KR102529924B1 - 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 device including a compound represented by 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. do. 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.

Materials used as organic layers in organic electric devices may be classified into light emitting materials and charge transport materials, such as hole injection materials, hole transport materials, electron transport materials, and electron injection materials, according to their functions. In addition, the light emitting materials can be classified into high molecular weight and low molecular weight according to molecular weight, and can be classified into fluorescent materials derived from singlet excited states of electrons and phosphorescent materials derived from triplet excited states of electrons according to light emitting mechanisms. there is. In addition, light emitting materials may be classified into blue, green, and red light emitting materials and yellow and orange light emitting materials required to realize better natural colors according to the light emitting color.

On the other hand, when only one material is used as a light emitting material, the maximum emission wavelength moves to a longer wavelength due to intermolecular interactions, and the color purity decreases or the efficiency of the device decreases due to the emission attenuation effect. Therefore, color purity increases and energy transfer A host/dopant system may be used as a light emitting material in order to increase luminous efficiency. The principle is that when a small amount of a dopant having a smaller energy band gap than the host forming the light emitting layer is mixed into the light emitting layer, excitons generated in the light emitting layer are transported to the dopant to emit light with high efficiency. At this time, since the wavelength of the host moves to the wavelength range of the dopant, light of a desired wavelength can be obtained according to the type of dopant used.

Currently, the size of the portable display market tends to increase with large-area displays, and as a result, power consumption greater than that required for existing portable displays is required. Therefore, power consumption has become a very important factor for portable displays that have a limited power supply source such as a battery, and efficiency and lifespan problems must also be solved.

Efficiency, lifespan, driving voltage, etc. are related to each other, and as efficiency increases, 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 T ₁ value between each organic material layer and the intrinsic properties of the material (mobility, interfacial property, etc.) is achieved. .

Therefore, it is necessary to develop a light emitting material that has high thermal stability and can efficiently balance charge in the light emitting layer. That is, in order to fully exhibit the excellent characteristics of organic electric devices, materials constituting the organic layer in the device, such as hole injection materials, hole transport materials, light emitting materials, electron transport materials, electron injection materials, etc. are supported by stable and efficient materials. Although this should be preceded, development of stable and efficient organic material layer materials for organic electric devices has not yet been sufficiently achieved, and in particular, development of a host material for a light emitting layer is urgently required.

An object of the present invention is to provide a compound capable of lowering the driving voltage of the device and improving the luminous efficiency 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, the driving voltage of the device can be lowered, and the luminous efficiency and lifetime of the device can be greatly improved.

1 is an exemplary diagram of an organic electroluminescent device according to the present invention.
2 shows a chemical formula according to one aspect of 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 may include 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 may include a fluorenyl group and the arylene group may include 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, in the present specification, numbers or alphabets indicating positions may be omitted when describing compound names or substituent names. For example, pyrido[4,3-d]pyrimidine to pyridopyrimidine, benzofuro[2,3-d]pyrimidine to benzofuropyrimidine, and 9,9-dimethylfluorene to dipyrimidine. It can be described as methyl fluorene or the like. Therefore, both benzo[g]quinoxaline and benzo[f]quinoxaline can be described as benzoquinoxaline.

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 does not exist, and when a is an integer of 1, one substituent R ¹ is bonded to any one of the carbon atoms forming the benzene ring, and when a is an integer of 2 or 3 Each is bonded as follows, wherein R ¹ may be the same or different from each other, and when a is an integer of 4 to 6, it is bonded to the carbon of the benzene ring in a similar manner, while indicating the hydrogen bonded to the carbon forming the benzene ring. is omitted.

In addition, unless otherwise described herein, a ring formed by bonding adjacent groups to each other is a C ₆ ~ C ₆₀ aromatic ring 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 ₃ ~ C ₆₀ aliphatic ring and C ₆ ~ C ₆₀ aromatic ring fused ring group; And it may be selected from the group consisting of combinations thereof.

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.

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. An organic material layer containing the compound according to the present invention is included between the second electrodes 180 . In this case, the first electrode 120 may be an anode (anode), 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 include a hole injection layer 130, a hole transport layer 140, a light emitting layer 150, an electron transport layer 160, an electron injection layer 170, and the like sequentially stacked on the first electrode 120. . At this time, at least one of these layers may be omitted, or may further include a hole blocking layer, an electron blocking layer, a light emitting auxiliary layer 151, an electron transport auxiliary layer, a buffer layer 141, and the like. It may also serve as a hole blocking layer.

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

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

On the other hand, even for the same or similar core, since the band gap, electrical properties, interface properties, etc. may vary depending on which substituent is attached to which position, the selection of the core and the combination of sub-substituents bound thereto Research is needed, 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 using the compound represented by Formula 1 as a host of the light emitting layer, the lifespan of the organic electric device is optimized by optimizing the energy level and T ₁ value between each organic material layer, and the intrinsic properties of the material (mobility, interfacial property, etc.) and efficiency can be improved at the same time.

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.

An organic electric device according to an embodiment of the present invention may be a top emission type, a bottom emission type, or a double side emission type depending on the material used.

In addition, the organic electric device according to an embodiment of the present invention may be selected from the group consisting of an organic light emitting device, an organic solar cell, an organic photoreceptor, an organic transistor, a device for monochromatic lighting, and an 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 controller, a navigation device, a game machine, various TVs, and various computers.

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 the above formula, each symbol can be defined as follows.

R ₁ to R ₈ are each independently hydrogen; heavy hydrogen; halogen; cyano group; 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 ₃ ~ C ₆₀ aliphatic ring and C ₆ ~ C ₆₀ aromatic ring fused ring group; C ₁ ~ C ₅₀ Alkyl group; A C ₂ ~C ₂₀ alkenyl group; A 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 ); selected from the group consisting of, adjacent groups may be bonded to each other to form a ring.

A ring formed by bonding adjacent groups to each other is a C ₆ ~ C ₆₀ aromatic ring 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; Alternatively, it may be a fused ring group of a C ₃ ~ C ₆₀ aliphatic ring and a C ₆ ~ C ₆₀ aromatic ring. For example, adjacent R ₁ and R ₂ , adjacent R ₂ and R ₃ , adjacent R ₃ and R ₄ , adjacent R ₅ and R ₆ , adjacent R ₆ and R ₇ , adjacent R ₇ and R ₈ may combine with each other to form an aromatic ring such as benzene, naphthalene, or phenanthrene. Preferably, adjacent R ₁ and R ₂ , adjacent R ₂ and R ₃ , adjacent R ₃ and R ₄ , or adjacent R ₆ and R ₇ may bond to each other to form a ring.

When R ₁ to R ₈ are aryl groups, preferably C ₆ to C ₃₀ aryl groups, more preferably C ₆ to C ₁₈ aryl groups, such as phenyl, naphthyl, biphenyl, terphenyl, and phenanthrene. etc. When R ₁ to R ₈ are a heterocyclic group, preferably a C ₂ to C ₃₀ heterocyclic group, more preferably a C ₂ to C ₉ heterocyclic group, such as pyrimidine, pyrazine, quinoline, quinazoline, and quinone. It can be a salvaged light. When R ₁ to R ₈ are alkyl groups, they are preferably C ₂ to C ₁₀ alkyl groups such as methyl, t-butyl, and the like.

Ar ₁ is hydrogen; heavy hydrogen; halogen; cyano group; 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 ₃ ~ C ₆₀ aliphatic ring and C ₆ ~ C ₆₀ aromatic ring fused ring group; C ₁ ~ C ₅₀ Alkyl group; A C ₂ ~C ₂₀ alkenyl group; A 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 ); may be selected from the group consisting of. Preferably Ar ¹ is a substituent other than hydrogen.

When Ar ₁ is an aryl group, it may be preferably a C ₆ -C ₃₀ aryl group, more preferably a C ₆ -C ₁₈ aryl group, such as phenyl, naphthyl, biphenyl, terphenyl, phenanthrene, and the like. . When Ar ₁ is a heterocyclic group, it is preferably a C ₂ ~ C ₃₀ heterocyclic group, more preferably a C ₂ ~ C ₁₆ heterocyclic group, such as triazine, quinoxaline, carbazole, phenylcarbazole, and the like. there is.

Ar ₂ 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; C ₃ ~ C ₆₀ aliphatic ring and C ₆ ~ C ₆₀ aromatic ring fused ring group; C ₁ ~ C ₅₀ Alkyl group; A C ₂ ~C ₂₀ alkenyl group; A C ₂ ~C ₂₀ alkynyl group; C ₁ ~ C ₃₀ alkoxy group; And it may be selected from the group consisting of a C ₆ ~ C ₃₀ aryloxy group.

When Ar ₂ is an aryl group, it may be preferably a C ₆ -C ₃₀ aryl group, more preferably a C ₆ -C ₁₈ aryl group, such as phenyl, naphthyl, biphenyl, terphenyl, and the like. When Ar ₂ is a heterocyclic group, preferably a C ₂ ~ C ₃₀ heterocyclic group, more preferably a C ₂ ~ C ₁₆ heterocyclic group, such as triazine, pyrimidine, pyridine, quinazoline, quinoxaline, dibenzothiophene, dibenzofuran, carbazole, phenylcarbazole, benzothienopyrimidine, and the like. When Ar ₂ is a fluorenyl group, it may be 9,9-dimethylfluorene, 9,9-diphenylfluorene, 9,9'-spirofluorene or the like.

L and L' are each independently 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; C ₃ ~ C ₆₀ aliphatic ring group; and C ₃ ~ C ₆₀ aliphatic ring and C ₆ ~ C ₆₀ aromatic ring fused ring group; may be selected from the group consisting of.

When L and L' are arylene groups, they are preferably C ₆ -C ₃₀ arylene groups, more preferably C ₆ -C ₁₈ arylene groups, such as phenyl, naphthyl, biphenyl, terphenyl, etc. . When L and L' are heterocyclic groups, preferably C ₂ ~ C ₃₀ heterocyclic groups, more preferably C ₂ ~ C ₁₆ heterocyclic groups such as triazine, pyrimidine, quinazoline, quinoxaline, benzothienopyrimidine, carbazole, phenylcarbazole, and the like.

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; C ₃ ~ C ₆₀ aliphatic ring group; and C ₃ ~ C ₆₀ aliphatic ring and C ₆ ~ C ₆₀ aromatic ring fused ring group; may be selected from the group consisting of.

Ar ₁ , Ar ₂ , R ₁ to R ₈ , L, L', R _a , R _b , and a ring formed by bonding adjacent groups to each other are 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; C ₁ -C ₂₀ Alkylthio group; C ₁ -C ₂₀ alkoxy 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; And it may be further substituted with one or more substituents selected from the group consisting of combinations thereof.

Formula 1 may be represented by one of Formulas 2 to 3 below.

<Formula 2> <Formula 3>

<Formula 4>

In the above formula, R ₁ to R ₈ , L, Ar ₁ and Ar ₂ are as defined in Formula 1, Z ₁ to Z ₈ are N or CR', X is O, S, NR' or C(R ')(R").

Wherein R' and R" are each independently hydrogen; heavy hydrogen; halogen; cyano group; nitro group; C ₆ ~ C ₂₀ aryl group; fluorenyl group; at least one heteroatom selected from O, N, S, Si and P C ₂ ~ C ₂₀ heterocyclic group containing; C ₃ ~ C ₂₀ aliphatic ring group; C ₃ ~ C ₂₀ aliphatic ring and C ₆ ~ C ₂₀ aromatic ring fused ring group; C ₁ ~ C ₂₀ Alkyl group; C ₂ ~ C ₂₀ alkenyl group; C ₂ ~ C ₂₀ alkynyl group; C ₁ ~ C ₂₀ alkoxy group; and C ₆ ~ C ₃₀ selected from the group consisting of an aryloxy group, adjacent to R' Each other or R' and R" may be bonded to each other to form a ring.

In addition, Formula 1 may be represented by one of Formulas 5 to 10 below.

<Formula 5> <Formula 6>

<Formula 7> <Formula 8>

<Formula 9> <Formula 10>

In the above formula, R ₁ to R ₈ , L, Ar ₁ and Ar ₂ are as defined in Formula 1.

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

.

.

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 above. contains a compound that is Preferably, the organic material layer includes a light emitting layer containing the compound. Also, preferably, the compound is used as a red host material of the light emitting layer.

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

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 Sub 1 and Sub 2 as in Scheme 1 below, but is not limited thereto.

<Scheme 1>

1. of Sub 1 synthesis example

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

<Scheme 2>

Sub A-1 synthesis example

(1) Sub A-1-2 synthesis example

Sub A-1-1 (100 g, 512 mmol), benzene-1,2-diamine (55.3 g, 512 mmol), and PPTsOH (8.8 g, 51.2 mmol) were added to a round bottom flask and dissolved in EtOH (1000 mL). and then refluxed for 12 hours. When the reaction was completed, the temperature of the reactant was cooled to room temperature, and the precipitated organic matter was filtered to remove the organic solvent to obtain compound Sub A-1-2 (119.5 g, 82%).

(2) Sub A-1-3 synthesis example

After dissolving Sub A-1-2 (119.5 g, 422 mmol) in THF (800 mL), the temperature was lowered to 0 ° C, NaH (11.1 g, 464.2 mmol) was added thereto, and the mixture was stirred for 1 hour. (Bromoethynyl)triisopropylsilane (90 g, 506.4 mmol) was dissolved in THF, injected into the reaction mixture, and stirred at room temperature for 4 hours. When the reaction is complete, water is added for quenching, the water in the product is removed, and the product is filtered under reduced pressure. Then, the organic layer was dried over MgSO ₄ and concentrated to obtain the product Sub A-1-3 (118.5 g, 74%).

(3) Sub A-1-4 synthesis example

After dissolving Sub A-1-3 (118.5 g, 312.2 mmol) in CH ₂ Cl ₂ (500 mL), the temperature of the reactant was lowered to -20 ° C, and TBAF (81.6 g, 312.2 mmol) was dissolved in 100 m of THF. Then, it was slowly added dropwise to the reactants. Thereafter, after stirring for 1 hour, water was added and quenched to remove water in the reactants. Then, after filtering under reduced pressure, the organic layer was dried over MgSO ₄ and concentrated. Then, recrystallization from ethanol gave the product Sub A-1-3 (62.4 g (yield: 65%)).

(4) Sub A-1 synthesis example

Sub A-1-4 (62.4 g, 203 mmol), PdOAc ₂ (1.37 g, 6.09 mmol), P(Ph) ₃ (3.21 g, 12.18 mmol), and NaOH (23.4 g, 609 mmol) were dissolved in toluene (1000 mL), and the reaction mixture was refluxed for 12 hours. When the reaction was completed, water was added to the reactant for quenching, water in the reactant was removed, filtered under reduced pressure, and the organic layer was dried over MgSO ₄ and concentrated to obtain Sub A-1 (48 g, 77%).

Sub B-1 synthesis example

(1) Sub B-1-2 synthesis example

Sub B-1-1 (126 g, 512 mmol), benzene-1,2-diamine (55.3 g, 512 mmol), PPTsOH (8.8 g, 51.2 mmol) were prepared in the same manner as in the synthesis of Sub A-1-2. The reaction was carried out to obtain 135 g of product (yield: 79%).

(2) Sub B-1-3 synthesis example

Sub B-1-2 (135 g, 405 mmol), NaH (10.7 g, 445.5 mmol), (Bromoethynyl)triisopropylsilane (90 g, 506.4 mmol) were reacted in the same manner as in the synthesis method of Sub A-1-3. Proceed to obtain 121.8 g of product (yield: 70%).

(3) Sub B-1-4 synthesis example

Sub B-1-3 (121.8 g, 283.7 mmol) and TBAF (74 g, 312.2 mmol) were reacted in the same manner as in the synthesis of Sub A-1-4 to obtain 65 g of product (yield: 64%) got it

(4) Sub B-1 synthesis example

Sub B-1-4 (65 g, 181.9 mmol), PdOAc ₂ (1.25 g, 5.46 mmol), P(Ph) ₃ (2.86 g, 10.92 mmol), and NaOH (21.8 g, 545.7 mmol) were reacted in the same manner as in the synthesis method of Sub A-1 to obtain a product of 52 g (yield). : 80%) was obtained.

Synthesis of Sub C-1

(1) Sub C-1-2 synthesis example

Sub C-1-1 (126 g, 512 mmol), benzene-1,2-diamine (55.3 g, 512 mmol), PPTsOH (8.8 g, 51.2 mmol) were prepared in the same manner as in the synthesis method of Sub A-1-2. The reaction was carried out to obtain 141.7 g of product (yield: 83%).

(2) Sub C-1-3 synthesis example

Sub C-1-2 (141.7 g, 425 mmol), NaH (11.2 g, 467.5 mmol), and (Bromoethynyl)triisopropylsilane (90 g, 506.4 mmol) were reacted in the same manner as in the synthesis method of Sub A-1-3. Proceed to obtain 137 g of product (yield: 75%).

(3) Sub C-1-4 synthesis example

Sub C-1-3 (137 g, 318.8 mmol) and TBAF (72 g, 318.8 mmol) were reacted in the same manner as in the synthesis method of Sub A-1-4 to obtain a product of 78.6 g (yield: 64%) got it

(4) Sub C-1 synthesis example

Sub C-1-4 (78.6 g, 220 mmol), PdOAc ₂ (1.25 g, 5.46 mmol), P(Ph)3 (2.86 g, 10.92 mmol), and NaOH (21.8 g, 545.7 mmol) were added to Sub A The reaction was carried out in the same manner as in the synthesis method of -1 to obtain 65 g of product (yield: 82%).

Synthesis example of Sub D-1

(1) Sub D-1-2 synthesis example

Sub D-1-1 (126 g, 512 mmol), benzene-1,2-diamine (55.3 g, 512 mmol), and PPTsOH (8.8 g, 51.2 mmol) were prepared in the same manner as in the synthesis method of Sub A-1-2. The reaction was carried out to obtain 141.2 g of product (yield: 83%).

(2) Sub D-1-3 synthesis example

Sub D-1-2 (141.2 g, 425 mmol), NaH (11.2 g, 467.5 mmol), and (Bromoethynyl)triisopropylsilane (90 g, 506.4 mmol) were reacted in the same manner as in the synthesis method of Sub A-1-3. Proceed to obtain 122.4 g of product (yield: 67%).

(3) Sub D-1-4 synthesis example

Sub D-1-3 (122.4 g, 284.8 mmol) and TBAF (74 g, 312.2 mmol) were reacted in the same manner as in the synthesis method of Sub A-1-4 to obtain a product of 65.2 g (yield: 64%) got it

(4) Sub D-1 synthesis example

Sub D-1-4 (65.2 g, 182.3 mmol), PdOAc ₂ (1.25 g, 5.46 mmol), P(Ph)3 (2.86 g, 10.92 mmol), and NaOH (21.8 g, 545.7 mmol) were added to Sub A The reaction was carried out in the same manner as in the synthesis method of -1 to obtain 47 g of product (yield: 72%).

Synthesis of Sub E-1

(1) Sub E-1-2 synthesis example

Sub E-1-1 (100 g, 512 mmol), naphthalene-2,3-diamine (81 g, 512 mmol), and PPTsOH (8.8 g, 51.2 mmol) were prepared in the same manner as in the synthesis method of Sub A-1-2. The reaction was carried out to obtain 150 g of product (yield: 88%).

(2) Sub E-1-3 synthesis example

Sub E-1-2 (150 g, 450.6 mmol), NaH (11.2 g, 495.7 mmol), and (Bromoethynyl)triisopropylsilane (90 g, 506.4 mmol) were reacted in the same manner as in the synthesis method of Sub A-1-3. Proceed to obtain 141.7 g of product (yield: 76%).

(3) Sub E-1-4 synthesis example

Sub E-1-3 (141.7 g, 342.5 mmol) and TBAF (77.5 g, 342.5 mmol) were reacted in the same manner as in the synthesis method of Sub A-1-4 to obtain 85.7 g of product (yield: 70%) got it

(4) Sub E-1 synthesis example

Sub E-1-4 (85.7 g, 239.8 mmol), PdOAc ₂ (1.6 g, 7.2 mmol), P(Ph)3 (3.77 g, 14.4 mmol), and NaOH (28.8 g, 719.4 mmol) were added to Sub A The reaction was carried out in the same manner as in the synthesis method of -1 to obtain 66 g of product (yield: 77%).

Example of Sub 2

Compounds belonging to Sub 2 used in Scheme 1 are as follows, but are not limited thereto.

The FD-MS values of the compounds belonging to Sub 2 are shown in Table 1 below.

[Table 1]

of the final compound synthesis example

A-2 synthesis example

Sub A-1 (20.0 g, 65 mmol) and 4-iodo-1,1'-biphenyl (18.2 g, 65 mmol), Pd ₂ (dba) ₃ (1.79 g, 1.95 mmol), (t-Bu) ₃ P (0.79 g, 3.9 mmol) and Nat-BuO (18.7 g, 195 mmol) were put into a round bottom flask, dissolved in toluene (250 mL), and refluxed at 110 °C for 12 hours. When the reaction was completed, the temperature was lowered to room temperature, extracted with CH ₂ Cl ₂ and washed with water. Thereafter, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was separated using a silica gel column to obtain product A-2 (20.2 g, 67%).

A-10 synthesis example

Sub A-1 (20.0 g, 65 mmol) and Sub 2 (A-10) (25.7 g, 65 mmol) were reacted in the same manner as in the synthesis method of Compound A-2 to obtain the product A-10 (26.7 g, 65 mmol). 66%) was obtained.

A-19 Synthesis Example

Sub A-1 (20.0 g, 65 mmol) and Sub 2 (A-19) (20.9 g, 65 mmol) were reacted in the same manner as in the synthesis method of Compound A-2 to obtain the product A-19 (22.1 g, 65 mmol). 66%) was obtained.

B-10 synthesis example

Sub B-1 (23.2 g, 65 mmol) and Sub 2 (A-19) (25.7 g, 65 mmol) were reacted in the same manner as in the synthesis method of Compound A-2 to produce product B-10 (23.5 g, 65 mmol). 58%) was obtained.

E-18 synthesis example

Sub E-1 (23.2 g, 65 mmol) and Sub 2 (A-18) (20.9 g, 65 mmol) were reacted in the same manner as in the synthesis method of Compound A-2 to obtain the product E-18 (22.6 g, 65 mmol). 58%) was obtained.

F-2 synthesis example

Sub A-1 (20.0 g, 65 mmol) and Sub 2 (F-2) (22.3 g, 65 mmol) were reacted in the same manner as in the synthesis method of Compound A-2 to obtain the product F-2 (30.3 g, 65 mmol). 76%) was obtained.

Synthesis example of F-7

Sub A-1 (20.0 g, 65 mmol) and Sub 2 (F-7) (23.2 g, 65 mmol) were reacted in the same manner as in the synthesis method of Compound A-2 to obtain the product F-7 (32.7 g, 65 mmol). 80%) was obtained.

Synthesis example of G-7

Sub B-1 (23.2 g, 65 mmol) and Sub 2 (F-7) (23.2 g, 65 mmol) were reacted in the same manner as in the synthesis method of Compound A-2 to obtain the product G-7 (26.4 g, 65 mmol). 61%) was obtained.

H-2 Synthesis Example

Sub C-1 (23.2 g, 65 mmol) and Sub 2 (F-2) (22.3 g, 65 mmol) were reacted in the same manner as in the synthesis method of Compound A-2 to obtain the product H-2 (26.4 g, 65 mmol). 61%) was obtained.

J-5 synthesis example

Product J-5 (34 g, 34 g, 77%) was obtained.

FD-MS values for the compounds of the present invention synthesized by the above synthesis method are shown in Table 2 below.

[Table 2]

Manufacturing evaluation of organic electric devices

[ Example One] red organic light emitting device

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

Next, a light emitting layer having a thickness of 30 nm was formed on the hole transport layer. Compound A-1 of the present invention was used as a host and bis-(1-phenylisoquinolyl)iridium(III)acetylacetonate (hereinafter referred to as (piq) ₂ Ir(acac) was about Flag) was used as a dopant, but the host and dopant were used in a weight ratio of 95:5.

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

[ Example 2] to [ Example 21]

An organic light emitting device was manufactured in the same manner as in Example 1, except that the compound of the present invention described in Table 3 was used instead of Compound A-1 as a host material of the light emitting layer.

[ comparative example 1] to [ comparative example 3]

An organic light emitting device was manufactured in the same manner as in Example 1, except that one of Comparative Compounds 1 to 3 was used instead of Compound A-1 of the present invention as a host material for the light emitting layer.

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

Electroluminescence (EL) characteristics were measured with PR-650 of Photoresearch Co., Ltd. by applying a forward bias DC voltage to the organic electroluminescent devices manufactured by Examples 1 to 21 and Comparative Examples 1 to 3 of the present invention. , 2500cd/m ² The life of T95 was measured through the life measurement equipment of McScience at the standard luminance. The measurement results are shown in Table 3 below.

[Table 3]

From Table 3, it can be seen that when the compound of the present invention is used as a phosphorescent host material, the driving voltage of the organic light emitting device can be lowered and the efficiency and lifespan can be improved compared to the case of using Comparative Compound A to Comparative Compound C. can

Comparative Compounds A to C are similar to the compounds of the present invention, but differ in the number of core rings and condensed positions of the additional rings. Due to this difference, a difference in electrochemical properties such as HOMO, LUMO, T1 and energy band gap of the compound occurs, which acts as a major factor in improving performance during device deposition. Therefore, it is determined that device characteristics are improved when the compound of the present invention is used as a red host material compared to the case of using the comparative compound.

Table 4 below shows the HOMO, LUMO, Eg and T1 values of Comparative Compounds A and C and Compound F-2 of the present invention.

[Table 4]

Referring to Table 4, Comparative Compound A has one more ring formed in the middle ring of the core compared to Compound F-2 of the present invention. As such, one more ring is formed, so that both HOMO and LUMO are much lower than that of the compound.

In addition, while the 6 rings, which are the cores of the compound of the present invention, are linearly condensed, Comparative Compound C is different in that the benzene ring is condensed in the middle ring of the 5 rings. Due to these differences, Comparative Compound C tended to have both HOMO and LUMO values higher than those of the compound of the present invention, as opposed to Comparative Compound A.

Therefore, depending on the shape of the mother nucleus, a difference occurs in the physical properties of the compound as shown in Table 4, and the characteristics of the device change due to this difference. It will not be easy to predict the beneficial effect of

In the above, the present invention has been described as an example, and those skilled in the art will be able to make various modifications without departing from the essential characteristics of the present invention. Therefore, 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 techniques 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 (10)

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

In the above formula,
R ₁ to R ₈ are each independently hydrogen; heavy hydrogen; halogen; cyano group; 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 ₃ ~ C ₆₀ aliphatic ring and C ₆ ~ C ₆₀ aromatic ring fused ring group; C ₁ ~ C ₅₀ Alkyl group; A C ₂ ~C ₂₀ alkenyl group; A C ₂ ~C ₂₀ alkynyl group; C ₁ ~ C ₃₀ alkoxy group; C ₆ ~ C ₃₀ aryloxy group; And -L'-N (R _a ) (R _b ); is selected from the group consisting of, adjacent groups may be bonded to each other to form a ring,
Ar ₁ is hydrogen; heavy hydrogen; halogen; cyano group; 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 ₃ ~ C ₆₀ aliphatic ring and C ₆ ~ C ₆₀ aromatic ring fused ring group; C ₁ ~ C ₅₀ Alkyl group; A C ₂ ~C ₂₀ alkenyl group; A 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,
Ar ₂ 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; C ₃ ~ C ₆₀ aliphatic ring and C ₆ ~ C ₆₀ aromatic ring fused ring group; C ₁ ~ C ₅₀ Alkyl group; A C ₂ ~C ₂₀ alkenyl group; A C ₂ ~C ₂₀ alkynyl group; C ₁ ~ C ₃₀ alkoxy group; And C ₆ ~ C ₃₀ It is selected from the group consisting of an aryloxy group,
L and L' are each independently 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; C ₃ ~ C ₆₀ aliphatic ring group; and C ₃ ~ C ₆₀ aliphatic ring and C ₆ ~ C ₆₀ aromatic ring fused ring group; is selected from the group consisting of;
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; C ₃ ~ C ₆₀ aliphatic ring group; and C ₃ ~ C ₆₀ aliphatic ring and C ₆ ~ C ₆₀ aromatic ring fused ring group; may be selected from the group consisting of. According to claim 1,
A compound characterized in that Formula 1 is represented by one of the following Formulas 2 to 3:
<Formula 2><Formula3>

<Formula 4>

In the above formula, R ₁ to R ₈ , L, Ar ₁ and Ar ₂ are as defined in claim 1,
Z ₁ to Z ₈ are N or CR';
X is O, S, NR' or C(R')(R");
Wherein R' and R" are each independently hydrogen; heavy hydrogen; halogen; cyano group; nitro group; C ₆ ~ C ₂₀ aryl group; fluorenyl group; at least one heteroatom selected from O, N, S, Si and P C ₂ ~ C ₂₀ heterocyclic group containing; C ₃ ~ C ₂₀ aliphatic ring group; C ₃ ~ C ₂₀ aliphatic ring and C ₆ ~ C ₂₀ aromatic ring fused ring group; C ₁ ~ C ₂₀ Alkyl group; C ₂ ~ C ₂₀ alkenyl group; C ₂ ~ C ₂₀ alkynyl group; C ₁ ~ C ₂₀ alkoxy group; and C ₆ ~ C ₃₀ selected from the group consisting of an aryloxy group, adjacent to R' Each other or R' and R" may be bonded to each other to form a ring. According to claim 1,
A compound characterized in that Formula 1 is represented by one of the following Formulas 5 to 10:
<Formula 5><Formula6>

<Formula 7><Formula8>

<Formula 9><Formula10>

In the above formula, R ₁ to R ₈ , L, Ar ₁ and Ar ₂ are as defined in claim 1. According to claim 1,
A compound, characterized in that Ar ₁ is a substituent other than hydrogen. According to claim 1,
A compound characterized in that adjacent R ₁ and R ₂ , adjacent R ₂ and R ₃ , adjacent R ₃ and R ₄ , or adjacent R ₆ and R ₇ bond to each other to form a ring. According to claim 1,
Formula 1 is a compound characterized in that 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 compound represented by the formula (1) of claim 1. According to claim 7,
The organic material layer includes a light emitting layer, and the organic electric device, characterized in that the compound is included in the light emitting layer. 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 9,
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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