CN116891441A - Compound for organic electronic element, organic electronic element using same, and electronic device using same - Google Patents

Compound for organic electronic element, organic electronic element using same, and electronic device using same Download PDF

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Publication number
CN116891441A
CN116891441A CN202310333088.8A CN202310333088A CN116891441A CN 116891441 A CN116891441 A CN 116891441A CN 202310333088 A CN202310333088 A CN 202310333088A CN 116891441 A CN116891441 A CN 116891441A
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compound
layer
organic
electronic element
integer
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Inventor
秦孝旻
金哉昊
李炯东
苏己镐
李善希
李允硕
文成允
李学荣
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DukSan Neolux Co Ltd
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DukSan Neolux Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/14—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom
    • C07D251/24—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to three ring carbon atoms
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/16—Electron transporting layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/18—Carrier blocking layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Optics & Photonics (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

The present invention provides a novel compound capable of improving luminous efficiency, stability and lifetime of an element, an organic electronic element using the same, and an electronic device thereof.

Description

Compound for organic electronic element, organic electronic element using same, and electronic device using same
Technical Field
The present invention relates to a compound for an organic electronic element, an organic electronic element using the compound, and an electronic device thereof.
Background
In general, an organic light emitting phenomenon refers to a phenomenon in which electric energy is converted into light energy by using an organic material. An organic electronic element using an organic light emitting phenomenon generally has a structure including an anode, a cathode, and an organic material layer interposed therebetween. Here, in order to increase efficiency and stability of the organic electronic element, the organic material layer is generally composed of a multi-layer structure composed of different materials, and may include, for example, a hole injection layer, a hole transport layer, an emission layer, an electron transport layer, an electron injection layer, and the like.
Materials used as the organic material layer in the organic electronic element may be classified into a light emitting material and a charge transporting material, such as a hole injecting material, a hole transporting material, an electron injecting material, and the like, according to their functions. The light emitting material may be classified into a high molecular weight type and a low molecular weight type according to molecular weight, and may be classified into a fluorescent material derived from a singlet excited state of electrons and a phosphorescent material derived from a triplet excited state of electrons according to a light emitting mechanism. Further, the light emitting material may be classified into a blue light emitting material, a green light emitting material, and a red light emitting material according to emission colors, and a yellow light emitting material and an orange light emitting material necessary for realizing more natural colors.
However, when only one material is used as a light emitting material, the maximum emission wavelength is shifted to a longer wavelength due to intermolecular interaction, and there is a problem in that color purity is lowered or device efficiency is lowered due to an emission attenuation effect, so in order to increase color purity and increase light emitting efficiency by energy transfer, a host/dopant system may be used as a light emitting material. The principle is as follows: when a small amount of dopant having a smaller energy band gap than that of the host forming the emission layer is mixed in the emission layer, excitons generated in the emission layer are transferred to the dopant to efficiently emit light. At this time, since the wavelength of the host is shifted to the wavelength band of the dopant, light having a desired wavelength can be obtained according to the type of the dopant used.
Currently, the portable display market is a large display and its size is increasing, and thus, larger power consumption than that required for the existing portable display is required. Therefore, for portable displays with a limited power supply such as a battery, power consumption becomes a very important factor, and also problems of efficiency and lifetime have to be solved.
The efficiency, the service life, and the driving voltage are related to each other, and as the efficiency increases, the driving voltage relatively decreases, and as the driving voltage decreases, crystallization of the organic material due to joule heating generated during driving decreases, and thus the service life tends to increase. However, efficiency cannot be maximized simply by improving the organic material layer. This is because, when the energy level and T1 value between the organic material layers and the intrinsic properties of the material (mobility, interface properties, etc.) are optimally combined, a long service life and high efficiency can be achieved at the same time.
Therefore, although permeation and diffusion of a metal oxide from an anode electrode (ITO) into an organic layer, which is one of the reasons for shortening the service life of an organic electronic element, should have stable characteristics against joule heating generated during device driving, and an OLED device is mainly formed by a deposition method, and it is necessary to develop a material that can withstand long-time deposition, i.e., a material having strong heat resistance.
In other words, in order to fully exhibit excellent characteristics of the organic electronic element, materials such as a hole injecting material, a hole transporting material, a light emitting material, an electron transporting material, an electron injecting material, and the like, which constitute an organic material layer in the device, should be preferentially qualified, but development of stable and effective organic material layer materials for the organic electronic device has not been sufficiently achieved. Therefore, development of new materials, and in particular, development of host materials for an emission layer is urgently required.
Disclosure of Invention
In order to solve the above-described problems of the background art, the present invention discloses a compound having a novel structure, and when the compound is applied to an organic electronic element, it has been found that the luminous efficiency, stability and lifetime of the device can be significantly improved.
It is therefore an object of the present invention to provide novel compounds, organic electronic elements using the same, and electronic devices thereof.
Technical proposal
The present invention provides a compound represented by formula (2).
(2)
In another aspect, the present invention provides an organic electronic element comprising the compound represented by formula (2) and an electronic device thereof.
Effects of the invention
By using the compound according to the present invention, high luminous efficiency, low driving voltage and high heat resistance of the device can be achieved, and color purity and service life of the device can be greatly improved.
Drawings
Fig. 1 to 3 are exemplary views of an organic electroluminescent device according to the present invention.
The numerals in the drawings represent:
100. 200, 300: organic electronic element 110: first electrode
120: hole injection layer 130: hole transport layer
140: emission layer 150: electron transport layer
160: electron injection layer 170: second electrode
180: light efficiency enhancement layer 210: buffer layer
220: emission assistance layer 320: first hole injection layer
330 first hole transport layer 340 first emissive layer
350: first electron transport layer 360: a first charge generation layer
361: the second charge generation layer 420: a second hole injection layer
430: second hole transport layer 440: second emissive layer
450: second electron transport layer CGL: charge generation layer
ST1: first stacked body ST1: a second stack
Detailed Description
Hereinafter, some embodiments of the present invention will be described in detail. Furthermore, in the following description of the present invention, a detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear.
Further, when describing the components of the present invention, terms such as first, second, A, B, (a), (b), and the like may be used herein. Each of these terms is not intended to limit the substance, order, or sequence of corresponding components, but is merely intended to distinguish the corresponding components from other components. It should be noted that if a component is described as being "connected," "coupled," or "connected" to another component, the component may be directly connected or connected to the other component, but another component may be "connected," "coupled," or "connected" between the components.
As used in the specification and the appended claims, the following are the meanings of the following terms, unless otherwise indicated.
The term "halo" or "halogen" as used herein includes fluoro, bromo, chloro or iodo unless otherwise indicated.
The term "alkyl" or "alkyl group" as used herein has a single bond of 1 to 60 carbon atoms, unless otherwise specified, and means a saturated aliphatic functionality, including a straight chain alkyl group, a branched alkyl group, a cycloalkyl group (alicyclic), a cycloalkyl group substituted with an alkyl group, or an alkyl group substituted with a cycloalkyl group.
The term "alkenyl" or "alkynyl" as used herein has a double or triple bond of 2 to 60 carbon atoms, unless otherwise specified, but is not limited thereto and includes straight or branched chain groups.
The term "cycloalkyl" as used herein means, unless otherwise specified, an alkyl group forming a ring having 3 to 60 carbon atoms, but is not limited thereto.
The term "alkoxy", "alkoxy group" or "alkyloxy group" as used herein means an oxy group attached to an alkyl group and having from 1 to 60 carbon atoms, unless otherwise specified, but is not limited thereto.
The term "aryloxy group" or "aryloxy group" as used herein means an oxy group attached to an aryl group and having 6 to 60 carbon atoms, unless otherwise specified, but is not limited thereto.
The terms "aryl group" and "arylene group" as used in the present invention have 6 to 60 carbon atoms, respectively, unless otherwise specified, but are not limited thereto. In the present invention, an aryl group or arylene group means a monocyclic or polycyclic aromatic group and includes an aromatic ring formed by linking or participating in a reaction through adjacent substituents.
For example, the aryl group may be a phenyl group, a biphenyl group, a fluorene group, or a spirofluorene group.
The prefix "aryl" or "aryl" means a group substituted with an aryl group. For example, an arylalkyl group may be an alkyl group substituted with an aryl group, and an arylalkenyl group may be an alkenyl group substituted with an aryl group, with the aryl-substituted group having the number of carbon atoms as defined herein.
Furthermore, when the prefixes are named sequentially, this means that the substituents are listed in the order first described. For example, arylalkoxy means alkoxy substituted with aryl, alkoxycarbonyl means carbonyl substituted with alkoxy, and arylcarbonylalkenyl also means alkenyl substituted with arylcarbonyl, wherein arylcarbonyl may be carbonyl substituted with aryl.
The term "heterocyclic group" as used herein contains one or more heteroatoms having from 2 to 60 carbon atoms, unless otherwise specified, but is not limited thereto, including any of monocyclic and polycyclic, and may include heteroalicyclic and heteroaromatic rings. In addition, it is also possible to combine with adjacent groups to form heterocyclic groups.
The term "heteroatom" as used herein means at least one of N, O, S, P or Si unless otherwise specified.
Furthermore, the term "heterocyclic group" may include a group comprising SO 2 Instead of the carbon ring constituting the ring. For example, "heterocyclic group" includes the following compounds.
Unless otherwise indicated, the term "fluorenyl group" or "fluorenylene group" as used herein means a monovalent or divalent functional group in which both R, R ' and R "are hydrogen in the following structures, and the term" substituted fluorenyl group "or" substituted fluorenylene group "means that at least one of the substituents R, R ', R" is a substituent other than hydrogen, and includes those in which R and R ' are bonded to each other to form a spiro compound together with the carbon to which they are bonded.
The term "spiro compound" as used herein has a "spiro" and spiro means a connection in which two rings share only one atom. At this time, the atoms shared in both rings are referred to as "spiro atoms", and these compounds are referred to as "mono-, bi-, and" trispiro- "respectively, depending on the number of spiro atoms in the compound.
The term "aliphatic" as used herein means an aliphatic hydrocarbon having 1 to 60 carbon atoms, and the term "aliphatic ring" as used herein means an aliphatic hydrocarbon ring having 3 to 60 carbon atoms, unless otherwise specified.
The term "ring" as used herein means an aliphatic ring having 3 to 60 carbon atoms, or an aromatic ring having 6 to 60 carbon atoms, or a heterocyclic ring having 2 to 60 carbon atoms, or a condensed ring formed by a combination thereof, and includes saturated or unsaturated rings, unless otherwise specified.
In addition to the hetero compounds mentioned above, other hetero compounds or groups include, but are not limited to, one or more heteroatoms.
Furthermore, unless explicitly specified, the term "substituted" in the term "substituted or unsubstituted" as used herein means substituted with one or more substituents selected from deuterium, halogen, amino groups, nitrile groups, nitro groups, C 1 -C 20 Alkyl group, C 1 -C 20 Alkoxy groups, C 1 -C 20 Alkyl amine group, C 1 -C 20 Alkyl thiophene group, C 6 -C 20 Arylthiophene group, C 2 -C 20 Alkenyl group, C 2 -C 20 Alkynyl radicals, C 3 -C 20 Cycloalkyl radicals, C 6 -C 20 Aryl group, C substituted with deuterium 6 -C 20 Aryl group, C 8 -C 20 An arylalkenyl group, a silane group, a boron group, a germanium group, and C 2 -C 20 Heterocyclic groups, but are not limited to, these substituents.
In addition, unless explicitly explained, the formula used in the present invention is the same as the definition of substituents by the typical definition (exponent definition) of the following formula.
Here, when a is an integer of zero, the substituent R 1 Absent, when a is an integer of 1, the only substituent R 1 Any one of carbons attached to carbon constituting a benzene ring, when a is an integer of 2 or 3, each are combined as follows, wherein R 1 Which may be the same or different from each other, when a is an integer of 4 to 6, it is bonded to a carbon of a benzene ring in a similar manner, but the indication of hydrogen bonded to the carbon forming the benzene ring is omitted.
Hereinafter, a compound according to aspects of the present invention and an organic electronic element including the compound will be described.
The present invention provides a compound represented by formula (2).
(2)
Wherein,,
1)R 1 、R 2 、R 3 、R 4 and R is 5 Are identical or different from each other and are, independently of each other, hydrogen or deuterium;
2) L is a single bond; or C 6 -C 60 An arylene group;
3) Ar is C 6 -C 60 An aryl group;
4) c is an integer from 0 to 5, d is an integer from 0 to 6, e and f are each independently an integer from 0 to 4, and g is an integer from 0 to 7,
5) Wherein the arylene group and the aryl group may be further substituted with one or more substituents selected from deuterium; c (C) 6 -C 20 An aryl group; c substituted with deuterium 6 -C 20 An aryl group.
Furthermore, the present invention provides compounds wherein formula (2) is represented by formulas (2-1) to (2-3).
Wherein,,
R 1 、R 2 、R 3 、R 4 、R 5 l, ar, c, d, e, f and g are as defined above.
Furthermore, the present invention provides a compound wherein L is represented by any one of the following formulas a-1 to a-20.
Wherein,,
1)R 7 selected from deuterium; c (C) 6 -C 20 An aryl group; c substituted with deuterium 6 -C 20 An aryl group;
2) h, i and j are each independently an integer from 0 to 4, k is an integer from 0 to 6, l is an integer from 0 to 8,
3) Meaning the position where triazine or Ar is bonded.
Further, the present invention provides a compound wherein Ar is represented by any one of the following formulas b-1 to b-8.
Wherein,,
1)R 8 selected from deuterium; c (C) 6 -C 20 An aryl group; c substituted with deuterium 6 -C 20 An aryl group;
2) m is an integer of 0 to 5, n is an integer of 0 to 7, o is an integer of 0 to 9,
3)meaning the position where it binds to L.
Furthermore, the present invention provides a compound having a recombination energy value of 0.240 to 0.300, which is a compound represented by formula (2). Preferably, it may be a compound having a recombination energy value of 0.246 to 0.300.
Further, the present invention provides a compound in which the compound represented by the formula (2) is represented by any one of the following compounds S-1 to S-56.
Referring to fig. 1, the organic electronic element (100) according to the present invention includes a first electrode (110), a second electrode (170), and an organic material layer including a single compound represented by formula (2) or two or more compounds between the first electrode (110) and the second electrode (170). In this case, the first electrode (110) may be an anode, and the second electrode (170) may be a cathode. In the case of the inversion type, the first electrode may be a cathode and the second electrode may be an anode.
The organic material layer may include a hole injection layer (120), a hole transport layer (130), an emission layer (140), an electron transport layer (150), and an electron injection layer (160) on the first electrode (110) in this order. In this case, the remaining layers other than the emission layer (140) may not be formed. A hole blocking layer, an electron blocking layer, an emission assisting layer (220), a buffer layer (210), and the like may also be included, and an electron transporting layer (150) and the like may be used as the hole blocking layer. (see FIG. 2)
In addition, the organic electronic element according to an embodiment of the present invention may further include a protective layer or a light efficiency enhancing layer (180). The light efficiency enhancing layer may be formed on one of the two surfaces of the first electrode that is not in contact with the organic material layer, or on one of the two surfaces of the second electrode that is not in contact with the organic material layer. The compound according to an embodiment of the present invention, which is suitable for an organic material layer, may be used as a host or dopant for a hole injection layer (120), a hole transport layer (130), an emission auxiliary layer (220), an electron transport auxiliary layer, an electron transport layer (150) and an electron injection layer (160), an emission layer (140), or as a material for a light efficiency enhancing layer. Preferably, for example, the compound according to formula (2) of the present invention may be used as a host material for an emission layer, a hole blocking layer, or an electron transport layer.
The organic material layer may include two or more stacks including a hole transport layer, an emission layer, and an electron transport layer sequentially formed on the anode, and a charge generation layer formed between the two or more stacks (see fig. 3).
In addition, even in the case of the same core, band gap, electric characteristics, interface characteristics, and the like may vary depending on the position where the substituents are bonded, and therefore, selection of the combination of the core and the sub-substituents bonded thereto is also very important, and in particular, when an optimal combination of the energy level and T1 value of each organic material layer and unique properties (mobility, interface characteristics, and the like) of the material are achieved, both long service life and high efficiency can be achieved.
The organic electroluminescent device according to the embodiment of the present invention may be manufactured using a PVD (physical vapor deposition) method. For example, after forming an anode by depositing a metal or a metal oxide having conductivity or an alloy thereof on a substrate and forming an organic material layer including a hole injection layer (120), a hole transport layer (130), an emission layer (140), an electron transport layer (150), and an electron injection layer (160) thereon, an organic electroluminescent device may be prepared by depositing a material that can function as a cathode thereon.
Further, in the present invention, the organic material layer is formed by any one of a spin coating process, a nozzle printing process, an inkjet printing process, a slit coating process, a dip coating process, and a roll-to-roll process, and the organic material layer provides an organic electric element including the compound as an electron transport material.
As another specific example, the same or different compounds of the compounds represented by formula (2) are mixed and used in the organic material layer.
Furthermore, the present invention provides an emission layer composition including the compound represented by formula (2), and an organic electronic element including the emission layer.
Further, the present invention provides a hole blocking layer composition comprising the compound represented by formula (2), and an organic electronic element including the hole blocking layer.
Further, the present invention provides an electron transport layer composition comprising the compound represented by formula (2), and an organic electronic element including the electron transport layer.
Furthermore, the present invention provides an electronic device including a display device including an organic electronic element; and a control unit for driving the display device.
In another aspect, the organic electronic element is at least one of an organic electroluminescent device, an organic solar cell, an organic photoreceptor, an organic transistor, and a device for monochromatic or white illumination. At this time, the electronic device may be a current or future wired/wireless communication terminal, and covers all kinds of electronic devices including mobile communication terminals such as mobile phones, personal Digital Assistants (PDAs), electronic dictionaries, point-to-multipoint (PMPs), remote controllers, navigation units, game machines, various TVs, and various computers.
Hereinafter, a synthesis example of the compound represented by formula 2 of the present invention and a production example of the organic electronic element of the present invention will be described in detail with reference to examples, but the present invention is not limited to the following examples.
Synthesis example
The compound represented by formula 2 (final product 1) according to the present invention is synthesized by reacting Sub3 and Sub4 as shown in scheme 1 below, but is not limited thereto.
< reaction scheme 1>
Synthesis of Sub3
Sub3 of scheme 1 is synthesized by the reaction pathway of scheme 2 below, but is not limited thereto.
< reaction scheme 2>
Synthesis example of Sub3-1
After Sub3a-1 (25.0 g,88.3 mmol) was dissolved in THF (tetrahydrofuran) (440 mL) in a round bottom flask, sub3b-1 (29.1 g,88.3 mmol), naOH (10.6 g,264.9 mmol), pd (PPh) was added 3 ) 4 (6.12 g,5.30 mmol), water (220 mL), and the mixture was stirred at 80℃0. When the reaction is complete, the mixture is taken up in CH 2 Cl 2 And water extraction and the organic layer was subjected to MgSO 4 Drying and concentrating. After this time, after application of the silica gel column, the obtained compound was recrystallized to obtain 31.6g (yield 88.2%) of a product.
Synthesis example of Sub3-2
After Sub3a-1 (10.0 g,35.3 mmol) was dissolved in THF (180 mL) in a round bottom flask, sub3b-2 (11.8 g,35.3 mmol), naOH (4.2 g,105.9 mmol), pd (PPh) were added 3 ) 4 (2.45 g,2.12 mmol), water (90 mL), and by using the sameThe process to Sub3-1 gave 12.5g (86.5% yield) of product.
Synthesis example of Sub3-4
After Sub3a-1 (25.0 g,88.3 mmol) was dissolved in THF (440 mL) in a round bottom flask, sub3b-4 (29.1 g,88.3 mmol), naOH (10.6 g,264.9 mmol), pd (PPh) were added 3 ) 4 (6.12 g,5.30 mmol), water (220 mL), and 30.4g (yield 84.8%) of a product was obtained by a method using synthetic Sub 3-1.
Synthesis example of Sub3-6
After Sub3a-1 (25.0 g,88.3 mmol) was dissolved in THF (440 mL) in a round bottom flask, sub3b-6 (29.1 g,88.3 mmol), naOH (10.6 g,264.9 mmol), pd (PPh) were added 3 ) 4 (6.12 g,5.30 mmol), water (220 mL), and 27.0g (yield 75.3%) of a product was obtained by a method using synthetic Sub 3-1.
The compound belonging to Sub3 may be the following compound, but is not limited thereto, and table 1 below shows the field desorption-mass spectrometry (FD-MS) values of the compound belonging to Sub 3.
TABLE 1
Synthesis of Sub4
Sub4 of scheme 1 is synthesized by the reaction pathway of the following reaction scheme 3, but is not limited thereto.
< reaction scheme 3>
Synthesis example of Sub4-1
After Sub4b-1 (17.1 g,75.7 mmol) was dissolved in THF (380 mL) in a round bottom flask, sub4a-1 (25.0 g,75.7 mmol), naOH (9.1 g,227.1 mmol), pd (PPh) was added 3 ) 4 (5.25 g,4.54 mmol), water (190 mL), and the mixture was stirred at 80 and under stirring. When the reaction is complete, the mixture is taken up in CH 2 Cl 2 And water extraction and the organic layer was subjected to MgSO 4 Drying and concentrating. After this time, after application of the silica gel column, the resulting compound was recrystallized to obtain 21.5g (yield 72.1%) of a product.
Synthesis of Sub4-17
(1) Synthesis example of Sub4b-17
After Sub4c-1 (8.4 g,45.4 mmol) was dissolved in THF (230 mL) in a round bottom flask, sub4a-1 (15.0 g,45.4 mmol), naOH (5.5 g,136.3 mmol), pd (PPh) were added 3 ) 4 (3.15 g,2.73 mmol), water (115 mL), and 10.2g (yield 63.7%) of a product was obtained by a method using synthetic Sub 4-1.
(2) Synthesis example of Sub4-17
After Sub4b-17 (10.2 g,28.9 mmol) was dissolved in THF (145 mL) in a round bottom flask, sub4a-1 (9.6 g,28.9 mmol), naOH (3.5 g,86.8 mmol), pd (PPh) were added 3 ) 4 (2.01 g,1.74 mmol), water (72 mL), and by allowing10.7g (71.0% yield) of product were obtained by synthesizing Sub 4-1.
Synthesis of Sub4-20
After Sub4b-20 (16.0 g,45.4 mmol) was dissolved in THF (230 mL) in a round bottom flask, sub4a-1 (15.0 g,45.4 mmol), naOH (5.5 g,136.3 mmol), pd (PPh) were added 3 ) 4 (3.15 g,2.73 mmol), water (115 mL), and 17.1g (yield 72.6%) of a product was obtained by a method using synthetic Sub 4-1.
Synthesis of Sub4-31
(1) Synthesis example of Sub4a-31
After Sub4e-31 (10.7 g,65.8 mmol) was dissolved in THF (330 mL) in a round bottom flask, sub4c-31 (25.0 g,65.8 mmol), naOH (7.9 g,197.3 mmol), pd (PPh) were added 3 ) 4 (4.56 g,3.95 mmol), water (165 mL), and 17.9g (yield 81.1%) of a product was obtained by a method using synthetic Sub 4-1.
(2) Synthesis example of Sub4-31
After Sub4b-1 (12.1 g,53.3 mmol) was dissolved in THF (270 mL) in a round bottom flask, sub4a-31 (17.9 g,53.3 mmol), naOH (6.4 g,160.0 mmol), pd (PPh) were added 3 ) 4 (3.70 g,3.20 mmol), water (135 mL), and 15.8g (yield 74.4%) of a product was obtained by a method using synthetic Sub 4-1.
Synthesis of Sub4-35
After Sub4b-35 (9.3 g,30.3 mmol) was dissolved in THF (151 mL) in a round bottom flask, sub4a-1 (10.0 g,30.3 mmol), naOH (3.6 g,90.8 mmol), pd (PPh) were added 3 ) 4 (2.10 g,1.82 mmol), water (76 mL), and 11g (yield 76.7%) of a product was obtained by a method using synthesis of Sub 4-1.
The compound belonging to Sub4 may be, but is not limited to, the following compound, and table 2 below shows the field desorption-mass spectrometry (FD-MS) values of the compound belonging to Sub 4.
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TABLE 2
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III Synthesis of final product 1
Synthesis example of S-1
After Sub4-1 (2.9 g,7.4 mmol) was dissolved in THF (tetrahydrofuran) (37 mL) in a round bottom flask, sub3-1 (3.0 g,7.4 mmol), naOH (0.9 g,22.1 mmol), pd (PPh) was added 3 ) 4 (0.51 g,0.44 mmol), water (18 mL), and stirred at 80 and under.
When the reaction is complete, the mixture is taken up in CH 2 Cl 2 And water extraction and the organic layer was subjected to MgSO 4 Drying and concentrating. After this time, after application of the silica gel column, the resulting compound was recrystallized to obtain 3.7g (yield 78%) of a product.
2.S-9 Synthesis example
After Sub4-35 (3.5 g,7.4 mmol) was dissolved in THF (37 mL) in a round bottom flask, sub3-1 (3.0 g,7.4 mmol), naOH (0.9 g,22.1 mmol), pd (PPh) was added 3 ) 4 (0.51 g,0.44 mmol), water (18 mL), and 4.0g (yield 76%) of a product was obtained by a synthetic method using S-1.
3.S-12 Synthesis example
After Sub4-20 (3.8 g,7.4 mmol) was dissolved in THF (37 mL) in a round bottom flask, sub3-1 (3.0 g,7.4 mmol), naOH (0.9 g,22.1 mmol), pd (PPh) was added 3 ) 4 (0.51 g,0.44 mmol), water (18 mL), and 4.4g (78% yield) of the product was obtained using the synthetic method of S-1 above.
Synthesis example of S-21
After Sub4-1 (2.9 g,7.4 mmol) was dissolved in THF (37 mL) in a round bottom flask, sub3-4 (3.0 g,7.4 mmol), naOH (0.9 g,22.1 mmol), pd (PPh) were added 3 ) 4 (0.51 g,0.44 mmol), water (18 mL), and 3.8g (yield 80%) of a product was obtained by a synthetic method using S-1.
Synthesis example of 5.S-33
After Sub4-17 (3.8 g,7.4 mmol) was dissolved in THF (37 mL) in a round bottom flask, sub3-4 (3.0 g,7.4 mmol), naOH (0.9 g,22.1 mmol), pd (PPh) were added 3 ) 4 (0.51 g,0.44 mmol), water (18 mL), and by a synthetic method using S-14.3g (77% yield) of product are obtained.
Synthesis example of 6.S-36
After Sub4-31 (2.9 g,7.4 mmol) was dissolved in THF (37 mL) in a round bottom flask, sub3-4 (3.0 g,7.4 mmol), naOH (0.9 g,22.1 mmol), pd (PPh) were added 3 ) 4 (0.51 g,0.44 mmol), water (18 mL), and 3.7g (yield 78%) of a product was obtained by a synthetic method using S-1.
Synthesis example of 7.S-41
After Sub4-1 (2.9 g,7.4 mmol) was dissolved in THF (37 mL) in a round bottom flask, sub3-6 (3.0 g,7.4 mmol), naOH (0.9 g,22.1 mmol), pd (PPh) were added 3 ) 4 (0.51 g,0.44 mmol), water (18 mL), and 3.0g (yield 63%) of the product was obtained by the synthetic method of S-1.
Meanwhile, FD-MS values of the inventive compounds S-1 to S-56 prepared according to the above synthesis examples are shown in Table 3 below.
TABLE 3
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Example 25 Red organic light-emitting device (phosphorescent host)
The organic electroluminescent device is manufactured according to a conventional method using a compound obtained by synthesis as a light-emitting host material of a light-emitting layer.
First, after a film of N1- (naphthalen-2-yl) -N4, N4-bis (4- (naphthalen-2-yl (phenyl) amino) phenyl) -N1-phenylbenzene-1, 4-diamine (hereinafter, 2-TANA) was vacuum deposited on an ITO layer (anode) formed on a glass substrate to form a hole injection layer having a thickness of 60nm, 4-bis [ N- (1-naphthyl) -N-phenylamino ] as a hole transport compound was vacuum deposited on the hole injection layer]Biphenyl (hereinafter, NPD) to a thickness of 50nm to form a hole transport layer. The emission assistance layer was formed by vacuum depositing tris (4- (9H-carbazol-9-yl) phenyl) amine (hereinafter, TCTA) as an emission assistance layer material to a thickness of 10nm on the hole transport layer. After forming the emission assisting layer, the compound S-1 of the present invention represented by formula 2 as a host and (piq) as a dopant material were doped at a weight ratio of 95:5 in the upper portion of the emission assisting layer 2 Ir (acac), an emissive layer was deposited to a thickness of 30 nm.
Subsequently, (1, 1' -biphenyl) -4-bond) bis (2-methyl-8-quinolinolato) aluminum (hereinafter, BAlq) was vacuum deposited to a thickness of 10nm as a hole blocking layer, and bis (10-hydroxybenzo [ h ] quinolinolato) beryllium (hereinafter, beBq 2) was formed as an electron transport layer having a thickness of 25 nm. Then, liF as an alkali metal halide was deposited to a thickness of 0.2nm as an electron injection layer, and then Al was deposited to a thickness of 150nm and used as a cathode, thereby preparing an organic electroluminescent device.
Examples 26 to 29
An organic electroluminescent device was fabricated in the same manner as in example 25, but using the compound of the present invention described in table 4 as a host material of the emission layer instead of the compound S-1 of the present invention.
Example 30
An organic electroluminescent device was manufactured in the same manner as in example 25, but using the first compound (the compound S-1 of the present invention) and the compound C-1 of the present invention as host materials of the emission layer in a weight ratio of 5:5.
Examples 31 to 41
An organic electroluminescent device was manufactured in the same manner as in example 25, but using the compound of the present invention and the compound C-1 or the compound C-2 shown in Table 4 below as a host material of an emission layer in a weight ratio of 5:5 instead of the compound S-1 of the present invention as a first compound.
Comparative examples 13 to 14
An organic electroluminescent device was fabricated in the same manner as in example 25, except that comparative compound E or comparative compound F was used as a host material of the emission layer instead of the compound S-1 of the present invention.
Comparative examples 15 to 18
An organic electroluminescent device was manufactured in the same manner as in example 25, but using comparative compound E or comparative compound F and compound C-1 or compound C-2 as host materials of the emission layer in a weight ratio of 5:5.
By applying a forward bias DC voltage to the organic electronic devices prepared in examples 25 to 41 and comparative examples 13 to 18 prepared in this manner, and measuring Electroluminescent (EL) characteristics with PR-650 of Photo Research, as a measurement result, a life measuring device manufactured by McScience was used at 2500cd/m 2 The T95 lifetime was measured at standard brightness. Table 4 below shows the device manufacturing and evaluation results.
TABLE 4
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As can be seen from table 4, when the compound of the present invention is used as an emission layer host material, it can be seen that the driving voltage is reduced and the efficiency and the service life are significantly improved as compared to the case of using the comparative compound E or the comparative compound F.
Referring to the examples, it can be seen that the overall performance of the device is better when multiple compounds are mixed and used than when the emissive layer host compound is used alone. In the comparative example, it was confirmed that properties were improved when a plurality of compounds were mixed and used.
As can be seen from the above, when a plurality of compounds are mixed to form a body of an emission layer, characteristics are different according to types of a first compound and a second compound, and when the same compound is applied to the second compound, it can be seen that characteristic differences are significantly exhibited according to the type of the first compound. Similarly, the second compound exhibits differences in driving voltage, efficiency, and lifetime depending on the type.
Recombination energy (hereinafter abbreviated as RE) refers to energy lost due to a change in molecular structural arrangement when charges (electrons, holes) move. It depends on molecular geometry and has a characteristic that the value decreases as the difference between the potential energy surface in the neutral state (hereinafter abbreviated as PES) and the PES in the charge state decreases. RE value can be obtained by the following formula.
RE The cavity ：λ + ＝(E NOCE -E COCE )+(E CONE -E NONE )
RE Electronic device ：λ - ＝(E NOAE -E AOAE )+( EAONE -E NONE )
Each factor may be defined as follows.
Neutral geometry of neutral molecule (hereinafter, NO opt.)
Anionic geometry of neutral molecules
Cationic geometry of neutral molecules
Neutral geometry of AONE anionic molecules
Anionic geometry of anionic molecules (hereinafter, AO opt.)
Neutral geometry of the cationic molecule
Cationic geometry of cationic molecule (hereinafter, CO opt.)
The recombination energy and mobility are inversely proportional to each other and the RE value directly affects the mobility of each material under the condition that they have the same r and T values. The relationship between RE value and mobility is expressed as follows.
Each factor may be defined as follows.
Recombinant energy
-mu. Mobility
-r dimer shift
-t: intermolecular charge transfer matrix element
As can be seen from the above equation, the lower the RE value, the faster the mobility.
RE values require simulation tools that can calculate potential energy from molecular structure, and we use the Gaussian09 (hereinafter G09) and Jaguar (hereinafter JG) modules of Schrodinger Materials Science. Both G09 and JG are tools for analyzing molecular properties by quantum mechanical (hereinafter, QM) computation, and have a function of optimizing a molecular structure or computing energy (single-point energy) of a given molecular structure.
The process of computing QM of a molecular architecture requires a lot of computing resources and we use two cluster servers to do these computations. Each cluster server is composed of 4 node workstations and 1 master workstation, and each node performs molecular QM computations by Symmetric Multiprocessing (SMP) parallel computation using 36 or more core Central Processing Units (CPUs).
The potential energy in neutral state/charge state (NONE/COCE) required to optimize the molecular structure and its recombination energy was calculated using G09. The state of charge potential (NOCE) and the state of neutral potential (CONE) of the structure optimized for the neutral state are calculated by changing the charge of only two optimized structures. The recombination energy is then calculated according to the following relationship.
RE Electric charge ：λ＝(E NOCE -E COCE )+(E CONE -E NONE )
Since schrodinger provides a function of automatically performing such a calculation process, potential energy according to each state is sequentially calculated through the JG module by providing a molecular structure (NO) of a ground state, and an RE value is calculated.
Calculated recombination energy values for comparative compound E, comparative compounds F and S-21 are described in Table 5 below. The RE values shown in Table 5 are RE Electronic device Is a calculated value of (a).
TABLE 5
Compounds of formula (I) Recombinant Energy (RE)
Comparative Compound E 0.2213
Comparative Compound F 0.2378
S-21 0.2462
Referring to Table 5 above, S-21 has a higher RE value than either comparative compound E or comparative compound F. These RE values vary depending on the triazine substituents, in particular, it can be seen that the compounds S-21 of the invention have the highest RE values. In other words, when it has a high RE value, this means low mobility and slow EOD.
When the emission layer is composed of a plurality of mixtures, the driving efficiency and the service life are determined according to the easiness of injecting the hole and the electron into the dopant, and when the hole and electron ratio (charge balance) is properly maintained, the efficiency and the service life are significantly increased.
In other words, since it has a relatively high RE value, the compound of the present invention represented by chemical formula 2 is expected to be better in charge balance, and thus the performance of the device is improved.
It was confirmed that the characteristics of the triazine were very different depending on the type of substituent and the bonding position of the substituent. In particular, when the-naphthyl-phenyl structure and the-biphenyl-1-naphthyl structure are simultaneously substituted with the substituent of the triazine as in the present invention, this effect is considered to be the maximization of the synergistic effect.
Although exemplary embodiments of the present invention have been described for illustrative purposes, those skilled in the art will appreciate that various modifications, additions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims. Accordingly, the embodiments disclosed in the present invention are intended to exemplify the scope of the technical idea of the present invention, and the scope of the present invention is not limited by the embodiments. The scope of the present invention should be construed based on the appended claims, and should be construed as including all technical ideas within the scope equivalent to the claims.

Claims (14)

1. A compound represented by the formula (2),
(2)
Wherein,,
1)R 1 、R 2 、R 3 、R 4 and R is 5 Are identical or different from each other and are, independently of each other, hydrogen or deuterium;
2) L is a single bond; or C 6 -C 60 An arylene group;
3) Ar is C 6 -C 60 An aryl group;
4) c is an integer from 0 to 5, d is an integer from 0 to 6, e and f are each independently an integer from 0 to 4, and g is an integer from 0 to 7,
5) Wherein the arylene group and the aryl group may be further substituted with one or more substituents selected from deuterium; c (C) 6 -C 20 An aryl group; c substituted with deuterium 6 -C 20 An aryl group.
2. The compound according to claim 1, wherein the formula (2) is represented by any one of formulas (2-1) to (2-3):
(2-3)
Wherein,,
R 1 、R 2 、R 3 、R 4 、R 5 l, ar, c, d, e, f and g are the same as defined in claim 1.
3. The compound of claim 1, wherein L is represented by any one of the following formulas a-1 to a-20:
wherein,,
1)R 7 selected from deuterium; c (C) 6 -C 20 An aryl group; c substituted with deuterium 6 -C 20 An aryl group;
2) h, i and j are each independently an integer from 0 to 4, k is an integer from 0 to 6, l is an integer from 0 to 8,
3) Meaning the position where triazine or Ar is bonded.
4. The compound of claim 1, wherein Ar is represented by any one of the following formulas b-1 to b-8:
wherein,,
1)R 8 selected from deuterium; c (C) 6 -C 20 An aryl group; c substituted with deuterium 6 -C 20 An aryl group;
2) m is an integer of 0 to 5, n is an integer of 0 to 7, o is an integer of 0 to 9,
3)meaning the position where it binds to L.
5. The compound according to claim 1, wherein the compound represented by the formula (2) is any one of the following compounds S-1 to S-56:
6. the compound of claim 1, wherein the recombination energy value is 0.240 to 0.300.
7. An organic electronic element comprising a first electrode, a second electrode, and an organic material layer formed between the first electrode and the second electrode, wherein the organic material comprises an emission layer, a hole blocking layer, and an electron transport layer, wherein the emission layer, the hole blocking layer, or the electron transport layer comprises the compound represented by formula (2) of claim 1.
8. The organic electronic element according to claim 7, wherein the emission layer contains the compound represented by formula (2) according to claim 1.
9. The organic electronic element of claim 7 wherein the emissive layer comprises a first host compound; a second host compound; wherein the first host compound or the second host compound includes the compound represented by formula (2) according to claim 1.
10. The organic electronic element according to claim 7, further comprising a light efficiency enhancing layer formed on at least one of surfaces of the first electrode and the second electrode opposite to the organic material layer.
11. The organic electronic element according to claim 7, wherein the organic material layer includes at least two or more stacks including a hole transport layer, an emission layer, and an electron transport layer sequentially formed on the first electrode.
12. The organic electronic element according to claim 11, wherein the organic material layer further comprises a charge generation layer formed between the two or more stacks.
13. An electronic device, comprising: a display device comprising the organic electronic element of claim 7; and a control unit for driving the display device.
14. The organic electronic element according to claim 13, wherein the organic electronic element is any one of an organic electroluminescent device (OLED), an organic solar cell, an Organic Photoreceptor (OPC), an organic transistor (organic TFT), and an element for monochromatic or white illumination.
CN202310333088.8A 2022-04-01 2023-03-31 Compound for organic electronic element, organic electronic element using same, and electronic device using same Pending CN116891441A (en)

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