WO2022231299A1 - Compound for organic electric element, organic electric element using same, and electronic device thereof - Google Patents

Abstract

The present invention provides: a novel compound which can improve the luminous efficiency, stability, and service life of an element; an organic electric element using same; and an electronic device thereof.

Description

Compound for organic electric device, organic electric device using 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 electric energy is converted into light energy using an organic material. An organic electric device using an organic light emitting phenomenon generally has a structure including an anode and a cathode and an organic material layer therebetween. Here, the organic layer is often formed of a multi-layered structure composed of different materials in order to increase the efficiency and stability of the organic electric device, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer.

A material used as an organic layer in an organic electric device may be classified into a light emitting material and a charge transport material, such as a hole injection material, a hole transport material, an electron transport material, an electron injection material, according to their function.

Lifespan and efficiency are the most problematic for organic light emitting diodes, and as displays become larger, these problems of efficiency and life must be solved. Efficiency, lifespan, and driving voltage are related to each other, and when the efficiency is increased, the driving voltage is relatively decreased. It shows a tendency to increase the lifespan.

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

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

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, most of the materials used for the hole transport layer have a low T1 value because they should have a low HOMO value. As a result, excitons generated in the emission layer are transferred to the hole transport layer, resulting in charge unbalance in the emission layer. This results in light emission at the hole transport layer interface.

When light is emitted at the hole transport layer interface, the color purity and efficiency of the organic electric device are lowered, and the lifespan is shortened. Therefore, it is urgently required to develop a light emitting auxiliary layer having a high T1 value and having a HOMO level between the HOMO energy level of the hole transport layer and the HOMO energy level of the emission layer.

On the other hand, while delaying the penetration and diffusion of metal oxide from the anode electrode (ITO) into the organic layer, which is one of the causes of shortening the lifespan of the organic electric device, stable characteristics against Joule heating generated during device driving, that is, high glass transition There is a need for development of a hole injection layer material having a temperature. The low glass transition temperature of the hole transport layer material has a characteristic of lowering the uniformity of the thin film surface when driving the device, which is reported to have a significant effect on the device lifespan. In addition, OLED devices are mainly formed by a deposition method, and there is a need to develop a material that can withstand a long time during deposition, that is, a material with strong heat resistance.

That is, in order to sufficiently exhibit the excellent characteristics of the organic electric device, the material constituting the organic layer in the device, for example, a hole injection material, a hole transport material, a light emitting material, an electron transport material, an electron injection material, a light emitting auxiliary layer material, etc. is stable and efficient. Supported by materials should be preceded, but the development of stable and efficient organic layer materials for organic electric devices has not yet been sufficiently made. Therefore, the development of new materials continues to be demanded.

In order to solve the problems of the above-mentioned background art, the present invention has revealed a compound having a novel structure, and the fact that when this compound is applied to an organic electric device, the luminous efficiency, stability and lifespan of the device can be greatly improved has revealed

Accordingly, an object of the present invention is to provide a novel compound, an organic electric device using the same, and an electronic device thereof.

The present invention provides a compound represented by the following formula (1).

Formula 1

In another aspect, the present invention provides an organic electric device comprising the compound represented by Formula 1 and an electronic device thereof.

By using the compound according to the present invention, high luminous efficiency, low driving voltage and high heat resistance of the device can be achieved, and color purity and lifespan of the device can be greatly improved.

1 to 3 are exemplary views of an organic electroluminescent device according to the present invention.

4 shows a chemical formula according to an aspect of the present invention.

5 shows a measurement result of the bond dissociation energy according to an embodiment of the present invention.

100, 200, 300: organic electric device 110: first electrode

120: hole injection layer 130: hole transport layer

140: light emitting layer 150: electron transport layer

160: electron injection layer 170: second electrode

180: light efficiency improvement layer 210: buffer layer

220: light emitting auxiliary layer 320: first hole injection layer

330: first hole transport layer 340: first light emitting layer

350: first electron transport layer 360: first charge generation layer

361: second charge generation layer 420: second hole injection layer

430: second hole transport layer 440: second light emitting layer

450: second electron transport layer CGL: charge generation layer

ST1: first stack ST2: second stack

Hereinafter, it will be described in detail with reference to embodiments of the present invention. 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 thereof will be omitted.

In addition, in describing the components of the present invention, terms such as first, second, A, B, (a), (b), etc. may be used. These terms are only for distinguishing the elements from other elements, and the essence, order, or order of the elements are not limited by the terms. When it is described that a component is “connected”, “coupled” or “connected” to another component, the component may be directly connected or connected to the other component, but another component is between each component. It should be understood that elements may be “connected,” “coupled,” or “connected.”

As used in this specification and the appended claims, unless stated otherwise, the following terms have the following meanings:

As used herein, the term “halo” or “halogen” refers to fluorine (F), bromine (Br), chlorine (Cl) or iodine (I), unless otherwise specified.

The term "alkyl" or "alkyl group" as used herein, unless otherwise specified, has a single bond of 1 to 60 carbon atoms, a straight chain alkyl group, a branched chain alkyl group, a cycloalkyl (alicyclic) group, an alkyl-substituted cyclo means a radical of saturated aliphatic functional groups including alkyl groups, cycloalkyl-substituted alkyl groups.

As used herein, the terms "alkenyl group", "alkenyl group" or "alkynyl group" have a double or triple bond of 2 to 60 carbon atoms, respectively, unless otherwise specified, and include a straight or branched chain group, , but not limited thereto.

As used herein, the term “cycloalkyl” refers to an alkyl forming a ring having 3 to 60 carbon atoms unless otherwise specified, but is not limited thereto.

As used herein, the term "alkoxyl group", "alkoxy group", or "alkyloxy group" refers to an alkyl group to which an oxygen radical is attached, and has 1 to 60 carbon atoms, unless otherwise specified. it is not

As used herein, the term “aryloxyl group” or “aryloxy group” refers to an aryl group to which an oxygen radical is attached, and has 6 to 60 carbon atoms unless otherwise specified, but is not limited thereto.

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, an aryl group or an arylene group means a single ring or multiple ring aromatic, and includes an aromatic ring formed by a neighboring substituent joining or participating in a reaction. For example, the aryl group may be a phenyl group, a biphenyl group, a fluorene group, or a spirofluorene group.

The prefix “aryl” or “ar” refers to a radical substituted with an aryl group. For example, an arylalkyl group is an alkyl group substituted with an aryl group, an arylalkenyl group is an alkenyl group substituted with an aryl group, and the radical substituted with an aryl group has the number of carbon atoms described herein.

Also, when prefixes are named consecutively, it is meant that the substituents are listed in the order listed first. For example, an arylalkoxy group means an alkoxy group substituted with an aryl group, an alkoxylcarbonyl group means a carbonyl group substituted with an alkoxyl group, and an arylcarbonylalkenyl group means an alkenyl group substituted with an arylcarbonyl group and wherein the arylcarbonyl group is a carbonyl group substituted with an aryl group.

The term "heterocyclic group" as used in the present invention, unless otherwise specified, contains one or more heteroatoms, has 2 to 60 carbon atoms, includes at least one of a single ring and multiple rings, and includes a heteroaliphatic ring and a heteroaliphatic ring aromatic rings. It may be formed by combining adjacent functional groups.

As used herein, the term "heteroatom" refers to N, O, S, P or Si, unless otherwise specified.

In addition, the "heterocyclic group" may include a ring containing SO ₂ instead of carbon forming the ring. For example, "heterocyclic group" includes the following compounds.

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

The term "spiro compound" used in the present invention has a 'spiro union', and the spiro linkage means a connection formed by sharing only one atom in two rings. At this time, the atoms shared by the two rings are called 'spiro atoms', and depending on the number of spiro atoms in a compound, they are respectively 'monospiro-', 'dispiro-', 'trispiro-' ' It's called a compound.

Unless otherwise specified, as used herein, the term "aliphatic" refers to an aliphatic hydrocarbon having 1 to 60 carbon atoms, and "aliphatic ring" refers to an aliphatic hydrocarbon ring having 3 to 60 carbon atoms.

Unless otherwise specified, the term "ring" as used herein refers to a fused ring consisting of an aliphatic ring having 3 to 60 carbon atoms, an aromatic ring having 6 to 60 carbon atoms, a heterocycle having 2 to 60 carbon atoms, or a combination thereof, Contains saturated or unsaturated rings.

Other heterocompounds or heteroradicals other than the above-mentioned heterocompounds include one or more heteroatoms, but are not limited thereto.

In addition, unless otherwise explicitly stated, in the term "substituted or unsubstituted" used in the present invention, "substitution" means deuterium, halogen, amino group, nitrile group, nitro group, C ₁ ~ C ₂₀ alkyl group, C ₁ ~ C ₂₀ Alkoxyl group, C ₁ ~ C 20 Alkylamine group, C ₁ ~ C ₂₀ Alkylthiophene group, C ₆ ~ C _{20 Arylthiophene} group, C ₂ ~ C ₂₀ Alkenyl group, C ₂ ~ C ₂₀ alkynyl group, C ₃ ~ C ₂₀ cycloalkyl group, C ₆ ~ C ₂₀ aryl group, C ₆ ~ C ₂₀ aryl group substituted with deuterium, C ₈ ~ C ₂₀ arylalkenyl group, silane group, boron It means substituted with one or more substituents selected from the group consisting of a group, a germanium group, and a C ₂ ~ C ₂₀ heterocyclic group, but is not limited to these substituents.

In addition, unless there is an explicit explanation, the formula used in the present invention is the same as the definition of the substituent by the exponent definition of the following formula.

Here, when a is an integer of 0, the substituent R ¹ is absent, and when a is an integer of 1, one substituent R ¹ is bonded to any one carbon of the carbons forming the benzene ring, and when a is an integer of 2 or 3 Each is bonded as follows, where 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 the hydrogen bonded to the carbon forming the benzene ring is omitted.

Bond-Dissociation Energy (BDE) is a calculation of the bond energy for acyclic bonds within a molecule. To this end, the electrical potential energy of the target molecule is calculated, and the electrical potential energy for each is calculated by dividing it into two radical molecules based on an acyclic bond, and the bond dissociation energy can be expressed as follows.

All calculations are performed assuming an electrically neutral state, and since solid-phase molecules extracted through molecular dynamics simulation do not have an optimized structure unlike gas-phase molecules, all calculations are performed with single-point energy ( Single-point energy , SPE) and calculate the bond dissociation energy while maintaining the structure.

As used herein, the term “average bond-dissociation energy in solid state amorphous ” is, unless otherwise specified, the quantum mechanical average binding energy (Quantum) of amorphous solid phase molecules through molecular dynamics simulation. -Mechanics-based Average Bond-dissociation Energy of Molecules in Molecular Dynamically simulated solid-state amorphous).

Since the average bond dissociation energy in the amorphous solid phase is a statistical data set (a set of multiple energy values), the value may be quantified differently depending on the data processing method. Therefore, in the present specification, for quantification, the average value of the bond dissociation energy distribution in the amorphous solid phase is used, which is statistically reliable because there are many samples, and the characteristic difference between materials is clearly displayed, and the value is obtained through the following process do.

The average bond dissociation energy in the amorphous solid phase is a value derived by placing a certain number of monomolecules in a unit cell with a periodic boundary condition (PBC) and performing molecular dynamics simulations on this. Preferably, the number of monomolecules in the unit cell may be several tens to several thousand.

Molecular dynamics simulation was performed in a total of 4 steps, and the first step was conducted at a temperature of 10 Kelvin under conditions of constant volume according to Brownian mechanics. The second step is similarly performed according to Brownian mechanics, but at a temperature of 100 Kelvin under constant atmospheric pressure (1.01325 bar). After that, in the third step, molecular dynamics according to the force field is calculated, and similarly, it proceeds by 0.1 nanoseconds (ns) at a constant pressure (atmospheric pressure) and temperature (room temperature). Finally, under the same conditions as in the third step (atmospheric pressure, room temperature), the molecular dynamics process is performed in units of 2 femtoseconds (fs), and the simulation is performed until a certain time is required. In this case, the predetermined time means a time for the amorphous solid structure to sufficiently reach the equilibrium state, and may preferably be several hundred nanoseconds to several thousand nanoseconds, more preferably 100 nanoseconds to 150 nanoseconds, and even more preferably For example, it may be 120 nanoseconds. Thereafter, structural data at the final time point are extracted, and some monomolecules are extracted (sampling) from the corresponding structure. Single-point energy calculation for a single molecule extracted through quantum mechanics simulation is performed, and the bond-dissociation energy (BDE) for an acyclic bond within a molecule is calculated. Calculate. By taking all the obtained bond dissociation energies, the set of bond dissociation energies G = {E ₁ … E _N } is constructed and the average value of the set of bond dissociation energies

is used as an indicator of the bond dissociation energy of a solid state substance.

In the present specification, the average bond dissociation energy value in the amorphous solid phase

The unit of is eV, and can be converted to kcal/mol by multiplying the eV value by 23.061.

As used herein, the term “ Bulk density of solid-state amorphous ” refers to the bulk density of Molecular Dynamically simulated obtained through molecular dynamics simulation, unless otherwise specified. solid-state amorphous ), and its value is obtained through the following process.

It is a value derived by placing a certain number of monomolecules in a unit cell with periodic repeat boundary conditions (PBC) and performing molecular dynamics simulations on them. Preferably, the monomolecules in the unit cell are It may be tens to thousands.

Molecular dynamics simulation was performed in a total of 4 steps, and the first step was conducted at a temperature of 10 Kelvin under conditions of constant volume according to Brownian mechanics. The second step is similarly performed according to Brownian mechanics, but at a temperature of 100 Kelvin under constant atmospheric pressure (1.01325 bar). After that, in the third step, molecular dynamics according to the force field is calculated, and similarly, it proceeds by 0.1 nanoseconds (ns) at a constant pressure (atmospheric pressure) and temperature (room temperature). Finally, under the same conditions as in the third step (atmospheric pressure, room temperature), the molecular dynamics process is performed in units of 2 femtoseconds (fs), and the simulation is performed until a certain time is required. In this case, the predetermined time means the time for the amorphous solid structure to sufficiently reach the equilibrium state, and may preferably be several hundred nanoseconds to several thousand nanoseconds, more preferably 100 nanoseconds to 150 nanoseconds, and even more preferably may be 120 nanoseconds. After that, the average bulk density for the final 20% of the time was calculated, and the final 20% of the time may be preferably several tens of nanoseconds to several thousand nanoseconds, more preferably 80 nanoseconds to 150 nanoseconds. and even more preferably 120 nanoseconds.

In the present specification, the unit of the volume density value of the amorphous solid molecular structure is g/cm ³ .

As used herein, the term “radial distribution function (RDF) g(r) ” refers to the probability of finding another molecule separated by a certain distance r from one molecule. The radial distribution function is expressed as a function according to the distance, and the equation is defined as follows.

In the above formula, ρ is the bulk density, dr is the micro-thickness of the sphere having the radius r , and dn _r is the number of molecules included in the shell of the sphere having the micro-thickness of dr . In order to quantify the radial distribution function, the distance at which the radial distribution function has the largest value in the amorphous solid phase is used as an index, and the intermolecular distance r is the center-of-mass distance of each molecule. The amorphous solid phase structure for obtaining the radial distribution function is obtained through molecular dynamics simulation, and the distribution function was calculated using only the structure for the last 20% of the total simulation time, and the final 20% of the time is preferably several tens. It may be nanoseconds to several thousand nanoseconds, more preferably 80 nanoseconds to 150 nanoseconds, and even more preferably 120 nanoseconds.

In the present specification, the unit of the value of the radial distribution function is Å.

The average dissociation energy of the amorphous solid phase described herein, the volume density of the molecular structure of the amorphous solid phase, and the radial distribution function values were obtained through molecular simulation (Gaussian09 Rev. C.01, Schrodinger Materials Science Suite 4.1.161), and the molecular Desmond package was used for dynamics simulation. Quantum chemical properties based on the first principle were calculated by extracting single molecules from the structure obtained through molecular dynamics simulation, and Gaussian and Jaguar packages were used in this process.

Charge mobility is a generalized effective medium model (GEMM), charge mobility for a uniform medium is an analytical method of the master equation according to the effective medium approximation (Effective medium approximation) It can be obtained from the solution, and the expression is expressed as:

where e is the amount of charge, β is a thermodynamic constant given by the Boltzmann constant and the reciprocal of temperature (1/k _B T), M is the average number of nearest-neighbor molecules, H _ab is the charge transfer matrix element ), n is the charge transfer dimension ( n = 3 in a three-dimensional system), ħ is the Planck constant, λ is the reorganization energy, σ is the disorder parameter, and C is the correction constant. Therefore, the charge mobility has the following proportional relationship.

If it is assumed that the molecules in the amorphous solid state are sufficiently uniformly distributed (σ≪1), the charge transfer matrix element (H _ab ) between each dimer is constant, so the above proportional expression can be expressed as follows.

At this time, it is known a priori that the charge transfer matrix element has a proportional relationship with the intermolecular distance as follows.

where η is the decay constant, and r is the intermolecular distance. Therefore, for a uniform medium, the charge mobility has a relationship that is proportional to the exponential decay with respect to the intermolecular distance, and as the intermolecular distance is shorter, the charge mobility tends to increase.

Also, since the volume density is inversely proportional to the volume ( ρ ∝1/ V ), this is used to determine the average intermolecular distance (

), and the smaller the volume density, the shorter the intermolecular distance.

Therefore, by examining the radial distribution function in the amorphous solid-phase structure obtained through molecular dynamics simulation, the distribution section with the maximum intermolecular distance can be confirmed, and the position of the peak value of the radial distribution function can be used as an intermolecular distance index to compare charge mobility. can be utilized

The charge mobility is described in Friederich, Pascal, et al. "Ab initio treatment of disorder effects in amorphous organic materials: Toward parameter free materials simulation", Journal of chemical theory and computation 10.9 (2014): 3720-3725], [Friederich, Pascal, et al. “Molecular origin of the charge carrier mobility in small molecule organic semiconductors”, Advanced Functional Materials 26.31 (2016): 5757-5763], Oberhofer, Harald, and Jochen Blumberger. "Electronic coupling matrix elements from charge constrained density functional theory calculations using a plane wave basis set", The Journal of Chemical Physics 133.24 (2010): 244105], [Albinsson, Bo, et al. "Electron and energy transfer in donor-acceptor systems with conjugated molecular bridges", Physical Chemistry Chemical Physics 9.44 (2007): 5847-5864 and Cave, Robert J., and Marshall D. Newton. See "Calculation of electronic coupling matrix elements for ground and excited state electron transfer reactions: comparison of the generalized Mulliken-Hush and block diagonalization methods", The Journal of chemical physics 106.22 (1997): 9213-9226, which includes The entirety of which is incorporated herein by reference.

Hereinafter, a compound according to an aspect of the present invention and an organic electric device including the same will be described.

The present invention relates to quantum-mechanical average bond dissociation energy of amorphous solid-phase molecules.

It provides a compound represented by the following formula (1) is 3.650 eV or more.

In addition, the present invention is an organic electric device comprising an anode, a cathode, and an organic material layer formed between the anode and the cathode, wherein the organic material layer comprises a single compound or two or more compounds represented by the following formula (1), and in the organic material layer, the compound is Quantum-mechanical mean bond dissociation energy of amorphous solid-phase molecules

It provides an organic electric device, characterized in that 3.650 eV or more.

Formula 1

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

1) X ¹ and X ² are each independently O or S.

2) Ar ¹ , Ar ² and Ar ³ are each independently a C ₆ ~ C ₆₀ aryl group, preferably a C ₆ ~ C ₃₀ aryl group, more preferably a C ₆ ~ C ₂₅ aryl group, such as phenylene, biphenyl, naphthalene, terphenyl, and the like.

3) L ¹ and L ² are each independently a single bond or a C ₆ ~ C ₆₀ arylene group, and when L ¹ and L ² are an arylene group, preferably a C ₆ ~ C ₃₀ arylene group, more preferably may be a C ₆ ~ C ₂₄ arylene group, for example, phenylene, biphenyl, naphthalene, terphenyl, and the like.

4) wherein the aryl group and the arylene group are each deuterium; halogen; silane 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 ₁ ~ C ₂₀ A heteroalkyl group; C ₁ ~ C ₂₀ Heteroalkenyl group; C ₁ ~ C ₂₀ Heteroalkynyl group; C ₆ ~ C ₂₀ Aryl group; C ₆ ~ C ₂₀ Aryl group substituted with deuterium; fluorenyl group; C ₂ ~ C ₂₀ A heterocyclic group; C ₃ ~ C ₂₀ Cycloalkyl group; C ₇ ~ C ₂₀ Arylalkyl group; And C ₈ ~ C ₂₀ Aryl alkenyl group; may be further substituted with one or more substituents selected from the group consisting of, and these substituents may be combined with each other to form a ring, where 'ring' means C ₃ ~ C ₆₀ of an aliphatic ring or a C ₆ ~ C ₆₀ aromatic ring or a C ₂ ~ C ₆₀ heterocyclic ring or a fused ring consisting of a combination thereof, and includes a saturated or unsaturated ring.

Quantum-mechanical average bond dissociation energy of the amorphous solid-phase molecule of the compound represented by Formula 1 in the present invention

is preferably 3.650 eV or more, more preferably 3.650 eV to 4.500 eV, and even more preferably 3.655 eV to 3.800 eV.

In addition, the present invention provides a compound having a volume density of 1.110 g/cm ³ or more of the amorphous solid molecular structure of the compound represented by Formula 1 above. The volume density of the amorphous solid molecular structure of the compound represented by Formula 1 may be preferably 1.110 g/cm ³ or more, more preferably 1.110 g/cm ³ to 1.200 g/cm ³ , and even more preferably preferably 1.140 g/cm ³ to 1.160 g/cm ³ .

In addition, the present invention provides a compound having a radial distribution function value of less than 11.0 Å of the compound represented by Formula 1 above. The value of the radial distribution function of the compound represented by Formula 1 may be preferably less than 11.0 Å, more preferably 8.0 Å to 13.0 Å, and even more preferably 9.0 Å to 11.0 Å.

In addition, the present invention provides a compound in which the compound represented by Formula 1 is represented by any one of the following Formulas 1-1 to 1-3.

Formula 1-1 Formula 1-2

Formula 1-3

{In Formulas 1-1 to 1-3, Ar ¹ , Ar ² , Ar ³ , L ¹ and L ² are the same as defined in Formula 1 above.}

In addition, the present invention provides a compound in which at least one of Ar ¹ to Ar ³ is represented by any one of the following Chemical Formulas Ar-1 to Ar-13.

Formula Ar-1 Formula Ar-2 Formula Ar-3 Formula Ar-4

Formula Ar-5 Formula Ar-6 Formula Ar-7

Formula Ar-8 Formula Ar-9 Formula Ar-10

Formula Ar-11 Formula Ar-12 Formula Ar-13

In Formulas Ar-1 to Ar-13, each symbol may be defined as follows.

1) R ¹ , R ² , and R ³ are the same or different from each other, and each independently hydrogen; deuterium, halogen; cyano group; nitro group; C ₆ ~ C ₆₀ Aryl group; fluorenyl group; O, N, S, Si and P containing at least one heteroatom C ₂ ~ C ₆₀ A heterocyclic group; C ₃ ~ C ₆₀ A fused ring group of an aliphatic ring and a C ₆ ~ C ₆₀ aromatic ring; C ₃ ~ C ₂₀ Cycloalkyl group; C ₁ ~ C ₅₀ Alkyl group; C ₂ ~ C ₂₀ Alkenyl group; C ₂ ~ C ₂₀ alkynyl group; C ₁ ~ C ₃₀ An alkoxyl group; And C ₆ ~ C ₃₀ Aryloxy group; is selected from the group consisting of.

When R ¹ , R ² and R ³ are aryl groups, preferably a C ₆ ~ C ₃₀ aryl group, more preferably a C ₆ ~ C ₂₅ aryl group, such as phenylene, biphenyl, naphthalene, terphenyl etc.

When R ¹ , R ² and R ³ are a heterocyclic group, preferably a C ₂ ~ C ₃₀ heterocyclic group, more preferably a C ₂ ~ C ₂₄ heterocyclic group, illustratively pyrazine, cy Offene, pyridine, pyrimidoindole, 5-phenyl-5H-pyrimido[5,4-b]indole, quinazoline, benzoquinazoline, carbazole, dibenzoquinazole, dibenzofuran, dibenzothiophene, benzo thienopyrimidine, benzofuropyrimidine, phenothiazine, phenylphenothiazine, and the like.

When R ¹ , R ² and R ³ are a fused ring group, preferably a fused ring group of a C ₃ ~ C ₃₀ aliphatic ring and a C ₆ ~ C ₃₀ aromatic ring, more preferably a C ₃ ~ C ₂₄ It may be a fused ring group of an aliphatic ring and a C ₆ ~ C ₂₄ aromatic ring.

When R ¹ , R ² and R ³ are an alkyl group, it may be preferably a C ₁ to C ₃₀ alkyl group, and more preferably a C ₁ to C ₂₄ alkyl group.

When R ¹ , R ² and R ³ are an alkoxyl group, it may be preferably a C ₁ to C ₂₄ alkoxyl group.

When R ¹ , R ² and R ³ are an aryloxy group, it may be preferably a C ₆ ~ C ₂₄ aryloxy group.

2) a is an integer from 0 to 5, b and c are independently integers from 0 to 4,

3) * means the bonding position.

In addition, the present invention provides a compound in which at least one of L ¹ and L ² is represented by any one of the following Chemical Formulas L-1 to L-3.

Formula L-1 Formula L-2 Formula L-3

{In the above formulas L-1 to L-3,

1) R ⁴ is the same as the definition of R ¹ above,

2) d is an integer from 0 to 4,

3) * means the bonding position.}

In addition, the present invention provides a compound in which the compound represented by Formula 1 is represented by any one of the following compounds P-1 to P-90.

Referring to FIG. 1 , the organic electric device 100 according to the present invention includes a first electrode 110 , a second electrode 170 , and between the first electrode 110 and the second electrode 170 by Chemical Formula 1 An organic material layer including a single compound or two or more compounds represented by In this case, the first electrode 110 may be an anode or an anode, and the second electrode 170 may be a cathode or a cathode. 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 120 , a hole transport layer 130 , a light emitting layer 140 , an electron transport layer 150 , and an electron injection layer 160 on the first electrode 110 . In this case, the remaining layers except for the light emitting layer 140 may not be formed. It may further include a hole blocking layer, an electron blocking layer, a light emission auxiliary layer 220 , a buffer layer 210 , and the like, and the electron transport layer 150 and the like may serve as a hole blocking layer. (See Fig. 2)

In addition, the organic electric device according to an embodiment of the present invention may further include a protective layer or a light efficiency improving layer 180 . The light efficiency improving layer may be formed on a surface of both surfaces of the first electrode that does not contact the organic material layer or on a surface of both surfaces of the second electrode that does not contact the organic material layer. The compound according to an embodiment of the present invention applied to the organic layer is a hole injection layer 120, a hole transport layer 130, a light emitting auxiliary layer 220, an electron transport auxiliary layer, an electron transport layer 150, an electron injection layer ( 160), a host or dopant of the emission layer 140, or a material of the light efficiency improving layer. Preferably, for example, the compound according to Chemical Formula 1 of the present invention may be used as a material for a light emitting auxiliary layer or a hole transport layer.

The organic material layer may include two or more stacks including a hole transport layer, a light emitting layer, and an electron transport layer sequentially formed on the anode, and may further include a charge generating layer formed between the two or more stacks. (See Fig. 3)

On the other hand, even with the same core, the band gap, electrical properties, interface properties, etc. may vary depending on which position the substituent is bonded to, so the selection of the core and the combination of the sub-substituents coupled thereto are also very In particular, when the energy level and T1 value between each organic material layer and the intrinsic properties of the material (mobility, interfacial properties, etc.) are optimally combined, a long lifespan and high efficiency can be achieved at the same time.

The organic electroluminescent device according to an embodiment of the present invention may be manufactured using a PVD (physical vapor deposition) method. For example, an anode is formed by depositing a metal or a metal oxide having conductivity or an alloy thereof on a substrate, and the hole injection layer 120, the hole transport layer 130, the light emitting layer 140, the electron transport layer 150 and After forming the organic material layer including the electron injection layer 160, it may be manufactured by depositing a material that can be used as a cathode thereon.

In addition, in the present invention, the organic layer is formed by any one of a spin coating process, a nozzle printing process, an inkjet printing process, a slot coating process, a dip coating process, and a roll-to-roll process, and the organic layer contains the compound as an electron transport material. It provides an organic electric device, characterized in that.

As another specific example, the present invention provides an organic electric device, characterized in that the compound of the same or different types of the compound represented by Formula 1 is mixed and used in the organic material layer.

In addition, the present invention provides a light-emitting auxiliary layer composition comprising the compound represented by Formula 1, and provides an organic electric device including the light-emitting auxiliary layer.

In addition, the present invention provides a hole transport layer composition comprising the compound represented by Formula 1, and provides an organic electric device including the hole transport layer.

In addition, the present invention provides a light efficiency improving layer composition comprising the compound represented by Formula 1, and provides an organic electric device including the light efficiency improving layer.

In addition, the present invention is a display device including the organic electric device described above; and a controller for driving the display device.

In another aspect, the present invention provides an electronic device, characterized in that the organic electroluminescent device is at least one of an organic electroluminescent device, an organic solar cell, an organic photoreceptor, an organic transistor, and a device for single color or white lighting. In this case, 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 system, a game machine, various TVs, and various computers.

Hereinafter, a synthesis example of the compound represented by Formula 1 of the present invention and a manufacturing example of the organic electric device of 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 1]

The compound (Final Product) represented by Formula 1 according to the present invention is synthesized as shown in Scheme 1 below, but is not limited thereto.

<Scheme 1>

{In Scheme 1,

1) Hal is I, Br or Cl;

2) X is the same as the definition of X ¹ in Formula 1,

3) Ar is the same as the definition of Ar ¹ in Formula 1,

4) L is the same as the definition of L ¹ in Formula 1,

5) Sub 1 may be the same or different from each other.}

I. Synthesis of Sub 1

Sub 1 of Scheme 1 is synthesized by the reaction route of Scheme 2 below, but is not limited thereto. Hal is I, Br or Cl.

<Scheme 2>

In Scheme 2, when L of Sub 1 does not exist, the step of reacting Sub 1B and Sub 1B' may be omitted.

1. Sub 1-1 Synthesis Example

Sub 1-1A (50.0 g, 177.6 mmol) was placed in a round-bottom flask and dissolved in THF (888 ml), followed by Sub 1-1A' (21.7 g, 177.6 mmol), Pd(PPh ₃ ) ₄ (12.3 g, 10.7). mmol), NaOH (21.3 g, 532.8 mmol), and water (444 ml) are added, and the reaction proceeds at 80°C. After completion of the reaction, extraction with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ , concentrated, and the resulting organic material was recrystallized by silicagel column to obtain 40.1 g of a product. (Yield: 81.1%)

2. Sub 1-2 Synthesis Example

Put Sub 1-1 (30.0 g, 107.6 mmol) in a round-bottom flask and dissolve in THF (538 ml), Sub 1-2B' (16.8 g, 107.6 mmol), Pd(PPh ₃ ) ₄ (7.5 g, 6.5 mmol), NaOH (12.9 g, 322.9 mmol), and water (269 ml) were added, and the experiment was performed in the same manner as in Sub 1-1 to obtain 30.9 g of the product. (Yield: 80.8%)

3. Sub 1-31 Synthesis Example

Put Sub 1-31A (50.0 g, 168.0 mmol) in a round-bottom flask and dissolve in THF (840 ml), Sub 1-31A' (58.8 g, 168.0 mmol), Pd(PPh ₃ ) ₄ (11.7 g, 10.1) mmol), NaOH (20.2 g, 504.0 mmol), and water (420 ml) were added, and the experiment was performed in the same manner as in Sub 1-1 to obtain 67.5 g of the product. (Yield: 76.8%)

4. Sub 1-39 Synthesis Example

1) Synthesis of Sub 1-39B

Put Sub 1-31A (50.0 g, 168.0 mmol) in a round-bottom flask and dissolve in THF (840 ml), Sub 1-39A' (39.3 g, 168.0 mmol), Pd(PPh ₃ ) ₄ (11.7 g, 10.1) mmol), NaOH (20.2 g, 504.0 mmol), and water (420 ml) were added, and the experiment was performed in the same manner as in Sub 1-1 to obtain 56.3 g of the product. (Yield: 82.3%)

2) Synthesis of Sub 1-39

Sub 1-39B (56.3 g, 138.3 mmol) obtained in the above reaction was placed in a round-bottom flask and dissolved in THF (692 ml), Sub 1-39B' (21.6 g, 138.3 mmol), Pd(PPh ₃ ) ₄ ( 9.6 g, 8.3 mmol), NaOH (16.6 g, 415.0 mmol), and water (346 ml) were added, and the experiment was performed in the same manner as in Sub 1-1 to obtain 54.5 g of the product. (Yield: 81.5%)

5. Sub 1-46 Synthesis Example

1) Synthesis of Sub 1-49

Put Sub 1-46A (50.0 g, 173.9 mmol) in a round-bottom flask and dissolve in THF (869 ml), Sub 1-46A' (22.1 g, 173.9 mmol), Pd(PPh ₃ ) ₄ (12.1 g, 10.4) mmol), NaOH (20.9 g, 521.6 mmol), and water (435 ml) were added, and the experiment was performed in the same manner as in Sub 1-1 to obtain 41.2 g of the product. (Yield: 81.8%)

2) Synthesis of Sub 1-46

Sub 1-49 (41.2 g, 142.2 mmol) obtained in the above reaction was placed in a round-bottom flask and dissolved in THF (711 ml), Sub 1-2B' (22.2 g, 142.2 mmol), Pd(PPh ₃ ) ₄ ( 9.9 g, 8.5 mmol), NaOH (17.1 g, 426.5 mmol), and water (355 ml) were added, and the experiment was performed in the same manner as in Sub 1-1 to obtain 42.1 g of the product. (Yield: 80.9%)

The compound belonging to Sub 1 may be the following compounds, but is not limited thereto, and Table 1 below shows Field Desorption-Mass Spectrometry (FD-MS) values of the compounds belonging to Sub 1.

compound	FD-MS	compound	FD-MS
Sub 1-1	m/z=278.05 (C 18 H 11 ClO=278.74)	Sub 1-2	m/z=354.08 (C 24 H 15 ClO=354.83)
Sub 1-3	m/z=354.08 (C 24 H 15 ClO=354.83)	Sub 1-4	m/z=354.08 (C 24 H 15 ClO=354.83)
Sub 1-5	m/z=334.11 (C 22 H 19 ClO=334.84)	Sub 1-6	m/z=354.08 (C 24 H 15 ClO=354.83)
Sub 1-7	m/z=354.08 (C 24 H 15 ClO=354.83)	Sub 1-8	m/z=354.08 (C 24 H 15 ClO=354.83)
Sub 1-9	m/z=430.11 (C 30 H 19 ClO=430.93)	Sub 1-10	m/z=430.11 (C 30 H 19 ClO=430.93)
Sub 1-11	m/z=430.11 (C 30 H 19 ClO=430.93)	Sub 1-12	m/z=430.11 (C 30 H 19 ClO=430.93)
Sub 1-13	m/z=430.11 (C 30 H 19 ClO=430.93)	Sub 1-14	m/z=430.11 (C 30 H 19 ClO=430.93)
Sub 1-15	m/z=430.11 (C 30 H 19 ClO=430.93)	Sub 1-16	m/z=430.11 (C 30 H 19 ClO=430.93)
Sub 1-17	m/z=430.11 (C 30 H 19 ClO=430.93)	Sub 1-18	m/z=390.18 (C 26 H 27 ClO=390.95)
Sub 1-19	m/z=486.18 (C 34 H 27 ClO=487.04)	Sub 1-20	m/z=430.11 (C 30 H 19 ClO=430.93)
Sub 1-21	m/z=506.14 (C 36 H 23 ClO=507.03)	Sub 1-22	m/z=370.06 (C 24 H 15 ClS=370.89)
Sub 1-23	m/z=370.06 (C 24 H 15 ClS=370.89)	Sub 1-24	m/z=370.06 (C 24 H 15 ClS=370.89)
Sub 1-25	m/z=294.03 (C 18 H 11 ClS=294.8)	Sub 1-26	m/z=426.12 (C 28 H 23 ClS=427)
Sub 1-27	m/z=312.02 (C 18 H 10 ClFS=312.79)	Sub 1-28	m/z=376.11 (C 24 H 21 ClS=376.94)
Sub 1-29	m/z=303.05 (C 19 H 10 ClNO=303.75)	Sub 1-30	m/z=446.09 (C 30 H 19 ClS=446.99)
Sub 1-31	m/z=522.12 (C 36 H 23 ClS=523.09)	Sub 1-32	m/z=430.11 (C 30 H 19 ClO=430.93)
Sub 1-33	m/z=444.13 (C 31 H 21 ClO=444.96)	Sub 1-34	m/z=426.12 (C 28 H 23 ClS=427)
Sub 1-35	m/z=502.15 (C 34 H 27 ClS=503.1)	Sub 1-36	m/z=430.11 (C 30 H 19 ClO=430.93)
Sub 1-37	m/z=410.14 (C 28 H 23 ClO=410.94)	Sub 1-38	m/z=430.11 (C 30 H 19 ClO=430.93)
Sub 1-39	m/z=482.18 (C 32 H 31 ClS=483.11)	Sub 1-40	m/z=506.14 (C 36 H 23 ClO=507.03)
Sub 1-41	m/z=370.06 (C 24 H 15 ClS=370.89)	Sub 1-42	m/z=406.15 (C 26 H 27 ClS=407.01)
Sub 1-43	m/z=359.11 (C 24 H 10 D 5 ClO=359.86)	Sub 1-44	m/z=522.12 (C 36 H 23 ClS=523.09)
Sub 1-45	m/z=446.09 (C 30 H 19 ClS=446.99)	Sub 1-46	m/z=365.15 (C 24 H 4 D 11 ClO=365.9)
Sub 1-47	m/z=358.11 (C 24 H 11 D 4 ClO=358.86)	Sub 1-48	m/z=374.08 (C 24 H 11 D 4 ClS=374.92)
Sub 1-49	m/z=289.12 (C 18 D 11 ClO=289.8)	Sub 1-50	m/z=381.13 (C 24 H 4 D 11 ClS=381.96)
Sub 1-51	m/z=299.06 (C 18 H 6 D 5 ClS=299.83)	Sub 1-52	m/z=354.11 (C 22 H 15 D 4 ClS=354.93)

II. Synthesis of Sub 2

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

<Scheme 3>

{In Scheme 3,

1) Hal is I, Br or Cl;

2) R ¹⁰¹ is the same as the definition of Ar ³ in Formula 1,

3) n is an integer from 0 to 5.}

The compound belonging to Sub 2 may be the following compounds, but is not limited thereto, and Table 2 below shows FD-MS (Field Desorption-Mass Spectrometry) values of the compounds belonging to Sub 2 .

compound	FD-MS	compound	FD-MS
Sub 2-1	m/z=169.09 (C 12 H 11 N=169.23)	Sub 2-2	m/z=169.09 (C 12 H 11 N=169.23)
Sub 2-3	m/z=93.06 (C 6 H 7 N=93.13)	Sub 2-4	m/z=169.09 (C 12 H 11 N=169.23)
Sub 2-5	m/z=245.12 (C 18 H 15 N=245.33)	Sub 2-6	m/z=245.12 (C 18 H 15 N=245.33)
Sub 2-7	m/z=225.15 (C 16 H 19 N=225.34)	Sub 2-8	m/z=281.21 (C 20 H 27 N=281.44)
Sub 2-9	m/z=245.12 (C 18 H 15 N=245.33)	Sub 2-10	m/z=321.15 (C 24 H 19 N=321.42)
Sub 2-11	m/z=245.12 (C 18 H 15 N=245.33)	Sub 2-12	m/z=245.12 (C 18 H 15 N=245.33)
Sub 2-13	m/z=245.12 (C 18 H 15 N=245.33)	Sub 2-14	m/z=245.12 (C 18 H 15 N=245.33)
Sub 2-15	m/z=245.12 (C 18 H 15 N=245.33)	Sub 2-16	m/z=245.12 (C 18 H 15 N=245.33)
Sub 2-17	m/z=321.15 (C 24 H 19 N=321.42)	Sub 2-18	m/z=321.15 (C 24 H 19 N=321.42)
Sub 2-19	m/z=149.12 (C 10 H 15 N=149.24)	Sub 2-20	m/z=245.12 (C 18 H 15 N=245.33)
Sub 2-21	m/z=183.1 (C 13 H 13 N=183.25)	Sub 2-22	m/z=281.21 (C 20 H 27 N=281.44)
Sub 2-23	m/z=321.15 (C 24 H 19 N=321.42)	Sub 2-24	m/z=303.2 (C 22 H 25 N=303.45)
Sub 2-25	m/z=265.15 (C 18 H 19 NO=265.36)	Sub 2-26	m/z=187.08 (C 12 H 10 FN=187.22)
Sub 2-27	m/z=185.08 (C 12 H 11 NO=185.23)	Sub 2-28	m/z=195.1 (C 14 H 13 N=195.27)
Sub 2-29	m/z=245.12 (C 18 H 15 N=245.33)	Sub 2-30	m/z=174.12 (C 12 H 6 D 5 N=174.26)
Sub 2-31	m/z=258.2 (C 18 H 2 D 13 N=258.4)	Sub 2-32	m/z=178.15 (C 12 H 2 D 9 N=178.28)
Sub 2-33	m/z=233.2 (C 16 H 11 D 8 N=233.38)	Sub 2-34	m/z=245.12 (C 18 H 15 N=245.33)
Sub 2-35	m/z=321.15 (C 24 H 19 N=321.42)	Sub 2-36	m/z=321.15 (C 24 H 19 N=321.42)
Sub 2-37	m/z=225.15 (C 16 H 19 N=225.34)	Sub 2-38	m/z=321.15 (C 24 H 19 N=321.42)
Sub 2-39	m/z=321.15 (C 24 H 19 N=321.42)	Sub 2-40	m/z=175.14 (C 12 H 17 N=175.28)

III. Synthesis of Final Product

1. P-1 Synthesis Example

After dissolving Sub 1-1 (10.0 g, 35.9 mmol) with toluene (179 mL) in a round-bottom flask, Sub 2-1 (2.9 g, 17.9 mmol), Pd ₂ (dba) ₃ (1.0 g, 1.1 mmol) , P( t -Bu) ₃ (0.4 g, 2.2 mmol), and NaO t -Bu (6.9 g, 71.8 mmol) were added and stirred at 120°C. Upon completion of the reaction, the mixture was extracted with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ , concentrated, and the resulting compound was recrystallized by silicagel column to obtain 17.7 g of the product. (Yield: 75.4%)

2. P-5 Synthesis Example

1) Synthesis of Intermediate-5

Sub 1-1 (10.0 g, 35.9 mmol), Sub 2-1 (2.9 g, 17.9 mmol), Pd ₂ (dba) ₃ (1.0 g, 1.1 mmol), P( t -Bu) ₃ ( 0.4 g, 2.2 mmol), NaO t -Bu (6.9 g, 71.8 mmol), and toluene (179 mL) were tested in the same manner as in P-1 to obtain 8.4 g of the product. (Yield: 56.8%)

2) Synthesis of P-5

In a round-bottom flask, Intermediate-5 (8.4 g, 20.4 mmol) obtained in the above synthesis, Sub 1-2 (7.0 g, 20.4 mmol), Pd ₂ (dba) ₃ (0.6 g, 0.6 mmol), P(t-Bu) ) ₃ (0.3 g, 1.2 mmol), NaOt-Bu (3.9 g, 40.8 mmol), and toluene (102 mL) were tested in the same manner as in P-1 to obtain 11.5 g of the product. (Yield: 77.1%)

3. P-20 Synthesis Example

Sub 1-1 (10.0 g, 35.9 mmol), Sub 2-14 (4.3 g, 17.9 mmol), Pd ₂ (dba) ₃ (1.0 g, 1.1 mmol), P( t -Bu) ₃ ( 0.4 g, 2.2 mmol), NaO t -Bu (6.9 g, 71.8 mmol), and toluene (179 mL) were tested in the same manner as in P-1 to obtain 19.2 g of the product. (Yield: 73.5%)

4. P-67 Synthesis Example

1) Synthesis of Intermediate-67

Sub 1-25 (10.0 g, 33.9 mmol), Sub 2-20 (8.0 g, 33.9 mmol), Pd ₂ (dba) ₃ (0.9 g, 1.0 mmol), P( t -Bu) ₃ ( 0.4 g, 2.0 mmol), NaO t -Bu (6.5 g, 67.8 mmol), and toluene (170 mL) were tested in the same manner as in P-1 to obtain 9.5 g of the product. (Yield: 55.7%)

2) Synthesis of P-67

Intermediate-67 (9.5 g, 18.9 mmol) obtained in the above synthesis and Sub 1-30 (8.1 g, 18.9 mmol), Pd ₂ (dba) ₃ (0.5 g, 0.6 mmol), P(t-Bu) in a round-bottom flask ) ₃ (0.2 g, 1.1 mmol), NaOt-Bu (3.6 g, 37.7 mmol), and toluene (94 mL) were tested in the same manner as in P-1 to obtain 12.4 g of the product. (Yield: 72.1%)

5. P-74 Synthesis Example

1) Synthesis of Intermediate-74

Sub 1-25 (10.0 g, 33.9 mmol), Sub 2-1 (2.8 g, 17.0 mmol), Pd ₂ (dba) ₃ (0.9 g, 1.0 mmol), P( t -Bu) ₃ ( 0.4 g, 2.0 mmol), NaO t -Bu (6.5 g, 67.8 mmol), and toluene (170 mL) were tested in the same manner as in P-1 to obtain 8.1 g of the product. (Yield: 56.0%)

2) Synthesis of P-74

Intermediate-74 (8.1 g, 18.9 mmol) obtained in the above synthesis and Sub 1-38 (7.9 g, 18.9 mmol), Pd ₂ (dba) ₃ (0.5 g, 0.6 mmol), P(t-Bu) in a round-bottom flask ) ₃ (0.2 g, 1.1 mmol), NaOt-Bu (3.6 g, 37.9 mmol), and toluene (95 mL) were tested in the same manner as in P-1 to obtain 11.4 g of the product. (Yield: 72.9%)

6. P-86 Synthesis Example

Sub 1-49 (10.0 g, 28.0 mmol), Sub 2-32 (2.4 g, 14.0 mmol), Pd ₂ (dba) ₃ (0.8 g, 0.8 mmol), P( t -Bu) ₃ ( 0.3 g, 1.7 mmol), NaO t -Bu (5.4 g, 55.9 mmol), and toluene (140 mL) were tested in the same manner as in P-1 to obtain 14.4 g of the product. (Yield: 75.4%)

Meanwhile, FD-MS values of compounds P-1 to P-90 of the present invention prepared according to the above synthesis examples are shown in Table 3 below.

compound	FD-MS	compound	FD-MS
P-1	m/z=653.24 (C 48 H 31 NO 2 =653.78)	P-2	m/z=653.24 (C 48 H 31 NO 2 =653.78)
P-3	m/z=577.2 (C 42 H 27 NO 2 =577.68)	P-4	m/z=653.24 (C 48 H 31 NO 2 =653.78)
P-5	m/z=729.27 (C 54 H 35 NO 2 =729.88)	P-6	m/z=805.3 (C 60 H 39 NO 2 =805.98)
P-7	m/z=805.3 (C 60 H 39 NO 2 =805.98)	P-8	m/z=805.3 (C 60 H 39 NO 2 =805.98)
P-9	m/z=729.27 (C 54 H 35 NO 2 =729.88)	P-10	m/z=729.27 (C 54 H 35 NO 2 =729.88)
P-11	m/z=805.3 (C 60 H 39 NO 2 =805.98)	P-12	m/z=709.3 (C 52 H 39 NO 2 =709.89)
P-13	m/z=765.36 (C 56 H 47 NO 2 =766)	P-14	m/z=709.3 (C 52 H 39 NO 2 =709.89)
P-15	m/z=729.27 (C 54 H 35 NO 2 =729.88)	P-16	m/z=805.3 (C 60 H 39 NO 2 =805.98)
P-17	m/z=729.27 (C 54 H 35 NO 2 =729.88)	P-18	m/z=729.27 (C 54 H 35 NO 2 =729.88)
P-19	m/z=729.27 (C 54 H 35 NO 2 =729.88)	P-20	m/z=729.27 (C 54 H 35 NO 2 =729.88)
P-21	m/z=729.27 (C 54 H 35 NO 2 =729.88)	P-22	m/z=729.27 (C 54 H 35 NO 2 =729.88)
P-23	m/z=805.3 (C 60 H 39 NO 2 =805.98)	P-24	m/z=805.3 (C 60 H 39 NO 2 =805.98)
P-25	m/z=709.3 (C 52 H 39 NO 2 =709.89)	P-26	m/z=729.27 (C 54 H 35 NO 2 =729.88)
P-27	m/z=805.3 (C 60 H 39 NO 2 =805.98)	P-28	m/z=805.3 (C 60 H 39 NO 2 =805.98)
P-29	m/z=819.31 (C 61 H 41 NO 2 =820)	P-30	m/z=729.27 (C 54 H 35 NO 2 =729.88)
P-31	m/z=805.3 (C 60 H 39 NO 2 =805.98)	P-32	m/z=833.33 (C 62 H 43 NO 2 =834.03)
P-33	m/z=881.33 (C 66 H 43 NO 2 =882.08)	P-34	m/z=881.33 (C 66 H 43 NO 2 =882.08)
P-35	m/z=729.27 (C 54 H 35 NO 2 =729.88)	P-36	m/z=729.27 (C 54 H 35 NO 2 =729.88)
P-37	m/z=709.3 (C 52 H 39 NO 2 =709.89)	P-38	m/z=897.45 (C 66 H 59 NO 2 =898.2)
P-39	m/z=957.36 (C 72 H 47 NO 2 =958.17)	P-40	m/z=805.3 (C 60 H 39 NO 2 =805.98)
P-41	m/z=669.21 (C 48 H 31 NOS=669.84)	P-42	m/z=685.19 (C 48 H 31 NS 2 =685.9)
P-43	m/z=593.18 (C 42 H 27 NOS=593.74)	P-44	m/z=669.21 (C 48 H 31 NOS=669.84)
P-45	m/z=761.22 (C 54 H 35 NS 2 =762)	P-46	m/z=821.28 (C 60 H 39 NOS=822.04)
P-47	m/z=821.28 (C 60 H 39 NOS=822.04)	P-48	m/z=837.25 (C 60 H 39 NS 2 =838.1)
P-49	m/z=761.22 (C 54 H 35 NS 2 =762)	P-50	m/z=745.24 (C 54 H 35 NOS=745.94)
P-51	m/z=821.28 (C 60 H 39 NOS=822.04)	P-52	m/z=725.28 (C 52 H 39 NOS=725.95)
P-53	m/z=933.4 (C 68 H 55 NOS=934.25)	P-54	m/z=893.31 (C 64 H 47 NS 2 =894.21)
P-55	m/z=821.28 (C 60 H 39 NOS=822.04)	P-56	m/z=821.28 (C 60 H 39 NOS=822.04)
P-57	m/z=837.25 (C 60 H 39 NS 2 =838.1)	P-58	m/z=821.28 (C 60 H 39 NOS=822.04)
P-59	m/z=819.3 (C 58 H 45 NS 2 =820.13)	P-60	m/z=781.25 (C 54 H 39 NOS 2 =782.03)
P-61	m/z=703.18 (C 48 H 30 FNS 2 =703.89)	P-62	m/z=685.21 (C 48 H 31 NO 2 S=685.84)
P-63	m/z=695.23 (C 50 H 33 NOS=695.88)	P-64	m/z=779.21 (C 54 H 34 FNS 2 =779.99)
P-65	m/z=731.32 (C 52 H 45 NOS=732)	P-66	m/z=694.21 (C 49 H 30 N 2 OS=694.85)
P-67	m/z=913.28 (C 66 H 43 NS 2 =914.2)	P-68	m/z=913.28 (C 66 H 43 NS 2 =914.2)
P-69	m/z=835.29 (C 61 H 41 NOS=836.07)	P-70	m/z=743.28 (C 55 H 37 NO 2 =743.91)
P-71	m/z=801.31 (C 58 H 43 NOS=802.05)	P-72	m/z=933.4 (C 68 H 55 NOS=934.25)
P-73	m/z=821.28 (C 60 H 39 NOS=822.04)	P-74	m/z=821.28 (C 60 H 39 NOS=822.04)
P-75	m/z=797.31 (C 56 H 47 NS 2 =798.12)	P-76	m/z=897.31 (C 66 H 43 NOS=898.14)
P-77	m/z=801.31 (C 58 H 43 NOS=802.05)	P-78	m/z=833.41 (C 58 H 59 NS 2 =834.24)
P-79	m/z=989.31 (C 72 H 47 NS 2 =990.3)	P-80	m/z=837.25 (C 60 H 39 NS 2 =838.1)
P-81	m/z=734.3 (C 54 H 30 D 5 NO 2 =734.91)	P-82	m/z=816.37 (C 60 H 28 D 11 NO 2 =817.04)
P-83	m/z=826.31 (C 60 H 34 D 5 NOS=827.07)	P-84	m/z=829.33 (C 60 H 31 D 8 NOS=830.09)
P-85	m/z=742.35 (C 54 H 22 D 13 NO 2 =742.96)	P-86	m/z=684.43 (C 48 D 31 NO 2 =684.97)
P-87	m/z=848.32 (C 60 H 28 D 11 NS 2 =849.17)	P-88	m/z=749.3 (C 52 H 31 D 8 NS 2 =750.06)
P-89	m/z=786.37 (C 56 H 42 D 5 NOS=787.09)	P-90	m/z=734.33 (C 52 H 30 D 9 NOS=735)

Manufacturing evaluation of organic electric devices

[Example 1] Green organic electroluminescent device (light emitting auxiliary layer)

On the ITO layer (anode) formed on the glass substrate, 4,4',4"-tris[2-naphthyl(phenyl)amino]triphenylamine (hereinafter abbreviated as 2-TNATA) was vacuum-deposited on it, and a 60 nm-thick hole was injected. After forming the 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.

Then, the compound P-1 of the present invention was vacuum-deposited on the hole transport layer to a thickness of 20 nm to form a light emitting auxiliary layer, and then, as a host material, 4,4'-N,N'-dicarbazole-biphenyl (hereinafter, CBP), tris(2-phenylpyridine)-iridium (hereinafter, abbreviated as Ir(ppy) ₃ ) is used as a dopant material, but a dopant is doped at a weight of 95:5 to form a light emitting layer with a thickness of 30 nm did.

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

[Example 2] to [Example 15]

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

[Comparative Example 1] to [Comparative Example 6]

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that the following comparative compounds A to F were used instead of the compound P-1 of the present invention as a light emitting auxiliary layer material.

[Comparative compound A] [Comparative compound B] [Comparative compound C]

[Comparative compound D] [Comparative compound E] [Comparative compound F]

By applying a forward bias DC voltage to the organic electroluminescent devices manufactured by Examples 1 to 15 and Comparative Examples 1 to 6 of the present invention, the electroluminescence (EL) characteristics were obtained with PR-650 of photoresearch. was measured, and as a result of the measurement, the T95 lifetime was measured using a lifetime measuring device manufactured by McScience at 5000 cd/m ² standard luminance. Table 4 below shows the device fabrication and evaluation results.

	compound	drive voltage	Current (mA/cm 2 )	Luminance (cd/m 2 )	Efficiency (cd/A)	T(95)
Comparative Example (1)	Comparative compound A	6.1	13.9	5000.0	36.1	100.9
Comparative Example (2)	Comparative compound B	5.8	13.6	5000.0	36.7	102.2
Comparative Example (3)	Comparative compound C	6.1	13.5	5000.0	37.0	103.6
Comparative Example (4)	Comparative compound D	5.9	12.9	5000.0	38.8	101.3
Comparative Example (5)	Comparative compound E	5.7	12.9	5000.0	37.9	104.5
Comparative Example (6)	Comparative compound F	5.8	13.2	5000.0	35.4	105.7
Example (1)	P-1	4.9	9.9	5000.0	50.5	131.9
Example (2)	P-2	5.0	10.3	5000.0	48.6	130.3
Example (3)	P-3	4.9	9.9	5000.0	50.7	130.8
Example (4)	P-4	4.9	9.8	5000.0	51.2	131.1
Example (5)	P-5	5.0	10.0	5000.0	49.8	131.4
Example (6)	P-6	5.3	11.1	5000.0	44.9	132.3
Example (7)	P-14	5.1	10.4	5000.0	48.1	125.3
Example (8)	P-25	5.1	10.5	5000.0	47.8	127.5
Example (9)	P-41	5.3	9.9	5000.0	50.6	128.1
Example (10)	P-52	5.2	10.9	5000.0	46.0	123.9
Example (11)	P-56	5.3	11.2	5000.0	44.5	125.4
Example (12)	P-59	5.3	11.4	5000.0	43.8	122.5
Example (13)	P-74	5.2	10.8	5000.0	46.3	128.6
Example (14)	P-80	5.3	11.1	5000.0	45.0	129.8
Example (15)	P-86	5.0	9.8	5000.0	50.8	132.0

As can be seen from the results of Table 4, when a green organic light emitting device is manufactured using the material for an organic electroluminescent device of the present invention as a light emitting auxiliary layer material, Comparative Compounds A to having a similar basic skeleton to the compound of the present invention The driving voltage, luminous efficiency, and lifetime of the organic electroluminescent device can be improved compared to Comparative Examples using Comparative Compound F. In other words, Comparative Examples 1 to Comparative Examples using the light emitting auxiliary layer using Comparative Compounds A to F. When the compound of the present invention was used as a light emitting auxiliary layer material than in case 6, the driving voltage of the organic electroluminescent device was lowered, and the luminous efficiency and especially the lifespan were significantly improved.

Comparative compounds A to F are the same as the compounds of the present invention in that dibenzofuran is substituted in the tertiary amine compound, but have at least one substituent at the 8th position of dibenzofuran or dibenzothiophene, At the same time, it is different from the compound of the present invention in that it is a tertiary amine compound in which two groups having an amine group bonded to the 1-position of dibenzofuran or dibenzothiophene are necessarily present.

Table 5 below shows the quantum mechanical average dissociation energies of the amorphous solid phase molecules of the compounds of the present invention and comparative compounds A to E having similar compound structures.

(hereinafter, Avg. BDE, unit: eV), the volume density of the amorphous solid-state molecular structure (hereinafter, Bulk Density, unit: g/cm ³ ) and the value of the radial distribution function (RDF, unit: Å) Data measured using molecular simulation (Gaussian09 Rev. C.01, Schrodinger Materials Science Suite 4.1.161).

5 is a value obtained by extracting a part of a molecule in a unit cell having a periodic boundary condition (PBC) and calculating the bond dissociation energy of each molecule. The set of bond dissociation energies G = {E ₁ … After constructing E _N }, the average value of the set of bond dissociation energies

was used as an indicator of the bond dissociation energy of the solid state.

	Avg. BDE (eV)	Bulk Density (g/cm 3 )	RDF (Å)
P-1	3.67004	1.152	9.9
P-2	3.65907	1.146	10.07
P-3	3.73561	1.153	9.53
P-4	3.75642	1.151	9.03
P-5	3.72987	1.149	9.95
Comparative compound A	3.47846	1.109	10.72
Comparative compound B	3.51261	1.122	10.63
Comparative compound C	3.50228	1.109	10.47
Comparative compound D	3.61524	1.121	10.16
Comparative compound E	3.60679	1.142	10.19

From Table 5, it can be seen that the quantum mechanical average bond dissociation energy value of the amorphous solid phase molecules in the compounds P-1 to P-5 of the present invention is higher than that of the comparative compounds A to E. In an organic electric device, the lower the crystallinity of the thin film, the more an amorphous state can be created. can be faster However, depending on the structure of the molecule, even in the same amorphous state, the quantum mechanical average bond dissociation energy of a solid-state molecule in the amorphous state may be different due to intermolecular interactions in the solid-state, and the higher the value, the higher the stability of the compound itself. do. Therefore, when the compound of the present invention is used as a light emitting auxiliary layer of an organic electric device, the stability of electrons passing through the light emitting layer is significantly increased compared to Comparative Examples using Comparative Compounds A to E having similar basic skeletons to the compound of the present invention. Thus, it is judged that the lifetime of the device is maximized. In addition, the volume density value of the amorphous solid molecular structure of the compounds P-1 to P-5 of the present invention is higher than that of the comparative compounds A to E, and the radial distribution It can be seen from Table 5 that the function value is formed low. This is because when the compound of the present invention is in the amorphous solid state than the comparative compounds, the intermolecular distance is closer and the charge transfer is relatively quick. considered to be improved.

These results show that the basic skeleton of the molecule, such as Comparative Compound A to Comparative Compound F and the compound of the present invention, has Hole characteristics, light efficiency characteristics, energy levels, hole injection and mobility characteristics, hole This suggests that the properties of the compound such as charge balance of electrons and electrons, bulk density, and intermolecular distance may vary, and as a result, the properties of the device may also vary.

In the case of the light-emitting auxiliary layer, it is necessary to understand the correlation between the hole transport layer and the light-emitting layer (host). It will be very difficult.

In addition, in the evaluation results of the above-described device fabrication, the device characteristics in which the compound of the present invention is applied only to the light emitting auxiliary layer has been described, but the compound of the present invention may be applied to the hole transport layer or both the hole transport layer and the light emission auxiliary layer may be applied.

The above description is merely illustrative of the present invention, and those of ordinary skill in the art to which the present invention pertains will be able to make various modifications without departing from the essential characteristics of the present invention. Accordingly, the embodiments disclosed herein are for illustrative purposes rather than limiting 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 descriptions within an equivalent scope should be construed as being included in the scope of the present invention.

According to the present invention, it is possible to manufacture an organic device having excellent device characteristics of high luminance, high luminescence and long life, and thus has industrial applicability.

Claims (18)

1. A compound represented by the following formula (1)

   Formula 1

   

   {In Formula 1,

   1) X ¹ and X ² are each independently O or S,

   2) Ar ¹ , Ar ² and Ar ³ are each independently a C ₆ ~ C ₆₀ aryl group,

   3) L ¹ and L ² are each independently a single bond or a C ₆ ~ C ₆₀ arylene group,

   4) wherein the aryl group and the arylene group are each deuterium; halogen; silane 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 ₁ ~ C ₂₀ A heteroalkyl group; C ₁ ~ C ₂₀ Heteroalkenyl group; C ₁ ~ C ₂₀ Heteroalkynyl group; C ₆ ~ C ₂₀ Aryl group; C ₆ ~ C ₂₀ Aryl group substituted with deuterium; fluorenyl group; C ₂ ~ C ₂₀ A heterocyclic group; C ₃ ~ C ₂₀ Cycloalkyl group; C ₇ ~ C ₂₀ Arylalkyl group; And C ₈ ~ C ₂₀ Aryl alkenyl group; may be further substituted with one or more substituents selected from the group consisting of, and these substituents may be combined with each other to form a ring, where 'ring' means C ₃ ~ C ₆₀ of an aliphatic ring or C ₆ ~ C ₆₀ aromatic ring or C ₂ ~ C ₆₀ heterocyclic ring or a fused ring consisting of a combination thereof, including saturated or unsaturated rings.}
2. According to claim 1, wherein the compound represented by Formula 1 is the quantum mechanical average dissociation energy of the amorphous solid-state molecule

   

   A compound characterized in that 3.650 eV or more
3. The compound according to claim 1, wherein the compound represented by Formula 1 has a volume density of 1.110 g/cm ³ or more of the amorphous solid molecular structure.
4. The compound according to claim 1, wherein the value of the radial distribution function of the compound represented by Formula 1 is less than 11.0 Å.
5. The compound according to claim 1, wherein the compound represented by Formula 1 is represented by any one of the following Formulas 1-1 to 1-3.

   Formula 1-1 Formula 1-2

   

   Formula 1-3

   

   {In Formulas 1-1 to 1-3, Ar ¹ , Ar ² , Ar ³ , L ¹ and L ² are the same as defined in claim 1 above.}
6. The compound according to claim 1, wherein at least one of Ar ¹ to Ar ³ is represented by any one of the following Chemical Formulas Ar-1 to Ar-13.

   Formula Ar-1 Formula Ar-2 Formula Ar-3 Formula Ar-4

   

   Formula Ar-5 Formula Ar-6 Formula Ar-7

   

   Formula Ar-8 Formula Ar-9 Formula Ar-10

   

   Formula Ar-11 Formula Ar-12 Formula Ar-13

   

   {In the formulas Ar-1 to Ar-13,

   1) R ¹ , R ² , and R ³ are the same or different from each other, and each independently hydrogen; deuterium, halogen; cyano group; nitro group; C ₆ ~ C ₆₀ Aryl group; fluorenyl group; O, N, S, Si and P containing at least one heteroatom C ₂ ~ C ₆₀ A heterocyclic group; C ₃ ~ C ₆₀ A fused ring group of an aliphatic ring and a C ₆ ~ C ₆₀ aromatic ring; C ₃ ~ C ₂₀ Cycloalkyl group; C ₁ ~ C ₅₀ Alkyl group; C ₂ ~ C ₂₀ Alkenyl group; C ₂ ~ C ₂₀ alkynyl group; C ₁ ~ C ₃₀ An alkoxyl group; And C ₆ ~ C ₃₀ An aryloxy group; is selected from the group consisting of,

   2) a is an integer from 0 to 5, b and c are independently integers from 0 to 4,

   3) * means the bonding position.}
7. The compound according to claim 1, wherein at least one of L ¹ and L ² is represented by any one of the following Chemical Formulas L-1 to L-3.

   Formula L-1 Formula L-2 Formula L-3

   

   {In the above formulas L-1 to L-3,

   1) R ⁴ is the same as the definition of R ¹ in claim 5,

   2) d is an integer from 0 to 4,

   3) * means the bonding position.}
8. The compound according to claim 1, wherein Formula 1 is represented by any one of the following compounds P-1 to P-90.

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   
9. In an organic electric device comprising an anode, a cathode, and an organic material layer formed between the anode and the cathode, the organic material layer comprises a single compound or two or more compounds represented by Formula 1 of claim 1, wherein the compound in the organic material layer is an amorphous solid phase Quantum mechanical average dissociation energy of molecules

   

   Organic electric device, characterized in that 3.650 eV or more
10. The organic electric device according to claim 9, wherein the organic material layer comprises at least one of a hole injection layer, a hole transport layer, a light emission auxiliary layer, a light emitting layer, an electron transport auxiliary layer, an electron transport layer, and an electron injection layer.
11. The organic electric device according to claim 9, wherein the organic material layer is a light emitting auxiliary layer.
12. The organic electric device according to claim 9, wherein the organic material layer is a hole transport layer.
13. The organic electric device according to claim 9, further comprising a light efficiency improving layer formed on at least one surface opposite to the organic material layer among one surface of the anode and the cathode.
14. The organic electric device according to claim 9, wherein the organic material layer is a light efficiency improving layer.
15. The organic electric device according to claim 9, wherein the organic material layer comprises at least two stacks including a hole transport layer, a light emitting layer, and an electron transport layer sequentially formed on the anode.
16. The organic electric device according to claim 9, wherein the organic material layer further comprises a charge generating layer formed between the two or more stacks.
17. A display device comprising the organic electric device of claim 9; and a controller configured to drive the display device.
18. 18. The method of claim 17, wherein the organic electric device is at least one of an organic electroluminescent device (OLED), an organic solar cell, an organophotoreceptor (OPC), an organic transistor (organic TFT), and a device for monochromatic or white lighting. electronic device

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