U.S. patent application number 16/517830 was filed with the patent office on 2019-11-07 for materials for electronic devices.
The applicant listed for this patent is Merck Patent GmbH. Invention is credited to Joachim KAISER, Teresa MUJICA-FERNAUD, Christof PFLUMM, Frank STIEBER, Philipp STOESSEL, Frank VOGES.
Application Number | 20190341559 16/517830 |
Document ID | / |
Family ID | 54260714 |
Filed Date | 2019-11-07 |
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United States Patent
Application |
20190341559 |
Kind Code |
A1 |
VOGES; Frank ; et
al. |
November 7, 2019 |
MATERIALS FOR ELECTRONIC DEVICES
Abstract
The present application relates to a material comprising a
monoarylamine of a defined formula and a p-dopant of a defined
formula. The present application further relates to the use of said
material in an organic layer of an electronic device, the device
preferably being an organic electroluminescent device (OLED).
Inventors: |
VOGES; Frank; (Bad
Duerkheim, DE) ; STIEBER; Frank; (Einhausen, DE)
; STOESSEL; Philipp; (Frankfurt Am Main, DE) ;
MUJICA-FERNAUD; Teresa; (Darmstadt, DE) ; PFLUMM;
Christof; (Darmstadt, DE) ; KAISER; Joachim;
(Darmstadt, DE) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Merck Patent GmbH |
Darmstadt |
|
DE |
|
|
Family ID: |
54260714 |
Appl. No.: |
16/517830 |
Filed: |
July 22, 2019 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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15521026 |
Apr 21, 2017 |
10396297 |
|
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PCT/EP2015/001910 |
Sep 25, 2015 |
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16517830 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
H01L 51/5036 20130101;
Y02P 70/521 20151101; H01L 51/56 20130101; H01L 51/0061 20130101;
Y02E 10/549 20130101; H01L 51/0077 20130101; H01L 51/005 20130101;
C07F 9/94 20130101; H01L 51/0059 20130101; H01L 51/506 20130101;
H01L 51/5056 20130101; H01L 51/006 20130101; Y02P 70/50 20151101;
H01L 51/5012 20130101 |
International
Class: |
H01L 51/00 20060101
H01L051/00; C07F 9/94 20060101 C07F009/94; H01L 51/56 20060101
H01L051/56; H01L 51/50 20060101 H01L051/50 |
Foreign Application Data
Date |
Code |
Application Number |
Oct 24, 2014 |
EP |
14003629.4 |
Aug 7, 2015 |
EP |
15180258.4 |
Claims
1-21. (canceled)
22. A material comprising a compound P which is a complex of
bismuth and a compound A of a formula (A-I), (A-IV), (A-V), (A-VII)
or (A-IX) ##STR00157## where one or more R.sup.1 radicals may be
bonded to any of the unsubstituted positions shown, and the
variables that occur are as follows: Z is the same or different at
each instance and is CR.sup.1; X is the same or different at each
instance and is a single bond, O, S, C(R.sup.1).sub.2,
Si(R.sup.1).sub.2, PR.sup.1, C(R.sup.1).sub.2--C(R.sup.1).sub.2, or
CR.sup.1.dbd.CR.sup.1; Y is the same or different at each instance
and is O, S, C(R.sup.1).sub.2, Si(R.sup.1).sub.2, NR.sup.1,
C(R.sup.1).sub.2--C(R.sup.1).sub.2, or CR.sup.1.dbd.CR.sup.1;
Ar.sup.1 is the same or different at each instance and is an
aromatic ring system which has 6 to 60 aromatic ring atoms and may
be substituted by one or more R.sup.1 radicals, or a heteroaromatic
ring system which has 5 to 60 aromatic ring atoms and may be
substituted by one or more R.sup.1 radicals; Ar.sup.2 is an
aromatic ring system which has 6 to 20 aromatic ring atoms and may
be substituted by one or more R.sup.1 radicals, or a heteroaromatic
ring system which has 5 to 20 aromatic ring atoms and may be
substituted by one or more R.sup.1 radicals; n, p, q are the same
or different and are each 0 or 1; where the sum of the value of the
indices p and q is 1; R.sup.1 is the same or different at each
instance and is selected from H, D, F, C(.dbd.O)R.sup.2, CN,
Si(R.sup.2).sub.3, P(.dbd.O)(R.sup.2).sub.2, OR.sup.2,
S(.dbd.O)R.sup.2, S(.dbd.O).sub.2R.sup.2, straight-chain alkyl or
alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl
or alkoxy groups having 3 to 20 carbon atoms, alkenyl or alkynyl
groups having 2 to 20 carbon atoms, aromatic ring systems having 6
to 40 aromatic ring atoms, and heteroaromatic ring systems having 5
to 40 aromatic ring atoms; where the alkyl, alkoxy, alkenyl and
alkynyl groups mentioned and the aromatic ring systems and
heteroaromatic ring systems mentioned may each be substituted by
one or more R.sup.2 radicals; and where one or more CH.sub.2 groups
in the alkyl, alkoxy, alkenyl and alkynyl groups mentioned may be
replaced by --R.sup.2C.dbd.CR.sup.2--, --C.ident.C--,
Si(R.sup.2).sub.2, C.dbd.O, C.dbd.NR.sup.2, --C(.dbd.O)O--,
--C(.dbd.O)NR.sup.2--, P(.dbd.O)(R.sup.2), --O--, --S--, SO or
SO.sub.2; R.sup.2 is the same or different at each instance and is
selected from H, D, F, CN, alkyl groups having 1 to 20 carbon
atoms, aromatic ring systems having 6 to 40 aromatic ring atoms and
heteroaromatic ring systems having 5 to 40 aromatic ring atoms; and
where the alkyl groups, aromatic ring systems and heteroaromatic
ring systems mentioned may be substituted by F or CN.
23. The material according to claim 22, wherein the compound A has
a single amino group.
24. The material according to claim 22, wherein the compound A does
not contain a fused aryl group having more than 10 aromatic ring
atoms nor a fused heteroaryl group having more than 14 aromatic
ring atoms.
25. The material according to claim 22, wherein in the compound A,
the Ar.sup.1 group is the same or different at each instance and is
an aromatic ring system which has 6 to 40 aromatic ring atoms and
may be substituted by one or more R.sup.1 radicals, or a
heteroaromatic ring system which has 5 to 40 ring atoms and may be
substituted by one or more R.sup.1 radicals.
26. The material according to claim 22, wherein, in the compound A,
the Ar.sup.1 group is a group which is optionally substituted by
one or more R.sup.1 radicals and is selected from phenyl, biphenyl,
terphenyl, quaterphenyl, naphthyl, phenanthryl, fluoranthenyl,
fluorenyl, indenofluorenyl, spirobifluorenyl, dibenzofuranyl,
dibenzothiophenyl, carbazolyl, acridyl and phenanthridyl.
27. The material according to claim 22, wherein in the compound A,
group X is the same or different at each instance and is a single
bond or O.
28. The material according to claim 22, wherein in the compound A,
group Y is C(R.sup.1).sub.2.
29. The material according to claim 22, wherein the compound A
conforms to a formula (A-I), and groups Ar.sup.1 are selected,
identically or differently, from phenyl, biphenyl, terphenyl,
quaterphenyl, naphthyl, dibenzofuranyl, dibenzothiophenyl, and
carbazolyl, each of which is optionally substituted by one or more
R.sup.1 radicals.
30. The material according to claim 22, wherein the compound A
conforms to a formula (A-IV), and one of groups X is a single bond,
and the other one of groups X is O.
31. The material according to claim 22, wherein the compound A
conforms to a formula (A-V), and group X is a single bond.
32. The material according to claim 22, wherein groups Ar.sup.1 are
selected, identically or differently, from the following groups
##STR00158## ##STR00159## ##STR00160## ##STR00161## ##STR00162##
##STR00163## ##STR00164## ##STR00165## ##STR00166## ##STR00167##
##STR00168## ##STR00169## ##STR00170## ##STR00171## ##STR00172##
each of which may be substituted by one or more R.sup.1 radicals at
any of the unsubstituted positions shown.
33. The material according to claim 22, wherein groups Ar.sup.2 are
selected, identically or differently, from the following groups
##STR00173## ##STR00174## ##STR00175## ##STR00176## each of which
may be substituted by one or more R.sup.1 radicals at any of the
unsubstituted positions shown.
34. The material according to one claim 22, wherein the compound P
is a complex of bismuth in the (III) oxidation state.
35. The material according to claim 22, wherein the compound P is a
complex of bismuth having at least one ligand L which is an organic
compound.
36. The material according to claim 35, wherein the ligand L is
singly negatively charged.
37. The material according to claim 35, wherein the group in the
ligand L that binds to the bismuth atom is selected from carboxylic
acid groups, thiocarboxylic acid groups, carboxamide groups and
carboximide groups.
38. The material according to claim 35, wherein the ligand L is
selected from fluorinated benzoic acid derivatives, fluorinated or
non-fluorinated phenylacetic acid derivatives and fluorinated or
non-fluorinated acetic acid derivatives.
39. The material according to claim 22, wherein the compound P is
present in the material as a dopant in a concentration of 0.1% to
20%.
40. A layer comprising the material according to claim 22.
41. A formulation comprising the material according to claim 22 and
at least one solvent.
42. A process for producing the layer according to claim 40,
wherein compound A and compound P are applied together from the gas
phase, or in that a formulation comprising the material of the
invention is applied from the liquid phase.
44. Electronic device selected from organic electroluminescent
devices, organic integrated circuits, organic field-effect
transistors, organic thin-film transistors, organic light-emitting
transistors, organic solar cells, organic optical detectors,
organic photoreceptors, organic field-quench devices, organic
light-emitting electrochemical cells and organic laser diodes,
comprising the material according to claim 22.
45. An organic electroluminescent device comprising the material
according to claim 22, wherein the device includes the material in
a hole-transporting layer disposed between anode and emitting
layer, with one or more further layers present between the layer
comprising the material and the emitting layer.
46. The organic electroluminescent device according to claim 45,
wherein the HOMO levels of the hole-transporting layer (HTL) and
the one layer between hole-transporting layer and emitting layer
(EBL) meet the following condition: HOMO(HTL)<=HOMO(EBL).
47. The organic electroluminescent device according to claim 45,
wherein the one or more further layers disposed between the layer
comprising the material and the emitting layer comprise one or more
identical or different compounds of the formula (A).
48. The organic electroluminescent device according to claim 45,
wherein the device comprises the material in a layer directly
adjoining the anode.
Description
[0001] The present application relates to a material comprising a
monoarylamine of a defined formula and a metal complex of a defined
formula. The present application further relates to the use of said
material in an organic layer of an electronic device, the device
preferably being an organic electroluminescent device (OLED).
[0002] The term "comprising" is understood in the context of this
application to mean that further constituents or steps may be
present. The indefinite article "a" does not exclude the
plural.
[0003] Electronic devices in the context of this application are
understood to mean what are called organic electronic devices,
which contain organic semiconductor materials as functional
materials.
[0004] The structure of OLEDs in which organic compounds are used
as functional materials is described, for example, in U.S. Pat.
Nos. 4,539,507, 5,151,629, EP 0676461 and WO 98/27136. In general,
the term OLEDs is understood to mean electronic devices which have
one or more layers comprising organic compounds and emit light on
application of electrical voltage.
[0005] A great influence on the performance data of electronic
devices is possessed by layers having a hole-transporting function
(hole-transporting layers), for example hole injection layers, hole
transport layers and electron blocker layers.
[0006] The prior art discloses use of monoarylamines as materials
for hole-transporting layers. Such monoarylamines are described,
for example, in JP 1995/053955, WO 2006/123667, JP 2010/222268, WO
2012/034627, WO 2013/120577, WO 2014/015938 and WO 2014/015935.
[0007] In addition, the prior art discloses use of p-dopants in
combination with hole transport materials in hole-transporting
layers of OLEDs. A p-dopant is understood here to mean a compound
which, when added as a minor component to a main component,
significantly increases the conductivity thereof for holes.
[0008] p-Dopants known in the prior art are organic electron
acceptor compounds, for example
7,7,8,8-tetracyano-2,3,5,6-tetrafluoroQuinodimethane (F4TCNQ). The
prior art further discloses, as p-dopants, metal complexes of
transition metal cations and main group metal cations, for example
in WO 2011/33023 and WO 2013/182389.
[0009] The hole transport materials known in the prior art and the
p-dopants known in the prior art result in a great variety of
potentially possible combinations. Of these, only some are
disclosed in the prior art. Mention may be made here by way of
example of the combination of main group metal complexes as
p-dopants with tetraamines, for example
2,2',7,7'-tetra(N,N-di-p-tolyl)amino-9,9-spirobifluorene in the
hole transport layer of an OLED. This is disclosed in WO
2013/182389. A further example from the prior art is the
combination of F4TCNQ with monoarylamines, for example
tris-para-biphenylamine in the hole transport layer of an OLED.
This is disclosed in WO 2013/135352.
[0010] However, OLEDs comprising these materials in the hole
transport layer are in need of improvement in relation to lifetime
and efficiency.
[0011] There is additionally a need for p-dopants capable of
efficiently doping hole transport materials having a low-lying
HOMO, especially those having a HOMO within the range from -5.2 to
-5.7 eV, such that it is possible to obtain dopant-hole transport
material combinations having both a suitable conductivity and a low
HOMO energy level. Suitable and preferred conductivities here are
in the range from 10.sup.-4 S/m to 10.sup.-3 S/m. The use of hole
transport materials having a low-lying HOMO is highly desirable
because this dispenses with the necessity of inserting a further
layer having a low HOMO between hole transport layer and emitting
layer. This enables a simpler construction of the OLED and hence a
more efficient production process. If a further layer is inserted
between hole transport layer and emitting layer, it is possible in
the desired case of a hole transport layer having a low HOMO to
avoid a hole barrier and hence a voltage drop between the hole
transport layer and the emitting layer by virtue of the HOMO of the
hole transport layer being no higher than the HOMO of the layer
between the hole transport layer and emitting layer. This is
possible, for example, through the use of the same material in the
hole transport layer and the further layer between the hole
transport layer and emitting layer.
[0012] There is additionally a need for hole transport
material-dopant combinations having only low absorption in the
visible region (VIS region). The p-dopants known in the prior art,
for example NDP-2 or molybdenum oxide dopants, in combination with
the standard hole transport materials have absorptions in the VIS
region. Low absorption bands in the VIS region are highly desirable
since absorptions in the VIS region affect the emission
characteristics of the OLEDs and worsen the efficiency thereof.
[0013] In studies of possible combinations of p-dopants and hole
transport materials for use in hole transport layers, it has now
been found that, unexpectedly, a material comprising a
monoarylamine of a specific formula (A) and a bismuth complex gives
excellent values compared to the prior art in relation to lifetime
and efficiency. In addition, the inventive material has lower
leakage currents when used in OLEDs than materials according to the
prior art. Without being bound to this theory, this may be caused
by a lower lateral conductivity of the doped layer of the OLED.
With pixels in displays becoming ever smaller, leakage currents are
a great problem since they can lead to crosstalk between the
pixels. The avoidance thereof is therefore desirable. Yet another
feature of the inventive material is no absorption band in the VIS
region. Yet another feature is that it is possible with the
inventive material, because of the low HOMO position of the
monoarylamine, to produce OLEDs which need not have any additional
layer between the hole transport layer comprising the inventive
material and the emitting layer and can therefore be produced in a
more efficient manner.
[0014] The present application therefore provides a material
comprising a compound P which is a complex of bismuth and a
compound A of a formula (A)
##STR00001##
[0015] where the variables that occur are: [0016] A.sup.1 is the
same or different at each instance and is H, an alkyl group which
has 1 to 20 carbon atoms and may be substituted by one or more
R.sup.1 radicals, or Ar.sup.1; [0017] Ar.sup.2 is the same or
different at each instance and is an aromatic ring system which has
6 to 60 aromatic ring atoms and may be substituted by one or more
R.sup.1 radicals, or a heteroaromatic ring system which has 5 to 60
aromatic ring atoms and may be substituted by one or more R.sup.1
radicals; Ar.sup.1 and/or A.sup.1 groups here may be bonded to one
another via R.sup.1 radicals; [0018] R.sup.1 is the same or
different at each instance and is selected from H, D, F,
C(.dbd.O)R.sup.2, CN, Si(R.sup.2).sub.3, P(.dbd.O)(R.sup.2).sub.2,
OR.sup.2, S(.dbd.O)R.sup.2, S(.dbd.O).sub.2R.sup.2, straight-chain
alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or
cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, alkenyl
or alkynyl groups having 2 to 20 carbon atoms, aromatic ring
systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring
systems having 5 to 40 aromatic ring atoms; where two or more
R.sup.1 radicals may be joined to one another and may form a ring;
where the alkyl, alkoxy, alkenyl and alkynyl groups mentioned and
the aromatic ring systems and heteroaromatic ring systems mentioned
may each be substituted by one or more R.sup.2 radicals; and where
one or more CH.sub.2 groups in the alkyl, alkoxy, alkenyl and
alkynyl groups mentioned may be replaced by
--R.sup.2C.dbd.CR.sup.2--, --C.ident.C--, Si(R.sup.2).sub.2,
C.dbd.O, C.dbd.NR.sup.2, --C(.dbd.O)O--, --C(.dbd.O)NR.sup.2--,
P(.dbd.O)(R.sup.2), --O--, --S--, SO or SO.sub.2; [0019] R.sup.2 is
the same or different at each instance and is selected from H, D,
F, CN, alkyl groups having 1 to 20 carbon atoms, aromatic ring
systems having 6 to 40 aromatic ring atoms and heteroaromatic ring
systems having 5 to 40 aromatic ring atoms; where two or more
R.sup.2 radicals may be joined to one another and may form a ring;
and where the alkyl groups, aromatic ring systems and
heteroaromatic ring systems mentioned may be substituted by F or
CN;
[0020] where the scope of the formula (A) excludes compounds of the
following formula (B)
##STR00002##
[0021] in which the new variables that occur are: [0022] V is
CR.sup.1; [0023] Ara is the same or different at each instance and
is an aromatic ring system which has 6 to 30 aromatic ring atoms
and may be substituted by one or more R.sup.1 radicals, or a
heteroaromatic ring system which has 5 to 30 aromatic ring atoms
and may be substituted by one or more R.sup.1 radicals; Ar.sup.1
groups here may be bonded to one another via R.sup.1 radicals.
[0024] An aromatic ring system in the context of this invention
contains 6 to 60 carbon atoms in the ring system. It does not
comprise any heteroatoms as aromatic ring atoms. An aromatic ring
system in the context of this invention therefore does not contain
any heteroaryl groups. An aromatic ring system in the context of
this invention shall be understood to mean a system which does not
necessarily contain only aryl groups but in which it is also
possible for a plurality of aryl groups to be bonded by a single
bond or by a non-aromatic unit, for example one or more optionally
substituted C, Si, N, O or S atoms. In this case, the nonaromatic
unit comprises preferably less than 10% of the atoms other than H,
based on the total number of atoms other than H in the system. For
example, systems such as 9,9'-spirobifluorene, 9,9'-diarylfluorene,
triarylamine, diaryl ethers and stilbene are also to be regarded as
aromatic ring systems in the context of this invention, and
likewise systems in which two or more aryl groups are joined, for
example, by a linear or cyclic alkyl, alkenyl or alkynyl group or
by a silyl group. In addition, systems in which two or more aryl
groups are joined to one another via single bonds are also to be
regarded as aromatic ring systems in the context of this invention,
for example systems such as biphenyl and terphenyl.
[0025] A heteroaromatic ring system in the context of this
invention contains 5 to 60 aromatic ring atoms, at least one of
which is a heteroatom. The heteroatoms of the heteroaromatic ring
system are preferably selected from N, o and/or S. A heteroaromatic
ring system corresponds to the abovementioned definition of an
aromatic ring system, but has at least one heteroatom as one of the
aromatic ring atoms. In this way, it differs from an aromatic ring
system in the sense of the definition of the present application,
which, according to this definition, cannot contain any heteroatom
as aromatic ring atom.
[0026] An aryl group in the context of this invention contains 6 to
40 aromatic ring atoms of which none is a heteroatom. An aryl group
in the context of this invention is understood to mean either a
simple aromatic cycle, i.e. benzene, or a fused aromatic polycycle,
for example naphthalene, phenanthrene or anthracene. A fused
aromatic polycycle in the context of the present application
consists of two or more simple aromatic cycles fused to one
another. Fusion between cycles is understood here to mean that the
cycles share at least one edge with one another.
[0027] A heteroaryl group in the context of this invention contains
5 to 40 aromatic ring atoms of which at least one is a heteroatom.
The heteroatoms of the heteroaryl group are preferably selected
from N, O and S. A heteroaryl group in the context of this
invention is understood to mean either a simple heteroaromatic
cycle, for example pyridine, pyrimidine or thiophene, or a fused
heteroaromatic polycycle, for example quinoline or carbazole. A
fused heteroaromatic polycycle in the context of the present
application consists of two or more simple heteroaromatic cycles
fused to one another. Fusion between cycles is understood to mean
that the cycles share at least one edge with one another.
[0028] An aromatic ring system having 6 to 40 aromatic ring atoms
or a heteroaromatic ring system having 5 to 40 aromatic ring atoms
are especially understood to mean groups derived from the groups
mentioned above under aryl groups and heteroaryl groups, and from
biphenyl, terphenyl, quaterphenyl, fluorene, spirobifluorene,
dihydrophenanthrene, dihydropyrene, tetrahydropyrene,
indenofluorene, truxene, isotruxene, spirotruxene, spiroisotruxene,
indenocarbazole, or from combinations of these groups.
[0029] An aryl or heteroaryl group, each of which may be
substituted by the abovementioned radicals and which may be joined
to the aromatic or heteroaromatic system via any desired positions,
is especially understood to mean groups derived from benzene,
naphthalene, anthracene, phenanthrene, pyrene, dihydropyrene,
chrysene, perylene, triphenylene, fluoranthene, benzanthracene,
benzophenanthrene, tetracene, pentacene, benzopyrene, furan,
benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene,
isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole,
carbazole, pyridine, quinoline, isoquinoline, acridine,
phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline,
benzo-7,8-quinoline, phenothiazine, phenoxazine, pyrazole,
indazole, imidazole, benzimidazole, naphthimidazole,
phenanthrimidazole, pyridimidazole, pyrazinimidazole,
quinoxalinimidazole, oxazole, benzoxazole, naphthoxazole,
anthroxazole, phenanthroxazole, isoxazole, 1,2-thiazole,
1,3-thiazole, benzothiazole, pyridazine, benzopyridazine,
pyrimidine, benzopyrimidine, quinoxaline, pyrazine, phenazine,
naphthyridine, azacarbazole, benzocarboline, phenanthroline,
1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2,3-oxadiazole,
1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole,
1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole,
1,3,4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine,
tetrazole, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine,
purine, pteridine, indolizine and benzothiadiazole.
[0030] In the context of the present invention, a straight-chain
alkyl group having 1 to 20 carbon atoms and a branched or cyclic
alkyl group having 3 to 20 carbon atoms and an alkenyl or alkynyl
group having 2 to 20 carbon atoms in which individual hydrogen
atoms or CH.sub.2 groups may also be replaced by the groups
mentioned above in the definition of the radicals are preferably
understood to mean the methyl, ethyl, n-propyl, i-propyl, n-butyl,
i-butyl, s-butyl, t-butyl, 2-methylbutyl, n-pentyl, s-pentyl,
cyclopentyl, neopentyl, n-hexyl, cyclohexyl, neohexyl, n-heptyl,
cycloheptyl, n-octyl, cyclooctyl, 2-ethyihexyl, trifluoromethyl,
pentafluoroethyl, 2,2,2-trifluoroethyl, ethenyl, propenyl, butenyl,
pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl,
cycloheptenyl, octenyl, cyclooctenyl, ethynyl, propynyl, butynyl,
pentynyl, hexynyl or octynyl radicals.
[0031] An alkoxy or thioalkyl group having 1 to 20 carbon atoms in
which individual hydrogen atoms or CH.sub.2 groups may also be
replaced by the groups mentioned above in the definition of the
radicals is preferably understood to mean methoxy,
trifluoromethoxy, ethoxy, n-propoxy, propoxy, n-butoxy, i-butoxy,
s-butoxy, t-butoxy, n-pentoxy, s-pentoxy, 2-methylbutoxy, n-hexoxy,
cyclohexyloxy, n-heptoxy, cycloheptyloxy, n-octyloxy,
cyclooctyloxy, 2-ethylhexyloxy, pentafluoroethoxy,
2,2,2-trifluoroethoxy, methylthio, ethylthio, n-propylthio,
i-propylthio, n-butylthio, i-butylthio, s-butylthio, t-butylthio,
n-pentylthio, s-pentylthio, n-hexylthio, cyclohexylthio,
n-heptylthio, cycloheptylthio, n-octylthio, cyclooctylthio,
2-ethylhexylthio, trifluoromethylthio, pentafluoroethylthio,
2,2,2-trifluoroethylthio, ethenylthio, propenylthio, butenylthio,
pentenylthio, cyclopentenylthio, hexenylthio, cyclohexenylthio,
heptenylthio, cycloheptenylthio, octenylthio, cyclooctenylthio,
ethynylthio, propynylthio, butynylthio, pentynylthio, hexynylthio,
heptynylthio or octenylthio.
[0032] The wording that two or more radicals together may form a
ring, in the context of the present application, shall be
understood to mean, inter alia, that the two radicals are joined to
one another by a chemical bond. In addition, however, the
abovementioned wording shall also be understood to mean that, if
one of the two radicals is hydrogen, the second radical binds to
the position to which the hydrogen atom was bonded, forming a
ring.
[0033] The compound A is preferably a monoarylamine, A
monoarylamine is understood here to mean a compound having a single
arylamino group and not more than one. Preferably, the compound is
a monotriarylamino compound, meaning that it has a single
triarylamino group. The term "triarylamino group" is preferably
also understood to mean compounds containing heteroaryl groups
bonded to the amino nitrogen. Further preferably, the compound A
has a single amino group. Itshould be noted that, according to the
definition of the present application, carbazole groups do not
count as arylamino groups or amino groups.
[0034] According to a further preferred embodiment of the
invention, the compound A does not contain a fused aryl group
having more than 10 aromatic ring atoms nor a fused heteroaryl
group having more than 14 aromatic ring atoms.
[0035] Preferably, A.sup.1 is the same or different at each
instance and is an alkyl group which has 1 to 20 carbon atoms and
may be substituted by one or more R.sup.1 radicals, or AR.sup.1.
Preferably, at least one A.sup.1 group in the compound A is
Ar.sup.1; more preferably, both A.sup.1 groups in the compound A
are AR.sup.1.
[0036] Ar.sup.1 is preferably the same or different at each
instance and is an aromatic ring system which has 6 to 40 aromatic
ring atoms and may be substituted by one or more R.sup.1 radicals,
or a heteroaromatic ring system which has 5 to 40 aromatic ring
atoms and may be substituted by one or more R.sup.1 radicals.
[0037] Preferably, at least one Ar.sup.1 group in the compound of
the formula (A) is a group which is optionally substituted by one
or more R.sup.1 radicals and is selected from phenyl, biphenyl,
terphenyl, quaterphenyl, naphthyl, phenanthryl, fluoranthenyl,
fluorenyl, indenofluorenyl, spirobifluorenyl, furanyl,
benzofuranyl, isobenzofuranyl, dibenzofuranyl, thiophenyl,
benzothiophenyl, isobenzothiophenyl, dibenzothiophenyl, indolyl,
isoindolyl, carbazolyl, indolocarbazolyl, indenocarbazolyl,
pyridyl, quinolinyl, isoquinolinyl, acridyl, phenanthridyl,
benzimidazolyl, pyrimidyl, pyrazinyl and triazinyl; particular
preference among these is given to phenyl, biphenyl, terphenyl,
quaterphenyl, naphthyl, phenanthryl, fluoranthenyl, fluorenyl,
indenofluorenyl, spirobifluorenyl, dibenzofuranyl,
dibenzothiophenyl, carbazolyl, acridyl and phenanthridyl.
[0038] R.sup.1 is preferably the same or different at each instance
and is selected from H, D, F, CN, Si(R.sup.2).sub.3, straight-chain
alkyl or alkoxy groups having 1 to 10 carbon atoms, branched or
cyclic alkyl or alkoxy groups having 3 to 10 carbon atoms, aromatic
ring systems having 6 to 40 aromatic ring atoms and heteroaromatic
ring systems having 5 to 40 aromatic ring atoms; where the alkyl
and alkoxy groups mentioned, the aromatic ring systems mentioned
and the heteroaromatic ring systems mentioned may each be
substituted by one or more R.sup.2 radicals; and where one or more
CH.sub.2 groups in the alkyl or alkoxy groups mentioned may be
replaced by --C.ident.C--, --R.sup.2C.dbd.CR.sup.2--,
Si(R.sup.2).sub.2, C.dbd.O, C.dbd.NR.sup.2, --O--, --S--,
--C(.dbd.O)O-- or --C(.dbd.O)NR.sup.2--.
[0039] Preferably, at least one Ar.sup.1 group, more preferably all
the Ar.sup.1 groups, in the compound of the formula (A) are the
same or different at each instance and are selected from the
following groups, each of which may be substituted by one or more
R.sup.1 radicals at any of the unsubstituted positions shown:
##STR00003## ##STR00004## ##STR00005## ##STR00006## ##STR00007##
##STR00008## ##STR00009## ##STR00010## ##STR00011## ##STR00012##
##STR00013## ##STR00014## ##STR00015##
[0040] Preferably, compound A corresponds to one of the following
formulae, excluding compounds of the formula (B) as defined
above:
##STR00016## ##STR00017##
[0041] where one or more R.sup.1 radicals may be bonded to any of
the unsubstituted positions shown, and the variables that occur are
as follows: [0042] Z is the same or different at each instance and
is CR.sup.1 or N; [0043] X is the same or different at each
instance and is a single bond, O, S, C(R.sup.1).sub.2,
Si(R.sup.1).sub.2, C(R.sup.1).sub.2--C(R.sup.1).sub.2, or
CR.sup.1.dbd.CR.sup.1; [0044] Y is the same or different at each
instance and is O, S, C(R.sup.1).sub.2, Si(R.sup.1).sub.2,
PR.sup.1, NR.sup.1, C(R.sup.1).sub.2--C(R.sup.1).sub.2, or
CR.sup.1.dbd.CR.sup.1; [0045] AR.sup.1 is as defined above; [0046]
Ar.sup.2 is an aromatic ring system which has 6 to 20 aromatic ring
atoms and may be substituted by one or more R.sup.1 radicals, or a
heteroaromatic ring system which has 5 to 20 aromatic ring atoms
and may be substituted by one or more R.sup.1 radicals; [0047] n,
p, q are the same or different and are each 0 or 1.
[0048] It is preferable that not more than three Z groups in one
ring are N. Preferably not more than 2 adjacent Z groups are N.
More preferably, Z is CR.sup.1.
[0049] It is preferable that X is the same or different at each
instance and is a single bond, o, S or (CR.sup.1).sub.2.
[0050] Preferably, at least one of the indices p and q is 1.
Preferably, the sum total of the indices p and q is 1.
[0051] Preferably, AR.sup.1 in the abovementioned formulae is (A-I)
to (A-IX) selected from the abovementioned preferred embodiments of
AR.sup.1.
[0052] Preferably, Ar.sup.2 comprises at least one group selected
from benzene, naphthalene, phenanthrene, fluoranthene, biphenyl,
terphenyl, quaterphenyl, fluorene, indenofluorene, spirobifluorene,
furan, benzofuran, isobenzofuran, dibenzofuran, thiophene,
benzothiophene, isobenzothiophene, dibenzothiophene, indole,
isoindole, carbazole, indolocarbazole, indenocarbazole, pyridine,
quinoline, isoquinoline, acridine, phenanthridine, benzimidazole,
pyrimidine, pyrazine and triazine, where the groups mentioned may
be substituted by one or more R.sup.1 radicals. Preferably,
Ar.sup.2 consists exclusively of one of the abovementioned groups
or of a combination of a plurality of the abovementioned
groups.
[0053] Preferably, Ar.sup.2 is the same or different at each
instance and is selected from the following groups, each of which
may be substituted by one or more R.sup.1 radicals at any of the
unsubstituted positions shown:
##STR00018## ##STR00019## ##STR00020## ##STR00021##
[0054] Preferred embodiments of compounds of the formula (A) are
the following compounds:
##STR00022## ##STR00023## ##STR00024## ##STR00025## ##STR00026##
##STR00027## ##STR00028## ##STR00029## ##STR00030## ##STR00031##
##STR00032## ##STR00033## ##STR00034## ##STR00035## ##STR00036##
##STR00037## ##STR00038## ##STR00039## ##STR00040## ##STR00041##
##STR00042## ##STR00043## ##STR00044## ##STR00045## ##STR00046##
##STR00047## ##STR00048## ##STR00049## ##STR00050## ##STR00051##
##STR00052## ##STR00053## ##STR00054## ##STR00055## ##STR00056##
##STR00057## ##STR00058## ##STR00059## ##STR00060## ##STR00061##
##STR00062## ##STR00063## ##STR00064## ##STR00065## ##STR00066##
##STR00067## ##STR00068## ##STR00069## ##STR00070## ##STR00071##
##STR00072## ##STR00073## ##STR00074## ##STR00075## ##STR00076##
##STR00077## ##STR00078##
##STR00079## ##STR00080## ##STR00081## ##STR00082## ##STR00083##
##STR00084## ##STR00085## ##STR00086## ##STR00087## ##STR00088##
##STR00089## ##STR00090## ##STR00091## ##STR00092## ##STR00093##
##STR00094## ##STR00095## ##STR00096## ##STR00097## ##STR00098##
##STR00099## ##STR00100## ##STR00101## ##STR00102## ##STR00103##
##STR00104## ##STR00105## ##STR00106## ##STR00107## ##STR00108##
##STR00109## ##STR00110## ##STR00111## ##STR00112## ##STR00113##
##STR00114## ##STR00115## ##STR00116## ##STR00117## ##STR00118##
##STR00119## ##STR00120## ##STR00121## ##STR00122## ##STR00123##
##STR00124## ##STR00125## ##STR00126## ##STR00127## ##STR00128##
##STR00129## ##STR00130## ##STR00131## ##STR00132## ##STR00133##
##STR00134## ##STR00135## ##STR00136## ##STR00137##
##STR00138##
[0055] Preparation processes for the various embodiments of
compound A are known in the prior art. Among other documents, the
person skilled in the art may make reference to the disclosure of
documents WO 2006/122630, WO 2006/100896, EP 1661888, WO
2012/034627, WO 2013/120577, WO 2014/015937, WO 2014/015938, WO
2014/015935, WO 2013/083216 and WO 2012/150001.
[0056] The compound P is a p-dopant in the sense of the
abovementioned definition. Without being bound to this theory, it
is assumed that the compound P is a Lewis acid which, when present
mixed with the compound A, forms a complex with the compound A. The
compound A acts here as a Lewis base. Without being bound to this
theory, the complex is formed by virtue of a free electron pair in
compound A interacting with the bismuth metal atom of compound
P.
[0057] The compound P may be a mononuclear complex of bismuth, a
binuclear complex of bismuth or a polynuclear complex of bismuth.
It is possible that the compound P is a mononuclear complex of
bismuth if it is present in the gas phase and a polynuclear complex
of bismuth if it is in the solid phase. This means that the
compound P may polymerize or depolymerize according to the state of
matter.
[0058] The complex of bismuth is preferably a complex of bismuth in
the (II), (III) or (V) oxidation state. It is more preferably a
complex of bismuth in the (III) oxidation state.
[0059] Preferably, the complex of bismuth has at least one ligand L
which is an organic compound. The ligand L is preferably selected
from monodentate, bidentate and tridentate ligands, more preferably
from monodentate ligands. Further preferably, the ligand L is
negatively charged, preferably triply, doubly or singly negatively
charged, more preferably singly negatively charged.
[0060] The group of the ligand L that binds to the bismuth atom is
preferably selected from carboxylic acid groups, thiocarboxylic
acid groups, in particular thiolic acid groups, thionic acid groups
and dithiolic acid groups, carboxamide groups and carboximide
groups, more preferably from carboxylic acid groups.
[0061] Preferably, the ligand L corresponds to one of the following
formulae (L-I), (L-II), (L-III) and (L-IV)
##STR00139##
[0062] where:
[0063] W is selected from carboxylic acid groups, thiocarboxylic
acid groups, in particular thiolic acid groups, thionic acid groups
and dithiolic acid groups, carboxamide groups and carboximide
groups, more preferably from carboxylic acid groups;
[0064] U is the same or different at each instance and is selected
from N and CR.sup.3 if no W group is bonded thereto, and U is C
when a W group is bonded thereto; and
[0065] R.sup.3 is the same or different at each instance and is
selected from H, D, F, Cl, Br, I, CN, NO.sup.2, CF.sub.3,
straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms,
branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon
atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms,
aromatic ring systems having 6 to 40 aromatic ring atoms, and
heteroaromatic ring systems having 5 to 40 aromatic ring atoms;
where the alkyl, alkoxy, alkenyl and alkynyl groups mentioned and
the aromatic ring systems and heteroaromatic ring systems mentioned
may each be substituted by one or more R.sup.4 radicals; and where
one or more CH.sub.2 groups in the alkyl, alkoxy, alkenyl and
alkynyl groups mentioned may be replaced by
--R.sup.4C.dbd.CR.sup.4--, --C.ident.C--, Si(R.sup.4).sub.2,
C.dbd.O, C.dbd.NR.sup.4, --C(.dbd.O)O--, --C(.dbd.O)NR.sup.4--,
P(.dbd.O)(R.sup.4), --O--, --S--, SO or SO.sub.2; and
[0066] R.sup.4 is the same or different at each instance and is
selected from H, D, F, Cl, CN, NO.sub.2, alkyl groups having 1 to
20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring
atoms and heteroaromatic ring systems having 5 to 40 aromatic ring
atoms; where two or more R.sup.4 radicals may be joined to one
another and may form a ring; and where the alkyl groups, aromatic
ring systems and heteroaromatic ring systems mentioned may be
substituted by F, Cl, CN and NO.sub.2; and
[0067] R.sup.5 is the same or different at each instance and is
selected from H, D, F, C(.dbd.O)R.sup.4, CN, Si(R.sup.4).sub.3,
P(.dbd.O)(R.sup.4).sub.2, OR.sup.4, S(.dbd.O)R.sup.4,
S(.dbd.O).sub.2R.sup.4, straight-chain alkyl or alkoxy groups
having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy
groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups
having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40
aromatic ring atoms, and heteroaromatic ring systems having 5 to 40
aromatic ring atoms; where two or more R.sup.1 radicals may be
joined to one another and may form a ring; where the alkyl, alkoxy,
alkenyl and alkynyl groups mentioned and the aromatic ring systems
and heteroaromatic ring systems mentioned may each be substituted
by one or more R.sup.4 radicals; and where one or more CH.sub.2
groups in the alkyl, alkoxy, alkenyl and alkynyl groups mentioned
may be replaced by --R.sup.4C.dbd.CR.sup.4--, --C.ident.C--,
Si(R.sup.4).sub.2, C.dbd.O, C.dbd.NR.sup.4, --C(.dbd.O)O--,
--C(.dbd.O)NR.sup.4--, P(.dbd.O)(R.sup.4), --O--, --S--, SO or
SO.sub.2; and
[0068] R.sup.6 is the same or different at each instance and is
selected from H, D, F, Cl, Br, I, CN, NO.sub.2, CF.sub.3,
straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms,
branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon
atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms,
aromatic ring systems having 6 to 40 aromatic ring atoms, and
heteroaromatic ring systems having 5 to 40 aromatic ring atoms;
where the alkyl, alkoxy, alkenyl and alkynyl groups mentioned and
the aromatic ring systems and heteroaromatic ring systems mentioned
may each be substituted by one or more R.sup.4 radicals; and where
one or more CH.sub.2 groups in the alkyl, alkoxy, alkenyl and
alkynyl groups mentioned may be replaced by
--R.sup.4C.dbd.CR.sup.4--, Si(R.sup.4).sub.2, C.dbd.O,
C.dbd.NR.sup.4, --C(.dbd.O)O--, --C(.dbd.O)NR.sup.4--,
P(.dbd.O)(R.sup.4), --O--, --S--, SO or SO.sub.2.
[0069] Preferably, in each of the formulae (L-I) to (L-III), at
least one R.sup.3 group is present, selected from F, Cl, Br, I, CN,
NO.sub.2 and alkyl groups which have 1 to 20 carbon atoms and at
least one substituent selected from F, Cl, CN and NO.sub.2. Among
the groups mentioned, particular preference is given to F, Cl, CN
and CF.sub.3.
[0070] More preferably, one, two or three R.sup.3 groups of this
kind are present, most preferably three.
[0071] Preferably, in formula (L-IV), at least one R.sup.6 group is
present, selected from F, Cl, Br, I, CN, NO.sub.2 and alkyl groups
which have 1 to 20 carbon atoms and at least one substituent
selected from F, Cl, CN and NO.sub.2. Among the groups mentioned,
particular preference is given to F, Cl, CN and CF.sub.3.
[0072] More preferably, one, two or three R.sup.6 groups of this
kind are present, most preferably three.
[0073] Preferred ligands L are selected from fluorinated benzoic
acid derivatives, fluorinated or non-fluorinated phenylacetic acid
derivatives and fluorinated or non-fluorinated acetic acid
derivatives.
[0074] Examples of preferred fluorinated benzoic acid derivatives
are: 2-(trifluoromethyl)benzoic acid; 3,5-difluorobenzoic acid;
3-hydroxy-2,4,6-triiodobenzoic acid; 3-fluoro-4-methylbenzoic acid;
3-(trifluoromethoxy)benzoic acid; 4-(trifluoromethoxy)benzoic acid;
4-chloro-2,5-difluorobenzoic acid; 2-chloro-4,5-difluorobenzoic
acid; 2,4,5-trifluorobenzoic acid; 2-fluorobenzoic acid;
4-fluorobenzoic acid; 2,3,4-trifluorobenzoic acid;
2,3,5-trifluorobenzoic acid; 2,3-difluorobenzoic acid;
2,4-bis(trifluoromethyl)benzoic acid; 2,4-difluorobenzoic acid;
2,5-difluorobenzoic acid; 2,6-bis(trifluoromethyl)benzoic acid;
2,6-difluorobenzoic acid; 2-chloro-6-fluorobenzoic acid;
2-fluoro-4-(trifluoromethyl)benzoic acid;
2-fluoro-5-(trifluoromethyl)benzoic acid;
2-fluoro-6-(trifluoromethyl)benzoic acid; 3,4,5-trifluorobenzoic
acid; 3,4-difluorobenzoic acid; 3,5-bis(trifluoromethyl)benzoic
acid; 3-(trifluoromethyl)benzoic acid; 3-chloro-4-fluorobenzoic
acid; 3-fluoro-5-(trifluoromethyl)benzoic acid; 3-fluorobenzoic
acid; 4-fluoro-2-(trifluoromethyl)benzoic acid;
4-fluoro-3-(trifluoromethyl)benzoic acid; 5-fluoro-2-methylbenzoic
acid; 2-(trifluoromethoxy)benzoic acid; 2,3,5-trichlorobenzoic
acid; 4-(trifluoromethyl)benzoic acid; pentafluorobenzoic acid; and
2,3,4,5-tetrafluorobenzoic acid.
[0075] Examples of fluorinated or non-fluorinated phenylacetic acid
derivatives are: 2-fluorophenylacetic acid; 3-fluorophenylacetic
acid; 4-fluorophenylacetic acid; 2,3-difluorophenylacetic acid;
2,4-difluorophenylacetic acid; 2,6-difluorophenylacetic acid;
3,4-difluorophenylacetic acid; 3,5-difluorophenylacetic acid;
pentafluoro-phenylacetic acid; 2-chloro-6-fluorophenylacetic acid;
2-chloro-3,6-difluorophenylacetic acid;
3-chloro-2,6-difluorophenylacetic acid;
3-chloro-4-fluorophenylacetic acid; 5-chloro-2-fluorophenylacetic
acid; 2,3,4-trifluorophenylacetic acid; 2,3,5-trifluorophenylacetic
acid; 2,3,6-trifluorophenylacetic acid; 2,4,5-trifluorophenylacetic
acid; 2,4,6-trifluorophenylacetic acid; 3,4,5-trifluorophenylacetic
acid; 3-chloro-2-fluorophenylacetic acid; 6-fluorophenylacetic
acid; 4-chloro-2-fluorophenylacetic acid;
2-chloro-4-fluorophenylacetic acid.
[0076] Examples of fluorinated or non-fluorinated acetic acid
derivatives are: difluoroacetic acid; trifluoroacetic acid;
chlorodifluoroacetic acid; (3-chlorophenyl)difluoroacetic acid;
(3,5-difluorophenyl)difluoroacetic acid; (4-butylphenyl)
difluoroacetic acid; (4-tert-butylphenyl)difluoroacetic acid;
(3,4-dimethylphenyl)difluoroacetic acid;
(3-chloro-4-fluorophenyl)-difluoroacetic acid;
(4-chlorophenyl)-difluoroacetic acid;
2-biphenyl-3',5'-difluoroacetic acid;
3-biphenyl-3',5'-difluoroacetic acid;
4-biphenyl-3',5'-difluoroacetic acid;
2-biphenyl-3',4'-difluoroacetic acid;
3-biphenyl-3',4'-difluoroacetic acid;
4-biphenyl-3',4'-difluoroacetic acid and 2,2-difluoropropionic acid
and higher homologues thereof.
[0077] The compounds mentioned in deprotonated form in the above
list may also be present in protonated form in accordance with the
invention. They are preferably in deprotonated form. The compounds
mentioned in protonated form in the above list may also be present
in deprotonated form, which is preferred in accordance with the
invention.
[0078] The material of the invention may contain further compounds.
It preferably contains essentially exclusively exactly one compound
A and exactly one compound P. If further compounds are present,
these are preferably compounds according to formula (A). In one
possible embodiment of the invention, exactly two different
compounds A and exactly one compound P are present in the material
of the invention.
[0079] The compound P is preferably present as a dopant in the
material of the invention. It is preferable that the material of
the invention contains the compound P in a concentration of 0.1% to
20%, more preferably 0.5% to 12%, even more preferably 1% to 8% and
most preferably of 2% to 6%.
[0080] Percentages in the context of the present application are
stated such that they mean % by volume in the case of gas phase
deposition and % by weight in the case of application from the
liquid phase.
[0081] The material of the invention is preferably in the form of a
thin layer, more preferably of a functional layer of an electronic
device. The present invention therefore also provides a layer,
preferably a semiconductor layer, comprising the material of the
invention.
[0082] The layer comprising the material of the invention
preferably has a thickness of 1 to 500 nm, more preferably of 5 to
300 nm and most preferably of 8 to 250 nm. Itis preferably used as
hole-transporting layer in an electronic device, preferably of an
OLED, as laid out in detail further down.
[0083] The material of the invention can be applied in the form of
a layer from the gas phase, for example by means of the OVPD
(organic vapour phase deposition) method or with the aid of carrier
gas sublimation. In this case, the materials are applied at a
pressure between 10.sup.-5 mbar and 1 bar. A special case of this
method is the OVJP (organic vapour jet printing) method, in which
the materials are applied directly by a nozzle and thus structured
(for example M. S. Arnold et al., Appl. Phys. Lett. 2008, 92,
053301). Alternatively, the material can also be produced from the
liquid phase, for example by spin-coating, or by any printing
method, for example screen printing, flexographic printing, nozzle
printing or offset printing, preferably LITI (light-induced thermal
imaging, thermal transfer printing) or inkjet printing.
[0084] For the processing of the material of the invention from the
liquid phase, for example by the abovementioned methods,
formulations are required. These formulations may, for example, be
solutions, dispersions or emulsions. For this purpose, itmay be
preferable to use mixtures of two or more solvents. Suitable and
preferred solvents are, for example, toluene, anisole, o-, m- or
p-xylene, methyl benzoate, mesitylene, tetralin, veratrole, THF,
methyl-THF, THP, chlorobenzene, dioxane, phenoxytoluene, especially
3-phenoxytoluene, (-)-fenchone, 1,2,3,5-tetramethylbenzene,
1,2,4,5-tetramethylbenzene, 1-methylnaphthalene,
2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidinone,
3-methylanisole, 4-methylanisole, 3,4-dimethylanisole,
3,5-dimethylanisole, acetophenone, .alpha.-terpineol,
benzothiazole, butyl benzoate, cumene, cyclohexanol, cyclohexanone,
cyclohexylbenzene, decalin, dodecylbenzene, ethyl benzoate, indane,
methyl benzoate, NMP, p-cymene, phenetole, 1,4-diisopropylbenzene,
dibenzyl ether, diethylene glycol butyl methyl ether, triethylene
glycol butyl methyl ether, diethylene glycol dibutyl ether,
triethylene glycol dimethyl ether, diethylene glycol monobutyl
ether, tripropylene glycol dimethyl ether, tetraethylene glycol
dimethyl ether, 2-isopropyl naphthalene, pentylbenzene,
hexylbenzene, heptylbenzene, octylbenzene,
1,1-bis(3,4-dimethylphenyl)ethane or mixtures of these
solvents.
[0085] The invention therefore further provides a formulation,
especially a solution, dispersion or emulsion, comprising the
material of the invention and at least one solvent, preferably an
organic solvent. The way in which such a formulation, especially
such solutions, can be prepared is known to those skilled in the
art and is described, for example, in WO 2002/072714, WO
2003/019694 and the literature cited therein.
[0086] In the case of gas phase deposition, both compound P and
compound A are coevaporated, preferably from different vapour
deposition sources, and deposited as a layer. In the case of
application from the liquid phase, the compound P and the compound
A are dissolved in solvent and then applied by means of the
abovementioned printing techniques. The layer comprising the
material of the invention is finally obtained by evaporating the
solvent.
[0087] The present application therefore also provides a process
for producing a layer comprising the material of the invention,
characterized in that compound A and compound P are applied
together from the gas phase, or in that a formulation comprising
the material of the invention is applied from the liquid phase.
[0088] The material of the invention is suitable for use in
electronic devices, preferably selected from the group consisting
of organic integrated circuits (OLCs), organic field-effect
transistors (OFETs), organic thin-film transistors (OTFTs), organic
light-emitting transistors (OLETs), organic solar cells (OSCs),
organic optical detectors, organic photoreceptors, organic
field-quench devices (OFQDs), organic light-emitting
electrochemical cells (OLECs), organic laser diodes (O-lasers) and
more preferably organic electroluminescent devices (OLEDs).
[0089] This material may be used in different functions. Preference
is given to the use of the material in a hole-transporting layer,
for example a hole injection layer, a hole transport layer, an
exciton blocker layer or an electron blocker layer. The
above-described use of the material likewise forms part of the
subject-matter of the invention.
[0090] A hole transport layer according to the present application
is a layer having a hole-transporting function between the anode
and emitting layer.
[0091] Hole injection layers and electron blocker layers are
understood in the context of the present application to be specific
embodiments of hole transport layers. A hole injection layer, in
the case of a plurality of hole transport layers between the anode
and emitting layer, is a hole transport layer which directly
adjoins the anode or is separated therefrom only by a single
coating of the anode. An electron blocker layer, in the case of a
plurality of hole transport layers between the anode and emitting
layer, is that hole transport layer which directly adjoins the
emitting layer on the anode side.
[0092] The invention further provides an electronic device
comprising the material of the invention, preferably in the form of
a layer. This electronic device is preferably selected from the
abovementioned devices. More preferably, the electronic device is
an OLED comprising anode, cathode and at least one emitting layer,
characterized in that at least one layer, preferably a
hole-transporting layer, comprises the material of the
invention.
[0093] Apart from the cathode, anode and emitting layer, the OLED
preferably comprises still further functional layers. These are
selected, for example, from in each case one or more hole injection
layers, hole transport layers, hole blocker layers, electron
transportlayers, electron injection layers, electron blocker
layers, exciton blocker layers, interlayers, charge generation
layers (IDMC 2003, Taiwan; Session 21 OLED (5), T. Matsumoto, T.
Nakada, J. Endo, K. Mori, N. Kawamura, A. Yoko', J. Kido,
Multiphoton Organic EL Device Having Charge Generation Layer)
and/or organic or inorganic pin junctions.
[0094] The sequence of the layers of the OLED comprising the
material of the invention is preferably as follows: [0095] anode
[0096] hole injection layer [0097] hole transportlayer [0098]
optionally further hole transport layer [0099] optionally electron
blocker layer [0100] emitting layer [0101] optionally hole blocker
layer [0102] electron transportlayer [0103] electron injection
layer [0104] cathode.
[0105] However, it is not necessary for all the layers mentioned to
be present, and further layers may additionally be present.
[0106] The OLED of the invention may comprise several emitting
layers. More preferably, these emission layers in this case have
several emission maxima between 380 nm and 750 mm overall, such
that the overall result is white emission; in other words, various
emitting compounds which may fluoresce or phosphoresce and which
emit blue, yellow, green, orange or red light are used in the
emitting layers. Especially preferred are three-layer systems, i.e.
systems having three emitting layers, where the three layers show
blue, green and orange or red emission (for the basic construction
see, for example, WO 2005/011013).
[0107] Preferably, the OLED comprises the material of the invention
in a hole-transporting layer disposed between the anode and
emitting layer, with one or more further layers preferably present
between the layer comprising the material of the invention and the
emitting layer. Preferably, these further layers are hole transport
layers, more preferably electron blocker layers. The further layers
mentioned may be p-doped or non-p-doped.
[0108] In a preferred embodiment of the invention, the HOMO levels
of the hole-transporting layer (HTL) and the layer between the
hole-transporting layer and emitting layer (EBL) meet the following
condition:
HOMO(HTL)<=HOMO(EBL).
[0109] In this way, it is possible to avoid a hole barrier and
hence a voltage drop between the hole transport layer and the
emitting layer. This is advantageously possible, for example,
through the use of the same material in the hole transport layer
and the further layer between the hole transport layer and emitting
layer.
[0110] However, it may also be preferable that the material of the
invention is disposed in a hole-transporting layer directly
adjoining the emitting layer.
[0111] The hole transport layers disposed between the layer
comprising the material of the invention and the emitting layer
preferably comprise one or more identical or different compounds of
the formula (A), preferably different compounds of the formula
(A).
[0112] The OLED of the invention may have a multitude of hole
transport layers. There are preferably one, two, three, four or
five hole transport layers, more preferably two, three or four hole
transport layers, at least one of which comprises the material of
the invention.
[0113] It is further preferable that the OLED comprises the
material of the invention in a layer directly adjoining the
anode.
[0114] More preferably, the OLED of the invention comprises one of
the following layer structures:
[0115] a) anode--layer comprising the material of the
invention--electron blocker layer--emitting layer;
[0116] b) anode--layer comprising the material of the
invention--hole transport layer--electron blacker layer--emitting
layer;
[0117] c) anode--first layer comprising the material of the
invention--hole transport layer--second layer comprising the
material of the invention--electron blocker layer--emitting
layer.
[0118] Those layers that preferably adjoin the emitting layer on
the cathode side correspond to the abovementioned preferred layers
in these positions, namely one or more hole blocker layers,
electron transport layers and electron injection layers.
[0119] In structure a), it is possible for both the layer
comprising the material of the invention and the electron blocker
layer to comprise the same compound of the formula (A). In
structure c), both the layer comprising the material of the
invention and the hole transport layer may comprise the same
compound of the formula (A) and/or both the second layer comprising
the material of the invention and the electron blocker layer may
comprise the same compound of the formula (A).
[0120] It is additionally preferable that the electron blocker
layer in the OLED of the invention, or that layer which directly
adjoins the emitting layer on the anode side, comprises a compound
of the formula (A), especially a compound of the formula (A) which
is a monoarylamine.
[0121] It is preferable when the material of the invention is used
in an OLED comprising one or more phosphorescent emitting
compounds. The term "phosphorescent emitting compounds" typically
encompasses compounds where the emission of light is effected
through a spin-forbidden transition, for example a transition from
an excited triplet state or a state having a higher spin quantum
number, for example a quintet state.
[0122] Suitable phosphorescent emitting compounds (=triplet
emitters) are especially compounds which, when suitably excited,
emit light, preferably in the visible region, and also contain at
least one atom of atomic number greater than 20, preferably greater
than 38, and less than 84, more preferably greater than 56 and less
than 80. Preferred phosphorescent emitting compounds are compounds
containing copper, molybdenum, tungsten, rhenium, ruthenium,
osmium, rhodium, iridium, palladium, platinum, silver, gold or
europium, especially compounds containing iridium, platinum or
copper. In the context of the present invention, all luminescent
iridium, platinum or copper complexes are considered to be
phosphorescent emitting compounds.
[0123] Examples of the above-described emitting compounds can be
found in applications WO 00/70655, WO 01/41512, WO 02/02714, WO
02/15645, EP 1191613, EP 1191612, EP 1191614, WO 05/033244, WO
05/019373 and US 2005/0258742. In general, all phosphorescent
complexes as used for phosphorescent OLEDs according to the prior
art and as known to those skilled in the art in the field of
organic electroluminescent devices are suitable. It is also
possible for the person skilled in the art, without exercising
inventive skill, to use further phosphorescent complexes in
combination with the material of the invention in an OLED.
[0124] In an alternative embodiment, it is preferable that the
material is used in an OLED comprising a fluorescent emitting
compound in its emitting layer. Preferably, the emitting layer in
this case comprises an arylamino compound as fluorescent emitting
compound, more preferably in combination with a host material. The
host material in this case is preferably selected from compounds
comprising one or more anthracene groups.
[0125] Preferred embodiments of the different functional materials
in the electronic device are listed hereinafter.
[0126] Preferred phosphorescent emitting compounds are the
abovementioned compounds.
[0127] Preferred fluorescent emitting compounds are selected from
the class of the arylamines. An arylamine or an aromatic amine in
the context of this invention is understood to mean a compound
containing three substituted or unsubstituted aromatic or
heteroaromatic ring systems bonded directly to the nitrogen.
Preferably, at least one of these aromatic or heteroaromatic ring
systems is a fused ring system, more preferably having at least 14
aromatic ring atoms. Preferred examples of these are aromatic
anthraceneamines, aromatic anthracenediamines, aromatic
pyreneamines, aromatic pyrenediamines, aromatic chryseneamines or
aromatic chrysenediamines. An aromatic anthraceneamine is
understood to mean a compound in which a diarylamino group is
bonded directly to an anthracene group, preferably in the 9
position. An aromatic anthracenediamine is understood to mean a
compound in which two diarylamino groups are bonded directly to an
anthracene group, preferably in the 9,10 positions. Aromatic
pyreneamines, pyrenediamines, chryseneamines and chrysenediamines
are defined analogously, where the diarylamino groups in the pyrene
are bonded preferably in the 1 position or 1,6 positions. Further
preferred emitting compounds are indenofluoreneamines or -diamines,
for example according to WO 2006/108497 or WO 2006/122630,
benzoindenofluoreneamines or -diamines, for example according to WO
2008/006449, and dibenzoindenofluoreneamines or -diamines, for
example according to WO 2007/140847, and the indenofluorene
derivatives having fused aryl groups disclosed in WO 2010/012328.
Likewise preferred are the pyrenearylamines disclosed in WO
2012/048780 and in WO 2013/185871. Likewise preferred are the
benzoindenofluoreneamines disclosed in WO 2014/037077, the
benzofluoreneamines disclosed in WO 2014/106522 and the extended
benzoindenofluorenes disclosed in WO 2014/111269.
[0128] Useful matrix materials, preferably for fluorescent emitting
compounds, include materials of various substance classes.
Preferred matrix materials are selected from the classes of the
oligoarylenes (e.g. 2,2',7,7'-tetraphenylspirobifluorene according
to EP 676461 or dinaphthylanthracene), especially of the
oligoarylenes containing fused aromatic groups, the
oligoarylenevinylenes (e.g. DPVBi or spiro-DPVBi according to EP
676461), the polypodal metal complexes (for example according to WO
2004/081017), the hole-conducting compounds (for example according
to WO 2004/058911), the electron-conducting compounds, especially
ketones, phosphine oxides, sulphoxides, etc. (for example according
to WO 2005/084081 and WO 2005/084082), the atropisomers (for
example according to WO 2006/048268), the boronic acid derivatives
(for example according to WO 2006/117052) or the benzanthracenes
(for example according to WO 2008/145239). Particularly preferred
matrix materials are selected from the classes of the oligoarylenes
comprising naphthalene, anthracene, benzanthracene and/or pyrene or
atropisomers of these compounds, the oligoarylenevinylenes, the
ketones, the phosphine oxides and the sulphoxides. Very
particularly preferred matrix materials are selected from the
classes of the oligoarylenes comprising, anthracene,
benzanthracene, benzophenanthrene and/or pyrene or atropisomers of
these compounds. An oligoarylene in the context of this invention
shall be understood to mean a compound in which at least three aryl
or arylene groups are bonded to one another. Preference is further
given to the anthracene derivatives disclosed in WO 2006/097208, WO
2006/131192, WO 2007/065550, WO 2007/110129, WO 2007/065678, WO
2008/145239, WO 2009/100925, WO 2011/054442 and EP 1553154, and the
pyrene compounds disclosed in EP 1749809, EP 1905754 and US
2012/0187826.
[0129] Preferred matrix materials for phosphorescent emitting
compounds are aromatic ketones, aromatic phosphine oxides or
aromatic sulphoxides or sulphones, for example according to WO
2004/013080, WO 2004/093207, WO 2006/005627 or WO 2010/006680,
triarylamines, carbazole derivatives, e.g. CBP
(N,N-biscarbazolylbiphenyl) or the carbazole derivatives disclosed
in WO 2005/039246, US 2005/0069729, JP 2004/288381, EP 1205527 or
WO 2008/086851, indolocarbazole derivatives, for example according
to WO 2007/063754 or WO 2008/056746, indenocarbazole derivatives,
for example according to WO 2010/136109, WO 2011/000455 or WO
2013/041176, azacarbazole derivatives, for example according to EP
1617710, EP 1617711, EP 1731584, JP 2005/347160, bipolar matrix
materials, for example according to WO 2007/137725, silanes, for
example according to WO 2005/111172, azaboroles or boronic esters,
for example according to WO 2006/117052, triazine derivatives, for
example according to WO 2010/015306, WO 2007/063754 or WO
2008/056746, zinc complexes, for example according to EP 652273 or
WO 2009/062578, diazasilole or tetraazasilole derivatives, for
example according to WO 2010/054729, diazaphosphole derivatives,
for example according to WO 2010/054730, bridged carbazole
derivatives, for example according to US 2009/0136779, WO
2010/050778, WO 2011/042107, WO 2011/088877 or WO 2012/143080,
triphenylene derivatives, for example according to WO 2012/048781,
or lactams, for example according to WO 2011/116865 or WO
2011/137951.
[0130] Suitable charge transport materials as usable in the hole
injection or hole transport layer or electron blocker layer or in
the electron transport layer of the electronic device of the
invention are, as well as the compounds of the formula (A), for
example, the compounds disclosed in Y. Shirota et al., Chem. Rev.
2007, 107(4), 953-1010, or other materials as used in these layers
according to the prior art.
[0131] Examples of preferred materials which can be used in a hole
transport, hole injection or electron blocker layer in the
electroluminescent device of the invention are, as well as the
compounds of the formula (A), indenofluorenamine derivatives (for
example according to WO 06/122630 or WO 06/100896), the amine
derivatives disclosed in EP 1661888, hexaazatriphenylene
derivatives (for example according to WO 01/049806), amine
derivatives having fused aromatic systems (for example according to
U.S. Pat. No. 5,061,569), the amine derivatives disclosed in WO
95/09147, monobenzoindenofluoreneamines (for example according to
WO 08/006449), dibenzoindenofluoreneamines (for example according
to WO 07/140847), spirobifluoreneamines (for example according to
WO 2012/034627 and WO 2013/120577), fluoreneamines (for example
according to WO 2014/015937, WO 2014/015938 and WO 2014/015935),
spirodibenzopyranamines (for example according to WO 2013/083216)
and dihydroacridine derivatives (for example according to WO
2012/150001).
[0132] Materials used for the electron transport layer may be any
materials as used according to the prior artas electron transport
materials in the electron transport layer. Especially suitable are
aluminium complexes, for example Alq.sub.3, zirconium complexes,
for example Zrq.sub.4, lithium complexes, for example Liq,
benzimidazole derivatives, triazine derivatives, pyrimidine
derivatives, pyridine derivatives, pyrazine derivatives,
quinoxaline derivatives, quinoline derivatives, oxadiazole
derivatives, aromatic ketones, lactams, boranes, diazaphosphole
derivatives and phosphine oxide derivatives. Further suitable
materials are derivatives of the abovementioned compounds as
disclosed in JP 2000/053957, WO 2003/060956, WO 2004/028217, WO
2004/080975 and WO 2010/072300.
[0133] Preferred cathodes of the electronic device are metals
having a low work function, metal alloys or multilayer structures
composed of various metals, for example alkaline earth metals,
alkali metals, main group metals or lanthanoids (e.g. Ca, Ba, Mg,
Al, In, Mg, Yb, Sm, etc.). Additionally suitable are alloys
composed of an alkali metal or alkaline earth metal and silver, for
example an alloy composed of magnesium and silver. In the case of
multilayer structures, in addition to the metals mentioned, it is
also possible to use further metals having a relatively high work
function, for example Ag or Al, in which case combinations of the
metals such as Ca/Ag, Mg/Ag or Ba/Ag, for example, are generally
used. It may also be preferable to introduce a thin interlayer of a
material having a high dielectric constant between a metallic
cathode and the organic semiconductor. Examples of useful materials
for this purpose are alkali metal or alkaline earth metal
fluorides, but also the corresponding oxides or carbonates (e.g.
LiF, Li.sub.2O, BaF.sub.2, MgO, NaF, CsF, Cs.sub.2CO.sub.3, etc.).
It is also possible to use lithium quinolinate (LiQ) for this
purpose. The layer thickness of this layer is preferably between
0.5 and 5 nm.
[0134] Preferred anodes are materials having a high work function.
Preferably, the anode has a work function of greater than 4.5 eV
versus vacuum. Firstly, metals having a high redox potential are
suitable for this purpose, for example Ag, Pt or Au. On the other
hand, metal/metal oxide electrodes (e.g. Al/Ni/NiO.sub.x,
Al/PtO.sub.x) may also be preferred. For some applications, at
least one of the electrodes has to be transparent or partly
transparent in order to enable the irradiation of the organic
material (organic solar cell) or the emission of light (OLED,
O-LASER). Preferred anode materials here are conductive mixed metal
oxides. Particular preference is given to indium tin oxide (ITO) or
indium zinc oxide (IZO). Preference is further given to conductive
doped organic materials, especially conductive doped polymers. In
addition, the anode may also consist of two or more layers, for
example of an inner layer of ITO and an outer layer of a metal
oxide, preferably tungsten oxide, molybdenum oxide or vanadium
oxide.
[0135] The device is structured appropriately (according to the
application), contact-connected and finally sealed, in order to
rule out damaging effects by water and air.
[0136] In a preferred embodiment, the electronic device is
characterized in that one or more layers are coated by a
sublimation process. In this case, the materials are applied by
vapour deposition in vacuum sublimation systems at an initial
pressure of less than 10.sup.-5 mbar, preferably less than
10.sup.-6 mbar. In this case, however, it is also possible that the
initial pressure is even lower, for example less than 10.sup.-7
mbar. Preferred methods for application of layers from the gas
phase are described further up, and apply generally to the
production of layers in the OLEDs of the invention.
[0137] In an alternative embodiment, the electronic device is
characterized in that one or more layers are applied from solution.
Preferred methods for application of layers from solution are
described further up, and apply generally to the production of
layers in the OLEDs of the invention.
[0138] It is further preferable that an electronic device of the
invention is produced by applying one or more layers from solution
and one or more layers by a sublimation method.
[0139] The OLEDs of the invention can be used in displays, as light
sources in lighting applications and as lightsources in medical
and/or cosmetic applications (for example light therapy).
WORKING EXAMPLES
A) Synthesis of
bis[[3,5-bis(trifluoromethyl)benzoyl]oxy]bismuthanyl
3,5-bis(trifluoromethyl)benzoate
##STR00140##
[0141] 50 g (113.56 mmol) of triphenylbismuthane (CAS No.:
603-33-8) and 89.40 g of 3,5-bis(trifluoromethyl)benzoic acid
(340.36 mmol) are initially charged in a flask inertized under
argon and 11 of dried toluene is added. The mixture is heated
gradually to 80.degree. C. and then stirred at this temperature for
a further 12 hours. The mixture is subsequently cooled to room
temperature and filtered through a protective gas frit, washed
three times with toluene, dried at the vacuum pump and then
sublimed under high vacuum.
B) Device Examples
[0142] In examples I1 to I8 and C1 to C2 which follow, the data of
various OLEDs are presented. Examples C1 to C2 are comparative
examples according to the prior art; examples I1 to I8 show data of
OLEDs of the invention.
[0143] OLEDs of the invention and OLEDs according to the prior art
are produced by a general method according to WO 2004/058911, which
is adapted to the circumstances described here (variation in layer
thickness, materials). Glass plaques which have been coated with
structured ITO (indium tin oxide) in a thickness of 50 nm are the
substrates for the OLEDs. The substrates are subjected to wet
cleaning (cleaning machine, detergent: Merck Extran), then baked at
250.degree. C. for 15 min and, prior to the coating, treated with
an oxygen plasma.
[0144] Various layers are applied to the pretreated substrates:
first hole transport layer (NTLI)/second hole transport layer
(HTL2)/emission layer (EML)/electron transport layer (ETL)/electron
injection layer (EIL) and finally a 100 nm-thick aluminium cathode.
The exact structure of the OLEDs can be found in Table 1. The
materials used for production of the OLEDs are shown in Table
2.
[0145] All materials are applied by thermal vapour deposition in a
vacuum chamber. In this case, the emission layer always consists of
at least one matrix material and an emitting compound which is
added to the matrix material(s) in a particular proportion by
volume by co-evaporation. Details given in such a form as M1:D1
(95%:5%) mean here that the material M1 is present in the layer in
a proportion by volume of 95% and D1 in a proportion by volume of
5%. Analogously, the electron transport layer may also consist of a
mixture of two materials.
[0146] The OLEDs are characterized in a standard manner. For this
purpose, the electroluminescence spectra and the external quantum
efficiency (EQE, measured in percent) are determined as a function
of luminance, calculated from current-voltage-luminance
characteristics (IUL characteristics) assuming Lambertian radiation
characteristics, and the lifetime. The electroluminescence spectra
are determined at a luminance of 1000 cd/m.sup.2, and the CIE 1931
x and y color coordinates are calculated therefrom. The lifetime
LT80 is defined as the time after which the luminance drops from
the starting luminance to 80% of the start value in the course of
operation with constant current density.
TABLE-US-00001 TABLE 1 Structure of the OLEDs HTL1 HTL2 EML ETL EIL
Ex. thickness thickness thickness thickness thickness V1 NPB:BiC
NPB M1:D1 ST1:LiQ (50%:50%) LiQ (95%:5%) 20 nm 180 nm (95%:5%) 20
nm 30 nm 1 nm V2 DA1:BiC DA1 M1:D1 ST1:LiQ (50%:50%) LiQ (95%:5%)
20 nm 180 nm (95%:5%) 20 nm 30 nm 1 nm E1 MA2:BiC MA2 M1:D1 ST1:LiQ
(50%:50%) LiQ (95%:5%) 20 nm 180 nm (95%:5%) 20 nm 30 nm 1 nm E2
MA4:BiC MA4 M1:D1 ST1:LiQ (50%:50%) LiQ (95%:5%) 20 nm 180 nm
(95%:5%) 20 nm 30 nm 1 nm E3 MA5:BiC MA5 M1:D1 ST1:LiQ (50%:50%)
LiQ (95%:5%) 20 nm 180 nm (95%:5%) 20 nm 30 nm 1 nm E4 MA6:BiC MA6
M1:D1 ST1:LiQ (50%:50%) LiQ (95%:5%) 20 nm 180 nm (95%:5%) 20 nm 30
nm 1 nm E5 MA7:BiC MA7 M1:D1 ST1:LiQ (50%:50%) LiQ (95%:5%) 20 nm
180 nm (95%:5%) 20 nm 30 nm 1 nm E6 MA8:BiC MA8 M1:D1 ST1:LiQ
(50%:50%) LiQ (95%:5%) 20 nm 180 nm (95%:5%) 20 nm 30 nm 1 nm E7
MA9:BiC MA9 M1:D1 ST1:LiQ (50%:50%) LiQ (95%:5%) 20 nm 180 nm
(95%:5%) 20 nm 30 nm 1 nm E8 DA2:BiC DA2 M1:D1 ST1:LiQ (50%:50%)
LiQ (95%:5%) 20 nm 180 nm (95%:5%) 20 nm 30 nm 1 nm
TABLE-US-00002 TABLE 2 Structural formulae of the materials for the
OLEDs ##STR00141## F4TCNQ ##STR00142## BiC ##STR00143## M1
##STR00144## D1 ##STR00145## ST1 ##STR00146## LiQ ##STR00147## NPB
##STR00148## DA1 ##STR00149## DA2 ##STR00150## MA2 ##STR00151## MA4
##STR00152## MA5 ##STR00153## MA6 ##STR00154## MA7 ##STR00155## MA8
##STR00156## MA9
[0147] The examples are elucidated in detail hereinafter, in order
to illustrate the advantages of the OLEDs of the invention.
[0148] The inventive samples II to 18 are compared with the
comparative samples C1 and C2. The former differ from C1 and C2 in
that they contain a monoarylamine as material for the HTL, and no
diamine or tetraamine. In all cases, the p-dopant BiC is used in
the first of the two hole-transporting layers present. All
inventive samples II to 18 have a better lifetime and efficiency
than the comparative samples C1 and C2 (Table 3), with similar
values for voltage.
TABLE-US-00003 TABLE 3 Results for the OLEDs Ex. U @ 10 mA/cm.sup.2
EQE @ 10 mA/cm.sup.2 LT80 @ 60 mA/cm.sup.2 C1 4.3 5.7 195 C2 3.8
4.1 50 I1 4.2 8.3 310 I2 4.0 7.1 375 I3 4.2 7.9 365 I4 4.6 7.7 270
I5 4.2 7.0 250 I6 4.3 8.4 270 I7 3.9 7.3 330 I8 4.2 7.8 210
[0149] The examples shown illustrate the advantages of the
inventive combination of bismuth complexes with monoarylamines of
the formula (A) as hole transport materials in OLEDs. They should
not be interpreted in a restrictive manner. The advantages of the
inventive combination extend over the whole scope of the material
combinations defined in the claims.
* * * * *