KR102555747B1 - Compound for organic electronic element, organic electronic element comprising the same, and electronic device thereof - Google Patents

Abstract

Disclosed are an organic electric device including 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 device including the organic electric device. By including the compound represented by Chemical Formula 1 in the organic material layer, the driving voltage of the organic electric element can be lowered and the luminous efficiency and lifetime can be improved.

Description

Compound for organic electric element, organic electric element using the same, and 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, the organic light emitting phenomenon refers to a phenomenon in which electrical energy is converted into light energy using an organic material. An organic electric device using an organic light emitting phenomenon usually has a structure including an anode, 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 include, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer.

Lifespan and efficiency are the most problematic issues in organic electroluminescent devices, and as displays become larger, these efficiency and lifespan problems must be solved.

Efficiency, lifespan, driving voltage, etc. are related to each other. As the efficiency increases, the driving voltage relatively decreases. indicates a tendency to increase life expectancy.

However, efficiency cannot be maximized by simply improving the organic layer. This is because long life and high efficiency can be achieved at the same time when the optimal combination of the energy level and T1 value between each organic material layer and the intrinsic properties (mobility, interfacial property, etc.) of the material is achieved.

In addition, in order to solve the light emitting problem in the hole transport layer in recent organic electroluminescent devices, an auxiliary light emitting layer must exist between the hole transport layer and the light emitting layer, and different light emission auxiliary layers 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, since the materials used in the hole transport layer must have a low HOMO value, most of them have a low T1 value. As a result, excitons generated in the light emitting layer are transferred to the hole transport layer, resulting in charge unbalance in the light emitting layer. ), resulting in light emission at the interface of the hole transport layer.

When light is emitted from the interface of the hole transport layer, the color purity and efficiency of the organic electric element are lowered and the lifetime is shortened. Therefore, there is an urgent need to develop a light emitting auxiliary layer having a high T1 value and a HOMO level between the HOMO energy level of the hole transport layer and the HOMO energy level of the light emitting layer.

On the other hand, it delays the penetration and diffusion of metal oxide into the organic layer from the anode electrode (ITO), which is one of the causes of life shortening of organic electric devices, and has stable characteristics against Joule heating generated during device operation, that is, high glass transition. It is necessary to develop a hole injection layer material having a temperature. The low glass transition temperature of the hole transport layer material has a property of reducing the uniformity of the surface of the thin film when the device is driven, which is reported to have a great effect on the lifespan of the device. In addition, OLED devices are mainly formed by a deposition method, and there is a need to develop materials that can endure for a long time during deposition, that is, materials with strong heat resistance.

That is, in order to fully exhibit the excellent characteristics of organic electric devices, materials constituting the organic material layer in the device, such as hole injection materials, hole transport materials, light emitting materials, electron transport materials, electron injection materials, and light emitting auxiliary layer materials, etc. are stable and efficient. Although supporting by materials should precede, the development of stable and efficient organic material layer materials for organic electric devices has not yet been sufficiently achieved. Therefore, the development of new materials is continuously required, and in particular, the development of materials for the light emitting auxiliary layer is 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 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 formula below.

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

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, color purity and lifetime of the device can be greatly improved.

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

The terms "aryl group" and "arylene group" used in the present invention have 6 to 60 carbon atoms, respectively, unless otherwise specified, but are not limited thereto. In the present invention, the aryl group or arylene group includes a single ring, a ring assembly, a conjugated multiple ring system, a spiro compound, and the like. In addition, unless otherwise specified in the present specification, the aryl group includes a fluorenyl group and the arylene group includes a fluorenyl group.

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 structure, respectively, unless otherwise specified, " Substituted fluorenyl group" or "substituted fluorenyl 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 This includes cases where they form a spy compound together.

As used herein, the term "spiro compound" has a 'spiro linkage', and the spiro linkage means a linkage formed by sharing only one atom between two rings. At this time, the atoms shared by the two rings are called 'spiro atoms', and according to the number of spiro atoms in a compound, they are called 'monospiro-', 'dispiro-', and 'trispiro-', respectively. ' It's called a compound.

As used herein, the term "heterocyclic group" includes not only aromatic rings such as "heteroaryl group" or "heteroarylene group" but also non-aromatic rings, and unless otherwise specified, the carbon number each containing at least one heteroatom. It means 2 to 60 rings, but is not limited thereto. As used herein, the term "heteroatom" refers to N, O, S, P, or Si, unless otherwise specified, and a heterocyclic group includes a single ring containing a heteroatom, a ring assembly, a fused multi-ring system, a spy means a compound, etc.

As used herein, the term "heterocyclic group" refers to a ring containing heteroatoms such as N, O, S, P or Si instead of carbon forming a ring, and is referred to as a "heteroaryl group" or "heteroarylene group". It includes not only an aromatic ring but also a non-aromatic ring, such as the following compound instead of carbon forming a ring, SO ₂ , and a compound containing a heteroatom group such as P=O may also be included.

As used herein, the term "alicyclic group" refers to cyclic hydrocarbons other than aromatic hydrocarbons, and includes monocyclics, ring aggregates, bonded multiple ring systems, spiro compounds, etc., unless otherwise specified, carbon atoms It means rings of 3 to 60, but is not limited thereto. For example, even when benzene, which is an aromatic ring, and cyclohexane, which is a non-aromatic ring, are fused, it corresponds to an 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 be described as a 'name of a group reflecting a valence', but described as a 'parent compound name' You may. For example, in the case of 'phenanthrene', which is a kind of aryl group, the name of the group may be described by dividing the valence, such as 'phenanthryl' for a monovalent group and 'phenanthrylene' for a divalent group, but the valence and Regardless, it can also be described as 'phenanthrene', which is the name of the parent compound. Similarly, in the case of pyrimidine, it can also be described as 'pyrimidine' regardless of the valence, or as the 'name of the group' of the corresponding valence, such as a pyrimidinyl group in the case of monovalent, or pyrimidinylene in the case of divalent. there is.

In addition, unless explicitly stated otherwise, the chemical formula used in the present invention applies the same as the substituent definition by the exponent definition of the following formula.

Here, when a is an integer of 0, substituent R ¹ means that it does not exist, that is, when a is 0, it means that hydrogen is bonded to all carbons forming the benzene ring. It may be omitted and the chemical formula or compound may be described. In addition, when a is an integer of 1, one substituent R ¹ is bonded to any one of carbon atoms forming a benzene ring, and when a is an integer of 2 or 3, for example, it may be bonded as follows, and a is 4 to 6 Even if it is an integer of, it is bonded to the carbon of the benzene ring in a similar way, and when a is an integer of 2 or more, R ¹ may be the same as or different from each other.

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

In describing the present invention, if it is determined that a detailed description of a related known configuration or function may obscure the gist of the present invention, the detailed description will be omitted.

Also, when a component such as a layer, film, region, or plate is said to be “on” or “on” another component, this is not only when it is “directly on” the other component, but also when there is another component in between. It should be understood that the case may also be included. Conversely, when an element is said to be “directly on” another part, it should be understood that there is no intervening part.

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

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 element 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, and An organic material layer containing the compound according to the present invention is provided between the two electrodes 180 . In this case, the first electrode 120 may be an anode (anode), and the second electrode 180 may be a cathode (negative electrode), 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 sequentially 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 on the first electrode 120 . At this time, at least one of these layers may be omitted, or may further include a hole blocking layer, an electron blocking layer, a light emitting auxiliary layer 151, an electron transport auxiliary layer, a buffer layer 141, and the like. It may also serve as a hole blocking layer.

In addition, although not shown, the organic electric device according to an embodiment of the present invention further includes a protective layer or a light efficiency improving layer (Capping layer) formed on a surface opposite to the organic material layer among at least one surface of the first electrode and the second electrode. can do.

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 material of the light emitting layer 150, or the material of the light efficiency improvement layer, but is preferably used as the hole transport layer 140 and / or the light emitting auxiliary layer 151 material, More preferably, it can be used as a material for the light emitting auxiliary layer 151.

On the other hand, since the band gap, electrical properties, interface properties, etc. may vary depending on which substituent is attached to which position even in the same core, the selection of the core and the combination of sub-substituents bound thereto Research is required, and in particular, long life and high efficiency can be achieved at the same time when the optimal combination of the energy level and T ₁ value between each organic material layer and the intrinsic properties of the material (mobility, interfacial property, etc.) is achieved.

Therefore, in the present invention, by forming the light emitting auxiliary layer 151 using the compound represented by Formula 1, the energy level and T ₁ value between each organic material layer, and the intrinsic properties of the material (mobility, interface property, etc.) are optimized to optimize organic properties. It is possible to simultaneously improve the lifespan and efficiency of an electric device.

An organic light emitting device according to an embodiment of the present invention may be manufactured using various deposition methods. It can be manufactured using a deposition method such as PVD or CVD, for example, depositing a metal or a metal oxide having conductivity 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 a hole transport layer 140, a light emitting layer 150, an electron transport layer 160 and an electron injection layer 170, it can be manufactured by depositing a material that can be used as the cathode 180 thereon. there is. In addition, an auxiliary light emitting layer 151 may be further formed between the hole transport layer 140 and the light emitting layer 150 and an auxiliary electron transport layer may be further formed between the light emitting layer 150 and the electron transport layer 160 .

In addition, the organic material layer is formed by a solution process or a solvent process other than a deposition method using various polymer materials, such as a spin coating process, a nozzle printing process, an inkjet printing process, a slot coating process, a dip coating process, a roll-to-roll process, and a doctor blading process. It can be manufactured with a smaller number of layers by a method such as a printing process, a screen printing process, or a thermal transfer method. Since the organic layer according to the present invention can be formed in various ways, the scope of the present invention is not limited by the forming method.

The organic electric device according to the present invention may be one of an organic light emitting device (OLED), an organic solar cell, an organic photoconductor (OPC), an organic transistor (organic TFT), a device for monochromatic or white lighting, and a device for quantum dot display.

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 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 a mobile communication terminal such as a mobile phone, a PDA, an electronic dictionary, a PMP, a remote control, a navigation device, a game machine, various TVs, and various computers. The display device may include an organic light emitting display, a quantum dot display, and the like.

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

A compound according to one aspect of the present invention is represented by Formula 1 below.

<Formula 1>

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

X and Y are independently of each other O or S.

R ¹ to R ³ are each independently hydrogen; heavy hydrogen; halogen; C ₆ ~ C ₆₀ aryl group; fluorenyl group; a C ₂ ~C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si, and P; C ₃ ~ C ₆₀ aliphatic ring group; C ₁ ~ C ₅₀ Alkyl group; A C ₂ ~C ₂₀ alkenyl group; C ₁ ~ C ₃₀ alkoxyl group; C ₆ ~ C ₃₀ aryloxy group; And -L'-N (R _a ) (R _b ) It is selected from the group consisting of, adjacent groups may be bonded to each other to form a ring.

When adjacent groups combine with each other to form a ring, a C ₆ ~ C ₆₀ aromatic ring, a C ₂ ~ C ₆₀ hetero atom including at least one hetero atom selected from fluorene, O, N, S, Si and P A ring or a C ₃ ~ C ₆₀ aliphatic ring may be formed. When adjacent R ¹ , adjacent R ² , or adjacent R ³ bonds to each other to form an aromatic ring, preferably a C ₆ to C ₃₀ aromatic ring, more preferably a C ₆ to C ₁₀ aromatic ring rings, such as benzene, naphthalene, and the like.

a and c are each an integer of 0 to 3, b is an integer of 0 to 4, and when each of a, b, and c is an integer of 2 or more, each of a plurality of R ¹ , each of a plurality of R ² , each of a plurality of R ³ may be the same as or different from each other.

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

When L ¹ and L ² are arylene groups, they are preferably C ₆ -C ₃₀ arylene groups, more preferably C ₆ -C ₁₈ arylene groups, such as phenyl, naphthalene, biphenyl terphenyl, and the like. When L ¹ and L ² are heterocyclic groups, preferably C ₂ ~ C ₃₀ heterocyclic groups, more preferably C ₂ ~ C ₁₈ heterocyclic groups, such as dibenzothiophene, dibenzofuran, and carba sol, phenylcarbazole, and the like.

Ar ¹ to Ar ⁴ are each independently a C ₆ to C ₆₀ aryl group; fluorenyl group; A C ₂ ~C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si, and P; C ₃ ~ C ₆₀ aliphatic ring group; -L'-N(R _a )(R _b ); And it may be selected from the group consisting of combinations thereof.

When Ar ¹ to Ar ⁴ are aryl groups, they are preferably C ₆ -C ₃₀ aryl groups, more preferably C ₆ -C ₁₈ aryl groups, such as phenyl, naphthyl, biphenyl, triphenylene, etc. there is. When Ar ¹ to Ar ⁴ are heterocyclic groups, preferably C ₂ to C ₃₀ heterocyclic groups, more preferably C ₂ to C ₁₈ heterocyclic groups such as pyridine, pyrimidine, pyrazine, triazine, Dibenzothiophene, dibenzofuran, carbazole, phenylcarbazole, benzonaphthothiophene, benzonaphthofuran, and the like may be used. When Ar ¹ to Ar ⁴ are fluorenyl groups, they may be 9,9-dimethylfluorene, 9,9-diphenylfluorene, 9,9'-spirofluorene or the like.

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

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

The rings formed by combining R ¹ to R ³ , Ar ¹ to Ar ⁴ , R _a , R _b , L ¹ , L ² , L' and neighboring groups each contain 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 group; boron group; Germanium group; cyano group; nitro group; A phosphine oxide group unsubstituted or substituted with a C ₁ -C ₂₀ alkyl group or a C ₆ -C ₂₀ aryl group; C ₁ -C ₂₀ Alkylthio group; C ₁ -C ₂₀ alkoxyl group; C ₆ -C ₂₀ aryloxy 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; A deuterium-substituted C ₆ -C ₂₀ aryl group; fluorenyl group; A C ₂ -C ₂₀ heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si and P; C ₃ -C ₂₀ aliphatic ring group; C ₇ -C ₂₀ arylalkyl group; C ₈ -C ₂₀ arylalkenyl group; -L'-N(R _a )(R _b ); And it may be further substituted with one or more substituents selected from the group consisting of combinations thereof. Here, L', R _a and R _b are as defined above.

Preferably, Formula 1 may be represented by one of Formulas 2 to 5 below.

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

In Formulas 2 to 5, X, Y, R ¹ to R ³ , Ar ¹ to Ar ⁴ , L ¹ , L ² , a, b, and c are the same as those defined in Formula 1.

Preferably, Formula 1 may be represented by Formula 6 below.

<Formula 6>

In Formula 6, each symbol may be defined as follows.

R ⁴ and R ⁵ are each independently hydrogen; heavy hydrogen; halogen; C ₆ ~ C ₆₀ aryl group; fluorenyl group; a C ₂ ~C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si, and P; C ₃ ~ C ₆₀ aliphatic ring group; C ₁ ~ C ₅₀ Alkyl group; A C ₂ ~C ₂₀ alkenyl group; C ₁ ~ C ₃₀ alkoxyl group; C ₆ ~ C ₃₀ aryloxy group; And -L'-N (R _a ) (R _b ) It is selected from the group consisting of, adjacent groups may be bonded to each other to form a ring.

Preferably, R ⁴ and R ⁵ are each independently hydrogen; heavy hydrogen; halogen; C ₁ -C ₂₀ alkoxyl group; C ₆ -C ₂₀ aryloxy 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; A C ₂ -C ₂₀ heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si and P; C ₃ -C ₂₀ aliphatic ring group; -L'-N(R _a )(R _b ); And it may be further substituted with one or more substituents selected from the group consisting of combinations thereof.

d is an integer of 0 to 3, e is an integer of 0 to 4, and when each of d and e is an integer of 2 or greater, a plurality of R ⁴ and a plurality of R ⁵ are the same as or different from each other.

Z is N(R'), O, S or C(R ^a )(R ^b );

Wherein R' is a C ₆ ~ C ₆₀ aryl group; fluorenyl group; a C ₂ ~C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si, and P; C ₃ ~ C ₆₀ aliphatic ring group; And it may be selected from the group consisting of combinations thereof.

Preferably, R' is a C ₆ ~ C ₂₀ aryl group; a C ₂ ~C ₂₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si, and P; C ₃ ~ C ₂₀ aliphatic ring group; And it may be selected from the group consisting of combinations thereof.

Wherein R ^a and R ^b are each independently hydrogen; heavy hydrogen; halogen; C ₆ ~ C ₆₀ aryl group; fluorenyl group; a C ₂ ~C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si, and P; C ₃ ~ C ₆₀ aliphatic ring group; C ₁ ~ C ₅₀ Alkyl group; A C ₂ ~C ₂₀ alkenyl group; C ₁ ~ C ₃₀ alkoxyl group; C ₆ ~ C ₃₀ aryloxy group; And -L'-N (R _a ) (R _b ) It is selected from the group consisting of, R ^a and R ^b may be bonded to each other to form a ring.

Preferably, R ^a and R ^b are independently of each other hydrogen; heavy hydrogen; halogen; C ₆ ~ C ₂₀ aryl group; a C ₂ ~C ₂₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si, and P; C ₃ ~ C ₂₀ aliphatic ring group; C ₁ ~ C ₂₀ Alkyl group; A C ₂ ~C ₂₀ alkenyl group; C ₁ ~ C ₂₀ alkoxyl group; C ₆ ~ C ₂₀ aryloxy group; And -L'-N (R _a ) (R _b ) It may be selected from the group consisting of.

X, Y, R ¹ to R ³ , Ar ¹ to Ar ³ , L ¹ , L ² , a, b, c, L', R _a and R _b are as defined in Formula 1.

Preferably, Chemical Formula 1 may be asymmetric about the axis of the covalent side of naphthalene. At this time, the covalent side of naphthalene means the dotted line portion in Formula 1 below.

Therefore, when the naphthalene is asymmetric about the common side (dotted line part) as an axis, for example, when X and Y are different, when R ¹ and R ³ are different, when L ¹ and L ² are different, N(Ar ¹ ) ( Ar ² ) group and N (Ar ³ ) (Ar ⁴ ) group may be different.

More preferably, X and Y in Formula 1 may be different from each other.

Specifically, the compound represented by Formula 1 may be one of the following compounds.

.

.

As another embodiment of the present invention, there is provided 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 1 represented by Formula 1 A single species compound or a compound of two or more species is included.

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 supplement, an electron transport layer, and an electron injection layer, and preferably, the compound is included in the light emitting auxiliary layer or the hole transport layer. do.

As another embodiment of the present invention, an electronic device including a display device including the organic electric element and a control unit driving the display device is provided.

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

synthesis example

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

<Scheme 1>

In the case of symmetry around naphthalene in the center, synthesis is performed by reacting 1 equivalent of Core 1 with about 2 equivalents of Sub 1, and in the case of asymmetric, the above process is repeated, respectively.

I. Synthesis of Core 1

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

<Scheme 2>

In the case of a symmetric compound, synthesis is performed by reacting 1 equivalent of Core1-I with 2 equivalents of Core 1-II, and in the case of an asymmetric compound, the above process is repeated.

In addition, Core 1-I of Reaction Scheme 2 may be synthesized by the reaction pathways of Reaction Schemes 3 to 5 below, but is not limited thereto.

<Scheme 3> (When X and Y are S)

<Scheme 4> (When X and Y are O and S, respectively)

<Scheme 5> (When X and Y are O)

of Core 1 synthesis example

(1) Synthesis of Core 1-1

1) After putting 2,7-diiodonaphthalene (30 g, 79.0 mmol) in a round bottom flask and dissolving it with 260 mL of THF, (2-chloro-6-(methylthio)phenyl)boronic acid (16.8 g, 82.9 mmol), Pd (PPh ₃ ) ₄ (1.8 g, 1.6 mmol), K ₂ CO ₃ (21.8 g, 157.9 mmol) and 85 mL of water were added and stirred at 80 °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 and concentrated. Thereafter, impurities were removed from the concentrate by recrystallization with a silica gel column to obtain 27.5 g (yield: 85%) of (3-chloro-2-(7-iodonaphthalen-2-yl)phenyl)(methyl)sulfane.

2) Put (3-chloro-2-(7-iodonaphthalen-2-yl)phenyl)(methyl)sulfane (25 g, 60.9 mmol) in a round bottom flask, dissolve in 200 mL of THF, and (2-bromo-6 -(methylthio)phenyl)boronic acid (15.8 g, 63.92 mmol), Pd(PPh ₃ ) ₄ (1.4 g, 1.2 mmol), K ₂ CO ₃ (16.8 g, 121.7 mmol) and 80 mL of water were added and stirred at 80 °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 and concentrated. Thereafter, impurities were removed from the concentrate by a silica gel column and recrystallization to obtain 25.5 g of 2-(2-bromo-6-(methylsulfinyl)phenyl)-7-(2-chloro-6-(methylsulfinyl)phenyl)naphthalene (yield: 83%) was obtained.

3) 2-(2-bromo-6-(methylsulfinyl)phenyl)-7-(2-chloro-6-(methylsulfinyl)phenyl)naphthalene (20 g, 41.0 mmol) was added to a round bottom flask and dissolved in 130 mL of AcOH. After that, H ₂ O ₂ (3 g, 90.6 mmol) was added and stirred at room temperature. After the reaction was completed, the solvent was removed, neutralized with 1M NaOH, extracted with ethyl acetate, and recrystallized to form (3-bromo-2-(7-(2-chloro-6-(methylthio)phenyl)naphthalen-2-yl). 19.2 g of phenyl)(methyl)sulfane (yield: 90%) was obtained.

4) (3-bromo-2-(7-(2-chloro-6-(methylthio)phenyl)naphthalen-2-yl)phenyl)(methyl)sulfane (19.0 g, 36.7 mmol) in H ₂ SO ₄ 200 g and stirred at 65°C. When the reaction was completed, it was neutralized using an aqueous NaOH solution, and then impurities were removed by a silica gel column and recrystallization to obtain 14.8 g of Core1-1 (yield: 89%).

(2) Synthesis of Core 1-12

After dissolving Core1-13 (20 g, 44.0 mmol) in 150 mL of THF, (3-bromophenyl)boronic acid (9.3 g, 46.3 mmol), Pd(PPh ₃ ) ₄ (1.0 g, 0.9 mmol), K ₂ CO ₃ (12.2 g, 88.1 mmol) and 50 mL of water were added and stirred at 80 °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 and concentrated. Thereafter, impurities were removed from the concentrate by recrystallization with a silica gel column to obtain 19.9 g of Core1-12 (yield: 85%).

(3) Synthesis of Core 1-14

1) Put 10-bromobenzo[b]naphtho[2,1-d]thiophen-1-ol (20 g, 40.1 mmole) in a round bottom flask, dissolve in 270 mL of DMF, and then add 1-chloro-4-iodobenzene (7.5 g). , 44.2 mmol), K ₂ CO ₃ (11.1 g, 80.3 mmol), Cu (1.3 g, 20.1 mmol), and Dibenzo-18-crown-6 (0.87 g, 2.4 mmole) were added and stirred at 120 °C. After the reaction was completed, the solvent was removed, extracted with CH ₂ Cl ₂ and water, and the organic layer was dried over MgSO ₄ and concentrated. Thereafter, impurities were removed from the concentrate using a silica gel column to obtain 13.9 g of 10-bromo-1-(4-chlorophenoxy)benzo[b]naphtho[2,1-d]thiophene (yield: 79%).

2) Pd(OAc) ₂ (0.31 g, 1.4 mol), K ₂ CO in 10-bromo-1-(4-chlorophenoxy)benzo[b]naphtho[2,1-d]thiophene (12 g, 27.3 mmol) ₃ 7.5 g, 54.6 mol) into 200 mL of acetic acid and stirred at 120 ° C for 48 hours. After the reaction was completed, the mixture was extracted with EA and water, and the organic layer was dried over MgSO ₄ and concentrated. Thereafter, impurities were removed from the concentrate by a silica gel column to obtain 5.3 g of Core1-14 (yield: 44%).

(3) Synthesis of Core 1-16

1) Naphthalene-1,8-diol (20 g, 124.9 mmole) was put in a round bottom flask and dissolved in 400 mL of DMF, followed by 1-bromo-2-iodobenzene (35.3 g, 124.9 mmole) and K ₂ CO ₃ (34.5 g). 249.7 mmol), Cu (4.0 g, 62.4 mmol), and Dibenzo-18-crown-6 (2.3 g, 6.3 mmole) were added and stirred at 120°C. After the reaction was completed, the solvent was removed, extracted with CH ₂ Cl ₂ and water, and the organic layer was dried over MgSO ₄ and concentrated. Thereafter, impurities were removed from the concentrate using a silica gel column to obtain 27.5 g (yield: 70%) of 8-(2-bromophenoxy)naphthalen-1-ol.

2) 8-(2-bromophenoxy)naphthalen-1-ol (25 g, 79.3 mmole) was put in a round bottom flask and dissolved in 260 mL of DMF, followed by 1-chloro-2-iodobenzene (20.8 g, 87.3 mmole), K ₂ CO ₃ (21.9 g 158.6 mmol), Cu (2.5 g, 40.0 mmol), and Dibenzo-18-crown-6 (1.4 g, 4.0 mmole) were added and stirred at 120°C. After the reaction was completed, the solvent was removed, extracted with CH ₂ Cl ₂ and water, and the organic layer was dried over MgSO ₄ and concentrated. Thereafter, impurities were removed from the concentrate using a silica gel column to obtain 24.3 g of 1-(2-bromophenoxy)-8-(2-chlorophenoxy)naphthalene (yield: 72%).

3) 1-(2-bromophenoxy)-8-(2-chlorophenoxy)naphthalene (20 g, 47.0 mmol), Pd(OAc) ₂ (0.5 g, 2.4 mol), K ₂ CO ₃ 13.0 g, 94.0 mol) 160 mL of acetic acid was added and stirred at 120°C for 48 hours. After the reaction was completed, the mixture was extracted with EA and water, and the organic layer was dried over MgSO ₄ and concentrated. Thereafter, impurities were removed from the concentrate by a silica gel column to obtain 8.3 g of Core1-16 (yield: 42%).

(4) Synthesis of Core 1-20

After putting Core1-1 (20 g, 44.1 mmol) in a round bottom flask and dissolving it in 150 mL of THF, (9-chlorodibenzo[b,d]thiophen-1-yl)boronic acid (12.2 g, 46.3 mmol), Pd( PPh ₃ ) ₄ (1.0 g, 0.9 mmol), K ₂ CO ₃ (12.2 g, 88.2 mmol) and 50 mL of water were added and stirred at 80 °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 and concentrated. Thereafter, impurities were removed from the concentrate by a silica gel column and recrystallization to obtain 21.1 g of Core1-20 (yield: 81%).

The compound belonging to Core 1 may be the following compounds, but is not limited thereto, and the FD-MS values for the following compounds are shown in Table 1.

[Table 1]

II. of Sub 1 synthesis example

Sub 1 of Reaction Scheme 1 may be synthesized by the reaction pathway of Reaction Scheme 6 below, but is not limited thereto.

<Scheme 6>

(1) Sub 1-5 synthesis example

aniline (9.2 g, 98.8 mmol), Pd ₂ (dba) ₃ (1.4 g, 1.5 mmol), 50% P( t -Bu) ₃ ( 1.2 ml, 3.0 mmol), NaO t -Bu (14.6 g, 152.0 mmol), and toluene (500 ml) were added and stirred at 80°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 and concentrated. Thereafter, impurities were removed from the concentrate by a silica gel column and recrystallization to obtain 17.0 g of Sub1-5 (yield: 81%).

(2) Sub 1-21 synthesis example

3-bromo-7-iododibenzo[b,d]thiophene (20 g, 51.4 mmol), diphenylamine (11.3 g, 66.8 mmol), Pd ₂ (dba) ₃ (0.9 g, 1.0 mmol), 50% P( t - Bu) ₃ (0.8 ml, 2.0 mmol), NaO t -Bu (9.9 g, 102.8 mmol), and toluene (350 ml) were added and stirred at 80°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 and concentrated. Thereafter, impurities were removed from the concentrate by a silica gel column and recrystallization to obtain 18.4 g of Sub1-21 (yield: 83%).

(3) Sub 1-25 synthesis example

Diphenylamine (9.8 g, 58.0 mmol), Pd ₂ (dba) ₃ (0.8 g, 0.9 mmol), 50% P( t -Bu) ₃ (0.7 ml, 1.8 mmol), NaO t -Bu (8.6 g, 89.3 mmol), and toluene (300 ml) were added and stirred at 80°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 and concentrated. Thereafter, impurities were removed from the concentrate by a silica gel column and recrystallization to obtain 17.3 g of Sub1-25 (yield: 79%).

(4) Sub 1-47 synthesis example

aniline (14.8 g, 87.5 mmol), Pd ₂ (dba) ₃ (1.2 g, 1.4 mmol), 50% P( t -Bu) in 2-bromonaphtho[2,3-b]benzofuran (20 g, 67.3 mmol) ₃ (1.1 ml, 2.70 mmol), NaO t -Bu (13.0 g, 134.6 mmol), and toluene (450 ml) were added and stirred at 80°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 and concentrated. Thereafter, impurities were removed from the concentrate by a silica gel column and recrystallization to obtain 16.0 g of Sub1-47 (yield: 77%).

Compounds belonging to Sub 1 may be the following compounds, but are not limited thereto, and FD-MS values for the following compounds are shown in Table 2.

[Table 2]

III. of the final compound synthesis example

(1) P-1 synthesis example

Core1-1 (20 g, 44.1 mmol), diphenylamine (18.7 g, 110.2 mmol), Pd ₂ (dba) ₃ (1.6 g, 1.8 mmol), 50% P( t -Bu) ₃ (1.4 ml, 3.5 mmol) , NaO t -Bu (12.7 g, 132.2 mmol) and toluene (300 ml) were added and stirred at 80 °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 and concentrated. Thereafter, impurities were removed from the concentrate by a silica gel column and recrystallization to obtain 20.5 g of P1 (yield: 69%).

(2) P-65 synthesis example

1) Core1-14 (20 g, 45.7 mmol) Sub1-30 (14.9 g, 45.7 mmol), Pd ₂ (dba) ₃ (0.8 g, 0.9 mmol), 50% P( t -Bu) ₃ (0.7 ml , 1.8 mmol), NaO t -Bu (13.2 g, 137.1 mmol), and toluene (300 ml) were added and stirred at 80 °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 and concentrated. Thereafter, the concentrate was subjected to a silica gel column and recrystallization to remove impurities, resulting in N-(benzo[b]naphtho[1,2-d]thiophen-9-yl)-10-chloro-N-phenylbenzo[4',5' 26.5 g (yield: 85%) of ]thieno[3',2':7,8]naphtho[1,2-b]benzofuran-1-amine was obtained.

2) N-(benzo[b]naphtho[1,2-d]thiophen-9-yl)-10-chloro-N-phenylbenzo[4',5']thieno[3',2':7,8] Sub1-31 (12.5 g, 40.3 mmol), Pd ₂ (dba) ₃ (0.7 g, 0.7 mmol), 50% P( t -Bu) ₃ (0.6 ml, 1.5 mmol), NaO t -Bu (10.6 g, 110.0 mmol), and toluene (250 ml) were added and stirred at 80°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 and concentrated. Thereafter, impurities were removed from the concentrate by a silica gel column and recrystallization to obtain 25.6 g of P30 (yield: 73%).

The FD-MS values of the compounds P1 to P39 of the present invention prepared according to the Synthesis Example as described above are shown in Table 3 below.

[Table 3]

Manufacturing evaluation of organic electric devices

[ Example One] red organic light emitting device ( Light emitting auxiliary layer )

First, 4,4',4''-Tris[2-naphthyl(phenyl)amino]triphenylamine (hereinafter abbreviated as 2-TNATA) was vacuum deposited to a thickness of 60 nm on an ITO layer (anode) formed on a glass substrate. After forming a hole injection layer, N,N'-Bis(1-naphthalenyl)-N,N'-bis-phenyl-(1,1'-biphenyl)-4,4'- Diamine (hereinafter abbreviated as NPB) was vacuum deposited to a thickness of 60 nm to form a hole transport layer. Subsequently, the compound P1 of the present invention was vacuum deposited on the hole transport layer to a thickness of 20 nm to form an auxiliary light emitting layer, and then 4,4'-N, N'-dicarbazole-biphenyl (hereinafter referred to as Abbreviated as “CBP”) as a host material and bis-(1-phenylisoquinolyl)iridium(III)acetylacetonate (hereinafter abbreviated as “(piq) ₂ Ir(acac)”) as a dopant material. A light emitting layer was formed by doping a dopant in a weight ratio and vacuum depositing to a thickness of 30 nm.

Next, (1,1'-biphenyl-4-olato)bis(2-methyl-8-quinolinolato)aluminum (hereinafter abbreviated as "BAlq") was vacuum-deposited to a thickness of 10 nm on the light emitting layer to form a hole blocking layer. was formed, and tris-(8-hydroxyquinoline)aluminum (hereinafter abbreviated as "Alq ₃ ") was vacuum deposited on the hole blocking layer to a thickness of 40 nm to form an electron transport layer. Thereafter, LiF was deposited to a thickness of 0.2 nm to form an electron injection layer, and then Al was deposited to a thickness of 150 nm to form a cathode.

[ Example 2] to [ Example 14]

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 P1 of the present invention as a material for the light emitting auxiliary 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 Comparative Compound C was used instead of Compound P1 of the present invention as a material for the light emitting auxiliary layer.

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

By applying a forward bias DC voltage to the organic light emitting device manufactured by Examples 1 to 14 and Comparative Examples 1 to 3 of the present invention, electroluminescence (EL) characteristics were measured with Photoresearch's PR-650. It was measured, and as a result of the measurement, the T95 life was measured through a life measurement equipment manufactured by McScience at a standard luminance of 2500 cd / m ² , and the measurement results are shown in Table 4 below.

[Table 4]

As can be seen from Table 4, when manufacturing a red organic light emitting device using the organic light emitting device material of the present invention as a light emitting auxiliary layer material, compared to Comparative Examples using Comparative Compounds A to C, organic electroluminescence The driving voltage of the light emitting device can be lowered, and the luminous efficiency and lifetime can be remarkably improved.

Comparative Compound A has a different structure from that of the present invention, and also different types of heteroelements included in the core. Comparative Compound B and Comparative Compound C have the same core as the compound of the present invention, but are different from the compound of the present invention in that they have only one amine group bonded to the core.

Due to this difference, the device characteristics of Comparative Example 2 or Comparative Example 3 using Comparative Compound B or Comparative Compound C were superior to Comparative Example 1 using Comparative Compound A as the light emitting auxiliary layer material, and in the case of Examples using the compound of the present invention Device characteristics were the best.

This is because the physical properties of the compound vary significantly depending on the skeleton of the core and the type of heteroelements included in the core, and the physical properties of the compound, such as hole injection and mobility, are also changed due to the amine group bonded to the core, and the difference in physical properties of these compounds As a result, it is determined that the device characteristics are changed by acting as a major factor in improving performance during device deposition.

The above description is only illustrative of the present invention, and those skilled in the art will be able to make various modifications without departing from the essential characteristics of the present invention. Accordingly, the embodiments disclosed in this specification are intended to explain, not limit, the present invention, and the spirit and scope of the present invention are not limited by these embodiments. The protection scope of the present invention should be construed by the following claims, and all technologies within the equivalent range 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)

A compound represented by Formula 1 below:
<Formula 1>

In Formula 1,
X and Y are independently of each other O or S,
R ¹ to R ³ are each independently hydrogen; heavy hydrogen; halogen; C ₆ ~ C ₆₀ aryl group; a C ₂ ~C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si, and P; C ₃ ~ C ₆₀ aliphatic ring group; C ₁ ~ C ₅₀ Alkyl group; And it is selected from the group consisting of C ₂ ~ C ₂₀ alkenyl groups, adjacent groups may be bonded to each other to form a ring,
a and c are each an integer of 0 to 3, b is an integer of 0 to 4, and when each of a, b, and c is an integer of 2 or greater, each of a plurality of R ¹ , each of a plurality of R ² , each of a plurality of R ³ the same as or different from each other,
L ¹ and L ² are each independently a single bond; C ₆ ~ C ₆₀ arylene group; C ₃ ~ C ₆₀ aliphatic ring group; And it is selected from the group consisting of a C ₂ ~C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P,
Ar ¹ to Ar ⁴ are each independently a C ₆ to C ₆₀ aryl group; A C ₂ ~C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si, and P; C ₃ ~ C ₆₀ aliphatic ring group; And -L'-N (R _a ) (R _b ); is selected from the group consisting of,
L' is a single bond; C ₆ ~ C ₆₀ arylene group; Fluorenylene group; A C ₂ ~C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si, and P; And C ₃ ~ C ₆₀ It is selected from the group consisting of an aliphatic ring group,
Wherein R _a and R _b are each independently a C ₆ ~ C ₆₀ aryl group; fluorenyl group; A C ₂ ~C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si, and P; And C ₃ ~ C ₆₀ It is selected from the group consisting of an aliphatic ring group. According to claim 1,
A compound characterized in that Formula 1 is represented by one of the following Formulas 2 to 5:
<Formula 2><Formula3><Formula4><Formula5>

In Formulas 2 to 5,
X, Y, R ¹ to R ³ , Ar ¹ to Ar ⁴ , L ¹ , L ² , a, b and c are the same as defined in claim 1. According to claim 1,
Formula 1 is a compound characterized in that represented by the following formula (6):
<Formula 6>

In Formula 6,
R ⁴ and R ⁵ are each independently hydrogen; heavy hydrogen; halogen; C ₆ ~ C ₂₀ aryl group; a C ₂ ~C ₂₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si, and P; C ₃ ~ C ₂₀ aliphatic ring group; C ₁ ~ C ₂₀ Alkyl group; And it is selected from the group consisting of C ₂ ~ C ₂₀ alkenyl groups, adjacent groups may be bonded to each other to form a ring,
d is an integer of 0 to 3, e is an integer of 0 to 4, and when each of d and e is an integer of 2 or more, a plurality of R ⁴ and a plurality of R ⁵ are the same as or different from each other;
Z is N(R'), O, S or C(R ^a )(R ^b );
R' is a C ₆ ~ C ₂₀ aryl group; a C ₂ ~C ₂₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si, and P; And C ₃ ~ C ₂₀ It is selected from the group consisting of an aliphatic ring group,
Wherein R ^a and R ^b are each independently hydrogen; heavy hydrogen; halogen; C ₆ ~ C ₂₀ aryl group; a C ₂ ~C ₂₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si, and P; C ₃ ~ C ₂₀ aliphatic ring group; C ₁ ~ C ₂₀ Alkyl group; And C ₂ ~ C ₂₀ It is selected from the group consisting of alkenyl, R ^a and R ^b may be bonded to each other to form a ring,
X, Y, R ¹ to R ³ , Ar ¹ to Ar ³ , L ¹ , L ² , a, b and c are the same as defined in claim 1. According to claim 1,
Formula 1 is a compound, characterized in that asymmetric about the axis of the covalent side of naphthalene. According to claim 1,
A compound characterized in that X and Y of Formula 1 are different from each other. According to claim 1,
A compound, characterized in that the compound represented by Formula 1 is one of the following compounds:

. a first electrode; a second electrode; and an organic material layer positioned between the first electrode and the second electrode.
The organic material layer is an organic electric device characterized in that it comprises a compound represented by the formula (1) of claim 1. According to claim 7,
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. According to claim 8,
The organic electric device, characterized in that the compound is included in the light emitting auxiliary layer. According to claim 7,
The organic 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 electric element of claim 7; and
An electronic device comprising a controller for driving the display device. According to claim 11,
The electronic device, characterized in that the organic electric device is selected from the group consisting of organic light emitting devices, organic solar cells, organic photoreceptors, organic transistors, devices for monochromatic lighting and devices for quantum dot displays.

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