DE102020108402B4 - Organic electronic device, organic semiconducting material, a trioxatriborinane compound and their use - Google Patents

Abstract

An organic electronic device comprising a first electrode, a second electrode and an organic semiconducting layer, wherein the organic semiconducting layer is arranged between the first electrode and the second electrode; the organic semiconducting layer is a hole injection layer, a hole transport layer or a hole generation layer; and- the organic semiconducting layer comprises a 1,3,5-trioxatriborinane-containing compound; wherein the 1,3,5-trioxatriborinane-containing compound is represented by the following formula (II) wherein R4, R5 and R6 are independently selected from the group consisting of fully substituted aryl and fully substituted heteroaryl; - it is provided for each of R4, R5 and R6 that at least one of the substituents is CN and / or at least one of the substituents is a hydrocarbon which comprises at least one sp3-hybridized carbon atom and is completely substituted by halogen atoms is; and- the remaining substituents of R4, R5 and R6 are independently selected from the group consisting of F, Cl, Br, I and CN, alternatively are independently selected from the group consisting of F, Cl, Br and I.

Description

The present invention relates to an organic electronic device, an organic semiconducting material, a trioxatriborinane compound and the use thereof.

STATE OF THE ART

Organic light-emitting diodes (OLEDs), which are self-emitting components, have a wide viewing angle, excellent contrast, quick response, high brightness, excellent drive voltage characteristics and color rendering. A typical OLED includes an anode, a hole transport layer (HTL), an emission layer (EML), an electron transport layer (ETL), and a cathode that are sequentially stacked on a substrate. The HTL, the EML and the ETL are thin films that are formed from organic and / or organometallic compounds.

When a voltage is applied to the anode and cathode, holes injected from the anode electrode move to the EML, via the HTL, and electrons injected from the cathode electrode move to the EML, via the ETL. The holes and electrons recombine in the EML to create excitons. When the excitons fall from an excited state to a ground state, light is emitted. The injection and flow of holes and electrons should be balanced so that an OLED having the structure described above has excellent efficiency.

WO 2016/097017 A1 discloses organic compounds which, due to their lowest unoccupied molecular orbitals (LUMO), are capable of being comparable to HOMO (most occupied molecular orbital) energy levels of compounds typically used as majority components (matrices) in organic hole-transporting semiconducting materials are to act as so-called charge transfer or redox p-dopants.

WO 2017/029370 A1 and WO 2017/029366 A1 disclose the use of sulfonylimide metal complexes comprising at least one sulfonylimide anionic ligand as hole injection materials.

Frohn et al., Z. Anorg Allg. Chemie, 2002, 628, pp. 2827-2833 discloses polyfluoro-organic boron-oxygen compounds, in particular polyfluorinated aryl (dihydroxy) boranes and tri (aryl) boroxines.

WO 2006/117 052 A1 discloses the use of aromatic boric acid or boric acid derivatives in organic electronic components, in particular electroluminescent components.

However, there still remains an unmet need for p-type dopants and hole injection materials that meet various and often conflicting practical requirements. For example, such requirements could be the provision of a hole injection material that enables good hole injection without significantly increasing the concentration of free holes in the doped material or on the doped phase interface. Such materials could be very useful for limiting electrical pixel crosstalk in displays that include an electrically doped hole transport layer adjacent to the patterned, pixel-defining anode.

In addition, there is still a need to improve the performance of organic electronic devices and / or organic semiconducting materials, in particular of optoelectronic devices that comprise an organic charge transport material, such as organic light emitting diodes (OLEDs) or organic photovoltaic (OPV) devices , and complex devices comprising the optoelectronic devices such as OLED displays.

It is therefore the object of the present invention to provide an organic electronic device, an organic semiconducting material and a compound for use therein which overcome the disadvantages of the prior art, in particular to provide p-dopants and / or hole injection materials in order to improve the performance of a corresponding device to improve, in particular to improve the initial tension, efficiency or tension stability thereof.

SUMMARY OF THE INVENTION

• - die organische halbleitende Schicht zwischen der ersten Elektrode und der zweiten Elektrode angeordnet ist;
• - die organische halbleitende Schicht eine Lochinjektionsschicht, eine Lochtransportschicht oder eine Locherzeugungsschicht ist; und
• - die organische halbleitende Schicht eine 1,3,5-Trioxatriborinan enthaltende Verbindung umfasst;

wobei die 1,3,5-Trioxatriborinan enthaltende Verbindung durch die folgende Formel (II) dargestellt ist

wobei

• - R⁴, R⁵ und R⁶ unabhängig ausgewählt sind aus der Gruppe bestehend aus vollständig substituiertem Aryl und vollständig substituiertem Heteroaryl;
• - es für jeden von R⁴, R⁵ und R⁶ vorgesehen ist, dass mindestens einer der Substituenten CN ist und/oder mindestens einer der Substituenten ein Kohlenwasserstoff ist, der mindestens ein sp³-hybridisiertes Kohlenstoffatom umfasst und vollständig mit Halogenatomen substituiert ist; und
• - die verbleibenden Substituenten von R⁴, R⁵ und R⁶ unabhängig ausgewählt sind aus der Gruppe bestehend aus F, Cl, Br, I und CN, alternativ unabhängig ausgewählt sind aus der Gruppe bestehend aus F, Cl, Br und I.

The above object is achieved by an organic electronic device which comprises a first electrode, a second electrode and an organic semiconducting layer, wherein

• - the organic semiconducting layer is arranged between the first electrode and the second electrode;
• the organic semiconducting layer is a hole injection layer, a hole transport layer or a hole generation layer; and
• the organic semiconducting layer comprises a compound containing 1,3,5-trioxatriborinane;

wherein the 1,3,5-trioxatriborinane-containing compound is represented by the following formula (II)

whereby

• - R ⁴ , R ⁵ and R ^{6 are} independently selected from the group consisting of fully substituted aryl and fully substituted heteroaryl;
• it is provided for each of R ⁴ , R ⁵ and R ⁶ that at least one of the substituents is CN and / or at least one of the substituents is a hydrocarbon which ^{comprises at least one sp 3} -hybridized carbon atom and is completely substituted by halogen atoms; and
• - the remaining substituents of R ⁴ , R ⁵ and R ^{6 are} independently selected from the group consisting of F, Cl, Br, I and CN, alternatively are independently selected from the group consisting of F, Cl, Br and I.

It has surprisingly been found by the inventors that 1,3,5-trioxatriborinane-containing compounds can be used in organic electronic devices (and in organic semiconducting materials) and that this use, especially when the 1,3,5-trioxatriborinane-containing compounds as p-dopants or used as hole injection materials, can be helpful to improve key properties of such devices and materials and thus their performance.

For the purposes of the present invention, a compound containing 1,3,5-trioxatriborinane is a compound which comprises the following 1,3,5-trioxatriborinane unit:

• - R⁴, R⁵ und R⁶ unabhängig ausgewählt sind aus der Gruppe bestehend aus vollständig substituiertem Aryl und vollständig substituiertem Heteroaryl;
• - es für jeden von R⁴, R⁵ und R⁶ vorgesehen ist, dass mindestens einer der Substituenten CN ist und/oder mindestens einer der Substituenten ein Kohlenwasserstoff ist, der mindestens ein sp³-hybridisiertes Kohlenstoffatom umfasst und vollständig mit Halogenatomen substituiert ist; und
• - die verbleibenden Substituenten von R⁴, R⁵ und R⁶ unabhängig ausgewählt sind aus der Gruppe bestehend aus F, Cl, Br, I und CN, alternativ unabhängig ausgewählt sind aus der Gruppe bestehend aus F, Cl, Br und I.

The 1,3,5-trioxatriborinane-containing compound contains three further groups which are bonded to the trivalent boron atoms. The 1,3,5-trioxatriborinane-containing compound is represented by the following formula (II) where

• - R ⁴ , R ^5, and R ^{6 are} independently selected from the group consisting of fully substituted aryl and fully substituted heteroaryl;
• it is provided for each of R ⁴ , R ⁵ and R ⁶ that at least one of the substituents is CN and / or at least one of the substituents is a hydrocarbon which ^{comprises at least one sp 3} -hybridized carbon atom and is completely substituted by halogen atoms; and
• - the remaining substituents of R ⁴ , R ⁵ and R ^{6 are} independently selected from the group consisting of F, Cl, Br, I and CN, alternatively are independently selected from the group consisting of F, Cl, Br and I.

(II) The remaining substituent (s), if present in one or more of R ⁴ , R ⁵ and R ⁶ , can be independently selected from the group consisting of halogen and CN. In this connection, halogen is F, Cl, Br and I. In this way, the electronic properties of the compound can be improved to improve its usefulness in organic electronic devices.

In one embodiment, at least 50%, preferably at least 66%, more preferably at least 75%, more preferably at least 80%, even more preferably at least 90%, most preferably 100% of the total number of hydrogen atoms present in at least one of R ⁴ , R ⁵ and R ^{6 are} included, may be replaced by substituents independently selected from F, Cl, Br, 1 and CN. The percentage of substitution here refers to a situation in which an unsubstituted group R ¹ , R ² , R ³ (hypothetical) is first provided and then a specific percentage of the hydrogen atoms contained in the respective unsubstituted group is replaced by substituents will. In this way, the electronic properties of the compound can be improved to improve its usefulness in organic electronic devices.

In another embodiment, at least 50%, preferably at least 66%, more preferably at least 75%, more preferably at least 80%, even more preferably at least 90%, most preferably 100% of the total number of hydrogen atoms in at least one of R ⁴ , R ⁵ and R ^{6 are} included, may be replaced by substituents independently selected from F and CN. In this way, the electronic properties of the compound can be improved to improve its usefulness in organic electronic devices.

In various embodiments, at least 50%, preferably at least 66%, more preferably at least 75%, more preferably at least 80%, even more preferably at least 90%, most preferably 100% of the total number of hydrogen atoms present in all of R ⁴ , R ⁵ and R ^{6 are} contained, can be replaced together by substituents which are independently selected from the group consisting of F, Cl, Br, 1 and CN. In this way, the electronic properties of the compound can be improved to improve its usefulness in organic electronic devices.

In various embodiments, at least 50%, preferably 66%, more preferably at least 75%, more preferably at least 80%, even more preferably at least 90%, most preferably 100% of the total number of hydrogen atoms present in all R ⁴ , R ⁵ and R ⁶ are contained together, be replaced by substituents which are independently selected from the group consisting of F and CN. In this way, the electronic properties of the compound can be improved to improve its usefulness in organic electronic devices.

oder eine Mischung davon sein. Auf diese Weise können die elektronischen Eigenschaften der Verbindung verbessert werden, um deren Verwendbarkeit in organischen elektronischen Vorrichtungen zu verbessern.The 1,3,5-trioxatriborinane containing compound can

or a mixture of these. In this way, the electronic properties of the compound can be improved to improve its usefulness in organic electronic devices.

• - die organische elektronische Vorrichtung eine lichtemittierende Schicht umfasst;
• - die lichtemittierende Schicht zwischen der ersten Elektrode und der zweiten Elektrode angeordnet ist;
• - die organische halbleitende Schicht zwischen der ersten Elektrode und der lichtemittierenden Schicht angeordnet ist; und
• - die organische halbleitende Schicht eine Lochinjektionsschicht oder Lochtransportschicht ist.

It can be provided that

• the organic electronic device comprises a light-emitting layer;
• the light-emitting layer is arranged between the first electrode and the second electrode;
• the organic semiconducting layer is arranged between the first electrode and the light-emitting layer; and
• the organic semiconducting layer is a hole injection layer or hole transport layer.

As disclosed herein, when reference is made to a specific layer of the organic electronic device, for example a light emitting layer, a hole injection layer, an organic semiconducting layer, etc., it can be provided that the organic electronic device comprises more than one of the respective layers . For example, the term “organic electronic device comprising one light emitting layer” also includes organic electronic devices comprising two light emitting layers, organic electronic devices comprising three light emitting layers, etc.

• - die organische elektronische Vorrichtung eine erste lichtemittierende Schicht und eine zweite lichtemittierende Schicht umfasst;
• - die erste lichtemittierende Schicht und die zweite lichtemittierende Schicht zwischen der ersten Elektrode und der zweiten Elektrode angeordnet sind;
• - die organische halbleitende Schicht zwischen der ersten lichtemittierenden Schicht und der zweiten lichtemittierenden Schicht angeordnet ist; und
• - die organische halbleitende Schicht eine Locherzeugungsschicht ist.

It can be provided that

• the organic electronic device comprises a first light-emitting layer and a second light-emitting layer;
• the first light-emitting layer and the second light-emitting layer are arranged between the first electrode and the second electrode;
• the organic semiconducting layer is arranged between the first light-emitting layer and the second light-emitting layer; and
• the organic semiconducting layer is a hole-generating layer.

The organic electronic device can be an organic electroluminescent device, an organic transistor, an organic diode, or an organic photovoltaic device.

The organic electroluminescent device may be an organic light emitting diode.

The object is also achieved by a display device which comprises the organic electronic device according to the invention.

The display device can comprise at least two organic electronic devices according to the invention.

• - das organische halbleitende Material eine Matrixverbindung und einen elektrischen Dotanden umfasst; und
• - der elektrische Dotand eine 1,3,5-Trioxatriborinan enthaltende Verbindung ist.

The object is also achieved by an organic semiconducting material, wherein

• the organic semiconducting material comprises a matrix compound and an electrical dopant; and
• the electrical dopant is a compound containing 1,3,5-trioxatriborinane.

The matrix compound contained in the organic semiconducting material can comprise or consist of a hole transport matrix compound.

The organic semiconducting material can be a hole transport material and the matrix compound can be a hole transport matrix compound.

The hole transport matrix compound can be an organic hole transport matrix compound. The organic hole transport matrix compound can comprise a conjugate system of at least 6 delocalized electrons, alternatively at least 10 delocalized electrons, alternatively at least 14 delocalized electrons.

The organic hole transport matrix compound can be selected from organic compounds comprising at least one amine nitrogen substituted with groups independently selected from C6 to C42 aryl and C3 to C42 heteroaryl.

oder eine Mischung davon sein. Auf diese Weise können die elektronischen Eigenschaften der Verbindung verbessert werden, um deren Verwendbarkeit in organischen halbleitenden Materialien zu verbessern.The 1,3,5-trioxatriborinane containing compound can

or a mixture of these. In this way, the electronic properties of the compound can be improved in order to improve its usefulness in organic semiconducting materials.

wobei

• - R⁴, R⁵ und R⁶ unabhängig ausgewählt sind aus der Gruppe bestehend aus vollständig substituiertem Aryl und vollständig substituiertem Heteroaryl;
• - es für jedes von R⁴, R⁵ und R⁶ vorgesehen ist, dass mindestens einer der Substituenten CN ist und/oder mindestens einer der Substituenten ein Kohlenwasserstoff ist, der mindestens ein sp³-hybridisiertes Kohlenstoffatom umfasst und vollständig mit Halogenatomen substituiert ist; und
• - die verbleibenden Substituenten von R⁴, R⁵ und R⁶ unabhängig ausgewählt sind aus der Gruppe bestehend aus F, Cl, Br, I und CN, alternativ unabhängig ausgewählt sind aus der Gruppe bestehend aus F, Cl, Br und I, alternativ alle F sind.

The object is also achieved by a compound of the following formula (II):

whereby

• - R ⁴ , R ⁵ and R ^{6 are} independently selected from the group consisting of fully substituted aryl and fully substituted heteroaryl;
• it is provided for each of R ⁴ , R ⁵ and R ⁶ that at least one of the substituents is CN and / or at least one of the substituents is a hydrocarbon which ^{comprises at least one sp 3} -hybridized carbon atom and is completely substituted by halogen atoms; and
• - the remaining substituents of R ⁴ , R ⁵ and R ^{6 are} independently selected from the group consisting of F, Cl, Br, I and CN, alternatively are independently selected from the group consisting of F, Cl, Br and I, alternatively all F are.

In this context, fully substituted means that in a situation in which an unsubstituted group R ⁴ , R ⁵ and R ^{6 is provided first} (hypothetical), then all hydrogen atoms contained in the respective unsubstituted group are replaced by substituents.

• -Ar ein vollständig substituiertes Aryl oder ein vollständig substituiertes Heteroaryl ist;
• - mindestens einer der Substituenten von Ar ein Hydrocarbyl ist, das vollständig mit Halogenatomen substituiert ist und mindestens ein sp³-hybridisiertes Kohlenstoffatom umfasst; und
• - die verbleibenden Substituenten von Ar unabhängig ausgewählt sind aus der Gruppe bestehend aus F, Cl, Br, I und CN, alternativ unabhängig ausgewählt sind aus der Gruppe bestehend aus F, Cl, Br und I, alternativ alle F sind. Die Aufgabe wird ferner gelöst durch die Verwendung einer 1,3,5-Trioxatriborinan enthaltenden Verbindung als p-Dotand in einer elektronischen Vorrichtung, wobei die 1,3,5-Trioxatriborinan enthaltende Verbindung durch die folgende Formel (II) dargestellt ist
  

wobei

• - R⁴, R⁵ und R⁶ unabhängig ausgewählt sind aus der Gruppe bestehend aus vollständig substituiertem Aryl und vollständig substituiertem Heteroaryl;
• - es für jeden von R⁴, R⁵ und R⁶ vorgesehen ist, dass mindestens einer der Substituenten CN ist und/oder mindestens einer der Substituenten ein Kohlenwasserstoff ist, der mindestens ein sp³-hybridisiertes Kohlenstoffatom umfasst und vollständig mit Halogenatomen substituiert ist; und
• - die verbleibenden Substituenten von R⁴, R⁵ und R⁶ unabhängig ausgewählt sind aus der Gruppe bestehend aus F, Cl, Br, I und CN, alternativ unabhängig ausgewählt sind aus der G

The object is also achieved by a compound of the following formula (III) Ar-B (OH) ₂ (III), whereby

• -Ar is a fully substituted aryl or a fully substituted heteroaryl;
• - At least one of the substituents of Ar is a hydrocarbyl which is completely substituted with halogen atoms and ^{comprises at least one sp 3} hybridized carbon atom; and
• the remaining substituents of Ar are independently selected from the group consisting of F, Cl, Br, I and CN, alternatively are independently selected from the group consisting of F, Cl, Br and I, alternatively all are F. The object is also achieved by using a compound containing 1,3,5-trioxatriborinane as a p-dopant in an electronic device, the 1,3,5-trioxatriborinane-containing compound being represented by the following formula (II)
  

whereby

• - R ⁴ , R ⁵ and R ^{6 are} independently selected from the group consisting of fully substituted aryl and fully substituted heteroaryl;
• it is provided for each of R ⁴ , R ⁵ and R ⁶ that at least one of the substituents is CN and / or at least one of the substituents is a hydrocarbon which ^{comprises at least one sp 3} -hybridized carbon atom and is completely substituted by halogen atoms; and
• - The remaining substituents of R ⁴ , R ⁵ and R ^{6 are} independently selected from the group consisting of F, Cl, Br, I and CN, alternatively are independently selected from G

Preferred embodiments relating to the 1,3,5-trioxatriborinane-containing compound which can be used in this context are disclosed above in relation to the organic electronic device according to the invention, the organic semiconducting material according to the invention and the compound according to the invention.

wobei

• - R⁴, R⁵ und R⁶ unabhängig ausgewählt sind aus der Gruppe bestehend aus vollständig substituiertem Aryl und vollständig substituiertem Heteroaryl;
• - es für jeden von R⁴, R⁵ und R⁶ vorgesehen ist, dass mindestens einer der Substituenten CN ist und/oder mindestens einer der Substituenten ein Kohlenwasserstoff ist, der mindestens ein sp³-hybridisiertes Kohlenstoffatom umfasst und vollständig mit Halogenatomen substituiert ist; und
• - die verbleibenden Substituenten von R⁴, R⁵ und R⁶ unabhängig ausgewählt sind aus der Gruppe bestehend aus F, Cl, Br, I und CN, alternativ unabhängig ausgewählt sind aus der G.

The object is also achieved by the use of a compound containing 1,3,5-trioxatriborinane as a hole-injecting material in an electronic device,
wherein the 1,3,5-trioxatriborinane-containing compound is represented by the following formula (II)

whereby

• - R ⁴ , R ⁵ and R ^{6 are} independently selected from the group consisting of fully substituted aryl and fully substituted heteroaryl;
• it is provided for each of R ⁴ , R ⁵ and R ⁶ that at least one of the substituents is CN and / or at least one of the substituents is a hydrocarbon which ^{comprises at least one sp 3} -hybridized carbon atom and is completely substituted by halogen atoms; and
• - The remaining substituents of R ⁴ , R ⁵ and R ^{6 are} independently selected from the group consisting of F, Cl, Br, I and CN, alternatively are independently selected from G.

Preferred embodiments in relation to the 1,3,5-trioxatriborinane-containing compound which can be used in this context are disclosed above in relation to the organic electronic device according to the invention, the organic semiconducting material according to the invention and the compound according to the invention.

The object is also achieved by using a compound of the following formula (III) Ar-B (OH) ₂ (III), as a precursor compound for the preparation of a compound containing 1,3,5-trioxatriborinane.

More layers

According to the invention, the organic electronic device can comprise further layers in addition to the layers already mentioned above. Exemplary embodiments of corresponding layers are described below:

Substrate

The substrate can be any substrate commonly used in the manufacture of organic electronic devices such as organic light emitting diodes. If light is to be emitted through the substrate, the substrate is a transparent or semitransparent material, for example a glass substrate or a transparent plastic substrate. If light is to be emitted through the top surface, the substrate can be both a transparent and a non-transparent material, for example a glass substrate, a plastic substrate, a metal substrate or a silicon substrate.

Anode electrode

The first electrode or the second electrode can be an anode electrode. The anode electrode can be formed by depositing or sputtering a material used to form the anode electrode. The material used to form the anode electrode can be a high work function material to facilitate hole injection. The anode material can also be selected from a low work function material (ie, aluminum). The anode electrode can be a transparent or reflective electrode. Transparent conductive oxides, such as indium tin oxide (ITO), indium zinc oxide (IZO), tin dioxide (SnO ₂ ), aluminum zinc oxide (AlZO), and zinc oxide (ZnO), can be used to form of the anode electrode. The anode electrode can also be formed using metals, typically silver (Ag), gold (Au), or metal alloys. Another alternative material for the anode electrode can be graphene.

Hole injection layer

According to the invention, the hole injection layer can comprise the 1,3,5-trioxatriborinane-containing compound, as described in detail above. The hole injection layer (HIL) can be formed on the anode electrode by vacuum deposition, spin coating, printing, casting, slot die coating, Langmuir-Blodgett (LB) deposition, or the like. When the HIL is formed using vacuum deposition, the deposition conditions can vary according to the compound used to form the HIL and the desired structure and thermal properties of the HIL. In general, however, conditions for vacuum deposition may include a deposition temperature of 100 ° C to 500 ° C, a pressure of 10 ^-8 to 10 ^-3 Torr (1 Torr corresponds to 133.322 Pa), and a deposition rate of 0.1 to 10 nm / sec.

When the HIL is formed using spin coating or printing, coating conditions can vary according to the compound used to form the HIL and the desired structure and thermal properties of the HIL. For example, the coating conditions can include a coating speed of about 2000 rpm to about 5000 rpm and a heat treatment temperature of about 80 ° C to about 200 ° C. Heat treatment removes a solvent after coating is performed.

The HIL can be formed from any compound commonly used to form an HIL, particularly when the organic electronic device comprises another layer comprising the 1,3,5-trioxatriborinane-containing compound. Examples of compounds that can be used to form the HIL include a phthalocyanine compound such as copper phthalocyanine (CuPc), 4,4 ', 4 "-ris (3-methylphenylphenylamino) triphenylamine (M-MTDATA), TDATA, 2T- NATA, polyaniline / dodecylbenzenesulfonic acid (Pani / DBSA), poly (3,4-ethylenedioxythiophene) / poly (4-styrene sulfonate) (PEDOT / PSS), polyaniline / camphorsulfonic acid (Pani / CSA) and polyaniline) / poly (4-styrene sulfonate ( PANI / PSS).

In such a case, the HIL can be a pure layer of a p-dopant or can be selected from a hole-transporting matrix compound which is doped with a p-dopant. Typical examples of known redox-doped hole transport materials are: copper phthalocyanine (CuPc), where the HOMO level is approximately -5.2 eV, that is doped with tetrafluoro-tetracyanoquinone dimethane (F4TCNQ), where the LUMO level is approximately -5.2 eV is; Zinc phthalocyanine (ZnPc) (HOMO = -5.2 eV) doped with F4TCNQ is; α-NPD (N, N'-bis (naphthalen-1-yl) -N, N'bis (phenyl) -benzidine) doped with F4TCNQ. α-NPD doped with 2,2 '- (perfluoronaphthalene-2,6-diylidene) dimalononitrile (PD1). α-NPD which is doped with 2,2 ', 2 "- (cyclopropane-1,2,3-triylidene) tris (2- (p-cyanotetrafluorophenyl) acetonitrile) (PD2). Dopant concentrations can range from 1 to 20 wt. -%, more preferably from 3% by weight to 10% by weight.

The thickness of the HIL can range from about 1 nm to about 100 nm and, for example, from about 1 nm to about 25 nm. When the thickness of the HIL is in this range, the HIL can have excellent hole injection properties without being significantly disadvantageous in terms of operating voltage.

Hole transport layer

According to the invention, the hole transport layer can comprise the 1,3,5-trioxatriborinane-containing compound, as described in detail above.

The hole transport layer (HTL) can be formed on the HIL by vacuum deposition, spin coating, slot die coating, printing, casting, Langmuir-Blodgett (LB) deposition, or the like. When the HTL is formed by vacuum deposition or spin coating, the conditions for deposition and coating may be similar to the conditions for the formation of the HIL. However, the conditions for vacuum or solution deposition can vary according to the compound used to form the HTL.

In the event that the HTL does not comprise the 1,3,5-trioxatriborinane-containing compound according to the invention, but the 1,3,5-trioxatriborinane-containing compound is included in another layer, the HTL can be formed by any compound commonly used to form an HTL. Compounds that can be suitably used are disclosed in, for example, Yasuhiko Shirota and Hiroshi Kragyama, Chem. Rev. 2007, 107, 953-1010. and incorporated herein by reference. Examples of the compound that can be used to form the HTL are: carbazole derivatives such as N-phenylcarbazole or polyvinylcarbazole; Benzidine derivatives, such as N, N'-bis (3-methylphenyl) -N, N'diphenyl- [1,1-biphenyl] -4,4'-diamine (TPD) or N, N'-di (naphthalene- 1-yl) -N, N'diphenylbenzidine (alpha-NPD); and a triphenylamine-based compound such as 4,4 ', 4 "-tris (N-carbazolyl) triphenylamine (TCTA). Among these compounds, TCTA can transport holes and prevent excitons from being diffused into the EML.

The thickness of the HTL can be in the range from about 5 nm to about 250 nm, preferably about 10 nm to about 200 nm, further about 20 nm to about 190 nm, further about 40 nm to about 180 nm, further about 60 nm to about 170 nm, further about 80 nm to about 160 nm, further about 100 nm to about 160 nm, further about 120 nm to about 140 nm. A preferred thickness of the HTL can be 170 nm to 200 nm.

If the thickness of the HTL is in this range, the HTL can have excellent hole transport properties without any significant disadvantage with regard to the operating voltage.

Electron blocking layer

The function of the electron blocking layer (EBL) is to prevent electrons from being transferred from the emission layer to the hole transport layer and thereby to limit electrons to the emission layer. This improves the efficiency, the operating voltage and / or the service life. Typically the electron blocking layer comprises a triarylamine compound. The triarylamine compound can have a LUMO level which is closer to the vacuum level than the LUMO level of the hole transport layer. The electron blocking layer can have a HOMO level that is further removed from the vacuum level compared to the HOMO level of the hole transport layer. The thickness of the electron blocking layer can be selected between 2 and 20 nm.

The electron blocking layer may comprise a compound represented by the formula (Z) given below.

In formula Z, CY1 and CY2 are identical or different from one another and each independently represent a benzene ring or a naphthalene ring, Ar1 to Ar3 are identical or different from one another and are each independently selected from the group consisting of hydrogen; a substituted or unsubstituted aryl group having 6 to 30 carbon atoms; and a substituted or unsubstituted heteroaryl group having 5 to 30 carbon atoms, Ar4 is selected from the group consisting of a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted triphenylene group and a substituted or unsubstituted triphenylene group 5 to 30 carbon atoms, L is a substituted or unsubstituted arylene group having 6 to 30 carbon atoms.

If the electron blocking layer has a high triplet level, it can also be referred to as a triplet control layer.

The function of the triplet control layer is to reduce triplet quenching when a green or blue emissive phosphorescent layer is used. This makes it possible to achieve a higher efficiency of the light emission from a phosphorescent emission layer. The triplet control layer is selected from triarylamine compounds with a triplet level above the triplet level of the phosphorescent emitter in the adjacent emission layer. Suitable compounds for the triplet control layer, in particular the triarylamine compounds, are in the EP 2 722 908 A1 described.

Emission Layer (EML)

The EML can be formed on the HTL by vacuum deposition, spin coating, slot die coating, printing, casting, LB deposition, or the like. When the EML is formed by vacuum deposition or spin coating, the conditions for deposition and coating may be similar to the conditions for the formation of the HIL. However, the deposition and coating conditions can vary according to the compound used to form the EML.

The emission layer (EML) can be formed from a combination of a host and an emitter dopant. Examples of the host are Alq3, 4,4'-N, N'-dicarbazole biphenyl (CBP), poly (n-vinylcarbazole) (PVK), 9,10-di (naphthalen-2-yl) anthracene (ADN), 4 , 4 ', 4 "-Tris (carbazol-9-yl) -triphenylamine (TCTA), 1,3,5-tris (N-phenylbenzimidazol-2-yl) benzene (TPBI), 3-tert-butyl-9, 10-di-2-naphthylanthracene (TBADN), distyrylarylene (DSA), bis (2- (2-hydroxyphenyl) benzo-thiazolate) zinc (Zn (BTZ) 2), G3 below, compound 1 below and compound 2 below.

The emitter dopant can be a phosphorescent or fluorescent emitter. Phosphorescent emitters and emitters that emit light via a thermally activated delayed fluorescence (TADF) mechanism may be preferred because of their higher efficiency. The emitter can be a small molecule or a polymer.

Examples of red emitter dopants are PtOEP, Ir (piq) ₃ and Btp ₂ Ir (acac), but are not restricted to these. These compounds are phosphorescent emitters, but fluorescent red emitter dopants could also be used.

Examples of phosphorescent green emitter dopants are Ir (ppy) ₃ (ppy = phenylpyridine), Ir (ppy) ₂ (acac), Ir (mpy) ₃ are shown below. Compound 3 is an example of a fluorescent green emitter and the structure is shown below.

Examples of phosphorescent blue emitter dopants are F2Irpic, (F2ppy) 2Ir (tmd) and Ir (dfppz) ₃ , ter-fluorene, the structures are shown below. 4,4'-bis (4-diphenylamiostyryl) biphenyl (DPAVBi), 2,5,8,11-tetra-tert-butylperylene (TBPe), and compound 4 as shown below are examples of fluorescent blue emitter dopants.

The amount of emitter dopant can range from about 0.01 to about 50 parts by weight based on 100 parts by weight of the host. Alternatively, the emission layer can consist of a light-emitting polymer. The EML can have a thickness of about 10 nm to about 100 nm, for example from about 20 nm to about 60 nm. If the thickness of the EML is in this range, the EML can exhibit excellent light emission without any significant disadvantage in terms of operating voltage.

Hole blocking layer (HBL)

A hole blocking layer (HBL) can be formed on the EML using vacuum deposition, spin coating, slot die coating, printing, casting, LB deposition, or the like to prevent the diffusion of holes into the EML. If the EML comprises a phosphorescent dopant, the HBL can also have a triplet exciton blocking function.

When the HBL is formed by vacuum deposition or spin coating, the conditions for deposition and coating may be similar to the conditions for the formation of the HIL. However, the deposition and coating conditions may vary according to the compound used to form the HBL. Any compound commonly used to form an HBL can be used. Examples of compounds for forming HBL include oxadiazole derivatives, triazole derivatives and phenanthroline derivatives.

The HBL can have a thickness in the range from approximately 5 nm to approximately 100 nm, for example from approximately 10 nm to approximately 30 nm. If the thickness of the HBL is in this range, the HBL can have excellent hole blocking properties without being significantly disadvantageous in terms of the operating voltage.

Electron transport layer (ETL)

The OLED according to the present invention can contain an electron transport layer (ETL).

According to various embodiments, the OLED can comprise an electron transport layer or an electron transport layer stack which comprises at least one first electron transport sublayer and at least one second electron transport sublayer.

By properly adjusting the energy levels of certain layers of the ETL, the injection and transport of electrons can be controlled and the holes can be blocked efficiently. As a result, the OLED can have a long service life.

The electron transport layer of the organic electronic device can comprise an organic electron transport matrix material (ETM). Furthermore, the electron transport layer can comprise one or more n-dopants. Suitable compounds for the ETM are not particularly limited. In one embodiment, the electron transport matrix compounds consist of covalently bonded atoms. Preferably the electron transport matrix compound comprises a conjugate system of at least 6, more preferably at least 10 delocalized electrons. In one embodiment, the conjugated system can be comprised of delocalized electrons in aromatic or heteroaromatic structural units, as for example in the publications EP 1970 371 A1 or WO 2013/079217 A1 disclosed.

In one embodiment, the electron transport layer can be electrically doped with an electrical n-dopant. In another embodiment, the electron transport layer can be the second Electron transport sublayer located closer to the cathode than the first electron transport sublayer, and only the second electron transport sublayer may comprise the n-type electrical dopant.

The electrical n-dopant can be selected from electropositive elemental metals and / or from metal salts and metal complexes of electropositive metals, in particular from elemental forms, salts and / or metal complexes selected from alkali metals, alkaline earth metals and rare earth metals.

Electron injection layer (EIL)

The optional EIL, which can facilitate the injection of electrons from the cathode, can be formed on the ETL, preferably directly on the electron transport layer. Examples of materials for forming the EIL include lithium 8-hydroxyquinolinolate (LiQ), LiF, NaCl, CsF, Li ₂ O, BaO, Ca, Ba, Yb, Mg, which are known in the art. Deposition and coating conditions for forming the EIL are similar to those for forming the EIL, although the deposition and coating conditions may vary according to the material used to form the EIL.

The thickness of the EIL can be in the range from about 0.1 nm to about 10 nm, for example in the range from about 0.5 nm to about 9 nm. If the thickness of the EIL is in this range, the EIL can exhibit satisfactory electron injection properties without being significantly disadvantageous in terms of operating voltage.

Cathode electrode

The cathode electrode, if present, is formed on the EIL. The cathode electrode can be formed from a metal, an alloy, an electrically conductive compound or a mixture thereof. The cathode electrode can have a low work function. For example, the cathode electrode made of lithium (Li), magnesium (Mg), aluminum (Al), aluminum (Al) -Lithium (Li), calcium (Ca), barium (Ba), ytterbium (Yb), magnesium (Mg) - Indium (In), magnesium (Mg) -silver (Ag) or the like. Alternatively, the cathode electrode can be formed from a transparent conductive oxide such as ITO or IZO.

The thickness of the cathode electrode can be in the range from approximately 5 nm to approximately 1000 nm, for example in the range from approximately 10 nm to approximately 100 nm. When the thickness of the cathode electrode is in the range of about 5 nm to about 50 nm, the cathode electrode may be transparent or semitransparent even if it is formed from a metal or a metal alloy.

It goes without saying that the cathode electrode is not part of an electron injection layer or the electron transport layer.

Charge generation layer / hole generation layer

The charge generation layer (CGL) can consist of a double layer. In the case that the charge generation layer is a p-type charge generation layer (hole generation layer), it may comprise the 1,3,5-trioxatriborinane-containing compound as defined herein.

Typically, the charge generation layer is a pn junction connecting an n-type charge generation layer (electron generation layer) and a hole generation layer. The n-side of the pn-junction generates electrons and injects them into the layer that is adjacent in the direction towards the anode. Similarly, the p-side of the pn-junction creates holes and injects them into the layer that is adjacent in the direction of the cathode.

Charge generation layers are used in tandem devices, for example in tandem OLEDs which have two or more emission layers between two electrodes. In a tandem OLED, which comprises two emission layers, the n-type charge generation layer provides electrons for the first light emission layer, which is arranged near the anode, while the hole generation layer provides holes for the second light emission layer, which is between the first emission layer and the cathode is arranged.

According to the invention it can be provided that the organic electronic device comprises a hole injection layer and a hole generation layer. If any layer other than the hole generation layer comprises the 1,3,5-trioxatriborinane-containing compound as defined herein, it is not It is imperative that the hole-generating layer also comprises the compound containing 1,3,5-trioxatriborinane, as defined here. In such a case, the hole generation layer can consist of an organic matrix material which is doped with a p-type dopant. Suitable matrix materials for the hole generation layer can be materials which are customarily used as hole injection and / or hole transport matrix materials. Conventional materials can also be used for the hole generation layer. For example, the p-type dopant can be one selected from a group consisting of tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4-TCNQ), derivatives of tetracyanoquinodimethane, quinenodienemethane derivatives, iodine, FeCl3, FeF3 and SbCl5. Also, the host can be one selected from the group consisting of N, N'-di (naphthalen-1-yl) -N, N-diphenyl-benzidine (NPB), N, N'-diphenyl-N, N'-bis (3-methylphenyl) -1,1-biphenyl-4,4'-diamine (TPD) and N, N ', N'-tetranaphthyl-benzidine (TNB).

In one embodiment, the hole transport layer comprises the 1,3,5-trioxatriborinane-containing compound as defined in detail above.

The n-type charge generation layer may be a layer of a pure n-dopant, for example an electropositive metal, or it may consist of an organic matrix material doped with the n-dopant. In one embodiment, the n-dopant can be alkali metal, alkali metal compound, alkaline earth metal or alkaline earth metal compound. In another embodiment, the metal can be one selected from the group consisting of Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, La, Ce, Sm, Eu, Tb, Dy, and Yb consists. Specifically, the n-type dopant may be one selected from a group consisting of Cs, K, Rb, Mg, Na, Ca, Sr, Eu, and Yb. Suitable matrix materials for the electron generation layer can be the materials which are customarily used as matrix materials for electron injection or electron transport layers. The matrix material may, for example, be one selected from a group consisting of triazine compounds, hydroxyquinoline derivatives such as tris (8-hydroxyquinoline) aluminum, benzazole derivatives, and silol derivatives.

wobei jedes von A1 bis A6 Wasserstoff, ein Halogenatom, Nitril (-CN), Nitro (-NO₂), Sulfonyl (-SO₂R), Sulfoxid (-SOR), Sulfonamid (-SO₂NR₂), Sulfonat (-SO₃R), Trifluormethyl (-CF₃), Ester (-COOR), Amid (-CONHR oder -CONRR"), substituiertes oder unsubstituiertes geradkettiges oder verzweigtkettiges C1-C12-Alkoxy, substituiertes oder unsubstituiertes geradkettiges oder verzweigtkettiges C1-C12-Alkyl, substituiertes oder unsubstituiertes geradkettiges oder verzweigtkettiges C2-C12-Alkenyl, ein substituiertes oder unsubstituierter aromatischer oder nichtaromatischer Heteroring, substituiertes oder unsubstituiertes Aryl, substituiertes oder unsubstituiertes Mono- oder Diarylamin, substituiertes oder unsubstituiertes Aralkyl oder dergleichen sein kann. Dabei kann jedes der obigen R und R' substituiertes oder unsubstituiertes C1-C60-Alkyl, substituiertes oder unsubstituiertes Aryl oder ein substituierter oder unsubstituierter 5- bis 7-gliedriger Heteroring oder dergleichen sein.In one embodiment, the p-type charge generation layer may contain compounds represented by chemical formula X below.

where each from A1 to A6 is hydrogen, a halogen atom, nitrile (-CN), nitro (-NO ₂ ), sulfonyl (-SO ₂ R), sulfoxide (-SOR), sulfonamide (-SO ₂ NR ₂ ), sulfonate (- SO ₃ R), trifluoromethyl (-CF ₃ ), ester (-COOR), amide (-CONHR or -CONRR "), substituted or unsubstituted straight-chain or branched-chain C1-C12-alkoxy, substituted or unsubstituted straight-chain or branched-chain C1-C12- Alkyl, substituted or unsubstituted straight-chain or branched-chain C2-C12-alkenyl, a substituted or unsubstituted aromatic or non-aromatic hetero ring, substituted or unsubstituted aryl, substituted or unsubstituted mono- or diarylamine, substituted or unsubstituted aralkyl or the like R and R 'be substituted or unsubstituted C1-C60-alkyl, substituted or unsubstituted aryl or a substituted or unsubstituted 5- to 7-membered hetero ring or the like.

An example of such a p-type charge generation layer may be a layer comprising CNHAT.

The hole generation layer may be disposed on the n-type charge generation layer.

Organic Light Emitting Diode (OLED)

According to one aspect of the present invention, there is provided an organic light emitting diode (OLED) comprising: a substrate; an anode electrode formed on the substrate; a hole injection layer, a hole transport layer, an emission layer and a cathode electrode.

According to another aspect of the present invention, there is provided an OLED comprising: a substrate; an anode electrode formed on the substrate; a hole injection layer, a hole transport layer, an electron blocking layer, an emission layer, a hole blocking layer, and a cathode electrode.

According to another aspect of the present invention, there is provided an OLED comprising: a substrate; an anode electrode formed on the substrate; a hole injection layer, a hole transport layer, an electron blocking layer, an emission layer, a hole blocking layer, an electron transport layer, and a cathode electrode.

According to another aspect of the present invention, there is provided an OLED comprising: a substrate; an anode electrode formed on the substrate; a hole injection layer, a hole transport layer, an electron blocking layer, an emission layer, a hole blocking layer, an electron transport layer, an electron injection layer, and a cathode electrode.

According to various embodiments of the present invention, OLEDs can be provided which comprise layers which are arranged between the above-mentioned layers, on the substrate or on the upper electrode.

According to one aspect, the OLED can comprise a layer structure of a substrate which is arranged adjacent to an anode electrode, the anode electrode is arranged adjacent to a first hole injection layer, the first hole injection layer is arranged adjacent to a first hole transport layer, the first hole transport layer is arranged adjacent to a first electron blocking layer the first electron blocking layer is disposed adjacent to a first emission layer, the first emission layer is disposed adjacent to a first electron transport layer, the first electron transport layer is disposed adjacent to an n-type charge generation layer, the n-type charge generation layer is disposed adjacent to a hole generation layer , the hole generation layer is arranged adjacent to a second hole transport layer, the second hole transport layer is arranged adjacent to a second electron blocking layer, the second electron blocking layer is arranged adjacent to a second emission layer, an optional electron transport layer and / or an optional injection layer are arranged between the second emission layer and the cathode electrode.

For example, the OLED according to 2 be formed by a process whereby on a substrate ( 110 ), an anode ( 120 ), a hole injection layer ( 130 ), a hole transport layer ( 140 ), an electron blocking layer ( 145 ), an emission layer ( 150 ), a hole blocking layer ( 155 ), an electron transport layer ( 160 ), an electron injection layer ( 180 ) and the cathode electrode ( 190 ) are formed one after the other in this order.

Details and Definitions of the Invention

The organic electronic device of the present invention comprises at least one (semiconducting) layer which can comprise a hole transport matrix compound and the compound containing 1,3,5-trioxatriborinane. The 1,3,5-trioxatriborinane-containing compound can be embedded in the matrix material; H. the matrix material is the predominant material in such a layer. It can also be provided that the matrix material and the 1,3,5-trioxatriborinane-containing compound in the semiconducting layer in a first sub-layer, which includes the matrix material, and a second sub-layer, which the 1,3,5-trioxatriborinane-containing compound as Comprises dopant, are separated from one another, or, in a preferred embodiment, each consist of these. It can also be provided that the layer consists of the compound containing 1,3,5-trioxatriborinane.

The 1,3,5-trioxatriborinane-containing compound can diffuse into the adjacent layers after deposition, in particular the 1,3,5-trioxatriborinane-containing compound can diffuse into the layer on which it is deposited.

The organic electronic device described here can be an organic electronic device based on semiconducting layers. In particular, the hole injection layer, the hole transport layer and the hole generation layer are semiconducting layers.

The term “carbon-containing group” as used here is to be understood to include any organic group that includes carbon atoms, in particular organic groups such as alkyl, aryl, heteroaryl, heteroalkyl, in particular those groups that appear in the organic Electronics are common substituents.

The term "hydrocarbon" as used here is to be understood to include any organic monovalent group that only includes carbon and hydrogen atoms, for example organic groups such as alkyl, aryl, arylalkyl, cycloalkyl, alkenyl, alkynyl, Arylalkenyl, arylalkynyl, and the like.

As used herein, the term "alkyl" is intended to encompass linear, branched and cyclic alkyl. For example, C3-alkyl can be selected from n-propyl and iso-propyl. Likewise, C4-alkyl includes n-butyl, sec-butyl and t-butyl. Likewise, C6-alkyl includes n-hexyl and cyclo-hexyl.

The subscript n in C _n relates to the total number of carbon atoms in the respective alkyl, arylene, heteroarylene or aryl group.

The term “aryl” as used here is intended to _{encompass phenyl (C 6} -aryl) and monovalent groups derived from condensed aromatics, such as naphthalene, anthracene, phenanthrene, tetracene, etc. Also included are biphenyl and oligo - or polyphenyl, such as terphenyl, etc. Also included is any hydrocarbyl group which comprises at least one aromatic ring, if the single bond which bonds the hydrocarbyl group to another structural unit results from the aromatic ring which is included in the hydrocarbyl group . Examples can be, for example, 2-fluorenyl, 3-fluorenyl, 9,9 "-dimethyl-2-fluorenyl etc. Arylene or heteroarylene refers analogously to divalent aromatic groups which are derived from an arene or a heteroarene, so that two hydrogen atoms originally attached to aromatic rings of the arene or heteroarenes are replaced by two more structural units.

The term “heteroaryl” as used herein relates to aryl groups in which at least one carbon atom has been replaced by a heteroatom, preferably selected from N, O, S, B or Si.

The term “halogenated” refers to an organic compound in which one hydrogen atom has been replaced by a halogen atom. The term “perhalogenated” refers to an organic compound in which all of its hydrogen atoms have been replaced with halogen atoms. The meaning of the terms “fluorinated” and “perfluorinated” is to be understood analogously.

The subscript n in C _n -heteroaryl refers only to the number of carbon atoms, with the exception of the number of heteroatoms. In this context, it is clear that a C ₃ heteroarylene group is an aromatic compound comprising three carbon atoms, such as pyrazole, imidazole, oxazole, thiazole and the like.

For the purposes of the invention, the expression “between” in relation to a layer that lies between two other layers does not exclude the presence of further layers that can be arranged between the one layer and one of the two other layers. In the context of the invention, the expression “in direct contact” with reference to two layers that are in direct contact with one another means that no further layer is arranged between these two layers. A layer deposited on top of another layer is considered to be in direct contact with that layer.

In the context of the present description, the expression “essentially non-emitting” or “non-emitting” means that the proportion of the compound or layer to the visible emission spectrum from the device is less than 10%, preferably less than 5%, based on the visible emission spectrum , amounts to. The visible emission spectrum is an emission spectrum with a wavelength of approximately ≥ 380 nm to approximately ≤ 780 nm.

The organic semiconducting layer, which comprises at least one electrical dopant, is preferably essentially non-emissive or non-emissive.

With regard to the electronic device according to the invention, the compounds mentioned in the experimental part can be most preferred.

The electronic device according to the invention can comprise semiconducting devices, the charge transport consisting solely in the movement of electrons and / or holes.

The electronic device according to the invention can be an organic electroluminescent device (OLED), an organic photovoltaic device (OPV) or an organic field effect transistor (OFET).

According to a further aspect, the organic electroluminescent device according to the present invention can comprise more than one emission layer, preferably two or three emission layers. An OLED that comprises more than one emission layer is also referred to as a tandem OLED or stacked OLED.

The organic electroluminescent device (OLED) can be a bottom or top emitting device.

Another aspect relates to a device which comprises at least one organic electroluminescent device (OLED). A device that comprises organic light-emitting diodes is, for example, a display or a lighting panel.

In the present invention, the following defined terms are to be used, and these definitions apply unless a different definition is given in the claims or otherwise in this description.

In connection with the present description, the term “different” or “differs” in connection with the matrix material means that the matrix material differs in its structural formula.

The energy levels of the highest occupied molecular orbital, also known as HOMO, and the lowest occupied molecular orbital, also known as LUMO, are measured in electron volts (eV).

The terms “OLED” and “organic light-emitting diode” are used at the same time and have the same meaning. The term “organic electroluminescent device” as used herein can include both organic light-emitting diodes and organic light-emitting transistors (OLETs).

As used herein, “percent by weight”, “% by weight”, “% by weight”, “percent by weight”, “% by weight” and variations thereof refer to a composition, component, substance or agent as the weight thereof Component, substance or the agent of the respective electron transport layer divided by the total weight of the respective electron transport layer thereof and multiplied by 100. It is understood that the total weight percentage of all components, substances and the agent of the respective electron transport layer and the electron injection layer are selected to be 100 Wt .-% does not exceed.

As used herein, "percent by volume", "percent by volume", "percent in volume", "% in volume" and their variations refer to a composition, component, substance or agent as the volume of that component, substance or substance By means of the respective electron transport layer, divided by the total volume of the respective electron transport layer thereof and multiplied by 100. It goes without saying that the total volume percentage of all components, substances and the means of the cathode layer are selected so that they do not exceed 100% by volume.

All numerical values are assumed herein to be modified by the term “about”, not even explicitly stated. As used herein, the term "about" refers to the variation in the amount of numbers that can occur. Whether or not modified by the term "about" of the claims encompass equivalents to the amounts.

It should be noted that, as used in this specification and the appended claims, the singular forms “a,” “an,” and “the” include the plural, unless the contents clearly indicate otherwise .

The terms “free of”, “does not contain”, “does not include” do not exclude impurities. Impurities have no technical effect in relation to the object achieved by the present invention.

Figure list

• 1 eine schematische Schnittansicht einer organischen Leuchtdiode (OLED) gemäß einem Ausführungsbeispiel der vorliegenden Erfindung;
• 2 eine schematische Schnittansicht einer OLED gemäß einem Ausführungsbeispiel der vorliegenden Erfindung.
• 3 eine schematische Schnittansicht einer Tandem-OLED mit einer Ladungserzeugungsschicht gemäß einem Ausführungsbeispiel der vorliegenden Erfindung.

These and / or other aspects and advantages of the present invention will become clearer and clearer from the following description of the exemplary embodiments in conjunction with the accompanying drawings. Show it:

• 1 a schematic sectional view of an organic light emitting diode (OLED) according to an embodiment of the present invention;
• 2 a schematic sectional view of an OLED according to an embodiment of the present invention.
• 3 a schematic sectional view of a tandem OLED with a charge generation layer according to an embodiment of the present invention.

EMBODIMENTS OF THE DEVICE ACCORDING TO THE INVENTION

Reference will now be made in detail to the embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like numerals refer to like elements throughout. The exemplary embodiments are described below in order to explain the aspects of the present invention with reference to the figures.

Where herein a first element is referred to as being formed or disposed “on” a second element, the first element may be disposed directly on the second element, or one or more other elements may be disposed therebetween. When a first element is referred to as being formed or disposed “directly on” a second element, no other elements are disposed therebetween.

1 shows a schematic sectional view of an organic light emitting diode (OLED) 100 according to an embodiment of the present invention. The OLED 100 comprises a substrate 110 , an anode 120 , a hole injection layer (HIL) 130 , a hole transport layer (HTL) 140 , an emission layer (EML) 150 , an electron transport layer (ETL) 160 . The electron transport layer (ETL) 160 is right on the EML 150 educated. On the electron transport layer (ETL) 160 is an electron injection layer (EIL) 180 arranged. The cathode 190 is directly on the electron injection layer (EIL) 180 arranged.

Instead of a single electron transport layer 160 an electron transport layer stack (ETL) can optionally be used.

2 shows a schematic sectional view of an OLED 100 according to a further embodiment of the present invention. 2 differs from 1 in that the OLED 100 the 2 an electron blocking layer (EBL) 145 and a hole blocking layer (HBL) 155 having.

Referring to 2 includes the OLED 100 a substrate 110 , an anode 120 , a hole injection layer (HIL) 130 , a hole transport layer (HTL) 140 , an electron blocking layer (EBL) 145 , an emission layer (EML) 150 , a hole blocking layer (HBL) 155 , an electron transport layer (ETL) 160 , an electron injection layer (EIL) 180 and a cathode electrode 190 .

3 shows a schematic sectional view of a tandem OLED 200 according to a further embodiment of the present invention. 3 differs from 2 in that the OLED 100 the 3 further comprises a charge generation layer and a second emission layer.

Referring to 3 includes the OLED 200 a substrate 110 , an anode 120 , a first hole injection layer (HIL) 130 , a first hole transport layer (HTL) 140 , a first electron blocking layer (EBL) 145 , a first emission layer (EML) 150 , a first hole blocking layer (HBL) 155 , a first electron transport layer (ETL) 160 , an n-type charge generation layer (n-type CGL) 185 , a p-type charge generation layer (p-type GCL) 135 , a second hole transport layer (HTL) 141 , a second electron blocking layer (EBL) 146 , a second emission layer (EML) 151 , a second hole blocking layer (EBL) 156 , a second electron transport layer (ETL) 161 , a second electron injection layer (EIL) 181 and a cathode 190 .

Although in 1 , 2 and 3 not shown, can be on the cathode electrodes 190 Furthermore, a sealing layer can be formed around the OLEDs 100 and 200 to seal. In addition, various other modifications can be applied thereto.

In the following, one or more exemplary embodiments of the present invention are described in detail with reference to the following examples. However, these examples are not intended to limit the purpose and scope of the claims to one or more exemplary embodiments of the present invention.

EXPERIMENTAL PART

Supporting materials

(Poly[(9,9-Dioctylfluorenyl-2,7-diyl)-CO-(4,4'-(N-(4-sec-butylphenyl)diphenylamin)], kommerziell erhältlich von Solaris Chem Inc., Kanada)

N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-9H-fluoren-2-amine, CAS 1242056-42-3;

8-(4-(4,6-Di(naphthalen-2-yl)-1,3,5-triazin-2-yl)phenyl)chinolin, CAS 1312928-44-1;

N,N-Di([1,1'-Biphenyl]-4-yl)-3'-(9H-carbazol-9-yl)-[1,1'-biphenyl]-4-amin, CAS 1464822-27-2;

2-(3'-(9,9-Dimethyl-9H-fluoren-2-yl)-[1,1'-biphenyl]-3-yl)-4,6-diphenyl-1,3,5-triazin, CAS 1955543-57-3;

4'-(4-(4-(4,6-Diphenyl-1,3,5-triazin-2-yl)phenyl)naphthalen-1-yl)-[1,1'-biphenyl]-,4-carbonitril, CAS 2032421-37-5.The support materials formulas below are as follows:

(Poly [(9,9-dioctylfluorenyl-2,7-diyl) -CO- (4,4 '- (N- (4-sec-butylphenyl) diphenylamine)], commercially available from Solaris Chem Inc., Canada)

N - ([1,1'-biphenyl] -4-yl) -9,9-dimethyl-N- (4- (9-phenyl-9H-carbazol-3-yl) phenyl) -9H-fluorene-2- amine, CAS 1242056-42-3;

8- (4- (4,6-di (naphthalen-2-yl) -1,3,5-triazin-2-yl) phenyl) quinoline, CAS 1312928-44-1;

N, N-di ([1,1'-biphenyl] -4-yl) -3 '- (9H-carbazol-9-yl) - [1,1'-biphenyl] -4-amine, CAS 1464822-27 -2;

2- (3 '- (9,9-dimethyl-9H-fluoren-2-yl) - [1,1'-biphenyl] -3-yl) -4,6-diphenyl-1,3,5-triazine, CAS 1955543-57-3;

4 '- (4- (4- (4,6-Diphenyl-1,3,5-triazin-2-yl) phenyl) naphthalen-1-yl) - [1,1'-biphenyl] -, 4-carbonitrile , CAS 2032421-37-5.

ABH-113 and Ho9 are emitter hosts and DB-370 and DB-200 are blue fluorescent emitter dopants, all commercially available from SFC, Korea.

ITO is indium tin oxide, LiQ stands for lithium 8-hydroxyquinolinolate.

für die getesteten erfindungsgemäßen Verbindungen als Benchmarking-p-Dotand- oder Lochinjektionsmaterial nach dem Stand der Technik verwendet.In device tests, the connection was

used for the tested compounds according to the invention as benchmarking p-dopant or hole injection material according to the prior art.

Standard procedure

Fixture preparation

Fl layer, comprising the tested and / or comparative electrical dopant, was produced by spin coating on a standard glass substrate provided with an ITO layer; 1.5% by weight of F1 stock solution in anisole and 2% by weight of F1 stock solution of electrical dopant in benzonitrile were filtered through PTFE syringe filters with 0.2 μm pore size and mixed in the desired volume ratio before use.

Other layers were deposited by thermal vacuum evaporation (VTE).

Tension stability

OLEDs are powered by constant electrical circuits. These circuits can deliver a constant current over a given voltage range. The wider the voltage range, the wider the power losses of such devices. Therefore, the change in the drive voltage during operation must be minimized.

The drive voltage of an OLED is temperature-dependent. Therefore, the voltage stability in thermal equilibrium must be assessed. Thermal equilibrium is reached after one hour of operation.

The voltage stability is measured by measuring the difference in the drive voltage after 50 hours and after 1 hour at a constant current density. A current density of 30 mA / cm ^{2 is} used here. Measurements are carried out at room temperature. $$\text{you}\left[\text{V}\right]=\text{U}\left(50\text{H}\text{, 30 mA}/{\text{cm}}^2\right)-\text{U}\left(\text{1 h}\text{, 30 mA}/{\text{cm}}^2\right)$$

Synthesis of trioxatriborinane compounds

Production of E1 (not according to the invention)

Step 1: Synthesis of (perfluorophenyl) boronic acid

Bromopentafluorobenzene (1.00 g, 4.0 mmol) was added to a suspension of magnesium (0.10 g, 4.1 mmol) in ether (10 mL) at 0 ° C. The mixture was stirred at the same temperature for 2 hours and then refluxed for 1 hour. The reaction mixture was cooled to 0 ° C. and added portionwise to a cooled solution of B (OMe) 3 (0.60 g, 6.0 mmol) in ether (5 ml). The suspension was stirred at 0 ° C. for 1 h and then poured into 5% HCl (20 ml). After stirring at room temperature for 10 min, the organic layer was separated, the aqueous layer extracted with ether (5 ml) and the combined extracts dried _{over MgSO 4.} After concentration under reduced pressure and recrystallization of the resulting solid from toluene, (perfluorophenyl) boronic acid was obtained as a white solid (0.37 g, 43%).

¹¹ BNMR (600 MHz, acetone-d ₆ ) δ 26.3; ¹⁹ FNMR (377 MHz, acetone-d ₆ ) δ -132.6 (m, 2F), -154.8 (m, 1F), -163.5 (m, 2F); IR (ATR): v = 3308, 1648, 1524, 1482, 1396, 1332, 1270, 1096, 970, 856, 775, 741, 603, 565.

Step 2: Synthesis of Tris (perfluorophenyl) boroxyin (E1)

(Perfluorophenyl) boric acid (0.21 g, 1.0 mmol) was heated for 40 min at 120 ° C under reduced pressure (700 mbar) to provide tris (perfluorophenyl) boroxyyne (0.18 g, 94% yield). Response can be monitored by IR analysis. ¹¹ BNMR (600 M Hz, acetone-d6) δ 19.1; ¹⁹ FNMR (377 MHz, acetone-d6) δ -133.1 (m, 2F), -157.7 (m, 1F), -163.8 (m, 2F); IR (ATR): v ^-1 = 1648, 1524, 1481, 1344, 1222, 1091, 978, 885, 756, 707, 625,565,482; EIMS: m / z (%) = 581 (15) [M +], 489 (5), 378 (12), 212 (40), 184 (55), 168 (100), 136 (50), 105 (43 ), 91 (25). EI-MS: m / z (%) = 582 (100) [M +], 194 (40), 148 (19).

Making E2

Step 1: Synthesis of (4-cyano-2,3,5,6-tetrafluorophenyl) boronic acid

IPrMgCl (2.1 mL, 4.1 mmol, 2 M in Ether) was added at -95 ° C. and the reaction mixture was stirred at the same temperature. After 3 h, a solution of B (OMe) 3 (0.61 g, 5.9 mmol) in ether (5 mL) was added to the reaction mixture. The suspension was stirred at -95 ° C. for 2 h, warmed to room temperature (overnight) and then poured into 5% HCl (20 mL). After stirring at room temperature for 10 min, the organic layer was separated, the aqueous layer was extracted with ether (5 mL) and the combined extracts were dried _{over MgSO 4.} After concentration under reduced pressure, (4-cyano-2,3,5,6-tetrafluorophenyl) boronic acid was obtained as a white solid (0.44 g, 51%).

¹¹ BNMR (600 MHz, acetone-d ₆ ) δ 26.2; ¹⁹ FNMR (377 MHz, acetone-d ₆ ) δ -131.0 (m, 2F), -136.7 (m, 2F); IR (ATR): v = 3191, 1679, 1408, 1381, 1280, 1190, 884, 706, 634, 545,474.

Step 2: Synthesis of Tris (4-cyano-2,3,5,6-tetrafluorophenyl) boroxyin (E2)

(4-Cyano-2,3,5,6-tetrafluorophenyl) boronic acid (0.22 g, 1.0 mmol) was heated at 120 ° C. under reduced pressure (800 mbar) for 2.5 h to give tris (4 Cyano-2,3,5,6-tetrafluorophenyl) boroxyin (0.18 g, 88%). (The reaction was monitored by IR analysis). ¹¹ BNMR (600 MHz, acetone-d6) δ 19.7; IR (ATR): v = 1702, 1465, 1382, 1269, 1153, 971, 942, 812, 703, 65,4,581; EI-MS: m / z (%) = 603 (15) [M +], 376 (10), 190 (20), 174 (100), 100 (65).

Manufacture of E3

Step 1: Synthesis of (2,3,5,6-tetrafluoro-4- (trifluoromethyl) phenyl) boronic acid

To a solution of 1-bromo-2,3,5,6-tetrafluoro-4- (trifluoromethyl) benzene (1.00 g, 3.4 mmol) in 15 mL ether, iPrMgCl (1.9 mL, 3rd , 7 mmol, 2 M in ether) was added at -30 ° C and the reaction mixture was stirred at the same temperature for 2 h and then warmed to 0 ° C. After 1 h, a solution of B (OMe) 3 (0.52 g, 5.1 mmol) in ether (5 mL) was added to the reaction mixture. The suspension was stirred at 0 ° C. for 2 h, warmed to room temperature (overnight) and then poured into 5% HCl (20 mL). After stirring at room temperature for 10 min, the organic layer was separated, the aqueous layer was extracted with ether (5 mL) and the combined extracts were dried _{over MgSO 4.} After evaporation of the solvent under reduced pressure, (2,3,5,6-tetrafluoro-4- (trifluoromethyl) phenyl) boronic acid was obtained as a white solid (0.74 g, 84%). ¹¹ BNMR (600 MHz, acetone-d6) δ 26.1; ¹⁹ FNMR (377 MHz, acetone-d6) δ-58.3 (t, J = 21.8 Hz, 3F), -132.4 (m, 2F), 138.3 (m, 2F); IR (ATR): v = 3340, 1464, 1430, 1345, 1312, 1161, 1033, 970, 942, 792, 713, 598, 432.

Step 2: Synthesis of Tris (2,3,5,6-Tetrafluoro-4- (trifluoromethyl) phenyl) boroxyin (E3)

2,3,5,6-Tetrafluoro-4- (trifluoromethyl) phenyl) boric acid (0.26 g, 1.0 mmol) was heated for 20 min at 120 ° C. under reduced pressure (800 mbar) to give tris (2, 3,5,6-tetrafluoro-4- (trifluoromethyl) phenyl) boroxyin (0.21 g, 87%). (The reaction was monitored by IR analysis).

¹¹ BNMR (600 MHz, acetone-d ₆ ) δ 19.7; ¹⁹ FNMR (57 MHz, acetone-d ₆ ) δ -45.3 - -82.8 (m), -120.4 - -153.1 (m). IR (ATR): v = 1468, 1329, 1147, 973, 804, 713, 620; EI-MS: m / z (%) = 732 (25) [M +], 481 (20), 265 (30), 234 (100), 218 (60), 184 (27), 98 (40).

Device experiments

1) Blue fluorescent OLED comprising a trioxatriborinane compound as p-dopant in a trioxatriborinane compound as p-dopant in a hole injection layer

The layer containing the tested materials (45 nm HTL doped with 8 mol% of each dopant, mol% based on the molecular weight of the tested p-dopant and the molecular weight of the structural unit of F1, as shown above) was used directly applied to the top of an ITO anode by the general procedure described above. After 10 min burnout at 100 ° C, the experimental devices were transferred to the vacuum chamber of the VTE tool; an undoped HTL, made from F2 and all other layers, was then deposited by VTE.

The device structure is described schematically in Table 1: Table 1 material c d [% By volume] [nm] ITO 90 F1: p-dopant Different 45 (8 mol%) F2 85 SFC_ABH113: SFC_NUBD370 3 20th Q3: LiQ 50 36 Al 100

Experimental OLED data are listed in Table 2 below. With regard to the initial voltage U and the external quantum efficiency EQE, E1 works at least as well or even better than the comparison material LiTFSI. In addition, there is better performance in terms of voltage stability for both connections E1 and E2 compared to Li (TFSI) observed. Table 2 p-dopant U EQE you you (10 mA / cm ² ) (10 mA / cm ² ) (10 h, 30 mA / cm ² ) (50 h, 30 mA / cm ² ) [V] [%] [V] [V] B2 ref. 4.1 5.9 2.9 6.9 E1 (not according to the invention) 4.1 6.0 1.7 4.3 E2 4.4 5.8 0.4 1.6

2) Blue fluorescent OLED comprising a trioxatriborinane compound as a p-hole injection layer

The sublimed sample of E1 was tested in a model device below, made entirely by vacuum processing and described schematically in Table 3: Table 3 material c d [% By volume] [nm] ITO 90 E1 (not according to the invention) 100 F2 128 F4 5 H09: BD200 3 20th F5 5 Q6: LiQ 50 31 Yb 2 A1 100

Experimental OLED data are presented in Table 4: Table 4 HIL U EQE CIE-y (10 mA / cm ² ) (10 mA / cm ² ) [V] [V] 2 nm E1 (not according to the invention) 3.85 8.2 0.101

The features disclosed in the above description and in the dependent claims can be essential both individually and in any combination thereof for the realization of the inventive ideas set out in the independent claims in diverse forms thereof.

Claims (8)

An organic electronic device comprising a first electrode, a second electrode and an organic semiconducting layer, wherein the organic semiconducting layer is arranged between the first electrode and the second electrode; the organic semiconducting layer is a hole injection layer, a hole transport layer or a hole generation layer; and - the organic semiconducting layer comprises a 1,3,5-trioxatriborinane-containing compound; wherein the 1,3,5-trioxatriborinane-containing compound is represented by the following formula (II)

where - R ⁴ , R ⁵ and R ^{6 are} independently selected from the group consisting of fully substituted aryl and fully substituted heteroaryl; it is provided for each of R ⁴ , R ⁵ and R ⁶ that at least one of the substituents is CN and / or at least one of the substituents is a hydrocarbon which ^{comprises at least one sp 3} -hybridized carbon atom and is completely substituted by halogen atoms; and - the remaining substituents of R ⁴ , R ⁵ and R ^{6 are} independently selected from the group consisting of F, Cl, Br, I and CN, alternatively are independently selected from the group consisting of F, Cl, Br and I. Organic electronic device according to Claim 1 wherein - the organic electronic device comprises a light emitting layer; the light-emitting layer is arranged between the first electrode and the second electrode; the organic semiconducting layer is arranged between the first electrode and the light-emitting layer; and the organic semiconducting layer is a hole injection layer or hole transport layer. Organic electronic device according to one of the preceding claims, wherein the organic electronic device is an organic electroluminescent device, an organic transistor, an organic diode or an organic photovoltaic device. A display device comprising at least one organic electronic device according to any one of the preceding claims. Organic semiconducting material, wherein the organic semiconducting material comprises a matrix compound and an electrical dopant; and the electrical dopant is a compound containing 1,3,5-trioxatriborinane; wherein the 1,3,5-trioxatriborinane-containing compound is represented by the following formula (II)

where - R ⁴ , R ⁵ and R ^{6 are} independently selected from the group consisting of fully substituted aryl and fully substituted heteroaryl; it is provided for each of R ⁴ , R ⁵ and R ⁶ that at least one of the substituents is CN and / or at least one of the substituents is a hydrocarbon which ^{comprises at least one sp 3} -hybridized carbon atom and is completely substituted by halogen atoms; and - the remaining substituents of R ⁴ , R ⁵ and R ^{6 are} independently selected from the group consisting of F, Cl, Br, I and CN, alternatively are independently selected from the group consisting of F, Cl, Br and I. Compound represented by the following formula (II)

where - R ⁴ , R ⁵ and R ^{6 are} independently selected from the group consisting of fully substituted aryl and fully substituted heteroaryl; it is provided for each of R ⁴ , R ⁵ and R ⁶ that at least one of the substituents is CN and / or at least one of the substituents is a hydrocarbon which ^{comprises at least one sp 3} -hybridized carbon atom and is completely substituted by halogen atoms; and - the remaining substituents of R ⁴ , R ⁵ and R ^{6 are} independently selected from the group consisting of F, Cl, Br, I and CN, alternatively are independently selected from the group consisting of F, Cl, Br and I. Compound represented by the following formula (III) Ar-B (OH) ₂ (III), whereby - Ar is fully substituted aryl or fully substituted heteroaryl; - at least one of the substituents of Ar is a hydrocarbyl which is completely substituted with halogen atoms and ^{comprises at least one sp 3} hybridized carbon atom; and - the remaining substituents of Ar are independently selected from the group consisting of F, Cl, Br, I and CN, alternatively are independently selected from the group consisting of F, Cl, Br and I. Use of a compound containing 1,3,5-trioxatriborinane as p-dopant and / or as hole injection material in an electronic device; wherein the 1,3,5-trioxatriborinane-containing compound is represented by the following formula (II)

where - R ⁴ , R ⁵ and R ^{6 are} independently selected from the group consisting of fully substituted aryl and fully substituted heteroaryl; it is provided for each of R ⁴ , R ⁵ and R ⁶ that at least one of the substituents is CN and / or at least one of the substituents is a hydrocarbon which ^{comprises at least one sp 3} -hybridized carbon atom and is completely substituted by halogen atoms; and - the remaining substituents of R ⁴ , R ⁵ and R ^{6 are} independently selected from the group consisting of F, Cl, Br, I and CN, alternatively are independently selected from the group consisting of F, Cl, Br and I.

Images