Mixtures of matrix materials and organic semiconductors capable of emission, use of the same and electronic components containing said mixtures
View Patent ↗The present invention describes new types of material mixtures composed of at least two substances, one serving as a matrix material and the other being an emission material capable of emission, the latter comprising at least one element of atomic number greater than 20, and the use thereof in organic electronic components such as electroluminescent elements and displays.
1. Mixtures comprising
at least one matrix material A which contains a structural unit of the form C═Q in which Q has at least one non-bonding electron pair and represents the element O, S, Se or N, and
at least one emission material B which is capable of emission and is a compound which, upon suitable excitation, emits light, and contains at least one element of atomic number greater than 20.
2. The mixture as claimed in claim 1 , characterized in that the matrix material A can form glasslike layers.
3. The mixture as claimed in claim 1 , characterized in that the matrix material A has a glass transition temperature T g (measured as the pure substance) greater than 70° C.
4. The mixture as claimed in claim 1 , characterized in that the matrix material A used is at least one compound of the formula (1), formula (2) and/or formula (3)
where the symbols and indices are each defined as follows:
X is the same or different at each instance and is O, S or Se;
Y at each instance is N;
R 1 , R 2 and R 3 are the same or different at each instance and is H, CN, a straight-chain, branched or cyclic alkyl, alkoxy or alkylamino group having from 1 to 40 carbon atoms, in which one or more nonadjacent CH 2 groups is optionally replaced by —R 4 C═CR 4 —, —C≡C—, C═O, C═S, C═Se, C═NR 4 , —O—, —S—, —NR 5 — or —CONR 6 —, and in which one or more hydrogen atoms is optionally replaced by F, Cl, Br, I, or
an aromatic or heteroaromatic system having from 1 to 40 carbon atoms, in which one or more hydrogen atoms is optionally replaced by F, Cl, Br, I, and which is optionally substituted by one or more nonaromatic R 1 radicals, and a plurality of substituents R 1 and/or R 1 , R 2 , either on the same ring or on the two different rings, optionally together in turn form a further mono- or polycyclic, aliphatic or aromatic ring system; with the proviso that R 1 =R 2 =R 3 ≠hydrogen;
R 4 , R 5 and R 6 are the same or different at each instance and are H or an aliphatic or aromatic hydrocarbon radical having from 1 to 20 carbon atoms.
5. The mixture as claimed in claim 1 , characterized in that the matrix material A used is at least one compound of the formula (4) to (9)
where
X is the same or different at each instance and is O, S or Se;
Y at each instance is N;
R 1 , R 2 and R 3 are the same or different at each instance and are H, CN, a straight-chain, branched or cyclic alkyl, alkoxy or alkylamino group having from 1 to 40 carbon atoms, in which one or more nonadjacent CH 2 groups is optionally replaced by —R 4 C═CR 4 —, —C≡C—, C═O, C═S, C═Se, C═NR 4 , —O—, —S—, —NR 5 — or —CONR 6 —, and in which one or more hydrogen atoms is optionally replaced by F, Cl, Br, I, or
an aromatic or heteroaromatic system having from 1 to 40 carbon atoms, in which one or more hydrogen atoms is optionally replaced by F, Cl, Br, I, and which is optionally substituted by one or more nonaromatic R 1 radicals, and a plurality of substituents R 1 and/or R 1 , R 2 , either on the same ring or on the two different rings, optionally together in turn form a further mono- or polycyclic, aliphatic or aromatic ring system; with the proviso that R 1 =R 2 =R 3 ≠hydrogen;
R 4 , R 5 and R 6 are the same or different at each instance and are H or an aliphatic or aromatic hydrocarbon radical having from 1 to 20 carbon atoms and
Z is the same or different at each instance and is CR 1 or N.
6. The mixture as claimed in claim 5 , characterized in that the matrix material A used is at least one compound of the formula (1) to (9) in which the symbols used are:
X is the same or different at each instance and is O or S,
Y at each instance is N;
Z at each instance is CR 1 ;
R 1 , R 2 and R 3 are the same or different at each instance and are H, a straight-chain, branched or cyclic alkyl group which has from 1 to 40 carbon atoms and no hydrogen atoms in the α-position to the keto or imine function, in which one or more nonadjacent CH 2 groups is optionally replaced by —R 4 C═CR 4 —, —C≡C—, C═O, C═S, C═Se, C═NR 4 , —O—, —S—, —NR 5 — or —CONR 6 —, and in which one or more hydrogen atoms is optionally replaced by F, Cl, Br, I, or
an aromatic or heteroaromatic system having from 1 to 40 carbon atoms, in which one or more hydrogen atoms may be replaced by F, Cl, Br, I, and which is optionally substituted by one or more nonaromatic R 1 radicals, and a plurality of substituents R 1 and/or R 1 , R 2 , either on the same ring or on the different rings, optionally together in turn form a further mono- or polycyclic, aliphatic or aromatic ring system,
R 4 , R 5 and R 6 are the same or different at each instance and are H or an aliphatic or aromatic hydrocarbon radical having from 1 to 20 carbon atoms.
7. The mixture as claimed in claim 1 , characterized in that the matrix material A used is at least one compound of the formula (10) to (15)
where
Y at each instance is N;
Z is the same or different at each instance and is CR 1 or N;
R 1 , R 2 and R 3 are the same or different at each instance and are H, CN, a straight-chain, branched or cyclic alkyl, alkoxy or alkylamino group having from 1 to 40 carbon atoms, in which one or more nonadjacent CH 2 , groups is optionally replaced by —R 4 C═CR 4 —, —C≡C—, C═O, C═S, C═Se, C═NR 4 , —O—, —S—, —NR 5 — or —CONR 6 —, and in which one or more hydrogen atoms is optionally replaced by F, Cl, Br, I, or
an aromatic or heteroaromatic system having from 1 to 40 carbon atoms, in which one or more hydrogen atoms is optionally replaced by F, Cl, Br, I, and which is optionally substituted by one or more nonaromatic R 1 radicals, and a plurality of substituents R 1 and/or R 1 , R 2 , either on the same ring or on the two different rings, optionally together in turn form a further mono- or polycyclic, aliphatic or aromatic ring system; with the proviso that R 1 =R 2 =R 3 ≠hydrogen;
R 4 , R 5 and R 6 are the same or different at each instance and are H or an aliphatic or aromatic hydrocarbon radical having from 1 to 20 carbon atoms,
Ar is the same or different at each instance and is an aromatic or heteroaromatic system having from 2 to 40 carbon atoms, in which one or more hydrogen atoms is optionally replaced by F, Cl, Br, I, and which is optionally substituted by one or more nonaromatic R 1 radicals, and a plurality of substituents R 1 , either on the same ring or on different rings, optionally together in turn form a further mono- or polycyclic, aliphatic or aromatic ring system;
n is the same or different at each instance and is 0 or 1.
8. The mixture as claimed in claim 1 , characterized in that the emitter B used is at least one compound which, upon suitable excitation, emits light and contains at least one atom of atomic number greater than 38 and less than 84.
9. The mixture as claimed in claim 8 , characterized in that the emitter B used is at least one compound which, upon suitable excitation, emits light and contains at least one atom of atomic number greater than 56 and less than 80.
10. The mixture as claimed in claim 9 , characterized in that the emitter B used is at least one compound which, upon suitable excitation, emits light and contains at least one atom from the group of molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold or europium.
11. The mixture as claimed in claim 1 , characterized in that the emitter B used is at least one compound of the formula (16) to (19)
where the symbols used are:
DCy is the same or different at each instance and is a cyclic group which contains at least one donor atom via which the cyclic group is bonded to the metal atom, and which optionally bear one or more substituents R 9 ; the DCy and CCy groups are joined together via a covalent bond;
CCy is the same or different at each instance and is a cyclic group which contains a carbon atom via which the cyclic group is bonded to the metal and which optionally bear one or more substituents R 9 ;
R 9 is the same or different at each instance and is H, F, Cl, Br, I, NO 2 , CN, a straight-chain or branched or cyclic alkyl or alkoxy group having from 1 to 40 carbon atoms, in which one or more nonadjacent CH 2 groups is optionally replaced by —CR 4 ═CR 4 —, —C≡C—, C═O, C═S, C═Se, C═NR 4 , —O—, —S—, —NR 5 — or —CONR 6 —, and in which one or more hydrogen atoms is optionally replaced by F, or an aromatic or heteroaromatic system which has from 4 to 40 carbon atoms and is optionally substituted by one or more nonaromatic R 9 radicals; and a plurality of substituents R 9 , either on the same ring or on the two different rings, optionally together in turn form a further mono- or polycyclic, aliphatic or aromatic ring system;
L is the same or different at each instance and is a bidentate chelating ligand;
R 4 , R 5 and R 6 are the same or different at each instance and is H or an aliphatic or aromatic hydrocarbon radical having from 1 to 20 carbon atoms.
12. The mixture as claimed in claim 1 , characterized in that the matrix material contains one or more polymers or dentrimers.
13. The mixture as claimed in claim 12 , characterized in that the polymer is conjugated, semiconjugated or nonconjugated.
14. The mixture as claimed in claim 12 , characterized in that the polymer is selected from the group of the polyfluorenes, poly-spiro-bifluorenes, poly-para-phenylenes, polycarbazoles, polyvinylcarbazoles, polythiophenes, or else from copolymers which have a plurality of these units.
15. The mixture as claimed in claim 1 , characterized in that the mixture contains between 1 to 99% by weight of emitter B based on the overall mixture of emitter B and matrix material A.
16. An electronic component comprising at least one mixture as claimed in claim 1 .
17. The electronic component as claimed in claim 16 , characterized in that it is an organic light-emitting diode (OLED), an organic integrated circuit (O-IC), an organic field-effect transistor (OFET), an organic thin-film transistor (OTFT), an organic solar cell (O-SC) or an organic laser diode (O-laser).
18. The electronic component as claimed in claim 16 , characterized in that the electronic component is an organic light-emitting diode (OLED) which comprises at least one hole injection layer and/or at least one hole transport layer and/or at least one hole blocking layer and/or at least one electron transport layer and/or at least one electron injection layer and/or further layers, and which comprises at least one mixture comprising
at least one matrix material A which contains a structural unit of the form C═Q in which Q has at least one non-bonding electron pair and represents the element O, S, Se or N, and
at least one emission material B which is capable of emission and is a compound which, upon suitable excitation, emits light, and contains at least one element of atomic number greater than 20 in the emission layer.
19. Compounds of the formula (10a) to (15)
in which the symbols
Y at each instance is N;
Z is the same or different at each instance and is CR 1 or N;
R 1 , R 2 and R 3 are the same or different at each instance and are H, CN, a straight-chain, branched or cyclic alkyl, alkoxy or alkylamino group having from 1 to 40 carbon atoms, in which one or more nonadjacent CH 2 groups is optionally replaced by —R 4 C═CR 4 —, —C≡C—, C═O, C═S, C═Se, C═NR 4 , —O—, —S—, —NR 5 — or —CONR 6 —, and in which one or more hydrogen atoms is optionally replaced by F, Cl, Br, I, or
an aromatic or heteroaromatic system having from 1 to 40 carbon atoms, in which one or more hydrogen atoms is optionally replaced by F, Cl, Br, I, and which is optionally substituted by one or more nonaromatic R 1 radicals, and a plurality of substituents R 1 and/or R 1 , R 2 , either on the same ring or on the two different rings, optionally together in turn form a further mono- or polycyclic, aliphatic or aromatic ring system; with the proviso that R 1 =R 2 =R 3 ≠hydrogen;
R 4 , R 5 and R 6 are the same or different at each instance and are H or an aliphatic or aromatic hydrocarbon radical having from 1 to 20 carbon atoms,
Ar is the same or different at each instance and is an aromatic or heteroaromatic system having from 2 to 40 carbon atoms, in which one or more hydrogen atoms is optionally replaced by F, Cl, Br, I, and which is optionally substituted by one or more nonaromatic R 1 radicals, and a plurality of substituents R 1 , either on the same ring or on different rings, optionally together in turn form a further mono- or polycyclic, aliphatic or aromatic ring system;
E is the same or different at each instance and is C or N;
R 7 is the same or different at each instance and is an alkyl, alkoxy or alkylamino group having from 1 to 40 carbon atoms, in which one or more CH 2 groups is optionally replaced by —R 4 C═CR 4 —, —C≡C—, C═O, C═S, C═Se, C═NR 4 , —O—, —S—, —NR 4 or —CONR 4 —, and in which one or more hydrogen atoms is optionally replaced by F, Cl, Br, I, with the proviso that no hydrogen atoms are bonded in the α-position to the carbonyl group, or
an aromatic group which may optionally be substituted by halogen, alkyl, trifluoromethyl, hydroxyl, —SH, —S-alkyl, alkoxy, nitro, cyano, —COOH, —COOalkyl, —NH 2 , -Nalkyl, benzyl or benzoyl, or
a larger aromatic system having from 2 to 40 carbon atoms, in which one or more hydrogen atoms is optionally replaced by F, Cl, Br, I, and which is optionally substituted by one or more nonaromatic R 1 radicals, and a plurality of substituents R 1 may in turn form a further mono- or polycyclic, aliphatic or aromatic ring system;
A 1 at each instance is R 8 or CO—R 7 when X═C or is a free electron pair when X═N;
A 2 at each instance is R 8 or CO—R 7 when X═C or is a free electron pair when X═N;
A 3 at each instance is R 8 or CO—R 7 when X═C or is a free electron pair when X═N;
R 8 is the same or different at each instance and is H, F, Cl, Br, I, CN, NO 2 , a straight-chain or branched or cyclic alkyl group having from 1 to 40 carbon atoms, in which one or more nonadjacent CH 2 groups is optionally replaced by —R 4 C═CR 4 —, —C≡C—, C═S, C═Se, C═NR 4 , —O—, —S—, —NR 4 — or —CONR 4 —, and in which one or more hydrogen atoms is optionally replaced by F, Cl, Br, I, or
an aromatic or heteroaromatic system having from 1 to 40 carbon atoms, in which one or more hydrogen atoms is optionally replaced by F, Cl, Br, I, and which is optionally substituted by one or more nonaromatic R 1 radicals, and a plurality of substituents R 1 and/or R 1 /R 4 , either on the same ring or on the different rings, optionally together in turn form a further mono- or polycyclic, aliphatic or aromatic ring system;
with the proviso that, for the compound of the formula (10a), only the following combinations are permitted for the symbols described, where R 8 and R 4 can be selected freely according to the definition:
when R 7 is an alkyl group without α-hydrogen atoms, the symbols Z, E, A 1 , A 2 and A 3 can be selected freely according to the definition;
when R 7 is an aromatic group and at least one Z is N, the symbols E, A 1 , A 2 and A 3 can be selected freely according to the definition;
when R 7 is an aromatic group and at least one Z is a CR 1 group where R 1 is other than H, the symbols E, A 1 , A 2 and A 3 can be selected freely according to the definition;
when R 7 is an aromatic group and all Z are CH and at least one symbol E is N, the symbols A 1 , A 2 and A 3 can be selected freely according to the definition;
when R 7 is an aromatic group, all Z are CH and all E are C, at least one of the symbols A 1 , A 2 and/or A 3 has to be an R 8 group other than alkyl, while the two other groups can be selected freely according to the definition;
when R 7 is an aromatic group, all Z are CH, all E are C and the two symbols A 1 and A 2 are selected freely according to the definition, at least one of the two symbols being a group other than H, the symbol A 3 is a CO—R 7 group where R 7 here can be selected freely according to the definition;
when R 7 is a larger aromatic system, for example fluorene, spirobifluorene, triarylamine, etc., the symbols Z, E, A 1 , A 2 and A 3 can be selected freely according to the definition.
20. The electronic component as claimed in claim 19 , characterized in that a mixture comprising
at least one matrix material A which contains a structural unit of the form C═Q in which Q has at least one non-bonding electron pair and represents the element O, S, Se or N, and
at least one emission material B which is capable of emission and is a compound which, upon suitable excitation, emits light, and contains at least one element of atomic number greater than 20 without the use of a separate hole blocking layer directly adjoins an electron transport layer.
21. The electronic component as claimed in claim 19 , characterized in that the mixture comprising
at least one matrix material A which contains a structural unit of the form C═Q in which Q has at least one non-bonding electron pair and represents the element O, S, Se or N, and
at least one emission material B which is capable of emission and is a compound which, upon suitable excitation, emits light, and contains at least one element of atomic number greater than 20 without use of a separate hole blocking layer and of a separate electron transport layer directly adjoins an electron injection layer or the cathode.