CN114094023A - Organic electroluminescent element containing triphenyltriindene-based compound - Google Patents

Organic electroluminescent element containing triphenyltriindene-based compound Download PDF

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CN114094023A
CN114094023A CN202111353380.3A CN202111353380A CN114094023A CN 114094023 A CN114094023 A CN 114094023A CN 202111353380 A CN202111353380 A CN 202111353380A CN 114094023 A CN114094023 A CN 114094023A
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CN114094023B (en
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姜卫东
张海威
曹建华
董焕章
唐怡杰
邸庆童
边坤
郭文龙
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Shanghai 800 Million Spacetime Advanced Material Co ltd
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    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
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Abstract

The invention discloses a hole transport layer and a charge blocking layer containing a triphenyltriindene-based compound. By using a compound containing a triphenyltriindene base in the hole transport layer, the voltage, efficiency and lifetime of the OLED can be improved. Furthermore, the voltage, efficiency and lifetime of the OLED can be further improved by using a compound comprising a triphenyltriindene base in the charge blocking layer in the tandem OLED structure.

Description

Organic electroluminescent element containing triphenyltriindene-based compound
Technical Field
The present invention relates to a hole injection layer and a charge generation layer of an organic electroluminescent element. And more particularly, to a hole injection layer and a charge generation layer including a tribenzotriindene-based compound.
Background
In general, the organic light emitting phenomenon refers to a phenomenon in which light is emitted when electric energy is applied to an organic substance. That is, when an organic layer is disposed between an anode and a cathode, if a voltage is applied between the two electrodes, holes are injected from the anode into the organic layer, and electrons are injected from the cathode into the organic layer. When the injected holes and electrons meet, excitons are formed, and when the excitons transition to a ground state, light and heat are emitted.
As one method for efficiently manufacturing an organic electroluminescent element, studies have been made to manufacture an organic layer in the element using a multilayer structure instead of a single layer. In 1987, tang proposed an organic electroluminescent element having a laminated structure of a hole layer and a functional layer of a light-emitting layer, and most of the organic electroluminescent elements currently used include: the light emitting device includes a substrate, an anode, a hole injection layer receiving holes from the anode, a hole transport layer transporting holes, a light emitting layer emitting light by recombination of holes and electrons, an electron transport layer transporting electrons, an electron injection layer receiving electrons from the cathode, and a cathode. The reason why the organic electroluminescent element is formed in a multilayer structure is that since the moving speeds of holes and electrons are different, if the hole injection layer and the transport layer, and the electron transport layer and the electron injection layer are appropriately formed, holes and electrons can be efficiently transported, and the balance between holes and electrons can be achieved in the element, thereby improving the exciton utilization rate.
In an OLED element, a Hole Injection Layer (HIL) facilitates hole injection from the ITO anode to the organic layers. In order to achieve a low element driving voltage, it is important to have a minimum charge injection barrier from the anode. Various HIL materials have been developed, such as triarylamine compounds having shallow HOMO levels, heterocyclic compounds that are very electron deficient, and triarylamine compounds doped with P-type conductivity dopants. In order to improve OLED performance, such as longer element lifetime, higher efficiency and lower voltage, it is important to develop HIL materials with better performance.
Accordingly, in order to overcome the above-described problems of the conventional techniques and further improve the characteristics of the organic electroluminescent element, development of a more stable and effective substance which can be used as a substance for hole injection and transport in the organic electroluminescent element is continuously required.
Disclosure of Invention
The present invention is directed to improving the voltage, efficiency and lifetime of an OLED by using a hole injection layer comprising a triphenyltriindene-based compound. In addition, a charge injection layer comprising the tribenzotriindene-based compound is provided, which can be used for connecting p-type charge generation layers in series OLED structures, and further improves the voltage, efficiency and lifetime of the OLED.
According to an embodiment of the present invention, there is disclosed an organic electroluminescence element including: an anode, a cathode, a hole injection layer disposed between the anode and the cathode, wherein the hole injection layer comprises a compound represented by general formula (I):
Figure BDA0003356603930000021
wherein:
R0～R11each independently selected from hydrogen, deuterium, halogen, nitrile group, substituted or unsubstituted C1-C40Alkyl, substituted or unsubstituted C3-C40With branched alkyl or cycloalkyl, substituted or unsubstituted C1-C40With heteroalkyl, substituted or unsubstituted C2-C40Alkenyl of (a), substituted or unsubstituted C6-C60Aryl, substituted or unsubstituted C6-C60Aryloxy, substituted or unsubstituted C7-C60Aralkyl, substituted or unsubstituted C3-C40Alkylsilyl group, substituted or unsubstituted C6-C60Aryl silyl group of (1), substituted or unsubstituted having C0-C40Or an amine group ofSubstituted or unsubstituted C2-C60Heterocyclic aryl, acyl, carbonyl, carboxylic acid, ester, isonitrile, thio, sulfinyl, sulfonyl, phosphino groups, wherein two or more adjacent groups may optionally be joined or fused to form a further substituted or unsubstituted ring or rings, free from or containing one or more heteroatoms N, P, B, O or S in the formed ring. Preferably R0～R11Not all of hydrogen and deuterium, more preferably said R0、R1And R4～R11Not all are hydrogen and deuterium.
In the present specification, a substituted or unsubstituted ring formed by bonding adjacent groups to each other, and a "ring" refers to a substituted or unsubstituted hydrocarbon ring or a substituted or unsubstituted heterocyclic ring.
According to another embodiment of the present invention, there is also disclosed a tandem organic electroluminescent element including:
an anode, a cathode, a hole injection layer disposed between the anode and the cathode, wherein the hole injection layer comprises a compound represented by general formula (I):
Figure BDA0003356603930000031
wherein:
R0～R11each independently selected from hydrogen, deuterium, halogen, nitrile group, substituted or unsubstituted C1-C40Alkyl, substituted or unsubstituted C3-C40With branched alkyl or cycloalkyl, substituted or unsubstituted C1-C40With heteroalkyl, substituted or unsubstituted C2-C40Alkenyl of (a), substituted or unsubstituted C6-C60Aryl, substituted or unsubstituted C6-C60Aryloxy, substituted or unsubstituted C7-C60Aralkyl, substituted or unsubstituted C3-C40Alkylsilyl group, substituted or unsubstituted C6-C60Aryl silyl group of (1), substituted or unsubstituted having C0-C40Or substituted or unsubstituted C2-C60Heterocyclic aryl, acyl, carbonyl, carboxylic acid, ester, isonitrile, thio, sulfinyl, sulfonyl, phosphino groups, wherein two or more adjacent groups may optionally be joined or fused to form a further substituted or unsubstituted ring or rings, free from or containing one or more heteroatoms N, P, B, O or S in the formed ring. Preferably R0～R11Not all are hydrogen and deuterium.
The hole injection layer and the charge generation layer comprise the tribenzotriindene-based compound or the tribenzotriindene-based compound, so that the voltage of an OLED element can be reduced, the efficiency of the element can be improved, and the service life of the element can be prolonged.
Drawings
Fig. 1 is a schematic diagram of an organic light emitting device that can contain the compound materials disclosed herein.
Fig. 2 is a schematic diagram of a tandem organic light emitting device that can contain the compound materials disclosed herein.
Fig. 3 is a schematic view of another tandem organic light emitting device that may contain the compound materials disclosed herein.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the scope of the present invention is not limited thereto.
OLEDs can be fabricated on a variety of substrates, such as glass, plastic, and metal. Fig. 1 schematically, but without limitation, illustrates an organic light emitting device 100. The figures are not necessarily to scale, and some of the layer structures in the figures may be omitted as desired. The device 100 may include a substrate 101, an anode 110, a hole injection layer 120, a hole transport layer 130, an electron blocking layer 140, an emissive layer 150, a hole blocking layer 160, an electron transport layer 170, an electron injection layer 180, and a cathode 190. The device 100 may be fabricated by sequentially depositing the described layers. The nature and function of the layers, as well as exemplary materials, are described in more detail in U.S. patent US7,279,704B2, columns 6-10, which is incorporated herein by reference in its entirety.
There are more instances of each of these layers. For example, a flexible and transparent substrate-anode combination is disclosed in U.S. Pat. No. 5,844,363, which is incorporated by reference in its entirety. An example of a p-doped hole transport layer is m-MTDATA doped with F4-TCNQ at a molar ratio of 50:1, as disclosed in U.S. patent application publication No. 2003/0230980, which is incorporated by reference in its entirety. Examples of host materials are disclosed in U.S. patent No. 6,303,238 to thompson et al, which is incorporated by reference in its entirety. An example of an n-doped electron transport layer is BPhen doped with Li at a molar ratio of 1:1, as disclosed in U.S. patent application publication No. 2003/0230980, which is incorporated by reference in its entirety. U.S. Pat. Nos. 5,703,436 and 5,707,745, which are incorporated by reference in their entirety, disclose examples of cathodes including composite cathodes having a thin layer of a metal such as Mg: Ag and an overlying layer of transparent, conductive, sputter-deposited ITO. The principles and use of barrier layers are described in more detail in U.S. patent No. 6,097,147 and U.S. patent application publication No. 2003/0230980, which are incorporated by reference in their entirety. Examples of injection layers are provided in U.S. patent application publication No. 2004/0174116, which is incorporated by reference in its entirety. A description of the protective layer may be found in U.S. patent application publication No. 2004/0174116, which is incorporated by reference in its entirety.
The above-described hierarchical structure is provided via non-limiting embodiments. The function of the OLED may be achieved by combining the various layers described above, or some layers may be omitted entirely. It may also include other layers not explicitly described. Within each layer, a single material or a mixture of materials may be used to achieve optimal performance. Any functional layer may comprise several sub-layers. For example, the light emitting layer may have two layers of different light emitting materials to achieve a desired light emission spectrum.
In one embodiment, an OLED may be described as having an "organic layer" disposed between a cathode and an anode. The organic layer may include one or more layers.
In one embodiment, two or more OLED cells can be connected in series to form a series OLED, as shown schematically and without limitation in FIG. 2 for a series OLED device 500. The apparatus 500 may include a substrate 101, an anode 110, a first unit 100, a charge generation layer 300, a second unit 200, and a cathode 290. The first unit 100 includes a hole injection layer 120, a hole transport layer 130, an electron blocking layer 140, an emission layer 150, a hole blocking layer 160, and an electron transport layer 170, the second unit 200 includes a hole injection layer 220, a hole transport layer 230, an electron blocking layer 240, an emission layer 250, a hole blocking layer 260, an electron transport layer 270, and an electron injection layer 280, and the charge generation layer 300 includes an N-type charge generation layer 310 and a P-type charge generation layer 320. The device 500 may be fabricated by sequentially depositing the described layers.
The OLED may also be provided with an encapsulation layer, as shown schematically and non-limitingly in fig. 3 for an organic light emitting device 600, which differs from fig. 2 in that an encapsulation layer 102 may also be included over the cathode 290 to protect against harmful substances from the environment, such as moisture and oxygen. Any material capable of providing an encapsulation function may be used as the encapsulation layer, such as glass or a hybrid organic-inorganic layer. The encapsulation layer should be placed directly or indirectly outside the OLED element. Multilayer film encapsulation is described in U.S. patent US7,968,146B2, the entire contents of which are incorporated herein by reference.
Elements manufactured according to embodiments of the present invention may be incorporated into various consumer products having one or more electronic component modules (or units) of the elements. Some examples of such consumer products include flat panel displays, monitors, medical monitors, televisions, billboards, lights for indoor or outdoor lighting and/or signaling, heads-up displays, fully or partially transparent displays, flexible displays, smart phones, tablet computers, tablet handsets, wearable devices, smart watches, laptop computers, digital cameras, camcorders, viewfinders, micro-displays, 3-D displays, vehicle displays, and taillights.
The materials and structures described herein may also be used in other organic electronic components as previously listed.
As used herein, "top" means furthest from the substrate, and "bottom" means closest to the substrate. Where a first layer is described as being "disposed on" a second layer, the first layer is disposed farther from the substrate. Other layers may be present between the first and second layers, unless it is specified that the first layer is "in contact with" the second layer. For example, a cathode can be described as being "disposed on" an anode even though various organic layers are present between the cathode and the anode.
As used herein, "solution processable" means capable of being dissolved, dispersed or transported in and/or deposited from a liquid medium in the form of a solution or suspension.
A ligand may be referred to as "photoactive" when it is believed that the ligand directly contributes to the photoactive properties of the emissive material. A ligand may be referred to as "ancillary" when it is believed that the ligand does not contribute to the photoactive properties of the emissive material, but the ancillary ligand may alter the properties of the photoactive ligand.
Definitions for substituent terms
Halogen or halide-as used herein, includes fluorine, chlorine, bromine and iodine.
Alkyl groups include straight and branched chain alkyl groups. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, neopentyl, 1-methylpentyl, 2-methylpentyl, 1-pentylhexyl, 1-butylpentyl, 1-heptyloctyl, 3-methylpentyl. In addition, the alkyl group may be optionally substituted. The carbons in the alkyl chain may be substituted with other heteroatoms. Among the above, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl and neopentyl are preferable.
Cycloalkyl groups as used herein comprise cyclic alkyl groups. Preferred cycloalkyl groups are those containing from 3 to 40 ring carbon atoms and include cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4, 4-dimethylcyclohexyl, 1-adamantyl, 2-adamantyl, 1-norbornyl, 2-norbornyl and the like. In addition, the cycloalkyl group may be optionally substituted. The carbon in the ring may be substituted with other heteroatoms.
Alkenyl, as used herein, encompasses straight chain, branched chain and cyclic olefin groups. Preferred alkenyl groups are those containing 2 to 40 carbon atoms. Examples of the alkenyl group include a vinyl group, an allyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, a1, 3-butadienyl group, a 1-methylvinyl group, a styryl group, a 2, 2-diphenylvinyl group, a 1-methylallyl group, a1, 1-dimethylallyl group, a 2-methylallyl group, a 1-phenylallyl group, a 3, 3-diphenylallyl group, a1, 2-dimethylallyl group, a 1-phenyl-1-butenyl group and a 3-phenyl-1-butenyl group. In addition, alkenyl groups may be optionally substituted.
Aryl or aromatic groups as used herein, non-fused and fused systems are contemplated. Preferred aryl groups are those containing from 6 to 60 carbon atoms, more preferably from 6 to 20 carbon atoms, and even more preferably from 6 to 12 carbon atoms. Examples of aryl groups include phenyl, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chicory, perylene and azulene, preferably phenyl, biphenyl, terphenyl, triphenylene, fluorene and naphthalene. In addition, the aryl group may be optionally substituted. Examples of non-fused aryl groups include phenyl, biphenyl-2-yl, biphenyl-3-yl, biphenyl-4-yl, p-terphenyl-4-yl, p-terphenyl-3-yl, p-triphenyl-2-yl, m-terphenyl-4-yl, m-terphenyl-3-yl, m-terphenyl-2-yl, o-tolyl, m-tolyl, p-tolyl, p- (2-phenylpropyl) phenyl, 4 '-methyldiphenyl, 4' -tert-butyl-p-terphenyl-4-yl, o-cumyl, m-cumyl, p-cumyl, 2, 3-xylyl, 3, 4-xylyl, 2, 5-xylyl, mesityl and m-quaterphenyl.
Heterocyclyl or heterocyclic as used herein, aromatic and non-aromatic cyclic groups are contemplated. Heteroaryl also refers to heteroaryl. Preferred non-aromatic heterocyclic groups are those containing 3 to 7 ring atoms, which include at least one heteroatom such as nitrogen, oxygen and sulfur. The heterocyclic group may also be an aromatic heterocyclic group having at least one hetero atom selected from a nitrogen atom, an oxygen atom, a sulfur atom and a selenium atom.
Heteroaryl as used herein, non-fused and fused heteroaromatic groups are contemplated that may contain 1 to 5 heteroatoms. Preferred heteroaryl groups are those containing from 2 to 60 carbon atoms, more preferably from 3 to 20 carbon atoms, more preferably from 3 to 12 carbon atoms. Suitable heteroaryl groups include dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridine indole, pyrrolopyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, bisoxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indoline, benzimidazole, indazole, indenozine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, benzothienopyridine, thienobipyridine, benzothiophenopyridine, cinnolinopyrimidine, selenobenzodipyridine, selenobenzene, preferably dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, triazine, benzimidazole, 1, 2-azaborine, 1, 3-azaborine, 1, 4-azaborine, borazole, and aza analogues thereof. In addition, the heteroaryl group may be optionally substituted.
Further preferably, said substituted or unsubstituted C2-C60The heterocyclic aryl groups are respectively and independently selected from one or more of the following groups II-1 to II-17:
Figure BDA0003356603930000061
wherein the content of the first and second substances,
Z1、Z2each independently selected from hydrogen, deuterium, halogen, hydroxyl, nitrile, nitro, amino, amidino, hydrazine, hydrazone, carboxyl or carboxylate thereof, sulfonic or sulfonate thereof, phosphoric or phosphate thereof, C1-C60Alkyl radical, C2-C60Alkenyl radical, C2-C60Alkynyl, C1-C60Alkoxy radical, C3-C60Cycloalkyl radical, C3-C60Cycloalkenyl radical, C6-C60Aryl, C containing at least one-F, -CN or C1-C10 alkyl group6-C60Aryl, substituted or unsubstituted C6-C60Aryloxy, substituted or unsubstituted C6-C60An arylthioether group, or a substituted or unsubstituted C2-C60A heterocyclic aryl group;
x1 represents an integer of 1 to 4; x2 represents an integer of 1 to 3; x3 represents 1 or 2; x4 represents an integer of 1 to 6; x5 represents an integer of 1 to 5;
T1represents an oxygen atom or a sulfur atom;
Figure BDA0003356603930000071
represents a bond between a substituent and the main structure.
Alkoxy is represented by-O-alkyl, and examples and preferred examples of alkyl are the same as described above. Examples of the alkoxy group having 1 to 40 carbon atoms, preferably 1 to 20 carbon atoms include methoxy, ethoxy, propoxy, butoxy, pentyloxy and hexyloxy. The alkoxy group having 3 or more carbon atoms may be linear, cyclic or branched.
Aryloxy is represented by-O-aryl or-O-heteroaryl. Examples and preferred examples of aryl and heteroaryl groups are the same as described above. Examples of the aryloxy group having 6 to 60 carbon atoms include a phenoxy group and a biphenyloxy group.
Aralkyl as used herein, an alkyl group having an aryl substituent. In addition, the aralkyl group may be optionally substituted. Examples of the aralkyl group include benzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylisopropyl, 2-phenylisopropyl, phenyl tert-butyl, α -naphthylmethyl, 1- α -naphthylethyl, 2- α -naphthylethyl, 1- α -naphthylisopropyl, 2- α -naphthylisopropyl, β -naphthylmethyl, 1- β -naphthylethyl, 2- β -naphthylethyl, 1- β -naphthylisopropyl, 2- β -naphthylisopropyl, p-methylbenzyl, m-methylbenzyl, o-methylbenzyl, p-chlorobenzyl, m-chlorobenzyl, o-chlorobenzyl, p-bromobenzyl, m-bromobenzyl, o-bromobenzyl, p-iodobenzyl, m-iodobenzyl, o-iodobenzyl, p-hydroxybenzyl, m-hydroxybenzyl, o-hydroxybenzyl, p-aminobenzyl, m-aminobenzyl, o-aminobenzyl, p-nitrobenzyl, m-nitrobenzyl, o-nitrobenzyl, p-cyanobenzyl, m-cyanobenzyl, o-cyanobenzyl, 1-2-hydroxy-2-phenylisopropyl and 1-chloro-2-phenylisopropyl. Among the above, benzyl, p-cyanobenzyl, m-cyanobenzyl, o-cyanobenzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylisopropyl and 2-phenylisopropyl are preferable.
The term "substituted or unsubstituted" as used herein means a compound selected from the group consisting of hydrogen, deuterium, a halogen atom, a hydroxyl group, a nitrile group, a nitro group, an amino group, an amidino group, a hydrazine group, a hydrazone group, a carboxyl group or a carboxylate thereof, a sulfonic acid group or a sulfonate thereof, a phosphoric acid group or a phosphate thereof, and C1-C60Alkyl radical, C2-C60Alkenyl radical, C2-C60Alkynyl, C1-C60Alkoxy radical, C3-C60Cycloalkyl radical, C3-C60Cycloalkenyl radical, C6-C60Aryl radical, C6-C60Aryloxy radical, C6-C60An arylthioether group and C2-C60The heterocyclic aryl group may be substituted or unsubstituted with 1 or more substituents, or may be substituted or unsubstituted with substituents formed by connecting 2 or more substituents among the above-exemplified substituents.
It will be understood that when a molecular fragment is described as a substituent or otherwise attached to another moiety, its name may be written depending on whether it is a fragment (e.g., phenyl, phenylene, naphthyl, dibenzofuranyl) or depending on whether it is an entire molecule (e.g., benzene, naphthalene, dibenzofuran). As used herein, these different ways of specifying substituents or linking fragments are considered to be equivalent.
In the compounds mentioned in the present disclosure, a hydrogen atom may be partially or completely replaced by deuterium. Other atoms such as carbon and nitrogen may also be replaced by their other stable isotopes. Substitution of other stable isotopes in the compounds may be preferred due to their efficiency and stability in enhancing elements.
In the compounds mentioned in the present disclosure, multiple substitution means that a double substitution is included up to the range of the maximum available substitutions.
According to an embodiment of the present invention, there is disclosed an organic electroluminescence element including: an anode, a cathode, a hole injection layer disposed between the anode and the cathode, wherein the hole injection layer comprises a compound represented by general formula (I):
Figure BDA0003356603930000081
wherein:
R0～R11each independently selected from hydrogen, deuterium, halogen, nitrile group, substituted or unsubstituted C1-C40Alkyl, substituted or unsubstituted C3-C40With branched alkyl or cycloalkyl, substituted or unsubstituted C1-C40With heteroalkyl, substituted or unsubstituted C2-C40Alkenyl of (a), substituted or unsubstituted C6-C60Aryl, substituted or unsubstituted C6-C60Aryloxy, substituted or unsubstituted C7-C60Aralkyl, substituted or unsubstituted C3-C40Alkylsilyl group, substituted or unsubstituted C6-C60Aryl silyl group of (1), substituted or unsubstituted having C0-C40Or substituted or unsubstituted C2-C60Heterocyclic aryl, acyl, carbonyl, carboxylic acid, ester, isonitrile, thio, sulfinyl, sulfonyl, phosphino groups, wherein two or more adjacent groups may optionally be joined or fused to form a further substituted or unsubstituted ring or rings, free from or containing one or more heteroatoms N, P, B, O or S in the formed ring.
According to another embodiment of the invention, wherein the hole injection layer comprising the compound of formula I is in contact with the anode.
According to another embodiment of the invention, wherein R0～R11Each independently selected from hydrogen, deuterium, nitro, fluoro, nitrile, trifluoromethyl, trifluoromethoxy or pentafluoro-sulfurizationThe group consisting of (a).
According to a preferred embodiment of the present invention, the compound of formula (I) is selected from the group consisting of the following formula CJHM 383-CJHM 514:
Figure BDA0003356603930000082
Figure BDA0003356603930000091
Figure BDA0003356603930000101
Figure BDA0003356603930000111
Figure BDA0003356603930000121
according to one embodiment of the present invention, wherein the hole injection layer is a layer entirely composed of the compound having the general formula I.
According to an embodiment of the present invention, wherein the hole injection layer further comprises an aromatic amine compound.
According to a preferred embodiment of the present invention, wherein the hole injection layer further comprises an aromatic amine compound; preferably, the aromatic amine compound is selected from the group consisting of the following structures:
Figure BDA0003356603930000131
Figure BDA0003356603930000141
Figure BDA0003356603930000151
the invention also provides a material, the raw material of the material comprises the triphenyltriindene-based compound, and preferably, the material is an organic electroluminescent material.
The materials described herein for a particular layer in an organic light emitting element can be used in combination with various other materials present in the element. Combinations of these materials are described in detail in U.S. patent application Ser. No. 0132-0161 of U.S. 2016/0359122A1, the entire contents of which are incorporated herein by reference. The materials described or referenced therein are non-limiting examples of materials that may be used in combination with the compounds disclosed herein, and one skilled in the art can readily review the literature to identify other materials that may be used in combination.
Materials described herein as being useful for particular layers in organic light emitting elements can be used in combination with a variety of other materials present in the element. For example, the light emitting dopants disclosed herein may be used in conjunction with a variety of hosts, transport layers, barrier layers, injection layers, electrodes, and other layers that may be present. Combinations of these materials are described in detail in paragraphs 0080-0101 of patent application US2015/0349273A1, which is incorporated herein by reference in its entirety. The materials described or referenced therein are non-limiting examples of materials that may be used in combination with the compounds disclosed herein, and one skilled in the art can readily review the literature to identify other materials that may be used in combination.
The present invention also provides an organic electroluminescent element comprising a first electrode, a second electrode, and one or more organic layers interposed between the first electrode and the second electrode; at least one of the organic layers contains the triphenyltriindene-based compound.
The organic electroluminescent element includes a cathode, an anode, and at least one light-emitting layer. In addition to these layers, it may also comprise further layers, for example in each case one or more hole-injecting layers, hole-transporting layers, hole-blocking layers, electron-transporting layers, electron-injecting layers, exciton-blocking layers, electron-blocking layers and/or charge-generating layers. An intermediate layer having, for example, exciton blocking function can likewise be introduced between the two light-emitting layers. However, it should be noted that each of these layers need not be present. The organic electroluminescent device described herein may include one light emitting layer, or it may include a plurality of light emitting layers. That is, a plurality of light-emitting compounds capable of emitting light are used in the light-emitting layer. Particularly preferred are systems with three light-emitting layers, wherein the three layers can exhibit blue, green and red light emission. If more than one light-emitting layer is present, at least one of these layers comprises, according to the invention, a compound according to the invention.
Further, the organic electroluminescent element according to the invention does not comprise a separate hole injection layer and/or hole transport layer and/or hole blocking layer and/or electron transport layer, i.e. the light-emitting layer is directly adjacent to the hole injection layer or the anode and/or the light-emitting layer is directly adjacent to the electron transport layer or the electron injection layer or the cathode.
In the other layers of the organic electroluminescent element according to the invention, in particular in the hole-injecting and hole-transporting layer and in the electron-injecting and electron-transporting layer, all materials can be used in the manner conventionally used according to the prior art. The person skilled in the art will thus be able to use all materials known for organic electroluminescent elements in combination with the light-emitting layer according to the invention without inventive effort.
Preference is furthermore given to organic electroluminescent arrangements which are characterized in that one or more layers are applied by means of a sublimation process, with a temperature of less than 10 ℃ in a vacuum sublimation apparatus-5Pa, preferably less than 10-6Pa is applied by vapor deposition. However, the initial pressure may also be even lower, e.g. below 10-7Pa。
Preference is likewise given to organic electroluminescent elements which are characterized in that one or more layers are applied by means of an organic vapor deposition method or by means of carrier gas sublimation, where 10 is-5Pressure between Pa and 1PaThe material is applied. A particular example of this method is the organic vapour jet printing method, in which the material is applied directly through a nozzle and is therefore structured.
Preference is furthermore given to organic electroluminescent elements in which one or more layers are produced from solution, for example by spin coating, or by means of any desired printing method, for example screen printing, flexographic printing, offset printing, photoinitiated thermal imaging, thermal transfer, ink-jet printing or nozzle printing. Soluble compounds, for example obtained by appropriate substitution. These methods are also particularly suitable for oligomers, dendrimers and polymers. Furthermore, hybrid methods are possible, in which, for example, one or more layers are applied from solution and one or more further layers are applied by vapor deposition.
These methods are generally known to those skilled in the art, and they can be applied to an organic electroluminescent element comprising the compound according to the present invention without inventive labor.
The invention therefore also relates to a method for producing an organic electroluminescent element according to the invention, characterized in that at least one layer is applied by means of a sublimation method and/or in that at least one layer is applied by means of an organic vapour deposition method or by means of carrier gas sublimation and/or in that at least one layer is applied from solution by spin coating or by means of a printing method.
Furthermore, the present invention relates to pharmaceutical compositions comprising at least one compound of the invention as indicated above. The same preferences as indicated above for the organic electroluminescent elements apply to the compounds according to the invention. In particular, the compounds may furthermore preferably comprise further compounds. The processing of the compounds according to the invention from the liquid phase, for example by spin coating or by printing methods, requires the preparation of the compounds according to the invention. These formulations may be, for example, solutions, dispersions or emulsions. For this purpose, it may be preferred to use a mixture of two or more solvents. Suitable and preferred solvents are, for example, toluene, anisole, o-xylene, m-xylene or p-xylene, methyl benzoate, mesitylene, tetralin, o-dimethoxybenzene, tetrahydrofuran, methyltetrahydrofuran, tetrahydropyran, chlorobenzene, dioxane, phenoxytoluene, in particular 3-phenoxytoluene, (-) -fenchytone, 1,2,3, 5-tetramethylbenzene, 1,2,4, 5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidone, 3-methylanisole, 4-methylanisole, 3, 4-dimethylanisole, 3, 5-dimethylanisole, acetophenone, alpha-terpineol, benzothiazole, butyl benzoate, cumene, cyclohexanol, cyclohexanone, cyclohexylbenzene, decalin, dodecylbenzene, ethyl benzoate, indane, methyl benzoate, 1-methylpyrrolidone, p-cymene, phenetole, 1, 4-diisopropylbenzene, dibenzyl ether, diethylene glycol butyl methyl ether, triethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 2-isopropylnaphthalene, pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, 1, 1-bis (3, 4-dimethylphenyl) ethane, or a mixture of these solvents.
In addition, unless otherwise specified, all starting materials for use in the present invention are commercially available, and any range recited herein includes any value between the endpoints and any subrange between the endpoints and any value between the endpoints or any subrange between the endpoints.
The invention has the following beneficial effects:
the material which is shown in the formula I and is composed of the tribenzotriindene-based compound or the tribenzotriindene-based compound can reduce the voltage of an OLED element, improve the efficiency of the element and prolong the service life of the element.
In the description of the present invention, "a plurality" means two or more unless otherwise specified; the terms "upper", "lower", and the like, indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, and are only for convenience in describing the present invention and simplifying the description, but do not indicate or imply that the referred devices or elements must have a specific orientation, be constructed and operated in a specific orientation, and thus, should not be construed as limiting the present invention.
The experimental procedures used in the following examples are conventional unless otherwise specified. The experimental raw materials and the related equipments used in the following examples are commercially available unless otherwise specified, and the percentages are by mass unless otherwise specified.
The following examples are provided for testing the performance of OLED materials and devices using the following test apparatus and method:
OLED element performance detection conditions:
luminance and chromaticity coordinates: testing with a photosresearch PR-715 spectrum scanner;
current density and lighting voltage: testing using a digital source table Keithley 2420;
power efficiency: tested using NEWPORT 1931-C.
Example 1
The preparation method of compound CJHM383 comprises the following steps:
the first step is as follows: preparation of Compound Int-1
Figure BDA0003356603930000171
20.0mmol of 4,5,6, 7-tetrafluoro-1H-indene-1, 3(2H) -dione (CAS:29045-72-5), 0.1mol of potassium bromide, 0.1mol of 1M dilute hydrochloric acid aqueous solution and 0.4mol of 30% hydrogen peroxide are mixed with 100mL of toluene, stirred at room temperature for reaction for 1 hour, 50mL of 5% sodium thiosulfate aqueous solution and 50mL of saturated sodium bicarbonate aqueous solution are added, extraction is carried out with ethyl acetate, the organic phase is dried, reduced pressure concentration is carried out, and separation and purification are carried out by a silica gel column, so that the compound Int-1 is obtained as a white solid with the yield of 98%.
The second step is that: preparation of Compound Int-2
Figure BDA0003356603930000181
20.0mmol of Int-1 is dissolved in 80mL of dry DMF, 24.0mmol of cuprous cyanide is added in batches under the protection of nitrogen, the temperature is raised to 55 ℃, the reaction solution is stirred for 10 hours, the reaction solution is poured into 150mL of water, the filtration is carried out, a filter cake is washed by ethyl acetate, a filtrate is collected, an organic phase is separated, an aqueous phase is extracted by ethyl acetate, the drying is carried out, the concentration under reduced pressure is carried out, and the compound Int-2 is obtained, namely a white solid, and the yield is 88%.
The third step: preparation of Compound Int-3
Figure BDA0003356603930000182
15.0mmol of Int-2 and 15.1mmol of benzhydrol (CAS:91-01-0) were dispersed in 150mL of toluene, 5.0mmol of p-toluenesulfonic acid was added, the reaction was stirred under reflux at elevated temperature for 24 hours, the water produced by the reaction was removed by a water separator, cooled to room temperature, 50mL of saturated aqueous potassium carbonate was added, extraction was performed with ethyl acetate, the organic phase was dried, concentrated under reduced pressure and dried, and separated and purified by a silica gel column to obtain compound Int-3 as a white solid with a yield of 85%.
The fourth step: preparation of Compound Int-4
Figure BDA0003356603930000183
42.0mmol of sodium hydride is dispersed in 20mL of dry DME, the temperature is reduced to 0 ℃, 40.0mmol of a solution of tert-butylmalononitrile (CAS:4210-60-0) dissolved in DME is added dropwise, the mixture is heated to room temperature and stirred for reaction for 30 minutes, 19.0mmol of an Int-3 solution dissolved in DME is added dropwise, the mixture is heated to reflux and stirred for reaction for 24 hours, the mixture is cooled to room temperature, 100mL of water is added, filtration is carried out, and a filter cake is washed by water to obtain a compound Int-4 which is an off-white solid with the yield of 80%.
The fifth step: preparation of Compound Int-5
Figure BDA0003356603930000191
15.0mmol of Int-4 is dissolved in 50mL of methanol and 50mL of THF, the temperature is reduced to 0 ℃, 30.0mmol of sodium borohydride is added in batches, the mixture is stirred for reaction for 2 hours, 200mL of saturated saline solution is added, extraction is carried out by ethyl acetate, the organic phase is dried and concentrated under reduced pressure, and the mixture is separated and purified by a silica gel column to obtain the compound Int-5, white solid with the yield of 87%.
And a sixth step: preparation of Compound Int-6
Figure BDA0003356603930000192
Mixing 5.0mL of polyphosphoric acid and 50mL of dry chlorobenzene, adding 10.0mmol of Int-5 in batches under the protection of nitrogen, heating, refluxing, stirring, reacting for 20 hours, cooling to room temperature, pouring the reaction solution into 200mL of saturated sodium bicarbonate aqueous solution, separating an organic phase, extracting an aqueous phase with ethyl acetate, combining and drying the organic phase, filtering, concentrating the filtrate under reduced pressure, and separating and purifying by using a silica gel column to obtain a compound Int-6, namely a white solid with the yield of 38%.
The seventh step: preparation of Compound Int-7
Figure BDA0003356603930000193
Dissolving 10.0mmol of Int-6 in 120mL of dry carbon tetrachloride, adding 31.0mmol of NBS and 1mg of AIBN under the protection of nitrogen, heating to reflux, stirring for reaction for 5 hours, cooling to room temperature, filtering, washing filtrate with saturated aqueous solution of sodium bisulfite, separating an organic phase, drying, filtering, concentrating the filtrate under reduced pressure to dryness, and separating and purifying by using a silica gel column to obtain a compound Int-7, namely a yellow solid, wherein the yield is 78%.
Eighth step: preparation of Compound Int-8
Figure BDA0003356603930000201
Dissolving 10.0mmol of Int-7 in 80mL of dry DMF, adding 32.0mmol of cuprous cyanide, stirring and reacting for 24 hours under the protection of nitrogen, pouring the reaction solution into 150mL of water, filtering, washing a filter cake with water, dissolving with dichloromethane, filtering, drying a filtrate, filtering, concentrating the filtrate under reduced pressure to dryness, and separating and purifying by using a silica gel column to obtain a compound Int-8, yellow solid, yield 88%.
The ninth step: preparation of compound CJHM383
Figure BDA0003356603930000202
Mixing 10.0mmol of Int-8 and 120mL of diphenyl ether, heating to reflux, stirring, reacting for 10 minutes, cooling to 40 ℃, adding 120mL of diethyl ether and 120mL of 4% sodium carbonate aqueous solution, separating an upper organic phase, extracting with 4% sodium carbonate aqueous solution, collecting an aqueous phase, filtering, acidifying the filtrate with concentrated hydrochloric acid to obtain a white precipitate, dropwise adding bromine water until the aqueous phase is purple red, filtering, washing the filter cake with water to neutrality to obtain a compound CJ383, sublimating and purifying to obtain a white solid with the yield of 68%, and obtaining MS (TOF-SIMS) m/z of 542.0846.
Example 2
Preparation of compound CJHM385
Compound CJHM385, MS (TOF-SIMS) m/z:878.0138 was prepared by referring to the synthetic method of example 1, i.e., the same procedure as in example 1 except that diphenylmethanol in the third step of example 1 was replaced with bis (3, 4-bis (trifluoromethoxy) phenyl) methanol and the mass amount of the compound was changed according to the molar amount.
Example 3
Preparation of compound CJHM389
Compound CJHM389, MS (TOF-SIMS) m/z:578.0644 was prepared according to the synthetic method of example 1, i.e., the same procedure as in example 1 except that diphenylmethanol in the third step of example 1 was replaced with bis (4-fluorophenyl) methanol and the mass amount of the compound was changed according to the molar amount.
Example 4
Preparation of compound CJHM390
Compound CJHM390, MS (TOF-SIMS) m/z:614.0471 was prepared by referring to the synthetic method of example 1, i.e., the same procedure as in example 1 except that diphenylmethanol in the third step of example 1 was replaced with bis (3, 4-difluorophenyl) methanol and the mass amount of the compound was changed according to the molar amount.
Example 5
Preparation of Compound CJHM405
Compound CJHM405, MS (TOF-SIMS) m/z:578.0658 was prepared by referring to the synthetic method of example 1, i.e., the same procedure as in example 1 except that diphenylmethanol in the third step of example 1 was replaced with bis (2-fluorophenyl) methanol and the mass amount of the compound was changed according to the molar amount.
Example 6
Preparation of Compound CJHM406
Compound CJHM406, MS (TOF-SIMS) m/z:592.0751 was prepared by referring to the synthetic method of example 1, i.e., the same procedure as in example 1 except that diphenylmethanol in the third step of example 1 was replaced with bis (2-cyanophenyl) methanol and the mass amount of the compound was changed according to the molar amount.
Example 7
Preparation of compound CJHM407
Compound CJHM407, MS (TOF-SIMS) m/z:710.0494 was prepared by referring to the synthetic method of example 1, i.e., the same procedure as in example 1 except that diphenylmethanol in the third step of example 1 was replaced with bis (2- (trifluoromethoxy) phenyl) methanol and the mass amount of the compound was changed according to the molar amount.
Example 8
Preparation of Compound CJHM408
Compound CJHM408, MS (TOF-SIMS) m/z:678.0596 was prepared by referring to the synthetic method of example 1, i.e., the same procedure as in example 1 except that diphenylmethanol in the third step of example 1 was replaced with bis (2- (trifluoromethyl) phenyl) methanol and the mass amount of the compound was changed according to the molar amount.
Example 9
Preparation of compound CJHM409
Compound CJHM409, MS (TOF-SIMS) m/z:878.0140 was prepared by referring to the synthetic method of example 1, i.e., the same procedure as in example 1 except that diphenylmethanol in the third step of example 1 was replaced with bis (2, 4-bis (trifluoromethoxy) phenyl) methanol and the mass amount of the compound was changed according to the molar amount.
Example 10
Preparation of compound CJHM435
Compound CJHM435, MS (TOF-SIMS) m/z:1045.9784 was prepared by referring to the synthetic method of example 1, i.e., the same procedure as in example 1 except that diphenylmethanol in the third step of example 1 was replaced with bis (2,3, 4-tris (trifluoromethoxy) phenyl) methanol and the mass amount of the compound was changed according to the molar amount.
Example 11
Preparation of compound CJHM445
The compound CJHM445, MS (TOF-SIMS) m/z:703.0445 was prepared by referring to the synthetic method of example 1, i.e., the same procedure as in example 1 except that Int-2 in the third step of example 1 was replaced with 2,4,5,6, 7-pentafluoro-1H-indene-1, 3(2H) -dione, diphenyl carbinol in the third step of example 1 was replaced with bis (4- (trifluoromethoxy) phenyl) carbinol, and the mass amount of the compound was changed according to the molar amount.
Example 12
Preparation of compound CJHM444
The compound CJHM444, MS (TOF-SIMS) m/z:535.0799 was prepared by referring to the synthetic method of example 1, i.e., the same procedure as in example 1 except that Int-2 in the third step of example 1 was replaced with 2,4,5,6, 7-pentafluoro-1H-indene-1, 3(2H) -dione, and the mass amount of the compound was changed in terms of molar amount.
Example 13
Preparation of compound CJHM446
The compound CJHM446, MS (TOF-SIMS) m/z:871.0093 was prepared by referring to the synthetic method of example 1, i.e., the same procedure as in example 1 except that Int-2 in the third step of example 1 was replaced with 2,4,5,6, 7-pentafluoro-1H-indene-1, 3(2H) -dione, diphenyl methanol in the third step of example 1 was replaced with bis (3, 4-bis (trifluoromethoxy) phenyl) methanol, and the mass usage of the compound was changed according to the molar amount.
Example 14
Preparation of compound CJHM450
The compound CJHM450, MS (TOF-SIMS) m/z:571.0611 was prepared by referring to the synthetic method of example 1, i.e., the same procedure as in example 1 except that Int-2 in the third step of example 1 was replaced with 2,4,5,6, 7-pentafluoro-1H-indene-1, 3(2H) -dione, diphenyl methanol in the third step of example 1 was replaced with bis (4-fluorophenyl) methanol, and the mass amount of the compound was changed according to the molar amount.
Example 15
Preparation of Compound CJHM451
The compound CJHM451, MS (TOF-SIMS) m/z:607.0424 was prepared by referring to the synthesis method of example 1, i.e., the same procedure as in example 1 except that Int-2 in the third step of example 1 was replaced with 2,4,5,6, 7-pentafluoro-1H-indene-1, 3(2H) -dione, diphenyl methanol in the third step of example 1 was replaced with bis (3, 4-difluorophenyl) methanol, and the mass amount of the compound was changed according to the molar amount.
Example 16
Preparation of Compound CJHM473
The compound CJHM473, MS (TOF-SIMS) m/z 571.0613 was prepared by referring to the synthetic method of example 1, i.e., the same procedure as in example 1 except that Int-2 in the third step of example 1 was replaced with 2,4,5,6, 7-pentafluoro-1H-indene-1, 3(2H) -dione, the diphenylmethanol in the third step of example 1 was replaced with bis (2-fluorophenyl) methanol, and the mass amount of the compound was changed according to the molar amount.
Example 17
Preparation of compound CJHM474
The compound CJHM474, MS (TOF-SIMS) m/z 585.0704 was prepared by referring to the synthetic method of example 1, i.e., the same procedure as in example 1 except that Int-2 in the third step of example 1 was replaced with 2,4,5,6, 7-pentafluoro-1H-indene-1, 3(2H) -dione, diphenyl methanol in the third step of example 1 was replaced with bis (2-cyanophenyl) methanol, and the mass amount of the compound was changed according to the molar amount.
Example 18
Preparation of compound CJHM475
The compound CJHM475, MS (TOF-SIMS) m/z:703.0447 was prepared by referring to the synthetic method of example 1, i.e., the same procedure as in example 1 except that Int-2 in the third step of example 1 was replaced with 2,4,5,6, 7-pentafluoro-1H-indene-1, 3(2H) -dione, diphenyl methanol in the third step of example 1 was replaced with bis (2-trifluoromethoxyphenyl) methanol, and the mass amount of the compound was changed according to the molar amount.
Example 19
Preparation of Compound CJHM476
The compound CJHM476, MS (TOF-SIMS) m/z:671.0547 was prepared by referring to the synthetic method of example 1, i.e., the method steps identical to example 1 except that Int-2 in the third step of example 1 was replaced with 2,4,5,6, 7-pentafluoro-1H-indene-1, 3(2H) -dione, diphenyl methanol in the third step of example 1 was replaced with bis (2-trifluoromethylphenyl) methanol, and the mass amount of the compound was changed depending on the molar amount.
Example 20
Preparation of Compound CJHM478
Compound CJHM478, MS (TOF-SIMS) m/z:871.0093 was prepared by referring to the synthesis method of example 1, i.e., the same procedure as in example 1 except that Int-2 in the third step of example 1 was replaced with 2,4,5,6, 7-pentafluoro-1H-indene-1, 3(2H) -dione, diphenyl methanol in the third step of example 1 was replaced with bis (2, 4-bis (trifluoromethoxy) phenyl) methanol, and the mass usage of this compound was changed according to the molar amount.
Example 21
Preparation of Compound CJHM482
The compound CJHM482, MS (TOF-SIMS) m/z 871.0091 was prepared by referring to the synthesis method of example 1, i.e., the same procedure as in example 1 except that Int-2 in the third step of example 1 was replaced with 2,4,5,6, 7-pentafluoro-1H-indene-1, 3(2H) -dione, diphenyl methanol in the third step of example 1 was replaced with bis (2, 5-bis (trifluoromethoxy) phenyl) methanol, and the mass amount of the compound was changed according to the molar amount.
Example 22
Preparation of Compound CJHM499
Compound CJHM499, MS (TOF-SIMS) m/z:1038.9739 was prepared by referring to the synthetic method of example 1, i.e., the method steps identical to example 1 except that Int-2 in the third step of example 1 was replaced with 2,4,5,6, 7-pentafluoro-1H-indene-1, 3(2H) -dione, diphenyl methanol in the third step of example 1 was replaced with bis (2,3, 4-tris (trifluoromethoxy) phenyl) methanol, and the mass amount of this compound was changed according to the molar amount.
Example 23
Preparation of compound CJHM515
Compound CJHM515, MS (TOF-SIMS) m/z:878.0140 was prepared by referring to the synthetic method of example 1, i.e., the same procedure as in example 1 except that diphenylmethanol in the third step of example 1 was replaced with bis (2, 5-bis (trifluoromethoxy) phenyl) methanol and the mass amount of the compound was changed according to the molar amount.
Example 24
Preparation of compound CJHM516
Compound CJHM516, MS (TOF-SIMS) m/z:1006.9904 was prepared by referring to the synthetic method of example 1, i.e., the same procedure as in example 1 except that diphenylmethanol in the third step of example 1 was replaced with bis (3, 4-bis (trifluoromethoxy) phenyl) methanol and the mass amount of the compound was changed according to the molar amount.
It will be appreciated by those skilled in the art that the above preparation methods are only illustrative examples and that those skilled in the art will be able to modify them to obtain other structures of the compounds of the invention.
Light emitting device embodiments
Firstly, the glass substrate coated with the ITO conductive layer is treated by ultrasonic in a cleaning agent for 30 minutes, washed in deionized water, treated by ultrasonic in an acetone/ethanol mixed solvent for 30 minutes, baked to be completely dried in a clean environment, irradiated by an ultraviolet light cleaning machine for 10 minutes, bombarded on the surface by a low-energy cation beam, then, the treated ITO glass substrate is placed on a bracket and is arranged in a vacuum chamber, and the vacuum chamber is vacuumized to 1 multiplied by 10-5～9×10-3Pa, in
Figure BDA0003356603930000241
The organic layers specified below are vacuum evaporated in sequence,
1) the compound (formula I) of the invention is 3% of HT09 mass as a doping material and HT09 as a host material are evaporated on the ITO anode layer film, the compound (formula I) is used as a Hole Injection Layer (HIL) of the element, and the thickness of the evaporated film is equal to that of the element
Figure BDA0003356603930000242
2) Continuously depositing HT09 on the hole injection layer to form a Hole Transport Layer (HTL) with a thickness of
Figure BDA0003356603930000243
3) H01 as a host material and RD as a dopant material are continuously evaporated on the hole transport layer, RD is 5% of H01 by mass, and the film thickness of the organic luminescent layer obtained by evaporation is equal to that of the organic luminescent layer of the device
Figure BDA0003356603930000244
4) Continuously evaporating a mixture of ET and LiQ on the organic light-emitting layer, wherein the mass ratio of ET to LiQ is 35:65, the mixture is used as an electron transport layer of the element, and the thickness of the evaporated film is equal to
Figure BDA0003356603930000245
5) Continuously evaporating a layer of LiF on the electron transport layer to form an electron injection layer, wherein the thickness of the evaporated film is
Figure BDA0003356603930000246
6) Depositing aluminum metal on the electron injection layer to form a cathode layer of the device, wherein the thickness of the deposited layer is
Figure BDA0003356603930000247
The element was then transferred to a glove box and encapsulated with a glass cover plate and a desiccant to complete the OLED element provided by the present invention.
Comparative example 1
Following the same procedure described above, the compound of the invention (formula I) in step 1) was replaced with F4-TCNQ to give comparative element 1;
comparative example 2
Replacing the compound of the present invention (formula I) in step 1) with S01 according to the same procedure as above to give comparative element 2;
the material structures used in the elements are as follows:
Figure BDA0003356603930000251
the IVL and lifetime characteristics of the elements were measured at different current densities and voltages. At a luminance of 1000cd/m2Under the conditions that the driving voltage, the current efficiency, the full width at half maximum (FWHM) and the emission maximum peak λ max of the light emitting element were measured, and data normalization processing was performed as compared with comparative element 1, the LT 95% lifetime of the element was 10000cd/m at the initial luminance2Measured under the conditions of (1), and subjected to data normalization processing as compared with comparative element 1.
TABLE 1 component data
Figure BDA0003356603930000252
Figure BDA0003356603930000261
Figure BDA0003356603930000271
Figure BDA0003356603930000281
Figure BDA0003356603930000291
As can be seen from the data of table 1 above, the compounds of the present invention show superiority in various aspects over the comparative compounds, as the examples of the present invention have lower driving voltages relative to the comparative examples, indicating that hole injection using the compounds of the present invention is much more efficient and energy efficient than the comparative compounds. Compared with a comparison example, the embodiment of the invention also has higher current efficiency and longer element life. The performance of the compound of the embodiment is far better than that of the comparative example 2, because the alkane ring has a larger electron-pulling substituent, and the redox stability of the material is improved.
Although the invention has been described in detail hereinabove by way of general description, specific embodiments and experiments, it will be apparent to those skilled in the art that many modifications and improvements can be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.

Claims (10)

1. An organic electroluminescent element comprising:
an anode, a cathode, a anode and a cathode,
a cathode electrode, which is provided with a cathode,
a hole injection layer disposed between the anode and the cathode, wherein the hole injection layer comprises a compound represented by general formula (I):
Figure FDA0003356603920000011
wherein:
R0～R11each independently selected from hydrogen, deuterium, halogen, nitrile group, substituted or unsubstituted C1-C40Alkyl, substituted or unsubstituted C3-C40With branched alkyl or cycloalkyl, substituted or unsubstituted C1-C40With heteroalkyl, substituted or unsubstituted C2-C40Alkenyl of (a), substituted or unsubstituted C6-C60Aryl, substituted or unsubstituted C6-C60Aryloxy, substituted or unsubstituted C7-C60Aralkyl, substituted or unsubstituted C3-C40Alkylsilyl group, substituted or unsubstituted C6-C60Aryl silyl group of (1), substituted or unsubstituted having C0-C40Or substituted or unsubstituted C2-C60Heterocyclic aryl, acyl, carbonyl, carboxylic acid, ester, isonitrile, thio, sulfinyl, sulfonyl, phosphino groups, wherein two or more adjacent groups may optionally be joined or fused to form a further substituted or unsubstituted ring or rings, free from or containing one or more heteroatoms N, P, B, O or S in the formed ring.
2. The organic electroluminescent element according to claim 1, wherein R is0～R11Each independently selected from the group consisting of hydrogen, deuterium, nitro, fluoro, nitrile, trifluoromethyl, trifluoromethoxy or pentafluorosulfide, preferably said R0～R11Not all of hydrogen and deuterium, more preferably said R0、R1And R4～R11Not all are hydrogen and deuterium.
3. The organic electroluminescent element according to claim 1, wherein the substituted or unsubstituted C is2-C60The heterocyclic aryl groups are each independently selected from the group consisting of groups represented by II-1 to II-17:
Figure FDA0003356603920000012
Figure FDA0003356603920000021
wherein the content of the first and second substances,
Z1、Z2each independently selected from hydrogen, deuterium, halogen, hydroxyl, nitrile, nitro, amino, amidino, hydrazine, hydrazone, carboxyl or carboxylate thereof, sulfonic or sulfonate thereof, phosphoric or phosphate thereof, C1-C60Alkyl radical, C2-C60Alkenyl radical, C2-C60Alkynyl, C1-C60Alkoxy radical, C3-C60Cycloalkyl radical, C3-C60Cycloalkenyl radical, C6-C60Aryl radicals containing at least one-F, -CN or C1-C10C of alkyl6-C60Aryl, substituted or unsubstituted C6-C60Aryloxy, substituted or unsubstituted C6-C60An arylthioether group, or a substituted or unsubstituted C2-C60A heterocyclic aryl group;
x1 represents an integer of 1 to 4; x2 represents an integer of 1 to 3; x3 represents 1 or 2; x4 represents an integer of 1 to 6; x5 represents an integer of 1 to 5;
T1represents an oxygen atom or a sulfur atom;
Figure FDA0003356603920000023
represents a bond between a substituent and the main structure.
4. The organic electroluminescent element according to claim 1, wherein the hole injection layer containing the compound of the general formula (I) is in contact with an anode.
5. The organic electroluminescent element according to claim 1, wherein the organic electroluminescent element comprises a compound of formula (I) selected from the group consisting of formula CJHM383 to CJHM 514:
Figure FDA0003356603920000022
Figure FDA0003356603920000031
Figure FDA0003356603920000041
Figure FDA0003356603920000051
Figure FDA0003356603920000061
6. the organic electroluminescent element as claimed in claim 1, wherein the hole injection layer is a layer entirely composed of the compound having the general formula (I).
7. The organic electroluminescent element according to claim 1, wherein the hole injection layer further comprises an aromatic amine compound; preferably, the aromatic amine compound is selected from the group consisting of the following structures:
Figure FDA0003356603920000071
Figure FDA0003356603920000081
Figure FDA0003356603920000091
8. an organic electroluminescent material, characterized in that the raw material of the organic electroluminescent material comprises a compound described by formula (I).
9. A tandem organic electroluminescent element comprising:
an anode, a cathode, a anode and a cathode,
a cathode electrode, which is provided with a cathode,
a hole injection layer disposed between the anode and the cathode, wherein the hole injection layer comprises a compound represented by general formula (I):
Figure FDA0003356603920000092
wherein:
R0～R11each independently selected from hydrogen, deuterium, halogen, nitrile group, substituted or unsubstituted C1-C40Alkyl, substituted or unsubstituted C3-C40With branched alkyl or cycloalkyl, substituted or unsubstituted C1-C40With heteroalkyl, substituted or unsubstituted C2-C40Alkenyl of (a), substituted or unsubstituted C6-C60Aryl, substituted or unsubstituted C6-C60Aryloxy, substituted or unsubstituted C7-C60Aralkyl, substituted or unsubstituted C3-C40Alkylsilyl group, substituted or unsubstituted C6-C60Aryl silyl group of (1), substituted or unsubstituted having C0-C40Or substituted or unsubstituted C2-C60Heterocyclic aryl, acyl, carbonyl, carboxylic acid, ester, isonitrile, thio, sulfinyl, sulfonyl, phosphino groups, wherein two or more adjacent groups may optionally be joined or fused to form a further substituted or unsubstituted ring or rings, free from or containing one or more heteroatoms N, P, B, O or S in the formed ring.
10. A consumer product comprising the organic electroluminescent element according to claim 1.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES359987A1 (en) * 1967-11-09 1970-10-01 Ciba Geigy Procedure for obtaining peptides of hypocalcenic effectiveness. (Machine-translation by Google Translate, not legally binding)
CN107353891A (en) * 2017-06-15 2017-11-17 华南理工大学 It is a kind of using three indenes fluorenes units as star-like bipolarity small molecule emitter material of core and preparation method and application

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES359987A1 (en) * 1967-11-09 1970-10-01 Ciba Geigy Procedure for obtaining peptides of hypocalcenic effectiveness. (Machine-translation by Google Translate, not legally binding)
CN107353891A (en) * 2017-06-15 2017-11-17 华南理工大学 It is a kind of using three indenes fluorenes units as star-like bipolarity small molecule emitter material of core and preparation method and application

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