KR20210022272A - Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof - Google Patents

Abstract

The present invention provides: an organic electric element containing a compound represented by chemical formula 1, and including a first electrode, a second electrode, and an organic material layer between the first electrode and the second electrode; and an electronic device including the organic electric element. By containing the compound represented by chemical formula 1 in the organic material layer, it is possible to lower a driving voltage, and improve luminous efficiency and lifespan of the organic electric element.

Description

Compound for organic electric device, organic electric device using the same, and electronic device thereof {COMPOUND FOR ORGANIC ELECTRONIC ELEMENT USING THE SAME, AND AN ELECTRONIC DEVICE THEREOF}

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

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

Materials used as an organic material layer in an organic electronic device can be classified into light-emitting materials and charge transport materials, such as hole injection materials, hole transport materials, electron transport materials, and electron injection materials, according to their functions. And the light-emitting material can be classified into a high molecular type and a low molecular type according to the molecular weight, and according to the light emitting mechanism, it can be classified into a fluorescent material derived from the singlet excited state of the electron and a phosphorescent material derived from the triplet excited state of the electron. have. In addition, the light-emitting material may be classified into blue, green, and red light-emitting materials and yellow and orange light-emitting materials necessary to realize a better natural color according to the light-emitting color.

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

Currently, the portable display market is increasing in size as a large-area display, and for this reason, more power consumption than the power consumption required by the existing portable display is required. Therefore, power consumption has become an important factor for portable displays that have a limited power supply source, such as a battery, and efficiency and life issues are also important factors that must be solved.

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

In addition, in order to solve the problem of light emission in the hole transport layer in recent organic electroluminescent devices, a method of using a light emitting auxiliary layer between the hole transport layer and the light emitting layer is being studied. Since material properties are different, it is time to develop a light-emitting auxiliary layer for each light-emitting layer.

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, and excitons are generated by recombination.

However, in the case of a material used in the hole transport layer, since it must have a low HOMO value, most have a low T ₁ value, and as a result, excitons generated in the light emitting layer pass to the hole transport layer interface or the hole transport layer, and as a result, the hole transport layer. It causes light emission at the interface or charge unbalance in the light emitting layer to emit light at the hole transport layer interface.

When light is emitted at the hole transport layer interface, the color purity and efficiency of the organic electric device are deteriorated, and the lifespan is shortened. Therefore, it must be a material having a HOMO level between the HOMO energy level of the hole transport layer and the HOMO energy level of the light emitting layer, has a high T1 value, and is within a suitable driving voltage range (within the driving voltage range of the blue device of the full device). Mobility) is required to develop a light-emitting auxiliary layer.

However, this cannot be achieved simply due to the structural characteristics of the core of the light-emitting auxiliary layer material, and the characteristics of the core and sub-substituent of the light-emitting auxiliary layer material, and a suitable combination between the light-emitting auxiliary layer and the hole transport layer, and the light-emitting auxiliary layer and the light-emitting layer are made. When it is lost, a high-efficiency and high-life device can be implemented.

Meanwhile, development of materials for a light-emitting layer and a light-emitting auxiliary layer having stable properties, that is, a high glass transition temperature, against Joule heating generated when the device is driven is also required. The low glass transition temperature of the light emitting layer and the light emitting auxiliary layer material decreases the uniformity of the thin film surface when the device is driven, and the material may be deformed due to heat generated when the device is driven, which has been reported to have a great influence on the life of the device.

Therefore, it is necessary to develop a material that can withstand a long time during evaporation, that is, a material with strong heat resistance, and materials that form the organic material layer in the device, such as hole injection materials, hole transport materials, and light emission, are required to fully exhibit the excellent characteristics of organic electronic devices. A material, an electron transport material, an electron injection material, a light-emitting auxiliary layer material, etc. must be supported by a stable and efficient material. In particular, development of materials used for a light-emitting auxiliary layer and a light-emitting layer is required.

An object of the present invention is to provide a compound capable of lowering a driving voltage of a device and improving luminous efficiency and lifetime of a device, an organic electric device using the same, and an electronic device thereof.

In one aspect, the present invention provides a compound represented by the following formula.

In another aspect, the present invention provides an organic electric device and an electronic device using the compound represented by the above formula.

By using the compound according to an embodiment of the present invention, not only can the driving voltage of the device be lowered, but also the luminous efficiency, color purity, stability, and lifespan of the device can be greatly improved.

1 to 3 are exemplary views of an organic electroluminescent device according to the present invention.
4 shows a chemical formula according to an aspect of the present invention.

The terms "aryl group" and "arylene group" used in the present invention each have 6 to 60 carbon atoms, and are not limited thereto. In the present invention, the aryl group or the arylene group may include a monocyclic type, a ring aggregate, a conjugated ring system, a spiro compound, and the like. In addition, unless otherwise stated in the specification, a fluorenyl group may be included in the aryl group, and a fluorenylene group may be included in the arylene group.

The terms "fluorenyl group", "fluorenylene group", and "fluorentriyl group" used in the present invention are monovalent, 2 in which R, R'and R" are all hydrogen in the following structures, respectively, unless otherwise specified. It means a valence or trivalent functional group, "substituted fluorenyl group", "substituted fluorenylene group" or "substituted fluorentriyl group" means that at least one of the substituents R, R', R" is other than hydrogen It means that it is a substituent, and includes the case where R and R'are bonded to each other to form a spy compound together with the carbon to which they are bonded. In the present specification, a fluorenyl group, a fluorenylene group, and a fluorenetriyl group may all be referred to as fluorene groups regardless of the valence.

The term "spyro compound" used in the present invention has a'spyro linkage', and the spyro linkage refers to a linkage made by two rings sharing only one atom. At this time, the atoms shared in the two rings are referred to as'spyro atoms', and depending on the number of spyro atoms in one compound, these are respectively referred to as'monospiro-','dispiro-', and'trispyro-'. 'It is called a compound.

The term "heterocyclic group" used in the present invention includes not only an aromatic ring such as a "heteroaryl group" or a "heteroarylene group", but also a non-aromatic ring, and unless otherwise stated, each carbon number including one or more heteroatoms It means a ring of 2 to 60, but is not limited thereto. The term "heteroatom" as used herein refers to N, O, S, P, or Si unless otherwise specified, and the heterocyclic group is a monocyclic type including a heteroatom, a ring aggregate, a conjugated ring system, spy It means a compound and the like. In addition, instead of carbon forming a ring, _{a compound including a heteroatom group such as SO 2} , P=O, and the like, such as the following compounds, may also be included in the heterocyclic group.

The term "aliphatic ring group" as used in the present invention refers to cyclic hydrocarbons excluding aromatic hydrocarbons, and includes monocyclic, cyclic aggregates, conjugated cyclic systems, spiro compounds, etc., unless otherwise stated, It refers to a ring of 3 to 60, but is not limited thereto. For example, even when benzene, which is an aromatic ring, and cyclohexane, which is a non-aromatic ring, are fused, it is an aliphatic ring.

In the present specification, the'group name' corresponding to the aryl group, arylene group, heterocyclic group, etc. exemplified as examples of each symbol and its substituent may describe'the name of the group reflecting the number', but is described as'parent compound name' You may. For example, in the case of'phenanthrene', which is a kind of aryl group, the monovalent'group' is'phenanthryl' and the divalent group can be labeled with the valence by dividing the valency such as'phenanthrylene'. Regardless, it may be described as the parent compound name'phenanthrene'. Similarly, in the case of pyrimidine, it may be described as'pyrimidine' regardless of the valence, or in the case of monovalent, it may be described as the'name of the group' of the corresponding valency, such as a pyrimidinyl group and in the case of divalent, pyrimidinylene. have.

In addition, in the present specification, when describing the name of the compound or the name of the substituent, numbers or alphabets indicating positions may be omitted. For example, pyrido[4,3-d]pyrimidine to pyridopyrimidine, benzofuro[2,3-d]pyrimidine to benzofuropyrimidine, 9,9-dimethyl-9H-flu Orene can be described as dimethylfluorene or the like. Therefore, both benzo[g]quinoxaline and benzo[f]quinoxaline can be described as benzoquinoxaline.

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

Here, when a is an integer of 0, the substituent R ¹ means that the substituent R 1 is absent, that is, when a is 0, it means that all hydrogens are bonded to the carbon forming the benzene ring. It may be omitted and the formula or compound may be described. In addition, when a is an integer of 1, one substituent R ¹ is bonded to any one of carbons forming a benzene ring, and when a is an integer of 2 or 3, it may be bonded, for example, as follows, and a is 4 to 6 In the case of an integer of, it is bonded to the carbon of the benzene ring in a similar manner, and when a is an integer of 2 or more, R ¹ may be the same or different from each other.

In addition, unless otherwise specified in the present specification, when indicating a condensed ring, a number in'number-condensed ring' indicates the number of condensed rings. For example, a form in which three rings are condensed with each other, such as anthracene, phenanthrene, benzoquinazoline, and the like, may be expressed as a 3-condensed ring.

In addition, unless otherwise specified in the specification, when a ring is expressed in the form of a'numeric resource' such as a five-membered ring, a six-membered ring, etc., the number in'number-atom' indicates the number of elements forming the ring. For example, thiophene or furan may correspond to a five-membered ring, and benzene or pyridine may correspond to a six-membered ring.

In addition, unless otherwise described in the present specification, the ring formed by bonding of adjacent groups to each other is a C ₆ ~ C ₆₀ aromatic ring group; Fluorenyl group; O, N, S, Si, and C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of P; And C ₃ ~ C ₆₀ aliphatic ring group; may be selected from the group consisting of.

At this time, unless otherwise described in the specification, the term'neighboring groups' refers to the following formula as an example, _{between R 1} and R _2, between R ₂ and R _3, between R ₃ and R ₄ , Not only R ₅ and R _{6 but also R 7} and R ₈ sharing one carbon are included, and are not immediately adjacent, such as between _{R 1} and R ₇ , R ₁ and R _8, or R ₄ and R _5. Substituents bonded to ring elements (such as carbon or nitrogen) may also be included. In other words, if there are substituents on a ring element such as carbon or nitrogen immediately adjacent to each other, they may be neighboring groups, but if no substituent is bonded to the ring element at the immediately adjacent position, it is bonded to the next ring element. It may be a group adjacent to the substituted substituent, and also the substituents bonded to the carbon constituting the same ring may be referred to as neighboring groups.

In the following formula, _{when substituents bonded to the same carbon as R 7} and R ₈ are bonded to each other to form a ring, a compound including a spiro moiety may be formed.

,

,

In addition, in the present specification, the expression'neighboring groups can be bonded to each other to form a ring' is used in the same meaning as'neighboring groups are bonded to each other to selectively form a ring', and at least one pair of It refers to a case where neighboring groups are bonded to each other to form a ring.

Hereinafter, a laminated structure of an organic electric device including the compound of the present invention will be described with reference to FIGS. 1 to 3.

In adding reference numerals to elements of each drawing, it should be noted that the same elements are assigned the same numerals as possible, even if they are indicated on different drawings. In addition, in describing the present invention, when it is determined that a detailed description of a related known configuration or function may obscure the subject matter of the present invention, a detailed description thereof will be omitted.

In describing the constituent elements of the present invention, terms such as first, second, A, B, (a), and (b) may be used. These terms are for distinguishing the constituent element from other constituent elements, and the nature, order, or order of the constituent element is not limited by the term. When a component is described as being "connected", "coupled" or "connected" to another component, that component may be directly connected or connected to that other component, but another component between each component It will be understood that elements may be “connected”, “coupled” or “connected”.

Also, when a component such as a layer, film, region, or plate is said to be "on" or "on" another component, it is not only "directly over" another component, but also when another component is in the middle. It should be understood that cases may also be included. Conversely, it should be understood that when an element is "directly above" another part, it means that there is no other part in the middle.

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

Referring to FIG. 1, an organic electric device 100 according to an embodiment of the present invention includes a first electrode 110, a second electrode 170, and a first electrode 110 formed on a substrate (not shown). ) And an organic material layer formed between the second electrode 170.

The first electrode 110 may be an anode (anode), the second electrode 170 may be a cathode (cathode), and in the case of an inverted type, a first electrode may be a cathode and a second electrode may be an anode.

The organic material layer may include a hole injection layer 120, a hole transport layer 130, a light emitting layer 140, an electron transport layer 150, and an electron injection layer 160. Specifically, a hole injection layer 120, a hole transport layer 130, a light emitting layer 140, an electron transport layer 150, and an electron injection layer 160 may be sequentially formed on the first electrode 110.

Preferably, the light efficiency improvement layer 180 may be formed on one side of both surfaces of the first electrode 110 or the second electrode 170 that is not in contact with the organic material layer, and when the light efficiency improvement layer 180 is formed The light efficiency of the organic electric device can be improved.

For example, the light efficiency improvement layer 180 may be formed on the second electrode 170. In the case of a top emission organic light emitting device, the light efficiency improvement layer 180 is formed to form the second electrode 170. ), optical energy loss due to surface plasmon polaritons (SPPs) can be reduced, and in the case of a bottom emission organic light emitting device, the light efficiency improvement layer 180 performs a buffering role for the second electrode 170 can do.

A buffer layer 210 or a light emission auxiliary layer 220 may be further formed between the hole transport layer 130 and the emission layer 140, which will be described with reference to FIG. 2.

Referring to FIG. 2, an organic electric device 200 according to another embodiment of the present invention includes a hole injection layer 120, a hole transport layer 130, a buffer layer 210, which are sequentially formed on the first electrode 110. A light-emitting auxiliary layer 220, a light-emitting layer 140, an electron transport layer 150, an electron injection layer 160, and a second electrode 170 may be included, and a light efficiency improvement layer 180 is formed on the second electrode. Can be.

Although not shown in FIG. 2, an electron transport auxiliary layer may be further formed between the light emitting layer 140 and the electron transport layer 150.

In addition, according to another embodiment of the present invention, the organic material layer may have a form in which a plurality of stacks including a hole transport layer, an emission layer, and an electron transport layer are formed. This will be described with reference to FIG. 3.

Referring to FIG. 3, in an organic electric device 300 according to another embodiment of the present invention, two stacks ST1 and ST2 formed of a multi-layered organic material layer are disposed between the first electrode 110 and the second electrode 170. A set or more may be formed, and a charge generation layer CGL may be formed between the stacks of the organic material layers.

Specifically, the organic electric device according to the embodiment of the present invention includes a first electrode 110, a first stack ST1, a charge generation layer (CGL), a second stack ST2, and a second electrode. 170 and a light efficiency improvement layer 180 may be included.

The first stack ST1 is an organic material layer formed on the first electrode 110, which is a first hole injection layer 320, a first hole transport layer 330, a first emission layer 340, and a first electron transport layer 350. ), and the second stack ST2 may include a second hole injection layer 420, a second hole transport layer 430, a second emission layer 440, and a second electron transport layer 450. . As described above, the first stack and the second stack may be organic material layers having the same laminated structure, but may be organic material layers having different laminated structures.

A charge generation layer CGL may be formed between the first stack ST1 and the second stack ST2. The charge generation layer CGL may include a first charge generation layer 360 and a second charge generation layer 361. The charge generation layer CGL is formed between the first emission layer 340 and the second emission layer 440 to increase current efficiency generated in each emission layer and smoothly distribute electric charges.

The first emission layer 340 may include a light emitting material including a blue fluorescent dopant in a blue host, and the second emission layer 440 includes a material doped with a greenish yellow dopant and a red dopant in a green host. It may be included, but the material of the first emission layer 340 and the second emission layer 440 according to an embodiment of the present invention is not limited thereto.

In FIG. 3, n may be an integer of 1 to 5. When n is 2, a charge generation layer CGL and a third stack may be additionally stacked on the second stack ST2.

When a plurality of light-emitting layers are formed by the multi-layer stack structure method as shown in FIG. 3, it is possible to manufacture an organic electroluminescent device in which white light is emitted by the mixing effect of light emitted from each of the light-emitting layers, as well as various colors of light. It is also possible to manufacture an organic electroluminescent device that emits light.

The compound represented by Formula 1 of the present invention is a hole injection layer (120, 320, 420), a hole transport layer (130, 330, 430), a buffer layer (210), a light emission auxiliary layer (220), an electron transport layer (150, 350). , 450), the electron injection layer 160, the light emitting layer 140, 340, 440, or may be used as a material for the light efficiency improvement layer 180, but preferably, the light emitting layer 140, 340, 440, the light emitting auxiliary layer 220 ) And/or the light efficiency improvement layer 180 may be used as a material.

Since the band gap, electrical properties, and interfacial properties can vary depending on which substituent is bonded to any position even with the same and similar core, a study on the selection of the core and the combination of sub-substituents bonded thereto _{In particular, long life and high efficiency can be achieved at the same time when the energy level and T 1} value between each organic material layer and the intrinsic properties of the material (mobility, interfacial properties, etc.) are optimally combined.

Therefore, in the present invention, by using the compound represented by Formula 1 as a material for the light emitting layer 140, 340, 440, the light emitting auxiliary layer 220, and/or the light efficiency improving layer 180, the energy level and T _{1 between each organic material layer} By optimizing the value and intrinsic properties of the material (mobility, interfacial properties, etc.), it is possible to improve the life and efficiency of the organic electric device at the same time.

The organic electroluminescent device according to an embodiment of the present invention may be manufactured using various deposition methods. It can be manufactured using a deposition method such as PVD or CVD, for example, by depositing a metal or a conductive metal oxide or an alloy thereof on a substrate to form the anode 110, and a hole injection layer 120 thereon. , After forming an organic material layer including the hole transport layer 130, the light emitting layer 140, the electron transport layer 150 and the electron injection layer 160, it can be prepared by depositing a material that can be used as the cathode 170 thereon. have. In addition, a light emitting auxiliary layer 220 between the hole transport layer 130 and the light emitting layer 140, and an electron transport auxiliary layer (not shown) between the light emitting layer 140 and the electron transport layer 150 may be further formed. It can also be formed in a stack structure as shown.

In addition, the organic material layer is a solution process or a solvent process other than a vapor deposition method using various polymer materials, such as a spin coating process, a nozzle printing process, an inkjet printing process, a slot coating process, a dip coating process, a roll-to-roll process, and a doctor blaze. It can be manufactured with fewer layers by a method such as a ding process, 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 method of forming the organic material layer.

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

In addition, the organic electric device according to an embodiment of the present invention may be selected from the group consisting of an organic electroluminescent device, an organic solar cell, an organic photoreceptor, an organic transistor, a monochromatic lighting device, and a quantum dot display device.

Another embodiment of the present invention may include a display device including the organic electric 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 or wireless communication terminal, and includes all electronic devices such as mobile communication terminals such as mobile phones, PDAs, electronic dictionaries, PMPs, remote controls, navigation, game consoles, various TVs, and various computers.

Hereinafter, a compound according to an aspect of the present invention will be described.

A compound according to an aspect of the present invention is represented by the following formula (1).

<Formula 1>

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

R ¹ to R ⁴ are each independently hydrogen; heavy hydrogen; halogen; Cyano group; Nitro group; C ₆ ~ C ₆₀ aryl group; Fluorenyl group; O, N, S, Si, and C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of P; C ₃ ~ C ₆₀ aliphatic ring group; C ₁ ~ C ₃₀ alkyl group; C ₂ ~ C ₃₀ alkenyl group; Alkynyl group of C ₂ ~ C _30; An alkoxyl group of C ₁ to C _30; C ₆ ~ C ₃₀ aryloxy group; And it is selected from the group consisting of -LN (R _a ) (R _b ), and neighboring groups may be bonded to each other to selectively form a ring.

a and b are each an integer of 0 to 2, c and d are each an integer of 0 to 3, and when each of them is an integer of 2 or more, each of R ^1, each of R ^2, each of R ^{3, and} each of R ⁴ is the same or different from each other Do.

The ring formed by bonding of adjacent groups to each other is an aromatic ring group of _{C 6} ~ C _60; Fluorenyl group; O, N, S, Si, and C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of P; And C ₃ ~ C ₆₀ aliphatic ring group; may be selected from the group consisting of.

When adjacent groups are bonded to each other to form an aromatic ring, preferably a C ₆ ~ C ₂₀ aromatic ring, more preferably a C ₆ ~ C ₁₄ aromatic ring, such as benzene, naphthalene, phenanthrene, etc., or , May form a ring containing a benzene moiety.

When R ¹ to R ⁴ are an aryl group, preferably a C ₆ to C ₃₀ aryl group, more preferably a C ₆ to C ₁₈ aryl group, such as phenyl, naphthyl, biphenyl, terphenyl, and the like.

When R ¹ to R ⁴ are heterocyclic _{groups, preferably a C 2} to C ₃₀ heterocyclic group, more preferably a C ₂ to C ₁₈ heterocyclic group such as triazine, quinazoline, benzoquinazoline, di Benzothiophene, dibenzofuran, naphthobenzofuran, naphthobenzothiophene, carbazole, phenylcarbazole, and the like.

When R ¹ to R ⁴ is an alkyl group, it is preferably a C ₁ to C ₁₀ alkyl group, and may be, for example, methyl, t-butyl, or the like.

L ¹ and L ² are each independently a single bond; C ₆ ~ C ₆₀ arylene group; Fluorenylene group; C ₃ ~ C ₆₀ aliphatic ring group; And O, N, S, Si and P may be selected from the group consisting of _{a C 2} ~ C _{60 heterocyclic group containing at least one heteroatom.}

When L ¹ and L ² are an arylene group, preferably a C ₆ to C ₃₀ arylene group, more preferably a C ₆ to C ₁₈ arylene group such as phenylene, naphthylene, biphenylene, terphenyl, etc. I can.

When L ¹ and L ² are heterocyclic _{groups, preferably a C 2} to C ₃₀ heterocyclic group, more preferably a C ₂ to C ₁₈ heterocyclic group such as pyridine, pyrimidine, triazine, pyrazine, carba Sol, phenylcarbazole, quinazoline, benzoquinazoline, quinoxaline, benzoquinoxaline, dibenzoquinoxaline, quinoline, isoquinoline, benzoquinoline, benzothienopyrimidine, benzofuropyrimidine, dibenzodioxin, Phenothiazine, phenoxatin, benzoimidazole, benzothiazole, indole, benzoxazole, dibenzothiophene, dibenzofuran, and the like.

Ar ¹ and Ar ² are each independently a C ₆ ~ C ₆₀ aryl group; Fluorenyl group; O, N, S, Si, and C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of P; C ₃ ~ C ₆₀ aliphatic ring group; And -LN (R _a ) (R _b ) It may be selected from the group consisting of.

When Ar ¹ and Ar ² are an aryl group, preferably a C ₆ to C ₃₀ aryl group, more preferably a C ₆ to C ₁₈ aryl group such as phenyl, naphthyl, biphenyl, terphenyl, phenanthrene, Triphenylene, pyrene, chrysene, anthracene, and the like.

When Ar ¹ and Ar ² are heterocyclic _{groups, preferably a C 2} to C ₃₀ heterocyclic group, more preferably a C ₂ to C ₂₂ heterocyclic group such as pyridine, pyrimidine, triazine, pyrazine, carba Sol, phenylcarbazole, phenylbenzocarbazole, quinazoline, benzoquinazoline, quinoxaline, benzoquinoxaline, dibenzoquinoxaline, quinoline, isoquinoline, benzoquinoline, benzothienopyrimidine, benzofuropyrimidine , Dibenzodioxin, phenothiazine, phenoxatin, benzoimidazole, benzothiazole, indole, benzoxazole, dibenzothiophene, dibenzofuran, naphthobenzothiophene, naphthobenzofuran, and the like.

When Ar ¹ and Ar ² are fluorenyl groups, 9,9-dimethyl-9 H -fluorene, 9,9-diphenyl-9 H -fluorenyl groups, 9,9'-spirobifluorene, etc. I can.

When Ar ¹ and Ar ² are an aliphatic ring group, preferably a C ₃ to C ₃₀ aliphatic ring group, more preferably a C ₃ to C ₁₀ aliphatic ring group, such as cyclohexane, adamantyl, and the like.

L is a single bond; C ₆ ~ C ₆₀ arylene group; Fluorenylene group; O, N, S, Si, and C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of P; C ₃ ~ C ₆₀ aliphatic ring group; And it may be selected from the group consisting of a combination thereof.

When L is an arylene group, preferably a C ₆ to C ₃₀ arylene group, more preferably a C ₆ to C ₁₈ arylene group, such as phenylene, naphthylene, biphenylene, terphenyl, and the like.

R _a and R _b are each independently a C ₆ ~ C ₆₀ aryl group; Fluorenyl group; O, N, S, Si, and C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of P; And C ₃ ~ C ₆₀ It may be selected from the group consisting of an aliphatic ring group.

When R _a and R _b are an aryl group, preferably a C ₆ to C ₃₀ aryl group, more preferably a C ₆ to C ₁₈ aryl group, such as phenyl, naphthyl, biphenyl, terphenyl, and the like.

When R _a and R _b are a heterocyclic group, preferably a C ₂ to C ₃₀ heterocyclic group, more preferably a C ₂ to C ₁₂ heterocyclic group, such as dibenzothiophene, dibenzofuran, etc. .

When R _a and R _b are fluorenyl groups, 9,9-dimethyl-9 H -fluorene, 9,9-diphenyl-9 H -fluorenyl groups, 9,9'-spirobifluorene, etc. I can.

The R ¹ ~R ⁴ , L ¹ , L ² , Ar ¹ , Ar ² , and the rings formed by bonding of adjacent groups to each other are deuterium, respectively; halogen; A silane group unsubstituted or substituted with a C ₁ -C ₂₀ alkyl group or a C ₆ -C _{20 aryl group;} Phosphine oxide unsubstituted or substituted with a C ₁ -C ₂₀ alkyl group or a C ₆ -C _{20 aryl group;} Siloxane group; Boron group; Germanium group; Cyano group; Nitro group; C ₁ -C ₂₀ alkylthio group; C ₁ -C ₂₀ alkoxy group; A C ₆ -C ₂₀ aryloxy group; C ₆ -C ₂₀ arylthio group; A C ₁ -C ₂₀ alkyl group; An alkenyl group of C ₂ -C _20; Alkynyl group of C ₂ -C _20; C ₆ -C ₂₀ aryl group; Fluorenyl group; _{A heterocyclic group of C 2} -C ₂₀ including at least one heteroatom selected from the group consisting of O, N, S, Si and P; An aliphatic ring group of C ₃ -C _20; A C ₇ -C ₂₀ arylalkyl group; And it may be further substituted with one or more substituents selected from the group consisting of _{C 8} -C _{20 arylalkenyl group.}

Illustratively, Formula 1 may be represented by one of Formulas 1-1 to 1-6 below.

<Formula 1-1> <Formula 1-2> <Formula 1-3>

<Formula 1-4> <Formula 1-5> <Formula 1-6>

In Formulas 1-1 to 1-6, R ¹ to R ⁴ , a to d, L ¹ , L ² , Ar ¹ , Ar ² , L, R _a , R _b are as defined in Formula 1.

As another example, Formula 1 may be represented by one of Formulas 2-1 to 2-6 below.

<Formula 2-1> <Formula 2-2> <Formula 2-3>

<Formula 2-4> <Formula 2-5> <Formula 2-6>

In Formulas 2-1 to 2-6, R ¹ to R ⁴ , a to d, L ¹ , L ² , Ar ¹ , Ar ² are the same as defined in Formula 1, and L ⁶ is a single bond; C ₆ ~ C ₆₀ arylene group; Fluorenylene group; O, N, S, Si, and C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of P; C ₃ ~ C ₆₀ aliphatic ring group; And it is selected from the group consisting of a combination thereof, X ¹ to X ⁶ are each independently C, C (R') or N, and at least one of ^{X 1} to X ^{6 is N.}

R'is independently of each other hydrogen; heavy hydrogen; halogen; A silane group unsubstituted or substituted with a C ₁ -C ₂₀ alkyl group or a C ₆ -C _{20 aryl group;} Cyano group; Nitro group; C ₁ -C ₂₀ alkylthio group; C ₁ -C ₂₀ alkoxy group; A C ₆ -C ₂₀ aryloxy group; A C ₁ -C ₂₀ alkyl group; An alkenyl group of C ₂ -C _20; Alkynyl group of C ₂ -C _20; C ₆ -C ₂₀ aryl group; Fluorenyl group; _{A heterocyclic group of C 2} -C ₂₀ including at least one heteroatom selected from the group consisting of O, N, S, Si and P; An aliphatic ring group of C ₃ -C _20; A C ₇ -C ₂₀ arylalkyl group; And it _{is selected from the group consisting of arylalkenyl group of C 8} -C ₂₀ , and neighboring groups may be bonded to each other to form a ring.

Exemplarily, the L ¹ , L ² and L may be independently selected from the group consisting of the following Formulas b-1 to b-13.

<Formula b-1> <Formula b-2> <Formula b-3>

<Formula b-4> <Formula b-5> <Formula b-6>

<Formula b-7> <Formula b-8> <Formula b-9> <Formula b-10>

<Formula b-11> <Formula b-12> <Formula b-13>

In Formulas b-1 to b-13, Z is O, S, N-(L'-Ar') or C(R')(R"), and Z ⁴⁹ to Z ⁵¹ are each independently C, C(R') or N, and at least one of ^{Z 49} to Z ^{51 is N.}

R ⁵ to R ⁷ , wherein R'and R" are each independently hydrogen; deuterium; halogen; a silane group unsubstituted or substituted with a _{C 1} -C ₂₀ alkyl group or a C ₆ -C _{20 aryl group; a cyano group; nitro} group; a C ₂ -C ₂₀ alkenyl;; C ₁ -C ₂₀ alkylthio Sy of; C ₁ -C ₂₀ alkoxy group; C ₆ -C ₂₀ aryloxy; C ₁ -C ₂₀ alkyl C ₂ -C ₂₀ alkynyl group; C ₆ -C _{20 aryl group; fluorenyl group; C 2} -C ₂₀ heterocycle containing at least one heteroatom selected from the group consisting of O, N, S, Si and P Group; C ₃ -C ₂₀ aliphatic ring group; C ₇ -C ₂₀ arylalkyl group; And C ₈ -C ₂₀ selected from the group consisting of arylalkenyl groups, neighboring groups can be bonded to each other to form a ring have.

a", c", d", e", g" is an integer of 0-4, b" is an integer of 0-6, f" is an integer of 0-3, h" is an integer of 0-2, i "Is an integer of 0 to 3, and when each of them is an integer of 2 or more, each of R ^5, each of R ^{6, and} each of R ⁷ is the same as or different from each other.

Ar' is a C ₆ ~ C ₂₀ aryl group; Fluorenyl group; O, N, S, Si, and C ₂ ~ C ₂₀ heterocyclic group containing at least one heteroatom of P; C ₃ ~ C ₂₀ aliphatic ring group; And it may be selected from the group consisting of a combination thereof.

L'is independently of each other a single bond; C ₆ ~ C ₂₀ arylene group; Fluorenylene group; O, N, S, Si, and C ₂ ~ C ₂₀ heterocyclic group containing at least one heteroatom of P; And C ₃ ~ C ₂₀ It may be selected from the group consisting of an aliphatic ring group.

Exemplarily _{, at least one of R a} and R _b may be represented by the following Formula B-1.

<Formula B-1>

In Formula B-1, ring A and ring B are independently of each other C ₆ ~ C _{20 aromatic ring group or C 4} ~ C ₂₀ hetero containing at least one hetero atom of O, N, S, Si and P And Z is O, S, N-(L'-Ar') or C(R')(R").

The R′ and R” are independently of each other hydrogen; deuterium; halogen; _{a silane group unsubstituted or substituted with a C 1} -C ₂₀ alkyl group or a C ₆ -C ₂₀ aryl group; a cyano group; a nitro group; C ₁ -C ₂₀ alkylthio group; C ₁ -C ₂₀ alkoxy group; C ₆ -C ₂₀ aryloxy group; C ₁ -C ₂₀ alkyl group; C ₂ -C ₂₀ alkenyl group; C ₂ -C ₂₀ alkynyl group ; C ₆ -C _{20 aryl group; fluorenyl group; C 2} -C ₂₀ heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; C ₃ -C _It is selected from the group consisting of an aliphatic ring group of _{20; C 7} -C ₂₀ arylalkyl group; And C ₈ -C ₂₀ arylalkenyl group, and neighboring groups may be bonded to each other to form a ring.

Ar' is a C ₆ ~ C ₂₀ aryl group; Fluorenyl group; O, N, S, Si, and C ₂ ~ C ₂₀ heterocyclic group containing at least one heteroatom of P; C ₃ ~ C ₂₀ aliphatic ring group; And it may be selected from the group consisting of a combination thereof.

L'is independently of each other a single bond; C ₆ ~ C ₂₀ arylene group; Fluorenylene group; O, N, S, Si, and C ₂ ~ C ₂₀ heterocyclic group containing at least one heteroatom of P; And C ₃ ~ C ₂₀ It may be selected from the group consisting of an aliphatic ring group.

Exemplarily ^{, at least one of R 1} to R ⁴ , Ar ¹ and Ar ² may be selected from the group consisting of the following Formulas A-1 to A-6.

<Formula A-1> <Formula A-2> <Formula A-3>

<Formula A-4> <Formula A-5> <Formula A-6>

In Formulas A-1 to A-6, L is the same as defined in Formula 1, X ¹ to X ⁶ are each independently C, C (R ₁ ) or N, and Y ₁ to Y ₈ are independent of each other By C(R ₁ ) or N.

Preferably, in Formula A-1, ^{at least one of X 1} to X ⁶ is N, and in Formula A-2, at least one of X ¹ to X ⁴ and Y ₁ to Y ₄ is N, and the formula In A-3, ^{at least one of X 1} to X ⁶ is N, and in Formula A-4, at least one of X ¹ to X ⁴ and Y ₁ to Y ₈ is N, and the formulas A-5 and A In -6, at least one of ^{X 1} to X ^{4 is N.}

V and W are O, S, N-(L'-Ar') or C(R')(R"), e and f are each 0 or 1, at least one of e and f is 1, and Y ¹ is O, S, N, N-(L'-Ar'), C(R') or C(R')(R"), and Y ² is N.

The R ₁ , R′ and R” are independently of each other hydrogen; deuterium; halogen; _{a silane group unsubstituted or substituted with a C 1} -C ₂₀ alkyl group or a C ₆ -C ₂₀ aryl group; a cyano group; a nitro group; C ₁ -C ₂₀ alkylthio group; C ₁ -C ₂₀ alkoxy group; C ₆ -C ₂₀ aryloxy group; C ₁ -C ₂₀ alkyl group; C ₂ -C ₂₀ alkenyl group; C ₂ -C ₂₀ Alkynyl group of; C ₆ -C _{20 aryl group; fluorenyl group; C 2} -C ₂₀ heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; C _It is selected from the group consisting of 3 -C ₂₀ aliphatic ring group; C ₇ -C ₂₀ arylalkyl group; And C ₈ -C ₂₀ arylalkenyl group, and neighboring groups may be bonded to each other to form a ring.

Ar' is a C ₆ ~ C ₂₀ aryl group; Fluorenyl group; O, N, S, Si, and C ₂ ~ C ₂₀ heterocyclic group containing at least one heteroatom of P; C ₃ ~ C ₂₀ aliphatic ring group; And it may be selected from the group consisting of a combination thereof.

L'is independently of each other a single bond; C ₆ ~ C ₂₀ arylene group; Fluorenylene group; O, N, S, Si, and C ₂ ~ C ₂₀ heterocyclic group containing at least one heteroatom of P; And C ₃ ~ C ₂₀ It may be selected from the group consisting of an aliphatic ring group.

Specifically, the compound represented by Formula 1 may be one of the following compounds, but is not limited thereto.

.

.

In another aspect of the present invention, the present invention provides an organic electric device comprising an anode, a cathode, and an organic material layer formed between the anode and the cathode, wherein the organic material layer is one single compound or two or more Contains compounds.

In another aspect of the present invention, the present invention provides an organic electric device including an anode, a cathode, an organic material layer formed between the anode and the cathode, and a light efficiency improvement layer. In this case, the light efficiency improvement layer is formed on one side of both surfaces of the anode or the cathode that is not in contact with the organic material layer, and the organic material layer or the light efficiency improvement layer includes the compound represented by Formula 1 above.

The organic material layer includes at least one of a hole injection layer, a hole transport layer, a light emission auxiliary layer, a light emitting layer, an electron transport auxiliary layer, an electron transport layer and an electron injection layer, and preferably, the compound is included in the emission layer and/or the emission auxiliary layer. Can be included.

The organic material layer may include two or more stacks including a hole transport layer, an emission layer, and an electron transport layer sequentially formed on the anode, and may further include a charge generation layer formed between the two or more stacks.

In another aspect of the present invention, the present invention provides an electronic device including a display device including an organic electric device represented by Formula 1 and a control unit for driving the display device.

Hereinafter, examples for synthesizing the compound represented by Chemical Formula 1 according to the present invention and an example for preparing an organic electric device according to the present invention will be described in detail, but the present invention is not limited to the following examples.

Synthesis example

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

<Reaction Scheme 1>

I. of Sub 1 Synthesis example

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

<Reaction Scheme 2>

Synthesis example of Sub 1-IV-1

(1) Sub 1-I-1 synthesis

1,8-dibromonaphthalene (50 g, 174.8 mmol) was added to a round bottom flask and dissolved in 350 mL of THF, followed by (2-nitrophenyl)boronic acid (29.2 g, 174.8 mmol), Pd(PPh ₃ ) ₄ (6.1 g, 5.3 mmol), NaOH (21 g, 524.5 mmol), and 175 mL of water were added, followed by stirring at 80°C. When the reaction was completed, the _{mixture was extracted with CH 2} Cl ₂ and water, and the organic layer was dried over _{MgSO 4 and concentrated.} Thereafter, the concentrate was separated by a silica gel column and recrystallized to obtain 40.7 g (yield: 71%) of the product.

(2) Sub 1-II-1 synthesis

Sub 1-I-1 (40.7 g, 124 mmol), (2-nitrophenyl) boronic acid (20.7 g, 124 mmol) was used as a reactant and proceeded in the same manner as for the synthesis of Sub 1-I-1, and the product 35.4 g (yield: 77%) was obtained.

(3) Sub 1-III-1 synthesis

Add Sub 1-II-1 (35.4 g, 95.6 mmol) to a round bottom flask and dissolve with 200 mL of DMF, then PPh ₃ (75.2 g, 286.8 mmol) was added and stirred at 165°C. When the reaction was completed, the _{mixture was extracted with CH 2} Cl ₂ and water, and the organic layer was dried over _{MgSO 4 and concentrated.} Thereafter, the concentrate was separated by a silica gel column and recrystallized to obtain 24.9 g (yield: 85%) of the product.

(4) Sub 1-IV-1 synthesis

Sub 1-III-1 (24.9 g, 81.3 mmol), NaCl (8.1 g, 203.2 mmol), and AlCl ₃ (54.2 g, 406.4 mmol) were dissolved in benzene, and the melt was hydrolyzed. When the reaction was completed, the benzene solution was _{washed with NaHCO 3} aqueous solution and water, dried over MgSO ₄ , concentrated, and dissolved with a small amount of hot p-xylene. Thereafter, the product was separated by a silica gel column and recrystallized with methylcyclohexane to obtain 9.2 g (yield: 37%) of the product.

Synthesis example of Sub 1-1

Sub 1-IV-1 (9.3 g, 30.6 mmol) was put in a round bottom flask and dissolved with toluene (100 mL), then iodobenzene (6.2 g, 30.6 mmol), Pd ₂ (dba) ₃ (0.8 g, 0.9 mmol) , P( t -Bu) ₃ (0.4 g, 1.8 mmol), NaO t -Bu (8.8 g, 91.7 mmol) was added and stirred at 100°C. After completion of the reaction, the organic layer extracted with _{CH 2} Cl _{2 and water was dried over MgSO 4} and concentrated with an evaporator. Thereafter, the concentrate was separated by a silica gel column and recrystallized to obtain 7.7 g (yield: 66%) of the product.

Synthesis example of Sub 1-9

Sub 1-IV-2 (7.8 g, 16.5 mmol) and chlorobenzene (1.9 g, 16.5 mmol) were used in the same manner as for the synthesis of Sub 1-1 to obtain 6.2 g (yield: 68%) of the product.

Synthesis example of Sub 1-30

Using Sub 1-IV-1 (7.8 g, 25.6 mmol) and 2-chlorobenzonaphthothiophene (6.9 g, 25.6 mmol), proceed in the same manner as for the synthesis of Sub 1-1 to obtain 7.8 g (yield: 57%) of the product. Got it.

Synthesis example of Sub 1-33

Same as the synthesis method of Sub 1-1 using Sub 1-IV-1 (14.5 g, 47.6 mmol) and 2-chloro-4,6-diphenyl-1,3,5-triazine (3.4 g, 47.6 mmol) Proceeding to the method to give the product 15.8 g (yield: 62%).

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

[Table 1]

II. Sub 2 example

The compound belonging to Sub 2 of Scheme 1 may be a compound as follows, but is not limited thereto, and Table 2 shows the FD-MS (Field Desorption-Mass Spectrometry) values of the following compounds.

[Table 2]

III. Of the final compound Synthesis example

Synthesis example of P-2

After dissolving Sub 1-IV-1 (9.3 g, 30.6 mmol) with toluene, Sub 2-2 (5 g, 26.5 mmol), Pd ₂ (dba) ₃ (0.8 g, 0.9 mmol), P( t -Bu ) ₃ (0.4 g, 1.8 mmol), NaO t -Bu (8.8 g, 91.7 mmol) was added and stirred at 100°C. After completion of the reaction, the organic layer extracted with _{CH 2} Cl _{2 and water was dried over MgSO 4} and concentrated with an evaporator. Thereafter, the concentrate was separated by a silica gel column and recrystallized to obtain 12.3 g (yield: 87%) of the product.

Synthesis example of P-7

Using Sub 1-1 (12.5 g, 32.9 mmol) and Sub 2-7 (7.2 g, 32.9 mmol), the product 13.5 g (yield: 73%) was obtained by proceeding according to the synthesis method of P-2.

Synthesis example of P-102

Using Sub 1-9 (11.2 g, 20.5 mmol) and Sub 2-73 (5.4 g, 20.5 mmol), the product 11.9 g (yield: 75%) was obtained by proceeding according to the synthesis method of P-2.

Synthesis example of P-121

Using Sub 1-26 (11.8 g, 25.8 mmol) and Sub 2-59 (6.5 g, 25.8 mmol), the product 13.9 g (yield: 80%) was obtained by proceeding according to the synthesis method of P-2.

Synthesis example of P-144

Using Sub 1-1 (10.8 g, 28.4 mmol) and Sub 2-94 (6.5 g, 28.4 mmol), the product 12.4 g (yield: 76%) was obtained by proceeding according to the synthesis method of P-2.

The FD-MS values of the compounds P-1 to P-157 of the present invention prepared according to the synthesis example as described above are shown in Table 3 below.

[Table 3]

Manufacturing evaluation of organic electric devices

[Example 1] Red organic light emitting device (phosphorescent host)

On the ITO layer (anode) formed on the glass substrate, N1-(naphthalen-2-yl)-N4,N4-bis(4-(naphthalen-2-yl(phenyl)amino)phenyl)-N1-phenylbenzene-1,4 -Diamine (hereinafter abbreviated as "2-TNATA") film was vacuum-deposited to form a hole injection layer with a thickness of 60 nm, and then N,N'-Bis(1-naphthalenyl)-N,N'-bis-phenyl- (1,1'-biphenyl)-4,4'-diamine (hereinafter abbreviated as "NPB") was vacuum deposited to a thickness of 60 nm to form a hole transport layer.

Then, the compound P-11 of the present invention as a host material on the hole transport layer, bis-(1-phenylisoquinolyl)iridium(III)acetylacetonate (hereinafter, _{abbreviated as "(piq) 2} Ir(acac)") as a dopant Although used as a material, a light emitting layer having a thickness of 30 nm was deposited by doping with a dopant so that the weight ratio was 94:6.

Next, (1,1'-biphenyl-4-olato)bis(2-methyl-8-quinolinolato)aluminum (hereinafter abbreviated as "BAlq") was vacuum-deposited to a thickness of 10 nm on the light-emitting layer to form a hole blocking layer. And tris(8-quinolinol)aluminum (hereinafter _{abbreviated as Alq 3} ) was deposited to a thickness of 40 nm on the hole blocking layer to form an electron transport layer.

Thereafter, LiF was deposited to a thickness of 0.2 nm on the electron transport layer to form an electron injection layer, and Al was deposited on the electron injection layer to a thickness of 150 nm to form a cathode.

[ Example 2] to [ Example 17]

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-11 of the present invention as a host material.

[Comparative Example 1] and [Comparative Example 2]

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that Comparative Compound 1 or Comparative Compound 2 was used instead of Compound P-11 of the present invention as a host material.

<Comparative compound 1> <Comparative compound 2>

By applying a forward bias DC voltage to the organic electroluminescent devices of Examples 1 to 17 and Comparative Examples 1 and 2 of the present invention prepared as described above, electroluminescence (EL) characteristics were measured with PR-650 of photoresearch, and , T95 life was measured with a life measurement equipment manufactured by McScience at a reference luminance of 2500 cd/m ^2. The measurement results are shown in Table 4 below.

[Table 4]

As can be seen from the results of Table 4, when the compound of the present invention is used as a host material for the light emitting layer, the driving voltage of the device is lowered and the efficiency and lifespan are significantly improved compared to the case of using Comparative Compound 1 or Comparative Compound 2.

The compounds of the present invention are structurally different from Comparative Compounds 1 and 2 in that the two carbazole moieties are a core condensed on the middle 7-membered ring. Due to these differences, the compounds of the present invention have improved hole properties and band gap. This narrowing seems to improve the driving voltage and efficiency, and the compound of the present invention has an increased planarity and a high Tg value compared to the comparative compound, so that the lifespan is also remarkably improved.

[ Example 18] to [ Example 26] Green organic electroluminescent device ( Light-emitting auxiliary layer )

A 2-TNATA film was vacuum-deposited on the ITO layer (anode) formed on the glass substrate to form a hole injection layer with a thickness of 60 nm, and then NPB was vacuum evaporated to form a hole transport layer having a thickness of 60 nm. Subsequently, the compound 1-75 of the present invention was vacuum-deposited to a thickness of 20 nm on the hole transport layer to form a light emission auxiliary layer.

Subsequently, after vacuum deposition of the compound of the present invention shown in Table 5 to a thickness of 20 nm on the hole transport layer to form a light emission auxiliary layer, 4,4'-N,N'- as a host on the light emission auxiliary layer. dicarbazole-biphenyl (hereinafter, abbreviated as CBP), tris(2-phenylpyridine)-iridium (hereinafter referred to as “Ir(ppy) ₃ ) as a dopant, but doped with a dopant so that the weight ratio is 93:7. An nm-thick light-emitting layer was formed.

Next, BAlq was vacuum deposited on the emission layer to a thickness of 10 nm to form a hole blocking layer, and Alq ₃ was deposited on the hole blocking layer to a thickness of 40 nm to form an electron transport layer.

Thereafter, LiF was deposited to a thickness of 0.2 nm on the electron transport layer to form an electron injection layer, and Al was deposited on the electron injection layer to a thickness of 150 nm to form a cathode.

[Comparative Example 3]

An organic electroluminescent device was manufactured in the same manner as in Example 18, except that the light emission auxiliary layer was not formed.

[ Comparative example 4] to [ Comparative example 6]

An organic electroluminescent device was manufactured in the same manner as in Example 18, except that one of the following Comparative Compounds 3 to 5 was used instead of the compound of the present invention as the light emitting auxiliary layer material.

<Comparative compound 3> <Comparative compound 4> <Comparative compound 5>

By applying a forward bias DC voltage to the organic electroluminescent devices prepared according to Examples 18 to 26 and Comparative Examples 3 to 6, electroluminescence (EL) characteristics were measured with a PR-650 of photoresearch, and 5000 cd/m ^{2 At the} reference luminance, the T95 life was measured with a life measurement equipment manufactured by McScience. The measurement results are shown in Table 5 below.

[Table 5]

From the results of Table 5, it can be seen that the compounds of the present invention are similar to Comparative Compounds 1 to 5, but the introduction of a pyrrolidine moiety containing N into the core acts as a major factor in improving the performance of the device.

When the light emission auxiliary layer is formed by using Comparative Compound 3 to Comparative Compound 5 rather than an organic electric device in which the light emission auxiliary layer is not formed (Comparative Examples 4 to 6), the driving voltage of the device is lowered and the efficiency and lifespan This was improved.

And, compared to the case of using one of Comparative Compounds 3 to 5, when the compound of the present invention is used as a light emitting auxiliary layer material, the driving voltage is lowered, the efficiency and lifespan are remarkably improved, and in particular, the lifespan is remarkably improved. This is because the compound of the present invention to which the pyrrolidine moiety is further introduced has improved hole transport capacity and narrower band gap than Comparative Compounds 3 to 5, and thus luminous efficiency and driving voltage were improved.

These results show that even if the basic skeleton is a similar compound, as the pyrrolidine ring is further introduced as in the present invention, the physical properties of the compound such as hole characteristics, light efficiency characteristics, energy level, etc. are changed, resulting in device results that are difficult to predict. Suggests that it can be done.

The descriptions in Tables 4 and 5 are merely illustrative of the present invention, and those of ordinary skill in the art to include other compounds in the light emitting layer within the range not departing from the essential characteristics of the present invention. Various variations are possible, including ways to improve performance.

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 in the present specification are not intended to limit the present invention, but to explain the present invention, and the spirit and scope of the present invention are not limited by these embodiments. The scope of protection of the present invention should be interpreted by the claims below, and all technologies within the scope equivalent thereto should be construed as being included in the scope of the present invention.

100, 200, 300: organic electric device 110: first electrode
120: hole injection layer 130: hole transport layer
140: light emitting layer 150: electron transport layer
160: electron injection layer 170: second electrode
180: light efficiency improvement layer 210: buffer layer
220: light emission auxiliary layer 320: first hole injection layer
330: first hole transport layer 340: first emission layer
350: first electron transport layer 360: first charge generation layer
361: second charge generation layer 420: second hole injection layer
430: second hole transport layer 440: second emission layer
450: second electron transport layer CGL: charge generation layer
ST1: first stack ST2: second stack

Claims (15)

Compound represented by the following formula (1):
<Formula 1>

In Formula 1,
R ¹ to R ⁴ are each independently hydrogen; heavy hydrogen; halogen; Cyano group; Nitro group; C ₆ ~ C ₆₀ aryl group; Fluorenyl group; O, N, S, Si, and C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of P; C ₃ ~ C ₆₀ aliphatic ring group; C ₁ ~ C ₃₀ alkyl group; C ₂ ~ C ₃₀ alkenyl group; Alkynyl group of C ₂ ~ C _30; An alkoxyl group of C ₁ to C _30; C ₆ ~ C ₃₀ aryloxy group; And it is selected from the group consisting of -LN (R _a ) (R _b ), and neighboring groups may be bonded to each other to form a ring,
a and b are each an integer of 0 to 2, c and d are each an integer of 0 to 3, and when each of them is an integer of 2 or more, each of R ^1, each of R ^2, each of R ^{3, and} each of R ⁴ is the same or different from each other And
L ¹ and L ² are each independently a single bond; C ₆ ~ C ₆₀ arylene group; Fluorenylene group; C ₃ ~ C ₆₀ aliphatic ring group; And O, N, S, Si and P is selected from the group consisting of a heterocyclic group of _{C 2} ~ C _{60 containing at least one heteroatom,}
Ar ¹ and Ar ² are each independently a C ₆ ~ C ₆₀ aryl group; Fluorenyl group; O, N, S, Si, and C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of P; C ₃ ~ C ₆₀ aliphatic ring group; And -LN (R _a ) (R _b ) is selected from the group consisting of,
L is a single bond; C ₆ ~ C ₆₀ arylene group; Fluorenylene group; O, N, S, Si, and C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of P; C ₃ ~ C ₆₀ aliphatic ring group; And it is selected from the group consisting of a combination thereof,
R _a and R _b are each independently a C ₆ ~ C ₆₀ aryl group; Fluorenyl group; O, N, S, Si, and C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of P; And C ₃ ~ C ₆₀ is selected from the group consisting of an aliphatic ring group,
The R ¹ ~R ⁴ , L ¹ , L ² , Ar ¹ , Ar ² , and the rings formed by bonding of adjacent groups to each other are deuterium, respectively; halogen; A silane group unsubstituted or substituted with a C ₁ -C ₂₀ alkyl group or a C ₆ -C _{20 aryl group;} Phosphine oxide unsubstituted or substituted with a C ₁ -C ₂₀ alkyl group or a C ₆ -C _{20 aryl group;} Siloxane group; Boron group; Germanium group; Cyano group; Nitro group; C ₁ -C ₂₀ alkylthio group; C ₁ -C ₂₀ alkoxy group; A C ₆ -C ₂₀ aryloxy group; C ₆ -C ₂₀ arylthio group; A C ₁ -C ₂₀ alkyl group; An alkenyl group of C ₂ -C _20; Alkynyl group of C ₂ -C _20; C ₆ -C ₂₀ aryl group; Fluorenyl group; _{A heterocyclic group of C 2} -C ₂₀ including at least one heteroatom selected from the group consisting of O, N, S, Si and P; An aliphatic ring group of C ₃ -C _20; A C ₇ -C ₂₀ arylalkyl group; And it may be further substituted with one or more substituents selected from the group consisting of arylalkenyl group of _{C 8} -C _20. The method of claim 1
Formula 1 is a compound characterized in that represented by one of the following formulas 1-1 to 1-6:
<Formula 1-1><Formula1-2><Formula1-3>

<Formula 1-4><Formula1-5><Formula1-6>

In Formulas 1-1 to 1-6, R ¹ to R ⁴ , a to d, L ¹ , L ² , Ar ¹ , Ar ² , L, R _a , R _b are the same as defined in claim 1 . The method of claim 1
Formula 1 is a compound characterized in that represented by one of the following formulas 2-1 to 2-6:
<Formula 2-1><Formula2-2><Formula2-3>

<Formula 2-4><Formula2-5><Formula2-6>

In Formulas 2-1 to 2-6, R ¹ to R ⁴ , a to d, L ¹ , L ² , Ar ¹ , Ar ² are the same as defined in claim 1,
L ⁶ is a single bond; C ₆ ~ C ₆₀ arylene group; Fluorenylene group; O, N, S, Si, and C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of P; C ₃ ~ C ₆₀ aliphatic ring group; And it is selected from the group consisting of a combination thereof,
X ¹ to X ⁶ are each independently C, C(R') or N, and at least one of ^{X 1} to X ^{6 is N,}
R'is independently of each other hydrogen; heavy hydrogen; halogen; A silane group unsubstituted or substituted with a C ₁ -C ₂₀ alkyl group or a C ₆ -C _{20 aryl group;} Cyano group; Nitro group; C ₁ -C ₂₀ alkylthio group; C ₁ -C ₂₀ alkoxy group; A C ₆ -C ₂₀ aryloxy group; A C ₁ -C ₂₀ alkyl group; An alkenyl group of C ₂ -C _20; Alkynyl group of C ₂ -C _20; C ₆ -C ₂₀ aryl group; Fluorenyl group; _{A heterocyclic group of C 2} -C ₂₀ including at least one heteroatom selected from the group consisting of O, N, S, Si and P; An aliphatic ring group of C ₃ -C _20; A C ₇ -C ₂₀ arylalkyl group; And it _{is selected from the group consisting of arylalkenyl group of C 8} -C ₂₀ , and neighboring groups may be bonded to each other to form a ring. The method of claim 1,
The L ¹ , L ² , L is a compound characterized in that it is selected from the group consisting of the following formulas b-1 to b-13:
<Formula b-1><Formulab-2><Formulab-3>

<Formula b-4><Formulab-5><Formulab-6>

<Formula b-7><Formulab-8><Formulab-9><Formulab-10>

<Formula b-11><Formulab-12><Formulab-13>

In Formulas b-1 to b-13,
Z is O, S, N-(L'-Ar') or C(R')(R"),
Z ⁴⁹ to Z ⁵¹ are each independently C, C (R') or N, at least one of ^{Z 49} to Z ^{51 is N,}
R ⁵ to R ⁷ , wherein R'and R" are each independently hydrogen; deuterium; halogen; a silane group unsubstituted or substituted with a _{C 1} -C ₂₀ alkyl group or a C ₆ -C _{20 aryl group; a cyano group; nitro} group; a C ₂ -C ₂₀ alkenyl;; C ₁ -C ₂₀ alkylthio Sy of; C ₁ -C ₂₀ alkoxy group; C ₆ -C ₂₀ aryloxy; C ₁ -C ₂₀ alkyl C ₂ -C ₂₀ alkynyl group; C ₆ -C _{20 aryl group; fluorenyl group; C 2} -C ₂₀ heterocycle containing at least one heteroatom selected from the group consisting of O, N, S, Si and P Group; C ₃ -C ₂₀ aliphatic ring group; C ₇ -C ₂₀ arylalkyl group; And C ₈ -C ₂₀ selected from the group consisting of arylalkenyl groups, neighboring groups can be bonded to each other to form a ring There is,
a", c", d", e", g" is an integer of 0-4, b" is an integer of 0-6, f" is an integer of 0-3, h" is an integer of 0-2, i "Is an integer of 0 to 3, and when each of them is an integer of 2 or more, each of R ^5, each of R ^{6, and} each of R ⁷ is the same as or different from each other,
Ar' is a C ₆ ~ C ₂₀ aryl group; Fluorenyl group; O, N, S, Si, and C ₂ ~ C ₂₀ heterocyclic group containing at least one heteroatom of P; C ₃ ~ C ₂₀ aliphatic ring group; And it is selected from the group consisting of a combination thereof,
L'is independently of each other a single bond; C ₆ ~ C ₂₀ arylene group; Fluorenylene group; O, N, S, Si, and C ₂ ~ C ₂₀ heterocyclic group containing at least one heteroatom of P; And C ₃ ~ C ₂₀ is selected from the group consisting of an aliphatic ring group. The method of claim 1
A compound characterized in that at least one of R _a and R _b is represented by the following formula B-1:
<Formula B-1>

In Formula B-1,
Ring A and Ring B are independently of each other an _{aromatic ring group of C 6} ~ C _{20 or a heterocyclic group of C 4} ~ C ₂₀ containing at least one heteroatom of O, N, S, Si and P,
Z is O, S, N-(L'-Ar') or C(R')(R"),
The R′ and R” are independently of each other hydrogen; deuterium; halogen; _{a silane group unsubstituted or substituted with a C 1} -C ₂₀ alkyl group or a C ₆ -C ₂₀ aryl group; a cyano group; a nitro group; C ₁ -C ₂₀ alkylthio group; C ₁ -C ₂₀ alkoxy group; C ₆ -C ₂₀ aryloxy group; C ₁ -C ₂₀ alkyl group; C ₂ -C ₂₀ alkenyl group; C ₂ -C ₂₀ alkynyl group ; C ₆ -C _{20 aryl group; fluorenyl group; C 2} -C ₂₀ heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; C ₃ -C _It is selected from the group consisting of an aliphatic ring group of _{20; C 7} -C ₂₀ arylalkyl group; And C ₈ -C ₂₀ arylalkenyl group, and neighboring groups may be bonded to each other to form a ring,
Ar' is a C ₆ ~ C ₂₀ aryl group; Fluorenyl group; O, N, S, Si, and C ₂ ~ C ₂₀ heterocyclic group containing at least one heteroatom of P; C ₃ ~ C ₂₀ aliphatic ring group; And it is selected from the group consisting of a combination thereof,
L'is independently of each other a single bond; C ₆ ~ C ₂₀ arylene group; Fluorenylene group; O, N, S, Si, and C ₂ ~ C ₂₀ heterocyclic group containing at least one heteroatom of P; And C ₃ ~ C ₂₀ is selected from the group consisting of an aliphatic ring group. The method of claim 1,
At least one of R ¹ to R ⁴ , Ar ¹ and Ar ² is selected from the group consisting of the following Formulas A-1 to A-6:
<Formula A-1><FormulaA-2><FormulaA-3>

<Formula A-4><FormulaA-5><FormulaA-6>

In Formulas A-1 to A-6, L is the same as defined in claim 1,
X ¹ ~ X ⁶ are each independently C, C (R ₁ ) or N,
Y ₁ to Y ₈ are independently of each other C(R ₁ ) or N,
In Formula A-1, at least one of ^{X 1} to X ^{6 is N,}
In Formula A-2, at least one of ^{X 1} to X ⁴ and Y ₁ to Y _{4 is N,}
In Formula A-3, at least one of ^{X 1} to X ^{6 is N,}
In Formula A-4, at least one of ^{X 1} to X ⁴ and Y ₁ to Y _{8 is N,}
In Formulas A-5 and A-6, at least one of ^{X 1} to X ^{4 is N,}
V and W are O, S, N-(L'-Ar') or C(R')(R"), e and f are each 0 or 1, at least one of e and f is 1,
Y ¹ is O, S, N, N-(L'-Ar'), C(R') or C(R')(R"), Y ² is N,
The R ₁ , R′ and R” are independently of each other hydrogen; deuterium; halogen; _{a silane group unsubstituted or substituted with a C 1} -C ₂₀ alkyl group or a C ₆ -C ₂₀ aryl group; a cyano group; a nitro group; C ₁ -C ₂₀ alkylthio group; C ₁ -C ₂₀ alkoxy group; C ₆ -C ₂₀ aryloxy group; C ₁ -C ₂₀ alkyl group; C ₂ -C ₂₀ alkenyl group; C ₂ -C ₂₀ Alkynyl group of; C ₆ -C _{20 aryl group; fluorenyl group; C 2} -C ₂₀ heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; C ₃ -C ₂₀ aliphatic ring group; C ₇ -C ₂₀ arylalkyl group; And C ₈ -C ₂₀ selected from the group consisting of arylalkenyl group, neighboring groups may be bonded to each other to form a ring,
Ar' is a C ₆ ~ C ₂₀ aryl group; Fluorenyl group; O, N, S, Si, and C ₂ ~ C ₂₀ heterocyclic group containing at least one heteroatom of P; C ₃ ~ C ₂₀ aliphatic ring group; And it is selected from the group consisting of a combination thereof,
L'is independently of each other a single bond; C ₆ ~ C ₂₀ arylene group; Fluorenylene group; O, N, S, Si, and C ₂ ~ C ₂₀ heterocyclic group containing at least one heteroatom of P; And C ₃ ~ C ₂₀ is selected from the group consisting of an aliphatic ring group. The method of claim 1,
The compound represented by Formula 1 is a compound characterized in that one of the following compounds:

. In an organic electric device comprising an anode, a cathode, and an organic material layer formed between the anode and the cathode,
The organic material layer is an organic electric device, characterized in that it contains a single compound or two or more compounds represented by the formula (1) of claim 1. In an organic electric device comprising an anode, a cathode, an organic material layer formed between the anode and the cathode, and a light efficiency improvement layer,
The light efficiency improvement layer is formed on one surface of both surfaces of the anode or the cathode that is not in contact with the organic material layer,
An organic electric device, wherein the organic material layer or the light efficiency improvement layer comprises a compound represented by Formula 1 of claim 1. The method of claim 8 or 9,
The organic material layer comprises at least one of a hole injection layer, a hole transport layer, a light emission auxiliary layer, a light emission layer, an electron transport auxiliary layer, an electron transport layer, and an electron injection layer. The method of claim 10,
The compound is an organic electric device, characterized in that included in at least one of the light-emitting layer and the light-emitting auxiliary layer. The method of claim 8 or 9,
The organic material layer comprises at least two stacks including a hole transport layer, a light emitting layer, and an electron transport layer sequentially formed on the anode. The method of claim 12,
The organic material layer further comprises a charge generation layer formed between the two or more stacks. A display device comprising the organic electric device of claim 8 or 9; And
Electronic device comprising a; a control unit for driving the display device. The method of claim 14,
The organic electric device is an electronic device, characterized in that selected from the group consisting of an organic electroluminescent device, an organic solar cell, an organic photoreceptor, an organic transistor, a monochromatic lighting device, and a quantum dot display device.

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