amino ] -9, 9-spirobifluorene (2,2' -spirobifluorene), 2' -bis (N, N-diphenylamino) -9, 9-spirobifluorene (Spiro-BPA), 2',7,7' -tetrakis (N, N-xylyl) aminospirobifluorene (Spiro-TTB), N, N, N ', n' -tetralin-2-yl benzidine (TNB), porphyrin compounds and phthalocyanines such as copper phthalocyanine and titanyl phthalocyanine. Commonly used hole transport materials are selected from polyvinylcarbazole, (phenylmethyl) polysilane and polyaniline. Hole-transporting polymers can also be obtained by doping hole-transporting molecules in polymers such as polystyrene and polycarbonate. Suitable hole-transporting molecules are the molecules already mentioned above.
In addition, in one embodiment, carbene complexes may be used as hole transport materials, wherein the band gap of at least one hole transport material is generally greater than the band gap of the emitter material used. Suitable carbene complexes are mentioned above.
In a preferred embodiment of the present invention, the hole transport layer (2) comprises at least one metal organic compound and at least one metal oxide, wherein the amounts of suitable metal organic compounds and suitable metal oxides and suitable metal organic compounds and suitable metal oxides are mentioned above.
The light-emitting layer (3) comprises at least one emitter material. In principle it can be a fluorescent or phosphorescent dispersion. Suitable emitter materials are known to those skilled in the art. The at least one emitter material is preferably a phosphorescent emitter. The phosphorescent emitter compounds preferably used are of importance based on metal complexes, in particular complexes of the metals Ru, Rh, Ir, Pd and Pt, in particular Ir.
Suitable metal complexes for the OLEDs of the invention are described, for example, in documents WO 02/60910 a1, US 2001/0015432 a1, US 2001/0019782 a1, US 2002/0055014 a1, US 2002/0024293 a1, US 2002/0048689 a1, EP 1191612 a2, EP 1191613 a2, EP 1211257 a2, US 2002/0094453 a1, WO 02/02714 a2, WO 00/70655 a2, WO 01/41512 a1, WO 02/15645 a1, WO 2005/019373 a2, WO 2005/113704 a2, WO 2006/115301 a1, WO 2006/067074 a1, WO 2006/056418, WO 2006121811 a1, WO 2007095118 a2, WO2007/115970, WO 2007/115981 and WO 2008/000727.
Further suitable metal complexes are the commercially available metal complexes tris (2-phenylpyridine) iridium (III), tris (2- (4-tolyl) pyridine-N, C2') Iridium (III), bis (2-phenylpyridine) (acetylacetone) Iridium (III), tris (1-phenylisoquinoline) Iridium (III), bis (2,2' -benzothiophene)pyridine-N, C3') (acetylacetone) iridium (III), tris (2-phenylquinoline) iridium (III), bis (2- (4, 6-difluorophenyl) pyridine-N, C2) Picoline iridium (III), bis (1-phenylisoquinoline) (acetylacetone) iridium (III), bis (2-phenylquinoline) (acetylacetone) iridium (III), bis (di-benzo [ f, h ]]Quinoxaline) (acetylacetone) Iridium (III), bis (2-methyldi-benzo [ f, h)]Quinoxaline) (acetylacetone) iridium (III) and tris (3-methyl-1-phenyl-4-trimethylacetyl-5-pyrazoline) terbium (III), bis [1- (9, 9-dimethyl-9H-fluoren-2-yl) isoquinoline]Iridium (III) acetylacetonate, iridium (III) bis (2-phenylbenzothiazole) (acetylacetonate), iridium (III) bis (2- (9, 9-dihexylfluorenyl) -1-pyridine) (acetylacetonate), and iridium (III) bis (2-benzo [ b ]]Thiophen-2-yl-pyridine) (acetylacetone) iridium (III).
In addition, the following commercially available materials are suitable: tris (dibenzoylacetone) mono (phenanthroline) europium (III), tris (dibenzoylmethane) -mono (phenanthroline) europium (III), tris (dibenzoylmethane) mono (5-aminophenanthryl) -europium (III), tris (di-2-naphthoylmethane) mono (phenanthroline) europium (III), tris (4-bromobenzoylmethane) mono (phenanthroline) europium (III), tris (di (biphenyl) methane) mono (phenanthroline) europium (III), tris (dibenzoylmethane) mono (4, 7-diphenylphenanthroline) europium (III), tris (dibenzoylmethane) mono (4, 7-di-methylphenanthryl) europium (III), tris (dibenzoylmethane) mono (4, 7-dimethylphenanthroline disulfonic acid) europium (III) disodium salt, tris [ bis (2- (2-ethoxyethoxy) ethoxy) benzoylmethane) ] mono (phenanthroline) europium (III) and tris [ bis (biphenyl-ethoxy) methane) [4- (2- (2-ethoxyethoxy) ethoxy) benzoylmethane) ] mono (5-aminophenanthryl) europium (III), osmium (II) bis (3- (trifluoromethyl) -5- (4-tert-butylpyridinyl) -1,2, 4-triazole) diphenylphosphine, osmium (II) bis (3- (trifluoromethyl) -5- (2-pyridyl) -1,2, 4-triazole) dimethylphenylphosphine, osmium (II) bis (3- (trifluoromethyl) -5- (4-tert-butylpyridinyl) -1,2, 4-triazole) dimethylphenylphosphine, osmium (II) bis (3- (trifluoromethyl) -5- (2-pyridyl) pyrazole), Tris [4,4 '-di-tert-butyl (2,2') -bipyridine ] ruthenium (III), osmium (II) bis (2- (9, 9-dibutylfluorenyl) -1-isoquinoline (acetylacetone).
Preferred triplet emitters are carbene complexes. Suitable carbene complexes are known to the person skilled in the art and are described, for example, in WO 2005/019373 a2, WO 2006/056418 a2, WO 2005/113704, WO2007/115970, WO 2007/115981 and WO 2008/000727. Preferred carbene complexes are those of the above formula (I). Particularly preferred carbene complexes are those of the formulae (Ia) and (Ib) described above.
Figure BDA0001074230950000181
The light-emitting layer may comprise other components in addition to the emitter material.
For example, fluorescent dyes may be present in the light-emitting layer to change the emission color of the emitter material. In addition, in a preferred embodiment, a matrix material may be used. The matrix material may be a polymer, such as poly (N-vinylcarbazole) or polysilane. However, the matrix material may be a small molecule, for example 4,4 '-N, N' -dicarbazole biphenyl (CDP ═ CBP) or a tertiary aromatic amine such as TCTA.
Suitable matrix materials, in addition to the above-mentioned matrix materials, are in principle the materials described below as hole-and electron-transporting materials, and also carbon complexes, for example the carbene complexes mentioned in WO 2005/019373. Particularly suitable are carbazole derivatives, such as 4,4' -bis (carbazol-9-yl) -2,2' -dimethylbiphenyl (CDBP), 4' -bis (carbazol-9-yl) biphenyl (CBP), 1, 3-bis (N-carbazolyl) benzene (mCP), and matrix materials described in the following applications: WO2008/034758 and WO 2009/003919.
In addition, dibenzofurans are suitable as matrix materials, for example those disclosed in US 2007/0224446 a1, for example those in which at least one of the radicals R1 to R8 is a heterocyclic group, for example the compounds a-15, and those disclosed in WO 2009/069442 a1, WO 2010/090077 a1 and JP 2006/321750 a.
Other matrix materials based on dibenzofurans are described, for example, in US2009066226, EP1885818B1, EP1970976, EP1998388 and EP 2034538.
Other suitable matrix materials which may be small molecules or (co) polymers of said small molecules are described in the following publications:
WO2007108459(H-1 to H-37), preferably H-20 to H-22 and H-32 to H-37, most preferably H-20, H-32, H-36, H-37, WO 2008035571A 1(Host 1 to Host 6), JP2010135467 (compounds 1 to 46 and Host-1 to Host-39 and Host-43), WO2009008100 compounds No.1 to No.67, preferably No.3, No.4, No.7 to No.12, No.55, No.59, No.63 to No.67, more preferably No.4, No.8 to No.12, No.55, No.59, No.64, No.65 and No.67, WO2009008099 compounds No.1 to No.110, WO2008140114 compounds 1 to 1-50, WO 90912 compounds OC-7 to H-36, Mo-42 to Mo 2009008099, polymers No.1 to No. 19, WO2008140114, Mo-19, WO 20080778 to No. 19, WO 20080776, 20080778 to No. 19, 20080778, Mo-7, and Mo-7, 32. 36, 39-44, WO201001830 polymers of monomers 1-1 to 1-9, preferably 1-3, 1-7 and 1-9, WO2008029729 compounds 1-1 to 1-36, (polymers of) WO20100443342HS-1 to HS-101 and BH-1 to BH-17, preferably BH-1 to BH-17, JP2009182298 based on (co) polymers of monomers 1 to 75, JP2009170764 based on (co) polymers of monomers 1-14, WO2009063757 preferably based on (co) polymers of monomers 1-1 to 1-26, WO2008146838 compounds a-1 to a-43 and 1-1 to 1-46, JP2008207520 based on (co) polymers of monomers 1-1 to 1-26, JP2008066569 based on (co) polymers of monomers 1-1 to 1-16, WO2008029652 based on (co) polymers of monomers 1 to 1-52, WO2007114244 is based on (co) polymers of monomers 1-1 to 1-18, JP2010040830 compounds HA-1 to HA-20, HB-1 to HB-16, HC-1 to HC-23 and (co) polymers based on monomers HD-1 to HD-12, JP2009021336, WO2010090077 compounds 1 to 55, WO2010079678 compounds H1 to H42, WO2010067746, WO2010044342 compounds HS-1 to HS-101 and Poly-1 to Poly-4, JP2010114180 compounds PH-1 to PH-36, US2009284138 compounds 1 to 111 and H1 to H71, WO2008072596 compounds 1 to 45, JP2010021336 compounds H-1 to H-38, preferably H-1, WO2010004877 compounds H-1 to H-60, JP 20067255 compounds 1 to 911-105, WO 20090910281 to 2000492028 compounds WO 2000492028 2009255, WO 20020092863 to 2009286413, WO 20020020020020092673,793,000, JP2009114369 compounds 2-1 to 2-40, JP2009114370 compounds 1 to 67, WO2009060742 compounds 2-1 to 2-56, WO2009060757 compounds 1-1 to 1-76, WO2009060780 compounds 1-1 to 1-70, WO2009060779 compounds 1-1 to 1-42, WO2008156105 compounds 1 to 54, JP2009059767 compounds 1 to 20, JP20080749 compounds 1 to 256, JP2008021687 compounds 1 to 50, WO2007119816 compounds 1 to 37, WO2010087222 compounds H-1 to H-31, WO2010095564 compounds HOST-1 to HOST-61, WO2007108362, WO2009003898, WO2009003919, WO2010040777, US2007224446 and WO 06128800.
In a particularly preferred embodiment, one or more compounds of the general formula (X) described below are used as matrix material. Preferred embodiments of the compounds of the general formula (X) are likewise described below.
In a preferred embodiment, the present invention therefore relates to organic electronic devices, preferably OLEDs, according to the invention which comprise at least one compound of the general formula (X), particularly preferably in combination with a carbene complex as triplet emitter:
Figure BDA0001074230950000201
wherein:
t is NR57S, O or PR57Preferably S or O, more preferably O;
R57is aryl, heteroaryl, alkyl, cycloalkyl or heterocycloalkyl;
q' is-NR58R59、-SiR70R71R72、-P(O)R60R61、-PR62R63、-S(O)2R64、-S(O)R65、-SR66OR-OR67preferably-NR58R59(ii) a More preferably
Figure BDA0001074230950000202
Wherein:
R68、R69each independently is alkyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl; preferably methyl, carbazolyl, dibenzofuranyl or dibenzothiophenyl;
y, z are each independently 0, 1,2,3 or 4, preferably 0 or 1;
R55、R56each independently is alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, SiR70R71R72A group Q' or a group having donor or acceptor action;
a "is 0, 1,2,3 or 4;
b' is 0, 1,2 or 3;
R58、R59together with the nitrogen atom, form a cyclic group having 3 to 10 ring atoms, which may be unsubstituted or substituted by one or more substituents selected from alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl and groups having donor or acceptor properties; and/or one or more further cyclic groups having 3 to 10 ring atoms can be fused, wherein the fused groups can be unsubstituted or substituted by one or more substituents selected from alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl and groups having donor or acceptor properties;
R70、R71、R72、R60、R61、R62、R63、R64、R65、R66、R67each independently is aryl, heteroaryl, alkyl, cycloalkyl or heterocycloalkyl,
or
The two units of the formula (X) are bridged to each other by a bond or by O via a linear or branched, saturated or unsaturated bridge, optionally interrupted by at least one heteroatom.
Preferred are compounds of formula (X) wherein:
t is S or O, preferably O, and
q' is
Figure BDA0001074230950000211
Wherein:
R68、R69each independently is alkyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl; preferably methyl, carbazolyl, dibenzofuranyl or dibenzothiophenyl;
y, z are each independently 0, 1,2,3 or 4, preferably 0 or 1.
Particularly preferred compounds of formula (X) have the following formula (Xa):
Figure BDA0001074230950000212
wherein the symbols and indices Q', T, R55、R56A 'and b' are each as defined above.
Very particularly preferred compounds of the formula (X) have the formula (Xaa):
Figure BDA0001074230950000221
wherein the symbols and the index R68、R69、y、z、T、R55、R56A 'and b' are each as defined above.
In a very particularly preferred embodiment, in formula (Xaa):
t is O or S, preferably O;
a' is 1;
b' is 0;
y, z are each independently 0 or 1; and is
R68、R69Each independently is methyl, carbazolyl, dibenzofuranyl or dibenzothiophenyl,
R55is a substituted phenyl, carbazolyl, dibenzofuranyl or dibenzothiophenyl group.
Another very particularly preferred compound of formula (X) has the formula (Xab):
Figure BDA0001074230950000222
wherein the symbols and the index R68、R69y、z、T、R55、R56A "and b' each independently have the meaning described above.
In a particularly preferred embodiment, the symbols and indices in formula (Xab) have the following meanings: t is O or S, preferably O;
a' is 0;
b' is 0;
y, z are independently 0 or 1; and is
R68、R69Independently a methyl group, a carbazolyl group, a dibenzofuranyl group, or a dibenzothiophenyl group.
Particularly preferred compounds of formula (Xab) are the following:
Figure BDA0001074230950000231
wherein T is O or S, preferably O.
The compounds of formula (X) can be prepared, for example, as described in WO2010079051, WO2007/077810, JP2009267255, respectively US20090017331 a1) and WO2009/003898 or analogously to the preparation methods described in the above-mentioned documents.
In a further preferred embodiment of the present invention, at least one compound of the formula (V) is used as matrix material, particularly preferably together with a carbene complex as triplet emitter:
Figure BDA0001074230950000232
wherein:
x is NR, S, O or PR;
r is aryl, heteroaryl, alkyl, cycloalkyl or heterocycloalkyl;
a is-NR6R7、-P(O)R8R9、-PR10R11、-S(O)2R12、-S(O)R13、-SR14OR-OR15；R1、R2And R3Independently of one another, are aryl, heteroaryl, alkyl, cycloalkyl or heterocycloalkyl, where the radicals R1、R2Or R3At least one is aryl or heteroaryl;
R4and R5Independently of one another, alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, the radical A or with a donor orA group characteristic of the acceptor;
n and m are independently of each other 0, 1,2 or 3;
R6、R7together with the nitrogen atom, form a cyclic group having 3 to 10 ring atoms, which may be unsubstituted or substituted by one or more substituents selected from alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl and groups having donor or acceptor properties; and/or it may be fused to one or more other cyclic groups having 3 to 10 ring atoms, wherein the fused groups may be unsubstituted or may be substituted by one or more substituents selected from alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl and groups having donor or acceptor properties; and is
R8、R9、R10、R11、R12、R13、R14And R15Independently of one another, aryl, heteroaryl, alkyl, cycloalkyl or heterocycloalkyl.
The compounds of formula (V) are described in WO2010079051(PCT/EP 2009/067120).
For compounds of the formula (X), especially for R55-R77Radicals, and for compounds of the formula (V), especially for R1-R15Group (b):
the terms aryl or group, heteroaryl or group, alkyl or group, cycloalkyl or group, heterocycloalkyl or group, alkenyl or group, alkynyl or group and group having donor and/or acceptor action are each defined as follows:
aryl (or group) is understood to mean a group having a basic skeleton of from 6 to 30 carbon atoms, preferably from 6 to 18 carbon atoms, and formed by an aromatic ring or by a plurality of fused aromatic rings. Suitable basic skeletons are, for example, phenyl, naphthyl, anthryl or phenanthryl, indenyl or fluorenyl. The base skeleton may be unsaturated (which means that all substitutable carbon atoms carry hydrogen atoms), or may be substituted at one, more than one or all substitutable positions of the base skeleton.
Suitable substituents are, for example, deuterium, alkoxy, aryloxy, alkylamino, arylamino, carbazolyl, silyl,SiR78R79R80Suitable silyl SiRs78R79R80Described hereinafter, alkyl, preferably alkyl having 1 to 8 carbon atoms, more preferably methyl, ethyl or isopropyl, aryl, preferably C6Aryl, which in turn may be substituted or unsubstituted, heteroaryl, preferably heteroaryl comprising at least one nitrogen atom, more preferably pyridyl and carbazolyl, alkenyl, preferably alkenyl with one double bond, more preferably alkenyl with one double bond and 1-8 carbon atoms, alkynyl, preferably alkynyl with one triple bond, more preferably alkynyl with one triple bond and 1-8 carbon atoms, or a group with donor or acceptor action. Suitable groups having donor or acceptor action are described below. Most preferably, the substituted aryl group bears a substituent selected from the group consisting of methyl, ethyl, isopropyl, alkoxy, heteroaryl, halogen, pseudohalogen and amino, preferably arylamino. Aryl or aryl groups are preferably C6-C18Aryl, more preferably C6Aryl, which is optionally substituted with at least one or more than one of the substituents described above. C6-C18Aryl, preferably C6Aryl more preferably has 0, 1,2,3 or 4, most preferably 0, 1 or 2 of the above substituents.
Heteroaryl or heteroaryl groups are understood to mean groups which differ from the abovementioned aryl radicals in that at least one carbon atom is replaced by a heteroatom in the basic skeleton of the aryl radical and the basic skeleton of the heteroaryl radical preferably has from 5 to 18 ring atoms. Preferred heteroatoms are N, O and S. Particularly preferred suitable heteroaryl groups are nitrogen-containing heteroaryl groups. Most preferably one or two carbon atoms of the basic skeleton are substituted by a heteroatom, preferably nitrogen. It is particularly preferred that the basic skeleton is selected from systems such as pyridine, pyrimidine and 5-membered heteroaromatic compounds such as pyrrole, furan, pyrazole, imidazole, thiophene,
Figure BDA0001074230950000251
Oxazole, thiazole, triazole. In addition, the heteroaryl group may be a condensed ring system, for example, a benzofuranyl group, a benzothienyl group, a benzopyrolyl group, a dibenzofuranyl group, a dibenzothienyl group, a phenanthrolinyl group, a carbazolyl group, an azacarbazolyl groupOr diazacarbazolyl. The basic skeleton may be substituted at one, more than one or all substitutable positions of the basic skeleton. Suitable substituents are the same as already described for aryl.
Alkyl or alkyl group is to be understood as meaning a group having from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms, more preferably from 1 to 8 carbon atoms, most preferably from 1 to 4 carbon atoms. The alkyl groups may be branched or unbranched and may optionally be interrupted by one or more heteroatoms, preferably Si, N, O or S, more preferably N, O or S. In addition, the alkyl group may be substituted with one or more substituents as described for the aryl group. In addition, the alkyl groups present according to the invention can have at least one halogen atom, for example F, Cl, Br or I, in particular F. In another embodiment, the alkyl groups present according to the present invention may be fully fluorinated. Likewise, an alkyl group may carry one or more (hetero) aryl groups. In the context of the present application, for example benzyl is alkyl which is thus substituted. In this context, all of the above (hetero) aryl groups are suitable. The alkyl group is more preferably selected from the group consisting of methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl and tert-butyl, very particularly preferably methyl and ethyl.
Cycloalkyl or cycloalkyl groups are to be understood as meaning groups having from 3 to 20 carbon atoms, preferably from 3 to 10 carbon atoms, more preferably from 3 to 8 carbon atoms. The basic skeleton may be unsubstituted (which means that all substitutable carbon atoms carry hydrogen atoms) or may be substituted in one, more than one or all substitutable positions of the basic skeleton. Suitable substituents are the groups already described above for aryl. Likewise, a cycloalkyl group may carry one or more (hetero) aryl groups. Examples of suitable cycloalkyl groups are cyclopropyl, cyclopentyl and cyclohexyl.
Heterocycloalkyl or heterocycloalkyl groups are understood to mean groups which differ from the above-mentioned cycloalkyl groups in that at least one carbon atom is replaced by a heteroatom in the basic skeleton of the cycloalkyl group. Preferred heteroatoms are N, O and S. Most preferably, one or two carbon atoms of the cycloalkyl backbone are substituted with a heteroatom. Examples of suitable heterocycloalkyl radicals are those derived from pyrrolidine, piperidine, piperazine, tetrahydrofuran, bis
Figure BDA0001074230950000261
The radical of an alkane.
Alkenyl or alkenyl group is understood to mean groups which correspond to the abovementioned alkyl groups having at least two carbon atoms, with the difference that at least one C-C single bond of the alkyl group is replaced by a C-C double bond. The alkenyl group preferably has one or two double bonds.
Alkynyl or alkynyl group is understood to mean a group corresponding to the above-mentioned alkyl groups having at least two carbon atoms, with the difference that at least one C-C single bond of the alkyl group is replaced by a C-C triple bond. Alkynyl groups preferably have one or two triple bonds.
SiR78R79R80The radicals are understood to mean silyl radicals, in which: r78、R79And R80Each independently is alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl OR OR73。
SiR74R75R76The radicals are understood to mean silyl radicals, in which: r74、R75And R76Each independently is alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl OR OR73。
In the context of the present application, a group or substituent having donor or acceptor action is understood to mean the following groups:
a group having a donor action is understood to mean a group having a + I and/or + M effect, and a group having an acceptor action is understood to mean a group having an-I and/or-M effect. Preferred suitable groups are selected from C1-C20Alkoxy radical, C6-C30Aryloxy radical, C1-C20Alkylthio radical, C6-C30Arylthio, SiR81 ' R82 ' R83 ', OR73Halogen group, halogeno C1-C20Alkyl, carbonyl (-CO (R81 ")), carbonylthio (-C ═ O (SR 81")), carbonyloxy (-C ═ O (OR81 ")), oxycarbonyl (-OC ═ O (R81")), thiocarbonyl (-SC ═ O (R81 ")), amino (-NR 81" R82 "), pseudohalogen group, amido (-C ═ O (NR 81")), -NR81 "C ═ O (R83"), phosphonate (-p (O)) (OR81 ")2Phosphoric acid esters(-OP(O)(OR81”)2) Phosphine (-PR81 "R82"), phosphine oxide (-P (O) R81) "2) Sulfuric acid ester (-OS (O)2OR81 "), sulfoxide (-S (O) R81"), sulfonate (-S (O)2OR81 "), sulfo (-S (O)2R81', sulfamide (-S (O))2NR81”R82”)、NO2Boronic acid ester (-OB (OR 81')2) Imino (-C ═ NR81 "R82")), boryl, stannyl, hydrazino, hydrazone, oxime, nitroso, bisazo, vinyl, sulfoximine, alane, germane, boroxine, and borazine.
The radicals R81 ", R82" and R83 "mentioned in the above-mentioned groups having donor or acceptor action are each independently:
substituted or unsubstituted C1-C20Alkyl or substituted or unsubstituted C6-C30Aryl, OR OR76Suitable and preferred alkyl and aryl groups are as described above. The radicals R81 ', R82 ' and R83 ' are more preferably C1-C6Alkyl groups, such as methyl, ethyl or isopropyl, or phenyl. In a preferred embodiment, in the case of SiR81 "R82" R83 ", R81", R82 "and R83" are preferably each independently substituted or unsubstituted C1-C20Alkyl or substituted or unsubstituted aryl, preferably phenyl.
Preferred substituents having donor or acceptor action are selected from:
C1-C20alkoxy, preferably C1-C6Alkoxy, more preferably ethoxy or methoxy; c6-C30Aryloxy radical, preferably C6-C10Aryloxy, more preferably phenoxy; SiR81 "R82" R83 ", for which R81", R82 "and R83" are preferably each independently a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, preferably phenyl; more preferably at least one of the groups R81 ", R82" and R83 "is a substituted or unsubstituted phenyl group, suitable substituents being as described above; halogen radicals, preferably F, Cl, more preferably F, halogeno C1-C20Alkyl, preferably halo C1-C6Alkyl, most preferably fluorinated C1-C6Alkyl radicals, e.g. CF3、CH2F、CHF2Or C2F5(ii) a An amino group, preferably a dimethylamino group, a diethylamino group, or a diarylamino group, more preferably a diarylamino group; pseudohalogen radicals, preferably CN, -C (O) OC1-C4Alkyl, preferably-C (O) OMe, P (O) R2Preferably P (O) Ph2。
Very particularly preferred substituents having donor or acceptor action are selected from methoxy, phenoxy, halogeno C1-C4Alkyl, preferably CF3、CH2F、CHF2、C2F5Halogen, preferably F, CN, SiR81 "R82" R83 ", suitable radicals R81", R82 "and R83" are as already described, diarylamino groups (NR84 "R85", in which R84 ", R85" are each C6-C30Aryl group, -C (O) OC1-C4Alkyl, preferably-C (O) OMe, P (O) Ph2。
Halogen groups are preferably understood to mean F, Cl and Br, more preferably F and Cl, most preferably F.
Pseudohalogen groups are preferably understood to mean CN, SCN and OCN, more preferably CN.
The above groups having donor or acceptor action do not exclude the possibility that other groups and substituents mentioned herein but not included in the above groups having donor or acceptor action have donor or acceptor action.
The aryl or group, heteroaryl or group, alkyl or group, cycloalkyl or group, heterocycloalkyl or group, alkenyl or group and the group having donor and/or acceptor action as described above may be substituted or unsubstituted. In the context of the present application, unsubstituted radicals are understood to mean radicals in which the substitutable atoms of the radical carry hydrogen atoms. In the context of the present application, a substituent group is understood to mean a group in which one or more substitutable atoms carry a substituent in place of a hydrogen atom in at least one position. Suitable substituents are those described above for aryl groups or groups.
When groups having the same numbering appear more than once in the compounds of the present application, these groups may each independently have the definitions described.
The group T in the compound of formula (X) is NR57S, O or PR57Preferably NR57S or O, more preferably O or S, most preferably O. The group X in formula (V) is NR, S, O or PR, more preferably O or S, most preferably O.
R57The group is aryl, heteroaryl, alkyl, cycloalkyl or heterocycloalkyl, preferably aryl, heteroaryl or alkyl, more preferably aryl, wherein the above groups may be unsubstituted or substituted. Suitable substituents are as described above. R57More preferred is a phenyl group which may be substituted or unsubstituted with the above-mentioned substituent. R57Most preferred is unsubstituted phenyl.
The R group is aryl, heteroaryl, alkyl, cycloalkyl or heterocycloalkyl, wherein the above groups may be unsubstituted or substituted. Suitable substituents are as described above. More preferably, R is a phenyl group which may be substituted or unsubstituted with the above-mentioned substituent. Most preferably, R is unsubstituted phenyl.
The group Q' in the compound of formula (X) is-NR58R59、-P(O)R60R61、-PR62R63、-S(O)2R64、-S(O)R65、-SR66OR-OR67(ii) a Preferably NR58R59、-P(O)R60R61OR-OR67More preferably-NR58R59。
The A group in the compound of formula (V) is-NR6R7、-P(O)R8R9、-PR10R11、-S(O)2R12、-S(O)R13、-SR14OR-OR15preferably-NR6R7、-P(O)R8R9OR-OR15More preferably-NR6R7。
R58-R67And R74-R76And R6-R15The groups are each defined as follows:
R58、R59、R6、R7together with nitrogen atoms to form a ring having 3-10A cyclic group of ring atoms, which may be unsubstituted or substituted by one or more substituents selected from alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl and groups having donor or acceptor properties; and/or one or more further cyclic groups having 3 to 10 ring atoms can be fused, wherein the fused groups can be unsubstituted or substituted by one or more substituents selected from alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl and groups having donor or acceptor properties;
R60、R61、R62、R63、R64、R65、R66、R67、R74、R75、R76、R8、R9、R10、R11、R12、R13、R14、R15each independently is aryl, heteroaryl, alkyl, cycloalkyl or heterocycloalkyl, preferably aryl or heteroaryl, wherein the groups may be unsubstituted or substituted with one or more groups selected from: alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl and groups having donor or acceptor action, more preferably unsubstituted or substituted phenyl, suitable substituents being as described above, for example tolyl or a group of the formula:
Figure BDA0001074230950000291
wherein the groups T and R70、R71And R72Each group is independently as defined for the compound of formula (X).
R60、R61、R62、R63、R64、R65、R66And R67And R8、R9、R10、R11、R12、R13、R14、R15Most preferably each independently phenyl, tolyl, or a group of the formula:
Figure BDA0001074230950000292
wherein T is NPh, S or O.
Preferably suitable-NR58R59Group and-NR6R7Examples of groups are selected from pyrrolyl, 2, 5-dihydro-1-pyrrolyl, pyrrolidinyl, indolyl, indolinyl, isoindolinyl, carbazolyl, azacarbazolyl, diazacazolyl, imidazolyl, imidazolinyl, benzimidazolyl, pyrazolyl, indazolyl, 1,2, 3-triazolyl, benzotriazolyl, 1,2, 4-triazolyl, tetrazolyl, 1,3-
Figure BDA0001074230950000293
Azolyl, 1, 3-thiazolyl, piperidinyl, morpholinyl, 9, 10-dihydroacridinyl and 1,4-
Figure BDA0001074230950000294
(ii) an oxazinyl group, wherein the above-mentioned groups may be unsubstituted or substituted by one or more substituents selected from the group consisting of alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl and a group having donor or acceptor action; -NR6R7Group and-NR58R59The radicals are independently preferably selected from carbazolyl, pyrrolyl, indolyl, imidazolyl, benzimidazolyl, azacarbazolyl and diazacarbazolyl, wherein the above-mentioned radicals may be unsubstituted or substituted by one or more substituents selected from alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl and a group having donor or acceptor action; -NR58R59Group and-NR6R7The groups are more preferably independently carbazolyl, which may be unsubstituted or substituted with one or more substituents selected from the group consisting of alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl and a group having donor or acceptor action.
Particularly preferred is-NR58R59and-NR6R7The groups are:
Figure BDA0001074230950000301
wherein:
R68、R69each independently is alkyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl; preferably methyl, carbazolyl, dibenzofuranyl or dibenzothiophenyl;
y, z are each independently 0, 1,2,3 or 4, preferably 0 or 1;
for example:
Figure BDA0001074230950000302
wherein X and T are independently NPh, S or O;
Figure BDA0001074230950000311
wherein T is NPh, S or O,
Figure BDA0001074230950000312
r in the Compound of formula (X)55、R56And R in the compound of formula (V)4、R5Each independently is alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, other A groups or groups having donor or acceptor action; preferably each independently of the others, an alkyl group, an aryl group, a heteroaryl group or a group having donor or acceptor action. For example R55Or R56Or R4Or R5May each independently be:
Figure BDA0001074230950000321
wherein T is NPh, S or O.
In the compounds of the formula (X), a 'R's may be present55Group and/or b' R56A group, wherein a "and b' are:
a "is 0, 1,2,3 or 4; preferably independently 0, 1 or 2;
b' is 0, 1,2 or 3; preferably independently 0, 1 or 2.
Most preferably at least a "or b ' is 0, very particularly preferably a" and b ' are each 0 or a "is 1 and b ' is 0.
In the compounds of the formula (V), m R may be present4A group and/or n' R5A group, wherein m and n are:
m is 0, 1,2,3 or 4; preferably independently 0, 1 or 2;
n is 0, 1,2 or 3; preferably independently 0, 1 or 2.
Most preferably at least m or n is 0, very particularly preferably m and n are each 0 or m is 1 and n is 0.
Other preferred compounds of the formula (V) correspond to the following formula (XI):
Figure BDA0001074230950000322
wherein:
R70、R71、R72each independently is aryl, heteroaryl, alkyl, cycloalkyl or heterocycloalkyl.
Preferred examples of compounds of formula (V) are:
Figure BDA0001074230950000331
the compounds are described in WO2010079051(PCT/EP 2009/067120; in particular the tables on pages 19 to 26, and on pages 27 to 34, 35 to 37 and 42 to 43).
Examples of particularly preferred matrix materials are shown below:
Figure BDA0001074230950000332
Figure BDA0001074230950000341
Figure BDA0001074230950000351
in the above compounds, T is O or S, preferably O. If T occurs more than 1 time in the molecule, all radicals T have the same meaning.
In addition, the light-emitting layer may comprise further carbene complexes as additional or only matrix material and/or as additional emitter material. Suitable further carbene complexes are the same carbene complexes as described above, in particular carbene complexes of the formula (I).
In a preferred embodiment, the light-emitting layer is formed from 2 to 70% by weight, preferably 5 to 40% by weight, of at least one of the abovementioned emitter materials and 30 to 98% by weight, preferably 60 to 95% by weight, of the abovementioned matrix material, in one embodiment of at least one compound of the formula (V), the sum of the emitter material and matrix material adding up to 100% by weight.
In a preferred embodiment, the light-emitting layer comprises at least one of the abovementioned matrix materials-in one embodiment compounds of the formula (V) -for example
Figure BDA0001074230950000361
And two carbene complexes, preferably of the formula:
Figure BDA0001074230950000362
in this embodiment, the light-emitting layer consists of 2 to 40% by weight, preferably 5 to 35% by weight
Figure BDA0001074230950000363
And 60 to 98% by weight, preferably 65 to 95% by weight, of at least one of the abovementioned matrix materials-in one embodiment compounds of the formula (V) -and
Figure BDA0001074230950000364
form, wherein the carbene complexAnd the sum of at least one of the abovementioned matrix materials-in one embodiment the compounds of the formula (V) -adds to 100% by weight.
In a preferred embodiment, the light-emitting layer comprises at least one of the abovementioned matrix materials, as described below in one embodiment compounds of the formula (V), as matrix material and one or two carbene complexes, preferably of the formula (Ia) and/or (Ib).
In a further embodiment, at least one of the above-described matrix materials, such as the compounds of the formula (V) in one embodiment described below, is used as hole/exciton blocker material, preferably together with a carbene complex as triplet emitter. At least one of the above-mentioned matrix materials, such as the compounds of the formula (V) in one embodiment described below, can also be used as matrix material and hole/exciton blocker material together with carbene complexes as triplet emitters.
If the hole/exciton blocking layer (4) does not comprise any of the above-mentioned matrix materials-or in addition to any of the above-mentioned matrix materials-in one embodiment as described below-any of the compounds of formula (V) in one embodiment as described below-the OLED has-if a hole blocking layer is present-hole blocker materials customary in OLEDs, for example 2, 6-bis (N-carbazolyl) pyridine (mCPy), 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline (bathocuproin, (BCP)), bis (2-methyl-8-quinoline) -4-phenylphenyl) aluminium (III) (BAIq), phenothiazine S, S-dioxide derivatives and 1,3, 5-tris (N-phenyl-2-benzylimidazolyl) benzene (TPBI), TPBI is also suitable as an electron conducting material. Other suitable hole blockers and/or electron transport materials are 2,2' - (1,3, 5-benzenetriyl) tris (1-phenyl-1-H-benzimidazole), 2- (4-biphenylyl) -5- (4-tert-butylphenyl) -1,3,4-
Figure BDA0001074230950000371
Diazole, 8-hydroxyquinoline lithium, 4- (naphthalen-1-yl) -3, 5-diphenyl-4H-1, 2, 4-triazole, 1, 3-bis [2- (2,2' -bipyridin-6-yl) -1,3,4-
Figure BDA0001074230950000372
Diazol-5-yl]Benzene, 4, 7-diphenyl-1, 10-phenanthroline,3- (4-biphenylyl) -4-phenyl-5-tert-butylphenyl-1, 2, 4-triazole, 6' -bis [5- (biphenyl-4-yl) -1,3,4-
Figure BDA0001074230950000373
Diazol-2-yl]2,2 '-bipyridine, 2-phenyl-9, 10-di (naphthalen-2-yl) anthracene, 2, 7-bis [2- (2,2' -bipyridin-6-yl) -1,3,4-
Figure BDA0001074230950000374
Diazol-5-yl]-9, 9-dimethylfluorene, 1, 3-bis [2- (4-tert-butylphenyl) -1,3,4-
Figure BDA0001074230950000375
Diazol-5-yl]Benzene, 2- (naphthalen-2-yl) -4, 7-diphenyl-1, 10-phenanthroline, tris (2,4, 6-trimethyl-3- (pyridin-3-yl) phenyl) borane, 2, 9-bis (naphthalen-2-yl) -4, 7-diphenyl-1, 10-phenanthroline, 1-methyl-2- (4- (naphthalen-2-yl) phenyl) -1H-imidazo [4, 5-f-l][1,10]Phenanthroline. In another embodiment, compounds comprising aromatic or heteroaromatic rings linked via a carbonyl-containing group as described in WO2006/100298 may be used, selected from the following disilyl compounds: disilylcarbazoles, disilylbenzofurans, disilylbenzothiophenes, disilylbenzophospholes, disilylbenzothiophen S-oxides and disilylbenzothiophen S, S-dioxides, as described, for example, in WO2009003919(PCT/EP2008/058207) and WO2009003898(PCT/EP2008/058106), and disilyl compounds as described in WO2008/034758 as hole/exciton blocking layers (4) or as matrix materials in the light-emitting layer (3).
In a preferred embodiment, the present invention relates to an OLED according to the invention comprising the layers: (1) an anode, (2) a hole-transporting layer, (3) a light-emitting layer, (4) a hole/exciton-blocking layer, (5) an electron-transporting layer and (6) a cathode, and, if appropriate, further layers, wherein the hole-transporting layer comprises at least one metal-organic compound and at least one metal oxide. Suitable organometallic compounds and metal oxides and suitable amounts are mentioned hereinbefore.
Suitable electron-transporting materials for the layer (5) of the OLED of the invention comprise metals chelated with a like octyl compound, for exampleSuch as 2,2' - (1,3, 5-phenylene) tris [ 1-phenyl-1H-benzimidazole](TPBI), tris (8-hydroxyquinoline) aluminum (Alq)3) Phenanthroline-based compounds such as 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline (DDPA ═ BCP) or 4, 7-diphenyl-1, 10-phenanthroline (DPA), and azole compounds such as 2- (4-biphenyl) -5- (4-tert-butylphenyl) -1,3,4-
Figure BDA0001074230950000381
Oxadiazole (PBD) and 3- (4-Biphenyl) -4-phenyl-5- (4-tert-butylphenyl) -1,2, 4-Triazole (TAZ), lithium 8-quinolinolate (Liq), 4, 7-diphenyl-1, 10-phenanthroline (BPhen), bis (2-methyl-8-quinoline) -4- (phenylphenol) aluminium (BALq), 1, 3-bis [2- (2,2' -bipyridin-6-yl) -1,3,4-
Figure BDA0001074230950000382
Diazol-5-yl]Benzene (Bpy-OXD), 6' -bis [5- (biphenyl-4-yl) -1,3,4-
Figure BDA0001074230950000383
Diazol-2-yl]-2,2 '-bipyridine (BP-OXD-Bpy), 4- (naphthalen-1-yl) -3, 5-diphenyl-4H-1, 2, 4-triazole (NTAZ), 2, 9-bis (naphthalen-2-yl) -4, 7-diphenyl-1, 10-phenanthroline (NBphen), 2, 7-bis [2- (2,2' -bipyridin-6-yl) -1,3,4-
Figure BDA0001074230950000384
Diazol-5-yl]-9, 9-dimethylfluorene (by-FOXD), 1, 3-bis [2- (4-tert-butylphenyl) -1,3,4-
Figure BDA0001074230950000385
Diazol-5-yl]Benzene (OXD-7), tris (2,4, 6-trimethyl-3- (pyridin-3-yl) phenyl) borane (3TPYMB), 1-methyl-2- (4- (naphthalen-2-yl) phenyl) -1H-imidazo [4,5-f [ ]][1,10]Phenanthroline (2-NPIP), 2-phenyl-9, 10-di (naphthalen-2-yl) anthracene (PADN), 2- (naphthalen-2-yl) -4, 7-diphenyl-1, 10-phenanthroline (HNBphen). Layer (5) may be used to facilitate electron transport and as a buffer or blocking layer to prevent quenching of excitons at layer interfaces of the OLED. Layer (5) preferably improves electron mobility and reduces exciton quenching. In a preferred embodiment, TPBI is used as the electron conductor material. In principle the electron-conductor layer may compriseAt least one compound of the formula (V) as electron conductor material.
In a preferred embodiment, the electron transport layer (5) of the OLED of the invention comprises an organometallic complex of the formula (II) and preferably a compound of the formula (III), (IVa) or (IVb). The layer (5) preferably improves the mobility of electrons. The compounds of formulae (II), (III), (IVa) and (IVb) and suitable amounts of said compounds in the organic layer, especially in the electron transport layer, are mentioned above.
Among the above-described materials as the hole transport material and the electron transport material, some may perform a plurality of functions. For example, when they have a low HOMO, then some of the electron transport materials are simultaneously hole blocking materials. These can be used, for example, in the hole/exciton blocking layer (4).
The charge transport layer can also be electron doped to improve the transport properties of the materials used, firstly to make the layer thickness thicker (to avoid pinholes/short circuits) and secondly to minimize the operating voltage of the device. For example, the hole transport material may be doped with an electron acceptor; for example, phthalocyanines or arylamines such as TPD or TDTA can be treated with tetrafluorotetrahydroquinodimethane (F4-TCNQ) or with MoO3Or WO3And (4) doping. Electron doping is known to those skilled in the art and is disclosed, for example, in w.gao, a.kahn, j.appl.phys., volume 94, No.1, 7/1/2003 (p-doped organic layer); werner, F.Li, K.Harada, M.Pfeiffer, T.Fritz, K.Leo.appl.Phys.Lett., Vol.82, No.25, 23.6.2003 and Pfeiffer et al, Organic Electronics 2003, 4, 89-103.
The cathode (6) is an electrode for introducing electrons or negative charge carriers. Suitable materials for the cathode are selected from the group consisting of the elements group (old IUPAC version) group Ia alkali metals such as Li, Cs, group IIa alkaline earth metals such as calcium, barium or magnesium, group IIb metals including the lanthanides and actinides, for example samarium. In addition, metals such as aluminum or indium, and combinations of all of the metals described, can also be used. In addition, lithium-containing organometallic compounds or potassium fluoride (KF) may be applied between the organic layer and the cathode to reduce the operating voltage.
The OLEDs of the present invention may also comprise other layers known to those skilled in the art. Layers which, for example, promote the transport of positive charges and/or match the band gaps of the layers to one another may be applied between the layer (2) and the light-emitting layer (3). Alternatively, the other layer may be used as a protective layer. Further layers may be present in a similar manner between the light-emitting layer (3) and the layer (4) to facilitate negative charge transport and/or to match the band gaps between the layers to each other. Alternatively, the layer may be used as a protective layer.
In a preferred embodiment, the OLED of the invention comprises, in addition to the layers (1) to (6), at least one of the following layers:
-a hole injection layer between the anode (1) and the hole transport layer (2);
-an electron blocking layer between the hole transport layer (2) and the light emitting layer (3);
-an electron injection layer between the electron transport layer (5) and the cathode (6).
The material for the hole injection layer may be selected from copper phthalocyanine, 4 '-tris (N-3-methylphenyl-N-phenylamino) triphenylamine (m-MTDATA), 4' -tris (N- (2-naphthyl) -N-phenylamino) triphenylamine (2T-NATA), 4 '-tris (N- (1-naphthyl) -N-phenylamino) triphenylamine (1T-NATA), 4' -tris (N, N-diphenylamino) triphenylamine (NATA), oxytitanium phthalocyanine, 2,3,5, 6-tetrafluoro-7, 7,8, 8-tetracyanoquinodimethane (F4-TCNQ), pyrazino [2,3-F ] [1,10] phenanthroline-2, 3-dinitrile (PPDN), N, N, N ', N' -tetrakis (4-methoxyphenyl) benzidine (MeO-TPD), 2, 7-bis [ N, N-bis (4-methoxyphenyl) amino ] -9, 9-spirobifluorene (MeO-Spiro-TPD), 2 '-bis [ N, N-bis (4-methoxyphenyl) amino ] -9, 9-spirobifluorene (2,2' -MeO-Spiro-TPD), N, N '-diphenyl-N, N' -bis- [4- (N, N-xylylamino) phenyl ] benzidine (NTNPB), N, N '-diphenyl-N, N' -bis- [4- (N, N-diphenylamino) phenyl ] benzidine (NPNPNPB), N, N '-di (naphthalen-2-yl) -N, N' -terphenyl-1, 4-diamine (α -NPP). In principle, the hole injection layer can comprise at least one metal-organic compound and at least one metal oxide. Suitable metal organic compounds and suitable metal oxides and suitable amounts of said metal organic compounds and said metal oxides are mentioned above.
As a material for the electron injection layer, KF or Liq may be selected, for example. KF is more preferred than Liq.
The skilled person knows how to select suitable materials (e.g. based on electrochemical studies). Suitable materials for the layers are known to the person skilled in the art, for example from WO 00/70655.
In addition, some of the layers used in the OLEDs of the present invention can be surface treated to increase the charge carrier transport efficiency. The choice of materials for the layers is preferably determined by the resulting OLED having high efficiency and lifetime.
The OLEDs of the present invention can be produced by methods known to those skilled in the art. In general, the OLEDs of the present invention are produced by sequential vapor deposition of the individual layers on a suitable substrate. Suitable substrates are, for example, glass, inorganic semiconductors such as ITO or IZO or polymer films. For vapor deposition, conventional techniques, such as thermal evaporation, Chemical Vapor Deposition (CVD), Physical Vapor Deposition (PVD), and others, may be used. In an alternative approach, the organic layers of the OLED may be applied from solutions or dispersions in suitable solvents using coating techniques known to those skilled in the art.
In general, the different layers have the following thicknesses: the anode (1) is 50-500nm, preferably 100-200 nm; a hole-conducting layer (2) of 5 to 100nm, preferably 20 to 80nm, a light-emitting layer (3) of 1 to 100nm, preferably 10 to 80nm, a hole/exciton-blocking layer (4) of 2 to 100nm, preferably 5 to 50nm, an electron-conducting layer (5) of 5 to 100nm, preferably 20 to 80nm, and a cathode (6) of 20 to 1000nm, preferably 30 to 500 nm. The relative position of the recombination zone of holes and electrons in the OLED of the invention with respect to the cathode and hence the emission spectrum of the OLED can be influenced by the relative thicknesses of the layers, among other factors. This means that the thickness of the electron transport layer should preferably be chosen such that the position of the recombination zone matches the optical cavity properties of the diode and thus the emission wavelength of the emitter. The ratio of the layer thicknesses of the individual layers in an OLED depends on the materials used. The layer thicknesses of any other layers used are known to those skilled in the art. The electron-conducting layer and/or the hole-conducting layer have a thickness which is greater than the thickness of the layers mentioned when they are electrically doped.
With the first organic layer, in particular the hole transport layer or the hole injection layer, of the present application, an OLED with high efficiency and with low operating voltage can be obtained. OLEDs which are generally obtained by using the first organic layer of the present application, in particular the hole transport layer or the hole injection layer, also have a high lifetime. The efficiency of the OLED can also be improved by optimizing the other layers of the OLED. Shaped substances and novel electron-transporting materials which lead to a reduction in the operating voltage or an increase in the quantum efficiency can also be used in the OLEDs of the invention. In addition, other layers may be present in the OLED to adjust the energy levels of the different layers and to facilitate electroluminescence.
The OLED may further comprise at least one second light emitting layer. The total emission of the OLED may consist of the emission of at least two light-emitting layers, and may also comprise white light.
OLEDs can be used in all devices where electroluminescence is useful. Suitable devices are preferably selected from stationary and mobile video display devices and lighting devices. Stationary video display devices are, for example, video display devices of computers, televisions, video display devices in printing presses, kitchen appliances and billboards, lighting devices and information boards. Mobile video display devices are for example radio telephones, laptops, digital cameras, MP3 players, video display devices in vehicles, and destination displays on buses and trains. Other devices in which the OLED of the invention can be used are for example keyboards; a part of a garment; furniture; wallpaper.
In addition, the electron transport layer of the present application can be used in an OLED having an inverted structure. The structure of inverted OLEDs and the materials typically used therein are known to those skilled in the art.
In addition, the invention relates to a device comprising an organic electronic device according to the invention or an organic layer according to the invention, in particular an electron transport layer, said device being selected from the group consisting of stationary video display devices such as video display devices of computers, televisions, video display devices in printers, kitchen appliances and billboards, lighting devices, information boards, and mobile video display devices such as radio telephones, laptops, digital cameras, MP3 players, video display devices in vehicles, and destination displays on buses and trains; an illumination device; a keyboard; clothing; furniture; wallpaper.
The following examples are included for illustrative purposes only and do not limit the scope of the claims. All parts and percentages are by weight unless otherwise indicated.
Examples
I conductivity of
Conductivity comparative example 1
The ITO substrate to be used as the anode was first washed with a commercial detergent for LCD production (
Figure BDA0001074230950000423
20NS, and 25
Figure BDA0001074230950000424
Neutralizer) and then rinsed in acetone/isopropanol in an ultrasonic bath. To eliminate any possible organic residues, the substrate was exposed to a continuous ozone flow in an ozone oven for another 25 minutes. This treatment also improves the hole injection properties of the ITO.
Thereafter, the organic material described below was deposited by vapor deposition at about 10 deg.f-8Is applied to the cleaning substrate at a rate of about 0.5-5nm/min under mbar. Mixing Ir (dppic)3(V1) was applied to the substrate at a thickness of 80 nm.
Figure BDA0001074230950000421
Ir(dpbic)3
(for preparation, see Ir complex (7) in application WO 2005/019373.)
Finally, a 100nm thick Al electrode was applied by vapor deposition.
Conductivity example 1
Device preparation and construction as in conductivity comparative example 1, except that instead of Ir (dpbic) alone3(V1) to be doped with 5% by weight of MoO3Ir (dpbic)3(V1) is applied to a substrate. Conductivity example 2
Device preparation and construction as in conductivity comparative example 1, except that instead of Ir (dpbic) alone3(V1) to be doped with 5% by weight of ReO3Ir (dpbic)3(V1) is applied to a substrate.
A at 2V, mA/cm at 2V measured with respect to devices of conductivity examples and conductivity comparative examples2The resistivity Ω · cm and the conductivity S/m are shown in table 1 below.
Figure BDA0001074230950000422
Figure BDA0001074230950000431
1)Ir(dpbic)3
Doped with metal oxides, especially with ReO3The conductivity of V1 is much higher than that of V1 alone.
Application examples
Application comparative example 1
The ITO substrate to be used as the anode was first washed with a commercial detergent for LCD production (
Figure BDA0001074230950000435
20NS, and 25
Figure BDA0001074230950000434
Neutralizer) and then rinsed in acetone/isopropanol in an ultrasonic bath. To eliminate any possible organic residues, the substrate was exposed to a continuous ozone flow in an ozone oven for another 25 minutes. This treatment also improves the hole injection properties of the ITO. AJ20-1000 (commercially available from Plexcore) was then spin coated and dried to form a hole injection layer (. about.40 nm).
Thereafter, the organic material described below was deposited by vapor deposition at about 10 deg.f-8Is applied to the cleaning substrate at a rate of about 0.5-5nm/min under mbar. As hole transport and exciton blocker, Ir (dppic)3(V1) was applied to the substrate at a thickness of 40 nm.
Figure BDA0001074230950000432
Ir(dpbic)3
(for preparation, see Ir complex (7) in application WO 2005/019373.)
Subsequently, 30% by weight of the slurry was converted toCompound (I)
Figure BDA0001074230950000433
(V2), 35% by weight of Compound (V1) and 35% by weight of Compound
Figure BDA0001074230950000441
The mixture of (V3, described in PCT/EP2009/067120) was applied by vapour deposition at a thickness of 40nm, with compound V2 acting as emitter material and compounds V1 and V3 as matrix material.
Subsequently mixing the materials
Figure BDA0001074230950000442
(V3) was applied as exciton and hole blocker by vapor deposition at a thickness of 5 nm.
Then, 25% by weight of
Figure BDA0001074230950000443
(8-Hydroxyquinoline-lithium (Liq)) and 75% by weight of
Figure BDA0001074230950000444
The mixture of (V4) was applied as an electron transport layer by vapor deposition at a thickness of 40nm, likewise a 2nm thick potassium fluoride layer (electron injection layer) and finally a 100nm thick Al electrode.
Application example 1
Preparation and construction of an OLED as applied comparative example 1, except that Ir (dppic)3(V1) was applied to the substrate at a thickness of 40nm, wherein initially 35nm was doped with MoO3(50 wt%) to form hole transport and exciton blocker.
Application example 2
Preparation and construction of an OLED as applied comparative example 1, except that Ir (dppic)3(V1) was applied to the substrate at a thickness of 40nm, with an initial 35nm doping with ReO3(50 wt%) to form hole transport and exciton blocker.
Application example 3
Preparation and construction of an OLED with the exception of Ir (d) comparative example 1 was appliedpbic)3(V1) was applied to the substrate at a thickness of 40nm, with an initial 35nm doping with ReO3(3 wt%) to form hole transport and exciton blocker.
Application example 4
Preparation and construction of an OLED as applied comparative example 1, except that Ir (dppic)3(V1) was applied to the substrate at a thickness of 40nm, with an initial 35nm doping with ReO3(5 wt%) to form hole transport and exciton blocker.
To characterize the OLEDs, electroluminescence spectra at different currents and voltages were recorded. In addition, the current-voltage characteristic is measured in combination with the emitted light output. The light output can be converted to photometric parameters by calibration with a photometer. To determine lifetime, the OLED was operated at constant current density and the decrease in light output was recorded. Lifetime is defined as the time to fall until the brightness falls to half of the initial value.
300cd/m measured with respect to devices of application examples and application comparative examples2V, 300cd/m2Lower lm/W, 300cd/m2EQE (%) below, 2000cd/m2Life (hours) of 300cd/m2The life (hours) and Color (CIE) of the following are shown in the following table 2, in which the measured data of the application comparative example is set as 100, and the data of the application example are described with respect to those of the application comparative example.
TABLE 2
Figure BDA0001074230950000451
Figure BDA0001074230950000461
1)Ir(dpbic)3
2)External Quantum Efficiency (EQE) is the # a of a photon generated by a substance or device/the # HT layer of electrons flowing through it ═ hole transport layer
The lifetime, power efficiency and quantum efficiency of the device to which the example was applied were excellent compared to the device to which the comparative example was applied.

Claims (11)

1. An organic electronic device comprising a first electrode, a second electrode and a first organic layer disposed between the first electrode and the second electrode, wherein the first organic layer comprises at least one metal organic compound and at least one metal oxide, wherein the at least one metal oxide is selected from the group consisting of ReO3Wherein the metal oxide is present in an amount of 1 to 1 based on the total weight of the first organic layer<8 wt% is used in the first organic layer, wherein the metal organic compound is a metal carbene compound of formula (I):
Figure FDA0003043382880000011
wherein the symbols have the following meanings:
M1is a metal atom selected from Rh, Ir, Pd, Pt, Ru and Os in any oxidation state possible for the corresponding metal atom;
the carbene is a carbene ligand, which may be uncharged or monoanionic and monodentate, bidentate or tridentate, wherein the carbene ligand may also be a bi-carbene or tri-carbene ligand;
l is a monoanionic or dianionic ligand, which may be monodentate or bidentate;
k is an uncharged monodentate or bidentate ligand selected from the group consisting of: a phosphine; a phosphonate; an arsenate salt; a phosphite salt; CO; pyridine; nitriles and with M1A conjugated diene forming a pi complex;
n is the number of carbene ligands, wherein n is at least 1, and when n >1, the carbene ligands in the complex of formula I may be the same or different;
m is the number of ligands L, where m can be 0 or ≧ 1 and when m >1, the ligands L can be the same or different;
o is the number of ligands K, where o can be 0 or ≧ 1, and when o >1, the ligands K can be the same or different;
wherein the sum n + m + o depends on the oxidation state and coordination number of the metal atom, and on the degree of denticity of the ligands carbene, L and K, and on the charge on the ligands carbene and L, with the proviso that n is at least 1.
2. An organic electronic device according to claim 1 wherein the metal carbene complex has the formula:
Figure FDA0003043382880000021
3. an organic electronic device according to claim 1, wherein the first organic layer comprising at least one metal organic compound and at least one metal oxide is a hole transport layer or a hole injection layer.
4. The organic electronic device of claim 1, further comprising a second organic layer comprising at least one compound of formula (II):
Figure FDA0003043382880000022
wherein:
R1and R2Independently of one another is F, C1-C8Alkyl or may be optionally substituted by one or more C1-C8Alkyl substituted C6-C14Aryl, or
Two substituents R1And/or R2Combined to form a mixture optionally substituted by one or more C1-C8An alkyl-substituted fused benzene ring group,
a and b are each independently of the other 0, or an integer from 1 to 3,
m is an alkali metal atom or an alkaline earth metal atom,
if M is an alkali metal atom, n is 1, and if M is an alkaline earth metal atom, n is 2.
5. An organic electronic device according to claim 4, wherein the second organic layer further comprises at least one compound of formula (III), (IVa) and/or (IVb):
Figure FDA0003043382880000031
wherein:
R81、R82、R83、R84、R81’、R82’、R83’and R84’Independently of one another is H, C1-C18Alkyl, C substituted by E and/or interrupted by D1-C18Alkyl radical, C6-C24Aryl, C substituted by G6-C24Aryl radical, C2-C20Heteroaryl, or C substituted by G2-C20(ii) a heteroaryl group, wherein,
q is arylene or heteroarylene, each of which may be optionally substituted with G;
d is-CO-; -COO-; -S-; -SO-; -SO2-；-O-；-NR25-；-SiR30R31-；-POR32-；-CR23＝CR24-; or-C ≡ C-; and is
E is-OR29；-SR29；-NR25R26；-COR28；-COOR27；-CONR25R26(ii) a -CN; or F; g is E, C1-C18Alkyl, C interrupted by D1-C18Alkyl radical, C1-C18Perfluoroalkyl group, C1-C18Alkoxy, or C substituted by E and/or interrupted by D1-C18Alkoxy, wherein:
R23and R24Independently of one another is H, C6-C18An aryl group; quilt C1-C18Alkyl or C1-C18Alkoxy-substituted C6-C18An aryl group; c1-C18An alkyl group; or C interrupted by-O-)1-C18An alkyl group;
R25and R26Independently of one another are C6-C18An aryl group; quilt C1-C18Alkyl or C1-C18Alkoxy-substituted C6-C18An aryl group; c1-C18An alkyl group; or C interrupted by-O-)1-C18An alkyl group; or
R25And R26Together form a 5-or 6-membered ring,
R27and R28Independently of one another are C6-C18An aryl group; quilt C1-C18Alkyl or C1-C18Alkoxy-substituted C6-C18An aryl group; c1-C18An alkyl group; or C interrupted by-O-)1-C18An alkyl group, a carboxyl group,
R29is C6-C18An aryl group; quilt C1-C18Alkyl or C1-C18Alkoxy-substituted C6-C18An aryl group; c1-C18An alkyl group; or C interrupted by-O-)1-C18An alkyl group, a carboxyl group,
R30and R31Independently of one another are C1-C18Alkyl radical, C6-C18Aryl radicals, or by C1-C18Alkyl substituted C6-C18An aryl group, a heteroaryl group,
R32is C1-C18Alkyl radical, C6-C18Aryl radicals, or by C1-C18Alkyl substituted C6-C18An aryl group;
Figure FDA0003043382880000032
Figure FDA0003043382880000041
wherein:
R89is phenanthryl, pyrenyl, triphenylene, 1, 10-phenanthroline, triazinyl, dibenzothienyl, or pyrimidyl, each of which may be anyIs selected by one or more C1-C18Alkyl radical, C6-C14Aryl or C2-C20A heteroaryl group is substituted by a heteroaryl group,
R90is phenanthryl, pyrenyl, triphenylenyl, 1, 10-phenanthrolinyl, triazinyl, dibenzothienyl, or pyrimidinyl, each of which may optionally be substituted by one or more C1-C18Alkyl radical, C6-C14Aryl or C2-C20A heteroaryl group is substituted by a heteroaryl group,
R91is phenanthryl, pyrenyl, triphenylenyl, 1, 10-phenanthrolinyl, triazinyl, dibenzothienyl, pyrimidinyl or dibenzofuranyl, each of which may optionally be substituted by one or more C1-C18Alkyl radical, C6-C14Aryl or C2-C20A heteroaryl group is substituted by a heteroaryl group,
R92is H, phenanthryl, pyrenyl, triphenylenyl, 1, 10-phenanthrolinyl, triazinyl, dibenzothienyl or pyrimidinyl, and each may optionally be substituted by one or more C1-C18Alkyl radical, C6-C14Aryl or C2-C20A heteroaryl group is substituted by a heteroaryl group,
a is a single bond, an arylene or heteroarylene group, each of which may optionally be substituted by one or more C1-C18Alkyl substitution; or-SiR87R88-, wherein R87And R88Independently of one another are C1-C18Alkyl, or may be optionally substituted by one or more C1-C18Alkyl substituted C6-C14And (4) an aryl group.
6. The organic electronic device according to claim 1, wherein the organic electronic device is selected from the group consisting of an organic solar cell, a switching element, and an organic light emitting diode.
7. The organic electronic device according to claim 6, wherein the organic electronic device is an OLED further comprising a light-emitting layer comprising at least one phosphorescent light-emitting material.
8. An organic electronic device according to claim 7 wherein the light-emitting layer further comprises as host material at least one compound of formula (X):
Figure FDA0003043382880000051
wherein:
t is NR57S, O or PR57；
R57Is aryl, heteroaryl, alkyl, cycloalkyl or heterocycloalkyl;
q' is-NR58R59、-SiR70R71R72、-P(O)R60R61、-PR62R63、-S(O)2R64、-S(O)R65、-SR66OR-OR67
R55、R56Each independently is alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, SiR70R71R72A group Q' or a group having donor or acceptor action;
a "is 0, 1,2,3 or 4;
b' is 0, 1,2 or 3;
R58、R59together with the nitrogen atom, form a cyclic group having 3 to 10 ring atoms, which may be unsubstituted or substituted by one or more substituents selected from alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl and groups having donor or acceptor properties; and/or one or more further cyclic groups having 3 to 10 ring atoms can be fused, wherein the fused groups can be unsubstituted or substituted by one or more substituents selected from alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl and groups having donor or acceptor properties;
R70、R71、R72、R60、R61、R62、R63、R64、R65、R66、R67each independently is aryl, heteroaryl, alkyl, cycloalkyl or heterocycloalkyl,
or
The two units of the formula (X) are bridged to each other by a bond or by O via a linear or branched, saturated or unsaturated bridge, optionally interrupted by at least one heteroatom.
9. An organic electronic device according to claim 7 wherein the light-emitting layer further comprises as host material at least one compound of formula (V):
Figure FDA0003043382880000061
wherein:
x is NR, S, O or PR;
r is aryl, heteroaryl, alkyl, cycloalkyl or heterocycloalkyl;
a is-NR6R7、-P(O)R8R9、-PR10R11、-S(O)2R12、-S(O)R13、-SR14OR-OR15；
R1、R2And R3Independently of one another, are aryl, heteroaryl, alkyl, cycloalkyl or heterocycloalkyl, where the radicals R1、R2Or R3At least one is aryl or heteroaryl;
R4and R5Independently of one another, alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, a group A, or a group having donor or acceptor properties;
n and m are independently of each other 0, 1,2 or 3;
R6、R7together with the nitrogen atom, form a cyclic group having 3 to 10 ring atoms, which may be unsubstituted or substituted by one or more substituents selected from alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl and groups having donor or acceptor properties; and/or it may be fused to one or more other cyclic groups having 3 to 10 ring atoms, where the fused groups may be unsubstituted or may be substituted by one or more groups selected from alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl and substituted with one or more groups selected from alkyl, cycloalkyl, heteroaryl and substituted with one or more groups selected from alkyl, heteroaryl and substituted with one or more groups selectedSubstituent substitution of groups having donor or acceptor properties; and is
R8、R9、R10、R11、R12、R13、R14And R15Independently of one another, aryl, heteroaryl, alkyl, cycloalkyl or heterocycloalkyl.
10. An apparatus comprising the organic electronic device according to claim 1.
11. A hole transport layer or hole injection layer comprising at least one metal organic compound and at least one metal oxide, wherein the at least one metal oxide is selected from ReO3Wherein the metal oxide is present in an amount of 1 to 1 based on the total weight of the first organic layer<8 wt% is used in the first organic layer, wherein the metal organic compound is a metal carbene compound of formula (I):
Figure FDA0003043382880000071
wherein the symbols have the following meanings:
M1is a metal atom selected from Rh, Ir, Pd, Pt, Ru and Os in any oxidation state possible for the corresponding metal atom;
the carbene is a carbene ligand, which may be uncharged or monoanionic and monodentate, bidentate or tridentate, wherein the carbene ligand may also be a bi-carbene or tri-carbene ligand;
l is a monoanionic or dianionic ligand, which may be monodentate or bidentate;
k is an uncharged monodentate or bidentate ligand selected from the group consisting of: a phosphine; a phosphonate; an arsenate salt; a phosphite salt; CO; pyridine; nitriles and with M1A conjugated diene forming a pi complex;
n is the number of carbene ligands, wherein n is at least 1, and when n >1, the carbene ligands in the complex of formula I may be the same or different;
m is the number of ligands L, where m can be 0 or ≧ 1 and when m >1, the ligands L can be the same or different;
o is the number of ligands K, where o can be 0 or ≧ 1, and when o >1, the ligands K can be the same or different;
wherein the sum n + m + o depends on the oxidation state and coordination number of the metal atom, and on the degree of denticity of the ligands carbene, L and K, and on the charge on the ligands carbene and L, with the proviso that n is at least 1.
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