KR102460259B1 - Organic electric element comprising compound for organic electric element and electronic device thereof - Google Patents

Abstract

Disclosed are an organic electric device including the compound represented by Formula 1 as a light emitting auxiliary layer material and an electronic device including the same. and can improve luminous efficiency and lifespan.

Description

Organic field device using compound for organic field device and electronic device thereof

The present invention relates to an organic field device using a compound for an organic field device and an electronic device thereof.

In general, the organic light emitting phenomenon refers to a phenomenon in which electric energy is converted into light energy using an organic material. An organic electric field device using an organic light emitting phenomenon usually has a structure including an anode and a cathode and an organic material layer therebetween. Here, the organic layer is often formed of a multilayer structure composed of different materials in order to increase the efficiency and stability of the organic field device, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer.

The current portable display market is a large-area display, and the size thereof is increasing, and thus, power consumption greater than that required by the existing portable display is required. Therefore, power consumption has become a very important factor for a portable display having a limited power supply such as a battery, and the problem of efficiency and lifespan must also be solved.

Efficiency, lifespan, and driving voltage are related to each other, and when the efficiency is increased, the driving voltage is relatively decreased. It shows a tendency to increase the lifespan. However, the efficiency cannot be maximized simply by improving the organic material layer. This is because, when the energy level and T1 value between each organic material layer, and the intrinsic properties (mobility, interfacial properties, etc.) of materials are optimally combined, long lifespan and high efficiency can be achieved at the same time.

In general, electrons are transferred from the electron transport layer to the light emitting layer and holes are transferred from the hole transport layer to the light emitting layer to generate excitons by recombination. However, most materials used for the hole transport layer have a low T ₁ value because they must have a low HOMO value. ) to emit light in the hole transport layer or at the interface of the hole transport layer, resulting in a decrease in color purity, a decrease in efficiency, and a decrease in lifespan.

In addition, when a material having high hole mobility is used to make a low driving voltage, the efficiency tends to decrease due to this. This is because hole mobility is faster than electron mobility in a general organic light emitting device, which causes charge unbalance in the light emitting layer, resulting in reduced efficiency and reduced lifespan.

Recently, in order to solve the problem of light emission in the hole transport layer in organic electroluminescent devices, a light emitting auxiliary layer is formed between the hole transport layer and the light emitting layer. It is time for development.

The light emitting auxiliary layer should be formed of a material having a hole mobility, a high electron block (T ₁ ) value, and a wide bandgap to have a suitable driving voltage to solve the problems of the hole transport layer. These requirements are not satisfied only with the structural characteristics of the core of the light emitting auxiliary layer material, but only when the characteristics such as the core and sub-substituents of the material are properly combined. In order to improve the light-emitting auxiliary layer material having a high T ₁ value and a wide bandgap, there is an urgent need for development.

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

An object of the present invention is to provide an organic electric field device using a compound capable of improving high luminous efficiency, low driving voltage, high heat resistance, color purity and lifespan as a light emitting auxiliary layer material and an electronic device thereof.

In one aspect, the present invention provides an organic electric field device including a first electrode, a second electrode, and an organic material layer formed between the first electrode and the second electrode. In this case, the organic layer includes a light-emitting auxiliary layer formed between the first electrode and the light-emitting layer, and the light-emitting auxiliary layer includes a compound represented by the following formula.

In another aspect, the present invention provides an electronic device including the organic field device.

By using the compound according to an embodiment of the present invention as a light emitting auxiliary layer material, it is possible to not only lower the driving voltage of the organic electric field device, but also greatly improve the luminous efficiency, color purity and lifespan of the device.

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

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

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

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

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

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

Hereinafter, the stacked structure of the organic field device including the compound of the present invention will be described with reference to FIG. 1 .

1 is a diagram illustrating a stacked structure of an organic field device according to an embodiment of the present invention.

Referring to FIG. 1 , the organic field device 100 according to the present invention includes a first electrode 120 , a second electrode 180 , and a first electrode 110 and a second electrode 180 formed on a substrate 110 . ), an organic layer containing the compound according to the present invention is provided. 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 material layer may sequentially include a hole injection layer 130 , a hole transport layer 140 , a light emitting layer 150 , an electron transport layer 160 , and an electron injection layer 170 on the first electrode 120 . At this time, at least one of these layers may be omitted, or a hole blocking layer, an electron blocking layer, a light emission auxiliary layer 151, a buffer layer 141, etc. may be further included, and the electron transport layer 160 and the like serve as a hole blocking layer. you might be able to

In addition, although not shown, the organic field device according to the present invention may further include a protective layer or a light efficiency improving layer (Capping layer) formed on 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 layer is a hole injection layer 130 , a hole transport layer 140 , an electron transport layer 160 , an electron injection layer 170 , a light emitting layer 150 , a light efficiency improving layer, a light emitting auxiliary layer, etc. could be used as a material for For example, the compound of the present invention may be used as a material for the hole transport layer 140 and/or the light emission auxiliary layer 151 .

On the other hand, even with the same core, the band gap, electrical properties, interface properties, etc. may vary depending on which position the substituent is bonded to, so the selection of the core and the combination of sub-substituents bonded thereto are very important, especially When the energy level and T ₁ value between each organic material layer, and the intrinsic properties (mobility, interfacial properties, etc.) of materials are optimally combined, long lifespan and high efficiency can be achieved at the same time.

As already described, in order to solve the light emitting problem in the hole transport layer in recent organic electroluminescent devices, it is preferable to form a light emitting auxiliary layer between the hole transport layer and the light emitting layer, and corresponding to each light emitting layer (R, G, B) Therefore, it is necessary to form different light emitting auxiliary layers. On the other hand, in the case of the light-emitting auxiliary layer, since the correlation between the hole transport layer and the light-emitting layer (host) must be understood, it will be very difficult to infer the characteristics if the organic material layer used is different even if a similar core is used.

Therefore, by forming a hole transport layer and/or a light emitting auxiliary layer using the compound of the present invention, the energy level and T ₁ value between each organic material layer, the intrinsic properties of the material (mobility, interfacial properties, etc.) It is possible to improve the lifetime and efficiency of the device at the same time.

The organic light emitting diode according to an embodiment of the present invention may be manufactured using various deposition methods. It can be manufactured using a deposition method such as PVD or CVD, for example, by depositing a metal or a metal oxide having conductivity or an alloy thereof on a substrate to form the anode 120, and the hole injection layer 130 thereon. , after forming an organic material layer including the hole transport layer 140, the light emitting layer 150, the electron transport layer 160, and the electron injection layer 170, it can be prepared by depositing a material that can be used as the cathode 180 thereon. have. In addition, a light emitting auxiliary layer 151 may be additionally formed between the hole transport layer 140 and the light emitting layer 150 .

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

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

Another embodiment of the present invention may include a display device including the organic field device 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/wireless communication terminal, and includes all electronic devices such as a mobile communication terminal such as a mobile phone, a PDA, an electronic dictionary, a PMP, a remote control, a navigation system, a game machine, various TVs, various computers, and the like. The display device may include an organic light emitting display, a quantum dot display, and the like.

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

In one embodiment of the present invention, there is provided an organic electric field device including a first electrode, a second electrode, and an organic material layer formed between the first electrode and the second electrode. In this case, the organic material layer includes a light-emitting auxiliary layer formed between the first electrode and the light-emitting layer, and the light-emitting auxiliary layer includes a compound represented by the following formula (1).

<Formula 1>

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

R ^a1 , R ^b1 , R ^a2 and R ^b2 are each independently a C ₁ ~ C ₅₀ alkyl group; C ₆ ~ C ₆₀ Aryl group; fluorenyl group; And O, N, S, Si and P containing at least one heteroatom C ₂ ~ C ₆₀ A heterocyclic group; may be selected from the group consisting of.

In addition, R ^a1 and R ^b1 may be bonded to each other to form a ring, and R ^a2 and R ^b2 may also be bonded to each other to form a ring, for example, C ₆ ~ C ₆₀ aromatic hydrocarbon; fluorenyl group; O, N, S, Si and P containing at least one heteroatom C ₂ ~ C ₆₀ A heterocyclic group; C ₃ ~ C ₆₀ aliphatic ring; C ₃ ~ C ₆₀ A fused ring group of an aliphatic ring and a C ₆ ~ C ₆₀ aromatic ring; Or it may form a ring consisting of a combination thereof. Preferably, R ^a1 and R ^b1 and/or R ^a2 and R ^b2 may be combined with each other to form a C ₆ -C ₆₀ ring including a benzene ring.

When R ^a1 , R ^b1 , R ^a2 and R ^b2 are an alkyl group, it may be preferably a C ₁ to C ₁₀ alkyl group, more preferably a C ₁ to C ₄ alkyl group, specifically methyl, ethyl, propyl, etc. have. When R ^a1 , R ^b1 , R ^a2 and R ^b2 are an aryl group, preferably a C ₆ -C ₃₀ aryl group or a C ₆ -C ₂₀ aryl group, more preferably a C ₆ -C ₁₈ aryl group, For example, it may be phenyl, naphthalene, biphenyl, terphenyl, etc., and most preferably phenyl.

When R ^a1 and R ^b1 and/or R ^a2 and R ^b2 combine with each other to form a ring including a benzene ring, preferably a C ₆ -C ₂₁ ring, more preferably a C ₆ -C ₁₃ ring may form, and when R ^b1 and/or R ^a2 and R ^b2 are combined with each other to form a fused ring of an aromatic ring and an aliphatic ring, preferably a C ₃ ~ C ₃₀ aliphatic ring and C ₆ ~ C ₃₀ A fused ring of aromatic hydrocarbons, more preferably a C ₃ ~ C ₁₈ aliphatic ring and a C ₆ ~ C ₁₈ fused ring of an aromatic hydrocarbon may be formed. For example, R ^a1 and R ^b1 and/or R ^a2 and R ^b2 may combine with each other to form dihydroindene or a derivative thereof, fluorene or a derivative thereof, and as a result share a carbon atom with the pentagonal ring to which they are attached By doing so, a spiro compound can be formed.

Preferably, at least one of R ^a1 , R ^b1 , R ^a2 and R ^b2 is a methyl group or phenyl, or R ^a1 and R ^b1 combine with each other to form fluorene, benzofluorene, or dibenzofluorene, R ^a2 and R ^b2 may combine with each other to form fluorene, benzofluorene, or dibenzofluorene. Also preferably, R ^a1 , R ^b1 , R ^a2 and R ^b2 may be all methyl groups, all phenyl, or both may be fluorene, R ^a1 and R ^bi1 are methyl or phenyl, R ^a2 and R ^b2 may form a fluorene ring, conversely, R ^a1 and R ^b1 may form a fluorene ring and both R ^a2 and R ^b2 may be methyl or phenyl.

R ¹ to R ⁷ are each independently hydrogen; heavy hydrogen; halogen; C ₆ ~ C ₆₀ Aryl group; fluorenyl group; O, N, S, Si and P containing at least one heteroatom C ₂ ~ C ₆₀ A heterocyclic group; C ₃ ~ C ₆₀ A fused ring group of an aliphatic ring and a C ₆ ~ C ₆₀ aromatic ring; C ₁ ~ C ₅₀ Alkyl group; C ₂ ~ C ₂₀ Alkenyl group; C ₂ ~ C ₂₀ alkynyl group; C ₁ ~ C ₃₀ An alkoxyl group; C ₆ ~ C ₃₀ Aryloxy group; and -L′-N(R′)(R″); or adjacent groups may be bonded to each other to form a ring.

Neighboring R ¹ , neighboring R ² , neighboring R ³ , neighboring R ⁴ , neighboring R ⁵ , neighboring R ⁶ , and/or neighboring R ⁷ bonds to each other to form a ring If so, C ₆ ~ C ₆₀ aromatic hydrocarbons; fluorenyl group; O, N, S, Si and P containing at least one heteroatom C ₂ ~ C ₆₀ A heterocyclic group; C ₃ ~ C ₆₀ aliphatic ring; C ₃ ~ C ₆₀ A fused ring group of an aliphatic ring and a C ₆ ~ C ₆₀ aromatic ring; Or it may be a ring selected from the group consisting of a combination thereof, preferably, a C ₆ ~ C ₂₀ aromatic hydrocarbon containing a benzene ring, more preferably a C ₆ ~ C ₁₈ aromatic hydrocarbon, such as benzene, naphthalene etc. Accordingly, preferably, adjacent groups are bonded to each other to form naphthalene, phenanthrene, and the like together with the benzene ring to which they are bonded.

Preferably, R ^a1 , R ^b1 , R ^a2 and R ^b2 are each independently a C ₁ -C ₁₀ alkyl group, a C ₆ -C ₂₀ aryl group, or R ^a1 and R ^b1 and/or R ^a2 and R ^b2 is bonded to each other to form a C ₆ ~ C ₂₁ ring including a benzene ring, and R ¹ to R ⁷ are independently bonded to each other to form a C ₆ ~ C ₂₀ ring including a benzene ring can be formed

More preferably, R ^a1 , R ^b1 , R ^a2 and R ^b2 are each independently a C ₁ -C ₄ alkyl group, a C ₆ -C ₁₈ aryl group, or R ^a1 and R ^b1 and/or R ^a2 and R ^b2 is bonded to each other to form a C ₆ to C ₁₃ ring including a benzene ring, and at least one pair of adjacent groups of R ¹ to R ⁷ are bonded to each other to form a C ₆ to C ₁₂ aromatic including a benzene ring hydrocarbons can be formed.

For example, R ^a1 , R ^b1 , R ^a2 and R ^b2 may each independently be a methyl group or a phenyl group, or R ^a1 and R ^b1 and/or R ^a2 and R ^b2 may combine with each other to form fluorene, and R ¹ to R At least one pair of adjacent groups of ⁷ may combine with each other to form a benzene ring.

a, c, e and g are each an integer from 0 to 4, b, d and f are each an integer from 0 to 3, each of which is an integer of 2 or more oral, each R ¹ to each R ⁷ of the plurality is Each may be identical to or identical to each other.

Ar ¹ is a C ₆ ~ C ₆₀ aryl group, preferably a C ₆ ~ C ₃₀ aryl group, more preferably a C ₆ ~ C ₁₈ aryl group, for example, phenyl, biphenyl, terphenyl, naphthyl , phenanthrene, pyrene, and the like.

Preferably, when Ar ¹ is a C ₆ ~ C ₃₀ aryl group, R ^a1 , R ^b1 , R ^a2 and R ^b2 are each independently a C ₁ ~ C ₁₀ alkyl group, a C ₆ ~ C ₂₀ aryl group, or , R ^a1 and R ^b1 and/or R ^a2 and R ^b2 may be combined with each other to form a C ₆ -C ₂₁ ring including a benzene ring.

More preferably, when Ar ¹ is a C ₆ ~ C ₁₈ aryl group, R ^a1 , R ^b1 , R ^a2 and R ^b2 are each independently a C ₁ ~ C ₄ alkyl group, or a C ₆ ~ C ₁₈ aryl group Alternatively, R ^a1 and R ^b1 and/or R ^a2 and R ^b2 may combine with each other to form a C ₆ -C ₁₃ ring including a benzene ring.

Also, preferably, when Ar ¹ is a C ₆ ~ C ₃₀ aryl group, R ¹ to R ⁷ are independently bonded to each other to form a C ₆ ~ C ₂₀ ring including a benzene ring. More preferably, when Ar ¹ is a C ₆ ~ C ₁₈ aryl group, at least one pair of adjacent groups of R ¹ to R ⁷ bond to each other to form a C ₆ ~ C ₁₂ aromatic hydrocarbon including a benzene ring. can be formed

Also, preferably, when Ar ¹ is a C ₆ ~ C ₃₀ aryl group, R ^a1 , R ^b1 , R ^a2 and R ^b2 are each independently a C ₁ ~ C ₁₀ alkyl group, or a C ₆ ~ C ₂₀ aryl group or R ^a1 and R ^b1 and/or R ^a2 and R ^b2 may combine with each other to form a C ₆ -C ₂₁ ring including a benzene ring, and R ¹ to R ⁷ are independently of each other adjacent groups They combine with each other to form a C ₆ ~ C ₂₀ ring including a benzene ring.

More preferably, when Ar ¹ is a C ₆ ~ C ₁₈ aryl group, R ^a1 , R ^b1 , R ^a2 and R ^b2 are each independently a C ₁ ~ C ₄ alkyl group, or a C ₆ ~ C ₁₈ aryl group or R ^a1 and R ^b1 and/or R ^a2 and R ^b2 may combine with each other to form a C ₆ -C ₁₃ ring including a benzene ring, and at least one pair of adjacent groups among R ¹ to R ⁷ . They combine with each other to form C ₆ ~ C ₁₂ aromatic hydrocarbons including a benzene ring.

For example, R ^a1 , R ^b1 , R ^a2 and R ^b2 are each independently a methyl group or a phenyl group, or R ^a1 and R ^b1 and/or R ^a2 and R ^b2 combine with each other to form fluorene, and among R ¹ to R ⁷ , At least a pair of neighboring groups are bonded to each other to form a benzene ring, and Ar ¹ may be phenyl, biphenyl, terphenyl, naphthyl, phenanthrene, or pyrene.

The L' is a single bond; C ₆ ~ C ₆₀ Arylene group; fluorenylene group; C ₃ ~ C ₆₀ A fused ring group of an aliphatic ring and a C ₆ ~ C ₆₀ aromatic ring; And C ₂ ~ C ₆₀ A heterocyclic group; may be selected from the group consisting of.

The R' and R" are each independently a C ₆ ~ C ₆₀ aryl group; a fluorenyl group; a C ₃ ~ C ₆₀ aliphatic ring and a C ₆ ~ C ₆₀ aromatic ring fused ring group; and O, N, It may be selected from the group consisting of; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of S, Si and P.

a ring formed by combining R ^a1 , R ^b1 , R ^a2 , R ^b2 , R ¹ to R ⁷ , Ar ¹ , L', R', R", R ^a1 and R ^b1 or R ^a2 and R ^b2 by bonding to each other; and a ring formed by bonding adjacent groups of R ¹ to R ⁷ each may be deuterium; a halogen; a silane group unsubstituted or substituted with a C ₁ -C ₂₀ alkyl group or a C ₆ -C ₂₀ aryl group; a siloxane group; Boron group; Germanium group; Cyano group; Nitro group; C ₁ -C ₂₀ Alkylthio group; C ₁ -C ₂₀ Alkoxy group; C ₁ -C ₂₀ Alkyl group; C ₂ -C ₂₀ Alkenyl group; C ₂ -C ₂₀ alkynyl group; C ₆ -C ₂₀ aryl group; C ₆ -C ₂₀ aryl group substituted with deuterium; fluorenyl group; at least one selected from the group consisting of O, N, S, Si and P One selected from the group consisting of a C ₂ -C ₂₀ heterocyclic group containing a heteroatom; a C ₃ -C ₂₀ cycloalkyl group; a C ₇ -C ₂₀ arylalkyl group; and a C ₈ -C ₂₀ arylalkenyl group; It may be further substituted with more than one substituent.

For example, Ar ¹ may be further substituted with an aryl group such as phenyl, biphenyl, terphenyl, or naphthyl, or deuterium, methyl, ethene, methoxy, F, CN, or the like.

Formula 1 is a compound characterized in that it is represented by one of the following Formulas 2 to 4:

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

In Formulas 2 to 4, R ^a1 , R ^b1 , R ^a2 , R ^b2 , R ¹ to R ⁷ , a, b, c, d, e, f, g and Ar ¹ are those defined in Formula 1 and same.

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

.

.

Preferably, the compound represented by Formula 1 may be included in the light-emitting auxiliary layer in the form of one single compound or a mixture of two or more, and more preferably used as a material for the green light-emitting auxiliary layer of the light-emitting auxiliary layer. .

In another aspect of the present invention, there may be provided an electronic device including a display device including an organic field device, and a control unit for driving the display device, wherein the organic field device includes the organic field device represented by Formula 1 compounds.

Hereinafter, examples of the synthesis of the compound represented by the formula according to the present invention and the preparation of the organic field device will be described in detail with reference to examples, but the present invention is not limited to the following examples.

Synthesis example

The compound (Product) represented by Formula 1 according to the present invention is prepared by reacting Sub 1 and Sub 2 as shown in Scheme 1 below, but is not limited thereto.

<Scheme 1>

I. Sub 1 of synthesis

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

<Scheme 2>

1. Sub 1-1 Synthesis example

bis(9,9-diphenyl-9H-fluoren-4-yl)amine (25.99 g, 40.0 mmol), 1-bromo-3-chlorobenzene (8.04 g, 42.0 mmol), Pd ₂ (dba) ₃ in a round-bottom flask (1.10 g, 1.2 mmol), 50% P(t-Bu) ₃ (1.2 mL, 2.4 mmol), NaO(t-Bu) (11.53 g, 120.0 mmol), and Toluene (130 mL) were added, and then 135°C Heat and reflux for 8 hours. When the reaction is complete, dilute by adding distilled water at room temperature and extract with toluene and water. Thereafter, the organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was recrystallized from toluene and acetone to obtain a product Sub 1-1 (18.25 g, 60%).

2. Sub 1-2 Synthesis example

N-(9,9-dimethyl-9H-fluoren-4-yl)-9,9-diphenyl-9H-fluoren-4-amine (21.03 g, 40.0 mmol), 1-bromo-3-chlorobenzene (8.04 g, 42.0 mmol), Pd ₂ (dba) ₃ (1.10 g, 1.2 mmol), 50% P(t-Bu) ₃ (1.2 mL, 2.4 mmol), NaO(t-Bu) (11.53 g, 120.0 mmol), Toluene (130 mL), The product Sub 1-2 (15.27 g, 60 %) was obtained by the same synthesis method as in Synthesis Example 1-1.

3. Sub 1-7 Synthesis example

N-(9,9-diphenyl-9H-fluoren-4-yl)-9,9'-spirobi[fluoren]-4-amine (25.91 g, 40.0 mmol), 1-bromo-3-chlorobenzene (8.04 g, 42.0 mmol), Pd ₂ (dba) ₃ (1.10 g, 1.2 mmol), 50% P(t-Bu) ₃ (1.2 mL, 2.4 mmol), NaO(t-Bu) (11.53 g, 120.0 mmol), Toluene (130 mL), The product Sub 1-7 (18.20 g, 60 %) was obtained by the same synthesis method as in Synthesis Example 1-1.

4. Sub 1-12 Synthesis example

N-(9,9-dimethyl-9H-fluoren-4-yl)-9,9-dimethyl-9H-fluoren-3-amine (16.06 g, 40.0 mmol), 1-bromo-3-chlorobenzene (8.04 g, 42.0 mmol), Pd ₂ (dba) ₃ (1.10 g, 1.2 mmol), 50% P(t-Bu) ₃ (1.2 mL, 2.4 mmol), NaO(t-Bu) (11.53 g, 120.0 mmol), Toluene (130 mL), The product Sub 1-12 (12.29 g, 60 %) was obtained by the same synthesis method as in Synthesis Example 1-1.

5. Sub 1-20 Synthesis example

N-(9,9-diphenyl-9H-fluoren-4-yl)-9,9-dimethyl-9H-fluoren-2-amine (21.03 g, 40.0 mmol), 1-bromo-3-chlorobenzene (8.04 g, 42.0 mmol), Pd ₂ (dba) ₃ (1.10 g, 1.2 mmol), 50% P(t-Bu) ₃ (1.2 mL, 2.4 mmol), NaO(t-Bu) (11.53 g, 120.0 mmol), Toluene (130 mL), The product Sub 1-20 (15.27 g, 60 %) was obtained by the same synthesis method as in Synthesis Example 1-1.

6. Sub 1-53 Synthesis example

N-(9,9-diphenyl-9H-fluoren-3-yl)-9,9-dimethyl-9H-fluoren-1-amine (21.03 g, 40.0 mmol), 1-bromo-3-chlorobenzene (8.04 g, 42.0 mmol), Pd ₂ (dba) ₃ (1.10 g, 1.2 mmol), 50% P(t-Bu) ₃ (1.2 mL, 2.4 mmol), NaO(t-Bu) (11.53 g, 120.0 mmol), Toluene (130 mL), the product Sub 1-53 (15.27 g, 60 %) was obtained by the same synthesis method as in the Sub 1-1 synthesis example.

7. Sub 1-68 Synthesis example

N-(9,9-diphenyl-9H-fluoren-2-yl)-9,9-diphenyl-9H-fluoren-1-amine (25.99 g, 40.0 mmol), 1-bromo-3-chlorobenzene (8.04 g, 42.0 mmol), Pd ₂ (dba) ₃ (1.10 g, 1.2 mmol), 50% P(t-Bu) ₃ (1.2 mL, 2.4 mmol), NaO(t-Bu) (11.53 g, 120.0 mmol), Toluene (130 mL), The product Sub 1-68 (15.21 g, 50 %) was obtained by the same synthesis method as in Synthesis Example 1-1.

8. Sub 1-75 Synthesis example

N-(9,9-dimethyl-9H-fluoren-1-yl)-9,9-diphenyl-9H-fluoren-1-amine (21.03 g, 40.0 mmol), 3-bromo-5-chloro-1,1 '-biphenyl (8.04 g, 42.0 mmol), Pd ₂ (dba) ₃ (1.10 g, 1.2 mmol), 50% P(t-Bu) ₃ (1.2 mL, 2.4 mmol), NaO(t-Bu) (11.53 g, 120.0 mmol), Toluene (130 mL), The product Sub 1-75 (17.10 g, 60 %) was obtained by the same synthesis method as in Synthesis Example 1-1.

The compound belonging to Sub 1 prepared by the above synthesis method may be a compound as follows, but is not limited thereto, and Table 1 shows the FD-MS values of the compound belonging to Sub 1.

[Table 1]

II. Sub 2 example

The compound belonging to Sub 2 may be the following compounds, but is not limited thereto, and Table 2 shows FD-MS values of the compounds belonging to Sub 2 .

[Table 2]

III. Product synthesis

1. Compound P-1 Synthesis example

Sub 1-1 (18.25 g, 24.0 mmol), Sub 2-1 (6.22 g, 24.0 mmol), Pd ₂ (dba) ₃ (0.66 g, 0.7 mmol), P(t-Bu) ₃ ( 0.7 mL, 1.4 mmol), NaO(t-Bu) (6.92 g, 72.0 mmol), and Toluene (80 mL) were added, and then heated to reflux at 135° C. for 8 hours. When the reaction is complete, dilute by adding distilled water at room temperature, and extract with toluene and water. Thereafter, the organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was dissolved in Toluene. Then, the solution dissolved in toluene was passed through a silica filter, concentrated, and then recrystallized from Toluene and Acetone to produce P-1 (17.7 g) , 70%) was obtained.

2. Compound P-3 Synthesis example

Sub 1-2 (18.25 g, 24.0 mmol), Sub 2-1 (6.22 g, 24.0 mmol), Pd ₂ (dba) ₃ (0.66 g, 0.7 mmol), P(t-Bu) ₃ (0.7 mL, 1.4 mmol), NaO(t-Bu) (6.92 g, 72.0 mmol), Toluene (80 mL), the compound P- 1 It was synthesized as in Synthesis Example to obtain a product P-3 (16.83 g, 75%).

3. Compound P-11 Synthesis example

Sub 1-7 (18.20 g, 24.0 mmol), Sub 2-11 (8.05 g, 24.0 mmol), Pd ₂ (dba) ₃ (0.66 g, 0.7 mmol), P(t-Bu) ₃ (0.7 mL, 1.4 mmol), NaO(t-Bu) (6.92 g, 72.0 mmol), Toluene (80 mL), the compound P- 1 It was synthesized as in Synthesis Example to obtain a product P-11 (17.76 g, 70%).

4. Compound P-19 Synthesis example

Sub 1-12 (12.29 g, 24.0 mmol), Sub 2-28 (6.34 g, 24.0 mmol), Pd ₂ (dba) ₃ (0.66 g, 0.7 mmol), P(t-Bu) ₃ (0.7 mL, 1.4 mmol), NaO(t-Bu) (6.92 g, 72.0 mmol), Toluene (80 mL), the compound P- 1 was synthesized as in Synthesis Example to obtain a product P-19 (10.66 g, 60%).

5. Compound P-28 Synthesis example

Sub 1-20 (15.27 g, 24.0 mmol), Sub 2-4 (8.05 g, 24.0 mmol), Pd ₂ (dba) ₃ (0.66 g, 0.7 mmol), P(t-Bu) ₃ (0.7 mL, 1.4 mmol), NaO(t-Bu) (6.92 g, 72.0 mmol), Toluene (80 mL), the compound P- 1 It was synthesized as in Synthesis Example to obtain a product P-28 (13.47 g, 60%).

6. Compound P-72 Synthesis example

Sub 1-53 (15.27 g, 24.0 mmol), Sub 2-29 (9.25 g, 24.0 mmol), Pd ₂ (dba) ₃ (0.66 g, 0.7 mmol), P(t-Bu) ₃ (0.7 mL, 1.4 mmol), NaO(t-Bu) (6.92 g, 72.0 mmol), Toluene (80 mL), the compound P- 1 was synthesized as in Synthesis Example to obtain a product P-72 (11.82 g, 50%).

7. Compound P-94 Synthesis example

Sub 1-68 (15.21 g, 20.0 mmol), Sub 2-2 (6.71 g, 20.0 mmol), Pd ₂ (dba) ₃ (0.55 g, 0.6 mmol), P(t-Bu) ₃ (0.6 mL, 1.2 mmol), NaO(t-Bu) (5.77 g, 60.0 mmol), Toluene (66 mL), the compound P- 1 was synthesized as in Synthesis Example to obtain a product P-94 (14.83 g, 70%).

8. Compound P-103 Synthesis example

Sub 1-75 (17.10 g, 24.0 mmol), Sub 2-3 (8.05 g, 24.0 mmol), Pd ₂ (dba) ₃ (0.66 g, 0.7 mmol), P(t-Bu) ₃ (0.7 mL, 1.4 mmol), NaO(t-Bu) (6.92 g, 72.0 mmol), Toluene (80 mL), the compound P- 1 It was synthesized as in Synthesis Example to obtain a product P-103 (13.35 g, 55%).

FD-MS values of compounds P-1 to P-108 of the present invention prepared according to the above synthesis examples are shown in Table 3 below.

[Table 3]

Manufacturing evaluation of organic electroluminescent device

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

N ¹ -(naphthalen-2-yl)-N ⁴ ,N ⁴ -bis(4-(naphthalen-2-yl(phenyl)amino)phenyl)-N ¹ -phenylbenzene on the ITO layer (anode) formed on the glass substrate After vacuum deposition of a -1,4-diamine (hereinafter abbreviated as "2-TNATA") film to form a 60 nm thick hole injection layer, N,N'-Bis(1-naphthalenyl)-N,N'- A bis-phenyl-(1,1'-biphenyl)-4,4'-diamine (hereinafter abbreviated as "NPB") film was vacuum-deposited to a thickness of 60 nm to form a hole transport layer. next,

Next, the compound P-1 of the present invention was vacuum-deposited to a thickness of 20 nm on the hole transport layer to form a light emitting auxiliary layer.

Next, on the light emitting auxiliary layer, 4,4'-N,N'-dicarbazole-biphenyl (hereinafter referred to as "CBP") as a host material and tris(2-phenylpyridine)-iridium (hereinafter, "Ir(ppy) ₃ ) was used in a 95:5 weight ratio to form a light emitting layer with a thickness of 30 nm.

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

[Example 2] to [Example 31]

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

[Comparative Example 1]

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that the light-emitting auxiliary layer was not formed.

[ comparative example 2] to [ comparative example 5]

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

[ comparative example 6]

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that the compound P-1 of the present invention was used as the material of the hole transport layer and NPB was used as the material of the light emission auxiliary layer.

<Comparative compound A> <Comparative compound B> <Comparative compound C> <Comparative compound D>

Electroluminescence (EL) characteristics by applying a forward bias DC voltage to the organic electroluminescent devices manufactured by Examples 1 to 21 and Comparative Examples 1 to 6 of the present invention and PR-650 from Photoresearch , at 5000cd/m ² standard luminance, the T95 lifetime was measured using a lifetime measuring device manufactured by McScience, and the measurement results are shown in Table 4 below.

[Table 4]

As can be seen from the results in Table 4, when a green organic light emitting device is manufactured using the material for an organic electroluminescent device of the present invention as a light emitting auxiliary layer material, the light emitting auxiliary layer is not formed or Comparative Compound A to Comparative Compound Compared to the comparative example using D, the driving voltage of the organic light emitting diode can be lowered, and the luminous efficiency and lifespan can be improved.

In the case of Comparative Examples 2 to 5, in which the light emitting auxiliary layer was formed using one of Comparative Compounds A to D, rather than Comparative Example 1 in which the light emitting auxiliary layer was not formed, the driving voltage, efficiency and lifespan were improved. Compared to Comparative Examples 1 to 5, in the case of Examples of the present invention in which NPB was used as the hole transport layer material and the compound of the present invention was used as the light emitting auxiliary layer material, the driving voltage, efficiency, and lifespan were significantly improved.

Comparative Compound A and Comparative Compound B differ only in the position where the amine group is bonded to dibenzofuran. It is bound to position 1 of this dibenzofuran. Looking at the device characteristics of Comparative Examples 2 and 3 using these compounds as a light emitting auxiliary layer material, it can be seen that the device characteristics of Comparative Example 3 are better.

In addition, comparing the comparative compound B and the comparative compound C, only the position at which both amines are bonded to the phenyl is different. ), on the other hand, Comparative Compound C is different in that both amine groups are non-linearly positioned (that is, the amine group is bonded to the meta position of phenyl). Looking at the device characteristics of Comparative Example 3 and Comparative Example 4 using these compounds as a light emitting auxiliary layer material, it can be seen that the device characteristics of Comparative Example 4 using Comparative Compound C were significantly improved.

In addition, comparing the comparative compound C and the comparative compound D, the comparative compound C has phenyl bonded to the nitrogen of the amine group to which dibenzofuran is bonded, whereas the comparative compound D has dimethyl fluorene deficient. Looking at the device characteristics of Comparative Examples 4 and 5 using these compounds as a light emitting auxiliary layer material, it can be seen that the device characteristics of Comparative Example 5 were slightly improved.

Therefore, from the device characteristics results of Comparative Examples 2 to 5, when two amine groups are bonded to the linker by phenyl, they are bonded to the linker at a meta position, and the same substituent fluorene is bonded to the nitrogen of both amines, respectively. It can be seen that the properties of the organic electroluminescent device can be improved when the compound in the present invention is used as the light emitting auxiliary layer material.

From these results, it can be seen that even compounds having a similar structure may have different characteristics of the device depending on the substitution position of the substituent and the type of the substituent. This seems to be because the physical properties of the compound act as a major factor (eg, energy balance) in improving device performance during compound deposition during the manufacturing process.

On the other hand, in the compound according to Formula 1 of the present invention, two amine groups are substituted at the meta position of phenyl, which is a linking group, 1-dibenzofuran is bonded to the nitrogen of one amine group, and the nitrogen of the other amine group is Two fluorenes are bonded to each other.

As can be seen in Comparative Examples 4 and 5 above, when 1-dibenzofuran is bonded to two amine group cores, a compound containing two fluorenes rather than one fluorene It was confirmed that the device characteristics of the fluorene were further improved. As in Comparative Example 5 of the present invention, two fluorenes were included in the compound, but the fluorene was not bonded to the nitrogen of different amine groups, but the nitrogen of the amine group. The difference is that each has a fluorene bonded thereto. However, as can be seen in Table 4, the compound of the present invention in which two fluorenes are bonded to one amine group rather than Comparative Example 5 in which fluorene is bonded to the nitrogen of both amine groups is used as a light emitting auxiliary layer material. In this case, the characteristics of the device were significantly improved.

This is because the physical properties of the compound, including LUMO, HOMO, band gap, and T1 value, are different depending on whether the two fluorenes are each bonded to the nitrogen of the amine group or both are bonded to one amine group. The difference in physical properties seems to be because it acts as a major factor influencing the device characteristics when a compound is deposited to form a light emitting auxiliary layer in the device manufacturing process.

Therefore, even for compounds having a similar structure, if slight differences in the type and position of substituents play a decisive role in the difference in physical properties, it can be seen that device characteristic results that are difficult for a person skilled in the art to be derived can be derived, and Comparative Example 6 and When comparing the examples of the present invention, it can be seen that even if the same compound is used, completely different device characteristic results can be derived depending on which material is used for which layer, that is, the combination of materials used for each layer.

The above description is merely illustrative of the present invention, and those of ordinary skill in the art to which the present invention pertains will be able to make various modifications without departing from the essential characteristics of the present invention. Accordingly, the embodiments disclosed herein are for illustrative purposes rather than limiting the present invention, and the spirit and scope of the present invention are not limited by these embodiments. The protection scope of the present invention should be construed by the following claims, and all descriptions within an equivalent scope should be construed as being included in the scope of the present invention.

100: organic electric device 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 (8)

An organic electric field device comprising a first electrode, a second electrode, and an organic material layer formed between the first electrode and the second electrode,
The organic material layer includes a light emitting auxiliary layer formed between the first electrode and the light emitting layer, wherein the light emitting auxiliary layer comprises a compound represented by the following formula (1):
<Formula 1>

In Formula 1,
R ^a1 , R ^b1 , R ^a2 and R ^b2 are each independently a C ₁ ~ C ₅₀ alkyl group; C ₆ ~ C ₆₀ Aryl group; fluorenyl group; and O, N, ^S , ^Si and ^P , a C ₂ ~ C ₆₀ heterocyclic group comprising at least one ^heteroatom ; may combine with each other to form a ring, wherein the ring is C ₆ ~ C ₆₀ aromatic hydrocarbon; fluorenyl group; O, N, S, Si and P containing at least one heteroatom C ₂ ~ C ₆₀ A heterocyclic group; C ₃ ~ C ₆₀ aliphatic ring; And C ₃ ~ C ₆₀ aliphatic ring and C ₆ ~ C ₆₀ It is selected from the group consisting of a fused ring group of an aromatic ring,
R ¹ to R ⁴ , R ⁶ and R ⁷ are each independently hydrogen; heavy hydrogen; halogen; C ₆ ~ C ₆₀ Aryl group; fluorenyl group; O, N, S, Si and P containing at least one heteroatom C ₂ ~ C ₆₀ A heterocyclic group; C ₃ ~ C ₆₀ A fused ring group of an aliphatic ring and a C ₆ ~ C ₆₀ aromatic ring; C ₁ ~ C ₅₀ Alkyl group; C ₂ ~ C ₂₀ Alkenyl group; C ₂ ~ C ₂₀ alkynyl group; C ₁ ~ C ₃₀ An alkoxyl group; C ₆ ~ C ₃₀ Aryloxy group; and -L'-N(R')(R"); and adjacent groups may combine with each other to form a ring, wherein the ring is a C ₆ ~ C ₆₀ aromatic hydrocarbon; fluorene Diary; O, N, S, Si and P containing at least one heteroatom ₂ ~ C ₆₀ heterocyclic group; C ₃ ~ C ₆₀ aliphatic ring; And C ₃ ~ C ₆₀ aliphatic ring and C ₆ ~ C ₆₀ is selected from the group consisting of a fused ring group of an aromatic ring,
R ⁵ are each independently hydrogen; heavy hydrogen; and C ₆ ~ C ₆₀ selected from the group consisting of an aryl group, and adjacent R ⁵ may combine with each other to form a C ₆ ~ C ₆₀ aromatic hydrocarbon ring,
a, c, e and g are each an integer from 0 to 4, b, d and f are each an integer from 0 to 3,
Ar ¹ is a C ₆ ~ C ₆₀ aryl group,
The L' is a single bond; C ₆ ~ C ₆₀ Arylene group; fluorenylene group; C ₃ ~ C ₆₀ A fused ring group of an aliphatic ring and a C ₆ ~ C ₆₀ aromatic ring; And C ₂ ~ C ₆₀ A heterocyclic group is selected from the group consisting of,
The R' and R" are each independently a C ₆ ~ C ₆₀ aryl group; a fluorenyl group; a C ₃ ~ C ₆₀ aliphatic ring and a C ₆ ~ C ₆₀ aromatic ring fused ring group; and O, N, Selected from the group consisting of; C ₂ ~ C ₆₀ heterocyclic group comprising at least one heteroatom of S, Si and P;
a ring formed by combining R ^a1 , R ^b1 , R ^a2 , R ^b2 , R ¹ to R ⁷ , Ar ¹ , L', R', R", R ^a1 and R ^b1 or R ^a2 and R ^b2 by bonding to each other; and a ring formed by bonding adjacent groups of R ¹ to R ⁷ each may be deuterium; a halogen; a silane group unsubstituted or substituted with a C ₁ -C ₂₀ alkyl group or a C ₆ -C ₂₀ aryl group; a siloxane group; Boron group; Germanium group; Cyano group; Nitro group; C ₁ -C ₂₀ Alkylthio group; C ₁ -C ₂₀ Alkoxy group; C ₁ -C ₂₀ Alkyl group; C ₂ -C ₂₀ Alkenyl group; C ₂ -C ₂₀ alkynyl group; C ₆ -C ₂₀ aryl group; C ₆ -C ₂₀ aryl group substituted with deuterium; fluorenyl group; at least one selected from the group consisting of O, N, S, Si and P One selected from the group consisting of a C ₂ -C ₂₀ heterocyclic group containing a heteroatom; a C ₃ -C ₂₀ cycloalkyl group; a C ₇ -C ₂₀ arylalkyl group; and a C ₈ -C ₂₀ arylalkenyl group; It may be further substituted with more than one substituent,
However, R ⁵ does not include a fluorenyl group or a heterocyclic group. The method of claim 1,
Formula 1 is an organic electric field device, characterized in that represented by one of the following Formulas 2 to 4:
<Formula 2><Formula3><Formula4>

In Formulas 2 to 4, R ¹ to R ⁷ , a, b, c, d, e, f, g, and Ar ¹ are as defined in claim 1. The method of claim 1,
The compound represented by Formula 1 is an organic electric field device, characterized in that one of the following compounds:

. The method of claim 1,
The compound represented by Formula 1 is an organic electric field device, characterized in that it comprises one type of compound or a mixture of two or more types in the light emitting auxiliary layer. The method of claim 1,
The compound is an organic electric field device, characterized in that used as a material of the green light emission auxiliary layer of the light emission auxiliary layer. The method of claim 1,
The organic material layer is an organic field device, characterized in that formed by a spin coating process, a nozzle printing process, an inkjet printing process, a slot coating process, a dip coating process or a roll-to-roll process. A display device comprising the organic field device of claim 1; and
An electronic device comprising a; a control unit for driving the display device. 8. The method of claim 7,
The organic electric device is an organic light emitting device, an organic solar cell, an organic photoreceptor, an organic transistor, an electronic device, characterized in that selected from the group consisting of a single color lighting device and a quantum dot display device.

Images