WO2017029366A1

WO2017029366A1 - Triaryl amine thick layer doped with metal amides for use as hil for an organic light-emitting diode (oled)

Info

Publication number: WO2017029366A1
Application number: PCT/EP2016/069631
Authority: WO
Inventors: Markus Hummert; Thomas Rosenow
Original assignee: Novaled Gmbh
Priority date: 2015-08-18
Filing date: 2016-08-18
Publication date: 2017-02-23
Also published as: JP6807379B2; JP2018530910A; CN107925013B; KR20180041695A; EP3338314B1; US10998518B2; US20180240995A1; CN107925013A; EP3133664A1; EP3338314A1; KR102658023B1

Abstract

The present invention relates to a hole injection layer for an OLED comprising a triarylamine compound doped with a charge neutral metal amide compound, characterized in that the hole injection layer has a thickness of at least about ≥ 20 nm to about ≤ 1000 nm and the charge neutral metal amide compound has the Formula Ia.

Description

TITLE

Triaryl amine thick layer doped with metal amides for use as HIL for an Organic light- emitting diode (OLED)

DESCRIPTION

The present invention relates to a triaryl amine thick layer doped with a metal amide for use as hole injection layer (HIL) for an Organic light-emitting diode (OLED), and a method of manufacturing Organic light-emitting diode (OLED) comprising the triaryl amine thick layer HIL doped with a metal amide.

DESCRIPTION OF THE RELATED ART

Organic solar cell as disclosed in EP 1 209 708 Al having the general structure:

substrate+EM/HTM/dye/SOL/EM, or

substrate+EM/SOL/dye/HTM/EM, or

substrate+EM/HTM/SOL/EM,

in which EM is the electrode material that may be a transparent conductive oxide (TCO) or metal, with at least one of the EM layer(s) of the cell being a TCO, HTM is the hole transport material, SOL is a semiconducting oxide layer, "dye" is a suitable dye, and the SOL layer is vapor deposited.

US 2013/0330632 Al refers to electrochemical devices comprising complexes of cobalt comprising at least one ligand with a 5- or six membered, N-containing heteroring. The complex are useful as p- and n-dopants, as over of electrochemical devices, in particular in organic semiconductors. The complexes are further useful as over-discharge prevention and overvoltage protection agents.

Organic light-emitting diodes (OLEDs), which are self-emitting devices, have a wide viewing angle, excellent contrast, quick response, high brightness, excellent driving voltage characteristics, and color reproduction. A typical OLED includes an anode, a hole injection layer (HIL), a hole transport layer (HTL), an emission layer (EML), an electron transport layer (ETL), and a cathode, which are sequentially stacked on a substrate. In this regard, the HIL, the HTL, the EML, and the ETL are thin films formed from organic compounds.

When a voltage is applied to the anode and the cathode, holes injected from the anode move to the EML, via the HIL and HTL, and electrons injected from the cathode move to the EML, via the ETL. The holes and electrons recombine in the EML to generate excitons. When the excitons drop 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 above- described structure has excellent efficiency and/or a long lifetime.

Dipyrazino[2,3 :2',3'-/z]quinoxaline-2,3,6,7,10,l 1-hexacarbonitrile (CNHAT (CAS 105598-27-4)) having the Formula A, which is typically used as hole injection layer has several drawbacks.

For example, if the HOMO level of the hole transport layer of an OLED comprising a CNHAT HIL-layer is further away from the vacuum level, the voltage of the OLED is too high. Further, effective hole injection even into very deep HOMO HTLs, that means the HOMO is further away from vacuum level, is not sufficiently achieved.

Efficient hole injection into very deep HOMO levels enables the use of high efficiency emission layers, in particular phosphorescent blue and green emitters and emission which relies on TADF (thermally activated delayed fluorescence).

Thus, it is still desired to provide a hole injection layer material that more effectively promotes the hole injection over a broader range of HOMO levels to vacuum level from the HIL-layer into the hole transport layer (HTL).

Additionally, it is still desired to provide a thick hole injection layer material that provides an effective smoothing layer and thereby provides a pinhole-free basis for deposition of subsequent layers, so that defect-free OLEDs can be obtained even if the substrate is nonuniform. SUMMARY

Aspects of the present invention provide a method of reducing the drive voltage and improving the voltage stability over time, especially for blue emitting OLEDs , and/or the external quantum efficiency EQE, for top and/or bottom emission organic light-emitting diodes (OLED). The invention relates to a hole injection layer (HIL) for use for an Organic light-emitting diode (OLED). The invention relates further to an organic light-emitting diode (OLED) comprising an anode, a hole injection layer (HIL), a hole transport layer (HTL), an emission layer (EML), optional a hole blocking layer (HBL), optional an electron transport layer (ETL), optional an electron injection layer (EIL), and a cathode as well as a method of manufacturing the same.

According to an aspect of the present invention, there is provided a hole injection layer (HIL) for an OLED comprising a triarylamine compound doped with a charge neutral metal amide compound, wherein the hole injection layer has a thickness of at least about > 20 nm to about < 1000 nm and the charge neutral metal amide com ound has the Formula la:

(la),

wherein:

G = halide O, alkoxylate or amine of Formula Ila to He:

are independently selected from the group comprising H, Ci to C₂o alkyl, Ci to C₂o heteroalkyl, unsubstituted or Ci to C₁₂ substituted C₆ to C₂₀ aryl, unsubstituted or Ci to C₁₂ substituted heteroaryl with 5 to 20 ring- forming atoms, halogenated or perhalogenated Ci to C₂₀ alkyl, halogenated or perhalogenated Ci to C₂₀ heteroalkyl, halogenated or perhalogenated C₆ to C₂₀ aryl, halogenated or perhalogenated heteroaryl with 5 to 20 ring- forming atoms; or at least one R¹ and R⁴ and/or R² and R³ and/or R¹ and R⁵ are bridged and form a 5 to 20 member ring;

m = 0, 1 , 2, 3 or 4;

M = a metal selected from the group comprising alkali metal, alkaline earth metal,

Al, Ga, In, transition metal or rare earth metal;

L = charge neutral ligand which coordinates to the metal M, selected from the

group comprising H₂0, C₂ to C₄o mono- or multi-dentate ethers and C₂ to C₄₀ thioethers, C₂ to C₄₀ amines, C₂ to C₄₀ phosphine, C₂ to C₂o alkyl nitrile or C₂ to C₄o aryl nitrile, or a compound according to Formula (III);

R⁶

(HI),

wherein R⁶ and R⁷ are independently selected from Ci to C₂o alkyl, Ci to C₂o heteroalkyl, C₆ to C₂o aryl, heteroaryl with 5 to 20 ring-forming atoms, halogenated or perhalogenated Ci to C₂o alkyl, halogenated or perhalogenated Ci to C₂o heteroalkyl, halogenated or perhalogenated C₆ to C₂o aryl, halogenated or perhalogenated heteroaryl with 5 to 20 ring-forming atoms, or at least one R⁶ and R⁷ are bridged and form a 5 to 20 member ring, or the two R⁶ and/or the two R⁷ are bridged and form a 5 to 40 member ring or form a 5 to 40 member ring comprising an unsubstituted or Ci to C₁₂ substituted phenanthroline;

p = 0, 1 , 2 or 3;

A¹, A², A³ and A⁴ are independently selected from CO, S0₂ or POR ;

Q

R = electron withdrawing group selected from the group comprising halide, nitrile, halogenated or perhalogenated Ci to C₂o alkyl, halogenated or perhalogenated C₆ to C₂o aryl, or halogenated or perhalogenated heteroaryl with 5 to 20 ring- forming atoms;

n = 1 , 2, 3, 4 or 5;

B¹, B², B³ and B⁴ are same or independently selected from substituted or unsubstituted Ci to C₂o alkyl, substituted or unsubstituted Ci to C₂o heteroalkyl, substituted or unsubstituted C₆ to C₂o aryl, substituted or unsubstituted C₅ to C₂o

1 2

heteroaryl, or B and B are bridged; 1 2

wherein B and B are bridged, then:

- M, N, A 1 , B1 , B2 , A 2 and N form a 7 to 10 member ring according to Formula lb;

N, A 1 , B1 , B2 and A 2 form a 5 to 10 member ring according to Formula Ic,

- N, A 1 , B1 , B2 and A 2 form a first 5 to 10 member ring and B 1 and B2 form a second 5 to 20 member ring according to Formula Id:

According to another aspect of the present invention, there is provided a hole injection layer (HIL) for an OLED, wherein the hole injection layer comprises one triarylamine compound.

According to another aspect of the present invention, there is provided a hole injection layer (HIL) for an OLED, wherein the hole injection layer comprises one charge neutral metal amide compound.

According to another aspect of the present invention, there is provided a hole injection layer (HIL) for an OLED, wherein the hole injection layer comprises one triarylamine compound and one charge neutral metal amide compound.

According to another aspect of the present invention, there is provided a hole injection layer (HIL) for an OLED comprising a triarylamine compound with a HOMO more negative than -5 eV and more positive than -6 eV, when measured by cyclic voltammetry in

dichloromethane vs. Fc/Fc⁺, preferably more negative than -5.05 eV and more positive than - 5.9 eV. Under these conditions the HOMO of spiro-MeO-TAD (CAS 207739-72-8) is -4.71 eV.

According to another aspect of the present invention, there is provided a hole injection layer (HIL) for an OLED comprising a triarylamine compound with an oxidation potential more positive than - 0.2 V and more negative than 1.22 V, when measured by cyclic voltammetry in dichloromethane vs. Fc/Fc⁺, preferably more positive than - 0.18 V and more negative than 1.12 V. Under these conditions the oxidation potential of spiro-MeO-TAD (CAS 207739-72-8) is -0.07 V.

According to another aspect of the present invention, there is provided a hole injection layer (HIL) for an OLED comprising a triarylamine compound doped with a charge neutral metal amide compound, wherein the hole injection layer has a thickness of at least about > 20 nm to about < 1000 nm and the char e neutral metal amide compound has the Formula la:

(la),

wherein:

G = halide, O, alkoxylate or amine of Formula Ila to He:

(Ila) (lib) (lie) (lid) (He);

R¹ to R⁵ are independently selected from the group comprising H, Ci to C₂o alkyl, Ci to

C₂o heteroalkyl, unsubstituted or Ci to C₁₂ substituted C₆ to C₂₀ aryl, unsubstituted or Ci to C₁₂ substituted heteroaryl with 5 to 20 ring- forming atoms, halogenated or perhalogenated Ci to C₂₀ alkyl, halogenated or perhalogenated Ci to C₂₀ heteroalkyl, halogenated or perhalogenated C₆ to C₂₀ aryl, halogenated or perhalogenated heteroaryl with 5 to 20 ring- forming atoms; or

at least one R¹ and R⁴ and/or R² and R³ and/or R¹ and R⁵ are bridged and form a 5 to 20 member ring;

m = 0, 1 , 2, 3 or 4; a metal selected from the group comprising alkali metal, alkaline earth metal, Al, Ga, In, transition metal or rare earth metal;

charge neutral ligand which coordinates to the metal M, selected from the group comprising H₂0, C₂ to C40 mono- or multi-dentate ethers and C₂ to C40 thioethers, C₂ to C40 amines, C₂ to C40 phosphine, C₂ to C₂₀ alkyl nitrile or C₂ to C40 aryl nitrile, or a compound according to Formula (III);

6

R⁶

(HI),

wherein R⁶ and R⁷ are independently selected from Ci to C₂₀ alkyl, Ci to C₂₀ heteroalkyl, C₆ to C₂₀ aryl, heteroaryl with 5 to 20 ring-forming atoms, halogenated or perhalogenated Ci to C₂₀ alkyl, halogenated or perhalogenated Ci to C₂o heteroalkyl, halogenated or perhalogenated C₆ to C₂₀ aryl, halogenated or perhalogenated heteroaryl with 5 to 20 ring-forming atoms, or at least one R⁶ and R⁷ are bridged and form a 5 to 20 member ring, or the two R⁶ and/or the two R⁷ are bridged and form a 5 to 40 member ring or form a 5 to 40 member ring comprising an unsubstituted or Ci to C₁₂ substituted phenanthroline;

p = 0, 1, 2 or 3;

A¹, A², A³ and A⁴ are independently selected from CO, S0₂ or POR ;

Q

R = electron withdrawing group selected from the group comprising halide, nitrile, halogenated or perhalogenated Ci to C₂₀ alkyl, halogenated or perhalogenated C₆ to C₂o aryl, or halogenated or perhalogenated heteroaryl with 5 to 20 ring- forming atoms;

n = 1, 2, 3, 4 or 5;

B³ and B⁴ are same or independently selected from substituted or unsubstituted Ci to C₂₀ alkyl, substituted or unsubstituted Ci to C₂₀ heteroalkyl, substituted or unsubstituted C₆ to C₂₀ aryl, substituted or unsubstituted C₅ to C₂₀ heteroaryl;

1 2

B and B" are bridged, wherein: - M, N, A 1 , B1 , B2 , A 2 and N form a 7 to 10 member ring according to Formula lb;

N, A 1 , B1 , B2 and A 2 form a 5 to 10 member ring according to Formula Ic,

According to another aspect of the present invention, there is provided a hole injection layer (HIL) comprising a triarylamine compound doped with a charge neutral metal amide compound, wherein the hole injection layer has a thickness of at least about > 20 nm to about

< 1000 nm;

- wherein the triarylamine compound has the Formula Vila:

wherein:

1 2

Ar and Ar = independently selected from substituted or unsubstituted C₆ to C₂o arylene;

Ar³ and Ar⁴ = independently selected from substituted or unsubstituted C₆ to C₂₀ aryl; Ar⁵ and Ar⁶ = independently selected from substituted or unsubstituted C₆ to C₂₀ aryl or C₅ to C₄o heteroaryl; R⁹ = a single chemical bond, a unsubstituted or substituted Ci to C₆ alkyl and unsubstituted or substituted Ci to C₅ heteroalkyl;

q = 0, 1 or 2;

r = 0 or 1 ;

wherein

- the substituents for Ar¹ to Ar⁶ are independently selected from Ci to C₂o alkyl, Ci to C₂o heteroalkyl, or halide; and

- the substitutents for R⁹ are independently selected from Ci to C₆ alkyl, Ci to C₅ heteroalkyl, C₆ to C₂₀ aryl and C₅ to C₂₀ heteroaryl;

wherein the charge neutral metal amide compound has the Formula la:

(la),

wherein:

G = halide O, alkoxylate or amine of Formula Ila to He:

(Ila) (lib) (lie) (lid) (He);

R¹ to R⁵ are independently selected from the group comprising H, Ci to C₂₀ alkyl, Ci to

m = 0, 1, 2, 3 or 4; a metal selected from the group comprising alkali metal, alkaline earth metal, Al, Ga, In, transition metal or rare earth metal;

wherein the bond between N and the metal M is a covalent bond or N forms a non-covalent interaction to the metal M;

(HI),

p = 0, 1, 2 or 3;

A¹, A², A³ and A⁴ are independently selected from CO, S0₂ or POR ;

Q

n = 1, 2, 3, 4 or 5;

B¹, B², B³ and B⁴ are same or independently selected from substituted or unsubstituted Ci to C₂o alkyl, substituted or unsubstituted Ci to C₂₀ heteroalkyl, substituted or unsubstituted C₆ to C₂₀ aryl, substituted or unsubstituted C₅ to C₂₀ heteroaryl, or B 1 and B 2 are bridged;

1 2

wherein B and B are bridged, then: - M, N, A 1 , B1 , B2 , A 2 and N form a 7 to 10 member ring according to Formula lb;

N, A 1 , B1 , B2 and A 2 form a 5 to 10 member ring according to Formula Ic,

- N, A 1 , B1 , B2 and A 2 form a first 5 to 10 member ring and B 1 and B2 form a second 5 to 20 member ring accordin to Formula Id:

According to another aspect of the present invention, there is provided a hole injection layer (HIL) comprising a triarylamine compound doped with a charge neutral metal amide compound, wherein the hole injection layer has a thickness of at least about > 20 nm to about < 1000 nm;

- wherein the triarylamine compound has the Formula Vila

wherein:

1 2

q = 0, 1 or 2;

r = 0 or 1 ;

wherein

wherein the charge neutral metal amide compound has the Formula la:

(la),

wherein:

G = halide O, alkoxylate or amine of Formula Ila to He:

(Ila) (lib) (lie) (lid) (He);

(HI),

p = 0, 1, 2 or 3;

A¹, A², A³ and A⁴ are independently selected from CO, S0₂ or POR ;

Q

n = 1, 2, 3, 4 or 5;

1 2

N, A 1 , B1 , B2 and A 2 form a 5 to 10 member ring according to Formula Ic,

wherein in the hole injection layer (HIL) the wt.-% of the triarylamine compound according to Formula Vila is higher than the wt.-% of the charge neutral metal amide compound according to Formula la; wherein the weight-% of the components are based on the total weight of the hole injection layer.

It has been surprisingly found that the thick hole injection layer (HIL) of a

triarylamine compound doped with a metal amide improves performance of OLEDs compared to a thick hole injection layer (HIL) of CNHAT (Dipyrazino[2,3- 2',3'-/z]quinoxaline- 2,3,6,7,10,11-hexacarbonitrile (CAS 105598-27-4)). CNHAT is a standard hole injection layer. Surprisingly, a hole injection layer (HIL) of a triarylamine compound doped with a metal amide of at least 20 nm are required to achieve good voltage stability.

It has been found that the thickness of the triarylamine hole injection layer (HIL) doped with an metal amide can be selected very thick, for example up to 450 nm, without a dramatic increase in voltage.

It has been further found that the thick hole injection layer (HIL) of a triarylamine compound doped with a metal amide according to the invention may be beneficially used for large area lighting panels, where the ITO is not sufficiently conductive, for example a copper grid.

Additionally, the thick hole injection layer material according to the invention may provide an effective smoothing layer and thereby provides a pinhole-free basis for deposition of subsequent layers. Thereby, defect-free OLEDs can be obtained even if the substrate is non-uniform.

In particular, the invention may provide an uniform hole injection layer on top of an anode layer which comprises metal oxides, for example indium-tin oxide (ITO), or a metal grid.

Further, the thick hole injection layer (HIL) of a triarylamine compound doped with a metal amide inserted between the anode and the hole transport layer effectively promotes hole injection into the hole transport layer. For example, if the HOMO level of the hole transport layer is further away from vacuum level, the performance of metal amides is superior to CNHAT, in particular the voltage. Furthermore, effective hole injection even into very deep HOMO HTLs (HOMO further away from vacuum level) can be achieved. This cannot be achieved with prior art materials, such as CNHAT, which is typically used as a HIL material. Efficient hole injection into very deep HOMO levels enables the use of high efficiency emission layers, in particular phosphorescent blue and green emitters and emission which relies on TADF (thermally activated delayed fluorescence).

A very deep HOMO in the sense of the present invention is a HOMO which is more negative than -5 eV, preferably more negative than -5.2 eV when measured by cyclic voltammetry in dichloromethane vs. Fc/Fc⁺.

- wherein the triarylamine com ound has the Formula Vila:

(Vila),

wherein:

1 2

Ar and Ar = independently selected from substituted or unsubstituted C₆ to C₂o arylene; Ar³ and Ar⁴ = independently selected from substituted or unsubstituted C₆ to C₂o aryl; Ar⁵ and Ar⁶ = independently selected from substituted or unsubstituted C₆ to C₂₀ aryl or C₅ to C40 heteroaryl;

R⁹ = a single chemical bond, a unsubstituted or substituted Ci to C₆ alkyl; q = 0, 1 or 2;

r = 0 or 1 ;

wherein

- the substituents for Ar¹ to Ar⁶ are independently selected from Ci to C₂₀ alkyl or halide; and

- the substitutents for R⁹ are independently selected from Ci to C₆ alkyl, C₆ to C₂₀ aryl and C₅ to C₂₀ heteroaryl;

wherein the charge neutral metal amide compound has the Formula la:

(la),

wherein:

G = halide O, alkoxylate or amine of Formula Ila to He:

at least one R¹ and R⁴ and/or R² and R³ and/or R¹ and R⁵ are bridged and form a 5 to 20 member ring; m = 0, 1 , 2, 3 or 4;

Al, Ga, In, transition metal or rare earth metal;

L = charge neutral ligand which coordinates to the metal M, selected from the

R⁶

(HI),

p = 0, 1 , 2 or 3;

A¹, A², A³ and A⁴ are independently selected from CO, S0₂ or POR ;

Q

n = 1 , 2, 3, 4 or 5;

1 2

heteroaryl, or B and B are bridged; 1 2

wherein B and B are bridged, then:

N, A 1 , B1 , B2 and A 2 form a 5 to 10 member ring according to Formula Ic,

The organic light-emitting diode (OLED) can be a bottom emission OLED or a top emission OLED.

For the following defined terms, these definitions shall be applied, unless a different definition is given in the claims or elsewhere in this specification.

The bond between N and the metal M, as indicated for example in Formula la, lb, lc, and Id, can be a covalent bond or N forms a non-covalent interaction to the metal M. Without being bond to a specific theory it is assumed by the inventors that this kind of compounds may form a covalent bond between N and M or N forms a non-covalent interaction to the metal M, as can be seen from the example below:

The dotted line and/or an arrow symbolizes a non-covalent interaction. A non-covalent interaction differs from a covalent bond in that it does not involve the sharing of electrons, but rather involves more dispersed variations of electromagnetic interactions between molecules or within a molecule. Non-covalent interactions can be generally classified into four categories, electrostatic, π-effects, van der Waals forces, and hydrophobic effects.

The voltage, also named U, is measured in Volt (V) at 10 milliAmpere per square centimeter (mA/cm 2 ) in bottom emission devices and at 15 niA/cm 2 in top emission devices.

The voltage stability over time U(50 h)-U(0 h) is measured in Volt (V) at 15 mA/cm². To calculate the voltage stability over time, the voltage at the start of the stability test (U(0 h)) is subtracted from the voltage after 50 hours (h) (U(50 h)). The smaller the value U(50 h)-U(0 h) is the better is the voltage stability over time.

The external quantum efficiency, also named EQE, is measured in percent (%). The color space is described by coordinates CIE-x and CIE-y (International Commission on Illumination 1931). For blue emission the CIE-y is of particular importance. A smaller CIE-y denotes a deeper blue color.

The highest occupied molecular orbital, also named HOMO, and lowest unoccupied molecular orbital, also named LUMO, are measured in electron volt (eV).

The term "OLED" and "organic light-emitting diode" is simultaneously used and having the same meaning.

The term "transition metal" means and includes any element in the d-block of the periodic table, which includes groups 3 to 12 elements on the periodic table.

As used herein,„weight percent",„wt.-%",„percent by weight",„% by weight", and variations thereof refer to a composition, component, substance or agent as the weight of that composition, component, substance or agent of the respective electron transport layer divided by the total weight of the composition thereof and multiplied by 100. It is understood that the total weight percent amount of all components, substances or agents of the respective electron transport layer are selected such that it does not exceed 100 wt.-%. As used herein,„volume percent",„vol.-%",„percent by volume",„% by volume", and variations thereof refer to an elemental metal, a composition, component, substance or agent as the volume of that elemental metal, component, substance or agent of the respective electron transport layer divided by the total volume of the respective electron transport layer thereof and multiplied by 100. It is understood that the total volume percent amount of all elemental metal, components, substances or agents of the respective electron transport layer are selected such that it does not exceed 100 vol.-%.

All numeric values are herein assumed to be modified by the term "about", whether or not explicitly indicated. As used herein, the term "about" refers to variation in the numerical quantity that can occur. Whether or not, modified by the term„about", the claims include equivalents to the quantities.

It should be noted that, as used in this specification and the appended claims, the singular forms„a",„an", and„the" include plural referents unless the content clearly dictates otherwise.

The term "free of, "does not contain", "does not comprise" does not exclude impurities. Impurities have no technical effect with respect to the object achieved by the present invention.

The term "alkyl" refers to straight-chain or branched alkyl groups.

The term " 1 to 20 carbon atoms" as used herein refers to straight-chain or branched alkyl groups having 1 to 20 carbon atoms. The alkyl groups can be selected from the group comprising methyl, ethyl and the isomers of propyl, butyl or pentyl, such as isopropyl, isobutyl, tert.-butyl, sec. -butyl and/or isopentyl. The term "aryl" refers to aromatic groups for example phenyl or naphthyl.

Herein, when a first element is referred to as being formed or disposed "on" a second element, the first element can be disposed directly on the second element or one or more other elements may be disposed there between. When a first element is referred to as being formed or disposed "directly on" a second element, no other elements are disposed there between.

According to another aspect, there is provided a hole injection layer (HIL) comprising a triarylamine compound doped with a charge neutral metal amide compound, wherein the hole injection layer has a thickness of at least about > 20 nm to about < 1000 nm:

- wherein the triarylamine compound has the Formula Vila:

wherein:

1 2

Ar³ and Ar⁴ = independently selected from substituted or unsubstituted C₆ to C₂₀ aryl; Ar⁵ and Ar⁶ = independently selected from substituted or unsubstituted C₆ to C₂₀ aryl or C₅ to C₄o heteroaryl;

R⁹ = a single chemical bond, a unsubstituted or substituted Ci to C₆ alkyl and unsubstituted or substituted Ci to C₅ heteroalkyl;

q = 0, 1 or 2;

r = 0 or 1 ;

wherein

- the substituents for Ar¹ to Ar⁶ are independently selected from Ci to C₂₀ alkyl, Ci to C₂o heteroalkyl, or halide; and

- wherein the charge neutral metal amide compound has the Formula la:

(la),

wherein:

G = halide O, alkoxylate or amine of Formula Ila to He:

(lib) (lie) (lid) (He); are independently selected from the group comprising H, Ci to C₂₀ alkyl, Ci to C₂o heteroalkyl, unsubstituted or Ci to C₁₂ substituted C₆ to C₂₀ aryl, unsubstituted or Ci to C₁₂ substituted heteroaryl with 5 to 20 ring- forming atoms, halogenated or perhalogenated Ci to C₂o alkyl, halogenated or perhalogenated Ci to C₂₀ heteroalkyl, halogenated or perhalogenated C₆ to C₂₀ aryl, halogenated or perhalogenated heteroaryl with 5 to 20 ring- forming atoms; or

0, 1, 2, 3 or 4;

a metal selected from the group comprising alkali metal, alkaline earth metal, Al, Ga, In, transition metal or rare earth metal;

charge neutral ligand which coordinates to the metal M, selected from the group comprising H₂0, C₂ to C₄o mono- or multi-dentate ethers and C₂ to C₄₀ thioethers, C₂ to C₄₀ amines, C₂ to C₄₀ phosphine, C₂ to C₂₀ alkyl nitrile or C₂ to C₄o aryl nitrile, or a compound according to Formula (III);

(HI),

p = 0, 1, 2 or 3;

A¹, A², A³ and A⁴ are independently selected from CO, S0₂ or POR ;

n = 1, 2, 3, 4 or 5;

B¹, B², B³ and B⁴ are same or independently selected from substituted or unsubstituted Ci to C20 alkyl, substituted or unsubstituted Ci to C₂o heteroalkyl, substituted or unsubstituted C₆ to C₂o aryl, substituted or unsubstituted C₅ to C₂o heteroaryl. According to another aspect there is provided a hole injection layer for an OLED comprising a charge neutral metal amide compound, wherein the charge neutral metal amide compound has the Formula lb, Ic or Id:

wherein:

1 2

B and B are bridged;

B³ and B⁴ are same or independently selected from substituted or unsubstituted Ci to C₂o alkyl, substituted or unsubstituted Ci to C₂o heteroalkyl, substituted or unsubstituted C₆ to C₂o aryl, substituted or unsubstituted C₅ to C₂o heteroaryl;

- M, N, A 1 , B1 , B2 , A 2 and N form a 7 to 10 member rin according to Formula lb;

- N, A 1 , B1 , B2 and A 2 form a 5 to 10 member ring according to Formula Ic,

wherein: G = halide, O, alkoxylate or amine of Formula Ila to He:

(Ila) (lib) (lie) (lid) (He); are independently selected from the group comprising H, Ci to C₂o alkyl, Ci to C₂o heteroalkyl, unsubstituted or Ci to C₁₂ substituted C₆ to C₂₀ aryl, unsubstituted or Ci to C₁₂ substituted heteroaryl with 5 to 20 ring- forming atoms, halogenated or perhalogenated Ci to C₂₀ alkyl, halogenated or perhalogenated Ci to C₂₀ heteroalkyl, halogenated or perhalogenated C₆ to C₂₀ aryl, halogenated or perhalogenated heteroaryl with 5 to 20 ring- forming atoms; or

m =

Al, Ga, In, transition metal or rare earth metal;

heteroalkyl, C₆ to C₂₀ aryl, heteroaryl with 5 to 20 ring-forming atoms, halogenated or perhalogenated Ci to C₂₀ alkyl, halogenated or perhalogenated Ci to C₂o heteroalkyl, halogenated or perhalogenated C₆ to C₂₀ aryl, halogenated or perhalogenated heteroaryl with 5 to 20 ring-forming atoms, or at least one R⁶ and R⁷ are bridged and form a 5 to 20 member ring, or the two R⁶ and/or the two R⁷ are bridged and form a 5 to 40 member ring or form a 5 to 40 member ring comprising an unsubstituted or Ci to C₁₂ substituted phenanthroline;

p = 0, 1, 2 or 3;

A¹, A², A³ and A⁴ are independently selected from CO, S0₂ or POR ;

n = 1, 2, 3, 4 or 5;

wherein the hole injection layer comprises:

- at least about > 1 wt.-% to about < 50 wt.-%, preferably about > 1 wt.-% to about < 25 wt.- %, and more preferred about > 2 wt.-% to about < 15 wt.-%, of a charge neutral metal amide compound according to Formula la, and

- at least about > 50 wt.-% to about < 99 wt.-%, preferably about > 75 wt.-% to about < 99 wt.-%, and more preferred about > 85 wt.-% to about < 98 wt.-%, of a triarylamine compound according to Formula Vila; wherein the weight-% of the components are based on the total weight of the hole injection layer.

According to another aspect there is provided a hole injection layer (HIL) comprising a triarylamine compound doped with a charge neutral metal amide compound, wherein the hole injection layer has a thickness of at least about > 20 nm to about < 1000 nm:

- wherein the triarylamine compound has the Formula Vila:

wherein:

Ar¹ and Ar² independently selected from substituted or unsubstituted C₆ to C₂₀ arylene;

q = 0, 1 or 2;

r = 0 or 1 ;

wherein

wherein the charge neutral metal amide compound has the Formula lb:

wherein:

1 2

B and B are bridged; and

1 1 2 2

M, N, A , B , B , A and N form a 7 to 10 member ring according to Formula lb;

wherein:

G = halide, O, alkoxylate or amine of Formula Ila to He:

(Ila) (lib) (lie) (lid) (He); R¹ to R⁵ are independently selected from the group comprising H, Ci to C₂o alkyl, Ci to C₂o heteroalkyl, unsubstituted or Ci to C₁₂ substituted C₆ to C₂₀ aryl, unsubstituted or Ci to C₁₂ substituted heteroaryl with 5 to 20 ring- forming atoms, halogenated or perhalogenated Ci to C₂₀ alkyl, halogenated or perhalogenated Ci to C₂₀ heteroalkyl, halogenated or perhalogenated C₆ to C₂₀ aryl, halogenated or perhalogenated heteroaryl with 5 to 20 ring- forming atoms; or

m = 0, 1, 2, 3 or 4;

Al, Ga, In, transition metal or rare earth metal;

L = charge neutral ligand which coordinates to the metal M, selected from the group comprising H₂0, C₂ to C₄o mono- or multi-dentate ethers and C₂ to C₄₀ thioethers, C₂ to C₄₀ amines, C₂ to C₄₀ phosphine, C₂ to C₂₀ alkyl nitrile or C₂ to C₄o aryl nitrile, or a compound according to Formula (III);

R⁶

(HI),

p = 0, 1, 2 or 3;

1 2 8

A and A are independently selected from CO, S0₂ or POR ; R = electron withdrawing group selected from the group comprising halide, nitrile, halogenated or perhalogenated Ci to C20 alkyl, halogenated or perhalogenated C₆ to C20 aryl, or halogenated or perhalogenated heteroaryl with 5 to 20 ring- forming atoms;

n = 1 , 2, 3, 4 or 5.

- wherein the triarylamine compound has the Formula Vila:

wherein:

1 2

Ar and Ar = independently selected from substituted or unsubstituted C₆ to C20 arylene;

Ar³ and Ar⁴ = independently selected from substituted or unsubstituted C₆ to C₂o aryl; Ar⁵ and Ar⁶ = independently selected from substituted or unsubstituted C₆ to C₂o aryl or C₅ to C40 heteroaryl;

a single chemical bond, a unsubstituted or substituted Ci to C₆ alkyl and unsubstituted or substituted Ci to C₅ heteroalkyl;

q = 0, 1 or 2;

r = 0 or 1 ;

wherein

- the substitutents for R⁹ are independently selected from Ci to C₆ alkyl, Ci to C₅ heteroalkyl, C₆ to C₂o aryl and C₅ to C₂o heteroaryl;

- wherein the charge neutral metal amide com ound has the Formula Ic:

wherein: 1 2

B and B are bridged; and

1 1 2 2

N, A , B , B and A form a 5 to 10 member ring according to Formula Ic,

wherein:

G = halide O, alkoxylate or amine of Formula Ila to He:

(lib) (lie) (lid) are independently selected from the group comprising H, Ci to C₂o alkyl, Ci to C₂o heteroalkyl, unsubstituted or Ci to C₁₂ substituted C₆ to C₂o aryl, unsubstituted or Ci to C₁₂ substituted heteroaryl with 5 to 20 ring- forming atoms, halogenated or perhalogenated Ci to C₂o alkyl, halogenated or perhalogenated Ci to C₂o heteroalkyl, halogenated or perhalogenated C₆ to C₂o aryl, halogenated or perhalogenated heteroaryl with 5 to 20 ring- forming atoms; or

0, 1 , 2, 3 or 4;

M = a metal selected from the group comprising alkali metal, alkaline earth metal, Al, Ga, In, transition metal or rare earth metal;

charge neutral ligand which coordinates to the metal M, selected from the group comprising H₂0, C₂ to C₄o mono- or multi-dentate ethers and C₂ to C₄₀ thioethers, C₂ to C₄₀ amines, C₂ to C₄₀ phosphine, C₂ to C₂o alkyl nitrile or C₂ to C₄o aryl nitrile, or a compound according to Formula (III);

(HI),

wherein R⁶ and R⁷ are independently selected from Ci to C₂o alkyl, Ci to C₂₀ heteroalkyl, C₆ to C₂₀ aryl, heteroaryl with 5 to 20 ring-forming atoms, halogenated or perhalogenated Ci to C₂₀ alkyl, halogenated or perhalogenated Ci to C₂o heteroalkyl, halogenated or perhalogenated C₆ to C₂₀ aryl, halogenated or perhalogenated heteroaryl with 5 to 20 ring-forming atoms, or at least one R⁶ and R⁷ are bridged and form a 5 to 20 member ring, or the two R⁶ and/or the two R⁷ are bridged and form a 5 to 40 member ring or form a 5 to 40 member ring comprising an unsubstituted or Ci to C₁₂ substituted phenanthroline;

p = 0, 1, 2 or 3;

1 2 8

A and A are independently selected from CO, S0₂ or POR ;

Q

n = 1, 2, 3, 4 or 5.

- wherein the triarylamine compound has the Formula Vila:

wherein:

1 2

Ar and Ar = independently selected from substituted or unsubstituted C₆ to C₂₀ arylene;

Ar³ and Ar⁴ = independently selected from substituted or unsubstituted C₆ to C₂₀ aryl; Ar⁵ and Ar⁶ = independently selected from substituted or unsubstituted C₆ to C₂o aryl or C₅ to C40 heteroaryl;

q = 0, 1 or 2;

r = 0 or 1 ;

wherein

- wherein the charge neutral metal amide com ound has the Formula Id:

wherein:

1 2

B and B are bridged; and

1 1 2 2 1 2

N, A , B , B and A form a first 5 to 10 member ring and B and B form a second 5 to 20 member ring according to Formula Id:

wherein:

G = halide O, alkoxylate or amine of Formula Ila to He:

C₂o heteroalkyl, unsubstituted or Ci to C₁₂ substituted C₆ to C₂₀ aryl, unsubstituted or Ci to C₁₂ substituted heteroaryl with 5 to 20 ring- forming atoms, halogenated or perhalogenated Ci to C₂₀ alkyl, halogenated or perhalogenated Ci to C₂o heteroalkyl, halogenated or perhalogenated C₆ to C₂₀ aryl, halogenated or perhalogenated heteroaryl with 5 to 20 ring- forming atoms; or

0, 1, 2, 3 or 4;

(HI),

p = 0, 1, 2 or 3;

1 2 8

A and A are independently selected from CO, S0₂ or POR ;

Q

R = electron withdrawing group selected from the group comprising halide, nitrile, halogenated or perhalogenated Ci to C₂₀ alkyl, halogenated or perhalogenated C₆ to C₂o aryl, or halogenated or perhalogenated heteroaryl with 5 to 20 ring- forming atoms; n = 1 , 2, 3, 4 or 5.

- wherein the triarylamine compound has the Formula Vila:

wherein:

1 2

q = 0, 1 or 2;

r = 0 or 1 ;

wherein

- wherein the charge neutral metal amide compound has the Formula lb, Ic, or Id:

wherein:

G = halide O, alkoxylate or amine of Formula Ila to He:

are independently selected from the group comprising H, Ci to C₂₀ alkyl, Ci to C₂₀ heteroalkyl, unsubstituted or Ci to C₁₂ substituted C₆ to C₂o aryl, unsubstituted or Ci to C₁₂ substituted heteroaryl with 5 to 20 ring- forming atoms, halogenated or perhalogenated Ci to C₂o alkyl, halogenated or perhalogenated Ci to C₂o heteroalkyl, halogenated or perhalogenated C₆ to C₂o aryl, halogenated or perhalogenated heteroaryl with 5 to 20 ring- forming atoms; or

0, 1, 2, 3 or 4;

wherein the bond between N and the metal M is a covalent bond or N forms a non-covalent interaction to the metal M; L = charge neutral ligand which coordinates to the metal M, selected from the group comprising H₂0, C₂ to C40 mono- or multi-dentate ethers and C₂ to C40 thioethers, C₂ to C40 amines, C₂ to C40 phosphine, C₂ to C₂₀ alkyl nitrile or C₂ to C40 aryl nitrile, or a compound according to Formula (III);

(HI),

p = 0, 1, 2 or 3;

A¹, A², A³ and A⁴ are independently selected from CO, S0₂ or POR ;

Q

n = 1, 2, 3, 4 or 5;

B³ and B⁴ are same or independently selected from substituted or unsubstituted Ci to

C₂o alkyl, substituted or unsubstituted Ci to C₂₀ heteroalkyl, substituted or unsubstituted C₆ to C₂₀ aryl, substituted or unsubstituted C₅ to C₂₀ heteroaryl;

1 2

B and B are bridged,

wherein: - M, N, A 1 , B1 , B2 , A 2 and N form a 7 to 10 member ring according to Formula lb;

N, A 1 , B1 , B2 and A 2 form a 5 to 10 member ring according to Formula Ic,

According to another aspect for the charge neutral metal amide compound according to the invention B¹, B², B³ and B⁴ can be independently selected from a substituted Ci to C₂o alkyl, substituted Ci to C₂₀ heteroalkyl, substituted C₆ to C₂₀ aryl, or substituted C₅ to C₂₀ heteroaryl; wherein the substituent of the substituted Ci to C₂₀ alkyl, substituted Ci to C₂₀ heteroalkyl, substituted C₆ to C₂₀ aryl, or substituted C₅ to C₂₀ heteroaryl;

- wherein the substituent can be an electron withdrawing group selected from the group comprising a halide, nitrile, perhalogenated Ci to C₂₀ alkyl, perhalogenated C₆ to C₂₀ aryl, perhalogenated heteroaryl with 6 to 20 ring-forming atoms, preferably the electron withdrawing group is a fluoride, perfluroinated Ci to C₂₀ alkyl, perfluorinated C₆ to C₂₀ aryl, or perfluorinated heteroaryl with 5 to 20 ring-forming atoms.

In order to increase the vacuum vaporization it can be preferred that according to one embodiment for the charge neutral metal amide compound the substituent can be a Ci to C₆ alkyl or Ci to C₆ heteroalkyl, and more preferred an Ci to C₄ alkyl or Ci to C₄ heteroalkyl. In order to improve the solution processing it can be preferred that according to one embodiment for the charge neutral metal amide compound the substituent can be a C₄ to C20 alkyl or C₄ to C20 heteroalkyl, and more preferred an C₆ to C₁₈ alkyl or C₆ to C₁₈ heteroalkyl.

According to one aspect the charge neutral ligand L may be selected from the group comprising C₂ to C₂o glycole ethers, C₂ to C₂o ethylendiamine derivatives, and more preferred

1 1 2 2

bis(2-methoxyethyl) ether, tetrahydrofurane, tetrahydrothiophen, N ,N ,N ,N -tetramethyl-1 , 2-ethanediamine, N-((E,2E)-2- { [(E)- 1 , 1 -dimethyl ethyljimino} ethylidene)-2-methyl-2- propanamine, acetonitrile, trisphenylphosphine, trismethylphosphine,

tris(cylcohexyl)phosphine, 1 ,2-bis(diphenylphosphino)ethane, bispyridine, phenanthroline, (2E,3E)-N²,N³-diphenylbutane-2,3-diimine or ( \E,2E)-N^l ,N², 1 ,2-tetraphenylethane- 1 ,2- diimine.

According to one aspect of the charge neutral metal amide compound "m" may be selected that m = 0, 1 or 2.

According to one aspect of the charge neutral metal amide compound "M" may be selected from Li(I), Na(I), K(I), Cs(I), Mg(II), Ca(II), Sr(II), Ba(II), Sc(III), Y(III), Ti(IV), V(III-V), Cr(III-VI), Mn(II), Mn(III), Fe(II), Fe(III), Co(II), Co(III), Ni(II), Cu(I), Cu(II), Zn(II), Ag(I), Au(I), Au(III), Al(III), Ga(III), In(III), Sn(II), Sn(IV), or Pb(II); preferably M is selected from Li (I), Mg (II), Mn (II) or Ag (I); and more preferred M is selected from Mg (II) and Li (I).

According to one aspect of the charge neutral metal amide compound, wherein may be (G)_m for m = 1 , then G is CI; or may be (G)_m for m = 2, then G is O.

According to one aspect of the charge neutral metal amide compound, wherein may be (G)m-M is Cl-Al, Cl-Mg, 0=V or 0₂U.

According to one aspect of the charge neutral metal amide compound, wherein may be for n > 2 then:

1 1 2 2

N, A , B , A and B form a 5 to 10 member ring; or

M, N, A¹, B¹, A² and B² form a 7 to 10 member ring; or

M, N, A¹, B¹, A² and B² form a 7 to 10 member ring and A³, B³, A⁴ and B⁴ form a 5 to 10 member ring.

According to another aspect the char e neutral ligand L may the Formula la,

(la), wherein:

1 2 8 1

A and A are same or independently selected from CO, POR and S0₂, preferably A

2 8

and A are selected same from CO, POR , S0₂; or

1 2 8

A and A are independently selected from CO, POR , S0₂, and

N, A 1 , B1 , A2 and B 2 form a 5 to 10 member ring.

According to another aspect the charge neutral metal amide compound of the hole injection layer may be selected from at least one compound according to Formula Ila, lib, lie, lid, He, Ilf, Ilg and/or Ilh,

wherein for:

- p = 0, m = 1, 2, 3 or 4 and n = 1, 2, 3 or 4, the charge neutral metal amide compound has the Formula Ila:

p = 1, 2 or 3, and n = 1, 2, 3 or 4 and m = 0, the charge neutral metal amide compound has the Formula lib:

p = l, 2 or 3, n = 1, 2, 3 or 4, m = 1, 2, 3 or 4 and N, A¹, B¹, B² and A² form a 5 to 10 member ring, the charge neutral metal amide compound has the Formula lie:

p = 1, 2 or 3, n = 1, 2, 3 or 4, m = 1, 2, 3 or 4 and N, A¹, B¹, B² and A² form a first 5 to

1 2

10 member ring and B and B are bridged to form a second 5 to 20 member ring, the charge neutral metal amide compound has the Formula lid:

p= l,2or3,n= l,m= 1,2, 3 or 4, and M, N, A¹, B¹, B², A² and N form a 7 to 10 member ring, the charge neutral metal amide compound has the Formula He:

1 1 2 2

p = 1, 2 or 3, n = 1, 2, 3 or 4, m = 0 and N, A , B , B and A form a 5 to 10 member ring, the charge neutral metal amide compound has the Formula Ilf:

(ilf); p = 1, 2 or 3, n = 1, 2, 3 or 4, m = 0 andN, A¹, B¹, B² and A² form a first 5 to 10

1 2

member ring, and B and B are bridged to form a second 5 to 20 member ring, the charge neutral metal amide compound has the Formula Ilg:

- p = 1, 2 or 3, n = 1, m = 0 and M, N, A¹, B¹, B², A² and N form a 7 to 10 member ring, the charge neutral metal amide compound has the Formula Ilh:

According to another aspect the charge neutral metal amide compound of the hole injection layer may be selected from at least one compound according to Formula Ilia, Illb, IIIc, Hid, Hie, Illf, Illg, Illh and/or Illi,

wherein for A 1 and A 2 are S0₂:

- p = 1, 2 or 3, n = 1, 2, 3 or 4, m = 1, 2, 3 or 4, the charge neutral metal amide compound has the Formula Ilia:

- p = 0, n = 1, 2, 3 or 4, m = 1, 2, 3 or 4, the charge neutral metal amide compound has the Formula Illb:

p = 1, 2 or 3, n = 1, 2, 3 or 4, m = 0, the charge neutral metal amide compound has the Formula IIIc:

p = 1, 2 or 3, n = 1, 2, 3 or 4, m = 1, 2, 3 or 4 and N, S0₂, B¹, B² and S0₂ form a 5 to 10 member ring, the charge neutral metal amide compound has the Formula Hid:

p = 1, 2 or 3, n = 1, 2, 3 or 4, m = 1, 2, 3 or 4 and N, S0₂, B¹, B² and S0₂ form a first 5 to 10 member ring, and B 1 and B 2 are bridged to form a second 5 to 20 member ring, the charge neutral metal amide compound has the Formula Hie:

p = 1, 2 or 3, n = 1, m = 1, 2, 3 or 4 and M, N, S0₂, B¹, B², S0₂ and N form a 7 to 10 member ring, the charge neutral metal amide compound has the Formula Illf:

(Illf);

- p = 1, 2 or 3, n = 1, 2, 3 or 4, m = 0 and N, S0₂, B 1 , B 2 and S0₂ form a 5 to 10 member ring, the charge neutral m tal amide compound has the Formula Illg:

- p = 1, 2 or 3, n = 1, 2, 3 or 4, m = 0 and N, S0₂, B¹, B² and S0₂ form a first 5 to 10 member ring, and B 1 and B 2 are bridged to form a second 5 to 20 member ring, the charge neutral metal amide compound has the Formula Illh:

- p = 1, 2 or 3, n = 1, 2, 3 or 4, m = 0 and M, N, S0₂, B¹, B², S0₂ and N form a 7 to 10 member ring, the charge neutral metal amide compound has the Formula IIIi:

According to another aspect the charge neutral metal amide compound of the hole injection layer may be selected from at least one compound according to Formula IVa, IVb, IVc, IVd and/or IVe,

wherein for A 1 and A2 are POR 8 :

- p = 1 , 2 or 3, m = 1 , 2, 3 or 4 and n = 1 , 2, 3 or 4, the charge neutral metal amide compound has the Formula IVa:

- p = 0, m = 1, 2, 3 or 4 and n = 1, 2, 3 or 4, the charge neutral metal amide compound has the Formula IVb:

- p = l, 2 or 3, m = 0 and n = 1, 2, 3 or 4, the charge neutral metal amide compound has the Formula IVc:

p = 1, 2 or 3, n = 1, 2, 3 or 4, m = 1, 2, 3 or 4 and N, POR⁸, B¹, B² and POR⁸ form a 5 to 10 member ring, the charge neutral metal amide compound has the Formula (IVd):

- p = 1, 2 or 3, n = 1, 2, 3 or 4, m = 0 and N, POR⁸, B¹, B² and POR⁸ form a 5 to 10 member ring, the charge neutral metal amide com ound has the Formula (IVe):

According to another aspect the charge neutral metal amide compound of the hole injection layer may be selected from at least one compound according to Formula Va, Vb, Vc, Vd, Ve, Vf, Vg, Vh and/or Vi,

wherein for A 1 and A 2 are CO:

- p = 1 , 2 or 3, m = 1 , 2, 3 or 4 and n = 1 , 2, 3 or 4, the charge neutral metal amide compound has the Form la Va:

- p = 0, n = 1, 2, 3 or 4, m = 1, 2, 3 or 4, the charge neutral metal amide compound has the Formula Vb:

(Vb); p=l,2or3,n=l,2,3or4,m = 0, the charge neutral metal amide compound has the Formula Vc:

p = 1, 2 or 3, n = 1, 2, 3 or 4, m = 1, 2, 3 or 4 and N, CO, B¹, B² and CO form a 5 to 10 member ring, the charge neutral metal amide compound has the Formula Vd:

p = 1, 2 or 3, n = 1, 2, 3 or 4, m = 1, 2, 3 or 4 and N, CO, B¹, B² and CO form a first 5 to

1 2

10 member ring, and B and B are bridged to form a second 5 to 20 member ring, the charge neutral metal amide com ound has the Formula Ve:

p= l,2or3,n= l,m= 1,2, 3 or 4 and M, N, CO, B¹, B², CO and N form a 7 to 10 member ring, the charge neutral metal amide com ound has the Formula Vf:

p = 1 , 2 or 3, n = 1 , 2, 3 or 4, m = 0 and N, CO, B 1 , B 2 and CO form a 5 to 10 member ring, the charge neutral metal amide compound has the Formula (Vg):

p = 1, 2 or 3, n = 1, 2, 3 or 4, m = 0 and N, CO, B¹, B² and CO form a first 5 to 10 member ring, and B 1 and B 2 form a second 5 to 20 member ring, the charge neutral metal amide compound has the Formula Vh:

p = l, 2 or 3, n = 1, 2, 3 or 4, m = 0 and M, N, CO, B¹, B², CO and N form a 7 to 10 member ring, the charge neutral metal amide compound has the Formula (Vi):

According to another aspect the charge neutral metal amide compound of the hole injection layer may be selected from at least one compound according to Formula Via, wherein for A¹ is S0₂ and A² is POR⁸:

- p = 1 , 2 or 3, m = 1 , 2, 3 or 4 and n = 1 , 2, 3 or 4, the charge neutral metal amide compound has the Formula Via:

According to another aspect the charge neutral metal amide compound of the hole injection layer may be selected from at least one compound according to Formula lb:

wherein:

3 4 8 3

A and A are same or independently selected from CO, POR or S0₂, preferably A

4 8

and A are selected same from CO, POR or S0₂;

B³ and B⁴ are independently selected from substituted or unsubstituted Ci to C₂₀ alkyl, substituted or unsubstituted Ci to C₂₀ heteroalkyl, substituted or unsubstituted C₆ to C₂₀ aryl, substituted or unsubstituted C₆ to C₂₀ heteroaryl, preferably B³ and B⁴ are selected same; and

M, N, A¹, B¹, A² and B² form a 7 to 10 member ring.

According to another aspect the charge neutral metal amide compound of the hole injection layer may be selected from at least one compound according to Formula Id, wherein

N, A 1 , B1 , A2 and B 2 form a first 5 to 10 member ring and B 1 and B2 are bridged to form a second ring of a substituted or unsubstituted C₆ to C₂₀ aryl, or of a substituted or unsubstituted C₆ to C₂o heteroaryl ring:

(Id).

According to another aspect the charge neutral metal amide compound of the hole injection layer may be selected from at least one fluorinated compound according to:

- Formula CI to C16, based on general formula la, wherein p = 0, m = 0, n = 1, 2, 3 or 4 and A¹ and A² are S0₂:

(C14) (C15) (C16)

- Formula C17 to C23, based on general Formula la, wherein n = 1, 2, 3 or 4, A 1 and A 2 are CO:

(CI 9)

(C22) (C23)

Formula C24 to C25, based on general Formula la, wherein n = 1, 2, 3 or 4, A 1 and A 2 are POR⁸:

According to another aspect the charge neutral metal amide compound of the hole injection layer may be selected from at least one fluorinated compound, based on general formula la, having the Formula Dl to D24:

1 2

wherein p = 0, m = 0, n = 1 , 2, 3 or 4 and A and A are S0₂:

(D9) (D10) (Dl l)

(D12) (D13)

(D15) (D16) (D17)

(D18) (D19) (D20)

(D21) (D22) (D23)

According to another aspect the charge neutral metal amide compound of the hole injection layer may be selected from at least one fluorinated compound, based on general formula la, having the Formula Fl to F23:

wherein the charge neutral ligand L coordinates to the metal M:

(Fl) (F2) (F3)

(F4) (F5)

(F7) (F8) (F9)

(F10) (Fll) (F12)

(F17),

wherein

R⁶ and R⁷ are independently selected from Ci to C20 alkyl, Ci to C20 heteroalkyl, C₆ to C20 aryl, heteroaryl with 5 to 20 ring- forming atoms, halogenated or perhalogenated Ci to C20 alkyl, halogenated or perhalogenated Ci to C20 heteroalkyl, halogenated or perhalogenated C₆ to C20 aryl, halogenated or perhalogenated heteroaryl with 5 to 20 ring-forming atoms, or at least one R⁶ and R⁷ are bridged and form a 5 to 20 member ring , or the two R⁶ and/or the two R⁷ are bridged and form a 5 to 40 member ring or form a 5 to 40 member ring comprising an unsubstituted or Ci to C12 substituted phenanthroline.

Charge neutral metal amide compounds which contain a charge-neutral ligand L selected from mono and multidental ethers or amines forming a 5 to 7 membered ring system with the metal, preferably glycole ethers, ethylendiamine derivatives, even more preferred diglyme, and/or N 1 ,N 1 ,N2,N2-tetramethyl- 1 ,2-ethanediamine, N-((E,2E)-2- { [(E)- 1,1- dimethylethyl]imino}ethylidene)-2-methyl-2-propanamine can be preferably used as HIL- material.

Examples of charge neutral metal amides compounds with a charge-neutral ligand L selected from mono and/or multidental ethers or amines that can be preferably used as HIL- material having the Formula Fl, F2, F3, F4, F5 and/or F6:

(Fl) (F2) (F4)

(F5) (F6),

wherein

R⁶ and R⁷ are independently selected from Ci to C₂₀ alkyl, Ci to C₂₀ heteroalkyl, C₆ to C₂₀ aryl, heteroaryl with 5 to 20 ring- forming atoms, halogenated or perhalogenated Ci to C₂₀ alkyl, halogenated or perhalogenated Ci to C₂₀ heteroalkyl, halogenated or perhalogenated C₆ to C₂₀ aryl, halogenated or perhalogenated heteroaryl with 5 to 20 ring-forming atoms, or at least one R⁶ and R⁷ are bridged and form a 5 to 20 member ring , or the two R⁶ and/or the two R⁷ are bridged and form a 5 to 40 member ring or form a 5 to 40 member ring comprising an unsubstituted or Ci to C₁₂ substituted phenanthroline.

According to another aspect the charge neutral metal amide compound of the hole injection layer may be selected preferably from at least one fluorinated compound, based on general formula la, having the Formula F18 to F23:

(F18) (F19) (F20)

(F21) (F22)

(F23).

According to another aspect the charge neutral metal amide compound of the hole injection layer may be selected preferably from at least one fluorinated compound, based on general formula la, having the Formula F24 to F45:

wherein a halide, O, alkoxylate or amine bonds to the metal M:

(F24) (F25) (F26)

R¹ to R⁵ are independently selected from the group comprising H, Ci to C₂o alkyl, Ci to C₂₀ heteroalkyl, unsubstituted or Ci to C₁₂ substituted C₆ to C₂₀ aryl, unsubstituted or Ci to C₁₂ substituted heteroaryl with 5 to 20 ring-forming atoms, halogenated or perhalogenated Ci to C₂₀ alkyl, halogenated or perhalogenated Ci to C₂₀ heteroalkyl, halogenated or perhalogenated C₆ to C₂₀ aryl, halogenated or perhalogenated heteroaryl with 5 to 20 ring-forming atoms; or at least one R¹ and R⁴ and/or R² and R³ and/or R¹ and R⁵ are bridged and form a 5 to 20 member cyclic ring.

More preferred are compounds which comprise a ligand G. Ligand G is selected from group VII elements, preferably chloride CI. Furthermore preferred are compounds wherein ligand G is selected from an alkoxylate of formula F30, F31 and F35:

(F30) (F31) (F35),

wherein

R¹ is selected from the group comprising H, Ci to C₂₀ alkyl, Ci to C₂₀ heteroalkyl,

unsubstituted or Ci to C₁₂ substituted C₆ to C₂₀ aryl, unsubstituted or Ci to C₁₂ substituted heteroaryl with 5 to 20 ring-forming atoms, halogenated or perhalogenated Ci to C₂₀ alkyl, halogenated or perhalogenated Ci to C₂₀ heteroalkyl, halogenated or

perhalogenated C₆ to C₂₀ aryl, halogenated or perhalogenated heteroaryl with 5 to 20 ring-forming atoms.

According to another aspect the charge neutral metal amide compound of the hole injection layer may be selected preferably from at least one fluorinated compound, based on general formula la, having the Formula F36 to F46:

(F39) (F40) (F41)

(F42) (F43) (F44)

(F45) (F46).

In Table 1 below metal amide compounds according to formula la are listed, which can be preferably used as hole injection layer (HIL) material.

Table 1

Compounds of formula (la) which can be suitable used for an hole injection layer (HIL)

Metal amide Structure CAS number

Particularly preferred are metal amide compounds for use as HIL-material listed in Table 2.

Table 2

According to one aspect, the hole injection layer (HIL) may comprises the charge neutral metal amide compound according to formula la, lb, Ic and/or Id in the range of about > 0.1 wt.-% to about < 49 wt.-%, preferably about > 0.5 wt.-% to about < 45 wt.-%, further preferred about > 1 wt.-% to about < 40 wt.-%, in addition preferred about > 1.5 wt.-% to about < 30 wt.-%, or about > 2 wt.-% to about < 20 wt.-%, or about > 2.5 wt.-% to about < 10 wt.-%, or about > 3 wt.-% to about < 7 wt.-%, and more preferred about > 3.5 wt.-% to about < 5 wt.-% or about > 4 wt.-% to about < 4.5 wt.-%.

Triarylamine compounds used in the hole transport layer (HIL)

According to a preferred aspect, the hole injection layer (HIL) comprises a

triarylamine compound having the Formula Vila:

wherein:

1 2

Ar and Ar = independently selected from substituted or unsubstituted C₆ to C20 arylene; Ar³ and Ar⁴ = independently selected from substituted or unsubstituted C₆ to C₂o aryl; Ar⁵ and Ar⁶ = independently selected from substituted or unsubstituted C₆ to C₂o aryl or

C₅ to C40 heteroaryl; R⁹ = a single chemical bond, a unsubstituted or substituted Ci to C₆ alkyl and unsubstituted or substituted Ci to C₅ heteroalkyl;

q = 0, 1 or 2;

r = 0 or 1 ;

wherein

- the substituents for Ar¹ to Ar⁶ are independently selected from Ci to C₂o alkyl, Ci to C₂₀ heteroalkyl, or halide; and

- the substitutents for R⁹ are independently selected from Ci to C₆ alkyl, Ci to C₅ heteroalkyl, C₆ to C₂o aryl and C₅ to C₂₀ heteroaryl.

According to a further preferred aspect, the hole injection layer may comprises a triarylamine compound of Formula Vila, wherein Ar¹ and Ar² are Ph; Ar³ to Ar⁶ are selected from phenyl, tolyl, xylyl, mesityl, biphenyl, 1-naphthyl, 2-napthyl, 2-( 9,9-dialkyl-fluorenyl), 2-( 9-alkyl-9'-aryl-fluorenyl) and 2-( 9,9-diaryl-fluorenyl); R⁹ = single bond; r = 1 and q= 1.

According to a further preferred aspect, the hole injection layer may comprises a

1 2

triarylamine compound of Formula Vila, wherein Ar and Ar are independently selected from phenyl and biphenyl; Ar³ to Ar⁶ are selected from phenyl, tolyl, xylyl, mesityl, biphenyl, 1-naphthyl, 2-napthyl, 2-( 9,9-dialkyl-fluorenyl), 2-( 9-alkyl-9'-aryl-fluorenyl) and 2-( 9,9- diaryl-fluorenyl); R⁹ = single bond; r = 1 and q= 1.

According to a further preferred aspect, the hole injection layer may comprises a triarylamine compound of Formula Vila, wherein Ar¹ and Ar² are phenyl; Ar³ to Ar⁶ are selected from phenyl, tolyl, xylyl, mesityl, biphenyl, 1-naphthyl, 2-napthyl, 2-( 9,9-dialkyl- fluorenyl), 2-( 9-alkyl-9'-aryl-fluorenyl) and 2-( 9,9-diaryl-fluorenyl); R⁹ = 9,9'-fluorenyl; r = 1 and q= 1.

According to a further preferred aspect, the hole injection layer may comprises a triarylamine compound of Formula Vila, wherein Ar¹ is phenyl; Ar³ to Ar⁶ are selected from phenyl, tolyl, xylyl, mesityl, biphenyl, 1-naphthyl, 2-napthyl, 2-( 9,9-dialkyl-fluorenyl), 2-( 9- alkyl-9'-aryl-fluorenyl) and 2-( 9,9-diaryl-fluorenyl); R⁹ = single bond; r = 0 and q= 1. The substituent on Ar¹ is selected from phenyl, biphenyl, 2-( 9,9-dialkyl-fluorenyl), 2-( 9-alkyl-9'- aryl-fluorenyl) and 2-( 9,9-diaryl-fluorenyl).

1 3 2 triarylamine compound of Formula Vila, wherein N, Ar and Ar form a carbazole ring; Ar is phenyl or biphenyl; Ar³ to Ar⁶ are selected from phenyl, tolyl, xylyl, mesityl, biphenyl, 1- naphthyl, 2-napthyl, 2-( 9,9-dialkyl-fluorenyl), 2-( 9-alkyl-9'-aryl-fluorenyl) and 2-( 9,9- diaryl-fluorenyl); R⁹ = single bond; r = 1 and q= 1.

Preferably in Formula Vila the q may be selected from 1 or 2.

Compounds of formula Vila that can be suitable used as HIL-material may have an molecular weight suitable for thermal vacuum deposition and HOMO levels that provides a good hole injection performance into the emission layer. Compounds of formula Vila that can be preferably used as HIL-material may have an molecular weight that is about > 243 g/mol and about < 2000 g/mol, even more preferred is about > 412 g/mol and about < 1800 g/mol, also preferred about > 488 g/mol and about < 1500 g/mol.

According to a more preferred embodiment the Ar 1 and Ar 2 of Formula Vila may be independently selected from phenylene, biphenylene, naphthylene, anthranylene,

carbazolylene, or fluorenylene, preferably from phenylene or biphenylene.

According to a more preferred embodiment the Ar³ to Ar⁶ of Formula Vila may be independently selected from phenyl, biphenyl, terphenyl, quartphenyl, fluorenyl, napthyl, anthranyl, phenanthryl, thiophenyl, fluorenyl, or carbazolyl.

Even more preferred, Ar³ to Ar⁶ of Formula Vila may be independently selected from phenyl, biphenyl, fluorenyl, napthyl, thiopheneyl, fluorenyl, or carbazolyl.

At least two of Ar¹ to Ar⁶ of Formula Vila may form a cyclic structure, for example Ar¹ and Ar³; or Ar¹ and Ar⁴; or Ar² and Ar⁵; or Ar² and Ar⁶; may be a carbazole, phenazoline or phenoxazine ring.

According to a further preferred embodiment the triarylamine compound having the Formula Vila, wherein:

1 2

Ar and Ar are independently selected from phenylene, biphenylene, naphthylene, anthranylene, carbazolylene and fluorenylene, preferably selected from phenylene and biphenylene;

Ar³ to Ar⁶ are independently selected from phenyl, biphenyl, terphenyl, quartphenyl, fluorenyl, napthyl, anthranyl, phenanthryl, thiophenyl, fluorenyl, 9- carbazolyl; preferably

Ar³ to Ar⁶ are independently selected from phenyl, biphenyl, fluorenyl, napthyl, thiophenyl, fluorenyl, carbazolyl.

Furthermore preferred, at least one of Ar¹ to Ar⁶ of Formula Vila may be

unsubstituted, even more preferred at least two of Ar¹ to Ar⁶ of Formula VII may be unsubstituted. According to an additional preferred embodiment the triarylamine compound having the Formula Vila:

- Ar³ and Ar⁴ and/or Ar⁵ and Ar⁶ are linked to form a carbazole, phenazoline or phenoxazine ring.

According to a furthermore preferred embodiment the triarylamine compound has the Formula Vllb to Vllk.

(Vlld) (Vile)

(Vllj) (Vllk).

Compounds of formula Vila, wherein not all Ar to Ar are substituted are particularly suited for vacuum thermal deposition.

Preferably, the hole injection layer (HIL) may comprises a triarylamine compound of formula Vila, wherein the substituents on Ar³ to Ar⁶ are independently selected from Ci to C alkyl, Ci to C₁₂ alkoxy or halide, preferably from Ci to C₈ alkyl or Ci to C₈ heteroalkyl, even more preferred from Ci to C₅ alkyl or Ci to C₅ heteroalkyl. Preferably, the hole injection layer comprises a triarylamine compound of formula Vila, wherein the substituents on Ar³ to Ar⁶ are independently selected from Ci to C₁₂ alkyl or halide, preferably from Ci to C₈ alkyl or fluoride, even more preferred from Ci to C₅ alkyl or fluoride. When the substituents are selected from alkyl groups, the HOMO level of the hole injection layer may have a HOMO level suitable for good hole injection into the emission layer, in particular of phosphorescent blue and green emitters and emission which relies on TADF (thermally activated delayed fluorescence) and the OLED may have low voltage, high efficiency and good stability.

Examples of particularly preferred compounds of Formula Vila are shown in Table 3.

Table 3

Triarylamine compounds of formula Vila

According to another aspect, the hole injection layer (HIL) may have a layer thickness of at least about > 30 nm to about < 1000 nm, preferably of about > 40 nm to about < 500 nm, also preferred of about > 50 nm to about < 750 nm.

According to another aspect, the hole injection layer (HIL) may have a layer thickness of at least about > 40 nm to about < 1000 nm, preferably of about > 60 nm to about < 500 nm, also preferred of about > 80 nm to about < 750 nm. According to another aspect, the hole injection layer (HIL) may have a layer thickness of at least about > 70 nm to about < 1000 nm, preferably of about > 90 nm to about < 500 nm, also preferred of about > 100 nm to about < 600 nm.

According to another aspect, the hole injection layer (HIL) may have a layer thickness of at least about > 100 nm to about < 1000 nm, preferably of about > 150 nm to about < 500 nm, also preferred of about > 200 nm to about < 450 nm.

According to another aspect, the hole injection layer (HIL) may comprises:

- at least about > 0.1 wt.-% to about < 50 wt.-%, preferably about > 1 wt.-% to about < 25 wt.-%, and more preferred about > 2 wt.-% to about < 15 wt.-%, of a charge neutral metal amide compound according to Formula la, lb, Ic or Id, and

- at least about > 50 wt.-% to about < 99 wt.-%, preferably about > 75 wt.-% to about < 99 wt.-%, and more preferred about > 85 wt.-% to about < 98 wt.-%, of a triarylamine compound; preferably the wt.-% of the triarylamine compound is higher than the wt.-% of the charge neutral metal amide compound; wherein the weight-% of the components are based on the total weight of the hole injection layer.

According to another aspect, the hole injection layer (HIL) may comprises:

- at least about > 0.5 wt.-% to about < 50 wt.-%, preferably about > 1 wt.-% to about < 25 wt.-%, and more preferred about > 1.5 wt.-% to about < 15 wt.-%, of a charge neutral metal amide compound according to Formula la, lb, Ic or Id, and

- at least about > 50 wt.-% to about < 99.5 wt.-%, preferably about > 75 wt.-% to about < 99 wt.-%, and more preferred about > 85 wt.-% to about < 98.5 wt.-%, of a triarylamine compound; wherein the weight-% of the components are based on the total weight of the hole injection layer.

According to another aspect, the hole injection layer (HIL) may comprises:

- at least about > 50 wt.-% to about < 99 wt.-%, preferably about > 75 wt.-% to about < 99 wt.-%, and more preferred about > 85 wt.-% to about < 98 wt.-%, of a triarylamine compound according to Formula Vila; preferably the wt.-% of the triarylamine compound is higher than the wt.-% of the charge neutral metal amide compound; wherein the weight- % of the components are based on the total weight of the hole injection layer.

According to another aspect, the hole injection layer (HIL) may comprises: - at least about > 0.5 wt.-% to about < 50 wt.-%, preferably about > 1 wt.-% to about < 25 wt.-%, and more preferred about > 1.5 wt.-% to about < 15 wt.-%, of a charge neutral metal amide compound according to Formula la, lb, Ic or Id, and

- at least about > 50 wt.-% to about < 99.5 wt.-%, preferably about > 75 wt.-% to about < 99 wt.-%, and more preferred about > 85 wt.-% to about < 98.5 wt.-%, of a triarylamine compound according to Formula Vila; wherein the weight-% of the components are based on the total weight of the hole injection layer.

According to another aspect, the hole injection layer (HIL) may comprises the triarylamine compound according to Formula Vila in the range of about > 60 wt.-% to about

< 100 wt.-%, further preferred about > 70 wt.-% to about < 100 wt.-%, in addition preferred about > 80 wt.-% to about < 100 wt.-%, or about > 95 wt.-% to about < 100 wt.-%, or about > 98 wt.-% to about < 100 wt.-%, or about > 99 wt.-% to about < 100 wt.-%, and more preferred about > 90 wt.-% to about < 100 wt.-% or about > 95 wt.-% to about < 99 wt.-%.

According to another aspect, the hole injection layer (HIL) may comprises the triarylamine compound according to Formula Vila in the range of about > 70 wt.-% to about

< 100 wt.-%, in addition preferred about > 80 wt.-% to about < 100 wt.-%, or about > 95 wt.- % to about < 100 wt.-%, or about > 98 wt.-% to about < 100 wt.-%, or about > 99 wt.-% to about < 100 wt.-%, and more preferred about > 90 wt.-% to about < 100 wt.-% or about > 95 wt.-% to about < 99 wt.-%.

According to another aspect, the hole injection layer (HIL) may comprises the triarylamine compound according to Formula Vila in the range of about > 80 wt.-% to about

< 100 wt.-%, or about > 95 wt.-% to about < 100 wt.-%, or about > 98 wt.-% to about < 100 wt.-%, or about > 99 wt.-% to about < 100 wt.-%, and more preferred about > 90 wt.-% to about < 100 wt.-% or about > 95 wt.-% to about < 99 wt.-%.

According to another aspect, the hole injection layer (HIL) may comprises the triarylamine compound according to Formula Vila in the range of about > 95 wt.-% to about

< 100 wt.-%, or about > 98 wt.-% to about < 100 wt.-%, or about > 99 wt.-% to about < 100 wt.-%, and more preferred about > 90 wt.-% to about < 100 wt.-% or about > 95 wt.-% to about < 99 wt.-%.

According to another aspect, the hole injection layer (HIL) may comprises the triarylamine compound according to Formula Vila in the range of about > 98 wt.-% to about

< 100 wt.-%, or about > 99 wt.-% to about < 100 wt.-%, and more preferred about > 90 wt.-% to about < 100 wt.-% or about > 95 wt.-% to about < 99 wt.-%. According to another aspect, the hole injection layer (HIL) may comprises the triarylamine compound according to Formula Vila in the range of about > 99 wt.-% to about < 100 wt.-%, and more preferred about > 90 wt.-% to about < 100 wt.-% or about > 95 wt.-% to about < 99 wt.-%.

According to another aspect, the hole injection layer comprises:

- at least about > 1 wt.-% to about < 50 wt.-%, preferably about > 1 wt.-% to about < 25 wt.- %, and more preferred about > 2 wt.-% to about < 15 wt.-%, of a charge neutral metal amide compound according to claims 1 to 18, and

- at least about > 50 wt.-% to about < 99 wt.-%, preferably about > 75 wt.-% to about < 99 wt.-%, and more preferred about > 85 wt.-% to about < 98 wt.-%, of a triarylamine compound; preferably the wt.-% of the triarylamine compound is higher than the wt.-% of the charge neutral metal amide compound; wherein the weight-% of the components are based on the total weight of the hole injection layer; or

- at least about > 1 wt.-% to about < 4 wt.-%, and more preferred about > 2 wt.-% to about < 3 wt.-%, of the charge neutral metal amide compound; and

- at least about < 99 wt.-% to about > 96 wt.-%, and more preferred about < 98 wt.-% to about > 97 wt.-%, of the triarylamine compound; preferably the wt.-% of the triarylamine compound is higher than the wt.-% of the charge neutral metal amide compound; wherein the weight-% of the components are based on the total weight of the hole injection layer.

Compounds used in the hole transport layer (HTL)

The HTL may be formed of any compound that is commonly used to form a HTL. Compound that can be suitably used is disclosed for example in Y. Shirota and H. Kageyama, Chem. Rev. 2007, 107, 953-1010 and incorporated by reference. Examples of the compound that may be used to form the HTL 140 are: a carbazole derivative, such as N-phenylcarbazole or polyvinylcarbazole; an amine derivative having an aromatic condensation ring, such as N,N'-bis(3-methylphenyl)-N,N'-diphenyl-[l,l-biphenyl]-4,4'-diamine (T-l), or Ν,Ν'- di(naphthalene-l-yl)-N,N'-diphenyl benzydine (alpha -NPD, T-4); and a triphenylamine- based compound, such as 4,4',4"-tris(N-carbazolyl)triphenylamine (T-10). Among these compounds, T-10 can transport holes and inhibit excitons from being diffused into the EML.

Other examples of the compounds that may be used forming the HTL 140 are oligothiophenes and phthalocyanines disclosed for example in Yasuhiko Shirota and Hiroshi Kageyama, Chem. Rev. 2007, 107, 953-1010 and in Facchetti, MaterialsToday 10, 2007, 28 and incorporated by reference.

Compounds used in the electron transport layer (ETL)

The OLED according to the present invention may not contain an electron transport layer (ETL). However, the OLED according to the present invention may optional contain an electron transport layer (ETL).

According to various embodiments the OLED may comprises an electron transport layer or an electron transport layer stack comprising at least a first electron transport layer and at least a second electron transport layer.

According to various embodiments of the OLED of the present invention the electron transport layer may comprises at least one matrix compound.

According to various embodiments of the OLED the matrix compound may be selected from:

- an anthracene based compound or a heteroaryl substituted anthracene based compound, preferably 2-(4-(9, 10-di(naphthalen-2-yl)anthracene-2-yl)phenyl)- 1 -phenyl- 1 H- benzo[d]imidazole and/or N4,N4"-di(naphthalen- 1 -yl)-N4,N4"-diphenyl-[ 1 , Γ:4', 1 "- terphenyl]-4,4"-diamine;

- a phosphine oxide based compound, preferably (3-(dibenzo[c,h]acridin-7- yl)phenyl)diphenylphosphine oxide and/or phenyl bis(3-(pyren-l-yl)phenyl)phosphine oxide and/or 3-Phenyl-3H-benzo[b]dinaphtho[2,l-d: r,2^'-fJphosphepine-3-oxide; or

- a substituted phenanthroline compound, preferably 2,4,7,9-tetraphenyl- 1,10- phenanthroline, 4,7-diphenyl-2,9-di-p-tolyl-l,10-phenanthroline, or 2,9-di(biphenyl-4-yl)- 4,7-diphenyl- 1 , 10-phenanthroline.

According to various embodiments of the OLED the matrix compound of the electron transport layer may be preferably selected from:

- a phosphine oxide based compound, preferably (3-(dibenzo[c,h]acridin-7- yl)phenyl)diphenylphosphine oxide, 3-phenyl-3H-benzo[b]dinaphtho[2,l-d: l ',2'- f]phosphepine-3 -oxide and/or phenyl bis(3-(pyren-l-yl)phenyl)phosphine oxide; or

- a substituted phenanthroline compound, preferably 2,4,7,9-tetraphenyl- 1,10- phenanthroline, 4, 7-diphenyl-2,9-di-p-tolyl- 1,10-phenanthroline, or 2,9-di(biphenyl-4-yl)- 4,7-diphenyl- 1 , 10-phenanthroline. According to various embodiments of the OLED the matrix compound of the electron transport layer may be more preferred selected from:

- a phosphine oxide based compound, preferably (3-(dibenzo[c,h]acridin-7- yl)phenyl)diphenylphosphine oxide, 3-phenyl-3H-benzo[b]dinaphtho[2,l-d: l ',2'- fJphosphepine-3 -oxide and/or phenyl bis(3-(pyren-l-yl)phenyl)phosphine oxide.

According to various embodiments of the OLED of the present invention the thicknesses of the electron transport layer may be in the range of about > 0.5 nm to about < 95 nm, preferably of about > 3 nm to about < 80 nm, further preferred of about > 5 nm to about < 60 nm, also preferred of about > 6 nm to about < 40 nm, in addition preferred about > 8 nm to about < 20 nm and more preferred of about > 10 nm to about < 18 nm.

According to various embodiments of the OLED of the present invention the thicknesses of the electron transport layer stack can be in the range of about > 25 nm to about < 100 nm, preferably of about > 30 nm to about < 80 nm, further preferred of about > 35 nm to about < 60 nm, and more preferred of about > 36 nm to about < 40 nm.

According to various embodiments of the OLED of the present invention the electron transport layer may comprises:

a) about > 10 wt.-% to about < 70 wt.-%, preferably about > 20 wt.-% to about < 65 wt.- % and also preferred about > 50 wt.-% to about < 60 wt.-% of a lithium halide or an lithium organic complex of a lithium quinolate, a lithium borate, a lithium phenolate and/or a lithium Schiff base, preferably of a lithium quinolate complex has the formula I, II or III:

wherein

- Al to A6 are same or independently selected from CH, CR, N, O, - R is same or independently selected from hydrogen, halogen, alkyl or aryl or heteroaryl with 1 to 20 carbon atoms, and more preferred of a lithium 8- hydroxyquinolate;

b) about < 90 wt.-% to about > 30 wt.-%, preferably about < 80 wt.-% to about > 35 wt.- % and also preferred about < 50 wt.-% to about > 40 wt.-% of a matrix compound of:

- an anthracene based compound or a hetero substituted anthracene based compound, preferably 2-(4-(9, 10-di(naphthalen-2-yl)anthracene-2-yl)phenyl)- 1 -phenyl- 1 H- benzo[d]imidazole and/or N4,N4"-di(naphthalen- 1 -yl)-N4,N4"-diphenyl-[ 1 , Γ:4', 1 "- terphenyl]-4,4"-diamine; or

- a phosphine oxide based compound, preferably (3-(dibenzo[c,h]acridin-7- yl)phenyl)diphenylphosphine oxide and/or phenyl bis(3-(pyren-l- yl)phenyl)phosphine oxide and/or 3-Phenyl-3H-benzo[b]dinaphtho[2,l-d:l ',2'- f]phosphepine-3 -oxide; or

- a substituted phenanthroline compound, preferably 2,4,7,9-tetraphenyl- 1,10- phenanthroline, 4,7-diphenyl-2,9-di-p-tolyl-l,10-phenanthroline, or 2,9- di(biphenyl-4-yl)-4,7-diphenyl- 1 , 10-phenanthroline; whereby

more preferred is a phosphine oxide based compound and most preferred is (3-

(dibenzo[c,h]acridin-7-yl)phenyl)diphenylphosphine oxide;

based on the total weight of the electron transport layer.

According to one embodiment of the OLED, the electron transport layer comprises of about > 50 wt.-% to about < 60 wt.-% of a first lithium halide or a first lithium organic complex and about < 50 wt.-% to about > 40 wt.-% of a matrix compound of:

- a phosphine oxide based compound, preferably (3-(dibenzo[c,h]acridin-7- yl)phenyl)diphenylphosphine oxide, 3-phenyl-3H-benzo[b]dinaphtho[2,l-d: l ',2'- fJphosphepine-3 -oxide and/or phenyl bis(3-(pyren-l-yl)phenyl)phosphine oxide; or

- a substituted phenanthroline compound, preferably 2,4,7,9-tetraphenyl- 1,10- phenanthroline, 4, 7-diphenyl-2,9-di-p-tolyl- 1,10-phenanthroline, or 2,9-di(biphenyl-4- yl)-4,7-diphenyl- 1 , 10-phenanthroline.

The light-emitting diode (OLED) may comprises at least two electrodes, an anode electrode and a second cathode electrode.

The electron transport layer/s or electron transport layer stack is not an electrode. The electron transport layer/s or electron transport layer are sandwiched between two electrodes, namely sandwiched between an anode and a second cathode. The ETL may be formed optional on an EML or on the HBL if the HBL is formed. The ETL includes a first layer including a first lithium halide or a first lithium organic complex; and optional a second electron transport layer including a second lithium halide or a second lithium organic complex, wherein optional the first lithium organic complex is not the same as the second lithium organic complex and wherein the first lithium halide is not the same as the second lithium halide.

The ETL includes a first layer comprising a first matrix compound and a lithium halide or a lithium organic complex; and optional a second electron transport layer comprising a second matrix compound and a metal dopant selected from a group comprising alkali, alkaline earth and rare earth metals.

The ETL includes a first layer comprising a first matrix compound and a lithium halide or a lithium organic complex; and optional a second electron transport layer comprising a second matrix compound and is free of dopant.

The ETL may have a stacked structure, preferably of two ETL-layers, so that injection and transport of electrons may be balanced and holes may be efficiently blocked. In a conventional OLED, since the amounts of electrons and holes vary with time, after driving is initiated, the number of excitons generated in an emission area may be reduced. As a result, a carrier balance may not be maintained, so as to reduce the lifetime of the OLED.

However, in the ETL, the first layer and the second layer may have similar or identical energy levels, so that the carrier balance may be uniformly maintained, while controlling the electron-transfer rate.

Matrix compound for the electron layer that can be suitable used are selected from the group comprising anthracene compounds, preferably 2-(4-(9,10-di(naphthalen-2-yl)anthracen- 2-yl)phenyl)- 1 -phenyl- 1 H-benzo[d]imidazole

Anthracene compounds that can be used as matrix materials are disclosed in US 6878469 B.

Other matrix compounds that can be used are diphenylphosphine oxide, preferably (3- (dibenzo[c,h]acridin-7-yl)phenyl)diphenylphosphine oxide, phenylbis(3-(pyren-l- yl)phenyl)phosphine oxide, 3-phenyl-3H-benzo[b]dinaphtho[2,l-d:r,2^'-f]phosphepine-3- oxide, phenyldi(pyren-l-yl)phosphine oxide.

Diphenylphosphine oxide compounds that can be used as matrix materials are disclosed in EP 2395571 Al, WO2013079217 Al, EP 13187905, EP13199361 and

JP2002063989 Al . Other suitable matrix compounds that can be used are phenanthrolme compounds, preferably selected from the group comprising of 2,4,7,9-tetraphenyl-l,10-phenanthroline, 4,7-diphenyl-2,9-di-p-tolyl-l,10-phenanthroline, and 2,9-di(biphenyl-4-yl)-4,7-diphenyl-l,10- phenanthroline. Phenanthrolme compounds that can be used as matrix materials are disclosed in EP 1786050 Al .

The matrix compound of the electron transport layer may be a compound that efficiently transports electrons, such as an anthracene-based compound, diphenylphosphine oxide based compound, or a phenanthrolme based compound, preferably a matrix compound mentioned in Table 4. For example, the matrix compound of the electron transport layer may be selected from the group consisting of Compound 5, a compound represented by Formula 2, and a compound represented by Formula 3 below:

Formula 2

Formula 3

In Formulae 2 and 3, Ri to R₆ are each independently a hydrogen atom, a halogen atom, a hydroxy group, a cyano group, a substituted or unsubstituted C₁-C30 alkyl group, a substituted or unsubstituted C₁-C30 alkoxy group, a substituted or unsubstituted C₁-C30 acyl group, a substituted or unsubstituted C₂-C30 alkenyl group, a substituted or unsubstituted C₂- C30 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a substituted or unsubstituted C3-C30 heteroaryl group. At least two adjacent Ri to R₆ groups are optionally bonded to each other, to form a saturated or unsaturated ring. Li is a bond, a substituted or unsubstituted C₁-C30 alkylene group, a substituted or unsubstituted C6-C30 arylene group, or a substituted or unsubstituted C3-C30 hetero arylene group. Qi through Q are each

independently a hydrogen atom, a substituted or unsubstituted C6-C30 aryl group, or a substituted or unsubstituted C3-C30 hetero aryl group, and "a" is an integer from 1 to 10.

For example, Ri to R₆ may be each independently selected from the group consisting of a hydrogen atom, a halogen atom, a hydroxy group, a cyano group, a methyl group, an ethyl group, a propyl group, a butyl group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a phenyl group, a naphthyl group, an anthryl group, a pyridinyl group, and a pyrazinyl group.

In particular, in Formula 2 and/or 3, Ri to R4 may each be a hydrogen atom, R5 may be selected from the group consisting of a halogen atom, a hydroxy group, a cyano group, a methyl group, an ethyl group, a propyl group, a butyl group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a phenyl group, a naphthyl group, an anthryl group, a pyridinyl group, and a pyrazinyl group. In addition, in Formula 3, Ri to R₆ may each be a hydrogen atom. For example, in Formula 2 and/or 3, Qi to Q are each independently a hydrogen atom, a phenyl group, a naphthyl group, an anthryl group, a pyridinyl group, and a pyrazinyl group. In particular, in Formulae 2 and/or 3, Qi, Q3-Q6, Qs and Q9 are hydrogen atoms, and Q₂ and Q₇ may be each independently selected from the group consisting of a phenyl group, a naphthyl group, an anthryl group, a pyridinyl group, and a pyrazinyl group.

For example, L_ls in Formula 2 and/or 3, may be selected from the group consisting of a phenylene group, a naphthylene group, an anthrylene group, a pyridinylene group, and a pyrazinylene group. In particular, Li may be a phenylene group or a pyridinylene group. For example, "a" may be 1, 2, or, 3.

The matrix compound for the ETL-layer may be further selected from Compound 5, 6, or 7 belo

Compound 6 Compound 7.

Table 4

Chemical structures of matrix materials that can be suitable used for ETL-layer

Referred IUPAC name Structure Reference to as:

MX 2 (3-(dibenzo[c,h]acridin-7- EP 2395571B1, yl)phenyl)diphenylphosphine WO2013079217A1 oxide

MX 3 Phenylbis(3 -(pyren- 1 - EP13187905.8 yl)phenyl)phosphine oxide

MX 4 3-Phenyl-3H- EP13199361.0 b enzo [b] dinaphtho [2,1- d: ,2^'-f]phosphepine-3- oxide

MX 5 Phenyldi(pyren- 1 - JP4876333

yl)phosphine oxide

Referred IUPAC name Structure Reference to as:

MX 6 2,4,7,9-tetraphenyl-l , 10- EP1786050

phenanthroline

MX 8 2,9-di(biphenyl-4-yl)-4,7- EP1786050

diphenyl-1,10- phenanthroline

MX 9 4,7-diphenyl-2,9-di-p-tolyl- EP1786050

1 , 10-phenanthroline

H3C CH3

The electron transport layer may comprises a lithium halide or a lithium organic complex.

Suitable organic ligands to form a lithium organic complex that can be used for the electron transport layer are disclosed, for example in US 2014/0048792 and

Kathirgamanathan, Poopathy; Arkley, Vincent; Surendrakumar, Sivagnanasundram; Chan, Yun F.; Ravichandran, Seenivasagam; Ganeshamurugan, Subramaniam; Kumaraverl, Muttulingam; Antipan-Lara, Juan; Paramaswara, Gnanamolly; Reddy, Vanga R., Digest of Technical Papers - Society for Information Display International Symposium (2010), 41(Bk. 1), 465-468.

Table 5 Lithium organic complex that can be suitable used for the ETL-layer

The organic ligand of the lithium organic complex of the electron transport layer may be selected from the group comprising a quinolate, a borate, a phenolate, a pyridinolate or a Schiff base ligand, or Table 5;

- preferably the lithium quinolate complex has the formula I:

wherein

Al to A6 are same or independently selected from CH, CR, N, O;

R is same or independently selected from hydrogen, halogen, alkyl or aryl or heteroaryl with 1 to 20 carbon atoms; and more preferred Al to A6 are CH;

- preferably the borate based organic ligand is a tetra(lH-pyrazol-l-yl)borate;

- preferably the phenolate is a 2-(pyridin-2-yl)phenolate or a 2- (diphenylphosphoryl)phenolate;

- preferably the lithium Schiff base has the structure 100, 101 , 102 or 103 :

The lithium halide of the electron transport layer may be selected from the group comprising a LiF, LiCl, LiBr or LiJ, and preferably LiF.

The ETL may be formed on the EML by vacuum deposition, spin coating, slot-die coating, printing, casting, or the like. When the ETL is formed by vacuum deposition or spin coating, the deposition and coating conditions may be similar to those for formation of the HIL 130. However, the deposition and coating conditions may vary, according to a compound that is used to form the ETL.

Substrate The substrate may be any substrate that is commonly used in manufacturing of organic light-emitting diodes. If light is emitted through the substrate, the substrate may be a transparent material, for example a glass substrate or a transparent plastic substrate, having excellent mechanical strength, thermal stability, transparency, surface smoothness, ease of handling, and waterproofness. If light is emitted through the top surface, the substrate may be a transparent or non-transparent material, for example a glass substrate, a plastic substrate, a metal substrate or a silicon substrate.

Anode electrode

The anode electrode may be formed by depositing or sputtering a compound that is used to form the anode electrode. The compound used to form the anode electrode may be a high work-function compound, so as to facilitate hole injection. The anode material may also be selected from a low work function material (i.e. Aluminum). The anode electrode may be a transparent or reflective electrode. Transparent conductive compounds, such as indium tin oxide (ITO), indium zinc oxide (IZO), tin-dioxide (Sn0₂), and zinc oxide (ZnO), may be used to form the anode electrode 120. The anode electrode 120 may also be formed using magnesium (Mg), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium- indium (Mg-In), magnesium-silver (Mg-Ag), silver (Ag), gold (Au), or the like.

The anode electrode may be formed from a high conductivity metal, for example copper (Cu) or silver (Ag).

The HIL may 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 may vary according to the compound that is 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 equals 133.322 Pa), and a deposition rate of 0.1 to 10 nm/sec.

HIL - forming conditions

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

HTL - forming conditions

The hole transport layer (HTL) may 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 those for the formation of the HIL. However, the conditions for the vacuum or solution deposition may vary, according to the compound that is used to form the HTL.

Emission layer (EML)

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

The emission layer (EML) may be formed of a combination of a host and a dopant. Example of the host are Alq3, 4,4'-N,N'- dicarbazole-biphenyl (CBP), poly(n-vinylcarbazole) (PVK), 9, 10-di(naphthalene-2-yl)anthracenee (ADN), 4,4',4"-Tris(carbazol-9-yl)-triphenylamine (TCTA), l,3,5-tris(N-phenylbenzimidazole-2-yl)benzene (TPBI), 3-tert-butyl-9,10-di- 2-naphthylanthracenee (TBADN), distyrylarylene (DSA), Bis(2-(2-hydroxyphenyl)benzo- thiazolate)zinc (Zn(BTZ) 2), E3 below, AND, Compound 1 below, and Compound 2 below.

E3

AND

Compound 2

The dopant may be a phosphorescent or fluorescent emitter. Phosphorescent emitters are preferred due to their higher efficiency

Examples of a red dopant are PtOEP, Ir(piq) 3, and Btp 21r(acac), but are not limited thereto. These compounds are phosphorescent emitters, however, fluorescent red dopants could also be used.

PtOEP lr i€i ¾ Bt 2ir acac) Examples of a phosphorescent green dopant are Ir(ppy) 3 (ppy = phenylpyridine), Ir(ppy) 2(acac), Ir(mpyp) 3 are shown below. Compound 3 is an example of a fluorescent green emitter and the structure is shown below.

Compound 3

Examples of a phosphorescent blue dopant are F₂Irpic, (F₂ppy) ₂Ir(tmd) and Ir(dfppz) 3, ter-fluorene, the structures are shown below. 4.4'-bis(4-diphenyl amiostyryl)biphenyl (DPAVBi), 2,5,8,11-tetra-tert-butyl perylene (TBPe), and Compound 4 below are examples of fluorescent blue dopants.

F₂Irpic (F₂ppy) ₂Ir(tmd) Ir(dfppz) 3

Compound 4

The amount of the dopant may be in the range of about 0.01 to about 50 parts by weight, based on 100 parts by weight of the host. The EML may have a thickness of about 10 nm to about 100 nm, for example, about 20 nm to about 60 nm. When the thickness of the EML is within this range, the EML may have excellent light emission, without a substantial increase in driving voltage.

Hole blocking layer (HBL)

When the EML comprises a phosphorescent dopant, a hole blocking layer (HBL) may be formed on the EML, by using vacuum deposition, spin coating, slot-die coating, printing, casting, LB deposition, or the like, in order to prevent the diffusion of triplet excitons or holes into the ETL.

When the HBL is formed using vacuum deposition or spin coating, the conditions for deposition and coating may be similar to those for the formation of the HIL. However, the conditions for deposition and coating may vary, according to the compound that is used to form the HBL. Any compound that is commonly used to form a HBL may be used. Examples of compounds for forming the HBL include an oxadiazole derivative, a triazole derivative, and a phenanthroline derivative. The HBL may have a thickness of about 5 nm to about 100 nm, for example, about 10 nm to about 30 nm. When the thickness of the HBL is within this range, the HBL may have excellent hole-blocking properties, without a substantial increase in driving voltage.

Electron injection layer (EIL)

The optional EIL, which may facilitates injection of electrons from the cathode, may be formed on the ETL, preferably directly on the electron transport layer. Examples of materials for forming the EIL include LiF, NaCl, CsF, Li20, BaO, Ca, Ba, Yb, Mg which are known in the art. Deposition and coating conditions for forming the EIL are similar to those for formation of the HIL, although the deposition and coating conditions may vary, according to a material that is used to form the EIL.

The thickness of the EIL may be in the range of about 0.1 nm to 10 nm, for example, in the range of 0.5 nm to 9 nm. When the thickness of the EIL is within this range, the EIL may have satisfactory electron-injecting properties, without a substantial increase in driving voltage.

Cathode electrode

The cathode electrode is formed on the EIL if present. The cathode electrode may be a cathode, which is an electron-injecting electrode. The cathode electrode may be formed of a metal, an alloy, an electrically conductive compound, or a mixture thereof. The cathode electrode may have a low work function. For example, the cathode electrode may be formed 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. In addition, the cathode electrode may be formed of a transparent conductive material, such as ITO or IZO.

The thickness of the cathode electrode may be in the range of about 5 nm to 1000 nm, for example, in the range of 10 nm to 100 nm. When the cathode electrode is in the range of 5 nm to 50 nm, the electrode will transparent even if a metal or metal alloy is used.

Since the layers of the ETL have similar or identical energy levels, the injection and transport of the electrons may be controlled, and the holes may be efficiently blocked. Thus, the OLED may have long lifetime.

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

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

According to another aspect of the present invention, there is provided an organic light-emitting diode (OLED) comprising: a substrate; a anode electrode formed on the substrate; a hole injection layer comprising a charge neutral metal amide according to the invention, a hole transport layer, an emission layer, hole blocking layer, electron transport layer, and a cathode electrode.

According to another aspect of the present invention, there is provided an organic light-emitting diode (OLED) comprising: a substrate; a anode electrode formed on the substrate; a hole injection layer comprising a charge neutral metal amide according to the invention, a hole transport layer, an emission layer, hole blocking layer, electron transport layer, an electron injection layer, and a cathode electrode.

According to another aspect, there is provided an organic light-emitting diode (OLED) comprising: at least one layer selected from the group consisting of a hole injection layer, a hole transport layer, an emission layer, a hole blocking layer, an electron transport layer, exactly in that order between the anode electrode and the cathode electrode.

According to various embodiments of the present invention, there is provided an organic light-emitting diode (OLED) further comprising an electron injection layer formed between the electron transport layer and the cathode electrode.

According to various embodiments of the OLED of the present invention, the OLED may not comprises an electron injection layer.

According to various embodiments of the OLED of the present invention, the OLED may not comprises an electron transport layer.

According to various embodiments of the OLED of the present invention, the OLED may not comprises an electron transport layer and an electron injection layer.

According to another aspect of the present invention, there is provided a method of manufacturing an organic light-emitting diode (OLED), the method using: - at least one deposition source, preferably two deposition sources and more preferred at least three deposition sources; and/or

- deposition via vacuum thermal evaporation; and/or

- deposition via solution processing, preferably the processing is selected from spin-coating, printing, casting and/or slot-die coating.

Method of manufacture

According to various embodiments of the present invention, the method may further include forming on the anode electrode an hole injection layer, an hole transport layer, an emission layer and a cathode electrode, exactly in that order.

According to various embodiments of the present invention, the method may further include forming on the anode electrode an hole injection layer, an hole transport layer, an emission layer, an electron transport layer, and a cathode electrode, exactly in that order.

According to various embodiments of the present invention, the method may further include forming on the anode electrode an hole injection layer, an hole transport layer, hole blocking layer, an emission layer, an electron transport layer, and a cathode electrode, exactly in that order.

According to various embodiments of the present invention, the method may further include the steps for forming an organic light-emitting diode (OLED), wherein

- on a substrate a anode electrode is formed,

- on the anode electrode an hole injection layer is formed,

- on the hole injection layer an hole transport layer is formed,

- optional on the hole transport layer a hole blocking layer is formed,

- than an emission layer is formed thereon,

- on the emission layer optional an electron transport layer is formed, preferably an electron transport layer stack,

- finally a cathode electrode is formed thereon,

- optional an electron injection layer is formed between the electron transport layer and the cathode electrode.

The method of manufacturing the OLED may comprise the steps:

- the hole injection layer according to the invention is deposited on an anode layer, an optional hole transport layer is deposited on the hole injection layer, an emission layer is deposited on the hole transport layer, an optional hole blocking layer is deposited on the emission layer, an optional electron transport layer is deposited on the hole blocking layer, an optional electron injection layer is deposited on the electron transport layer and a cathode is deposited on the electron injection layer, wherein the layers are arranged in that order and sandwiched between the anode and the cathode.

However, according to one aspect the layers are deposited the other way around, starting with the cathode, and sandwiched between the cathode and the anode.

For example, starting with the cathode layer, optional electron injection layer, electron transport layer, optional hole blocking layer, emission layer, hole transport layer, hole injection layer, anode electrode, exactly in this order.

The anode electrode and/or the cathode electrode can be deposit on a substrate.

Preferably the anode is deposit on a substrate.

Additional aspects and/or advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.

BRIEF DESCRIPTION OF THE DRAWINGS

These and/or other aspects and advantages of the present invention will become apparent and more readily appreciated from the following description of the exemplary embodiments, taken in conjunction with the accompanying drawings, of which:

FIG. 1 is a schematic sectional view of an organic light-emitting diode (OLED), according to an exemplary embodiment of the present invention;

FIG. 2 is a schematic sectional view of an OLED, according to an exemplary embodiment of the present invention.

FIG. 3 is a schematic sectional view of an OLED, according to an exemplary embodiment of the present invention.

FIG. 4 is an overview of metal amides based on general Formula la that can be used according to the invention.

Fig. 5 is an overview of metal amides that can be used according to the invention

1 2 1 2

with specific A and A , wherein A and A are S0₂.

Fig. 6 is an overview of metal amides that can be used according to the invention

1 2 1 2 8

with specific A and A , wherein A and A are POR . Fig. 7 is an overview of metal amides that can be used according to the invention

1 2 1 2

with specific A and A , wherein A and A are CO.

Fig. 8 is an overview of metal amides that can be used according to the invention with specific A 1 and A2 , wherein A 1 and A2 are selected different, wherein A¹ is S0₂ and A² is POR⁸

DETAILED DESCRIPTION

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

Herein, when a first element is referred to as being formed or disposed "on" a second element, the first element can be disposed directly on the second element, or one or more other elements may be disposed there between. When a first element is referred to as being formed or disposed "directly on" a second element, no other elements are disposed there between.

FIG. 1 is a schematic sectional view of an organic light-emitting diode (OLED) 100, according to an exemplary embodiment of the present invention. The OLED 100 includes a substrate 110. On the substrate 110 an anode 120 is disposed. On the anode 120 a hole injection layer 130 containing or consisting of a metal amide compound according to the invention is disposed and thereon a hole transport layer 140. Onto the hole transport layer 140 an emission layer 150 and an cathode electrode 190, exactly in this order, are disposed.

FIG. 2 is a schematic sectional view of an organic light-emitting diode (OLED) 100, according to an exemplary embodiment of the present invention. The OLED 100 includes a substrate 110, a first electrode 120, a hole injection layer (HIL) 130, a hole transport layer (HTL) 140, an emission layer (EML) 150, an electron transport layer (ETL) 161. The electron transport layer (ETL) 161 is formed directly on the EML 150. Onto the electron transport layer (ETL) 161 a cathode electrode 190 is disposed.

Instead of a single electron transport layer 161, optional an electron transport layer stack (ETL) can be used. Fig. 3 is a schematic sectional view of an OLED 100, according to another exemplary embodiment of the present invention. Fig. 3 differs from Fig. 2 in that the OLED 100 of Fig. 3 comprises a hole blocking layer (HBL) 155 and an electron injection layer (E1L) 180.

Referring to Fig. 3 the OLED 100 includes a substrate 110, an anode electrode 120, a hole injection layer (HIL) 130, a hole transport layer (HTL) 140, an emission layer (EML) 150, a hole blocking layer (HBL) 155, an electron transport layer (ETL) 161, an electron injection layer (EIL) 180 and a cathode electrode 190. The layers are disposed exactly in the order as mentioned before.

In the description above the method of manufacture an OLED of the present invention is started with a substrate 110 onto which an anode electrode 120 is formed, on the anode electrode 120, an hole injection layer 130, hole transport layer 140, an emission layer 150, optional a hole blocking layer 155, optional at least one electron transport layer 161, optional at least one electron injection layer 180, and a cathode electrode 190 are formed, exactly in that order or exactly the other way around.

While not shown in Fig. 1, Fig. 2 and Fig. 3, a sealing layer may further be formed on the cathode electrodes 190, in order to seal the OLEDs 100. In addition, various other modifications may be applied thereto.

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

Examples

General procedure

For bottom emission devices, a 15Ω /cm glass substrate (available from Corning Co.) with 100 nm ITO was cut to a size of 50 mm x 50 mm x 0.7 mm, ultrasonically washed with isopropyl alcohol for 5 minutes and then with pure water for 5 minutes, and washed again with UV ozone for 30 minutes, to prepare a first electrode. For top emission devices, the anode electrode was formed from 100 nm silver on glass which was prepared by the same methods as described above.

Then, the hole injection layer, triaryl amine compound andcharge neutral metal amide compound according to the examples of Table 6 was vacuum co-deposited on the ITO electrode, to form a HIL having a thickness according to the examples 1 to 22 and comparative examples 1 to 5 of tables 6, 7 and 8. Then the corresponding hole injection layer according to the examples 1 to 22 and comparative examples 1 to 5 of tables 6, 7 and 8 was vacuum deposited on the HIL, to form a HTL having a thickness as mentioned in tables 6, 7 and 8, respectively.

The wt.-% of the HIL-compound/s and HTL-compound according to the examples 1 to 22 and comparative examples 1 to 5 can be taken from Tables 6, 7 and 8 below, whereby the wt.-% amount of the HIL-compound/s is 100 wt.-% based on the total weight amount of the HIL-layer, and the wt.-% amount of the HTL-compound/s is 100 wt.-% based on the total weight amount of the HTL-layer, if no not indicated otherwise the wt.-% of the components are indicated in Tables 6, 7 and 8, respectively. That means that the HIL according to examples 1 to 22 consist of the triarylamine compound and metal amide compound according to the invention. However, the hole injection layer may comprises traces of the compound of the hole transport layer, due to the process of manufacture.

97 wt.-% of ABH113 (Sun Fine Chemicals) as a host and 3 wt.-% of NUBD370 (Sun Fine Chemicals) as a dopant were deposited on the HTL, to form a blue-emitting EML with a thickness of 20 nm.

Then the ETL-layer of matrix compound of 50 wt.-% MX 2 and 50 wt.-% LiQ (50 wt.-% : 50 wt.-%) having a thickness of 36 nm is formed by deposing the matrix compound from a first deposition source and the lithium organic complex or lithium halide from a second deposition source directly on the EML.

For the comparative examples 1 to 5 and examples 1 to 22 only one electron transport layer is formed.

The cathode was evaporated at ultra-high vacuum of 10^"7 bar. Therefore, a thermal single co -evaporation of one or several metals was performed with a rate of 0, 1 to 10 nm/s (0,01 to 1 A/s ) in order to generate a homogeneous cathode with a thickness of 5 to 1000 nm. For top emission devices, the cathode electrode was formed from 13 nm magnesium (90 vol.- %)-silver (10 vol.-%) alloy. For bottom emission devices, the cathode electrode was formed from 100 nm aluminum.

The OLED stack is protected from ambient conditions by encapsulation of the device with a glass slide. Thereby, a cavity is formed, which includes a getter material for further protection. To assess the performance of the inventive examples compared to the prior art, the current efficiency is measured under ambient conditions (20°C). Current voltage

measurements are performed using a Keithley 2400 sourcemeter, and recorded in V. At 10 mA/cm² for bottom emission and 15 niA/cm² for top emission devices, a calibrated spectrometer CAS 140 from Instrument Systems is used for measurement of CIE coordinates and brightness in Candela. Lifetime LT of the device is measured at ambient conditions (20°C) and 15 mA/cm², using a Keithley 2400 sourcemeter, and recorded in hours. The brightness of the device is measured using a calibrated photo diode. The lifetime LT is defined as the time till the brightness of the device is reduced to 97 % of its initial value.

In bottom emission devices, the emission is predominately Lambertian and quantified in percent external quantum efficiency (EQE). To determine the efficiency EQE in % the light output of the device is measured using a calibrated photodiode at 10 mA/cm .

In top emission devices, the emission is forward directed, non-Lambertian and also highly dependent on the mirco-cavity. Therefore, the efficiency EQE will be higher compared to bottom emission devices. To determine the efficiency EQE in % the light output of the device is measured using a calibrated photodiode at 15 mA/cm .

Technical Effect of the invention

Effect of the layer thickness of the HIL on device performance without cavity control

In order to test the performance of very thick hole injection layers (HIL), bottom emission OLED-devices are fabricated with a HIL thickness ranging from 100 nm to 450 nm. The HTL thickness is given in Table 6. The cavity, and thereby light out coupling, varies depending on HIL thickness, therefore no data are provided on efficiency EQE. In Table 6 the effect of the HIL thickness without cavity control is shown. As can be seen in Example 1 to 8, only a comparatively small increase in voltage is observed even for very thick layers.

Table 6

Effect of HIL thickness on device performance without cavity control HIL HIL dopant HIL dopant HIL HTL HTL U compound concentration thickness thickness [V]

[wt.-%] [nm] [nm]

Example T-3 Li(TFSI) 2 100 T-3 30 4.7 1

Example T-3 Li(TFSI) 2 150 T-3 30 4.8 2

Example T-3 Li(TFSI) 2 200 T-3 30 4.9 3

Example T-3 Li(TFSI) 2 250 T-3 30 5 4

Example T-3 Li(TFSI) 2 300 T-3 30 5 5

Example T-3 Li(TFSI) 2 350 T-3 30 5.1 6

Example T-3 Li(TFSI) 2 400 T-3 30 5.2 7

Example T-3 Li(TFSI) 2 450 T-3 30 5.3 8

Effect of the layer thickness of the HIL on device performance at constant cavity

In Table 7 is shown the effect of the HIL and HTL thickness on performance of bottom emission devices. The thickness of the layers is selected in such a way that the sum of the thickness of HIL and HTL is kept constant at 130 nm. Thereby, the cavity does not change and light outcoupling and efficiency EQE are not impacted.

In comparative examples 1 and 2, the compound CNHAT (CAS 105598-27-4) has been used as a hole injection layer. In comparative example 1, a 10 nm layer of CNHAT was used. The efficiency EQE of 4.9 % was obtained at a voltage of 5.4 V. However, it is desired to provide a thick HIL which can smooth over non-uniformities in the anode layer. Therefore, a 100 nm layer of CNHAT was tested. The efficiency EQE of 4.2 % was achieved at 4.7 V. In summary, the efficiency EQE is reduced at thicknesses which would level out non- uniformities.

Example 9 to 15 shows the effect of increased thickness of the HIL comprising triarylamine T-3 and metal amide Li(TFSI) on efficiency, voltage and voltage stability over time. As can be seen in Table 7, the efficiency is always higher than the efficiency obtained for devices containing a CNHAT HIL layer. Additionally, the efficiency EQE remains constant for a HIL thickness ranging from 20 to 120 nm. The voltage for a 20 nm HIL layer is slightly higher compared to the comparative examples but surprisingly, the voltage decreases to 4.8 to 4.9 V for thicker layers (example 10 to 15). The voltage stability of all examples is at an acceptable level, for example less than 0.35V over 50 hours stability test at 15 mA/cm .

Table 7

Effect of HIL thickness on device performance at constant cavity

Effect of the metal cation on device performance

In Table 8, the effect of the metal cation in the metal amide on performance of bottom emission devices. For ease of comparison, a 100 nm HIL was used in all examples. In Examples 16 to 20 are compared triarylamine T-3 doped with Li(TFSI), Ag(TFSI),

Mg(TFSI)₂, Mn(TFSI)₂ and Li(cTFSI) (CAS 189217-62-7). The efficiency EQE is always higher than for comparative example 3 with CNHAT. Particularly high efficiency is obtained for a Ag(TFSI) doped HIL (example 18), while the lowest voltage and least voltage increase over time is achieved for Mg(TFSI) and Mn(TFSI)₂ (example 17 and 19, respectively).

Effect of the HOMO level of the hole transport layer on device performance

In order to achieve light output in different colours, a large variety of materials is available for application in the emission layer of OLEDs. Each emission layer composition comes with different demands on the HTL (for example band-gap or triplet level). Therefore, the HTL materials of different OLEDs may differ in their HOMO level. Consequently, a good hole injection layer enables hole injection in to a large variety of HTL materials.

In a second step, triarylamine compounds with deeper HOMO levels are tested in the hole injection layer and hole transport layer, see Table 8. For ease of comparison, a 100 nm HIL was used in all examples. HTLs which show low performance with the fluorescent blue EML used here may show unique performance with a different EML composition, for example phosphorescent blue or green EML, or for TADF (thermally activated delayed fluorescence) emitters. In the following examples, the hole injection performance is evaluated relative to CNHAT which is not suitable for injection into deep HOMO HTLs. In comparative examples 4 and 5, CNHAT HIL is used together with deeper HOMO triarylamine compound T-8 (HOMO -5.25 eV) and T-9 (HOMO -5.33 eV). Compared to comparative example 3, where a triarylamine compound with a HOMO closer to vacuum level was used (T-3, HOMO -5.10 eV), the efficiency is slightly increased, however the voltage is so high, that a commercial application cannot be considered. As the voltage is very high, the voltage stability over time has not been measured. In example 21 and 22, the effect of a HIL comprising deep HOMO triarylamines and metal amide Mg(TFSI) is evaluated. As can be seen in Table 8, the efficiency is significantly higher than for CNHAT HIL and the voltage is significantly lower (5.2 compared to 6.1 V and 6.2 compared to 8.6 V, respectively). In summary, a wide range of metal amides with various metal cations can be successfully used as HIL dopant.

Additionally, both open-chain and cyclic amide ligands show the desired effect (Li(TFSI) compared to Li(cTFSI), example 16 and 20, respectively). Furthermore, the invention is particularly useful for efficient hole injection into deeper HOMO HTLs which are required for OLEDs which rely on phosphorescent or TADF emitters, in particular green and blue emitters.

Table 8

Effect of metal cation and HOMO level of HTL on device performance

Another aspect is directed to an organic light-emitting diode (OLED) comprising more than one emission layer (EML) 150, for example two, three or four emission layers may be present. An organic light-emitting diode (OLED) comprising more than one emission layer is also described as a tandem OLED or stacked OLED.

Another aspect is directed to a device comprising at least one organic light-emitting diode (OLED). A device comprising organic light-emitting diodes (OLED) is for example a display or a lighting panel.

From the foregoing detailed description and examples, it will be evident that modifications and variations can be made to the compositions and methods of the invention without departing from the spirit and scope of the invention. Therefore, it is intended that all modifications made to the invention without departing from the spirit and scope of the invention come within the scope of the appended claims.

Claims

1. A hole injection layer for an OLED comprising a triarylamine compound (Vila) doped with a charge neutral metal amide compound (la), characterized in that the hole injection layer has a thickness of at least about > 20 nm to about < 1000 nm and the charge neutral metal amide compound has the Formula la:

(la),

wherein:

G = halide O, alkoxylate or amine of Formula Ila to He:

(Ila) (lib) (lie) (lid) (He);

m = 0, 1 , 2, 3 or 4;

Al, Ga, In, transition metal or rare earth metal;

L = charge neutral ligand which coordinates to the metal M, selected from the group comprising H₂0, C₂ to C₄o mono- or multi-dentate ethers and C₂ to C₄₀ thioethers, C₂ to C40 amines, C₂ to C40 phosphine, C₂ to C₂₀ alkyl nitrile or C₂ to C40 aryl nitrile, or a compound according to Formula (III);

R⁶

(HI),

p = 0, 1, 2 or 3;

A¹, A², A³ and A⁴ are independently selected from CO, S0₂ or POR ;

Q

n = 1, 2, 3, 4 or 5;

1 2

wherein B and B are bridged, then: 1 1 2 2

- M, N, A , B , B , A and N form a 7 to 10 member ring according to Formula lb;

1 1 2 2

- N, A , B , B and A form a 5 to 10 member ring according to Formula Ic,

1 1 2 2 1 2

N, A , B , B and A form a first 5 to 10 member ring and B and B form a second 5 to 20 member ring accordin to Formula Id:

2. The hole injection layer according to claim 1 ,

- wherein the triarylamine compound has the Formula Vila:

wherein:

1 2

R⁹ = aa ssiinnggllee cchheemmiiccaall bboonndd, a unsubstituted or substituted Ci to C₆ alkyl and unsubstituted or substituted Ci to C₅ heteroalkyl;

q = 0, 1 or 2; r = 0 or 1 ;

wherein

- wherein the charge neutral metal amide compound has the Formula la, lb, Ic or Id.

The hole injection layer according to claim 1 or 2, wherein:

- the hole injection layer comprises one triaryl amine compound; or

- the hole injection layer comprises one charge neutral metal amide compound; or

- the hole injection layer comprises one triaryl amine compound and one charge neutral metal amide compound.

The hole injection layer according to claims 1 to 3, wherein the charge neutral metal amide compound has the Formula la

(la), wherein:

1 2 8 1

A and A are same or independently selected from CO, POR and S0₂, preferably A

2 8

and A are selected same from CO, POR , S0₂; or

1 2 8

A and A are independently selected from CO, POR , S0₂, and

N, A 1 , B1 , A2 and B 2 form a 5 to 10 member ring.

The hole injection layer according to any of claims 1 to 4,

wherein for:

p = 1, 2 or 3, n = 1, 2, 3 or 4, m = 1, 2, 3 or 4 and N, A¹, B¹, B² and A² form member ring, the charge neutral metal amide compound has the Formula lie

1 2

10 member ring and B and B are bridged to form a second 5 to 20 member ring, the charge neutral metal amide com ound has the Formula lid:

p = l, 2 or 3, n = l, m = 1, 2, 3 or 4, and M, N, A¹, B¹, B², A² and N form a 7 to 10 member ring, the charge neutral metal amide compound has the Formula He:

1 1 2 2

(ilf); p = 1, 2 or 3, n = 1, 2, 3 or 4, m = 0 and N, A¹, B¹, B² and A² form a first 5 to 10

1 2

(ilg);

6. The hole injection layer according to any of claims 1 to 5,

1 2

wherein for A and A are S0₂:

(Ilia); p = 0, n = l,2,3or4,m = 1,2, 3 or 4, the charge neutral metal amide compound has the Formula Illb:

p=l,2or3,n=l,2,3or4,m = 0, the charge neutral metal amide compound has the Formula IIIc:

O O (iiid p = 1, 2 or 3, n = 1, 2, 3 or 4, m = 1, 2, 3 or 4 and N, S0₂, B¹, B² and S0₂ form a first 5

1 2

to 10 member ring, and B and B are bridged to form a second 5 to 20 member ring, the charge neutral metal amide compound has the Formula Hie:

(Illf);

- p = 1, 2 or 3, n = 1, 2, 3 or 4, m = 0 and N, S0₂, B 1 , B 2 and S0₂ form a 5 to 10 member ring, the charge neutral metal amide compound has the Formula Illg:

wherein for A 1 and A2 are POF £ p = l, 2 or 3, m = l, 2, 3 or 4 and n = 1, 2, 3 or 4, the charge neutral metal amide compound has the Formula IVa:

p = 0, m = 1, 2, 3 or 4 and n = 1, 2, 3 or 4, the charge neutral metal amide compound has the Formula IVb:

p = 1, 2 or 3, m = 0 and n = 1, 2, 3 or 4, the charge neutral metal amide compound has the Formula IVc:

- p = 1, 2 or 3, n = 1, 2, 3 or 4, m = 0 and N, POR⁸, B¹, B² and POR⁸ form a 5 to 10 member ring, the charge neutral metal amide compound has the Formula (IVe):

wherein for A 1 and A 2 are CO: p=l,2or3,m=l,2, 3 or 4 and n = 1, 2, 3 or 4, the charge neutral metal amide compound has the Formula Va:

p = 0,n = 1, 2, 3 or 4, m = 1,2, 3 or 4, the charge neutral metal amide compound has the Formula Vb:

p=l,2or3,n=l,2,3or4,m = 0, the charge neutral metal amide compound has the Formula Vc:

p = 1, 2 or 3, n = 1, 2, 3 or 4, m = 1, 2, 3 or 4 and N, CO, B¹, B² and CO form a 5 to 10 member ring, the charge neutral metal amide com ound has the Formula Vd:

1 2

10 member ring, and B and B are bridged to form a second 5 to 20 member ring, the charge neutral metal amide compound has the Formula Ve:

p = l,2or3,n= l,m= 1,2, 3 or 4 and M, N, CO, B¹, B², CO and N form a 7 to 10 member ring, the charge neutral metal amide compound has the Formula Vf:

p = 1, 2 or 3, n = 1, 2, 3 or 4, m = 0 andN, CO, B¹, B² and CO form a first 5 to 10 member ring, and B 1 and B 2 form a second 5 to 20 member ring, the charge neutral metal amide compo nd has the Formula Vh:

p= l,2or3,n = 1,2, 3 or4,m = 0 and M, N, CO, B¹, B², CO and N form a 7 to 10 member ring, the charge neutral metal amide compound has the Formula (Vi):

1 2

wherein for A is S0₂ and A i; - p = 1 , 2 or 3, m = 1 , 2, 3 or 4 and n = 1 , 2, 3 or 4, the charge neutral metal amide compound has the Formula Via:

7. The hole injection layer according to any of claims 1 to 6, wherein

B¹, B², B³ and B⁴ are independently selected from a substituted Ci to C₂o alkyl, substituted Ci to C₂₀ heteroalkyl, substituted C₆ to C₂₀ aryl, or substituted C₅ to C₂₀ heteroaryl;

wherein

the substituent is an electron withdrawing group selected from the group comprising a halide, nitrile, perhalogenated Ci to C₂₀ alkyl, perhalogenated C₆ to C₂₀ aryl, perhalogenated heteroaryl with 6 to 20 ring-forming atoms, preferably the electron withdrawing group is a fluoride, perfluroinated Ci to C₂₀ alkyl, perfluorinated C₆ to C₂o aryl, or perfluorinated heteroaryl with 5 to 20 ring-forming atoms.

8. The hole injection layer according to any of claims 1 to 7, wherein m = 0, 1 or 2.

9. The hole injection layer according to any of claims 1 to 8, wherein M is selected from Li(I), Na(I), K(I), Cs(I), Mg(II), Ca(II), Sr(II), Ba(II), Sc(III), Y(III), Ti(IV), V(III-V), Cr(III-VI), Mn(II), Mn(III), Fe(II), Fe(III), Co(II), Co(III), Ni(II), Cu(I), Cu(II), Zn(II), Ag(I), Au(I), Au(III), Al(III), Ga(III), In(III), Sn(II), Sn(IV), or Pb(II); preferably M is selected from Li (I), Mg (II), Mn (II) or Ag (I); and more preferred M is selected from Mg (II) and Li(I).

10. The hole injection layer according to any of claims 1 to 9, wherein the charge neutral metal amide compound has the Formula lb:

wherein

3 4 8 3

A and A are same or independently selected from CO, POR or S0₂, preferably A

4 8

and A are selected same from CO, POR or S0₂;

M, N, A¹, B¹, A² and B² form a 7 to 10 member ring.

11. The hole injection layer according to any of claims 1 to 10, wherein N, A 1 , B1 , A2 and B 2 form a first 5 to 10 member ring and B 1 and B 2 according to Formula Id:

(Id)

are bridged to form a second ring of a substituted or unsubstituted C₆ to C₂₀ aryl, or of a substituted or unsubstituted C₆ to C₂₀ heteroaryl ring.

12. The hole injection layer according to any of claims 1 to 11, wherein the charge neutral metal amide compound is selected from at least one of the fluorinated compounds according to Formula C 1 to C25 :

wherein

- Formula CI to C16, wherein p = 0, m = 0, n = 1, 2, 3 or 4 and A 1 and A 2 are S0₂:

117 (C14) (C15) (C16)

Formula C17 to C23, wherein n = 1, 2, 3 or 4, A 1 and A 2 are CO:

(CI 7) (CI 8)

(CI 9) (C20) (C21)

(C22) (C23)

- Formula C24 to C25, wherein n = 1 , 2, 3 or 4, A¹ and A² are POR⁸:

(C24) (C25).

The hole injection layer according to any of claims 1 to 12, wherein the charge neutral metal amide compound is selected from at least one fluorinated compound according to Formula Dl to D24:

1 2

wherein p = 0, m = 0, n = 1 , 2, 3 or 4 and A and A are S0₂:

(D5) (D6) (D7) (D8)

(D9) (D10) (Dl l)

(D18) (D19) (D20)

(D21) (D22) (D23)

14. The hole injection layer according to any of claims 1 to 13, wherein the charge neutral metal amide compound is selected from at least one fluorinated compound according to Formula Fl to F23:

wherein the charge neutral ligand L coordinates to the metal M:

(Fl) F2) (F3)

(F4) (F5) (F6)

(F10) (Fl l) (F12)

F15) (F16)

(F17),

wherein

R⁶ and R⁷ are independently selected from Ci to C20 alkyl, Ci to C20 heteroalkyl, C₆ to C20 aryl, heteroaryl with 5 to 20 ring- forming atoms, halogenated or perhalogenated Ci to C20 alkyl, halogenated or perhalogenated Ci to C20 heteroalkyl, halogenated or perhalogenated C₆ to C20 aryl, halogenated or perhalogenated heteroaryl with 5 to 20 ring-forming atoms, or at least one R⁶ and R⁷ are bridged and form a 5 to 20 member ring , or the two R⁶ and/or the two R⁷ are bridged and form a 5 to 40 member ring or form a 5 to 40 member ring comprising an unsubstituted or Ci to C12 substituted phenanthroline;

wherein the fluorinated compounds according to Formula F18 to F23 are preferred:

(F18) (F19) (F20)

(F21) (F22)

(F23).

The hole injection layer according to any of claims 1 to 14, wherein the charge neutral metal amide compound is selected from at least one fluorinated compound according to Formula F24 to F45 :

wherein a halide, O, alkoxylate or amine bonds to the metal M:

(F24) (F25) (F26)

(F27) (F28) (F29)

(F33) (F34) (F35), wherein

C₂o heteroalkyl, unsubstituted or Ci to C₁₂ substituted C₆ to C₂₀ aryl, unsubstituted or Ci to C₁₂ substituted heteroaryl with 5 to 20 ring- forming atoms, halogenated or perhalogenated Ci to C₂₀ alkyl, halogenated or perhalogenated Ci to C₂₀ heteroalkyl, halogenated or perhalogenated C₆ to C₂₀ aryl, halogenated or perhalogenated heteroaryl with 5 to 20 ring- forming atoms; or at least one R¹ and R⁴ and/or R² and R³ and/or R¹ and R⁵ are bridged and form a 5 to 20 member cyclic ring;

wherein the fluorinated compounds according to Formula F36 to F46 are preferred:

(F36) (F37) (F38)

(F39) (F40) (F41)

(F42) (F43) (F44)

16. The hole injection layer according to any of claims 1 to 15, wherein for the triarylamine compound having the Formula Vila:

1 2

17. The hole injection layer according to any of claims 1 to 16, wherein the triarylamine compound has the Formula Vllb to Vllk:

125

(viij) (Vllk).

18. The hole injection layer according to any of claims 1 to 17, wherein the hole injection layer has a layer thickness of at least about > 30 nm to about < 1000 nm, preferably of about > 40 nm to about < 500 nm, also preferred of about > 50 nm to about < 750 nm.

19. The hole injection layer according to any of claims 1 to 18, wherein the hole injection layer comprises:

- at least about > 1 wt.-% to about < 4 wt.-%, and more preferred about > 2 wt.-% to about < 3 wt.-%, of a charge neutral metal amide compound (la); and

- at least about < 99 wt.-% to about > 96 wt.-%, and more preferred about < 98 wt.-% to about > 97 wt.-%, of a triarylamine compound (Vila);

wherein the weight-% of the components are based on the total weight of the hole injection layer.

20. The hole injection layer according to any of claims 1 to 19, wherein the hole injection layer is free of a triarylamine compound of:

21. An OLED (100) according to claims 1 to 20, comprising:

- an anode (120), a hole injection layer (130) and an emission layer (150), wherein the hole injection layer is in direct contact with the anode and the emission layer is in direct contact with the hole injection layer; or

- an anode (120), a hole injection layer (130), a hole transport layer (140) and an emission layer (150), wherein the hole injection layer is in direct contact with the anode and the hole transport layer is in direct contact with the hole injection layer; and wherein the composition of the hole injection layer is different to the composition of the hole transport layer.

22. A method of manufacturing an OLED (100), wherein

- the hole injection layer (130) according to claims 1 to 20 is deposited on an anode layer (120), an optional hole transport layer (140) is deposited on the hole injection layer (130), an emission layer (150) is deposited on the hole transport layer (140), an optional hole blocking layer (155) is deposited on the emission layer (150), an optional electron transport layer (161) is deposited on the hole blocking layer (155), an optional electron injection layer (180) is deposited on the electron transport layer (161) and a cathode (190) is deposited on the electron injection layer (180), wherein the layers are arranged in that order and sandwiched between the anode (120) and the cathode (190); or

- the layers are deposited the other way around, starting with the cathode (190), and sandwiched between the cathode Π 90"» and the anode (120).