Organic molecules for photoelectronic devices, compositions, photoelectronic devices, and methods for generating light.
Patent Information
- Authority / Receiving Office
- JP · JP
- Patent Type
- Patents
- Current Assignee / Owner
- SAMSUNG DISPLAY CO LTD
- Filing Date
- 2022-04-25
- Publication Date
- 2026-08-07
Smart Images
Figure 0007902197000001 
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Abstract
Description
[Technical Field]
[0001] This invention relates to light-emitting organic molecules, organic light-emitting diodes (OLEDs), and their applications in other optoelectronic devices. [Overview of the project] [Problems that the invention aims to solve]
[0002] The problem that this invention aims to solve is to provide a molecule suitable for use in optoelectronic devices. [Means for solving the problem]
[0003] Such objectives are achieved by the present invention, which provides novel organic molecules.
[0004] According to the present invention, the organic molecule is a pure organic molecule, that is, unlike metal complexes known to be used in optoelectronic devices, it does not contain any metal ions. [Effects of the Invention]
[0005] According to the present invention, the organic molecule exhibits maximum emission in the blue or sky blue spectral range. The organic molecule exhibits maximum emission particularly in the range of 420 nm to 520 nm, preferably 440 nm to 495 nm, and more preferably 450 nm to 470 nm. The photoluminescence quantum yield of the organic molecule according to the present invention is particularly 50% or more. The use of the molecule according to the present invention in optoelectronic devices, such as organic light-emitting diodes (OLEDs), results in higher efficiency of the device or higher color purity expressed by the full width at half maximum (FWHM) of the emission. The corresponding OLED has even higher stability than known emitter materials and OLEDs with similar hues. [Modes for carrying out the invention]
[0006] The organic luminescent molecule of the present invention contains or consists of the structure of chemical formula I: [ka] ···Chemical formula I Here, R , 5 , 5 , 5 , 5 , 5 , 5 , 40 , 5 , , , 5 , 5 , 5 , 5 , 5 , 5 , 5 , 5 is C6-C 12 aryl, which is selectively substituted with one or more C1-C6 alkyl substituents that selectively form a monocyclic aliphatic ring system in the C6-C 12 aryl (as a result, for example, a structure represented by Chemical formula I-5 or I-6 is formed), R a is, in each case, independently selected from the group consisting of hydrogen, deuterium, N(R 5 )2, OR 5 , Si(R 5 )3, B(OR 5 )2, B(R 5 )2, OSO2R 5 , CF3, CN, F, Br, I, Cl, C1-C 40 alkyl, which is selectively substituted with one or more substituents R 5 , where one or more non-adjacent CH2 groups are selectively R 5 C=CR 5 , C≡C, Si(R 5 )2, Ge(R 5 )2, Sn(R 5 )2, C=O, C=S, C=Se, C=NR 5 , P(=O)(R 5 ), SO, SO2, NR 5 , O, S or CONR 5 substituted, C1-C 40 alkoxy, which is selectively substituted with one or more substituents R 5 , where one or more non-adjacent CH2 groups are selectively R 5 C=CR 5 , C≡C, Si(R 5 )2, Ge(R 5 )2, Sn(R 5 )2, C=O, C=S, C=Se, C=NR 5, P(=O)(R 5 ), SO, SO2, NR 5 , O, S or CONR 5 Replaced by, C1-C 40 Thioalkoxy, This selectively involves one or more substituents R 5 Replaced by, Here, one or more non-adjacent CH2 groups are selectively R 5 C=CR 5 , C≡C, Si(R 5 )2, Ge(R 5 )2, Sn(R 5 )2, C=O, C=S, C=Se, C=NR 5 , P(=O)(R 5 ), SO, SO2, NR 5 , O, S or CONR 5 Replaced by, C2-C 40 Alkenil, This selectively involves one or more substituents R 5 Replaced by, Here, one or more non-adjacent CH2 groups are selectively R 5 C=CR 5 , C≡C, Si(R 5 )2, Ge(R 5 )2, Sn(R 5 )2, C=O, C=S, C=Se, C=NR 5 , P(=O)(R 5 ), SO, SO2, NR 5 , O, S or CONR 5 Replaced by, C2-C 40 Alkinil, This selectively involves one or more substituents R 5 Replaced by, Here, one or more non-adjacent CH2 groups are selectively R 5 C=CR 5 , C≡C, Si(R 5 )2, Ge(R 5 )2, Sn(R 5 )2, C=O, C=S, C=Se, C=NR 5 , P(=O)(R 5 ), SO, SO2, NR5 、 O, S or CONR 5 and is substituted with optionally one or more substituents R 5 to give C6-C 60 aryl, and optionally one or more substituents R 5 to give C2-C 57 heteroaryl, R 5 in each case, independently of one another, is selected from the group consisting of hydrogen, deuterium, N(R 6 )2, OR 6 , Si(R 6 )3, B(OR 6 )2, B(R 6 )2, OSO2R 6 , CF3, CN, F, Br, I, C1-C<00, O, S or CONR 6 Replaced by, C1-C 40 Thioalkoxy, This selectively involves one or more substituents R 6 Replaced by, Here, one or more non-adjacent CH2 groups are selectively R 6 C=CR 6 , C≡C, Si(R 6 )2, Ge(R 6 )2, Sn(R 6 )2, C=O, C=S, C=Se, C=NR 6 , P(=O)(R 6 ), SO, SO2, NR 6 , O, S or CONR 6 Replaced by, C2-C 40 Alkenil, This selectively involves one or more substituents R 6 Replaced by, Here, one or more non-adjacent CH2 groups are selectively R 6 C=CR 6 , C≡C, Si(R 6 )2, Ge(R 6 )2, Sn(R 6 )2, C=O, C=S, C=Se, C=NR 6 , P(=O)(R 6 ), SO, SO2, NR 6 , O, S or CONR 6 Replaced by, C2-C 40 Alkinil, This selectively involves one or more substituents R 6 Replaced by, Here, one or more non-adjacent CH2 groups are selectively R 6 C=CR 6 , C≡C, Si(R 6 )2, Ge(R 6 )2, Sn(R 6 )2, C=O, C=S, C=Se, C=NR 6 , P(=O)(R 6 ), SO, SO2, NR 6 , O, S or CONR 6 Replaced by, Selectively one or more substituents R 6 C6-C replaced by 60 Aryl, and Selectively one or more substituents R 6 C2-C replaced by 57 Heteroaryl, R 6 In each case, the following groups are selected independently from each other: Hydrogen, deuterium, OPh (Ph=phenyl), CF3, CN, F, C1-C5 alkyl, Here, one or more hydrogen atoms are selectively and independently substituted with deuterium, CN, CF3, or F. C1-C5 alkoxy, Here, one or more hydrogen atoms are selectively and independently substituted with deuterium, CN, CF3, or F. C1-C5 thioalkoxy, Here, one or more hydrogen atoms are selectively and independently substituted with deuterium, CN, CF3, or F. C2-C5 alkenyl, Here, one or more hydrogen atoms are selectively and independently substituted with deuterium, CN, CF3, or F. C2-C5 alkynyl, Here, one or more hydrogen atoms are selectively and independently substituted with deuterium, CN, CF3, or F. C6-C molecules selectively substituted with one or more C1-C5 alkyl substituents 18 Ariel, C2-C molecules selectively substituted with one or more C1-C5 alkyl substituents 17 Heteroaryl, N(C6-C 18 Ariel) 2, N(C2-C 17 Heteroaryl)2, and N(C2-C 17 (Heteroaryl)(C6-C 18 Ariel), Here, substituent R a , R 5 and R 6 One of these independently has one or more substituents Ra , R 5 and / or R 6 Together, monocyclic or polycyclic, aliphatic, aromatic, heteroaromatic, and / or benzo-condensed ring systems can be formed. For example, one substituent R a is the other substituent R a It forms a ring system with, or one substituent R 5 is a substituent R a It can form a ring system.
[0007] In certain embodiments, the organic molecule of the present invention comprises or consists of the structure of chemical formula Ia, Ib, or Ic: [ka] ...Chemical formula Ia [ka] ...Chemical formula Ib [ka] ...Chemical formula Ic.
[0008] In a preferred embodiment, the organic molecule of the present invention comprises or consists of the structure of chemical formula Ia.
[0009] In one embodiment, R 1 This is a phenyl molecule selectively substituted with one or more C1-C6 alkyl groups.
[0010] In one embodiment, R 1 It selectively uses methyl, i Propyl, cyclohexyl and t It is a phenyl compound substituted with one or more substituents selected from butyl.
[0011] In one embodiment, R 1 It selectively uses methyl, i Propyl and t It is a phenyl compound substituted with one or more substituents selected from butyl.
[0012] In one embodiment, R 1 It is hydrogen.
[0013] In a preferred embodiment, the organic molecule includes or consists of the structure of chemical formula I-1, chemical formula I-2, chemical formula I-3, chemical formula I-4, chemical formula I-5, chemical formula I-6, chemical formula I-7, chemical formula I-8, chemical formula I-9, or chemical formula I-10: [ka] ...Chemical formula I-1 [ka] ...Chemical formula I-2 [ka] ...Chemical formula I-3 [ka] ...Chemical formula I-4 [ka] ...Chemical formula I-5 [ka] ...Chemical formula I-6 [ka] ...Chemical formula I-7 [ka] ...Chemical formula I-8 [ka] ...Chemical formula I-9 [ka] ...Chemical formula I-10.
[0014] In one embodiment, the organic molecule contains or consists of the structure of chemical formula II: [ka] ...Chemical formula II.
[0015] In a preferred embodiment, the organic molecule has or comprises the structure of chemical formula IIa. [ka] ...Chemical formula IIa Here, R c In each case, the following groups are selected independently of each other: hydrogen, Me, i Pr, t Bu, CN Sofa CF3, Me, i Pr, t Ph is selectively substituted with one or more substituents independently selected from the group consisting of Bu, CN, CF3, and Ph. Me, i Pr, t Pyridinyl molecules selectively substituted with one or more substituents independently selected from the group consisting of Bu, CN, CF3, and Ph. Me, i Pr, t Pyrimidinyl molecules selectively substituted with one or more substituents independently selected from the group consisting of Bu, CN, CF3, and Ph. Me, i Pr, t Carbazolyl, selectively substituted with one or more substituents independently selected from the group consisting of Bu, CN, CF3, and Ph. Me, i Pr, tTriazinyl selectively substituted with one or more substituents independently selected from the group consisting of Bu, CN, CF3, and Ph, and N(Ph)2.
[0016] In a preferred embodiment, the organic molecule comprises or consists of the structure of Chemical Formula IIa-1 or Chemical Formula IIa-2:
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[0017] In one embodiment, the organic molecule comprises or consists of the structure of Chemical Formula III,
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[0018] In a preferred embodiment, the organic molecule comprises or consists of the structure of Chemical Formula IIIa or Chemical Formula IIIb:
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[0019] In a preferred embodiment, the organic molecule comprises or consists of a structure of Chemical Formula III-1, Chemical Formula III-2, Chemical Formula III-3, Chemical Formula III-4, Chemical Formula III-5, Chemical Formula III-6, Chemical Formula III-7 or Chemical Formula III-8:
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[0020] In one embodiment, the organic molecule comprises or consists of a structure of Chemical Formula IV,
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[0021] In one embodiment, the organic molecule includes or consists of the structure of chemical formula IVa, chemical formula IVb, or chemical formula IVc: [ka] ...Chemical formula IVa [ka] ...Chemical formula IVb [ka] ...Chemical formula IVc.
[0022] In a preferred embodiment, the organic molecule contains or comprises a structure of chemical formula IVc.
[0023] In a preferred embodiment, the organic molecule includes or comprises the structure of chemical formula IV-1, chemical formula IV-2, chemical formula IV-3, chemical formula IV-4, chemical formula IV-5, chemical formula IV-6, chemical formula IV-7, chemical formula IV-8, chemical formula IV-9, or chemical formula IV-10: [ka] ...Chemical formula IV-1 [ka] ...Chemical formula IV-2 [ka] ...Chemical formula IV-3 [ka] ...Chemical formula IV-4 [ka] ...Chemical formula IV-5 [ka] ...Chemical formula IV-6 [ka] ...Chemical formula IV-7 [ka] ...Chemical formula IV-8 [ka] ...Chemical formula IV-9 [ka] ...Chemical formula IV-10
[0024] In one embodiment, the organic molecule contains or consists of a structure of chemical formula V. [ka] ...Chemical formula V Here, R b In each case, the following groups are selected independently of each other: hydrogen, Me, i Pr, t Bu, CN Sofa CF3, Me, i Pr, tPh is selectively substituted with one or more substituents independently selected from the group consisting of Bu, CN, CF3, and Ph. Me, i Pr, t Pyridinyl molecules selectively substituted with one or more substituents independently selected from the group consisting of Bu, CN, CF3, and Ph. Me, i Pr, t Pyrimidinyl molecules selectively substituted with one or more substituents independently selected from the group consisting of Bu, CN, CF3, and Ph. Me, i Pr, t Carbazolyl, selectively substituted with one or more substituents independently selected from the group consisting of Bu, CN, CF3, and Ph. Me, i Pr, t Triazinyls selectively substituted with one or more substituents independently selected from the group consisting of Bu, CN, CF3, and Ph, and N(Ph)2.
[0025] In one embodiment, the organic molecule contains or consists of the structure of chemical formula Va: [ka] ...Chemical formula Va.
[0026] In a preferred embodiment, the organic molecule comprises or consists of the structure of chemical formula V-1 or chemical formula V-2: [ka] ...Chemical formula V-1 [ka] ...Chemical formula V-2.
[0027] In one embodiment of the present invention, R a In each case, the following groups are selected independently of each other: hydrogen, Me, i Pr, t Bu, CN Sofa CF3, Me, i Pr, t Ph is selectively substituted with one or more substituents independently selected from the group consisting of Bu, CN, CF3, and Ph. Me, i Pr, t Pyridinyl molecules selectively substituted with one or more substituents independently selected from the group consisting of Bu, CN, CF3, and Ph. Me, i Pr, t Pyrimidinyl molecules selectively substituted with one or more substituents independently selected from the group consisting of Bu, CN, CF3, and Ph. Me, i Pr, t Carbazolyl, selectively substituted with one or more substituents independently selected from the group consisting of Bu, CN, CF3, and Ph. Me, i Pr, t Triazinyls selectively substituted with one or more substituents independently selected from the group consisting of Bu, CN, CF3, and Ph, and N(Ph)2.
[0028] In a preferred embodiment, the organic luminescent molecule of the present invention comprises or consists of the structure of chemical formula VI. [ka] ...Chemical formula VI Here, R d In each case, hydrogen and R e Selected from the group, where R e In each case, the following group is selected: Me, i Pr, t Bu, Me,i Pr, t Ph is selectively substituted with one or more substituents independently selected from the group consisting of Bu, CN, CF3, and Ph.
[0029] In a preferred embodiment, the organic luminescent molecule of the present invention comprises or consists of the structure of chemical formula VI, where exactly 2, 3, 4, 5, or 6 substituents R d In each case, R is independent of each other. e Selected from.
[0030] definition Here, the term "layer" refers to a body having a wide-ranging planar geometric structure. The fact that optoelectronic elements are composed of multiple layers is part of common knowledge for those skilled in the art.
[0031] In the context of the present invention, an EML is a layer of a photoelectronic device, where light emission from the layer is observed when a voltage and current are applied to the device. Those skilled in the art will understand that light emission from a photoelectronic device is attributable to light emission from at least one EML. Skilled technicians will understand that light emission from an EML is not typically attributable to (primarily) all materials contained in the EML, but to a specific emitter material.
[0032] In the context of the present invention, the “emitter material” (also referred to as the “emitter”) is a material that emits light when contained in the light-emitting layer (EML) of a photoelectronic device under given voltage and current conditions (see below). Those skilled in the art will know that the emitter material is generally a “luminescent dopant” material, and that the dopant material (whether luminescent or not) is typically a material incorporated into a matrix material called a host material (as used herein). Here, the host material is generally H when contained in a photoelectronic device, preferably an OLED, that contains at least one organic molecule according to the present invention. B It is called that.
[0033] In the context of the present invention, the term "cyclic group" is understood in its broadest sense to refer to any monocyclic, bicyclic, or polycyclic part.
[0034] In the context of this invention, when referring to a chemical structure, the term "ring" is understood in its broadest sense as any monocyclic part. From the same viewpoint, when referring to a chemical structure, the term "ring" is understood in its broadest sense as any bicyclic or polycyclic part.
[0035] In the context of this invention, the term "ring system" is understood in its broadest sense to refer to any monoring, biring, or polyring portion.
[0036] In the context of this invention, the term "ring atom" refers to any atom that is part of a cyclic core of a ring or ring system and is not part of an acyclic substituent selectively bonded to the cyclic core.
[0037] In the context of the present invention, the term "carbocyclic" is understood in its broadest sense as any cyclic group whose cyclic core structure consists only of carbon atoms that can be substituted with any other substituents as defined in the particular embodiments of the present invention, not to mention hydrogen. The term "carbocyclic" is an adjective and is also understood as referring to a cyclic group whose cyclic core structure consists only of carbon atoms that can be substituted with any other substituents as defined in the particular embodiments of the present invention, not to mention hydrogen.
[0038] In the context of the present invention, the term “heterocyclic” is understood in its broadest sense as any cyclic group whose cyclic core structure contains not only carbon atoms but also at least one heteroatom. The term “heterocyclic” is an adjective and is also understood as referring to a cyclic group whose cyclic core structure contains not only carbon atoms but also at least one heteroatom. The heteroatom may be the same or different in each case, unless otherwise specifically mentioned in a particular embodiment, and may be individually selected from the group consisting of B, Si, N, O, S, and Se, more preferably B, N, O, and S, and most preferably N, O, and S. Not to mention all carbon atoms or heteroatoms contained in a heterocyclic in the context of the present invention, but they may be substituted with hydrogen or any other substituent as defined in a particular embodiment of the present invention.
[0039] Those skilled in the art will understand that any cyclic group (i.e., any carbon ring and heteroring) can be aliphatic, aromatic, or heteroaromatic.
[0040] In the context of the present invention, when referring to a cyclic group (i.e., one ring, multiple rings, cyclic system, carbocyclic, heterocyclic), the term “aliphatic” includes at least one ring atom that is not part of an aromatic or heteroaromatic ring or cyclic system of the cyclic core structure (excluding selectively bonded substituents). Preferably, most of the ring atoms in the aliphatic cyclic group, more preferably all of the ring atoms, are not part of an aromatic or heteroaromatic ring or cyclic system (e.g., in cyclohexane or piperidine). Herein, when referring to an aliphatic ring or cyclic system in general, no distinction is made between carbocyclic and heterocyclic groups, and the term “aliphatic” is also used as an adjective describing a carbocyclic or heterocyclic to indicate whether or not a heteroatom is included within the aliphatic cyclic group.
[0041] As understood by skilled technicians, the terms “aryl” and “aromatic” in their broadest sense are understood as any monocyclic, bicyclic, or polycyclic aromatic moiety, i.e., a ring group in which all ring atoms are part of an aromatic ring system, preferably as part of the same aromatic ring system. However, throughout this application, the terms “aryl” and “aromatic” are limited to monocyclic, bicyclic, or polycyclic aromatic moieties in which all aromatic ring atoms are carbon atoms. In contrast, in this application, the terms “heteroaryl” and “heteroaromatic” refer to any monocyclic, bicyclic, or polycyclic aromatic moiety in which one or more aromatic carbocyclic atoms are substituted by heteroatoms (i.e., non-carbons). Unless specifically mentioned in particular embodiments of the present invention, at least one heteroatom in a “heteroaryl” or “heteroaromatic” may be identical or different in each case and may be individually selected from the group consisting of N, O, S, and Se, more preferably N, O, and S. Those skilled in the art will understand that the adjectives “aromatic” and “heteroaromatic” are also used to describe any cyclic group (i.e., any ring system). That is, an aromatic cyclic group (i.e., an aromatic ring system) is an aryl group, and a heteroaromatic cyclic group (i.e., a heteroaromatic ring system) is a heteroaryl group.
[0042] Unless otherwise specifically mentioned in a particular embodiment of the present invention, in this application, an aryl group preferably comprises 6 to 60 aromatic ring atoms, more preferably 6 to 40 aromatic ring atoms, and even more preferably 6 to 18 aromatic ring atoms. Unless otherwise specifically mentioned in a particular embodiment of the present invention, in this application, a heteroaryl group preferably comprises 5 to 60 aromatic ring atoms, more preferably 5 to 40 aromatic ring atoms, and even more preferably 5 to 20 aromatic ring atoms, of which at least one is a heteroatom, preferably selected from N, O, S, and Se, and more preferably from N, O, and S. If one or more heteroatoms are included in the heteroaromatic group, all heteroatoms are preferably selected independently from each other from N, O, S, and Se, and more preferably from N, O, and S.
[0043] In the context of the present invention, for both aromatic groups and heteroaromatic groups (e.g., aryl substituents or heteroaryl substituents), the number of aromatic ring carbon atoms is given as a subscript in the definition of a particular substituent, for example, "C6-C 60 The form is given as "aryl". This means that each aryl substituent contains 6 to 60 aromatic carbon ring atoms. The same subscript is used to indicate the number of carbon atoms allowed for all other types of substituents, whether aliphatic, aromatic, or heteroaromatic. For example, "C1-C 40 The term "alkyl" refers to alkyl substituents containing 1 to 40 carbon atoms.
[0044] Preferred examples of aryl groups include benzene, naphthalene, anthracene, phenanthrene, pyrene, dihydropyrene, chrysene, perylene, fluoranthene, benzanthracene, benzophenanthrene, tetracene, pentacene, benzopyrene, or combinations thereof.
[0045] Preferred examples of heteroaryl groups include furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene; pyrrole, indole, isoindole, carbazole, indolocarbazole, pyridine, quinoline, isoquinoline, acridine, phenantholidine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, phenothiazine, phenoxazine, pyrazole, indazole, imidazole, benzimidazole, naphthoimidazole, phenanthroimidazole, pyridoimidazole, pyrazinoimidazole, quinoxalinoimidazole, oxazole, benzoxazole, naphthoxazole, anthroxazole This includes zole, phenanthroxazole, isoxazole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, benzopyridazine, pyrimidine, benzopyrimidine, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, quinoxaline, pyrazine, phenazine, naphthyridine, carboline, benzocarbolin, phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,2,3,4-tetrazine, 1,2,4,5-tetrazine, purine, pteridine, indoridine, and benzothiadiazole, or combinations thereof.
[0046] As used throughout this specification, the term “arylene” refers to a divalent aryl substituent that has two binding sites to other molecular structures and acts as a linker structure. From the same viewpoint, the term “heteroarylene” refers to a divalent aryl substituent that has two binding sites to other molecular structures and acts as a linker structure.
[0047] In the context of the present invention, when referring to an aromatic ring system or a heteroaromatic ring system, the term “condensed” means that the “condensed” aromatic ring or heteroaromatic ring shares at least one bond that is part of both ring systems. For example, naphthalene (or, when referred to as a substituent, naphthyl) or benzothiophene (or, when referred to as a substituent, benzothiophenyl) are considered in the context of the present invention to be a condensed aromatic ring system, where the two benzene rings (in the case of naphthalene) or thiophene and benzene (in the case of benzothiophene) share one bond. Also, in such a context, sharing a bond is understood to include sharing two atoms that make up each bond, and a condensed aromatic ring system or a heteroaromatic ring system is also understood to be a single aromatic system or a heteroaromatic system. It is also understood that one or more bonds are shared by the aromatic rings or heteroaromatic rings that make up a condensed aromatic ring system or a heteroaromatic ring system (e.g., pyrene). Furthermore, aliphatic ring systems can also be condensed, which can be understood as having the same meaning as aromatic ring systems or heteroaromatic ring systems, except that the condensed aliphatic ring system is not aromatic. Also, aromatic ring systems or heteroaromatic ring systems can be condensed with aliphatic ring systems (i.e., they share at least one bond).
[0048] In the context of this invention, the term "condensed" ring system has the same meaning as "fused" ring system.
[0049] In certain embodiments of the present invention, adjacent substituents bonded to a ring or ring system may form further monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring systems fused to the aromatic or heteroaromatic ring or ring system to which the substituents are bonded. A fused ring system selectively formed in this manner may also be understood as larger (meaning containing more ring atoms) than the aromatic or heteroaromatic ring or ring system to which the adjacent substituents are bonded. In that case (and where such figures are provided), the “total” number of ring atoms contained in the fused ring system should be understood as the sum of the ring atoms contained in the aromatic or heteroaromatic ring or ring system. Adjacent substituents are bonded, and the ring atoms of the additional ring system are formed by the adjacent substituents, but ring atoms shared by the fused ring are counted once, not twice. For example, a benzene ring may have two adjacent substituents that form yet another benzene ring so that a naphthalene core is formed. The naphthalene core will contain 10 ring atoms, since two carbon atoms are shared by two benzene rings and are counted only once, not twice.
[0050] Generally, in the context of the present invention, the terms “adjacent substituent” or “adjacent group” mean a substituent or group bonded to the same or adjacent atom.
[0051] In the context of the present invention, the term "alkyl group" is understood in its broadest sense as any linear, branched, or cyclic alkyl substituent. In particular, the term "alkyl group" is understood as a substituent such as methyl (Me), ethyl (Et), n-propyl ( n Pr), i-propyl( i Pr), cyclopropyl, n-butyl ( n Bu), i-butyl ( i Bu), s-butyl ( s Bu), t-butyl ( tBu), cyclobutyl, 2-methylbutyl, n-pentyl, s-pentyl, t-pentyl, 2-pentyl, neo-pentyl, cyclopentyl, n-hexyl, s-hexyl, t-hexyl, 2-hexyl, 3-hexyl, neo-hexyl, cyclohexyl, 1-methylcyclopentyl, 2-methylpentyl, n-heptyl, 2-heptyl, 3-heptyl, 4-heptyl, cycloheptyl, 1-methylcyclohexyl, n -Octyl, 2-ethylhexyl, cyclooctyl, 1-bicyclo[2,2,2]octyl, 2-bicyclo[2,2,2]octyl, 2-(2,6-dimethyl)octyl, 3-(3,7-dimethyl)octyl, adamantyl, 2,2,2-trifluoroethyl, 1,1-dimethyl-n-hex-1-yl, 1,1-dimethyl-n-hept-1-yl, 1,1-dimethyl-n-octo-1-yl, 1,1-dimethyl-n- Des-1-yl, 1,1-dimethyl-n-dodes-1-yl, 1,1-dimethyl-n-tetrades-1-yl, 1,1-dimethyl-n-hexades-1-yl, 1,1-dimethyl-n-octades-1-yl, 1,1-diethyl-n-hex-1-yl, 1,1-diethyl-n-hept-1-yl, 1,1-diethyl-n-octo-1-yl, 1,1-diethyl-n-des-1-yl, 1,1-diethyl-n-dodes- This includes 1-yl, 1,1-diethyl-n-tetrades-1-yl, 1,1-diethyl-n-hexades-1-yl, 1,1-diethyl-n-octades-1-yl, 1-(n-propyl)-cyclohex-1-yl, 1-(n-butyl)-cyclohex-1-yl, 1-(n-hexyl)-cyclohex-1-yl, 1-(n-octyl)-cyclohex-1-yl, and 1-(n-decyl)-cyclohex-1-yl.
[0052] For example, in s-butyl, s-pentyl, and s-hexyl, "s" means "secondary," that is, s-butyl, s-pentyl, and s-hexyl are identical to sec-butyl, sec-pentyl, and sec-hexyl, respectively. For example, in t-butyl, t-pentyl, and t-hexyl, "t" means "tertiary," that is, t-butyl, t-pentyl, and t-hexyl are identical to tert-butyl, tert-pentyl, and tert-hexyl, respectively.
[0053] As used throughout this specification, the term “alkenyl” includes linear, branched, and cyclic alkenyl substituents. The term “alkenyl group” includes, for example, substituents such as ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, or cyclooctadienyl.
[0054] As used throughout this specification, the term “alkynyl” includes linear, branched, and cyclic alkynyl substituents. The term “alkynyl group” includes, for example, ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl, or octinyl.
[0055] As used throughout this specification, the term “alkoxy” includes linear, branched, and cyclic alkoxy substituents. The term “alkoxy group” includes, for example, methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, and 2-methylbutoxy.
[0056] As used throughout this specification, the term “thioalkoxy” includes linear, branched, and cyclic thioalkoxy substituents, where the oxygen in the exemplary alkoxy group is replaced by sulfur.
[0057] As used throughout this specification, the term “halogen” (or, in chemical nomenclature, “halo” when referring to a substituent) is also understood in its broadest sense to mean any atom of the elements of the seventh major group (i.e., Group 17) of the periodic table, preferably fluorine, chlorine, bromine, or iodine.
[0058] When a molecular fragment is described as being bonded to substituents or other parts, its name may be described as if it were the fragment itself (e.g., naphthyl, dibenzofuryl) or as the whole molecule (e.g., naphthalene, dibenzofuran). As used herein, the aforementioned methods of describing substituents or bonded fragments are considered equivalent.
[0059] Furthermore, in this application, "C6-C 60 "Aryl" or "C1-C" 40 Whenever a substituent like "alkyl" is mentioned without a name indicating the bonding site within that substituent, it means that each substituent is bonded via any atom. For example, "C6-C 60 The "aryl" substituent is bonded via any 6 to 60 aromatic carbon atoms, and is "C1-C 40 Alkyl substituents are bonded via any 1 to 40 aliphatic carbon atoms. On the other hand, 2-cyanophenyl substituents are bonded only in a manner that their CN group is adjacent to the bonding site, in order to allow for precise chemical nomenclature.
[0060] In the context of this invention, whenever a substituent such as "butyl," "biphenyl," or "terphenyl" is mentioned without further detail, this means that any isomorph of each substituent is acceptable as a specific substituent. In this regard, for example, the term "butyl" as a substituent includes n-butyl, s-butyl, t-butyl, and isobutyl as substituents. Similarly, the term "biphenyl" as a substituent includes ortho-biphenyl, meta-biphenyl, or para-biphenyl, where ortho, meta, and para are defined with respect to the bonding site of the biphenyl substituent to the respective chemical part having the biphenyl substituent. Similarly, as substituents, the term "terphenyl" includes 3-ortho-terphenyl, 4-ortho-terphenyl, 4-meta-terphenyl, 5-meta-terphenyl, 2-para-terphenyl, or 3-para-terphenyl, where, as is known to skilled technicians, ortho, meta, and para indicate the positions of the two Ph moieties within the terphenyl group relative to each other, and "2-", "3-", "4-", and "5-" indicate the bonding positions of the terphenyl substituent to the respective chemical moieties having the terphenyl substituent.
[0061] All the groups defined above and, in fact, all chemical parts, whether cyclic or acyclic, aliphatic, aromatic or heteroaromatic, are understood to be further replaceable by the specific embodiments described herein.
[0062] All hydrogen atoms (H) in any structure referred to in this application are also substituted with deuterium (D) in each case, independently of each other, unless otherwise specifically stated. Substituting hydrogen with deuterium is common practice and is obvious to those skilled in the art. Accordingly, there are many well-known methods and some review articles that can achieve this.
[0063] When comparing experimental or computational data, the values must be determined using the same methodology. For example, experimental ΔE obtained by a specific method STIf the energy is determined to be less than 0.4 eV, the comparison is only valid if the same identification method is used, including the same conditions. For example, a comparison of the photoluminescence quantum yield (PLQY) of different compounds is only valid if the PLQY determination is performed under the same reaction conditions (e.g., room temperature, measurement on a 10% PMMA film). Similarly, the calculated energy values must be determined by the same calculation method (along with the same function and the same base set).
[0064] Photoelectronic device comprising at least one organic molecule according to the present invention A further aspect of the present invention relates to a photoelectronic device comprising at least one organic molecule according to the present invention.
[0065] In one embodiment, a photoelectronic device comprising at least one organic molecule according to the present invention is selected from the group consisting of the following: • Organic light-emitting diode (OLED) • Light-emitting electrochemical cell • OLED sensors, particularly gas and vapor sensors that are not completely isolated from the outside. • Organic diode ·Organic solar cells • Organic transistors • Organic field-effect transistor • Organic laser • Down-conversion element.
[0066] The light-emitting electrochemical cell consists of three layers: a cathode, an anode, and an active layer containing the organic molecule according to the present invention.
[0067] In a preferred embodiment, the photoelectronic device comprising at least one organic molecule according to the present invention is selected from the group consisting of organic light-emitting diodes (OLEDs), light-emitting electrochemical cells (LECs), organic lasers, and light-emitting transistors.
[0068] In a more preferred embodiment, the photoelectronic device comprising at least one organic molecule according to the present invention is an organic light-emitting diode (OLED).
[0069] In one embodiment, the photoelectronic device comprising at least one organic molecule according to the present invention is an OLED having the following layer structure: 1. Circuit board 2. Anode layer A 3. Hole Injection Layer (HIL) 4. Hole transport layer (HTL) 5.Electron blocking layer (EBL) 6. Emitting Layer (EML) 7. Hole Blocking Layer (HBL) 8.Electron transport layer (ETL) 9.Electron injection layer (EIL) 10. Cathode layer C
[0070] Here, the OLED selectively includes each of the layers except for the anode layer A, the cathode layer C, and the light-emitting layer EML, with different layers being merged, and the OLED also includes one or more layers from each of the layer types defined above.
[0071] Furthermore, the photoelectronic element comprising at least one organic molecule according to the present invention may selectively include one or more protective layers to protect the element from damage exposure to harmful substances in the environment, such as moisture, vapor, and / or gas.
[0072] In one embodiment, a photoelectronic device comprising at least one organic molecule according to the present invention is an OLED having the following inverted layer structure: 1. Circuit board 2. Cathode layer C 3.Electron injection layer (EIL) 4.Electron transport layer (ETL) 5. Hole Blocking Layer (HBL) 6. Emitting Layer (EML) 7.Electron blocking layer (EBL) 8. Hole Transport Layer (HTL) 9. Hole Injection Layer (HIL) 10. Anode layer A
[0073] Here, the OLED (having an inverse stacked structure) selectively includes each of the layers except for the anode layer A, the cathode layer C, and the light-emitting layer EML, with different layers being merged, and the OLED also includes one or more layers from each of the layer types defined above.
[0074] The organic molecules according to the present invention (as described in the embodiments above) can be used in various layers by specific structures and substitutions. When used, the fraction of the organic molecules according to the present invention in each layer of a photoelectronic device, particularly an OLED, is 0.1% to 99% by weight, more preferably 1% to 80% by weight. In an alternative embodiment, the proportion of the organic molecules in each layer is 100% by weight.
[0075] In one embodiment, a photoelectronic device comprising at least one organic molecule according to the present invention is an OLED that may have a stacked structure. In this structure, unlike the general arrangement in which OLEDs are arranged side by side, individual units are stacked on top of each other. Mixed light is generated by OLEDs exhibiting a stacked structure, and in particular, white light is generated by stacking blue OLEDs, green OLEDs, and red OLEDs. The OLEDs exhibiting a stacked structure may also selectively include a charge generation layer (CGL), which is generally located between two OLED subunits and is generally composed of an n-doped layer and a p-doped layer. Generally, the n-doped layer of one CGL is located closer to the anode layer.
[0076] In one embodiment, a photoelectronic device comprising at least one organic molecule according to the present invention is an OLED comprising two or more light-emitting layers between an anode and a cathode. In particular, a so-called tandem OLED comprises three light-emitting layers, where one light-emitting layer emits red light, one light-emitting layer emits green light, and one light-emitting layer emits blue light, and additional layers such as charge generation layers, charge blocking layers, or charge transport layers may be selectively included between the individual light-emitting layers. In a further embodiment, the light-emitting layers are stacked adjacent to each other. In a further embodiment, the tandem OLED includes a charge generation layer between each of the two light-emitting layers. Also, adjacent light-emitting layers, or light-emitting layers separated by a charge generation layer, may be merged.
[0077] In one embodiment, a photoelectronic device comprising at least one organic molecule according to the present invention is also essentially a white photoelectronic device, meaning that the device emits white light. For example, such a white photoelectronic device also comprises at least one (deep) blue emitter molecule and one or more emitter molecules emitting green and / or red light. Furthermore, selective energy transfer may occur between two or more molecules, as described in later sections of this text (see below).
[0078] In the case of a photoelectronic device containing at least one organic molecule according to the present invention, at least one organic molecule according to the present invention is contained in the light-emitting layer (EML) of the photoelectronic device, most preferably the EML of an OLED. However, the organic molecule according to the present invention may also be used, for example, in an electron transport layer (ETL) and / or electron blocking layer (EBL) or an exciton blocking layer and / or hole transport layer (HTL) and / or hole blocking layer (HBL). When used, the fraction of the organic molecule according to the present invention in each layer of the photoelectronic device, particularly an OLED, is 0.1% to 99% by weight, more preferably 0.5% to 80% by weight, and particularly 0.5% to 10% by weight. In an alternative embodiment, the proportion of the organic molecule in each layer is 100% by weight.
[0079] The criteria for selecting materials suitable for individual layers of optoelectronic devices, particularly OLEDs, are common knowledge to those skilled in the art. The latest technology demonstrates a wide range of materials for use in individual layers, indicating which materials are suitable for use together. It is understood that any material used in the latest technology can also be used in the optoelectronic devices containing organic molecules according to the present invention. Below are preferred examples of materials for individual layers. It is understood that this does not mean that all types of layers listed below must be present in the optoelectronic device containing at least one organic molecule according to the present invention. Furthermore, it is understood that the optoelectronic device containing at least one organic molecule according to the present invention includes one or more of the layers listed below, such as two or more light-emitting layers (EMLs). It is also understood that two or more layers of the same type (e.g., two or more EMLs, or two or more HTLs) do not necessarily contain the same material, or more preferably, the same proportion of the same material. Additionally, the optoelectronic device containing at least one organic molecule according to the present invention does not need to include all types of layers listed below, where the anode layer, cathode layer, and light-emitting layer are generally present in all cases.
[0080] The substrate may also be formed from any material or a composition thereof. Most often, a glass slide is used as the substrate. Alternatively, a thin metal layer (e.g., copper, gold, silver, or aluminum film), or a plastic film or plastic slide may be used. This can allow for an even higher level of flexibility. The anode layer A is composed of a material from which a nearly (essentially) transparent film can be obtained. Since at least one of the two electrodes must be (essentially) transparent in order to allow light emission from the OLED, one of the anode layer A or cathode layer C is transparent. Preferably, the anode layer A contains or consists of a large amount of transparent conductive oxides (TCOs). Such anode layer A may also include, for example, indium tin oxide, aluminum zinc oxide, fluorine-doped tin oxide, indium zinc oxide, PbO, SnO, zirconium oxide, molybdenum oxide, vanadium oxide, tungsten oxide, graphite, doped Si, doped Ge, doped GaAs, doped polyaniline, doped polypyrrole and / or doped polythiophene.
[0081] Preferably, the anode layer A is (essentially) indium tin oxide (ITO) (e.g., (InO3) 0.9 (SnO2) 0.1The anode layer A is composed of transparent conductive oxide (TCO). The roughness of the anode layer A due to the transparent conductive oxide (TCO) can also be mitigated by using a hole injection layer (HIL). The HIL also facilitates the injection of similar charge carriers (i.e., holes) from the TCO to the hole transport layer (HTL). The hole injection layer (HIL) may also contain poly-3,4-ethylenedioxythiophene (PEDOT), polystyrene sulfonic acid (PSS), MoO2, V2O5, CuPC, or CuI, in particular a mixture of PEDOT and PSS. The hole injection layer (HIL) can also prevent the diffusion of metal from the anode layer A to the hole transport layer (HTL). For example, the HIL is poly-3,4-ethylenedioxythiophene:polystyrene sulfonic acid (PEDOT:PSS), poly-3,4-ethylenedioxythiophene (PEDOT), 4,4',4”-tris[phenyl(m-tolyl)amino]triphenylamine (mMTDATA), 2,2',7,7'-tetrakis(n,n-diphenylamino)-9,9'-spirobifluorene (Spiro-TAD), N1,N1'-(biphenyl-4,4'-diyl)bis(N1-phenyl-N4,N4-di-m-tolylbenzene-1,4-diamine (DNTPD), N,N'-nis-(1-naph It is also composed of thalenyl)-N,N'-bis-phenyl-(1,1'-biphenyl)-4,4'-diamine (NPB), N,N'-diphenyl-N,N'-di-[4-(N,N-diphenylamino)phenyl]benzidine (NPNPB), N,N,N',N'-tetrakis(4-methoxyphenyl)benzidine (MeO-TPD), 1,4,5,8,9,11-hexaazatriphenylene-hexacarbonnitrile (HAT-CN), and / or N,N'-diphenyl-N,N'-bis-(1-naphthyl)-9,9'-spirobifluorene-2,7-diamine (Spiro-NPD).
[0082] Adjacent to the anode layer A or hole injection layer (HIL), a hole transport layer (HTL) is typically located. Here, any hole transport compound can be used. For example, electron-rich heteroaromatic compounds such as triarylamines and / or carbazoles can also be used as hole transport compounds. The HTL can reduce the energy barrier between the anode layer A and the light-emitting layer (EML). The hole transport layer (HTL) is also an electron blocking layer (EBL). Preferably, the hole transport compound has a triplet state T1 with a relatively high energy level. For example, the hole transport layer (HTL) includes tris(4-carbazolyl-9-ylphenyl)amine (TCTA), poly(4-butylphenyl-diphenylamine) (poly-TPD), poly(4-butylphenyl-diphenylamine) (α-NPD), 4,4'-cyclohexyllidene-bis[N,N-bis(4-methylphenyl)benzeneamine] (TAPC), and 4,4',4”-tris[2-naphthyl(phenyl)-amine]. [N]triphenylamine (2-TNATA), 2,2',7,7'-tetrakis(n,n-diphenylamino)-9,9'-spirobifluorene (Spiro-TAD), N1,N1'-(biphenyl-4,4'-diyl)bis(N1-phenyl-N4,N4-di-m-tolylbenzene-1,4-diamine (DNTPD), N,N'-bis-(1-naphthalenyl)-N,N'-bis-phenyl-(1,1'-biphenyl The HTL also contains star-shaped heterocycles such as )-4,4'-diamine (NPB), N,N'-diphenyl-N,N'-di-[4-(N,N-diphenylamino)phenyl]benzidine (NPNPB), N,N,N',N'-tetrakis(4-methoxyphenyl)benzidine (MeO-TPD), 1,4,5,8,9,11-hexaazatriphenylene-hexacarbonnitrile (HAT-CN) and / or 9,9'-diphenyl-6-(9-phenyl-9H-carbazole-3-yl)-9H,9'H-3,3'-bicarbazole (TrisPcz). The HTL also contains a p-doped layer composed of inorganic or organic dopants within the organic hole transport matrix. Transition metal oxides such as vanadium oxide, molybdenum oxide, or tungsten oxide can be used as the inorganic dopant.Examples of organic dopants that can be used include tetrafluorotetracyanoquinodimethane (F4-TCNQ), copper-pentafluorobenzoic acid (Cu(I)pFBz), or transition metal complexes.
[0083] EBL also includes, for example, 1,3-bis(carbazole-9-yl)benzene (mCP), tris(4-carbazoyl-9-ylphenyl)amine (TCTA), 4,4',4”-tris[2-naphthyl(phenyl)amino]triphenylamine (2-TNATA), 3,3-di(9H-carbazole-9-yl)biphenyl (mCBP), 9-phenyl-3,6-bis(9-phenyl-9H-carbazole-3-yl)-9H-carbazole (tris-Pcz), 9-(4-tert-butylphenyl)-3,6-bis(triphenylsilyl)-9H-carbazole (CzSi), and / or N,N'-dicarbazolyl-1,4-dimethylbenzene (DCB).
[0084] Adjacent to the hole transport layer (HTL) or (if present) the electron blocking layer (EBL), the emissive layer (EML) is typically located. The emissive layer (EML) contains at least one emissive molecule (i.e., emitter material). Generally, the EML further contains one or more host materials (also called matrix materials). For example, the host materials are 4,4'-bis-(N-carbazolyl)-biphenyl (CBP), 1,3-bis(carbazole-9-yl)benzene (mCP), 3,3-di(9H-carbazole-9-yl)biphenyl (mCBP), dibenzo[b,d]thiophen-2-yltriphenylsilane (Sif87), 9-(4-tert-butylphenyl)-3,6-bis(triphenylsilyl)-9H-carbazole (CzSi), dibenzo[b,d]thiophen-2-yl)diphenylsilane (Sif88), bis[2-(diphenylphosphinofino)phenyl]ether oxide (DPEPO), and 9-[3-(dibenzofuran-2-yl)phenyl]-9H-carbazole. Selected from ruvasol, 9-[3-(dibenzofuran-2-yl)phenyl]-9H-carbazole, 9-[3-(dibenzothiophen-2-yl)phenyl]-9H-carbazole, 9-[3,5-bis(2-dibenzofuranyl)phenyl]-9H-carbazole, 9-[3,5-bis(2-dibenzothiophenyl)phenyl]-9H-carbazole, 2,4,6-tris(biphenyl-3-yl)-1,3,5-triazine (T2T), 2,4,6-tris(triphenyl-3-yl)-1,3,5-triazine (T3T), and / or 2,4,6-tris(9,9'-spirobifloren-2-yl)-1,3,5-triazine (TST). As is known to those skilled in the art, the host material must generally be selected to exhibit a first (i.e., lowest) excited triplet state (T1) and a first (i.e., lowest) excited singlet state (S1) energy level, which is higher in energy than the first (i.e., lowest) excited triplet state (T1) and first (i.e., lowest) excited singlet state (S1) energy levels of at least one luminescent molecule incorporated into the respective host material.
[0085] As described above, in the context of the present invention, it is preferable that at least one EML of the photoelectronic device contains at least one molecule according to the present invention. Preferred compositions of EMLs of photoelectronic devices containing at least one organic molecule according to the present invention will be described in more detail in later sections of this text (see below).
[0086] Adjacent to the luminescent layer (EML), an electron transport layer (ETL) may be located. Here, any electron transporter can be used. Exemplary examples include electron-deficient compounds such as benzimidazole, pyridine, triazole, triazine, oxadiazole (e.g., 1,3,4-oxadiazole), phosphine oxide, and sulfone. The electron transporter is also a star-shaped heterocycle, such as 1,3,5-tri(1-phenyl-1H-benzo[d]imidazole-2-yl)phenyl (TPBi). The ETL may also include, for example, 2,9-bis(naphthalene-2-yl)-4,7-diphenyl-1,10-phenanthroline (NBphen), aluminum-tris(8-hydroxyquinoline) (Alq3), diphenyl-4-triphenylsilylphenylphosphine oxide (TSPO1), 2,7-di(2,2'-bipyridine-5-yl)triphenyl (BPyTP2), dibenzo[b,d]thiophen-2-yltriphenylsilane (Sif87), dibenzo[b,d]thiophen-2-yl)diphenylsilane (Sif88), 1,3-bis[3,5-di(pyridine-3-yl)phenyl]benzene (BmPyPhB) and / or 4,4'-bis-[2-(4,6-diphenyl-1,3,5-triazinyl)]-1,1'-biphenyl (BTB). Selectively, the ETL may also be doped with a substance such as 8-hydroxyquinolinolatritium (Liq). The electron transport layer (ETL) can also block holes. Alternatively, a hole blocking layer (HBL) is generally introduced between the EML and the ETL.
[0087] Hole blocking layers (HBLs) include, for example, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline=basocupproine (BCP), 4,6-diphenyl-2-(3-(triphenylsilyl)phenyl)-1,3,5-triazine, 9,9'-(5-(6-([1,1'-biphenyl]-3-yl)-2-phenylpyrimidine-4-yl)-1,3-phenylene)bis(9H-carbazole), bis(8-hydroxy-2-methylquinoline)-(4-phenylphenoxy)aluminum (BAlq), and 2,9-bis(naphthalene-2-yl)-4,7-diphenyl-1,10-phenanthroline (NBphe). n) also contains aluminum-tris(8-hydroxyquinoline) (Alq3), diphenyl-4-triphenylsilylphenylphosphine oxide (TSPO1), 2,4,6-tris(biphenyl-3-yl)-1,3,5-triazine (T2T), 2,4,6-tris(triphenyl-3-yl)-1,3,5-triazine (T3T), 2,4,6-tris(9,9'-spirobifluoren-2-yl)-1,3,5-triazine (TST), and / or 1,3,5-tris(N-carbazol)benzol / 1,3,5-tris(carbazole)-9-yl)benzene (TCB / TCP).
[0088] Adjacent to the electron transport layer (ETL), a cathode layer C may be located. The cathode layer C may contain or consist of, for example, a metal (e.g., Al, Au, Ag, Pt, Cu, Zn, Ni, Fe, Pb, LiF, Ca, Ba, Mg, In, W, or Pd) or a metal alloy. For practical reasons, the cathode layer C may also consist of (essentially) opaque metals such as Mg, Ca, or Al. Alternatively or additionally, the cathode layer C may also contain graphite and / or carbon nanotubes (CNTs). Alternatively, the cathode layer C may also contain or consist of nanoscale silver wires.
[0089] An OLED comprising at least one organic molecule according to the present invention may optionally further include a protective layer (also referred to as an electron injection layer (EIL)) between the electron transport layer (ETL) and the cathode layer C. The layer may also contain lithium fluoride, cesium fluoride, silver, 8-hydroxyquinolinolatritium (Liq), Li2O, BaF2, MgO and / or NaF.
[0090] Selectively, the electron transport layer (ETL) and / or hole blocking layer (HBL) also contain one or more host compounds.
[0091] As used herein, unless otherwise specifically defined in a particular context, the hue designation of emitted and / or absorbed light is as follows: Purple: Wavelength range of >380~420nm Deep blue: Wavelength range >420~480nm Sky blue: Wavelength range of >480~500nm Green: Wavelength range >500~560nm Yellow: Wavelength range >560~580nm Orange: Wavelength range >580~620nm Red: Wavelength range of >620~800nm.
[0092] In relation to the emitter molecule (i.e., the emitter material), such hues exhibit maximum emission at the main emission peak. Therefore, for example, a deep blue emitter has maximum emission in the >420-480 nm range, a sky blue emitter has maximum emission in the >480-500 nm range, a green emitter has maximum emission in the >500-560 nm range, and a red emitter has maximum emission in the >620-800 nm range.
[0093] The deep blue emitter may have a maximum emission of less than 475 nm, more preferably less than 470 nm, even more preferably less than 465 nm, and still more preferably less than 460 nm. It is generally greater than 420 nm, preferably greater than 430 nm, more preferably greater than 440 nm, and still more preferably greater than 450 nm. In a preferred embodiment, the organic molecule according to the present invention exhibits maximum emission at 420-500 nm, preferably 430-490 nm, more preferably 440-480 nm, and most preferably 450-470 nm, and is generally measured at room temperature (i.e., about 20°C) from a film spin-coated with 1-5% by weight, preferably 2% by weight, of the organic molecule according to the present invention in poly(methyl methacrylate) (PMMA), mCBP, or alternatively, from 0.001 mg / mL of the organic molecule according to the present invention in an organic solvent, preferably DCM or toluene.
[0094] Further embodiments relate to an OLED comprising at least one organic molecule according to the present invention, which emits light having CIEx and CIEy color coordinates close to the color coordinates of primary blue (CIEx=0.131 and CIEy=0.046) as defined by ITU-R Recommendation BT.2020 (Rec.2020), which is suitable for use in UHD (Ultra High Definition) displays, such as UHD-TVs. Therefore, a further aspect of the present invention relates to an OLED comprising at least one organic molecule according to the present invention, wherein the luminescence exhibits CIEx color coordinates of 0.02 to 0.30, preferably 0.03 to 0.25, more preferably 0.05 to 0.20, even more preferably 0.08 to 0.18, and even more preferably 0.10 to 0.15, and / or CIEy color coordinates of 0.00 to 0.45, preferably 0.01 to 0.30, more preferably 0.02 to 0.20, even more preferably 0.03 to 0.15, and even more preferably 0.04 to 0.10.
[0095] Another embodiment is 1000 cd / m². 2 In this case, it exhibits an external quantum efficiency of more than 8%, preferably more than 10%, more preferably more than 13%, even more preferably more than 15%, and even more preferably more than 20%, and / or exhibits maximum emission at 420nm to 500nm, preferably 430nm to 490nm, more preferably 440nm to 480nm, and even more preferably 450nm to 470nm, and / or 500 cd / m 2 The present invention relates to an OLED containing at least one organic molecule according to the present invention that exhibits an LT80 value exceeding 100h, preferably exceeding 200h, more preferably exceeding 400h, even more preferably exceeding 750h, and even more preferably exceeding 1000h.
[0096] The green emitter material can preferably have a maximum emission of 500-560 nm, more preferably 510-550 nm, and even more preferably 520-540 nm.
[0097] Further embodiments relate to an OLED comprising at least one organic molecule according to the present invention and emitting light at distinct color points. Preferably, the OLED emits light having a narrow emission band (small full width at half maximum (FWHM)). In a preferred embodiment, the OLED comprising at least one organic molecule according to the present invention emits light having an FWHM of a main emission peak of less than 0.30 eV, preferably less than 0.25 eV, more preferably less than 0.20 eV, even more preferably less than 0.1 eV, or less than 0.17 eV.
[0098] According to the present invention, a photoelectronic element comprising at least one organic molecule according to the present invention can be used, for example, as a light source in the field of displays, lighting applications, and medical and / or cosmetic applications (e.g., phototherapy).
[0099] Combination of organic molecules and additional materials according to the present invention The fact that any layer within a photoelectronic device (preferably an OLED), particularly an emissive layer (EML), consists of a single material or a combination of different materials, is part of the general knowledge of those skilled in the art.
[0100] For example, a person skilled in the art will understand that an EML is composed of a single material that emits light when a voltage (and current) is applied to the element. However, a person skilled in the art will understand that in an EML of a photoelectronic element (wherein preferably an OLED), different materials, in particular one or more host materials (i.e., matrix materials; wherein which the host material H is included when the photoelectronic element contains at least one organic molecule according to the present invention) are used. B It is understood that when voltage and current are applied to the element, coupling with one or more dopant materials (i.e., emitter materials) that emit light at least one of them is advantageous.
[0101] In a preferred embodiment of the use of the organic molecule according to the present invention in a photoelectronic device, the photoelectronic device includes at least one organic molecule according to the present invention in an EML, a layer directly adjacent to the EML, or one or more layers of those layers.
[0102] In a preferred embodiment of the use of the organic molecule according to the present invention in a photoelectronic device, the photoelectronic device is an OLED and contains at least one organic molecule according to the present invention in an EML, a layer directly adjacent to the EML, or one or more layers of those layers.
[0103] In a more preferred embodiment of the use of organic molecules according to the present invention in a photoelectronic device, the photoelectronic device is an OLED and the EML contains at least one organic molecule according to the present invention.
[0104] In one embodiment relating to a photoelectronic device, preferably an OLED, comprising at least one organic molecule according to the present invention, at least one, preferably each organic molecule according to the present invention, is used as an emitter material in a light-emitting layer (EML), which emits light when a voltage (and current) is applied to the device.
[0105] As is known to those skilled in the art, for example, in an organic light-emitting diode (OLED), the emission from the emitter material (i.e., the luminescent dopant) includes fluorescence from an excited singlet state (generally the lowest excited singlet state S1) and phosphorescence from an excited triplet state (generally the lowest excited triplet state T1).
[0106] A fluorescent emitter F can emit light at room temperature (i.e., about 20°C) when electronically excited (e.g., in a photoelectronic device), and the luminescent excited state is a singlet state. Fluorescent emitters generally exhibit immediate (i.e., direct) fluorescence on a nanosecond timescale when the initial electronic excitation (e.g., by electron-hole recombination) provides the excited singlet state of the emitter.
[0107] In the context of the present invention, a delayed fluorescence material is a material that can reach an excited singlet state (generally the lowest excited singlet state S1) from an excited triplet state (generally the lowest excited singlet state S1) via reverse intersystem crossing (RISC; i.e., up-system crossing or reverse intersystem crossing), and can emit light when returning from the excited singlet state (generally S1) to the electronic ground state. The timescale (generally in the microsecond range) at which fluorescence emission occurs after RISC from the excited triplet state (generally T1) to the excited singlet state (generally S1) occurs is slower than the timescale (generally in the nanosecond range) at which direct (i.e., immediate) fluorescence occurs, and is therefore called delayed fluorescence (DF). When RISC from the excited triplet state (generally from T1) to the excited singlet state (generally up to S1) occurs via thermal activation, and the thus filled excited singlet state emits light (delayed fluorescence emission), the process is called thermally activated delayed fluorescence (TADF). Therefore, TADF materials are materials that can emit thermally activated delayed fluorescence (TADF) as described above. The lowest excited singlet state energy level E(S1) of the fluorescent emitter F E ) and the lowest excited triplet state energy level E(T1 E ) Energy difference ΔE STThose skilled in the art know that if ΔE decreases, the RISC-mediated switching from the lowest excited singlet state to the lowest excited triplet state occurs with high efficiency. Therefore, TADF materials generally have a small ΔE. ST Having a value forms part of the general knowledge of those skilled in the art (see below). As is known to those skilled in the art, TADF materials are not simply materials capable of their own RISC from an excited triplet state to an excited singlet state, along with the subsequent emission of TADF as described above. TADF materials consist of virtually two types of materials, preferably two host materials H B More preferably, p-host material H P and n-host material H N Those skilled in the art know that it is an excyplex formed from (see below).
[0108] The generation of (thermally activated) delayed fluorescence is analyzed based on decay curves obtained, for example, from time-resolved (i.e., transient) photoluminescence (PL) measurements. For this purpose, spin-coated films of 1–10 wt%, particularly 10 wt%, of each emitter (i.e., assumed TADF material) in poly(methyl methacrylate) (PMMA) are used as samples. The analysis is performed, for example, using an Edinburgh Instruments FS5 fluorescence spectrometer. A nitrogen atmosphere is maintained while the sample PMMA film is placed in a cuvette for measurement. Data acquisition is performed using the well-established time-correlated single-photon counting (TCSPC, see below) technique. To collect the overall decay dynamics over multiple orders of magnitude in time and signal intensity, measurements can be performed and coupled in four time domains (200 ns, 1 μs, 20 μs, and longer measurement periods >80 μs) (see below).
[0109] The TADF material preferably satisfies the following two conditions in relation to the overall damping mechanics described above: (i) Damping dynamics exhibit two time domains, one in the nanosecond (ns) range and the other in the microsecond (μs) range, and (ii) The morphology of the emission spectrum is identical in the two time domains.
[0110] Here, some of the light emitted in the first decay region is taken as immediate fluorescence, and some of the light emitted in the second decay region is taken as delayed fluorescence.
[0111] The ratio of delayed fluorescence to immediate fluorescence is expressed in the form of a so-called n-value, which is calculated by integrating the respective photoluminescence decays over time using the following equation:
number
[0112] In the context of the present invention, the TADF material is preferably greater than 0.05 (n>0.05), more preferably greater than 0.1 (n>0.1), even more preferably greater than 0.15 (n>0.15), particularly preferably greater than 0.2 (n>0.20), and even more preferably greater than 0.25 (n>0.25).
[0113] In a preferred embodiment, the organic molecule according to the present invention exhibits an n value greater than 0.05 (n>0.05) (ratio of delayed fluorescence to immediate fluorescence).
[0114] In the context of the present invention, TADF material E B This is the lowest excited singlet state energy level E(S1 E ) and the lowest excited triplet state energy level E(T1 E ΔE corresponds to the energy difference with ) ST It is characterized by exhibiting a value of less than 0.4 eV, preferably less than 0.3 eV, more preferably less than 0.2 eV, even more preferably less than 0.1 eV, and even more preferably less than 0.05 eV. TADF material E B ΔE ST The method for determining the value is explained in a later section of this text.
[0115] One common approach to designing TADF materials is to covalently bond one or more (electron) donor regions where the HOMO is distributed and one or more (electron) acceptor regions where the LUMO is distributed to the same bridge, which is referred to in this application as a linker group. B For example, it includes two or three linker groups bonded to the same acceptor portion, and further donor and acceptor portions may be bonded to each of those two or three linker groups.
[0116] Furthermore, one or more donor portions and one or more acceptor portions can be directly bonded to each other (without the presence of a linker group).
[0117] Typical donor moieties include diphenylamine, indole, carbazole, acridine, phenoxazine, and derivatives of related structures. In particular, aliphatic, aromatic, or heteroaromatic ring systems are condensed into the aforementioned donor precursors to reach, for example, indolocarbazole.
[0118] Benzene, biphenyl, and to some extent, derivatives of terphenyl are common linker groups.
[0119] Nitrile groups are very common acceptor moieties in TADF materials, and well-known examples include: (i) Carbazolyl dicyanobenzene compounds 2CzPN (4,5-di(9H-carbazole-9-yl)phthalonitrile), DCzIPN (4,6-di(9H-carbazole-9-yl)isophthalonitrile), 4CzPN (3,4,5,6-tetra(9H-carbazole-9-yl)phthalonitrile), 4CzIPN (2,4,5,6-tetra(9H-carbazole-9-yl)isophthalonitrile), 4CzTPN (2,4,5,6-tetra(9H-carbazole-9-yl)terephthalonitrile) and its derivatives, (ii) Carbazolylcyanopyridine compounds 4CzCNPy(2,3,5,6-tetra(9H-carbazole-9-yl)-4-cyanopyridine) and its derivatives, (iii) Carbazolylcyanobiphenyl compounds CNBPCz (4,4',5,5'-tetra(9H-carbazol-9-yl)-[1,1'-biphenyl]-2,2'-dicarbonitrile), CzBPCN (4,4',6,6'-tetra(9H-carbazol-9-yl)-[1,1'-biphenyl]-3,3'-dicarbonitrile), DDCzIPN (3,3',5,5'-tetra(9H-carbazol-9-yl)-[1,1'-biphenyl]-2,2',6,6'-tetracarbonitrile) and its derivatives, Here, in these materials, one or more nitrile groups can be replaced with fluorine (F) or trifluoromethyl (CF3) as the acceptor moiety.
[0120] Furthermore, nitrogen heterocycles such as triazines, pyrimidines, triazoles, oxadiazoles, thiadiazoles, heptadine, 1,4-diazatriphenylene, benzothiazoles, benzoxazoles, quinoxalines, and diazafluorene derivatives are well-known acceptor moieties used in the construction of TADF molecules. For example, known examples of TADF molecules containing a triazine acceptor include PIC-TRZ(7,7'-(6-([1,1'-biphenyl]-4-yl)-1,3,5-triazine-2,4-diyl)bis(5-phenyl-5,7-dihydroindoro[2,3-b]carbazole)), mBFCzTrz(5-(3-(4,6-diphenyl-1,3,5-triazine-2-yl))phenyl)-5H-benzofl[3,2-c]carbazole), and DCzTrz(9,9'-(5-(4,6-diphenyl-1,3,5-triazine-2-yl)-1,3-phenylene)bis(9H-carbazole)).
[0121] Another group of TADF materials includes diaryl ketones such as benzophenone, or (heteroaryl)aryl ketones and their derivatives such as 4-benzoylpyridine, 9,10-anthraquinone, and 9H-xanthene-9-one, to which the donor moiety (mainly a carbazolyl substituent) is attached as an acceptor moiety. Examples of such TADF molecules include BPBCz (bis(4-(9'-phenyl-9H,9'H-[3,3'-bicarbazole]-9-yl)phenyl)methanone), mDCBP ((3,5-di(9H-carbazole-9-yl)phenyl)(pyridine-4-yl)methanone), AQ-DTBu-Cz (2,6-bis(4-(3,6-di-tert-butyl-9H-carbazole-9-yl)phenyl)anthracene-9,10-dione), and MCz-XT (3-(1,3,6,8-tetramethyl-9H-carbazole-9-yl)-9H-xanthene-9-one), respectively.
[0122] Furthermore, sulfoxides, particularly diphenyl sulfoxides, are commonly used as acceptor moieties for the composition of TADF materials. Well-known examples include 4-PC-DPS (9-phenyl-3-(4-(phenylsulfonyl)phenyl)-9H-carbazole), DitBu-DPS (9,9'-(sulfonylbis(4,1-phenylene))bis(9H-carbazole)), and TXO-PhCz (2-(9-phenyl-9H-carbazole-3-yl)-9H-thioxanthene-9-one 10,10-dioxide).
[0123] The fluorescent emitter F may also exhibit TADF as defined herein, and furthermore, TADF material E as defined herein. B It is understood that this is the case. As a result, a small FWHM emitter S as defined herein B This refers to TADF material E as defined herein. B It may be so, or it may not be.
[0124] Phosphorescence, that is, emission from an excited triplet state (generally the lowest excited triplet state T1), is a spin-prohibition process. As is known to those skilled in the art, phosphorescence is promoted (enhanced) by utilizing (intramolecular) spin-orbit interactions (the so-called (internal) heavy atom effect). In the context of this invention, phosphorescent material P B This is a phosphorescent emitter that can emit phosphorescence at room temperature (i.e., approximately 20°C).
[0125] Here, phosphorescent material P B Preferably, it contains at least one atom of an element having a standard atomic weight greater than the standard atomic weight of calcium (Ca). More preferably, in the context of the present invention, phosphorescent material P B This includes transition metal atoms, particularly transition metal atoms of elements having a standard atomic weight greater than that of zinc (Zn). Phosphorescent material P B The transition metal atoms preferably included exist in any oxidation state (and can also exist as ions of each element).
[0126] Phosphorescent material P used in organic electroluminescent elements B It is common knowledge to those skilled in the art that the phosphorescent material P is Ir, Pd, Pt, Au, Os, Eu, Ru, Re, Ag, and Cu, preferably Ir, Pt, and Pd, and more preferably a complex of Ir and Pt, in the context of the present invention. Those skilled in the art will know that any material in a photoelectronic device is a phosphorescent material P B It is known whether they are suitable for use as phosphorescent materials and how to synthesize them. Furthermore, those skilled in the art are familiar with the design principles of phosphorescent complexes for use as phosphorescent materials in optoelectronic devices and know how to control the emission of the complexes through structural changes.
[0127] Those skilled in the art will know that phosphorescent material P used in photoelectronic devices B It is known what materials are suitable for this purpose and how to synthesize them. In connection with this, those skilled in the art will know, in particular, that phosphorescent material P in optoelectronic devices is suitable. B We are familiar with the design principles of phosphorescent complexes for use as such, and we know how to regulate the release of the complex through structural changes.
[0128] Phosphorescent material P usable with organic molecules according to the present invention B Examples of these (for example, in the form of a composition or in an EML of a photoelectronic device, see below) are disclosed in the latest art. For example, the following metal complexes are phosphorescent materials P that can be used with the organic molecules according to the present invention. B is: [ka]
[0129] In the context of the present invention, a small half-width (FWHM) emitter S B This refers to any emitter (i.e., emitter material) having an emission spectrum exhibiting an FWHM of 0.35 eV or less (≤0.35 eV), preferably 0.30 eV or less (≤0.30 eV), and particularly 0.25 eV or less (≤0.25 eV). Unless otherwise specified, this is determined based on the emission spectrum of each emitter at room temperature (i.e., (approximately) 20°C) and is generally measured in 1-5 wt%, particularly 2 wt%, emitters in poly(methyl methacrylate) (PMMA) or mCBP. Alternatively, a small FWHM emitter S B The emission spectrum is generally obtained at room temperature (i.e., (approximately) 20°C) with 0.001-0.2 mg / mL of emitter S in dichloromethane or toluene. B It can be measured in a solution containing [the specified value].
[0130] Small FWHM emitter S B These are fluorescent emitters F and phosphorescent emitters (for example, phosphorescent material P). B ) and / or TADF emitters (e.g., TADF material E B ) is the aforementioned TADF material E B and phosphorescent material P B In this case, the emission spectrum is obtained at room temperature (i.e., (approximately) 20°C) for each material E at 10 wt% within poly(methyl methacrylate) (PMMA). B or P B Measurements are taken from each of the spin-coated films.
[0131] As is known to those skilled in the art, emitters (for example, small FWHM emitters S B The full width at half maximum (FWHM) of the emission spectrum can be easily determined from the respective emission spectra (fluorescence spectrum for a fluorescent emitter and phosphorescence spectrum for a phosphorescent emitter). All recorded FWHM values generally indicate the main emission peak (i.e., the peak with the highest intensity). The means of determining the FWHM (where preferably recorded in electron volts eV) is part of the common sense of those skilled in the art. For example, if the main emission peak of the emission spectrum reaches half of the maximum emission (i.e., 50% of the maximum emission intensity) at two wavelengths λ1 and λ2 obtained from the emission spectrum in nanometers (nm), the FWHM in electron volts (eV) is generally (and here) determined using the following equation:
number
[0132] In the context of the present invention, a small FWHM emitter S B This is an organic emitter, which in the context of the present invention means that it does not contain any transition metals. Preferably, in the context of the present invention, a small FWHM emitter S B It is mainly composed of the elements hydrogen (H), carbon (C), nitrogen (N), and boron (B), but may also contain, for example, oxygen (O), silicon (Si), fluorine (F), and bromine (Br).
[0133] Furthermore, in the context of the present invention, a small FWHM emitter S B It is preferable that the fluorescent emitter F may or may not exhibit TADF.
[0134] Preferably, in the context of the present invention, a small FWHM emitter S B It must satisfy at least one of the following requirements: (i) Boron (B) containing emitters, which are each small FWHM emitters S B This means that at least one atom inside is boron (B), (ii) comprising a polycyclic aromatic or heteroaromatic core structure in which at least two aromatic rings are condensed together (e.g., anthracene, pyrene, or aza derivatives thereof).
[0135] As is known to those skilled in the art, the host material H of EML B It can pass through the EML and transport electrons or positive charges, and the host material H B It is possible to transfer excitation energy to at least one emitter material doped with H. Those skilled in the art will know that the host material H included in the EML of a photoelectronic device (e.g., OLED) B However, it is understood that when voltage and current are applied, they do not significantly affect the light emission from the element. Those skilled in the art will also understand that any host material H B However, p-host H exhibits high hole mobility. P n-host H exhibits high electron mobility N , or bipolar host material H exhibiting both high hole mobility and high electron mobility BP It is known that this is the case.
[0136] As is known to those skilled in the art, EML also has at least one p-host H P and one n-host H N This includes a so-called mixed host system having exactly one emitter material and n-host H according to the present invention. N 2,4,6-Tris(biphenyl-3-yl)-1,3,5-triazine (T2T), p-host H PThe system comprises a mixed host system containing a host selected from CBP, mCP, mCBP, 4,6-diphenyl-2-(3-(triphenylsilyl)phenyl)-1,3,5-triazine, 9-[3-(dibenzofuran-2-yl)phenyl]-9H-carbazole, 9-[3-(dibenzofuran-2-yl)phenyl]-9H-carbazole, 9-[3-(dibenzothiophen-2-yl)phenyl]-9H-carbazole, 9-[3,5-bis(2-dibenzofuranyl)phenyl]-9H-carbazole, and 9-[3,5-bis(2-dibenzothiophenyl)phenyl]-9H-carbazole.
[0137] EML is at least one p-host H P and one n-host H N This includes a so-called mixed host system having n-host H. N It contains groups derived from pyridine, pyrimidine, benzopyrimidine, 1,3,5-triazine, 1,2,4-triazine and 1,2,3-triazine, and p-host H P The group comprises indole, isoindole, and preferably a group derived from carbazole.
[0138] Those skilled in the art know what materials are suitable host materials for use in organic electroluminescent devices. Any host material used in the latest technology is a suitable host material H in the context of the present invention. B It is understood to be that.
[0139] p-host material H in the context of the present invention P Material H B Examples are listed below: [ka] [ka] [ka] [ka] [ka] [ka]
[0140] n-host material H in the context of the present invention N Material H B Examples are listed below: [ka] [ka] [ka]
[0141] Those skilled in the art will understand that not only any material contained in the same layer, particularly the same EML, but also materials in adjacent layers that are in very close proximity at the interface between those adjacent layers can form an excyplex together. Those skilled in the art will understand that a pair of materials forming an excyplex, particularly p-host H P and n-host H N A method for selecting a pair of materials, as well as selection criteria for the two components of the material pair, including HOMO and / or LUMO energy requirements, are known. That is, when excyplex formation is required, one component, for example, p-host material H P The HOMO is other components, for example, n-host material H N The energy is at least 0.20 eV higher than the HOMO, and one component, for example, p-host material H P The LUMO is other components, for example, n-host material H NThe energy is at least 0.20 eV higher than the LUMO. It is common knowledge to those skilled in the art that if an exciplex is present in a photoelectronic device, particularly in the EML of an OLED, the exciplex functions as an emitter material and can emit light when voltage and current are applied to the device. As is known from the latest technology and generally, an exciplex can also be non-luminescent and, for example, if it is included in the EML of a photoelectronic device, can transfer excitation energy to the emitter material.
[0142] As is known to those skilled in the art, TTA (triplet-triplet annihilation) materials are host materials H B It is also used as a TTA material. TTA materials enable triplet-triplet annihilation. Triplet-triplet annihilation can preferably cause photon upconversion. Thus, two, three or more photons can be converted into TTA material H TTA The lowest excited triplet state (T1 TTA ) to the first excited singlet state (S1 TTA Facilitates photon upconversion to ). In a preferred embodiment, two photons are converted to T1 TTA From S1 TTA This facilitates photon upconversion to triplet. Therefore, triplet-triplet annihilation is also a process in which two (or more selectively two) low-frequency photons can be coupled into one high-frequency photon through a number of energy transfer steps.
[0143] Selectively, the TTA material may also include an absorbent moiety, a sensitiver moiety, and an emitter moiety (or disappearance moiety). In this regard, the emitter moiety may also be a polycyclic aromatic moiety such as benzene, biphenyl, triphenyl, triphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, or azulene. In preferred embodiments, the polycyclic aromatic moiety includes an anthracene moiety or a derivative thereof. The sensitiver moiety and the emitter moiety may be located in two different chemical compounds (i.e., separate chemical entities) or may be two moies contained within a single chemical compound.
[0144] According to the present invention, the triplet-triplet annihilation (TTA) material undergoes triplet-triplet annihilation to reach the first excited triplet state T1 N From the first excited singlet state S1 N It converts energy into [something].
[0145] According to the present invention, the TTA material is in the lowest excited triplet state (T1 N ) then exhibits triplet-triplet annihilation, resulting in the first excited singlet state S1 after triplet-triplet annihilation. N Generate T1 N It is characterized by having up to twice the energy of [the other element].
[0146] In one embodiment of the present invention, the TTA material is T1 N From there, we show triplet-triplet annihilation, S1 N Generate T1 N It is characterized by having energy 1.01 to 2 times, 1.1 to 1.9 times, 1.2 to 1.5 times, 1.4 to 1.6 times, or 1.5 to 2 times the energy of the original.
[0147] In this specification, the terms "TTA material" and "TTA compound" may be used interchangeably.
[0148] Typical "TTA materials" can be found in cutting-edge technologies related to blue fluorescent OLEDs, as described by Kondakov (Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, 2015, 373: 20140321). Such blue fluorescent OLEDs use aromatic hydrocarbons, such as anthracene derivatives, as the main component (host) of the EML.
[0149] In a preferred embodiment, the TTA material enables sensitive triplet-triplet annihilation. Selectively, the TTA material may contain one or more polycyclic aromatic structures. In a preferred embodiment, the TTA material contains at least one polycyclic aromatic structure and at least one further aromatic residue.
[0150] In a preferred embodiment, the TTA material has a larger singlet-triplet energy split, i.e., at least 1.1 times, at least 1.2 times, at least 1.3 times, at least 1.5 times, preferably 2 times or less, for the first excited singlet state S1 N and the lowest excited triplet state T1 N It has an energy difference with respect to
[0151] In a preferred embodiment of the present invention, TTA material H TTA It is an anthracene derivative.
[0152] In one embodiment, the TTA material H TTA It is an anthracene derivative of the following chemical formula 4, [ka] ...chemical formula 4 Here, Each Ar is independently selected from the following group: C6-C 60 Ariel, C3-C 57 Heteroaryls, halogens, and C1-C 40 C6-C 60 Aryl, and C6-C 60 Ariel, C3-C 57 Heteroaryls, halogens, and C1-C 40 C3-C 57 Heteroaryl, Each A1 is independently selected from the following group: hydrogen, deuterium, C6-C 60 Ariel, C3-C 57 Heteroaryls, halogens, and C1-C 40 C6-C 60 Ariel, C6-C 60 Ariel, C3-C 57 Heteroaryls, halogens, and C1-C 40 C3-C 57 Heteroaryls, and C6-C 60 Ariel, C3-C 57 Heteroaryls, halogens, and C1-C 40 C1-C11 is selectively substituted with one or more residues selected from the group consisting of (hetero)alkyl groups. 40 (Hetero)alkyl.
[0153] In one embodiment, the TTA material H TTA It is an anthracene derivative of the following chemical formula 4, Here, Each Ar is independently selected from the following group: C6-C 20 Ariel, C3-C 20 Heteroaryls, halogens, and C1-C 210 C6-C 20 Aryl, and C6-C 20 Ariel, C3-C 20 Heteroaryls, halogens, and C1-C 10 C3-C 20 Heteroaryl, Each A1 is independently selected from the following group: hydrogen, deuterium, C6-C 20Ariel, C3-C 20 Heteroaryls, halogens, and C1-C 10 C6-C 20 Ariel, C6-C 20 Ariel, C3-C 20 Heteroaryls, halogens, and C1-C 10 C3-C 20 Heteroaryls, and C6-C 60 Ariel, C3-C 57 Heteroaryls, halogens, and C1-C 40 C1-C11 is selectively substituted with one or more residues selected from the group consisting of (hetero)alkyl groups. 10 (Hetero)alkyl.
[0154] In one embodiment, H TTA is an anthracene derivative of the following chemical formula 4, where at least one A1 is hydrogen. In one embodiment, H TTA is an anthracene derivative of the following chemical formula 4, where at least two A1s are hydrogen. In one embodiment, H TTA is an anthracene derivative of the following chemical formula 4, where at least three A1s are hydrogen. In one embodiment, H TTA This is an anthracene derivative of the chemical formula 4 below, where all A1s are hydrogen atoms. In one embodiment, H TTA This is an anthracene derivative of the following chemical formula 4, where at least one Ar is a residue selected from the group consisting of phenyl, naphthyl, phenanthryl, pyrenyl, triphenylenyl, dibenzoanthracenyl, fluorenyl, benzofluorenyl, anthracenyl, phenantrenyl, benzonaphthofuranil, benzonaphthothiophenyl, dibenzofuranil, and dibenzothiophenyl, which is C6-C 60 Ariel, C3-C 57 Heteroaryls, halogens, and C1-C 40It can be selectively substituted with one or more residues selected from the group consisting of (hetero)alkyl groups.
[0155] In one embodiment, H TTA This is an anthracene derivative of the chemical formula 4 below, where the two Ar groups are each independently selected residues from the group consisting of phenyl, naphthyl, phenanthryl, pyrenyl, triphenylenyl, dibenzoanthracenyl, fluorenyl, benzofluorenyl, anthracenyl, phenantrenyl, benzonaphthofuranyl, benzonaphthothiophenyl, dibenzofuranyl, and dibenzothiophenyl, and this is C6-C 60 Ariel, C3-C 57 Heteroaryls, halogens, and C1-C 40 It can be selectively substituted with one or more residues selected from the group consisting of (hetero)alkyl groups.
[0156] In one embodiment, TTA material H TTA is an anthracene derivative selected from the following: [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka]
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[0157] A composition comprising at least one organic molecule according to the present invention One aspect of the present invention relates to a composition comprising at least one organic molecule according to the present invention. Another aspect of the present invention relates to the use of the composition in a photoelectronic device, preferably an OLED, and more particularly in an EML of the device.
[0158] In describing the compositions mentioned above, the content of specific materials in each composition will, where applicable, be referred to in the form of a percentage. It should be noted that, unless otherwise specified in a particular embodiment, all percentages refer to weight percentages, which are synonymous with weight % ((weight / weight), (w / w), wt%). For example, if the content of one or more organic molecules according to the present invention is mentioned as 30% in a particular composition, this is understood to mean that the total weight of one or more organic molecules according to the present invention (i.e., all of those molecules combined) is 30% by weight, i.e., 30% of the total weight of each composition. By providing preferred content of components in weight %, it is understood that, each time a composition is specified, the total content of all components will be summed up to 100% by weight (i.e., the total weight of the composition).
[0159] In describing embodiments of the present invention relating to compositions comprising at least one organic molecule according to the present invention, when the composition is used in a photoelectronic device, preferably in an EML of a photoelectronic device, most preferably in an EML of an OLED, we will refer to the energy transfer process that occurs between the components in the composition. Those skilled in the art will understand that such excitation energy transfer processes can improve the luminescence efficiency when the composition is used in an EML of a photoelectronic device.
[0160] When describing a composition comprising at least one organic molecule according to the present invention, it will also be noted that certain materials are "different" from other materials. This means that materials that are "different" from each other do not have the same chemical structure.
[0161] In one embodiment, the composition comprises or consists of the following: (a) One or more organic molecules according to the present invention (b) One or more host materials H different from the organic molecules in (a) B , and (c) One or more solvents selectively.
[0162] In one embodiment, the composition comprises or consists of the following: (a) One or more organic molecules according to the present invention, and (b) One or more host materials H different from the organic molecules in (a) B , Here, the host material H in the composition B The fraction (weight %) of is higher than the fraction (weight %) of the organic molecule according to the present invention, and preferably the host material H in the composition. B The fraction (weight %) of this molecule is more than twice as high as the fraction (weight %) of the organic molecule according to the present invention.
[0163] In one embodiment, the composition comprises or consists of the following: (a) 0.1 to 30% by weight, preferably 0.8 to 15% by weight, and particularly 1.5 to 5% by weight of the organic molecule according to the present invention, (b) Host material H according to the following chemical formula 4 B TTA material as: [ka] ...Chemical formula 4.
[0164] In one embodiment, the composition comprises or consists of the following: (a) Organic molecule according to the present invention, (b) The organic molecule in (a) and a different host material H B , and (c)TADF material E B and / or phosphorescent material P B .
[0165] In one embodiment, the composition comprises or consists of the following: (a) 0.1 to 20% by weight, preferably 0.5 to 12% by weight, and especially 1 to 5% by weight of the organic molecule according to the present invention. (b) 0-98.8% by weight, preferably 35-94% by weight, and particularly 60-88% by weight, of one or more host materials H different from the organic molecules according to the present invention. B , (c) 0.1 to 20% by weight, preferably 0.5 to 10% by weight, and especially 1 to 3% by weight, one or more phosphorescent materials P different from the organic molecules in (a). B , (d) 1 to 99.8% by weight, preferably 5 to 50% by weight, and especially 10 to 30% by weight, of one or more TADF materials E different from the organic molecules of (a). B , and (e) One or more solvents in an amount of 0 to 98.8% by weight, preferably 0 to 59% by weight, and especially 0 to 28% by weight.
[0166] In a further aspect, the present invention relates to photoelectronic devices comprising the types of organic molecules or compositions described herein, in particular to devices selected from the group consisting of organic light-emitting diodes (OLEDs), light-emitting electrochemical cells, OLED sensors, in particular gas sensors and vapor sensors not completely isolated from the outside, organic diodes, organic solar cells, organic transistors, organic field-effect transistors, organic lasers, and down-conversion devices.
[0167] In a preferred embodiment, the photoelectronic element is an element selected from the group consisting of organic light-emitting diodes (OLEDs), light-emitting electrochemical cells (LECs), and light-emitting transistors.
[0168] In one embodiment of the photoelectronic device of the present invention, the organic molecule E according to the present invention is used as an emitter material in the light-emitting layer EML.
[0169] In one embodiment of the photoelectronic device of the present invention, the light-emitting layer EML comprises the composition according to the present invention as described herein.
[0170] If the photoelectronic element is an OLED, it may have, for example, the following layer structure: 1. Circuit board 2. Anode layer A 3. Hole Injection Layer (HIL) 4. Hole transport layer (HTL) 5.Electron blocking layer (EBL) 6. Emitting Layer (EML) 7. Hole Blocking Layer (HBL) 8.Electron transport layer (ETL) 9.Electron injection layer (EIL) 10. Cathode layer C
[0171] Here, the OLED selectively includes each layer selected from the group of HIL, HTL, EBL, HBL, ETL, and EIL, with different layers being merged, and the OLED also includes one or more layers from each of the layer types defined above.
[0172] In one embodiment, the photoelectronic element may selectively include one or more protective layers to protect the element from damage exposure to harmful substances in the environment, such as moisture, vapor, and / or gases.
[0173] In one embodiment of the present invention, the optoelectronic element is an OLED having the following inverted layer structure: 1. Circuit board 2. Cathode layer 3.Electron injection layer (EIL) 4.Electron transport layer (ETL) 5. Hole Blocking Layer (HBL) 6. Emitting layer B 7.Electron blocking layer (EBL) 8. Hole Transport Layer (HTL) 9. Hole Injection Layer (HIL) 10. Anode layer A
[0174] Here, the OLED selectively includes each layer selected from the group of HIL, HTL, EBL, HBL, ETL, and EIL, with different layers being merged, and the OLED also includes one or more layers from each of the layer types defined above.
[0175] In one embodiment of the present invention, the optoelectronic element is an OLED that may have a stacked structure. In this structure, unlike the general arrangement in which OLEDs are arranged side by side, individual units are stacked on top of each other. Mixed light is generated by the OLED exhibiting the stacked structure, and in particular, white light is generated by stacking blue OLEDs, green OLEDs, and red OLEDs. The OLED exhibiting the stacked structure may also include a charge generation layer (CGL), which is generally located between two OLED subunits and is generally composed of an n-doped layer and a p-doped layer. Generally, the n-doped layer of one CGL is located closer to the anode layer.
[0176] In one embodiment of the present invention, the photoelectronic element is an OLED including two or more light-emitting layers between the anode and the cathode. In particular, a so-called tandem OLED includes three light-emitting layers, where one light-emitting layer emits red light, one light-emitting layer emits green light, and one light-emitting layer emits blue light, and additional layers such as charge generation layers, charge blocking layers, or charge transport layers may be selectively included between the individual light-emitting layers. In a further embodiment, the light-emitting layers are stacked adjacent to each other. In a further embodiment, the tandem OLED includes a charge generation layer between each of the two light-emitting layers. Also, adjacent light-emitting layers, or light-emitting layers separated by a charge generation layer, may be merged.
[0177] The substrate may also be formed from any material or a composition thereof. Most often, a glass slide is used as the substrate. Alternatively, a thin metal layer (e.g., copper, gold, silver, or aluminum film), or a plastic film or plastic slide may be used. This can allow for an even higher level of flexibility. The anode layer A is composed of a material from which a nearly (essentially) transparent film can be obtained. Since at least one of the two electrodes must be (essentially) transparent in order to allow light emission from the OLED, one of the anode layer A or cathode layer C is transparent. Preferably, the anode layer A contains or consists of a large amount of transparent conductive oxides (TCOs). Such anode layer A may also include, for example, indium tin oxide, aluminum zinc oxide, fluorine-doped tin oxide, indium zinc oxide, PbO, SnO, zirconium oxide, molybdenum oxide, vanadium oxide, tungsten oxide, graphite, doped Si, doped Ge, doped GaAs, doped polyaniline, doped polypyrrole and / or doped polythiophene.
[0178] Anode layer A is (essentially) indium tin oxide (ITO) (e.g., (InO3) 0.9 (SnO2) 0.1The anode layer A is composed of transparent conductive oxide (TCO). The roughness of the anode layer A due to the transparent conductive oxide (TCO) can also be mitigated by using a hole injection layer (HIL). The HIL also facilitates the injection of similar charge carriers (i.e., holes) from the TCO to the hole transport layer (HTL). The hole injection layer (HIL) may also contain poly-3,4-ethylenedioxythiophene (PEDOT), polystyrene sulfonic acid (PSS), MoO2, V2O5, CuPC, or CuI, in particular a mixture of PEDOT and PSS. The hole injection layer (HIL) can also prevent the diffusion of metal from the anode layer A to the hole transport layer (HTL). For example, the HIL is poly-3,4-ethylenedioxythiophene:polystyrene sulfonic acid (PEDOT:PSS), poly-3,4-ethylenedioxythiophene (PEDOT), 4,4',4”-tris[phenyl(m-tolyl)amino]triphenylamine (mMTDATA), 2,2',7,7'-tetrakis(n,n-diphenylamino)-9,9'-spirobifluorene (Spiro-TAD), N1,N1'-(biphenyl-4,4'-diyl)bis(N1-phenyl-N4,N4-di-m-tolylbenzene-1,4-diamine (DNTPD), N,N'-nis-(1-naph It is also composed of thalenyl)-N,N'-bis-phenyl-(1,1'-biphenyl)-4,4'-diamine (NPB), N,N'-diphenyl-N,N'-di-[4-(N,N-diphenylamino)phenyl]benzidine (NPNPB), N,N,N',N'-tetrakis(4-methoxyphenyl)benzidine (MeO-TPD), 1,4,5,8,9,11-hexaazatriphenylene-hexacarbonnitrile (HAT-CN), and / or N,N'-diphenyl-N,N'-bis-(1-naphthyl)-9,9'-spirobifluorene-2,7-diamine (Spiro-NPD).
[0179] Adjacent to the anode layer A or hole injection layer (HIL), a hole transport layer (HTL) is typically located. Here, any hole transport compound can be used. For example, electron-rich heteroaromatic compounds such as triarylamines and / or carbazoles can also be used as hole transport compounds. The HTL can reduce the energy barrier between the anode layer A and the light-emitting layer (EML). The hole transport layer (HTL) is also an electron blocking layer (EBL). Preferably, the hole transport compound has a triplet state T1 with a relatively high energy level. For example, the hole transport layer (HTL) is tris(4-carbazolyl-9-ylphenyl)amine (TCTA), poly(4-butylphenyl-diphenylamine) (poly-TPD), poly(4-butylphenyl-diphenylamine) (α-NPD), 4,4'-cyclohexyllidene-bis[N,N-bis(4-methylphenyl)benzeneamine] (TAPC), 4,4',4”-tris[2-naphthyl(phenyl)-amino]triphenylamine (2-TNATA), Spiro-TAD, DNTPD, NPB, NPNPB, MeO-TPD, HAT-CN and / or 9,9'-diphenyl-6-(9-phenyl-9H The HTL may also contain a star-shaped heterocycle such as -carbazole-3-yl)-9H,9'H-3,3'-bicarbazole (TrisPcz). The HTL may also contain a p-doped layer composed of inorganic or organic dopants within the organic hole transport matrix. Examples of inorganic dopants include transition metal oxides such as vanadium oxide, molybdenum oxide, or tungsten oxide. Examples of organic dopants include tetrafluorotetracyanoquinodimethane (F4-TCNQ), copper-pentafluorobenzoic acid (Cu(I)pFBz), or transition metal complexes.
[0180] EBL also includes, for example, 1,3-bis(carbazole-9-yl)benzene (mCP), TCTA, 2-TNATA, 3,3-di(9H-carbazole-9-yl)biphenyl (mCBP), tris-Pcz, 9-(4-tert-butylphenyl)-3,6-bis(triphenylsilyl)-9H-carbazole (CzSi) and / or N,N'-dicarbazolyl-1,4-dimethylbenzene (DCB).
[0181] The luminescent layer (EML) is generally located adjacent to the hole transport layer (HTL). The luminescent layer (EML) contains at least one luminescent molecule. In particular, the EML contains at least one luminescent molecule E according to the present invention. In one embodiment, the luminescent layer contains only the organic molecule according to the present invention. Generally, the EML further contains one or more host materials H. For example, the host material H is 4,4'-bis-(N-carbazolyl)-biphenyl (CBP), mCP, mCBP, dibenzo[b,d]thiophen-2-yltriphenylsilane (Sif87), CzSi, dibenzo[b,d]thiophen-2-yl)diphenylsilane (Sif88), bis[2-(diphenylphosphino)phenyl]ether oxide (DPEPO), 9-[3-(dibenzofuran-2-yl)phenyl]-9H-carbazole, 9-[3-(dibenzofuran-2-yl)phenyl]-9H-carbazole, 9-[3-(dibenzo The following are selected from zothiophen-2-yl)phenyl]-9H-carbazole, 9-[3,5-bis(2-dibenzofuranyl)phenyl]-9H-carbazole, 9-[3,5-bis(2-dibenzothiophenyl)phenyl]-9H-carbazole, 2,4,6-tris(biphenyl-3-yl)-1,3,5-triazine (T2T), 2,4,6-tris(triphenyl-3-yl)-1,3,5-triazine (T3T), and / or 2,4,6-tris(9,9'-spirobifluoren-2-yl)-1,3,5-triazine (TST). The host material H must generally be selected to exhibit first triplet (T1) and first singlet (S1) energy levels that are energetically higher than the first triplet (T1) and first singlet (S1) energy levels of the organic molecule.
[0182] In one embodiment of the present invention, the EML includes a so-called mixed host system having at least one hole-dominant host and one electron-dominant host. In a particular embodiment, the EML includes exactly one luminescent organic molecule according to the present invention, T2T as the electron-dominant host, and a mixed host system comprising a host selected from CBP, mCP, mCBP, 9-[3-(dibenzofuran-2-yl)phenyl]-9H-carbazole, 9-[3-(dibenzofuran-2-yl)phenyl]-9H-carbazole, 9-[3-(dibenzothiophen-2-yl)phenyl]-9H-carbazole, 9-[3,5-bis(2-dibenzofuranyl)phenyl]-9H-carbazole and 9-[3,5-bis(2-dibenzothiophenyl)phenyl]-9H-carbazole as the hole-dominant host. In further embodiments, the EML contains 50-80% by weight, preferably 60-75% by weight, of CBP, mCP, mCBP, a host selected from 9-[3-(dibenzofuran-2-yl)phenyl]-9H-carbazole, 9-[3-(dibenzofuran-2-yl)phenyl]-9H-carbazole, 9-[3-(dibenzothiophen-2-yl)phenyl]-9H-carbazole, 9-[3,5-bis(2-dibenzofuranyl)phenyl]-9H-carbazole and 9-[3,5-bis(2-dibenzothiophenyl)phenyl]-9H-carbazole, 10-45% by weight, preferably 15-30% by weight, of T2T, and 5-40% by weight, preferably 10-30% by weight, of the luminescent molecule according to the present invention.
[0183] Adjacent to the luminescent layer (EML), an electron transport layer (ETL) may be located. Here, any electron transporter can be used. Exemplary examples include electron-deficient compounds such as benzimidazole, pyridine, triazole, triazine, oxadiazole (e.g., 1,3,4-oxadiazole), phosphine oxide, and sulfone. The electron transporter is also a star-shaped heterocycle, such as 1,3,5-tri(1-phenyl-1H-benzo[d]imidazole-2-yl)phenyl (TPBi). The ETL also contains 2,9-bis(naphthalene-2-yl)-4,7-diphenyl-1,10-phenanthroline (NBphen), aluminum-tris(8-hydroxyquinoline) (Alq3), diphenyl-4-triphenylsilylphenylphosphine oxide (TSPO1), 2,7-di(2,2'-bipyridine-5-yl)triphenyl (BPyTP2), dibenzo[b,d]thiophen-2-yltriphenylsilane (Sif87), dibenzo[b,d]thiophen-2-yl)diphenylsilane (Sif88), 1,3-bis[3,5-di(pyridine-3-yl)phenyl]benzene (BmPyPhB) and / or 4,4'-bis-[2-(4,6-diphenyl-1,3,5-triazinyl)]-1,1'-biphenyl (BTB). Selectively, the ETL can also be doped with a substance such as Liq. The electron transport layer (ETL) can also block holes. Alternatively, a hole blocking layer (HBL) can be introduced.
[0184] HBLs include, for example, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline=basocupproine (BCP), bis(8-hydroxy-2-methylquinoline)-(4-phenylphenoxy)aluminum (BAlq), 2,9-bis(naphthalene-2-yl)-4,7-diphenyl-1,10-phenanthroline (NBphen), aluminum-tris(8-hydroxyquinoline)(Alq3), and diphenyl-4-triphenylsilylphenylphosphine oxy It also contains said (TSPO1), 2,4,6-tris(biphenyl-3-yl)-1,3,5-triazine (T2T), 2,4,6-tris(triphenyl-3-yl)-1,3,5-triazine (T3T), 2,4,6-tris(9,9'-spirobifloren-2-yl)-1,3,5-triazine (TST), and / or 1,3,5-tris(N-carbazol)benzol / 1,3,5-tris(carbazole)-9-yl)benzene (TCB / TCP).
[0185] Adjacent to the electron transport layer (ETL), a cathode layer C may be located. The cathode layer C may contain or consist of, for example, a metal (e.g., Al, Au, Ag, Pt, Cu, Zn, Ni, Fe, Pb, LiF, Ca, Ba, Mg, In, W, or Pd) or a metal alloy. For practical reasons, the cathode layer C may also consist of (essentially) opaque metals such as Mg, Ca, or Al. Alternatively or additionally, the cathode layer C may also contain graphite and / or carbon nanotubes (CNTs). Alternatively, the cathode layer C may also contain or consist of nanoscale silver wires.
[0186] The OLED may optionally further include a protective layer (also called an electron injection layer (EIL)) between the electron transport layer (ETL) and the cathode layer C. This layer may also contain lithium fluoride, cesium fluoride, silver, 8-hydroxyquinoline tritium (Liq), Li2O, BaF2, MgO, and / or NaF.
[0187] Selectively, the electron transport layer (ETL) and / or hole blocking layer (HBL) also contain one or more host compounds H.
[0188] To further modify the emission and / or absorption spectra of the emissive layer EML, the emissive layer EML may further contain one or more additional emitter molecules F. Such emitter molecules F may be any emitter molecules known in the art. Preferably, such emitter molecule F is a molecule having a different structure from molecule E according to the present invention. Emitter molecule F is selectively also a TADF emitter. Alternatively, emitter molecule F is also a fluorescent and / or phosphorescent emitter molecule that can selectively shift the emission and / or absorption spectra of the emissive layer EML. For example, triplet and / or singlet excitons can be transferred from the organic emitter molecule according to the present invention to emitter molecule F before relaxing to the ground state S0, and can emit light that is typically red-shifted compared to the light emitted by the organic molecule. Selectively, emitter molecule F can also induce a two-photon effect (i.e., absorption of two photons that are half of the maximum absorption energy).
[0189] Selectively, a photoelectronic device (e.g., an OLED) is, for example, essentially a white photoelectronic device. For example, such a white photoelectronic device also contains at least one (deep) blue emitter molecule and one or more emitter molecules that emit green and / or red light. And selectively, as mentioned above, there may be energy transfer between two or more molecules.
[0190] As used herein, unless otherwise specifically defined in a particular context, the hue designation of emitted and / or absorbed light is as follows: Purple: Wavelength range of >380~420nm Deep blue: Wavelength range >420~480nm Sky blue: Wavelength range of >480~500nm Green: Wavelength range >500~560nm Yellow: Wavelength range >560~580nm Orange: Wavelength range >580~620nm Red: Wavelength range of >620~800nm.
[0191] In relation to the emitter molecule, such hues exhibit maximum emission. For example, a deep blue emitter has maximum emission in the >420-480 nm range, a sky blue emitter has maximum emission in the >480-500 nm range, a green emitter has maximum emission in the >500-560 nm range, and a red emitter has maximum emission in the >620-800 nm range.
[0192] The deep blue emitter can preferably have a maximum emission of less than 480 nm, more preferably less than 470 nm, even more preferably less than 465 nm, and still more preferably less than 460 nm. It is also generally greater than 420 nm, preferably greater than 430 nm, more preferably greater than 440 nm, and still more preferably greater than 450 nm.
[0193] The green emitter has a maximum emission of less than 560 nm, more preferably less than 550 nm, even more preferably less than 545 nm, and still more preferably less than 540 nm. It is also generally greater than 500 nm, more preferably greater than 510 nm, even more preferably greater than 515 nm, and still more preferably greater than 520 nm.
[0194] Therefore, a further aspect of the present invention is 1000 cd / m². 2 In this case, it exhibits an external quantum efficiency of more than 8%, preferably more than 10%, more preferably more than 13%, even more preferably more than 15%, and even more preferably more than 20%, and / or exhibits maximum emission at 420nm to 500nm, preferably 430nm to 490nm, more preferably 440nm to 480nm, and even more preferably 450nm to 470nm, and / or 500 cd / m 2The present invention relates to an OLED exhibiting an LT80 value exceeding 100h, preferably exceeding 200h, more preferably exceeding 400h, even more preferably exceeding 750h, and still more preferably exceeding 1000h. Therefore, a further aspect of the present invention relates to an OLED exhibiting a CIEy color coordinate of less than 0.45, preferably less than 0.30, more preferably less than 0.20, even more preferably less than 0.15, and still more preferably less than 0.10.
[0195] A further aspect of the present invention relates to an OLED that emits light at distinct color points. According to the present invention, the OLED emits light having a narrow emission band (small full width at half maximum (FWHM)). In one embodiment, the OLED according to the present invention emits light having a main emission peak FWHM of less than 0.25 eV, preferably less than 0.20 eV, more preferably less than 0.17 eV, even more preferably less than 0.15 eV, and even more preferably less than 0.13 eV.
[0196] A further aspect of the present invention relates to an OLED that emits light having CIEx and CIEy color coordinates close to the CIEx (=0.131) and CIEy (=0.046) color coordinates of primary blue (CIEx=0.131 and CIEy=0.046) as defined by ITU-R Recommendation BT.2020 (Rec.2020), which is suitable for use in UHD (Ultra High Definition) displays, such as UHD-TVs. Therefore, a further aspect of the present invention relates to an OLED in which the light emission exhibits CIEx color coordinates of 0.02 to 0.30, preferably 0.03 to 0.25, more preferably 0.05 to 0.20, even more preferably 0.08 to 0.18, and even more preferably 0.10 to 0.15, and / or CIEy color coordinates of 0.00 to 0.45, preferably 0.01 to 0.30, more preferably 0.02 to 0.20, even more preferably 0.03 to 0.15, and even more preferably 0.04 to 0.10.
[0197] In further embodiments of the present invention, the composition has a photoluminescence quantum yield (PLQY) of more than 20%, preferably more than 30%, more preferably more than 35%, more preferably more than 40%, more preferably more than 45%, more preferably more than 50%, more preferably more than 55%, even more preferably more than 60%, and even more preferably more than 70% at room temperature.
[0198] In one embodiment, the composition includes the following: (a) an organic molecule according to any one of claims 1 to 7, particularly in the form of an emitter, (b) A host material different from the organic molecule, and (c) Selectively, dyes and / or solvents.
[0199] In particular, the material includes a material selected from the group consisting of at least TADF materials and phosphorescent materials.
[0200] In a further embodiment of the present invention, the composition contains 0.1 to 30% by weight, preferably 0.8 to 15% by weight, and particularly 1.5 to 5% by weight of the organic molecule.
[0201] In a further embodiment of the present invention, the composition comprises a material selected from the group consisting of at least TADF materials and phosphorescent materials.
[0202] In a further embodiment of the present invention, the host material of the composition comprises a structure represented by chemical formula 4, [ka] ...chemical formula 4 Here, Each Ar is independently selected from the following group: C6-C 60 Ariel, C3-C 57 Heteroaryls, halogens, and C1-C 40 C6-C 60 Aryl, and C6-C 60 Ariel, C3-C 57 Heteroaryls, halogens, and C1-C 40 C3-C 57 Heteroaryl, Each A1 is independently selected from the following group: hydrogen, deuterium, C6-C 60 Ariel, C3-C 57 Heteroaryls, halogens, and C1-C 40 C6-C 60 Ariel, C6-C 60 Ariel, C3-C 57 Heteroaryls, halogens, and C1-C 40 C3-C 57 Heteroaryls, and C6-C 60 Ariel, C3-C 57 Heteroaryls, halogens, and C1-C 40 C1-C11 is selectively substituted with one or more residues selected from the group consisting of (hetero)alkyl groups. 40 (Hetero)alkyl.
[0203] In a further embodiment, the present invention relates to a method for manufacturing optoelectronic components. In this case, the organic molecules of the present invention are used.
[0204] In a further embodiment, the present invention relates to a method for generating light in the wavelength range of 440 nm to 470 nm, comprising the following steps: (i) A step of providing a photoelectronic device containing the organic molecule of the present invention, and (ii) The step of applying an electric current to the photoelectronic element.
[0205] Optoelectronic devices, in particular OLEDs according to the present invention, can also be manufactured by vapor deposition and / or liquid processes of any means. Therefore, at least one layer is - Manufactured by a sublimation process, - Manufactured by an organic vapor deposition process, - Manufactured by a carrier gas sublimation process, - Processed with a solution or printed.
[0206] The method used to manufacture optoelectronic devices, particularly OLEDs, according to the present invention is publicly known in the industry. Different layers are individually and sequentially deposited on a suitable substrate by a subsequent deposition process. The individual layers may be identical or deposited using different deposition methods.
[0207] For example, the vapor deposition process includes thermal (co)deposition, chemical vapor deposition, and physical vapor deposition. In the case of active-matrix OLED displays, an AMOLED backplane is used as the substrate. Individual layers are also processed from solutions or dispersions using appropriate solvents. For example, solution deposition processes include spin coating, dip coating, and jet printing. Solution processing is selectively carried out in an inert atmosphere (e.g., a nitrogen atmosphere), and the solvent is completely or partially removed by means known to the art.
[0208] In yet another embodiment, the present invention also relates to an organic luminescent molecule comprising or comprising the structure of the following chemical formula 100: [ka] ...Chemical formula 100 Here, n=0 or 1, X is independent in each case, directly joined, CR 3 R 4 , C=CR 3 R 4 , C=O, C=NR 3 , NR 3 , O, SiR3 R 4 Selected from the group consisting of S, S(O), and S(O)2, R 1 , R 2 , R 3 , R 4 , R I , R II , R III , R IV and R V The group is selected from the following: Hydrogen, deuterium, N(R) 5 )2, OR 5 , Si(R 5 )3, B(OR 5 )2, B(R 5 )2, OSO2R 5 CF3, CN, F, Br, I, C1-C 40 Alkyl, This selectively involves one or more substituents R 5 Replaced by, Here, one or more non-adjacent CH2 groups are selectively R 5 C=CR 5 , C≡C, Si(R 5 )2, Ge(R 5 )2, Sn(R 5 )2, C=O, C=S, C=Se, C=NR 5 , P(=O)(R 5 ), SO, SO2, NR 5 , O, S or CONR 5 Replaced by, C1-C 40 Alkoxy, This selectively involves one or more substituents R 5 Replaced by, Here, one or more non-adjacent CH2 groups are selectively R 5 C=CR 5 , C≡C, Si(R 5 )2, Ge(R 5 )2, Sn(R 5 )2, C=O, C=S, C=Se, C=NR 5 , P(=O)(R 5 ), SO, SO2, NR 5 , O, S or CONR 5Replaced by, C1-C 40 Thioalkoxy, This selectively involves one or more substituents R 5 Replaced by, Here, one or more non-adjacent CH2 groups are selectively R 5 C=CR 5 , C≡C, Si(R 5 )2, Ge(R 5 )2, Sn(R 5 )2, C=O, C=S, C=Se, C=NR 5 , P(=O)(R 5 ), SO, SO2, NR 5 , O, S or CONR 5 Replaced by, C2-C 40 Alkenil, This selectively involves one or more substituents R 5 Replaced by, Here, one or more non-adjacent CH2 groups are selectively R 5 C=CR 5 , C≡C, Si(R 5 )2, Ge(R 5 )2, Sn(R 5 )2, C=O, C=S, C=Se, C=NR 5 , P(=O)(R 5 ), SO, SO2, NR 5 , O, S or CONR 5 Replaced by, C2-C 40 Alkinil, This selectively involves one or more substituents R 5 Replaced by, Here, one or more non-adjacent CH2 groups are selectively R 5 C=CR 5 , C≡C, Si(R 5 )2, Ge(R 5 )2, Sn(R 5 )2, C=O, C=S, C=Se, C=NR 5 , P(=O)(R 5 ), SO, SO2, NR 5 , O, S or CONR 5 Replaced by, Selectively one or more substituents R5 C6-C replaced by 60 Aryl, and Selectively one or more substituents R 5 C2-C replaced by 57 Heteroaryl, R d and R e They are independently selected from the following group: Hydrogen, deuterium, CF3, CN, F, Br, I, C1-C 40 Alkyl, This selectively involves one or more substituents R a Replaced by, Here, one or more non-adjacent CH2 groups are selectively R 5 C=CR 5 , C≡C, Si(R 5 )2, Ge(R 5 )2, Sn(R 5 )2, C=O, C=S, C=Se, C=NR 5 , P(=O)(R 5 ), SO, SO2, NR 5 , O, S or CONR 5 Replaced by, Selectively one or more substituents R a C6-C replaced by 60 Aryl, and Selectively one or more substituents R a C2-C replaced by 57 Heteroaryl, R a In each case, independently, a group consisting of the following is selected: Hydrogen, deuterium, N(R) 5 )2, OR 5 , Si(R 5 )3, B(OR 5 )2, B(R 5 )2, OSO2R 5 CF3, CN, F, Br, I, C1-C 40 Alkyl, This selectively involves one or more substituents R 5 Replaced by, Here, one or more non-adjacent CH2 groups are selectively R 5C=CR 5 , C≡C, Si(R 5 )2, Ge(R 5 )2, Sn(R 5 )2, C=O, C=S, C=Se, C=NR 5 , P(=O)(R 5 ), SO, SO2, NR 5 , O, S or CONR 5 Replaced by, C1-C 40 Alkoxy, This selectively involves one or more substituents R 5 Replaced by, Here, one or more non-adjacent CH2 groups are selectively R 5 C=CR 5 , C≡C, Si(R 5 )2, Ge(R 5 )2, Sn(R 5 )2, C=O, C=S, C=Se, C=NR 5 , P(=O)(R 5 ), SO, SO2, NR 5 , O, S or CONR 5 Replaced by, C1-C 40 Thioalkoxy, This selectively involves one or more substituents R 5 Replaced by, Here, one or more non-adjacent CH2 groups are selectively R 5 C=CR 5 , C≡C, Si(R 5 )2, Ge(R 5 )2, Sn(R 5 )2, C=O, C=S, C=Se, C=NR 5 , P(=O)(R 5 ), SO, SO2, NR 5 , O, S or CONR 5 Replaced by, C2-C 40 Alkenil, This selectively involves one or more substituents R 5 Replaced by, Here, one or more non-adjacent CH2 groups are selectively R 5 C=CR 5 , C≡C, Si(R5 )2, Ge(R 5 )2, Sn(R 5 )2, C=O, C=S, C=Se, C=NR 5 , P(=O)(R 5 ), SO, SO2, NR 5 , O, S or CONR 5 Replaced by, C2-C 40 Alkinil, This selectively involves one or more substituents R 5 Replaced by, Here, one or more non-adjacent CH2 groups are selectively R 5 C=CR 5 , C≡C, Si(R 5 )2, Ge(R 5 )2, Sn(R 5 )2, C=O, C=S, C=Se, C=NR 5 , P(=O)(R 5 ), SO, SO2, NR 5 , O, S or CONR 5 Replaced by, Selectively one or more substituents R 5 C6-C replaced by 60 Aryl, and Selectively one or more substituents R 5 C2-C replaced by 57 Heteroaryl, R 5 In each case, the following groups are selected independently from each other: Hydrogen, deuterium, N(R) 6 )2, OR 6 , Si(R 6 )3, B(OR 6 )2, B(R 6 )2, OSO2R 6 CF3, CN, F, Br, I, C1-C 40 Alkyl, This selectively involves one or more substituents R 6 Replaced by, Here, one or more non-adjacent CH2 groups are selectively R 6 C=CR 6 , C≡C, Si(R 6)2, Ge(R 6 )2, Sn(R 6 )2, C=O, C=S, C=Se, C=NR 6 , P(=O)(R 6 ), SO, SO2, NR 6 , O, S or CONR 6 Replaced by, C1-C 40 Alkoxy, This selectively involves one or more substituents R 6 Replaced by, Here, one or more non-adjacent CH2 groups are selectively R 6 C=CR 6 , C≡C, Si(R 6 )2, Ge(R 6 )2, Sn(R 6 )2, C=O, C=S, C=Se, C=NR 6 , P(=O)(R 6 ), SO, SO2, NR 6 , O, S or CONR 6 Replaced by, C1-C 40 Thioalkoxy, This selectively involves one or more substituents R 6 Replaced by, Here, one or more non-adjacent CH2 groups are selectively R 6 C=CR 6 , C≡C, Si(R 6 )2, Ge(R 6 )2, Sn(R 6 )2, C=O, C=S, C=Se, C=NR 6 , P(=O)(R 6 ), SO, SO2, NR 6 , O, S or CONR 6 Replaced by, C2-C 40 Alkenil, This selectively involves one or more substituents R 6 Replaced by, Here, one or more non-adjacent CH2 groups are selectively R 6 C=CR 6 , C≡C, Si(R 6 )2, Ge(R 6 )2, Sn(R6 )2, C=O, C=S, C=Se, C=NR 6 , P(=O)(R 6 ), SO, SO2, NR 6 , O, S or CONR 6 Replaced by, C2-C 40 Alkinil, This selectively involves one or more substituents R 6 Replaced by, Here, one or more non-adjacent CH2 groups are selectively R 6 C=CR 6 , C≡C, Si(R 6 )2, Ge(R 6 )2, Sn(R 6 )2, C=O, C=S, C=Se, C=NR 6 , P(=O)(R 6 ), SO, SO2, NR 6 , O, S or CONR 6 Replaced by, Selectively one or more substituents R 6 C6-C replaced by 60 Aryl, and Selectively one or more substituents R 6 C2-C replaced by 57 Heteroaryl, R 6 In each case, the following groups are selected independently from each other: Hydrogen, deuterium, OPh, CF3, CN, F, C1-C5 alkyl, Here, one or more hydrogen atoms are selectively and independently substituted with deuterium, CN, CF3, or F. C1-C5 alkoxy, Here, one or more hydrogen atoms are selectively and independently substituted with deuterium, CN, CF3, or F. C1-C5 thioalkoxy, Here, one or more hydrogen atoms are selectively and independently substituted with deuterium, CN, CF3, or F. C2-C5 alkenyl, Here, one or more hydrogen atoms are selectively and independently substituted with deuterium, CN, CF3, or F. C2-C5 alkynyl, Here, one or more hydrogen atoms are selectively and independently substituted with deuterium, CN, CF3, or F. C6-C molecules selectively substituted with one or more C1-C5 alkyl substituents 18 Ariel, C2-C molecules selectively substituted with one or more C1-C5 alkyl substituents 17 Heteroaryl, N(C6-C 18 Ariel) 2, N(C2-C 17 Heteroaryl)2, and N(C2-C 17 (Heteroaryl)(C6-C 18 Ariel), Here, substituent R a , R d , R e and R 5 These are, independently of each other, one or more substituents R a , R d , R e and R 5 Along with selectively forming monocyclic or polycyclic, aliphatic, aromatic, heteroaromatic and / or benzo-condensed ring systems, Here, substituent R 1 , R 2 , R 3 , R 4 , R 5 , R I , R II , R III , R IV and R V These are, independently of each other, one or more substituents R 1 , R 2 , R 3 , R 4 , R 5 , R I , R II , R III , R IV and R V Along with this, it selectively forms monocyclic or polycyclic, aliphatic, aromatic, heteroaromatic, and / or benzo-condensed ring systems.
[0209] Examples General synthesis method I [ka]
[0210] General procedure for synthesis: AAV1: In a mixture of toluene and water (volume ratio 4:1), suspensions of I-1 (1.3 equivalents), I-2 (1.0 equivalent), tetrakis(triphenylphosphine)-palladium(0) (CAS-No. 14221-01-3, 0.05 equivalents), and K2CO3 (CAS-No. 584-08-7, 2.0 equivalents) were stirred under reflux for 5 hours. After cooling to room temperature, an aqueous workup was performed, and the crude product was purified by recrystallization or column chromatography. The desired compound I-3 was obtained as a solid.
[0211] AAV2: In degassed xylene, a suspension of I-3 (1.0 equivalent), I-4 (1.0 equivalent), tris(dibenzylideneacetone)-dipalladium(0) (CAS-No. 51364-51-3, 0.01 equivalent), tri-tert-butylphosphonium tetrafluoroborate (CAS-No. 131274-22-1, 0.04 equivalent), and sodium tert-butoxide (CAS-No. 865-48-5, 3.0 equivalent) was stirred at 130°C for 24 hours. After cooling to room temperature, an aqueous workup was performed, and the crude product was purified by recrystallization or column chromatography. The desired compound I-5 was obtained as a solid.
[0212] AAV3: In a degassed mixture of toluene and water (volume ratio 4:1), suspensions of I-5 (1.0 equivalent), I-6 (1.25 equivalent), tris(dibenzylideneacetone)-dipalladium(0) (CAS-No. 51364-51-3, 0.01 equivalent), X-Phos (CAS-No. 564483-18-7, 0.04 equivalent), and K3PO4 (CAS-No. 7778-53-2, 3.5 equivalent) were stirred under reflux for 5 hours. After cooling to room temperature, an aqueous workup was performed, and the crude product was purified by recrystallization or column chromatography. The desired compound I-7 was obtained as a solid.
[0213] At AAV4:0°C, the I-7 solution in anhydrous tert-butylbenzene (30 mL per 1 mmol of I-7) was stirred with n-butyllithium (2.5 M in hexane, CAS No. 109-72-8, 1.1 equivalents) for 15 minutes. Then, tert-butyllithium (1.6 M in pentane, CAS No. 594-19-4, 2.2 equivalents) was added at 0°C, and the mixture was stirred at 60°C for 1 hour. After lithiation was complete, the mixture was cooled to <-60°C, boron tribromide (99%, CAS No. 10294-33-4, 1.5 equivalents) was added, and the mixture was warmed to room temperature. After stirring at room temperature for 18 hours, the reaction product was quenched with 5% NH3(aq) and extracted with dichloromethane. The combined organic layers were dried over MgSO4, filtered, and concentrated. The target compound P-1 was obtained as a solid by purification using recrystallization or column chromatography.
[0214] General synthesis method II [ka]
[0215] General procedure for synthesis: A suspension of AAV-5:I-8 (1.0 equivalent), bis(pinacolate)diborone (CAS-No. 73183-34-3, 1.7 equivalents), [1,1'-bis(diphenylphosphino)ferrocene]palladium(II) dichloride (CAS-No. 72287-26-4, 0.02 equivalents), and potassium acetate (KOAc, CAS-No. 127-08-2, 4.5 equivalents) was stirred under reflux in degassed dioxane for 18 hours. After cooling to room temperature, an aqueous workup was performed, and the crude product was purified by recrystallization or column chromatography. The desired compound I-2 was obtained as a solid.
[0216] Depending on the circumstances, tris(dibenzylideneacetone)-dipalladium(0) (CAS-No. 51364-51-3, 0.01 equivalents) and X-Phos (CAS-No. 564483-18-7, 0.04 equivalents) may be used as catalysts instead of [1,1'-bis(diphenylphosphino)ferrocene]palladium(II) dichloride.
[0217] General synthesis method III [ka]
[0218] General procedure for synthesis: AAV6: In a degassed mixture of toluene and water (volume basis 4:1), suspensions of I-9 (1.0 equivalent), I-10 (2.2 equivalents), tris(dibenzylideneacetone)-dipalladium(0) (CAS-No. 51364-51-3, 0.01 equivalent), X-Phos (CAS-No. 564483-18-7, 0.04 equivalent), and K3PO4 (CAS-No. 7778-53-2, 3.0 equivalents) were stirred under reflux for 2 hours. After cooling to room temperature, an aqueous workup was performed, and the crude product was purified by recrystallization or column chromatography. The desired compound I-4 was obtained as a solid.
[0219] Cyclic voltammetry A cyclic volmogram is obtained when the concentration of organic molecules is 10 in dichloromethane or a suitable solvent and a suitable supporting electrolyte (e.g., 0.1 mol / L tetrabutylammonium hexafluorophosphate). -3 The measurement is performed using a mol / L solution. The measurement is carried out at room temperature in a nitrogen atmosphere using a three-electrode assembly (working electrode and counter electrode: Pt wire, reference electrode: Pt wire), with FeCp2 / FeCp2 as the internal standard. + Correction is performed using [this method]. HOMO data was corrected using ferrocene as an internal standard related to saturated calomel electrodes (SCE).
[0220] Density function theory calculation The molecular structure was optimized using the BP86 function and the RI (Resolution of Identity) approach. Excitation energies were calculated using the (BP86) optimized structure via the TD-DFT (Time-Dependent DFT) method. Orbital energies and excited-state energies were calculated using the B3LYP function. The Def2-SVP basic set and m4-grid were used for numerical integration. The Turbomole program package was used for all calculations.
[0221] optical physical measurements Sample preparation: Spin coating Equipment: Spin150, SPS euro The sample concentration is 10 mg / ml when dissolved in a suitable solvent. Program: 1) 400 U / min for 3 seconds, then 1000 U / min for 20 seconds (1000 Upm / s). 3) 4000 U / min for 10 seconds (1000 Upm / s). After coating, the film was dried at 70°C for 1 minute.
[0222] Photoluminescence spectroscopy and time-correlated single-photon counting (TCSPC) Steady-state emission spectroscopy is recorded using a Model FluoroMax-4 (Horiba Scientific) equipped with a 150W xenon-Arc lamp, excitation and emission monochromator, Hamamatsu R928 photomultiplier tube, and time-correlated single-photon counting option. Standard correction fits are used to correct the emission and excitation spectra.
[0223] The excited state lifetime is determined using the same system employing the TCSPC method, along with the FM-2013 equipment and the Horiba Yvon TCSPC hub.
[0224] Excitation light source: NanoLED 370 (Wavelength: 371nm, Pulse duration: 1.1ns) NanoLED 290 (Wavelength: 294nm, Pulse duration: <1ns) SpectraLED 310 (wavelength: 314nm) SpectraLED 355 (wavelength: 355nm) Data analysis (exponential fitting) is performed using the DataStation and DAS6 analysis software suites. The fit is determined using the chi-squared test.
[0225] Photoluminescence quantum yield measurement For photoluminescence quantum yield (PLQY) measurements, the Absolute PL quantum yield measurement system C9920-03G (Hamamatsu Photonics) was used. Quantum yield and CIE coordinates were determined using software U6039-05 version 3.6.0.
[0226] The maximum emission is expressed in nm, the quantum yield Φ is expressed in %, and the CIE coordinates are expressed in x,y values.
[0227] PLQY is determined using the following protocol: 1) Quality Assurance: Anthracene (known concentration) in ethanol will be used as the standard. 2) Excitation wavelength: The maximum absorption of the organic molecule is determined, and this wavelength is used to excite the molecule. 3) Measurement Quantum yield is measured for a solution or film sample in a nitrogen atmosphere. The yield is calculated using the following equation:
number
[0228] Manufacturing and characterization of optoelectronic devices Optoelectronic elements, such as OLED elements containing organic molecules according to the present invention, can also be manufactured by a vacuum deposition method. When a layer contains one or more compounds, the weight percentage of one or more compounds is expressed in %. Since the total weight percentage value is 100%, if no value is specified, the fraction of the compound is the same as the difference between the specified value and 100%.
[0229] Unoptimized OLEDs are characterized by measuring their electroluminescence spectrum using standard methods and determining their intensity and current-dependent external quantum efficiency (%), calculated using the light and current detected by the photodiode. The lifetime of the OLED element is extracted from the change in brightness while operating at a constant current density. The LT50 value corresponds to the time when the measured brightness has decreased to 50% of the initial brightness; similarly, LT80 corresponds to the time when the measured brightness has decreased to 80% of the initial brightness, and LT95 corresponds to the time when the measured brightness has decreased to 95% of the initial brightness.
[0230] Accelerated lifetime measurements are performed (e.g., by applying increased current density). For example, 500 cd / m². 2 In this case, the LT80 value is determined using the following formula:
number
[0231] HPLC-MS HPLC-MS analysis is performed using an Agilent HPLC (1100 series) equipped with an MS detector (Thermo LTQ XL).
[0232] For example, a typical HPLC method is as follows: From Agilent (ZORBAX Eclipse Plus 95Å C18, 4.6×150mm, 3.5μm HPLC column), a reversed-phase column of 4.6mm×150mm and a particle size of 3.5μm are used for HPLC. HPLC-MS measurements are performed at room temperature (rt) according to the following gradient. [Table 1] The following solvent mixture was used: [Table 2] Take a 5 μL injection volume from a 0.5 mg / mL concentration analyte solution for measurement. The ionization of the probe is positive (APCI + ) Ionization mode or negative (APCI - In ionization mode, this is performed using an APCI (Atmospheric Pressure Chemical Ionization) source.
[0233] Example 1 [ka]
[0234] Example 1 was synthesized as follows: AAV1 (44% yield), where starting materials I-1 and I-2 are represented as 1,3-dibromo-2,5-dichlorobenzene (CAS-No. 81067-41-6) and 8-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-7H-benzo[c]carbazole (CAS-No. 2259354-30-6), where the latter is synthesized in 80% yield from 8-bromo-7H-benzo[c]carbazole (CAS-No. 1686099-80-8) by AAV5. AAV2 (39% yield), where I-4 is represented as 4'-(1,1-dimethylethyl)-N-[4'-(1,1-dimethylethyl)[1,1'-biphenyl]-4-yl]-[1,1'-biphenyl]-4-amine (CAS-No. 1078705-10-8), where the latter was synthesized in 90% yield from bis(4-bromophenyl)amine (CAS-No. 16292-17-4) and 4-tert-butylbenzeneboronic acid (CAS-No. 123324-71-0) by AAV6. AAV3 (57% yield), where compound I-6 is represented as 4-tert-butylbenzeneboronic acid (CAS-No. 123324-71-0), and AAV4 (14% yield). MS (LC-MS, APPI ion source): rt: 8.8 mins at 866 m / z.
[0235] In Example 1 (2 wt%), the maximum emission was 460 nm, the CIEx coordinate was 0.14, and the CIEy coordinate was 0.12. The photoluminescence quantum yield (PLQY) was 64%.
[0236] Additional examples of organic molecules of the present invention [ka] [ka] JPEG0007902197000102.jpg105139 [ka] [ka] [ka]
Claims
1. Organic molecules with the structure of chemical formula V: 【Transformation 5】 ...Chemical formula V Here, R ｂ In each case, it is hydrogen, R1 is a Ph selectively substituted with one or more substituents independently selected from the group consisting of Me, iPr, and tBu. Ra is independently selected in each case from the following group: hydrogen, t Bu, and, Ph is selectively substituted with one or more substituents independently selected from the group consisting of Me, i Pr, and t Bu.
2. Composition including the following: (a) The organic molecule according to claim 1, particularly in emitter form, (b) A host material different from the organic molecule, and (c) Selectively, dyes and / or solvents, In particular, the composition comprises at least one material selected from the group consisting of TADF materials and phosphorescent materials.
3. The composition according to claim 2, comprising 0.1 to 30% by weight, preferably 0.8 to 15% by weight, and particularly 1.5 to 5% by weight of the organic molecule, and further comprising at least one material selected from the group consisting particularly of TADF materials and phosphorescent materials.
4. The host material comprises a structure represented by chemical formula 4, according to claim 2: 【Transformation 7】 ...Chemical formula 4 Here, Each Ar is independently selected from the following group: C ６ -C ６０ aryl, C ３ -C ５７ heteroaryl, halogen and C １ -C ４０ optionally substituted with one or more residues selected from the group consisting of (hetero)alkyl, C ６ -C ６０ aryl, and C ６ -C ６０ Ariel, C ３ -C ５７ Heteroaryls, halogens, and C １ -C ４０ C is selectively substituted with one or more residues selected from the group consisting of (hetero)alkyl groups. ３ -C ５７ Heteroaryl, Each A １ These are selected independently from the following group: hydrogen, deuterium, C ６ -C ６０ Ariel, C ３ -C ５７ Heteroaryls, halogens, and C １ -C ４０ C is selectively substituted with one or more residues selected from the group consisting of (hetero)alkyl groups. ６ -C ６０ Ariel, C ６ -C ６０ Ariel, C ３ -C ５７ Heteroaryls, halogens, and C １ -C ４０ C is selectively substituted with one or more residues selected from the group consisting of (hetero)alkyl groups. ３ -C ５７ Heteroaryls, and C ６ -C ６０ Ariel, C ３ -C ５７ Heteroaryls, halogens, and C １ -C ４０ C is selectively substituted with one or more residues selected from the group consisting of (hetero)alkyl groups. １ -C ４０ (Hetero)alkyl.
5. A photoelectronic element comprising, in particular, an organic molecule according to claim 1 or a composition according to claim 4, as a light-emitting emitter.
6. The photoelectronic element is selected from the group consisting of the following, as described in claim 5: Organic diodes Organic light-emitting diode (OLED) • Light-emitting electrochemical cell OLED sensor ・Organic solar cells Organic transistors Organic field-effect transistor • Organic lasers, and - Down-conversion element.
7. The optoelectronic device according to claim 5, comprising a host material having a structure represented by chemical formula 4: 【Transformation 8】 ...Chemical formula 4 Here, Each Ar is independently selected from the following group: C ６ -C ６０ Ariel, C ３ -C ５７ Heteroaryls, halogens, and C １ -C ４０ C is selectively substituted with one or more residues selected from the group consisting of (hetero)alkyl groups. ６ -C ６０ Aryl, and C ６ -C ６０ Ariel, C ３ -C ５７ Heteroaryls, halogens, and C １ -C ４０ C is selectively substituted with one or more residues selected from the group consisting of (hetero)alkyl groups. ３ -C ５７ Heteroaryl, Each A １ These are selected independently from the following group: hydrogen, deuterium, C ６ -C ６０ Ariel, C ３ -C ５７ Heteroaryls, halogens, and C １ -C ４０ C is selectively substituted with one or more residues selected from the group consisting of (hetero)alkyl groups. ６ -C ６０ Ariel, C ６ -C ６０ Ariel, C ３ -C ５７ Heteroaryls, halogens, and C １ -C ４０ C is selectively substituted with one or more residues selected from the group consisting of (hetero)alkyl groups. ３ -C ５７ Heteroaryls, and C ６ -C ６０ Ariel, C ３ -C ５７ Heteroaryls, halogens, and C １ -C ４０ C is selectively substituted with one or more residues selected from the group consisting of (hetero)alkyl groups. １ -C ４０ (Hetero)alkyl.
8. -substrate, -anode, - Cathode, and - Includes a light-emitting layer, The anode or cathode is disposed on the substrate, The photoelectronic element according to claim 5, wherein the light-emitting layer is disposed between the anode and the cathode and contains the organic molecule or the composition.
9. (i) the step of providing the optoelectronic element according to claim 5, (ii) A method for generating light in the wavelength range of 440 nm to 470 nm, comprising the step of applying an electric current to the photoelectronic element.
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Organic molecules for optoelectronic devices
WO2020135953A1