KR20190140586A - Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof - Google Patents

Abstract

Disclosed are: an organic electronic device comprising a compound represented by chemical formula 1, a first electrode, a second electrode, and an organic material layer between the first electrode and the second electrode; and an electronic apparatus comprising the organic electronic device. By comprising the compound represented by chemical formula 1 in the organic material layer, it is possible to lower a driving voltage and improve luminous efficiency and lifespan of the organic electronic device.

Description

COMPONENT 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 device, an organic electric device using the same, and an electronic device thereof.

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

The material used as the organic material layer in the organic electric element may be classified into a light emitting material and a charge transport material such as a hole injection material, a hole transport material, an electron transport material, an electron injection material and the like according to a function. The light emitting material may be classified into a polymer type and a low molecular 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. have. In addition, the light emitting material may be classified into blue, green, and red light emitting materials and yellow and orange light emitting materials required to achieve a better natural color according to the light emitting color.

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

Currently, the portable display market is increasing in size with large-area displays, which requires more power consumption than is required for conventional portable displays. Therefore, power consumption has become a very important factor for a portable display having a limited power supply such as a battery, and the problem of efficiency and lifespan must also be solved.

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

Therefore, there is a need for development of a light emitting material having high thermal stability and efficiently achieving a charge balance in the light emitting layer. That is, in order to fully exhibit the excellent characteristics of the organic electric device, a material forming the 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, etc., is supported by a stable and efficient material. Although this should be preceded, the development of a stable and efficient organic material layer for an organic electric device has not been sufficiently achieved. Among them, the development of the host material of the light emitting layer is particularly urgently required.

An object of the present invention is to provide a compound capable of lowering the driving voltage of the device and improving the luminous efficiency, color purity, stability, and lifetime of the device, an organic electric device using the same, and an electronic device thereof.

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

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

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

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

As used herein, the terms "aryl group" and "arylene group" have a carbon number of 6 to 60 unless otherwise stated, but is not limited thereto. In the present invention, the aryl group or arylene group includes monocyclic, ring aggregate, conjugated ring system, spiro compound and the like.

As used herein, the term "heterocyclic group" includes not only aromatic rings, such as "heteroaryl groups" or "heteroarylene groups," but also non-aromatic rings, and unless otherwise stated, carbon number each including one or more heteroatoms. It means a ring of 2 to 60, but is not limited thereto. As used herein, the term “heteroatom” refers to N, O, S, P or Si unless otherwise indicated, and heterocyclic groups are monocyclic, ring aggregates, conjugated multiple ring systems, spies, including heteroatoms. Means a compound or the like.

As used herein, the term "heterocyclic group" refers to a ring containing a hetero atom such as N, O, S, P or Si, instead of the carbon forming the ring, "heteroaryl group" or "heteroarylene group" In addition to the aromatic ring, such as a non-aromatic ring, and may include a compound containing a hetero atom group, such as SO ₂ , P = O and the like instead of the carbon forming the ring.

As used herein, the term "fluorenyl group" or "fluorenylene group" means a monovalent or divalent functional group in which R, R 'and R "are all hydrogen in the following structures, unless otherwise stated, and" Substituted fluorenyl group "or" substituted fluorenylene group "means that at least one of the substituents R, R ', and R" is a substituent other than hydrogen, and R and R' are bonded to each other to form a carbon It includes the case of forming a compound by spying together.

As used herein, the term "spiro compound" has a "spiro union", and a spiro linkage means a linkage formed by two rings sharing one atom only. In this case, the atoms shared by the two rings are called spiro atoms, and according to the number of spiro atoms in a compound, they are respectively referred to as 'monospyro-', 'diespyro-' and 'trispyro-' It is called a compound.

The group name corresponding to the aryl group, arylene group, heterocyclic group, etc. exemplified in each symbol and examples of the substituents in this specification may describe 'the name of the group reflecting the singer', but is described as 'the parent compound name'. You may. For example, in the case of phenanthrene, which is a kind of aryl group, the monovalent group is phenanthryl and the divalent group may be grouped with a singer, such as phenanthryl, to describe the group name. Regardless, it may be described as the parent compound name 'phenanthrene'. Similarly, in the case of pyrimidine, it may be described as 'pyrimidine' irrespective of the valence, or as the 'name of the group' of the singer, such as pyrimidinyl group in the case of monovalent and pyrimidinylene in the case of divalent. have.

In addition, unless otherwise stated, the formulas used in the present invention apply equally to the substituent definitions based on the exponential definitions of the following formulas.

Herein, when a is an integer of 0, the substituent R ¹ is absent, when a is an integer of 1, one substituent R ¹ is bonded to any one of carbons forming the benzene ring, and a is an integer of 2 or 3 Each combine as follows, where R ¹ may be the same or different. When a is an integer of 4 to 6, it is bonded to the carbon of the benzene ring in a similar manner. In addition, the indication of the hydrogen couple | bonded with the carbon which forms the benzene ring can be abbreviate | omitted.

Hereinafter, a lamination 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 the detailed description of the related well-known configuration or function may obscure the gist of the present invention, the detailed description thereof will be omitted.

In addition, 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 "on top of" but also another component in between. It is to be understood that this may also include cases. On the contrary, when a component is said to be "directly above" another part, it should be understood to mean that there is no other part in the middle.

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 may include a first electrode 120, a second electrode 180, and a first electrode 120 formed on a substrate 110. An organic material layer including the compound according to the present invention is included between the second electrodes 180. 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, an electron injection layer 170, etc. sequentially stacked on the first electrode 120. . In this case, 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, and the like. It may also serve as a hole blocking layer.

In addition, although not shown, the organic electronic 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 not in contact with the organic material layer on both surfaces of the first electrode or on a surface not in contact with the organic material layer on both surfaces of the second electrode.

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, the host or dopant of the light emitting layer 150, or may be used as a material of the light efficiency improving layer. Preferably, the compound according to Formula 1 of the present invention can be 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, interfacial characteristics, etc. may vary depending on which substituents are bonded at which positions, so that the selection of the cores and the combination of sub-substituents bonded thereto are required. In particular, long life and high efficiency can be simultaneously achieved when an optimal combination of energy level, T ₁ value, and intrinsic properties (mobility, interfacial properties, etc.) of each organic material layer is achieved.

Therefore, in the present invention, by using the compound represented by the formula (1) as a host of the light emitting layer, the lifetime of the organic electric device by optimizing the energy level and T ₁ value between each organic material layer, the intrinsic properties (mobility, interface properties, etc.) 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, the anode 120 is formed by depositing a metal or conductive metal oxide or an alloy thereof on a substrate, and the hole injection layer 130 thereon. , By forming an organic material layer including a hole transport layer 140, a light emitting layer 150, an electron transport layer 160 and an electron injection layer 170, and then 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 an 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 or solvent process (e.g., spin coating process, nozzle printing process, inkjet printing process, slot coating process, dip coating process, roll-to-roll process, doctor blading), using various polymer materials. It can be produced in fewer layers by methods such as ding process, screen printing process, or thermal transfer method. Since the organic material layer according to the present invention may be formed in various ways, the scope of the present invention is not limited by the forming method.

The organic electric element according to an embodiment of the present invention may be a top emission type, a bottom emission type or a double-sided emission type according to 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 photosensitive member, an organic transistor, a monochromatic lighting device and a quantum dot display device.

Another embodiment of the present invention may include a display device including the organic electric element of the present invention described above, and an electronic device including a control unit for controlling the display device. In this case, the electronic device may be a current or future wired or wireless communication terminal, and includes all electronic devices such as a mobile communication terminal such as a mobile phone, a PDA, an electronic dictionary, a PMP, a remote controller, a navigation device, a game machine, various TVs, and various computers.

Hereinafter, the compound which concerns on one aspect of this invention is demonstrated.

Compound according to an aspect of the present invention is represented by the following formula (1).

<Formula 1>

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

Ring A and Ring B independently from each other C ₆ ~ C ₆₀ aromatic hydrocarbons; Fluorene; C ₂ -C ₆₀ heterocycle including at least one heteroatom of O, N, S, Si, and P; Aliphatic rings of C ₃ -C ₃₀ ; And combinations thereof may be selected from the group.

When ring A and ring B are aromatic hydrocarbons, it may be preferably C ₆ to C ₃₀ aromatic hydrocarbons, more preferably C ₆ to C ₁₄ aromatic hydrocarbons such as benzene, naphthalene, phenanthrene and the like. When ring A and ring B are heterocycles, preferably C ₂ to C ₃₀ heterocycle, more preferably C ₂ to C ₂₂ heterocycle, such as dibenzothiophene, carbazole, phenylcarbazole, dibenzo Furan, benzonaphthothiophene, dynaphthothiophene, phenanthrothiophene, benzocarbazole, phenylbenzocarbazole and the like. When ring A and ring B are fluorene, it may be dimethyl fluorene, diphenyl fluorene, or the like.

The C ring is C ₆ -C ₃₀ aromatic hydrocarbon or C ₂ -C ₃₀ heterocycle.

When the C ring is an aromatic hydrocarbon, preferably C ₆ -C ₁₈ aromatic hydrocarbons, more preferably C ₆ -C ₁₄ aromatic hydrocarbons, such as benzene, naphthalene, phenanthrene and the like. When the C ring is a hetero ring, preferably a C ₂ to C ₁₈ hetero ring, more preferably a C ₂ to C ₁₆ hetero ring such as benzothiophene, naphthothiophene, phenanthrothiophene, benzofuran, Naphthofuran and the like.

X ¹ to X ³ are independently of each other N or C, two of X ¹ to X ³ are N and the other is C. When one of X ¹ to X ³ is C, such C binds to L ₁ .

L ₁ is independently of each other a single bond; C ₆ ~ C ₆₀ arylene group; Fluorenylene groups; Aliphatic ring group of C ₃ ~ C ₆₀ ; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; And combinations thereof may be selected from the group.

When L ₁ is an arylene group, it may be preferably an arylene group of C ₆ to C ₃₀ , more preferably an arylene group of C ₆ to C ₁₂ , such as phenylene, naphthalene, biphenyl and the like. When L ₁ is a heterocyclic group, preferably a C ₂ to C ₃₀ heterocyclic group, more preferably a C ₂ to C ₉ heterocyclic group such as pyridine, pyrimidine, triazine, quinazoline, quinoline, quinox It may be saved.

Ar ₁ and Ar ₂ are each independently 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; Aliphatic ring group of C ₃ ~ C ₆₀ ; C ₁ ~ C ₅₀ Alkyl group; C ₂ ~ C ₂₀ Alkenyl group; Alkynyl groups of C ₂ to C ₂₀ ; C ₁ ~ C ₃₀ Alkoxy group; C ₆ -C ₃₀ aryloxy group; And -L'-N (R _a ) (R _b ).

When Ar ₁ and Ar ₂ are aryl groups, preferably an aryl group of C ₆ to C ₃₀ , more preferably an aryl group of C ₆ to C ₁₈ , such as phenyl, naphthyl, biphenyl, phenanthrene, triphenylene , Terphenyl, and the like. When Ar ₁ and Ar ₂ are heterocyclic groups, preferably C ₂ to C ₃₀ heterocyclic groups, more preferably C ₂ to C ₁₆ heterocyclic groups such as dibenzothiophene, dibenzofuran, carbazole , Phenylcarbazole, benzonaphthothiophene, benzothiophene and the like. When Ar ₁ and Ar ₂ are fluorenyl groups, they may be dimethyl fluorene, diphenyl fluorene, spirofluorene, or the like.

L 'is a single bond; C ₆ ~ C ₆₀ arylene group; Fluorenylene groups; Aliphatic ring group of C ₃ ~ C ₆₀ ; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; And combinations thereof may be selected from the group.

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

Ring A, ring B, ring C, L ₁ , Ar ₁ , Ar ₂ , L ', R _a and R _b are each deuterium; halogen; A silane group unsubstituted or substituted with a C ₁ -C ₂₀ alkyl group or a C ₆ -C ₂₀ aryl group; Siloxane groups; Boron group; Germanium group; Cyano group; Nitro group; Import alkylthio of C ₁ -C _20; An alkoxy group of C ₁ -C ₂₀ ; C ₆ -C ₂₀ arylalkoxy group; An alkyl group of C ₁ -C ₂₀ ; Alkenyl groups of C ₂ -C ₂₀ ; An alkynyl group of C ₂ -C ₂₀ ; Aryl group of C ₆ -C ₂₀ ; C ₆ -C ₂₀ aryl group substituted with deuterium; Fluorenyl groups; C ₂ -C ₂₀ heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; Aliphatic ring groups of C ₃ -C ₂₀ ; C ₇ -C ₂₀ arylalkyl group; Arylalkenyl group of C ₈ -C ₂₀ ; And one or more substituents selected from the group consisting of a combination thereof.

Preferably, Formula 1 may be represented by one of the following Formula 2 to Formula 5.

  <Formula 2> <Formula 3> <Formula 4> <Formula 5>

In Formulas 2 to 5, A ring, B ring, L ₁ , Ar ₁ and Ar ₂ are the same as defined in Formula 1, Y ₁ and Y ₂ is O or S, n and m are each 0 or It is an integer of 1 except n + m is an integer of 1 or more. In Formula 5, when n and m are 0, it means a single bond.

Preferably, at least one of the A ring and the B ring is a C ₁₀ or more aryl group.

Preferably, Formula 1 may be represented by one of the following Formula 6 to Formula 21.

<Formula 6> <Formula 7> <Formula 8> <Formula 9>

<Formula 10> <Formula 11> <Formula 12> <Formula 13>

<Formula 14> <Formula 15> <Formula 16> <Formula 17>

<Formula 18> <Formula 19> <Formula 20> <Formula 21>

In Chemical Formulas 6 to 21, each symbol may be defined as follows.

C ring, L ₁ , Ar ₁ , Ar ₂ and X ¹ to X ³ are the same as defined in Chemical Formula 1.

R ² and R ³ are independently of each other hydrogen; heavy hydrogen; halogen; Cyano group; Nitro 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; Aliphatic ring group of C ₃ ~ C ₆₀ ; C ₁ ~ C ₅₀ Alkyl group; C ₂ ~ C ₂₀ Alkenyl group; Alkynyl groups of C ₂ to C ₂₀ ; C ₁ ~ C ₃₀ Alkoxy group; C ₆ -C ₃₀ aryloxy group; And -L'-N (R _a ) (R _b ), and neighboring groups may be bonded to each other to form a ring, wherein the ring is C ₆ -C ₆₀ aromatic ring; C ₂ -C ₆₀ heterocycle including at least one heteroatom of O, N, S, Si, and P; Aliphatic rings of C ₃ -C ₆₀ ; And combinations thereof, wherein L ′, R _a and R _b are as defined in formula (1).

a is an integer of 0-4, b is an integer of 0-6, c is an integer of 0-8, and when each of these is an integer of 2 or more, each R <^2> and each R <^3> is mutually same or different.

Preferably, L ₁ may be selected from the group consisting of Formulas A-1 to A-12.

In Formulas A-1 to A-12, each symbol may be defined as follows.

R ⁶ to R ⁸ are each independently hydrogen; heavy hydrogen; halogen; Cyano group; Nitro 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; Aliphatic ring group of C ₃ ~ C ₆₀ ; C ₁ ~ C ₅₀ Alkyl group; C ₂ ~ C ₂₀ Alkenyl group; Alkynyl groups of C ₂ to C ₂₀ ; C ₁ ~ C ₃₀ Alkoxy group; C ₆ -C ₃₀ aryloxy group; And -L'-N (R _a ) (R _b ), and neighboring groups may be bonded to each other to form a ring, wherein the ring is C ₆ -C ₆₀ aromatic ring; C ₂ -C ₆₀ heterocycle including at least one heteroatom of O, N, S, Si, and P; Aliphatic rings of C ₃ -C ₆₀ ; And combinations thereof.

a ', c', d 'and e' are each an integer from 0 to 4, b 'is an integer from 0 to 6, f' and g 'are each an integer from 0 to 3, h' is 0 or 1 May be the same as or different from each other when each of R ⁶ , each R ⁷ and each R ⁸ is an integer of 2 or more.

Y is N (R '), O, S or C (R') (R ").

Z ¹ to Z ³ are C, CR 'or N, and at least one of Z ¹ to Z ³ is N.

R ′ and R ″ are each independently hydrogen; deuterium; halogen; cyano group; nitro group; C ₆ ~ C ₆₀ aryl group; fluorenyl group; at least one heteroatom of O, N, S, Si, and P; C ₂ ~ C ₆₀ Heterocyclic group containing, C ₃ ~ C ₆₀ Alicyclic group; C ₁ ~ C ₅₀ Alkyl group; C ₂ ~ C ₂₀ Alkenyl group; C ₂ ~ C ₂₀ Alkynyl group; C An alkoxy group of ₁ to C ₃₀ ; an aryloxy group of C ₆ to C ₃₀ ; and -L'-N (R _a ) (R _b ), wherein R 'and R "are bonded to each other to bond Together with C to form a ring.

L ′, R _a and R _b are the same as defined in Chemical Formula 1.

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

.

.

In another aspect, 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 Formula 1 It includes a 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, and preferably the compound is included in the light emitting layer.

Synthesis Example

Compounds represented by Chemical Formula 1 according to the present invention are synthesized by reacting Sub 1 and Sub 2 as in Scheme 1 below, but are not limited thereto.

<Scheme 1>

I. Synthesis of Sub 1

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

<Scheme 2>

Synthesis examples of the compound belonging to Sub 1 are as follows.

One. Sub1 -2 Synthesis Example

<Scheme 3>

(1) Sub1-I-2

Naphthalen-2-ylboronic acid (100 g, 0.58 mol) was added to a round bottom flask and dissolved with THF / H ₂ O (1000/300 mL), then 1-bromo-2-nitrobenzene (117 g, 0.58 mol), Pd (pph ₃ ) ₄ (20 g, 0.017 mol), NaOH (69 g, 1.74 mol) was added and stirred at 80 ° C. After completion of the reaction, the mixture was extracted with CH ₂ Cl ₂ and water, and the organic layer was dried over MgSO ₄ and concentrated. The concentrate was then recrystallized after applying a silica gel column to give 110 g (yield: 76%) of product Sub1-I-2.

(2) Sub1 -2 synthesis

Sub-I-1 (100 g, 0.40 mol) was added to DCB (300 ml), triphenylphosphane (316 g, 1.2 mol) was added thereto, and stirred at 200 ° C. After removing the solvent and synthesized in the same manner as the synthesis method of Sub-I-2 to give 81 g (yield: 92%) of the product Sub 1-1.

2. Sub1-13 Synthesis Example

<Scheme 4>

3-bromo-9H-carbazole (50 g, 0.20 mol) was added to a round bottom flask and dissolved with THF / H ₂ O (400/100 mL), then phenylboronic acid (25 g, 0.20 mol), Pd (pph ₃ ) ₄ (7 g, 0.006 mol), NaOH (24 g, 0.61 mol) was added and stirred at 80 ° C. When the reaction was completed, the synthesis was carried out in the same manner as in the synthesis of Sub-I-2, to obtain 44 g (yield: 89%) of the product Sub1-13.

3. Sub1-21 Synthesis Example

Scheme 5

(1) Sub1-I-21 Synthesis

(9-phenyl-9H-carbazol-3-yl) boronic acid (50 g, 0.17 mol) was added to a round bottom flask and dissolved with THF / H ₂ O (350/80 mL), followed by 1-bromo-2-nitrobenzene (35 g, 0.17 mol), Pd (pph ₃ ) ₄ (6 g, 0.005 mol), NaOH (21 g, 0.52 mol) were added and stirred at 80 ° C. When the reaction was completed, it was synthesized by the same method as the synthesis of Sub-I-2 to give 55 g (yield: 86.7%) of the product Sub1-I-21.

(2) Sub1-II-21 Synthesis

Sub-I-21 (50 g, 0.14 mol) was added to DCB (200 ml), triphenylphosphane (108 g, 0.41 mol) was added thereto, and the mixture was stirred at 200 ^° C. After removing the solvent and synthesized in the same manner as the synthesis of Sub-I-2 to give the product Sub 1-21 21 g (yield: 46%).

4. Sub1-35 Synthesis Example

<Scheme 6>

(1) Sub1-I-35 synthesis

6-bromodinaphtho [1,2-b: 1 ', 2'-d] thiophene (100 g, 0.28 mol), 2-chloroaniline (35 g, 0.28 mol), Pd ₂ (dba) ₃ (7.5 g, 0.008 mol ), 50% P ( t -Bu) ₃ (6.7 ml, 0.01 mol), NaO t -Bu (79 g, 0.82 mol) was added to toluene (550 ml) and stirred at 90 ° C. Thereafter, 90 g (yield: 80%) of the product Sub 1-I-35 was obtained by synthesis in the same manner as in the synthesis of Sub1-I-2.

(2) Sub1-35 Synthesis

Sub-I-35 (50 g, 0.24 mol) was added to DMA (490 mL) followed by Pd (OAc) ₂ (1.64 g, 0.007 mol), K ₂ CO ₃ (100 g, 0.733 mol) and at 90 ° C. Stirred. Thereafter, 90 g (yield: 80%) of the product Sub 1-I-35 was obtained by synthesis in the same manner as in the synthesis of Sub1-I-2.

The compound belonging to Sub 1 may be, but is not limited to, the following compounds. Table 1 shows FD-MS values of compounds belonging to Sub 1.

 TABLE 1

Ⅱ. Synthesis of Sub 2

Sub 2 of Scheme 1 may be synthesized by the reaction route of Scheme 7, but is not limited thereto.

Scheme 7

Synthesis examples of the compound belonging to Sub 2 are as follows.

1. Sub2-1 Synthesis Example

Scheme 8

4- (diphenylamino) phenyl) boronic acid (50 g, 0.17 mol) and 2,4-dichloroquinazoline (34.5 g, 0.17 mol) were added to a round bottom flask and dissolved with THF (350 mL) and H ₂ O (100 mL). Then Pd (PPh ₃ ) ₄ (6 g, 0.005 mol), K ₂ CO ₃ (71 g, 0.51 mol) was added and stirred at 75 ° C. After completion of the reaction, the mixture was extracted with CH ₂ Cl ₂ and water, and the organic layer was dried over MgSO ₄ and concentrated. The concentrate was then recrystallized after applying a silica gel column to give 67 g (yield: 95.5%) of product.

2. Sub2-6 Synthesis Example

Scheme 9

3- (dibenzo [b, d] thiophen-2-yl (phenyl) amino) phenyl) boronic acid (100 g, 0.25 mol) and 2,4-dichloroquinazoline (50 g, 0.25 mol) with THF (506 mL) After dissolving with H ₂ O (150 mL), Pd (PPh ₃ ) ₄ (8.8 g, 0.008 mol) and K ₂ CO ₃ (104 g, 0.76 mol) were added and stirred at 75 ° C. Then, the synthesis in the same manner as in the Sub2-1 synthesis method to give a product 88 g (yield: 67.6%).

3. Synthesis Example of Sub2-18

Scheme 10

4- (phenyl (4- (pyridin-2-yl) phenyl) amino) phenyl) boronic acid (70 g, 0.19 mol) and 2,3-dichloroquinoxaline (38 g, 0.19 mol) were dissolved in THF (380 mL) and H After dissolving with ₂ O (120 mL) Pd (PPh ₃ ) ₄ (6.6 g, 0.005 mol), K ₂ CO ₃ (79 g, 0.57 mol) was added and stirred at 75 ° C. Thereafter, 80 g (yield: 86.4%) of the product Sub2-18 was obtained by synthesis in the same manner as in the above Sub2-1 synthesis.

4. Sub2-31 Synthesis Example

Scheme 11

4- (9,9'-spirobi [fluoren] -3-yl (dibenzo [b, d] furan-1-yl) amino) phenyl) boronic acid (65 g, 0.1 mol) with 2,3-dichlorodibenzo [f , h] quinoxaline (31 g, 0.1 mol) was dissolved in THF (210 mL) and H ₂ O (70 mL), then Pd (PPh ₃ ) ₄ (3.6 g, 0.003 mol), K ₂ CO ₃ (43.6 g, 0.32 mol) was added and stirred at 75 ° C. Thereafter, 80 g (yield: 90%) of product Sub2-31 was obtained by synthesis in the same manner as in the above Sub2-1 synthesis.

5. Sub2-63 Synthesis Example

Scheme 12

(4- (diphenylamino) phenyl) boronic acid (30 g, 0.1 mol) and 2,4-dichlorobenzofuro [3,2-d] pyrimidine (25 g, 0.1 mol) were dissolved in THF (210 mL) and H ₂ O (70 mL) and then Pd (PPh ₃ ) ₄ (3.6 g, 0.003 mol) and K ₂ CO ₃ (43.6 g, 0.32 mol) were added and stirred at 75 ° C. Subsequently, 40 g (yield: 80%) of product Sub2-63 was obtained by synthesis in the same manner as in the synthesis of Sub2-1.

TABLE 2

III. Synthesis of Final Compound

1.P-1 Synthesis Example

Scheme 13

Sub 1-1 (20 g, 0.11 mol) is dissolved in toluene (240 ml), then Sub 2-1 (49 g, 0.11 mol), Pd ₂ (dba) ₃ (3.3 g, 0.003 mol), 50% P ( t- Bu) ₃ (3 ml, 0.007 mol), NaO t -Bu (34.5 g, 0.359 mol) were added and stirred at 135 ° C. After completion of the reaction, the mixture was extracted with toluene and water, and the organic layer was dried over MgSO ₄ and concentrated. The concentrate was then recrystallized after applying a silica gel column to give 60 g (yield: 93%) of product P-1.

2. P-10 Synthesis Example

Scheme 14

Sub 1-8 (12 g, 0.045 mol) is dissolved in toluene (100 ml), then Sub 2-10 (22 g, 0.045 mol), Pd ₂ (dba) ₃ (1 g, 0.001 mol), 50% P ( t- Bu) ₃ (1 ml, 0.002 mol), NaO t -Bu (13 g, 0.13 mol) were added and stirred at 135 ° C. Thereafter, the compound was synthesized in the same manner as in the synthesis of P-1, to obtain 21 g (yield: 64%) of product P-10.

3. P-24 Synthesis Example

Scheme 15

Sub 1-29 (15 g, 0.055 mol) is dissolved in toluene (120 ml), then Sub 2-23 (27 g, 0.055 mol), Pd ₂ (dba) ₃ (1.3 g, 0.001 mol), 50% P ( t- Bu) ₃ (1.1 ml, 0.002 mol), NaO t -Bu (15 g, 0.16 mol) were added and stirred at 135 ° C. After the synthesis in the same manner as the synthesis method of P-1 to give 30 g (yield: 73%) of the product P-24.

4. P-26 Synthesis Example

Scheme 16

Sub 1-9 (20 g, 0.064 mol) is dissolved in toluene (130 ml), then Sub 2-25 (27 g, 0.064 mol), Pd ₂ (dba) ₃ (1.7 g, 0.002 mol), 50% P ( t- Bu) ₃ (1.5 ml, 0.004 mol), NaO t -Bu (18 g, 0.18 mol) were added and stirred at 135 ° C. After the synthesis in the same manner as the synthesis method of P-1 to give 40 g (yield: 89.8%) of the product P-26.

5. P-30 Synthesis Example

Scheme 17

After dissolving Sub1-36 (18 g, 0.07 mol) and Sub2-29 (37.5 g, 0.07 mol) with toluene (140 ml), Pd ₂ (dba) ₃ (1.9 g, 0.002 mol), 50% P ( t- Bu) ₃ (1.7 ml, 0.004 mol), NaO t -Bu (20 g, 0.21 mol) were added and stirred at 135 ° C. Thereafter, 43 g (yield: 81%) of product P-30 was obtained by synthesis in the same manner as in the synthesis of P-1.

6. Synthesis of P-40

Scheme 18

After dissolving Sub1-37 (26 g, 0.07 mol) and Sub2-40 (49 g, 0.07 mol) with toluene (140 ml), Pd ₂ (dba) ₃ (1.9 g, 0.002 mol), 50% P ( t- Bu) ₃ (1.7 ml, 0.004 mol), NaO t -Bu (20 g, 0.21 mol) were added and stirred at 135 ° C. Thereafter, 62 g (yield: 85%) of product P-40 was obtained by synthesis in the same manner as in the synthesis of P-1.

7. Synthesis Example of P-51

Scheme 19

After dissolving Sub1-39 (30 g, 0.08 mol) and Sub2-46 (40 g, 0.08 mol) with toluene (145 ml), Pd ₂ (dba) ₃ (2 g, 0.002 mol), 50% P ( t- Bu) ₃ (1.8 ml, 0.004 mol), NaO t -Bu (25 g, 0.23 mol) were added and stirred at 135 ° C. Thereafter, the compound was synthesized in the same manner as in the synthesis of P-1, to obtain 50 g (yield: 75%) of product P-51.

8. P-65 Synthesis Example

Scheme 20

After dissolving Sub1-5 (26 g, 0.1 mol) and Sub2-59 (52 g, 0.1 mol) with toluene (200 ml), Pd ₂ (dba) ₃ (2.7 g, 0.003 mol), 50% P ( t- Bu) ₃ (2.5 ml, 0.006 mol), NaO t -Bu (28 g, 0.29 mol) were added and stirred at 135 ° C. Thereafter, the compound was synthesized in the same manner as in the synthesis of P-1, to obtain 50 g (yield: 66%) of product P-65.

9. Synthesis Example of P-74

Scheme 21

After dissolving Sub1-26 (50 g, 0.1 mol) and Sub2-66 (46 g, 0.1 mol) with toluene (200 ml), Pd ₂ (dba) ₃ (2.7 g, 0.003 mol), 50% P ( t- Bu) ₃ (2.5 ml, 0.006 mol), NaO t -Bu (28 g, 0.29 mol) were added and stirred at 135 ° C. Thereafter, 80 g (yield: 86%) of product P-74 was obtained by synthesis in the same manner as in the synthesis of P-1.

The FD-MS values of the compounds P-1 to P-72 of the present invention prepared according to the synthesis examples as described above are shown in Table 2 below.

TABLE 3

Manufacturing Evaluation of Organic Electrical Device

[ Example  One] Red  Organic electroluminescent device (host)

N ^1- (naphthalen-2-yl) -N ⁴ , N ⁴ -bis (4- (naphthalen-2-yl (phenyl) amino) phenyl) -N ¹ -phenylbenzene on the ITO layer (anode) formed on the glass substrate. -1,4-diamine (hereinafter abbreviated as "2-TNATA") was vacuum deposited to a thickness of 60 nm to form a hole injection layer, and then 4,4-bis [N- (1) on the hole injection layer. -Naphthyl) -N-phenylamino] biphenyl (hereinafter abbreviated as "NPB") was vacuum deposited to a thickness of 60 nm to form a hole transport layer.

Subsequently, bis- (1-phenylisoquinolyl) iridium (III) acetylacetonate (hereinafter abbreviated as “(piq) ₂ Ir (acac)”) as a host material and a dopant material on the hole transport layer A light emitting layer having a thickness of 30 nm was deposited by doping with a dopant such that the weight ratio was 95: 5.

Next, (1,1'-biphenyl-4-olato) bis (2-methyl-8-quinolinolato) aluminum (hereinafter abbreviated as "BAlq") on the light emitting layer by vacuum deposition to a thickness of 10 nm hole blocking layer And tris (8-quinolinol) aluminum (hereinafter abbreviated as Alq ₃ ) was deposited to a thickness of 40 nm on the hole blocking layer to form an electron transport layer.

Thereafter, LiF was deposited to a thickness of 0.2 nm on the electron transport layer to form an electron injection layer, and Al was deposited to a thickness of 150 nm on the electron injection layer to form a cathode.

[ Example  2] to [ Example  26]

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 was used instead of the compound P-1 as a host material of the emission layer.

[Comparative Example 1] to [Comparative Example 3]

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that one of Comparative Compounds A to C was used instead of Compound P-1 of the present invention as a host material of the emission layer.

<Comparative Compound A> <Comparative Compound B> <Comparative Compound C>

The electroluminescence (EL) characteristics of the organic electroluminescent devices prepared according to Examples 1 to 1 and Comparative Examples of the present invention were applied to the PR-650 of photoresearch, and 2500cd / The T95 lifetime was measured using the McScience Lifetime Measurement Equipment at m ² standard luminance, and the measurement results are shown in Table 4 below.

TABLE 4

From the results of Table 4, it can be seen that when the organic electroluminescent device material of the present invention is used as a phosphorescent host, the luminous efficiency, lifespan and driving voltage of the device can be significantly improved. That is, specific ET units, such as quinazoline and quinoxaline, are compared to comparative compounds A to C having simple ET (electron transfer) units such as pyridine, pyrimidine, and triazine bonded to N of the carbazole mother nucleus. It can be seen that the properties of the device are remarkably improved when the compound of the present invention having an amine group bonded thereto is used as a host.

It is quinazoline, benzoquinazolin, dibenzoquinazolin, quinoxaline, benzoquinoxaline, dibenzoquinoxaline, benzothienopyrimidine, benzothienoparazine, naphthothienopyrazine, phenanthrosyeno When certain substituents, such as pyrazine, benzopuropyrimidine, benzofuropyrazine, naphthopuropyrazine, and the like are bound to the N of the carbazole nucleus, LUMO or band gap as compared to when the simple ET substituent is substituted This is because the back is changed. Even in the case of a compound having a similar structure, there are differences in physical properties depending on the type of the substituent and the bonding position, and this difference acts as a major factor (for example, energy balance) in improving device performance during device deposition.

The above description is merely illustrative of the present invention, and those skilled in the art will appreciate that various modifications can be made without departing from the essential features of the present invention. Accordingly, the embodiments disclosed herein are not intended to limit the present invention but to describe 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 descriptions within the scope equivalent thereto should be construed as being included in the scope of the present invention.

100: organic electric 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 (12)

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

In Chemical Formula 1,
Ring A and Ring B independently from each other C ₆ ~ C ₆₀ aromatic hydrocarbons; Fluorene; C ₂ -C ₆₀ heterocycle including at least one heteroatom of O, N, S, Si, and P; Aliphatic rings of C ₃ -C ₃₀ ; And combinations thereof,
C ring is C ₆ ~ C ₃₀ aromatic hydrocarbons or C ₂ ~ C ₃₀ heterocyclic ring,
X ¹ to X ³ are independently of each other N or C, two of X ¹ to X ³ is N,
L ₁ is independently of each other a single bond; C ₆ ~ C ₆₀ arylene group; Fluorenylene groups; Aliphatic ring group of C ₃ ~ C ₆₀ ; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; And combinations thereof.
Ar ₁ and Ar ₂ are each independently 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; Aliphatic ring group of C ₃ ~ C ₆₀ ; C ₁ ~ C ₅₀ Alkyl group; C ₂ ~ C ₂₀ Alkenyl group; Alkynyl groups of C ₂ to C ₂₀ ; C ₁ ~ C ₃₀ Alkoxy group; C ₆ -C ₃₀ aryloxy group; And -L'-N (R _a ) (R _b ),
L 'is a single bond; C ₆ ~ C ₆₀ arylene group; Fluorenylene groups; Aliphatic ring group of C ₃ ~ C ₆₀ ; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; And combinations thereof.
R _a and R _b are each independently a C ₆ ~ C ₆₀ aryl group; Fluorenyl group; Aliphatic ring group of C ₃ ~ C ₆₀ ; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; And combinations thereof.
Ring A, ring B, ring C, L ₁ , Ar ₁ , Ar ₂ , L ', R _a and R _b are each deuterium; halogen; A silane group unsubstituted or substituted with a C ₁ -C ₂₀ alkyl group or a C ₆ -C ₂₀ aryl group; Siloxane groups; Boron group; Germanium group; Cyano group; Nitro group; Import alkylthio of C ₁ -C _20; An alkoxy group of C ₁ -C ₂₀ ; C ₆ -C ₂₀ arylalkoxy group; An alkyl group of C ₁ -C ₂₀ ; Alkenyl groups of C ₂ -C ₂₀ ; An alkynyl group of C ₂ -C ₂₀ ; Aryl group of C ₆ -C ₂₀ ; C ₆ -C ₂₀ aryl group substituted with deuterium; Fluorenyl group; C ₂ -C ₂₀ heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; Aliphatic ring groups of C ₃ -C ₂₀ ; C ₇ -C ₂₀ arylalkyl group; Arylalkenyl group of C ₈ -C ₂₀ ; And one or more substituents selected from the group consisting of a combination thereof. The method of claim 1,
Formula 1 is a compound, characterized in that represented by one of the formula
<Formula 2><Formula3><Formula4><Formula5>

In Chemical Formulas 2 to 5,
Ring A, ring B, L ₁ , Ar ₁ and Ar ₂ are the same as defined in claim 1,
Y ₁ and Y ₂ are O or S, n and m are each an integer of 0 or 1, provided that n + m is an integer of 1 or more. The method of claim 1,
At least one of the A ring and B ring is a compound characterized in that it is a C ₁₀ or more aryl group. The method of claim 1,
Formula 1 is a compound characterized in that represented by one of the following formula 6 to formula 21:
<Formula 6><Formula7><Formula8><Formula9>

<Formula 10><Formula11><Formula12><Formula13>

<Formula 14><Formula15><Formula16><Formula17>

<Formula 18><Formula19><Formula20><Formula21>

In Chemical Formulas 6 to 21,
C ring, L ₁ , Ar ₁ , Ar ₂ and X ¹ to X ³ are as defined in claim 1,
R ² and R ³ are independently of each other hydrogen; heavy hydrogen; halogen; Cyano group; Nitro 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; Aliphatic ring group of C ₃ ~ C ₆₀ ; C ₁ ~ C ₅₀ Alkyl group; C ₂ ~ C ₂₀ Alkenyl group; Alkynyl groups of C ₂ to C ₂₀ ; C ₁ ~ C ₃₀ Alkoxy group; C ₆ -C ₃₀ aryloxy group; And -L'-N (R _a ) (R _b ), and neighboring groups may be bonded to each other to form a ring, wherein the ring is C ₆ -C ₆₀ aromatic ring; C ₂ -C ₆₀ heterocycle including at least one heteroatom of O, N, S, Si, and P; Aliphatic rings of C ₃ -C ₆₀ ; And combinations thereof,
L ', R _a and R _b are the same as defined in claim 1,
a is an integer of 0-4, b is an integer of 0-6, c is an integer of 0-8, and when each of these is an integer of 2 or more, each R <^2> and each R <^3> is mutually same or different. The method of claim 1,
L ₁ is a compound characterized in that it is selected from the group consisting of Formulas A-1 to A-12:

In Chemical Formulas A-1 to A-12,
R ⁶ to R ⁸ are each independently hydrogen; heavy hydrogen; halogen; Cyano group; Nitro 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; Aliphatic ring group of C ₃ ~ C ₆₀ ; C ₁ ~ C ₅₀ Alkyl group; C ₂ ~ C ₂₀ Alkenyl group; Alkynyl groups of C ₂ to C ₂₀ ; C ₁ ~ C ₃₀ Alkoxy group; C ₆ -C ₃₀ aryloxy group; And -L'-N (R _a ) (R _b ), and neighboring groups may be bonded to each other to form a ring, wherein the ring is C ₆ -C ₆₀ aromatic ring; C ₂ -C ₆₀ heterocycle including at least one heteroatom of O, N, S, Si, and P; Aliphatic rings of C ₃ -C ₆₀ ; And combinations thereof,
a ', c', d 'and e' are each an integer from 0 to 4, b 'is an integer from 0 to 6, f' and g 'are each an integer from 0 to 3, h' is 0 or 1 Each of R ⁶ , each R ⁷ and each R ⁸ are the same as or different from each other,
Y is N (R '), O, S or C (R') (R "),
Z ¹ to Z ³ is C, C (R ') or N, at least one of Z ¹ to Z ³ is N,
R ′ and R ″ are each independently hydrogen; deuterium; halogen; cyano group; nitro group; C ₆ ~ C ₆₀ aryl group; fluorenyl group; at least one heteroatom of O, N, S, Si, and P; C ₂ ~ C ₆₀ Heterocyclic group containing, C ₃ ~ C ₆₀ Alicyclic group; C ₁ ~ C ₅₀ Alkyl group; C ₂ ~ C ₂₀ Alkenyl group; C ₂ ~ C ₂₀ Alkynyl group; C An alkoxy group of ₁ to C ₃₀ ; an aryloxy group of C ₆ to C ₃₀ ; and -L'-N (R _a ) (R _b ), wherein R 'and R "are bonded to each other to bond Form a ring with C,
L ′, R _a and R _b are as defined in claim 1. The method of claim 1,
Compound represented by Formula 1 is one of the following compounds:

. An organic electric device comprising a first electrode, a second electrode, and an organic material layer formed between the first electrode and the second electrode.
The organic material layer comprises an organic electroluminescent device comprising a single compound or two or more compounds represented by Formula 1 of claim 1. The method of claim 7, wherein
The organic material layer comprises 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. The method of claim 8,
The compound of claim 1, wherein the compound is included in the light emitting layer. The method of claim 7, wherein
The organic material layer is formed by a spin coating process, a nozzle printing process, an inkjet printing process, a slot coating process, a dip coating process or a roll-to-roll process. A display device comprising the organic electronic device of claim 7; And
And a controller for driving the display device. The method of claim 11,
The organic electroluminescent device is selected from the group consisting of an organic electroluminescent device, an organic solar cell, an organic photoconductor, an organic transistor, a monochromatic lighting device and a quantum dot display device.

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