KR102015037B1 - Stacked organic light emitting device - Google Patents

Abstract

The present specification relates to a stacked organic light emitting device including a charge generating layer.

Description

Multilayer Organic Light-Emitting Element {STACKED ORGANIC LIGHT EMITTING DEVICE}

The present specification relates to a laminated organic light emitting device.

The organic light emitting phenomenon is an example of converting an electric current into visible light by an internal process of a specific organic molecule. The principle of the organic light emitting phenomenon is as follows.

When the organic material layer is placed between the anode and the cathode, when a voltage is applied between the two electrodes, electrons and holes are injected into the organic material layer from the cathode and the anode, respectively. Electrons and holes injected into the organic material layer recombine to form excitons, and the excitons fall back to the ground to shine. An organic light emitting device using this principle may generally be composed of an organic material layer including a cathode and an anode, and an organic material layer disposed therebetween, such as a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer.

An organic light emitting device refers to a self-luminous device using an electroluminescence phenomenon that emits light when a current flows through a light emitting organic compound, and has attracted attention as a next generation material in various industrial fields such as display and lighting.

In the case of a stacked organic light emitting device in which two or more light emitting units are stacked, a process is complicated because the number of layers of each light emitting unit is different from each other, and the material cost of the light emitting unit is increased because the materials of the light emitting units are different. There is a problem and a problem that the efficiency is lowered by increasing the driving voltage due to the increase in the number of layers (layer).

Most of the materials used in the organic light emitting device are pure organic materials or complex compounds in which organic materials and metals are complexed, and depending on the purpose, hole injection materials, hole transport materials, light emitting materials, electron transport materials, electron injection materials, etc. It can be divided into. Here, as the hole injection material or the hole transport material, an organic material having a p-type property, that is, an organic material which is easily oxidized and has an electrochemically stable state during oxidation, is mainly used. On the other hand, as an electron injection material or an electron transport material, organic materials having n-type properties, that is, organic materials that are easily reduced and have an electrochemically stable state at the time of reduction are mainly used. As the light emitting layer material, a material having a p-type property and an n-type property at the same time, that is, a material having a stable form in both oxidation and reduction states, and a material having high luminous efficiency that converts it to light when excitons are formed desirable.

There is a need in the art for the development of high efficiency organic light emitting devices.

Applied Physics Letters 51, p. 913, 1987

The present specification provides a laminated organic light emitting device.

The present specification is a cathode; An anode provided opposite the cathode; Two or more light emitting units provided between the cathode and the anode; And a charge generating layer provided between at least two light emitting units adjacent to each other among the two or more light emitting units, wherein the charge generating layer includes a p-type organic compound layer, an n-type organic compound layer, and an intermediate layer. It provides an organic light emitting device comprising a compound represented by.

[Formula 1]

In Chemical Formula 1,

At least one of X, Y and Z is represented by the following formula (2),

Among X, Y and Z, a group other than Formula 2 may be a substituted or unsubstituted aryl group; Or a substituted or unsubstituted nitrogen-containing heterocyclic group,

[Formula 2]

In Chemical Formula 2,

L is a direct bond; Substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,

A is a direct bond; Or C = O,

a is an integer from 1 to 7,

when a is 2 or more, two or more R1 are the same as or different from each other,

R 1 is hydrogen; heavy hydrogen; Halogen group; Nitrile group; Nitro group; Imide group; Amide group; Hydroxyl group; Substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted alkoxy group; Substituted or unsubstituted aryloxy group; Substituted or unsubstituted alkylthioxy group; Substituted or unsubstituted arylthioxy group; Substituted or unsubstituted alkenyl group; Substituted or unsubstituted silyl group; Substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; Substituted or unsubstituted arylamine group; Substituted or unsubstituted heteroarylamine group; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroring group.

In addition, the present disclosure provides a display device including the organic light emitting device.

In addition, the present specification provides a lighting device including the organic light emitting device.

The organic light emitting diode according to the exemplary embodiment of the present specification can minimize the increase in the driving voltage.

In addition, the organic light emitting device of the present specification introduces an intermediate layer to reduce the concentration of the n-type dopant, thereby increasing the process efficiency, thereby reducing the material cost.

In addition, the tandem organic light emitting device of the present specification can operate even if each light emitting unit has a simple configuration, thereby reducing the manufacturing cost and increasing the driving voltage due to the energy barrier between each interface.

1 illustrates an example of a stacked organic light emitting diode according to an exemplary embodiment of the present specification.
2 illustrates an example of a stacked organic light emitting diode according to an exemplary embodiment of the present specification.
3 shows an example of a charge generating layer of the present specification.
4 is a diagram illustrating a voltage-current graph of an organic light emitting diode according to the thickness of an intermediate layer of the present specification.
5 is a diagram illustrating a voltage-current graph according to Examples and Comparative Examples of the present specification.

Hereinafter, the present specification will be described in detail.

In this specification, when a member is located "on" another member, this includes not only when one member is in contact with another member but also when another member exists between the two members.

In the present specification, when a part "includes" a certain component, it means that it may further include other components, without excluding the other components unless otherwise stated.

The present specification is a cathode; An anode provided opposite the cathode; Two or more light emitting units provided between the cathode and the anode; And a charge generating layer provided between two light emitting units adjacent to each other among the two or more light emitting units, wherein the charge generating layer includes a p-type organic compound layer, an n-type organic compound layer, and an intermediate layer, wherein the intermediate layer is represented by Formula 1 above. It provides an organic light emitting device comprising the compound represented.

In this specification, n-type means n-type semiconductor characteristics. In other words, n-type is a property that electrons are injected or transported through a lower unoccupied molecular orbital (LUMO) energy level, which can be defined as a property of a material in which electron mobility is greater than hole mobility. In contrast, p-type means p-type semiconductor characteristics. In other words, p-type is a property of injecting or transporting holes through a high occupied molecular orbital (HOMO) energy level, which may be defined as a property of a material in which the hole mobility is greater than the electron mobility. In the present specification, the compound or organic compound layer having n-type characteristics may be referred to as an n-type compound or n-type organic compound layer. In addition, the compound or organic compound layer having a p-type characteristic may be referred to as a p-type compound or p-type organic compound layer. Also, n-type doping means that it is doped to have n-type characteristics.

In the present specification, the term “adjacent” means an arrangement relationship of the nearest layers among the layers mentioned as adjacent. For example, two adjacent light emitting units mean an arrangement relationship of two light emitting units disposed closest to each other among a plurality of light emitting units. The adjacency may mean a case where two layers are in physical contact with each other in some cases, and another layer not mentioned between the two layers may be disposed. For example, the light emitting unit adjacent to the cathode means a light emitting unit disposed closest to the cathode among the light emitting units. In addition, although the cathode and the light emitting unit may be physically in contact with each other, a layer other than the light emitting unit may be disposed between the cathode and the light emitting unit.

In the organic light emitting diode according to the exemplary embodiment of the present specification, at least one charge generating layer is provided between at least two adjacent light emitting units.

In the present specification, the light emitting unit is not particularly limited as long as it is a unit having a function capable of emitting light. For example, the light emitting unit may include one or more light emitting layers, and the light emitting layer in the light emitting unit corresponds to a light emitting region as a point where electrons transported from the cathode and holes transported from the anode meet together to form excitons. If necessary, the light emitting unit may include one or more organic material layers other than the light emitting layer.

In one embodiment of the present specification, the light emitting unit may further include one or more organic material layers in addition to the light emitting layer. The additional organic layer may be a hole transport layer, a hole injection layer, a layer for transporting and injecting holes, a buffer layer, an electron blocking layer, an electron transporting layer, an electron injection layer, a layer for transporting and injecting electrons, a hole blocking layer, and the like. Here, the hole transport layer, the hole injection layer, the layer for transporting and injecting holes or the electron blocking layer may be disposed closer to the anode than the light emitting layer. The electron transport layer, the electron injection layer, the layer for transporting and injecting electrons or the hole blocking layer may be disposed closer to the cathode than the light emitting layer. Whether to use the hole blocking layer may be determined depending on the nature of the light emitting layer. For example, when the property of the light emitting layer is close to n type, the hole blocking layer may not be used. However, when the property of the light emitting layer is p type, the use of the hole blocking layer may be considered. In addition, in consideration of the relationship between the HOMO energy level of the light emitting layer and the HOMO energy level of the electron transport layer, it may be determined whether to use the hole blocking layer. When the HOMO energy level of the light emitting layer has a larger value than the HOMO energy level of the electron transport layer, introduction of a hole blocking layer may be considered. However, in this case, when the HOMO level of the electron transport layer is greater than the HOMO level of the light emitting layer, the electron transport layer itself may serve as a hole blocking layer. As one example, by using two or more materials of the electron transport layer may play a role of the electron transport layer and the hole blocking layer at the same time.

In one embodiment of the present specification, the light emitting unit includes a light emitting layer; And a hole injection layer, a hole transport layer. It further comprises one or two or more layers selected from the group consisting of an electron transport layer, an electron injection layer, an electron blocking layer and a hole blocking layer.

In one embodiment, the light emitting unit includes a hole transport layer, a light emitting layer and an electron transport layer, the electron transport layer is provided in contact with the intermediate layer.

Specifically, in the present specification, the hole transport layer is provided close to the anode, the electron transport layer is provided close to the cathode, and the light emitting layer is provided between the hole transport layer and the electron transport layer.

In one embodiment of the present specification, the electron transport layer included in the light emitting unit includes two or more electron transport layers, and the electron transport layer provided in contact with the intermediate layer among the two or more electron transport layers is doped with an n-type dopant.

When the electron transport layer doped with the n-type dopant is included, driving characteristics of the charge generation layer may be improved.

In another exemplary embodiment, the electron transport layer included in the light emitting unit includes two or more electron transport layers, and the materials of the two or more electron transport layers are the same or different from each other.

In the present specification, the two or more light emitting units may each independently emit one or more colors.

In one embodiment of the present specification, the two or more light emitting units may each include different light emitting dopants. In the present specification, the light emitting dopant may be a phosphorescent or fluorescent dopant, and may be selected according to the needs of those skilled in the art.

In the present specification, the charge generating layer is a layer that generates charge without applying an external voltage, and generates two or more charges between the light emitting units so that two or more light emitting units included in the organic light emitting device can emit light.

The charge generation layer according to the exemplary embodiment of the present specification may include an n-type organic compound layer, a p-type organic compound layer, and an intermediate layer.

In one embodiment of the present specification, the p-type organic compound layer is provided closer to the anode than the intermediate layer, the intermediate layer is provided closer to the cathode than the p-type organic compound layer, the n-type organic compound layer is provided between the p-type organic compound layer and the intermediate layer.

1 and 2 illustrate an example of an organic light emitting diode according to one embodiment.

In FIG. 1, two light emitting units 301 and 302 are provided between an anode 101 and a cathode 201, and a charge generation layer 401 is provided between the two light emitting units. The structure may further include a light emitting unit, in which case a charge generation layer may be provided between at least two adjacent light emitting units.

In FIG. 2, two light emitting units 301 and 302 are provided between the anode 101 and the cathode 201, and a charge generation layer 401 is provided between the two light emitting units. In addition, an electron transport layer 801 doped with an n-type dopant may be provided between the charge generating layer and the light emitting unit 301 near the anode and the charge generating layer 401. The structure may further include a light emitting unit, in which case a charge generation layer may be provided between at least two adjacent light emitting units.

3, in the charge generation layer 401, the p-type organic layer 701 is disposed closer to the anode 101, the intermediate layer 501 is disposed closer to the cathode 201, and the n-type organic compound layer 601. Is provided between the p-type organic compound layer and the intermediate layer.

In the present specification, the energy level means the magnitude of energy. Therefore, even when the energy level is displayed in the negative (-) direction from the vacuum level, the energy level is interpreted to mean the absolute value of the corresponding energy value. For example, the HOMO energy level means the distance from the vacuum level to the highest occupied molecular orbital. In addition, the LUMO energy level means the distance from the vacuum level to the lowest unoccupied molecular orbital.

In the present specification, the measurement of the HOMO energy level may use a UV photoelectron spectroscopy (UPS) for measuring the ionization potential of a material by irradiating UV on the surface of the thin film and detecting the protruding electrons. Alternatively, the HOMO energy level may be measured by cyclic voltammetry (CV) which measures an oxidation potential through a voltage sweep after dissolving a target material in a solvent together with an electrolyte. In the case of measuring the HOMO energy level in the form of a thin film, the UPS can measure more accurate values than the CV, and the HOMO energy level of the present specification was measured by the UPS method.

In the present specification, the LUMO energy level may be obtained by measuring inverse photoelectron spectroscopy (IPES) or electrochemical reduction potential. IPES is a method of irradiating an electron beam (electron beam) to a thin film and measuring the light emitted at this time to determine the LUMO energy level. In addition, the electrochemical reduction potential may be measured by dissolving a substance to be measured in a solvent together with an electrolyte and then measuring a reduction potential through a voltage sweep. Alternatively, the LUMO energy level may be calculated using the singlet energy level obtained by measuring the HOMO energy level and the degree of UV absorption of the target material.

In one embodiment of the present specification, the thickness of the intermediate layer including the compound of Formula 1 is 0.5nm to 10nm. The driving voltage of the organic light emitting element is reduced within the above range thickness.

4 is a diagram illustrating a voltage-current of an organic light emitting diode according to the thickness of an intermediate layer. 4, it can be seen that the current-voltage characteristics are excellent within the above range.

As used herein, the thickness means the width between one surface facing the anode or the cathode and one surface facing the anode or cathode.

In one embodiment of the present specification, the p-type organic compound layer, the n-type organic compound layer and the intermediate layer of the charge generating layer is provided in contact with each other.

In one embodiment of the present specification, the p-type organic compound layer is provided closer to the anode than the intermediate layer, the intermediate layer is provided closer to the cathode than the p-type organic compound layer, the n-type organic compound layer is provided between the p-type organic compound layer and the intermediate layer. The p-type organic compound layer and the n-type organic compound layer form an NP junction.

In an exemplary embodiment of the present specification, the p-type organic compound layer and the n-type organic compound layer may be provided in contact with each other, and a charge may be generated by forming an NP junction. In this case, the LUMO energy level of the n-type organic compound layer and the HOMO energy level of the p-type organic compound layer may be adjusted in consideration of the energy level relationship between neighboring organic compound layers.

Holes generated between the n-type organic compound layer and the p-type organic compound layer are easily injected into the HOMO energy level of the p-type organic compound layer. When the LUMO energy level of the n-type organic compound layer is greater than the HOMO energy level of the p-type organic compound layer, NP junctions are easily generated, thereby preventing an increase in driving voltage. In the present specification, NP junction may occur when the n-type organic compound layer 512 and the p-type organic compound layer 511 are not only in physical contact but also satisfy the above-described energy relationship.

In one embodiment of the present specification, the HOMO energy level of the p-type organic compound layer has a value equal to or greater than the LUMO energy level of the n-type organic compound layer. In this case, it is more effective for charge generation.

When the NP junction is formed, holes or electrons are easily formed by an external voltage or a light source. That is, due to the NP junction, holes and electrons are simultaneously generated, that is, charge generation between the n-type organic compound layer and the p-type organic compound layer. Electrons are transported in the electron transport layer direction through the n-type organic compound layer, and holes are transported in the p-type organic compound layer direction. That is, when the HOMO energy level of the p-type organic compound layer is greater than the LUMO energy level of the n-type organic compound layer, the electrons of the HOMO level of the p-type organic compound layer may be spontaneously moved by the energy difference to the empty LUMO level of the n-type organic compound layer. In this case, holes are generated at the HOMO level of the p-type organic compound layer, and electrons are generated at the LUMO level of the n-type organic compound layer, so that holes or electrons are easily generated, and a rise in driving voltage for hole injection can be prevented.

In one embodiment of the present specification, the Fermi level of the n-type organic compound layer is the same as or larger than the Fermi level of the p-type organic compound layer. In this case, it is more effective for charge generation.

In one embodiment of the present specification, the n-type organic compound layer and the p-type organic compound layer satisfy the following formula (1).

[Equation 1]

In Equation 1, E _pH is the HOMO energy level of the p-type organic compound layer, E _nL is LUMO energy level of the n-type organic compound layer.

In one embodiment of the present specification, the n-type organic compound layer and the p-type organic compound layer satisfy the following formula (2).

[Equation 2]

In Formula 2, E _nF is a Fermi level of the n-type organic compound layer, E _pF is a Fermi level of the p-type organic compound layer.

In one embodiment of the present specification, the n-type organic compound layer and the p-type organic compound layer satisfies Equation 1 and 2.

In the present specification, in order to measure the HOMO energy level and the Fermi level, an ultraviolet photoelectron spectroscopy (UPS) method was used. This method analyzes the kinetic energy of electrons from the sample when the sample is irradiated with vacuum UV rays (21.20 eV) from the He lamp under ultra-vacuum (<10 ^-8 Torr). In this case, the ionization energy, that is, the HOMO level and the Fermi energy level can be determined. That is, when the vacuum UV ray (21.20 eV) is irradiated to the sample, the kinetic energy of the electrons emitted from the sample becomes a difference between the vacuum UV energy 21.2 eV and the electron binding energy of the sample to be measured. Accordingly, by analyzing the kinetic energy distribution of electrons emitted from the sample, it is possible to know the distribution of intramolecular binding energy of the material in the sample. At this time, when the maximum energy value of the kinetic energy of the electron has a minimum binding energy of the sample. This can be used to determine the work function (Fermi energy level) and HOMO level of the sample.

In the present specification, when the HOMO energy level and the Fermi level are large, X-ray photoelectron spectroscopy (XPS) was used, and X-ray photoelectron spectroscopy may be measured by a method used in the art.

In a stacked organic light emitting device including a charge generation layer, an electron injection barrier is a problem when electrons generated in an n-type organic compound layer are transferred to an electron transport layer. Therefore, an attempt was made to increase the electron density of the electron transport layer by doping the n-type dopant to the electron transport layer to lower its energy barrier.

However, when the doping concentration is increased by the n-type dopant, which is a material of alkali metal or alkaline earth metal having a low work function, the driving characteristics of the charge generating layer are improved, but in the process, it is not economical in terms of time and cost. There is a problem that the life is reduced, the efficiency is reduced.

In the organic light emitting device according to the exemplary embodiment of the present specification, the intermediate layer including the compound represented by Formula 1 is introduced into the charge generating layer, thereby lowering the electron injection barrier, thereby lowering the n-type doping concentration of the electron transport layer. Therefore, the driving characteristics are improved, the process is economical, and there is an advantageous effect in terms of the life of the device and the efficiency of the light emitting device.

5 is a diagram showing a voltage-current density with or without an intermediate layer. In the case of including an intermediate layer in FIG. 5, it can be seen that an organic light emitting device having a low driving voltage can be configured while using an electron transport layer having a low doping concentration.

In one embodiment of the present specification, the organic light emitting device is a hole injection layer, a hole transport layer. It may further include one or two or more layers selected from the group consisting of an electron transport layer, an electron injection layer, an electron blocking layer and a hole blocking layer.

In one embodiment of the present specification, the at least one light emitting unit further includes an electron transport layer, and the electron transport layer is provided in contact with the intermediate layer. In this case, when electrons formed in the electron transport layer direction are transferred from the n-type organic compound layer to the electron transport layer, the intermediate layer serves to lower the energy barrier between the n-type organic compound layer and the electron transport layer, thereby facilitating electron transfer.

In one embodiment of the present specification, at least one of the X, Y and Z is any one of the following substituents.

In the substituent,

L1 to L3 are the same as or different from each other, and each independently a direct bond; Substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,

R2 and R3 are the same as or different from each other, and each independently a substituted or unsubstituted aryl group; Substituted or unsubstituted heterocyclic group; Or Formula 2,

b is an integer from 1 to 7,

c is an integer of 1 to 3,

d is an integer of 1 to 6,

when b is 2 or more, two or more R5 are the same or different from each other,

when c is 2 or more, two or more R 7 are the same as or different from each other,

when d is 2 or more, two or more R8 are the same or different from each other,

R4 to R8 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; Nitrile group; Nitro group; Imide group; Amide group; Hydroxyl group; Substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted alkoxy group; Substituted or unsubstituted aryloxy group; Substituted or unsubstituted alkylthioxy group; Substituted or unsubstituted arylthioxy group; Substituted or unsubstituted alkenyl group; Substituted or unsubstituted silyl group; Substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; Substituted or unsubstituted arylamine group; Substituted or unsubstituted heteroarylamine group; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroring group.

Examples of the substituents are described below, but are not limited thereto.

The term "substituted" means that a hydrogen atom bonded to a carbon atom of the compound is replaced with another substituent, and the position to be substituted is not limited to a position where the hydrogen atom is substituted, that is, a position where a substituent can be substituted, if two or more substituted , Two or more substituents may be the same or different from each other.

As used herein, the term "substituted or unsubstituted" is deuterium; Halogen group; Nitrile group; Nitro group; Imide group; Amide group; Hydroxyl group; Substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted alkoxy group; Substituted or unsubstituted aryloxy group; Substituted or unsubstituted alkylthioxy group; Substituted or unsubstituted arylthioxy group; Substituted or unsubstituted alkyl sulfoxy group; Substituted or unsubstituted aryl sulfoxy group; Substituted or unsubstituted alkenyl group; Substituted or unsubstituted silyl group; Substituted or unsubstituted boron group; Substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; Substituted or unsubstituted arylamine group; Substituted or unsubstituted heteroarylamine group; Substituted or unsubstituted aryl group; And it means substituted or unsubstituted with one or more substituents selected from the group consisting of a substituted or unsubstituted heterocyclic group.

In the present specification, the halogen group may be fluorine, chlorine, bromine or iodine.

In this specification, although carbon number of an imide group is not specifically limited, It is preferable that it is C1-C25. Specifically, it may be a compound having a structure as follows, but is not limited thereto.

In the present specification, the amide group may be substituted with one or two of the nitrogen of the amide group is hydrogen, a linear, branched or cyclic alkyl group having 1 to 25 carbon atoms or an aryl group having 6 to 25 carbon atoms. Specifically, it may be a compound of the following structural formula, but is not limited thereto.

In the present specification, the alkyl group may be linear or branched chain, carbon number is not particularly limited, but is preferably 1 to 50. Specific examples include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl , Isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n -Heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethyl Heptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, and the like.

In the present specification, the cycloalkyl group is not particularly limited, but preferably 3 to 60 carbon atoms, specifically, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like, but are not limited thereto. Do not.

In the present specification, the alkoxy group may be linear, branched or cyclic. Although carbon number of an alkoxy group is not specifically limited, It is preferable that it is C1-C20. Specifically, methoxy, ethoxy, n-propoxy, isopropoxy, i-propyloxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, Isopentyloxy, n-hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, benzyloxy, p-methylbenzyloxy and the like It may be, but is not limited thereto.

In the present specification, the alkenyl group may be linear or branched chain, the carbon number is not particularly limited, but is preferably 2 to 40. Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1- Butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2- ( Naphthyl-1-yl) vinyl-1-yl, 2,2-bis (diphenyl-1-yl) vinyl-1-yl, stilbenyl group, styrenyl group and the like, but are not limited thereto.

In the present specification, specifically, the silyl group includes trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, phenylsilyl group, and the like. However, the present invention is not limited thereto.

In the present specification, the aryl group may be a monocyclic aryl group or a polycyclic aryl group, and may include a case where a substituent such as an alkyl group having 1 to 25 carbon atoms and an alkoxy group having 1 to 25 carbon atoms is further substituted. In addition, the aryl group in the present specification may mean an aromatic ring.

When the aryl group is a monocyclic aryl group, carbon number is not particularly limited, but preferably 6 to 25 carbon atoms. Specifically, the monocyclic aryl group may be a phenyl group, a biphenyl group, a terphenyl group, etc., but is not limited thereto.

Carbon number is not particularly limited when the aryl group is a polycyclic aryl group. It is preferable that it is C10-24. Specifically, the polycyclic aryl group may be a naphthyl group, anthracenyl group, phenanthryl group, pyrenyl group, perylenyl group, chrysenyl group, fluorenyl group, and the like, but is not limited thereto.

In the present specification, the fluorenyl group may be substituted, and adjacent substituents may be bonded to each other to form a ring.

,

,

및

등이 될 수 있다. 다만, 이에 한정되는 것은 아니다.When the fluorenyl group is substituted,

,

,

And

And so on. However, the present invention is not limited thereto.

In the present specification, the heterocyclic group includes one or more atoms other than carbon and hetero atoms, and specifically, the hetero atoms may include one or more atoms selected from the group consisting of O, N, and S, and the like. Although carbon number of a heterocyclic group is not specifically limited, It is preferable that it is C2-C60. Examples of heterocyclic groups include thiophene group, furan group, pyrrole group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, bipyridyl group, pyrimidyl group, triazine group, triazole group, Acridyl group, pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidinyl group, pyrido pyrazinyl group, pyrazino pyrazinyl group, isoquinoline group , Indole group, carbazole group, benzoxazole group, benzimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group (phenanthroline), thiazolyl group, Isooxazolyl group, oxdiazolyl group, thiadiazolyl group, benzothiazolyl group, phenothiazinyl group, dibenzofuranyl group and the like, but is not limited thereto.

The heterocyclic group may be monocyclic or polycyclic, and may be aromatic, aliphatic or a condensed ring of aromatic and aliphatic.

In the present specification, examples of the arylamine group include a substituted or unsubstituted monoarylamine group, a substituted or unsubstituted diarylamine group, or a substituted or unsubstituted triarylamine group. The aryl group in the arylamine group may be a monocyclic aryl group, may be a polycyclic aryl group. The arylamine group including two or more aryl groups may simultaneously include a monocyclic aryl group, a polycyclic aryl group, or a monocyclic aryl group and a polycyclic aryl group.

Specific examples of the aryl amine group include phenylamine, naphthylamine, biphenylamine, anthracenylamine, 3-methyl-phenylamine, 4-methyl-naphthylamine, 2-methyl-biphenylamine, 9-methyl-anthra Cenylamine, diphenyl amine group, phenyl naphthyl amine group, ditolyl amine group, phenyl tolyl amine group, carbazole and triphenyl amine group and the like, but are not limited thereto.

In the present specification, the heteroaryl group in the heteroarylamine group may be selected from the examples of the heterocyclic group described above.

In the present specification, the aryl group in the aryloxy group, arylthioxy group, and aralkylamine group is the same as the example of the aryl group described above. Specifically, as the aryloxy group, phenoxy, p-tolyloxy, m-tolyloxy, 3,5-dimethyl-phenoxy, 2,4,6-trimethylphenoxy, p-tert-butylphenoxy, 3-biphenyl Oxy, 4-biphenyloxy, 1-naphthyloxy, 2-naphthyloxy, 4-methyl-1-naphthyloxy, 5-methyl-2-naphthyloxy, 1-anthryloxy, 2-anthryl Oxy, 9-anthryloxy, 1-phenanthryloxy, 3-phenanthryloxy, 9-phenanthryloxy, and the like. Examples of the arylthioxy group include a phenylthioxy group, 2-methylphenylthioxy group, and 4-tert-butylphenyl. Thioxy group and the like, but is not limited thereto.

In this specification, the alkyl group in the alkylthioxy group is the same as the example of the alkyl group mentioned above. Specifically, the alkyl thioxy group includes a methyl thioxy group, an ethyl thioxy group, a tert-butyl thioxy group, a hexyl thioxy group, an octyl thioxy group, and the like, but is not limited thereto.

The arylene group and the heteroarylene group of the present specification mean two divalent groups having two bonding positions, respectively, in the aryl group and the heteroaryl group. The description of the aryl group and heterocyclic group described above can be applied except that they are each divalent.

In one embodiment of the present specification, L is a direct bond or a phenylene group.

In one embodiment L is a direct bond.

In another exemplary embodiment, L is a phenylene group.

In one embodiment of the present specification, L is a phenylene group, and there is a bonding position in a para position.

In one embodiment of the present specification, A is a direct bond.

In another embodiment, A is C = O.

In one embodiment of the present specification, R1 is hydrogen.

이다. In one embodiment of the present specification, at least one of X, Y and Z is

to be.

이다. In another embodiment, at least one of X, Y and Z is

to be.

이다. In another embodiment, at least one of X, Y and Z is

to be.

In one embodiment of the present specification, the remainder other than Formula 2 in X, Y, and Z is a substituted or unsubstituted aryl group.

In one embodiment of the present specification, the remainder other than Formula 2 in X, Y, and Z is a substituted or unsubstituted phenyl group.

In one embodiment, the remaining non-formula 2 of X, Y and Z is a phenyl group.

In one embodiment of the present specification, L1 is a substituted or unsubstituted arylene group.

In one embodiment, L1 is a substituted or unsubstituted biphenylylene group.

In one embodiment, L1 is a biphenylylene group.

이다. In another embodiment, L1 is

to be.

In one embodiment of the present specification, R2 and R3 are the same as or different from each other, and are each independently a substituted or unsubstituted aryl group.

In one embodiment of the present specification, R2 is a substituted or unsubstituted aryl group.

In another embodiment, R2 is a substituted or unsubstituted phenyl group.

In another embodiment, R2 is a phenyl group.

In one embodiment of the present specification, R2 is a substituted or unsubstituted naphthyl group.

In another embodiment, R2 is a naphthyl group.

이다. In one embodiment of the present specification, R2 is

to be.

In another embodiment, R3 is a substituted or unsubstituted phenyl group.

In another embodiment, R3 is a phenyl group.

In one embodiment of the present specification, R3 is a substituted or unsubstituted naphthyl group.

In another embodiment, R3 is a naphthyl group.

이다. In one embodiment of the present specification, R3 is

to be.

In one embodiment of the present specification, L2 is a substituted or unsubstituted arylene group.

In another embodiment, L2 is a substituted or unsubstituted phenylene group.

In another exemplary embodiment, L2 is a phenylene group.

In one embodiment of the present specification, L2 is a phenylene group, and there is a bonding position at a para position.

In one embodiment of the present specification, R4 is a substituted or unsubstituted aryl group.

In another exemplary embodiment, R4 is a substituted or unsubstituted phenyl group.

In one embodiment of the present specification, R4 is a phenyl group.

In one embodiment of the present specification, R5 is hydrogen.

In one embodiment of the present specification, L3 is a substituted substituted or unsubstituted arylene group.

In another embodiment, L3 is a substituted or unsubstituted phenylene group.

In another exemplary embodiment, L3 is a phenylene group.

In one embodiment of the present specification, L3 is a phenylene group, and there is a bonding position at a para position.

In one embodiment of the present specification, R6 is a substituted or unsubstituted aryl group.

In another exemplary embodiment, R6 is a substituted or unsubstituted phenyl group.

In one embodiment of the present specification, R6 is a phenyl group.

In one embodiment of the present specification, R7 is hydrogen.

In one embodiment of the present specification, R8 is hydrogen.

In one embodiment of the present specification, the compound represented by Chemical Formula 1 is represented by any one of the following Chemical Formulas 1-1 to 1-14.

In one embodiment of the present specification, the n-type organic compound layer includes a compound of Formula 3 below.

 [Formula 3]

R10 to R15 are the same as or different from each other, and each independently hydrogen; Halogen group; Nitrile group (-CN); Nitro group (-NO ₂ ); Sulfonyl group (-SO ₂ R); Sulfoxide group (-SOR); Sulfonamide groups (-SO ₂ NR ₂ ); Sulfonate groups (-SO ₃ R); Trifluoromethyl group (-CF ₃ ); Ester group (-COOR); Amide groups (-CONHR or -CONRR '); Substituted or unsubstituted linear or branched C1-C12 alkoxy group; Substituted or unsubstituted linear or branched C1 to C12 alkyl group; Substituted or unsubstituted linear or branched C2 to C12 alkenyl group; Substituted or unsubstituted aromatic or non-aromatic heterocyclic group; Substituted or unsubstituted aryl group; Substituted or unsubstituted mono- or di-arylamine group; And it is selected from the group consisting of a substituted or unsubstituted aralkylamine group,

R and R 'are the same as or different from each other, and each independently a substituted or unsubstituted C1 to C60 alkyl group; Substituted or unsubstituted aryl group; And it is selected from the group consisting of a substituted or unsubstituted 5 to 7 membered heterocyclic group.

In one embodiment of the present specification, R10 to R15 are the same as or different from each other, and each independently a nitrile group; Sulfonyl group; Nitro group; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted alkenyl group.

In one embodiment of the present specification, R10 to R15 are the same as or different from each other, and each independently a nitrile group; Sulfonyl groups substituted with aryl groups; Nitro group; Aryl groups substituted with nitro or nitrile groups; Or an alkenyl group substituted with a nitrile group.

In one embodiment of the present specification, R10 is a nitrile group.

In another exemplary embodiment, R10 is a sulfonyl group (-SO ₂ R).

In one embodiment of the present specification, R10 is a nitro group.

In another exemplary embodiment, R10 is a substituted or unsubstituted aryl group.

In one embodiment of the present specification, R10 is an aryl group which is substituted with a nitro group.

In another exemplary embodiment, R10 is a phenyl group substituted with a nitro group.

In one embodiment of the present specification, R10 is an aryl group which is substituted with a nitrile group.

In another exemplary embodiment, R10 is a phenyl group substituted with a nitrile group.

In one embodiment of the present specification, R10 is a substituted or unsubstituted alkenyl group.

In another exemplary embodiment, R10 is an alkenyl group substituted with a nitrile group.

In one embodiment of the present specification, R11 is a nitrile group.

In another exemplary embodiment, R11 is a sulfonyl group (-SO ₂ R).

In one embodiment of the present specification, R11 is a nitro group.

In another exemplary embodiment, R11 is a substituted or unsubstituted aryl group.

In one embodiment of the present specification, R11 is an aryl group which is substituted with a nitro group.

In another exemplary embodiment, R11 is a phenyl group substituted with a nitro group.

In one embodiment of the present specification, R11 is an aryl group which is substituted with a nitrile group.

In another exemplary embodiment, R11 is a phenyl group substituted with a nitrile group.

In one embodiment of the present specification, R11 is a substituted or unsubstituted alkenyl group.

In another exemplary embodiment, R11 is an alkenyl group substituted with a nitrile group.

In one embodiment of the present specification, R12 is a nitrile group.

In another exemplary embodiment, R12 is a sulfonyl group (-SO ₂ R).

In one embodiment of the present specification, R12 is a nitro group.

In another exemplary embodiment, R12 is a substituted or unsubstituted aryl group.

In one embodiment of the present specification, R12 is an aryl group which is substituted with a nitro group.

In another exemplary embodiment, R12 is a phenyl group substituted with a nitro group.

In one embodiment of the present specification, R12 is an aryl group which is substituted with a nitrile group.

In another exemplary embodiment, R12 is a phenyl group substituted with a nitrile group.

In one embodiment of the present specification, R12 is a substituted or unsubstituted alkenyl group.

In another exemplary embodiment, R12 is an alkenyl group substituted with a nitrile group.

In one embodiment of the present specification, R13 is a nitrile group.

In another exemplary embodiment, R13 is a sulfonyl group (-SO ₂ R).

In one embodiment of the present specification, R13 is a nitro group.

In another exemplary embodiment, R13 is a substituted or unsubstituted aryl group.

In one embodiment of the present specification, R13 is an aryl group which is substituted with a nitro group.

In another exemplary embodiment, R13 is a phenyl group substituted with a nitro group.

In one embodiment of the present specification, R13 is an aryl group which is substituted with a nitrile group.

In another exemplary embodiment, R13 is a phenyl group substituted with a nitrile group.

In one embodiment of the present specification, R13 is a substituted or unsubstituted alkenyl group.

In another exemplary embodiment, R13 is an alkenyl group substituted with a nitrile group.

In one embodiment of the present specification, R14 is a nitrile group.

In another exemplary embodiment, R14 is a sulfonyl group (-SO ₂ R).

In one embodiment of the present specification, R14 is a nitro group.

In another exemplary embodiment, R14 is a substituted or unsubstituted aryl group.

In one embodiment of the present specification, R14 is an aryl group which is substituted with a nitro group.

In another exemplary embodiment, R14 is a phenyl group substituted with a nitro group.

In one embodiment of the present specification, R14 is an aryl group which is substituted with a nitrile group.

In another exemplary embodiment, R14 is a phenyl group substituted with a nitrile group.

In one embodiment of the present specification, R14 is a substituted or unsubstituted alkenyl group.

In another exemplary embodiment, R14 is an alkenyl group substituted with a nitrile group.

In one embodiment of the present specification, R15 is a nitrile group.

In another exemplary embodiment, R15 is a sulfonyl group (-SO ₂ R).

In one embodiment of the present specification, R15 is a nitro group.

In another exemplary embodiment, R15 is a substituted or unsubstituted aryl group.

In one embodiment of the present specification, R15 is an aryl group which is substituted with a nitro group.

In another exemplary embodiment, R15 is a phenyl group substituted with a nitro group.

In one embodiment of the present specification, R15 is an aryl group which is substituted with a nitrile group.

In another exemplary embodiment, R15 is a phenyl group substituted with a nitrile group.

In one embodiment of the present specification, R15 is a substituted or unsubstituted alkenyl group.

In another exemplary embodiment, R15 is an alkenyl group substituted with a nitrile group.

In one embodiment of the present specification, R is a substituted or unsubstituted aryl group.

In another embodiment, R is a phenyl group.

In one embodiment of the present specification, the n-type organic compound layer represented by Chemical Formula 3 is represented by any one of the following Chemical Formulas 3-1 to 3-6.

In one embodiment of the present specification, the p-type organic compound layer may generally use a material of a hole transport material.

In one embodiment of the present specification, the p-type organic compound layer is an aromatic amine group; Ditoliamine group; Aromatic aniline groups; Indolo acridine groups; And one or more substituents selected from the group consisting of aromatic silane groups. In one embodiment of the present specification, the p-type organic compound layer may use an arylamine-based compound. In one embodiment, the p-type organic compound layer may use the following NPB.

[NPB]

In another exemplary embodiment, the p-type organic compound layer may use TAPC (1,1-bis- (4-bis (4-methyl-phenyl) -amino-phenyl) -cyclohexane), TAPC, and the like. Metal oxides having a Fermi level of 4.5 eV or more, such as p-type dopants such as molybdenum oxide (MoO _x ), rhenium oxide (ReO _x ), tungsten oxide (WO _x ), etc. ) Or a layer doped with a transition metal complex may be used, but is not limited thereto.

The organic light emitting device according to the present specification may be a top emission type, a bottom emission type, or a double side emission type according to a material used.

In addition, the organic light emitting diode according to the present disclosure may be a normal type in which the lower electrode is an anode and the upper electrode is a cathode, or may be an inverted type in which the lower electrode is a cathode and the upper electrode is an anode.

In an exemplary embodiment of the present specification, the substrate further includes a substrate provided on a surface opposite to the surface on which the organic material layer of the anode is provided, and further includes an internal light extraction layer provided between the substrate and the anode.

In another exemplary embodiment, the apparatus may further include a substrate provided on a surface of the anode facing the surface on which the organic material layer is provided, and further include an external light extracting layer on a surface of the substrate facing the surface of the anode. .

In one embodiment of the present specification, the internal light extraction layer includes a flat layer.

In another exemplary embodiment, the external light extraction layer includes a flat layer.

According to one embodiment of the present specification, the internal light scattering layer or the external light extracting layer is not particularly limited so long as it has a structure that can induce light scattering and improve the light extraction efficiency of the organic light emitting device. Specifically, according to one embodiment of the present specification, the light extraction layer may have a structure in which scattering particles are dispersed in a binder.

According to one embodiment of the present specification, the light scattering layer may be directly formed on the substrate by a method such as spin coating, bar coating, slit coating, or the like, and may be formed by attaching the film.

According to an exemplary embodiment of the present specification, the organic light emitting device may be a flexible organic light emitting device. In this case, the substrate may comprise a flexible material. Specifically, the substrate may be a glass, plastic substrate, or film substrate in the form of a thin film that can be bent.

The material of the plastic substrate is not particularly limited, but generally, a film such as PET, PEN, PEEK, and PI may be included in the form of a single layer or a multilayer.

An exemplary embodiment of the present specification provides a display device including the organic light emitting device. In the display device, the organic light emitting diode may serve as a pixel or a backlight. In addition, the configuration of the display device may be applied to those known in the art.

One embodiment of the present specification provides a lighting device including the organic light emitting device. In the lighting device, the organic light emitting diode serves as a light emitting unit. In addition, the configurations required for the lighting device may be applied to those known in the art.

The structure according to the exemplary embodiment of the present specification may act on a principle similar to that applied to an organic light emitting device in an organic electronic device including an organic solar cell, an organic photoconductor, and an organic transistor.

The organic light emitting device of the present specification may be manufactured by materials and methods known in the art, except for including the aforementioned charge generating layer.

For example, the organic light emitting device of the present specification may be manufactured by sequentially stacking an anode, an organic material layer, and a cathode on a substrate. At this time, the anode is formed by depositing a metal or conductive metal oxide or an alloy thereof on the substrate by using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation. And an organic material layer including a hole injection layer, a hole transporting layer, a light emitting layer, and an electron transporting layer thereon, and then depositing a material that can be used as a cathode thereon. In addition to the above method, an organic light emitting device may be manufactured by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate.

In addition, according to one embodiment of the present specification, the organic material layer is a solvent process (e.g., spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer method) using various polymer materials instead of a deposition method. It is possible to produce a smaller number of layers by such a method.

The organic material layer of the organic light emitting device of the present specification may have a multilayer structure in which two or more organic material layers are stacked.

In the present specification, the substrate may be a glass substrate or a transparent plastic substrate having excellent transparency, surface smoothness, ease of handling, and waterproofness, but is not limited thereto. The substrate is not limited as long as it is a substrate commonly used in organic light emitting devices.

As the anode material, a material having a large work function is generally preferred to facilitate hole injection into the organic material layer. Specific examples of the positive electrode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc and gold or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO); ZnO: Al or SNO ₂ : Combination of metals and oxides such as Sb; Conductive polymers such as poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDOT), polypyrrole and polyaniline, and the like, but are not limited thereto.

The cathode material is generally a material having a small work function to facilitate electron injection into the organic material layer. Specific examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead or alloys thereof; Multilayer structure materials such as LiF / Al or LiO ₂ / Al, and the like, but are not limited thereto.

The cathode may be formed of the same material as the anode. In this case, the cathode may be formed of the above-described anode materials. Or the cathode or anode may comprise a transparent material.

The hole injection material is a layer for injecting holes from an electrode, and the hole injection material has a capability of transporting holes, and has a hole injection effect at an anode, an excellent hole injection effect with respect to a light emitting layer or a light emitting material, and is generated in a light emitting layer. The compound which prevents the movement of the excited excitons to the electron injection layer or the electron injection material, and is excellent in thin film formation ability is preferable. Preferably, the highest occupied molecular orbital (HOMO) of the hole injection material is between the work function of the positive electrode material and the highest occupied molecular orbital (HOMO) of the surrounding organic material layer. Specific examples of the hole injection material include metal porphyrin, oligothiophene, arylamine-based organic material, hexanitrile hexaazatriphenylene-based organic material, quinacridone-based organic material, and perylene-based Organic materials, anthraquinone, and polyaniline and polythiophene-based conductive polymers, but are not limited thereto.

The hole transport layer is a layer that receives holes from the hole injection layer and transports holes to the light emitting layer. As a hole transport material, the hole transport material is a material capable of transporting holes from the anode or the hole injection layer to the light emitting layer. The material is suitable. Specific examples thereof include an arylamine-based organic material, a conductive polymer, and a block copolymer having a conjugated portion and a non-conjugated portion together, but are not limited thereto.

In the light emitting layer, since the hole transfer and the electron transfer occur at the same time, the light emitting layer may have both n-type characteristics and p-type characteristics. For convenience, it may be defined as an n-type light emitting layer when electron transport is faster than hole transport, and a p-type light emitting layer when hole transport is faster than electron transport.

The light emitting material is a material capable of emitting light in the visible region by transporting and combining holes and electrons from the hole transport layer and the electron transport layer, respectively, and a material having good quantum efficiency with respect to fluorescence or phosphorescence is preferable. Specific examples thereof include 8-hydroxyquinoline aluminum complex (Alq ₃ ); Carbazole series compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzoquinoline-metal compound; Benzoxazole, benzthiazole and benzimidazole series compounds; Poly (p-phenylenevinylene) (PPV) -based polymers; Spiro compounds; Polyfluorene, rubrene and the like, but are not limited thereto.

The light emitting layer may include a host material and a dopant material. The host material is a condensed aromatic ring derivative or a heterocyclic containing compound. Specifically, the condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, and fluoranthene compounds, and the heterocyclic containing compounds include carbazole derivatives, dibenzofuran derivatives and ladder types. Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.

Dopant materials include organic compounds, metals or metal compounds.

Organic compounds as dopant materials include aromatic amine derivatives, styrylamine compounds, boron complexes, fluoranthene compounds and the like. Specifically, the aromatic amine derivatives include condensed aromatic ring derivatives having a substituted or unsubstituted arylamino group, and include pyrene, anthracene, chrysene, and periplanthene having an arylamino group, and a styrylamine compound may be substituted or unsubstituted. At least one arylvinyl group is substituted with the substituted arylamine, and one or two or more substituents selected from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group and an arylamino group are substituted or unsubstituted. Specifically, styrylamine, styryldiamine, styryltriamine, styryltetraamine and the like, but is not limited thereto. In addition, as the metal or the metal compound, a general metal or a metal compound may be used, and specifically, a metal complex may be used. The metal complex includes, but is not limited to, an iridium complex, a platinum complex, and the like.

The electron transporting material is a layer that receives electrons from the electron injection layer and transports electrons to the light emitting layer. The electron transporting material is a material that can inject electrons well from the cathode and move them to the light emitting layer. This is suitable. Specific examples thereof include Al complexes of 8-hydroxyquinoline; Complexes including Alq ₃ ; Organic radical compounds; Hydroxyflavone-metal complexes and the like, but are not limited thereto. The electron transport layer can be used with any desired cathode material as used in accordance with the prior art. In particular, examples of suitable cathode materials are conventional materials having a low work function followed by an aluminum or silver layer. Specifically cesium, barium, calcium, ytterbium and samarium, followed by aluminum layers or silver layers in each case.

The electron injection layer is a layer that injects electrons from an electrode, has an ability of transporting electrons, has an electron injection effect from a cathode, an electron injection effect with respect to a light emitting layer or a light emitting material, and hole injection of excitons generated in the light emitting layer The compound which prevents the movement to a layer and is excellent in thin film formation ability is preferable. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone and the like and derivatives thereof, metal Complex compounds, nitrogen-containing five-membered ring derivatives, and the like, but are not limited thereto.

Examples of the metal complex compound include 8-hydroxyquinolinato lithium, bis (8-hydroxyquinolinato) zinc, bis (8-hydroxyquinolinato) copper, bis (8-hydroxyquinolinato) manganese, Tris (8-hydroxyquinolinato) aluminum, tris (2-methyl-8-hydroxyquinolinato) aluminum, tris (8-hydroxyquinolinato) gallium, bis (10-hydroxybenzo [h] Quinolinato) beryllium, bis (10-hydroxybenzo [h] quinolinato) zinc, bis (2-methyl-8-quinolinato) chlorogallium, bis (2-methyl-8-quinolinato) ( o-cresolato) gallium, bis (2-methyl-8-quinolinato) (1-naphtolato) aluminum, bis (2-methyl-8-quinolinato) (2-naphtolato) gallium, It is not limited to this.

The hole blocking layer is a layer for blocking the arrival of the cathode of the hole, and may be generally formed under the same conditions as the hole injection layer. Specifically, there are oxadiazole derivatives, triazole derivatives, phenanthroline derivatives, BCP, aluminum complexes, and the like, but are not limited thereto.

The present invention will be described in more detail with reference to the following examples. However, the following examples are only intended to illustrate the invention, and are not intended to limit the scope of the invention by the examples.

Example  One.

The device was configured to include a charge generating layer as follows.

Device structure: ITO / NPB / Chemical Formula 3-1 / Chemical Formula 1-1 / ETL / Al

4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (NPB) (500 Pa) of the chemical formula was vacuum deposited on the ITO electrode (1300 Pa) to form a p-type organic compound layer. . An n-type organic compound layer of Formula 3-1 (200 kPa) was formed on the p-type organic compound layer. In addition, an intermediate layer (1 nm) of Formula 1-1 was formed, and an electron transport layer (250 Hz) was formed of BCP. Finally the cathode consisted of aluminum (1000 kPa).

In the above process, the deposition rate of the organic material was maintained at 0.5 ~ 1 Å / sec, the aluminum was maintained at a deposition rate of 1 Å / sec, the vacuum during deposition was maintained at 2 × 10 ^-7 ~ 4 × 10 ^-8 torr Thus, an organic light emitting device was produced.

[Formula 3-1]

[NPB]

[BCP]

Example  2.

A device was manufactured in the same manner as in Example 1, except that the thickness of the intermediate layer was 3 nm.

Example  3.

A device was manufactured in the same manner as in Example 1, except that the thickness of the intermediate layer was 5 nm.

Example  4.

A device was manufactured in the same manner as in Example 1, except that the thickness of the intermediate layer was 10 nm.

Comparative example  One.

A device was manufactured in the same manner as in Example 1, except that the intermediate layer was not present.

4 is a diagram illustrating a voltage-current graph of the organic light emitting diodes of Examples 1 to 4 and Comparative Example 1. FIG.

Example  5.

In Example 1, Li was used as the n-type dopant in the electron transport layer, and the device was manufactured in the same manner as in Example 1 except that the concentration of the dopant was 1%.

Comparative example  2.

A device was manufactured in the same manner as in Example 5, except that there was no intermediate layer in Example 5.

Comparative example  3.

The device was manufactured in the same manner as in Example 5, except that the concentration of the n-type dopant was set to 7% in Example 5, and the intermediate layer was not included.

5 is a diagram showing voltage-current of organic light emitting diodes of Example 5, Comparative Examples 2 and 3. FIG.

101: anode
201: cathode
301 and 302: light emitting unit
401: charge generating layer
501: middle layer
601: n-type organic compound layer
701: p-type organic compound layer
801: electron transport layer doped with n-type dopant

Claims (20)

Cathode;
An anode provided opposite the cathode;
Two or more light emitting units provided between the cathode and the anode; And
A charge generation layer provided between at least two light emitting units adjacent to each other among the two or more light emitting units,
The charge generating layer includes a p-type organic compound layer, an n-type organic compound layer and an intermediate layer,
The intermediate layer is an organic light emitting device comprising a compound represented by the following formula (1):
[Formula 1]

In Chemical Formula 1,
At least one of X, Y and Z is represented by the following formula (2),
Among X, Y and Z, a group other than Formula 2 may be a substituted or unsubstituted aryl group; Or a substituted or unsubstituted nitrogen-containing heterocyclic group,
[Formula 2]

In Chemical Formula 2,
L is a direct bond; Substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,
A is a direct bond; Or C = O,
a is an integer from 1 to 7,
when a is 2 or more, two or more R1 are the same as or different from each other,
R 1 is hydrogen; heavy hydrogen; Halogen group; Nitrile group; Nitro group; Imide group; Amide group; Hydroxyl group; Substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted alkoxy group; Substituted or unsubstituted aryloxy group; Substituted or unsubstituted alkylthioxy group; Substituted or unsubstituted arylthioxy group; Substituted or unsubstituted alkenyl group; Substituted or unsubstituted silyl group; Substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; Substituted or unsubstituted arylamine group; Substituted or unsubstituted heteroarylamine group; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroring group. The method according to claim 1,
The p-type organic compound layer is provided closer to the anode than the intermediate layer,
The intermediate layer is provided closer to the cathode than the p-type organic compound layer,
The n-type organic compound layer is provided between the p-type organic compound layer and the intermediate layer. The method according to claim 1,
At least one of X, Y and Z is any one of the following substituents:

In the substituent,
L1 to L3 are the same as or different from each other, and each independently a direct bond; Substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,
R2 and R3 are the same as or different from each other, and each independently a substituted or unsubstituted aryl group; Substituted or unsubstituted heterocyclic group; Or Formula 2,
b is an integer from 1 to 7,
c is an integer of 1 to 3,
d is an integer of 1 to 6,
when b is 2 or more, two or more R5 are the same or different from each other,
when c is 2 or more, two or more R 7 are the same as or different from each other,
when d is 2 or more, two or more R8 are the same or different from each other,
R4 to R8 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; Nitrile group; Nitro group; Imide group; Amide group; Hydroxyl group; Substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted alkoxy group; Substituted or unsubstituted aryloxy group; Substituted or unsubstituted alkylthioxy group; Substituted or unsubstituted arylthioxy group; Substituted or unsubstituted alkenyl group; Substituted or unsubstituted silyl group; Substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; Substituted or unsubstituted arylamine group; Substituted or unsubstituted heteroarylamine group; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroring group. The method according to claim 1,
The compound represented by Chemical Formula 1 is represented by any one of the following Chemical Formulas 1-1 to 1-14.

The method according to claim 1,
The n-type organic compound layer is an organic light emitting device comprising a compound of the formula
[Formula 3]

R10 to R15 are the same as or different from each other, and each independently hydrogen; Halogen group; Nitrile group (-CN); Nitro group (-NO ₂ ); Sulfonyl group (-SO ₂ R); Sulfoxide group (-SOR); Sulfonamide groups (-SO ₂ NR ₂ ); Sulfonate groups (-SO ₃ R); Trifluoromethyl group (-CF ₃ ); Ester group (-COOR); Amide groups (-CONHR or -CONRR '); Substituted or unsubstituted linear or branched C1-C12 alkoxy group; Substituted or unsubstituted linear or branched C1 to C12 alkyl group; Substituted or unsubstituted linear or branched C2 to C12 alkenyl group; Substituted or unsubstituted aromatic or non-aromatic heterocyclic group; Substituted or unsubstituted aryl group; Substituted or unsubstituted mono- or di-arylamine group; And it is selected from the group consisting of a substituted or unsubstituted aralkylamine group,
R and R 'are the same as or different from each other, and each independently a substituted or unsubstituted C1 to C60 alkyl group; Substituted or unsubstituted aryl group; And it is selected from the group consisting of a substituted or unsubstituted 5 to 7 membered heterocyclic group. The method according to claim 5,
The n-type organic compound layer represented by the formula (3) is an organic light emitting device represented by any one of the following formulas 3-1 to 3-6:

The method according to claim 1,
The thickness of the intermediate layer is 0.5 nm to 10 nm organic light emitting device. The method according to claim 1,
The p-type organic compound layer, the n-type organic compound layer and the intermediate layer is provided in contact with each other. The method according to claim 1,
And the p-type organic compound layer and the n-type organic compound layer to form an NP junction. The method according to claim 1,
The light emitting unit includes a light emitting layer; And
Hole injection layer, hole transport layer. The organic light emitting device further comprises one or two or more layers selected from the group consisting of an electron transport layer, an electron injection layer, an electron blocking layer and a hole blocking layer. The method according to claim 1,
The light emitting unit includes a hole transport layer, a light emitting layer and an electron transport layer,
The electron transport layer is provided in contact with the intermediate layer. The method according to claim 11,
The electron transport layer includes at least two electron transport layer,
The electron transport layer provided in contact with the intermediate layer of the two or more electron transport layer is doped with an n-type dopant. The method according to claim 1,
The organic light emitting device is a hole injection layer, a hole transport layer. The organic light emitting device further comprises one or two or more layers selected from the group consisting of an electron transport layer, an electron injection layer, an electron blocking layer and a hole blocking layer. The method according to claim 1,
Further comprising a substrate provided on the side facing the surface on which the organic layer of the anode is provided,
Organic light emitting device further comprises an internal light extraction layer provided between the substrate and the anode. The method according to claim 14,
The internal light extraction layer is an organic light emitting device comprising a flat layer. The method according to claim 1,
Further comprising a substrate provided on the side facing the surface on which the organic layer of the anode is provided,
Organic light emitting device further comprises an external light extraction layer on a surface of the substrate facing the surface of the anode. The method according to claim 16,
The external light extraction layer is an organic light emitting device comprising a flat layer. The method according to claim 1,
The organic light emitting device is an organic light emitting device that is a flexible organic light emitting device. A display device comprising the organic light emitting device according to any one of claims 1 to 18. An illumination device comprising the organic light emitting device according to any one of claims 1 to 18.

Images