# US 11,993,572 B2 · Composition for organic electronic devices

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- Number: US 11,993,572 B2
- Document ID: US11993572B2
- Status: Granted
- Kind: B2
- Application number: 16/628,297
- Filed: 2018-07-02
- Published: 2020-07-09
- Granted: 2024-05-28
- Earliest claimed: 2017-07-05
- Assignees: Merck Patent GmbH
- Applicants: Merck Patent GmbH
- Inventors: Amir Parham; Jonas Kroeber; Tobias Grossmann; Anja Jatsch; Christian Eickhoff; Christian Ehrenreich
- Web page: https://patentgrep.com/patent/US11993572B2

## CPC

- C09K 11/06: containing organic luminescent materials
- C07D 209/82: Carbazoles; Hydrogenated carbazoles
- C07D 403/04: directly linked by a ring-member-to-ring-member bond
- C07D 403/14: containing three or more hetero rings
- C07D 407/14: containing three or more hetero rings
- C07D 409/14: containing three or more hetero rings
- H10K 85/654: {comprising only nitrogen as heteroatom (H10K85/652 takes precedence)}
- H10K 85/6572: {comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole}
- C09K 2211/1007: Non-condensed systems
- C09K 2211/1029: containing one nitrogen atom as the heteroatom
- C09K 2211/185: of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
- H10K 30/353: {comprising blocking layers, e.g. exciton blocking layers}
- H10K 30/50: Photovoltaic [PV] devices
- H10K 50/11: characterised by the electroluminescent [EL] layers
- H10K 50/15: Hole transporting layers
- H10K 50/171: {Electron injection layers}
- H10K 85/342: {comprising iridium}
- H10K 85/633: {comprising polycyclic condensed aromatic hydrocarbons as substituents on the nitrogen atom}
- H10K 85/6574: {comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes}
- H10K 2101/10: Triplet emission
- H10K 2101/90: {Multiple hosts in the emissive layer}
- Y02E 10/549: Organic PV cells
- Y02P 70/50: Manufacturing or production processes characterised by the final manufactured product
- C09K: MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08)
- H10K: ORGANIC ELECTRIC SOLID-STATE DEVICES
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

The present invention relates to a composition which comprises an electron-transporting host and a hole-transporting host, to the use thereof in electronic devices and to electronic devices containing this composition. The electron-transporting host is particularly preferably selected from the class of the lactams. The hole-transporting host is preferably selected from the class of the biscarbazoles.

## Claims

### Claim 1

A composition comprising at least one compound of the formula (1a) and at least one compound of the formula (2)
where the following applies to the symbols and indices used:
V is a bond, C(R0)2, O or S;
v is 0 or 1;
X2 is on each occurrence, identically or differently, CR1 or N;
Z is C(R0)2, NR1, O or S;
N is 0 or 1;
Ar1 and Ar2 are in each case, independently of one another, selected from aromatic or heteroaromatic ring systems from Ar-1 to Ar-15 and Ar-20 to Ar-22
Y3 on each occurrence, identically or differently, denotes O, NR#, S or C(#)2, where the radical
R# is on each occurrence, identically or differently, H, D, F, Cl, Br, I, CN, NO2, N(Ar)2, N(R2)2, C(═O)Ar, C(═O)R2, P(═O)(Ar)2, P(Ar)2, B(Ar)2, Si(Ar)3, Si(R2)3, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 C atoms or an alkenyl group having 2 to 20 C atoms, which may in each case be substituted by one or more radicals R2, where one or more non-adjacent CH2 groups may be replaced by R2C═CR2, Si(R2)2, C═O, C═S, C═NR2, P(═O)(R2), SO, SO2, NR2, O, S or CONR2 and where one or more H atoms maybe replaced by D, F, Cl, Br, I, CN or NO2, an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, which may in each case be substituted by one or more radicals R2,
dashed bond represents the bond to the C atom which carries the respective substituent R;
R0 is on each occurrence, identically or differently, a straight-chain or branched alkyl group having 1 to 4 C atoms or both R0 form a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system, which may be substituted by one or more radicals R2;
R is selected on each occurrence, identically or differently, from the group consisting of H, D, F, Cl, Br, I, CN, NO2, N(Ar)2, N(R2)2, C(═O)Ar, C(═O)R2, P(═O)(Ar)2, P(Ar)2, B(Ar)2, Si(Ar)3, Si(R2)3, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 C atoms, a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 C atoms and an alkenyl group having 2 to 20 C atoms, which may in each case be substituted by one or more radicals R2, where one or more non-adjacent CH2 groups may be replaced by R2C═CR2, Si(R2)2, C═O, C═S, C═NR2, P(═O)(R2), SO, SO2, NR2, O, S or CONR2 and where one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO2, an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, which may in each case be substituted by one or more radicals R2, or an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms, which may be substituted by one or more radicals R2, or an aralkyl or heteroaralkyl group having 5 to 40 aromatic ring atoms, which may be substituted by one or more radicals R2;
two substituents R which are bonded to the same carbon atom or to adjacent carbon atoms may optionally form a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system, which may be substituted by one or more radicals R2;
R1 is selected on each occurrence, identically or differently, from the group consisting of H, D, F, Cl, Br, I, CN, NO2, N(Ar)2, N(R2)2, C(═O)Ar, C(═O)R2, P(═O)(Ar)2, P(Ar)2, B(Ar)2, Si(Ar)3, Si(R2)3, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 C atoms, a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 C atoms and an alkenyl group having 2 to 20 C atoms, which may in each case be substituted by one or more radicals R2, where one or more non-adjacent CH2 groups may be replaced by R2C═CR2, Si(R2)2, C═O, C═S, C═NR2, P(═O)(R2), SO, SO2, NR2, O, S, or CONR2 and where one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO2, an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, which may in each case be substituted by one or more radicals R2, or an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms, which may be substituted by one or more radicals R2, or an aralkyl or heteroaralkyl group having 5 to 40 aromatic ring atoms, which may be substituted by one or more radicals R2, where the heteroaromatic ring system having 5 to 40 aromatic ring atoms in R1 is dibenzofuran, dibenzothiophene or 9-phenylcarbazole, which may be substituted by one or more radicals R2;
R2 is selected on each occurrence, identically or differently, from the group consisting of H, D, F, Cl, Br, I, CN, NO2, N(Ar)2, NH2, N(R3)2, C(═O)Ar, C(═O)H, C(═O)R3, P(═O)(Ar)2, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms, a branched or cyclic alkyl, alkoxy or thioalkyl group thioalkyl group having 3 to 40 C atoms and an alkenyl or alkynyl group having 2 to 40 C atoms, which may in each case be substituted by one or more radicals R3, where one or more non-adjacent CH2 groups may be replaced by HC═CH, R3C═CR3, C═C, Si(R3)2, Ge(R3)2, Sn(R3)2, C═O, C═S, C═Se, C═NR3, P(═O)(R3), SO, SO2, NH, NR3, O, S, CONH or CONR3 and where one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO2, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R3, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R3, or a combination of these systems, where two or more adjacent substituents R2 may optionally form a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system, which may be substituted by one or more radicals R3;
R3 is selected on each occurrence, identically or differently, from the group consisting of H, D, F, CN, an aliphatic hydrocarbon radical having 1 to 20 C atoms, an aromatic ring system having 6 to 30 ring atoms and a heteroaromatic ring system having 10 to 30 ring atoms, in which one or more H atoms may be replaced by D, F, Cl, Br, I or CN and which may be substituted by one or more alkyl groups, each having 1 to 4 carbon atoms; two or more adjacent substituents R3 may form a mono- or polycyclic, aliphatic ring system with one another; and
with the proviso the substituent R3 in structures Ar-1 to Ar-15 and Ar-20 to Ar-22 is selected on each occurrence, identically or differently, from the group consisting of H, D, F, CN, an aliphatic hydrocarbon radical having 1 to 20 C atoms and an aromatic or heteroaromatic ring system having 6 to 30 aromatic ring atoms, in which one or more H atoms maybe replaced by D, F, Cl, Br, I or CN and which may be substituted by one or more alkyl groups, each having 1 to 4 carbon atoms and where the heteroaromatic ring system is selected from dibenzofuran, dibenzothiophene or 9-phenylcarbazole;
Ar is on each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which may be substituted by one or more non-aromatic radicals R3; two radicals Ar which are bonded to the same N atom, P atom or B atom may also be bridged to one another by a single bond or a bridge selected from N(R3), C(R3)2, O or S.

### Claim 2 (depends on 1)

The composition according to claim 1, wherein the compound of the formula (2) corresponds to the formula (2a),
where the symbols and indices used have a meaning as in claim 1, q and t in each case is 4 and r and sin each case, is 3.

### Claim 3 (depends on 1)

The composition according to claim 1, wherein one of the substituents Ar1 and Ar2 denotes an aromatic ring system or a heteroaromatic ring system selected from Ar-1 to Ar-15 and Ar-20 to Ar-22; and the other substituent denotes an aromatic ring system selected from Ar-1 to Ar-11, and Ar-22.

### Claim 4 (depends on 1)

The composition according to claim 1, wherein the substituents Ar1 and Ar2 in each case, independently of one another, denote an aromatic ring system selected from Ar-1 to Ar11, and Ar-22.

### Claim 5 (depends on 1)

The composition according to claim 1, wherein the composition comprises at least one further compound selected from the group consisting of hole-injection materials, hole-transport materials, hole-blocking materials, wide bandgap materials, fluorescent emitters, phosphorescent emitters, host materials, electron-blocking materials, electron-transport materials and electron-injection materials, n-dopants and p-dopants.

### Claim 6 (depends on 1)

The composition according to claim 1, wherein the compound of the formula (1a) corresponds to the formulae (1b), (1c), (1d) or (1e),
where the symbols and indices used have a meaning as in claim 1 and V in formula (1e) is C(R0)2, O or S.

### Claim 7 (depends on 1)

The composition according to claim 1, wherein R1 is H or D.

### Claim 8 (depends on 2)

The composition according to claim 2, wherein R1 is H or D.

### Claim 9 (depends on 1)

The composition according to claim 1, wherein the compound of the formula (1a) is selected from the group consisting of:

### Claim 10

A composition comprising at least one compound of the formula (1a) and at least one compound of the formula (2)
V is a bond, C(R0)2, O or S;
v is 0 or 1;
R0 is on each occurrence, identically or differently, a straight-chain or branched alkyl group having 1 to 4 C atoms or both R0 form a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system, which may be substituted by one or more radicals R2;
R is selected on each occurrence, identically or differently, from the group consisting of H, D, F, Cl, Br, I, CN, NO2, N(Ar)2 N(R2)2, C(═O)Ar, C(═O)R2, P(═O)(Ar)2, P(Ar)2B(Ar)2, Si(Ar)3, Si(R2)3, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 C atoms or an alkenyl group having 2 to 20 C atoms, which may in each case be substituted by one or more radicals R2, where one or more non-adjacent CH2 groups may be replaced by R2C═CR2, Si(R2)2, C═O, C═S, C═NR2, P(═O)(R2), SO, SO2, NR2, O, S or CONR2 and where one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO2, an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, which may in each case be substituted by one or more radicals R2, or an aryloxy or 40 heteroaryloxy group having 5 to 40 aromatic ring atoms, which may be substituted by one or more radicals R2, or an aralkyl or heteroaralkyl group having 5 to 40 aromatic ring atoms, which may be substituted by one or more radicals R2;
two substituents R which are bonded to the same carbon atom or to adjacent carbon atoms may optionally form a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system, which may be substituted by one or more radicals R2;
R2 is selected on each occurrence, identically or differently, from the group consisting of H, D, F, Cl, Br, I, CN, NO2, N(Ar)2, NH2, N(R3)2, C(═O)Ar, C(═O)H, C(═O)R3, P(═O)(Ar)2, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 C atoms or an alkenyl or alkynyl group having 2 to 40 C atoms, which may in each case be substituted by one or more radicals R3, where one or more non-adjacent CH2 groups may be replaced by HC═CH, R3C═CR3, C≡C, Si(R3)2, Ge(R3)2, Sn(R3)2, C═O, C═S, C═Se, C═NR3, P(═O)(R3), SO, SO2, NH, NR3, O, S, CONH or CONR3 and where one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO2, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R3, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R3, or a combination of these systems, where two or more adjacent substituents R2 may optionally form a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system, which may be substituted by one or more radicals R3;
R3 is selected on each occurrence, identically or differently, from the group consisting of H, D, F, CN, an aliphatic hydrocarbon radical having 1 to 20 C atoms or an aromatic ring system having 6 to 30 ring atoms or a heteroaromatic ring system having 10 to 30 ring atoms, in which one or more H atoms may be replaced by D, F, Cl, Br, I or CN and which may be substituted by one or more alkyl groups, each having 1 to 4 carbon atoms; two or more adjacent substituents R3 may form a mono- or polycyclic, aliphatic ring system with one another;
Ar is on each occurrence, identically or differently, an aromatic or hetero aromatic ring system having 5 to 30 aromatic ring atoms, which may be substituted by one or more non-aromatic radicals R3; two radicals Ar which are bonded to the same N atom, P atom or B atom may also be bridged to one another by a single bond or a bridge selected from N(R3), C(R3)2, O or S;
wherein the compound of the formula (2) is selected from the group consisting of:

### Claim 11 (depends on 1)

A formulation comprising a composition according to claim 1 and at least one solvent.

### Claim 12 (depends on 1)

An organic electronic device containing at least one composition according to claim 1.

### Claim 13 (depends on 12)

The device according to claim 12, wherein the device is selected from the group consisting of organic integrated circuits (OICs), organic field-effect transistors (OFETs),organic thin-film transistors (OTFTs), organic electroluminescent devices, organic solar cells (OSCs), organic optical detectors and organic photoreceptors.

### Claim 14 (depends on 12)

The device according to claim 12, wherein the device is an electroluminescent device selected from organic light-emitting transistors (OLETs), organic field-quench devices (OFQDs), organic light-emitting electrochemical cells (OLECs, LECs, LEECs), organic laser diodes (O-lasers) and organic light-emitting diodes (OLEDs).

### Claim 15 (depends on 12)

The device according to claim 12, wherein the device contains the composition in an emission layer (EML), in an electron-transport layer (ETL), in an electron-injection layer (EIL) and/or in a hole-blocking layer (HBL).

### Claim 16 (depends on 12)

The device according to claim 12, wherein the device contains the composition in the emission layer together with a phosphorescent emitter.

### Claim 17 (depends on 12)

A process for the production of the device according to claim 12, which comprises applying at least one organic layer comprising the composition by gas-phase deposition or from solution.

### Claim 18 (depends on 17)

The process according to claim 17, wherein the at least one compound of the formula (1) and the at least one compound of the formula (2) are deposited from the gas phase successively or simultaneously from at least two material sources, optionally with further materials, and form the organic layer.

### Claim 19 (depends on 1, 17)

The process according to claim 17, wherein the composition according to claim 1 is utilized as material source for the gas-phase deposition and forms the organic layer.

### Claim 20 (depends on 11, 17)

The process according to claim 17, wherein the formulation according to claim 11 is used in order to apply the organic layer.