KR20220105911A - Organic electroluminescent device - Google Patents

Abstract

An organic electroluminescent device is disclosed. The organic electroluminescent device comprises a specific combination of organic layers in which a hole transport material is doped with a p-type conductivity doping material. The organic electroluminescent device can provide better device performance, such as improved lifespan and reduced voltage. The organic electroluminescent device may include: an anode; a cathode; a light emitting layer disposed between the anode and the cathode; and a first organic layer disposed between the anode and the light emitting layer.

Description

Organic electroluminescent device {ORGANIC ELECTROLUMINESCENT DEVICE}

The present invention relates to an organic electroluminescent device. In particular, it relates to an organic electroluminescent device and a display assembly having a hole injection layer doped with a p-type conductive material.

An organic electroluminescent device converts electrical energy into light by applying a voltage across the device. In general, an organic electroluminescent device includes an anode, a cathode, and an organic layer interposed between the anode and the cathode. The organic layer of the electroluminescent device includes a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer (including a host material and a doping material), an electron buffer layer, a hole blocking layer, an electron transport layer and an electron injection layer. According to the different functions of the material, the material constituting the organic layer can be divided into a hole injection material, a hole transport material, an electron blocking material, a host material, a light emitting material, an electron buffering material, a hole blocking material, an electron transporting material, a hole blocking material, etc. . When a bias is applied to the device, holes are injected from the anode into the emission layer, and electrons are injected from the cathode into the emission layer. Holes and electrons meet to form excitons, and the excitons recombine to emit light.

The hole injection layer may be a single material layer or may be several types of material layers, where, among the various types of material layers, a hole transport layer material doped with a p-type conductive doping material of a certain proportion is most commonly used, and generally doping The proportion is lower than 5%, but the most common doping proportion is between 1% and 3%. The p-type doping effect is achieved through the strong electron trapping ability of the p-type conductive doping material, and the hole injection and conduction performance is improved. As such, the hole injection layer doped with the p-type conductive material generally has a lower voltage than that of the single layer material, and thus is widely applied. The LUMO energy level of a commercially available p-type conductive material is -5.1eV right and left, and it can be combined with hole transporting materials with a HOMO energy level of -5.1eV left and right in general. There is a wide range of types of hole transport materials used in industry today, including HOMOs with energy levels of -5.2 eV or deeper. However, a p-type conductive material having a LUMO energy level of -5.1 eV or shallower may not achieve the p-type doping effect because the HOMO energy level is effectively matched with a hole transporting material having a HOMO energy level of -5.2 eV or deeper. Therefore, for the wide application of the p-type doping technology, it is necessary to develop and use a p-type conductive doping material whose LUMO energy level is deeper than -5.1 eV. On the other hand, in most OLED devices, the host material of the light emitting layer has a HOMO energy level of -5.4 eV to -5.6 eV left and right, which is much deeper than the hole transport layer material. Therefore, a relatively high potential barrier when holes enter the emission layer from the transport layer. will meet In order to solve this problem, in general, an electron blocking layer (or referred to as a second hole transport layer) having a HOMO energy level between them is inserted between the hole transport layer and the light emitting layer, that is, between the hole injection layer and the light emitting layer. The first hole transport layer and the second hole transport layer are formed to form a structure in which potential energy is gradual. However, hole injection in this structure still faces a total potential barrier height of the same size from the HOMO energy level of the first hole transport layer to the HOMO energy level of the host material of the light emitting layer, and the additionally increased material has more of the interface. It can lead to defects, affecting the lifespan and increasing the complexity of the process. Therefore, if a hole transport material with a deeper HOMO energy level can be used as the only hole transport material layer between the hole injection layer and the light emitting layer, a material in which the potential barrier of holes from the hole injection layer to the light emitting layer is reduced and further increased. may be reduced. Furthermore, if the same hole transport material having a deep HOMO energy level is used for the hole injection layer and doping using a p-type conductive doping material having a LUMO energy level matching the hole transport material, hole injection is also performed with a combination of both. A simple and effective device that can omit the use of various types of hole transport materials can be realized due to the low total potential barrier of

의 HOMO 에너지준위는 -5.28eV이고, JP2009076817A에서 정공 수송층재료로 사용되는 것을 개시하였고, WO2013129835A1에서 전자 차단층재료로 사용되는 것을 개시하였으며 US20150364696A1에서는 호스트 재료로 사용되는 것을 개시하였다. 화합물

의 HOMO 에너지준위는 -5.29eV이고, WO2019088231A1에서 전자 차단층재료로 사용되는 것을 개시하였고, US10103338 및 US20140319472A1에서는 정공 수송층재료로 사용되는 것을 개시하였다. 그러나, 현재 상기 깊은 에너지준위의 수송재료를 정공 주입층재료로 사용하는 동시에 깊은 에너지준위의 p형 전도재료를 도핑하는 것에 대한 개시 및 보도는 없다.In OLED devices, an organic material with a deep HOMO energy level is often used as a transport material, for example, a compound

HOMO energy level of -5.28 eV, JP2009076817A discloses its use as a hole transport layer material, WO2013129835A1 discloses its use as an electron blocking layer material, and US20150364696A1 discloses its use as a host material. compound

has a HOMO energy level of -5.29 eV, and was disclosed to be used as an electron blocking layer material in WO2019088231A1, and used as a hole transport layer material in US10103338 and US20140319472A1. However, there is currently no disclosure or report on using the transport material of the deep energy level as the hole injection layer material and doping the p-type conductive material of the deep energy level.

After in-depth research by applying the above-mentioned ideas, the present inventors included an organic layer of a specific combination of a p-type conductive doping material having a deep LUMO energy level and a hole transporting material having a deep HOMO energy level, and improved device performance. Disclosed is an organic electroluminescent device that can provide and has a simpler manufacturing process.

The present invention provides an organic electroluminescent device having an organic layer of a specific combination in which a p-type conductive doping material of a deep LUMO energy level is doped into a hole transporting material of a deep HOMO energy level in order to solve at least a part of the above problems The purpose. The organic electroluminescent device may provide better device performance, such as an increase in lifetime and a decrease in voltage.

According to an embodiment of the present invention, an organic electroluminescent device is disclosed, which comprises:

anode;

cathode;

a light emitting layer disposed between the anode and the cathode; and

a first organic layer disposed between the anode and the light emitting layer; including,

Here, the first organic layer further contains the compound of Formula 1 and the compound of Formula 2.

Here in Equation 1,

X and Y, identically or differently each time they appear, are selected from NR', CR''R"', O, S or Se;

Z ₁ and Z ₂ are identically or differently each time they appear are selected from O, S or Se;

R, R', R" and R"' are identically or differently each time they appear hydrogen, deuterium, halogen, nitroso group, nitro group, acyl group, carbonyl group, carboxylic acid group, ester group, cyano group, isocyano group, SCN, OCN, SF ₅ , boranyl group, sulfinyl group, sulfonyl group, phosphoroso group, substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, 3 to 20 ring carbon atoms atoms), a substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, 1 to 20 A substituted or unsubstituted alkoxy group having 6 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms A substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted group having 3 to 20 carbon atoms selected from the group consisting of an alkylsilyl group, a substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms, and combinations thereof;

each R can be the same or different, and at least one of R, R', R" and R"' is a group having at least one electron withdrawing group;

In Formula 1, adjacent substituents may be optionally connected to form a ring.

Here, in Equation 2,

X ₁ to X ₈ are identically or differently selected from CR ₁ or N whenever they appear;

L is, identically or differently, each occurrence selected from a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 3 to 30 carbon atoms, or a combination thereof;

Ar ₁ and Ar ₂ , identically or differently each time they appear, are selected from a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms;

R ₁ is identically or differently each time it appears hydrogen, deuterium, halogen, substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, substituted or unsubstituted cyclo having 3 to 20 ring carbon atoms A cycloalkyl group, a substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms group, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, 3~ A substituted or unsubstituted heteroaryl group having 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms ( arylsilyl group), a substituted or unsubstituted amine group having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a nitrile group, an isonitrile group, a thiol group, a sulfinyl group, a sulfonyl group , is selected from the group consisting of a phosphino group and combinations thereof;

In Formula 2, adjacent substituents may be optionally connected to form a ring.

According to another embodiment of the present invention, a display assembly including the above-described organic electroluminescent device is further disclosed.

The present invention discloses an OLED device with a simple structure, comprising an organic layer having a p-type conductive doping material having a relatively deep LUMO energy level and a hole transporting material having a relatively deep HOMO energy level, and is suitable for effective matching of two specific materials. It is advantageous for hole injection and transport. In addition, since the HOMO energy level of the specified hole transport material is similar to the HOMO energy level of the host material of the light emitting layer, the use of the electron blocking layer can be omitted, so that the device structure, that is, the process procedure can be simplified. In addition, since the energy level is better matched, the voltage can be reduced by making it more smooth for holes to be injected from the anode and transported to the light emitting layer. Finally, since the generation of defects at the interface is reduced due to the saving of materials, the lifetime of the device is also improved.

1 is a schematic diagram of an organic electroluminescent device 100 .

OLEDs can be fabricated on several types of substrates (eg, glass, plastic, and metal). 1 schematically and non-limitingly shows an organic electroluminescent device 100 . The drawings are not necessarily drawn to scale, and some layer structures in the drawings may be omitted if necessary. The organic electroluminescent device 100 includes an anode layer 101 , a hole injection layer (HIL) 102 , a hole transport layer (HTL) 103 , an electron blocking layer (also referred to as a second hole transport layer) (EBL) 104 . ), an emission layer (EML) 105 , a hole blocking layer (HBL) 106 , an electron transport layer (ETL) 107 , an electron injection layer (EIL) 108 , and a cathode layer 109 . Device 100 may be fabricated by sequentially depositing the described layers. The properties and functions of each layer and exemplary materials are described in more detail in US Patent US7279704B2 columns 6-10, the entire contents of which are incorporated herein by reference.

Each layer in these layers has more examples. An example is the flexible and transparent substrate-anode combination disclosed in US 5844363, incorporated by reference in its entirety. An example of a p-doped hole transport layer is m-MTDATA doped with F4-TCNQ in a molar ratio of 50:1, as disclosed in US Patent Application Publication No. 2003/0230980, which is incorporated by way of reference in its entirety. US Patent No. 6303238 (to Thompson et al.), incorporated by reference in its entirety, discloses an example of a host material. An example of an n-doped electron transport layer is BPhen doped with Li in a molar ratio of 1:1 as disclosed in U.S. Patent Application Publication No. 2003/0230980, incorporated by reference in its entirety. U.S. Pat. Nos. 5703436 and 5707745, incorporated by reference in their entirety, disclose examples of a cathode, which is a thin layer of metal such as Mg:Ag, overlying a transparent, conductive, sputter-deposited layer. and a composite cathode having an ITO layer deposited thereon. U.S. Patent No. 6097147 and U.S. Patent Application Publication No. 2003/0230980, which are incorporated by reference in their entirety, describe the principle and use of the barrier layer in more detail. US Patent Application Publication No. 2004/0174116, incorporated by reference in its entirety, provides an example of an injection layer. A description of the protective layer may be found in US Patent Application Publication No. 2004/0174116, incorporated by reference in its entirety.

The hierarchical structure is provided through a non-limiting example. The function of the OLED can be realized by combining the various types of layers described above, or some layers can be completely omitted. It may further include other layers not explicitly described. Optimal performance can be achieved by using a single material or a mixture of several types of materials within each layer. Any functional layer may include several sub-layers. For example, the light emitting layer may include two different light emitting materials to realize a desired emission spectrum.

In one embodiment, an OLED can be described as having an “organic layer” disposed between a cathode and an anode. The organic layer may include one or a plurality of layers.

A device manufactured according to an embodiment of the present invention may be integrated into various types of consumer goods having one or a plurality of electronic member modules (or units) of the device. Some examples of such consumer goods include flat panel displays, monitors, medical monitors, televisions, billboards, indoor or outdoor lighting and/or signal launch lights, head-up displays, fully transparent or partially transparent displays, flexible displays, Smartphones, tablets, tablet phones, wearable devices, smart watches, laptop computers, digital cameras, camcorders, viewfinders, micro displays, 3D displays, vehicle displays and tail lights.

The materials and structures described herein may also be used in other organic electronic devices listed above.

As used herein, "top" means located furthest from the substrate, and "bottom" means located closest to the substrate. When a first layer is described as being “disposed” “on” a second layer, the first layer is disposed relatively remote from the substrate. Other layers may exist between the first layer and the second layer, unless it is specified that the first layer “and” the second layer “contact”. For example, it can be explained that even if there are several kinds of organic layers between the cathode and the anode, the cathode is still "disposed" "on" the anode.

As used herein, “solution treatable” means capable of being dissolved, dispersed or transported in and/or precipitated from a liquid medium in the form of a solution or suspension.

In this context, the work function of a metal means the minimum energy required to move one electron from the inside of an object to the surface of the object. All “metal work functions” in the text are negative values, that is, the smaller the number (ie, the larger the absolute value), the greater the energy required to attract electrons to the vacuum level. For example, "the metal work function is less than -5 eV" means that an energy greater than 5 eV is required to attract electrons to the vacuum level.

In the text, the numerical values of the HOMO energy level (highest occupied orbit) and LUMO energy level (lowest unoccupied orbital) are measured by the electrochemical cyclic voltammetry method, and the electrochemical cyclic voltammetry method is the most commonly used organic material energy level. method of measurement. The test method is as follows: Platinum disk electrode as working electrode, Ag/AgNO ₃ The electrode is used as the reference electrode, the platinum wire electrode is the auxiliary electrode, the scan rate is 100 mV/s, the test temperature is 25→, and the solvent is anhydrous DMF. For example, the LUMO energy level of HATCN measured by this method is -4.2eV. In the text, the fact that the energy levels of all “HOMO energy levels” and “LUMO energy levels” all take negative values means that the smaller the number (that is, the greater the absolute value), the deeper the energy level.

Regarding the definition of the term substituent,

Halogen or halide - as used herein includes fluorine, chlorine, bromine and iodine.

The alkyl group includes a straight-chain alkyl group and a branched alkyl group. Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, t-butyl group, n-pentyl group, n-hexyl group, n -heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexa Decyl group, n-heptadecyl group, n-octadecyl group, neopentyl group, 1-methylpentyl group, 2-methylpentyl group, 1-pentylhexyl group, 1-butylpentyl group, 1-heptyloctyl group, 3 -Contains a methylpentyl group. Also, the alkyl group may be optionally substituted. Carbons in the alkyl group chain may be substituted by other heteroatoms. In the above, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, t-butyl group, n-pentyl group and neopentyl group are preferable.

Cycloalkyl groups as used herein include cyclic alkyl groups. Preferred cycloalkyl groups are cycloalkyl groups containing 4 to 10 ring carbon atoms, which are cyclobutyl group, cyclopentyl group, cyclohexyl group, 4-methylcyclohexyl group, 4,4-dimethylcyclohexyl group, 1-adaman tyl group, 2-adamantyl group, 1-norbornyl group (1-norbornyl), 2-norbornyl group, and the like. In addition, the cycloalkyl group may be optionally substituted. Carbons in the ring may be substituted by other heteroatoms.

Alkenyl groups, as used herein, include straight chain olefin groups and branched olefin groups. Preferred alkenyl groups are alkenyl groups containing from 2 to 15 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, a 1,3-butadienyl group (1,3-butadienyl), a 1-methylvinyl group, a styryl group, 2,2-diphenylvinyl group, 1,2-diphenylvinyl group, 1-methylallyl group, 1,1-dimethylallyl group, 2-methylallyl group, 1-phenylallyl group, 2-phenylallyl group, 3-phenylallyl group, 3,3-diphenylallyl group, 1,2-dimethylallyl group, 1-phenyl-1-butenyl group and 3-phenyl-1-butenyl group. Also, the alkenyl group may be optionally substituted.

Alkynyl groups, as used herein, include straight-chain alkynyl groups and branched alkynyl groups. A preferred alkynyl group is an alkynyl group containing from 2 to 15 carbon atoms. Also, the alkynyl group may be optionally substituted.

Aryl or aromatic groups contemplate condensed and unfused systems as used herein. A preferred aryl group is an aryl group containing 6 to 60 carbon atoms, more preferably an aryl group containing 6 to 20 carbon atoms, and still more preferably an aryl group containing 6 to 12 carbon atoms. Examples of the aryl group include a phenyl group, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene (perylene) and azulene (azulene), and preferably includes a phenyl group, biphenyl, terphenyl, triphenylene, fluorene and naphthalene. Also, the aryl group may be optionally substituted. Examples of the non-fused aryl group include a phenyl group, a biphenyl-2-yl group, a biphenyl-3-yl group, a biphenyl-4-yl group, a p-terphenyl-4-yl group, and a p-ter Phenyl-3-yl group, p-terphenyl-2-yl group, m-terphenyl-4-yl group, m-terphenyl-3-yl group, m-terphenyl-2-yl group, o-tolyl group, m-tol Lyl group, p-tolyl group, p-(2-phenylpropyl)phenyl group, 4'-methylbiphenylyl group, 4''-tertbutyl group-p-terphenyl-4-yl group, o-cumenyl group (o-cumenyl group ), m-cumenyl group, p-cumenyl group, 2,3-xylyl group, 3,4-xylyl group, 2,5-xylyl group, mesityl group and m-quaterphenyl group (m -quaterphenyl).

Heterocyclic group or heterocyclyl, as used herein, contemplates aromatic cyclic groups and non-aromatic cyclic groups. A heteroaromatic group also refers to a heteroaryl group. Preferred non-aromatic heterocyclic groups are those containing 3-7 ring atoms and contain at least one heteroatom such as nitrogen, oxygen and sulfur. The heterocyclic group may be an aromatic heterocyclic group having at least one heteroatom selected from a nitrogen atom, an oxygen atom, a sulfur atom and a selenium atom.

Heteroaryl groups, as used herein, are contemplated to include unfused and fused heteroaromatic groups which may contain 1-5 heteroatoms. A preferred heteroaryl group is a heteroaryl group containing 3 to 30 carbon atoms, more preferably a heteroaryl group containing 3 to 20 carbon atoms, even more preferably a heteroaryl group containing 3 to 12 carbon atoms. to be. Suitable heteroaryl groups include dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole ), indolocarbazole, pyridine indole, pyrrolopyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, Oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine (oxadiazine), indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnamon Noline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, benzofuranopyridine, Furanodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, selenophenopyridine, selenophenodipyridine, preferably dibenzothiophene. Dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, triazine, benzimidazole, 1,2-azaborane, 1,3-azaborane, 1,4-azaborane, borazine and their aza analogues. Also, the heteroaryl group may be optionally substituted.

The alkoxy group- is represented by an -O-alkyl group. Examples and preferred examples of the alkyl group are as described above. Examples of the alkoxy group having 1 to 20 carbon atoms and preferably having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group and a hexyloxy group. Alkoxy groups having 3 or more carbon atoms may be straight-chain, cyclic or branched.

The aryloxy group- is represented by an -O-aryl group or an -O-heteroaryl group. Examples and preferred examples of the aryl group and the heteroaryl group are as described above. Examples of the aryloxy group having 6 to 40 carbon atoms include a phenoxy group and a biphenyloxy group.

Arylalkyl group is an alkyl group having an aryl substituent as used herein. In addition, the aralkyl group may be optionally substituted. Examples of the aralkyl group include benzyl group, 1-phenylethyl group, 2-phenylethyl group, 1-phenylisopropyl group, 2-phenylisopropyl group, phenylt-butyl group, α-naphthylmethyl group, 1-α-naphthyl group -Ethyl group, 2-α-naphthylethyl group, 1-α-naphthylisopropyl group, 2-α-naphthylisopropyl group, β-naphthylmethyl group, 1-β-naphthyl-ethyl group, 2-β- Naphthyl-ethyl group, 1-β-naphthylisopropyl group, 2-β-naphthylisopropyl group, p-methylbenzyl group, m-methylbenzyl group, o-methylbenzyl group, p-chlorobenzyl group (p -chlorobenzyl), m-chlorobenzyl group, o-chlorobenzyl group, p-bromobenzyl group (p-bromobenzyl), m-bromobenzyl group, o-bromobenzyl group, p-iodobenzyl group (p- iodobenzyl), m-iodobenzyl group, o-iodobenzyl group, p-hydroxybenzyl group (p-hydroxybenzyl), m-hydroxybenzyl group, o-hydroxybenzyl group, p-aminobenzyl group, m-amino Benzyl group, o-aminobenzyl group, p-nitrobenzyl group, m-nitrobenzyl group, o-nitrobenzyl group, p-cyanobenzyl group, m-cyanobenzyl group, o-cyanobenzyl group, 1- hydroxy-2-phenylisopropyl group and 1-chloro-2-phenylisopropyl group. In the above, the benzyl group, p-cyanobenzyl group, m-cyanobenzyl group, o-cyanobenzyl group, 1-phenylethyl group, 2-phenylethyl group, 1-phenylisopropyl group and 2-phenylisopropyl group desirable.

The term "aza" in azadibenzofuran, aza-dibenzothiophene and the like means that one or more C-H groups in the corresponding aromatic fragment are replaced by a nitrogen atom. For example, azatriphenylene includes dibenzo[f, h]quinoxaline, dibenzo[f,h]quinoline and other analogs having two or more nitrogens in the ring system. Other nitrogen analogs of the above-described aza derivatives can readily be conceived by those skilled in the art, and all such analogs are intended to be encompassed by the terms set forth herein.

In the present invention, unless otherwise defined, a substituted alkyl group, a substituted cycloalkyl group, a substituted heteroalkyl group, a substituted aralkyl group, a substituted alkoxy group, a substituted aryloxy group, a substituted alkenyl group, a substituted aquinyl group, Substituted aryl group, substituted heteroaryl group, substituted alkylsilyl group, substituted arylsilyl group, substituted amino group, substituted acyl group, substituted carbonyl group, substituted carboxylic acid group, substituted ester group, substituted sulfide When any one term from the group consisting of a nyl group, a substituted sulfonyl group, a substituted phosphoroso group is used, it is an alkyl group, a cycloalkyl group, a heteroalkyl group, an aralkyl group, an alkoxy group, an aryloxy group, an alkenyl group, an aquinyl group , an aryl group, a heteroaryl group, an alkylsilyl group, an arylsilyl group, an amino group, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a sulfinyl group, a sulfonyl group and a phosphoroso group. , an unsubstituted alkyl group having 1 to 20 carbon atoms, an unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, an unsubstituted heteroalkyl group having 1 to 20 carbon atoms, unsubstituted aralkyl group having 7 to 30 carbon atoms, unsubstituted alkoxy group having 1 to 20 carbon atoms, unsubstituted aryloxy group having 6 to 30 carbon atoms, unsubstituted aralkyl group having 2 to 20 carbon atoms an alkenyl group, an unsubstituted aquinyl group having 2 to 20 carbon atoms, an unsubstituted aryl group having 6 to 30 carbon atoms, an unsubstituted heteroaryl group having 3 to 30 carbon atoms, 3 to 20 carbon atoms An unsubstituted alkylsilyl group, an unsubstituted arylsilyl group having 6 to 20 carbon atoms, an unsubstituted amino group having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, It means that it may be substituted by one or more selected from an ester group, a cyano group, an isocyano group, a thiol group, a sulfinyl group, a sulfonyl group, a phosphoroso group, and combinations thereof.

It is to be understood that when a molecular fragment is described with a substituent or linked to other moieties in other forms, it is a fragment (eg, a phenyl group, a phenylene group, a naphthyl group, a dibenzofuran group) or whether it is the whole molecule (eg , benzene, naphthalene, or dibenzofuran). As used herein, these different ways of designating a substituent or a fragment linkage are considered equivalent.

In the compounds referred to in the present application, hydrogen atoms may be partially or completely replaced by deuterium. Other elements such as carbon and nitrogen may also be replaced with other stable isotopes thereof. As this improves the efficiency and stability of the device, it may be desirable to substitute other stable isotopes in the compound.

In the compounds mentioned in this application, polysubstitution refers to a range up to the maximum usable substitution including disubstitution. In the compounds mentioned in this application, when any substituent represents polysubstitution (including disubstitution, trisubstitution, tetrasubstitution, etc.), it indicates that the substituent may exist at a plurality of available substitution positions in the linking structure, Substituents present at a plurality of available substitution positions may be of the same structure or of different structures.

In the compounds mentioned herein, for example, adjacent substituents in the compounds cannot be optionally joined to form a ring, unless it is expressly defined that adjacent substituents may optionally be joined to form a ring. In the compounds mentioned in the present invention, that adjacent substituents may be optionally joined to form a ring includes the case where adjacent substituents may be joined to form a ring, and also when adjacent substituents are joined to not form a ring also includes When adjacent substituents are optionally connected to connect the rings, the formed ring may be a monocyclic ring, a polycyclic ring, an alicyclic ring, a heteroalicyclic ring, an aromatic ring or a heteroaromatic ring. In this expression, adjacent substituents may refer to substituents bonded to the same atom, substituents bonded to carbon atoms bonded directly to each other, or substituents bonded to more distant carbon atoms. Preferably, adjacent substituents refer to substituents bonded to the same carbon atom and substituents bonded to carbon atoms bonded directly to each other.

The intention of the expression that adjacent substituents may be optionally linked to form a ring is also intended to contemplate that two substituents bonded to the same carbon atom are linked to each other by a chemical bond to form a ring, which is illustrated by the formula :

The intent of the statement that adjacent substituents may be optionally linked to form a ring is also intended to contemplate that two substituents bonded to a carbon atom directly bonded to each other are linked to each other by a chemical bond to form a ring, which has the formula It is exemplified through:

In addition, the intention of the expression that adjacent substituents may be optionally connected to form a ring is also intended to mean that when one of the two substituents bonded to a carbon atom directly bonded to each other represents hydrogen, the second substituent is on the side where the hydrogen atom is bonded It is intended to assume that they are joined to form a ring. This is exemplified through the formula:

According to an embodiment of the present invention, an organic electroluminescent device is disclosed, which comprises:

anode;

cathode;

a light emitting layer disposed between the anode and the cathode; and

a first organic layer disposed between the anode and the light emitting layer; including,

wherein the first organic layer contains a compound of formula 1 and a compound of formula 2:

Here in Equation 1,

X and Y, identically or differently each time they appear, are selected from NR', CR''R"', O, S or Se;

Z ₁ and Z ₂ are identically or differently each time they appear are selected from O, S or Se;

R, R', R" and R"' are identically or differently each time they appear hydrogen, deuterium, halogen, nitroso group, nitro group, acyl group, carbonyl group, carboxylic acid group, ester group, cyano group, isocyano group, SCN, OCN, SF ₅ , boranyl group, sulfinyl group, sulfonyl group, phosphoroso group, substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, 3 to 20 ring carbon atoms atoms), a substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, 1 to 20 A substituted or unsubstituted alkoxy group having 6 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms A substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted group having 3 to 20 carbon atoms It is selected from the group consisting of an alkylsilyl group, a substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms, and combinations thereof.

each R can be the same or different, and at least one of R, R', R" and R"' is a group having at least one electron withdrawing group;

In Formula 1, adjacent substituents may be optionally connected to form a ring.

Here, in Equation 2,

X ₁ to X ₈ are identically or differently selected from CR ₁ or N whenever they appear;

L is, identically or differently, each occurrence selected from a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 3 to 30 carbon atoms, or a combination thereof;

Ar ₁ and Ar ₂ , identically or differently each time they appear, are selected from a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms;

R ₁ is identically or differently each time it appears hydrogen, deuterium, halogen, substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, substituted or unsubstituted cyclo having 3 to 20 ring carbon atoms A cycloalkyl group, a substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms group, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, 3~ A substituted or unsubstituted heteroaryl group having 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms ( arylsilyl group), a substituted or unsubstituted amine group having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a nitrile group, an isonitrile group, a thiol group, a sulfinyl group, a sulfonyl group , is selected from the group consisting of a phosphino group and combinations thereof;

In Formula 2, adjacent substituents may be optionally connected to form a ring.

In the embodiment, the fact that adjacent substituents in Formula 1 may be optionally connected to form a ring means that there is a case in which adjacent substituents R'' and R"' may be connected to form a ring. For those skilled in the art, it is obvious that the adjacent substituents R'' and R"' in Formula 1 may not be connected to each other to form a ring.

In the embodiment, the fact that adjacent substituents in Formula 2 may be optionally connected to form a ring means that there are cases in which adjacent substituents R ₁ in Formula 2 may be connected to form a ring. For those skilled in the art, it is obvious that the adjacent substituents R ₁ in Formula 2 may not be connected to each other to form a ring.

According to an embodiment of the present invention, X and Y are identically or differently selected from NR' or CR''R"' whenever they appear, and R', R" and R"' have at least one electron withdrawing group. is a group; preferably, R, R', R" and R"' are a group having at least one electron withdrawing group.

According to an embodiment of the present invention, X and Y are identically or differently selected from O, S or Se whenever they appear, and at least one of R is a group having at least one electron withdrawing group; Preferably all R are groups having at least one electron withdrawing group.

According to an embodiment of the present invention, the Hammett constant of the electron withdrawing group is 0.05 or more, preferably 0.3 or more, and more preferably 0.5 or more. The Hammett substituent constant value of the electron withdrawing group of the present invention is 0.05 or more, preferably 0.3 or more, and more preferably 0.5 or more, and the electron withdrawing ability is relatively strong, and the LUMO energy level of the compound is significantly reduced to increase the charge mobility. improving effect can be achieved. It should be explained that the Hammett substituent constant value includes the Hammett substituent para constant and/or meta constant, and as long as one of the para constant and the meta constant satisfies the condition of 0.05 or more, in the present invention It can be used as a selected group.

According to an embodiment of the present invention, the electron withdrawing group is halogen; nitroso group; nitro group; acyl group; carbonyl group; carboxylic acid group; ester group; cyano group; isocyano group; SCN; OCN; SF ₅ ; Boranyl group (Boranyl); sulfinyl group; sulfonyl group; phosphoroso group; aza aromatic ring; and halogen, nitroso group, nitro group, acyl group, carbonyl group, carboxylic acid group, ester group, cyano group, isocyano group, SCN, OCN, SF5, boranyl group, sulfinyl group, sulfonyl group, phosphoroso group ( phosphoroso), any one of the following groups substituted with one or a plurality of azaaromatic rings: an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 ring carbon atoms, A heteroalkyl group having 1 to 20 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, an alkenyl group having 2 to 20 carbon atoms , an aquinyl group having 2 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, a heteroaryl group having 3 to 30 carbon atoms, an alkylsilyl group having 3 to 20 carbon atoms, 6 to 20 an arylsilyl group having two carbon atoms; and combinations thereof;

Preferably, the electron withdrawing group is from the group consisting of F, CF ₃ , OCF ₃ , SF ₅ , SO ₂ CF ₃ , cyano group, isocyano group, SCN, OCN, pyrimidyl group, triazinyl group, and combinations thereof. is chosen

According to an embodiment of the present invention, wherein X and Y are identically or differently each time they appear are selected from the group consisting of:

Here, R ₂ is the same or different whenever it appears hydrogen, deuterium, halogen, nitroso group, nitro group, acyl group, carbonyl group, carboxylic acid group, ester group, cyano group, isocyano group, SCN, OCN, SF5, purple Nyl group (Boranyl), sulfinyl group, sulfonyl group, phosphoroso group (phosphoroso), substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, substituted or unsubstituted having 3 to 20 ring carbon atoms cycloalkyl group, substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, substituted or unsubstituted having 1 to 20 carbon atoms an alkoxy group, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aquinyl group having 2 to 20 carbon atoms, A substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms , is selected from the group consisting of a substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms and combinations thereof;

Preferably, R ₂ is identically or differently each time it appears F, CF ₃ , OCF ₃ , SF ₅ , SO ₂ CF ₃ , cyano group, isocyano group, SCN, OCN, pentafluorophenyl group, 4-cyanotetra It is selected from the group consisting of a fluorophenyl group, a tetrafluoropyridyl group, a pyrimidyl group, a triazinyl group, and combinations thereof;

wherein V and W are identically or differently each time they appear selected from CR _v R _w , NR _v , O, S, Se;

wherein Ar is, identically or differently each time it appears, selected from a substituted or unsubstituted aryl group having 6 to 30 carbon atoms or a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms;

where A, R _a , R _b , R _c , R _d , Re _e , R _f , R _g , R _h , R _v and R _w are identically or differently each time they appear hydrogen, deuterium, halogen, nitroso group, Nitro group, acyl group, carbonyl group, carboxylic acid group, ester group, cyano group, isocyano group, SCN, OCN, SF ₅ , boranyl group, sulfinyl group, sulfonyl group, phosphoroso group, 1- A substituted or unsubstituted alkyl group having 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, a substituted or unsubstituted group having 1 to 20 carbon atoms a heteroalkyl group, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, A substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aquinyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, 3 to 30 carbon atoms A substituted or unsubstituted heteroaryl group having a character, a substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms and combinations thereof;

wherein A is a group having at least one electron withdrawing group, and in any of the above structures, R _a , R _b , R _c , R _d , Re _e , R _f , R _g , R _h , R _v and R _w When one or more of R _a , R _b , R _c , R _d , _Re , R _f , R _g , R _h , R _v and R _w are present, at least one of R a , R b , R c , R d , R g , R h , R v and R w is a group having at least one electron withdrawing group is; Preferably, the group having at least one electron withdrawing group is F, CF ₃ , OCF ₃ , SF ₅ , SO ₂ CF ₃ , cyano group, isocyano group, SCN, OCN, pentafluorophenyl group, 4-cyanotetra It is selected from the group consisting of a fluorophenyl group, a tetrafluoropyridyl group, a pyrimidyl group, a triazinyl group, and combinations thereof.

In this embodiment, "*" represents a position at which the X and Y groups are connected to the dehydrobenzodioxazole ring, dehydrobenzodithiazole ring or dehydrobenzodithiazole ring in Formula 1.

According to an embodiment of the present invention, X and Y are identically or differently each time they appear are selected from the group consisting of:

In this embodiment, "*" represents a position at which the X and Y groups are connected to the dehydrobenzodioxazole ring, dehydrobenzodithiazole ring or dehydrobenzodithiazole ring in Formula 1.

According to an embodiment of the present invention, wherein R is identically or differently each time it appears hydrogen; deuterium; halogen; nitroso group; nitro group; acyl group; carbonyl group; carboxylic acid group; ester group; cyano group; isocyano group; SCN; OCN; SF ₅ ; Boranyl group (Boranyl); sulfinyl group; sulfonyl group; phosphoroso group; an unsubstituted alkyl group having 1 to 20 carbon atoms; an unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms; an unsubstituted alkoxy group having 1 to 20 carbon atoms; an unsubstituted alkenyl group having 2 to 20 carbon atoms; an unsubstituted aryl group having 6 to 30 carbon atoms; an unsubstituted heteroaryl group having 3 to 30 carbon atoms; and halogen, nitroso group, nitro group, acyl group, carbonyl group, carboxylic acid group, ester group, cyano group, isocyano group, SCN, OCN, SF ₅ , boranyl group, sulfinyl group, sulfonyl group and phosphoroso group (phosphoroso) any one of the following groups substituted with one or a plurality of groups: an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 ring carbon atoms, 1 to 20 an alkoxy group having 2 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, a heteroaryl group having 3 to 30 carbon atoms; and combinations thereof.

Preferably, R is identically or differently each time it appears hydrogen; deuterium; methyl group; isopropyl group; NO ₂ ; SO ₂ CH ₃ ; SCF ₃ ; C ₂ F ₅ ; OC ₂ F ₅ ; OCH ₃ ; diphenylmethylsilyl group; phenyl group; methoxyphenyl group; p-methylphenyl group; 2,6-diisopropylphenyl group; biphenyl group; polyfluorophenyl group; difluoropyridyl group; nitrophenyl group; dimethylthiazole group; a vinyl group substituted with one or a plurality of CN or CF ₃ ; an ethynyl group substituted with one of CN or CF ₃ ; dimethylphosphonooxy; diphenylphosphonooxy; F; CF ₃ ; OCF ₃ ; SF ₅ ; SO ₂ CF ₃ ; cyano group; isocyano group; SCN; OCN; trifluoromethylphenyl group; trifluoromethoxyphenyl group; a bis(trifluoromethyl)phenyl group; bis(trifluoromethoxy)phenyl group; 4-cyanotetrafluorophenyl group; a phenyl group or a biphenyl group substituted with one or more of F, CN, or CF ₃ ; tetrafluoropyridyl group; pyrimidyl group; triazinyl group; diphenyl boranyl group; Oxaboraanthryl group (Oxaboraanthryl); and combinations thereof.

이다.According to an embodiment of the present invention, X and Y are

to be.

According to one embodiment of the present invention, wherein R is selected from the group consisting of the same or different each time it appears:

"는 상기 R 그룹이 식 1에서의 데하이드로벤조디옥사졸 고리, 데하이드로벤조디티아졸 고리 또는 데하이드로벤조디티아졸 고리와 연결되는 위치를 나타낸다.In that example, "

" represents the position at which the R group is connected to the dehydrobenzodioxazole ring, dehydrobenzodithiazole ring or dehydrobenzodithiazole ring in Formula 1.

According to an embodiment of the present invention, two R in one compound represented by Formula 1 are the same.

According to one embodiment of the present invention, the compound of Formula 1 has a structure represented by Formula 3:

wherein, two Z structures in Formula 3 are the same, two R structures are the same or different, and Z, X, Y, and R each correspond to an atom or group selected from the atoms or groups shown in the table of claim 11;

Here, the compound having the structure of Formula 3 is selected from Compound 1 to Compound 1356, and for specific structures of Compound 1 to Compound 1356, refer to claim 11.

According to an embodiment of the present invention, L is a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted terphenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted fluorenylidene group, substituted or unsubstituted silafluorenylidene, substituted or unsubstituted carbazolylene, substituted or unsubstituted dibenzofuranylene, substituted or unsubstituted a dibenzothiophenylene group, a substituted or unsubstituted dibenzoselenophenylene group, a substituted or unsubstituted phenanthrylene group, a substituted or unsubstituted triphenylene group, a substituted or unsubstituted a pyridinylene group, a substituted or unsubstituted spirobifluorenylene group, a substituted or unsubstituted anthrylene group, a substituted or unsubstituted pyrenylene group, or a combination thereof; Preferably, L is a substituted or unsubstituted phenylene group, or a substituted or unsubstituted biphenylene group; More preferably, L is a phenylene group or a biphenylene group.

According to an embodiment of the present invention, R ₁ is hydrogen, deuterium, halogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted having 3 to 20 ring carbon atoms selected from a cycloalkyl group, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms; Preferably R ₁ is selected from hydrogen, deuterium, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms.

According to an embodiment of the present invention, Ar ₁ and Ar ₂ are selected from a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 20 carbon atoms; Preferably, Ar ₁ and Ar ₂ are a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a fluorenyl group, a dibenzothienyl group, a spirobifluorenyl group, a pyridyl group or a pyrimidyl group.

According to an embodiment of the present invention, the compound having the structure of Formula 2 is selected from the group consisting of Compound H-1 to Compound H-176, wherein the specific structure of Compound H-1 to Compound H-176 is claimed in claim 15 see

According to an embodiment of the present invention, the organic electroluminescent device further includes a second organic layer disposed between the anode and the light emitting layer, wherein the second organic layer contains the compound of Formula 2.

According to an embodiment of the present invention, the first organic layer is in contact with the anode.

According to an embodiment of the present invention, the weight ratio of the compound of Formula 1 contained in the first organic layer to the total first organic layer is 5% or less, 3% or less, more preferably 2% or less, or 1% or less to be.

According to an embodiment of the present invention, the second organic layer is in contact with the light emitting layer.

According to an embodiment of the present invention, it further includes a third organic layer disposed between the anode and the light emitting layer, wherein the third organic layer contains a compound different from that of the second organic layer.

According to another embodiment of the present invention, a display assembly including the organic electroluminescent device according to any one of the above-described embodiments is further disclosed.

A typical OLED device structure is shown in FIG. 1 . Here, the OLED device 100 includes an anode layer 101 , a hole injection layer (HIL) 102 , a hole transport layer (HTL) 103 , an electron blocking layer (also referred to as a second hole transport layer) (EBL) 104 . ), an emission layer (EML) 105 , a hole blocking layer (HBL) 106 , an electron transport layer (ETL) 107 , an electron injection layer (EIL) 108 , and a cathode layer 109 . Here, the light-emitting layer 105 generally contains at least one host material and at least one light-emitting material, and the electron blocking layer 104 and the hole blocking layer 106 are selectable layers. The hole injection layer 102 may be a single material layer, such as commercially available HATCN; The hole injection layer 102 may also be a hole transport material doped with a p-type conductive doping material of a certain proportion, and generally the doping ratio is 5% or less, but the commonly used doping ratio is between 1% and 3%. A hole injection layer doped with a type conductive material generally has a lower voltage than a single layer material, and therefore has a wide range of applications. A commercially available hole transport layer material, such as a compound HT material with a HOMO energy level generally left and right of -5.1 eV, approximates the work function of a commercially available anode layer ITO of -4.8 eV, resulting in effective injection of holes from the anode layer. to secure However, most of the host materials of the light emitting layer have a HOMO energy level much deeper than that of the hole transport layer material, generally -5.4 eV to -5.6 eV left and right, so that holes encounter a relatively high potential barrier when entering the light emitting layer from the transport layer. In order to solve this problem, in general, a second hole transport layer having a HOMO energy level between them is inserted between the hole transport layer and the light emitting layer to form a gradual form of potential energy. However, the holes in this structure still face the same total potential barrier height, and the additionally increased material results in more interface defects, which affects the lifetime and increases the complexity of the process. If the HOMO energy level of the hole injection layer can also approach the host energy level, the potential barrier before the holes are transported and enter the light emitting layer can be reduced and even disappeared. However, if the HOMO energy level is excessively deep, it is difficult for holes to be injected from the anode layer, and the ohmic contact is dropped, resulting in an increase in voltage. This phenomenon can be alleviated by injecting a p-type conductive doping material into a hole injection material with a deep energy level [Lussem et al. PSS A 210, No. 1, 9-43 (2013)], a commercially available p-type conductive doping material such as compound PD having a LUMO energy level of only -5.06 eV cannot achieve a very good doping effect with a hole transport material having a deep energy level. For better matching, the LUMO energy level of the p-type conductive doping material should also be deeper.

The present invention relates to a p-type conductive doping material having a deeper LUMO energy level (the LUMO energy level of the compound shown in Equation 1 is -5.2 eV left and right) and a hole transporting material having a deeper HOMO energy level (the compound shown in Equation 2) HOMO energy level is -5.2 eV left and right) to form a hole injection layer by co-deposition, and then, using the hole transport material as a hole transport layer, a light emitting layer is directly deposited thereon. Energy levels are better matched, and film layers and materials are reduced, reducing device voltages, improving lifetime, and simplifying processes.

Example

Hereinafter, the present invention will be described in more detail with reference to the following examples. Since the compounds used in the examples below can be readily obtained by those skilled in the art, the synthesis method thereof is not further described in the text, and can be found, for example, in Chinese Patent CN201911046002.3, the contents of which are incorporated by reference in their entirety. It is very clear that the following examples are used for illustrative purposes only and are not used to limit the scope of the present invention, and those skilled in the art can obtain other examples of the present invention by practicing them.

Example 1-1: First, a 0.7 mm thick glass substrate having a pre-patterned 80 nm thick indium tin oxide (ITO) anode was used, and the substrate was washed with deionized water and detergent, followed by oxygen plasma and UV ozone. Treat the ITO surface with Then, the substrate is dried in a glove box to remove moisture, mounted on a bracket, and transferred into a vacuum chamber. Through vacuum thermal evaporation at a rate of 0.1-5 Å/s at a vacuum degree of about 10 ^-8 torr, the following designated organic layers are sequentially deposited on the ITO anode layer: Compound H-26 and Compound 70 are simultaneously deposited to form holes Injection layer (HIL, 97:3, 100Å), compound H-26 is deposited to form a hole transport layer (HTL, 1250Å), and compound BH and compound BD are simultaneously deposited to light emitting layer (EML, 96:4, 250Å) and depositing compound HB to form a hole blocking layer (HBL, 50 Å), and co-depositing compound ET and 8-hydroxyquinoline-lithium (Liq) to form an electron transport layer (ETL, 40: 60, 300 Å), Finally, Liq with a thickness of 10 Å is deposited to form an electron injection layer (EIL), and 120 nm aluminum is deposited as a cathode. Next, the device is transferred back to the glove box and encapsulated using a glass lid to complete the device.

Comparative Example 1-1: It is the same as the manufacturing method of Example 1-1, except that compound PD and compound H-26 are simultaneously deposited as a hole injection layer (HIL, 3:97, 100 Å).

Comparative Example 1-2: Simultaneous deposition of compound PD and compound HT as a hole injection layer (HIL, 3:97, 100 Å), deposition of compound HT as a hole transport layer (HTL, 1200 Å), and compound H- on HTL 26 is deposited to form the second hole transport layer (HTL2, 50 Å), but is the same as the manufacturing method of Example 1-1.

Some layer structures and thicknesses of the detailed devices are shown in the table below. Here, a layer in which two or more materials are used is obtained by doping different compounds in the weight ratios mentioned therein.

Device structures of Example 1-1, Comparative Examples 1-1 and 1-2 Device ID HIL HTL HTL2 EML HBL ETL Example 1-1 H-26:70 (97:3)
(100Å) H-26
(1250Å) BH:BD (96:4)
(250Å) HB (50Å) ET: Liq (40:60) (300Å) Comparative Example 1-1 H-26:PD (97:3)
(100Å) H-26
(1250Å) BH:BD (96:4)
(250Å) HB (50Å) ET: Liq (40:60) (300Å) Comparative Example 1-2 HT:PD (97:3)
(100Å) HT
(1200Å) H-26
(50Å) BH:BD (96:4)
(250Å) HB (50Å) ET: Liq (40:60) (300Å)

The structural formulas of compound 70, H-26, HT, PD, BH, BD, HB, ET and Liq are as follows:

Table 2 summarizes the device performance of Example 1-1 and Comparative Examples 1-1 and 1-2. Here, the color coordinates and voltage are measured at a current density of 15 mA/cm ² , and the device lifetime (LT95) is a measure of the time it takes for the luminance to decay to 95% of the initial luminance under the driving condition of 80 mA/cm ² .

Device performance data of Example 1-1, Comparative Examples 1-1 and 1-2 At 15 mA/cm ² At 80 mA/cm ² CIEx CIEy voltage [V] LT95 [h] Example 1-1 0.138 0.094 4.2 14.7 Comparative Example 1-1 0.138 0.093 4.5 6.8 Comparative Example 1-2 0.139 0.094 4.3 7.2

In Example 1-1, Compound 70 having a LUMO energy level of -5.20 eV was used as a p-type conductive doping material, and Compound H-26 having a HOMO energy level of -5.28 eV was doped as a hole transport material. For comparison, 1-1 used compound PD having a LUMO energy level of -5.06 eV as a p-type conductive doping material and doped compound H-26 having a HOMO energy level of -5.28 eV as a hole transport material. Both have similar colors, but the voltage of Example 1-1 is 0.3V lower than the voltage of Comparative Example 1-1, and the lifespan is more than doubled. This is because when a hole transporting material having a relatively deep HOMO energy level and a p-type conductive doping material having a relatively deep LUMO energy level are combined, it is advantageous for hole injection and transport and the device performance is a p-type conductive doping material having a shallow LUMO energy level. and the combination of hole transport materials with relatively deep HOMO energy levels.

Since the p-type conductive doping material having a shallow LUMO energy level and a hole transporting material having a relatively shallow HOMO energy level are a better combination, the embodiment of the present invention is also compared thereto. Comparative Example 1-2 uses a compound PD having a LUMO energy level of -5.06 eV as a p-type conductive doping material, and doping a compound HT having a HOMO energy level -5.14 eV as a hole transport material to form a hole injection layer. Although compound HT was added as the transport layer, the HOMO energy level of the compound HT has a relatively large potential barrier compared to the HOMO energy level (-5.66 eV) of the light emitting layer BH. to help the injection of holes into the light emitting layer. The device structure is also a method frequently used in the industry. As a result, the voltage of Example 1-1 was 0.1V lower than the voltage of Comparative Example 1-2, and the lifetime was increased by more than twice. Although this uses a combination of a p-type conductive doping material with a shallow LUMO energy level and a hole transport material with a relatively shallow HOMO energy level and a gradual potential energy with the addition of a second hole transport layer, the method commonly used in this industry is still the method of the present invention. It lags behind the embodiment, and explains that the advantages of the present invention are obvious, especially in terms of life.

Example 2-1: It is the same as the preparation method of Example 1-1, except that all compounds H-26 are all replaced with compound H-124.

Comparative Example 2-1: It is the same as the preparation method of Example 2-1, except that the compound PD and the compound H-124 are used as a hole injection layer (HIL, 3:97, 100 Å).

Comparative Example 2-2: Compound PD and Compound HT as a hole injection layer (HIL, 3:97, 100 Å), Compound HT as a hole transport layer (HTL, 1200 Å), and Compound H-124 was deposited on HTL It is the same as the manufacturing method of Example 2-1, except that the second hole transport layer (HTL2, 50 Å) is formed.

Some layer structures and thicknesses of the detailed devices are shown in the table below. Here, a layer in which two or more materials are used is obtained by doping different compounds in the weight ratios mentioned therein.

Device structures of Example 2-1 and Comparative Examples 2-1 and 2-2 Device ID HIL HTL HTL2 EML HBL ETL Example 2-1 H-124:70 (97:3)
(100Å) H-124
(1250Å) BH:BD (96:4)
(250Å) HB (50Å) ET: Liq (40:60) (300Å) Comparative Example 2-1 H-124:PD (97:3) (100 Å) H-124
(1250Å) BH:BD (96:4)
(250Å) HB (50Å) ET: Liq (40:60) (300Å) Comparative Example 2-2 HT:PD (97:3)
(100Å) HT
(1200Å) H-124
(50Å) BH:BD (96:4)
(250Å) HB (50Å) ET: Liq (40:60) (300Å)

Examples of compound H-124 are:

Table 4 summarizes the device performance of Example 2-1 and Comparative Examples 2-1 and 2-2. Here, the color coordinates and voltage are measured at a current density of 15 mA/cm ² , and the device lifetime (LT95) is a measure of the time it takes for the luminance to decay to 95% of the initial luminance under the driving condition of 80 mA/cm ² .

Device performance data of Example 2-1, Comparative Examples 2-1 and 2-2 At 15mA/cm ² At 80 mA/cm ² CIEx CIEy voltage [V] LT95 [h] Example 2-1 0.140 0.098 4.4 128 Comparative Example 2-1 0.140 0.100 6.1 107 Comparative Example 2-2 0.138 0.094 4.3 18

In Example 2-1, Compound 70 having a LUMO energy level of -5.20 eV was used as a p-type conductive doping material, and Compound H-124 having a HOMO energy level of -5.29 eV was doped as a hole transport material. In Comparative Example 2-1, compound PD having a LUMO energy level of -5.06 eV was used as a p-type conductive doping material, and compound H-124 having a HOMO energy level of -5.29 eV was doped as a hole transport material. Both have similar colors, but as a result, the voltage of Example 2-1 was 1.7V lower than the voltage of Comparative Example 2-1, and the lifespan was 20% longer. This is because when a hole transporting material having a relatively deep HOMO energy level and a p-type conductive doping material having a relatively deep LUMO energy level are combined, it is advantageous for hole injection and transport and the device performance is a p-type conductive doping material having a shallow LUMO energy level. and the combination of hole transport materials with relatively deep HOMO energy levels.

Since the p-type conductive doping material having a shallow LUMO energy level and a hole transporting material having a relatively shallow HOMO energy level are a better combination, the embodiment of the present invention is also compared thereto. Comparative Example 2-2 uses a compound PD having a LUMO energy level of -5.06 eV as a p-type conductive doping material, and doping a compound HT having a HOMO energy level -5.14 eV as a hole transport material to form a hole injection layer. Although compound HT was added as the transport layer, the HOMO energy level of compound HT has a relatively larger potential barrier than the HOMO energy level (-5.66 eV) of the light emitting layer BH. It helps to inject holes into the light emitting layer. The device structure is also a method frequently used in the industry. As a result, the voltage of Example 2-1 was 0.1V higher than that of Comparative Example 2-2, but the lifetime was increased by more than 6 times. Although this uses a combination of a p-type conductive doping material with a shallow LUMO energy level and a hole transport material with a relatively shallow HOMO energy level and a gradual potential energy with the addition of a second hole transport layer, the method commonly used in this industry is still the method of the present invention. It lags behind the embodiment, and explains that the advantages of the present invention are obvious, especially in terms of life.

Example 3-1: It is the same as the preparation method of Example 1-1, except that all compounds H-26 are all replaced with compound H-176.

Comparative Example 3-1: It is the same as the preparation method of Example 3-1, except that compound PD and compound H-176 are used as a hole injection layer (HIL, 3:97, 100 Å).

Comparative Example 3-2: Compound PD and Compound HT as a hole injection layer (HIL, 3:97, 100 Å), Compound HT as a hole transport layer (HTL, 1200 Å), and Compound H-176 was deposited on HTL It is the same as the manufacturing method of Example 3-1, except that the second hole transport layer (HTL2, 50 Å) is formed.

Some layer structures and thicknesses of the detailed devices are shown in the table below. Here, a layer in which two or more materials are used is obtained by doping different compounds in the weight ratios mentioned therein.

Device structures of Example 3-1 and Comparative Examples 3-1 and 3-2 Device ID HIL HTL HTL2 EML HBL ETL Example 3-1 H-176:70 (97:3) (100 Å) H-176
(1250Å) BH:BD (96:4)
(250Å) HB (50Å) ET: Liq (40:60) (300Å) Comparative Example 3-1 H-176:PD (97:3) (100 Å) H-176
(1250Å) BH:BD (96:4)
(250Å) HB (50Å) ET: Liq (40:60) (300Å) Comparative Example 3-2 HT:PD (97:3)
(100Å) HT
(1200Å) H-176
(50Å) BH:BD (96:4)
(250Å) HB (50Å) ET: Liq (40:60) (300Å)

Examples of compound H-176 are:

Table 6 summarizes the device performance of Example 3-1 and Comparative Examples 3-1 and 3-2. Here, the color coordinates, quantum efficiency, and voltage are measured at a current density of 15mA/cm ² , and the device lifetime (LT95) is a measurement of the time it takes for the luminance to decay to 95% of the initial luminance under the driving condition of 80mA/cm ² .

Device performance data of Example 3-1, Comparative Examples 3-1 and 3-2 At 15 mA/cm ² At 80 mA/cm ² CIEx CIEy voltage [V] EQE [%] LT95 [h] Example 3-1 0.137 0.093 4.7 9.4 40 Comparative Example 3-1 0.140 0.097 6.1 8.7 1.3 Comparative Example 3-2 0.139 0.089 4.3 9.1 20

In Example 3-1, Compound 70 having a LUMO energy level of -5.20 eV was used as a p-type conductive doping material, and Compound H-176 having a HOMO energy level of -5.29 eV was doped as a hole transport material. In Comparative Example 3-1, compound PD having a LUMO energy level of -5.06 eV was used as a p-type conductive doping material, and compound H-176 having a HOMO energy level of -5.29 eV was doped as a hole transport material. Both have similar colors, but the voltage of Example 3-1 is 1.4V lower than the voltage of Comparative Example 3-1, and the lifespan is increased by more than 30 times. This is because when a hole transporting material having a relatively deep HOMO energy level and a p-type conductive doping material having a relatively deep LUMO energy level are combined, it is advantageous for hole injection and transport and the device performance is a p-type conductive doping having a relatively shallow LUMO energy level. It demonstrates superiority to the combination of materials and hole transport materials with relatively deep HOMO energy levels.

Since the p-type conductive doping material having a shallow LUMO energy level and a hole transporting material having a relatively shallow HOMO energy level are a better combination, the embodiment of the present invention is also compared thereto. Comparative Example 3-2 uses a compound PD having a LUMO energy level of -5.06 eV as a p-type conductive doping material, and doping a compound HT having a HOMO energy level -5.09 eV as a hole transport material to form a hole injection layer. Although compound HT was added as a transport layer, the HOMO energy level of compound HT has a relatively larger potential barrier than the HOMO energy level (-5.66 eV) of the light emitting layer BH, so by adding compound H-176 as a second hole transport layer, a gradual potential energy It helps to inject holes into the light emitting layer. The device structure is also a method frequently used in the industry. The voltage of Example 3-1 was 0.4V higher than the voltage of Comparative Example 3-2, but the lifetime was doubled. Although this uses a combination of a p-type conductive doping material with a shallow LUMO energy level and a hole transport material with a relatively shallow HOMO energy level and a gradual potential energy with the addition of a second hole transport layer, the method commercially available in this industry is still the method of the present invention. It is inferior to the embodiment, and in particular, it will be explained that the advantages of the present invention are highlighted again in terms of lifespan.

Example 4-1: First, a 0.7 mm thick glass substrate having a pre-patterned 120 nm thick indium tin oxide (ITO) anode was used, and the substrate was washed with deionized water and detergent, followed by oxygen plasma and UV ozone. Treat the ITO surface with Then, the substrate is dried in a glove box to remove moisture, mounted on a bracket, and transferred into a vacuum chamber. Through vacuum thermal evaporation at a rate of 0.1 to 5 Å/s at a vacuum degree of about 10 ^-8 torr, the following designated organic layers are sequentially deposited on the ITO anode layer: Compound H-124 and Compound 70 are simultaneously deposited to form holes Injection layer (HIL, 97:3, 100Å), compound H-124 is deposited to form a hole transport layer (HTL, 450Å), and compound RH and compound RD are simultaneously deposited to light emitting layer (EML, 98:2, 400Å) and depositing compound GH2 to form a hole blocking layer (HBL, 50Å), and co-depositing compound ET2 and 8-hydroxyquinoline-lithium (Liq) to form an electron transport layer (ETL, 40:60, 350Å), Finally, Liq with a thickness of 10 Å is deposited to form an electron injection layer (EIL), and 120 nm aluminum is deposited as a cathode. Next, the device is transferred back to the glove box and encapsulated using a glass lid to complete the device.

Comparative Example 4-1: Compound HATCN as a hole injection layer (HIL, 100 Å), Compound HT as a hole transport layer (HTL, 400 Å), and Compound H-124 as a second hole transport layer (HTL2, 50 Å) Except that, the manufacturing method of Example 4-1 is the same.

Device structure of Example 4-1 and Comparative Example 4-1 Device ID HIL HTL HTL2 EML HBL ETL Example 4-1 H-124:70 (97:3) (100 Å) H-124 (450Å) RH:RD (98:2) (400 Å) GH2
(50Å) ET2 : Liq (40:60) (350Å) Comparative Example 4-1 HATCN
(100Å) HT
(400Å) H-124
(50Å) RH:RD (98:2) (400 Å) GH2
(50Å) ET2 : Liq (40:60) (350Å)

Examples of compounds HATCN, RH, RD, GH2, ET2 are as follows:

Table 8 summarizes the device performance of Example 4-1 and Comparative Example 4-1. Here, the color coordinates, quantum efficiency, and voltage are measured at a current density of 15mA/cm ² , and the device lifetime (LT95) is a measurement of the time it takes for the luminance to decay to 95% of the initial luminance under the driving condition of 80mA/cm ² .

Device performance data of Example 4-1 and Comparative Example 4-1 At 15 mA/cm ² At 80 mA/cm ² CIEx CIEy voltage [V] EQE [%] LT95 [h] Example 4-1 0.682 0.317 4.8 22.9 160 Comparative Example 4-1 0.681 0.317 4.8 23.2 140

In Example 4-1, in a red light device, Compound 70 having a LUMO energy level of -5.20 eV was used as a p-type conductive doping material, and Compound H-124 having a HOMO energy level of -5.29 eV was doped as a hole transport material. Comparative Example 4-1 has a structure of a red light device used in the industry, and it can be seen from the device data that it achieved relatively high red light device performance in the industry. Compared with Comparative Example 4-1, but under the premise of securing the color, the voltage and efficiency of Example 4-1 were almost maintained, and the lifespan was improved by 14%. That is, by using a simple device structure using a combination of a hole transporting material having a relatively deep HOMO energy level and a p-type conductive doping material having a relatively deep LUMO energy level as well, the device performance can be significantly improved even in a red light device. It can be significantly improved in terms of device lifetime.

Example 5-1: It is the same as the preparation method of Example 4-1, except that all compounds H-124 were replaced with all compounds H-176.

Comparative Example 5-1: Compound HATCN as a hole injection layer (HIL, 100 Å), compound HT as a hole transport layer (HTL, 400 Å), and Compound H-176 as a second hole transport layer (HTL2, 50 Å) Except that, it is the same as the manufacturing method of Example 5-1.

Device structure of Example 5-1 and Comparative Example 5-1 Device ID HIL HTL HTL2 EML HBL ETL Example 5-1 H-176:70 (97:3) (100 Å) H-176 (450Å) RH:RD (98:2) (400 Å) GH2
(50Å) ET2 : Liq (40:60) (350Å) Comparative Example 5-1 HATCN
(100Å) HT
(400Å) H-176
(50Å) RH:RD (98:2) (400 Å) GH2
(50Å) ET2 : Liq (40:60) (350Å)

Table 10 summarizes the device performance of Example 5-1 and Comparative Example 5-1. Here, the color coordinates, quantum efficiency, and voltage are measured at a current density of 15mA/cm ² , and the device lifetime (LT95) is a measurement of the time it takes for the luminance to decay to 95% of the initial luminance under the driving condition of 80mA/cm ² .

Device performance data of Example 5-1 and Comparative Example 5-1 At 15 mA/cm ² At 80 mA/cm ² CIEx CIEy voltage [V] EQE [%] LT95 [h] Example 5-1 0.681 0.318 4.8 23.7 150 Comparative Example 5-1 0.681 0.317 4.8 23.6 135

In Example 5-1, Compound 70 having a LUMO energy level of -5.20 eV was used as a p-type conductive doping material in a red light device, and Compound H-176 having a HOMO energy level of -5.29 eV was doped as a hole transport material. Comparative Example 5-1 has a structure of a red light device used in the industry, and it can be seen from the device data that it achieved relatively high red light device performance in the industry. Compared with Comparative Example 5-1, but under the premise of securing the color, the voltage and efficiency of Example 5-1 were almost maintained, and the lifespan was improved by 11%. That is, by using a simple device structure using a combination of a hole transporting material having a relatively deep HOMO energy level and a p-type conductive doping material having a relatively deep LUMO energy level as well, the device performance can be significantly improved even in a red light device. It further demonstrates that significant improvements can be made in terms of device lifetime.

In summary, combining a hole transporting material having a relatively deep HOMO energy level and a p-type conducting doping material having a relatively deep LUMO energy level is advantageous for hole injection and transport and device performance is improved by a p-type conduction having a shallow LUMO energy level. It is superior to the combination of the doping material and the hole transport material with a relatively deep HOMO energy level. And, when the combination of the present invention is applied to various kinds of organic electroluminescent devices, all of them can effectively improve device performance, which is a material combination with a relatively large development potential.

It should be understood that the various embodiments described herein are illustrative only and are not intended to limit the scope of the present invention. Accordingly, it will be apparent to those skilled in the art that the claimed invention may include modifications of the specific and preferred embodiments described herein. Many of the materials and structures described herein may be substituted for other materials and structures without departing from the spirit of the present invention. It should be understood that the various theories as to why the present invention works are not limiting.

Claims (21)

anode;
cathode;
a light emitting layer disposed between the anode and the cathode; and
a first organic layer disposed between the anode and the light emitting layer; including,
Here, the first organic layer contains a compound of Formula 1 and a compound of Formula 2,

Here in Equation 1,
X and Y, identically or differently each time they appear, are selected from NR', CR''R"', O, S or Se;
Z ₁ and Z ₂ are identically or differently each time they appear are selected from O, S or Se;
R, R', R" and R"' are identically or differently each time they appear hydrogen, deuterium, halogen, nitroso group, nitro group, acyl group, carbonyl group, carboxylic acid group, ester group, cyano group, isocyano group, SCN, OCN, SF ₅ , boranyl group, sulfinyl group, sulfonyl group, phosphoroso group, substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, 3 to 20 ring carbon atoms atoms), a substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, 1 to 20 A substituted or unsubstituted alkoxy group having 6 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms A substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted group having 3 to 20 carbon atoms selected from the group consisting of an alkylsilyl group, a substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms, and combinations thereof;
each R can be the same or different, and at least one of R, R', R" and R"' is a group having at least one electron withdrawing group;
Adjacent substituents in Formula 1 may be optionally linked to form a ring;

Here, in Equation 2,
X ₁ to X ₈ are identically or differently selected from CR ₁ or N whenever they appear;
L is, identically or differently, each occurrence selected from a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 3 to 30 carbon atoms, or a combination thereof;
Ar ₁ and Ar ₂ , identically or differently each time they appear, are selected from a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms;
R ₁ is identically or differently each time it appears hydrogen, deuterium, halogen, substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, substituted or unsubstituted cyclo having 3 to 20 ring carbon atoms A cycloalkyl group, a substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms group, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, 3~ A substituted or unsubstituted heteroaryl group having 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms ( arylsilyl group), a substituted or unsubstituted amine group having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a nitrile group, an isonitrile group, a thiol group, a sulfinyl group, a sulfonyl group , is selected from the group consisting of a phosphino group and combinations thereof;
In Formula 2, adjacent substituents are optionally connected to an organic electroluminescent device that can form a ring. The method of claim 1,
X and Y are, identically or differently, each occurrence selected from CR''R"' or NR', and R', R" and R"' are groups having at least one electron withdrawing group; preferably, R, R', R" and R"' are groups having at least one electron withdrawing group. The method of claim 1,
X and Y are identically or differently selected from O, S or Se at each occurrence, and at least one of R is a group having at least one electron withdrawing group; Preferably, all R is a group having at least one electron withdrawing group. 4. The method according to any one of claims 1 to 3,
The Hammett constant of the electron withdrawing group is 0.05 or more, preferably 0.3 or more, and more preferably 0.5 or more. 5. The method according to any one of claims 1 to 4,
The electron withdrawing group is halogen; nitroso group; nitro group; acyl group; carbonyl group; carboxylic acid group; ester group; cyano group; isocyano group; SCN; OCN; SF ₅ ; Boranyl group (Boranyl); sulfinyl group; sulfonyl group; phosphoroso group; aza aromatic ring; and halogen, nitroso group, nitro group, acyl group, carbonyl group, carboxylic acid group, ester group, cyano group, isocyano group, SCN, OCN, SF5, boranyl group, sulfinyl group, sulfonyl group, phosphoroso group ( phosphoroso), any one of the following groups substituted with one or a plurality of azaaromatic rings: an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 ring carbon atoms, A heteroalkyl group having 1 to 20 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, an alkenyl group having 2 to 20 carbon atoms , an aquinyl group having 2 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, a heteroaryl group having 3 to 30 carbon atoms, an alkylsilyl group having 3 to 20 carbon atoms, 6 to 20 an arylsilyl group having two carbon atoms; and combinations thereof;
Preferably, the electron withdrawing group is from the group consisting of F, CF ₃ , OCF ₃ , SF ₅ , SO ₂ CF ₃ , cyano group, isocyano group, SCN, OCN, pyrimidyl group, triazinyl group, and combinations thereof. Organic electroluminescent device of choice. 6. The method of any one of claims 1, 4, 5,
X and Y are the same or different whenever they appear organic electroluminescent device selected from the group consisting of:

Here, R ₂ is the same or different whenever it appears hydrogen, deuterium, halogen, nitroso group, nitro group, acyl group, carbonyl group, carboxylic acid group, ester group, cyano group, isocyano group, SCN, OCN, SF5, purple Nyl group (Boranyl), sulfinyl group, sulfonyl group, phosphoroso group (phosphoroso), substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, substituted or unsubstituted having 3 to 20 ring carbon atoms cycloalkyl group, substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, substituted or unsubstituted having 1 to 20 carbon atoms an alkoxy group, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aquinyl group having 2 to 20 carbon atoms, A substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms , is selected from the group consisting of a substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms and combinations thereof;
Preferably, R ₂ is identically or differently each time it appears F, CF ₃ , OCF ₃ , SF ₅ , SO ₂ CF ₃ , cyano group, isocyano group, SCN, OCN, pentafluorophenyl group, 4-cyanotetra It is selected from the group consisting of a fluorophenyl group, a tetrafluoropyridyl group, a pyrimidyl group, a triazinyl group, and combinations thereof;
wherein V and W are identically or differently each time they appear selected from CR _v R _w , NR _v , O, S or Se;
wherein Ar is, identically or differently each time it appears, selected from a substituted or unsubstituted aryl group having 6 to 30 carbon atoms or a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms;
where A, R _a , R _b , R _c , R _d , Re _e , R _f , R _g , R _h , R _v and R _w are identically or differently each time they appear hydrogen, deuterium, halogen, nitroso group, Nitro group, acyl group, carbonyl group, carboxylic acid group, ester group, cyano group, isocyano group, SCN, OCN, SF ₅ , boranyl group, sulfinyl group, sulfonyl group, phosphoroso group, 1- A substituted or unsubstituted alkyl group having 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, a substituted or unsubstituted group having 1 to 20 carbon atoms a heteroalkyl group, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, A substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aquinyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, 3 to 30 carbon atoms A substituted or unsubstituted heteroaryl group having a character, a substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms and combinations thereof;
wherein A is a group having at least one electron withdrawing group, and in any of the above structures, R _a , R _b , R _c , R _d , Re _e , R _f , R _g , R _h , R _v and R _w When one or more of R _a , R _b , R _c , R _d , _Re , R _f , R _g , R _h , R _v and R _w are present, at least one of R a , R b , R c , R d , R g , R h , R v and R w is a group having at least one electron withdrawing group is; Preferably, the group having at least one electron withdrawing group is F, CF ₃ , OCF ₃ , SF ₅ , SO ₂ CF ₃ , cyano group, isocyano group, SCN, OCN, pentafluorophenyl group, 4-cyanotetra It is selected from the group consisting of a fluorophenyl group, a tetrafluoropyridyl group, a pyrimidyl group, a triazinyl group, and combinations thereof;
Here, "*" represents a position where the X and Y groups are connected to the dehydrobenzodioxazole ring, dehydrobenzodithiazole ring or dehydrobenzodithiazole ring in Formula 1. 6. The method of any one of claims 1, 4, 5,
X and Y, identically or differently whenever they appear, are selected from the group consisting of:

Here, "*" represents a position in which the X and Y groups are connected to a dehydrobenzodioxazole ring, a dehydrobenzodithiazole ring or a dehydrobenzodithiazole ring in Formula 1; 8. The method according to any one of claims 1 to 7,
R is identically or differently each time it appears hydrogen; deuterium; halogen; nitroso group; nitro group; acyl group; carbonyl group; carboxylic acid group; ester group; cyano group; isocyano group; SCN; OCN; SF ₅ ; Boranyl group (Boranyl); sulfinyl group; sulfonyl group; phosphoroso group; an unsubstituted alkyl group having 1 to 20 carbon atoms; an unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms; an unsubstituted alkoxy group having 1 to 20 carbon atoms; an unsubstituted alkenyl group having 2 to 20 carbon atoms; an unsubstituted aryl group having 6 to 30 carbon atoms; an unsubstituted heteroaryl group having 3 to 30 carbon atoms; and halogen, nitroso group, nitro group, acyl group, carbonyl group, carboxylic acid group, ester group, cyano group, isocyano group, SCN, OCN, SF ₅ , boranyl group, sulfinyl group, sulfonyl group and phosphoroso group (phosphoroso) any one of the following groups substituted with one or a plurality of groups: an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 ring carbon atoms, 1 to 20 an alkoxy group having 2 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, a heteroaryl group having 3 to 30 carbon atoms, and combinations thereof;
Preferably, R is identically or differently each time it appears hydrogen; deuterium; methyl group; isopropyl group; NO ₂ ; SO ₂ CH ₃ ; SCF ₃ ; C ₂ F ₅ ; OC ₂ F ₅ ; OCH ₃ ; diphenylmethylsilyl group; phenyl group; methoxyphenyl group; p-methylphenyl group; 2,6-diisopropylphenyl group; biphenyl group; polyfluorophenyl group; difluoropyridyl group; nitrophenyl group; dimethylthiazole group; a vinyl group substituted with one or a plurality of CN or CF ₃ ; an ethynyl group substituted with one of CN or CF ₃ ; dimethylphosphonooxy; diphenylphosphonooxy; F; CF ₃ ; OCF ₃ ; SF ₅ ; SO ₂ CF ₃ ; cyano group; isocyano group; SCN; OCN; trifluoromethylphenyl group; trifluoromethoxyphenyl group; a bis(trifluoromethyl)phenyl group; bis(trifluoromethoxy)phenyl group; 4-cyanotetrafluorophenyl group; a phenyl group or a biphenyl group substituted with one or more of F, CN, or CF ₃ ; tetrafluoropyridyl group; pyrimidyl group; triazinyl group; diphenyl boranyl group; Oxaboraanthryl group (Oxaboraanthryl); And an organic electroluminescent device selected from the group consisting of combinations thereof. 9. The method of claim 8,
X and Y are

Phosphorus organic electroluminescent device. 10. The method according to any one of claims 1 to 9,
R is the same or different whenever it appears organic electroluminescent device selected from the group consisting of the following structures:

Preferably, two R in one compound represented by formula 1 are the same;
here, "

" represents the position at which the R group is connected to the dehydrobenzodioxazole ring, dehydrobenzodithiazole ring or dehydrobenzodithiazole ring in Formula 1. 11. The method of claim 10,
The compound of Formula 1 has a structure represented by Formula 3;

two Z structures in Formula 3 are the same, and two R structures are the same or different, wherein Z, X, Y, and R correspond to each selected from the atoms or groups shown in the table below;
Here, the compound having the structure of Formula 3 is an organic electroluminescent device selected from the group consisting of the following compounds:

The method of claim 1,
L is a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted terphenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted fluorenylidene group, a substituted or unsubstituted A substituted silafluorenylidene group, a substituted or unsubstituted carbazolylene group, a substituted or unsubstituted dibenzofuranylene group, a substituted or unsubstituted dibenzothiophenylene group, a substituted or Unsubstituted dibenzoselenophenylene group, substituted or unsubstituted phenanthrylene group, substituted or unsubstituted triphenylene group, substituted or unsubstituted pyridinylene group, substituted or unsubstituted selected from a spirobifluorenylene group, a substituted or unsubstituted anthrylene group, a substituted or unsubstituted pyrenylene group, or a combination thereof; Preferably L is selected from a substituted or unsubstituted phenylene group, or a substituted or unsubstituted biphenylene group; More preferably L is a phenylene group or a biphenylene group organic electroluminescent device. 13. The method of claim 1 or 12,
R ₁ is hydrogen, deuterium, halogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, 6 a substituted or unsubstituted aryl group having -30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3-30 carbon atoms; Preferably, R ₁ is hydrogen, deuterium, an organic electroluminescent device selected from a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms. 14. The method of any one of claims 1, 12, 13,
Ar ₁ and Ar ₂ are selected from a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 20 carbon atoms; Preferably, Ar ₁ and Ar ₂ are selected from a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a fluorenyl group, a dibenzothienyl group, a spirobifluorenyl group, a pyridyl group or a pyrimidyl group. The method of claim 1,
The compound having the structure of Formula 2 is an organic electroluminescent device selected from the group consisting of the following compounds:

The method of claim 1,
An organic electroluminescent device further comprising a second organic layer disposed between the anode and the light emitting layer, wherein the second organic layer contains the compound of Formula 2. 17. The method of claim 1 or 16,
The first organic layer is an organic electroluminescent device in contact with the anode. The method of claim 1,
The weight ratio of the compound of Formula 1 contained in the first organic layer to the total first organic layer is 5% or less, 3% or less, 2% or less, or 1% or less of the organic electroluminescent device. 17. The method of claim 16,
The second organic layer is an organic electroluminescent device in contact with the light emitting layer. The method of claim 1,
An organic electroluminescent device further comprising a third organic layer disposed between the anode and the light emitting layer, wherein the third organic layer contains a compound different from the second organic layer. A display assembly comprising the organic electroluminescent device according to claim 1 .

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