KR102054162B1 - An organic electronic element using compound for organic electronic element, and an electronic device thereof - Google Patents

Abstract

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

Description

Organic electronic device using organic compound and electronic device thereof {AN ORGANIC ELECTRONIC ELEMENT USING COMPOUND FOR ORGANIC ELECTRONIC ELEMENT, AND AN ELECTRONIC DEVICE THEREOF}

The present invention relates to an organic electric device using the compound for organic electric devices and an electronic device thereof.

In general, organic light emitting phenomenon refers to a phenomenon of converting electrical energy into light energy using an organic material. An organic electric device using an organic light emitting phenomenon usually has a structure including an anode, a cathode, and an organic material layer therebetween. The organic layer is often made of a multi-layer structure composed of different materials in order to increase the efficiency and stability of the organic electrical device, for example, it may be made of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer.

Materials used as the organic material layer in the organic electric element may be classified into light emitting materials and charge transport materials such as hole injection materials, hole transport materials, electron transport materials, electron injection materials and the like according to their functions.

The biggest problem for organic electroluminescent devices is lifetime and efficiency. As the display becomes larger, these efficiency and lifetime problems must be solved.

Efficiency, lifespan, and driving voltage are related to each other.As the efficiency increases, the driving voltage decreases relatively, and the crystallization of organic materials due to Joule heating generated during driving decreases as the driving voltage decreases. It shows a tendency to increase the lifetime.

However, simply improving the organic material layer does not maximize the efficiency. This is because long life and high efficiency can be simultaneously achieved when an optimal combination of energy level, T1 value, and intrinsic properties (mobility, interfacial properties, etc.) of each organic material layer is achieved.

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

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

However, in the case of the material used in the hole transport layer, it has a low T1 value because it has to have a low HOMO value, which causes the exciton generated in the light emitting layer to pass to the hole transport layer, resulting in charge unbalance in the light emitting layer. This causes light emission at the hole transport layer interface.

When the light is emitted from the hole transport layer interface, the color purity and efficiency of the organic electric element is lowered and the lifespan is shortened. Therefore, the development of a light emitting auxiliary layer having a high T1 value and a HOMO level between the hole transport layer HOMO energy level and the light emitting layer HOMO energy level is urgently required.

On the other hand, while delaying the diffusion of metal oxide into the organic layer from the anode electrode (ITO), which is one of the causes of shortening the life of the organic electronic device, stable characteristics, that is, high glass transition even for Joule heating generated when driving the device. 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 the property of lowering the uniformity of the surface of the thin film when the device is driven, which has been reported to have a great influence on the device life. In addition, the OLED device is mainly formed by a deposition method, which requires development of a material that can withstand a long time during deposition, that is, a material having strong heat resistance.

In other words, in order to fully exhibit the excellent characteristics of the organic electric device, the materials constituting the organic material layer in the device, such as a hole injection material, a hole transport material, a light emitting material, an electron transport material, an electron injection material, a light emitting auxiliary layer material, etc., are stable and efficient. Supported by the material should be preceded, but development of a stable and efficient organic material layer for an organic electric device has not been made yet. Therefore, the development of new materials is continuously required, and in particular, the development of the light emitting auxiliary layer and the material combination of the light emitting layer is urgently required.

An object of the present invention is to provide an organic electric element and its electronic device capable of improving the high luminous efficiency, low driving voltage, high heat resistance, color purity and lifetime of the device.

In one aspect, the present invention provides an organic electronic device and its electronic device, the organic electronic device includes a first electrode, a second electrode, and an organic material layer positioned between the first electrode and the second electrode, The organic material layer includes a hole transport layer, a light emitting auxiliary layer and a light emitting layer, wherein the light emitting auxiliary layer is positioned between the hole transport layer and the light emitting layer and includes a compound represented by Formula (1), and the light emitting layer is represented by Formulas (2) to ( 4) Provides an organic electric device comprising at least one of the compounds represented.

Formula (1) Formula (2)

Formula (3) Formula (4)

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 life of the device can be greatly improved.

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

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings.

In adding reference numerals to the components of each drawing, it should be noted that the same reference numerals are used to refer to the same components as much as possible, even if displayed on different drawings. In addition, in describing the present invention, if it is determined that the detailed description of the related well-known configuration or function may obscure the gist of the present invention, the detailed description thereof will be omitted.

In addition, in describing the component of this invention, terms, such as 1st, 2nd, A, B, (a), (b), can be used. These terms are only for distinguishing the components from other components, and the nature, order or order of the components are not limited by the terms. If a component is described as being "connected", "coupled" or "connected" to another component, that component may be directly connected to or connected to that other component, but there may be another configuration between each component. It is to be understood that the elements may be "connected", "coupled" or "connected".

As used in this specification and the appended claims, unless otherwise indicated, the meanings of the following terms are as follows:

As used herein, the term "halo" or "halogen" is fluorine (F), bromine (Br), chlorine (Cl) or iodine (I) unless otherwise indicated.

As used herein, the term "alkyl" or "alkyl group" has a single bond of 1 to 60 carbon atoms, unless otherwise specified, and is a straight chain alkyl group, branched chain alkyl group, cycloalkyl (alicyclic) group, alkyl-substituted cyclo Radicals of saturated aliphatic functional groups, including alkyl groups, cycloalkyl-substituted alkyl groups.

As used herein, the term "haloalkyl group" or "halogenalkyl group" means an alkyl group substituted with halogen unless otherwise specified.

As used herein, the term "heteroalkyl group" means that at least one of the carbon atoms constituting the alkyl group has been replaced with a heteroatom.

As used herein, the term "alkenyl group" or "alkynyl group", unless stated otherwise, has a double or triple bond of 2 to 60 carbon atoms, and includes a straight or branched chain group, and is not limited thereto. It is not.

The term "cycloalkyl" as used herein, unless otherwise indicated, refers to alkyl forming a ring having 3 to 60 carbon atoms, without being limited thereto.

As used herein, the term "alkoxyl group," "alkoxy group," or "alkyloxy group" means an alkyl group to which an oxygen radical is attached, and unless otherwise specified, has a carbon number of 1 to 60, and is limited herein. It is not.

As used herein, the term "alkenoxyl group", "alkenyloxy group", "alkenyloxyl group", or "alkenyloxy group" means an alkenyl group to which an oxygen radical is attached, and unless otherwise stated, 2 to 60 It has carbon number of, It is not limited to this.

As used herein, the term "aryloxyl group" or "aryloxy group" means an aryl group to which an oxygen radical is attached, and unless otherwise specified, has a carbon number of 6 to 60, but is not limited thereto.

As used herein, the terms "aryl group" and "arylene group" each have a carbon number of 6 to 60 unless otherwise stated, it is not limited thereto. In the present invention, an aryl group or an arylene group means an aromatic of a single ring or multiple rings, and includes an aromatic ring formed by neighboring substituents participating in a bond or a reaction. For example, the aryl group may be a phenyl group, a biphenyl group, a fluorene group, a spirofluorene group.

The prefix "aryl" or "ar" means 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 carbon number described herein.

Also, when prefixes are named consecutively, it means that substituents are listed in the order described 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. Wherein the arylcarbonyl group is a carbonyl group substituted with an aryl group.

As used herein, the term “heteroalkyl” means an alkyl including one or more heteroatoms unless otherwise indicated. As used herein, the term "heteroaryl group" or "heteroarylene group" means an aryl group or arylene group having 2 to 60 carbon atoms, each containing one or more heteroatoms, unless otherwise specified. It may include at least one of a single ring and multiple rings, and may be formed by combining adjacent functional groups.

As used herein, the term “heterocyclic group” includes one or more heteroatoms, unless otherwise indicated, and has from 2 to 60 carbon atoms, and includes at least one of single and multiple rings, heteroaliphatic rings and hetero Aromatic rings. Adjacent functional groups may be formed in combination.

The term "heteroatom" as used herein refers to N, O, S, P or Si unless otherwise stated.

"Heterocyclic groups" may also include rings comprising SO ₂ instead of carbon forming the ring. For example, a "heterocyclic group" includes the following compounds.

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

Unless otherwise stated, the term "saturated or unsaturated ring" as used herein means a saturated or unsaturated aliphatic ring or an aromatic ring or heterocyclic ring having 6 to 60 carbon atoms.

Other heterocompounds or heteroradicals other than the aforementioned heterocompounds include, but are not limited to, one or more heteroatoms.

Unless otherwise stated, the term "carbonyl" used in the present invention is represented by -COR ', where R' is hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, and 3 to 30 carbon atoms. Cycloalkyl group, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, or a combination thereof.

Unless otherwise stated, the term "ether" as used herein is represented by -RO-R ', wherein R or R' are each independently of each other hydrogen, an alkyl group having 1 to 20 carbon atoms, a group having 6 to 30 carbon atoms. It is an aryl group, a C3-C30 cycloalkyl group, a C2-C20 alkenyl group, a C2-C20 alkynyl group, or a combination thereof.

In addition, unless otherwise stated, the term "substituted" in the term "substituted or unsubstituted" is 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, C ₃ ~ C ₂₀ cycloalkyl group, C ₆ ~ C ₂₀ aryl group, of a C ₆ ~ C ₂₀ substituted by deuterium aryl group, a C ₈ ~ C ₂₀ aryl alkenyl group, a silane group, a boron Group, germanium group, and C ₂ ~ C _{20 It} is meant to be substituted with one or more substituents selected from the group consisting of, but not limited to these substituents.

Also, unless otherwise stated, the formulas used in the present invention apply equally to the definitions of substituents based on the exponential definitions of the formula

Herein, when a is an integer of 0, the substituent R ¹ is absent, when a is an integer of 1, one substituent R ¹ is bonded to any one of carbons forming the benzene ring, and a is an integer of 2 or 3 Are each bonded as follows, where R ¹ may be the same or different from each other, and when a is an integer from 4 to 6, it is bonded to the carbon of the benzene ring in a similar manner, while the indication of hydrogen bonded to the carbon forming the benzene ring Is omitted.

1 is an exemplary view of an organic electric device according to an embodiment of the present invention.

Referring to FIG. 1, the organic electric device 100 according to the present invention includes a first electrode 120, a second electrode 180, a first electrode 110, and a second electrode 180 formed on a substrate 110. ) Is provided with an organic material layer containing a compound according to the present invention. In this case, the first electrode 120 may be an anode (anode), the second electrode 180 may be a cathode (cathode), and in the case of an inverted type, the first electrode may be a cathode and the second electrode may be an anode.

The organic layer may include a hole injection layer 130, a hole transport layer 140, a light emitting layer 150, an electron transport layer 160, and an electron injection layer 170 on the first electrode 120 in sequence. At this time, the remaining layers except for the light emitting layer 150 may not be formed. The hole blocking layer, the electron blocking layer, the light emitting auxiliary layer 151, and the buffer layer 141 may be further included, and the electron transport layer 160 may serve as the hole blocking layer.

In addition, although not shown, the organic electronic device according to the present invention may further include a protective layer or a light efficiency improving layer formed on one surface of the at least one surface of the first electrode and the second electrode opposite to the organic material layer.

The compound according to the present invention applied to the organic material layer of the hole injection layer 130, the hole transport layer 140, the electron transport layer 160, the electron injection layer 170, the host of the dopant or light efficiency improving layer of the light emitting layer 150 It may be used as a material. Preferably, the compound of the present invention may be used as the light emitting layer 150 or the light emitting auxiliary layer 151.

Meanwhile, even in the same core, band gaps, electrical characteristics, and interface characteristics may vary depending on which substituents are bonded at which positions, so the selection of cores and the combination of sub-substituents bound thereto are also very significant. Importantly, long life and high efficiency can be achieved at the same time when an optimal combination of energy level and T1 value and intrinsic properties (mobility, interfacial properties, etc.) of each organic material layer is achieved.

As described above, in order to solve the problem of light emission in the hole transport layer in the organic electroluminescent device, it is preferable to form a light emitting auxiliary layer between the hole transport layer and the light emitting layer, and according to each light emitting layer (R, G, B) It is time to develop different emission auxiliary layers. On the other hand, in the case of the light emitting auxiliary layer, it is very difficult to infer its characteristics when the organic material layer used is different even if a similar core is used because the correlation between the hole transport layer and the light emitting layer (host) must be understood.

Therefore, in the present invention, by forming a light emitting layer or an auxiliary light emitting layer using a compound represented by the formula (1) to (4), the energy level (T) and T1 value between each organic material layer, the intrinsic properties (mobility, interface characteristics, etc.) of the material By optimizing, the life and efficiency of the organic electric element can be improved at the same time.

The organic electroluminescent device according to an embodiment of the present invention may be manufactured using a PVD method. For example, the anode 120 is formed by depositing a metal or conductive metal oxide or an alloy thereof on the substrate, and the hole injection layer 130, the hole transport layer 140, the light emitting layer 150, and the electron transport layer are formed thereon. After forming the organic material layer including the 160 and the electron injection layer 170, it can be prepared by depositing a material that can be used as the cathode 180 thereon.

In addition, the organic material layer is a solution or solvent process, such as spin coating process, nozzle printing process, inkjet printing process, slot coating process, dip coating process, roll-to-roll process, doctor blade using various polymer materials It can be produced in fewer layers by methods such as ding process, screen printing process, or thermal transfer method. Since the organic material layer according to the present invention may be formed in various ways, the scope of the present invention is not limited by the forming method.

The organic electric element according to the present invention may be a top emission type, a bottom emission type or a double side emission type according to the material used.

WOLED (White Organic Light Emitting Device) is easy to realize high resolution and excellent in processability, while there is an advantage that can be manufactured using the color filter technology of the existing LCD. Various structures for white organic light emitting devices mainly used as backlight devices have been proposed and patented. Typically, R (Red), G (Green), B (Blue) light emitting parts in a side-by-side parallel arrangement (side-by-side) method, stacking method in which the R, G, B light emitting layer is stacked up and down And a color conversion material (CCM) method using photo-luminescence of an inorganic phosphor by using electroluminescence by a blue (B) organic light emitting layer and light therefrom. May also be applied to such WOLEDs.

In addition, the organic electroluminescent device according to the present invention may be one of an organic electroluminescent device (OLED), an organic solar cell, an organic photoconductor (OPC), an organic transistor (organic TFT), a device for monochrome or white illumination.

Another embodiment of the present invention may include a display device including the organic electric element of the present invention described above, and an electronic device including a control unit for controlling the display device. In this case, the electronic device may be a current or future wired or wireless communication terminal, and includes all electronic devices such as a mobile communication terminal such as a mobile phone, a PDA, an electronic dictionary, a PMP, a remote controller, a navigation device, a game machine, various TVs, and various computers.

Hereinafter, an organic electric device according to an aspect of the present invention will be described.

According to an embodiment of the present invention, in an organic electric device comprising a first electrode, a second electrode, and an organic material layer located between the first electrode and the second electrode,

The organic layer includes a hole transport layer, a light emitting auxiliary layer and a light emitting layer, wherein the light emitting auxiliary layer is located between the hole transport layer and the light emitting layer and comprises a compound represented by the formula (1), the light emitting layer is represented by the formula (2) to An organic electric device comprising at least one of the compounds represented by (4) is provided.

Formula (1) Formula (2)

Formula (3) Formula (4)

In the above formula (1),

으로 표현되며,A is

Represented by

n and z are each independently an integer from 0 to 4,

R ⁰ and R ¹ are each the same as or different from each other when n and z are 2 or more, and iii) each independently deuterium; halogen; C ₆ ~ C ₆₀ aryl group; Fluorenyl groups; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; Fused ring group of an aromatic ring of C ₃ ~ C ₆₀ of aliphatic rings and C ₆ ~ C _60; C ₁ ~ C ₅₀ Alkyl group; C ₂ ~ C ₂₀ Alkenyl group; Alkynyl groups of C ₂ to C ₂₀ ; C ₁ -C ₃₀ alkoxyl group; C ₆ -C ₃₀ aryloxy group; And -L ^a -N (R _a ) (R _b ); (wherein L ^a is a single bond; C ₆ ~ C ₆₀ arylene group; Fluorenylene group; C ₃ ~ C ₆₀ A divalent fused ring group of an aliphatic ring and an aromatic ring of C ₆ to C ₆₀ , and a C ₂ to C ₆₀ divalent hetero ring group including at least one hetero atom of O, N, S, Si, and P; Selected from the group consisting of, R _a and R _b are each independently a C ₆ ~ C ₆₀ aryl group; fluorenyl group; C ₃ ~ C ₆₀ aliphatic ring and C ₆ ~ C ₆₀ aromatic ring fused ring group And C ₂ to C ₆₀ heterocyclic group including at least one heteroatom of O, N, S, Si, and P; or ii) when n and z are 2 or more, R ⁰ groups, or adjacent R ¹ groups, may each combine with each other to form a ring (where a group that does not form a ring is as defined in iii),

L ¹ and L ² are each independently a single bond; C ₆ ~ C ₆₀ arylene group; Fluorenylene groups; Divalent fused ring group of an aromatic ring of C ₃ ~ C ₆₀ of aliphatic rings and C ₆ ~ C _60; And C ₂ ~ C ₆₀ A bivalent heterocyclic group containing at least one heteroatom of O, N, S, Si and P; selected from the group consisting of,

Ar ¹ and Ar ² are each independently ⅰ) a C ₁ ~ C ₂₀ Alkyl group; C ₆ ~ C ₃₀ An aryl group; And a C ₂ -C ₂₀ heterocyclic group including at least one heteroatom of O, N, S, Si, and P; or ii) Ar ¹ and Ar ² are bonded to each other to form a spy; Can form compounds,

Ar ³ and Ar ⁴ are each independently hydrogen; heavy hydrogen; halogen; C ₆ ~ C ₆₀ aryl group; Fluorenyl groups; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; Fused ring group of an aromatic ring of C ₃ ~ C ₆₀ of aliphatic rings and C ₆ ~ C _60; C ₁ ~ C ₅₀ Alkyl group; C ₂ ~ C ₂₀ Alkenyl group; Alkynyl groups of C ₂ to C ₂₀ ; C ₁ -C ₃₀ alkoxyl group; C ₆ -C ₃₀ aryloxy group; And -L ^b -N (R _c ) (R _d ); wherein L ^b , R _c and R _d are the same as the definitions of L ^a , R _a and R _b , respectively,

In formula (2),

a and b are independently of each other an integer of 0 or 1, provided that a + b = 1 or greater,

m is an integer of 1 or 2,

q and o are each independently an integer from 1 to 4,

X and Y are each independently a single bond; S; O; NR ', CR'R "or SiR'R",

R 'and R "are independently of each other hydrogen; C ₆ ~ C ₆₀ aryl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; and C _It is selected from the group consisting of; alkyl group of ₁ ~ C ₅₀ ,

R ² to R ⁴ are each the same as or different from each other when m, o and p are 2 or more, and iii) each independently deuterium; halogen; C ₆ ~ C ₆₀ aryl group; Fluorenyl groups; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; Fused ring group of an aromatic ring of C ₃ ~ C ₆₀ of aliphatic rings and C ₆ ~ C _60; C ₁ ~ C ₅₀ Alkyl group; C ₂ ~ C ₂₀ Alkenyl group; Alkynyl groups of C ₂ to C ₂₀ ; C ₁ -C ₃₀ alkoxyl group; C ₆ -C ₃₀ aryloxy group; And -L ^c -N (R _e ) (R _f ); wherein each is the same as defined above for L ^a , R _a and R _b , or ii) or R ² , R ³ and R ⁴ , when m, o, p is 2 or more, neighboring R ² , neighboring R ³ , or neighboring R ⁴ may be bonded to each other to form a ring (where no ring is formed) Qi is as defined in i)),

L ³ is a single bond; C ₆ ~ C ₆₀ arylene group; A C ₂ to C _{60 divalent} heterocyclic group including at least one hetero atom of O, N, S, Si, or P; And divalent C ₁ to C ₆₀ aliphatic hydrocarbon group;

Ar ⁵ is hydrogen; heavy hydrogen; halogen; C ₆ ~ C ₆₀ aryl group; Fluorenyl groups; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; Fused ring group of an aromatic ring of C ₃ ~ C ₆₀ of aliphatic rings and C ₆ ~ C _60; C ₁ ~ C ₅₀ Alkyl group; C ₂ ~ C ₂₀ Alkenyl group; Alkynyl groups of C ₂ to C ₂₀ ; C ₁ -C ₃₀ alkoxyl group; C ₆ -C ₃₀ aryloxy group; And -L ^d -N (R _g ) (R _h ); wherein L ^d , R _g and R _h are the same as the definitions of L ^a , R _a and R _b , respectively,

In formula (3),

Z ¹ to Z ¹⁶ are independently of each other CR ⁵ or N,

R ⁵ is i) hydrogen; C ₆ ~ C ₆₀ aryl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si, P; C ₁ ~ C ₅₀ Alkyl group; -L ^e -N (R _i ) (R _j ); And a fluorenyl group; wherein L ^e , R _i and R _j are the same as the definitions of L ^a , R _a and R _b , respectively, and ii) adjacent R ⁵ is bonded to each other. Can form a ring (where a group that does not form a ring is as defined in iii),

L ⁴ is a single bond; C ₆ ~ C ₆₀ arylene group; A C ₂ to C _{60 divalent} heterocyclic group including at least one hetero atom of O, N, S, Si, or P; And divalent C ₁ to C ₆₀ aliphatic hydrocarbon group;

W is NAr ⁷ , O or S,

Ar ⁶ and Ar ⁷ are each independently of the other C ₆ ~ C ₆₀ An aryl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si, P; C ₁ ~ C ₅₀ Alkyl group; Fluorenyl groups; And -L ^f -N (R _k ) (R _l ); wherein L ^f , R _k and R _l are the same as the definitions of L ³ , R _a and R _b , respectively,

In formula (4),

R ^{6 to 17} are each independently hydrogen; heavy hydrogen; C ₆ ~ C ₆₀ aryl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si, P; C ₁ ~ C ₅₀ Alkyl group; An alkoxyl group of C ₁ to C ₅₀ ; C ₂ ~ C ₂₀ Alkenyl group; And -L ^g -N (R _m ) (R _n ); wherein L ^g , R _m and R _n are the same as the definitions of L ³ , R _a and R _b , respectively,

The aryl group, fluorenyl group, heterocyclic group, fused ring group, alkyl group, alkenyl group, alkynyl group, alkoxyl group, aryloxy group, arylene group, fluorenyl described in the definition of the formulas (1) to (4) The ethylene group and aliphatic hydrocarbon group are deuterium, halogen, silane group, siloxane group, boron group, germanium group, cyano group, nitro group, -L ⁷ -N (R _i ) (R _j ), where L ⁷ , R _i and R _j are also each as defined the above L ^3, R _a and R _b), C ₁ ~ a C ₂₀ come alkylthio, C ₁ ~ C ₂₀ alkoxy group, C alkyl group of ₁ ~ C _20, C ₂ ~ C ₂₀ of Alkenyl group, C ₂ ~ C ₂₀ Alkynyl group, C ₆ ~ C ₂₀ An aryl group, substituted with a C ₂ ~ C ₂₀ heterocyclic group containing at least one hetero atom of O, N, S, Si, P a C ₆ ~ C ₂₀ aryl group, of a C ₆ ~ C ₂₀ substituted by deuterium aryl group, fluorene group, O, N, S, Si, C ₂ ~ C ₂₀ comprising at least one hetero atom of the P a heterocyclic group, C ₆ ~ C ₂₀ aryl group being substituted in the O, N, S, Si, group at least one heteroatom C ₂ ~ C ₂₀ containing heterocycle of the P, C ₃ ~ C ₂₀ cycloalkyl group, C ₇ ~ arylalkyl group of C ₂₀ and C ₈ ~ C It may be further substituted with one or more substituents selected from the group consisting of ₂₀ arylalkenyl groups.

In another embodiment of the present invention, at least one of the compounds represented by the formula (2) to formula (4) provides an organic electric device, characterized in that the host material of the light emitting layer.

In another embodiment of the present invention, the compound represented by the formula (1) may be any one of the following formulas (5) to (8).

In the above formula, Ar ¹ to Ar ⁴ , L ² , R ⁰ , R ¹ , z and n are the same as Ar ¹ to Ar ⁴ , L ² , R ⁰ , R ¹ , z and n defined in Formula (1) same.

In another embodiment of the present invention, when R ¹ of Formula (1) forms a ring, Formula (1) may be any one of the following Formulas (9) to (12) .

In the above formula, Ar ¹ to Ar ⁴ , z, R ⁰ , L ¹ and L ² are the same as Ar ¹ to Ar ⁴ , z, R ⁰ , L ¹ and L ² defined in the formula (1).

In another embodiment of the present invention, the compounds represented by the formula (1) and formula (5) to formula (8) may be any one of those represented by the following formula independently of each other.

In an embodiment of the present invention, the compound represented by the formula (2) may be any one represented by the following formula.

In another embodiment of the present invention, the compound represented by the formula (3) may be any one represented by the following formula.

In another embodiment of the present invention, the compound represented by the formula (4) may be any one represented by the following formula.

In another embodiment of the present invention, the light emitting auxiliary layer contains a compound represented by Chemical Formula (1), and the light emitting layer is any of the compounds represented by Chemical Formulas (2) to (4) as a host material. The present invention provides an organic electric device comprising a mixture of two.

In another embodiment of the present invention, an organic electric including a light efficiency improving layer on at least one side of the one side of the first electrode opposite to the organic material layer or one side of the second electrode opposite to the organic material layer Provided is an element.

In another embodiment of the present invention, the organic layer provides an organic electroluminescent device, characterized in that 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 do.

In another embodiment of the present invention, in the organic electroluminescent device comprising a first electrode, a second electrode, and an organic material layer positioned between the first electrode and the second electrode, the organic material layer is a hole transport layer, a light emitting auxiliary layer and A light emitting layer, wherein the light emitting auxiliary layer is positioned between the hole transport layer and the light emitting layer and includes a compound represented by Formula (1), and the light emitting layer is at least one of compounds represented by Formulas (2) to (4) Display device including an organic electric element comprising a; And a controller for driving the display device.

The organic electroluminescence device according to another embodiment of the present invention may be at least one of an organic electroluminescent device (OLED), an organic solar cell, an organic photoconductor (OPC), an organic transistor (organic TFT), and a device for monochrome or white illumination. .

Synthesis Example

Synthesis of the compound was carried out in the following manner.

Final product ( Final Product Example of synthesis method

Compounds according to the present invention were prepared by reacting Sub 1 and Sub 2 as shown in Scheme 1 below.

<Scheme 1>

(Ar ¹ to Ar ⁴ , L ² , R ⁰ , R ¹ , z and n are the same as defined respectively in formula (1))

One. Sub  Synthesis Example of 1

Sub 1 of Scheme 1 may be synthesized by, but is not limited to, the following Scheme 2 reaction route.

<Scheme 2>

(Ar ⁴ , L ¹ , R ¹ and n are the same as defined respectively in formula (1))

Sub  1-2 synthetic

Sub 1-1 (1 equiv) was dissolved in DMF in a round bottom flask, then Bis (pinacolato) diboron (1.1 equiv), Pd (dppf) Cl ₂ (0.03 equiv) and KOAc (3 equiv) were added at 90 ° C. Stirred When the reaction was completed, the DMF was removed by distillation and extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ , concentrated, and the resulting compound was subjected to silicagel column and recrystallization to obtain Sub 1-2.

Sub  1 synthetic

Sub 1-2 (1 equiv), IL ¹ -Br compound (1 equiv), Pd (PPh ₃ ) ₄ (0.03 equiv) and K ₂ CO ₃ (3 equiv) were dissolved in anhydrous THF and a small amount of water, It was refluxed for 24 hours. After the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with CH ₂ Cl ₂ , and washed with water. A small amount of water was removed with anhydrous MgSO ₄ , filtered under reduced pressure, and the organic solvent was concentrated and the resulting product was separated using column chromatography to obtain the desired Sub 1.

Examples of Sub 1 are as follows, but are not limited thereto, and their FD-MSs are shown in Table 1 below.

2. Sub  Synthesis Example of 2

Examples of Sub 2 are as follows, but are not limited thereto, and their FD-MS are shown in Table 2 below.

<Scheme 3>

(Ar ¹ to Ar ³ , L ² , R ⁰ , R ¹ , z and n are the same as defined respectively in the formula (1))

Sub  2-2 Synthesis

In a round bottom flask, add 4-bromo-2-hydroxybenzoic acid (200 g, 1159 mmol), potassium carbonate (80 g, 579 mmol), and 1000 mL of DMF and stir. When the mixture is dissolved, methyl iodide (172 g, 1217 mmol) is added dropwise at room temperature, and the reaction is completed after 4.5 hours at room temperature. Extracted with Ether and water, and the organic layer was removed with MgSO ₄ and filtered through silica gel. The filtered organic layer was evaporated and dried in vacuo to yield Sub 2-2 (185 g of colorless crystal (yield: 85.5%)).

Sub  2-3 synthetic

In a round bottom flask, methyl 4-bromo-2-hydroxybenzoate (100 g, 537 mmol) was dissolved in 1000 mL of methylene chloride and triethylamine (113 mL, 805 mmol) was added trifluoromethanesulfonic anhydride (99 mL, 590 mmol) at -78 ° C. After the reaction, the temperature is gradually increased to room temperature, and extracted with water, and the organic layer is extracted with MgSO ₄ and then filtered, and the organic solvent is removed, dissolved with ether, silicagel filter is used to remove the dark color, the solvent is removed, and then vacuum dried. 166 g of Sub 2-3 were obtained (yield: 97.1%).

Sub  2-4 Synthesis

In a round bottom flask, methyl 4-bromo-2-(((trifluoromethyl) sulfonyl) oxy) benzoate (156 g, 492 mmol) and Phenylbronicacid (492 mmol) substituted with (R ⁰ ) _z and Pd (PPh ₃ ) ₄ ( 11 g, 10 mmol) and potassium carbonate (102 g, 738 mmol) were added and 1000 mL of DMF was added and stirred at 110 ° C. After the reaction, the mixture was extracted with ether and water, and the organic layer was removed with MgSO ₄ and filtered. The organic solvent was removed, the silicagel column was separated, the solvent was removed, and then vacuum dried to obtain 96.65 g of Sub 2-4 (yield: 80%).

Sub  2-5 Synthesis

After Sub 2-4 (1 equivalent) obtained in the above synthesis was dissolved in THF, the temperature of the reactant was lowered to -75 ° C and Li compound (2 equivalents) substituted with Ar ¹ or Ar ² was added thereto. After stirring for 4 hours, dilute with water and add 2N HCl. After the reaction was completed, the mixture was extracted with ethyl acetate and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic substance was purified by silicagel column and recrystallized to obtain Sub 2-5.

Sub  2-6 Synthesis

Sub 2-5 (1 equivalent) obtained in the above synthesis was added to Acetic acid, and the temperature of the reaction was lowered to 0 ° C. for 10 minutes. After adding phosphoric acid, it is stirred at 20 ° C for 1 hour. Finally add sodium hydroxide to terminate the reaction. After completion of the reaction, the mixture was extracted with ethyl acetate and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was purified by silicagel column and recrystallized to obtain Sub 2-6.

Sub  2-7 Synthesis

Sub 2-6 (1 equivalent) obtained in the above synthesis was dissolved in DMF in a round bottom flask, followed by addition of Bis (pinacolato) diboron (1.1 equiv), Pd (dppf) Cl ₂ (0.03 equiv) and KOAc (3 equiv) And stirred at 90 ° C. After completion of the reaction, DMF was removed by distillation and extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ , concentrated, and the resulting compound was subjected to silicagel column and recrystallization to obtain Sub 2-7.

Sub  2-8 Synthesis

Sub 2-7 (1 equivalent), IL ² -NH ₂ compound (1 equivalent), Pd (PPh ₃ ) ₄ (0.03 equivalent) and K ₂ CO ₃ (3 equivalent) obtained in the above synthesis were anhydrous THF and a small amount of water. After dissolving in, it was refluxed for 24 hours. After the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with CH ₂ Cl ₂ , and washed with water. After removing a small amount of water with anhydrous MgSO ₄ and filtered under reduced pressure, the organic solvent was concentrated and the resulting product was separated by column chromatography to give the desired Sub 2-8.

Sub  2 synthesis

Sub 2-8 (1 equivalent) and Sub 2-9 (1.1 equivalent) obtained in the above synthesis were dissolved in toluene in a round bottom flask, followed by Pd ₂ (dba) ₃ (0.3 equivalent), 50% P ( t -Bu) ₃ (9 equiv), NaO t -Bu (3 equiv) were added and stirred at 40 ° C. After the reaction was completed, the mixture was extracted with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was purified by silicagel column and recrystallized to obtain Sub 2.

Examples of Sub 2 are as follows, but are not limited thereto, and their FD-MS are shown in Table 2 below.

3. Final product ( Final Products Example of synthesis

1) Synthesis of Formula (1)

Sub 1 compound (1 equiv), Sub 2 compound (1.2 equiv), Pd ₂ (dba) ₃ (0.05 equiv), P (t-Bu) ₃ (0.1 equiv), NaO t -Bu (3 equiv) in a round bottom flask ), add toluene (10.5 mL / 1 mmol) and proceed with the reaction at 100 ℃. After the reaction was completed, the mixture was extracted with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was purified by silicagel column and recrystallized to obtain a final product.

1-19 Synthesis Example

2-bromo-9-phenyl-9H-carbazole (7.7g, 24mmol), N-([1,1'-biphenyl] -4-yl) -9,9-dimethyl-9H-fluoren-3 in a round bottom flask -amine (7.2 g, 20 mmol), Pd ₂ (dba) ₃ (0.03-0.05 mmol), P (t-Bu) ₃ (0.1 equiv), NaO t -Bu (3 equiv), toluene (10.5 mL / 1 mmol ) Is added and the reaction proceeds at 100 ° C. After the reaction was completed, the mixture was extracted with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic substance was purified by silicagel column and recrystallized to give 8.2g (yield: 68%) of the product.

1-37 Synthesis Example

3-bromo-9- (pyridin-2-yl) -9H-carbazole (7.8g, 24mmol), 9,9-dimethyl-N-phenyl-9H-fluoren-3-amine (5.7g, 20mmol) in a round bottom flask ), Pd ₂ (dba) ₃ (0.03 ~ 0.05 mmol), P (t-Bu) ₃ (0.1 equiv), NaO t -Bu (3 equiv), toluene (10.5 mL / 1 mmol) and then at 100 ° C Proceed with the reaction. After the reaction was completed, the mixture was extracted with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic substance was purified by silicagel column and recrystallized to obtain 7.5g (yield: 71%) of the product.

2-19 Synthesis Example

2- (3-bromophenyl) -9-phenyl-9H-carbazole (9.6g, 24mmol), 9,9-dimethyl-N- (naphthalen-2-yl) -9H-fluoren-3-amine ( 6.7 g, 20 mmol), Pd ₂ (dba) ₃ (0.03-0.05 mmol), P (t-Bu) ₃ (0.1 equiv), NaO t -Bu (3 equiv), toluene (10.5 mL / 1 mmol) After the reaction proceeds at 100 ℃. After completion of the reaction, the mixture was extracted with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic substance was purified by silicagel column and recrystallized to obtain 8.5g (yield: 65%) of the product.

2-33 Synthesis Example

3- (4-bromophenyl) -9-phenyl-9H-carbazole (9.6g, 24mmol), N-([1,1'-biphenyl] -4-yl) -9,9-dimethyl-9H in a round bottom flask -fluoren-3-amine (7.2 g, 20 mmol), Pd ₂ (dba) ₃ (0.03-0.05 mmol), P (t-Bu) ₃ (0.1 equiv), NaO t -Bu (3 equiv), toluene (10.5 mL / 1 mmol) and the reaction at 100 ℃ proceed. After the reaction was completed, the mixture was extracted with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic substance was purified by silicagel column and recrystallized to obtain 9.8 g (yield: 72%) of the product.

3-12 Synthesis Example

3- (3'-bromo- [1,1'-biphenyl] -3-yl) -9-phenyl-9H-carbazole (11.4g, 24mmol), N-([1,1'-biphenyl) in a round bottom flask ] -4-yl) -9,9'-spirobi [fluoren] -3-amine (9.7 g, 20 mmol), Pd ₂ (dba) ₃ (0.03 to 0.05 mmol), P (t-Bu) ₃ (0.1 equivalent ), NaO t -Bu (3 equiv) and toluene (10.5 mL / 1 mmol) were added and the reaction was carried out at 100 ° C. After completion of the reaction, the mixture was extracted with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic substance was purified by silicagel column and recrystallized to obtain 11.6g (yield: 66%) of the product.

4-1 Synthesis Example

3- (7-bromodibenzo [b, d] thiophen-3-yl) -9-phenyl-9H-carbazole (12.1g, 24mmol), 9,9-dimethyl-N-phenyl-9H-fluoren- in a round bottom flask 3-amine (5.7 g, 20 mmol), Pd ₂ (dba) ₃ (0.03-0.05 mmol), P (t-Bu) ₃ (0.1 equiv), NaO t -Bu (3 equiv), toluene (10.5 mL / 1 mmol), followed by reaction at 100 ° C. After the reaction was completed, the mixture was extracted with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was purified by silicagel column and recrystallized to obtain 9.1g (yield: 64%).

Examples of the compound represented by the formula (1) are compounds 1-1 to 5-8, but are not limited thereto, and their FD-MS are shown in Table 3 below.

2) Synthesis of Formula (2)

Of final product 6-9 Synthesis Example

Synthesis example of Product 6-9 in Chemical Formula 2 according to the present invention is the same as in Scheme 4.

<Scheme 4>

Sub  6-2 Synthesis

Sub 6-1 was dissolved in anhydrous THF, the temperature of the reaction was lowered to -78 ° C, n-BuLi (2.5 M inhexane) was slowly added dropwise, and the reaction was stirred at 0 ° C for 1 hour. Then, the temperature of the reaction was lowered to -78 ℃, trimethyl borate was added dropwise, and stirred at room temperature for 12 hours. Upon completion of the reaction, 2N-HCl aqueous solution was added, stirred for 30 minutes, and extracted with ether. After removal of water in the reaction with anhydrous MgSO ₄ and filtration under reduced pressure, the resulting product was concentrated by separation of the organic solvent using column chromatography to give the desired Sub 6-2.

Sub  6-3 Synthesis

Sub 6-2 and 1-iodo-2-nitrobenzene, Pd (PPh ₃ ) ₄ and K ₂ CO ₃ obtained in the above synthesis were dissolved in anhydrous THF and a small amount of water, and then refluxed for 24 hours. After the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with CH ₂ Cl ₂ , and washed with water. After removing a small amount of water with anhydrous MgSO ₄ and filtered under reduced pressure, the organic solvent was concentrated and the resulting product was separated by column chromatography to give the desired Sub 6-3.

Sub  6-4 Synthesis

Sub 6-3 and triphenylphosphine obtained in the above synthesis were dissolved in o-dichlorobenzene, and refluxed for 24 hours. After completion of the reaction, the solvent was removed using distillation under reduced pressure, and the concentrated product was separated using column chromatography to obtain the desired Sub 6-4.

Product  6-9 synthesis

Sub 6-4 (1 equiv) and Sub 6-5 (1.1 equiv) were added to toluene and Pd ₂ (dba) ₃ (0.05 equiv), PPh ₃ (0.1 equiv) and NaO t -Bu (3 equiv) were added respectively, followed by stirring under reflux for 24 hours at 100 ° C. After extraction with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was purified by silicagel column and recrystallized to obtain Product 6-9 (yield 68%).

Examples of the compound represented by the formula (2) are compounds 6-1 to 6-32, but are not limited thereto, and their FD-MS are shown in Table 4 below.

3) Synthesis of Formula (3)

Of final product 7-1 Synthesis Example

Synthesis example of Product 7-1 in Chemical Formula 3 according to the present invention is the same as in Scheme 5.

Scheme 5

3-bromo-9-phenyl-9H-carbazole (6.4 g, 20 mmol) was dissolved in THF, followed by (9- (4,6-diphenyl-1,3,5-triazin-2-yl) -9H-carbazol- 3-yl) boronic acid (8.8 g, 20 mmol), Pd (PPh ₃ ) ₄ (0.03 equiv), K ₂ CO ₃ (3 equiv), and water were added, followed by stirring under reflux. After the reaction was completed, the mixture was extracted with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic substance was purified by silicagel column and recrystallized to obtain 9.2g (yield: 72%).

Examples of the compound represented by the formula (3) are compounds 7-1 to 7-24, but are not limited thereto, and their FD-MS are shown in Table 5 below.

4) Synthesis of Formula (4)

Of the final product 8-6 Synthesis Example

Synthesis example of Product 8-6 in Chemical Formula 4 according to the present invention is the same as in Scheme 6.

<Scheme 6>

triphenylen-2-ylboronic acid (5.4g, 20mmol) was dissolved in THF and then 2- (4-bromophenyl) -4,6-diphenyl-1,3,5-triazine (7.8g, 20mmol), Pd (PPh ₃ ) ₄ (0.03 equiv), K ₂ CO ₃ (3 equiv), and water were added, followed by stirring under reflux. After the reaction was completed, the mixture was extracted with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic substance was purified by silicagel column and recrystallized to obtain 7.5g (yield: 70%) of the product.

Examples of the compound represented by the formula (4) are compounds 8-1 to 8-12, but are not limited thereto, and their FD-MS are shown in Table 6 below.

Manufacturing Evaluation of Organic Electrical Device

[ Example  Ⅰ] Red organic light emitting diode Luminous auxiliary layer )

First, on the ITO layer (anode) formed on the glass substrate, N ^1- (naphthalen-2-yl) -N ⁴ , N ⁴ -bis (4- (naphthalen-2-yl (phenyl) amino) phenyl as a hole injection layer. ) -N ¹ -phenylbenzene-1,4-diamine (abbreviated as 2-TNATA) membrane was vacuum deposited to form a thickness of 60 nm. Subsequently, 4,4-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (hereinafter abbreviated as -NPD) was vacuum-deposited to a thickness of 60 nm on the film as a hole transporting compound. Formed. Subsequently, the compound of the present invention (one of 2-1 to 2-40) was vacuum deposited to a thickness of 20 nm as a light emitting auxiliary layer material to form a light emitting auxiliary layer. Then, Compound (6-5) of the present invention is used as a host on the light emitting auxiliary layer, and (piq) ₂ Ir (acac) [bis- (1-phenylisoquinolyl) iridium (III) acetylacetonate] is used as a host. A 30 nm thick light emitting layer was deposited by doping at 5 weights. Thereafter, (1,1'bisphenyl) -4-oleito) bis (2-methyl-8-quinolineoleito) aluminum (hereinafter abbreviated as BAlq) was vacuum-deposited to a thickness of 10 nm on the light emitting layer. A blocking layer was formed and tris (8-quinolinol) aluminum (hereinafter abbreviated as Alq3) was deposited to a thickness of 40 nm on the hole blocking layer to form an electron transport layer. Subsequently, LiF, an alkali metal halide, was deposited to a thickness of 0.2 nm as an electron injection layer on the electron transport layer, and then an Al was deposited to a thickness of 150 nm to prepare an organic electroluminescent device.

[ Comparative example  One]

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

PR- Photoresearch Co., Ltd. was fabricated by applying a forward bias DC voltage to the organic electroluminescent devices according to [Example I] (Examples (1) to (40)) and [Comparative Example 1] prepared as described above. The electroluminescence (EL) characteristics were measured at 650, and the T95 lifetime was measured using a life-time measuring instrument manufactured by McScience Inc. at a luminance of 2500 cd / m2.

Table 7 below shows device fabrication and evaluation results of [Example I] (Examples (1) to (40)) and [Comparative Example 1] to which the compound according to the invention was applied.

As can be seen from the results of Table 7, when the red organic electroluminescent device was manufactured using the organic electroluminescent device material of the present invention as the light emitting auxiliary layer material, the organic electroluminescent device was compared to the comparative example without using the light emitting auxiliary layer. In addition to lowering the driving voltage, the luminous efficiency and lifespan can be significantly improved.

When the compound of the present invention is used as a light emitting auxiliary layer alone, it has a high T1 energy level and a deep HOMO energy level. As a result, holes and electrons achieve a charge balance, and light emission is not generated inside the light emitting layer, but instead of the hole transport layer interface. It is believed that this is because it maximizes higher efficiency and lifespan.

[ Example  Ⅱ] Green Organic Light Emitting Diode (Light emitting auxiliary layer)

First, on the ITO layer (anode) formed on the glass substrate, N ^1- (naphthalen-2-yl) -N ⁴ , N ⁴ -bis (4- (naphthalen-2-yl (phenyl) amino) phenyl as a hole injection layer. ) -N ¹ -phenylbenzene-1,4-diamine (abbreviated as 2-TNATA) membrane was vacuum deposited to form a thickness of 60 nm. Subsequently, 4,4-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (hereinafter abbreviated as -NPD) was vacuum-deposited to a thickness of 60 nm on the film as a hole transporting compound. Formed. Subsequently, the compound of the present invention (one of 1-1 to 1-64) was vacuum deposited to a thickness of 20 nm as a light emitting auxiliary layer material to form a light emitting auxiliary layer. Then, a light emitting layer having a thickness of 30 nm was formed by doping compound (7-1) as a host and Ir (ppy) 3 [tris (2-phenylpyridine) -iridium] as 95: 5 weight on the light emitting auxiliary layer. Deposited. Thereafter, (1,1'bisphenyl) -4-oleito) bis (2-methyl-8-quinolineoleito) aluminum (hereinafter abbreviated as BAlq) was formed as a hole blocking layer on the emission layer to a thickness of 10 nm. Vacuum deposition and tris (8-quinolinol) aluminum (hereinafter abbreviated as Alq3) were formed into a 40 nm thick film by an electron transport layer. Subsequently, LiF, which is an alkali metal halide, was deposited to a thickness of 0.2 nm as an electron injection layer, and then Al was deposited to a thickness of 150 nm to prepare an organic electroluminescent device.

[ Comparative example  2]

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

The PR-photoresearch company PR- was applied by applying a forward bias DC voltage to the organic electroluminescent devices according to [Example II] (Examples 41 to 104) and [Comparative Example 2] thus prepared. The electroluminescence (EL) characteristics were measured at 650, and the T95 lifetime was measured using a life-time measuring instrument manufactured by McScience Inc. at a luminance of 2500 cd / m2.

Table 8 below shows device fabrication and evaluation results of [Example II] (Examples (41) to (104)) and [Comparative Example 2] to which the compound according to the invention was applied.

As can be seen from the results of Table 8, when the green organic electroluminescent device was manufactured using the organic electroluminescent device material of the present invention as the light emitting auxiliary layer material, the organic electroluminescent device was compared to the comparative example without using the light emitting auxiliary layer. In addition to lowering the driving voltage, the luminous efficiency and lifespan can be significantly improved.

When the compound of the present invention is used as a light emitting auxiliary layer alone, it has a high T1 energy level and a deep HOMO energy level. As a result, holes and electrons achieve a charge balance, and light emission is not generated inside the light emitting layer, but instead of the hole transport layer interface. It is believed that this is because it maximizes higher efficiency and lifespan.

Example III Green Organic Light Emitting Device Luminous auxiliary layer )

First, on the ITO layer (anode) formed on the glass substrate, N ^1- (naphthalen-2-yl) -N ⁴ , N ⁴ -bis (4- (naphthalen-2-yl (phenyl) amino) phenyl as a hole injection layer. ) -N ¹ -phenylbenzene-1,4-diamine (abbreviated as 2-TNATA) membrane was vacuum deposited to form a thickness of 60 nm. Subsequently, 4,4-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (hereinafter abbreviated as -NPD) was vacuum-deposited to a thickness of 60 nm on the film as a hole transporting compound. Formed. Subsequently, the compound of the present invention (any one of 3-1 to 3-24, 4-1 to 4-8, and 5-1 to 5-4) as a light emitting auxiliary layer material was vacuum-deposited to a thickness of 20 nm to emit light. An auxiliary layer was formed. After the light emitting auxiliary layer was formed, the compound was doped with a compound (8-1) as a host and Ir (ppy) 3 [tris (2-phenylpyridine) -iridium] as a dopant at a weight of 95: 5. A light emitting layer having a thickness of 30 nm was deposited on the light emitting auxiliary layer. Then, (1,1'bisphenyl) -4-oleito) bis (2-methyl-8-quinolinoleito) aluminum (hereinafter abbreviated as BAlq) was vacuum-deposited to a hole blocking layer to a thickness of 10 nm, Tris (8-quinolinol) aluminum (hereinafter abbreviated as Alq3) was formed into an electron transport layer to a thickness of 40 nm. Subsequently, LiF, which is an alkali metal halide, was deposited to a thickness of 0.2 nm as an electron injection layer, and then Al was deposited to a thickness of 150 nm to prepare an organic electroluminescent device.

[ Comparative example  3]

An organic electroluminescent device was manufactured in the same manner as in Example III, except that no light emitting auxiliary layer was used.

The PR-photoresearch company PR- was applied by applying a forward bias DC voltage to the organic electroluminescent devices according to [Example III] (Examples 105 to 140) and [Comparative Example 3] prepared as described above. The electroluminescence (EL) characteristics were measured at 650, and the T95 lifetime was measured using a life-time measuring instrument manufactured by McScience Inc. at a luminance of 2500 cd / m2.

Table 9 below shows device fabrication and evaluation results of [Example III] (Examples 105 to 140) and [Comparative Example 3] to which the compound according to the invention was applied.

As can be seen from the results of Table 9, when the green organic electroluminescent device was manufactured using the organic electroluminescent device material of the present invention as the light emitting auxiliary layer material, the organic electroluminescent device was compared to the comparative example without using the light emitting auxiliary layer. In addition to lowering the driving voltage, the luminous efficiency and lifespan can be significantly improved.

When the compound of the present invention is used as a light emitting auxiliary layer alone, it has a high T1 energy level and a deep HOMO energy level. As a result, holes and electrons achieve a charge balance, and light emission is not generated inside the light emitting layer, but instead of the hole transport layer interface. It is believed that this is because it maximizes higher efficiency and lifespan.

EXAMPLE IV Green Organic Light Emitting Diode ( Light emitting layer  Mixed host)

First, on the ITO layer (anode) formed on the glass substrate, N ^1- (naphthalen-2-yl) -N ⁴ , N ⁴ -bis (4- (naphthalen-2-yl (phenyl) amino) phenyl as a hole injection layer. ) -N ¹ -phenylbenzene-1,4-diamine (abbreviated as 2-TNATA) membrane was vacuum deposited to form a thickness of 60 nm. Subsequently, 4,4-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (hereinafter abbreviated as -NPD) was vacuum-deposited to a thickness of 60 nm on the film as a hole transporting compound. Formed. Subsequently, the compound of the present invention (one of 1-1 to 1-64) was vacuum deposited to a thickness of 20 nm as a light emitting auxiliary layer material to form a light emitting auxiliary layer. Then, compound (6-5) and compound (7-1) were mixed as a host on the light emitting auxiliary layer, and Ir (ppy) 3 [tris (2-phenylpyridine) -iridium] was added as a dopant 95: 5. A light emitting layer having a thickness of 30 nm was deposited on the light emitting auxiliary layer by doping by weight. Thereafter, (1,1'bisphenyl) -4-oleito) bis (2-methyl-8-quinolineoleito) aluminum (hereinafter abbreviated as BAlq) was formed as a hole blocking layer on the light emitting layer to a thickness of 10 nm. Vacuum deposition and tris (8-quinolinol) aluminum (hereinafter abbreviated as Alq3) were formed into a 40 nm thick film by an electron transport layer. Subsequently, LiF, which is an alkali metal halide, was deposited to a thickness of 0.2 nm as an electron injection layer, and then Al was deposited to a thickness of 150 nm to prepare an organic electroluminescent device.

[ Comparative example  4]

An organic electroluminescent device was manufactured in the same manner as in Example 4, except that the light emitting auxiliary layer was not used.

The PR-photoresearch company PR- was applied by applying a forward bias DC voltage to the organic electroluminescent devices according to [Example IV] (Examples 141 to 180) and [Comparative Example 4] prepared as described above. The electroluminescence (EL) characteristics were measured at 650, and the T95 lifetime was measured using a life-time measuring instrument manufactured by McScience Inc. at a luminance of 2500 cd / m2.

Table 10 below shows device fabrication and evaluation results of [Example IV] (Examples (141) to (180)) and [Comparative Example 4] to which the compound according to the invention was applied.

As can be seen from the results of Table 10, the organic electroluminescent device using the organic electroluminescent device material of the present invention as a light emitting auxiliary layer material has a compound of Formula (2) and Formula (3) than when using a single host. It can be seen that when used in combination, it is used as a green light emitting layer material to significantly improve higher luminous efficiency, low driving voltage and lifetime. It is believed that the efficiency and lifespan are increased due to the wider band gap and higher charge balance in the light emitting layer than the single host due to the mixed two hosts.

[ Example  Ⅴ] Green Organic Light Emitting Diode  ( Light emitting layer  Mixed host)

First, on the ITO layer (anode) formed on the glass substrate, N ^1- (naphthalen-2-yl) -N ⁴ , N ⁴ -bis (4- (naphthalen-2-yl (phenyl) amino) phenyl as a hole injection layer. ) -N ¹ -phenylbenzene-1,4-diamine (abbreviated as 2-TNATA) membrane was vacuum deposited to form a thickness of 60 nm. Subsequently, 4,4-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (hereinafter abbreviated as -NPD) was vacuum-deposited to a thickness of 60 nm on the film as a hole transporting compound. Formed. Subsequently, the compound of the present invention (any one of 3-1 to 3-24, 4-1 to 4-8 and 5-1 to 5-4) was vacuum-deposited to a thickness of 20 nm as the light emitting auxiliary layer material. Formed. Then, a compound (8-1) and a compound (7-1) are mixed and used as a host on the light emitting auxiliary layer, and Ir (ppy) 3 [tris (2-phenylpyridine) -iridium] is used as a dopant. A light emitting layer of 30 nm thickness was deposited by doping at 5: weight. Thereafter, (1,1'bisphenyl) -4-oleato) bis (2-methyl-8-quinolineoleito) aluminum (abbreviated as BAlq) was vacuumed to a thickness of 10 nm as a hole blocking layer on the light emitting layer. A tris (8-quinolinol) aluminum (hereinafter abbreviated as Alq3) was deposited to a thickness of 40 nm as an electron transport layer. Subsequently, LiF, which is an alkali metal halide, was deposited to a thickness of 0.2 nm as an electron injection layer, and then Al was deposited to a thickness of 150 nm to prepare an organic electroluminescent device.

[ Comparative Example 5 ]

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

The PR-photoresearch Company PR- was applied by applying a forward bias DC voltage to the organic electroluminescent devices according to [Example V] (Examples 181 to 216) and [Comparative Example 5] prepared as described above. The electroluminescence (EL) characteristics were measured at 650, and the T95 life was measured using a life-time measurement device manufactured by McScience Inc. at 2500 cd / m2 reference luminance.

Table 11 below shows device fabrication and evaluation results of [Example V] (Examples 181 to 216) and [Comparative Example 5] to which the compound according to the invention was applied.

As can be seen from the results of Table 11, the organic electroluminescent device using the organic electroluminescent device material of the present invention as the light emitting auxiliary layer material is mixed with the compound of formula (3) and formula (4) than when using a single host. Therefore, it can be seen that when used as a host (applied to the green organic light emitting device), the luminous efficiency, low driving voltage and lifespan are significantly improved. It is believed that the efficiency and lifespan are increased due to the wider band gap and higher charge balance in the light emitting layer than the single host material due to the mixed two host materials.

The above description is merely illustrative of the present invention, and those skilled in the art to which the present invention pertains may various modifications without departing from the essential characteristics of the present invention. Accordingly, the embodiments disclosed herein are not intended to limit the present invention but to describe the present invention, and the spirit and scope of the present invention are not limited thereto.

The protection scope of the present invention should be interpreted by the following claims, and all the technologies within the equivalent scope should be interpreted as being included in the scope of the present invention.

100: organic electric element 110: substrate
120: first electrode 130: hole injection layer
140: hole transport layer 141: buffer layer
150: light emitting layer 151: light emitting auxiliary layer
160: electron transport layer 170: electron injection layer
180: second electrode

Claims (13)

In an organic electric device comprising a first electrode, a second electrode, and an organic material layer positioned between the first electrode and the second electrode,
The organic material layer includes a hole transport layer, a light emitting auxiliary layer and a light emitting layer, wherein the light emitting auxiliary layer is positioned between the hole transport layer and the light emitting layer and includes at least one of compounds represented by formulas (9) to (12), The light emitting layer is an organic electric device comprising at least one of the compounds represented by the formula (2) to (4).

Formula (2)

Formula (3) Formula (4)

[In the above formulas (9) to (12),
z is an integer from 0 to 4,
R ⁰ is a plurality or the same as or different from each other when z is 2 or more, and iii) each independently deuterium; halogen; C ₆ ~ C ₆₀ aryl group; Fluorenyl groups; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; Fused ring group of an aromatic ring of C ₃ ~ C ₆₀ of aliphatic rings and C ₆ ~ C _60; C ₁ ~ C ₅₀ Alkyl group; C ₂ ~ C ₂₀ Alkenyl group; Alkynyl groups of C ₂ to C ₂₀ ; C ₁ -C ₃₀ alkoxyl group; C ₆ -C ₃₀ aryloxy group; And -L ^a -N (R _a ) (R _b ); (wherein L ^a is a single bond; C ₆ ~ C ₆₀ arylene group; Fluorenylene group; C ₃ ~ C ₆₀ A divalent fused ring group of an aliphatic ring and an aromatic ring of C ₆ to C ₆₀ , and a C ₂ to C ₆₀ divalent hetero ring group including at least one hetero atom of O, N, S, Si, and P; Selected from the group consisting of, R _a and R _b are each independently a C ₆ ~ C ₆₀ aryl group; fluorenyl group; C ₃ ~ C ₆₀ aliphatic ring and C ₆ ~ C ₆₀ aromatic ring fused ring group And C ₂ to C ₆₀ heterocyclic group including at least one heteroatom of O, N, S, Si, and P); or ii) when z is 2 or more, adjacent R ^0. The groups may combine with each other to form a ring (where a group that does not form a ring is as defined in iii),
L ¹ and L ² are each independently a single bond; C ₆ ~ C ₆₀ arylene group; Fluorenylene groups; Divalent fused ring group of an aromatic ring of C ₃ ~ C ₆₀ of aliphatic rings and C ₆ ~ C _60; And C ₂ ~ C ₆₀ A bivalent heterocyclic group containing at least one heteroatom of O, N, S, Si and P; selected from the group consisting of,
Ar ¹ and Ar ² are each independently ⅰ) a C ₁ ~ C ₂₀ Alkyl group; C ₆ ~ C ₃₀ An aryl group; And a C ₂ -C ₂₀ heterocyclic group including at least one heteroatom of O, N, S, Si, and P; or ii) Ar ¹ and Ar ² are bonded to each other to form a spy; Can form compounds,
Ar ³ and Ar ⁴ are each independently hydrogen; heavy hydrogen; halogen; C ₆ ~ C ₆₀ aryl group; Fluorenyl groups; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; Fused ring group of an aromatic ring of C ₃ ~ C ₆₀ of aliphatic rings and C ₆ ~ C _60; C ₁ ~ C ₅₀ Alkyl group; C ₂ ~ C ₂₀ Alkenyl group; Alkynyl groups of C ₂ to C ₂₀ ; C ₁ -C ₃₀ alkoxyl group; C ₆ -C ₃₀ aryloxy group; And -L ^b -N (R _c ) (R _d ); wherein L ^b , R _c and R _d are the same as the definitions of L ^a , R _a and R _b , respectively,
In formula (2),
a and b are independently of each other an integer of 0 or 1, provided that a + b = 1 or greater,
m is an integer of 1 or 2,
q and o are each independently an integer from 1 to 4,
X and Y are each independently a single bond; S; O; NR ', CR'R "or SiR'R",
R 'and R "are independently of each other hydrogen; C ₆ ~ C ₆₀ aryl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; and C _It is selected from the group consisting of; alkyl group of ₁ ~ C ₅₀ ,
R ² to R ⁴ are each the same as or different from each other when m, o and p are 2 or more, and iii) deuterium; halogen; C ₆ ~ C ₆₀ aryl group; Fluorenyl groups; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; Fused ring group of an aromatic ring of C ₃ ~ C ₆₀ of aliphatic rings and C ₆ ~ C _60; C ₁ ~ C ₅₀ Alkyl group; C ₂ ~ C ₂₀ Alkenyl group; Alkynyl groups of C ₂ to C ₂₀ ; C ₁ -C ₃₀ alkoxyl group; C ₆ -C ₃₀ aryloxy group; And -L ^c -N (R _e ) (R _f ); wherein L ^c , Re and Rf are the same as the definitions of L ^a , R _a and R _b , respectively, or ii) Or R ² , R ³ and R ⁴ , when m, o, p is 2 or more, neighboring R ² , neighboring R ³ , or neighboring R ⁴ may be bonded to each other to form a ring ( Where a group that does not form a ring is as defined in i)),
L ³ is a single bond; C ₆ ~ C ₆₀ arylene group; A C ₂ to C _{60 divalent} heterocyclic group including at least one hetero atom of O, N, S, Si, or P; And divalent C ₁ to C ₆₀ aliphatic hydrocarbon group;
Ar ⁵ is hydrogen; heavy hydrogen; halogen; C ₆ ~ C ₆₀ aryl group; Fluorenyl groups; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; Fused ring group of an aromatic ring of C ₃ ~ C ₆₀ of aliphatic rings and C ₆ ~ C _60; C ₁ ~ C ₅₀ Alkyl group; C ₂ ~ C ₂₀ Alkenyl group; Alkynyl groups of C ₂ to C ₂₀ ; C ₁ -C ₃₀ alkoxyl group; C ₆ -C ₃₀ aryloxy group; And -L ^d -N (R _g ) (R _h ); wherein L ^d , R _g and R _h are the same as the definitions of L ^a , R _a and R _b , respectively,
In formula (3),
Z ¹ to Z ¹⁶ are independently of each other CR ⁵ or N,
R ⁵ is i) hydrogen; C ₆ ~ C ₆₀ aryl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si, P; C ₁ ~ C ₅₀ Alkyl group; -L ^e -N (R _i ) (R _j ); And a fluorenyl group; wherein L ^e , R _i and R _j are the same as the definitions of L ^a , R _a and R _b , respectively, and ii) adjacent R ⁵ is bonded to each other. Can form a ring (where a group that does not form a ring is as defined in iii),
L ⁴ is a single bond; C ₆ ~ C ₆₀ arylene group; A C ₂ to C _{60 divalent} heterocyclic group including at least one hetero atom of O, N, S, Si, or P; And divalent C ₁ to C ₆₀ aliphatic hydrocarbon group;
W is NAr ⁷ , O or S,
Ar ⁶ and Ar ⁷ are each independently of the other C ₆ ~ C ₆₀ An aryl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si, P; C ₁ ~ C ₅₀ Alkyl group; Fluorenyl groups; And -L ^f -N (R _k ) (R _l ); wherein L ^f , R _k and R _l are the same as the definitions of L ³ , R _a and R _b , respectively,
In formula (4),
R ^{6 to 17} are each independently hydrogen; heavy hydrogen; C ₆ ~ C ₆₀ aryl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si, P; C ₁ ~ C ₅₀ Alkyl group; An alkoxyl group of C ₁ to C ₅₀ ; C ₂ ~ C ₂₀ Alkenyl group; And -L ^g -N (R _m ) (R _n ); wherein L ^g , R _m and R _n are the same as the definitions of L ³ , R _a and R _b , respectively,
The aryl group, fluorenyl group, heterocyclic group, fused ring group, alkyl group, alkenyl group, alkynyl group, alkoxyl group, aryloxy group, arylene group, fluorenyl described in the definition of the formulas (2) to (4) The ethylene group and aliphatic hydrocarbon group are deuterium, halogen, silane group, siloxane group, boron group, germanium group, cyano group, nitro group, -L ⁷ -N (R _i ) (R _j ), where L ⁷ , R _i and R _j are also each as defined the above L ^3, R _a and R _b), C ₁ ~ a C ₂₀ come alkylthio, C ₁ ~ C ₂₀ alkoxy group, C alkyl group of ₁ ~ C _20, C ₂ ~ C ₂₀ of Alkenyl group, C ₂ ~ C ₂₀ Alkynyl group, C ₆ ~ C ₂₀ An aryl group, substituted with a C ₂ ~ C ₂₀ heterocyclic group containing at least one hetero atom of O, N, S, Si, P a C ₆ ~ C ₂₀ aryl group, of a C ₆ ~ C ₂₀ substituted by deuterium aryl group, fluorene group, O, N, S, Si, C ₂ ~ C ₂₀ comprising at least one hetero atom of the P Heterocyclic group, C ₆ ~ C _{20 It} is substituted with an aryl group C ₂ ~ C ₂₀ heterocyclic group containing at least one heteroatom of O, N, S, Si, P, C ₃ ~ C ₂₀ cycloalkyl group, C ₇ ~ C ₂₀ arylalkyl group and C ₈ ~ C May be further substituted with one or more substituents selected from the group consisting of ₂₀ arylalkenyl groups.] The method of claim 1,
At least one of the compounds represented by the above formulas (2) to (4) is a host material of the light emitting layer. delete delete The method of claim 1,
The compound represented by the formula (9) to formula (12) is an organic electric device, characterized in that any one of the compounds represented by the following formula independently.

The method of claim 1,
The compound represented by the formula (2) is an organic electric device, characterized in that any one of the following formula.

The method of claim 1,
The compound represented by the formula (3) is an organic electric device, characterized in that any one of the following formula.

The method of claim 1,
The compound represented by the formula (4) is an organic electric device, characterized in that any one of the following formula.

The method of claim 1,
The light emitting auxiliary layer contains at least one of the compounds represented by the formulas (9) to (12), and the light emitting layer is any two of the compounds represented by the formulas (2) to (4) as host materials. An organic electric element comprising a mixture of dogs. The method of claim 1,
An organic electric device comprising a light efficiency improving layer on at least one of one side of the first electrode opposite to the organic material layer or one side of the second electrode opposite to the organic material layer. The method of claim 1,
The organic material 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. A display device comprising the organic electroluminescent element of claim 1; And
And a controller for driving the display device. The method of claim 12,
The organic electroluminescent device is at least one of an organic electroluminescent device (OLED), an organic solar cell, an organic photoconductor (OPC), an organic transistor (organic TFT), and a monochromatic or white illumination element.

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