# US 11,309,495 B2 · Semiconducting material comprising a phosphine oxide matrix and metal salt

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- Number: US 11,309,495 B2
- Document ID: US11309495B2
- Status: Granted
- Kind: B2
- Application number: 15/564,782
- Filed: 2016-04-07
- Published: 2018-04-26
- Granted: 2022-04-19
- Earliest claimed: 2015-04-08
- Assignees: Novaled GmbH
- Applicants: Novaled GmbH
- Inventors: Julien Frey; Domagoj Pavicic; Ulrich Denker; Vygintas Jankus; Carsten Rothe; Francois Cardinali; Katja Gräf; Ulrich Heggemann; Omrane Fadhel
- Web page: https://patentgrep.com/patent/US11309495B2

## CPC

- H10K 85/615: {Polycyclic condensed aromatic hydrocarbons, e.g. anthracene}
- C07F 9/5325: {Aromatic phosphine oxides or thioxides (P-C aromatic linkage)}
- C07F 9/65517: {condensed with carbocyclic rings or carbocyclic ring systems}
- H10K 50/16: Electron transporting layers
- H10K 50/165: comprising dopants
- H10K 85/30: Coordination compounds
- H10K 85/322: {comprising boron}
- H10K 85/622: {containing four rings, e.g. pyrene}
- H10K 85/626: {containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene}
- H10K 85/6574: {comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes}
- H10K 50/171: {Electron injection layers}
- H10K 50/18: Carrier blocking layers
- H10K 2101/30: Highest occupied molecular orbital [HOMO], lowest unoccupied molecular orbital [LUMO] or Fermi energy values
- H10K: ORGANIC ELECTRIC SOLID-STATE DEVICES
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)

## Abstract

The present invention is directed to a semiconducting material comprising: i) a compound according to formula (I) wherein R1, R2 and R3 are independently selected from C1-C30-alkyl, C3-C30 cycloalkyl, C2-C30-heteroalkyl, C6-C30-aryl, C2-C30-heteroaryl, C1-C30-alkoxy, C3-C30-cycloalkyloxy, C6-C30 aryloxy, and from structural unit having general formula E-A-, wherein—A is a C6-C30 phenylene spacer unit, and—E is an electron transporting unit that is selected from C10-C60 aryl and C6-C60 heteroaryl comprising up to 6 heteroatoms independently selected from O, S, P, Si and B and that comprises a conjugated system of at least 10 delocalized electrons, and—at least one group selected from R1, R2 and R3 has the general formula E-A-; and ii) at least one complex of a monovalent metal having formula (II) wherein—M+ is a positive metal ion bearing a single elementary charge, and each of A1, A2, A3 and A4 is independently selected from H, substituted or unsubstituted C6-C20 aryl and substituted or unsubstituted C2-C20 heteroaryl, wherein a heteroaryl ring of at least 5 ring-forming atoms of the substituted or unsubstituted C2-C20 heteroaryl comprises at least one hetero atom selected from O, S and N.

## Claims

### Claim 1

A compound having the structure according to formula (I)
wherein in structure (I):
R1, R2 and R3 are independently selected from C1-C30-alkyl, C3-C30 cycloalkyl, C2-C30-heteroalkyl, C6-C30-aryl, C2-C30-heteroaryl, C1-C30-alkoxy, C3-C30-cycloalkyloxy, C6-C30-aryloxy, and from a structural unit having general formula E-A-, and at least one group selected from R1, R2 and R3 has the general formula E-A;
wherein
A is a C6-C30 phenylene spacer unit, and
E is an electron transport unit having the structure (Ib), (Ic), (Id) and/or (Ie):
wherein in structure (Ib)
X is a single bond and
Z is selected from a group comprising dibenzo[b,d]furanyl, dibenzo[b,d]thiophenyl, 9-anthranyl, pyren-1-yl, pyren-2-yl, 9,9′-dialkylfluoren-2-yl, 9,9′-diarylfluoren-2-yl, 9-alkyl-9′-arylfluoren-2-yl, 9,9′-dialkylfluoren-3-yl, 9,9′-diarylfluoren-3-yl, 9-alkyl-9′-arylfluoren-3-yl, phenanthren-1-yl and phenanthren-3-yl; or
wherein in structure (Ib)
X is selected from a group comprising phenylene, biphenyl, naphthalen-1,8-diyl, naphthalen-2,6-diyl, 9,9′-dialkylfluoren-2,7-diyl, 9,9′-diarylfluoren-2,7-diyl, 9-alkyl-9′-arylfluoren-2,7-diyl, 9,9′-dialkylfluoren-3,6-diyl, 9,9′-diarylfluoren-3,6-diyl and 9-alkyl-9′-arylfluoren-3,6-diyl; and
Z is selected from a group comprising hydrogen,
dibenzo[b,d]furanyl, dibenzo[b,d]thiophenyl, 9-anthranyl, pyren-1-yl, pyren-2-yl, 9,9′-dialkylfluoren-2-yl, 9,9′-diarylfluoren-2-yl, 9-alkyl-9′-arylfluoren-2-yl, 9,9′-dialkylfluoren-3-yl, 9,9′-diarylfluoren-3-yl, 9-alkyl-9′-arylfluoren-3-yl, phenanthren-1-yl and phenanthren-3-yl;
wherein in structure (Ic)
X is selected from a single bond, phenylene and 1,1′-biphenyl-diyl; and
Y is phenylene;
wherein in structure (Id)
X is selected from a group comprising phenylene, 1,1′-biphenyl-diyl, naphthalen-1,8-diyl, naphthalen-2,6-diyl, 9,9′-dialkylfluoren-2,7-diyl, 9,9′-diarylfluoren-2,7-diyl, 9-alkyl-9′-arylfluoren-2,7-diyl, 9,9′-dialkylfluoren-3,6-diyl, 9,9′-diarylfluoren-3,6-diyl and 9-alkyl-9′-arylfluoren-3,6-diyl;
wherein in structure (Ie)
X is a single bond; and
Z1 and Z2 are independently selected from a group comprising phenyl, naphthyl, dibenzo[b,d]furanyl, dibenzo[b,d]thiophenyl, 9-anthranyl, pyren-1-yl, pyren-2-yl, 9,9′-dialkylfluoren-2-yl, 9,9′-diarylfluoren-2-yl, 9-alkyl-9′-arylfluoren-2-yl, 9,9′-dialkylfluoren-3-yl, 9,9′-diarylfluoren-3-yl, 9-alkyl-9′-arylfluoren-3-yl, phenanthrene-1-yl and phenanthrene-3-yl;
wherein the following structures are excluded:

### Claim 2 (depends on 1)

Compound according to claim 1, wherein at least one of substituents R1, R2 and/or R3 is a phenyl.

### Claim 3 (depends on 1)

Compound according to claim 1, wherein A is selected from the group comprising a phenylene spacer unit, m-phenylene spacer unit, p-phenylene spacer unit, biphenyl spacer unit, m-biphenyl spacer unit, p-biphenyl spacer unit, terphenyl spacer unit, m-terphenyl spacer unit or p-terphenyl spacer unit.

### Claim 4 (depends on 1)

Compound according to claim 1, wherein
in structure (I):
R1, R2 and R3 are independently selected from C1-C12-alkyl, C6-C20-aryl, and from the structural unit having general formula E-A-, wherein and at least one group selected from R1, R2 and R3 has the general formula E-A.

### Claim 5 (depends on 1)

Compound according to claim 1, wherein the compound of formula (I) is represented by any of the following formulas:

### Claim 6 (depends on 1)

Semiconducting material comprising:
i) a compound according to claim 1; and
ii) at least one complex of a monovalent metal having formula (II):
wherein
M+ is a positive metal ion bearing a single elementary charge, and
each of A1, A2, A3 and A4 is independently selected from H and substituted or unsubstituted C2-C20 heteroaryl, wherein a heteroaryl ring of at least 5 ring-forming atoms of the substituted or unsubstituted C2-C20 heteroaryl comprises at least one hetero atom selected from O, S and N.

### Claim 7 (depends on 1, 6)

Semiconducting material according to claim 6, comprising:
i) a compound according to claim 1,
wherein
R1, R2 and R3 are independently selected from C6-C30-aryl or C2-C30-heteroaryl; and from structural unit having general formula E-A-;
wherein
in compound (I), at least one of substituents R1, R2 and/or R3 is phenyl,
at least one group selected from R1, R2 and R3 has the general formula E-A-; and
ii) at least one complex of a monovalent metal having formula (II):
wherein
M+ is a lithium cation (Li+), and
each of A1, A2, A3 and A4 is a heteroaryl ring of at least 5 ring-forming atoms comprises at least one hetero atom N.

### Claim 8 (depends on 6)

Semiconducting material according to claim 6, wherein in the compound (I) A is a C6-C30 phenylene spacer unit, or a C6-C30 m-phenylene spacer unit or C6-C30 p-phenylene spacer unit.

### Claim 9 (depends on 8)

Semiconducting material according to claim 8, wherein A is a spacer unit selected from a group comprising phenylene, biphenyl, naphthalen-1,8-diyl, naphthalen-2,6-diyl, 9,9′-dialkylfluoren-2,7-diyl, 9,9′-diarylfluoren-2,7-diyl, 9-alkyl-9′-arylfluoren-2,7-diyl, 9,9′-dialkylfluoren-3,6-diyl, 9,9′-diarylfluoren-3,6-diyl and 9-alkyl-9′-arylfluoren-3,6-diyl, wherein alkyl is C1-C12 alkyl and aryl is C6-C20 aryl.

### Claim 10 (depends on 6)

Semiconducting material according to claim 6, wherein in the compound (I), in any general formula E-A-
i) A is a C6-C30 m-phenylene or a p-phenylene spacer unit; or
ii) A is a C6-C30 m-phenylene spacer unit.

### Claim 11 (depends on 6)

Semiconducting material according to claim 6, wherein the compound of formula (I) is represented by any of the following formulas:

### Claim 12 (depends on 6)

Semiconducting material according to claim 6, wherein in the compound (II), each nitrogen containing heteroaryl is attached to the central boron atom through a boron-nitrogen bond.

### Claim 13 (depends on 6)

Electronic device comprising a cathode, an anode and the semiconducting material according to claim 6, wherein the semiconducting material is arranged between the cathode and the anode.

### Claim 14 (depends on 13)

Electronic device according to claim 13, wherein the semiconducting material is contained in an electron transporting layer and/or electron injecting layer.

### Claim 15 (depends on 13)

Electronic device according to claim 13, which is a light emitting device.