Organic light emitting diode and device comprising the same

TECHNICAL FIELD

The present invention relates to an organic light emitting diode and a device comprising the same.

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 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 HTL, the EML, and the ETL are thin films formed from organic and / or organometallic compounds.

When a voltage is applied to the anode and the cathode, holes injected from the anode electrode move to the EML, via the HTL, and electrons injected from the cathode electrode move to the EML, via the ETL. The holes and electrons recombine in the EML to 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.

A variety of organic electronic diodes comprising different electron transport materials are well known in the art. However, there is still a need to improve the performance of such devices, in particular to improve the performance of single-emission-layer top emission OLEDs, specifically with regard to efficiency and voltage.

It is, therefore, the object of the present invention to provide an organic light emitting diode overcoming drawbacks of the prior art, in particular a single-emission-layer top emission OLED with improved performance, that with improved efficiency and improved voltage.

DISCLOSURE

The object is achieved by an organic light emitting diode comprising a non-transparent substrate, an anode, a cathode, an emission layer, an electron injection layer and an electron transport layer stack; wherein the electron transport layer stack is arranged between the emission layer and the electron injection layer; the electron transport layer stack comprises a first electron transport layer and a second electron transport layer; the first electron transport layer comprises a compound of Formula (I)

- a and b are independently 1 or 2; - c is independently o or 1;

- Ar ¹ is independently selected from C ₆ to C _6o aryl or C ₂ to C ₄₂ heteroaryl,

- wherein each Ar ¹ may be substituted with one or two substituents independently selected from the group consisting of C ₆ to C ₁₂ aryl, C ₃ to C ₁₁ heteroaryl, and C ₁ to C ₆ alkyl, D, C ₁ to C ₆ alkoxy, C ₃ to C ₆ branched alkyl, C ₃ to C ₆ cyclic alkyl, C ₃ to C ₆ branched alkoxy, C ₃ to C ₆ cyclic alkoxy, partially or perfluorinated C ₁ to C ₆ alkyl, partially or perfluorinated C ₁ to C ₆ alkoxy, partially or perdeuterated C ₁ to C ₆ alkyl, partially or perdeuterated C ₁ to C ₆ alkoxy, halogen, CN or PY(R ¹⁰ ) ₂ , wherein Y is selected from O, S or Se, preferably O and R ¹⁰ is independently selected from C ₆ to C ₁₂ aryl, C ₃ to C ₁₂ heteroaryl, C ₁ to C ₆ alkyl, C ₁ to C ₆ alkoxy, partially or perfluorinated C ₁ to C ₆ alkyl, partially or perfluorinated C ₁ to C ₆ alkoxy, partially or perdeuterated C ₁ to C ₆ alkyl, partially or perdeuterated C ₁ to C ₆ alkoxy; wherein each C ₆ to C ₁₂ aryl substituent on Ar ¹ and each C ₃ to C ₁₁ heteroaryl substituent on Ar ¹ may be substituted with C ₁ to C ₄ alkyl or halogen;

A is independently selected from C ₆ to C ₃₀ aryl,

- wherein each A may be substituted with one or two substituents independently selected from the group consisting of C ₆ to C ₁₂ aryl and C ₁ to C ₆ alkyl, D, C ₁ to C ₆ alkoxy, C ₃ to C ₆ branched alkyl, C ₃ to C ₆ cyclic alkyl, C ₃ to C ₆ branched alkoxy, C ₃ to C ₆ cyclic alkoxy, partially or perfluorinated C ₁ to C ₆ alkyl, partially or perfluorinated C ₁ to C ₆ alkoxy, partially or perdeuterated C ₁ to C ₆ alkyl, partially or perdeuterated C ₁ to C ₆ alkoxy, halogen, CN or PY(R ¹⁰ ) ₂ , wherein Y is selected from O, S or Se, preferably O, andR ¹⁰ is independently selected from C ₆ to C ₁₂ aryl, C ₃ to C ₁₂ heteroaryl, C ₁ to C ₆ alkyl, C ₁ to C ₆ alkoxy, partially or perfluorinated C ₁ to C ₆ alkyl, partially or perfluorinated C ₁ to C ₆ alkoxy, partially or perdeuterated C ₁ to C ₆ alkyl, partially or perdeuterated C ₁ to C ₆ alkoxy;

- wherein each C ₆ to C ₁₂ aryl substituent on A may be substituted with C ₁ to C ₄ alkyl or halogen;

- X is independently selected from the group consisting of C ₂ to C ₄₂ heteroaryl and C ₆ to C ₆₀ aryl,

- wherein each X may be substituted with one or two substituents independently selected from the group consisting of C ₆ to C ₁₂ aryl, C ₃ to C ₁₁ heteroaryl, and C ₁ to C ₆ alkyl, D, C ₁ to C ₆ alkoxy, C ₃ to C ₆ branched alkyl, C ₃ to C ₆ cyclic alkyl, C ₃ to C ₆ branched alkoxy, C ₃ to C ₆ cyclic alkoxy, partially or perfluorinated C ₁ to C ₆ alkyl, partially or perfluorinated C ₁ to C ₆ alkoxy, partially or perdeuterated C ₁ to C ₆ alkyl, partially or perdeuterated C ₁ to C ₆ alkoxy, halogen, CN or PY(R ¹⁰ ) ₂ , wherein Y is selected from O, S or Se, preferably O, and R ¹⁰ is independently selected from C ₆ to C _ut aryl, C ₃ to C ₁₂ heteroaryl, C ₁ to C ₆ alkyl, C ₁ to C ₆ alkoxy, partially or perfluorinated C ₁ to C ₆ alkyl, partially or perfluorinated C ₁ to C ₆ alkoxy, partially or perdeuterated C ₁ to C ₆ alkyl, partially or perdeuterated C ₁ to C ₆ alkoxy;

2 wherein each C ₆ to C ₁₂ aryl substituent on X and each C ₃ to C ₁₁ heteroaryl substituent on X may be substituted with C ₁ to C ₄ alkyl or halogen;

- the molecular dipole moment of the compound of formula (I) is > o D and < 4 D;

- the second electron transport layer comprises a compound of Formula (II)

- m and n are independently 1 or 2;

- k is independently o, 1 or 2;

Ar ² is independently selected from the group consisting of C ₂ to C ₄₂ heteroaryl and C ₆ to C ₆ o aryl,

- wherein each Ar ² may be substituted with one or two substituents independently selected from the group consisting of C ₆ to C ₁₂ aryl, C ₃ to C ₁₁ heteroaryl, and C ₁ to C ₆ alkyl, D, C ₁ to C ₆ alkoxy, C ₃ to C ₆ branched alkyl, C ₃ to C ₆ cyclic alkyl, C ₃ to C ₆ branched alkoxy, C ₃ to C ₆ cyclic alkoxy, partially or perfluorinated C ₁ to C ₆ alkyl, partially or perfluorinated C ₁ to C ₆ alkoxy, partially or perdeuterated C ₁ to C ₆ alkyl, partially or perdeuterated C ₁ to C ₆ alkoxy, halogen, CN or PY(R ¹⁰ ) ₂ , wherein Y is selected from O, S or Se, preferably O, and R ¹⁰ is independently selected from C ₆ to C ₁₂ aryl, C ₃ to C ₁₂ heteroaryl, C ₁ to C ₆ alkyl, C ₁ to C ₆ alkoxy, partially or perfluorinated C ₁ to C ₆ alkyl, partially or perfluorinated C ₁ to C ₆ alkoxy, partially or perdeuterated C, to C ₆ alkyl, partially or perdeuterated C ₁ to C ₆ alkoxy;

- wherein each C ₆ to C ₁₂ aryl substituent on Ar ² and each C ₃ to C ₁₁ heteroaryl substituent on Ar ² may be substituted with C ₁ to C ₄ alkyl or halogen;

- Z is independently selected from C ₆ to C ₃₀ aryl, wherein each Z may be substituted with one or two substituents independently selected from the group consisting of C ₆ to C ₁₂ aryl and C ₁ to C ₆ alkyl, D, C ₁ to C ₆ alkoxy, C ₃ to C ₆ branched alkyl, C ₃ to C ₆ cyclic alkyl, C ₃ to C ₆ branched alkoxy, C ₃ to C ₆ cyclic alkoxy, partially or perfluorinated C ₁ to C ₆ alkyl, partially or perfluorinated C ₁ to C ₆ alkoxy, partially or perdeuterated C ₁ to C ₆ alkyl, partially or perdeuterated C ₁ to C ₆ alkoxy, halogen, CN or PY(R ¹⁰ ) ₂ , wherein Y is selected from O, S or Se, preferably O, and R ¹⁰ is independently selected from C ₆ to C ₁₂ aryl, C ₃ to C ₁₂ heteroaryl, C ₁ to C ₆ alkyl, C, to C ₆ alkoxy, partially or perfluorinated C, to C ₆ alkyl, partially or perfluorinated C ₁ to C ₆ alkoxy, partially or perdeuterated C, to C ₆ alkyl, partially or perdeuterated C, to C ₆ alkoxy; wherein each C ₆ to C ₁₂ aryl substituent on Z may be substituted with C ₁ to C ₄ alkyl or halogen;

G is chosen so that the dipole moment of a compound G-phenyl is ≥ 1 D and < 7 D; and

3 the first electron transport layer and the second electron transport layer are free of an electrical dopant.

The object is further achieved by a device comprising the inventive organic light emitting diode, wherein the device is a display device or a lighting device.

First electron transport layer

The first electron transport layer comprises a compound of Formula (I)

(Ar ¹ -Ac)a-X _b (I).

The first electron transport layer may consist of the compound of Formula (I). Alternatively, the first electron transport layer may consist of a mixture of the compound of Formula (I) and one or more further compounds, provided that none of the further compounds is an electrical dopant. The first electron transport layer may comprise more than one compound of Formula (I). In particular, the first electron transport layer may consist of a mixture of the compound of Formula (I) and further compounds known in the art as electron transport matrix compounds. Exemplary further electron transport matrix compounds which maybe contained are disclosed below.

In the compound of Formula (I), the group “A” is spacer moiety connecting (if present, that is in case that c > 1) the group Ar ¹ and X. In case that the compound of Formula (I) comprises more than one groups (Ar'-A _c ), the groups may or may not independently comprise the spacer

A.

In the compound of Formula (I), a and b are independently l or 2. Alternatively, a and b may both be 1.

In the compound of Formula (I), c is independently o or 1.

Ar ¹ is independently selected from C ₆ to C _6o aryl or C ₂ to C ₄₂ heteroaryl, alternatively C ₆ to C ₅₄ aryl or C ₂ to C ₃₉ heteroaryl, alternatively C ₆ to C ₄₈ aryl or C ₂ to C ₃₆ heteroaryl, alternatively C ₆ to C ₄₂ aryl or C ₂ to C ₃₆ heteroaryl, alternatively C ₆ to C ₃₆ aryl or C ₂ to C ₃₀ heteroaryl, alternatively C ₆ to C _3o aryl or C ₂ to C ₂₄ heteroaryl.

Ar ¹ may be independently C ₆ to aryl, optionally C ₆ to C ₄₈ aryl, optionally C ₆ to C ₄₂ aryl, optionally C ₆ to C ₃₆ aryl, optionally C ₆ to C ₃₀ aryl, and optionally C ₆ to C ₂₄ aryl.

Ar ¹ may be independently C ₂ to C ₄₂ hetroaryl, optionally C ₂ to C ₄₀ hetroaryl, optionally C ₂ to C ₃₆ hetroaryl, optionally C ₂ to C ₃₀ hetroaryl, and optionally C ₂ to C ₂₄ hetroaryl.

In an embodiment Ar ¹ is different from X.

Ar ¹ may comprise a system of two or more anellated aromatic rings, preferably three or more anellated aromatic rings.

4 Ar ¹ may comprise at least one sp ³ -hypridized carbon atom.

Ar ¹ may comprise at least one carbon-carbon sp ² alkene bond which is not integrated into an aromatic ring structure.In an embodiment where Ar ¹ is independently selected from unsubstituted C ₂ to C ₄₂ heteroaryl, the heteroatoms are bound into the molecular structure of

Ar ¹ by single bonds.

Ar ¹ may be independently selected from the group consisting of phenyl, naphthyl, anthracenyl, fluoranthenyl, xanthenyl, spiro-xanthenyl, fluorenyl, spiro-fluorenyl, triphenylsilyl, tetraphenylsilyl, dibenzo-fiiranyl, di-dibenzofuranyl, pyrimidinyl, pyrazinyl, aryl-alkenyl or a group having the formula (Ila) wherein the asterisk symbol represents the binding position for binding the group of formula (Ha) to A; and

R ¹ to R5 are independently selected from the group consisting of H, C ₆ to C ₁₂ aryl and C ₃ to Cm, alternatively C ₄ to C ₅ heterorayl.

Ar ¹ may be independently selected from the group consisting of phenyl, anthracenyl, fluorenyl or the group of the formula (Ila) wherein R ¹ to R ⁵ are independently selected from H and phenyl.

Ar ¹ may be a group of Formula (Ha)

5 and at least two of R ¹ to R ⁵ are not H.

In the group of Formula (Ila), at least two of R ¹ to R ⁵ which are not H may be in ortho-position to each other. At least one of R ¹ to R ⁵ which is not H may be in ortho-position to the *-position. In this regard, two groups are in ortho position to each other if bound to adjacent carbon atoms of the benzene ring in Formula (Ila), respectively.

Ar ¹ may be selected independently from one of the following groups

6

wherein the asterisk symbol represents the binding position for binding the to A, respectively.

In case that Ar ¹ is substituted, each of the substituents may be independently selected from the group consisting of phenyl, naphtyl, biphenyl, pyridyl, picolinyl, lutidinyl, dibenzofuranyl, dibenzothiophene-yl, and benzothiophene-yl.

A maybe independently selected from substituted or unsubstituted C ₆ to C ₃₀ aryl, alternatively C ₆ to C ₂₄ aryl, alternatively C ₆ to C ₁₈ aryl.

A may be selected independently from the group consisting of phenylene, naphthylene, biphenylene and terphenylene which may be substituted or unsubstituted, respectively.

A may be selected independently from one of the following groups or combinations thereof wherein the binding positions for binding to Ar ¹ and X can be freely selected, preferably

7

In case that A is substituted, each substituent on A may be independently selected from the group consisting of phenyl and C ₁ to C ₄ alkyl.

X may be independently selected from the group consisting of C ₂ to C ₃₉ heteroaryl and C ₆ to C ₅₄ aryl, optionally C ₂ > to C ₃₆ heteroaryl and C ₆ to C ₄ e aryl, optionally C ₃ to C ₃₀ heteroaryl and C ₆ to C ₄₂ aryl, optionally C ₃ to C ₂₇ heteroaryl and C ₆ to C ₃₆ aryl, optionally C ₃ to C ₂₄ heteroaryl and C ₆ to C ₃₀ aryl, and optionally C ₃ to C ₂₁ heteroaryl and C ₆ to C ₂₄ aryl, wherein the respective group maybe substituted or unsubstituted.

X may be independently selected from the group consisting of C ₂ to C ₃₉ N-containing heteroaryl, C ₂ to C ₃₉ O-containing heteroaryl and C ₆ to C ₅₄ aryl, optionally C _z to C ₃₆ N- containing heteroaryl, C ₂ to C ₃₆ O-containing heteroaryl and C ₆ to C ₄₈ aryl, optionally C ₃ to C ₃₀ N-containing heteroaryl, C ₃ to C ₃₀ O-containing heteroaryl and C ₆ to C ₄₂ aryl, optionally C ₃ to C ₂₇ N-containing heteroaryl, C ₃ to C ₂₇ O-containing heteroaryl and C ₆ to C ₃₆ aryl, optionally C ₃ to C ₂₄ N-containing heteroaryl, C ₃ to C ₂₄ O-containing heteroaryl and C ₆ to C ₃₀ aryl, and optionally C ₃ to C ₂₁ N-containing heteroaryl, C ₃ to C ₂₁ O-containing heteroaryl and C ₆ to C ₂₄ aryl.

X may be independently selected from the group consisting of Q> to C ₃₉ N-containing heteroaryl and C ₆ to C ₅₄ aryl, optionally C ₂ to C ₃₆ N-containing heteroaryl, and C ₆ to C ₄₈ aryl, optionally C ₃ to C _3o N-containing heteroaryl and C ₆ to C ₄₂ aryl, optionally C ₃ to C ₂₇ N-containing heteroaryl and C ₆ to C ₃₆ aryl, optionally C ₃ to C ₂₄ N-containing heteroaryl and C ₆ to C ₃₀ aryl, and optionally C ₃ to C ₂₁ N-containing heteroaryl and C ₆ to C ₂₄ aryl. In this regard, it may be provided that a respective N-containing heteroaryl comprises one or more N-atoms as the only heteroatom(s).

X may be independently selected from the group consisting of triazinyl, 1,2-diazinyl, 1,3- diazinyl, 1,4-diazinyl, quinazolinyl, benzoquinazolinyl, benzimidazolyl, quinolinyl, benzoquinolinyl benzoacridinyl, dibenzoacridinyl, fluoranthenyl, anthracenyl, naphthyl, triphenylenyl, phenathrolinyl, and dinaphthofuranyl which may be substituted or unsubstituted, respectively.

X may be independently selected from the group consisting of triazinyl, 1,2-diazinyl, 1,3- diazinyl, 1,4-diazinyl, quinazolinyl, benzoquinazolinyl, benzoacridinyl, dibenzoacridinyl, fluoranthenyl, anthracenyl, naphthyl, triphenylenyl, phenathrolinyl, and dinaphthofuranyl which maybe substituted or unsubstituted, respectively.

8 X may be independently selected from the group consisting of triazinyl, 1,2-diazinyl, 1,3- diazinyl, 1,4-diazinyl, quinazolinyl, benzoquinazolinyl, benzoacridinyl, dibenzoacridinyl, fluoranthenyl which may be substituted or unsubstituted, respectively.

X may be selected independently from one of the following groups wherein the asterisk symbol represents the binding position for binding the group to A, respectively.

In case that X is substituted, each substituent on X may be independently selected from the group consisting of phenyl, naphthyl and biphenyl-yl. In case that X is substituted, each substituent on X may be independently selected from the group consisting of phenyl and biphenyl-yl.

In case that X is substituted, respective substituted X groups may be

9 wherein the asterisk symbol represents the binding position for binding the group to A, respectively.

It may be provided that the compound of Formula (I) does not contain a moiety P=0. It may be provided that the compound of Formula (I) does not contain P(-0)Aryl ₂ . It maybe provided that the compound of Formula (I) does not contain P(=0)Alkyl ₂ . It may be provided that the compound of Formula (I) does not contain P(=0)Ph ₂ . It may be provided that the compound of Formula (I) does not contain P(=0)(CH ₃ ) ₂ . It may be provided that the compound of Formula (I) does not contain R’P(=0)R” wherein R’ and R” are connected with each other to form a ring, that is, does not contain ring-phosphine oxide. It may be provided that the compound of Formula (I) does not contain R’P(=0)R” wherein R’ and R” are connected with each other to form a 7-membered ring.

It may be provided that the compound of Formula (I) does not contain two moieties P=0. It maybe provided that wherein the compound of Formula (I) does not contain two P(=0)Aryl ₂ . It may be provided that wherein the compound of Formula (I) does not contain two P(=0)Alkyl ₂ . It may be provided that wherein the compound of Formula (I) does not contain two P(-0)Ph ₂ . It may be provided that wherein the compound of Formula (I) does not contain two P(=0)(CH ₃ ) ₂ . It may be provided that wherein the compound of Formula (I) does not contain CN.

It may be provided that one or more of the following formulas are excluded from the scope of the Compound of Formula (I)

10

The compound of Formula (I) may comprise 6 to 14 aromatic or heteroaromatic rings, optionally 7 to 13 aromatic or heteroaromatic rings, optionally 7 to 12 aromatic or heteroaromatic rings, optionally 9 to 11 aromatic or heteroaromatic rings. In this regard, an aromatic, respectively heteroaromatic ring, is a single aromatic ring, for example a 6- membered aromatic ring such as phenyl, a 6 -member ed heteroaromatic ring, an example would be pyridyl, a 5-membered heteroaromatic ring an example would be pyrrolyl etc. In a system of condensed (hetero)aromatic rings, each ring is considered as a single ring in this regard. For example, naphthalene comprises two aromatic rings.

The molecular dipole moment, computed by the TURBOMOLE V6.5 program package using hybrid functional B3LYP and Gaussian 6-31G* basis set, of the compound of formula (I) may be > o D and ≤ 4 D; alternatively > o D and ≤ 3.5 D; alternatively > o D and ≤ 3.0 D; alternatively > o D and ≤ 2.5 D; alternatively ≥ O D and ≤ 2.0 D. In this regards, the dipole moment of a molecule containing N atoms is given by:

11 where qi and are the partial charge and position of atom i in the molecule. The dipole moment is determined by a semi-empirical molecular orbital method. The geometries of the molecular structures are optimized using the hybrid functional B3LYP with the 6-3 lG* basis set in the gas phase as implemented in the program package TURBOMOLE V6.5 (TURBOMOLE GmbH, Litzenhardtstrasse 19, 76135 Karlsruhe, Germany). If more than one conformation is viable, the conformation with the lowest total energy is selected to determine the bond lengths of the molecules.

In an embodiment the LUMO energy level of the compound of formula (I) in the absolute scale taking vacuum energy level as zero, computed by the TURBOMOLE V6.5 program package using hybrid functional B3LYP and Gaussian 6-31G* basis set, is in the range from -1.90 eV to -1.60 eV, preferably from -1.87 eV to -1.65 eV, preferably from -1.85 eV to -1.65 eV.

The compound of Formula (I) maybe selected from the compounds A-l to A-29 of the following Table 1.

Table 1:

13

14

15

16

In an embodiment the LUMO energy level of the compound of formula (I) in the absolute scale taking vacuum energy level as zero, computed by the TURBOMOLE V6.5 program package using hybrid functional B3LYP and Gaussian 6-31G* basis set, is in the range from -1.90 eV to -1.60 eV, preferably from -1.85 eV to -1.65 eV.

The first electron transport layer may be arranged between the emission layer and the second electron transport layer. The first electron transport layer may be arranged in direct contact with the emission layer. The first electron transport layer may be arranged “contacting sandwiched” between the emission layer and the second electron transport layer.

The first electron transport layer may have a thickness of < 50 nm, optionally between 1 and 30 nm, optionally between 1 and lonm, optionally between 1 and 5 nm.

Second electron transport layer

The second electron transport layer comprises a compound of Formula (II)

17

The second electron transport layer may consist of the compound of Formula (II). Alternatively, the second electron transport layer may consist of a mixture of the compound of Formula (II) and one or more further compounds, provided that none of the further compounds is an electrical dopant. The first electron transport layer may comprise more than one compound of Formula (II). The second electron transport layer may consist of a mixture of the compound of Formula (II) and further compounds known in the art as electron transport matrix compounds. Exemplary further electron transport matrix compounds which may be contained are disclosed below.

In the compound of Formula (II), the group “Z” is a spacer moiety connecting (if present, that is in case that k > 1) the groups Ar ² and G. In case that the compound of Formula (II) comprises more than one groups (Z _k -G) the groups may or may not independently comprise the spacer Z.

In Formula (II), m and n are independently 1 or 2. In Formula (II), m and n may be 1.

In Formula (II), k is independently o, 1 or 2. In Formula (Π), k may be independently 1 or 2.

Ar ² may be independently selected from the group consisting of C ₂ to C ₃₉ heteroaryl and C ₆ to C ₅₄ aryl, optionally C ₂ to C ₃₆ heteroaryl and C ₆ to C ₄₈ aryl, optionally C ₃ to C ₃₀ heteroaryl and C ₆ to C ₄₂ aryl, optionally C ₃ to C ₂₇ heteroaryl and C ₆ to C ₃₆ aryl, optionally C ₃ to C ₂₄ heteroaryl and C ₆ to C ₃ o aryl, and optionally C ₃ to C ₂₁ heteroaryl and C ₆ to C ₂₄ aryl.

Ar ² may be independently selected from the group consisting of C ₂ to C ₃₉ N-containing heteroaryl and C ₆ to aryl, optionally C ₂ to C ₃₆ N-containing heteroaryl and C ₆ to C ₄₈ aryl, optionally C ₃ to C ₃₀ N-containing heteroaryl and C _& to C ₄₂ aryl, optionally C ₃ to C ₂₇ N-containing heteroaryl and C ₆ to C ₃₆ aryl, optionally C ₃ to C ₂₄ N-containing heteroaryl and C ₆ to C ₃₀ aryl, and optionally C ₃ to C ₂₁ N-containing heteroaryl and C ₆ to C ₂₄ aryl. In this regard, it may be provided that a respective N-containing heteroaryl comprises one or more N-atoms as the only heteroatom(s).

Ar ² may comprise at least two annelated 5- or 6-membered rings.

Ar ² may be independently selected from the group consisting of pyiidinyl, triazinyl, 1,2- diazinyl, 1,3-diazinyl, 1,4-diazinyl, quinazolinyl, benzoquinazolinyl, benzimidazolyl, quinolinyl, benzoquinolinyl benzoacridinyl, dibenzoacridinyl, fluoranthenyl, anthracenyl, naphthyl, triphenylenyl, phenathrolinyl, and dinaphthofuranyl which may be substituted or unsubstituted, respectively.

Ar ² maybe independently selected from the group consisting of dibenzoacridinyl, 1,3-diazinyl, 1,4-diazinyl, anthracenyl, triazinyl, phenathrolinyl, triphenylenyl, pyridinyl, dinaphthofuranyl.

Ar ² may be selected independently from one of the following groups

18

wherein the asterisk symbol represents the binding position for binding the to Z, respectively.

In case that Ar ² is substituted, each substituent on Ar ² may be independently selected from the group consisting of phenyl, naphthyl, optionally β-naphthyl, pyridinyl and biphenyl-yl which maybe substituted or unsubstituted, respectively.

In case that Ar ² is substituted, each substituent on Ar ² may be independently selected from the group consisting of phenyl, pyridinyl and biphenyl-yl, optionally para-biphenyl-yl.

Z may be independently selected from C _& to C ₂₄ aryl, alternatively C ₆ to C ₁₈ aryl, alternatively C ₆ to C ₁₂ aryl, which may be substituted or unsubstituted.

Z may be selected from the group consisting of phenylene, naphthylene, phenylene- naphthylene, biphenylene and terphenylene which may be substituted or unsubstituted, respectively.

Z may be selected independently from one of the following groups

19

wherein the binding positions for binding to Ar ² and G can be freely selected.

In case that Z is substituted, each substituent on Z may be independently selected from the group consisting of phenyl and C ₁ to C ₄ alkyl.

G is chosen so that the dipole moment, computed by the TURBOMOLE V6.5 program package using hybrid functional B3LYP and Gaussian 6-31G* basis set, of a compound G-phenyl is ≥ 1 D and < 7 D. The unit for the dipole moment “Debye” is abbreviated with the symbol “D”. The inventors have found that it is advantageous if the compound of Formula (Π) comprises a group having a certain polarity, that is a specific dipole moment within the above range or the ranges mentioned below. It was further found that it is still advantageous that the compound of Formula (Π) comprises such a polar group (first polar group) if the compound of Formula (If) comprises, in addition, a further polar group (second polar group) which is suitable to balance the dipole moment of the first polar group in a way that the total dipole moment of the compound of Formula (H) is low, for example, in case that the compound is a symmetrical molecule comprising a first polar group and a second polar group which are the same, the dipole moment could be o Debye. Therefore, the compound of Formula (II) cannot be characterized be referring to the total dipole moment of the compound. As a consequence, reference is made instead to an artificial compound comprising the polar group “G” and an unpolar group “phenyl”. In this regards, the dipole moment | of a compound containing N atoms is given by: where q _t and \ are the partial charge and position of atom i in the molecule. The dipole moment is determined by a semi-empirical molecular orbital method. The geometries of the molecular structures are optimized using the hybrid functional B3LYP with the 6-31G* basis set in the gas phase as implemented in the program package TURBOMOLE V6.5 (TURBOMOLE GmbH, Litzenhardtstrasse 19, 76135 Karlsruhe, Germany). If more than one

20 conformation is viable, the conformation with the lowest total energy is selected to determine the bond lengths of the molecules. In this regard, the entire moiety G encompasses all possible substituents which maybe comprised.

G may be selected so that the dipole moment of a compound G-phenyl is > 1 D; optionally ≥ 2 D; optionally ≥ 2.5 D, optionally > 2.5 D, optionally ≥ 3 D, and optionally ≥ 3.5 D. G maybe chosen so that the dipole moment of a compound G-phenyl is ≤ 7 D, optionally ≤ 6.5 D, optionally ≤ 6 D, optionally ≤ 5.5 D, optionally ≤ 5 D. If more than one conformational isomer of the compound G-phenyl is viable then the average value of the dipole moments of the conformational isomers of G-phenyl is selected to be in this range. Conformational isomerism is a form of stereoisomerism in which the isomers can be interconverted just by rotations about formally single bonds.

By selecting the G such that the dipole moment of a compound G-phenyl lies in the above range it is provided that the electron injection from the adjacent, distinct electron injection layer (EIL) is improved and voltage of the OLED device is decreased and the cd/A efficiency of the OLED device is increased.

Exemplary compounds “G-phenyl” are listed in the following Table 2, wherein the moiety in the respective compound specifies the “phenyl” part in “G-phenyl”

Table 2:

21

22

23

24

25

26

27

28

29

G may be selected from the group consisting of dialkylphosphinyl, diarylphosphinyl, alkylarylphosphinyl, diheteroarylphosphinyl, arylheteroarylphosphinyl, cyclic diarylphosphinyl, phosphine oxide, aryl-containing phosphine oxide, heteroaryl-containing phosphine oxide, cyclic arylheteroarylphosphinyl, cyclic heteroaryl-containing phosphine

30 oxide, nitrile, benzonitrile, nicotinonitrile, amide, carbamide, and C ₂ to C ₄₂ heteroaryl; wherein G may include one or more substituents attached to the group, wherein the one or more substituents are selected from the group consisting of C ₆ to C ₁₈ aryl, C ₁ to C ₁₀ alkyl, C ₂ to C, ₄ heteroaryl. In this regard, “cyclic means that the “P=0” of the phosphinyl, respectively the phosphine oxide is part of a ring formed with further moieties of the group.

G may be selected from the group consisting of di-C ₁ to C _1o -alkylphosphinyl, di-C _& to Cm C ₁₀ arylphosphinyl, C ₁₀ -C ₄₂ diheteroarylphosphinyl, C ₇ -C ₄₂ arylheteroarylphosphinyl, C ₈ -C ₄₂ phosphine oxide, C ₈ -C ₄₂ aryl-containing phosphine oxide, C ₆ -C ₆ s heteroaryl-containing phosphine oxide, C ₁₂ -C ₆₃ cyclic arylphosphinyl, C ₇ -C ₄₂ cyclic arylheteroarylphosphinyl, C ₇ -C ₄₂ cyclic heteroaryl-containing phosphine oxide, and C ₂ to C ₃₉ heteroaryl, optionally C ₂ to C ₃₅ heteroaryl, optionally C ₂ to C ₃₂ heteroaryl, optionally C ₂ to C ₂₉ heteroaryl, optionally C ₂ to C ₂₅ heteroaryl; G may include one or more substituents attached to the group, wherein the one or more substituents are selected from the group consisting of C ₆ to C ₁₂ aryl, C ₁ to C ₆ alkyl, C ₂ to C ₁₁ heteroaryl.

G may be selected from the group consisting of di-C ₁ to C ₄ -alkylphosphinyl, di-C ₆ to C ₁₀ - arylphosphinyl, C ₁₀ diheteroarylphosphinyl, C ₇ -C ₂₅ arylheteroarylphosphinyl, C ₈ -C ₄₂ phosphine oxide, C ₈ -C ₂₄ aryl-containing phosphine oxide, C ₈ -C ₂₄ heteroaryl-containing phosphine oxide, C ₁₂ -C ₄₂ cydic arylphosphinyl, CyC ₂₄ cyclic arylheteroarylphosphinyl, Cy-C ₂₄ cyclic heteroaryl-containing phosphine oxide, and C ₂ to C ₂₅ heteroaryl; wherein the respective G may include one or more substituents attached to the group, wherein the one or more substituents are selected from the group consisting of C ₆ to C ₁₀ aryl, C ₄ to C ₄ alkyl, C ₂ to C ₅ heteroaryl.

G is selected from the group consisting of dialkylphosphinyl, diarylphosphinyl, alkylarylphosphinyl, diheteroarylphosphinyl, arylheteroarylphosphinyl, cyclic diarylphosphinyl, phosphine oxide, aryl-containing phosphine oxide, heteroaryl-containing phosphine oxide, cyclic arylheteroarylphosphinyl, cyclic heteroaryl-containing phosphine oxide, nitrile, benzonitrile, nicotinonitrile, amide-yl, carbamide-yl and C ₂ to C, ₇ heteroaryl; wherein the respective G may include one or more substituents attached to the group, wherein the one or more substituents are selected from the group consisting of phenyl, methyl, ethyl, and pyridyl.

G may be selected independently from the group consisting of dimethylphosphinyl, diphenylphosphinyl, nitrile, benzonitrile, nicotinonitrile, di-hydro-benzoimidazolone-yl, diphenyl-propane-yl, N,N -dimethylacetamid, amide, carbamide, imidazolyl, phenylbenzoimidazolyl, ethylbenzoimidazolyl phenylbenzoquinolinyl, phenylbenzoimidazoquinolinyl, pyridinyl, bipyiidinyl, picolinyl, lutidenyl, pyridazinyl, pyrimidinyl, pyrazinyl, triphenyl-pyrazinyl, benzoquinolinyl, phenanthrolinyl, phenylphenanthrolinyl, quinazolinyl, benzoxazolyl, benzimidazolyl, pyridinyl- imidazopyridinyl;

31

32

33

34

wherein the asterisk symbol represents the binding position.

G may be selected independently from the group consisting of dimethylphosphinyl, diphenylphosphinyl, 2-phenyl-iH-benzo[d]imidazolyl, 2-ethyl-1H-benzo[d]imidazolyl, 2- phenylbenzo [h] quinolinyl, pyridinyl, 2,2’-bipyridinyl, 5-phenylbenzo[4,5]imidazo [1,2- ajquinolinyl, 9-phenyl-i,io-phenanthrolinyl, 2-quinazolinyl, 4-quinazolinyl, 4-phenyl-2- quinazolinyl and (pyridine-2-yl)imidazo[l,5-a]pyridinyl;

35

36

37

38

39

wherein the asterisk symbol represents the binding position.

The compound of Formula (II) may be selected from the compounds B-1 to B-26 of the following Table 3.

Table 3:

40

41

42

43

44

In an embodiment the LUMO energy level of the compound of formula (II) in the absolute scale taking vacuum energy level as zero, computed by the TURBOMOLE V6.5 program package using hybrid functional B3LYP and Gaussian 6-31G* basis set, is in the range from - 2.30 eV to -1.20 eV, preferably from -2.10 eV to -1.28 eV.

In an embodiment the compound of formula (II) comprises one polar group “G”.

It may be provided that the compound of Formula (II) does not contain a moiety P=0. It may be provided that the compound of Formula (Π) does not contain P(-0)Aryl ₂ . It may be provided that the compound of Formula (II) does not contain P(=0)Alkyl ₂ . It maybe provided that the compound of Formula (II) does not contain P(=0)Ph ₂ . It may be provided that the compound of Formula (II) does not contain P(=0)(CH ₃ ) ₂ . It may be provided that the compound of Formula (II) does not contain R’P(=0)R” wherein R’ and R” are connected with each other to form a ring, that is, does not contain ring-phosphine oxide. It may be provided that the compound of Formula (II) does not contain R’P(=0)R” wherein R’ and R” are connected with each other to form a 7-membered ring.

45 It may be provided that the compound of Formula (II) does not contain two moieties P=0. It may be provided that wherein the compound of Formula (II) does not contain two P(=0)Aryl _a . It may be provided that wherein the compound of Formula (II) does not contain two P(=0)Alkyl ₂ . It may be provided that wherein the compound of Formula (Π) does not contain two P(= 0)Ph ₂ . It may be provided that wherein the compound of Formula (Π) does not contain two P(=0)(CH ₃ ) _a . It may be provided that wherein the compound of Formula (Π) does not contain CN.

It may be provided that one or more of the following formulas are excluded from the scope of the Compound of Formula (II)

46

It may be provided that if the second electron transport layer comprises a compound of Formula (II) and a compound (III), the following combinations of compounds (with reference to Tables 3 and 4) in the specified amounts are excluded:

The following organic light emitting diodes a) and b) comprising the following compounds

47

may be excluded: a) tandem OLED, wherein the electron transport layer is arranged adjacent to and in direct contact with a n-doped charge generation layer made of compound E and metallic lithium in weight ratio E:Li equal to 98:2, the composition of the electron transport layer is selected from B-24:C-3, B-10:C-3, B-24:C-5, B- 11 :C-5, B-24:C-6, B-11 ;C-6; and weight ratio of the first and the component in each of these compositions is 30:70; b) top emitting blue OLED having structure

48 wherein

49

H09 is a commercial blue emitter host and BD200 is a commercial blue emitter, both supplied by SFC, Korea.

The second electron transport layer may further comprise a compound (III), wherein the compound (III) comprises 8 to 13 aromatic or heteroaromatic rings, optionally 8 to 11 aromatic or heteroaromatic rings, optionally 9 to 11 aromatic or heteroaromatic rings, and optionally 9 aromatic or heteroaromatic rings, wherein one or more of the aromatic or heteroaromatic rings maybe substituted with C ₁ to C ₄ alkyl. In this regard, an aromatic, respectively heteroaromatic ring is a single aromatic ring, for example a 6-membered aromatic ring such as phenyl, a 6- membered heteroaromatic ring such as pyridyl, a 5-membered heteroaromatic ring such as pyrrolyl etc. In a system of condensed (hetero)aromatic rings, each ring is considered as a single ring in this regard. For example, naphthalene comprises two aromatic rings.

The compound (III) may comprise at least one heteroaromatic ring, optionally 1 to 5 heteroaromatic rings, optionally 1 to 4 heteroaromatic rings, optionally 1 to 3 heteroaromatic rings, and optionally 1 or 2 heteroaromatic rings.

The aromatic or heteroaromatic rings of the compound (III) may be 6-membered rings.

50 The heteroaromatic rings of the compound (ΠΙ) may be a N-containing heteroaromatic ring, optionally all of the heteroaromatic rings are N-containing heteroaromatic rings, optionally all of the heteroaromatic rings heteroaromatic rings contain N as the only type of heteroatom.

The compound (III) may comprise at least one 6-membered heteroaromatic ring containing one to three N-atoms in each heteroaromatic ring, optionally one to three 6-membered heteroaromatic rings containing one to three N-atoms in each heteroaromatic ring, respectively.

The at least one 6-membered heteroaromatic ring comprised in the compound (III) maybe an azine. The at least one 6-membered heteroaromatic ring comprised in the compound (III) may be triazine, diazine, pyrazine.

If the compound (III) comprises two or more heteroaromatic rings, the heteroaromatic rings may be separated from each other by at least one aromatic ring which is free of a heteroatom.

In an embodiment, the heteroatoms in the heteroaromatic rings of compound (III) are bound into the molecular structure of compound (III) by at least one double bond.

The molecular dipole moment, computed by the TURBOMOLE V6.5 program package using hybrid functional B3LYP and Gaussian 6-31G* basis set, of the compound (III) maybe > o D and ≤ 4 D; alternatively > 0.1 D and ≤ 3.9 D; alternatively > 0.2 D and ≤ 3.7 D; alternatively > 0.3 D and ≤ 3.5 D.

By choosing compound (III) according to these embodiments it is provided that the mobility of the second electron transport layer is further improved and voltage of the OLED device is decreased and the cd/A efficiency of the OLED device is increased.

In an embodiment the compound (III) is not a compound of formula (II). The compound of Formula (III) maybe selected from the compounds C-i to C-6 of the following Table 4.

Table 4:

51

52 In case that the second electron transport layer comprises both the compound of Formula (II) and compound (III), the weight ratio of Formula (II) to compound (ΠΙ) may be 1:99 to 99:1, alternatively 10:90 to 60:40, alternatively 20:80 to 50:50, alternatively 25:75 to 40:60, alternatively about 30:70.

In an embodiment the LUMO energy level of the compound of formula (ΠΙ) in the absolute scale taking vacuum energy level as zero, computed by the TURBOMOLE V6.5 program package using hybrid functional B3LYP and Gaussian 6-31G* basis set, is in the range from - 2.00 eV to -1.70 eV, preferably from -1.95 eVto -1.80 eV.

In an embodiment the compound (III) comprises one nitrogen-containing six-membered ring.

In another embodiment the compound (ΠΙ) comprises two nitrogen-containing six-membered rings.

In an embodiment the compound of formula (I) is not a compound of formula (II). In a further embodiment the compound of formula (II) is not a compound (III). In another embodiment the compound of formula (I) is not a compound (III) . In a further embodiment of the invention all three compounds, namely the compound of formula (I), the compound of formula (II) and compound (III), are different from each other in that they have different molecular structure formulas.

The second electron transport layer may be arranged between the first electron transport layer and the electron injection layer. The second electron transport layer may be arranged in direct contact with the first electron transport layer. The second electron transport layer may be arranged “contacting sandwiched” between the first electron transport layer and the electron injection layer.

The second electron transport layer may have a thickness of < 100 nm , optionally between 10 and 90 nm, optionally between 10 and 6onm, optionally between 10 and 50 nm.

Further possible characteristics of the OLED

In terms of the present disclosure, a layer stack is an arrangement of two or more distinct layers. The layers of the layer stack may be distinguished from each other by the chemical nature of the materials comprised in the respective layers, that is, may be made of different compounds. An electron transport layer stack in terms of the present disclosure comprises at least two different layers made of electron transport materials, respectively.

The compound of Formula (I) and the compound of Formula (II) may be different from each other. That is, that the compounds of Formula (I) and the compound of Formula (II) may differ from each other with respect to at least one structural aspect from each other, in particular may differ from each other by at least one atom and/or group.

53 The first electron transport layer and the second electron transport layer are free of an electrical dopant. In this regard, “free of’ means that respective compounds (electrical dopants) are only contained in the respective layers which cannot be avoided by standard purification methods and common technical means during preparation of the respective layer. In this regards, electrical dopants are in particular, but not limited thereto, electrical n- dopants. The electrical n-dopant may be selected from a metal, alternatively an alkali metal, a metal salt alternatively an alkaline earth metal salt and/or rare earth metal salt, or an organic alkali metal complex, alternatively an alkali metal complex, alternatively LiF, LiCl, LiBr, Lil, LiQ, a metal borate, or mixtures thereof. In particular, the first electron transport layer and the second electron transport layer may be free of an electrical n-dopant. The electrical n-dopant may be a metal salt comprising at least one metal cation and at least one anion. The metal cation of the metal salt may be selected from the group consisting of alkali metals, alkaline earth metals, and rare earth metals, alternatively from the group consisting of Li, Na, K, Rb, Cs, Mg, Ca, Sr, and Ba; alternatively from Li, Mg, Ca, and Sr. The anion of the metal salt may be selected from the group consisting of quinolinolate, phosphine oxide phenolate and borate.

In this regard, electrical n-dopants are in particular, but not limited thereto, an elemental metal, alternatively an electropositive metal selected from alkali metals, alkaline earth metals, rare earth metals and transition metals, transition metals; a metal salt, alternatively an alkali metal salt, alkaline earth metal salt and/or rare earth metal salt, or a metal complex, alternatively an alkali metal complex, alkaline earth metal complex, transition metal complex and/or rare earth metal complex. Examples of n-doping metal salts can be LiF, LiCl, LiBr, Lil, metal borates, metal quinolinolates or mixtures thereof. Further examples of electrical n- dopants are strong chemical reducing agents. This class of "redox" n-dopants may be genetically characterized by energy level of the highest occupied molecular orbital (HOMO) comparable with lowest unoccupied molecular orbital Energy Level of corresponding electron transport matrices, which is in usual OLED transport materials about -3.0 eV or less. It is to be understood that the term "about -3.0 eV or less" means less negative values than -3.0 eV, for example -2.8 eV, -2.5 eV, -2.3 eV, -2.1 eV or vales less negative than -2.0 eV.

Electrical n-dopants may be organic compounds as disclosed in EP1837926A1, WO07107306A1 or WO07107356A1.

It is provided that the electrical dopant is essentially non-emissive.

The first electron transport layer and the second electron transport layer may be in direct contact with each other.

The electron transport layer stack may consist of the first electron transport layer and the second electron transport layer.

The second electron transport layer may be in direct contact with the electron injection layer.

The electron injection layer may consist of a number of individual electron injection sublayers.

The electron injection layer may comprise a metal, alternatively an alkali metal, a metal salt alternatively an alkaline earth metal salt and/or rare earth metal salt, or an organic alkali metal

54 complex, alternatively an alkali metal complex, alternatively LiF, LiCI, LiBr, Lil, LiQ, a metal borate, or mixtures thereof.

The electron injection layer may consist of a metal, alternatively an alkali metal, a metal salt alternatively an alkaline earth metal salt and/or rare earth metal salt, or an organic alkali metal complex, alternatively an alkali metal complex, alternatively LiF, LiCl, LiBr, Lil, LiQ, a metal borate, or mixtures thereof.

It may be provided that the compound of Formula (II) is not comprised in the electron injection layer. It may be provided that the compound of Formula (I) is not comprised in the electron injection layer. It may be provided that compound (III) is not comprised in the electron injection layer.

The compound of Formula (I), the compound of Formula (II) and the compound (III) maybe different from each other, and/or may not be comprised in the electron injection layer, respectively.

Exemplary embodiments

According to one embodiment, there is provided an organic light emitting diode comprising a non-transparent substrate, an anode, a cathode, an emission layer, an electron injection layer and an electron transport layer stack; wherein the electron transport layer stack is arranged between the emission layer and the electron injection layer;

- the electron transport layer stack comprises a first electron transport layer and a second electron transport layer; the first electron transport layer comprises a compound of Formula (I)

(Ar ¹ -Ac)a-X _b (I);

- a and b are independently 1 or 2;

- c is independently o or l;

Ar ¹ is independently selected from C ₆ to C _3o aryl or C ₂ to C ₂₄ heteroaryl, wherein each Ar ¹ may be substituted with one or two substituents independently selected from the group consisting of C ₆ to C ₁₂ aryl, C ₃ to C ₁₁ heteroaryl, and C ₁ to C ₆ alkyl, D, C ₁ to C ₆ alkoxy, C ₃ to C ₆ branched alkyl, C ₃ to C ₆ cyclic alkyl, C ₃ to C ₆ branched alkoxy, C ₃ to C ₆ cyclic alkoxy, partially or perfluorinated C ₁ to C ₆ alkyl, partially or perfluorinated C ₁ to C ₆ alkoxy, partially or perdeuterated C ₁ to C ₆ alkyl, partially or perdeuterated C ₁ to C ₆ alkoxy, halogen, CN or PY(R ¹⁰ ) ₂ , wherein Y is selected from O, S or Se, preferably O and R ¹⁰ is independently selected from C ₆ to C ₁₂ aryl, C ₃ to C ₁₂ heteroaryl, C ₁ to C ₆ alkyl, C ₁ to C ₆ alkoxy, partially or perfluorinated C ₁ to C ₆ alkyl, partially or perfluorinated C ₁ to C ₆ alkoxy, partially or perdeuterated C ₁ to C ₆ alkyl, partially or perdeuterated C ₁ to C ₆ alkoxy;

55 wherein each C ₆ to C ₁₂ aryl substituent on Ar ¹ and each C ₃ to C ₁₁ heteroaryl substituent on Ar ¹ may be substituted with C ₁ to C ₄ alkyl or halogen;

- A is independently selected from C ₆ to C ₁₈ aryl, wherein each A may be substituted with one or two substituents independently selected from the group consisting of C ₆ to C ₁₂ aryl and C ₁ to C ₆ alkyl, D, C ₁ to C ₆ alkoxy, C ₃ to C ₆ branched alkyl, C ₃ to C ₆ cyclic alkyl, C ₃ to C ₆ branched alkoxy, C ₃ to C ₆ cyclic alkoxy, partially or perfluorinated C ₁ to C ₆ alkyl, partially or perfluorinated C ₁ to C ₆ alkoxy, partially or perdeuterated C _a to C ₆ alkyl, partially or perdeuterated C, to C ₆ alkoxy, halogen, CN or PY(R ¹⁰ ) ₂ , wherein Y is selected from O, S or Se, preferably O, and R ¹⁰ is independently selected from C ₆ to C ₁₂ aryl, C ₃ to C ₁₂ heteroaryl, C ₁ to C ₆ alkyl, C _t to C ₆ alkoxy, partially or perfluorinated C _t to C ₆ alkyl, partially or perfluorinated C ₁ to C ₆ alkoxy, partially or perdeuterated C ₁ to C ₆ alkyl, partially or perdeuterated C ₁ to C ₆ alkoxy; wherein each C ₆ to C ₁₂ aryl substituent on A may be substituted with C ₁ to C ₄ alkyl or halogen;

X is independently selected from the group consisting of C ₃ to C ₂ i heteroaryl and C ₆ to C ₂₄ aryl, wherein each X may be substituted with one or two substituents independently selected from the group consisting of C ₆ to C ₁₂ aryl, C ₃ to C ₁₁ heteroaryl, and C ₁ to C ₆ alkyl, D, C ₁ to C ₆ alkoxy, C ₃ to C ₆ branched alkyl, C ₃ to C ₆ (ydic alkyl, C ₃ to C ₆ branched alkoxy, C ₃ to C ₆ cyclic alkoxy, partially or perfluorinated C ₁ to C ₆ alkyl, partially or perfluorinated C ₁ to C ₆ alkoxy, partially or perdeuterated C ₁ to C ₆ alkyl, partially or perdeuterated C ₁ to C ₆ alkoxy, halogen, CN or PY(R ¹⁰ ) ₂ , wherein Y is selected from O, S or Se, preferably O, and R“ is independently selected from C ₆ to C ₁₂ aryl, C ₃ to C ₁₂ heteroaryl, C ₁ to C ₆ alkyl, C ₁ to C ₆ alkoxy, partially or perfluorinated C ₁ to C ₆ alkyl, partially or perfluorinated C ₁ to C ₆ alkoxy, partially or perdeuterated C ₁ to C ₆ alkyl, partially or perdeuterated C ₁ to C ₆ alkoxy; wherein each C ₆ to C ₁₂ aryl substituent on X and each C ₃ to C ₁₁ heteroaryl substituent on X maybe substituted with C ₁ to C ₄ alkyl or halogen;

- the molecular dipole moment of the compound of formula (I) is > o D and ≤ 3.5 D;

- the second electron transport layer comprises a compound of Formula (II)

(Ar ² )m-(Zk-G) _n (II);

- m and n are independently 1 or 2;

- k is independently o, 1 or 2;

- Ar ² is independently selected from the group consisting of C ₃ to C ₃₀ heteroaryl and C ₆ to C ₄₂ aryl,

56 wherein each Ar ² may be substituted with one or two substituents independently selected from the group consisting of C ₆ to C ₁₂ atyl, C ₃ to C ₁₁ heteroaryl, and C ₁ to C ₆ alkyl, D, C ₁ to C ₆ alkoxy, C ₃ to C ₆ branched alkyl, C ₃ to C ₆ cyclic alkyl, C ₃ to C ₆ branched alkoxy, C ₃ to C ₆ cyclic alkoxy, partially or perfluorinated C ₁ to C ₆ alkyl, partially or perfluorinated C ₁ to C ₆ alkoxy, partially or perdeuterated C ₁ to C ₆ alkyl, partially or perdeuterated C ₁ to C ₆ alkoxy, halogen, CN or PY(R ¹⁰ ) ₂ , wherein Y is selected from O, S or Se, preferably O, and R“ is independently selected from C ₆ to C ₁₂ aryl, C ₃ to C ₁₂ heteroaryl, C ₁ to C ₆ alkyl, C ₁ to C ₆ alkoxy, partially or perfluorinated C ₁ to C ₆ alkyl, partially or perfluorinated C ₁ to C ₆ alkoxy, partially or perdeuterated C ₁ to C ₆ alkyl, partially or perdeuterated C ₁ to C ₆ alkoxy;

- wherein each C ₆ to C ₁₂ aryl substituent on Ar ² and each C ₃ to C ₁₂ heteroaryl substituent on Ar ² may be substituted with C ₁ to C ₄ alkyl or halogen;

- Z is independently selected from C ₆ to C ₁₈ aryl, wherein each Z may be substituted with one or two substituents independently selected from the group consisting of C ₆ to C ₁₂ aryl and C ₁ to C ₆ alkyl, D, C ₁ to C ₆ alkoxy, C ₃ to C ₆ branched alkyl, C ₃ to C ₆ cyclic alkyl, C ₃ to C ₆ branched alkoxy, C ₃ to C ₆ cyclic alkoxy, partially or perfluorinated C ₁ to C ₆ alkyl, partially or perfluorinated Cx to C ₆ alkoxy, partially or perdeuterated C ₁ to C ₆ alkyl, partially or perdeuterated C ₁ to C ₆ alkoxy, halogen, CN or PY(R ¹⁰ ) ₂ , wherein Y is selected from O, S or Se, preferably O, and R ¹⁰ is independently selected from C ₆ to C ₁₂ aryl, C ₃ to C ₁₂ heteroaryl, C ₁ to C ₆ alkyl, C ₁ to C ₆ alkoxy, partially or perfluorinated C ₁ to C ₆ alkyl, partially or perfluorinated C ₁ to C ₆ alkoxy, partially or perdeuterated C ₁ to C ₆ alkyl, partially or perdeuterated C ₁ to C ₆ alkoxy;

- wherein each C ₆ to C ₁₂ aryl substituent on Z may be substituted with C ₁ to C ₄ alkyl or halogen;

G is chosen so that the dipole moment of a compound G-phenyl is ≥ 2 D and ≤ 6 D; and the first electron transport layer and the second electron transport layer are free of an electrical dopant.

According to one embodiment, there is provided an organic light emitting diode comprising a non-transparent substrate, an anode, a cathode, an emission layer, an electron injection layer and an electron transport layer stack; wherein the electron transport layer stack is arranged between the emission layer and the electron injection layer; the electron transport layer stack comprises a first electron transport layer and a second electron transport layer; the first electron transport layer comprises a compound of Formula (I)

(Ar1-A _c ) _a -X _b (I)

57 - a and b are independently 1 or 2;

- c is independently o or 1;

- Ar ¹ is independently selected from C ₆ to C ₃₀ aryl, wherein each Ar ¹ may be substituted with one or two substituents independently selected from the group consisting of phenyl, naphtyl, biphenyl, pyridyl, picolinyl, lutidinyl, dibenzofuranyl, dibenzothiophene-yl, and benzothiophene-yl;

- A is independently selected from C ₆ to C ₁₈ aryl, wherein each A may be substituted with one or two substituents independently selected from the group consisting of phenyl and C ₁ to C ₄ alkyl;

- X is independently selected from the group consisting of C ₃ to C ₂₁ N-containing heteroaryl, C ₃ to C ₂₁ O-containing heteroaryl and C ₆ to aryl, wherein each X may be substituted with one or two substituents independently selected from the group consisting of phenyl, naphthyl and biphenyl-yl;

- the molecular dipole moment of the compound of formula (I) is > o D and ≤ 3.0 D;

- the second electron transport layer comprises a compound of Formula (II)

(Ar ² ) _m -(Z _k -G) _n (II)

- m and n are independently 1 or 2;

- k is independently o, 1 or 2;

- Ar ² is independently selected from the group consisting of C ₃ to C ₂₁ heteroaryl and C ₆ to C ₂₄ aryl, wherein each Ar ² may be substituted with one or two substituents independently selected from the group consisting of phenyl, pyiidinyl and biphenyl-yl, optionally para-biphenyl- yl·;

Z is independently selected from C ₆ to C ₁₈ aryl, wherein each Z may be substituted with one or two substituents independently selected from the group consisting of phenyl and C ₁ to C ₄ alkyl;

G is selected from the group consisting of dialkylphosphinyl, diarylphosphinyl, alkylarylphosphinyl, nitrile, benzonitrile, nicotinonitrile, amide, carbamide, and C ₂ to C ₄₂ heteroaryl; wherein G may include one or more substituents attached to the group,

58 wherein the one or more substituents are selected from the group consisting of C ₆ to C ₁₈ aryl, C ₁ to C ₁₀ alkyl, C ₂ to C ₁₄ heteroaryl; and the first electron transport layer and the second electron transport layer are free of an electrical dopant.

According to one embodiment, there is provided an organic light emitting diode comprising a non-transparent substrate, an anode, a cathode, an emission layer, an electron injection layer and an electron transport layer stack; wherein the electron transport layer stack is arranged between the emission layer and the electron injection layer;

- the electron transport layer stack comprises a first electron transport layer and a second electron transport layer; the first electron transport layer comprises a compound of Formula (I)

(Ar ¹ -A _c )a-Xb (I);

- a and b are independently 1 or 2;

- c is independently o or 1;

Ar ¹ is independently selected from phenyl, naphthyl, anthracenyl, fluoranthenyl, xanthenyl, spiro-xanthenyl, fluorenyl, spiro-fluorenyl, triphenylsilyl, tetraphenylsilyl or a group having the formula (Ila) wherein

- the asterisk symbol represents the binding position for binding the group of formula

(Ila) to A; and

R ¹ to R5 are independently selected from the group consisting of H, C ₆ to C ₁₂ aryl and C ₃ to C ₁₀ , alternatively C ₄ to C ₅ heterorayl,

- wherein each Ar ¹ may be substituted with one or two substituents independently selected from the group consisting of phenyl, naphtyl, biphenyl, pyridyl, picolinyl, lutidinyl, dibenzofuranyl, dibenzothiophene-yl, and benzothiophene-yl;

59 A is independently selected from phenylene, naphthylene, biphenylene and terphenylene,

- wherein each A may be substituted with one or two substituents independently selected from the group consisting of phenyl and C ₁ to C ₄ alkyl;

X is independently selected from the group consisting of C ₃ to C ₂₁ N-containing heteroaryl and C ₆ to C ₂₄ aryl,

- wherein each X may be substituted with one or two substituents independently selected from the group consisting of phenyl, naphthyl and biphenyl-yl;

- the molecular dipole moment of the compound of formula (I) is > o D and ≤ 2.5 D;

- the second electron transport layer comprises a compound of Formula (II)

(Ar=)m-(Z _k -G)n (ID;

- m and n are independently 1 or 2;

- k is independently 1 or 2;

Ar ² is independently selected from the group consisting of C ₃ to C ₂₁ N-containing heteroaryl and C ₆ to C ₂₄ aryl, wherein each Ar ² may be substituted with one or two substituents independently selected from the group consisting of phenyl, pyridinyl and biphenyl-yl, optionally para-biphenyl- yl·;

- Z is independently selected from the group consisting of phenylene, naphthylene, phenylene-naphthylene, biphenylene and terphenylene, wherein each Z may be substituted with one or two substituents independently selected from the group consisting of phenyl and C ₁ to C ₄ alkyl;

G is selected from the group consisting of C ₂ to C ₂₅ heteroaryl; G may include one or more substituents attached to the group, wherein the one or more substituents are selected from the group consisting of C ₆ to C ₁₂ aryl, C ₁ to C ₆ alkyl, C ₂ to C ₁₁ heteroaryl; and the first electron transport layer and the second electron transport layer are free of an electrical dopant.

According to one embodiment, there is provided an organic light emitting diode comprising a non-transparent substrate, an anode, a cathode, an emission layer, an electron injection layer and an electron transport layer stack; wherein the electron transport layer stack is arranged between the emission layer and the electron injection layer;

60 the electron transport layer stack comprises a first electron transport layer and a second electron transport layer;

- the first electron transport layer comprises a compound of Formula (I)

(Ar ¹ -Ac)a-Xb (I);

- a and b are independently i or 2;

- c is independently o or i;

- Ar ¹ is independently selected from the group consisting of phenyl, anthracenyl, fluorenyl or the group of the formula (Ila) wherein R ¹ to R ⁵ are independently selected from H and phenyl,

- wherein each Ar ¹ may be substituted with one or two substituents independently selected from the group consisting of phenyl, naphtyl, biphenyl, pyridyl, picolinyl, lutidinyl, dibenzofuranyl, dibenzothiophene-yl, and benzothiophene-yl;

A is independently selected from phenylene, naphthylene, biphenylene and terphenylene, wherein each A may be substituted with one or two substituents independently selected from the group consisting of phenyl and C ₁ to C ₄ alkyl;

X is independently selected from the group consisting of triazinyl, 1,2-diazinyl, 1,3- diazinyl, 1,4-diazinyl, quinazolinyl, benzoquinazolinyl, benzimidazolyl, quinolinyl, benzoquinolinyl benzoacridinyl, dibenzoacridinyl, fluoranthenyl, anthracenyl, naphthyl, triphenylenyl, phenathrolinyl, and dinaphthofuranyl, wherein each X may be substituted with one or two substituents independently selected from the group consisting of phenyl, naphthyl and biphenyl-yl; the molecular dipole moment of the compound of formula (I) is > o D and < 2.0 D; the second electron transport layer comprises a compound of Formula (Π)

(Ar ² ) _m -(Zk-G)n (II);

61 - m and n are independently 1 or 2;

- k is independently l or 2;

Ar ² is independently selected from the group consisting of pyridinyl, triazinyl, 1,2-diazinyl, 1,3-diazinyl, 1,4-diazinyl, quinazolinyl, benzoquinazolinyl, benzimidazolyl, quinolinyl, benzoquinolinyl benzoacridinyl, dibenzoacridinyl, fluoranthenyl, anthracenyl, naphthyl, triphenylenyl, phenathrolinyl, and dinaphthofuranyl, wherein each Ar ² may be substituted with one or two substituents independently selected from the group consisting of phenyl, pyridinyl and biphenyl-yl, optionally para-biphenyl- yl.;

Z is independently selected from the group consisting of phenylene, naphthylene, phenylene-naphthylene, biphenylene and terphenylene,

- wherein each Z may be substituted with one or two substituents independently selected from the group consisting of phenyl and C ₁ to C ₄ alkyl;

G is selected from the group consisting of di-C ₁ to C ₄ -alkylphosphinyl, di-C ₆ to C ₁₀ - arylphosphinyl, and C ₂ to C ₂₅ heteroaryl; wherein the respective G may include one or more substituents attached to the group, wherein the one or more substituents are selected from the group consisting of C ₆ to C ₁₀ aryl, C ₁ to C ₄ alkyl, C ₂ to C ₅ heteroaryl; and the first electron transport layer and the second electron transport layer are free of an electrical dopant.

According to one embodiment, there is provided an organic light emitting diode comprising a non-transparent substrate, an anode, a cathode, an emission layer, an electron injection layer and an electron transport layer stack; wherein the electron transport layer stack is arranged between the emission layer and the electron injection layer; the electron transport layer stack comprises a first electron transport layer and a second electron transport layer; the first electron transport layer comprises a compound of Formula (I)

(Ar ¹ -A _c ) _a -Xb (I)

- a and b are independently 1 or 2;

- c is independently o or 1;

Ar ¹ is a group of Formula (Ila)

62 and at least two of R ¹ to R ⁵ are not H;

- wherein each Ar ¹ may be substituted with one or two substituents independently selected from the group consisting of phenyl, naphtyl, biphenyl, pyridyl, picolinyl, lutidinyl, dibenzofuranyl, dibenzothiophene-yl, and benzothiophene-yl;

- A is independently selected from phenylene and biphenylene;

- wherein each A may be substituted with one or two substituents independently selected from the group consisting of phenyl and C ₁ to C ₄ alkyl;

- X is independently selected from the group consisting of triazinyl, 1,2-diazinyl, 1,3- diazinyl, 1,4-diazinyl, quinazolinyl, benzoquinazolinyl, benzoacridinyl, dibenzoacridinyl, fluoranthenyl, anthracenyl, naphthyl, triphenylenyl, phenathrolinyl, and dinaphthofuranyl, wherein each X may be substituted with one or two substituents independently selected from the group consisting of phenyl, naphthyl and biphenyl-yl; the molecular dipole moment of the compound of formula (I) is > o D and ≤ 2.0 D; the second electron transport layer comprises a compound of Formula (II)

(Ar ² ) _m -(Zk-G) _n (II);

- m and n are independently 1 or 2;

- k is independently 1 or 2;

Ar ² is independently selected from the group consisting of dibenzoacridinyl, 1,3-diazinyl, 1,4-diazinyl, anthracenyl, triazinyl, phenathrolinyl, triphenylenyl, pyridinyl, dinaphthofuranyl, wherein each Ar ² may be substituted with one or two substituents independently selected from the group consisting of phenyl, pyridinyl and biphenyl-yl, optionally para-biphenyl- yl.;

Z is independently selected from the group consisting of phenylene, naphthylene, phenylene-naphthylene, biphenylene and terphenylene,

63 wherein each Z may be substituted with one or two substituents independently selected from the group consisting of phenyl and C ₁ to C ₄ alkyl;

G is selected from the group consisting of dimethylphosphinyl, diphenylphosphinyl, nitrile, benzonitrile, nicotinonitrile, di-hydro-benzoimidazolone-yl, diphenyl-propane-yl, iV _^ ZV-dimethylacetamid, amide, carbamide, imidazolyl, phenylbenzoimidazolyl, ethylbenzoimidazolyl phenylbenzoquinolinyl, phenylbenzoimidazoquinolinyl, pyridinyl, bipyridinyl, picolinyl, lutidenyl, pyridazinyl, pyrimidinyl, pyrazinyl, triphenyl-pyrazinyl, benzoquinolinyl, phenanthrolinyl, phenylphenanthrolinyl and pyridinyl- imidazopyridinyl; and the first electron transport layer and the second electron transport layer are free of an electrical dopant.

According to one embodiment, there is provided an organic light emitting diode comprising a non-transparent substrate, an anode, a cathode, an emission layer, an electron injection layer and an electron transport layer stack; wherein the electron transport layer stack is arranged between the emission layer and the electron injection layer; the electron transport layer stack comprises a first electron transport layer and a second electron transport layer; the first electron transport layer comprises a compound of Formula (I)

(Ar ¹ Ac) a-Xb (I);

- a and b are independently 1 or 2;

- c is independently o or 1;

Ar ¹ is a group of Formula (Ila) and at least two of R ¹ to R5 are not H, wherein at least two of R ¹ to R5 which are not H are in ortho-position to each other and/or at least one of R ¹ to R5 which is not H is in ortho- position to the “-position;

64 wherein each Ar ¹ may be substituted with one or two substituents independently selected from the group consisting of phenyl, naphtyl, biphenyl, pyridyl, picolinyl, lutidinyl, dibenzofuranyl, dibenzothiophene-yl, and benzothiophene-yl;

- A is independently selected from phenylene and biphenylene; wherein each A may be substituted with one or two substituents independently selected from the group consisting of phenyl and C ₁ to C ₄ alkyl;

X is independently selected from the group consisting triazinyl, 1,2-diazinyI, 1,3-diazinyl, 1,4-diazinyl, quinazolinyl, benzoquinazolinyl, benzoacridinyl, dibenzoacridinyl, fluoranthenyl, wherein each X may be substituted with one or two substituents independently selected from the group consisting of phenyl, naphthyl and biphenyl-yl;

- the molecular dipole moment of the compound of formula (I) is > o D and ≤ 2.0 D; the second electron transport layer comprises a compound of Formula (Π)

(Ar ² )m-(Zk-G)n (II);

- m and n are independently 1 or 2;

- k is independently 1 or 2;

- Ar ² is independently selected from the group consisting of dibenzoacridinyl, 1,3-diazinyl, 1,4-diazinyl, anthracenyl, triazinyl, phenathrolinyl, triphenylenyl, pyridinyl, dinaphthofuranyl, wherein each Ar ² may be substituted with one or two substituents independently selected from the group consisting of phenyl, pyridinyl and biphenyl-yl, optionally para-biphenyl- yl.;

- Z is independently selected from the group consisting of phenylene, naphthylene, phenylene-naphthylene, biphenylene and terphenylene,

- wherein each Z may be substituted with one or two substituents independently selected from the group consisting of phenyl and C ₁ to C ₄ alkyl;

G is selected from the group consisting of dimethylphosphinyl, diphenylphospinyl, 2- phenyl-lH-benzo[d]imidazolyl, 2-ethyl-iH-benzo[d]imidazolyl, 2- phenylbenzo [h] quinolinyl, pyridinyl, 2 , 2’-bipyridinyl, 5-phenylbenzo[4,s]imidazo[i,2- ajquinolinyl, 9-phenyl-i,lo-phenanthrolinyI and (pyridine-2-yl)imidazo [1 ,5-a]pyridinyl; and

65 the first electron transport layer and the second electron transport layer are free of an electrical dopant.

According to one embodiment, there is provided an organic light emitting diode comprising a non-transparent substrate, an anode, a cathode, an emission layer, an electron injection layer and an electron transport layer stack; wherein the electron transport layer stack is arranged between the emission layer and the electron injection layer; the electron transport layer stack comprises a first electron transport layer and a second electron transport layer;

- the first electron transport layer comprises a compound selected from the compounds A- 1 to A-8 shown in Table 1;

- the second electron transport layer comprises a compound selected from the compounds B-1 to B-26 shown in Table 3; and the first electron transport layer and the second electron transport layer are free of an electrical dopant.

According to one embodiment, there is provided an organic light emitting diode comprising a non-transparent substrate, an anode, a cathode, an emission layer, an electron injection layer and an electron transport layer stack; wherein the electron transport layer stack is arranged between the emission layer and the electron injection layer; the electron transport layer stack comprises a first electron transport layer and a second electron transport layer; the first electron transport layer comprises a compound of Formula (I)

(Ar ¹ -A _c ) _a -X _b (I)

- a and b are independently 1 or 2;

- c is independently o or 1;

Ar ¹ is independently selected from C ₆ to C ₃₀ aryl or C ₂ to C ₂₄ heteroaryl, wherein each Ar ¹ maybe substituted with one or two substituents independently selected from the group consisting of C ₆ to C ₁₂ aryl, C ₃ to C ₁₁ heteroaryl, and C ₁ to C ₆ alkyl, D, C ₁ to C ₆ alkoxy, C ₃ to C ₆ branched alkyl, C ₃ to C ₆ cyclic alkyl, C ₃ to C ₆ branched alkoxy, C ₃ to C ₆ cyclic alkoxy, partially or perfluorinated C ₁ to C ₆ alkyl, partially or perfluorinated C ₁ to C ₆ alkoxy, partially or perdeuterated C ₁ to C ₆ alkyl, partially or perdeuterated C ₁ to C ₆ alkoxy,

66 halogen, CN or PY(R ¹⁰ ) ₂ , wherein Y is selected from O, S or Se, preferably O and R ¹⁰ is independently selected from C ₆ to C ₁₂ aryl, C ₃ to C ₁₂ heteroaryl, C ₁ to C ₆ alkyl, C ₁ to C ₆ alkoxy, partially or perfluorinated C ₁ to C ₆ alkyl, partially or perfluorinated C ₁ to C ₆ alkoxy, partially or perdeuterated C ₁ to C ₆ alkyl, partially or perdeuterated C ₁ to C ₆ alkoxy; wherein each C ₆ to C ₁₂ aryl substituent on Ar ¹ and each C ₃ to C ₁₁ heteroaryl substituent on Ar ¹ may be substituted with C ₁ to C ₄ alkyl or halogen;

A is independently selected from C ₆ to C ₁₈ aryl, wherein each A may be substituted with one or two substituents independently selected from the group consisting of C ₆ to C ₁₂ aryl and C ₁ to C ₆ alkyl, D, C, to C ₆ alkoxy, C ₃ to C ₆ branched alkyl, C ₃ to C ₆ cyclic alkyl, C ₃ to C ₆ branched alkoxy, C ₃ to C ₆ cyclic alkoxy, partially or perfluorinated C ₁ to C ₆ alkyl, partially or perfluorinated C ₁ to C ₆ alkoxy, partially or perdeuterated C ₁ to C ₆ alkyl, partially or perdeuterated C ₁ to C ₆ alkoxy, halogen, CN or PY(R ¹⁰ ) ₂ , wherein Y is selected from O, S or Se, preferably O, and R ¹⁰ is independently selected from C ₆ to C ₁₂ aryl, C ₃ to C ₁₂ heteroaryl, C ₁ to C ₆ alkyl, C ₁ to C ₆ alkoxy, partially or perfluorinated C ₁ to C ₆ alkyl, partially or perfluorinated C ₁ to C ₆ alkoxy, partially or perdeuterated C ₁ to C ₆ alkyl, partially or perdeuterated C ₁ to C ₆ alkoxy;

- wherein each C ₆ to C ₁₂ aryl substituent on A may be substituted with C ₁ to C ₄ alkyl or halogen;

X is independently selected from the group consisting of C ₂ to C ₂₁ heteroaryl and C ₆ to C ₂₄ aryl, wherein each X may be substituted with one or two substituents independently selected from the group consisting of C ₆ to C ₁₂ aryl, C ₃ to C ₁₁ heteroaryl, and C ₁ to C ₆ alkyl, D, C ₁ to C ₆ alkoxy, C ₃ to C ₆ branched alkyl, C ₃ to C ₆ cyclic alkyl, C ₃ to C ₆ branched alkoxy, C ₃ to C ₆ cyclic alkoxy, partially or perfluorinated C ₁ to C ₆ alkyl, partially or perfluorinated C ₁ to C ₆ alkoxy, partially or perdeuterated C ₁ to C ₆ alkyl, partially or perdeuterated C ₁ to C ₆ alkoxy, halogen, CN or PY(R ¹⁰ ) ₂ , wherein Y is selected from O, S or Se, preferably O, and R ¹⁰ is independently selected from C ₆ to C ₁₂ aryl, C ₃ to C ₁₂ heteroaryl, C ₁ to C ₆ alkyl, C ₁ to C ₆ alkoxy, partially or perfluorinated C ₁ to C ₆ alkyl, partially or perfluorinated C ₁ to C ₆ alkoxy, partially or perdeuterated C ₁ to C ₆ alkyl, partially or perdeuterated C ₁ to C ₆ alkoxy;

- wherein each C ₆ to C ₁₂ aryl substituent on X and each C ₃ to C ₁₁ heteroaryl substituent on X may be substituted with C ₁ to C ₄ alkyl or halogen;

- the molecular dipole moment of the compound of formula (I) is > o D and ≤ 3.5 D;

- the second electron transport layer comprises a compound of Formula (II)

(Ar ² ) _m -(Zk-G)n (II);

- m and n are independently 1 or 2;

67 - k is independently o, 1 or 2;

Ar ² is independently selected from the group consisting of C ₃ to C ₃₀ heteroaryl and C ₆ to C ₄₂ aryl, wherein each Ar ² may be substituted with one or two substituents independently selected from the group consisting of C ₆ to C ₁₂ aryl, C ₃ to C ₁₁ heteroaryl, and C ₁ to C ₆ alkyl, D, C ₁ to C ₆ alkoxy, C ₃ to C ₆ branched alkyl, C ₃ to C ₆ cyclic alkyl, C ₃ to C ₆ branched alkoxy, C ₃ to C ₆ cyclic alkoxy, partially or perfluorinated C ₁ to C ₆ alkyl, partially or perfluorinated C ₁ to C ₆ alkoxy, partially or perdeuterated C ₁ to C ₆ alkyl, partially or perdeuterated C ₁ to C ₆ alkoxy, halogen, CN or PY(R ¹⁰ ) ₂ , wherein Y is selected from O, S or Se, preferably O, and R ¹⁰ is independently selected from C ₆ to C ₁₂ aryl, C ₃ to C ₁₂ heteroaryl, C ₁ to C ₆ alkyl, C ₁ to C ₆ alkoxy, partially or perfluorinated C ₁ to C ₆ alkyl, partially or perfluorinated C ₁ to C ₆ alkoxy, partially or perdeuterated C ₁ to C ₆ alkyl, partially or perdeuterated C ₁ to C ₆ alkoxy; wherein each C ₆ to C ₁₂ aryl substituent on Ar ² and each C ₃ to C ₁₁ heteroaryl substituent on Ar ² may be substituted with C ₁ to C ₄ alkyl or halogen;

Z is independently selected from C ₆ to C ₁₈ aryl, wherein each Z may be substituted with one or two substituents independently selected from the group consisting of C ₆ to C ₁₂ aryl and C ₁ to C ₆ alkyl, D, C ₁ to C ₆ alkoxy, C ₃ to C ₆ branched alkyl, C ₃ to C ₆ cyclic alkyl, C ₃ to C ₆ branched alkoxy, C ₃ to C ₆ cyclic alkoxy, partially or perfluorinated C ₁ to C ₆ alkyl, partially or perfluorinated C ₁ to C ₆ alkoxy, partially or perdeuterated C ₁ to C ₆ alkyl, partially or perdeuterated C ₁ to C ₆ alkoxy, halogen, CN or PY(R ¹⁰ ) ₂ , wherein Y is selected from O, S or Se, preferably O, and R ¹⁰ is independently selected from C ₆ to C ₁₂ aryl, C ₃ to C ₁₂ heteroaryl, C ₁ to C ₆ alkyl, C ₁ to C ₆ alkoxy, partially or perfluorinated C ₁ to C ₆ alkyl, partially or perfluorinated C ₁ to C ₆ alkoxy, partially or perdeuterated C ₁ to C ₆ alkyl, partially or perdeuterated C ₁ to C ₆ alkoxy; wherein each C ₆ to C ₁₂ aryl substituent on Z may be substituted with C ₁ to C ₄ alkyl or halogen;

G is chosen so that the dipole moment of a compound G-phenyl is ≥ 2 D and ≤ 6 D; the second electron transport layer may further comprises a compound (III), wherein the compound (III) comprises 8 to 13 aromatic or heteroaromatic rings; and the first electron transport layer and the second electron transport layer are free of an electrical dopant.

According to one embodiment, there is provided an organic light emitting diode comprising a non-transparent substrate, an anode, a cathode, an emission layer, an electron injection layer and an electron transport layer stack; wherein the electron transport layer stack is arranged between the emission layer and the electron injection layer;

68 the electron transport layer stack comprises a first electron transport layer and a second electron transport layer; the first electron transport layer comprises a compound of Formula (I)

(Ar ^1_ Ac)a-X _b (I);

- a and b are independently l or 2;

- c is independently o or 1;

Ar ¹ is independently selected from C ₆ to C ₃₀ aryl, wherein each Ar ¹ may be substituted with one or two substituents independently selected from the group consisting of phenyl, naphtyl, biphenyl, pyridyl, picolinyl, lutidinyl, dibenzofiiranyl, dibenzothiophene-yl, and benzothiophene-yl;

- A is independently selected from C ₆ to C _IB aryl, wherein each A may be substituted with one or two substituents independently selected from the group consisting of phenyl and C ₁ to C ₄ alkyl;

X is independently selected from the group consisting of C ₃ to C ₂₁ N-containing heteroaryl, C ₃ to C ₂₁ 0-containing heteroaryl and C ₆ to C ₂₄ aryl, wherein each X may be substituted with one or two substituents independently selected from the group consisting of phenyl, naphthyl and biphenyl-yl;

- the molecular dipole moment of the compound of formula (I) is > o D and ≤ 3.0 D;

- the second electron transport layer comprises a compound of Formula (II)

(Ar ² ) _m -(Z _k -G)n (ID;

- m and n are independently 1 or 2;

- k is independently o, l or 2;

Ar ² is independently selected from the group consisting of C ₃ to C ₂₁ heteroaryl and C ₆ to C ₂₄ aryl, wherein each Ar ² may be substituted with one or two substituents independently selected from the group consisting of phenyl, pyridinyl and biphenyl-yl, optionally para-biphenyl- yl·;

Z is independently selected from C ₆ to C ₂₄ aryl,

69 wherein each Z may be substituted with one or two substituents independently selected from the group consisting of phenyl and C ₁ to C ₄ alkyl;

G is selected from the group consisting of dialkylphosphinyl, diarylphosphinyl, alkylarylphosphinyl, nitrile, benzonitrile, nicotmonitrile, amide, carbamide, and C ₂ to C ₄₂ heteroaryl; wherein G may include one or more substituents attached to the group, wherein the one or more substituents are selected from the group consisting of C ₆ to C ₁₈ aryl, C ₁ to C ₁₀ alkyl, C ₂ to C ₁₄ heteroaryl; the second electron transport layer may further comprises a compound (III), wherein the compound (III) comprises 8 to 13 aromatic or heteroaromatic rings; compound (III) comprises at least one heteroaromatic ring; and the first electron transport layer and the second electron transport layer are free of an electrical dopant.

According to one embodiment, there is provided an organic light emitting diode comprising a non-transparent substrate, an anode, a cathode, an emission layer, an electron injection layer and an electron transport layer stack; wherein the electron transport layer stack is arranged between the emission layer and the electron injection layer; the electron transport layer stack comprises a first electron transport layer and a second electron transport layer; the first electron transport layer comprises a compound of Formula (I)

(Ar1-Ac)a-Xb (I);

- a and b are independently 1 or 2;

- c is independently o or 1;

Ar ¹ is independently selected from phenyl, naphthyl, anthracenyl, fluoranthenyl, xanthenyl, spiro-xanthenyl, fluorenyl, spiro-fluorenyl, triphenylsilyl, tetraphenylsilyl or a group having the formula (Ila)

70 wherein the asterisk symbol represents the binding position for binding the group of formula

(Ila) to A; and

R ¹ to R ⁵ are independently selected from the group consisting of H, C ₆ to C ₁₂ aryl and C ₃ to C ₁₀ , alternatively C ₄ to C ₅ heterorayl,

- wherein each Ar ¹ may be substituted with one or two substituents independently selected from the group consisting of phenyl, naphtyl, biphenyl, pyridyl, picolinyl, lutidinyl, dibenzofuranyl, dibenzothiophene-yl, and benzothiophene-yl;

- A is independently selected from phenylene, naphthylene, biphenylene and terphenylene, wherein each A may be substituted with one or two substituents independently selected from the group consisting of phenyl and C ₁ to C ₄ alkyl;

X is independently selected from the group consisting of C ₃ to C ₂₁ N-containing heteroaryl and C ₆ to C ₂₄ aryl,

- wherein each X may be substituted with one or two substituents independently selected from the group consisting of phenyl, naphthyl and biphenyl-yl;

- the molecular dipole moment of the compound of formula (I) is > o D and ≤ 2.5 D;

- the second electron transport layer comprises a compound of Formula (II)

(Ar ² ) _m -(Z _k -G)„ (II);

- m and n are independently 1 or 2;

- k is independently l or 2;

Ar ² is independently selected from the group consisting of C ₃ to C ₂₁ N-containing heteroaryl and C ₆ to C ₂₄ aryl,

- wherein each Ar ² may be substituted with one or two substituents independently selected from the group consisting of phenyl, pyridinyl and biphenyl-yl, optionally para-biphenyl- yl.;

- Z is independently selected from the group consisting of phenylene, naphthylene, phenylene-naphthylene, biphenylene and terphenylene,

- wherein each Z may be substituted with one or two substituents independently selected from the group consisting of phenyl and C ₁ to C ₄ alkyl;

71 G is selected from the group consisting of C ₂ to C ₂₅ heteroaryl; G may include one or more substituents attached to the group, wherein the one or more substituents are selected from the group consisting of C ₆ to C ₁₂ aryl, C ₁ to C ₆ alkyl, C ₂ to C ₁₁ heteroaryl;

- the second electron transport layer may further comprises a compound (III), wherein the compound (III) comprises 8 to 13 aromatic or heteroaromatic rings; compound (III) comprises at least one heteroaromatic ring; the aromatic or heteroaromatic rings of the compound (III) are 6-membered rings; and

- the first electron transport layer and the second electron transport layer are free of an electrical dopant.

According to one embodiment, there is provided an organic light emitting diode comprising a non-transparent substrate, an anode, a cathode, an emission layer, an electron injection layer and an electron transport layer stack; wherein

- the electron transport layer stack is arranged between the emission layer and the electron injection layer; the electron transport layer stack comprises a first electron transport layer and a second electron transport layer; the first electron transport layer comprises a compound of Formula (I)

(Ar ¹ Ac)a-Xb (I);

- a and b are independently 1 or 2;

- c is independently o or 1;

Ar ¹ is independently selected from the group consisting of phenyl, anthracenyl, fluorenyl or the group of the formula (Ila) wherein R ¹ to R5 are independently selected from H and phenyl,

72 wherein each Ar ¹ maybe substituted with one or two substituents independently selected from the group consisting of phenyl, naphtyl, biphenyl, pyridyl, picolinyl, lutidinyl, dibenzofuranyl, dibenzothiophene-yl, and benzothiophene-yl;

- A is independently selected from phenylene, naphthylene, biphenylene and terphenylene, wherein each A may be substituted with one or two substituents independently selected from the group consisting of phenyl and Cx to C ₄ alkyl;

- X is independently selected from the group consisting of triazinyl, 1,2-diazinyl, 1,3- diazinyl, 1,4-diazinyl, quinazolinyl, benzoquinazolinyl, benzimidazolyl, quinolinyl, benzoquinolinyl benzoacridinyl, dibenzoacridinyl, fluoranthenyl, anthracenyl, naphthyl, triphenylenyl, phenathrolinyl, and dinaphthofuranyl, wherein each X may be substituted with one or two substituents independently selected from the group consisting of phenyl, naphthyl and biphenyl-yl; the molecular dipole moment of the compound of formula (I) is > o D and ≤ 2.0 D;

- the second electron transport layer comprises a compound of Formula (II)

(Ar ² )m-(Z _k -G) _n (II)

- m and n are independently 1 or 2;

- k is independently 1 or 2;

- Ar ² is independently selected from the group consisting of pyridinyl, triazinyl, 1, 2-diazinyl, 1,3-diazinyl, 1,4-diazinyl, quinazolinyl, benzoquinazolinyl, benzimidazolyl, quinolinyl, benzoquinolinyl benzoacridinyl, dibenzoacridinyl, fluoranthenyl, anthracenyl, naphthyl, triphenylenyl, phenathrolinyl, and dinaphthofuranyl, wherein each Ar ² may be substituted with one or two substituents independently selected from the group consisting of phenyl, pyridinyl and biphenyl-yl, optionally para-biphenyl- yl.;

- Z is independently selected from the group consisting of phenylene, naphthylene, phenylene-naphthylene, biphenylene and terphenylene, wherein each Z may be substituted with one or two substituents independently selected from the group consisting of phenyl and C ₁ to C ₄ alkyl;

G is selected from the group consisting of di-C ₁ to C ₄ -aIkylphosphinyl, di-C ₆ to C ₁₀ - arylphosphinyl, and C ₂ to C ₂₅ heteroaryl; wherein the respective G may include one or more substituents attached to the group, wherein the one or more substituents are selected from the group consisting of C ₆ to C _1o aryl, C ₁ to C ₄ alkyl, C ₂ to C ₅ heteroaryl;

73 - the second electron transport layer may further comprises a compound (III), wherein the compound (III) comprises 8 to 13 aromatic or heteroaromatic rings; compound (III) comprises at least one heteroaromatic ring; the aromatic or heteroaromatic rings of the compound (III) are 6-membered rings; the heteroaromatic rings of the compound (III) are N-containing heteroaromatic rings; and

- the first electron transport layer and the second electron transport layer are free of an electrical dopant.

According to one embodiment, there is provided an organic light emitting diode comprising a non-transparent substrate, an anode, a cathode, an emission layer, an electron injection layer and an electron transport layer stack; wherein the electron transport layer stack is arranged between the emission layer and the electron injection layer; the electron transport layer stack comprises a first electron transport layer and a second electron transport layer; the first electron transport layer comprises a compound of Formula (I)

(Ar ¹ -Ac)a ^_ X _b ) (I);

- a and b are independently 1 or 2;

- c is independently o or 1;

Ar ¹ is a group of Formula (Ila) and at least two of R ¹ to R5 are not H; wherein each Ar ¹ may be substituted with one or two substituents independently selected from the group consisting of phenyl, naphtyl, biphenyl, pyridyl, picolinyl, lutidinyl, dibenzofuranyl, dibenzothiophene-yl, and benzothiophene-yl;

74 A is independently selected from phenylene and biphenylene;

- wherein each A may be substituted with one or two substituents independently selected from the group consisting of phenyl and C ₁ to C ₄ alkyl;

- X is independently selected from the group consisting of triazinyl, 1,2-diazinyl, 1,3- diazinyl, 1,4-diazinyl, quinazolinyl, benzoquinazolinyl, benzoacridinyl, dibenzoacridinyl, fluoranthenyl, anthracenyl, naphthyl, triphenylenyl, phenathrolinyl, and dinaphthofuranyl, wherein each X may be substituted with one or two substituents independently selected from the group consisting of phenyl, naphthyl and biphenyl-yl; the molecular dipole moment of the compound of formula (I) is > o D and ≤ 2.0 D; the second electron transport layer comprises a compound of Formula (II)

(Ar ² )m-(Zk-G)n (II);

- m and n are independently 1 or 2;

- k is independently 1 or 2;

- Ar ² is independently selected from the group consisting of dibenzoacridinyl, 1,3-diazinyl, 1,4-diazinyl, anthracenyl, triazinyl, phenathrolinyl, triphenylenyl, pyridinyl, dinaphthofuranyl,

- wherein each Ar ² may be substituted with one or two substituents independently selected from the group consisting of phenyl, pyridinyl and biphenyl-yl, optionally para-biphenyl- yl·;

Z is independently selected from the group consisting of phenylene, naphthylene, phenylene-naphthylene, biphenylene and terphenylene, wherein each Z may be substituted with one or two substituents independently selected from the group consisting of phenyl and C ₁ to C ₄ alkyl;

G is selected from the group consisting of dimethylphosphinyl, diphenylphosphinyl, nitrile, benzonitrile, nicotinonitrile, di-hydro-benzoimidazolone-yl, diphenyl-propane-yl, N,N -dimethylacetamid, amide, carbamide, imidazolyl, phenylbenzoimidazolyl, ethylbenzoimidazolyl phenylbenzoquinolinyl, phenylbenzoimidazoquinolinyl, pyridinyl, bipyridinyl, picolinyl, lutidenyl, pyridazinyl, pyrimidinyl, pyrazinyl, triphenyl-pyrazinyl, benzoquinolinyl, phenanthrolinyl, phenylphenanthrolinyl and pyridinyl- imidazopyridinyl; the second electron transport layer may further comprises a compound (III), wherein the compound (III) comprises 8 to 13 aromatic or heteroaromatic rings;

75 compound (III) comprises at least one heteroaromatic ring; the aromatic or heteroaromatic rings of the compound (III) are 6-membered rings; the heteroaromatic rings of the compound (III) are N-containing heteroaromatic rings;

- the compound (III) may comprises at least one 6-membered heteroaromatic ring containing one to three N-atoms in each heteroaromatic ring; and the first electron transport layer and the second electron transport layer are free of an electrical dopant.

According to one embodiment, there is provided an organic light emitting diode comprising a non-transparent substrate, an anode, a cathode, an emission layer, an electron injection layer and an electron transport layer stack; wherein the electron transport layer stack is arranged between the emission layer and the electron injection layer;

- the electron transport layer stack comprises a first electron transport layer and a second electron transport layer;

- the first electron transport layer comprises a compound of Formula (I)

(Ar ¹ Ac)a-Xb (I)

- a and b are independently 1 or 2;

- c is independently o or 1;

Ar ¹ is a group of Formula (Ila) and at least two of R ¹ to R5 are not H, wherein at least two of R ¹ to R5 which are not H are in ortho-position to each other and/or at least one of R ¹ to R ⁵ which is not H is in orthoposition to the *-position;

- wherein each Ar ¹ may be substituted with one or two substituents independently selected from the group consisting of phenyl, naphtyl, biphenyl, pyridyl, picolinyl, lutidinyl, dibenzofuranyl, dibenzothiophene-yl, and benzothiophene-yl;

76 A is independently selected from phenylene and biphenylene; wherein each A may be substituted with one or two substituents independently selected from the group consisting of phenyl and C ₁ to C ₄ alkyl;

X is independently selected from the group consisting triazinyl, 1,2-diazinyl, 1,3-diazinyl, 1,4-diazinyl, quinazolinyl, benzoquinazolinyl, benzoacridinyl, dibenzoacridinyl, fluoranthenyl, wherein each X may be substituted with one or two substituents independently selected from the group consisting of phenyl, naphthyl and biphenyl-yl; the molecular dipole moment of the compound of formula (I) is ≥ o D and ≤ 2.0 D;

- the second electron transport layer comprises a compound of Formula (II)

(Ar ² )m-(Zk-G)n (II)

- m and n are independently 1 or 2;

- k is independently l or 2;

- Ar ² is independently selected from the group consisting of dibenzoacridinyl, 1,3-diazinyl, 1,4-diazinyl, anthracenyl, triazinyl, phenathrolinyl, triphenylenyl, pyridinyl, dinaphthofuranyl, wherein each Ar ² may be substituted with one or two substituents independently selected from the group consisting of phenyl, pyridinyl and biphenyl-yl, optionally para-biphenyl- yl.;

- Z is independently selected from the group consisting of phenylene, naphthylene, phenylene-naphthylene, biphenylene and terphenylene, wherein each Z may be substituted with one or two substituents independently selected from the group consisting of phenyl and C ₁ to C ₄ alkyl;

G is selected from the group consisting of dimethylphosphinyl, diphenylphosphinyl, 2- phenyl-iH-benzo[d]imidazolyl, 2-ethyl-iH-benzo[d] imidazolyl, 2- phenylbenzo[h]quinolinyl, pyridinyl, 2 , 2’-bipyridinyl, 5-phenylbenzo[4,5]imidazo[i,2- ajquinolinyl, 9-phenyl-i,lo-phenanthrolinyl and (pyridine-2-yl)imidazo[i,5-a]pyridinyl; the second electron transport layer may further comprise a compound (HI), wherein the compound (III) comprises 8 to 13 aromatic or heteroaromatic rings; compound (III) comprises at least one heteroaromatic ring; the aromatic or heteroaromatic rings of the compound (III) are 6-membered rings;

77 the heteroaromatic rings of the compound (HI) are N-containing heteroaromatic rings;

- the compound (III) may comprise at least one 6-membered heteroaromatic ring containing one to three N-atoms in each heteroaromatic ring; the compound (HI) comprises two or more heteroaromatic rings; and the first electron transport layer and the second electron transport layer are free of an electrical dopant.

According to one embodiment, there is provided an organic light emitting diode comprising a non-transparent substrate, an anode, a cathode, an emission layer, an electron injection layer and an electron transport layer stack; wherein

- the electron transport layer stack is arranged between the emission layer and the electron injection layer; the electron transport layer stack comprises a first electron transport layer and a second electron transport layer; the first electron transport layer comprises a compound selected from the compounds A- l to A-8 shown in Table l; the second electron transport layer comprises a compound selected from the compounds B-i to B-25 shown in Table 3; the and second electron transport layer further comprises a compound selected from the compounds l-i to C-6 shown in Table 4; and

- the first electron transport layer and the second electron transport layer are free of an electrical dopant.

Further layers

In accordance with the invention, the organic electronic device may comprise, besides the layers already mentioned above, further layers. Exemplary embodiments of respective layers are described in the fallowing:

Substrate

The non-transparent substrate may be any respective substrate that is commonly used in manufacturing of, electronic devices, such as organic light-emitting diodes. Since light is to be emitted through the top surface, the substrate is a non-transparent material, for example a plastic substrate, a metal substrate, a glass substrate coated with a non-transparent layer for example a non-transparent anode layer or a silicon substrate.

Anode electrode

78 Either a first electrode or a second electrode comprised in the inventive organic electronic device may be an anode electrode. The anode electrode may be formed by depositing or sputtering a material that is used to form the anode electrode. The material used to form the anode electrode may be a high work-function material, 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 oxides, such as indium tin oxide (ITΟ), indium zinc oxide (IZO), tin-dioxide (Sn02), aluminum zinc oxide (AlZO) and zinc oxide (ZnO), may be used to form the anode electrode. The anode electrode may also be formed using metals, typically silver (Ag), gold (An), or metal alloys.

Hole injection layer

A hole injection layer (HIL) maybe 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 ioo° 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.

When the HIL is formed using spin coating or printing, coating conditions may vary according to the 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 8o° C to about 200° C. Thermal treatment removes a solvent after the coating is performed.

The HIL may be formed of any compound that is commonly used to form a HIL. Examples of compounds that may be used to form the HIL include a phthalocyanine compound, such as copper phthalocyanine (CuPc), 4,4’,4"-tris (3-methylphenylphenylamino) triphenylamine (m- MTDATA), TDATA, 2T-NATA, polyaniline/ dodecylbenzenesulfonic acid (Pani/DBSA), poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate) (PEDOT/PSS), polyaniline/camphor sulfonic acid (Pani/CSA), and polyaniline)/poly(4-styrenesulfonate (PANI/PSS).

The HIL may comprise or consist of p-type dopant and the p-type dopant maybe selected from tetrafluoro-tetracyanoquinonedimethane (F4TCNQ), 2,2'-(perfluoronaphthalen-2,6- diylidene) dimalononitrile, 4,4 ^, ,4 ^,, -((lE,i ^, E,i”E)-cyclopropane-i,2,3- triylidenetris(cyanomethanylylidene))tris(2,3,5,6-tetrafluor obenzonitrile) or 2,2',2"-

(cyclopropane-l, 2, 3-triyhdene)tris(2-(p-cyanotetrafluorophenyl)acetonitrile) but not limited hereto. The HIL may be selected from a hole-transporting matrix compound doped with a p- type dopant. Typical examples of known doped hole transport materials are: copper phthalocyanine (CuPc), which HOMO level is approximately -5.2 eV, doped with tetrafluoro- tetracyanoquinonedimethane (F4TCNQ), which LUMO level is about -5.2 eV; zinc phthalocyanine (ZnPc) (HOMO = -5.2 eV) doped with F4TCNQ; α-NPD (N,N'-Bis(naphthalen- i-yl)-N,N'-bis(phenyl)-benzidine) doped with F4TCNQ. a-NPD doped with 2,2'- (perfluoronaphthalen-2,6-diylidene) dimalononitrile. The p-type dopant concentrations can be selected from 1 to 20 wt.-%, more preferably from 3 wt.-% to 10 wt.-%.

79 The thickness of the HIL may be in the range from about 1 nm to about 100 nm, and for example, from about 1 nm to about 25 nm. When the thickness of the HIL is within this range, the HIL may have excellent hole injecting characteristics, without a substantial penalty in driving voltage.

Hole transport layer

A 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.

The HTL maybe formed of any compound that is commonly used to form a HTL. Compounds that can be suitably used are disclosed for example in Yasuhiko Shirota and Hiroshi Kageyama, Chem. Rev. 2007, 107, 953-1010 and incorporated by reference. Examples of the compound that may be used to form the HTL are: carbazole derivatives, such as N-phenylcarbazole or polyvinylcarbazole; benzidine derivatives, such as N.N’-bists-methylphenyll-N^-diphenyl- [l,l-biphenyl]-4, 4 '-diamine (TPD), or N,N'-di(naphthalen-i-yl)-N,N' -diphenyl benzidine (alpha-NPD); and triphenylamine-based compound, such as 4,4',4"-tris(N- carbazolyl)triphenylamine (TCTA). Among these compounds, TCTA can transport holes and inhibit exdtons from being diffused into the EML.

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

When the thickness of the HTL is within this range, the HTL may have excellent hole transporting characteristics, without a substantial penalty in driving voltage.

Electron blocking layer

The function of an electron blocking layer (EBL) is to prevent electrons from being transferred from an emission layer to the hole transport layer and thereby confine electrons to the emission layer. Thereby, efficiency, operating voltage and/or lifetime are improved. Typically, the electron blocking layer comprises a triarylamine compound. The triarylamine compound may have a LUMO level closer to vacuum level than the LUMO level of the hole transport layer. The electron blocking layer may have a HOMO level that is further away from vacuum level compared to the HOMO level of the hole transport layer. The thickness of the electron blocking layer may be selected between 2 and 20 nm.

If the electron blocking layer has a high triplet level, it may also be described as triplet control layer.

80 The function of the triplet control layer is to reduce quenching of triplets if a phosphorescent green or blue emission layer is used. Thereby, higher efficiency of light emission from a phosphorescent emission layer can be achieved. The triplet control layer is selected from triarylamine compounds with a triplet level above the triplet level of the phosphorescent emitter in the adjacent emission layer. Suitable compounds for the triplet control layer, in particular the triarylamine compounds, are described in EP 2722908 A1.

Emission layer (EML)

The EML may be formed on the HTL by vacuum deposition, spin coating, slot-die coating, printing, casting, LB deposition, or the like. When the EML is formed 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.

It may be provided that the emission layer does not comprise the compound of Formulas (I), (II) and/or the compound (III).

The emission layer (EML) may be formed of a combination of a host and an emitter dopant. Example of the host are Alqs, 4,4'-N,N'-dicarbazole-biphenyl (CBP), poly(n-vinylcarbazole) (PVK), 9,io-di(naphthalene-2-yl)anthracene (ADN), 4,4’,4"-tris(carbazol-9-yl)- triphenylamine(TCTA), i,3,5-tris(N-phenylbenzimidazole-2-yl)benzene (TPBI), 3-tert-butyl- 9,10 -di-2-naphthylanthracenee (TBADN), distyrylarylene (DSA) and bis(2-(2- hydroxyphenyl)benzo-thiazolate)zinc (Zn(BTZ)2).

The emitter dopant maybe a phosphorescent or fluorescent emitter. Phosphorescent emitters and emitters which emit light via a thermally activated delayed fluorescence (TADF) mechanism may be preferred due to their higher efficiency. The emitter may be a small molecule or a polymer.

Examples of red emitter dopants are PtOEP, Ir(piq)3, and Btp2lr(acac), but are not limited thereto. These compounds are phosphorescent emitters, however, fluorescent red emitter dopants could also be used.

Examples of phosphorescent green emitter dopants are Ir(ppy)3 (ppy = phenylpyridine) , Ir(ppy)2(acac), Ir(mpyp)s.

Examples of phosphorescent blue emitter dopants are F2lrpic, (F2ppy)2lr(tmd) and Ir(dfppz)3 and ter-fluorene.4.4'-bis(4-diphenyl amiostyryl)biphenyl (DPAVBi), 2,5,8,11-tetra- tert-butyl perylene (TBPe) are examples of fluorescent blue emitter dopants.

The amount of the emitter dopant may be in the range from about 0.01 to about 50 parts by weight, based on 100 parts by weight of the host. Alternatively, the emission layer may consist of a light-emitting polymer. The EML may have a thickness of about 10 nm to about 100 nm, for example, from 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 penalty in driving voltage.

81 Hole blocking layer (HBL)

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 holes into the ETL. When the EML comprises a phosphorescent dopant, the HBL may have also a triplet exciton blocking function.

The HBL may also be named auxiliary ETL or a-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 oxadiazole derivatives, triazole derivatives, and phenanthroline derivatives.

The HBL may have a thickness in the range from about 5 nm to about 100 run, for example, from about 10 nm to about 30 nm. When the thickness of the HBL is within this range, the HBL may have excellent hole-bloddng properties, without a substantial penalty in driving voltage.

Electron transport layer (ETL)

The OLED according to the present invention comprises at least two electron transport layers (ETLs). At least two of the electron transport layers are the first electron transport layer and the second electron transport layer as defined herein. In addition, the OLED may comprise further ETLs which may or may not be as defined above. If the additional ETLfs) is/are not as defined above, the characteristics thereof may be as follows.

According to various embodiments the OLED may comprise an electron transport layer stack comprising at least a first electron transport layer (ETL-i) comprising the compound of formula (I) and at least a second electron transport layer (ETL-2) comprising a compound of formula (II).

By suitably adjusting energy levels of particular layers of the ETL, the injection and transport of the electrons may be controlled, and the holes may be efficiently blocked. Thus, the OLED may have long lifetime, improved performance and stability.

Electron injection layer (EIL)

An EIL, which may facilitate injection of electrons from the cathode into the electron transport layer stack, may be formed on the electron transport layer stack, preferably directly on the electron transport layer stack, preferably directly on the second electron transport layer, preferably in direct contact with the second electron transport layer. Examples of materials for forming the EIL or being comprised in the EIL indude lithium 8-hydroxyquinolinolate (LiQ), LiF, NaCl, CsF, L12O, 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

82 deposition and coating conditions may vary, according to the material that is used to form the EIL. The EIL may comprise an organic matrix material doped with an n-type dopant. The matrix material may be selected from materials conventionally used as matrix materials for electron transport layers.

The EIL may consist of a number of individual EIL sublayers. In case the EIL consists of a number of individual EIL sublayers, the number of sublayers is preferably 2. The individual EIL sublayers may comprise different materials for forming the EIL.

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

The electron transport stack of the present invention is not part of the electron injection layer.

Cathode electrode

The cathode electrode is formed on the EIL if present, preferably directly on the EIL, preferably in direct contact with the EIL. In the sense of this invention the cathode and the EIL can be regarded as one functional part enabling the injection of electrons into the electron transport layer stack. 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. Alternatively, the cathode electrode may be formed of a transparent conductive oxide, such as ITΟ or IZO.

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

It is to be understood that the cathode electrode and the electron injection layer are not part of the electron transport layer stack.

Organic light-emitting diode (OLED)

The organic electronic device according to the invention is an organic light-emitting device.

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

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

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

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

According to various embodiments of the present invention, there may be provided OLEDs layers arranged between the above mentioned layers, on the substrate or on the top electrode.

According to one aspect, the OLED can comprise a layer structure of a substrate that is adjacent arranged to an anode electrode, the anode electrode is adjacent arranged to a first hole injection layer, the first hole injection layer is adjacent arranged to a first hole transport layer, the first hole transport layer is adjacent arranged to a first electron blocking layer, the first electron blocking layer is adjacent arranged to a first emission layer, the first emission layer is adjacent arranged to a first electron transport layer, the first electron transport layer is adjacent arranged to a second electron transport layer, the second electron transport layer is adjacent arranged to an electron injection layer, the electron injection layer is adjacent arranged to the cathode electrode.

For example, the OLED (too) according to Fig. 1 may be formed by a process, wherein on a substrate (no), an anode (120), a hole injection layer (130), a hole transport layer (140), an emission layer (150), an electron transport layer stack (160) comprising a first electron transport layer (161) and a second electron transport layer (162), an electron injection layer (180) and the cathode electrode (190) are subsequently formed in that order.

For example, the OLED (100) according to Fig. 2 may be formed by a process, wherein on a substrate (110), an anode (120), a hole injection layer (130), a hole transport layer (140), an electron blocking layer (145), an emission layer (150), an electron transport layer stack (160) comprising a first electron transport layer (161) and a second electron transport layer (162), an electron injection layer (180) and the cathode electrode (190) are subsequently formed in that order.

According to another aspect of the present invention, there is provided a method of manufacturing an organic electronic device, the method using: at least one deposition source, preferably two deposition sources and more preferred at least three deposition sources.

84 The methods for deposition that can be suitable comprise: deposition via vacuum thermal evaporation; deposition via solution processing, preferably the processing is selected from spincoating, printing, casting; and/or slot-die coating.

In case the second electron transport layer comprises a compound (III) and a compound of formula (II) the two compounds may be deposited by co-deposition from two separate deposition sources or deposited as a pre-mix from one single deposition source. A pre-mix is a mixture of at least two compounds and that mixture was prepared prior to filling it into the deposition source.

According to various embodiments of the present invention, the method may further include forming on the anode electrode, an emission layer and at least one layer selected from the group consisting of forming a hole injection layer, forming a hole transport layer, or forming an electron hole blocking layer, between the anode electrode and the first electron transport layer.

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 first anode electrode is formed, on the first anode electrode an emission layer is formed, on the emission layer an electron transport layer stack is formed, optionally a hole blocking layer is formed on the emission layer and on the electron transport layer an electro injection layer is formed, and finally a cathode electrode is formed, optional a hole injection layer, a hole transport layer, and a hole blocking layer, formed in that order between the first anode electrode and the emission layer, an electron injection layer is formed between the electron transport layer stack and the cathode electrode.

According to various embodiments of the present invention, the method further comprises forming an electron injection layer on the organic semiconducting layer. According to various embodiments, the OLED may have the following layer structure, wherein the layers having the following order:

85 anode, hole injection layer, first hole transport layer, second hole transport layer, emission layer, optional hole blocking layer, the electron transport layer stack, an electron injection layer, and cathode.

According to another aspect of the invention, it is provided an electronic device comprising at least one organic light emitting device according to any embodiment described throughout this application, preferably, the electronic device comprises the organic light emitting diode in one of embodiments described throughout this application. More preferably, the electronic device is a display device.

In one embodiment, the organic electronic device according to the invention may further comprise a layer comprising a radialene compound and/or a quinodimethane compound.

In one embodiment, the radialene compound and/or the quinodimethane compound may be substituted with one or more halogen atoms and/or with one or more electron withdrawing groups. Electron withdrawing groups can be selected from nitrile groups, halogenated alkyl groups, alternatively from perhalogenated alkyl groups, alternatively from perfluorinated alkyl groups. Other examples of electron withdrawing groups may be acyl, sulfonyl groups or phosphoryl groups.

Alternatively, acyl groups, sulfonyl groups and/or phosphoryl groups may comprise halogenated and/or perhalogenated hydrocarbyl. In one embodiment, the perhalogenated hydrocarbyl may be a perfluorinated hydrocarbyl. Examples of a perfluorinated hydrocarbyl can be perfluormethyl, perfluorethyl, perfluorpropyl, perfluorisopropyl, perfluorobutyl, perfluorophenyl, perfluorotolyl; examples of sulfonyl groups comprising a halogenated hydrocarbyl may be trifluoromethylsulfonyl, pentafluoroethylsulfonyl, pentafluorophenylsulfonyl, heptafluoropropylsufonyl, nonafluorobutylsulfonyl, and like.

In one embodiment, the radialene and/or the quinodimethane compound may be comprised in a hole injection, hole transporting and/or a hole generation layer.

In one embodiment, the radialene compound may have Formula (XX) and/or the quinodimethane compound may have Formula (XXIa) or (XXIb): wherein R ¹ , R ² , R3, R4, Rs, R6, R7, R8, R11 R12 R15 R16, R20, R21 _are independently selected from above mentioned electron withdrawing groups and R9, R10, R13, R14, R17, R18, R19, R22, R23 and R24 are independently selected from H, halogen and above mentioned electron withdrawing groups.

86 Hereinafter, the embodiments are illustrated in more detail with reference to examples. However, the present disclosure is not limited to the following examples. Reference will now be made in detail to the exemplary aspects.

GENERAL DEFINITIONS

In the present specification, when a definition is not otherwise provided, an "alkyl group" may refer to an aliphatic hydrocarbon group. The alkyl group may refer to "a saturated alkyl group" without any double bond or triple bond. The term “alkyl” as used herein shall encompass linear as well as branched and cyclic alkyl. For example, C ₃ -alkyl may be selected from n-propyl and iso-propyl. Likewise, C ₄ -alkyl encompasses n-butyl, sec-butyl and t-butyl. Likewise, C ₆ -alkyl encompasses n-hexyl and cyco-hexyl.

As used herein if not explicitly mentioned else, the asterisk symbol represents a binding position at which the moiety labelled accordingly is bond to another moiety.

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

The term “aryl” or “arylene” as used herein shall encompass phenyl (C ₆ -aryl), fused aromatics, such as naphthalene, anthracene, phenanthrene, tetracene etc.. Further encompassed are biphenyl and oligo- or polyphenyls, such as terphenyl, phenyl-substituted biphenyl, phenyl- substituted terphenyl (such as tetraphenyl benzole groups) etc.. “Arylene” respectively “heteroarylene”, refers to groups to which two further moieties are attached. In the present specification, the term “aryl group” or “arylene group” may refer to a group comprising at least one hydrocarbon aromatic moiety, and all the elements of the hydrocarbon aromatic moiety may have p-orbitals which form conjugation, for example a phenyl group, a napthyl group, an anthracenyl group, a phenanthrenyl group, a pyrinyl group, a fluorenyl group and the like. Further encompoassed are spiro compounds in which two aromatic moieties are connected with each other via a spiro-atom, such as 9,9’-spirobi[9H-fluorene]yl. The aryl or arylene group may include a monocyclic or fused ring polycyclic (i.e., links sharing adjacent pairs of carbon atoms) functional group.

The term “heteroaryl” as used herein refers to aryl groups in which at least one carbon atom is substituted with a heteroatom. The term “heteroaryl” may refer to aromatic heterocycles with at least one heteroatom, and all the elements of the hydrocarbon heteroaromatic moiety may have p-orbitals which form conjugation. The heteroatom may be selected from N, O, S, B, Si, P, Se, preferably from N, O and S. A heteroarylene ring may comprise at least 1 to 3 heteroatoms. Preferably, a heteroarylene ring may comprise at least 1 to 3 heteroatoms individually selected from N, S and/or O. Just as in case of “aryl”/”arylene”, the term “heteroaryl” comprises, for example, spiro compounds in which two aromatic moieties are connected with each other, such as spiro[fluorene-9,9’-xanthene]. Further exemplary heteroaryl groups are diazine, triazine, dibenzofurane, dibenzothiofurane, acridine, benzoacridine, dibenzoacridine etc.

The term “alkenyl” as used herein refers to a group -CR ¹ = CR ² R ³ comprising a carbon-carbon double bond.

87 The term “perhalogenated” as used herein refers to a hydrocarbyl group wherein all of the hydrogen atoms of the hydrocarbyl group are replaced by halogen (F, Cl, Br, I) atoms.

The term “alkoxy” as used herein refers to a structural fragment of the Formula —OR with R being hydrocarbyl, preferably alkyl or cycloalkyl.

The term “thioalkyl” as used herein refers to a structural fragment of the Formula -SR with R being hydrocarbyl, preferably alkyl or cycloalkyl.

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

The term “heteroaryl” as used herewith shall encompass pyridine, quinoline, benzoquinoline, quinazoline, benzoquinazoline, pyrimidine, pyrazine, triazine, benzimidazole, benzothiazole, benzo[4,5]thieno[3, 2-d]pyrimidine, carbazole, xanthene, phenoxazine, benzoacridine, dibenzoacridine and the like.

In the present specification, the term single bond refers to a direct bond.

The term “fluorinated” as used herein refers to a hydrocarbon group in which at least one of the hydrogen atoms comprised in the hydrocarbon group is substituted by a fluorine atom. Fluorinated groups in which all of the hydrogen atoms thereof are substituted by fluorine atoms are referred to as perfluorinated groups and are particularly addressed by the term “fluorinated”.

In terms of the invention, a group is “substituted with” another group if one of the hydrogen atoms comprised in this group is replaced by another group, wherein the other group is the substituent.

In terms of the invention, the expression “between” with respect to one layer being between two other layers does not exclude the presence of further layers which may be arranged between the one layer and one of the two other layers. In terms of the invention, the expression “in direct contact” with respect to two layers being in direct contact with each other means that no further layer is arranged between those two layers. One layer deposited on the top of another layer is deemed to be in direct contact with this layer.

The term “contacting sandwiched” refers to an arrangement of three layers whereby the layer in the middle is in direct contact with the two adjacent layers.

With respect to the inventive electron transport layer stack the compounds mentioned in the experimental part are most preferred.

A lighting device may be any of the devices used for illumination, irradiation, signaling, or projection. They are correspondingly classified as illuminating, irradiating, signaling, and projecting devices. A lighting device usually consists of a source of optical radiation, a device

88 that transmits the radiant flux into space in the desired direction, and a housing that joins the parts into a single device and protects the radiation source and light-transmitting system against damage and the effects of the surroundings.

The organic electroluminescent device COLED) may be a bottom- or top-emission device. The organic electroluminescent device (OLED) may emit the light trough a transparent anode or through a transparent cathode.

Another aspect is directed to a device comprising at least one organic electroluminescent device (OLED).

A device comprising organic light-emitting diodes is for example a display or a lighting panel.

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

In the context of the present specification the term “different” or “differs” in connection with the matrix material means that the matrix material differs in their structural Formula.

The terms “OLED” and “organic light-emitting diode” are simultaneously used and have the same meaning. The term “organic electroluminescent device” as used herein may comprise both organic light emitting diodes as well as organic light emitting transistors (OLETs).

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 component, substance or agent of the respective electron transport layer divided by the total weight of the respective electron transport layer thereof and multiplied by too. It is under-stood that the total weight percent amount of all components, substances and agents of the respective electron transport layer and electron injection 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 a composition, component, substance or agent as the volume of that 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 loo. It is understood that the total volume percent amount of all components, substances and agents of the cathode 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 dearly dictates otherwise.

89 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.

In the context of the present specification the term “essentially non-emissive” or “non- emissive” means that the contribution of the compound or layer to the visible emission spectrum from the device is less than 10 %, preferably less than 5 % relative to the visible emission spectrum. The visible emission spectrum is an emission spectrum with a wavelength of about ≥ 380 nm to about ≤ 780 nm.

Preferably, the organic semiconducting layer comprising the compound of Formula (I) is essentially non-emissive or non-emitting.

The operating voltage, also named U, is measured in Volt (V) at 10 milliAmpere per square centimeter (mA/cm2).

The candela per Ampere efficiency, also named cd/A efficiency is measured in candela per ampere at 10 milliAmpere per square centimeter (mA/cm2).

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. Efficiency values are compared at the same CIE-y.

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”, “organic light emitting diode”, “organic light emitting device”, “organic optoelectronic device” and “organic light-emitting diode” are simultaneously used and have the same meaning.

The term “life-span” and “lifetime” are simultaneously used and have the same meaning.

The anode and cathode may be described as anode electrode / cathode electrode or anode electrode / cathode electrode or anode electrode layer / cathode electrode layer.

Room temperature, also named ambient temperature, is 23 ⁰ C.

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;

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

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" or “onto” 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" or “directly onto” 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 nontransparent substrate no, an anode 120, a hole injection layer (HIL) 130, a hole transport layer (HTL) 140, an emission layer (EML) 150, an electron transport layer (ETL) stack 160 comprising a first electron transport layer 161 and a second electron transport layer 162. The electron transport layer (ETL) 160 is formed on the EML 150. Onto the electron transport layer (ETL) 160, an electron injection layer (EIL) 180 is disposed. The cathode 190 is disposed directly onto the electron injection layer (EIL) 180.

Fig. 2 is a schematic sectional view of an OLED too, according to another exemplary embodiment of the present invention. Fig. 2 differs from Fig. 1 in that the OLED 100 of Fig. 2 comprises an electron blocking layer (EBL) 145.

Referring to Fig. 2, the OLED 100 includes a non-transparent substrate 110, an anode 120, a hole injection layer (HIL) 130, a hole transport layer (HTL) 140, an electron blocking layer (EBL) 145, an emission layer (EML) 150, an electron transport layer (ETL) stack 160 comprising a first electron transport layer 161 and a second electron transport layer 162, an electron injection layer (EIL) 180 and a cathode electrode 190.

While not shown in Fig. 1 and Fig. 2 a sealing layer may further be formed on the cathode electrodes 190, in order to seal the OLEDs 100 and 200. In addition, various other modifications maybe 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.

DETAILED DESCRIPTION

Dipole moment

91 The dipole moment of a molecule containing N atoms is given by: where q _i and are the partial charge and position of atom i in the molecule.

The dipole moment is determined by a semi-empirical molecular orbital method.

The geometries of the molecular structures are optimized using the hybrid functional B3LYP with the 6-31G* basis set in the gas phase as implemented in the program package TURBOMOLE V6.5 (TURBOMOLE GmbH, Litzenhardtstrasse 19, 76135 Karlsruhe, Germany). If more than one conformation is viable, the conformation with the lowest total energy is selected to determine the bond lengths of the molecules.

Calculated HOMO and LUMP

The HOMO and LUMO are calculated with the program package TURBOMOLE V6.5 (TURBOMOLE GmbH, Litzenhardtstrasse 19, 76135 Karlsruhe, Germany). The optimized geometries and the HOMO and LUMO energy levels of the molecular structures are determined by applying the hybrid functional B3LYP with a 6-31G* basis set in the gas phase. If more than one conformation is viable, the conformation with the lowest total energy is selected.

Measurement of QT.ED Performance

To assess the performance of the OLED devices the current efficiency is measured at 20°C. The current-voltage characteristic is determined using a Keithley 2635 source measure unit, by sourcing a voltage in V and measuring the current in mA flowing through the device under test. The voltage applied to the device is varied in steps of 0.1V in the range between oV and 10V. Likewise, the luminance-voltage characteristics and CIE coordinates are determined by measuring the luminance in cd/m ² using an Instrument Systems CAS-140CT array spectrometer (calibrated by Deutsche Akkreditierungsstelle (DAkkS)) for each of the voltage values. The cd/A efficiency at 10 mA/cm ² is determined by interpolating the luminance-voltage and current-voltage characteristics, respectively.

As applicable, Lifetime LT of the device can be measured at ambient conditions (20°C) and 30 mA/cm ² , 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.

The increase in operating voltage ΔU is used as a measure of the operating voltage stability of the device. This increase is determined during the LT measurement and by subtracting the

92 operating voltage at the start of operation of the device from the operating voltage after 50 hours.

ΔU = [U(50 h)-U(o h)]

The smaller the value of Δ U the better is the operating voltage stability.

General procedure for fabrication of OLEDs

For the top emission OLED devices a substrate with dimensions of 150 mm x 150 mm x 0.7 mm was ultrasonically cleaned with a 2% aqueous solution of Deconex FPD 211 for 7 minutes and then with pure water for 5 minutes, and dried for 15 minutes in a spin rinse dryer. Subsequently, Ag was deposited as anode at a pressure of 10-5 to 10-7 mbar.

Then, HT-i and D-i were vacuum co-deposited on the anode to form a HIL. Then, HT-i was vacuum deposited on the HIL to form an HTL. Then, HT-2 was vacuum deposited on the HTL to form an electron blocking layer (EBL).

Afterwards the emission layer was formed on the EBL by co-deposition of HOST-1 and EMITTER-i.

Then, the compound of Formula (I) was vacuum deposited onto the emission layer to form the first electron transport layer. Then, the second electron transport layer was formed on the first electron transport layer by depositing a compound of Formula (II) for examples OLED-1 to OLED-12, For the comparative OLED example the second electron transport layer was formed on the first electron transport layer by depositing the compound C-3.

For examples OLED-13 to OLED-20 the second electron transport layer was formed on the first electron transport layer by depositing a pre-mix compound of Formula (II) and compound

(HO-

Then, the electron injection layer is formed as a double layer on the second electron transport layer by depositing first LiQ and subsequently Yb.

Ag:Mg is then evaporated at a rate of 0.01 to 1 A/s at 10-7 mbar to form a cathode.

A cap layer of HT-3 is formed on the cathode.

The details of the layer stack in the top emission OLED devices are given below. A slash “/” separates individual layers. Layer thicknesses are given in squared brackets [...], mixing ratios in wt% given in round brackets (...):

Layer stack details used in the OLED device examples of Table 6:

Ag [100nm] / HT-l:NDP-9 (wt% 92:8) [lonm] / HT-1 [130nm] / HT-2( 5nm) / H09:BD200 (wt% 97:3) [20 nm] / Compound of Formula (I) (5nm] / Compound of Formula (II) or C-3 [30nm] / LiQ [inm] / Yb [2nm] / Ag:Mg (wt% 90:10) [13 nm] / HT-3 [75nm]

93 Layer stack details used in the OLED device examples of Table 7:

Ag [loonm] / HT-1:NDP-9 (wt% 92:8) [lonm] / HT-i [130nm] / HT-2 [511m] / H09:BD200 (wt% 97:3) [20 nm] / Compound of Formula (I) [5nm] / Compound of Formula (II): Compound of Formula (III) (wt% 30:70) [30n m] / UQ [nm] / Yb [2nm] / Ag:Mg (wt% 90:10) [13 nm] / HT-3 [75n m]

Table 5: List of compounds used 94

Table 6. Performance of an organic electroluminescent device comprising the compound of Formula (I) in the first electron transport layer and the compound of Formula (II) or the comparative compound C-3 in the second electron transport layer.

Table 7, Performance of an organic electroluminescent device comprising the compound of Formula (I) in the first electron transport layer and a mixture of compound of Formula (II) and compound of Formula (III) in the second electron transport layer.

95

Examples 15, 16, 19 and 20 show that the cd/A efficiency is further increased at comparable or lower voltage if a compound (III) is used in the second electron transport layer.

The features disclosed in the foregoing description and in the dependent claims may, both separately and in any combination thereof, be material for realizing the aspects of the disclosure made in the independent claims, in diverse forms thereof.

96