DE10317556A1 - Mixtures for use in organic electronic devices of simplified layer structure comprise matrix materials (some of which in e.g. (hetero)aromatic ketone form are new) and emitters containing an element of atomic number above 20 - Google Patents

Abstract

A mixture contains a matrix material containing specified units; and a material which is capable of emission and which contains an element of atomic number above 20. A mixture contains (a) a matrix material containing units of formula C:Q where Q = a non-bonding electron pair comprising O, S, Se or N; and (b) a material which is capable of emission and which contains an element of atomic number above 20. An independent claim is also included for novel aromatic or heteroaromatic compounds of formulae (10a)-(15). [Image] Z : CR 1> or N; Y : N; R 1> - R 3> which must be different from each other : (a) H, CN, optionally cyclic 1-40C alkyl, alkoxy or alkylamino optionally with one or more non-adjacent -CH 2- groups replaced by -R 4>C=CR 4>-, -Ctriple boundC-, C=O, C=S, C=Se, C=NR 4>, -O-, -S-, -NR 5>- or -CONR 6>- and optionally with one or more H replaced by F, Cl, Br or I or (b) a 1-40C (hetero)aromatic system optionally with one or more H replaced by F, Cl, Br or I and optionally substituted by one or more non- aromatic residue R 1> where one or more R 1> and/or R 1>, R 2> are on the same or different rings or stretch between a mono and poly-cyclic aliphatic or aromatic ring system; and R 4> - R 6>H or 1-20C aliphatic or aromatic hydrocarbon; Ar : a 2- 40C (hetero)aromatic system optionally with one or more H replaced by F, Cl, Br or I and optionally substituted with one or more non-aromatic residue R 1> as per (b) above; n : 0 or 1; E : C or N; R 7>(a) 1-40C alkyl, alkoxy or alkylamino optionally with one or more non-adjacent -CH 2- groups 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>-; (b) an aromatic group optionally substituted by halogen, alkyl, -CF 3, -OH, -SH, -S-alkyl, alkoxy, - NO 2, -CN, -COOH, -COOAlkyl, -NH 2, -Nalkyl, benzyl or benzoyl; or (c) a 2-40C large aromatic system optionally with one or more H replaced by F, Cl, Br or I and optionally substituted by one or more non-aromatic residue where several R 1> can stretch to a further mono- or poly-cyclic aliphatic or aromatic ring system; A 1> - A 3>R 8> or CO-R 7> when X = C or a free electron pair when X = N; R 8>(a) H, F, Cl, Br, I, CN, NO 2, an optionally cyclic 1-40C alkyl optionally with one or more non-adjacent -CH 2- groups replaced by -R 4>C=CR 4>-, -Ctriple boundC-, C=O, C=S, C=Se, C=NR 4>, -O-, -S-, -NR 4>- or -CONR 4>- and optionally with one or more H replaced by F, Cl, Br or I or (b) a 1-40C (hetero)aromatic system optionally with one or more H replaced by F, Cl, Br or I and optionally substituted by one or more non-aromatic residue R 1> where one or more R 1> and/or R 1>/R 4> are on the same or different rings or stretch between mono and poly-cyclic aliphatic or aromatic ring system; and with the provisos that for compound of formula (10a) only the following combinations hold : (i) when R 7>alkyl without an alpha -H atom then Z, E and A 1> - A 3> can any of the given definitions; (ii) when R 7> = an aromatic group and >=1 Z = N or CR 1> with R 1> not = H then E and A 1> - A 3> can be any of the given definitions; (iii) when R 7> = an aromatic group, all Z's = CH and >= E = N then A 1> - A 3> can any of the given definitions; (iv) when R 7> = an aromatic group, all Z's = CH and all E's = C then at least one of A 1> - A 3> = R 8> other than alkyl and the other two can be any of the given definitions; (v) when R 7> = an aromatic group, all Z's = CH, all E's = C and both A 1> and A 2> are as per the definitions with one other than H then A 3> = CO- R 7>; and (vi) when R 7> = a large aromatic group such as fluorene, spirobifluorene or triarylamine then Z, E and A 1> - A 3> are as per the definitions.

Description

The The present invention describes the use of new materials and material mixtures in organic electronic components such as Electroluminescent elements and their use in based thereon Displays.

In a number of different applications, the broadest Can be attributed to the electronics industry the use of organic semiconductors as active components (= functional materials) has been a reality for some time or is expected in the near future.

So have been finding light-sensitive organic materials for several years (e.g. phthalocyanines) as well as organic charge transport materials (usually triarylamine-based hole transporters) Use in copiers.

• 1. weiße oder farbige Hinterleuchtungen für monochrome oder mehrfarbige Anzeigeelemente (wie z.B. im Taschenrechner, Mobiltelefone und andere tragbare Anwendungen),
• 2. großflächige Anzeigen (wie z.B. Verkehrsschilder, Plakate und andere Anwendungen),
• 3. Beleuchtungselemente in allen Farben und Formen,
• 4. monochrome oder vollfarbige Passiv-Matrix-Displays für tragbare Anwendungen (wie z.B. Mobiltelefone, PDAs, Camcorder und andere Anwendungen),
• 5. vollfarbige großflächigen hochauflösenden Aktiv-Matrix-Displays für verschiedenste Anwendungen (wie z.B. Mobiltelefone, PDAs, Laptops, Fernseher und andere Anwendungen).

The use of special semiconducting organic compounds, some of which are also capable of emitting light in the visible spectral range, is just at the beginning of the market launch, for example in organic electroluminescent devices. Their individual components, the organic light-emitting diodes (OLEDs), have a very wide range of applications as:

• 1. white or colored backlighting for monochrome or multicolored display elements (such as in calculators, mobile phones and other portable applications),
• 2. large-scale advertisements (such as traffic signs, posters and other applications),
• 3. lighting elements in all colors and shapes,
• 4. monochrome or full-color passive matrix displays for portable applications (such as cell phones, PDAs, camcorders and other applications),
• 5. Full-color, large-area, high-resolution active matrix displays for a wide variety of applications (such as cell phones, PDAs, laptops, televisions and other applications).

at In some of these applications, the development is already very far advanced, but there is still a great need for technical improvements.

• 1. So ist v. a. die OPERATIVE LEBENSDAUER von OLEDs immer noch gering, so daß bis dato nur einfache Anwendungen kommerziell realisiert werden können.
• 2. Die Effizienzen von OLEDs sind zwar akzeptabel, aber auch hier sind – gerade für tragbare Anwendungen ("portable applications") – immer noch Verbesserungen erwünscht.
• 3. Die Farbkoordinaten von OLEDs, speziell im Roten, sind nicht gut genug. Besonders die Kombination von guten Farbkoordinaten mit hoher Effizienz muß noch verbessert werden.
• 4. Die Alterungsprozesse gehen i. d. R. mit einem Anstieg der Spannung einher. Dieser Effekt macht spannungsgetriebene organische Elektrolumineszenzvorrichtungen, z.B. Displays oder Anzeige-Elemente, schwierig bzw. unmöglich. Eine stromgetriebene Ansteuerung ist aber gerade in diesem Fall aufwendiger und teurer.
• 5. Die benötigte Betriebsspannung ist gerade bei effizienten phosphoreszierenden OLEDs recht hoch und muß daher verringert werden, um die Leistungseffizienz zu verbessern. Das ist gerade für tragbare Anwendungen von großer Bedeutung.
• 6. Der benötigte Betriebsstrom ist ebenfalls in den letzten Jahren verringert worden, muß aber noch weiter verringert werden, um die Leistungseffizienz zu verbessern. Das ist gerade für tragbare Anwendungen besonders wichtig.

The market launch for devices containing simpler OLEDs has already taken place, as evidenced by the car radios from Pioneer or a digital camera from Kodak with an "organic display". However, there are still significant problems that need urgent improvement:

• 1. The OPERATIVE LIFETIME of OLEDs is still short, so that only simple applications can be realized commercially up to now.
• 2. The efficiencies of OLEDs are acceptable, but improvements are still desired here, particularly for portable applications.
• 3. The color coordinates of OLEDs, especially in red, are not good enough. In particular, the combination of good color coordinates with high efficiency still needs to be improved.
• 4. The aging processes are usually accompanied by an increase in tension. This effect makes voltage-driven organic electroluminescent devices, for example displays or display elements, difficult or impossible. In this case, however, a current-driven control is more complex and expensive.
• 5. The operating voltage required is quite high, especially in the case of efficient phosphorescent OLEDs, and must therefore be reduced in order to improve the power efficiency. This is particularly important for portable applications.
• 6. The operating current required has also been reduced in recent years, but must be further reduced to improve performance efficiency. This is especially important for portable applications.

The The reasons given above under 1. to 6. make improvements necessary in the manufacture of OLEDs.

A This is a development that has emerged in recent years the use of organometallic complexes, phosphorescence show instead of fluorescence [M. A. Baldo, S. Lamansky, P.E. Burrows, M.E. Thompson, S.R. Forrest, Applied Physics Letters, 1999, 75, 4-6].

For quantum mechanical reasons, up to four times quantum, energy and power efficiency is possible using organometallic compounds. Whether this new development will prevail depends heavily on the one hand on whether suitable device compositions can be found which can also implement these advantages (triplet emission = phosphorescence over singlet emission = fluorescence) in the OLEDs. The essential conditions for practical use are, in particular, a long operational lifespan, high stability against thermal stress and a low operating and operating voltage to enable mobile applications.

• 1. Eine Trägerplatte = Substrat (üblicherweise Glas oder Kunststofffolien).
• 2. Eine Transparente Anode (üblicherweise Indium-Zinn-Oxid, ITO).
• 3. Eine Lochinjektions-Schicht (Hole Injection Layer = HIL): z. B. auf der Basis von Kupfer-phthalocyanin (CuPc), leitfähigen Polymeren, wie Polyanilin (PANI) oder Polythiophen-Derivaten (wie PEDOT).
• 4. Eine oder mehrere Lochtransport-Schichten (Hole Transport Layer = HTL): üblicherweise auf der Basis von Triarylamin-Derivaten z.B. 4,4',4''-Tris(N-1-naphthyl)N-phenyl-amino)-triphenylamin (NaphDATA) als erste Schicht und N,N'-Di(naphthalin-1-yl)-N,N'-diphenyl-benzidin (NPB) als zweite Lochtransportschicht.
• 5. Eine oder mehrere Emissions-Schichten (Emission Layer = EML): diese Schicht (bzw. Schichten) kann teilweise mit den Schichten 4 bis 8 zusammenfallen, besteht aber üblicherweise aus mit Fluoreszenzfarbstoffen, z.B. N,N'-Diphenyl quinacridone (QA), oder Phosphoreszenzfarbstoffen, z.B. Tris-(2-phenyl-pyridyl)-iridium (Ir(PPy)₃) oder Tris-(2-benzothiophenyl-pyridyl)-iridium (Ir(BTP)₃), dotierten Matrixmaterialien, wie 4,4'-Bis(carbazol-9-yl)-biphenyl (CBP). Die Emissions-Schicht kann aber auch aus Polymeren, Mischungen von Polymeren, Mischungen von Polymeren und niedermolekularen Verbindungen oder Mischungen verschiedener niedermolekularer Verbindungen bestehen.
• 6. Eine Loch-Blockier-Schicht (Hole-Blocking-Layer = HBL): diese Schicht kann teilweise mit den Schichten 7 und 8 zusammenfallen. Sie besteht üblicherweise aus BCP (2,9-Dimethyl-4,7-diphenyl-1,10-phenanthrolin = Bathocuproin) oder Bis-(2-methyl-8-quinolinolato)-4-(phenyl-phenolato)-aluminium-(III) (BAlq).
• 7. Eine Elektronentransport-Schicht (Electron Transport Layer = ETL): größtenteils auf Basis von Aluminium-tris-8-hydroxy-chinoxalinat (AlQ₃).
• 8. Eine Elektroneninjektions-Schicht (Electron Injection Layer = EIL): diese Schicht kann teilweise mit Schicht 4, 5, 6 und 7 zusammenfallen bzw. es wird ein kleiner Teil der Kathode speziell behandelt bzw. speziell abgeschieden.
• 9. Eine weitere Elektroneninjektions-Schicht (Electron Injection Layer = EIL): ein dünne Schicht bestehend aus einem Material mit einer hohen Dielektrizitätskonstanten, wie z.B. LiF, Li₂O, BaF₂, MgO, NaF.
• 10. Eine Kathode: hier werden in der Regel Metalle, Metallkombinationen oder Metalllegierungen mit niedriger Austrittsarbeit verwendet, so z. B. Ca, Ba, Cs, Mg, Al, In, Mg/Ag.

The general structure of organic electroluminescent devices is shown, for example, in US 4,539,507 and US 5,151,629 such as EP 01202358 described. An organic electroluminescent device usually consists of several layers which are applied to one another by means of vacuum methods or different printing methods. The individual layers are:

• 1. A carrier plate = substrate (usually glass or plastic films).
• 2. A transparent anode (usually indium tin oxide, ITO).
• 3. A hole injection layer (HIL): e.g. B. based on copper phthalocyanine (CuPc), conductive polymers such as polyaniline (PANI) or polythiophene derivatives (such as PEDOT).
• 4. One or more hole transport layers (HTL): usually based on triarylamine derivatives, for example 4,4 ', 4''- tris (N-1-naphthyl) N-phenylamino) -triphenylamine (NaphDATA) as the first layer and N, N'-di (naphthalin-1-yl) -N, N'-diphenyl-benzidine (NPB) as the second hole transport layer.
• 5. One or more emission layers (emission layer = EML): this layer (or layers) can partially coincide with layers 4 to 8, but usually consists of fluorescent dyes, for example N, N'-diphenyl quinacridone (QA) , or phosphorescent dyes, for example tris (2-phenyl-pyridyl) iridium (Ir (PPy) ₃ ) or tris (2-benzothiophenyl-pyridyl) iridium (Ir (BTP) ₃ ), doped matrix materials, such as 4.4 '-Bis (carbazol-9-yl) biphenyl (CBP). However, the emission layer can also consist of polymers, mixtures of polymers, mixtures of polymers and low-molecular compounds or mixtures of different low-molecular compounds.
• 6. A hole blocking layer (HBL): this layer can partially coincide with layers 7 and 8. It usually consists of BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline = bathocuproin) or bis- (2-methyl-8-quinolinolato) -4- (phenylphenolato) aluminum- ( III) (BAlq).
• 7. An electron transport layer (ETL): largely based on aluminum tris-8-hydroxy-quinoxalinate (AlQ ₃ ).
• 8. An electron injection layer (EIL): this layer can partly coincide with layers 4, 5, 6 and 7 or a small part of the cathode is specially treated or specially deposited.
• 9. Another electron injection layer (EIL): a thin layer consisting of a material with a high dielectric constant, such as LiF, Li ₂ O, BaF ₂ , MgO, NaF.
• 10. A cathode: usually metals, metal combinations or metal alloys with a low work function are used here. B. Ca, Ba, Cs, Mg, Al, In, Mg / Ag.

This entire device is structured accordingly (depending on the application), contacted and finally also hermetically sealed because the life of such devices drastically shortened in the presence of water and / or air. The The same applies to so-called inverted structures, in which the light from the cathode is decoupled. The anode exists in these inverted OLEDs e.g. from Al / Ni / NiOx or Al / Pt / PtOx or other metal / metal oxide combinations that a HOMO greater than 5 eV have. The cathode consists of the same materials, described in items 9 and 10, with the difference that the metal such as. Ca, Ba, Mg, Al, In etc. is very thin and therefore transparent. The layer thickness is less than 50 nm, better less than 30 nm, even better below 10 nm. Another can be placed on this transparent cathode transparent material is applied, e.g. ITO (indium tin oxide), IZO (indium zinc oxide) etc.

organic Electroluminescent devices in which the emission layer (EML) consists of more than one substance have been known for a long time.

in the The above structure comes from the matrix material of the emission layer (EML) play a special role. The matrix material must transport the charge of holes and enable electrons or improve and / or enable the charge carrier recombination or improve and, if necessary, the result of the recombination Transfer energy to the emitter. This task is based on the electroluminescent devices phosphorescent emitter so far of matrix materials, the carbazole units included, taken over.

However, matrix materials containing carbazole units, such as the frequently used 4,4'-bis (N-carbazol-yl) biphenyl (CBP), have some disadvantages in practice. These are often in the short to very short lifespan of the devices manufactured with them and the often high operating voltages that lead to low power efficiencies. Furthermore, it has been shown that, for energy reasons, CBP is unsuitable for blue-emitting electroluminescent devices, which results in poor efficiency.

It was now surprising found that the Use of certain matrix materials in combination with certain Emitters for significant improvements over the prior art, especially in terms of efficiency and in combination with a greatly increased Lifetime, lead.

The Use of the matrix materials described below in OLEDs, which contain phosphorescent emitters is as new as that underlying mix.

The use of analog materials in simple devices, as emission materials themselves or as materials in the emission layer in combination with fluorescent emitters has already been described in isolated cases (see, for example: JP 06192654 A2 19940712), however, the characteristic data achieved with it, in particular the efficiencies and operating voltages, are unsatisfactory.

The Invention described below is derived from the above descriptions not harmful to novelty touched, because the use of the matrix materials described below is new in OLEDs in combination with phosphorescent emitters.

• – mindestens ein Matrixmaterial A welches eine Struktureinheit der Form C = X bzw. C = Y- enthält, bei dem X bzw. Y mindestens ein nicht-bindendes Elektronenpaar aufweist, X für das Element O, S oder Se und Y für das Element N steht, und welche gegebenenfalls auch glasartige Schichten bilden kann, und
• – mindestens ein zur Emission befähigten Emissionsmaterial B welches eine Verbindung ist die bei geeigneter Anregung Licht emittiert und mindestens ein Element der Ordungszahl größer 20 enthält.

The invention therefore relates to mixtures

• - At least one matrix material A which contains a structural unit of the form C = X or C = Y-, in which X or Y has at least one non-binding electron pair, X for the element O, S or Se and Y for the element N. stands, and which can optionally also form glass-like layers, and
• - At least one emission material B capable of emission, which is a compound that emits light with suitable excitation and contains at least one element with an atomic number greater than 20.

The mixtures according to the invention are preferably those which contain at least one matrix material A in which A is a compound which contains a structural unit of the form C = X or C = Y-, characterized in that X or Y does not contain at least one -binding electron pair, X stands for the element O, S or Se and Y for the element N and the glass transition temperature T _{g of} the pure substance A is greater than 70 ° C.

wobei die Symbole und Indizes folgende Bedeutung haben:
X O, S oder Se;
Y N;
R¹, R², R³ ist gleich oder verschieden bei jedem Auftreten H, CN, eine geradkettige oder verzweigte oder cyclische Alkyl- oder Alkoxygruppe mit 1 bis 40 C-Atomen, wobei ein oder mehrere nicht benachbarte CH₂-Gruppen durch -HC=CH-, C=O, C=S, C=Se, C=NR⁴, -O-, -S-, -NR⁵-, oder -CONR⁶- ersetzt sein können und wobei ein oder mehrere H-Atome durch F, Cl, Br, I ersetzt sein können, oder eine Aryl- oder Heteroarylgruppe mit 1 bis 40 C-Atomen, wobei ein oder mehrere H-Atome durch F, Cl, Br, I ersetzt sein können und die durch einen oder mehrere, nicht aromatische Reste R¹ substituiert sein kann, wobei mehrere Substituenten R¹ und/oder R¹, R² sowohl am selben Ring als auch an den beiden unterschiedlichen Ringen zusammen wiederum ein weiteres mono- oder polycyclisches, aliphatisches oder aromatisches Ringsystem aufspannen können; mit der Maßgabe das R¹ = R² = R³ ungleich Wasserstoff ist
R⁴, R⁵, R⁶ sind gleich oder verschieden bei jedem Auftreten, H oder ein aliphatischer oder aromatischer Kohlenwasserstoffrest mit 1 bis 20 C-Atomen.The mixtures described above preferably contain at least one compound of the formula (1), formula (2) and / or formula (3) as matrix material A

where the symbols and indices have the following meaning:
XO, S or Se;
YN;
R ¹ , R ² , R ³ are the same or different with each occurrence H, CN, a straight-chain or branched or cyclic alkyl or alkoxy group with 1 to 40 C atoms, one or more non-adjacent CH ₂ groups denoted by -HC = CH-, C = O, C = S, C = Se, C = NR ⁴ , -O-, -S-, -NR ⁵ -, or -CONR ⁶ - can be replaced and where one or more H atoms can be replaced by F, Cl, Br, I, or an aryl or heteroaryl group having 1 to 40 C atoms, where one or more H atoms can be replaced by F, Cl, Br, I and those by one or more , non-aromatic radicals R ¹ can be substituted, it being possible for a plurality of substituents R ¹ and / or R ¹ , R ^{2 to} form a further mono- or polycyclic, aliphatic or aromatic ring system both on the same ring and on the two different rings; with the proviso that R ¹ = R ² = R ^{3 is} not hydrogen
R ⁴ , R ⁵ , R ⁶ are the same or different with each occurrence, H or an aliphatic or aromatic hydrocarbon radical having 1 to 20 carbon atoms.

wobei die Symbole X, Y, R¹, R², R³, R⁴, R⁵ und R⁶ die unter den Formeln (1) bis (3) genannten Bedeutungen haben, und
Z gleich oder verschieden bei jedem Auftreten CR¹ oder N ist,
enthalten.Mixtures which are also preferred as matrix material A, at least one compound of the formulas (4) to (9),

where the symbols X, Y, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ^{6 have} the meanings given under the formulas (1) to (3), and
Z is the same or different on each occurrence CR ¹ or N,
contain.

Organic mixtures which contain one of the matrix material A described above by formulas (1) to (9), in which
X O and S;
YN;
R ¹ , R ² , R ^{3 are the} same or different at each occurrence N, a straight-chain or branched or cyclic alkyl or alkoxy group with 1 to 40 C atoms, one or more non-adjacent CH ₂ groups being represented by -HC = CH- , C = O, C = S, C = Se, C = NR ⁴ , -O-, -S-, -NR ⁵ -, or -CONR ⁶ - and where one or more H atoms are replaced by F, Cl, Br, I can be replaced or an aryl or heteroaryl group with 1 to 40 C atoms, where one or more H atoms can be replaced by F, Cl, Br, I and that by one or more non-aromatic radicals R ¹ can be substituted, wherein a plurality of substituents R ¹ and / or R ¹ , R ² , both on the same ring and on the two different rings, can in turn form a further mono- or polycyclic, aliphatic or aromatic ring system,
R ⁴ , R ⁵ , R ^{6 are the} same or different and are Hoder an aliphatic or aromatic hydrocarbon radical having 1 to 20 carbon atoms.

enthalten, wobei
Z gleich oder verschieden bei jedem Auftreten CR¹ oder N ist,
R¹ gleich oder verschieden bei jedem Auftreten H, CN, eine geradkettige oder verzweigte oder cyclische Alkyl- oder Alkoxygruppe mit 1 bis 40 C-Atomen, wobei ein oder mehrere nicht benachbarte CH₂-Gruppen durch -HC=CH-, C=O, C=S, C=Se, C=NR⁴, -O-, -S-, -NR⁵-, oder -CONR⁶- ersetzt sein können und wobei ein oder mehrere H-Atome durch F, Cl, Br, I ersetzt sein können, oder eine Aryl- oder Heteroarylgruppe mit 1 bis 40 C-Atomen, wobei ein oder mehrere H-Atome durch F, Cl, Br, I ersetzt sein können und die durch einen oder mehrere, nicht aromatische Reste R¹ substituiert sein kann, wobei mehrere Substituenten R¹, sowohl am selben Ring als auch an den beiden unterschiedlichen Ringen zusammen wiederum ein weiteres mono- oder polycyclisches, aliphatisches oder aromatisches Ringsystem aufspannen können;
R⁴, R⁵, R⁶ gleich oder verschieden bei jedem Auftreten, H oder ein aliphatischer oder aromatischer Kohlenwasserstoffrest mit 1 bis 20 C-Atomen.Also preferred are mixtures which are used as matrix material A, at least one compound of the formula (10) and / or (11),

included, where
Z is the same or different on each occurrence CR ¹ or N,
R ^{1 the} same or different on each occurrence H, CN, a straight-chain or branched or cyclic alkyl or alkoxy group with 1 to 40 C atoms, one or more non-adjacent CH ₂ groups being represented by -HC = CH-, C = O , C = S, C = Se, C = NR ⁴ , -O-, -S-, -NR ⁵ -, or -CONR ⁶ - can be replaced and where one or more H atoms are replaced by F, Cl, Br, I can be replaced, or an aryl or heteroaryl group with 1 to 40 C atoms, where one or more H atoms can be replaced by F, Cl, Br, I and which are substituted by one or more non-aromatic radicals R ¹ can be, where a plurality of substituents R ¹ , both on the same ring and on the two different rings together can in turn span another mono- or polycyclic, aliphatic or aromatic ring system;
R ⁴ , R ⁵ , R ^{6 are the} same or different at each occurrence, H or an aliphatic or aromatic hydrocarbon radical having 1 to 20 carbon atoms.

The These materials are particularly preferred due to their high Justified glass transition temperatures. This are typically above 70 ° C and mostly depending on the substitution pattern above 100 ° C.

bei denen
Ar eine Aryl- oder Heteroarylgruppe mit 4 bis 40 C-Atomen, vorzugsweise mit 4 bis 20 C-Atomen, ist, wobei ein oder mehrere H-Atome durch F, Cl, Br, I ersetzt sein können und die durch einen oder mehrere, nicht aromatische Reste R¹ substituiert sein kann, wobei mehrere Substituenten R¹, sowohl am selben Ring als auch an den beiden unterschiedlichen Ringen zusammen wiederum ein weiteres mono- oder polycyclisches, aliphatisches oder aromatisches Ringsystem aufspannen können;
Z gleich oder verschieden bei jedem Auftreten CR¹ oder N ist,
R¹ gleich oder verschieden bei jedem Auftreten H, CN, eine geradkettige oder verzweigte oder cyclische Alkyl- oder Alkoxygruppe mit 1 bis 40 C-Atomen, wobei ein oder mehrere nicht benachbarte CH₂-Gruppen durch -HC=CH-, C=O, C=S, C=Se, C=NR⁴, -O-, -S-, -NR⁵-, oder -CONR⁶- ersetzt sein können und wobei ein oder mehrere H-Atome durch F, Cl, Br, I ersetzt sein können, oder eine Aryl- oder Neteroarylgruppe mit 1 bis 40 C-Atomen, wobei ein oder mehrere H-Atome durch F, Cl, Br, I ersetzt sein können und die durch einen oder mehrere, nicht aromatische Reste R¹ substituiert sein kann, wobei mehrere Substituenten R¹, sowohl am selben Ring als auch an den beiden unterschiedlichen Ringen zusammen wiederum ein weiteres mono- oder polycyclisches, aliphatisches oder aromatisches Ringsystem aufspannen können;
R⁴, R⁵, R⁶ gleich oder verschieden bei jedem Auftreten, N oder ein aliphatischer oder aromatischer Kohlenwasserstoffrest mit 1 bis 20 C-Atomen,
R⁷ gleich oder verschieden bei jedem Auftreten einer Aryl- oder Heteroarylgruppe mit 1 bis 40 C-Atomen, wobei ein oder mehrere H-Atome durch F, Cl, Br, I ersetzt sein können und die durch einen oder mehrere, nicht aromatische Reste R¹ substituiert sein kann, wobei mehrere Substituenten R¹, sowohl am selben Ring als auch an den beiden unterschiedlichen Ringen zusammen wiederum ein weiteres mono- oder polycyclisches, aliphatisches oder aromatisches Ringsystem aufspannen können, ist,
sind neu und damit ebenfalls Gegenstand der vorliegenden Erfindung,The compounds of the formulas (10), (11) and (12),

at them
Ar is an aryl or heteroaryl group with 4 to 40 C atoms, preferably with 4 to 20 C atoms, where one or more H atoms can be replaced by F, Cl, Br, I and which can be replaced by one or more, non-aromatic radicals R ¹ can be substituted, it being possible for a plurality of substituents R ¹ , both on the same ring and on the two different rings, to form a further mono- or polycyclic, aliphatic or aromatic ring system;
Z is the same or different on each occurrence CR ¹ or N,
R ^{1 the} same or different on each occurrence H, CN, a straight-chain or branched or cyclic alkyl or alkoxy group with 1 to 40 C atoms, one or more non-adjacent CH ₂ groups being represented by -HC = CH-, C = O , C = S, C = Se, C = NR ⁴ , -O-, -S-, -NR ⁵ -, or -CONR ⁶ - can be replaced and where one or more H atoms are replaced by F, Cl, Br, I can be replaced, or an aryl or heteroaryl group with 1 to 40 C atoms, where one or more H atoms can be replaced by F, Cl, Br, I and which are substituted by one or more non-aromatic radicals R ¹ can be, where a plurality of substituents R ¹ , both on the same ring and on the two different rings together can in turn span another mono- or polycyclic, aliphatic or aromatic ring system;
R ⁴ , R ⁵ , R ^{6 are the} same or different with each occurrence, N or an aliphatic or aromatic hydrocarbon radical with 1 to 20 C atoms,
R ^{7 is the} same or different each time an aryl or heteroaryl group with 1 to 40 C atoms occurs, it being possible for one or more H atoms to be replaced by F, Cl, Br, I and which are replaced by one or more non-aromatic radicals R ¹ can be substituted, with several substituents R ¹ , both on the same ring and on the two different rings together, in turn, a further mono- or polycyclic, aliphatic table or aromatic ring system is,
are new and thus also the subject of the present invention,

The present invention is explained in more detail by the following examples of matrix materials A, without wishing to restrict it thereto. The person skilled in the art can produce further matrix materials according to the invention from the description and the examples given without inventive step.

The Matrix materials according to the invention described above A - e.g. according to the examples 26, 27 and 28 - can for example as co-monomers to produce corresponding conjugated or partially conjugated polymers or as the core of dendrimers - e.g. according to the examples 29, 30 and 31 - use Find. The corresponding copolymerization is preferably carried out via the Halogen functionality.

So can she u. a. in soluble Polyfluorenes (e.g. according to EP-A-842208 or WO 00/22026), poly-spirobifluorenes (e.g. according to EP-A-707020 or EP-A-894107), poly-para-phenylenes (e.g. according to WO 92/18552), Poly-carbazoles or polythiophenes (e.g. according to EP-A-1028136) be polymerized.

The conjugated or partially conjugated polymers described above or Dendrimers which have one or more structural units of the formula (1) to (12) can contain used as matrix material in organic electroluminescent device become.

Farther can the matrix materials according to the invention A also by the example above. Reaction types further functionalized be converted into expanded matrix materials A. Here is an example of the functionalization with arylboronic acids acc. SUZUKI or with amines acc. To call HARTWIG-BUCHWALD.

Around The matrix materials according to the invention are used as functional material A or mixtures thereof or those containing matrix materials A. Polymers or dendrimers, optionally together with the emitters B, according to generally known methods known to the person skilled in the art, such as vacuum evaporation, Evaporation in the carrier gas stream, or from solution by spin coating or with various printing processes (e.g. inkjet printing, offset printing, LITI printing, etc.), in the form of a film on a substrate applied.

there The use of printing processes can provide advantages in terms of Scalability of production, as well as regarding the setting of mixing ratios in the blend layers used.

The matrix materials described above are used in combination with phosphorescence emitters. The organic electroluminescent devices represented in this way are characterized in that they contain as emitter B at least one compound which is characterized in that it emits light with suitable excitation and also contains at least one atom of atomic number greater than 20, preferably greater than 38 and less than 84, particularly preferably greater than 56 and less than 80.

Prefers are used as phosphorescence emitters in the organic described above Electroluminescent devices compounds containing molybdenum, tungsten, Rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, Containing silver, gold or europium.

worin
DCy eine zyklische Gruppe ist, die mindestens ein Donoratom, bevorzugt Stickstoff oder Phosphor, enthält, über welches die zyklische Gruppe an das Metall gebunden ist, und die wiederum ein oder mehrere Substituenten R⁸ tragen kann. Die Gruppen DCy und CCy sind über eine kovalente Bindung mit einander verbunden;
CCy eine zyklische Gruppe ist, die ein Kohlenstoffatom enthält, über welches die zyklischen Gruppe an das Metall gebunden ist und die wiederum ein oder mehrere Substituenten R⁸ tragen kann;
R⁸ gleich oder verschieden und bei jedem Auftreten H, F, Cl, Br, I, NO₂, CN, eine geradkettige oder verzweigte oder cyclische Alkyl- oder Alkoxygruppe mit 1 bis 40 C-Atomen, wobei ein oder mehrere nicht benachbarte CH₂-Gruppen durch C=O, C=S, C=Se, C=NR⁴, -O-, -S-, -NR⁵-, oder -CONR⁶- ersetzt sein können und wobei ein oder mehrere H-Atome durch F ersetzt sein können, oder eine Aryl- oder Heteroarylgruppe mit 4 bis 14 C-Atomen, die durch einen oder mehrere, nicht aromatische Reste R⁸ substituiert sein kann; wobei mehrere Substituenten R⁸, sowohl am selben Ring als auch an den beiden unterschiedlichen Ringen zusammen wiederum ein weiteres mono- oder polycyclisches Ringsystem aufspannen können; ist,
L ein zweizähnig, chelatisierender Ligand, bevorzugt ein Di-ketonatligand,
R⁴, R⁵, R⁶ gleich oder verschieden ist und bei jedem Auftreten, H oder ein aliphatischer oder aromatischer Kohlenwasserstoffrest mit 1 bis 20 C-Atomen ist.Particularly preferred mixtures containing, as emitter B, at least one compound of the formula (13) to (16),

wherein
DCy is a cyclic group which contains at least one donor atom, preferably nitrogen or phosphorus, via which the cyclic group is bonded to the metal and which in turn can carry one or more substituents R ⁸ . The groups DCy and CCy are connected to each other via a covalent bond;
CCy is a cyclic group which contains a carbon atom via which the cyclic group is bonded to the metal and which in turn can carry one or more substituents R ⁸ ;
R ^{8 are the} same or different and each occurrence is H, F, Cl, Br, I, NO ₂ , CN, a straight-chain or branched or cyclic alkyl or alkoxy group with 1 to 40 C atoms, one or more non-adjacent CH ₂ -Groups can be replaced by C = O, C = S, C = Se, C = NR ⁴ , -O-, -S-, -NR ⁵ -, or -CONR ⁶ - and where one or more H atoms by F can be replaced, or an aryl or heteroaryl group with 4 to 14 carbon atoms, which can be substituted by one or more non-aromatic radicals R ⁸ ; where a plurality of substituents R ⁸ , both on the same ring and on the two different rings together, can in turn span a further mono- or polycyclic ring system; is
L is a bidentate, chelating ligand, preferably a di-ketonate ligand,
R ⁴ , R ⁵ , R ^{6 are the} same or different and each occurrence is H or an aliphatic or aromatic hydrocarbon radical having 1 to 20 carbon atoms.

Examples of the emitters described above can be found, for example, in the following applications (WO 00/70655, WO 01/41512 A1, WO 02/02714 A2, WO 02/15645 A1, EP 1 191613 A2 . EP 1 191 612 A2 . EP 1 191 614 A2 ) are taken, and these are hereby considered as part of the registration via quotation. These are encompassed by the present invention.

The mixture according to the invention contains between 1 to 99% by weight, preferably 3 to 95% by weight, particularly preferably 5 to 50% by weight, in particular 7 to 20% by weight, of emitter B based on the total mixture of emitter B and matrix material A.

Another The present invention relates to electronic components, in particular organic electroluminescent devices (O-LED), organic solar cells (O-SCs), organic field effect transistors (O-FETs) or also organic laser diodes (O-lasers) containing the mixture according to the invention Matrix material A and emission material B.

• A eine Verbindung ist, welche eine Struktureinheit der Form C = X bzw. C = Y- enthält, dadurch gekennzeichnet, daß X bzw. Y mindestens ein nicht-bindendes Elektronenpaar aufweist, und gegebenenfalls auch glasartige Schichten bilden kann, und
• B eine Verbindung ist, dadurch gekennzeichnet, daß sie bei geeigneter Anregung Licht emittiert und welche mindestens ein Element der Ordungszahl größer 20 enthält.

Organic electroluminescent devices which have an emitting layer (EML) containing a mixture of at least one matrix material A and at least one emission material B capable of emission are particularly preferred,

• A is a compound which contains a structural unit of the form C = X or C = Y-, characterized in that X or Y has at least one non-binding pair of electrons and can optionally also form glass-like layers, and
• B is a compound, characterized in that it emits light with suitable excitation and which contains at least one element of an atomic number greater than 20.

• A eine Verbindung ist, welche eine Struktureinheit der Form C = X bzw. C = Y- enthält, dadurch gekennzeichnet, daß X bzw. Y mindestens ein nicht-bindendes Elektronenpaar aufweist, und dadurch gekennzeichnet, daß die Glastemperatur T_g der Reinsubstanz A größer 70°C ist, und
• B eine Verbindung ist, dadurch gekennzeichnet, daß sie bei geeigneter Anregung Licht emittiert und welche mindestens ein Element der Ordungszahl größer 20 enthält.

Organic electroluminescent devices which have an emitting layer (EML) containing a mixture of at least one matrix material A and at least one emission material B capable of emission are particularly preferred,

• A is a compound which contains a structural unit of the form C = X or C = Y-, characterized in that X or Y has at least one non-binding pair of electrons, and characterized in that the glass transition temperature T _{g of} the pure substance A is greater Is 70 ° C, and
• B is a compound, characterized in that it emits light with suitable excitation and which contains at least one element of an atomic number greater than 20.

The preferred embodiments of the mixtures according to the invention of matrix material A and emission material B are also for the electronic according to the invention Components, especially for the organic electroluminescent devices (O-LED), organic Solar cells (O-SCs), organic field effect transistors (O-FETs) or also given organic laser diodes (O-lasers). To avoid unnecessary repetitions will therefore be re-enumerated waived at this point.

in the present application text and also in the following examples is only on organic light emitting diodes and the corresponding displays targeted. Despite this limitation the description it is for possible to the person skilled in the art without further inventive intervention, corresponding layers according to the invention from the mixtures according to the invention to manufacture and use, especially in OLED-related or related Applications.

1. Synthesis of matrix materials A

The subsequent syntheses were - if not specified otherwise - under a protective gas atmosphere in dried solvent carried out. The starting materials were from ALDRICH [copper (I) cyanide, acetyl chloride, N-methylpyrolidinone (NMP)] related. 2-bromo-9,9'-spiro-bifluorene was based on literature methods Pei, Jian et al., J. Org. Chem., 2002, 67 (14), 4924-4936 shown.

Example 1: Di (9,9'-spirobifluoren-2-yl) ketone

A: 2-cyano-9,9'-spirobifluorene

A Suspension of 158.1 g (0.4 mol) of 2-bromo-9,9'-spirobifluorene and 89.6 g (1 mol) Copper (I) cyanide in 1100 ml of NMP was heated to 160 ° C. for 16 h. After cooling to 30 ° C became saturated with 1000 ml Ammonia solution added and 30 min. stirred. The precipitate was filtered off, saturated three times with 300 ml Ammonia solution and then washed three times with 300 ml of water and sucked dry. After loosening the solid in 1000 ml of dichloromethane was the solution over sodium sulfate dried, over Filtered silica gel and concentrated to dryness. The so obtained Crude product was recrystallized once from dioxane: ethanol (400 ml 750 ml). After drying the crystals in vacuo at 80 ° C, 81.0 g (237 mmol) became corresponding 59.3% of th.

¹ H-NMR (CDCl ₃ ): δ [ppm] = 7.92 - 7.85 (m, 4 H), 7.66 - 7.65 (m, 1 H), 7.44 - 7.39 (m, 3 H), 7.22 - 7.19 (m, 1 H), 7.15 - 7.11 (m, 2 H), 6.99 - 6.98 (m, 1 H), 6.79 - 6.78 (m, 1 H), 6.69 - 6.67 (m, 2 H).

B: Di (9,9'-spirobifluoren-2-yl) ketone

Out a solution of 98.8 g (250 mmol) of 2-bromo-9,9'-spirobifluorene and 6 ml 1,2-dichloroethane in 1000 ml THF and 7.1 g (290 mmol) magnesium the corresponding Grignard reagent was produced at the boiling point.

A solution of 85.4 g (250 mmol) of 2-cyano-9,9'-spirobifluorene in a mixture of 300 ml of THF and 1000 ml of toluene was added to this Grignad solution at 0-5 ° C. for 15 min. dropwise. The mixture was then heated under reflux for 6 h. After cooling, a mixture of 35 ml of 10N HCl in a mixture of 400 ml of water and 600 ml of ethanol was slowly added dropwise. After stirring for 16 h at room temperature temperature was suctioned off from the solid, which was washed three times with 200 ml of ethanol. The solid was recrystallized 4 times from NMP (5 ml / g) and then sublimed in a high vacuum (T = 385 ° C., p = 5 × 10 ^-5 mbar). The yield with a purity> 99.9% according to HPLC was 52.1 g (79 mmol) corresponding to 31.6% of th.

¹ H-NMR (CDCl ₃ ): δ [ppm] = 7.87 - 7.85 (m, 1 H), 7.83 - 7.81 (m, 2 H), 7.78 - 7.86 (m, 1 H), 7.60 - 7.58 (m, 1 H), 7.39 - 7.34 (m, 3 H), 7.18 - 7.17 (m, 1 H), 7.16 - 7.13 (m, 1 H), 7.10 - 7.07 (m, 2 H), 6.34 - 6.32 (m, 1 H), 6.70 - 6.69 (m, 2 H).

2. Production and characterization of organic electroluminescent devices, the compounds according to the invention contain

The OLEDs were produced in accordance with the following general procedure. Of course, this had to be done in individual cases particular circumstances (e.g. layer thickness variation in order to achieve optimal Efficiency or color).

• 1. ITO beschichtetes Substrat: Als Substrat wird bevorzugt mit ITO beschichtetes Glas verwendet, das einen möglichst niedrigen Gehalt bzw. keine ionischen Verunreinigungen enthält, wie z. B. Flachglas von den Firmen Merck-Balzers oder Akaii. Es können aber auch andere mit ITO beschichtete transparente Substrate, wie z.B. flexible Kunststofffolien oder Laminate verwendet werden. Das ITO muß eine möglichst hohe Leitfähigkeit mit einer hoher Transparenz verbinden. ITO-Schichtdicken zwischen 50 und 200 nm haben sich als besonders geeignet herausgestellt. Die ITO Beschichtung muß möglichst flach, bevorzugt mit einer Rauigkeit unter 2 nm, sein. Die Substrate werden zunächst mit einer 4%igen Dekonex-Lösung in entionisierten Wasser vorgereinigt. Danach wird das ITO beschichtete Substrat entweder mindestens 10 Minuten mit Ozon oder einige Minuten mit Sauerstoffplasma behandelt oder kurze Zeit mit einer Exzimer-Lampe bestrahlt.
• 2. Lochinjektions-Schicht (Hole Injection Layer = HIL): Als HIL wird entweder ein Polymer oder eine niedermolekulare Substanz verwendet. Besonders geeignet sind die Polymere Polyanilin (PANI) oder Polythiophen (PEDOT) und deren Derivate. Es handelt sich meist um 1 bis 5%ige wässrige Dispersionen, welche in dünnen Schichten zwischen 20 und 200 nm, bevorzugt zwischen 40 und 150 nm Schichtdicke auf das ITO-Substrat durch Spincoaten, Inkjet-Drucken oder andere Beschichtungsverfahren aufgebracht werden. Danach werden die mit PEDOT oder PANI beschichteten ITO-Substrate getrocknet. Für die Trocknung bieten sich mehrere Verfahren an. Herkömmlich werden die Filme im Trockenofen 1 bis 10 Minuten zwischen 110 und 200°C bevorzugt zwischen 150 und 180°C getrocknet. Aber auch neuere Trocknungsverfahren wie z.B. Bestrahlung mit IR-(Infrarot)-Licht führen zu sehr guten Resultaten, wobei die Bestrahlungsdauer im allgemeinen weniger als einige Sekunden dauert. Als niedermolekulares Material werden bevorzugt dünne Schichten, zwischen 5 und 30 nm, Kupferphthalocyanin (CuPc) verwendet. Herkömmlich wird CuPc in Vakuum-Sublimationsanlagen aufgedampft. Alle HIL müssen nicht nur sehr gut Löcher injizieren, sondern auch sehr gut auf ITO und Glas haften; dies ist sowohl für CuPc als auch für PEDOT und PANI der Fall. Eine besonders niedrige Absorption im sichtbaren Bereich und damit eine hohe Transparenz zeigen PEDOT und PANI, welches eine weitere notwendige Eigenschaft für die HIL ist.
• 3. Eine oder mehrere Lochtransport-Schichten (Hole Transport Layer = HTL): Bei den meisten OLEDs sind eine oder mehrere HTLs Voraussetzung für eine gute Effizienz und hohe Stabilität. Dabei erreicht man mit einer Kombination von zwei Schichten beispielsweise bestehend aus Triarylaminen wie MTDATA (4,4',4''-Tris(N-3-methyl-phenyl)-N-phenyl-amino)-triphenylamine) oder NaphDATA (4,4',4''-Tris(N-1-naphthyl)-N-phenyl-amino)-triphenylamine) als erste HTL und NPB (N,N'-Di(naphthalin-1-yl)-N,N'-diphenyl-benzidin) oder Spiro-TAD (Tetrakis-2,2',7,7'-diphenylamino-spiro-9'9'-bifluoren) als zweite HTL sehr gute Ergebnisse. MTDATA oder NaphDATA bewirken eine Erhöhung der Effizienz in den meisten OLEDs um ca. 20 – 40%; wegen der höheren Glastemperatur T_g wird NaphData (T_g = 130°C) gegenüber MTDATA (T_g = 100°C) bevorzugt. Als zweite Schicht wird Spiro-TAD (T_g = 130°C) wegen der höheren T_g gegenüber NPB (T_g = 95°C) bevorzugt. MTDATA bzw. NaphDATA haben eine Schichtdicke zwischen 5 und 100 nm, bevorzugt 10 und 60 nm, besonders bevorzugt zwischen 15 und 40 nm. Für dickere Schichten benötigt man etwas höhere Spannungen, um die gleiche Helligkeit zu erreichen; gleichzeitig verringert sich die Anzahl der Defekte. Spiro- TAD bzw. NPB haben eine Schichtdicke zwischen 5 und 150 nm, bevorzugt 10 und 100 nm, besonders bevorzugt zwischen 20 und 60 nm. Mit zunehmender Schichtdicke von NPB und den meisten anderen Triarylaminen benötigt man höhere Spannungen für gleiche Helligkeiten. Die Schichtdicke von Spiro-TAD hat jedoch nur einen geringfügigen Einfluß auf die Strom-Spannung-Elektrolumineszenz-Kennlinien, d.h. die benötigte Spannung, um ein bestimmte Helligkeit zu erreichen, hängt nur geringfügig von der Spiro-TAD Schichtdicke ab. Anstelle von niedermolekularen Triarylaminen können auch hochmolekulare Triarylaminen verwendet werden. Es handelt sich meist um 0.1 bis 30%ige Lösungen, welche in dünnen Schichten zwischen 20 und 500 nm, bevorzugt zwischen 40 und 150 nm Schichtdicke auf das ITO-Substrat oder die NIL (z.B. PEDOT- oder PANI-Schicht) durch Spincoaten, Inkjet-Drucken oder andere Beschichtungsverfahren aufgebracht werden.
• 4. Emissions-Schicht (Emission Layer = EML): Diese Schicht kann teilweise mit den Schichten 3 und/oder 5 zusammenfallen. Sie besteht z.B. aus einem niedermolekularen Wirtsmaterial und einem niedermolekularen Gastmaterial, dem phosphoreszierenden Dotanden, wie beispielsweise CBP oder eines der oben beschriebenen Matrixmaterialien A als Wirtsmaterial und Ir(PPy)₃ als Dotand. Gute Resultate erreicht man bei einer Konzentration von 5 – 30 % Ir(PPy)₃ in CBP oder eines der oben beschriebenen Matrixmaterialien A bei einer EML-Schichtdicke von 10 – 100 nm bevorzugt 10 – 50 nm. Anstelle von niedermolekularen Licht emittierenden Verbindungen können auch hochmolekulare Licht emittierenden Verbindungen (Polymere) verwendet werden, wobei eine oder auch beide Komponenten des Wirts-Gast-Systems hochmolekular sein können.
• 5. Eine Elektronentransport- und Lochblockier-Schicht (Hole Blocking Layer = HBL): Als HBL-Material hat sich besonders BCP (2,9-Dimethyl-4,7-diphenyl-1,10-phenanthrolin = Bathocuproin) oder BAIq als sehr wirkungsvoll gezeigt. Eine dünne Schicht von 3 – 30 nm, bevorzugt 5 – 20 nm erhöht die Effizienz sehr effektiv. Anstelle von niedemolekularen HBLs können auch hochmolekulare HBLs verwendet werden.
• 6. Elektronentransport-Schicht (Electron Transport Layer = ETL): Als ETL-Materialien sind Metall-hydroxy-chinolate gut geeignet; besonders Aluminium- tris-8-hydroxy-chinolat (Alq₃) hat sich als einer der stabilsten Elektronenleiter herausgestellt. Anstelle von niedemolekularen ETLs können auch hochmolekulare ETLs verwendet werden.
• 7. Elektroneninjektions-Schicht (Electron Injection Layer = EIL): Eine dünne Schicht mit einer Schichtdicke zwischen 0.2 und 8 nm bevorzugt 0.5 – 5 nm bestehend aus einem Material mit einer hohen Dielektrizitätskonstanten, insbesondere anorganische Fluoride und Oxide wie z.B. LiF, Li₂O, BaF₂, MgO, NaF und weiteren Materialien hat sich als EIL als besonders gut herausgestellt. Speziell in Kombination mit Al führt diese zusätzliche Schicht zu einer deutlichen Verbesserung der Elektroneninjektion, und damit zu verbesserten Resultaten bezüglich Lebensdauer, Quanten- und Leistungseffizienz.
• 8. Kathode: Hier werden in der Regel Metalle, Metallkombinationen oder Metalllegierungen mit niedriger Austrittsarbeit verwendet so z. B. Ca, Ba, Cs, K, Na, Mg, Al, In, Mg/Ag.
• 9. a) Herstellung dünner Schichten (2.–8.) niedermolekularer Verbindungen: Alle niedermolekularen Materialien der NIL, HTL, EML, HBL, ETL, EIL und Kathode werden in Vakuum-Sublimationsanlagen bei einem Druck kleiner 10^–5 mbar, bevorzugt kleiner 10^–6 mbar, besonders bevorzugt kleiner 10^–6 mbar aufgedampft. Die Aufdampfraten können zwischen 0.01 und 10nm/s bevorzugt 0.1 und 1 nm/s betragen. Neuere Verfahren wie die OPVD (Organic Physical Vapour Deposition) oder LITI (Light Induced Thermal Imaging) sind für die Beschichtung niedermolekularer Materialien ebenso geeignet, so wie weitere Drucktechniken. Für dotierte Schichten hat die OPVP ein großes Potential, weil das Einstellen von beliebigen Mischungsverhältnissen besonders gut gelingt. Ebenfalls lassen sich die Konzentrationen der Dotanden kontinuierlich verändern. Somit sind bei der OPVD die Voraussetzung für die Verbesserung der Elektrolumineszenz-Vorrichtung optimal. Wie oben beschrieben kann die Herstellung der erfindungsgemäßen Vorrichtungen auch durch spezielle Druckverfahren (wie das genannte LITI) durchgeführt werden. Dies hat sowohl Vorteile hinsichtlich der Skalierbarkeit der Fertigung, als auch bezüglich der Einstellung von Mischungsverhältnissen in verwendeten Blend-Schichten. Hierfür ist es aber in aller Regel nötig, entsprechende Schichten (für LITT: Transfer-Schichten) zu präparieren, welche dann erst auf das eigentliche Substrat übertragen werden.
• b) Herstellung dünner Schichten (2.–6.) hochmolekularer Verbindungen (Polymere): Es handelt sich meist um 0.1 bis 30%ige Lösungen, welche in dünnen Schichten zwischen 10 und 500 nm, bevorzugt zwischen 10 und 80 nm Schichtdicke auf das ITO-Substrat oder Barunterliegende Schichten durch Spincoaten, Inkjet-Drucken, LITT oder andere Beschichtungsverfahren und Drucktechniken aufgebracht werden.
• 10. Verkapselung: Eine effektive Einkapselung der organischen Schichten inklusive der EIL und der Kathode ist für organische Elektrolumineszenzvorrichtungen unerläßlich. Wenn das organische Display auf einem Glassubstrat aufgebaut ist, gibt es mehrere Möglichkeiten. Eine Möglichkeit ist das Verkleben des gesamten Aufbaus mit einer zweiten Glas- oder Metallplatte. Dabei haben sich Zwei-Komponenten- oder UV-härtende-Epoxykleber als besonders geeignet erwiesen. Dabei kann die Elektrolumineszenzvorrichtung vollständig oder aber auch nur am Rand verklebt werden. Wird das organische Display nur am Rand verklebt, kann man die Haltbarkeit zusätzlich verbessern, indem man einen sogenannten Getter hinzufügt. Dieser Getter besteht aus einem sehr hygroskopischen Material, insbesondere Metalloxide wie z.B. BaO, CaO usw., welches eindringendes Wasser und Wasserdämpfe bindet. Eine zusätzliche Bindung von Sauerstoff erreicht man mit Gettermaterialien wie z.B. Ca, Ba usw. Bei flexiblen Substraten ist besonders auf eine hohe Diffusionsbarriere gegenüber Wasser und Sauerstoff zu achten. Hier haben sich insbesondere Laminate aus alternierenden dünnen Kunststoff- und anorganischen Schichten (z.B. SiO_x oder SiN_x) bewährt.

Electroluminescent devices according to the invention can be represented, for example, as follows:

• 1. ITO-coated substrate: The substrate used is preferably ITO-coated glass which contains the lowest possible content or no ionic impurities, such as, for example, B. flat glass from Merck-Balzers or Akaii. However, other transparent substrates coated with ITO, such as, for example, flexible plastic films or laminates, can also be used. The ITO must combine the highest possible conductivity with high transparency. ITO layer thicknesses between 50 and 200 nm have proven to be particularly suitable. The ITO coating must be as flat as possible, preferably with a roughness below 2 nm. The substrates are first pre-cleaned with a 4% deconex solution in deionized water. The ITO-coated substrate is then either treated with ozone for at least 10 minutes or with oxygen plasma for a few minutes, or irradiated with an excimer lamp for a short time.
• 2. Hole Injection Layer (HIL): Either a polymer or a low-molecular substance is used as the HIL. The polymers polyaniline (PANI) or polythiophene (PEDOT) and their derivatives are particularly suitable. These are usually 1 to 5% aqueous dispersions, which are applied in thin layers between 20 and 200 nm, preferably between 40 and 150 nm, on the ITO substrate by spin coating, inkjet printing or other coating processes. The ITO substrates coated with PEDOT or PANI are then dried. Several methods are available for drying. Conventionally, the films are dried in the drying oven for 1 to 10 minutes between 110 and 200 ° C., preferably between 150 and 180 ° C. However, newer drying processes, such as irradiation with IR (infrared) light, also lead to very good results, the irradiation time generally taking less than a few seconds. Thin layers, between 5 and 30 nm, of copper phthalocyanine (CuPc) are preferably used as the low molecular weight material. Traditionally, CuPc is evaporated in vacuum sublimation systems. All HIL not only have to inject holes very well, they also have to adhere very well to ITO and glass; this is the case for CuPc as well as for PEDOT and PANI. PEDOT and PANI show a particularly low absorption in the visible range and thus a high level of transparency, which is another necessary property for the HIL.
• 3. One or more hole transport layers (HTL): Most OLEDs require one or more HTLs for good efficiency and high stability. A combination of two layers, for example consisting of triarylamines such as MTDATA (4,4 ', 4''- tris (N-3-methylphenyl) -N-phenylamino) triphenylamine) or NaphDATA (4, 4 ', 4''- tris (N-1-naphthyl) -N-phenyl-amino) -triphenylamine) as the first HTL and NPB (N, N'-di (naphthalin-1-yl) -N, N'- diphenyl-benzidine) or Spiro-TAD (Tetrakis-2,2 ', 7,7'-diphenylamino-spiro-9'9'-bifluorene) as second HTL very good results. MTDATA or NaphDATA increase the efficiency in most OLEDs by approx. 20 - 40%; Because of the higher glass temperature T _g , NaphData (T _g = 130 ° C) is preferred over MTDATA (T _g = 100 ° C). Spiro-TAD (T _g = 130 ° C) is preferred as the second layer because of the higher T _g compared to NPB (T _g = 95 ° C). MTDATA or NaphDATA have a layer thickness between 5 and 100 nm, preferably 10 and 60 nm, particularly preferably between 15 and 40 nm. For thicker layers, somewhat higher voltages are required in order to achieve the same brightness; at the same time, the number of defects is reduced. Spiro-TAD or NPB have a layer thickness between 5 and 150 nm, preferably 10 and 100 nm, particularly preferably between 20 and 60 nm. With increasing layer thickness of NPB and most other triarylamines, higher voltages are required for the same brightness. The layer thickness of Spiro-TAD, however, has only a minor influence on the current-voltage-electroluminescence characteristics, ie the voltage required to achieve a certain brightness depends only slightly on that Spiro-TAD layer thickness. Instead of low molecular weight triarylamines, high molecular weight triarylamines can also be used. These are usually 0.1 to 30% solutions, which are applied in thin layers between 20 and 500 nm, preferably between 40 and 150 nm, on the ITO substrate or the NIL (eg PEDOT or PANI layer) by spin coating, inkjet -Printing or other coating methods can be applied.
• 4. Emission Layer (Emission Layer = EML): This layer can partially coincide with layers 3 and / or 5. It consists, for example, of a low molecular weight host material and a low molecular weight guest material, the phosphorescent dopant such as CBP or one of the matrix materials A described above as the host material and Ir (PPy) ₃ as the dopant. Good results are achieved at a concentration of 5-30% Ir (PPy) ₃ in CBP or one of the matrix materials A described above with an EML layer thickness of 10-100 nm, preferably 10-50 nm. Instead of low molecular weight light-emitting compounds, it is also possible High molecular weight light-emitting compounds (polymers) are used, where one or both components of the host-guest system can be high molecular weight.
• 5. An electron transport and hole blocking layer (HBL): BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline = bathocuproin) or BAIq has proven to be a particularly good HBL material shown effectively. A thin layer of 3 - 30 nm, preferably 5 - 20 nm increases the efficiency very effectively. Instead of low molecular weight HBLs, high molecular weight HBLs can also be used.
• 6. Electron Transport Layer (ETL): Metal hydroxy-quinolates are well suited as ETL materials; aluminum tris-8-hydroxy-quinolate (Alq ₃ ) in particular has proven to be one of the most stable electron conductors. Instead of low-molecular ETLs, high-molecular ETLs can also be used.
• 7. Electron Injection Layer (EIL): A thin layer with a layer thickness between 0.2 and 8 nm, preferably 0.5 - 5 nm, consisting of a material with a high dielectric constant, in particular inorganic fluorides and oxides such as LiF, Li ₂ O. , BaF ₂ , MgO, NaF and other materials have proven to be particularly good as EIL. Especially in combination with Al, this additional layer leads to a significant improvement in the electron injection and thus to improved results with regard to service life, quantum and power efficiency.
• 8. Cathode: Usually metals, metal combinations or metal alloys with a low work function are used here. B. Ca, Ba, Cs, K, Na, Mg, Al, In, Mg / Ag.
• 9. a) Production of thin layers (2nd-8th) low-molecular compounds: All low-molecular materials of the NIL, HTL, EML, HBL, ETL, EIL and cathode are, preferably smaller, in vacuum sublimation systems at a pressure of less than 10 ^-5 mbar 10 ^-6 mbar, particularly preferably less than 10 ^-6 mbar evaporated. The evaporation rates can be between 0.01 and 10 nm / s, preferably 0.1 and 1 nm / s. Newer processes such as OPVD (Organic Physical Vapor Deposition) or LITI (Light Induced Thermal Imaging) are just as suitable for the coating of low-molecular materials, as are other printing techniques. OPVP has great potential for doped layers because it is particularly easy to set any mixture ratio. The concentrations of the dopants can also be changed continuously. Thus, the prerequisites for the improvement of the electroluminescent device are optimal with the OPVD. As described above, the devices according to the invention can also be produced by special printing processes (such as the LITI mentioned). This has advantages with regard to the scalability of the production as well as with regard to the setting of mixing ratios in the blend layers used. For this, however, it is generally necessary to prepare appropriate layers (for LITT: transfer layers), which are then only transferred to the actual substrate.
• b) Production of thin layers (2nd-6th) of high molecular weight compounds (polymers): These are mostly 0.1 to 30% solutions, which are in thin layers between 10 and 500 nm, preferably between 10 and 80 nm layer thickness on the ITO -Substrate or underlying layers can be applied by spin coating, inkjet printing, LITT or other coating processes and printing techniques.
• 10. Encapsulation: An effective encapsulation of the organic layers including the EIL and the cathode is essential for organic electroluminescent devices. If the organic display is built on a glass substrate, there are several options. One option is to glue the entire structure to a second glass or metal plate. Two-component or UV-curing epoxy adhesives have proven to be particularly suitable. The electroluminescent device can be glued completely or only at the edge. If the organic display is only glued on the edge, the durability can be further improved by adding a so-called getter. This getter consists of a very hygroscopic material, especially metal oxides such as BaO, CaO etc., which binds penetrating water and water vapors. An additional binding of oxygen can be achieved with getter materials such as Ca, Ba, etc. With flexible substrates, special attention must be paid to a high diffusion barrier against water and oxygen. Laminates of alternating thin plastic and inorganic layers (eg SiO _x or SiN _x ) have been found here in particular endures.

Examples

In This example shows the results of two different OLEDs compared. The basic structure, such as the materials used, degree of doping and their layer thickness was for the two sample experiments are identical for better comparability. It became exclusive the host material is exchanged in the emitter layer.

The first example describes a comparison standard according to the prior art, in which the emitter layer consists of the host material CBP and the guest material Ir (PPy) ₃ . Furthermore, an OLED with an emitter layer consisting of the host material di (9,9'-spirobifluoren-2-yl) ketone and the guest material Ir (PPy) ₃ (synthesized according to WO 02/060910) is described. The second example describes a further comparison between CBP and di (9,9'-spirobifluoren-2-yl) ketone (see Example 1) with the red emitter Ir (BTP) ₃ (synthesized according to WO 02/060910).

Analogous to the above general procedure, green and red emitting OLEDs with the following structure were produced:
PEDOT 60 nm (spun on water; PEDOT obtained from NC Starck; poly- [3,4-ethylenedioxy-2,5-thiophene]
NaphDATA 20 nm (evaporated; NaphDATA purchased from SynTec; 4,4 ', 4''- tris (N-1-naphthyl) N-phenylamino) triphenylamine
S-TAD 20 nm (evaporated; S-TAD manufactured according to WO 99/12888; 2,2 ', 7,7'-tetrakis (diphenylamino) -spirobifluorene)
Emitter layer:
CBP 20 nm (evaporated; CBP obtained from ALDRICH and further purified, finally sublimed twice; 4,4'-bis (N-carbazolyl) biphenyl) (comparison standard)
OR:
Di (9,9'-spiro-bi-fluoren-2-yl) ketone 20 nm (evaporated, synthesized and purified according to Example 1) each doped with 10% triplet emitter
Ir (PPy) ₃ (evaporated)
OR:
Ir (BTP) ₃ (evaporated)
Bathocuproin (BCP) 10 nm (evaporated; BCP obtained from ABCR, used as received; 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline)
AlQ ₃ 10 nm (evaporated: AlQ ₃ purchased from SynTec; Tris (quinoxalinato) aluminim (III))
Ba-Al 3 nm Ba on it 150 nm Al as cathode

This non-optimized OLEDs were characterized by default; for this were the electroluminescence spectra, the efficiency (measured in cd / A) dependent on the brightness, calculated from current-voltage-brightness characteristics (IUL characteristics), and determines the lifespan.

Application example 1: Ir (PPy) ₃

electroluminescence

The OLEDs, both the comparison standard, OLED with CBP, and the OLED with di (9,9'-spirobifluoren-2-yl) ketone as the host material show a green emission, resulting from the dopant Ir (PPy) ₃ .

Efficiency as a function of brightness

For OLEDs produced with the host material CBP, a maximum efficiency of about 25 cd / A is typically obtained and 4.8 V are required for the reference luminance of 100 cd / m ² . In contrast, OLEDs produced with the host material di (9,9'-spiro-bifluoren-2-yl) ketone show a maximum efficiency of over 30 cd / A, the voltage required for the reference luminance of 100 cd / m ² even 4.6 V is lowered.

Life comparison

The two life curves (see 1 ) were compared in the same illustration for better comparability shown. The figure shows the course of the luminance, measured in cd / m ² , over time. The lifespan is usually the time after which only 50% of the initial luminance is reached. Fig. 1

CBP as the host material has a lifespan of approx. 150 hours with an initial brightness of 1400 cd / m ² , which corresponds to an accelerated measurement, since the initial brightness is significantly higher than the brightness required for typical active matrix-controlled display applications ( 250 cd / m ² ). For di (9,9'-spirobifluoren-2-yl) ketone, a lifespan of approximately 2000 hours is obtained with the same initial brightness, which corresponds to an increase in lifespan of approximately 1300%.

From these two measured lifetimes, lifetimes can now be calculated for an initial brightness of 250 cd / m ² . In the case of the host material CBP, the service life is only 4700 hours, which is significantly less than the 10,000 hours required for display applications. In contrast, the di (9,9'-spirobifluoren-2-yl) ketone has a lifespan of over 60,000 hours, which clearly exceeds the minimum requirements.

Application example 2: Ir (BTP) ₃

Analogous experiments could be carried out with a red triplet emitter Ir (BTP) ₃ .

electroluminescence

The OLEDs, both the comparison standard, OLED with CBP, and the OLED with di (9,9'-spirobifluoren-2-yl) ketone as host material show a red emission, resulting from the dopant Ir (BTP) ₃ . The two spectra are in 2 shown. Fig. 2

Red Line: CBP; black line: di (9,9'-spiro-bifluoren-2-yl) ketone

Efficiency as a function of brightness

A maximum efficiency of about 8 cd / A is typically obtained for OLEDs produced with the host material CBP and 6.2 V are required for the reference luminance of 100 cd / m ² . In contrast, OLEDs produced with the host material di (9,9'-spirobifluoren-2-yl) ketone show a maximum efficiency of over 11 cd / A, the voltage required for the reference luminance of 100 cd / m ² even 5.2 V is reduced (see 3 ). Fig. 3

Life comparison

The two life curves (see 4 ) were shown in the same figure for better comparability. The figure shows the course of the luminance, measured in cd / m ² , over time. Fig. 4

CBP as the host material has a lifespan of approx. 53 hours with an initial brightness of almost 1300 cd / m ² , which also corresponds to an accelerated measurement in this example. For di (9,9'-spiro-bifluoren-2-yl) ketone, a lifespan of approximately 275 hours is obtained with the same initial brightness, which corresponds to an increase in lifespan of approximately 500%.

From these two measured lifetimes, lifetimes can now be calculated for an initial brightness of 250 cd / m ² . In the case of the host material CBP, the lifespan is only 1600 hours, which is significantly less than the 10,000 hours required for display applications. In contrast, the di (9,9'-spiro-bifluoren-2-yl) ketone has a lifespan of over 8200 hours, which is close to the minimum requirement.

Claims (18)

Containing mixtures - at least one matrix material A which contains a structural unit of the form C = X or C = Y- at X or Y has at least one non-binding pair of electrons, X for that Element O, S or Se and Y for the element N stands, and - at least one capable of emission Emission material B which is a compound with suitable excitation Light is emitted and contains at least one element with an atomic number greater than 20. Mixture according to claim 1, characterized in that the Matrix material A can form glass-like layers. Mixture according to claim 1 or 2, characterized in that the matrix material A has a glass transition temperature T _g (measured as pure substance) greater than 70 ° C. Mixture according to one or more of claims 1 to 3, characterized in that as matrix material A at least one compound according to formula (1), formula (2) and / or formula (3)

where the symbols and indices have the following meaning: XO, S or Se; YN; R ¹ , R ² , R ³ is the same or different with each occurrence N, CH, a straight-chain or branched or cy cical alkyl or alkoxy group with 1 to 40 C atoms, one or more non-adjacent CH ₂ groups being replaced by -HC = CH-, C = O, C = S, C = Se, C = NR ⁴ , -O- , -S-, -NR ⁵ -, or -CONR ⁶ - can be replaced and where one or more H atoms can be replaced by F, Cl, Br, I, or an aryl or heteroanl group with 1 to 40 C- Atoms, where one or more H atoms can be replaced by F, Cl, Br, I and which can be substituted by one or more, non-aromatic radicals R ¹ , where several substituents R ¹ and / or R ¹ , R ² both another mono- or polycyclic, aliphatic or aromatic ring system can in turn span on the same ring as well as on the two different rings; with the proviso that R ¹ = R ² = R ^{3 is} not hydrogen R ⁴ , R ⁵ , R ⁶ are the same or different in each occurrence, H or an aliphatic or aromatic hydrocarbon radical having 1 to 20 carbon atoms is used. Mixture according to one or more of claims 1 to 4, characterized in that as matrix material A at least one compound according to formula (4) to (9),

where the symbols X, Y, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ^{6 have} the meanings given under the formulas (1) to (3), and Z are the same or different each time CR ¹ or N is used. Mixture according to Claim 5, characterized in that at least one compound of the formula (4) to (9) is used as matrix material A in which X represents the element O and S, Y represents the element N, and R ¹ , R ² , R ^{3, the} same or different on each occurrence, N, a straight-chain or branched or cyclic alkyl or alkoxy group with 1 to 40 C atoms, one or more non-adjacent CH ₂ groups being represented by -HC = CH-, C = O, C = S, C = Se, C = NR ⁴ , -O-, -S-, -NR ⁵ -, or -CONR ⁶ - can be replaced and one or more H atoms by F, Cl, Br, I can be replaced or an aryl or heteroaryl group with 1 to 40 C atoms, where one or more H atoms can be replaced by F, Cl, Br, I and which can be substituted by one or more non-aromatic radicals R ¹ , where a plurality of substituents R ¹ and / or R ¹ , R ² , both on the same ring and on the two different rings, together in turn form a further mono- or polycyc can span, aliphatic or aromatic ring system, R ⁴ , R ⁵ , R ^{6 are the} same or different and is N or an aliphatic or aromatic hydrocarbon radical having 1 to 20 carbon atoms. Mixture according to claim 1, characterized in that as matrix material A at least one compound of the formula (10) and / or (11),

is used, where Z is the same or different at each occurrence CR ¹ or N, R ^{1 is} identical or different at each occurrence H, CN, a straight-chain or branched or cyclic alkyl or alkoxy group with 1 to 40 C atoms, where one or several non-adjacent CH ₂ groups replaced by -HC = CH-, C = O, C = S, C = Se, C = NR ⁴ , -O-, -S-, -NR ⁵ -, or -CONR ⁶ - and one or more H atoms can be replaced by F, Cl, Br, I, or an aryl or heteroaryl group having 1 to 40 C atoms, one or more H atoms being replaced by F, Cl, Br, I can be replaced and which can be substituted by one or more non-aromatic radicals R ¹ , where a plurality of substituents R ¹ , both on the same ring and on the two different rings, together in turn form a further mono- or polycyclic, aliphatic or aromatic ring system can span; R ⁴ , R ⁵ , R ^{6 are the} same or different at each occurrence, H or an aliphatic or aromatic hydrocarbon radical having 1 to 20 C atoms. Mix according to one or more of the claims 1 to 7, characterized in that as emitter B, at least a connection is used that with suitable excitation light emitted and at least one atom of atomic number greater than 38 and contains less than 84. Mix according to one or more of the claims 1 to 8, characterized in that as emitter B, at least a connection is used that with suitable excitation light emitted and at least one atom of atomic number greater than 56 and contains less than 80. Mix according to one or more of the claims 1 to 9, characterized in that as emitter B, at least a connection is used that with suitable excitation light emitted and at least one atom from the group molybdenum, tungsten, Rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, Is silver, gold or europium. Mixture according to one or more of claims 1 to 10, characterized in that at least one compound of the formula (13) to (16) as emitter B,

where DCy is a cyclic group which contains at least one donor atom, preferably nitrogen or phosphorus, via which the cyclic group is bonded to the metal and which in turn can carry one or more substituents R ⁸ . The groups DCy and CCy are connected to each other via a covalent bond; CCy is a cyclic group that contains a carbon atom via which the cyclic group attaches to the Metal is bound and which in turn can carry one or more substituents R ⁸ ; R ^{8 are the} same or different and each occurrence is H, F, Cl, Br, I, NO ₂ , CN, a straight-chain or branched or cyclic alkyl or alkoxy group with 1 to 40 C atoms, one or more non-adjacent CH ₂ -Groups can be replaced by C = O, C = S, C = Se, C = NR ⁴ , -O-, -S-, -NR ⁵ -, or -CONR ⁶ - and where one or more H atoms by F can be replaced, or an aryl or heteroaryl group with 4 to 14 carbon atoms, which can be substituted by one or more non-aromatic radicals R ⁸ ; where a plurality of substituents R ⁸ , both on the same ring and on the two different rings together, can in turn span a further mono- or polycyclic ring system; L is a bidentate, chelating ligand, preferably a di-ketonate ligand, R ⁴ , R ⁵ , R ^{6 is the} same or different and is H or an aliphatic or aromatic hydrocarbon radical having 1 to 20 C atoms in each occurrence becomes. Mix according to one or more of the claims 1 to 11, characterized in that the matrix material is one or contains several polymers or dendrimers. Mixture according to claim 12, characterized in that the Polymer conjugated or partially conjugated. Mixture according to claim 12 or 13, characterized in that the polymer from the group polyfluorenes, Poly-spirobifluorenes, poly-paraphenylenes, poly-carbazoles, poly-vinylcarbazoles, Polythiophenes or copolymers, several of those mentioned here Units selected is. Mix according to one or more of the claims 1 to 14, characterized in that the mixture between 1 to 99% by weight of emitter B based on the total mixture of emitter B and matrix material A contains. Compounds according to formulas (10), (11) and 12)

in which Ar is an aryl or heteroanl group with 4 to 40 C atoms, preferably with 4 to 20 C atoms, where one or more H atoms can be replaced by F, Cl, Br, I and which can be replaced by one or a plurality of non-aromatic radicals R ¹ can be substituted, it being possible for a plurality of substituents R ¹ , both on the same ring and on the two different rings, to form a further mono- or polycyclic, aliphatic or aromatic ring system; Z is the same or different at each occurrence, CR ¹ or N, R ^{1 is the} same or different at each occurrence, H, CN, a straight-chain or branched or cyclic alkyl or alkoxy group with 1 to 40 C atoms, one or more non-adjacent CH ₂ groups can be replaced by -HC = CH-, C = O, C = S, C = Se, C = NR ⁴ , -O-, -S-, -NR ⁵ -, or -CONR ⁶ - and where one or several H atoms can be replaced by F, Cl, Br, I, or an aryl or heteroanl group with 1 to 40 C atoms, where one or more H atoms can be replaced by F, Cl, Br, I and the can be substituted by one or more non-aromatic radicals R ¹ , it being possible for a plurality of substituents R ¹ , both on the same ring and on the two different rings, to form a further mono- or polycyclic, aliphatic or aromatic ring system; R ⁴ , R ⁵ , R ^{6 are the} same or different with each occurrence, N or an aliphatic or aromatic hydrocarbon radical with 1 to 20 C atoms, R ^{7 are} identical or different with each occurrence of an aryl or heteroaryl group with 1 to 40 C atoms , where one or more H atoms can be replaced by F, Cl, Br, I and which can be substituted by one or more non-aromatic radicals R ¹ , where several substituents R ¹ , both on the same ring and on the two different rings together can form another mono- or polycyclic, aliphatic or aromatic ring system. Electronic component containing at least one Mix according to one or more of the claims 1 to 15 and / or a compound according to claim 16. Electronic component according to claim 17, characterized in that it 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), preferably around an organic light-emitting diode (OLED) or an organic solar cell (O-SC).