KR20200082112A - Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof - Google Patents

Abstract

The present invention provides: an organic electric element comprising a compound represented by chemical formula 1, a first electrode, a second electrode, and an organic material layer disposed between the first electrode and the second electrode; and an electronic device comprising the organic electric element. By comprising the compound represented by chemical formula 1 in the organic material layer, a driving voltage can be lowered, and luminous efficiency and a lifespan of the organic electric element can be improved.

Description

Compounds for organic electrical devices, organic electrical devices using the same, and electronic devices thereof {COMPOUND FOR ORGANIC ELECTRONIC ELEMENT, ORGANIC ELECTRONIC ELEMENT USING THE SAME, AND AN ELECTRONIC DEVICE THEREOF}

The present invention relates to a compound for an organic electric element, an organic electric element using the same, and an electronic device thereof.

In general, the organic light emitting phenomenon refers to a phenomenon that converts electrical energy into light energy using an organic material. An organic electric device using an organic light emitting phenomenon usually has a structure including an anode and a cathode and an organic material layer therebetween. Here, the organic material layer is often composed of a multi-layer structure composed of different materials in order to increase the efficiency and stability of the organic electric device, and may be formed of, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer.

Materials used as the organic material layer in the organic electrical device may be classified into light emitting materials and charge transport materials, such as hole injection materials, hole transport materials, electron transport materials, and electron injection materials, depending on their function. In addition, the light-emitting material may be classified into a polymer type and a low-molecular type according to the molecular weight, and a fluorescent material derived from the singlet excited state of the electron and a phosphorescent material derived from the triplet excited state of the electron according to the light emission mechanism. have. In addition, the luminescent material may be divided into blue, green, and red luminescent materials and yellow and orange luminescent materials necessary for realizing a better natural color according to the luminous color.

On the other hand, when only one material is used as the light emitting material, the problem of the maximum light emission wavelength shifting to a long wavelength due to intermolecular interaction and a decrease in color purity or efficiency of the device due to the light emission attenuation effect occurs, so that the increase in color purity and energy transfer In order to increase the luminous efficiency through, a host/dopant system may be used as a luminescent material. The principle is that when a small amount of the dopant having a smaller energy band gap than the host forming the light emitting layer is mixed with the light emitting layer, excitons generated in the light emitting layer are transported to the dopant to produce light with high efficiency. At this time, since the wavelength of the host moves to the wavelength of the dopant, light of a desired wavelength can be obtained according to the type of dopant used.

Currently, the size of the portable display market is increasing as a large-area display, and accordingly, power consumption greater than that required in the existing portable display is required. Therefore, power consumption has become a very important factor for a portable display that has a limited power supply, such as a battery, and the efficiency and lifespan problems must also be solved.

Efficiency, life, and driving voltage are related to each other, and when the efficiency increases, the driving voltage decreases relatively, and as the driving voltage decreases, crystallization of organic substances due to Joule heating generated during driving decreases, and as a result, It shows a tendency to increase the life. However, simply improving the organic layer does not maximize efficiency. This is because long life and high efficiency can be achieved at the same time when the energy level and T ₁ value between each organic material layer and the intrinsic properties of materials (mobility, interfacial properties, etc.) are optimally combined. .

Therefore, there is a need to develop a light emitting material that has high thermal stability and can efficiently achieve charge balance in the light emitting layer. That is, in order to sufficiently exhibit the excellent characteristics of the organic electric device, materials constituting an organic material layer in the device, such as a hole injection material, a hole transport material, a light emitting material, an electron transport material, an electron injection material, are supported by stable and efficient materials It should be preceded, but the development of a stable and efficient organic material layer material for an organic electric device has not been sufficiently made, and among them, development of a host material of a light emitting layer is urgently required.

An object of the present invention is to provide a compound capable of lowering the driving voltage of a device and improving the luminous efficiency and life of the device, an organic electrical device using the same, and its electronic device.

In one aspect, the present invention provides a compound represented by the following formula.

In another aspect, the present invention provides an organic electric device using the compound represented by the formula and an electronic device thereof.

By using the compound according to the embodiment of the present invention, not only the driving voltage of the device can be lowered, but also the luminous efficiency and lifetime of the device can be greatly improved.

1 is an exemplary view of an organic electroluminescent device according to the present invention.
2 is a chemical formula according to an embodiment of the present invention.

The terms "aryl group" and "arylene group" used in the present invention have 6 to 60 carbon atoms, respectively, and are not limited thereto unless otherwise specified. In the present invention, an aryl group or an arylene group may include a monocyclic, ring aggregate, several conjugated ring systems, spiro compounds, and the like. In addition, unless otherwise specified herein, the aryl group may include a fluorenyl group and the arylene group may include a fluorenylene group.

The term "fluorenyl group" or "fluorenylene group" used in the present invention means a monovalent or divalent functional group in which R, R'and R" are both hydrogen in the following structures, unless otherwise specified. 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 R and R'are bonded to each other to form a bonded carbon. It includes the case where a compound was formed as a spy together.

The term "spyro compound" as used in the present invention has a'spyro linkage', and a spiro linkage refers to a linkage formed by two rings sharing only one atom. At this time, the atoms shared by the two rings are called'spyro atoms', and these are'monospyro-','dispiro-', and'trispyro' depending on the number of spy atoms in a compound. It is called a compound.

The term "heterocyclic group" used in the present invention includes aromatic rings such as "heteroaryl group" or "heteroarylene group" as well as non-aromatic rings, and carbon atoms each containing one or more heteroatoms unless otherwise specified. It means a ring of 2 to 60, but is not limited thereto. The term "heteroatom" as used herein refers to N, O, S, P or Si unless otherwise specified, and the heterocyclic group is a monocyclic, ring aggregate, heterozygous multiple ring system, spy containing heteroatoms. Means a compound and the like.

The term "heterocyclic group" used in the present invention means a ring containing a heteroatom such as N, O, S, P or Si instead of carbon forming a ring, and "heteroaryl group" or "heteroarylene group" In addition to the aromatic ring as well as non-aromatic ring, a compound containing a heteroatom group such as SO ₂ , P=O, etc. may be included instead of carbon forming a ring.

The term "aliphatic ring group" used in the present invention means a cyclic hydrocarbon excluding aromatic hydrocarbons, and includes monocyclic, ring aggregates, conjugated multiple ring systems, spiro compounds, and the like, unless otherwise specified. It means a 3 to 60 ring, but is not limited thereto. For example, even when the aromatic ring benzene and the non-aromatic ring cyclohexane are fused, it corresponds to the aliphatic ring.

In the present specification, the'group name' corresponding to an aryl group, an arylene group, a heterocyclic group, etc. exemplified as examples of each symbol and its substituent may describe'the name of a group reflecting a singer', but is described as a'parent compound name' You may. For example, in the case of'phenanthrene', which is a type of aryl group, the monovalent'group' is'phenanthryl' and the bivalent group is a singular such as'phenanthrylene', but the name of the group can be described. Regardless, the parent compound name may be described as'phenanthrene'. Similarly, in the case of pyrimidine, it can be described as'pyrimidine' regardless of the singer, or in the case of monovalent pyrimidinyl group, in the case of divalent pyrimidinylene, etc., as the'group name' of the corresponding singer. have.

In addition, in this specification, in describing the compound name or the substituent name, a number, an alphabet, or the like indicating the position may be omitted. For example, pyrido[4,3-d]pyrimidine as pyridopyrimidine, benzofuro[2,3-d]pyrimidine as benzofuropyrimidine, 9,9-dimethyl-9H-flu Oren can be described as dimethylfluorene or the like. Therefore, both benzo[g]quinoxaline and benzo[f]quinoxaline can be described as benzoquinoxaline.

In addition, unless expressly stated, the formula used in the present invention is applied in the same manner as the definition of a substituent based on the index definition of the following formula.

Here, when a is an integer of 0, the substituent R ¹ means non-existent, that is, when a is 0, it means that hydrogen is bonded to all of the carbons forming the benzene ring. The formula or compound may be omitted. In addition, when a is an integer of 1, one substituent R ¹ is bound to any one of carbons forming a benzene ring, and when a is an integer of 2 or 3, for example, it can be bonded as follows, and a is 4 to 6 Even in the case of an integer, it binds to the carbon of the benzene ring in a similar manner, and when a is an integer of 2 or more, R ¹ may be the same or different.

In addition, unless otherwise specified in the present specification, the rings formed by bonding with adjacent groups are C ₆ ~ C ₆₀ aromatic ring groups; Fluorenyl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C ₃ ~ C ₆₀ aliphatic ring group; C ₃ ~ C ₆₀ aliphatic ring and C ₆ ~ C ₆₀ aromatic ring fused ring group; And combinations thereof.

Hereinafter, a stacked structure of an organic electric device including the compound of the present invention will be described with reference to FIG. 1.

In describing the present invention, when it is determined that detailed descriptions of related known configurations or functions may obscure the subject matter of the present invention, detailed descriptions thereof will be omitted.

Also, if a component such as a layer, film, region, plate, etc. is said to be "on" or "on" another component, it is not only when the other component is "directly above", but also with another component in the middle. It should be understood that the case may be included. Conversely, it should be understood that when a component is said to be “just above” another part, it means that there is no other part in between.

1 is an exemplary view of an organic electric device according to an embodiment of the present invention.

Referring to FIG. 1, an organic electric device 100 according to an embodiment of the present invention includes a first electrode 120, a second electrode 180, and a first electrode 120 formed on a substrate 110. Between the second electrode 180 includes an organic material layer containing the compound according to the present invention. In this case, the first electrode 120 may be an anode (anode), the second electrode 180 may be a cathode (cathode), and in the case of an inverted 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 130, a hole transport layer 140, a light emitting layer 150, an electron transport layer 160, and an electron injection layer 170 sequentially stacked on the first electrode 120. . At this time, at least one of these layers may be omitted, or may further include a hole blocking layer, an electron blocking layer, a light emitting auxiliary layer 151, an electron transport auxiliary layer, a buffer layer 141, etc., and the electron transport layer 160, etc. It can also serve as a hole blocking layer.

In addition, although not shown, the organic electric device according to an embodiment of the present invention may further include a protective layer or a light efficiency improving layer. The light efficiency improving layer may be formed on a surface of both surfaces of the first electrode that does not contact the organic material layer or a surface of both surfaces of the second electrode that does not contact the organic material layer.

The compound according to an embodiment of the present invention applied to the organic layer is a hole injection layer 130, a hole transport layer 140, a light emitting auxiliary layer 151, an electron transport auxiliary layer, an electron transport layer 160, an electron injection layer ( 170), a host or dopant of the light-emitting layer 150, or may be used as a material for a light efficiency improving layer, but preferably, the compound according to Formula 1 of the present invention is used as a host of the light-emitting layer.

On the other hand, even in the case of the same core, the band gap, electrical characteristics, and interfacial characteristics may vary depending on which substituent is attached to which position, and thus, the selection of the core and the combination of sub-substituents coupled thereto. It is necessary to study, especially when the energy level and T ₁ value between each organic material layer and the intrinsic properties of materials (mobility, interfacial properties, etc.) are optimally combined, long life and high efficiency can be achieved simultaneously.

Therefore, in the present invention, by using the compound represented by the formula (1) as a host of the light emitting layer, the energy level and T ₁ value between each organic material layer, the properties of the material (mobility, interfacial properties, etc.) are optimized to optimize the life of the organic electric device. And efficiency can be improved at the same time.

The organic electroluminescent device according to an embodiment of the present invention may be manufactured using various deposition methods. It may be manufactured using a deposition method such as PVD or CVD, for example, by depositing a metal or conductive metal oxide or an alloy thereof on a substrate to form an anode 120, and a hole injection layer 130 thereon , After forming an organic material layer including the hole transport layer 140, the light emitting layer 150, the electron transport layer 160 and the electron injection layer 170, can be prepared by depositing a material that can be used as the cathode 180 thereon have. In addition, the light emitting auxiliary layer 151 may be further formed between the hole transport layer 140 and the light emitting layer 150, and the electron transport auxiliary layer may be further formed between the light emitting layer 150 and the electron transport layer 160.

In addition, the organic material layer is a solution process or a solvent process (e.g., spin coating process), nozzle printing process, inkjet printing process, slot coating process, dip coating process, roll-to-roll process, doctor blade using various polymer materials It can be produced with fewer layers by a method such as a ding process, a screen printing process, or a thermal transfer method. Since the organic material layer according to the present invention can be formed in various ways, the scope of the present invention is not limited by the formation method.

The organic electric device according to an embodiment of the present invention may be a front emission type, a back emission type, or a double-sided emission type depending on the material used.

In addition, the organic electroluminescent device according to an embodiment of the present invention may be selected from the group consisting of an organic electroluminescent device, an organic solar cell, an organic photoreceptor, an organic transistor, a monochromatic lighting device and a quantum dot display device.

Another embodiment of the present invention may include an electronic device including a display device including the above-described organic electric element of the present invention and a control unit for controlling the display device. At this time, the electronic device may be a current or future wired/wireless communication terminal, and includes all electronic devices such as mobile communication terminals such as mobile phones, PDAs, electronic dictionaries, PMPs, remote controls, navigation, game machines, various TVs, and various computers.

Hereinafter, a compound according to an aspect of the present invention will be described.

The compound according to an aspect of the present invention is represented by Formula 1 below.

<Formula 1>

In Chemical Formula 1, each symbol may be defined as follows.

R ₁ to R ₄ are independently of each other hydrogen; heavy hydrogen; halogen; Cyano group; C ₆ ~ C ₆₀ Aryl group; Fluorenyl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C ₃ ~ C ₆₀ aliphatic ring group; C ₁ ~ C ₅₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; C ₂ ~ C ₂₀ alkynyl group; C ₁ ~ C ₃₀ Alkoxy group; C ₆ ~ C ₃₀ Aryloxy group; And -L'-N (R _a ) (R _b ); is selected from the group consisting of, adjacent groups may be bonded to each other to form a ring.

Rings formed by combining adjacent R ₁ , neighboring R ₂ , neighboring R ₃ or neighboring R ₄ may include C ₆ to C ₆₀ aromatic hydrocarbons; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C ₃ ~ C ₆₀ aliphatic ring group; And combinations thereof.

When adjacent groups are combined with each other to form an aromatic hydrocarbon, preferably C ₆ ~ C ₃₀ aromatic hydrocarbons, more preferably C ₆ ~ C ₁₄ aromatic hydrocarbons, such as benzene, naphthalene, phenanthrene, anthracene, etc. Can form.

In addition, when adjacent groups are bonded to each other to form a heterocycle, preferably a C ₂ ~ C ₃₀ heterocyclic group, more preferably a C ₂ ~ C ₁₄ heterocyclic group, such as benzofuran, benzothiophene , Indole, phenyl-indole, and the like. Preferably, adjacent R ₃ may be bonded to each other to form a heterocycle.

a, b, c, and d are each integers of 0 to 4, and when each of these is an integer of 2 or more, each of R _1, each of R _2, each of R _{3, and} each of R ₄ is the same or different.

When R ₁ to R ₄ are aryl groups, preferably, C ₆ to C ₃₀ aryl groups, more preferably C ₆ to C ₁₈ aryl groups, such as phenyl, biphenyl, naphthyl, terphenyl, and the like.

When R ₁ to R ₄ are heterocyclic groups, preferably C ₂ to C ₃₀ heterocyclic groups, more preferably C ₂ to C ₁₈ heterocyclic groups, such as pyridine, pyrimidine, triazine, carbazole, Phenylcarbazole, quinoxaline, and the like.

When R ₁ to R ₄ are an alkyl group, preferably an alkyl group of C ₁ to C ₁₀ may be used, for example, methyl, t-butyl, and the like.

Ar ₁ is a C ₆ ~ C ₆₀ aryl group; Fluorenyl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C ₃ ~ C ₆₀ aliphatic ring group; C ₁ ~ C ₅₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; C ₂ ~ C ₂₀ alkynyl group; C ₁ ~ C ₃₀ Alkoxy group; C ₆ ~ C ₃₀ Aryloxy group; And -L'-N (R _a ) (R _b ); It may be selected from the group consisting of.

When Ar ₁ is an aryl group, preferably an aryl group of C ₆ to C ₃₀ , more preferably an aryl group of C ₆ to C ₁₈ , such as phenyl, biphenyl, naphthyl, terphenyl, phenanthrene, triphenylene , Fluoranthene, pyrene, and the like.

When Ar ₁ is a heterocyclic group, preferably a C ₂ to C ₃₀ heterocyclic group, more preferably a C ₂ to C ₂₄ heterocyclic group, such as pyridine, pyrimidine, triazine, quinazoline, quinoxaline, Benzoquinoxaline, dibenzoquinoxaline, quinoline, benzothiophene, dibenzothiophene, benzonaphthothiophene, benzofuran, dibenzofuran, benzonaphthofuran, carbazole, phenyl-carbazole, benzothieno Pyrimidine, benzofuropyrimidine, indolopyrimidine, indolopyrazine, imidazopyridine, benzoimidazopyridine, dihydrophenazine, dihydro-diphenylphenazine, phenoxazine, phenothiazine, thiarene , Dihydro-dimethyl-phenyl acrodine, and the like.

When Ar ₁ is a fluorenyl group, it may be 9,9-dimethyl-9 H -fluorene, 9,9-diphenyl-9 H -fluorenyl group, 9,9'-spirobifluorene, or the like.

L ₁ and L'are each independently a single bond; C ₆ ~ C ₆₀ Arylene group; Fluorylene group; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; And C ₃ ~ C ₆₀ It may be selected from the group consisting of an aliphatic ring group.

When L ₁ and L'are arylene groups, preferably an arylene group of C ₆ to C ₃₀ , more preferably an arylene group of C ₆ to C ₁₈ , such as phenylene, biphenyl, naphthalene, terphenyl, etc. .

When L ₁ and L'are heterocyclic groups, preferably a heterocyclic group of C ₂ to C ₃₀ , more preferably a heterocyclic group of C ₂ to C ₂₁ , such as pyridine, pyrimidine, triazine, quinoline, carba Sol, phenylcarbazole, quinazoline, quinoxaline, benzoquinoxaline, dibenzoquinoxaline, benzothienopyrimidine, benzofuropyrimidine, indolopyrimidine, indole, dihydrophenazine, dihydro-di Methyl acrodine, dihydro-phenyl acrodine, phenoxazin, phenothiazine, thiarene, and the like.

R _a and R _b are independently of each other C ₆ ~ C ₆₀ aryl group; Fluorenyl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; And C ₃ ~ C ₆₀ Aliphatic ring group; may be selected from the group consisting of.

Substituents indicated by each symbol may be further substituted. For example, the R ₁ ~ R ₄ , L ₁ , Ar ₁ , L', R _a , R _b , rings formed by bonding adjacent groups to each other are deuterium; halogen; A silane group unsubstituted or substituted with an alkyl group of C ₁ -C ₂₀ or an aryl group of C ₆ -C ₂₀ ; Siloxane groups; Boron group; Germanium group; Phosphine oxide unsubstituted or substituted with a C ₁ -C ₂₀ alkyl group or a C ₆ -C ₂₀ aryl group; Cyano group; Nitro group; C ₁ -C ₂₀ alkylthio; C ₁ -C ₂₀ Alkoxy group; C ₆ -C ₂₀ Arylalkoxy group; C ₁ -C ₂₀ alkyl group; Alkenyl group of C ₂ -C ₂₀ ; Alkynyl group of C ₂ -C ₂₀ ; C ₆ -C ₂₀ Aryl group; A C ₆ -C ₂₀ aryl group substituted with deuterium; Fluorenyl group; A C ₂ -C ₂₀ heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; C ₃ -C ₂₀ aliphatic ring group; C ₇ -C ₂₀ Arylalkyl group; C ₈ -C ₂₀ Arylalkenyl group; And it may be further substituted with one or more substituents selected from the group consisting of.

Preferably, the Chemical Formula 1 may be represented by one of the following Chemical Formulas 2 to 7.

<Formula 2> <Formula 3> <Formula 4>

<Formula 5> <Formula 6> <Formula 7>

In the above formula, R ₁ to R ₄ , Ar ₁ , L ₁ , a, b, c, d are as defined in Formula 1.

Specifically, the compound represented by Formula 1 may be one of the following compounds, but is not limited thereto.

.

.

In another aspect of the present invention, the present invention provides an organic electric device including a first electrode, a second electrode, and an organic material layer formed between the first electrode and the second electrode, wherein the organic material layer is represented by Chemical Formula 1 It contains one single compound or two or more compounds.

The organic material layer includes at least one layer of a hole injection layer, a hole transport layer, a light emitting auxiliary layer, a light emitting layer, an electron transport auxiliary layer, an electron transport layer, and an electron injection layer, preferably the compound is included in the light emitting layer, more preferably It is used as a host material for the light emitting layer.

In another aspect of the present invention, the present invention provides an electronic device including a display device including the organic electric element represented by Chemical Formula 1 and a control unit driving the display device.

Hereinafter, examples of the synthesis of the compound represented by Chemical Formula 1 according to the present invention and the manufacturing example of the organic electric device will be specifically described with reference to Examples, but the present invention is not limited to the following Examples.

Synthetic example

The compound represented by Chemical Formula 1 according to the present invention (final product 1) may be prepared by reacting Sub 1 and Sub 2 as shown in Reaction Scheme 1 below, but is not limited thereto.

<Scheme 1>

Exemplary compounds of Sub 1 and Synthetic example

The compound belonging to Sub 1 of Reaction Scheme 1 may be the following compound, but is not limited thereto.

The FD-MS values of the compounds belonging to Sub 1 are shown in Table 1 below.

[Table 1]

Sub 1 of Reaction Scheme 1 may be synthesized by the reaction route of Reaction Scheme 2 below, but is not limited thereto.

<Reaction Scheme 2>

Synthesis Example of Sub 1-I

After dissolving 2,7-dibromonaphthalene (40.0 g, 139.9 mmol) with 466 mL of THF, (2-nitrophenyl)boronic acid (25.7 g, 153.9 mmol), Pd(PPh ₃ ) ₄ (4.9 g, 4.2 mmol), K ₂ CO ₃ (58.0 g, 419.6 mmol), 233 mL of water was added and stirred at 80°C. After the reaction was completed, the organic layer was extracted with CH ₂ Cl ₂ and water, dried over MgSO ₄ and concentrated, and the resulting compound was separated by a silica gel column and recrystallized to obtain 38.6 g of product (yield: 84%).

Synthesis example of Sub 1-II

Sub 1-I (38.6 g, 117.6 mmol) is used instead of 2,7-dibromonaphthalene, and (4-chloro-2-nitrophenyl)boronic acid (26.0 g, 129.4 mmol) is used instead of (2-nitrophenyl)boronic acid, Sub 1 It proceeded in the same way as in the synthesis of -I to give the product 40.0 g (yield: 84%).

Synthesis Example of Sub 1-III

Sub 1-II (40.0 g, 98.8 mmol) was dissolved in 330 ml of o-DCB, triphenylphosphine (77.75 g, 296.4 mmol) was added and stirred at 180°C. When the reaction was completed, separation was performed using a silica gel column and recrystallization to obtain 25.9 g of product (yield: 77%).

Synthesis Example of Sub 1-IV

After dissolving Sub 1-III (25.9 g, 76.1 mmol) in 253 mL of toluene, 1,2-dichlorobenzene (12.3 g, 83.6 mmol), Pd(dba) ₃ (2.1 g, 2.3 mmol), NaOt-bu (21.9 g, 228.0 mmol) and tri tert-butylphosphine (1.5 g, 7.6 mmol) were added and stirred at 120°C. After the reaction was completed, the organic layer was extracted with CH ₂ Cl ₂ and water, dried and concentrated with MgSO ₄ , and the resulting compound was separated by a silica gel column and recrystallized to obtain 25.2 g of product (yield: 80%).

Synthesis example of Sub 1-V

Sub 1-IV (25.2 g, 60.8 mmol) was dissolved in 200 mL of toluene, 2-chloroaniline (8.5 g, 66.8 mmol), Pd(dba) ₃ (1.7 g, 1.8 mmol), NaOt-bu (17.5 g, 182.2) mmol), tri tert-butylphosphine (1.2 g, 6.1 mmol) was added and stirred at 120°C. After the reaction was completed, the mixture was extracted with CH ₂ Cl ₂ and water, and the organic layer was dried over MgSO ₄ , concentrated, and the resulting compound was separated by a silica gel column and recrystallized to obtain 24.6 g of product (yield: 80%).

Sub 1-1 Synthetic example

After dissolving Sub 1-V (24.6 g, 48.6 mmol) in 162 mL of DMA, Pd(OAc) ₂ (0.3 g, 1.5 mmol), K ₂ CO ₃ (20.2 g, 145.8 mmol), tri-tert-butylphosphonium tetrafluoroborate (1.4g, 4.9 mmol) was added and stirred at 160°C. When the reaction is completed, the mixture is extracted with CH ₂ Cl ₂ and water, and the organic layer is dried over MgSO ₄ and concentrated. Thereafter, the resultant compound was separated by a silica gel column and recrystallized to obtain 15.5 g (yield: 68%) of the product.

Sub 1-10 Synthetic example

(1) Sub 1-II-1 synthesis

Instead of 2,7-dibromonaphthalene, 2,9-dibromophenanthrene (40g, 119.0 mmol) was used, and (2-nitrophenyl)boronic acid (21.9g, 130.9 mmol) was used to proceed in the same manner as the synthesis method of Sub 1-I. Product 36.0 g (yield: 80%) was obtained.

(2) Sub 1-II-2 synthesis

Using Sub 1-II-1 (36.0 g, 95.2 mmol) instead of Sub 1-I and (4-chloro-2-nitrophenyl) boronic acid (21.1 g, 104.7 mmol), the synthesis method of Sub 1-II and The same method was carried out to obtain 33.3 g of product (yield: 77%).

(3) Sub 1-II-3 synthesis

Sub 1-II instead of Sub 1-II-2 (33.3 g, 73.3 mmol) was used to proceed in the same manner as in the synthesis method of Sub 1-III to obtain 19.5 g of product (yield: 68%).

(4) Sub 1-II-4 synthesis

Sub 1-III instead of Sub 1-II-3 (19.5g, 49.8 mmol)) was used and 1,2-dichlorobenzene (8.1g, 54.9 mmol) was used to proceed in the same way as in the synthesis of Sub 1-IV. 18.6 g of product (yield: 80%) was obtained.

(5) Sub 1-II-5 synthesis

Sub 1-IV instead of Sub 1-II-4 (18.6 g, 39.9 mmol) was used and 2-chloroaniline (5.6 g, 44 mmol) was used to proceed in the same way as in the synthesis method of Sub 1-V to give 17.8 g of product. (Yield: 80%).

(6) Sub 1-10 synthesis

Sub 1-V instead of Sub 1-II-5 (17.8 g, 32.0 mmol) was used to proceed in the same manner as in the synthesis method of Sub 1-1 to obtain 11.3 g of the product (yield: 68%).

Sub 1-20 Synthetic example

(1) Sub 1-III-1 synthesis

Sub 1-IV instead of Sub 1-IV (40 g, 96.4 mmol) was used and 2,4-dichloroaniline (17.2 g, 106.1 mmol) was used to proceed in the same manner as the synthesis method of Sub 1-V, resulting in 41.7 g of product ( Yield: 80%).

(2) Sub 1-III-2 synthesis

Sub 1-V instead of Sub 1-III-1 (41.7 g, 77.1 mmol) was used to proceed in the same manner as the synthesis method of Sub 1-1 to obtain 26.4 g of the product (yield: 68%).

(3) Sub 1-20 synthesis

Sub 1-IV instead of Sub 1-III-2 (26.4 g, 52.5 mmol), 2-chloroaniline instead of diphenylamine (9.8 g, 57.62 mmol) was used to proceed in the same way as the synthesis method of Sub 1-V, product 25.7. g (yield: 77%) was obtained.

Sub 1-23 Synthetic example

(1) Sub 1-IV-1 synthesis

Sub 1-III (40.0g, 117.4 mmol) was used, and instead of 1,2-dichlorobenzene, 2,3-dichlorodibenzo[b,d]furan (30.6g, 237.1 mmol) was used to synthesize Sub 1-IV. Proceed in the same way to give the product 47.4 g (yield: 80%).

(2) Sub 1-IV-2 synthesis

Sub 1-IV-1 (47.4 g, 93.9 mmol) was used instead of 2,7-dibromonaphthalene, and (2-nitrophenyl)boronic acid (17.2 g, 103.3 mmol) was used. Proceed with to give 42.8 g of product (yield: 77%).

(3) Sub 1-23 synthesis

Sub 1-II instead of Sub 1-IV-2 (42.8 g, 72.3 mmol) was used to proceed in the same manner as the synthesis method of Sub 1-III to obtain 27.5 g of the product (yield: 68%).

Sub 2 Exemplary Compound

Compound belonging to Sub 2 may be synthesized in the same manner as in Scheme 3 below, but is not limited thereto.

<Scheme 3> Hal ¹ = I, Br, Cl; Hal ² = Br, Cl

The compound belonging to Sub 2 may be the following compound, but is not limited thereto.

The FD-MS values of the compounds belonging to Sub 2 are shown in Table 2 below.

[Table 2]

3. Final compound Synthetic example

Synthesis example of P-1

Sub 1-1 (5 g, 10.6 mmol) and Sub 2-1 [Cas. 108-90-7] (1.3g, 11.7 mmol) was dissolved in 35 mL of toluene and then Pd ₂ (dba) ₃ (0.3 g, 0.3 mmol), P( t -Bu) ₃ (0.2 g, 1.1 mmol), NaO t- Bu (3.1 g, 31.9 mmol) was added and stirred at 100°C. After the reaction was completed, the organic layer was extracted with CH ₂ Cl ₂ and water, dried and concentrated with MgSO ₄ , and the resulting compound was separated by a silica gel column and recrystallized to obtain 4.6 g of product (yield: 80%).

Synthesis example of P-7

Sub 1-22 (5 g, 9.6 mmol) instead of Sub 1-1, Sub 2-7 [Cas. 68820-91-7] (2.3g, 10.6 mmol) was used to proceed in the same manner as in the synthesis method of P-1 to obtain 5.2 g of the product (yield: 77%).

P-15 Synthetic Example

Sub 1-1 (5 g, 10.6 mmol) instead of Sub 1-1, Sub 2-15 [Cas. 2060601-50-3] (4.1 g, 11.7 mmol) was used to proceed in the same manner as in the synthesis method of P-1 to obtain 6.7 g of product (yield: 80%).

Synthesis example of P-19

Sub 1-17 (5 g, 9.2 mmol) was replaced by Sub 2-19 [Cas. 29874-83-7] (2.4g, 10.1 mmol) was used to proceed in the same manner as in the synthesis method of P-1 to obtain 5.5 g of product (yield: 80%).

Synthesis example of P-34

Sub 1-1 (5 g, 10.6 mmol) instead of Sub 1-1, Sub 2-33 [Cas. 7342-86-1] (2.0 g, 11.7 mmol) was used to proceed in the same manner as in the synthesis method of P-1 to obtain 4.9 g (yield: 77%) of the product.

Synthesis example of P-44

Sub 1-2 (5 g, 10.6 mmol) instead of Sub 1-1, Sub 2-20 [Cas. 7065-92-1] (2.8 g, 11.7 mmol) was used to proceed in the same manner as in the synthesis method of P-1 to obtain 5.7 g of product (yield: 80%).

Synthesis example of P-55

Sub 1-2 (5 g, 10.6 mmol) instead of Sub 1-1, Sub 2-48 [Cas. 3114-55-4] (1.4g, 11.7 mmol) was used to proceed in the same manner as in the synthesis method of P-1 to obtain 4.7 g of the product (yield: 80%).

Synthesis example of P-59

Sub 1-2 (5g, 10.6 mmol) instead of Sub 1-1, Sub 2-52 [Cas. 1373116-37-0] (4.1 g, 11.7 mmol) was used to proceed in the same manner as in the synthesis method of P-1 to obtain 6.4 g of product (yield: 77%).

Synthesis example of P-68

Sub 1-1 (5 g, 7.0 mmol) instead of Sub 1-1, Sub 2-22 [Cas. 3842-55-5] (2.1 g, 7.7 mmol) was used to proceed in the same manner as in the synthesis method of P-1 to obtain 4.5 g of the product (yield: 68%).

Synthesis example of P-77

Sub 1-4 (5 g, 10.6 mmol) instead of Sub 1-1, Sub 2-21 [Cas. 2915-16-4] (3.1 g, 11.7 mmol) was used to proceed in the same manner as in the synthesis method of P-1 to obtain 5.1 g of the product (yield: 68%).

Synthesis example of P-87

Sub 1-5 (5 g, 10.6 mmol) instead of Sub 1-1, Sub 2-79 [Cas. 1801325-93-8] (3.3g, 11.7 mmol) was used to proceed in the same manner as in the synthesis method of P-1 to obtain 5.2 g of the product (yield: 68%).

Synthesis example of P-91

Sub 1-5 (5 g, 10.6 mmol) instead of Sub 1-1, Sub 2-66 [Cas. 106336-13-4] (3.3 g, 11.7 mmol) was used to proceed in the same manner as in the synthesis method of P-1 to give 5.2 g of the product (yield: 68%).

The FD-MS values of the compounds P-1 to P-106 of the present invention prepared according to the above synthesis examples are shown in Table 3 below.

[Table 3]

Manufacturing evaluation of organic electric devices

[ Example 1] to [ Example 15] Red organic light emitting device (Phosphorescent host)

4,4',4"-Tris[2-naphthyl(phenyl)amino]triphenylamine (hereinafter abbreviated as 2-TNATA) film is vacuum-deposited on the ITO layer (anode) formed on the glass substrate to form a hole injection layer with a thickness of 60 nm. Then, N,N'-Bis(1-naphthalenyl)-N,N'-bis-phenyl-(1,1'-biphenyl)-4,4'-diamine (hereinafter abbreviated as NPB) was formed. A hole transport layer was formed by vacuum deposition to a thickness of 60 nm.

Next, a 30 nm-thick light-emitting layer was formed on the hole transport layer, and the compound P-1 of the present invention was used as a host, and bis-(1-phenylisoquinolyl) iridium(III)acetylacetonat (hereinafter (piq) ₂ Ir(acac)) Flagship) as a dopant, but the host and the dopant were used in a weight ratio of 95:5.

Next, (1,1'-bisphenyl)-4-oleito)bis(2-methyl-8-quinolineoleito)aluminum (hereinafter abbreviated as BAlq) on the light emitting layer was vacuum-deposited to a thickness of 10 nm. A hole blocking layer was formed, and bis(10-hydroxybenzo[h]quinolinato)beryllium (hereinafter abbreviated as BeBq ₂ ) was deposited thereon to form a 40 nm thick electron transport layer. Subsequently, an organic electroluminescent device was manufactured by depositing LiF on the electron transport layer to a thickness of 0.2 nm to form an electron injection layer, and then depositing Al to a thickness of 150 nm to form a cathode.

[ Example 2] to [ Example 25]

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that the compound of the present invention shown in Table 4 below was used instead of the compound P-1 as the host material of the light emitting layer.

[ Comparative example 1] and [ Comparative example 2]

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that the following Comparative Compound 1 or Comparative Compound 2 was used instead of Compound P-1 of the present invention as the host material of the light emitting layer.

<Comparative compound 1> <Comparative compound 2>

Electro-luminescence (EL) characteristics of the organic electroluminescent device manufactured by Examples 1 to 25 and Comparative Examples 1 and 2 of the present invention were applied to PR-650 manufactured by Photoresearch by applying a direct bias DC voltage. The T95 lifespan was measured through a life measurement equipment of Max Science at a reference luminance of 2500 cd/m ² . The measurement results are shown in Table 4 below.

[Table 4]

As can be seen from the results in Table 4, it can be seen that when the compound of the present invention is used as the phosphorescent host of the light emitting layer, the driving voltage is lowered and the efficiency and lifespan are significantly improved compared to the case where Comparative Compound 1 or 2 is used.

That is, when the compound of the present invention is used as a host material, compared to the comparative compound 1, which is a CBP mainly used as a host material, and the comparative compound 2 having a structure having a basic skeleton similar to that of Formula 1 of the present invention as a host material, organic electroluminescence The luminous efficiency, lifespan and driving voltage of the device were significantly improved.

In more detail, when the comparative compound 2, which is an 8-ring heterocyclic compound, is used as a host material, rather than CBP (Comparative Compound 1), which is generally used as a host material, device characteristics are excellent. When the condensed compound of the present invention was used as a host material, it showed better results in terms of driving voltage, efficiency, and life.

These results show that even if the basic skeleton of the core is a similar compound, as the indole is further condensed as in the present invention, hole characteristics, light efficiency characteristics, energy levels (LUMO, HOMO levels, T1 levels), hole injection and mobility characteristics (hole injection) & mobility), the properties of compounds such as electron blocking (electron blocking) properties are different, it is suggested that this can lead to completely different device results.

The above description is merely illustrative of the present invention, and those skilled in the art to which the present invention pertains will be capable of various modifications without departing from the essential characteristics of the present invention. Therefore, the embodiments disclosed herein are not intended to limit the present invention, but to explain the present invention, and the spirit and scope of the present invention are not limited by these embodiments. The scope of protection of the present invention should be interpreted by the following claims, and all technologies within the equivalent range should be interpreted as being included in the scope of the present invention.

100: organic electrical element 110: substrate
120: first electrode 130: hole injection layer
140: hole transport layer 141: buffer layer
150: light emitting layer 151: light emitting auxiliary layer
160: electron transport layer 170: electron injection layer
180: second electrode

Claims (8)

Compound represented by the formula (1):
<Formula 1>

In the above formula,
R ₁ to R ₄ are independently of each other hydrogen; heavy hydrogen; halogen; Cyano group; C ₆ ~ C ₆₀ Aryl group; Fluorenyl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C ₃ ~ C ₆₀ aliphatic ring group; C ₁ ~ C ₅₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; C ₂ ~ C ₂₀ alkynyl group; C ₁ ~ C ₃₀ Alkoxy group; C ₆ ~ C ₃₀ Aryloxy group; And -L'-N (R _a ) (R _b ); is selected from the group consisting of, adjacent groups may be bonded to each other to form a ring,
a, b, c and d are each integers of 0 to 4, and when each of them is an integer of 2 or more, each of R _1, each of R _2, each of R _{3, and} each of R ₄ is the same or different from each other,
Ar ₁ is a C ₆ ~ C ₆₀ aryl group; Fluorenyl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C ₃ ~ C ₆₀ aliphatic ring group; C ₁ ~ C ₅₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; C ₂ ~ C ₂₀ alkynyl group; C ₁ ~ C ₃₀ Alkoxy group; C ₆ ~ C ₃₀ Aryloxy group; And -L'-N (R _a ) (R _b ); is selected from the group consisting of,
L ₁ and L'are each independently a single bond; C ₆ ~ C ₆₀ Arylene group; Fluorylene group; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; And C ₃ ~ C _{60 It} is selected from the group consisting of an aliphatic ring,
R _a and R _b are independently of each other C ₆ ~ C ₆₀ aryl group; Fluorenyl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; And C ₃ ~ C ₆₀ Aliphatic ring group; is selected from the group consisting of. According to claim 1,
Chemical Formula 1 is a compound characterized in that represented by one of the following Chemical Formulas 2 to 7:
<Formula 2><Formula3><Formula4>

<Formula 5><Formula6><Formula7>

In the above formula, R ₁ to R ₄ , Ar ₁ , L ₁ , a, b, c, d are as defined in claim 1. According to claim 1,
The compound represented by Formula 1 is one of the following compounds:

. In the organic electric device including a first electrode, a second electrode, and an organic material layer formed between the first electrode and the second electrode,
The organic material layer is characterized in that it comprises a single compound or two or more compounds represented by the formula (1) of claim 1. The method of claim 4,
The organic material layer comprises at least one of a hole injection layer, a hole transport layer, a light emitting auxiliary layer, a light emitting layer, an electron transport auxiliary layer, an electron transport layer and an electron injection layer. The method of claim 5,
The compound is an organic electrical device, characterized in that included in the light emitting layer. A display device comprising the organic electric device of claim 4; And
An electronic device comprising; a control unit for driving the display device. The method of claim 7,
The organic electric device is an electronic device, characterized in that selected from the group consisting of an organic electroluminescent device, an organic solar cell, an organic photoreceptor, an organic transistor, a monochromatic lighting device and a quantum dot display device.

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