Semiconductor material, method for preparing layer of semiconductor material, organic semiconductor device comprising organic semiconductor material, display device comprising organic semiconductor device, and compound

Abstract

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

Description

Technical Field

[0001] The present invention relates to a semiconductor material, a method for preparing a layer of the semiconductor material, an organic semiconductor device comprising the semiconductor material and a display device comprising the organic semiconductor device. The present invention also relates to a compound. Background of the Invention

[0003] Organic semiconductor devices such as organic light emitting diodes (OLEDs) as 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 sequentially stacked on a substrate. In this regard, HTL, EML, and ETL are thin films formed of organic compounds.

[0004] 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 an excited state to a 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 a long life.

[0005] The performance of an organic light emitting diode may be affected by the properties of the organic semiconductor layer, and in particular by the properties of the organic material of the organic semiconductor layer.

[0006] In particular, there is a need to develop an organic semiconductor layer capable of increasing electron mobility and simultaneously increasing electrochemical stability so that organic semiconductor devices such as organic light emitting diodes can be applied to large-sized flat panel displays.

[0007] In addition, there is a need to develop an organic semiconductor layer that can have an extended service life at higher current density and therefore at higher brightness. In particular, there is a need to develop an organic semiconductor material or semiconductor layer that can reduce the operating voltage of, for example, a mobile display device, which is very important for reducing power consumption and extending battery life.

[0008] Therefore, the object of the present invention is to provide an organic semiconductor device and an organic semiconductor material and compound for preparing the organic semiconductor device which overcome the disadvantages of the prior art, in particular to provide a compound for use in an organic semiconductor material and an electronic device containing the same to help improve its performance, in particular to improve its performance in terms of efficiency and / or operating voltage. Summary of the invention

[0009] This object is achieved by a semiconductor material comprising a first organic compound and a second organic matrix compound, wherein

[0010] - the first organic compound and the second organic matrix compound are different from each other; and

[0011] The first organic compound contains at least one group represented by the following formula (1):

[0012] (1)

[0013] in

[0014] - Squiggly line" " represents the position at which the group represented by formula (I) is bonded to the remaining structure of the first organic compound;

[0015] - and R 1 and R 2 are independently selected from alkyl; and

[0016] -R 1 and R 2 The total number of carbon atoms in is at least 3.

[0017] The first organic compound may further comprise at least one charge transporting moiety comprising at least one aromatic ring.

[0018] The charge transport moieties may be independently selected from:

[0019] - heteroaromatic moieties containing at least two heteroatoms;

[0020] - an aryl group comprising at least two, preferably at least three, fused aromatic rings; and

[0021] - a heteroaryl group comprising at least two, preferably at least three, fused aromatic rings.

[0022] The heteroaromatic moiety comprising at least two heteroatoms may be independently selected from diazines, triazines, quinazolines, quinoxalines, benzoquinazolines, benzoquinoxalines, azacarbazoles, azadibenzofurans, azadibenzothiophenes, naphthyridines, benzimidazoles, benzoxazoles, benzothiazoles, imidazopyridines and imidazopyrimidines.

[0023] The aryl group comprising at least two fused aromatic rings may be independently selected from anthracene, phenanthrene and pyrene.

[0024] The heteroaryl group comprising at least two fused aromatic rings may be independently selected from azaanthracene, azaphenanthracene, diazaanthracene, diazaphenanthracene, benzoacridine and dibenzoacridine.

[0025] R 1 and R 2 It may be independently selected from C4 alkyl and C5 alkyl, especially isobutyl and neopentyl.

[0026] R1 and R 2 You can choose the same.

[0027] The first organic compound can be represented by the following formula (2):

[0028] (2)

[0029] in

[0030] R 1 and R 2 are independently selected from alkyl;

[0031] R 1 and R 2 The total number of carbon atoms in is at least 3;

[0032] A is a charge transport moiety; and

[0033] L is a direct bond or a spacer.

[0034] L may be selected from an aromatic subgroup and a heteroaromatic subgroup.

[0035] L may be selected from a phenylene group and a 1,1'-biphenyl-diyl group.

[0036] The semiconductor material may also contain n-type electron dopants.

[0037] The object is also achieved by a method for producing a layer of semiconductor material according to the invention, said method comprising the step of depositing a first organic compound on a solid support.

[0038] The object is also achieved by an organic semiconductor device comprising at least one layer comprising the semiconductor material according to the invention.

[0039] The layer containing a semiconductor material may be an electron transport layer, an electron injection layer, or an electron generation layer.

[0040] The organic semiconductor device may be an organic diode, an organic transistor, an organic solar cell or an organic light emitting diode.

[0041] The object is also achieved by a display device comprising the organic semiconductor device according to the invention.

[0042] This object is also achieved by a compound selected from the group consisting of:

[0043] E1 E2 E3 E4 E-5 E-6 E-7 E-8 E-9 E-10 E-11 E-12 E-13 E-14 E-15 E-16 E-17 E-18 E-19 E-20 E-21 E-22 E-23 E-24 E-25 E-26 E-27 E-28 E-29 E-30 E-31 E-32 E-33 E-34 E-35 E-36 E-37 E-38 E-39 E-40 E-41 E-42 E-43 E-44 A2 A3 A4 A5 A6 A7.

[0044] Surprisingly, it was found that the semiconductor material according to the invention and the compound according to the invention as well as the organic semiconductor device according to the invention solve the underlying problem of the invention, so that the device is superior in all respects to the organic electroluminescent devices known from the prior art, in particular in terms of efficiency and / or operating voltage.

[0045] Semiconductor Materials

[0046] According to one aspect, the present invention relates to a semiconductor material comprising a first organic compound and a second organic compound. The first organic compound and the second organic compound are different from each other. In this regard, "different from each other" can have the meaning of "structurally different from each other", which means that the first organic compound and the second organic compound are formed by different atoms, or by the same atoms connected to each other in different ways. In other words, the first organic compound and the second organic compound can be completely different from each other, for example belong to different classes of matter, or can be isomers, in particular can be structural isomers.

[0047] The first organic compound contains at least one group represented by the following formula (1):

[0048] (1)

[0049] The wavy line " represents the position where the group represented by formula (I) is bonded to the remaining structure of the first organic compound; R 1 and R 2 are independently selected from alkyl; and R 1 and R 2 The total number of carbon atoms in is at least 3.

[0050] R 1 and R 2 The total number of carbon atoms in R 1 and R 2 That is, in R 1 is methyl (CH3) and R 2 In the case of ethyl (C2H5), the minimum total number of carbon atoms is 3.

[0051] The first organic compound includes, in addition to the group represented by formula (1), other parts, such as a charge transport structure part or another part, and, for example, a substituent connected to the charge transport structure part or the other part. In the case where the group represented by formula (1) is bonded to the charge transport structure part, the wavy line " " may represent a single bond through which the group represented by formula (1) is bonded to the charge transporting structure part. In the case where the group represented by formula (1) is bonded to another part of the first organic compound, the wavy line " " may represent a single bond through which the group represented by the formula (1) is bonded to the other part of the first organic compound.

[0052] The first organic compound may further comprise at least one charge transporting moiety comprising at least one aromatic ring.

[0053] The charge transport moiety may be a moiety comprising a molecular frontier orbital having a suitable energy level, particularly for transferring charges from the layer comprising the first organic compound to an adjacent layer.

[0054] For example, the first organic compound may be a matrix compound in a layer of an organic semiconductor device. In this case, the matrix compound (i.e., as the main (dominant) compound, e.g., with a content of more than 50% by weight or 50% by volume) forming the basis of a layer arranged between two electrodes in an organic semiconductor device may be "suitable" in the present invention, the frontier orbital energy level of which differs from the frontier orbital energy level of a matrix compound in an adjacent layer (arranged in contact with the layer comprising the first organic compound) by less than 1 eV, preferably less than 0.8 eV, more preferably less than 0.5 eV, and most preferably less than 0.3 eV.

[0055] The frontier orbital determining electron transport in an electron transport material is the lowest unoccupied molecular orbital (LUMO) of the corresponding electron transport host compound. Similarly, the frontier orbital determining hole transport in a hole transport material is the highest occupied molecular orbital (HOMO) of the corresponding hole transport host compound.

[0056] Advantageously, the frontier orbitals of the corresponding host compounds are delocalized on more than two atoms. In one embodiment, if the electron transport portion of the electron transport host comprises a conjugated system of at least four delocalized electrons, preferably at least six delocalized electrons, such frontier orbitals can be provided. Suitable LUMO energy levels in the frontier orbitals formed in such a small delocalized electron system can be adjusted by the presence of one or more heteroatoms, preferably by two or three nitrogen atoms. Examples of such electron transport portions may be diazines, triazines, diazoles, oxadiazoles and triazole portions.

[0057] In another embodiment, the electron transport portion of the electron transport matrix can contain a conjugated system of more than six delocalized electrons, such as ten delocalized electrons or fourteen delocalized electrons. In this embodiment, the requirements for suitable LUMO energy levels can be met in a broad spectrum of carbocyclic and heterocyclic structural moieties comprising at least two fused aromatic rings.

[0058] The charge transport moiety may be substituted with one or more substituents independently selected from C6 to C 12 Aryl, C3 to C 21 heteroaryl and C1 to C6 alkyl, D, C1 to C6 alkoxy, C3 to C6 branched alkyl, C3 to C6 cyclic alkyl, C3 to C6 branched alkoxy, C3 to C6 cyclic alkoxy, partially or perfluorinated C1 to C6 alkyl, partially or perfluorinated C1 to C6 alkoxy, partially or perdeuterated C1 to C6 alkyl, partially or perdeuterated C1 to C6 alkoxy, C3 to C 36 Silyl, halogen, CN or PY(R 10 )2, wherein Y is selected from O, S or Se, preferably O, and R 10 Independently selected from C6 to C 12 Aryl, C3 to C 12 heteroaryl, C1 to C6 alkyl, C1 to C6 alkoxy, partially or perfluorinated C1 to C6 alkyl, partially or perfluorinated C1 to C6 alkoxy, partially or perdeuterated C1 to C6 alkyl, partially or perdeuterated C1 to C6 alkoxy; and each C6 to C 12 The aryl substituent and each C3 to C 21 The heteroaryl substituents may be independently replaced by one or more C1 to C4 alkyl groups such as methyl, C3 to C 36 Silyl, CN and halogen substitution.

[0059] The charge transport moiety may be substituted with one or more substituents independently selected from C6 to C 12 Aryl such as C 10 Aryl (naphthyl) or C 12 (biphenyl) and / or C3 to C 21 Heteroaryl groups such as phenylene-pyridine or 2-phenylene-(4,6-diphenyl)triazine, which may or may not exclude C6 to C 12 Aryl and / or C3 to C 21 The presence of other substituents besides heteroaryl, such as methyl or CN.

[0060] The charge transport moieties may be independently selected from:

[0061] - heteroaromatic moieties containing at least two heteroatoms;

[0062] - an aryl group comprising at least two, preferably at least three, fused aromatic rings; and

[0063] - a heteroaryl group comprising at least two, preferably at least three, fused aromatic rings.

[0064] The term "heteroaryl" or "heteroaromatic moiety" may refer to an aromatic heterocycle having at least one heteroatom (or multiple if specifically specified), and all elements of the hydrocarbon heteroaromatic moiety may have a conjugated p orbital. The heteroatom may be independently selected from N, O, S, B, Si, P, Se, preferably selected from N, O and S, more preferably O and N, most preferably N.

[0065] The heteroaromatic moiety containing at least two heteroatoms may be C2 to C 42 Heteroaromatic moieties. Heteroaromatic moieties containing at least two heteroatoms may be C2 to C 39 Heteroaromatic moieties. Heteroaromatic moieties containing at least two heteroatoms may be C2 to C 36 Heteroaromatic moieties. Heteroaromatic moieties containing at least two heteroatoms may be C2 to C 33 Heteroaromatic moieties. Heteroaromatic moieties containing at least two heteroatoms may be C2 to C 30 Heteroaromatic moieties. Heteroaromatic moieties containing at least two heteroatoms may be C2 to C 27 Heteroaromatic moieties. Heteroaromatic moieties containing at least two heteroatoms may be C2 to C 24 Heteroaromatic moieties. Heteroaromatic moieties containing at least two heteroatoms may be C2 to C 21 Heteroaromatic moieties. Heteroaromatic moieties containing at least two heteroatoms may be C2 to C 17 Heteroaromatic moieties. Heteroaromatic moieties containing at least two heteroatoms may be C2 to C 14 Heteroaromatic moieties. Heteroaromatic moieties containing at least two heteroatoms may be C2 to C 11 Heteroaromatic moieties. The heteroaromatic moieties comprising at least two heteroatoms may be C2 to C9 heteroaromatic moieties. The heteroaromatic moieties comprising at least two heteroatoms may be C2 to C7 heteroaromatic moieties. The heteroaromatic moieties comprising at least two heteroatoms may be C2 to C5 heteroaromatic moieties. The heteroaromatic moieties comprising at least two heteroatoms may be C3 to C4 heteroaromatic moieties.

[0066] The aromatic heterocyclic moiety comprising at least two heteroatoms can be independently selected from diazine, triazine, quinazoline, quinoxaline, benzoquinazoline, benzoquinoxaline, azacarbazole, azadibenzofuran, azadibenzothiophene, naphthyridine, benzimidazole, benzothiazole, benzothiazole, imidazopyridine and imidazopyrimidine. The aromatic heterocyclic moiety comprising at least two heteroatoms can be triazine.

[0067] The aromatic heterocyclic moiety containing at least two heteroatoms can be independently selected from diazines, triazines, quinazolines, quinoxalines, benzoquinazolines, benzoquinoxalines, azacarbazoles, azadibenzofurans, azadibenzothiophenes, naphthyridines, benzimidazoles, benzoxazoles, benzothiazoles, imidazopyridines and imidazopyrimidines.

[0068] The aryl group comprising at least two, preferably at least three, fused aromatic rings may be C 10 To C 60 Aryl. The aryl group comprising at least two, preferably at least three fused aromatic rings may be C 10 To C 54 Aryl. The aryl group comprising at least two, preferably at least three fused aromatic rings may be C 10 To C 48 Aryl. The aryl group comprising at least two, preferably at least three fused aromatic rings may be C 10 To C 42 Aryl. The aryl group comprising at least two, preferably at least three fused aromatic rings may be C 10 To C 36 Aryl. The aryl group comprising at least two, preferably at least three fused aromatic rings may be C 10 To C 30 Aryl. The aryl group comprising at least two, preferably at least three fused aromatic rings may be C 10 To C 24 Aryl. The aryl group comprising at least two, preferably at least three fused aromatic rings may be C 10 To C 18 Aryl.

[0069] The aryl group comprising at least two condensed aromatic rings may be independently selected from anthracene, phenanthrene and pyrene. The aryl group comprising at least two condensed aromatic rings may be anthracene or phenanthrene.

[0070] The heteroaryl group containing at least two fused aromatic rings may be C6 to C 42 Heteroaryl. A heteroaryl group comprising at least two fused aromatic rings may be C6 to C 39 Heteroaryl. A heteroaryl group comprising at least two fused aromatic rings may be C6 to C 36 Heteroaryl. A heteroaryl group comprising at least two fused aromatic rings may be C6 to C 33 Heteroaryl. A heteroaryl group comprising at least two fused aromatic rings may be C6 to C 30 Heteroaryl. A heteroaryl group comprising at least two fused aromatic rings may be C6 to C 27 Heteroaryl. A heteroaryl group comprising at least two fused aromatic rings may be C6 to C 24Heteroaryl. A heteroaryl group comprising at least two fused aromatic rings may be C6 to C 21 Heteroaryl. A heteroaryl group comprising at least two fused aromatic rings may be C6 to C 17 Heteroaryl. A heteroaryl group comprising at least two fused aromatic rings may be C8 to C 17 Heteroaryl. A heteroaryl group comprising at least two fused aromatic rings may be C8 to C 12 Heteroaryl. The heteroaryl group comprising at least two fused aromatic rings may be a C8 to C9 heteroaryl.

[0071] The heteroaryl group comprising at least two fused aromatic rings may be independently selected from azaanthracene, azaphenanthracene, diazaanthracene, diazaphenanthracene, benzoacridine and dibenzoacridine.

[0072] R 1 and R 2 Can be independently selected from C1 alkyl to C 12 Alkyl, provided that R 1 and R 2 The total number of carbon atoms in R is at least 3. 1 and R 2 Can be independently selected from C1 alkyl to C 10 Alkyl, provided that R 1 and R 2 The total number of carbon atoms in R is at least 3. 1 and R 2 can be independently selected from C1 alkyl to C8 alkyl, provided that R 1 and R 2 The total number of carbon atoms in R is at least 3. 1 and R 2 can be independently selected from C1 alkyl to C6 alkyl, provided that R 1 and R 2 The total number of carbon atoms in is at least 3.

[0073] R 1 and R 2 R may be independently selected from C2 alkyl to C6 alkyl. 1 and R 2 R may be independently selected from C3 alkyl to C6 alkyl. 1 and R 2 It may be independently selected from C4 alkyl and C5 alkyl, in particular from isobutyl and neopentyl.

[0074] R 1 and R 2 You can choose the same, that is, for example, R 1 and R 2 Can be isobutyl or R 1 and R 2They may all be neopentyl.

[0075] The first organic compound can be represented by the following formula (2):

[0076] (2)

[0077] in

[0078] R 1 and R 2 are independently selected from alkyl;

[0079] R 1 and R 2 The total number of carbon atoms in is at least 3;

[0080] A is a charge transport moiety; and

[0081] L is a direct bond or a spacer.

[0082] R 1 and R 2 Preferred embodiments of are the same as described above with respect to formula (1).

[0083] A can be expressed as one of the following formulas,

[0084] ; ; ; ; ; ;

[0085] Among them, A is in " is bonded to L at "; and n is 1 or 2.

[0086] A can be expressed as one of the following formulas,

[0087] ; ; ; ; ; ; ;

[0088] Among them, A is in ” is bonded to L.

[0089] In the case where L is a spacer, L may be substituted by one or more substituents independently selected from: C6 to C 18 Aryl, C3 to C 15heteroaryl and C1 to C6 alkyl, D, C1 to C6 alkoxy, C3 to C6 branched alkyl, C3 to C6 cyclic alkyl, C3 to C6 branched alkoxy, C3 to C6 cyclic alkoxy, partially or perfluorinated C1 to C6 alkyl, partially or perfluorinated C1 to C6 alkoxy, partially or perdeuterated C1 to C6 alkyl, partially or perdeuterated C1 to C6 alkoxy, C3 to C 36 Silyl, halogen, CN or PY(R 10 )2, wherein Y is selected from O, S or Se, preferably O, and R 10 Independently select C6 to C 12 Aryl, C3 to C 12 heteroaryl, C1 to C6 alkyl, C1 to C6 alkoxy, partially or perfluorinated C1 to C6 alkyl, partially or perfluorinated C1 to C6 alkoxy, partially or perdeuterated C1 to C6 alkyl, partially or perdeuterated C1 to C6 alkoxy; and each C6 to C 18 The aryl substituent and each C3 to C 15 The heteroaryl substituents may be independently replaced by C1 to C4 alkyl, C3 to C 36 Silyl or halogen substituted.

[0090] In the case where L is a spacer, L (i.e., the spacer) may be selected from an aromatic subunit and a heteroaromatic subunit. In the case where L is a spacer, L may be selected from C6 to C 60 Aromatic subunits and C2 to C 42 In the case where L is a spacer, L can be selected from C6 to C 54 Aromatic subunits and C2 to C 39 In the case where L is a spacer, L can be selected from C6 to C 48 Aromatic subunits and C2 to C 36 In the case where L is a spacer, L can be selected from C6 to C 42 Aromatic subunits and C2 to C 33 In the case where L is a spacer, L can be selected from C6 to C 36 Aromatic subunits and C2 to C 30 In the case where L is a spacer, L can be selected from C6 to C 30 Aromatic subunits and C2 to C 24 In the case where L is a spacer, L can be selected from C6 to C 24 Aromatic subunits and C2 to C 21 In the case where L is a spacer, L can be selected from C6 to C 18 Aromatic subunits and C2 to C 17 In the case where L is a spacer, L can be selected from C6 to C 12 Aromatic subunits and C2 to C14 Heteroaromatic subunit.

[0091] In the case where L is a spacer, L (i.e., the spacer) may be an aromatic substituent. In the case where L is a spacer, L may be C6 to C 60 In the case where L is a spacer, L can be C6 to C 54 In the case where L is a spacer, L can be C6 to C 48 In the case where L is a spacer, L can be C6 to C 42 In the case where L is a spacer, L can be C6 to C 36 In the case where L is a spacer, L can be C6 to C 30 In the case where L is a spacer, L can be C6 to C 24 In the case where L is a spacer, L can be C6 to C 18 In the case where L is a spacer, L can be C6 to C 12 Aromatic subunit.

[0092] L may be selected from a phenylene group and a 1,1'-biphenyl-diyl group. L may be a phenylene group. L may be an m-phenylene group or a p-phenylene group.

[0093] The first organic compound may be selected from the following compounds E1 to E44 and A1 to A7:

[0094] E1 E2 E3 E4 E-5 E-6 E-7 E-8 E-9 E-10 E-11 E-12 E-13 E-14 E-15 E-16 E-17 E-18 E-19 E-20 E-21 E-22 E-23 E-24 E-25 E-26 E-27 E-28 E-29 E-30 E-31 E-32 E-33 E-34 E-35 E-36 E-37 E-38 E-39 E-40 E-41 E-42 E-43 E-44 A1 A2 A3 A4 A5 A6 A7.

[0095] According to one embodiment, the present invention relates to a semiconductor material comprising a first organic compound and a second organic compound, wherein

[0096] - the first organic compound and the second organic compound are different from each other; and

[0097] - The first organic compound is represented by the following formula (2):

[0098] (2)

[0099] in

[0100] R 1 and R 2Independently selected from C1 to C 12 alkyl;

[0101] R 1 and R 2 The total number of carbon atoms in is at least 3;

[0102] A is a charge transport structure;

[0103] The charge transport moieties are independently selected from:

[0104] - C2 to C containing at least two heteroatoms 42 Heteroaromatic moieties;

[0105] - C containing at least two, preferably at least three fused aromatic rings 10 To C 60 an aryl group; and

[0106] - C6 to C6 containing at least two, preferably at least three fused aromatic rings 42 heteroaryl groups;

[0107] The charge transport moiety may be substituted with one or more substituents independently selected from: C6 to C 12 Aryl, C3 to C 11 heteroaryl and C1 to C6 alkyl, D, C1 to C6 alkoxy, C3 to C6 branched alkyl, C3 to C6 cyclic alkyl, C3 to C6 branched alkoxy, C3 to C6 cyclic alkoxy, partially or perfluorinated C1 to C6 alkyl, partially or perfluorinated C1 to C6 alkoxy, partially or perdeuterated C1 to C6 alkyl, partially or perdeuterated C1 to C6 alkoxy, C3 to C 36 Silyl, halogen, CN or PY(R 10 )2, wherein Y is selected from O, S or Se, preferably O, and R 10 Independently selected from C6 to C 12 Aryl, C3 to C 12 heteroaryl, C1 to C6 alkyl, C1 to C6 alkoxy, partially or perfluorinated C1 to C6 alkyl, partially or perfluorinated C1 to C6 alkoxy, partially or perdeuterated C1 to C6 alkyl, partially or perdeuterated C1 to C6 alkoxy; and each C6 to C 12 The aryl substituent and each C3 to C 11 The heteroaryl substituents may be independently replaced by C1 to C4 alkyl, C3 to C 36 Silyl or halogen substitution;

[0108] L is a spacer group;

[0109] The spacer is C6 to C 60 an aromatic subunit; and

[0110] L may be substituted with one or more substituents independently selected from: C6 to C 18 Aryl, C3 to C 15 heteroaryl and C1 to C6 alkyl, D, C1 to C6 alkoxy, C3 to C6 branched alkyl, C3 to C6 cyclic alkyl, C3 to C6 branched alkoxy, C3 to C6 cyclic alkoxy, partially or perfluorinated C1 to C6 alkyl, partially or perfluorinated C1 to C6 alkoxy, partially or perdeuterated C1 to C6 alkyl, partially or perdeuterated C1 to C6 alkoxy, C3 to C 36 Silyl, halogen, CN or PY(R 10 )2, wherein Y is selected from O, S or Se, preferably O, and R 10 Independently selected from C6 to C 12 Aryl, C3 to C 12 heteroaryl, C1 to C6 alkyl, C1 to C6 alkoxy, partially or perfluorinated C1 to C6 alkyl, partially or perfluorinated C1 to C6 alkoxy, partially or perdeuterated C1 to C6 alkyl, partially or perdeuterated C1 to C6 alkoxy; and each C6 to C 18 The aryl substituent and each C3 to C 15 The heteroaryl substituents may be independently replaced by C1 to C4 alkyl, C3 to C 36 Silyl or halogen substituted.

[0111] According to one embodiment, the present invention relates to a semiconductor material comprising a first organic compound and a second organic compound, wherein

[0112] - the first organic compound and the second organic compound are different from each other; and

[0113] - The first organic compound is represented by the following formula (2):

[0114] (2)

[0115] in

[0116] R 1 and R 2 Independently selected from C3 to C6 alkyl;

[0117] R 1 and R 2 The total number of carbon atoms in is at least 3;

[0118] A is a charge transport structure;

[0119] The charge transport moiety is a C-containing at least two, preferably at least three fused aromatic rings. 10 To C60 Aryl groups;

[0120] The charge transport moiety may be substituted with one or more substituents independently selected from C6 to C 12 Aryl, wherein the presence of other substituents is not excluded, and the other substituents are independently selected from C3 to C 11 heteroaryl and C1 to C6 alkyl, D, C1 to C6 alkoxy, C3 to C6 branched alkyl, C3 to C6 cyclic alkyl, C3 to C6 branched alkoxy, C3 to C6 cyclic alkoxy, partially or perfluorinated C1 to C6 alkyl, partially or perfluorinated C1 to C6 alkoxy, partially or perdeuterated C1 to C6 alkyl, partially or perdeuterated C1 to C6 alkoxy, C3 to C 36 Silyl, halogen, CN or PY(R 10 )2, wherein Y is selected from O, S or Se, preferably O, and R 10 Independently selected from C6 to C 12 Aryl, C3 to C 12 heteroaryl, C1 to C6 alkyl, C1 to C6 alkoxy, partially or perfluorinated C1 to C6 alkyl, partially or perfluorinated C1 to C6 alkoxy, partially or perdeuterated C1 to C6 alkyl, partially or perdeuterated C1 to C6 alkoxy; and each C6 to C 12 The aryl substituent and each C3 to C 11 The heteroaryl substituents may be independently replaced by C1 to C4 alkyl, C3 to C 36 Silyl or halogen substitution;

[0121] L is a spacer group;

[0122] The spacer is C6 to C 18 an aromatic subunit; and

[0123] L may be substituted with one or more substituents independently selected from: C6 to C 18 Aryl, C3 to C 15 heteroaryl and C1 to C6 alkyl, D, C1 to C6 alkoxy, C3 to C6 branched alkyl, C3 to C6 cyclic alkyl, C3 to C6 branched alkoxy, C3 to C6 cyclic alkoxy, partially or perfluorinated C1 to C6 alkyl, partially or perfluorinated C1 to C6 alkoxy, partially or perdeuterated C1 to C6 alkyl, partially or perdeuterated C1 to C6 alkoxy, C3 to C 36 Silyl, halogen, CN or PY(R 10 )2, wherein Y is selected from O, S or Se, preferably O, and R 10 Independently selected from C6 to C 12 Aryl, C3 to C 12heteroaryl, C1 to C6 alkyl, C1 to C6 alkoxy, partially or perfluorinated C1 to C6 alkyl, partially or perfluorinated C1 to C6 alkoxy, partially or perdeuterated C1 to C6 alkyl, partially or perdeuterated C1 to C6 alkoxy; and each C6 to C 18 The aryl substituent and each C3 to C 15 The heteroaryl substituents may be independently replaced by C1 to C4 alkyl, C3 to C 36 Silyl or halogen substituted.

[0124] According to one embodiment, the present invention relates to a semiconductor material comprising a first organic compound and a second organic compound, wherein

[0125] - the first organic compound and the second organic compound are different from each other; and

[0126] - The first organic compound is represented by the following formula (2):

[0127] (2)

[0128] in

[0129] R 1 and R 2 independently selected from isobutyl and neopentyl;

[0130] A is a charge transport structure;

[0131] A is represented by one of the following formulas,

[0132] ; ; ; ; ; ;

[0133] Among them, A is in " is bonded to L; and n is 1 or 2;

[0134] A may be substituted with one or more substituents independently selected from C6 to C 12 Aryl, wherein the presence of other substituents is not excluded, and the other substituents are independently selected from C3 to C 11 heteroaryl and C1 to C6 alkyl, D, C1 to C6 alkoxy, C3 to C6 branched alkyl, C3 to C6 cyclic alkyl, C3 to C6 branched alkoxy, C3 to C6 cyclic alkoxy, partially or perfluorinated C1 to C6 alkyl, partially or perfluorinated C1 to C6 alkoxy, partially or perdeuterated C1 to C6 alkyl, partially or perdeuterated C1 to C6 alkoxy, C3 to C36 Silyl, halogen, CN or PY(R 10 )2, wherein Y is selected from O, S or Se, preferably O, and R 10 Independently selected from C6 to C 12 Aryl, C3 to C 12 heteroaryl, C1 to C6 alkyl, C1 to C6 alkoxy, partially or perfluorinated C1 to C6 alkyl, partially or perfluorinated C1 to C6 alkoxy, partially or perdeuterated C1 to C6 alkyl, partially or perdeuterated C1 to C6 alkoxy; and each C6 to C 12 The aryl substituent and each C3 to C 11 The heteroaryl substituents may be independently replaced by C1 to C4 alkyl, C3 to C 36 Silyl or halogen substitution;

[0135] L is a spacer group;

[0136] The spacer is selected from the group consisting of a phenylene group and a 1,1'-biphenyl-diyl group; and

[0137] L may be substituted with one or more substituents independently selected from: C6 to C 18 Aryl, C3 to C 15 heteroaryl and C1 to C6 alkyl, D, C1 to C6 alkoxy, C3 to C6 branched alkyl, C3 to C6 cyclic alkyl, C3 to C6 branched alkoxy, C3 to C6 cyclic alkoxy, partially or perfluorinated C1 to C6 alkyl, partially or perfluorinated C1 to C6 alkoxy, partially or perdeuterated C1 to C6 alkyl, partially or perdeuterated C1 to C6 alkoxy, halogen, CN or PY (R 10 )2, wherein Y is selected from O, S or Se, preferably O, and R 10 Independently selected from: C6 to C 12 Aryl, C3 to C 12 heteroaryl, C1 to C6 alkyl, C1 to C6 alkoxy, partially or perfluorinated C1 to C6 alkyl, partially or perfluorinated C1 to C6 alkoxy, partially or perdeuterated C1 to C6 alkyl, partially or perdeuterated C1 to C6 alkoxy; and each C6 to C 18 The aryl substituent and each C3 to C 15 The heteroaryl substituents may independently be substituted with C1 to C4 alkyl or halogen.

[0138] According to one embodiment, the present invention relates to a semiconductor material comprising a first organic compound and a second organic compound, wherein

[0139] - the first organic compound and the second organic compound are different from each other; and

[0140] - The first organic compound is represented by the following formula (2):

[0141] (2)

[0142] in

[0143] R 1 and R 2 independently selected from isobutyl and neopentyl;

[0144] A is represented by one of the following formulas:

[0145] ; ; ; ; ; ; ;

[0146] Among them, A is in " is bonded to L;

[0147] And L is an m-phenylene group or an o-phenylene group.

[0148] According to one embodiment, the present invention relates to a semiconductor material comprising a first organic compound and a second organic compound, wherein

[0149] - the first organic compound and the second organic compound are different from each other; and

[0150] - The first organic compound is represented by the following formula (2):

[0151] (2)

[0152] in

[0153] The first organic compound is selected from the following compounds E1 to E44 and A2 to A7:

[0154] E1 E2 E3 E4 E-5 E-6 E-7 E-8 E-9 E-10 E-11 E-12 E-13 E-14 E-15 E-16 E-17 E-18 E-19 E-20 E-21 E-22 E-23 E-24 E-25 E-26 E-27 E-28 E-29 E-30 E-31 E-32 E-33 E-34 E-35 E-36 E-37 E-38 E-39 E-40 E-41 E-42 E-43 E-44 A2 A3 A4 A5 A6 A7.

[0155] The second organic compound may be an organic matrix compound, that is, the second organic compound may also be referred to as a second organic matrix compound.

[0156] As the second organic compound, an electron transport material having a LUMO energy level similar to the LUMO energy level of the first organic compound may be particularly suitable. Similarity in this sense means that the difference between the LUMO energy levels of the first and second organic compounds is 1 eV or less, or 0.8 eV or less, or 0.5 eV or less, or 0.3 eV or less. In one embodiment, the dipole moment of the second organic compound is lower than the dipole moment of the first organic compound. In one embodiment, the second organic compound does not include a phosphine oxide group. The second organic compound can be a molecule, such as an organic molecule compound. Therefore, the element of the second organic compound can be bonded by a covalent bond. In one embodiment, the second organic compound does not include a metal. Therefore, the second organic compound may not be a metal organic complex.

[0157] The semiconductor material may be obtained by depositing the first organic compound and the second organic compound together from one deposition source.

[0158] Based on the total volume of the semiconductor material, the volume ratio of the second organic compound to the first organic compound in the semiconductor material, that is, the ratio of (second organic compound): (first organic compound) can be higher than 1, for example, based on the total volume of the semiconductor material, preferably in the range of 20:1 to 1:5, preferably in the range of 15:1 to 1:2, more preferably in the range of 10:1 to 1:1, even more preferably in the range of 5:1 to 3:2, and even more preferably in the range of 3:1 to 2:1.

[0159] If the n-type dopant is present in the semiconductor material, the volume ratio of the second organic compound and the n-type dopant in the semiconductor material, i.e., the ratio of (second organic compound):(n-type dopant) is higher than 1 based on the total volume of the semiconductor material. The second organic compound may be a main component of the semiconductor material to have good electron transport properties. An n-type dopant such as LiQ known in the prior art has poor electron transport properties, so a semiconductor material having a volume ratio of the second organic compound and the n-type dopant as described above may be preferred to have good electron transport properties.

[0160] The second organic compound may include a charge transport moiety selected from the group consisting of diazine, triazine, quinazoline, quinoxaline, benzoquinazoline, benzoquinoxaline, azacarbazole, azadibenzofuran, azadibenzothiophene, naphthyridine, benzimidazole, benzothiazole, benzothiazole, imidazopyridine, and imidazopyrimidine. Examples of compounds suitable for use as the second charge transport compound are disclosed in, for example, WO2020 / 120793 and / or WO2021 / 250276.

[0161] The semiconductor material may be an organic semiconductor material. The semiconductor material may be an electron transport material. The first organic compound may be an electron transport matrix material (electron transport matrix).

[0162] The semiconductor material may contain, in addition to the first organic compound and the second organic compound, an electronic dopant, such as an n-type electronic dopant, in particular a redox n-type dopant. An n-type dopant is a compound that, if embedded in an electron transport matrix material, improves the electronic properties of the resulting semiconductor material, in particular improved electronic properties in terms of electron injection and / or electron conductivity, compared to the pure electron transport matrix material under the same physical conditions.

[0163] In the context of the present invention, "embedded in the electron transport matrix" means uniformly mixed with the electron transport matrix.

[0164] The n-type dopant may be selected from elemental metals, metal salts, metal complexes and organic groups.

[0165] The metal salt may be selected from alkali metal salts and alkaline earth metal salts, and in one embodiment may be selected from salts of the following metals: Li, Na, K, Rb, Cs, Mg, Ca, Sr and Ba. The salt may contain anions selected from the following: halogen anions, complex borate anions, organic phenol anions. In one embodiment, the anions in the salt may be cationic chelated anions such as 8-hydroxyquinolate anions and / or 2-phosphorylphenol anions.

[0166] In one embodiment, the 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; still more preferably selected from lithium fluoride, lithium quinoline, lithium borate, lithium phenoxide, lithium pyridinolate or lithium complexes with Schiff base ligands; most preferably,

[0167] - The lithium complex has formula II, III or IV:

[0168]

[0169] in

[0170] A1 to A6 are identically or independently selected from CH, CR, N, O;

[0171] R are identical or independently selected from hydrogen, halogen, alkyl or aryl or heteroaryl having 1 to 20 carbon atoms; more preferably A1 to A6 are CH,

[0172] - The borate anion organic ligand is tetrakis(1H-pyrazol-1-yl)borate anion,

[0173] - the phenolate anion is a 2-(pyridin-2-yl)phenolate anion, a 2-phosphoryl-phenolate anion such as a 2-(diphenylphosphoryl)phenolate anion, an imidazophenol anion, a 2-(pyridin-2-yl)phenolate anion or a 2-(1-phenyl-1H-benzo[d]imidazol-2-yl)phenolate anion,

[0174] - The pyridinol anion is 2-(diphenylphosphoryl)pyridin-3-ol anion,

[0175] - The lithium Schiff base has structure 100, 101, 102 or 103:

[0176] .

[0177] According to one embodiment of the present invention, the semiconductor material of the present invention comprises a lithium organic complex or 8-hydroxyquinolate lithium (=LiQ).

[0178] According to one embodiment of the present invention, the semiconductor material comprises a metal, which is 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, still more preferably selected from Li, Na, Cs and Yb, and most preferably selected from Li, Na and Yb.

[0179] The most practical criterion for measuring the strength of an n-type dopant is its redox potential. There is no particular restriction on how negative the redox potential can be.

[0180] The reduction potential of commonly used electron transport substrates in organic semiconductors is generally in the range of about -0.8 V to about -3.1 V when measured by cyclic voltammetry relative to a ferrocene / ferrocene cation reference redox couple; the practically applicable range of redox potential for 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.

[0181] The measurement of redox potential is actually carried out on the corresponding redox couple composed of the reduced state and oxidized state of the same compound.

[0182] In the case where the n-type dopant is an electrically neutral metal complex and / or an electrically neutral organic free radical, the measurement of its redox potential is actually carried out on the redox couple formed as follows:

[0183] (i) a neutral metal complex and a cation radical thereof formed by abstracting an electron from the neutral metal complex; or

[0184] (ii) an electrically neutral organic radical and a cation thereof formed by abstracting an electron from the electrically neutral organic radical.

[0185] Preferably, the redox potential of the electrically neutral metal complex and / or electrically neutral organic free radical may have a value more negative than -0.5 V, preferably more negative than -1.2 V, more preferably more negative than -1.7 V, still more preferably more negative than -2.1 V, most preferably more negative than -2.5 V, if measured by cyclic voltammetry relative to a ferrocene / ferrocene cation reference redox couple for the corresponding redox couple consisting of:

[0186] (i) a neutral metal complex and a cation radical thereof formed by abstracting an electron from the neutral metal complex; or

[0187] (ii) an electrically neutral organic radical and a cation thereof formed by abstracting an electron from the electrically neutral organic radical.

[0188] 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 transporting host.

[0189] Electroneutral metal complexes suitable as n-type dopants may be, for example, strongly reducing complexes of some transition metals in a low oxidation state. As described in more detail in WO 2005 / 086251, particularly strong n-type dopants may be selected, for example, from Cr(II), Mo(II) and / or W(II) guanidine complexes such as W2(hpp)4.

[0190] As described in more detail in EP 1 837 926 B1, WO2007 / 107306 or WO2007 / 107356, the electrically neutral organic free radical suitable as an n-type dopant can be, for example, an organic free radical produced by supplying additional energy from its stable dimer, oligomer or polymer. Elemental metals are understood to be metals in the state of pure metals, metal alloys or in the state of free atoms or metal clusters. It is understood that the metal deposited by vacuum thermal evaporation from a metallic phase such as from a pure bulk metal is volatilized in its elemental form. It is also understood that if the volatilized elemental metal is deposited with a covalent matrix, the metal atoms and / or clusters are embedded in the covalent matrix. In other words, it is understood that any metal-doped covalent material prepared by vacuum thermal evaporation contains at least partially the metal in its elemental form.

[0191] For use in consumer electronics, only metals containing stable nuclides or nuclides with very long radioactive decay half-lives are suitable. As an acceptable level of nuclear stability, the nuclear stability of natural potassium can be used.

[0192] In one embodiment, the n-type dopant may be selected from an electropositive metal 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, still more preferably selected from Li, Na, Cs and Yb, most preferably selected from Li, Na and Yb.

[0193] In another embodiment, the semiconductor material of the present invention may be free of n-type dopants.In one embodiment, the semiconductor material of the present invention may be composed of the first and second organic compounds as the only components.

[0194] Method for producing a layer of semiconductor material

[0195] The invention also relates to a method for producing a layer of a semiconductor material according to the invention. The method comprises the step of depositing a first organic compound, preferably together with a second organic compound, on a solid support.

[0196] Embodiments described herein with respect to the semiconductor material according to the invention are also embodiments of the method according to the invention.

[0197] Deposition may include the use of:

[0198] - at least one deposition source, preferably two deposition sources, more preferably at least three deposition sources; and / or

[0199] - Deposition by vacuum thermal evaporation; and / or

[0200] - Deposition by solution processing, preferably selected from spin coating, printing, casting and / or slot die coating.

[0201] The solid support may be any layer of an organic semiconductor device on which a semiconductor material is deposited to form a layer, wherein the layer comprising the semiconductor material is directly adjacent to the solid support in the final device.

[0202] According to various embodiments of the present invention, there is provided a method using the following deposition source:

[0203] - a first deposition source to release a first organic compound according to the invention, preferably a first organic compound and a second organic compound; and

[0204] - 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;

[0205] The method comprises the steps of forming an organic semiconductor layer; wherein for an organic light emitting diode (OLED):

[0206] - The organic semiconductor layer is formed by releasing a first organic compound according to the invention (preferably together with a second organic compound) 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-hydroxyquinoline lithium from a second deposition source.

[0207] 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.

[0208] According to various embodiments of the present invention, the method may further include the step of forming an organic light emitting diode (OLED), wherein

[0209] - forming a first anode electrode on the substrate,

[0210] - forming a light emitting layer on the first anode electrode,

[0211] - 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,

[0212] - Finally, the cathode electrode is formed.

[0213] - 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,

[0214] - An optional electron injection layer is formed between the organic semiconductor layer and the cathode electrode.

[0215] 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 the electron injection layer.

[0216] According to various embodiments, the OLED may have the following layer structure, wherein the layers have the following order:

[0217] anode, hole injection layer, first hole transport layer, second hole transport layer, light-emitting layer, optional hole blocking layer, layer comprising or consisting of the first organic compound according to the invention, optional electron injection layer and cathode.

[0218] Organic semiconductor devices

[0219] The object is also achieved by an organic semiconductor device comprising at least one layer comprising the semiconductor material according to the invention.

[0220] Embodiments described herein relating to the semiconductor material according to the present invention also relate to embodiments of the organic semiconductor device according to the present invention.

[0221] The layer including the semiconductor material may be an electron transport layer, an electron injection layer, or an electron generation layer.

[0222] The organic semiconductor device may be an organic diode, an organic transistor, an organic solar cell or an organic light emitting diode, and in particular may be an organic light emitting diode.

[0223] According to the present invention, the organic semiconductor device may further comprise other layers in addition to the layers mentioned above, in particular, in addition to the electron transport layer and / or electron injection layer and / or electron generation layer comprising or consisting of the semiconductor material according to the present invention. Exemplary embodiments of the various layers are described below:

[0224] Base

[0225] The substrate may be any substrate commonly used to manufacture 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 may be either a transparent material or an opaque material, such as a glass substrate, a plastic substrate, a metal substrate, or a silicon substrate.

[0226] Anode electrode

[0227] The first electrode or the second electrode included in the organic semiconductor 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 used to form the anode electrode can be a high work function material, thereby facilitating 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 or 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 or a metal alloy, and the metal is typically silver (Ag) or gold (Au).

[0228] Hole injection layer

[0229] The hole injection layer (HIL) can be formed on the anode electrode by vacuum deposition, spin coating, printing, casting, slot die coating, Langmuir-Blodgett (LB) deposition, etc. When the HIL is formed using vacuum deposition, the deposition conditions may vary depending on the compound used to form the HIL and the desired structure and thermal properties of the HIL. However, in general, the vacuum deposition conditions may include a deposition temperature of 100° C. to 500° C., a ... -8 Up to 10 -3 Torr pressure (1 Torr equals 133.322 Pa) and a deposition rate of 0.1 nm / sec to 10 nm / sec.

[0230] When the HIL is formed using spin coating or printing, the coating conditions may vary depending on 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, heat treatment is performed to remove the solvent.

[0231] The HIL may be formed of any compound that is generally used to form a HIL. Examples of the compound 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).

[0232] 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 are: copper phthalocyanine (CuPc) doped with tetrafluoro-tetracyanoquinodimethane (F4TCNQ), the HOMO level of copper phthalocyanine (CuPc) being about -5.2 eV and the LUMO level of tetrafluoro-tetracyanoquinodimethane (F4TCNQ) being about -5.2 eV; zinc phthalocyanine (ZnPc) doped with F4TCNQ (HOMO=-5.2 eV); 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 concentration of the p-type dopant can be selected from 1 to 20 wt%, more preferably from 3 to 10 wt%.

[0233] The thickness of the HIL may be within a range of about 1 nm to about 100 nm, for example, within a range of 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.

[0234] Hole transport layer

[0235] The hole transport layer (HTL) can be formed on the HIL by vacuum deposition, spin coating, slot die coating, printing, casting, Langmuir-Blodgett (LB) deposition, etc. When the HTL is formed by vacuum deposition or spin coating, the conditions of deposition and coating can be similar to those of forming the HIL. However, the conditions of vacuum or solution deposition may vary depending on the compound used to form the HTL.

[0236] The HTL may be formed of any compound commonly used to form the HTL. For example, compounds that can be suitably used 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.

[0237] The thickness of the HTL may be in the range of about 5 nm to about 250 nm, preferably about 10 nm to about 200 nm, further about 20 nm to about 190 nm, further about 40 nm to about 180 nm, further about 60 nm to about 170 nm, further about 80 nm to about 160 nm, further about 100 nm to about 160 nm, further about 120 nm to about 140 nm. The preferred thickness of the HTL may be 170 nm to 200 nm.

[0238] When the thickness of the HTL is within this range, the HTL may have excellent hole transport characteristics without substantially deteriorating driving voltage.

[0239] Electron blocking layer

[0240] 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 limiting 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 is closer to the vacuum energy level than the LUMO energy level of the hole transport layer. Compared with the HOMO energy level of the hole transport layer, the electron blocking layer can have a HOMO energy level that is further away from the vacuum energy level. The thickness of the electron blocking layer can be selected between 2 nm and 20 nm.

[0241] If the electron blocking layer has a high triplet energy level, it can also be described as a triplet controlling layer.

[0242] If a phosphorescent green or blue emitting layer is used, the function of the triplet control layer is to reduce the quenching of the triplet state. Thus, a higher luminous efficiency from 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. Suitable compounds for triplet control layers, in particular triarylamine compounds, are described in EP 2 722 908 A1.

[0243] Photoactive Layer (PAL)

[0244] The photoactive layer converts electric current into photons or converts photons into electric current.

[0245] 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 by vacuum deposition or spin coating, the conditions of deposition and coating may be similar to those of forming the HIL. However, the conditions of deposition and coating may vary depending on the compound used to form the PAL.

[0246] The photoactive layer may not contain the compound of formula (1).

[0247] The photoactive layer can be a light emitting layer or a light absorbing layer.

[0248] Emission layer (EML)

[0249] 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 of deposition and coating may be similar to those of forming the HIL. However, the conditions of deposition and coating may vary depending on the compound used to form the EML.

[0250] The light-emitting layer may not contain the compound of formula (1).

[0251] The light-emitting layer (EML) can be formed by 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).

[0252] The emitter dopant may be a phosphorescent or fluorescent emitter. Phosphorescent emitters and emitters emitting 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.

[0253] 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.

[0254] Examples of phosphorescent green emitter dopants are Ir(ppy)3 (ppy=phenylpyridine), Ir(ppy)2(acac), Ir(mpyp)3.

[0255] 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.

[0256] The amount of the luminophore dopant may be in the range of about 0.01 to about 50 parts by weight based on 100 parts by weight of the host. Alternatively, the luminescent layer may be composed of a luminescent polymer. The EML may have a thickness of about 10 nm to about 100 nm, for example, about 20 nm to about 60 nm. When the thickness of the EML is within this range, the EML may have excellent luminescence without causing substantial damage to the driving voltage.

[0257] Hole Blocking Layer (HBL)

[0258] The 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 can also have a triplet exciton blocking function. The hole blocking layer can be an organic semiconductor layer of the present invention, which contains or consists of a compound of the present invention represented by the general formula (1) as defined above.

[0259] HBL can also be named as auxiliary ETL or a-ETL.

[0260] When vacuum deposition or spin coating is used to form HBL, the conditions of deposition and coating can be similar to those for forming HIL. However, the conditions of deposition and coating can vary with the compound used to form HBL. Any compound commonly used to form HBL can be used. Examples of compounds used to form HBL include oxadiazole derivatives, triazole derivatives, and phenanthroline derivatives.

[0261] The thickness of the HBL may be in a 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.

[0262] The hole blocking layer may also be described as an a-ETL or an auxiliary ETL.

[0263] According to one embodiment, a hole-blocking layer is arranged between the at least one photoactive layer and the layer which comprises or consists of the semiconductor material according to the invention.

[0264] According to one embodiment, a hole blocking layer is arranged between at least one photoactive layer and a layer comprising or consisting of a semiconductor material according to the invention, wherein the layer comprising the semiconductor material according to the invention comprises, in addition to the first organic compound and the second organic compound, an additive, which may be an n-type dopant.

[0265] According to one embodiment, a hole blocking layer is arranged between at least one photoactive layer and a layer comprising or consisting of a semiconductor material according to the invention, wherein the layer comprising a semiconductor material according to the invention also comprises a metal, a metal compound or a metal-organic complex, or a metal or lithium-organic complex.

[0266] According to one embodiment, the hole blocking layer is arranged between at least one photoactive layer and the layer comprising or consisting of the semiconductor material according to the invention, wherein the layer comprising or consisting of the semiconductor material according to the invention also comprises a metal.

[0267] Electron Transport Layer (ETL)

[0268] The semiconductor device according to the present invention may include an electron transport layer (ETL). According to a preferred embodiment of the present invention, the electron transport layer may be a layer including or consisting of the semiconductor material according to the present invention.

[0269] According to various embodiments, the OLED may comprise an electron transport layer or an electron transport layer stack comprising at least a first electron transport layer and at least a second electron transport layer.

[0270] 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, thereby allowing the OLED to have a long lifespan.

[0271] The electron transport layer of the semiconductor device may include the first organic compound and the second organic compound as defined above as organic electron transport matrix (ETM) materials. In addition to the first organic compound and the second organic compound or as a substitute thereof, the electron transport layer may also include other ETM materials known in the art. Similarly, the electron transport layer may include the first organic compound and the second organic compound as the only electron transport matrix materials. In the case where the organic semiconductor device of the present invention includes more than one electron transport layer, the first organic compound and the second organic compound may be included 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 include at least one additive as defined below.

[0272] In addition, the electron transport layer may include one or more dopants. The additive may be an n-type dopant. The additive can 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 one selected from the following: 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 one selected from the following: 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 suitable compounds of ETM (compounds that can be used in addition to the compounds of the present invention shown in the general formula (1) 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, for example, documents EP 1 970 371 A1 or WO 2013 / 079217 A1.

[0273] Electron injection layer (EIL)

[0274] An optional EIL may be formed on the ETL, preferably directly on the electron transport layer, which facilitates the injection of electrons from the cathode. Examples of materials 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 depending on the material used to form the EIL.

[0275] The thickness of the EIL may be in the range of about 0.1 nm to about 10 nm, for example, in the 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 performance without substantially deteriorating driving voltage.

[0276] Charge Generation Layer (CGL)

[0277] 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.

[0278] 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 adjacent layer in the anode direction. Similarly, the p-side of the pn junction generates holes and injects them into the adjacent layer in the cathode direction.

[0279] 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.

[0280] Suitable host materials for the hole generation layer may be materials conventionally used as hole injection and / or hole transport host materials. Moreover, conventional materials may be used as p-type dopants for the hole generation layer. For example, the p-type dopant may be one selected from the following: tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4-TCNQ), derivatives of tetracyanoquinodimethane, axialene derivatives, iodine, FeCl3, FeF3, and SbCl5. In addition, the host may be one selected from the following: N,N'-di(naphthalene-1-yl)-N,N-diphenylbenzidine (NPB), N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1-biphenyl-4,4'-diamine (TPD), and N,N',N'-tetranaphthylbenzidine (TNB). The p-type charge generation layer may be composed of CNHAT.

[0281] The n-type charge generation layer may be a layer comprising a semiconductor material according to the present invention or consisting of a semiconductor material according to the present invention. The n-type charge generation layer may be a layer of a pure n-type dopant such as a metal, 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 one selected from the following: 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 one selected from the following: Li, Cs, K, Rb, Mg, Na, Ca, Sr, Eu, and Yb. Suitable matrix materials for the electron generation layer may be materials conventionally used as matrix materials for electron injection or electron transport layers. The matrix material may be, for example, one selected from the following: triazine compounds, hydroxyquinoline derivatives such as tris (8-hydroxyquinoline) aluminum, benzoxazole derivatives, and silacyclopentane derivatives.

[0282] The hole generation layer is arranged in direct contact with the n-type charge generation layer.

[0283] According to one aspect of the present invention, the organic semiconductor layer is disposed between the first and second light emitting layers and further includes an n-type dopant.

[0284] According to one aspect of the present invention, the organic semiconductor layer is disposed between the first and second light emitting layers and further contains a metal.

[0285] According to one aspect of the present invention, the organic semiconductor layer is disposed between the first and second light-emitting layers, and further comprises a metal selected from the group consisting of alkali metals, alkaline earth metals, and rare earth metals.

[0286] According to one aspect of the present invention, a layer comprising or consisting of a semiconductor material according to the present invention is arranged between the first and second light-emitting layers, and other layers comprising or consisting of a semiconductor material according to the present invention are arranged between the second light-emitting layer and the cathode.

[0287] According to one aspect of the present invention, a layer containing a semiconductor material according to the present invention or consisting of a semiconductor material according to the present invention is arranged between the first and second light-emitting layers, and other layers containing a semiconductor material according to the present invention or consisting of a semiconductor material according to the present invention are arranged between the second light-emitting layer and the cathode; wherein the layer containing a semiconductor material according to the present invention or consisting of a semiconductor material according to the present invention further contains an n-type dopant.

[0288] According to one aspect of the present invention, a layer containing a semiconductor material according to the present invention or consisting of a semiconductor material according to the present invention is arranged between a first and a second light-emitting layer, and other layers containing a semiconductor material according to the present invention or consisting of a semiconductor material according to the present invention are arranged between the second light-emitting layer and the cathode; the other layers containing a semiconductor material according to the present invention or consisting of a semiconductor material according to the present invention further contain an n-type dopant.

[0289] According to one aspect of the present invention, a layer containing a semiconductor material according to the present invention or consisting of a semiconductor material according to the present invention is arranged between a first and a second light-emitting layer, and other layers containing a semiconductor material according to the present invention or consisting of a semiconductor material according to the present invention are arranged between the second light-emitting layer and the cathode; the layer containing a semiconductor material according to the present invention or consisting of a semiconductor material according to the present invention further contains an n-type dopant, and other layers containing a semiconductor material according to the present invention or consisting of a semiconductor material according to the present invention further contain an n-type dopant.

[0290] According to one aspect of the present invention, a layer containing a semiconductor material according to the present invention or consisting of a semiconductor material according to the present invention is arranged between a first and a second light-emitting layer, and other layers containing a semiconductor material according to the present invention or consisting of a semiconductor material according to the present invention are arranged between the second light-emitting layer and the cathode; wherein the layer containing a semiconductor material according to the present invention or consisting of a semiconductor material according to the present invention further contains a metal, and other layers containing a semiconductor material according to the present invention or consisting of a semiconductor material according to the present invention further contain an n-type dopant.

[0291] Method for preparing an organic semiconductor device

[0292] The present invention also relates to a method for preparing an organic semiconductor device according to the present invention, said method comprising the method for preparing a semiconductor material according to the present invention.

[0293] Organic Light Emitting Diodes

[0294] The organic semiconductor device according to the present invention may be an organic light emitting device.

[0295] According to one aspect of the present invention, an organic light emitting diode (OLED) is provided, which comprises: a substrate; an anode electrode formed on the substrate; a hole injection layer, a hole transport layer, a light emitting layer, a layer comprising or consisting of a semiconductor material according to the present invention, and a cathode electrode.

[0296] According to another aspect of the present invention, an OLED is provided, which includes: 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, a layer including or consisting of a semiconductor material according to the present invention, and a cathode electrode.

[0297] According to another aspect of the present invention, an OLED is provided, which includes: 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, a layer containing or consisting of the semiconductor material according to the present invention, an electron injection layer and a cathode electrode.

[0298] 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.

[0299] According to one aspect, an OLED may include a layer structure of a substrate arranged adjacent to an anode electrode, the anode electrode being arranged adjacent to a first hole injection layer, the first hole injection layer being arranged adjacent to a first hole transport layer, the first hole transport layer being arranged adjacent to a first electron blocking layer, the first electron blocking layer being arranged adjacent to a first light-emitting layer, the first light-emitting layer being arranged adjacent to a first electron transport layer, the first electron transport layer being arranged adjacent to an n-type charge generation layer, the n-type charge generation layer being arranged adjacent to the hole generation layer, the hole generation layer being arranged adjacent to a second hole transport layer, the second hole transport layer being arranged adjacent to a second electron blocking layer, the second electron blocking layer being arranged adjacent to a second light-emitting layer, and an optional electron transport layer and / or an optional injection layer being arranged between the second light-emitting layer and the cathode electrode.

[0300] The semiconductor layer according to the present invention, ie, the layer including the first organic compound and the second organic compound, may be an electron transport layer, a first electron transport layer, an n-type charge generation layer and / or a second electron transport layer.

[0301] For example, according to Figure 2The OLED can be formed by the following method: 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).

[0302] According to another aspect of the present invention, there is provided an organic semiconductor device, the organic semiconductor 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 embodiment described in the entire application. More preferably, the electronic device is a display device.

[0303] In one embodiment, the organic semiconductor device according to the present invention including a layer including or consisting of the semiconductor material according to the present invention may further include a layer including a radialene compound and / or a quinodimethane compound.

[0304] In one embodiment, the axialene compound and / or quinodimethane compound can be substituted with one or more halogen atoms and / or one or more electron withdrawing groups. The electron withdrawing group can be selected from nitrile group, haloalkyl group, or from perhaloalkyl group, or from perfluoroalkyl group. Other examples of electron withdrawing groups can be acyl group, sulfonyl group or phosphoryl group.

[0305] Alternatively, the acyl group, sulfonyl group and / or phosphoryl group may contain halogenated and / or perhalogenated hydrocarbon groups. In one embodiment, the perhalogenated hydrocarbon group may be a perfluoro hydrocarbon group. Examples of perfluoro 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.

[0306] In one embodiment, the radialene and / or quinodimethane compound may be included in a hole injection layer, a hole transport layer, and / or a hole generation layer.

[0307] In one embodiment, the radialene compound may have the formula (XX) and / or the quinodimethane compound may have the formula (XXIa) or (XXIb):

[0308]

[0309] where (as an exception to the above) R 1 , R 2 , R 3 , R4 , 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.

[0310] According to one embodiment of the present invention, a layer comprising or consisting of a semiconductor material according to the present invention is adjacent to a layer comprising a compound of the formula (XX), (XXIa) or (XXIb).

[0311] According to one embodiment of the present invention, the layer comprising or consisting of the semiconductor material according to the present invention is in direct contact with the layer comprising the compound of the formula (XX), (XXIa) or (XXIb).

[0312] Compound

[0313] According to other aspects, the present invention relates to a compound selected from compounds E1 to E44 and A2 to A7,

[0314] E1 E2 E3 E4 E-5 E-6 E-7 E-8 E-9 E-10 E-11 E-12 E-13 E-14 E-15 E-16 E-17 E-18 E-19 E-20 E-21 E-22 E-23 E-24 E-25 E-26 E-27 E-28 E-29 E-30 E-31 E-32 E-33 E-34 E-35 E-36 E-37 E-38 E-39 E-40 E-41 E-42 E-43 E-44 A2 A3 A4 A5 A6 A7.

[0315] common sense

[0316] 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 should encompass straight chain as well as branched and cyclic alkyl groups. For example, C3-alkyl groups may be selected from n-propyl and isopropyl. Similarly, C4-alkyl groups include n-butyl, sec-butyl and tert-butyl. Similarly, C6-alkyl groups include n-hexyl and cyclohexyl.

[0317] As used herein, unless otherwise expressly stated, an asterisk " ” indicates the binding position where the corresponding labeled moiety is bonded to another moiety.

[0318] C n The subscript number n in relates to the total number of carbon atoms in the corresponding alkyl, arylene, heteroarylene or aryl group.

[0319] As used herein, the term "aryl" or "aryl substituent" should cover: phenyl (C6-aryl); fused aromatic compounds such as naphthalene, anthracene, phenanthrene, tetracene, etc. Also covered are biphenyl and oligo- or poly-phenyl such as terphenyl, phenyl-substituted biphenyl, phenyl-substituted terphenyl such as phenyl groups of tetraphenyl, etc. "Aryl substituent", correspondingly "heteroaryl substituent" refers to a group connected to two other parts. In this specification, the term "aryl group" or "aryl substituent group" can refer to a group comprising at least one hydrocarbon aromatic part, and all elements of the hydrocarbon aromatic part can have a p orbital forming a conjugation, such as a phenyl group, a naphthyl group, an anthracene group, a phenanthrene group, a pyrenyl group, a fluorenyl group, etc. Also included are spiro compounds, in which two aromatic parts are connected to each other by spiro atoms, such as 9,9'-spiro two [9H-fluorene] base. Aryl or aryl substituent groups can include monocyclic or condensed ring polycyclic (i.e., sharing the connection of adjacent carbon atom pairs) functional groups.

[0320] 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 independently selected from N, S and / or O. As in the case of "aryl" / "aryl subunit", the term "heteroaryl" includes, for example, spiro compounds in which two aromatic moieties are interconnected, such as spiro[fluorene-9,9'-xanthene]. Other exemplary heteroaryl groups are diazines, triazines, dibenzofurans, dibenzothiophenes, acridines, benzoacridines and dibenzoacridines, etc.

[0321] As used herein, the term "alkenyl" refers to a group containing a carbon-carbon double bond -CR 1 =CR 2 R 3 .

[0322] 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.

[0323] 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.

[0324] 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.

[0325] C n The subscript number n in -heteroaryl refers only to the number of carbon atoms in addition to the number of heteroatoms. In this context, it is clear that the C3 heteroaryl group is an aromatic compound containing three carbon atoms such as pyrazole, imidazole, oxadiazole, thiazole, etc.

[0326] As used herein, the term "heteroaryl" shall include pyridine, quinoline, benzoquinoline, quinazoline, benzoquinazoline, pyrimidine, pyrazine, triazine, benzimidazole, benzothiazole, benzo[4,5]thieno[3,2-d]pyrimidine, carbazole, xanthene, phenazine, benzoacridine, dibenzoacridine, and the like.

[0327] In this specification, the term single bond means a direct bond.

[0328] As used herein, the term "fluorinated" refers to a hydrocarbon group in which at least one hydrogen atom contained in the hydrocarbon group is replaced by a fluorine atom. A fluorinated group in which all of its hydrogen atoms are replaced by fluorine atoms is called a perfluorinated group and is specifically represented by the term "fluorinated".

[0329] According to the present invention, a group is "substituted" by another group if one of the hydrogen atoms contained in the group is replaced by another group, wherein the other group is a substituent.

[0330] According to the present invention, in the formula showing the following bonding conditions, The group A may be bonded to any suitable bonding position. In the case where the bonds of A span more than one ring The group A may be bonded to any suitable bonding position of the respective ring spanned by the bond.

[0331] According to the invention, the expression "between" with respect to a layer between two other layers does not exclude the presence of other layers that may be arranged between the one layer and one of the two other layers. According to the invention, the expression "in direct contact" with respect to two layers in direct contact with each other means that no other layer is arranged between these two layers. A layer deposited on top of another layer is considered to be in direct contact with this layer.

[0332] The term "sandwiched in contact" refers to an arrangement of three layers wherein the middle layer is in direct contact with two adjacent layers.

[0333] With regard to the electron transport layer stack of the invention, the compounds mentioned in the experimental part are most preferred.

[0334] A lighting device can be any device used for illumination, radiation, signaling or projection. They are classified accordingly as lighting, radiation, signaling and projection devices. A lighting device is usually composed of the following elements: a source of optical radiation; a device that transmits the radiation flux into space in the desired direction; and a housing that connects the components into a single device and protects the radiation source and the optical transmission system from environmental damage and influences.

[0335] 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 referred to as tandem OLEDs or stacked OLEDs.

[0336] 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.

[0337] A further aspect relates to a device comprising at least one organic electroluminescent device (OLED).

[0338] Devices comprising organic light emitting diodes are, for example, displays or lighting panels.

[0339] For the present invention, for the following defined terms, these definitions shall apply unless a different definition is given in the claims or elsewhere in this specification.

[0340] In the context of this specification, the term "different" in relation to a host material means that the host materials differ in their structural formula.

[0341] 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 an organic light emitting diode as well as an organic light emitting transistor (OLET).

[0342] As used herein, "weight percent," "wt%" and variations thereof refer to expressing a composition, component, substance or agent as the weight of the component, substance or agent of the corresponding electron transport layer divided by the total weight of its corresponding electron transport layer, multiplied by 100. It is understood that the amount of the total weight percentage of all components, substances and agents of the corresponding electron transport layer and electron injection layer is selected in such a way that it does not exceed 100 wt%.

[0343] As used herein, "volume percent," "volume %," and variations thereof refer to expressing a composition, component, substance, or agent as the volume of the component, substance, or agent of the corresponding electron transport layer divided by the total volume of its corresponding electron transport layer, multiplied by 100. It is understood that the amount of the total volume percent of all components, substances, and agents of the cathode layer is selected in such a way that it does not exceed 100 volume %.

[0344] 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 variation in quantity that can occur. Whether or not modified by the term "about", the claims include equivalents of the quantities.

[0345] It must be noted that, as used in this specification and the appended claims, the singular forms "a," "an," "the," and "said" include plural referents unless the content clearly dictates otherwise.

[0346] The terms "does not contain", "does not contain", and "does not include" do not exclude impurities. Impurities have no technical influence on the purpose achieved by the present invention.

[0347] In the context of this specification, the term "substantially non-luminescent" or "non-luminescent" means that the compound or layer contributes less than 10%, preferably less than 5%, to the visible light emission spectrum from the device relative to the visible light emission spectrum. The visible light emission spectrum is the light emission spectrum with a wavelength of about ≥380 nm to about ≤780 nm.

[0348] Preferably, the organic semiconductor layer comprising the compound of formula (1) is substantially non-emissive or non-emissive.

[0349] The operating voltage, also called U, is 10 mA / cm2. 2 ) is measured in volts (V).

[0350] The candela efficiency per ampere, also called cd / A efficiency, is calculated at 10 mA / cm2. 2 ) is measured in candela per ampere.

[0351] External quantum efficiency, also called EQE, is measured in percent (%).

[0352] 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 luminescence. The smaller the CIE-y, the darker the blue. Efficiency values ​​are compared at the same CIE-y.

[0353] The highest occupied molecular orbital (also called HOMO) and the lowest unoccupied molecular orbital (also called LUMO) are measured in electron volts (eV).

[0354] 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.

[0355] The terms "lifetime" and "service life" are used concurrently and have the same meaning.

[0356] The anode and cathode may be described as anode electrode / cathode electrode or anode electrode / cathode electrode or anode electrode layer / cathode electrode layer.

[0357] Room temperature, also called ambient temperature, is 23°C.

[0358] Hereinafter, the embodiments are illustrated in more detail with reference to the examples. However, the present invention is not limited to the following examples. Reference will now be made in detail to the exemplary aspects. BRIEF DESCRIPTION OF THE DRAWINGS

[0359] The components described above and the components claimed for protection and used in the embodiments according to the invention are not limited by any special exceptions in terms of their size, shape, material selection and technical concept, so that selection criteria known in the relevant field can be applied without restriction.

[0360] Other details, features and advantages of the subject matter of the invention are disclosed in the dependent claims and in the description of the following drawings, which show preferred embodiments according to the invention in an exemplary manner. However, any embodiment does not necessarily represent the full scope of the invention, and therefore reference is made to the claims and this document to interpret the scope of the invention. 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 as claimed.

[0361] Figure 1 is a schematic cross-sectional view of an organic semiconductor device according to an exemplary embodiment of the present invention;

[0362] Figure 2 is a schematic cross-sectional view of an organic light emitting diode (OLED) according to an exemplary embodiment of the present invention;

[0363] Figure 3 is a schematic cross-sectional view of an OLED according to an exemplary embodiment of the present invention;

[0364] 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.

[0365] Hereinafter, the accompanying drawings will be described in more detail with reference to examples. However, the present invention is not limited to the following accompanying drawings.

[0366] Here, when a first element is referred to as being formed or disposed "on" a second element, the first element may be disposed directly on the second element, or one or more other elements may be disposed therebetween. When a first element is referred to as being formed or disposed "directly" on a second element, no other elements are disposed therebetween.

[0367] Figure 1 1 is a schematic cross-sectional view of an organic semiconductor device 100 according to an exemplary embodiment of the present invention. The organic semiconductor device 100 includes a substrate 110, an anode 120, a photoactive layer (PAL) 125, and a layer 160 including or consisting of a semiconductor material according to the present invention. The layer 160 including or consisting of a semiconductor material according to the present invention is formed on the PAL 125. On the organic semiconductor layer 160, a cathode 190 is provided.

[0368] 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. On the electron transport layer (ETL) 160, an electron injection layer (EIL) 180 is disposed. A cathode 190 is directly disposed on the electron injection layer (EIL) 180.

[0369] As an alternative to a single electron transport layer 160, a stack of electron transport layers (ETL) may optionally be used.

[0370] 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 that Figure 3 The OLED 100 includes an electron blocking layer (EBL) 145 and a hole blocking layer (HBL) 155 .

[0371] 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.

[0372] Preferably, the organic semiconductor layer including the compound of formula (1) may be an ETL.

[0373] 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).

[0374] See also 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.

[0375] Preferably, the layer comprising or consisting of the semiconductor material according to the present invention may be an n-type CGL.

[0376] Preferably, the layer including or consisting of the semiconductor material according to the present invention may be the first ETL, the n-type CGL and / or the second ETL.

[0377] Despite 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 variations may be applied thereto.

[0378] Hereinafter, the embodiments will be illustrated in more detail with reference to Examples. However, the present invention is not limited to the following Examples. DETAILED DESCRIPTION

[0379] The invention is further illustrated by the following examples, which are intended to be exemplary only and are not binding.

[0380] Experimental Section

[0381] Melting point

[0382] The melting point (mp) was determined as the peak temperature from the DSC curve of the above-mentioned TGA-DSC measurement or from 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 sample was placed in a 40 µL Mettler Toledo aluminum pan with a lid in which a hole of <1 mm was punched).

[0383] Glass transition temperature

[0384] The glass transition temperature (Tg) was measured as described in DIN EN ISO 11357, published in March 2010, in a Mettler Toledo DSC 822e differential scanning calorimeter under nitrogen and using a heating rate of 10 K / min.

[0385] Standard starting temperature

[0386] The standard onset temperature (TRO) is determined by loading 100 mg of the compound into a VTE source. As VTE source, organic material point sources provided by Kurt J. Lesker Company (www.Lesker.com) or CreaPhys GmbH (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 10 mbar and the temperature inside the 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 Å / s. To determine the standard onset temperature, the deposition rate is plotted against the VTE source temperature. The standard onset is the temperature at which significant deposition occurs on the QCM detector. To obtain accurate results, the VTE source is heated and cooled 3 times and only the results of the second and third runs are used to determine the standard onset starting temperature.

[0387] In order to well control the evaporation rate of the organic compound, the standard starting temperature may be in the range of 200 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 takt time, and the organic compound in the VTE source may decompose due to long-term exposure to high temperature.

[0388] 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.

[0389] Reduction potential

[0390] The reduction potential was determined at room temperature by cyclic voltammetry using a constant potential device Metrohm PGSTAT30 and software MetrohmAutolab GPES. The redox potential given under a specific compound is measured as follows: in a dry 0.1M THF solution of the experimental substance degassed with argon, under an argon atmosphere, a 0.1M tetrabutylammonium hexafluorophosphate supporting electrolyte is used between platinum working electrodes, and a Ag / AgCl pseudo-standard electrode (Metrohm silver rod electrode) consisting of a silver wire covered with silver chloride and directly immersed in the measurement solution is measured at a scan rate of 100mV / s. The first run was completed within the widest range of potentials set on the working electrode, and the range was then adjusted appropriately in subsequent runs. The last three runs were completed by adding ferrocene (0.1M concentration) as a standard. The average potential of the cathode and anode peaks corresponding to the compound under study was calculated after subtracting the potential of the standard Fc + The values ​​reported above were finally obtained by averaging the cathodic and anodic potentials observed for the α / Fc redox couple. All investigated compounds as well as the reported comparative compounds showed clear reversible electrochemical behavior.

[0391] Dipole moment

[0392] Dipole moment of a molecule containing N atoms Given by:

[0393]

[0394] in and is the partial charge and position of atom i in the molecule.

[0395] The dipole moments were determined by the semiempirical molecular orbital method.

[0396] The hybrid functionals B3LYP and 6-31G were used in the gas phase as implemented in the program package TURBOMOLE V6.5 (TURBOMOLE GmbH, Litzenhardtstrasse 19, 76135 Karlsruhe, Germany). The basis set optimizes the geometry of the molecular structure. If more than one conformation is feasible, the conformation with the lowest overall energy is chosen to determine the bond lengths of the molecule.

[0397] Calculated HOMO and LUMO

[0398] 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 as well as the HOMO and LUMO energy levels were calculated by applying the hybrid functional B3LYP and 6-31G in the gas phase. If more than one conformation is feasible, the one with the lowest total energy is chosen.

[0399] Measurement of OLED performance

[0400] To evaluate the performance of the OLED devices, the current efficiency was measured at 20°C. The current-voltage characteristics were determined using a Keithley 2635 source measurement unit by supplying a voltage in V and measuring the current in mA flowing through the device under test. The voltage applied to the device was varied in the range of 0 V to 10 V in steps of 0.1 V. Likewise, the luminance-voltage characteristics and CIE coordinates were measured in cd / m² for each voltage value using an Instrument Systems CAS-140CT array spectrometer (calibrated by Deutsche Akkreditierungsstelle (DAkkS)). 2 By interpolating the brightness-voltage and current-voltage characteristics, the brightness at 10 mA / cm 2 cd / A efficiency when

[0401] If applicable, use a Keithley 2400 source meter at ambient conditions (20°C) and 30 mA / cm 2 The device lifetime LT is measured and recorded in hours.

[0402] The brightness of the device is measured using a calibrated photodiode. The lifetime LT is defined as the time until the brightness of the device decreases to 97% of its initial value.

[0403] Synthesis steps

[0404] Diisobutyl (3-(10-(naphthalen-2-yl) anthracene-9-yl) phenyl) phosphine oxide (E1)

[0405]

[0406] (10-(Naphthalene-2-yl)anthracen-9-yl)boronic acid (6.44 g, 18.5 mmol), (3-bromophenyl)diisobutylphosphine oxide (6.45 g, 20.3 mmol), tetrakis(triphenylphosphine)palladium(0) (0.641 g, 0.555 mmol) and potassium carbonate (7.67 g, 55.5 mmol) were placed in a Schlenk flask under N2 and dissolved in a mixture of dioxane (120 mL) and water (30 mL) saturated with N2. The mixture was heated to 80°C for 23 hours. After removing the volatiles under reduced pressure, the resulting solid was extracted with CHCl3, and the filtrate was washed with water and dried over magnesium sulfate. The mixture was separated by flash column chromatography on a short silica gel column using CHCl2 and CHCl2 / MeOH (97:3) as eluents. The fractions containing the product were combined, the volume was concentrated, and the product was precipitated by adding n-hexane. The solid was purified by stirring with cyclohexane for 2 hours and drying under vacuum. The yield was 4.4 g (44%).

[0407] (3-(9,10-Di(naphthalene-2-yl)anthracen-2-yl)phenyl)diisobutylphosphine oxide (E2)

[0408]

[0409] 2-(9,10-Di(naphthalene-2-yl)anthracen-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (14.0 g, 25.2 mmol), (3-bromophenyl)diisobutylphosphine oxide (9.60 g, 30.2 mmol) and tetrakis(triphenylphosphine)palladium(0) were added to a flask containing N2-saturated dioxane (160 mL) and potassium carbonate (10.4 g, 75.5 mmol) in water (40 mL). The mixture was heated to 75°C for 44 hours. After cooling to room temperature, the volatiles were removed under reduced pressure. The semisolid residue was extracted with CHCl3 and washed with water. The organic phase was dried over magnesium sulfate, filtered through silica gel and reduced in volume under vacuum. Flash column chromatography was then performed on a short silica gel column using CHCl2 and CHCl / MeOH (97:3) as eluents. The fractions containing the product were combined, the volume was reduced, and a pale yellow solid was precipitated by the addition of n-hexane. The solid was recrystallized from toluene to give the product (8.9 g, 53%).

[0410] (3-(10-(Naphthalen-2-yl)anthracen-9-yl)phenyl)dineopentylphosphine oxide (E3)

[0411]

[0412] (10-(Naphthalen-2-yl)anthracen-9-yl)boronic acid (9.18 g, 26.4 mmol), (3-bromophenyl)di-neopentylphosphine oxide (7.00 g, 20.3 mmol), tetrakis(triphenylphosphine)palladium(0) (0.703 g, 0.608 mmol) and potassium carbonate (8.40 g, 60.8 mmol) were placed in a Schlenk flask under N2 and dissolved in a mixture of N2-saturated dioxane (120 mL) and water (30 mL). The mixture was heated to 85°C and maintained for 16 hours. A light-colored solid precipitated upon cooling, which was filtered off when the reaction mixture reached 30°C and subsequently washed with 1,4-dioxane. The solid was dissolved in CHCl, filtered through a pad of Florisil and reduced to dryness under vacuum. The residue was redissolved in CHCl (50 mL) at 50°C and n-hexane (75 mL) was added. The volume decreased by about 25 mL, resulting in the precipitation of the product as a light yellow solid, which was dried under vacuum. Yield 4.2 g (37%).

[0413] (3-(9,10-Di(naphthalene-2-yl)anthracen-2-yl)phenyl)dineopentylphosphine oxide (E4)

[0414]

[0415] Potassium carbonate (8.29 g, 60.0 mmol) was dissolved in 130 mL of deionized water, and argon was passed into the solution for 30 minutes. Glyme (200 mL) was placed in a 500 mL three-necked round-bottom flask and degassed with argon for 30 minutes. Then, 3-bromophenyl (di-neopentyl) phosphine oxide (7.25 g, 21.0 mmol), (9,10-di(naphthalene-2-yl) anthracene-2-yl) boronic acid (9.49 g, 20.0 mmol) and [Pd(PPh3)4] (694 mg, 0.60 mmol) were added to the flask under argon. The degassed potassium carbonate solution was added with a syringe, and the reaction mixture was heated to 85°C and maintained for 12 hours.

[0416] After cooling to room temperature, the obtained precipitate was collected by filtration, washed with water and methanol, and dried under vacuum at 40 ° C to obtain a light yellow solid. Using CH2Cl2 and CH2Cl2 / MeOH (98:2) as eluents, the product was purified by rapid column chromatography on silica gel. Finally, by impregnating in a mixture of petroleum ether, diethyl ether and CH2Cl2 and drying under high vacuum, the desired product was obtained as a light yellow powder. Yield 9.14 g (66%).

[0417] (3-(4-(4-(4,6-diphenyl-1,3,5-triazine-2-yl)phenyl)naphthalen-1-yl)phenyl)dineopentylphosphine oxide (E-19)

[0418]

[0419] (3-Bromophenyl)dineopentylphosphine oxide (18.6 g, 53.8 mmol), 2,4-diphenyl-6-(4-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)naphthalen-1-yl)phenyl)-1,3,5-triazine (34.5 g, 56.5 mmol) and potassium carbonate (18.6 g, 134.6 mmol) were suspended in 1,4-dioxane (650 ml) and water (110 ml) in a Schlenk flask, and the mixture was purged with N2. Subsequently, tetrakis(triphenylphosphine)palladium(0) (622 mg, 0.54 mmol) was added, and the mixture was heated at reflux for 60 hours. After cooling, the resulting precipitate was collected by filtration and washed with water and methanol. The solid was then purified with a short silica gel column using CH2Cl2 and CH2Cl2 / MeOH (9:1) as eluents. Evaporation of the solvent from appropriate fractions gave the desired product (35.0 g, 93%), ESI-MS: m / z = 700 [M+H].

[0420] (3-(4-(4-(4,6-diphenyl-1,3,5-triazine-2-yl)phenyl)naphthalen-1-yl)phenyl)dineopentylphosphine oxide (E-27)

[0421]

[0422] (4-Bromophenyl)dineopentylphosphine oxide (9.93 g, 28.8 mmol), 2,4-diphenyl-6-(3-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)naphthalen-1-yl)phenyl)-1,3,5-triazine (17.0 g, 30.2 mmol) and potassium carbonate (9.9 g, 71.9 mmol) were placed in a Schlenk flask, and the air was replaced with N2. Subsequently, tetrakis(triphenylphosphine)palladium(0) (332 mg, 0.30 mmol) was added, followed by 1,4-dioxane (220 ml) and water (40 ml). The mixture was then purged with N2 and heated to reflux for 16 hours. After cooling to room temperature, the resulting precipitate was collected by filtration and washed with water and methanol. The solid was then purified using a short silica gel column using CH2Cl2 and CH2Cl2 / MeOH (9:1) as eluents. Evaporation of the solvent from the appropriate fractions gave the desired product (13.4 g, 67%), ESI-MS: m / z = 700 [M+H] + .

[0423] (4'-(4-(6-(naphthalen-1-yl)-[1,1'-biphenyl]-3-yl)-6-phenyl-1,3,5-triazine-2-yl)-[1,1'-biphenyl]-3-yl)dineopentylphosphine oxide (E-29)

[0424]

[0425] (3-Bromophenyl)dineopentylphosphine oxide (10.3 g, 29.9 mmol), 2-(6-(naphthalen-1-yl)-[1,1'-biphenyl]-3-yl)-4-phenyl-6-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-1,3,5-triazine (20.0 g, 31.4 mmol) and potassium carbonate (10.3 g, 74.7 mmol) were suspended in 1,4-dioxane (220 ml) and water (40 ml) in a Schlenk flask, and the mixture was purged with N2. Subsequently, tetrakis(triphenylphosphine)palladium(0) (345 mg, 0.30 mmol) was added, and the mixture was heated to reflux for 60 hours. After cooling, the aqueous phase was separated and discarded, and the organic phase was evaporated to dryness under reduced pressure. The crude solid was purified by flash column chromatography using CH2Cl2 and CH2Cl2 / MeOH (9:1) as eluents, followed by recrystallization from toluene to give the pure product (16.4 g, 71%), ESI-MS: m / z = 611 [M+H] + .

[0426] (3-(9,10-Di(naphthalene-2-yl)anthracen-2-yl)phenyl)diethylphosphine oxide (A2)

[0427]

[0428] The flask was flushed with nitrogen and charged with 2-(9,10-di(naphthalene-2-yl)anthracen-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (20.0 g, 35.9 mmol), (3-bromophenyl)diethylphosphine oxide (11.3 g, 43.1 mmol), Pd(PPh3)4 (1.3 g, 1.1 mmol) and K2CO3 (14.9 g, 107.8 mmol). A mixture of degassed 1,4-dioxane / water (4:1, 270 mL) was added, and the reaction mixture was heated to reflux overnight under a nitrogen atmosphere. After cooling to room temperature, the solvent was removed under reduced pressure, and the crude product was extracted with a mixture of DCM / K2CO3 aqueous solution, then dried over MgSO4 and filtered through a silica gel pad. The impurities were rinsed with additional CH2Cl2, and the product was then rinsed with DCM / methanol (98:2, 800 mL). The filtrate was dried under reduced pressure, then dissolved in DCM, stirred with n-hexane overnight, and the solid was separated by suction filtration. i Further purification was achieved by recrystallization from PrOH / acetonitrile and toluene to give 9.4 g (43%) of a yellow solid after drying. Final purification was achieved by sublimation. HPLC / ESI-MS: m / z=611 [M+H] + .

[0429] (3-(9,10-Di(naphthalene-2-yl)anthracen-2-yl)phenyl)diisopropylphosphine oxide (A3)

[0430]

[0431] In a nitrogen flushed flask, (3-bromophenyl)diisopropylphosphine oxide (7.7 g, 26.6 mmol, 1.3 eq.), 2-(9,10-di(naphthalene-2-yl)anthracen-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (11.4 g, 20.5 mmol) were dissolved with Pd(PPh3)4 (0.71 g, 0.61 mmol, 0.03 eq.) and K2CO3 (8.5 g, 61.5 mmol, 3.0 eq.) in a degassed mixture of dioxane and water (3:1). The reaction mixture was stirred at reflux overnight. After cooling to room temperature, the reaction mixture was filtered through a pad of Florisil and the aqueous phase was separated. The organic phase was filtered again through Florisil, washed with CHCl3, and stirred in 3% NaDTC solution at room temperature. After removal of the aqueous phase, the organic solvent was filtered through silica gel and washed with MeOH. After precipitation with toluene, the product was finally purified by sublimation and 6.1 g (44%) of solid was isolated. HPLC / ESI-MS: 1277 [2M+H] + .

[0432] (3-(10-(3-(4,6-diphenyl-1,3,5-triazine-2-yl)phenyl)anthracen-9-yl)phenyl)diisopropylphosphine oxide (A4)

[0433]

[0434] The flask was flushed with nitrogen and (3-bromophenyl)diisopropylphosphine oxide (1.8 g, 6.4 mmol, 1.3 eq.), 2,4-diphenyl-6-(3-(10-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)anthracen-9-yl)phenyl)-1,3,5-triazine (3.0 g, 4.9 mmol) were dissolved in a degassed mixture of dioxane and water (4:1) together with Pd(dppf)Cl2 (0.036 g, 9.8 µmol, 0.01 eq.) and K2CO3 (1.4 g, 9.8 mmol, 2.0 eq.). The reaction mixture was stirred at reflux overnight. After cooling to room temperature, the aqueous phase was extracted three times with CH2Cl2. The combined organic phases were dried over MgSO4. After removal of the solvent, the crude product was purified by flash column chromatography (CH2Cl2:CH2Cl2 / MeOH 95:5). The off-white solid was then stirred in boiling isopropyl alcohol and washed with EtOH after filtration. After sublimation as a final purification step, 1.8 g (53%) of the product was isolated as a white solid. HPLC / ESI-MS: 1387 [2M+H] + .

[0435] (3'-(4,6-diphenyl-1,3,5-triazine-2-yl)-5'-(phenanthrene-9-yl)-[1,1'-biphenyl]-3-yl)diethylphosphine oxide (A5)

[0436]

[0437] In a nitrogen flushed flask, 2-(3-(phenanthrene-9-yl)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-4,6-diphenyl-1,3,5-triazine (10.0 g, 16.35 mmol), (3-bromophenyl)diethylphosphine oxide (4.7 g, 17.99 mmol, 1.1 eq.) were dissolved in a 2M mixture of degassed toluene, ethanol and water with Pd(PPh3)4 (0.82 mmol, 0.94 g, 0.05 eq.) and K2CO3 (3.3 g, 24.53 mmol, 1.5 eq.). The reaction mixture was heated at reflux overnight. After cooling to room temperature, the resulting precipitate was isolated by suction filtration and washed with water and MeOH. The crude product was then purified by flash liquid chromatography and 8 g of fine powder (80%) were isolated after grinding. HPLC / ESI-MS: 1331 [2M+H] + .

[0438] (3-(10-bromoanthracen-9-yl)phenyl)diisopropylphosphine oxide

[0439]

[0440] The flask was flushed with argon and charged with (3-bromophenyl)diisopropylphosphine oxide (14.5 g, 50.0 mmol), anthracene-9-ylboronic acid (12.2 g, 50.0 mmol), Pd(PPh3)4 (1.2 g, 1.0 mmol) and K2CO3 (13.8 g, 100.0 mmol). A mixture of degassed 1,4-dioxane / water (4:1, 250 mL) was added and the reaction mixture was heated to reflux overnight under an argon atmosphere. After cooling to room temperature, the resulting precipitate was separated by suction filtration, washed with water and dried under reduced pressure. Further purification was performed by flash column chromatography (DCM / acetone 1:1) and recrystallization from diethyl ether to obtain 14.9 g (74%) of a light ochre solid. The bromination reaction was completed by stirring NBS (10.1 g, 56.8 mmol) with chloroform (160 mL) at room temperature for 40 hours. The solution was washed with water (3×100 mL), dried over Na2SO4, and the solvent was removed under reduced pressure. Further purification was performed by flash column chromatography (CH2Cl2 / acetone 1:1), recrystallization from ether, and acetone maceration. A yellow solid was isolated by suction filtration to give 13.1 g (74%) of the product after drying.

[0441] (3-(10-(4-(2,6-dimethylpyridin-3-yl)phenyl)anthracen-9-yl)phenyl)diisopropylphosphine oxide (A6)

[0442]

[0443] The flask was flushed with nitrogen and charged with (3-(10-bromoanthracene-9-yl)phenyl)diisopropylphosphine oxide (12.3 g, 26.4 mmol), 2,6-dimethyl-3-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)pyridine (9.0 g, 29.1 mmol), Pd(dppf)Cl2 (80 mg, 0.2 mmol) and K2CO3 (7.3 g, 52.8 mmol). A degassed THF / water mixture (4:1, 150 mL) was added and the reaction mixture was heated to reflux overnight under a nitrogen atmosphere. After cooling to room temperature, the solvent was removed under reduced pressure and the crude product was extracted with a CH2Cl2 / K2CO3 aqueous solution mixture, then dried over MgSO4 and filtered through a silica gel pad. The filtrate was dried under reduced pressure, then dissolved in CH2Cl2 and stirred with n-hexane overnight. The solid was separated by suction filtration and dried to give 12.7 g (85%) of a white solid. The final purification was achieved by sublimation. m / z=568 [M+H] + .

[0444] 4'-(10-(3-(Diisopropylphosphoryl)phenyl)anthracen-9-yl)-[1,1'-biphenyl]-3-carbonitrile (A7)

[0445]

[0446] The flask was flushed with nitrogen and charged with (3-(10-bromoanthracene-9-yl)phenyl)diisopropylphosphine oxide (8.0 g, 17.2 mmol), 4'-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-[1,1'-biphenyl]-3-carbonitrile (5.8 g, 19.0 mmol), Pd(XPhos)(crotyl)Cl (0.2 g, 0.3 mmol) and K2CO3 (4.8 g, 34.4 mmol). A mixture of degassed 1,4-dioxane / water (4:1, 100 mL) was added, and the reaction mixture was heated to 70°C overnight under a nitrogen atmosphere. After cooling to room temperature, the solvent was removed under reduced pressure, and the crude product was extracted with a mixture of chloroform / K2CO3 aqueous solution, then dried over MgSO4 and filtered through a silica gel pad. The impurities were rinsed with additional chloroform, and the product was then rinsed with CH2Cl2 / methanol (95:5). The filtrate was dried under reduced pressure, then dissolved in CH2Cl2, stirred overnight with n-hexane, and the solid was isolated by suction filtration. Further purification was achieved by recrystallization from toluene and EtOH to obtain 4.2 g (43%) of a yellow solid after drying. Final purification was achieved by sublimation. m / z=564 [M+H] + .

[0447] Supporting materials for device experiments

[0448] C1 is CAS 2098308-14-4

[0449] C2 is CAS 2252183-63-2

[0450] C3 CAS 2253724-57-9

[0451] C4 CAS 2253724-95-5

[0452] C5

[0453] C6

[0454] A1 is CAS 2098710-88-2

[0455] F1 is CAS 1364603-07-5

[0456] F2 is CAS 1613079-70-1

[0457] F3 is CAS 2032364-64-8

[0458] F4 is CAS 1955543-57-3

[0459] F5 CAS 1242056-42-3

[0460] F6 CAS 721969-94-4

[0461] F7 CAS 2437303-42-7

[0462] PD2 CAS 1224447-88-4

[0463] LiQ is 8-hydroxyquinolate lithium, CAS 850918-68-2.

[0464] H09 is the emitter host and BD200 is the blue fluorescent emitter dopant, both of which are commercially available from SFC in Korea.

[0465] Preparation of model blue OLED devices

[0466] The device is prepared by depositing a 10 nm hole injection layer of F1 (the weight ratio of matrix to dopant is 98:2 volume %) doped with PD2 on a glass substrate with a silver anode, and then depositing a 128 nm thick undoped hole transport layer of F1. A 5 nm electron blocking layer of F2 is deposited on the HTL. Subsequently, a blue fluorescent light-emitting layer of the luminous body H09 (Sun Fine Chemicals) (97:3 volume %) doped with BD200 (Sun Fine Chemicals) is deposited with a thickness of 20 nm. On the light-emitting layer, a 5 nm layer made of F3 is deposited as a hole blocking layer. A 31 nm electron transport layer made of the test compound and F7 is co-deposited on the HBL with a volume ratio of 30:70. Subsequently, a 1 nm thick first electron injection layer and a 2 nm thick second electron injection layer made of F6 or LiQ doped with Li are deposited on the ETL, and then a 13 nm thick cathode consisting of a silver-magnesium alloy with a volume ratio of 90:10 is deposited. Finally, a 75 nm thick capping layer made of F5 was deposited on top of the cathode. All depositions were done by vacuum thermal evaporation.

[0467] Device Embodiment

[0468] 1) Blue fluorescent top-emitting OLED with Li salt EIL

[0469] Table 1a schematically describes the model device.

[0470] Table 1a

[0471]

[0472] The results are shown in Tables 1b to 1g.

[0473] Table 1b

[0474]

[0475] Compared to the semiconductor material comprising the first organic compound C1 containing a dimethylphosphine oxide group, similar semiconductor materials comprising compounds E3 and A1 comprising a dialkylphosphine oxide group having a higher alkyl group exhibit improved operating voltage and current efficiency.

[0476] Table 1c

[0477]

[0478] Compared to the semiconductor material comprising the first organic compound C2 containing a dimethylphosphine oxide group, similar semiconductor materials comprising compounds A2, A3 and E2 comprising a dialkylphosphine oxide group having a higher alkyl group exhibit improved operating voltage.

[0479] Table 1d

[0480]

[0481] Compared to the semiconductor material comprising the first organic compound C3 containing a dimethylphosphine oxide group, the similar semiconductor material comprising compound A4 comprising a dialkylphosphine oxide group having a higher alkyl group exhibits improved operating voltage and current efficiency.

[0482] Table

[0483]

[0484] Compared to the semiconductor material comprising the first organic compound C4 containing a dimethylphosphine oxide group, a similar semiconductor material comprising compound A5 comprising a dialkylphosphine oxide group having a higher alkyl group exhibits improved operating voltage and current efficiency.

[0485] Table 1f

[0486]

[0487] Compared to the semiconductor material comprising the first organic compound C5 containing a dimethylphosphine oxide group, the similar semiconductor material comprising compound A6 comprising a dialkylphosphine oxide group having a higher alkyl group exhibits improved operating voltage and current efficiency.

[0488] Table 1g

[0489]

[0490] Compared to a semiconductor material comprising the first organic compound C6 containing a dimethylphosphine oxide group, a similar semiconductor material comprising compound A7 comprising a dialkylphosphine oxide group having a higher alkyl group exhibits improved current efficiency.

[0491] 2) Blue fluorescent top-emitting OLEDs with redox-doped EIL

[0492] Table 2a schematically describes the model device.

[0493] Table 2a

[0494]

[0495] The results are shown in Tables 2b to 2g.

[0496] Table 2b

[0497]

[0498] Compared to the semiconductor material comprising the first organic compound C1 containing a dimethylphosphine oxide group, similar semiconductor materials comprising compounds E3 and A1 comprising a dialkylphosphine oxide group having a higher alkyl group exhibit improved operating voltage and current efficiency.

[0499] Table 2c

[0500]

[0501] Compared to the semiconductor material comprising the first organic compound C2 containing a dimethylphosphine oxide group, similar semiconductor materials comprising compounds A2, A3 and E2, which contain a dialkylphosphine oxide group with a higher alkyl group, exhibit improved operating voltage and improved current efficiency.

[0502] Table 2d

[0503]

[0504] Compared to the semiconductor material comprising the first organic compound C3 containing a dimethylphosphine oxide group, the similar semiconductor material comprising compound A4 comprising a dialkylphosphine oxide group having a higher alkyl group exhibits improved operating voltage and current efficiency.

[0505] Table 2e

[0506]

[0507] Compared to the semiconductor material comprising the first organic compound C4 containing a dimethylphosphine oxide group, a similar semiconductor material comprising compound A5 comprising a dialkylphosphine oxide group having a higher alkyl group exhibits improved operating voltage and current efficiency.

[0508] Table 2f

[0509]

[0510] Compared to the semiconductor material comprising the first organic compound C5 containing a dimethylphosphine oxide group, the similar semiconductor material comprising compound A6 comprising a dialkylphosphine oxide group having a higher alkyl group exhibits improved operating voltage and current efficiency.

[0511] Table 2g

[0512]

[0513] Compared to a semiconductor material comprising the first organic compound C6 containing a dimethylphosphine oxide group, a similar semiconductor material comprising compound A7 comprising a dialkylphosphine oxide group having a higher alkyl group exhibits improved current efficiency.

[0514] Adaptability of vacuum thermal evaporation manufacturing method

[0515] Advantageously for the production of organic semiconductor layers by vacuum thermal evaporation, the dineopentylphosphine oxide compounds of the invention exhibit a combination of high thermal stability and good volatility.

[0516] Table 7 shows that, although the molar masses of the dineopentylphosphine oxide compounds are significantly higher than those of their dimethylphosphine oxide analogs, the volatility of the compounds E3, E4 and E19 of the present invention is slightly higher than that of the corresponding dimethylphosphine analogs C1, C2 and C3 in terms of their standard onset evaporation temperature and the temperature of 50% weight loss in a standard high vacuum TGA test:

[0517] Table 7

[0518]

[0519] In terms of thermal stability to the onset of decomposition in standard TGA-DSC testing, compounds E3, E4 and E19 of the present invention and their dimethylphosphine oxide analogs C1, C2 and C3 showed no signs of decomposition at temperatures up to 415°C.

[0520] The features disclosed in the foregoing description and in the dependent claims may, both individually and in any combination thereof, be material for realizing aspects of the inventive content disclosed in the independent claims in their various forms.

Claims

1. A semiconductor material comprising a first organic compound and a second organic compound, wherein - the first organic compound and the second organic compound are different from each other; and - The first organic compound comprises at least one group represented by the following formula (1): (1) in - Wavy Line" " represents the position at which the group represented by formula (I) is bonded to the remaining structure of the first organic compound; -R 1 and R 2 are independently selected from alkyl; and -R 1 and R 2 The total number of carbon atoms in is at least 3. 2 . The semiconductor material of claim 1 , wherein the first organic compound further comprises at least one charge transport moiety comprising at least one aromatic ring.

3. The semiconductor material according to claim 2, wherein the charge transport moieties are independently selected from: - heteroaromatic moieties containing at least two heteroatoms; - an aryl group comprising at least two, preferably at least three, fused aromatic rings; and - a heteroaryl group comprising at least two, preferably at least three, fused aromatic rings.

4. The semiconductor material of claim 3, wherein the heteroaromatic moiety comprising at least two heteroatoms is independently selected from the group consisting of diazine, triazine, quinazoline, quinoxaline, benzoquinazoline, benzoquinoxaline, azacarbazole, azadibenzofuran, azadibenzothiophene, naphthyridine, benzimidazole, benzothiazole, benzoimidazolyl, and imidazopyridine.

5. The semiconductor material according to claim 3 or 4, wherein the aryl group comprising at least two fused aromatic rings is independently selected from: anthracene, phenanthrene and pyrene.

6. The semiconductor material according to any one of claims 3 to 5, wherein the heteroaryl group comprising at least two fused aromatic rings is independently selected from: azaanthracene, azaphenanthracene, diazaanthracene, diazaphenanthracene, benzoacridine and dibenzoacridine.

7. A semiconductor material according to any one of the preceding claims, wherein R 1 and R 2 Independently selected from C4 alkyl and C5 alkyl, especially selected from isobutyl and neopentyl.

8. A semiconductor material according to any one of the preceding claims, wherein R 1 and R 2 Select Same.

9. The semiconductor material according to any one of the preceding claims, wherein the first organic compound is represented by the following formula (2): (2) in R 1 and R 2 are independently selected from alkyl; R 1 and R 2 The total number of carbon atoms in is at least 3; A is a charge transport moiety; and L is a direct bond or a spacer.

10. The semiconductor material of claim 9, wherein L is selected from an aromatic subunit and a heteroaromatic subunit.

11. The semiconductor material according to claim 9 or 10, wherein L is selected from a phenylene group and a 1,1'-biphenyl-diyl group.

12. A semiconductor material according to any preceding claim, wherein the semiconductor material further comprises an n-type electron dopant.

13. A method for preparing a layer of semiconductor material according to any one of the preceding claims, the method comprising the step of depositing the first organic compound on a solid support.

14. An organic semiconductor device comprising at least one layer comprising the semiconductor material according to any one of claims 1 to 12. 15 . The organic semiconductor device according to claim 14 , wherein the layer comprising the semiconductor material is an electron transport layer, an electron injection layer or an electron generation layer. 16 . The organic semiconductor device according to claim 14 , wherein the organic semiconductor device is an organic diode, an organic transistor, an organic solar cell or an organic light emitting diode. 17 . A display device comprising the organic semiconductor device according to claim 14 .

18. A compound selected from: <h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> E1<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> E2 E3 E4 E-5 E-6 E-7 E-8 E-9 E-10 E-11 E-12 E-13 E-14 E-15 E-16 E-17 E-18 E-19 E-20 E-21 E-22 E-23 E-24 E-25 E-26 E-27 E-28 E-29 E-30 E-31 E-32 E-33 E-34 E-35 E-36 E-37 E-38 E-39 E-40 E-41 E-42 E-43 E-44 <h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> A2<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> A3 <h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> A4<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> A5 A6 A7。

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