KR20200089891A - 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, it is possible to lower a driving voltage, and improve luminous efficiency and a lifespan of the organic electric element.

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.

The most important issues in organic electroluminescent devices are life and efficiency, and as the display becomes larger, this efficiency or life problem must 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 T1 value between each organic material layer and the intrinsic properties of materials (mobility, interfacial properties, etc.) are optimally combined.

In addition, in order to solve the light emission problem in the hole transport layer in the recent organic electroluminescent device, there must be a light emitting auxiliary layer between the hole transport layer and the light emitting layer, and different light emission auxiliary according to each light emitting layer (R, G, B) It is time to develop the layer.

In general, electrons are transferred from the electron transport layer to the light emitting layer, and holes are transferred from the hole transport layer to the light emitting layer to generate excitons by recombination.

However, in the case of the material used for the hole transport layer, since it has to have a low HOMO value, most of them have a low T1 value, and as a result, exciton generated in the light emitting layer is transferred to the hole transport layer, resulting in charge unbalance in the light emitting layer. ) To emit light at the hole transport layer interface.

When emitting light at the interface of the hole transport layer, a problem arises in that the color purity and efficiency of the organic electric device decreases and the life is shortened. Therefore, the development of a light-emitting auxiliary layer having a high T1 value and having a HOMO level between the HOMO energy level of the hole transport layer and the HOMO energy level of the light-emitting layer is urgently required.

In order to fully 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, a light emitting auxiliary layer material, etc. It should be preceded by this, but the development of a stable and efficient organic material layer material for an organic electric device has not been sufficiently achieved. Therefore, the development of new materials continues to be demanded, and in particular, the development of light-emitting auxiliary layer materials 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 lifetime of the device, an organic electrical 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 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 can the driving voltage of the device 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 shows a chemical formula according to an aspect 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. As used herein, the term "heteroatom" refers to N, O, S, P or Si, unless otherwise specified, and the heterocyclic group is a monocyclic, ring aggregate, heterocyclic ring system containing heteroatoms, spies 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 is bonded 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 a detailed description of related known configurations or functions may obscure the subject matter of the present invention, the detailed description 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 is omitted, 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 may be further included, 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 that does not contact the organic material layer on both sides of the first electrode or a surface that does not contact the organic material layer on both surfaces of the second electrode.

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), the host or dopant of the light emitting layer 150, or may be used as a material for the light efficiency improving layer, but preferably, the compound represented by Formula 1 of the present invention is used as a material for the light emitting auxiliary layer 151.

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 material for the light-emitting auxiliary layer 151, the energy level and T ₁ value between each organic material layer, the material's intrinsic properties (mobility, interfacial properties, etc.) are optimized It is possible to simultaneously improve the life and efficiency of the organic electric device.

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>

<Formula 1-1> <Formula 1-2>

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

Ar ₁ and Ar ₂ 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; C ₃ ~ C ₆₀ aliphatic ring group; C ₁ ~ C ₆₀ 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; Formula 1-1; And it may be selected from the group consisting of formula 1-2. However, at least one of Ar ¹ and Ar ² is Chemical Formula 1-1 or Chemical Formula 1-2.

When Ar ₁ and Ar ₂ 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, phenanthrene, etc. Can.

When Ar ₁ and Ar ₂ are heterocyclic groups, preferably C ₂ to C ₃₀ heterocyclic groups, more preferably C ₂ to C ₁₈ heterocyclic groups, such as dibenzothiophene, dibenzofuran, carbazole , Phenylcarbazole, benzonaphthothiophene, benzonaphthofuran, and the like.

When Ar ₁ and Ar ₂ are fluorenyl groups, 9,9-dimethyl-9 H -fluorene, 9,9-diphenyl-9 H -fluorenyl group, 9,9'-spyrobifluorene, etc. Can.

When Ar ₁ and Ar ₂ are alkenyl groups, preferably, they may be C ₂ to C ₁₀ alkenyl groups, such as ethene and propene.

When Ar ₁ and Ar ₂ are aryloxy groups, preferably, they may be C ₆ to C ₃₀ aryloxy groups, and more preferably C ₆ to C ₁₈ aryloxy groups.

L ₁ and L ₂ are each independently a single bond; C ₆ ~ C ₆₀ Arylene group; Fluorylene group; C ₃ ~ C ₆₀ aliphatic ring group; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; And combinations thereof.

When L ₁ and L ₂ 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 phenyl, biphenyl, naphthalene, terphenyl, phenanthrene, etc. Can.

R ¹ to R ⁵ , R ₁ to R ₄ and R” are independently of each other hydrogen; deuterium, tritium; halogen; cyano group; nitro group; C ₆ to C ₆₀ aryl group; fluorenyl group; O, N, C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of 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 alkoxyl group; C ₆ ~ C ₃₀ aryloxy group; and -L'-N (R _a ) (R _b ); is selected from the group consisting of , Adjacent groups may combine with each other to form a ring.

a, m, o, and p are each an integer from 0 to 4, b is an integer from 0 to 2, c and n are integers from 0 to 3, and when each of these is an integer of 2 or more, each of R ¹ and R Each of ^2, each of R ^3, each of R ^4, each of R ^5, each of R _1, each of R _2, each of R _{3, and} each of R ₄ are the same or different from each other.

R ¹ and R ² are formed by bonding to each other, neighboring R ³ , neighboring R ⁴ , neighboring R ⁵ , neighboring R ₁ , neighboring R ₂ , neighboring R _3, or neighboring Rings formed by bonding with each other R ₄ is an aromatic ring group of C ₆ ~C ₆₀ ; 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; Or it may be a fused ring group of an aromatic ring of C ₃ ~ C ₆₀ of aliphatic rings and C ₆ ~ C _60.

When adjacent groups are bonded to each other to form an aromatic ring, preferably an aromatic ring of C ₆ ~C ₃₀ , more preferably an aromatic ring of C ₆ ~C ₁₄ , such as benzene, naphthalene, phenanthrene, etc. Aromatic rings can be formed. In addition, when adjacent R ¹ and R ² are bonded to each other to form an aliphatic ring, preferably C ₃ to C ₃₀ aliphatic ring groups, more preferably C ₃ to C ₁₇ aliphatic rings can be formed. .

When R ¹ to R ⁵ , R ₁ to R ₄ and R" 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, phenanthrene, and the like.

When R ¹ to R ⁵ and R ₁ to R ₄ are heterocyclic groups, preferably C ₂ to C ₃₀ heterocyclic groups, more preferably C ₂ to C ₂₂ heterocyclic groups, such as pyridine, quinazoline, Dibenzothiophene, dibenzofuran, carbazole, phenylcarbazole, and the like.

When R ¹ to R ⁵ , R ₁ to R ₄ and R" are alkyl groups, preferably C ₁ to C ₂₀ alkyl groups, more preferably C ₁ to C ₁₀ alkyl groups, such as methyl, t-butyl, and the like. have.

When R ¹ to R ⁵ and R ₁ to R ₄ are fluorenyl groups, 9,9-dimethyl-9 H -fluorene, 9,9-diphenyl-9 H -fluorenyl group, 9,9'- Spirobifluorene, and the like.

R'is independently a single bond; C ₆ ~ C ₆₀ Arylene group; Fluorylene group; C ₃ ~ C ₆₀ aliphatic ring group; And C ₂ to C ₆₀ heterocyclic groups including at least one hetero atom among O, N, S, Si, and P.

When R'is an arylene group, preferably an arylene group of C ₆ to C ₃₀ , more preferably an arylene group of C ₆ to C ₁₈ , such as phenyl, biphenyl, naphthalene, terphenyl, phenanthrene, and the like.

X is C(R _c )(R _d ), O or S.

R _c and R _d are independently of each other hydrogen; Deuterium, tritium; 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; 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, R _c and R _d may be bonded to each other to form a ring.

The ring formed by bonding of R _c and R _{d to} each other is an aromatic ring group of C ₆ ~C ₆₀ ; 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; Or it may be a fused ring group of an aromatic ring of C ₃ ~ C ₆₀ of aliphatic rings and C ₆ ~ C _60. When R _c and R _d are bonded to each other to form an aliphatic ring, preferably, an aliphatic ring group of C ₃ to C ₃₀ , more preferably an aliphatic ring of C ₃ to C ₁₇ may be formed.

When R _c and R _d 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, phenanthrene, etc. Can.

When R _c and R _d are fluorenyl groups, 9,9-dimethyl-9 H -fluorene, 9,9-diphenyl-9 H -fluorenyl group, 9,9'-spirobifluorene, etc. Can.

When R _c and R _d are alkyl groups, preferably an alkyl group of C ₁ to C ₂₀ , more preferably an alkyl group of C ₁ to C ₁₀ , such as methyl, t-butyl, and the like.

L'is a single bond; C ₆ ~ C ₆₀ Arylene group; Fluorylene group; C ₃ ~ C ₆₀ aliphatic ring group; 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 independently of each other C ₆ ~ C ₆₀ aryl group; Fluorenyl group; C ₃ ~ C ₆₀ aliphatic ring group; And C ₂ to C ₆₀ heterocyclic groups including at least one hetero atom among O, N, S, Si, and P.

Substituents indicated by each symbol may be further substituted. For example, Ar ₁ , Ar ₂ , R ¹ ~R ⁵ , R ₁ ~R ₄ , L ₁ , L ₂ , R', R", L', R _a , R _b , R _c , R _d , neighboring Rings formed by bonding with each other are deuterium; halogen; C ₁ -C ₂₀ alkyl group or C ₆ -C ₂₀ aryl group substituted or unsubstituted silane group; siloxane group; boron group; germanium group; C _1- Phosphine oxide unsubstituted or substituted with an alkyl group of C ₂₀ or an aryl group of C ₆ -C ₂₀ ; cyano group; nitro group; C ₁ -C ₂₀ alkylthio group; C ₁ -C ₂₀ alkoxy group; C _6- C ₂₀ -Arylalkoxy group; C ₁ -C ₂₀ alkyl group; C ₂ -C ₂₀ alkenyl group; C ₂ -C ₂₀ alkynyl group; C ₆ -C ₂₀ aryl group; C ₆ -C substituted with deuterium Aryl group of ₂₀ ; fluorenyl group; C ₂ -C ₂₀ heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si and P; aliphatic ring group of C ₃ -C ₂₀ ; C ₇ -C ₂₀ arylalkyl group; C ₈ -C ₂₀ arylalkenyl group; and combinations thereof 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 8.

<Formula 2> <Formula 3>

<Formula 4> <Formula 5>

<Formula 6> <Formula 7>

<Formula 8>

In Formulas 2 to 8, Ar ₁ , L ₁ , L ₂ , R ¹ to R ⁵ , R ₁ to R ₄ , R', R", a to c, n, m, o, p are defined in Formula 1 It's like that.

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 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 auxiliary 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 Formula 1 according to the present invention may be prepared by reacting Sub 1 and Sub 2 as shown in Reaction Scheme 1 below, but is not limited thereto.

<Scheme 1>

Ⅰ. 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 (Field Desorption-Mass Spectrometry) value of the compound belonging to Sub 1 is 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>

1.Sub 1- 1 Synthesis Example

(1) Sub 1-I-1 synthesis

After dissolving 4-bromo-9,9-dimethyl-9H-fluorene (200.0 g, 735.2mmol) in DMF (9000 mL) in an argon atmosphere, 2,3-dichlorophenol (179.77 g, 1102.9mmol), CuI (14.0 g. 73.5mmol), Fe(acac) ₃ (51.93 g, 147.0 mmol), K ₂ CO ₃ (203.22 g, 1470.5 mmol) was added and stirred at 130°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 using a silica gel column and recrystallized to obtain 167.17 g of product Sub 1-I-1 (yield: 64%). .

(2) Sub 1-1 synthesis

After dissolving Sub1-I-1 (167.17 g, 470.6 mmol) in DMF (2470 mL) in an argon atmosphere, Pd(OAc) ₂ (5.28 g, 23.5mmol), [(t-Bu) ₃ PH]BF ₄ ( 13.65 g. 47.1 mmol), K ₂ CO ₃ (195.09 g, 1411.7 mmol) was added and stirred at 190°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 52.20 g of product Sub 1-1 (yield: 58%).

2. Sub 1- 2 Synthesis Example

(1) Sub 1-I-2 synthesis

In an argon atmosphere, 4-bromo-9,9-diphenyl-9H-fluorene (80.0 g, 201 mmol) was dissolved in DMF (2500 mL), followed by 2,3-dichlorophenol (49.23 g, 302.0 mmol), CuI (3.83 g 20.1 mmol), Fe(acac) ₃ (14.22 g, 40.3 mmol), K ₂ CO ₃ (55.65 g, 402.7 mmol) was added and stirred at 130°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 57.92 g of product Sub 1-I-2 (yield: 60%). .

(2) Sub 1-2 synthesis

After dissolving Sub1-I-2 (57.92 g, 120.8 mmol) in DMF (634 mL) in an argon atmosphere, Pd(OAc) ₂ (1.36 g, 6.0 mmol), [(t-Bu) ₃ PH]BF ₄ ( 3.51 g, 12.1 mmol), K ₂ CO ₃ (50.09 g, 362.5 mmol) was added and stirred at 190°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 34.25 g of product Sub 1-2 (yield: 64%).

3. Sub 1- 3 Synthesis Example

(1) Sub 1-I-3 synthesis

In an argon atmosphere, 4-bromo-9,9'-spirobi[fluorene] (80.0 g, 202.4 mmol) was dissolved in DMF (2500 mL), followed by 2,3-dichlorophenol (49.48 g, 303.6 mmol), CuI (3.85 g.20.2 mmol), Fe(acac) ₃ (14.29 g, 40.5 mmol), K ₂ CO ₃ (55.94 g, 404.8 mmol) was added and stirred at 130°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 57.00 g of product Sub 1-I-3 (yield: 59%). .

(2) Sub 1-3 synthesis

After dissolving Sub1-I-3 (57.00 g, 119.4 mmol) in DMF (630 mL) in an argon atmosphere, Pd(OAc) ₂ (1.34 g, 6.0 mmol), [(t-Bu) ₃ PH]BF ₄ ( 3.46 g. 11.9 mmol), K ₂ CO ₃ (49.50 g, 358.2 mmol) was added and stirred at 190°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 31.59 g of product Sub 1-3 (yield: 60%).

Ⅱ. Exemplary compounds of Sub 2 and Synthetic example

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]

Sub 2 of Reaction Scheme 1 may be synthesized by the reaction route of Reaction Scheme 3 below, but is not limited thereto.

<Scheme 3>

1.Sub 2- 3 Synthesis Example

After dissolving 2-bromo-9,9-dimethyl-9H-fluorene (10.0 g, 36.6mmol) with toluene (460 ml), [1,1'-biphenyl]-4-amine (9.29 g, 54.9mmol), Pd ₂ (dba) ₃ (1.01 g, 1.1 mmol), 50% P( t -Bu) ₃ (1.1 ml, 2.2 mmol), NaO t -Bu (10.55 g, 109.8 mmol) was added and stirred at 50°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 10.85 g of product (yield: 82%).

2. Sub 2- 4 Synthesis Example

After dissolving 2-bromo-9,9-dimethyl-9H-fluorene (10.0 g, 36.6 mmol) with toluene (460 ml), [1,1'-biphenyl]-2-amine (9.29 g, 54.9 mmol), Pd ₂ (dba) ₃ (1.01 g, 1.1 mmol), 50% P( t -Bu) ₃ (1.1 ml, 2.2 mmol), NaO t -Bu (10.55 g, 109.8 mmol) was added and the Sub 2-3 By proceeding in the same manner as in Synthesis Example of to give the product 11.25 g (yield: 85%).

3. Sub 2- 6 Synthesis Example

After dissolving 2-bromo-9,9-dimethyl-9H-fluorene (12.0 g, 43.9mmol) with toluene (550 ml), dibenzo[b,d]thiophen-3-amine (13.13 g, 65.9mmol), Pd ₂ (dba) ₃ (1.21 g, 1.3 mmol), 50% P( t -Bu) ₃ (1.3 ml, 2.6 mmol), NaO t -Bu (12.67 g, 131.8 mmol) was added and Sub of 2-3 The process was performed in the same manner as in Synthesis Example to obtain 13.42 g (yield: 78%) of the product.

4. Sub 2- 8 Synthesis Example

After dissolving 2-bromo-9,9-dimethyl-9H-fluorene (15.0 g, 54.9mmol) with toluene (680 ml), dibenzo[b,d]furan-3-amine (15.09 g, 82.4mmol), Pd ₂ (dba) ₃ (1.51 g, 1.6 mmol), 50% P( t -Bu) ₃ (1.6 ml, 3.3 mmol), NaO t -Bu (15.83 g, 164.7 mmol) was added and the sub 2-3 Proceeding in the same manner as in Synthesis Example, the product was obtained 16.49 g (yield: 80%).

5. Sub 2- 14 Synthesis Example

After 4-bromo-9,9-dimethyl-9H-fluorene (8.5 g, 31.1 mmol) was dissolved with toluene (390 ml), 9,9-dimethyl-9H-fluoren-2-amine (9.77 g, 46.7 mmol) , Pd ₂ (dba) ₃ (0.85 g, 0.9 mmol), 50% P( t -Bu) ₃ (0.9 ml, 1.9 mmol), NaO t -Bu (8.973 g, 93.3 mmol) was added and the Sub 2- The same procedure as in Synthesis Example 3 was carried out to obtain 10.37 g (yield: 83%) of the product.

6. Sub 2- 19 Synthesis Example

After 2-bromo-9,9-diphenyl-9H-fluorene (15.0 g, 37.8mmol) was dissolved with toluene (470 ml), [1,1'-biphenyl]-4-amine (9.58 g, 56.6mmol), Pd ₂ (dba) ₃ (1.04 g, 1.1 mmol), 50% P( t -Bu) ₃ (1.1 ml, 2.3 mmol), NaO t -Bu (10.89 g, 113.3 mmol) was added and the Sub 2-3 By proceeding in the same manner as in Synthesis Example of to give the product 15.03 g (yield: 82%).

7. Sub 2- 25 Synthesis Example

After dissolving 2-bromo-9,9-diphenyl-9H-fluorene (25.0 g, 62.9mmol) with toluene (790 ml), dibenzo[b,d]furan-1-amine (17.29 g, 94.4mmol), Pd ₂ (dba) ₃ (1.73 g, 1.9 mmol), 50% P( t -Bu) ₃ (1.8 ml, 3.8 mmol), NaO t -Bu (18.14 g, 188.8 mmol) was added and Sub 2-3 It proceeded in the same manner as in Synthesis Example to obtain 25.78 g of product (yield: 82%).

8. Sub 2- 37 Synthesis Example

After 4-bromo-9,9-diphenyl-9H-fluorene (15.0 g, 37.9mmol) was dissolved with toluene (470 ml), dibenzo[b,d]thiophen-3-amine (11.34 g, 56.9mmol), Pd ₂ (dba) ₃ (1.04 g, 1.1 mmol), 50% P( t -Bu) ₃ (1.1 ml, 2.3 mmol), NaO t -Bu (10.97 g, 113.8 mmol) was added and Sub of 2-3 It proceeded in the same manner as in Synthesis Example to give 15.59 g of product (yield: 80%).

9. Sub 2- 42 Synthesis Example

After 4-bromo-9,9-diphenyl-9H-fluorene (10.0 g, 25.4mmol) was dissolved with toluene (310 ml), [1,1'-biphenyl]-2-amine (6.44 g, 38.0mmol) , Pd ₂ (dba) ₃ (0.70 g, 0.8 mmol), 50% P( t -Bu) ₃ (0.7 ml, 1.5 mmol), NaO t -Bu (7.31 g, 76.1 mmol) was added and the Sub 2- The same procedure as in Synthesis Example 3 was carried out to obtain 9.57 g (yield: 78%) of the product.

10. Sub 2- 48 Synthesis Example

After dissolving 9-(3-bromophenyl)-9-phenyl-9H-fluorene (15.0 g, 37.8 mmol) with toluene (470 ml), dibenzo[b,d]thiophen-3-amine (11.28 g, 56.6 mmol) , Pd ₂ (dba) ₃ (1.04 g, 1.1 mmol), 50% P( t -Bu) ₃ (1.1 ml, 2.3 mmol), NaO t -Bu (10.89 g, 113.3 mmol) was added and the Sub 2- It proceeded in the same manner as in Synthesis Example 3 to give 16.35 g of product (yield: 84%).

11.Sub 2- 52 Synthesis Example

After dissolving 9-(4-bromophenyl)-9-phenyl-9H-fluorene (10.0 g, 25.2mmol) with toluene (315 ml), [1,1'-biphenyl]-4-amine (6.39 g, 37.8mmol) ), Pd ₂ (dba) ₃ (0.69 g, 0.8 mmol), 50% P( t -Bu) ₃ (0.7 ml, 1.5 mmol), NaO t -Bu (7.26 g, 75.5 mmol) was added and the Sub 2 It proceeded in the same manner as in Synthesis Example of -3 to give 9.90 g of product (yield: 81%).

12. Sub 2- 60 Synthesis Examples

After dissolving 2-bromo-9,9-dimethyl-9H-fluorene (15.0 g, 54.9 mmol) with toluene (686 ml), 9,9-dimethyl-9H-fluoren-2-amine (17.24 g, 82.4 mmol) , Pd ₂ (dba) ₃ (1.51 g, 1.6 mmol), 50% P( t -Bu) ₃ (1.6 ml, 1.6 mmol), NaO t -Bu (15.83 g, 164.7 mmol) was added and the Sub 2- The same procedure as in Synthesis Example 3 was carried out to obtain 18.52 g of the product (yield: 84%).

13.Sub 2- 62 Synthesis Example

After dissolving 1-bromodibenzo[b,d]furan (10.0 g, 40.5mmol) with toluene (506 ml), 3-(9-phenyl-9H-fluoren-9-yl)aniline (20.24 g, 60.7mmol), Pd ₂ (dba) ₃ (1.11 g, 1.2 mmol), 50% P( t -Bu) ₃ (1.2 ml, 2.4 mmol), NaO t -Bu (11.67 g, 121.4 mmol) was added and the Sub 2-3 By proceeding in the same manner as in Synthesis Example of to give the product 17.39 g (yield: 86%).

14.Sub 2- 73 Synthesis Example

After dissolving 1-bromodibenzo[b,d]thiophene (10.0 g, 38.0mmol) with toluene (475 ml), dibenzo[b,d]thiophen-4-amine (11.36 g, 57.0mmol), Pd ₂ (dba) ₃ (1.04 g, 1.1mmol), 50% P( t -Bu) ₃ (1.1 ml, 2.3mmol), NaO t -Bu (10.96 g, 114.0mmol) was added and the same as the synthesis example of Sub 2-3 above. The process proceeded to give 11.74 g of product (yield: 81%).

Ⅲ. Of the final compound Synthetic example

1.P-1 Synthetic example

After dissolving Sub 1-1 (8.0 g, 25.1 mmol) with toluene (250 ml), Sub 2-3 (9.07 g, 25.1 mmol), Pd ₂ (dba) ₃ (0.69 g, 0.8 mmol), 50% P ( t -Bu) ₃ (0.60 ml, 1.5 mmol), NaO t -Bu (7.24 g, 75.3 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 12.12 g of product (yield: 75%).

2. P-2 Synthetic example

After dissolving Sub 1-1 (7.5 g, 23.5 mmol) with toluene (235 ml), Sub 2-4 (8.50 g, 23.5 mmol), Pd ₂ (dba) ₃ (0.65 g, 0.7 mmol), 50% P ( t -Bu) ₃ (0.58 ml, 1.4 mmol), NaO t -Bu (6.78 g, 70.6 mmol) was added and proceeded in the same manner as in the synthesis example of P-1 to give 11.81 g of product (yield: 78%). Got

3. P-9 Synthetic example

After dissolving Sub 1-1 (9.00 g, 28.2 mmol) with toluene (282 ml), Sub 2-8 (10.60 g, 28.2 mmol), Pd ₂ (dba) ₃ (0.78 g, 0.8 mmol), 50% P ( t -Bu) ₃ (1.7 ml, 0.78 mmol), NaO t -Bu (8.14 g, 84.7 mmol) was added and proceeded in the same manner as in the synthesis example of P-1 to obtain 13.19 g of product (yield: 71%). Got

4. P-15 Synthetic example

After dissolving Sub 1-1 (7.00 g, 22.0 mmol) with toluene (220 ml), Sub 2-25 (10.97 g, 22.0 mmol), Pd ₂ (dba) ₃ (0.60 g, 0.7 mmol), 50% P ( t -Bu) ₃ (0.54 ml, 1.3 mmol), NaO t -Bu (6.33 g, 65.9 mmol) was added and proceeded in the same manner as in the synthesis example of P-1 to obtain 11.35 g of product (yield: 66%). Got

5. P-22 Synthetic example

After dissolving Sub 1-1 (10.00 g, 31.4 mmol) with toluene (314 ml), Sub 2-48 (16.18 g, 31.4 mmol), Pd ₂ (dba) ₃ (0.86 g, 0.9 mmol), 50% P ( t -Bu) ₃ (0.76 ml, 1.9 mmol), NaO t -Bu (9.04 g, 94.1 mmol) was added and proceeded in the same manner as in the synthesis example of P-1 to give 15.02 g of product (yield: 60%). Got

6. P-27 Synthetic example

After dissolving Sub 1-1 (9.00 g, 28.2 mmol) with toluene (282 ml), Sub 2-19 (13.71 g, 28.2 mmol), Pd ₂ (dba) ₃ (0.78 g, 0.8 mmol), 50% P ( t -Bu) ₃ (0.68 ml, 1.7 mmol), NaO t -Bu (8.14 g, 84.7 mmol) was added and proceeded in the same manner as in the synthesis example of P-1 to obtain 18.89 g of product (yield: 75%) Got

7. P-32 Synthetic example

After dissolving Sub 1-2 (11.00 g, 24.8 mmol) with toluene (248 ml), Sub 2-6 (9.72 g, 24.8 mmol), Pd ₂ (dba) ₃ (0.68 g, 0.7 mmol), 50% P ( t -Bu) ₃ (0.6 ml, 1.5 mmol), NaO t -Bu (7.16 g, 74.5 mmol) was added and proceeded in the same manner as in the synthesis example of P-1 to give 15.46 g of product (yield: 78%). Got

8. P-39 Synthetic example

After dissolving Sub 1-2 (10.00 g, 22.6 mmol) with toluene (226 ml), Sub 2-37 (11.60 g, 22.6 mmol), Pd ₂ (dba) ₃ (0.62 g, 0.7 mmol), 50% P ( t -Bu) ₃ (0.54 ml, 1.4 mmol), NaO t -Bu (6.51 g, 67.7 mmol) was added and proceeded in the same manner as in the synthesis example of P-1 to give 14.13 g of product (yield: 68%). Got

9. P-43 Synthetic example

After dissolving Sub 1-2 (8.00 g, 18.1 mmol) with toluene (181 ml), Sub 2-52 (8.77 g, 18.1 mmol), Pd ₂ (dba) ₃ (0.50 g, 0.5 mmol), 50% P ( t -Bu) ₃ (0.44 ml, 1.1 mmol), NaO t -Bu (5.21 g, 54.2 mmol) was added and proceeded in the same manner as in the synthesis example of P-1 to obtain 11.44 g of product (yield: 71%). Got

10. P-52 Synthetic example

After dissolving Sub 1-3 (7.50 g, 17.0 mmol) with toluene (170 ml), Sub 2-14 (6.83 g, 17.0 mmol), Pd ₂ (dba) ₃ (0.47 g, 0.5 mmol), 50% P ( t -Bu) ₃ (0.42 ml, 1.0 mmol), NaO t -Bu (4.90 g, 51.0 mmol) was added and proceeded in the same manner as in the synthesis example of P-1 to obtain 9.05 g of product (yield: 66%). Got

11.P-60 Synthetic example

After dissolving Sub 1-3 (8.00 g, 18.1 mmol) with toluene (181 ml), Sub 2-42 (8.77 g, 18.1 mmol), Pd ₂ (dba) ₃ (0.50 g, 0.5 mmol), 50% P ( t -Bu) ₃ (0.44 ml, 1.0 mmol), NaO t -Bu (5.23 g, 54.4 mmol) was added and proceeded in the same manner as in the synthesis example of P-1 to obtain 9.35 g of product (yield: 0.58%). Got

12. P-63 Synthetic example

After dissolving Sub 1-3 (9.00 g, 20.4 mmol) with toluene (204 ml), Sub 2-25 (10.48 g, 20.4 mmol), Pd ₂ (dba) ₃ (0.56 g, 0.6 mmol), 50% P ( t -Bu) ₃ (0.50 ml, 1.2 mmol), NaO t -Bu (5.89 g, 61.2 mmol) was added and proceeded in the same manner as in the synthesis example of P-1 to give 14.06 g of product (yield: 75%). Got

13. P-73 Synthetic example

After dissolving Sub 1-1 (12.00 g, 37.7 mmol) with toluene (380 ml), Sub 2-60 (15.15 g, 37.7 mmol), Pd ₂ (dba) ₃ (1.04 g, 1.1 mmol), 50% P ( t -Bu) ₃ (1.1 ml, 2.3mmol), NaO t -Bu (10.88 g, 113.2mmol) was added and proceeded in the same manner as in the synthesis example of P-1 to give the product 20.12 g (Yield: 78%) Got

14. P-75 Synthetic example

After dissolving Sub 1-1 (10.00 g, 31.4 mmol) with toluene (310 ml), Sub 2-62 (15.71 g, 31.4 mmol), Pd ₂ (dba) ₃ (0.86 g, 0.9 mmol), 50% P ( t -Bu) ₃ (0.9 ml, 1.9mmol), NaO t -Bu (9.06 g, 94.3mmol) was added and proceeded in the same manner as in the synthesis example of P-1 to obtain 17.07 g of product (yield: 72%) Got

15. P-86 Synthetic example

After dissolving Sub 1-1 (9.00 g, 28.3mmol), Sub 2-73 (10.79 g, 28.3mmol), Pd ₂ (dba) ₃ (0.78 g, 0.8mmol), 50% P( t -Bu) ₃ (0.8 ml, 1.7 mmol), NaO t -Bu (8.16 g, 84.9 mmol) was added and the same procedure as in the synthesis example of P-1 was carried out to obtain 14.09 g (yield: 75%) of the product.

The FD-MS values of the compounds P-1 to P-104 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 One] Green organic electroluminescent device ( Light emitting auxiliary layer )

N1-(naphthalen-2-yl)-N4,N4-bis(4-(naphthalen-2-yl(phenyl)amino)phenyl)-N1-phenylbenzene-1,4 on ITO layer (anode) formed on glass substrate -After forming a hole injection layer by vacuum deposition of diamine (hereinafter abbreviated as 2-TNATA) to a thickness of 60 nm, N,N'-bis(1-naphthalenyl)-N,N'- on the hole injection layer A hole transport layer was formed by vacuum-depositing bis-phenyl-(1,1'-biphenyl)-4,4'-diamine (hereinafter abbreviated as NPB) to a thickness of 60 nm.

Subsequently, the compound P-1 of the present invention was vacuum-deposited to a thickness of 20 nm on the hole transport layer to form a light-emitting auxiliary layer, and then 4,4'-N,N'-dicarbazole- as a host on the light-emitting auxiliary layer Using biphenyl (hereinafter abbreviated as CBP) and dopant, tris(2-phenylpyridine)-iridium (hereinafter referred to as “Ir(ppy) ₃ ”) at a weight ratio of 95:5 to form a 30 nm thick light emitting layer.

Subsequently, a hole blocking layer is formed by vacuum-depositing (1,1'-biphenyl-4-olato)bis(2-methyl-8-quinolinolato)aluminum (hereinafter abbreviated as BAlq) to a thickness of 10 nm on the light emitting layer. Then, on the hole blocking layer, bis(10-hydroxybenzo[h]quinolinato)beryllium (hereinafter abbreviated as BeBq ₂ ) was vacuum-deposited to a thickness of 45 nm to form an electron transport layer.

Subsequently, an organic electroluminescent device was manufactured by depositing LiF 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 30]

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 of the present invention as the light-emitting auxiliary layer material.

[ Comparative example One]

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that the auxiliary light emitting layer was not formed.

[ Comparative example 2] to [ Comparative example 4]

Substitute for the compound P-1 of the present invention as a light-emitting auxiliary layer material, Ref. 1 to Ref. An organic electroluminescent device was manufactured in the same manner as in Example 1, except that one of the three was used.

<Ref. 1> <Ref. 2> <Ref. 3>

Electro-luminescence (EL) characteristics of the organic electroluminescent device manufactured by Examples 1 to 30 and Comparative Examples 1 to 4 of the present invention were applied to the PR-650 of photoresearch by applying a direct bias DC voltage. The T95 lifespan was measured with a lifespan measuring device manufactured by Max Science at a standard luminance of 5000 cd/m ² . The measurement results are shown in Table 4 below.

[Table 4]

As can be seen from the results of Table 4, when the organic electroluminescent device was manufactured using the material for an organic electroluminescent device of the present invention as a light-emitting auxiliary layer material, a light-emitting auxiliary layer was not formed or the compound Ref. 1 to Ref. The driving voltage of the organic electroluminescent device can be lower than that of the comparative example using 3, and the luminous efficiency and lifetime can be improved.

That is, Ref. 1 was compared with Comparative Example 1 in which no light-emitting auxiliary layer was formed. 1 to Ref. In Comparative Examples 2 to 4 in which the light-emitting auxiliary layer was formed by using one of 3, the driving voltage, efficiency, and life of the device were improved, and Ref. 1 to Ref. When the compound of the present invention was used as the light-emitting auxiliary layer material compared to the case where one of the 3 was used as the light-emitting auxiliary layer material, the luminous efficiency and life of the organic electroluminescent device were improved and the driving voltage was lowered.

Ref. 1 to Ref. The compound 3 is similar to the compound of the present invention in that the aryl amine group is bonded to the 5-membered core of the fluorenobenzofuran type, but the position where dimethylindene is fused to dibenzofuran (or dimethylfluorene) Benzofuran fused position) is different, Ref. 2 and Ref. 3 also differs from the compounds of the present invention where the amine group is attached.

That is, Ref. 1 is based on dibenzofuran, dimethylindene is fused at positions 2 and 3 of one benzene, but Ref. 2 and Ref. 3 has a difference in that dibenzofuran has a core in which dimethylindene is fused at positions 3 and 4 of one benzene. And, Ref. 2 and Ref. 3 has the same 5-ring core, but Ref. In the case of 2, the arylamine group was substituted at position 4 of the outer benzene of benzofuran, Ref. In the case of 3, the difference is that the arylamine group is substituted for the intermediate benzene of the 5-ring core.

Looking at the device properties of Comparative Examples 2 to 4 using these compounds as a light-emitting auxiliary layer material, Ref. 1 and Ref. 3 and Comparative Example 4 using the light-emitting auxiliary layer material than Ref. It can be seen that the device characteristics of Comparative Example 3 using 2 as the light-emitting auxiliary layer material are better. In addition, when looking at Comparative Examples 2 and 4, it can be seen that Comparative Example 2 has lower driving and efficiency characteristics than Comparative Example 4 devices, but has better characteristics in terms of life.

Through the above comparison, it can be seen that even the compound having a similar structure, the characteristics of the device may vary depending on the fusion form of the core, the substitution position of the substituent, etc. Due to this, it seems to be because the physical properties of the compound act as a major factor in improving device performance (e.g., energy balance) when depositing the compound in the device manufacturing process.

On the other hand, the compound of the present invention is ref. 2 and ref. 3 The substance and the core skeleton are the same, but there is a difference in the position at which the amine group is substituted. In addition, the compound of the present invention has at least any one of Ar ₁ and Ar ₂ of the amine group being fluorene, reverse fluorene, dibenzofuran, There is a difference in having a specific substituent such as dibenzothiophene. As described above, by introducing a specific substituent such as Chemical Formula 1-1 or Chemical Formula 1-2 instead of a general aryl group in the amine group, hole characteristics, light efficiency characteristics, energy levels (LUMO, HOMO levels, T1 levels), hole injection characteristics and transport characteristics , It can be seen that the physical properties of the compound such as electron blocking properties are more suitable for the light-emitting auxiliary layer.

In addition, when comparing the results of the device of the embodiment of the present invention, the device of Example 1 in which fluorene was introduced as a substituent of the amine group is the best in terms of driving voltage, but reverse fluorene, dibenzofuran and die as a substituent of the amine group Example 5, Example 18 and Example 19 in which one of the benzothiophenes was introduced was confirmed to have excellent efficiency and lifetime, and dibenzofuran or dibenzocyne than Example 5 in which reverse fluorene was introduced as a substituent. It can be seen that the efficiency and lifespan of the device of Example 18 and Example 19 in which the offen was introduced as a substituent were the best.

When reverse fluorene is introduced as a substituent of an amine group, HOMO values of Compound P-1 and Compound P-19 are similar due to the introduction of a specific substituent, but the excess is because the LUMO value of Compound P-19 has a relatively high value. By blocking the electrons from passing to the hole transport layer, it is judged that the luminous efficiency and lifetime are improved by increasing the charge balance in the light emitting layer.

In addition, when dibenzofuran or dibenzothiophene is introduced as a substituent of the amine group, luminescence efficiency and thermal stability are improved and life is improved because it exhibits a higher refractive index and higher Tg value than when the fluorene or reverse fluorene is substituted. It can be seen that this is increased.

Therefore, it can be seen that the physical properties of the compound change when the structure of the compound is changed according to the type of the substituent, the substitution position, and the substitution method, and thus the characteristics of the device are also changed when the light-emitting auxiliary layer is formed.

Comparison according to the amine group substituents of the compounds of the present invention was described by way of Example 1, Example 5, Example 18 and Example 19, but the above effects can be applied to all the examples using the compounds of the invention. have.

The above description is merely illustrative of the present invention, and those skilled in the art to which the present invention pertains may make various modifications without departing from the essential characteristics of the present invention. Accordingly, 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 scope equivalent thereto 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 (10)

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

<Formula 1-1><Formula1-2>

In the above formula,
Ar ₁ and Ar ₂ 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; C ₃ ~ C ₆₀ aliphatic ring group; C ₁ ~ C ₆₀ 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; Formula 1-1; And Formula 1-2, provided that at least one of Ar ₁ and Ar ₂ is Formula 1-1 or Formula 1-2,
L ₁ and L ₂ are each independently a single bond; C ₆ ~ C ₆₀ Arylene group; Fluorylene group; C ₃ ~ C ₆₀ aliphatic ring group; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; And combinations thereof,
R ¹ to R ⁵ , R ₁ to R ₄ and R” are independently of each other hydrogen; deuterium, tritium; halogen; cyano group; nitro group; C ₆ to C ₆₀ aryl group; fluorenyl group; O, N, C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of 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 alkoxyl group; C ₆ ~ C ₃₀ aryloxy group; and -L'-N (R _a ) (R _b ); is selected from the group consisting of , Adjacent groups can combine with each other to form a ring,
a, m, o, and p are each an integer from 0 to 4, b is an integer from 0 to 2, c and n are integers from 0 to 3, and each of them is an integer of 2 or more, each of R ¹ and R ² each, R ³ each, R ⁴ each, R ⁵ each, R ₁ each, R ₂ each, R ₃ each, R ₄ each is the same or different from each other,
R'is independently a single bond; C ₆ ~ C ₆₀ Arylene group; Fluorylene group; C ₃ ~ C ₆₀ aliphatic ring group; And O, N, S, Si and P is selected from the group consisting of a heterocyclic group of C ₂ ~ C ₆₀ containing at least one hetero atom,
X is C(R _c )(R _d ), O or S
R _c and R _d are independently of each other hydrogen; Deuterium, tritium; 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; 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, R _c and R _d may be bonded to each other to form a ring,
L'is a single bond; C ₆ ~ C ₆₀ Arylene group; Fluorylene group; C ₃ ~ C ₆₀ aliphatic ring group; 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 independently of each other C ₆ ~ C ₆₀ aryl group; Fluorenyl group; C ₃ ~ C ₆₀ aliphatic ring group; And O, N, S, Si and P is selected from the group consisting of a heterocyclic group of C ₂ ~ C ₆₀ containing at least one hetero atom,
Ar ₁ , Ar ₂ , R ¹ ~R ⁵ , R ₁ ~R ₄ , L ₁ , L ₂ , R', R", L', R _a , R _b , R _c , R _d , and neighboring groups Rings formed by bonding to each other are deuterium; halogen; silane groups unsubstituted or substituted with C ₁ -C ₂₀ alkyl groups or C ₆ -C ₂₀ aryl groups; siloxane groups; boron groups; germanium groups; C ₁ -C ₂₀ Phosphine oxide unsubstituted or substituted with an alkyl group or an aryl group of C ₆ -C ₂₀ ; cyano group; nitro group; C ₁ -C ₂₀ alkylthio group; C ₁ -C ₂₀ alkoxy group; C ₆ -C ₂₀ Arylalkoxy group; C ₁ -C ₂₀ alkyl group; C ₂ -C ₂₀ alkenyl group; C ₂ -C ₂₀ alkynyl group; C ₆ -C ₂₀ aryl group; C ₆ -C ₂₀ substituted with deuterium C ₂ -C ₂₀ heterocyclic group containing at least one heteroatom selected from the group consisting of aryl groups; fluorenyl groups; O, N, S, Si and P; aliphatic rings of C ₃ -C ₂₀ ; C ₇ -C ₂₀ arylalkyl group; C ₈ -C ₂₀ arylalkenyl group; and combinations thereof may be further substituted with one or more substituents selected from the group consisting of. According to claim 1,
Formula 1 is a compound characterized in that represented by one of the following formulas 2 to 5:
<Formula 2><Formula3>

<Formula 4><Formula5>

In the above formula, Ar ₁ , L ₁ , L ₂ , R ¹ ~R ⁵ , R ₁ ~R ₄ , R', R", a ~ c, n, m, o, p are those defined in claim 1 same. According to claim 1,
The compound represented by Chemical Formula 1 is a compound characterized in that it is one of the following Chemical Formulas 6 to 8:
<Formula 6><Formula7>

<Formula 8>

In the above formula, L ₁ , L ₂ , R ¹ ~R ⁵ , R ₁ ~R ₄ , R', R", a~c, n, m, o, p are as defined in claim 1. According to claim 2,
Ar ₁ is an aryl group, Ar ₂ is Chemical Formula 1-1 or Chemical Formula 1-2, L ₁ and L ₂ are each independently a single bond or an arylene group. 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 an organic electric device, 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 6,
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 7,
The compound is an organic electric device, characterized in that included in the light-emitting light-emitting auxiliary layer. A display device comprising the organic electroluminescent element of claim 6; And
An electronic device comprising; a control unit for driving the display device. The method of claim 9,
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.

Images