Compound, organic semiconductor material comprising same, organic electronic device comprising same, and method for preparing same

Abstract

The present invention relates to a compound, an organic semiconductor material comprising the compound, an organic electronic device comprising the organic semiconductor material, and a method for preparing the organic electronic device.

Description

Technical Field

[0001] The present invention relates to a compound, an organic semiconductor material comprising the compound, an organic electronic device comprising the organic semiconductor material, and a method for preparing the organic electronic device. Background Art

[0002] Organic electronic devices, such as organic light-emitting diodes (OLEDs), which are self-luminous devices, have wide viewing angles, excellent contrast, fast response, high brightness, excellent operating 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, HTL, EML, and ETL are thin films formed of organic compounds.

[0003] When voltage is applied to the anode and cathode, holes injected from the anode move to the EML through the HTL, and electrons injected from the cathode move to the EML through the ETL. Holes and electrons recombine in the EML to generate excitons. When the excitons drop from the excited state to the ground state, light is emitted. The injection and flow of holes and electrons should be balanced so that the OLED having the above structure has excellent efficiency and / or long life.

[0004] The performance of an organic light emitting diode may be affected by the characteristics of the organic semiconductor layer, and in particular, may be affected by the characteristics of the organic material of the organic semiconductor layer.

[0005] In particular, there is a need to develop an organic semiconductor layer that can increase electron mobility and simultaneously increase electrochemical stability so that organic electronic devices such as organic light-emitting diodes can be applied to large flat-panel displays.

[0006] In addition, it is necessary to develop organic semiconductor layers that can have an extended life at higher current density and thus at higher brightness. In particular, it is necessary to develop organic semiconductor materials or semiconductor layers to reduce the operating voltage, which is important for reducing the power consumption of, for example, mobile display devices and increasing their battery life.

[0007] There remains a need to improve the performance of organic semiconductor materials, organic semiconductor layers and organic electronic devices thereof, in particular to achieve increased efficiency by improving the properties of the compounds contained therein.

[0008] Therefore, an object of the present invention is to provide an organic light emitting diode that overcomes the disadvantages of the prior art, in particular to provide compounds for organic semiconductor materials and electronic devices comprising the organic semiconductor materials, thereby contributing to improving the driving voltage and / or efficiency of the electronic devices. Summary of the invention

[0009] This object is achieved by the following compounds of formula (I):

[0010] A-(Cy) n -Pz-FL(I)

[0011] in

[0012] -A is selected from substituted or unsubstituted C containing at least two condensed aromatic rings 10 To C 42 Aryl and selected from C2-C 42 Heteroaryl, excluding C2 to C 42 The case where the heteroaryl group is benzoxazolyl or carbazolyl;

[0013] - wherein, if A is substituted, one or more substituents are independently selected from C6-C 18 Aryl, C3-C 20 Heteroaryl, D, F, CN, C1-C 20 Alkyl, C1-C 20 Alkoxy, PY(R)2, OR, SR, (C=O)R, (C=O)N(R)2, Si(R)3, (S=O)R and

[0014] in

[0015] Y is O or S, and

[0016] R is independently selected from C1-C 20 Straight chain alkyl, C1-C 20 Alkoxy, C1-C 20 Thioalkyl, C3-C 20 Branched alkyl, C3-C 20 Cyclic alkyl, C3-C 20 Branched alkoxy, C3-C 20 Cyclic alkoxy, C3-C 20 Branched chain thioalkyl, C3-C 20 Cyclic thioalkyl, C6-C 20 Aryl and C3-C 20 heteroaryl;

[0017] -Cy is independently selected from substituted or unsubstituted monocyclic C3 to C 36 Hydrocarbyl, substituted or unsubstituted polycyclic C3 to C 36 Hydrocarbon, substituted or unsubstituted heteroatom-containing monocyclic C3 to C 36 A hydrocarbon group, or a substituted or unsubstituted polycyclic C3 to C 36 Hydrocarbon;

[0018] - wherein, if Cy is substituted, one or more substituents are independently selected from C6-C18 Aryl, C3-C 20 Heteroaryl, D, F, CN, C1-C 16 Alkyl, C1-C 16 Alkoxy, PY(R)2, OR, SR, (C=O)R, (C=O)N(R)2, Si(R)3, (S=O)R and

[0019] in

[0020] Y is O or S, and

[0021] R is independently selected from C1-C 20 Straight chain alkyl, C1-C 20 Alkoxy, C1-C 20 Thioalkyl, C3-C 20 Branched alkyl, C3-C 20 Cyclic alkyl, C3-C 20 Branched alkoxy, C3-C 20 Cyclic alkoxy, C3-C 20 Branched chain thioalkyl, C3-C 20 Cyclic thioalkyl, C6-C 20 Aryl and C3-C 20 heteroaryl;

[0022] -n is an integer from 0 to 4;

[0023] -Pz is a fully substituted pyrazine substituent;

[0024] - wherein the substituents on the pyrazine substituent are independently selected from groups having at least one carbon atom;

[0025] -FL is a substituted or unsubstituted fluorenyl group;

[0026] - wherein, if FL is substituted, one or more substituents are independently selected from C6-C 18 Aryl, C2-C 20 Heteroaryl, D, F, CN, C1-C 16 Alkyl, C1-C 16 Alkoxy, PY(R)2, OR, SR, (C=O)R, (C=O)N(R)2, Si(R)3, (S=O)R and

[0027] in

[0028] Y is O or S, and

[0029] R is independently selected from C1-C 20 Straight chain alkyl, C1-C 20 Alkoxy, C1-C20 Thioalkyl, C3-C 20 Branched alkyl, C3-C 20 Cyclic alkyl, C3-C 20 Branched alkoxy, C3-C 20 Cyclic alkoxy, C3-C 20 Branched chain thioalkyl, C3-C 20 Cyclic thioalkyl, C6-C 20 Aryl and C3-C 20 Heteroaryl.

[0030] The object is also achieved by an organic electronic semiconductor material comprising the compound according to the invention.

[0031] The object is also achieved by an organic electronic device comprising a semiconducting layer, wherein the semiconducting layer comprises the compound according to the invention.

[0032] The object is also achieved by a method for producing an organic electronic device according to the invention, comprising the step of depositing a compound according to the invention on a solid support.

[0033] Surprisingly, it was found that the organic electronic device according to the present invention solves the problems underlying the present invention by making the device superior to organic electroluminescent devices known in the art in several aspects, in particular in terms of efficiency and / or operating voltage.

[0034] The present invention particularly relates to a compound of the following formula (I):

[0035] A-(Cy) n -Pz-FL(I).

[0036] A is selected from substituted or unsubstituted C 10 To C 42 Aryl and selected from C2-C 42 According to the present invention, when A is C2-C 42 In the case of heteroaryl, C2-C 42 The heteroaryl group is a benzoxazolyl group or a carbazolyl group. It is also provided that A does not contain a benzoxazolyl group or a carbazolyl group. It may be further provided that the compound of formula (I) does not contain a benzoxazolyl group or a carbazolyl group. In view of device performance, it is found that it is advantageous to avoid the presence of a benzoxazolyl group or a carbazolyl group in the compound of formula (I), especially in the A part.

[0037] A may be selected from substituted or unsubstituted C 10 To C 36 Aryl and selected from C2-C 36 Heteroaryl, excluding C2 to C 36In the case where the heteroaryl group is benzoxazolyl or carbazolyl. A may be selected from substituted or unsubstituted C 10 To C 30 Aryl and selected from C3-C 30 Heteroaryl, excluding C2 to C 30 In the case where the heteroaryl group is benzoxazolyl or carbazolyl. A may be selected from substituted or unsubstituted C 10 To C 24 Aryl and selected from C3-C 24 Heteroaryl, excluding C2 to C 24 In the case where the heteroaryl group is benzoxazolyl or carbazolyl. A may be selected from substituted or unsubstituted C 10 To C 18 Aryl and selected from C3-C 21 Heteroaryl, excluding C2 to C 21 The heteroaryl group is a benzoxazolyl group or a carbazolyl group.

[0038] A may contain at least one six-membered N-containing aromatic ring.

[0039] A can be selected from C2-C 36 Heteroaryl, excluding C2 to C 36 When the heteroaryl group is benzoxazolyl or carbazolyl. A can be selected from C3-C 30 Heteroaryl, excluding C2 to C 30 When the heteroaryl group is benzoxazolyl or carbazolyl. A can be selected from C3-C 24 Heteroaryl, excluding C2 to C 24 When the heteroaryl group is benzoxazolyl or carbazolyl. A can be selected from C3-C 21 Heteroaryl, excluding C2 to C 21 The heteroaryl group is a benzoxazolyl group or a carbazolyl group.

[0040] A is selected from aryl groups containing 2, 3, 4 or 5 condensed aromatic rings, azinyl, diazinyl, triazinyl, naphthyrazinyl, naphthyrazinyl, triazinyl, azaanthryl, azaphenanthrenyl, diazaanthryl, diazaphenanthrenyl, triazaanthryl, triazaphenanthrenyl, benzofuranyl and its aza, diaza or triaza derivatives, benzothiophenyl and its aza, diaza or triaza derivatives, dibenzofuranyl and its aza, diaza or triaza derivatives, dibenzothiophenyl and its Aza, diaza or triaza derivatives, naphthofuranyl and its aza, diaza or triaza derivatives, naphthothienyl and its aza, diaza or triaza derivatives, naphthobenzofuranyl and its aza, diaza or triaza derivatives, naphthobenzothienyl and its aza, diaza or triaza derivatives, dinaphthofuranyl and its aza, diaza or triaza derivatives, and dinaphthothienyl and its aza, diaza or triaza derivatives, which are respectively substituted or unsubstituted.

[0041] The term "condensed aryl ring" is understood to mean when two aryl rings share at least two common sp 2 When carbon atoms are hybridized, they are considered fused or condensed.

[0042] The term "aza derivative" refers to a derivative of a specific moiety in which one carbon atom is replaced by a nitrogen atom. The term "diaza derivative" refers to a derivative of a specific moiety in which two carbon atoms are replaced by two nitrogen atoms, respectively. The term "triaza derivative" refers to a derivative of a specific moiety in which three carbon atoms are replaced by three nitrogen atoms, respectively.

[0043] A can be selected from azinyl, diazinyl, triazinyl, naphthazinyl, naphthazinyl, triazinyl, azaanthryl, azaphenanthrenyl, diazaanthryl, diazaphenanthrenyl, triazaanthryl, triazaphenanthrenyl, benzofuranyl and its aza, diaza or triaza derivatives, benzothienyl and its aza, diaza or triaza derivatives, dibenzofuranyl and its aza, diaza or triaza derivatives, dibenzothienyl and its aza, diaza or triaza derivatives derivatives, naphthofuranyl and its aza, diaza or triaza derivatives, naphthothienyl and its aza, diaza or triaza derivatives, naphthobenzofuranyl and its aza, diaza or triaza derivatives, naphthobenzothienyl and its aza, diaza or triaza derivatives, dinaphthofuranyl and its aza, diaza or triaza derivatives, and dinaphthothienyl and its aza, diaza or triaza derivatives, which are substituted or unsubstituted, respectively.

[0044] A can be selected from naphthyl, anthracenyl, phenanthrenyl, terphenylidene, acenaphthenyl, fluoranthenyl, pyrenyl, tetraphenyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, quinolyl, isoquinolyl, cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, naphthyridinyl, imidazopyridinyl, phenanthridinyl, phenanthrolinyl, acridinyl, benzoacridinyl, dibenzoacridinyl, which may be substituted or unsubstituted.

[0045] A can be selected from pyridinyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, quinolyl, isoquinolyl, cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, naphthyridinyl, imidazopyridinyl, phenanthridinyl, phenanthrolinyl, acridinyl, benzoacridinyl, dibenzoacridinyl, which may be substituted or unsubstituted.

[0046] A may be selected from pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl or triazinyl. A may be selected from pyrimidinyl or triazinyl.

[0047] If A is substituted, the one or more substituents are independently selected from C6-C 18 Aryl, C3-C 20 Heteroaryl, D, F, CN, C1-C 20 Alkyl, C1-C 20 Alkoxy, PY(R)2, OR, SR, (C=O)R, (C=O)N(R)2, Si(R)3, (S=O)R and

[0048] in

[0049] Y is O or S, and

[0050] R is independently selected from C1-C 20 Straight chain alkyl, C1-C 20 Alkoxy, C1-C 20 Thioalkyl, C3-C 20 Branched alkyl, C3-C 20 Cyclic alkyl, C3-C 20 Branched alkoxy, C3-C 20 Cyclic alkoxy, C3-C 20 Branched chain thioalkyl, C3-C 20 Cyclic thioalkyl, C6-C 20 Aryl and C3-C 20 In case one or more substituents on A comprise more than one radical R, the respective R may be selected independently of one another, ie may be independently identical or different from one another.

[0051] If A is substituted, the one or more substituents may be independently selected from C6-C 18 Aryl, C3-C 20Heteroaryl, D, F, CN, C1-C 20 If A is substituted, one or more substituents may be independently selected from C6-C 18 Aryl and C3-C 20 If A is substituted, one or more substituents may be independently selected from C6-C 18 If A is substituted, one or more substituents may be independently selected from C6-C 12 If A is substituted, then one or more of the substituents may each be phenyl.

[0052] Cy is independently selected from substituted or unsubstituted monocyclic C3 to C 36 Hydrocarbyl, substituted or unsubstituted polycyclic C3 to C 36 Hydrocarbon, substituted or unsubstituted heteroatom-containing monocyclic C3 to C 36 A hydrocarbon group, or a substituted or unsubstituted polycyclic C3 to C 36 Cy can be independently selected from substituted or unsubstituted monocyclic C6 to C 30 Hydrocarbyl, substituted or unsubstituted polycyclic C6 to C 30 Hydrocarbon, substituted or unsubstituted heteroatom-containing monocyclic C3 to C 30 A hydrocarbon group, or a substituted or unsubstituted polycyclic C3 to C 30 Cy can be independently selected from substituted or unsubstituted monocyclic C6 to C 24 Hydrocarbyl, substituted or unsubstituted polycyclic C6 to C 24 Hydrocarbon, substituted or unsubstituted heteroatom-containing monocyclic C3 to C 24 A hydrocarbon group, or a substituted or unsubstituted polycyclic C3 to C 24 Cy can be independently selected from substituted or unsubstituted monocyclic C6 to C 18 Hydrocarbyl, substituted or unsubstituted polycyclic C6 to C 18 Hydrocarbon, substituted or unsubstituted heteroatom-containing monocyclic C3 to C 18 A hydrocarbon group, or a substituted or unsubstituted polycyclic C3 to C 18 Cy can be independently selected from substituted or unsubstituted monocyclic C6 to C 12 Hydrocarbyl, substituted or unsubstituted polycyclic C6 to C 12 Hydrocarbon, substituted or unsubstituted heteroatom-containing monocyclic C3 to C 12 A hydrocarbon group, or a substituted or unsubstituted polycyclic C3 to C 12 Hydrocarbon.

[0053] Cy can be independently selected from C6-C 36 Aryl and C3-C 36Cy can be independently selected from C6-C 30 Aryl and C3-C 30 Cy can be independently selected from C6-C 24 Aryl and C3-C 24 Cy can be independently selected from C6-C 12 Aryl and C3-C 12 Heteroaryl.

[0054] Cy can be monocyclic or bicyclic. Cy can be monocyclic. Cy can be independently selected from phenylene and naphthalene. Cy can be phenylene.

[0055] n is an integer from 0 to 4. n may be an integer from 1 to 4. n may be an integer from 1 to 3. n may be an integer from 1 to 2. n may be 1.

[0056] Cy may be specified as a phenylene group and n may be 1. Cy may be specified as an o-phenylene group or an m-phenylene group and n may be 1. Cy may be specified as a m-phenylene group and n may be 1.

[0057] If Cy is substituted, the one or more substituents may be independently selected from C6-C 18 Aryl, C3-C 20 Heteroaryl, D, F, CN, C1-C 16 Alkyl and C1-C 16 If Cy is substituted, one or more substituents may be independently selected from D, F, CN, C1-C 16 Alkyl and C1-C 16 Alkoxy. If Cy is substituted, one or more substituents may be independently selected from D and C1-C4 alkyl. It may be provided that Cy is respectively unsubstituted.

[0058] Pz is a fully substituted pyrazine group. This means that the pyrazine group is (1.) connected to Cy via one of its carbon atoms (or to A when n is 0), (2.) connected to FL via another carbon atom thereof, and (3.) its two independently selected substituents are bonded to the two remaining carbon atoms. In particular, the fully substituted pyrazine group may have one of the following formulae:

[0059]

[0060] Among them, "Sub 1 " indicates a substituent, "Sub 2 " represents another substituent, and "*" represents the bonding position to Cy (or A) and FL, respectively. It is not foreseen that two or more substituents of the fully substituted pyrazine are linked to each other to form a ring.

[0061] The substituents of the fully substituted pyrazine substituents (Sub 1 and Sub 2 ) are independently selected from a group having at least one carbon atom. The substituents of the fully substituted pyrazine substituents may be independently selected from a hydrocarbyl group, a carbocyclic group or a heterocyclic group. In one embodiment, the substituents of the fully substituted pyrazine substituents are monocyclic or bicyclic.

[0062] The substituents of the fully substituted pyrazine substituent group may be independently selected from C6-C 36 Aryl and C3-C 36 The substituents of the fully substituted pyrazine substituent may be independently selected from C6-C 30 Aryl and C3-C 30 The substituents of the fully substituted pyrazine substituent may be independently selected from C6-C 24 Aryl and C3-C 24 The substituents of the fully substituted pyrazine substituent may be independently selected from C6-C 18 Aryl and C3-C 18 The substituents of the fully substituted pyrazine substituent may be independently selected from C6-C 12 Aryl and C3-C 12 Heteroaryl.

[0063] The substituents of the fully substituted pyrazine substituent group may be independently selected from C6-C 36 The substituents of the fully substituted pyrazine substituent may be independently selected from C6-C 30 The substituents of the fully substituted pyrazine substituent may be independently selected from C6-C 24 The substituents of the fully substituted pyrazine substituent may be independently selected from C6-C 18 The substituents of the fully substituted pyrazine substituent may be independently selected from C6-C 12 The substituents of the fully substituted pyrazine substituents may be phenyl.

[0064] FL may be a substituted or unsubstituted fluoren-1-yl group, a substituted or unsubstituted fluoren-2-yl group, a substituted or unsubstituted fluoren-3-yl group, or a substituted or unsubstituted fluoren-4-yl group.

[0065] The fluorenyl group may be substituted at position 9. The fluorenyl group may be substituted at position 9 by at least one hydrocarbon group, and in particular, by two hydrocarbon groups which may be connected to each other to form a ring.

[0066] Reference is made herein to the numbering of the fluorenyl moiety below.

[0067]

[0068] FL can be 9,9'-dialkyl-fluorenyl. FL can be 9,9'-C1 to C 16 Dialkyl-fluorenyl. FL can be 9,9'-C1 to C 10 Dialkyl-fluorenyl. FL may be 9,9'-C1 to C4 dialkyl-fluorenyl. FL may be 9,9'-dimethyl-fluorenyl.

[0069] The compound of formula (I) may be selected from the following E1 to E6.

[0070]

[0071] According to one embodiment, there is provided a compound of formula (I):

[0072] A-(Cy) n -Pz-FL(I),

[0073] in

[0074] A is selected from C3-C 30 Heteroaryl, excluding C2 to C 30 The case where the heteroaryl group is benzoxazolyl or carbazolyl;

[0075] Wherein, if A is substituted, one or more substituents are independently selected from C6-C 18 Aryl, C3-C 20 Heteroaryl, D, F, CN, C1-C 20 alkyl;

[0076] n is an integer from 1 to 4;

[0077] Cy is independently selected from C6-C 36 Aryl and C3-C 36 heteroaryl;

[0078] Wherein, if Cy is substituted, one or more substituents are independently selected from D, F, CN, C1-C 16 Alkyl and C1-C 16 Alkoxy;

[0079] Pz is a fully substituted pyrazine group, wherein the substituents of the fully substituted pyrazine group are independently selected from C6-C 36 Aryl and C3-C 36 heteroaryl; and

[0080] FL is substituted at the 9-position of the fluorenyl group with two hydrocarbon groups, and the two hydrocarbon groups may be connected to each other to form a ring.

[0081] According to one embodiment, there is provided a compound of formula (I):

[0082] A-(Cy) n -Pz-FL(I),

[0083] in

[0084] A is selected from naphthyl, anthracenyl, phenanthrenyl, terphenylidene, acenaphthenyl, fluoranthenyl, pyrenyl, naphthacene, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, quinolyl, isoquinolyl, cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, naphthyridinyl, imidazopyridinyl, phenanthridinyl, phenanthrolinyl, acridinyl, benzoacridinyl, dibenzoacridinyl, each of which is substituted or unsubstituted;

[0085] Wherein, if A is substituted, one or more substituents are independently selected from C6-C 18 Aryl;

[0086] n is 1 or 2;

[0087] Cy is independently selected from C6-C 12 Aryl and C3-C 12 heteroaryl;

[0088] wherein, if Cy is substituted, the one or more substituents are independently selected from D and C1-C4 alkyl;

[0089] Pz is a fully substituted pyrazine group, wherein the substituents of the fully substituted pyrazine group are independently selected from C6-C 36 aryl; and

[0090] FL is 9,9'-C1 to C 10 Dialkyl-fluorenyl.

[0091] According to one embodiment, there is provided a compound of formula (I):

[0092] A-(Cy) n -Pz-FL(I),

[0093] in

[0094] A is selected from pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl or triazinyl, in particular from pyrimidinyl or triazinyl, each of which is substituted or unsubstituted;

[0095] Wherein, if A is substituted, one or more substituents are independently selected from C6-C 12 Aryl, especially phenyl;

[0096] n is 1;

[0097] Cy is independently selected from unsubstituted phenylene groups and unsubstituted naphthalene groups, and can be in particular unsubstituted phenylene groups, such as metaphenylene groups;

[0098] Pz is a fully substituted pyrazine substituent, wherein the substituents of the fully substituted pyrazine substituent are independently selected from C6-C 12 Aryl, especially phenyl; and

[0099] FL is 9,9'-C1 to C4 dialkyl-fluorenyl, especially 9,9'-dimethyl-fluorenyl.

[0100] The object is also achieved by an organic semiconductor material comprising the compound of the formula (I) according to the invention.

[0101] In addition to the compound of formula (I), the organic semiconductor material may also contain an electrical dopant, in particular a redox n-dopant.

[0102] Redox n-dopants are understood to be compounds which, when embedded in an electron-transporting matrix, improve the electronic properties of the resulting organic material compared to the pure matrix under the same physical conditions, in particular with regard to electron injection and / or electron conductivity.

[0103] In the context of the present invention, "embedded in the electron transport matrix" means uniformly mixed with the electron transport matrix.

[0104] The redox n-type dopant may be selected from elemental metals, metal salts, metal complexes and organic groups.

[0105] In one embodiment, the redox n-type dopant is selected from alkali metal salts and alkali metal complexes; preferably selected from lithium salts and lithium organic complexes; more preferably selected from lithium halides and lithium organic chelates; even more preferably selected from lithium fluoride, lithium quinoline, lithium borate, lithium phenoxide, lithium pyridinolate or lithium complexes with Schiff base ligands; most preferably,

[0106] - The lithium complex has formula II, formula III or formula IV:

[0107]

[0108] in

[0109] A1 to A6 are identically or independently selected from CH, CR, N, O;

[0110] R are identically or independently selected from hydrogen, halogen, alkyl or aryl or heteroaryl having 1 to 20 carbon atoms; and more preferably A1 to A6 are CH,

[0111] - the borate anion organic ligand is a tetrakis(1H-pyrazol-1-yl)borate anion,

[0112] - the phenol anion is a 2-(pyridin-2-yl)phenol anion, a 2-(diphenylphosphoryl)phenol anion, an imidazophenol anion, a 2-(pyridin-2-yl)phenol anion or a 2-(1-phenyl-1H-benzo[d]imidazol-2-yl)phenol anion,

[0113] - the pyridinol anion is a 2-(diphenylphosphoryl)pyridin-3-ol anion,

[0114] - The lithium Schiff base has structure 100, 101, 102 or 103:

[0115]

[0116] According to one embodiment of the present invention, the organic semiconductor material of the present invention comprises a lithium organic complex, or LiQ.

[0117] According to one embodiment of the present invention, the organic semiconductor material comprises a metal, preferably selected from alkali metals, alkaline earth metals, rare earth metals and metals of the first transition period, Ti, V, Cr and Mn, especially selected from Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Sm, Eu, Tm, Yb; more preferably selected from Li, Na, K, Rb, Cs, Mg and Yb, even more preferably selected from Li, Na, Cs and Yb, most preferably selected from Li, Na and Yb.

[0118] The most practical reference to the strength of an n-type dopant is the value of its redox potential. There is no particular limit to how negative the redox potential can be.

[0119] Since the reduction potential of common electron transport substrates used in organic semiconductors is roughly in the range of about -0.8 V to about -3.1 V when measured by cyclic voltammetry for a ferrocene / ferrocene cation reference redox couple, the practical applicable range of redox potentials of n-type dopants that can effectively n-dope such substrates is in a slightly wider range of about -0.5 V to about -3.3 V.

[0120] The measurement of the redox potential is actually carried out on the corresponding redox couple consisting of the reduced form and the oxidized form of the same compound.

[0121] In the case where the redox n-type dopant is an electrically neutral metal complex and / or an electrically neutral organic group, the measurement of its redox potential is actually carried out on the redox couple formed by:

[0122] (i) an electrically neutral metal complex and a cationic group formed by extracting an electron from the electrically neutral metal complex, or

[0123] (ii) An electrically neutral organic group and a cation formed by extracting one electron from the electrically neutral organic group.

[0124] Preferably, the redox potential of the electrically neutral metal complex and / or electrically neutral organic group, when measured by cyclic voltammetry against a ferrocene / ferrocene cation reference redox couple, may have a value that is more negative than -0.5 V, preferably more negative than -1.2 V, more preferably more negative than -1.7 V, even more preferably more negative than -2.1 V, most preferably more negative than -2.5 V for the corresponding redox couple consisting of:

[0125] (i) an electrically neutral metal complex and a cationic group formed by extracting an electron from the electrically neutral metal complex, or

[0126] (ii) An electrically neutral organic group and a cation formed by extracting one electron from the electrically neutral organic group.

[0127] In a preferred embodiment, the redox potential of the n-type dopant is between about 0.5 V more positive and about 0.5 V more negative than the reduction potential of the selected electron transport host.

[0128] Suitable electrically neutral metal complexes as redox n-type dopants may be, for example, strongly reducing complexes of some transition metals in a low oxidation state. Particularly strong redox n-type dopants may be selected, for example, from Cr(II), Mo(II) and / or W(II) guanidine complexes, such as W2(hpp)4, as described in more detail in WO2005 / 086251.

[0129] The electrically neutral organic group suitable as a redox n-type dopant can be an organic group produced, for example, by supplying additional energy from its stable dimer, oligomer or polymer, as described in more detail in EP 1 837 926B1, WO2007 / 107306 or WO2007 / 107356. Elemental metals should be understood as metals in pure metal state, metal alloy state or free atom or metal cluster state. It should be understood that the metal deposited from the metal phase, for example, from pure bulk metal by vacuum thermal evaporation is vaporized in its elemental form. It should also be understood that if the vaporized elemental metal is deposited with a covalent matrix, the metal atoms and / or metal clusters are embedded in the covalent matrix. In other words, it should be understood that any metal-doped covalent material prepared by vacuum thermal evaporation contains at least a portion of the metal in its elemental form.

[0130] For use in consumer electronics, only metals containing stable nuclides or nuclides with extremely long radioactive decay half-lives are likely to be suitable. As an acceptable level of nuclear stability, the nuclear stability of natural potassium can be used.

[0131] In one embodiment, the n-type dopant may be selected from an electropositive metal, and the electropositive metal is selected from alkali metals, alkaline earth metals, rare earth metals, and metals of the first transition period Ti, V, Cr, and Mn. Preferably, the n-type dopant may be selected from Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Sm, Eu, Tm, Yb; more preferably selected from Li, Na, K, Rb, Cs, Mg, and Yb, even more preferably selected from Li, Na, Cs, and Yb, and most preferably selected from Li, Na, and Yb.

[0132] The object is also achieved by an organic electronic device comprising a semiconducting layer, wherein the semiconducting layer comprises a compound of the formula (I) according to the invention, in particular comprises an organic semiconducting material according to the invention or consists of an organic semiconducting material according to the invention.

[0133] According to one embodiment of the present invention, the organic semiconductor layer of the present invention is an electron transport layer, an electron injection layer or a charge generation layer; or is an electron transport layer or a charge generation layer.

[0134] The organic electronic device according to the present invention may be an organic light emitting diode. The present invention also relates to a display device comprising the organic electronic device according to the present invention.

[0135] Finally, the object is also achieved by a method for preparing an organic electronic device according to the invention, comprising the step of depositing the compound according to the invention on a solid support. In this context, a "solid support" can be any solid surface, in particular an organic electronic device layer arranged adjacent to an organic semiconductor layer in an organic electronic device.

[0136] Other layers

[0137] According to the present invention, in addition to the layers mentioned above, the organic electronic device may further comprise other layers. Exemplary embodiments of the corresponding layers are described below:

[0138] Base

[0139] The substrate can be any substrate commonly used in the manufacture of electronic devices such as organic light emitting diodes. If light is to be emitted through the substrate, the substrate should be a transparent or translucent material, such as a glass substrate or a transparent plastic substrate. If light is to be emitted through the top surface, the substrate can be a transparent as well as an opaque material, such as a glass substrate, a plastic substrate, a metal substrate or a silicon substrate.

[0140] Anode electrode

[0141] The first electrode or the second electrode included in the organic electronic device of the present invention can be an anode electrode. The anode electrode can be formed by depositing or sputtering a material for forming the anode electrode. The material for forming the anode electrode can be a high work function material to promote hole injection. The anode material can also be selected from a low work function material (i.e., aluminum). The anode electrode can be a transparent electrode or a reflective electrode. Transparent conductive oxides such as indium tin oxide (ITO), indium zinc oxide (IZO), tin dioxide (SnO2), aluminum zinc oxide (AlZO) and zinc oxide (ZnO) can be used to form the anode electrode. The anode electrode can also be formed using a metal, typically silver (Ag), gold (Au) or a metal alloy.

[0142] Hole injection layer

[0143] The hole injection layer (HIL) may be formed on the anode electrode by vacuum deposition, spin coating, printing, casting, slot die coating, Langmuir-Broghe (LB) deposition, etc. When the HIL is formed using vacuum deposition, the deposition conditions may vary according to the compound used to form the HIL and the desired structure and thermal properties of the HIL. However, in general, the conditions for vacuum deposition may include a deposition temperature of 100° C. to 500° C., a ... -8 Support up to 10 -3 Torr pressure (1 Torr equals 133.322 Pa) and a deposition rate of 0.1 to 10 nm / s.

[0144] When the HIL is formed using spin coating or printing, the coating conditions may vary according to the compound used to form the HIL and the desired structure and thermal properties of the HIL. For example, the coating conditions may include a coating speed of about 2000 rpm to about 5000 rpm and a heat treatment temperature of about 80° C. to about 200° C. After coating, the heat treatment removes the solvent.

[0145] The HIL may be formed of any compound commonly used to form a HIL. Examples of compounds that can be used to form the HIL include phthalocyanine compounds 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 / camphorsulfonic acid (Pani / CSA), and polyaniline / poly(4-styrenesulfonate) (PANI / PSS).

[0146] The HIL may include or consist of a p-type dopant, and the p-type dopant may be selected from tetrafluoro-tetracyanoquinodimethane (F4TCNQ), 2,2'-(perfluoronaphthalene-2,6-diylidene)dimalononitrile or 2,2',2"-(cyclopropane-1,2,3-triylidene)tris(2-(p-cyanotetrafluorophenyl)acetonitrile), but is not limited thereto. The HIL may be selected from a hole transport host compound doped with a p-type dopant. Typical examples of known doped hole transport materials include copper phthalocyanine (CuPc), which has a HOMO level of about -5.2 eV, and a doped Tetrafluorotetracyanoquinodimethane (F4TCNQ) with a LUMO level of about -5.2 eV; zinc phthalocyanine (ZnPc) (HOMO = -5.2 eV) doped with F4TCNQ; α-NPD (N,N'-bis(naphthalene-1-yl)-N,N'-bis(phenyl)-benzidine) doped with F4TCNQ. α-NPD doped with 2,2'-(perfluoronaphthalene-2,6-diylidene) dimalononitrile. The p-type dopant concentration may be selected from 1 wt% to 20 wt%, more preferably from 3 wt% to 10 wt%.

[0147] The thickness of the HIL may be in the range of about 1 nm to about 100 nm, for example, about 1 nm to about 25 nm. When the thickness of the HIL is within this range, the HIL may have excellent hole injection characteristics without substantially deteriorating driving voltage.

[0148] Hole transport layer

[0149] A hole transport layer (HTL) may be formed on the HIL by vacuum deposition, spin coating, slot die coating, printing, casting, Langmuir-Broghe (LB) deposition, etc. When the HTL is formed by vacuum deposition or spin coating, the conditions for deposition and coating may be similar to those for forming the HIL. However, the conditions for vacuum deposition or solution deposition may vary according to the compound used to form the HTL.

[0150] The HTL can be formed of any compound commonly used to form the HTL. For example, potentially applicable compounds are disclosed in Yasuhiko Shirota and Hiroshi Kageyama, Chem. Rev. 2007, 107, 953-1010 and are incorporated herein by reference. Examples of compounds that can be used to form the HTL are: carbazole derivatives, such as N-phenylcarbazole or polyvinylcarbazole; benzidine derivatives, such as N,N'-bis(3-methylphenyl)-N,N'-diphenyl-[1,1-biphenyl]-4,4'-diamine (TPD) or N,N'-di(naphthalene-1-yl)-N,N'-diphenylbenzidine (α-NPD); and triphenylamine compounds, such as 4,4',4"-tri(N-carbazolyl)triphenylamine (TCTA). Among these compounds, TCTA can transport holes and inhibit the diffusion of excitons into the EML.

[0151] 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, more preferably about 20 nm to about 190 nm, more preferably about 40 nm to about 180 nm, more preferably about 60 nm to about 170 nm, more preferably about 80 nm to about 160 nm, more preferably about 100 nm to about 160 nm, more preferably about 120 nm to about 140 nm. The preferred thickness of the HTL may be 170 nm to 200 nm.

[0152] When the thickness of the HTL is within this range, the HTL may have excellent hole transport characteristics without substantially deteriorating driving voltage.

[0153] Electron blocking layer

[0154] The function of the electron blocking layer (EBL) is to prevent electrons from being transferred from the light-emitting layer to the hole transport layer, thereby confining the electrons in the light-emitting layer. Thus, the efficiency, operating voltage and / or life are improved. Typically, the electron blocking layer comprises a triarylamine compound. The LUMO energy level of the triarylamine compound can be closer to the vacuum energy level than the LUMO energy level of the hole transport layer. The HOMO energy level of the electron blocking layer can be further away from the vacuum energy level than the HOMO energy level of the hole transport layer. The thickness of the electron blocking layer can be selected between 2nm and 20nm.

[0155] If the electron blocking layer has a high triplet energy level it can also be described as a triplet controlling layer.

[0156] If a phosphorescent green or blue emitting layer is used, the function of the triplet control layer is to reduce triplet quenching. Thus, a higher luminous efficiency of the phosphorescent emitting layer can be achieved. The triplet control layer is selected from triarylamine compounds whose triplet energy level is higher than the triplet energy level of the phosphorescent emitter in the adjacent emitting layer. EP 2 722 908 A1 describes compounds suitable for triplet control layers, in particular triarylamine compounds.

[0157] Photoactive Layer (PAL)

[0158] The photoactive layer converts electric current into photons or converts photons into electric current.

[0159] The PAL can be formed on the HTL by vacuum deposition, spin coating, slot die coating, printing, casting, LB deposition, etc. When the PAL is formed using vacuum deposition or spin coating, the conditions for deposition and coating may be similar to those for forming the HIL. However, the conditions for deposition and coating may vary depending on the compound used to form the PAL.

[0160] It may be provided that the photoactive layer comprises no compounds of the formula (I).

[0161] The photoactive layer can be a light emitting layer or a light absorbing layer.

[0162] Emission layer (EML)

[0163] The EML can be formed on the HTL by vacuum deposition, spin coating, slot die coating, printing, casting, LB deposition, etc. When the EML is formed using vacuum deposition or spin coating, the conditions for deposition and coating may be similar to those for forming the HIL. However, the conditions for deposition and coating may vary according to the compound used to form the EML.

[0164] It may be provided that the emitting layer comprises no compound of the formula (I).

[0165] The light-emitting layer (EML) may be formed of a combination of a host and a light-emitting dopant. Examples of the host are Alq3, 4,4'-N,N'-dicarbazole-biphenyl (CBP), poly(n-vinylcarbazole) (PVK), 9,10-di(naphthalene-2-yl)anthracene (ADN), 4,4',4"-tri(carbazole-9-yl)-triphenylamine (TCTA), 1,3,5-tri(N-phenylbenzimidazol-2-yl)benzene (TPBI), 3-tert-butyl-9,10-di-2-naphthylanthracene (TBADN), distyrylarene (DSA), and bis(2-(2-hydroxyphenyl)benzothiazole)zinc (Zn(BTZ)2).

[0166] The emitter dopant may be a phosphorescent or fluorescent emitter. Phosphorescent emitters and emitters that 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.

[0167] Examples of red emitter dopants are PtOEP, Ir(piq)3 and Btp2Ir(acac), but are not limited thereto. These compounds are phosphorescent emitters, however, fluorescent red emitter dopants may also be used.

[0168] Examples of phosphorescent green emitter dopants are Ir(ppy)3 (ppy=phenylpyridine), Ir(ppy)2(acac), Ir(mpyp)3.

[0169] Examples of phosphorescent blue emitter dopants are F2Irpic, (F2ppy)2Ir(tmd) and Ir(dfppz)3 and trifluorene. 4,4'-bis(4-diphenylaminophenylvinyl)biphenyl (DPAVBi), 2,5,8,11-tetra-tert-butylperylene (TBPe) are examples of fluorescent blue emitter dopants.

[0170] Based on 100 parts by weight of the host, the amount of the luminophore dopant may be in the range of about 0.01 to about 50 parts by weight. Alternatively, the luminescent layer may be composed of a luminescent polymer. The thickness of the EML may be about 10 nm to about 100 nm, for example, about 20 nm to about 60 nm. When the thickness of the EML is within this range, the EML may have excellent luminescence without causing substantial damage to the driving voltage.

[0171] Hole Blocking Layer (HBL)

[0172] A hole blocking layer (HBL) can be formed on the EML by using vacuum deposition, spin coating, slot die coating, printing, casting, LB deposition, etc. to prevent holes from diffusing into the ETL. When the EML contains a phosphorescent dopant, the HBL may also have a triplet exciton blocking function. The hole blocking layer can be an organic semiconductor layer of the present invention comprising or consisting of a compound of the present invention represented by the general formula (I) as defined above.

[0173] HBL may also be referred to as auxiliary ETL or a-ETL.

[0174] When vacuum deposition or spin coating is used to form HBL, the conditions for deposition and coating can be similar to those for forming HIL. However, the conditions for deposition and coating can vary according to the compound for forming HBL. Any compound commonly used to form HBL can be used. Examples of compounds for forming HBL include oxadiazole derivatives, triazole derivatives, and phenanthroline derivatives.

[0175] The thickness of the HBL may be in the range of about 5 nm to about 100 nm, for example, about 10 nm to about 30 nm. When the thickness of the HBL is within this range, the HBL may have excellent hole blocking properties without substantially deteriorating driving voltage.

[0176] According to one embodiment, the hole blocking layer is arranged between the at least one photoactive layer and the organic semiconductor layer comprising the compound of formula (I).

[0177] According to one embodiment, the hole blocking layer is arranged between at least one photoactive layer and the organic semiconductor layer comprising the compound of formula (I), wherein the organic semiconductor layer comprising the compound of formula (I) further comprises a redox n-dopant.

[0178] According to one embodiment, the hole blocking layer is arranged between at least one photoactive layer and the organic semiconductor layer comprising the compound of formula (I), wherein the organic semiconductor layer comprising the compound of formula (I) further comprises a metal or a metal organic complex, or a metal or lithium organic complex.

[0179] According to one embodiment, the hole blocking layer is arranged between at least one photoactive layer and the organic semiconductor layer comprising the compound of formula (I), wherein the organic semiconductor layer comprising the compound of formula (I) further comprises a metal.

[0180] Electron Transport Layer (ETL)

[0181] The OLED according to the present invention may comprise an electron transport layer (ETL). According to a preferred embodiment of the present invention, the electron transport layer may be an organic semiconductor layer of the present invention comprising the compound of the present invention represented by general formula (I) as defined herein.

[0182] According to various embodiments, the OLED may include an electron transport layer or an electron transport layer stack including at least a first electron transport layer and at least a second electron transport layer.

[0183] By properly adjusting the energy level of a specific layer of the ETL, the injection and transport of electrons can be controlled, and holes can be effectively blocked. As a result, the OLED can have a long lifespan.

[0184] The electron transport layer of the organic electronic device may contain a compound represented by the general formula (I) as defined above as an organic electron transport matrix (ETM) material. In addition to or instead of the compound represented by the general formula (I), the electron transport layer may also contain other ETM materials known in the art. Similarly, the electron transport layer may contain a compound represented by the general formula (I) as the only electron transport matrix material. In the case where the organic electronic device of the present invention comprises more than one electron transport layer, the compound represented by the general formula (I) may be contained only in one electron transport layer, in more than one electron transport layer, or in all electron transport layers. According to the present invention, in addition to the ETM material, the electron transport layer may also contain at least one additive as defined below.

[0185] In addition, the electron transport layer may also include one or more n-type dopants. The additive may be an n-type dopant. The additive may be an alkali metal, an alkali metal compound, an alkaline earth metal, an alkaline earth metal compound, a transition metal, a transition metal compound, or a rare earth metal. In another embodiment, the metal may be a metal selected from Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, La, Ce, Sm, Eu, Tb, Dy, and Yb. In another embodiment, the n-type dopant may be a dopant selected from Cs, K, Rb, Mg, Na, Ca, Sr, Eu, and Yb. In one embodiment, the alkali metal compound may be 8-hydroxyquinoline lithium (LiQ), tetrakis (1H-pyrazol-1-yl) lithium borate, or 2- (diphenylphosphoryl) phenol lithium. There is no particular restriction on compounds suitable for ETM (which may be used together with the compounds of the present invention represented by the general formula (I) as defined above). In one embodiment, the electron transport matrix compound is composed of covalently bonded atoms. Preferably, the electron transport matrix compound comprises a conjugated system of at least 6, more preferably at least 10 delocalized electrons. In one embodiment, the conjugated system of delocalized electrons may be contained in an aromatic or heteroaromatic moiety, as disclosed in documents EP 1 970 371 A1 or WO 2013 / 079217 A1, for example.

[0186] Electron injection layer (EIL)

[0187] An optional EIL that can facilitate electron injection from the cathode can be formed on the ETL, preferably directly on the electron transport layer. Examples of materials for forming the EIL include 8-hydroxyquinoline lithium (LiQ), LiF, NaCl, CsF, Li2O, BaO, Ca, Ba, Yb, Mg known in the art. The deposition and coating conditions for forming the EIL are similar to those for forming the HIL, but the deposition and coating conditions may vary according to the material for forming the EIL. The EIL may be an organic semiconductor layer comprising a compound of formula (I).

[0188] The thickness of the EIL may be within a range of about 0.1 nm to about 10 nm, for example, within a range of about 0.5 nm to about 9 nm. When the thickness of the EIL is within this range, the EIL may have satisfactory electron injection characteristics without substantially deteriorating driving voltage.

[0189] Cathode electrode

[0190] A cathode electrode is formed on the EIL (if present). The cathode electrode may be formed of a metal, an alloy, a 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), etc. Alternatively, the cathode electrode may be formed of a transparent conductive oxide such as ITO or IZO.

[0191] The thickness of the cathode electrode may be in the range of about 5 nm to about 1000 nm, for example, in the range of about 10 nm to about 100 nm. When the thickness of the cathode electrode is in the range of about 5 nm to about 50 nm, the cathode electrode may be transparent or translucent even if it is formed of a metal or a metal alloy.

[0192] It is to be understood that the cathode electrode is not part of the electron injection layer or the electron transport layer.

[0193] Charge Generation Layer (CGL)

[0194] The charge generation layer (CGL) may include a p-type charge generation layer (p-CGL) and an n-type charge generation layer (n-CGL). An intermediate layer may be disposed between the p-CGL and the n-CGL.

[0195] Typically, the charge generation layer is a pn junction connecting an n-type charge generation layer (electron generation layer) and a hole generation layer. The n-side of the pn junction generates electrons and injects them into the layer adjacent to the anode in the direction. Similarly, the p-side of the pn junction generates holes and injects them into the layer adjacent to the cathode in the direction.

[0196] Charge generation layers are used in tandem and stacked devices, for example in tandem or stacked OLEDs comprising two or more light-emitting layers between two electrodes. In a tandem or stacked OLED comprising two light-emitting layers, the n-type charge generation layer provides electrons to a first light-emitting layer arranged near the anode, while the hole generation layer provides holes to a second light-emitting layer arranged between the first light-emitting layer and the cathode.

[0197] The matrix material suitable for the hole generation layer can be a material conventionally used as a hole injection and / or hole transport matrix material. The p-type dopant for the hole generation layer can also be a conventional material. For example, the p-type dopant can be a dopant selected from tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4-TCNQ), tetracyanoquinodimethane derivatives, radialene derivatives, iodine, FeCl3, FeF3 and SbCl5. The host can also be a host selected from N,N'-di(naphthalene-1-yl)-N,N-diphenyl-benzidine (NPB), N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1-biphenyl-4,4'-diamine (TPD) and N,N',N'-tetranaphthyl-benzidine (TNB). The p-type charge generation layer can be composed of CNHAT.

[0198] The n-type charge generation layer may be a layer comprising a compound of formula (I). The n-type charge generation layer may be a pure n-type dopant (e.g., metal) layer, or may be composed of an organic matrix material doped with an n-type dopant. In one embodiment, the n-type dopant may be an alkali metal, an alkali metal compound, an alkaline earth metal, an alkaline earth metal compound, a transition metal, a transition metal compound, or a rare earth metal. In another embodiment, the metal may be a metal selected from Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, La, Ce, Sm, Eu, Tb, Dy, and Yb. More specifically, the n-type dopant may be a dopant selected from Li, Cs, K, Rb, Mg, Na, Ca, Sr, Eu, and Yb. The matrix material suitable for the electron generation layer may be a material conventionally used as a matrix material for an electron injection or electron transport layer. The matrix material may be, for example, a matrix material selected from triazine compounds, hydroxyquinoline derivatives such as tris (8-hydroxyquinoline) aluminum, indole derivatives, and silacyclopentane derivatives.

[0199] The hole generation layer is arranged in direct contact with the n-type charge generation layer.

[0200] According to one aspect of the present invention, the organic semiconductor layer is disposed between the first light-emitting layer and the second light-emitting layer, and further comprises a redox n-type dopant.

[0201] According to one aspect of the present invention, the organic semiconductor layer is disposed between the first light-emitting layer and the second light-emitting layer, and further contains a metal.

[0202] According to one aspect of the present invention, the organic semiconductor layer is disposed between the first light-emitting layer and the second light-emitting layer, and further comprises a metal selected from the group consisting of an alkali metal, an alkaline earth metal, and a rare earth metal.

[0203] According to one aspect of the present invention, an organic semiconductor layer comprising a compound of formula (I) is arranged between the first and second light-emitting layers, and another organic semiconductor layer comprising a compound of formula (I) is arranged between the second light-emitting layer and the cathode.

[0204] According to one aspect of the present invention, an organic semiconductor layer comprising a compound of formula (I) is arranged between a first light-emitting layer and a second light-emitting layer, and another organic semiconductor layer comprising a compound of formula (I) is arranged between the second light-emitting layer and a cathode; wherein the organic semiconductor layer comprising the compound of formula (I) also comprises a redox n-type dopant.

[0205] According to one aspect of the present invention, an organic semiconductor layer comprising a compound of formula (I) is arranged between a first light-emitting layer and a second light-emitting layer, and another organic semiconductor layer comprising a compound of formula (I) is arranged between the second light-emitting layer and a cathode; wherein the other organic semiconductor layer comprising a compound of formula (I) further comprises a redox n-type dopant.

[0206] According to one aspect of the present invention, an organic semiconductor layer comprising a compound of formula (I) is arranged between a first light-emitting layer and a second light-emitting layer, and another organic semiconductor layer comprising a compound of formula (I) is arranged between the second light-emitting layer and a cathode; wherein the organic semiconductor layer comprising the compound of formula (I) further comprises a redox n-type dopant, and the other organic semiconductor layer comprising the compound of formula (I) further comprises a redox n-type dopant.

[0207] According to one aspect of the present invention, an organic semiconductor layer comprising a compound of formula (I) is arranged between a first light-emitting layer and a second light-emitting layer, and another organic semiconductor layer comprising a compound of formula (I) is arranged between the second light-emitting layer and a cathode; wherein the organic semiconductor layer comprising the compound of formula (I) also comprises a metal, and the other organic semiconductor layer comprising the compound of formula (I) also comprises a redox n-type dopant.

[0208] Organic Light Emitting Diodes

[0209] The organic electronic device according to the present invention may be an organic light emitting device.

[0210] According to one aspect of the present invention, an organic light emitting diode (OLED) is provided, comprising: a substrate; an anode electrode formed on the substrate; a hole injection layer, a hole transport layer, a light emitting layer, an organic semiconductor layer comprising a compound of formula (I), and a cathode electrode.

[0211] According to another aspect of the present invention, an OLED is provided, comprising: a substrate; an anode electrode formed on the substrate; a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an organic semiconductor layer comprising a compound of formula (I), and a cathode electrode.

[0212] According to another aspect of the present invention, an OLED is provided, comprising: a substrate; an anode electrode formed on the substrate; a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an organic semiconductor layer comprising a compound of formula (I), an electron injection layer and a cathode electrode.

[0213] According to various embodiments of the present invention, an OLED layer may be provided that is arranged between the above-mentioned layers, on the substrate, or on the top electrode.

[0214] According to one aspect, the OLED may include the following layer structure: a substrate is arranged adjacent to an anode electrode, the anode electrode is arranged adjacent to a first hole injection layer, the first hole injection layer is arranged adjacent to a first hole transport layer, the first hole transport layer is arranged adjacent to a first electron blocking layer, the first electron blocking layer is arranged adjacent to a first light-emitting layer, the first light-emitting layer is arranged adjacent to a first electron transport layer, the first electron transport layer is arranged adjacent to an n-type charge generation layer, the n-type charge generation layer is arranged adjacent to a hole generation layer, the hole generation layer is arranged adjacent to a second hole transport layer, the second hole transport layer is arranged adjacent to a second electron blocking layer, the second electron blocking layer is arranged adjacent to a second light-emitting layer, and an optional electron transport layer and / or an optional injection layer are arranged between the second light-emitting layer and the cathode electrode.

[0215] The organic semiconductor layer according to the present invention may be an electron transport layer, a first electron transport layer, an n-type charge generation layer and / or a second electron transport layer.

[0216] For example, according to Figure 2 The OLED can be formed by the following method, wherein an anode (120), a hole injection layer (130), a hole transport layer (140), an electron blocking layer (145), a light emitting layer (150), a hole blocking layer (155), an electron transport layer (160), an electron injection layer (180) and a cathode electrode (190) are sequentially formed on a substrate (110).

[0217] Organic Electronic Devices

[0218] The organic electronic device according to the present invention may be a light emitting device or a photovoltaic cell, preferably a light emitting device.

[0219] According to another aspect of the present invention, there is provided a method for manufacturing an organic electronic device, the method using:

[0220] - at least one deposition source, preferably two deposition sources, more preferably at least three deposition sources.

[0221] Suitable deposition methods include:

[0222] -Deposition by vacuum thermal evaporation;

[0223] - deposition by solution processing, preferably selected from spin coating, printing, casting; and / or

[0224] -Slot die coating.

[0225] According to various embodiments of the present invention, there is provided a method, the method using:

[0226] - a first deposition source to release the compound of formula (I) according to the invention, and

[0227] - a second deposition source to release a metal, a metal salt or an alkali metal or alkaline earth metal complex, or an organic alkali metal or alkaline earth metal complex, or 8-hydroxyquinoline lithium;

[0228] The method comprises the steps of forming an organic semiconductor layer; wherein for an organic light emitting diode (OLED):

[0229] The organic semiconductor layer is formed by releasing the compound of formula (I) according to the invention from a first deposition source and releasing a metal, a metal salt or an alkali metal or alkaline earth metal complex, or an organic alkali metal or alkaline earth metal complex, or 8-hydroxyquinolate lithium from a second deposition source.

[0230] According to various embodiments of the present invention, the method may further include forming a light emitting layer on the anode electrode, and forming at least one layer selected from a hole injection layer, a hole transport layer or a hole blocking layer between the anode electrode and the first electron transport layer.

[0231] According to various embodiments of the present invention, the method may further include the step of forming an organic light emitting diode (OLED), wherein

[0232] - forming a first anode electrode on the substrate,

[0233] - forming a light emitting layer on the first anode electrode,

[0234] - forming an electron transport layer stack on the light-emitting layer, optionally forming a hole blocking layer on the light-emitting layer and forming an organic semiconductor layer,

[0235] -Finally, the cathode electrode is formed,

[0236] - forming an optional hole injection layer, a hole transport layer and a hole blocking layer in sequence between the first anode electrode and the light emitting layer,

[0237] - forming an optional electron injection layer between the organic semiconductor layer and the cathode electrode.

[0238] According to various embodiments of the present invention, the method may further include forming an electron injection layer on the organic semiconductor layer. However, according to various embodiments of the OLED of the present invention, the OLED may not include an electron injection layer.

[0239] According to various embodiments, the OLED may have the following layer structure, wherein the order of the layers is as follows:

[0240] an anode, a hole injection layer, a first hole transport layer, a second hole transport layer, a light-emitting layer, an optional hole blocking layer, an organic semiconductor layer comprising a compound of formula (I) according to the present invention, an optional electron injection layer and a cathode.

[0241] According to another aspect of the present invention, an electronic device is provided, the electronic device comprising at least one organic light-emitting device according to any embodiment described in the entire application, preferably, the electronic device comprises an organic light-emitting diode in one of the embodiments described in the entire application. More preferably, the electronic device is a display device.

[0242] In one embodiment, the organic electronic device according to the present invention comprising an organic semiconductor layer comprising a compound according to formula (I) may further comprise a layer comprising a radialene compound and / or a quinodimethane compound.

[0243] In one embodiment, the axialene compound and / or the quinodimethane compound can be substituted by one or more halogen atoms and / or one or more electron withdrawing groups. The electron withdrawing group can be selected from a nitrile group, a halogenated alkyl group, or a fully halogenated alkyl group, or a fully fluorinated alkyl group. Other examples of electron withdrawing groups can be acyl, sulfonyl or phosphoryl groups.

[0244] Alternatively, the acyl group, sulfonyl group and / or phosphoryl group may contain a halogenated and / or perhalogenated hydrocarbon group. In one embodiment, the perhalogenated hydrocarbon group may be a perfluorinated hydrocarbon group. Examples of perfluorinated hydrocarbon groups may be perfluoromethyl, perfluoroethyl, perfluoropropyl, perfluoroisopropyl, perfluorobutyl, perfluorophenyl, perfluorotolyl; Examples of sulfonyl groups containing halogenated hydrocarbon groups may be trifluoromethylsulfonyl, pentafluoroethylsulfonyl, pentafluorophenylsulfonyl, heptafluoropropylsulfonyl, nonafluorobutylsulfonyl, etc.

[0245] In one embodiment, the radialene compound and / or the quinodimethane compound may be included in the hole injection layer, the hole transport layer, and / or the hole generation layer.

[0246] In one embodiment, the radialene compound may have the formula (XX) and / or the quinodimethane compound may have the formula (XXIa) or (XXIb):

[0247]

[0248] where (as an exception to the above) R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 11 , R 12 , R 15 , R 16 , R 20 , R 21 are independently selected from the above electron withdrawing groups, and R 9 , R 10 , R 13 , R 14 , R 17 , R 18 , R 19 , R 22 , R 23 and R 24 Independently selected from H, halogen and the above-mentioned electron withdrawing groups.

[0249] According to one embodiment of the present invention, the organic semiconductor layer comprising the compound of formula (I) is adjacent to the layer comprising the compound of formula (XX), formula (XXIa) or formula (XXIb).

[0250] According to one embodiment of the present invention, the organic semiconductor layer comprising the compound of formula (I) is in direct contact with the layer comprising the compound of formula (XX), formula (XXIa) or formula (XXIb).

[0251] General Definition

[0252] In this specification, when no definition is provided otherwise, "alkyl group" may refer to an aliphatic hydrocarbon group. An alkyl group may refer to a "saturated alkyl group" without any double or triple bonds. The term "alkyl" as used herein will encompass straight chain alkyl groups as well as branched and cyclic alkyl groups. For example, a C3 alkyl group may be selected from n-propyl and isopropyl. Similarly, a C4 alkyl group encompasses n-butyl, sec-butyl and tert-butyl. Similarly, a C6 alkyl group encompasses n-hexyl and cyclohexyl.

[0253] If not explicitly mentioned, the asterisk symbol "*" as used herein indicates the binding position where the correspondingly marked moiety is bonded to another moiety.

[0254] C n The subscript number n in relates to the total number of carbon atoms in the corresponding alkyl, arylene, heteroarylene or aryl group.

[0255] As used herein, the term "aryl" or "aryl subunit" will cover phenyl (C6 aryl), fused aromatics, such as naphthalene, anthracene, phenanthrene, tetracene, etc. In addition, biphenyl and oligophenyl or polyphenyl are covered, such as terphenyl, phenyl-substituted biphenyl, phenyl-substituted terphenyl (such as tetraphenylphenyl group), etc. "aryl subunit" or "heteroaryl subunit" refers to a group connected to two other parts. In this specification, the term "aryl group" or "aryl subunit group" may refer to a group comprising at least one hydrocarbon aromatic part, and all elements of the hydrocarbon aromatic part may have a p orbital forming conjugation, such as a phenyl group, a naphthyl group, an anthracene group, a phenanthrene group, a pyridyl group, a fluorenyl group, etc. In addition, spiro compounds are covered, wherein two aromatic parts are connected to each other by spiral atoms, such as 9,9'-spiro two [9H-fluorene] base. Aryl or aryl subunit groups can include monocyclic or fused ring polycyclic (that is, sharing the connection of adjacent carbon atoms) functional groups.

[0256] As used herein, the term "heteroaryl" refers to an aryl group in which at least one carbon atom is replaced by a heteroatom. The term "heteroaryl" may refer to an aromatic heterocycle having at least one heteroatom, and all elements of the hydrocarbon heteroaromatic portion may have a p orbital forming a conjugation. The heteroatom may be selected from N, O, S, B, Si, P, Se, preferably selected from N, O and S. The heteroaryl subunit ring may contain at least 1 to 3 heteroatoms. Preferably, the heteroaryl subunit ring may contain at least 1 to 3 heteroatoms selected from N, S and / or O, respectively. As in the case of "aryl" / "aryl subunit", the term "heteroaryl" includes, for example, a spirocyclic compound in which two aromatic moieties are connected to each other, such as spiro[fluorene-9,9'-xanthene]. Other exemplary heteroaryl groups are diazines, triazines, dibenzofurans, dibenzothiophenes, acridines, benzoacridines, dibenzoacridines, etc.

[0257] As used herein, the term "alkenyl" refers to a group containing a carbon-carbon double bond -CR 1 =CR 2 R 3 .

[0258] As used herein, the term "perhalogenated" refers to a hydrocarbyl group in which all of the hydrogen atoms of the hydrocarbyl group are replaced by halogen (F, Cl, Br, I) atoms.

[0259] As used herein, the term "alkoxy" refers to a structural fragment of the formula -OR, wherein R is a hydrocarbon group, preferably an alkyl group or a cycloalkyl group.

[0260] As used herein, the term "thioalkyl" refers to a structural fragment of the formula -SR, wherein R is a hydrocarbon group, preferably an alkyl group or a cycloalkyl group.

[0261] C n The subscript number n in -heteroaryl refers only to the number of carbon atoms and does not include the number of heteroatoms. In this case, it is clear that the C3 heteroaryl substituent group is an aromatic compound containing three carbon atoms, such as pyrazole, imidazole, oxazole, thiazole, etc.

[0262] As used herein, the term "heteroaryl" is intended to 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.

[0263] In this specification, the term single bond means a direct bond.

[0264] As used herein, the term "fluorinated" refers to a hydrocarbon group in which at least one of the hydrogen atoms contained in the hydrocarbon group is replaced by a fluorine atom. A fluorinated group in which all hydrogen atoms are replaced by fluorine atoms is called a perfluorinated group, specifically referred to by the term "fluorinated".

[0265] For the purposes of the present invention, a group is "substituted" with another group if one of the hydrogen atoms contained in the group is replaced with another group, wherein the other group is a substituent.

[0266] For the purposes of the present invention, the expression "between" with respect to a layer being between two other layers does not exclude the presence of other layers which may be arranged between the one layer and one of the two other layers. For the purposes of the present invention, the expression "in direct contact" with respect to two layers being in direct contact with each other means that no other layer is arranged between the two layers. A layer deposited on top of another layer is considered to be in direct contact with this layer.

[0267] The term "sandwiched in contact" refers to a three-layer arrangement in which a layer in the middle is in direct contact with two adjacent layers.

[0268] For the electron transport layer stack according to the invention, the compounds mentioned in the experimental part are most preferred.

[0269] A lighting device can be any device used for illumination, irradiation, signal transmission or projection. They are classified accordingly as lighting devices, irradiation devices, signal transmission devices and projection devices. A lighting device usually consists of a light radiation source, a device that transmits the radiation flux into space in a desired direction, and a housing that connects the components into a single device and protects the radiation source and the light transmission system from damage and influence of the surrounding environment.

[0270] According to another aspect, the organic electroluminescent device according to the invention comprises two or three or more light-emitting layers. OLEDs comprising more than one light-emitting layer are also described as tandem OLEDs or stacked OLEDs.

[0271] Organic electroluminescent devices (OLEDs) can be bottom or top emitting devices. Organic electroluminescent devices (OLEDs) can emit light through a transparent anode or through a transparent cathode.

[0272] A further aspect relates to a device comprising at least one organic electroluminescent device (OLED).

[0273] Devices comprising organic light emitting diodes are, for example, displays or lighting panels.

[0274] In the present invention, the following defined terms shall apply unless a different definition is given in the claims or elsewhere in this specification.

[0275] In the context of this specification, the term "different" or "different" in relation to a host material means that the host materials differ in their structural formula.

[0276] The terms "OLED" and "organic light emitting diode" are used concurrently and have the same meaning. The term "organic electroluminescent device" as used herein may include organic light emitting diodes as well as organic light emitting transistors (OLETs).

[0277] As used herein, "weight percent," "wt %," "percent by weight," "% by weight," and variations thereof refer to a composition, component, substance, or agent expressed as the weight of the component, substance, or agent in the corresponding electron transport layer divided by the total weight of its corresponding electron transport layer and multiplied by 100. It is understood that the amount of the total weight percent of all components, substances, and agents of the corresponding electron transport layer and electron injection layer is selected so that it does not exceed 100 weight percent.

[0278] As used herein, "volume percent," "volume %," "percent by volume," "volume %," and variations thereof refer to a composition, component, substance, or agent expressed as the volume of the component, substance, or agent in the corresponding electron transport layer divided by the total volume of its corresponding electron transport layer and multiplied by 100. It is understood that the total volume percent amount of all components, substances, and agents of the cathode layer is selected so that it does not exceed 100 volume %.

[0279] Whether or not explicitly stated, it is assumed herein that all numerical values ​​are modified by the term "about". As used herein, the term "about" refers to the possible quantitative variation. Whether or not modified by the term "about", the claims include equivalents of the stated quantities.

[0280] It must be noted that as used in this specification and the claims, the singular forms "a," "an," "the," and "said" include plural referents unless the context clearly dictates otherwise.

[0281] The terms "does not contain", "does not contain", and "does not include" do not exclude impurities. Impurities have no technical influence on the purpose to be achieved by the present invention.

[0282] In the context of this specification, the term "substantially non-luminescent" or "non-luminescent" means that the contribution of a compound or layer to the visible emission spectrum of a device is less than 10%, preferably less than 5%, relative to the visible emission spectrum. The visible emission spectrum is the emission spectrum with a wavelength of about ≥380 nm to about ≤780 nm.

[0283] Preferably, the organic semiconductor layer comprising the compound of formula (I) is substantially non-luminescent or non-luminescent.

[0284] The working voltage is also called U, which is expressed in 10 mA / cm2. 2 ) is measured in volts (V).

[0285] Candela / ampere efficiency is also called cd / A efficiency, which is expressed in terms of 10 mA / cm2. 2 ) candela / ampere measurement under .

[0286] External quantum efficiency is also called EQE and is measured in percentage (%).

[0287] The color space is described by the coordinates CIE-x and CIE-y (International Commission on Illumination, 1931). CIE-y is particularly important for blue light. The smaller the CIE-y, the darker the blue color. Compare the efficiency values ​​at the same CIE-y.

[0288] The highest occupied molecular orbital (also known as HOMO) and the lowest unoccupied molecular orbital (also known as LUMO) are measured in electron volts (eV).

[0289] The terms "OLED", "organic light emitting diode", "organic light emitting device", "organic optoelectronic device" and "organic light emitting diode" are used concurrently and have the same meaning.

[0290] The terms "life span" and "lifetime" are used concurrently and have the same meaning.

[0291] The anode and cathode may be described as anode electrode / cathode electrode or anode electrode / cathode electrode or anode electrode layer / cathode electrode layer.

[0292] Room temperature, also known as ambient temperature, is 23°C.

[0293] The embodiments are described in more detail below 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. BRIEF DESCRIPTION OF THE DRAWINGS

[0294] The aforementioned components in the described embodiments as well as the components claimed and to be used according to the invention do not have any special exceptions in terms of their size, shape, material selection and technical principles, so that the selection criteria known in the relevant field can be applied without restriction.

[0295] Other details, characteristics and advantages of the purpose of the present invention are disclosed in the dependent claims and the following corresponding drawings, which illustrate preferred embodiments according to the present invention in an exemplary manner. However, any embodiment may not represent the full scope of the present invention, so the scope of the present invention is interpreted with reference to the claims and this article. It should be understood that the above general description and the following detailed description are only exemplary and explanatory, and are intended to further explain the invention claimed for protection.

[0296] Figure 1 is a schematic cross-sectional view of an organic electronic device according to an exemplary embodiment of the present invention;

[0297] Figure 2 is a schematic cross-sectional view of an organic light emitting diode (OLED) according to an exemplary embodiment of the present invention;

[0298] Figure 3 is a schematic cross-sectional view of an OLED according to an exemplary embodiment of the present invention.

[0299] Figure 4 is a schematic cross-sectional view of an OLED including a charge generation layer and two light emitting layers according to an exemplary embodiment of the present invention.

[0300] The accompanying drawings are described in more detail below with reference to embodiments. However, the present disclosure is not limited to the following drawings.

[0301] In this document, when a first element is referred to as being formed or disposed "on" or "over" a second element, the first element may be disposed directly on the second element, or one or more other elements may be disposed between them. When a first element is referred to as being formed or disposed "directly" on or "over" a second element, no other elements are disposed between them.

[0302] Figure 1 1 is a schematic cross-sectional view of an organic electronic device 100 according to an exemplary embodiment of the present invention. The organic electronic device 100 includes a substrate 110, an anode 120, a photoactive layer (PAL) 125, and an organic semiconductor layer 160 including a compound of formula (1). The organic semiconductor layer 160 including a compound of formula (1) is formed on the PAL 125. A cathode 190 is disposed on the organic semiconductor layer 160.

[0303] Figure 2 1 is a schematic cross-sectional view of an organic light emitting diode (OLED) 100 according to an exemplary embodiment of the present invention. The OLED 100 includes a substrate 110, an anode 120, a hole injection layer (HIL) 130, a hole transport layer (HTL) 140, an emission layer (EML) 150, and an electron transport layer (ETL) 160. The electron transport layer (ETL) 160 is formed on the EML 150. An electron injection layer (EIL) 180 is disposed on the electron transport layer (ETL) 160. A cathode 190 is disposed directly on the electron injection layer (EIL) 180.

[0304] Optionally, a stack of electron transport layers (ETL) may be used instead of the single electron transport layer 160 .

[0305] Figure 3 is a schematic cross-sectional view of an OLED 100 according to another exemplary embodiment of the present invention. Figure 3 and Figure 2 The difference is Figure 3 The OLED 100 includes an electron blocking layer (EBL) 145 and a hole blocking layer (HBL) 155 .

[0306] refer to Figure 3 , the OLED 100 includes a substrate 110, an anode 120, a hole injection layer (HIL) 130, a hole transport layer (HTL) 140, an electron blocking layer (EBL) 145, an emission layer (EML) 150, a hole blocking layer (HBL) 155, an electron transport layer (ETL) 160, an electron injection layer (EIL) 180 and a cathode electrode 190.

[0307] Preferably, the organic semiconductor layer including the compound of formula (1) may be an ETL.

[0308] Figure 4 is a schematic cross-sectional view of an OLED 100 according to another exemplary embodiment of the present invention. Figure 4 and Figure 3 The difference is that Figure 4 The OLED 100 further includes a charge generation layer (CGL) and a second light emitting layer (151).

[0309] refer to Figure 4 , the OLED 100 includes a substrate 110, an anode 120, a first hole injection layer (HIL) 130, a first hole transport layer (HTL) 140, a first electron blocking layer (EBL) 145, a first light emitting layer (EML) 150, a first hole blocking layer (HBL) 155, a first electron transport layer (ETL) 160, an n-type charge generation layer (n-type CGL) 185, a hole generation layer (p-type charge generation layer; p-type GCL) 135, a second hole transport layer (HTL) 141, a second electron blocking layer (EBL) 146, a second light emitting layer (EML) 151, a second hole blocking layer (EBL) 156, a second electron transport layer (ETL) 161, a second electron injection layer (EIL) 181 and a cathode 190.

[0310] Preferably, the organic semiconductor layer including the compound of formula (1) may be an n-type CGL.

[0311] Preferably, the organic semiconductor layer including the compound of formula (1) may be the first ETL, the n-type CGL and / or the second ETL.

[0312] although Figure 1 , Figure 2 , Figure 3 and Figure 4 Although not shown in the figure, a sealing layer may be further formed on the cathode electrode 190 to seal the OLED 100. In addition, various other modifications may be made thereto.

[0313] The embodiments are described in more detail below with reference to Examples. However, the present disclosure is not limited to the following Examples. DETAILED DESCRIPTION

[0314] The present invention is further illustrated by the following examples, which are intended to be illustrative only and not limiting.

[0315] Experimental Section

[0316] Melting point

[0317] The melting point (mp) was determined as the peak temperature of the DSC curve of the above TGA-DSC measurement or a separate DSC measurement (Mettler Toledo DSC822e, the sample was heated from room temperature to complete melting at a heating rate of 10 K / min under a pure nitrogen flow. An amount of 4 to 6 mg of the sample was placed in a 40 μL Mettler Toledo aluminum pan with a lid and a hole of <1 mm pierced in the lid).

[0318] Glass transition temperature

[0319] The glass transition temperature (Tg) was measured as described in DIN EN ISO 11357, published March 2010, in a Mettler Toledo DSC 822e differential scanning calorimeter under nitrogen using a heating rate of 10 K / min.

[0320] Standard starting temperature

[0321] The standard onset temperature (TRO) was determined by loading 100 mg of the compound into a VTE source. As VTE source, point sources for organic materials supplied by Kurt J. Lesker (www.lesker.com) or CreaPhys Ltd. (http: / / www.creaphys.com) can be used. -5 The VTE source is heated at a constant rate of 15 K / min at a pressure of mbar and the temperature inside the VTE source is measured with a thermocouple. The evaporation of the compound is detected with a QCM detector, which detects the deposition of the compound on the quartz crystal of the detector. The deposition rate on the quartz crystal is measured in angstroms / second. To determine the standard onset temperature, the deposition rate is plotted against the VTE source temperature. The standard onset is the temperature at which a significant deposition appears on the QCM detector. To obtain accurate results, the VTE source is heated and cooled three times and only the results of the second and third runs are used to determine the standard onset temperature.

[0322] In order to achieve good control of the evaporation rate of the organic compound, the standard starting temperature may be in the range of 200°C to 255°C. If the standard starting temperature is below 200°C, the evaporation may be too fast and thus difficult to control. If the standard starting temperature is above 255°C, the evaporation rate may be too low, which may result in a low cycle time, and the organic compounds in the VTE source may decompose due to long exposure to high temperature.

[0323] The standard onset temperature is an indirect measure of the volatility of a compound. The higher the standard onset temperature, the lower the volatility of the compound.

[0324] Reduction potential

[0325] The reduction potential was determined at room temperature using a constant potential device Metrohm PGSTAT30 and software Metrohm Autolab GPES by cyclic voltammetry. The redox potential given for a specific compound was measured in a 0.1M anhydrous THF solution of the substance being measured, degassed with argon, in an argon atmosphere, with a 0.1M tetrabutylammonium hexafluorophosphate supporting electrolyte, between platinum working electrodes and with an Ag / AgCl pseudo-standard electrode (Metrohm silver rod electrode) consisting of a silver wire covered with silver chloride and directly immersed in the solution being measured, at a scan rate of 100mV / s. The first run was performed within the widest potential range set on the working electrode, and then the range was appropriately adjusted in subsequent runs. The last three runs were performed with the addition of ferrocene (at a concentration of 0.1M) as a standard. The average potential of the cathode peak and the anode peak corresponding to the compound under study was measured after subtracting the potential for the standard Fc + The values ​​reported above were obtained by averaging the cathodic and anodic potentials observed for the 1 / Fc redox couple. All the compounds studied, as well as the reported comparative compounds, showed clear reversible electrochemical behavior.

[0326] Dipole moment

[0327] Dipole moment of a molecule containing N atoms It is derived from the following formula:

[0328]

[0329] where q i and is the partial charge and position of atom i in the molecule.

[0330] The dipole moments were determined by the semiempirical molecular orbital method.

[0331] The geometry of the molecular structure was optimized in the gas phase using the hybrid functional B3LYP with the 6-31G* basis set as implemented in the program package TURBOMOLE V6.5 (TURBOMOLE GmbH, Litzenhardtstrasse 19, 76135 Karlsruhe, Germany). If more than one conformation was feasible, the conformation with the lowest total energy was selected to determine the bond lengths of the molecule.

[0332] Calculated HOMO and LUMO

[0333] HOMO and LUMO were calculated using the program package TURBOMOLE V6.5 (TURBOMOLE GmbH, Litzenhardtstrasse 19, 76135 Karlsruhe, Germany). The optimized geometry of the molecular structure and the HOMO and LUMO energy levels were determined by applying the hybrid functional B3LYP with the 6-31G* basis set in the gas phase. If more than one conformation is feasible, the conformation with the lowest total energy is selected.

[0334] Preparation of the compounds of the present invention

[0335] 2-(3-(5-(9,9-dimethyl-9H-fluoren-2-yl)-3,6-diphenylpyrazin-2-yl)phenyl)-4,6-diphenylpyrimidine (E1)

[0336]

[0337] Step 1. Synthesis of 2-chloro-5-(9,9-dimethyl-9H-fluoren-2-yl)-3,6-diphenylpyrazine

[0338] A 3-necked round bottom flask was flushed with nitrogen and charged with 32.80 g of 2,5-dichloro-3,6-diphenylpyrazine (CAS 74134-61-5) (1 equiv.), 40.92 g of (9,9-dimethyl-9H-fluoren-2-yl)boric acid (CAS 333432-28-3) (1.6 equiv.), 3.15 g of tetrakis(triphenylphosphine)palladium(0) (CAS 14221-01-3) (0.025 equiv.), 30.11 g of potassium carbonate (CAS 584-08-7) (2 equiv.). A degassed mixture of 436 mL of dioxane and 109 mL of water was added. The reaction was carried out at 50° C. under a nitrogen atmosphere overnight. The formed suspension was filtered off and the solid was discarded. The filtrate was evaporated under reduced pressure, the crude product was dissolved in 400 mL of chloroform and extracted with water. The combined organic phases were dried and filtered through a pad of silica. The solvent was evaporated and the crude product was washed with 300 mL of acetonitrile at 80°C. Final purification was performed by sublimation, yield: 19.84 g (39.2%)

[0339] Step 2. Synthesis of 2-(3-(5-(9,9-dimethyl-9H-fluoren-2-yl)-3,6-diphenylpyrazin-2-yl)phenyl)-4,6-diphenylpyrimidine

[0340] A 3-necked round bottom flask was flushed with nitrogen and charged with 11.68 g of 2-chloro-5-(9,9-dimethyl-9H-fluoren-2-yl)-3,6-diphenylpyrazine (no CAS) (1 eq.), 10.49 g of 4,6-diphenyl-2-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)pyrimidine (CAS 1381862-91-4) (0.95 eq.), 0.74 g of tetrakis(triphenylphosphine)palladium(0) (CAS 14221-01-3) (0.025 eq.), 7.03 g of potassium carbonate (CAS 584-08-7) (2 eq.). A degassed mixture of 100 mL of dioxane and 25 mL of water was added. The reaction was carried out at 50° C. under a nitrogen atmosphere overnight. The next day, a yellow suspension was formed. The precipitate was filtered and washed with dioxane, water, methanol and acetonitrile. The crude product was dissolved in 900 mL of chloroform and filtered through a pad of silica. Final purification was performed by sublimation. Yield: 12.33 g (66.24%)

[0341] 2-(3-(3-(9,9-dimethyl-9H-fluoren-4-yl)-5,6-diphenylpyrazin-2-yl)phenyl)-4,6-diphenylpyrimidine (E2)

[0342]

[0343] Step 1. Synthesis of 2-(3-(3-chloro-5,6-diphenylpyrazin-2-yl)phenyl)-4,6-diphenylpyrimidine

[0344] A 3-necked round bottom flask was flushed with nitrogen and charged with 12.5 g of 2,3-dichloro-5,6-diphenylpyrazine (CAS 57038-62-7) (1 equivalent), 19.83 g of 4,6-diphenyl-2-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)pyrimidine (CAS 1381862-91-4) (1.1 equivalent), 0.62 g of [1,1'-bis(diphenylphosphino)ferrocene]-dichloropalladium(II) (CAS 72287-26-4) (0.02 equivalent), 11.46 g of potassium carbonate (CAS 584-08-7) (2 equivalents). A degassed mixture of 250 mL of dioxane and 83 mL of water was added. The reaction was carried out at 45° C. under a nitrogen atmosphere overnight. A yellow suspension was formed. The solid precipitate was collected by filtration and washed with dioxane, water and methanol. The solid was then dissolved in 700 mL of chloroform, the solution was filtered through a pad of silica and evaporated. Final purification was performed by sublimation. Yield: 11.11 g (48.43%)

[0345] Step 2. Synthesis of 2-(3-(3-(9,9-dimethyl-9H-fluoren-4-yl)-5,6-diphenylpyrazin-2-yl)phenyl)-4,6-diphenylpyrimidine

[0346] A 3-neck round bottom flask was flushed with nitrogen and charged with 10.2 g of 2-(3-(3-chloro-5,6-diphenylpyrazin-2-yl)phenyl)-4,6-diphenylpyrimidine (no CAS) (1 eq), 10.98 g of 2-(9,9-dimethyl-9H-fluoren-4-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (CAS 1365692-79-0) (1.93 eq), 0.513 g of tetrakis(triphenylphosphine)palladium(0) (CAS 14221-01-3) (0.025 eq), 4.92 g of potassium carbonate (CAS 584-08-7) (2 eq). A degassed mixture of 72 mL of THF and 18 mL of water was added. The reaction was carried out at 50° C. under a nitrogen atmosphere overnight. The next day, the dark suspension formed was filtered and the solid was washed with THF, water and methanol. The crude product was then dissolved in 400 mL of chloroform and filtered through a pad of silica. The solvent was evaporated to 100 mL and an additional 100 mL of methanol was added. The solid formed was filtered off and recrystallized from toluene. Final purification was performed by sublimation. Yield: 6.88 g (53.6%)

[0347] 2-(3-(5-(9,9-dimethyl-9H-fluoren-4-yl)-3,6-diphenylpyrazin-2-yl)phenyl)-4,6-diphenylpyrimidine (E3)

[0348]

[0349] Step 1. Synthesis of 2-(3-(5-chloro-3,6-diphenylpyrazin-2-yl)phenyl)-4,6-diphenylpyrimidine

[0350] A 3-necked round bottom flask was flushed with nitrogen and charged with 27.59 g of 2,5-dichloro-3,6-diphenylpyrazine (CAS 74134-61-5) (1.05 equivalents), 37.90 g of 4,6-diphenyl-2-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)pyrimidine (CAS 1381862-91-4) (1 equivalent), 2.51 g of tetrakis(triphenylphosphine)palladium(0) (CAS 14221-01-3) (0.025 equivalents), 30.15 g of potassium carbonate (CAS 584-08-7) (2.5 equivalents). A degassed mixture of 660 mL of dioxane and 110 mL of water was added. The reaction was carried out at 55° C. under a nitrogen atmosphere for 2 days. A yellow suspension is formed; the solid precipitate is filtered off and washed with water, dioxane and 2-methoxy-2-methylpropane. The crude product is extracted with toluene in a Soxhlet extractor. Final purification is carried out by sublimation. Yield: 20.63 g (41.27%)

[0351] Step 2. Synthesis of 2-(3-(5-(9,9-dimethyl-9H-fluoren-4-yl)-3,6-diphenylpyrazin-2-yl)phenyl)-4,6-diphenylpyrimidine

[0352] A 3-necked round bottom flask was flushed with nitrogen and charged with 12.5 g of 2-(3-(5-chloro-3,6-diphenylpyrazin-2-yl)phenyl)-4,6-diphenylpyrimidine (no CAS) (1 eq.), 8.38 g of 2-(9,9-dimethyl-9H-fluoren-4-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (CAS 1365692-79-0) (1.2 eq.), 0.504 g of tetrakis(triphenylphosphine)palladium(0) (CAS 14221-01-3) (0.02 eq.), 6.03 g of potassium carbonate (CAS 584-08-7) (2 eq.). A degassed mixture of 88 mL of THF and 22 mL of water was added. The reaction was carried out at 50° C. under a nitrogen atmosphere overnight. The reaction mixture was then cooled, the solvent evaporated and the resulting solid extracted in chloroform. The extract was washed with water, the organic phase was filtered through a pad of silica and evaporated under reduced pressure. Further purification was carried out by recrystallization of the crude solid from a toluene / acetonitrile 1:2 mixture and by sublimation. Yield: 12.70 g (82.65%)

[0353] 4-(3-(5-(9,9-dimethyl-9H-fluoren-4-yl)-3,6-diphenylpyrazin-2-yl)phenyl)-2,6-diphenylpyrimidine (E4)

[0354]

[0355] Step 1. Synthesis of 4-(3-(5-chloro-3,6-diphenylpyrazin-2-yl)phenyl)-2,6-diphenylpyrimidine.

[0356] A 3-necked round bottom flask was flushed with nitrogen and charged with 22 g of 2,5-dichloro-3,6-diphenylpyrazine (CAS 74134-61-5) (1.00 equiv), 31.7 g of 2,4-diphenyl-6-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)pyrimidine (CAS1342892-16-3) (1 equiv), 1.69 g of tetrakis(triphenylphosphine)palladium(0) (CAS14221-01-3) (0.02 equiv), 20.15 g of potassium carbonate (CAS 584-08-7) (2.0 equiv). A degassed mixture of 300 mL of THF and 75 mL of water was added. The reaction was carried out at 55° C. under a nitrogen atmosphere for 1 day. A yellow suspension was formed; the precipitate was filtered off and washed with water, THF and acetonitrile, dissolved in chloroform and the solution was filtered through a pad of silica. Further purification was carried out by sublimation. Yield: 17.3 g (38.6%)

[0357] Step 2. Synthesis of 4-(3-(5-(9,9-dimethyl-9H-fluoren-4-yl)-3,6-diphenylpyrazin-2-yl)phenyl)-2,6-diphenylpyrimidine

[0358] A 3-necked round bottom flask was flushed with nitrogen and charged with 11.5 g of 4-(3-(5-chloro-3,6-diphenylpyrazin-2-yl)phenyl)-2,6-diphenylpyrimidine (no CAS) (1 eq), 9.64 g of 2-(9,9-dimethyl-9H-fluoren-4-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (CAS 1365692-79-0) (1 eq), 0.45 g of tetrakis(triphenylphosphine)palladium(0) (CAS 14221-01-3) (0.02 eq), 5.52 g of potassium carbonate (CAS 584-08-7) (2 eq). A degassed mixture of 120 mL of THF and 20 mL of water was added. The reaction was carried out at 60° C. under a nitrogen atmosphere for 2 days. The reaction mixture is then cooled, the solvent evaporated and the solid extracted in chloroform, the extract washed with water. The organic phase is filtered through a pad of silica and evaporated under low pressure. Further purification is carried out by recrystallization from toluene and chlorobenzene in sequence and final sublimation. Yield: 6.61 g (45.3%).

[0359] Synthesis of 2-(3-(5-(9,9-dimethyl-9H-fluoren-4-yl)-3,6-diphenylpyrazin-2-yl)phenyl)-4,6-diphenyl-1,3,5-triazine (E5)

[0360]

[0361] Step 1. 2-(3-(5-chloro-3,6-diphenylpyrazin-2-yl)phenyl)-4,6-diphenyl-1,3,5-triazine

[0362] A 3-necked round bottom flask was flushed with nitrogen and charged with 40.0 g of 2,4-diphenyl-6-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-1,3,5-triazine (CAS 1269508-31-7) (1 equivalent), 26.29 g of 2,5-dichloro-3,6-diphenylpyrazine (CAS 74134-61-5) (0.95 equivalent), 2.65 g of tetrakis(triphenylphosphine)palladium(0) (CAS 14221-01-3) (0.025 equivalent), 25.40 g of potassium carbonate (CAS 584-08-7) (2 equivalents). A degassed mixture of 368 mL of dioxane and 92 mL of water was added. The reaction was carried out at 50° C. under a nitrogen atmosphere for 2 days. A yellow suspension was formed. The reaction mixture was cooled, the precipitate was filtered off and washed with dioxane, water and methanol. The crude solid product was stirred in chlorobenzene at room temperature, filtered and the solid was discarded. The organic filtrate was further filtered through a pad of silica and evaporated. Final purification was performed by sublimation. Yield: 22.8 g (44.8%)

[0363] Step 2. 2-(3-(5-(9,9-dimethyl-9H-fluoren-4-yl)-3,6-diphenylpyrazin-2-yl)phenyl)-4,6-diphenyl-1,3,5-triazine.

[0364] A 3-necked round bottom flask was flushed with nitrogen and charged with 25 g of 2-(3-(5-chloro-3,6-diphenylpyrazin-2-yl)phenyl)-4,6-diphenyl-1,3,5-triazine (no CAS) (1 eq), 18.1 g of 2-(9,9-dimethyl-9H-fluoren-4-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (CAS 1365692-79-0) (1.3 eq), 1.0 g of tetrakis(triphenylphosphine)palladium(0) (CAS 14221-01-3) (0.02 eq), 12.04 g of potassium carbonate (CAS 584-08-7) (2 eq). A degassed mixture of 160 mL of THF and 40 mL of water was added. The reaction was carried out at 60° C. under a nitrogen atmosphere for 3 days. A yellow suspension was formed. The reaction mixture was cooled, filtered, and washed with THF, water, and methanol. The solid was dissolved in chloroform and filtered through a pad of silica. The solvent was evaporated under low pressure and the crude white solid was further purified by sublimation. Yield: 19.09 g (78%).

[0365] 2-(3-(6-(9,9-dimethyl-9H-fluoren-4-yl)-3,5-diphenylpyrazin-2-yl)phenyl)-4,6-diphenylpyrimidine E6

[0366]

[0367] Step 1. Synthesis of 2-(3-(6-chloro-3,5-diphenylpyrazin-2-yl)phenyl)-4,6-diphenylpyrimidine.

[0368] A 3-necked round bottom flask was flushed with nitrogen and charged with 22 g of 2,6-dichloro-3,5-diphenylpyrazine (CAS 67714-55-0) (1.00 equiv), 31.7 g of 4,6-diphenyl-2-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)pyrimidine (CAS1381862-91-4) (1 equiv), 1.69 g of tetrakis(triphenylphosphine)palladium(0) (CAS14221-01-3) (0.02 equiv), 20.15 g of potassium carbonate (CAS 584-08-7) (2.0 equiv). A degassed mixture of 280 mL of dioxane and 70 mL of water was added. The reaction was carried out at 70° C. under a nitrogen atmosphere for 3 days. A yellow suspension was formed; the precipitate was filtered off, the collected solid was washed with water, dioxane and methanol and dissolved in chloroform. The solution was filtered through a pad of silica and evaporated. Further purification was carried out by recrystallization from toluene. Yield: 19.6 g (49%)

[0369] Step 2. Synthesis of 2-(3-(6-(9,9-dimethyl-9H-fluoren-4-yl)-3,5-diphenylpyrazin-2-yl)phenyl)-4,6-diphenylpyrimidine.

[0370] A 3-necked round bottom flask was flushed with nitrogen and charged with 15 g of 2-(3-(6-chloro-3,5-diphenylpyrazin-2-yl)phenyl)-4,6-diphenylpyrimidine (no CAS) (1 eq.), 10.9 g of 2-(9,9-dimethyl-9H-fluoren-4-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (CAS 1365692-79-0) (1.3 eq.), 0.61 g of tetrakis(triphenylphosphine)palladium(0) (CAS 14221-01-3) (0.02 eq.), 7.23 g of potassium carbonate (CAS 584-08-7) (2 eq.). A degassed mixture of 160 mL of THF and 25 mL of water was added. The reaction was carried out at 60° C. under a nitrogen atmosphere for 2 days. The reaction mixture was then cooled, the precipitated solid was filtered off, washed with water and extracted with chloroform. The organic phase was filtered through a pad of silica and evaporated under reduced pressure. Further purification was carried out by recrystallization from THF and final sublimation. Yield: 17 g (89%).

[0371] Device experiments

[0372] Comparison of compounds C1 to C3

[0373]

[0374] Compound C1 is known from WO2022 / 015047, and compounds C2 and C3 are known from WO2019 / 238858.

[0375] Carrier material

[0376] Support materials for device experiments

[0377] F1 is

[0378]

[0379] F2 is

[0380]

[0381] F3 is

[0382]

[0383] PD2

[0384] LiQ is 8-hydroxyquinolate lithium, CAS 850918-68-2.

[0385] H09 is the main luminescent body, and BD200 is the dopant for the blue fluorescent luminescent body, both of which can be purchased from SFC Company in South Korea.

[0386] Preparation of model blue OLED devices

[0387] The device was fabricated by depositing a 10 nm hole injection layer of F1 doped with PD2 (matrix to dopant weight ratio of 97.5:2.5 vol%) on an ITO glass substrate, followed by a 128 nm thick undoped hole transport layer of F1. A 5 nm layer of electron blocking layer of F2 was deposited on the HTL. Subsequently, a blue fluorescent emitting layer (97:3 vol%) of the luminophore host H09 (Sun Fine Chemicals) doped with BD200 (Sun Fine Chemicals) was deposited with a thickness of 20 nm. On the emitting layer, a 5 nm layer made of the test compound or comparative compound was deposited as a hole blocking layer. A 31 nm layer of electron transport layer made of F3 and LiQ was co-deposited on the HBL in a volume ratio of 50:50. Subsequently, a 100 nm thick aluminum layer was deposited as the cathode. All depositions were performed by vacuum thermal evaporation.

[0388] Table 1a schematically describes a model blue fluorescent bottom-emitting device.

[0389] Table 1a

[0390]

[0391] ITO is indium tin oxide.

[0392] Technical Effects

[0393] Surprisingly, it was found that the organic electronic device comprising an organic semiconductor layer comprising a compound of formula 1 according to the present invention solves the potential problems by outperforming organic electronic devices known in the art, in particular in terms of operating voltage, current and quantum efficiency.

[0394] The results obtained using the above model device are shown in Table 1b.

[0395] Table 1b

[0396]

[0397] Compared to state-of-the-art compounds C1 to C3, compounds E1 to E5 of the invention are able to achieve lower operating voltages as well as higher currents and quantum efficiencies.

[0398] The features disclosed in the above description and in the claims may, both alone and in any combination thereof, be material for implementing aspects of the disclosure in their different forms as set out in the independent claims.

Claims

1. A compound of formula (I): A-(Cy) n -Pz-FL (I), in -A is selected from substituted or unsubstituted C containing at least two condensed aromatic rings 10 To C 42 Aryl and selected from C2-C 42 Heteroaryl, excluding C2 to C 42 The case where the heteroaryl group is benzoxazolyl or carbazolyl; -in, If A is substituted, the one or more substituents are independently selected from C6-C 18 Aryl, C3-C 20 Heteroaryl, D, F, CN, C1-C 20 Alkyl, C1-C 20 Alkoxy, PY(R)2, OR, SR, (C=O)R, (C=O)N(R)2, Si(R)3, (S=O)R and in Y is O or S, and R is independently selected from C1-C 20 Straight chain alkyl, C1-C 20 Alkoxy, C1-C 20 Thioalkyl, C3-C 20 Branched alkyl, C3-C 20 Cyclic alkyl, C3-C 20 Branched alkoxy, C3-C 20 Cyclic alkoxy, C3-C 20 Branched chain thioalkyl, C3-C 20 Cyclic thioalkyl, C6-C 20 Aryl and C3-C 20 heteroaryl; -Cy is independently selected from substituted or unsubstituted monocyclic C3 to C 36 Hydrocarbyl, substituted or unsubstituted polycyclic C3 to C 36 Hydrocarbon, substituted or unsubstituted monocyclic C3 to C 36 A hydrocarbon group, or a substituted or unsubstituted polycyclic C3 to C 36 Hydrocarbon; - wherein, if Cy is substituted, one or more substituents are independently selected from C6-C 18 Aryl, C3-C 20 Heteroaryl, D, F, CN, C1-C 16 Alkyl, C1-C 16 Alkoxy, PY(R)2, OR, SR, (C=O)R, (C=O)N(R)2, Si(R)3, (S=O)R and in Y is O or S, and R is independently selected from C1-C 20 Straight chain alkyl, C1-C 20 Alkoxy, C1-C 20 Thioalkyl, C3-C 20 Branched alkyl, C3-C 20 Cyclic alkyl, C3-C 20 Branched alkoxy, C3-C 20 Cyclic alkoxy, C3-C 20 Branched chain thioalkyl, C3-C 20 Cyclic thioalkyl, C6-C 20 Aryl and C3-C 20 heteroaryl; -n is an integer from 0 to 4; -Pz is a fully substituted pyrazine substituent; - wherein the substituents on the pyrazine substituent are independently selected from groups having at least one carbon atom; -FL is a substituted or unsubstituted fluorenyl group; - wherein, if FL is substituted, one or more substituents are independently selected from C6-C 18 Aryl, C2-C 20 Heteroaryl, D, F, CN, C1-C 16 Alkyl, C1-C 16 Alkoxy, PY(R)2, OR, SR, (C=O)R, (C=O)N(R)2, Si(R)3, (S=O)R and in Y is O or S, and R is independently selected from C1-C 20 Straight chain alkyl, C1-C 20 Alkoxy, C1-C 20 Thioalkyl, C3-C 20 Branched alkyl, C3-C 20 Cyclic alkyl, C3-C 20 Branched alkoxy, C3-C 20 Cyclic alkoxy, C3-C 20 Branched chain thioalkyl, C3-C 20 Cyclic thioalkyl, C6-C 20 Aryl and C3-C 20 Heteroaryl.

2. The compound according to claim 1, wherein A comprises at least one six-membered N-containing aromatic ring.

3. The compound according to claim 1 or 2, wherein A is selected from an aryl group comprising 2, 3, 4 or 5 condensed aromatic rings, an azinyl, a diazinyl, a triazinyl, a naphthazinyl, a naphthazinyl, a triazinyl, an azathranyl, an azaphenanthrenyl, a diazathranyl, a diazathranyl, a triazathranyl, a triazaphenanthrenyl, a benzofuranyl and its aza, diaza or triaza derivatives, a benzothiophenyl and its aza, diaza or triaza derivatives, a dibenzofuranyl and its aza, diaza or triaza derivatives and triaza derivatives thereof, dibenzothiophenyl and its aza, diaza or triaza derivatives, naphthofuranyl and its aza, diaza or triaza derivatives, naphthothiophenyl and its aza, diaza or triaza derivatives, naphthobenzofuranyl and its aza, diaza or triaza derivatives, naphthobenzothiophenyl and its aza, diaza or triaza derivatives, dinaphthofuranyl and its aza, diaza or triaza derivatives, and dinaphthothiophenyl and its aza, diaza or triaza derivatives, which are respectively substituted or unsubstituted.

4. The compound according to any one of the preceding claims, wherein A is selected from naphthyl, anthracenyl, phenanthrenyl, terphenylidene, acenaphthenyl, fluoranthenyl, pyrenyl, naphthacene, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, quinolyl, isoquinolyl, cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, naphthyridinyl, imidazopyridinyl, phenanthridinyl, phenanthrolinyl, acridinyl, benzoacridinyl, dibenzoacridinyl, each of which is substituted or unsubstituted.

5. A compound according to any one of the preceding claims, wherein if A is substituted, one or more substituents are independently selected from C6-C 12 Aryl.

6. A compound according to any one of the preceding claims, wherein Cy is independently selected from C6-C 36 Aryl and C3-C 36 Heteroaryl.

7. The compound according to any one of the preceding claims, wherein Cy is respectively monocyclic or bicyclic.

8. The compound according to any one of the preceding claims, wherein the substituents of the fully substituted pyrazine group are independently selected from a hydrocarbyl group, a carbocyclic group or a heterocyclic group.

9. A compound according to any one of the preceding claims, wherein the substituents of the fully substituted pyrazine substituent are independently selected from C6-C 36 Aryl and C3-C 36 Heteroaryl.

10. The compound according to any one of the preceding claims, wherein the substituents of the persubstituted pyrazine group are monocyclic or bicyclic.

11. The compound according to any one of the preceding claims, wherein the fluorenyl group is substituted at its 9-position by two hydrocarbyl groups which can be connected to each other to form a ring.

12. The compound according to any one of the preceding claims, wherein the fluorenyl group is 9,9'-dimethyl-fluorenyl group.

13. An organic semiconductor material comprising a compound according to any one of the preceding claims. 14 . An organic electronic device comprising a semiconductor layer, wherein the semiconductor layer comprises the compound according to claim 1 . The organic electronic device according to claim 14 , wherein the semiconductor layer is an electron transporting layer.

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