WO2021060723A1 - Compound for organic electronic element, organic electronic element comprising same, and electronic device thereof - Google Patents

Abstract

The present invention provides: a compound represented by chemical formula 1; an organic electronic element comprising a first electrode, a second electrode, and an organic layer placed between the first and second electrodes; and an electronic device comprising the organic electronic element, wherein the organic layer includes a compound represented by chemical formula 1 so that the driving voltage of the organic electronic element can be reduced and the luminous efficiency and service life thereof can be improved.

Description

Compound for organic electric device, organic electric device including the same, and electronic device thereof

The present invention relates to a compound for an organic electric device, an organic electric device including 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 multi-layered 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, and an electron injection layer.

Lifespan and efficiency are the most problematic in organic electroluminescent devices, and as displays become large-area, such efficiency or lifetime problems must be solved.

Efficiency, lifespan, and driving voltage are related to each other. As the efficiency increases, the driving voltage decreases relatively, and 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, simply improving the organic material layer cannot maximize the efficiency. This is because the long life and high efficiency can be achieved at the same time when the energy level and T1 value between each organic material layer and the intrinsic properties of the material (mobility, interfacial properties, etc.) are optimally combined.

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 for the hole transport layer, since it must have a low HOMO value, most have a low T1 value, and this causes excitons generated in the emission layer to pass to the hole transport layer, resulting in charge unbalance in the emission 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.

In order to solve the problem of light emission in the hole transport layer in recent organic electroluminescent devices, an emission auxiliary layer must exist between the hole transport layer and the emission layer, and different emission auxiliary layers are provided for each emission layer (R, G, B). Is being developed.

In order to fully exhibit the excellent characteristics of organic electronic devices, materials that make up the organic material layer in the device, such as hole injection materials, hole transport materials, light-emitting materials, electron transport materials, electron injection materials, and light-emitting auxiliary layer materials, are suitable for stable and efficient materials. Supported by this should be preceded, and in particular, development of a light-emitting auxiliary layer material 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 including the compound represented by the above formula.

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

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

[Explanation of code]

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

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 term "fluorenyl group" used in the present invention refers to a substituted or unsubstituted fluorenyl group, and "fluorenylene group" refers to a substituted or unsubstituted fluorenyl group, and the fluorenyl group or The fluorenylene group includes a spiro compound formed by bonding of R and R′ to each other in the following structure, and also includes a compound in which adjacent R″ is bonded to each other to form a ring.

"Substituted fluorenyl group" and "substituted fluorenylene group" means that at least one of R, R', R" in the following structure is a substituent other than hydrogen, and in the formula below, R" is 1 to 8 days I can. In the present specification, a fluorenyl group, a fluorenylene group, a fluorenetriyl group, and the like may all be referred to as a fluorene group 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 layers 140, 340, 440, or may be used as a material for the light efficiency improvement layer 180, but preferably, the light emission auxiliary layer 220 and/or the light efficiency improvement layer 180 ) Can 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 emission auxiliary layer 220 and/or the light efficiency improvement layer 180, the energy level and T ₁ value between each organic layer, and the inherent properties of the material (mobility , Interface characteristics, etc.) can be optimized to improve the life and efficiency of organic electronic devices 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.

Z ₁ to Z ₄ are each independently a single bond, O, S, or C(R')(R").

A ring, B ring, C ring, and D ring are independently of each other C ₆ ~ C _{60 aromatic ring group or C 2} ~ C ₆₀ heterocycle containing at least one heteroatom of O, N, S, Si and P And at least one of the A ring, B ring, C ring and D ring is a C ₁₀ aromatic ring group.

When at least one of the A ring, B ring, C ring and D ring is an aromatic ring group, the aromatic ring group is, for example, C ₆ ~ C ₃₀ , C ₆ ~ C ₂₉ , C ₆ ~ C ₂₈ , C ₆ ~ C ₂₇ , C ₆ ~C ₂₆ , C ₆ ~C ₂₅ , C ₆ ~C ₂₄ , C ₆ ~C ₂₃ , C ₆ ~C ₂₂ , C ₆ ~C ₂₁ , C ₆ ~C ₂₀ , C ₆ ~C ₁₉ , C ₆ ~ C ₁₈ , C ₆ to C ₁₇ , C ₆ to C ₁₆ , C ₆ to C ₁₅ , C ₆ to C ₁₄ , C ₆ to C ₁₃ , C ₆ to C ₁₂ , C ₆ to C ₁₁ , C ₆ to C ₁₀ , C ₆ , C ₁₀ , C ₁₂ , C ₁₃ , C ₁₄ , C ₁₅ , C ₁₆ , C ₁₇ , C _{18 It} may be an aromatic ring group, such as, specifically, may be benzene, naphthalene, and the like.

When at least one of the A ring, B ring, C ring and D ring is a heterocyclic group, the heterocyclic group is, for example, C ₂ ~C ₃₀ , C ₂ ~C ₂₉ , C ₂ ~C ₂₈ , C ₂ ~C ₂₇ , C ₂ to C ₂₆ , C ₂ to C ₂₅ , C ₂ to C ₂₄ , C ₂ to C ₂₃ , C ₂ to C ₂₂ , C ₂ to C ₂₁ , C ₂ to C ₂₀ , C ₂ to C ₁₉ , C ₂ ~C ₁₈ , C ₂ ~C ₁₇ , C ₂ ~C ₁₆ , C ₂ ~C ₁₅ , C ₂ ~C ₁₄ , C ₂ ~C ₁₃ , C ₂ ~C ₁₂ , C ₂ ~C ₁₁ , C ₂ ~C ₁₀ , C ₂ ~ C ₉ , C ₂ ~ C ₈ , C ₂ ~ C ₇ , C ₂ ~ C ₆ , C ₂ ~ C ₅ , C ₂ ~ C ₄ , C ₂ ~ C ₃ , C ₂ , C ₃ , C ₄ , C ₅ , C ₆ , C ₇ , C ₈ , C ₉ , C ₁₀ , C ₁₁ , C ₁₂ , C ₁₃ , C ₁₄ , C ₁₅ , C ₁₆ , C ₁₇ , C ₁₈ , C ₁₉ , C ₂₀ , C ₂₁ , C ₂₂ , C ₂₃ , C ₂₄ , C ₂₅ , C ₂₆ , C ₂₇ , C ₂₈ , C _{29 It} may be a heterocyclic group such as, specifically, pyridine, pyrimidine, quinoline, isoquinoline, quinazoline , Quinoxaline, naphthyridine, and the like. It may be _{a C 4} ~ C _{9 heterocycle including N.}

L _a , L _b and L _c 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 C 2} ~ C _{60 heterocyclic group containing at least one heteroatom.}

Ar _a and Ar _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} is selected from the group consisting of an aliphatic ring group.

The R'and R" are independently of each other hydrogen; deuterium; halogen; cyano group; nitro group; C ₆ ~ C ₆₀ aryl group; fluorenyl group; O, N, S, Si, and at least one heteroatom of P C ₂ ~ C ₆₀ heterocyclic group; C ₃ ~ C ₆₀ aliphatic ring group; C ₁ ~ C ₃₀ alkyl group; C ₂ ~ C ₃₀ alkenyl group; C ₂ ~ C ₃₀ alkynyl group; C _It is selected from the group consisting of an alkoxyl group of 1 to C _{30 ; And an aryloxy group of C 6} to C ₃₀ , and R′ and R” may be bonded to each other to form a ring. When R'and R" are bonded to each other to form a ring, a compound may be formed as a spy.

When _{at least one of Ar a} , Ar _b , R', R" is an aryl group, the aryl group is C ₆ ~C ₃₀ , C ₆ ~C ₂₉ , C ₆ ~C ₂₈ , C ₆ ~C ₂₇ , C ₆ ~ C ₂₆ , C ₆ to C ₂₅ , C ₆ to C ₂₄ , C ₆ to C ₂₃ , C ₆ to C ₂₂ , C ₆ to C ₂₁ , C ₆ to C ₂₀ , C ₆ to C ₁₉ , C ₆ to C ₁₈ , C ₆ ~C ₁₇ , C ₆ ~C ₁₆ , C ₆ ~C ₁₅ , C ₆ ~C ₁₄ , C ₆ ~C ₁₃ , C ₆ ~C ₁₂ , C ₆ ~C ₁₁ , C ₆ ~C ₁₀ , C ₆ , C ₁₀ , C ₁₂ , C ₁₃ , C ₁₄ , C ₁₅ , C ₁₆ , C ₁₇ , C _{18 It} may be an aryl group such as, specifically, phenyl, biphenyl, naphthyl, terphenyl, phenanthrene, tri Phenylene and the like.

When at least one of the L _a , L _b , and L _c is an arylene group, the arylene group is C ₆ ~ C ₃₀ , C ₆ ~ C ₂₉ , C ₆ ~ C ₂₈ , C ₆ ~ C ₂₇ , C ₆ ~ C ₂₆ , C ₆ ~C ₂₅ , C ₆ ~C ₂₄ , C ₆ ~C ₂₃ , C ₆ ~C ₂₂ , C ₆ ~C ₂₁ , C ₆ ~C ₂₀ , C ₆ ~C ₁₉ , C ₆ ~C ₁₈ , C ₆ ~C ₁₇ , C ₆ ~C ₁₆ , C ₆ ~C ₁₅ , C ₆ ~C ₁₄ , C ₆ ~C ₁₃ , C ₆ ~C ₁₂ , C ₆ ~C ₁₁ , C ₆ ~C ₁₀ , C ₆ , C ₁₀ , C ₁₂ , C ₁₃ , C ₁₄ , C ₁₅ , C ₁₆ , C ₁₇ , C _{18 It} may be an arylene group, such as, and specifically, may be phenylene, biphenyl, naphthylene, terphenyl.

When _{at least one of Ar a} , Ar _b , R', R", L _a , L _b , and L _c is a heterocyclic group, the heterocyclic group is C ₂ ~C ₃₀ , C ₂ ~C ₂₉ , C ₂ ~C ₂₈ , C ₂ to C ₂₇ , C ₂ to C ₂₆ , C ₂ to C ₂₅ , C ₂ to C ₂₄ , C ₂ to C ₂₃ , C ₂ to C ₂₂ , C ₂ to C ₂₁ , C ₂ to C ₂₀ , C ₂ to C ₁₉ , C ₂ to C ₁₈ , C ₂ to C ₁₇ , C ₂ to C ₁₆ , C ₂ to C ₁₅ , C ₂ to C ₁₄ , C ₂ to C ₁₃ , C ₂ to C ₁₂ , C ₂ ~C ₁₁ , C ₂ ~C ₁₀ , C ₂ ~C ₉ , C ₂ ~C ₈ , C ₂ ~C ₇ , C ₂ ~C ₆ , C ₂ ~C ₅ , C ₂ ~C ₄ , C ₂ ~C ₃ , C ₂ , C ₃ , C ₄ , C ₅ , C ₆ , C ₇ , C ₈ , C ₉ , C ₁₀ , C ₁₁ , C ₁₂ , C ₁₃ , C ₁₄ , C ₁₅ , C ₁₆ , C ₁₇ , It may be a heterocyclic group such as _{C 18} , C ₁₉ , C ₂₀ , C ₂₁ , C ₂₂ , C ₂₃ , C ₂₄ , C ₂₅ , C ₂₆ , C ₂₇ , C ₂₈ , C _{29, and specifically, pyridine, pyrimidine} , Pyrazine, pyridazine, triazine, furan, pyrrole, silol, indene, indole, phenyl-indole, benzoindole, phenyl-benzoindole, pyrazinoindole, quinoline, isoquinoline, benzoquinoline, pyridoquinoline, quinazoline, Benzoquinazoline, dibenzoquinazoline, phenanthroquinazoline, quinoxaline, benzoquinoxaline, dibenzoquinoxaline, benzofuran, naphthobenzofuran, dibenzofuran, phenanthrobenzofuran, dynaphthofuran, thiophene, Benzothiophene, dibenzothiophene, naphthobenzothiophene, phenanthrobenzothiophene, dinapthothiophene, carbazole, phenyl-carbazole, benzocarbazole, phenyl-benzocarbazole, naphthyl-benzocarbazole , Dibenzocarbazole, indolocarbazole, benzofuropyridine, benzothienopyridine, benzofuropyridine, benzothienopyrimidine, benzofuropyrimidine, benzothienopyrazine, Benzofuropyrazine, benzoimidazole, benzothiazole, benzoxazole, benzosilol, phenanthroline, dihydro-phenylphenazine, 10-phenyl-10H-phenoxazine, phenoxazine, phenothiazine, dibenzodioxin , Benzodibenzodioxin, thianthrene, 9,9-dimethyl-9H-xanthrene, 9,9-dimethyl-9H-thioxanthrene, dihydrodimethylphenylacridine, spiro[fluorene-9 ,9'-xanthene] and the like.

When _{at least one of Ar a} , Ar _b , R', R" is an alkyl group, the alkyl group is C ₁ ~C ₂₀ , C ₁ ~C ₁₀ , C ₁ ~C ₄ , C ₁ , C ₂ , C ₃ , It _{may be an alkyl group such as C 4} , and specifically, it may be methyl, ethyl, propyl, t-butyl, and the like.

When _{at least one of Ar a} , Ar _b , R', R" is a fluorenyl group, or at least one of L _a , L _b , L _c , L'is a fluorenylene group, the fluorenyl group or fluorene ylene group is 9,9-dimethyl -9 H - fluorene, 9,9-diphenyl -9 H - fluorene as fluorene group, a 9,9'-bi-Spy fluorene, benzo fluorene, spy [benzo [b ]Fluorene-11,9'-fluorene], 11,11-diphenyl-11 H -benzo[ b ]fluorene, 9-(naphthalen-2-yl)9-phenyl-9 H -fluorene, etc. have.

When _{at least one of Ar a} , Ar _b , R', R", L _a , L _b , and L _c is an aliphatic ring group, the aliphatic ring group is C ₆ ~C ₃₀ , C ₆ ~C ₂₉ , C ₆ ~C ₂₈ , C ₆ ~C ₂₇ , C ₆ ~C ₂₆ , C ₆ ~C ₂₅ , C ₆ ~C ₂₄ , C ₆ ~C ₂₃ , C ₆ ~C ₂₂ , C ₆ ~C ₂₁ , C ₆ ~C ₂₀ , C ₆ ~C ₁₉ , C ₆ ~C ₁₈ , C ₆ ~C ₁₇ , C ₆ ~C ₁₆ , C ₆ ~C ₁₅ , C ₆ ~C ₁₄ , C ₆ ~C ₁₃ , C ₆ ~C ₁₂ , C ₆ ~ C ₁₁ , C ₆ ~ C ₁₀ , C ₆ , C ₁₀ , C ₁₂ , C ₁₃ , C ₁₄ , C ₁₅ , C ₁₆ , C ₁₇ , C _{18 It} may be an aliphatic ring group, such as, specifically, cyclohexanyl I can.

The aryl group, arylene group, aromatic ring group, fluorenyl group, fluorenylene group, heterocyclic group, aliphatic ring group, alkyl group, alkenyl group, alkynyl group, alkoxyl group, aryloxy group, and R'and R" are Each of the rings formed by bonding to each other is 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 siloxane group; a cyano group; a nitro group; C ₁ -C ₂₀ Alkylthio group of; C ₁ -C ₂₀ alkoxy group; C ₆ -C ₂₀ aryloxy group; C ₆ -C ₂₀ arylthio group; C ₁ -C ₂₀ alkyl group unsubstituted or substituted with halogen; C ₂ -C ₂₀ alkenyl group; C ₂ -C ₂₀ alkynyl group; C ₆ -C ₂₀ aryl group; fluorenyl group; At least one heteroatom selected from the group consisting of O, N, S, Si and P C ₂ -C ₂₀ heterocyclic group; C ₃ -C ₂₀ aliphatic ring group; C ₇ -C ₂₀ arylalkyl group; And C ₈ -C ₂₀ with one or more substituents selected from the group consisting of arylalkenyl group Can be substituted.

The aryl group, arylene group, aromatic ring group, fluorenyl group, fluorenylene group, heterocyclic group, aliphatic ring group, alkyl group, alkenyl group, alkynyl group, alkoxyl group, aryloxy group, and R'and R" are When at least one of the rings formed by bonding to each other is substituted with an aryl group, the aryl group is C ₆ ~ C ₂₀ , C ₆ ~ C ₁₉ , C ₆ ~ C ₁₈ , C ₆ ~ C ₁₇ , C ₆ ~ C ₁₆ , C ₆ ~C ₁₅ , C ₆ ~C ₁₄ , C ₆ ~C ₁₃ , C ₆ ~C ₁₂ , C ₆ ~C ₁₁ , C ₆ ~C ₁₀ , C ₆ , C ₁₀ , C ₁₂ , C ₁₃ , C ₁₄ , It may be an aryl group such as _{C 15} , C ₁₆ , C ₁₇ , C _18.

The aryl group, arylene group, aromatic ring group, fluorenyl group, fluorenylene group, heterocyclic group, aliphatic ring group, alkyl group, alkenyl group, alkynyl group, alkoxyl group, aryloxy group, and R'and R" are When at least one of the rings formed by bonding to each other is substituted with a heterocyclic group, the heterocyclic group is C ₂ ~ C ₂₀ , C ₂ ~ C ₁₉ , C ₂ ~ C ₁₈ , C ₂ ~ C ₁₇ , C ₂ ~ C ₁₆ , C ₂ to C ₁₅ , C ₂ to C ₁₄ , C ₂ to C ₁₃ , C ₂ to C ₁₂ , C ₂ to C ₁₁ , C ₂ to C ₁₀ , C ₂ to C ₉ , C ₂ to C ₈ , C ₂ to C ₇ , C ₂ to C ₆ , C ₂ to C ₅ , C ₂ to C ₄ , C ₂ to C ₃ , C ₂ , C ₃ , C ₄ , C ₅ , C ₆ , C ₇ , C ₈ , It may be a heterocyclic group such as _{C 9} , C ₁₀ , C ₁₁ , C ₁₂ , C ₁₃ , C ₁₄ , C ₁₅ , C ₁₆ , C ₁₇ , C ₁₈ , C ₁₉ , C _20.

The aryl group, arylene group, aromatic ring group, fluorenyl group, fluorenylene group, heterocyclic group, aliphatic ring group, alkyl group, alkenyl group, alkynyl group, alkoxyl group, aryloxy group, and R'and R" are When at least one of the rings formed by bonding to each other is substituted with an alkyl group, the alkyl group is C ₁ to C ₂₀ , C ₁ to C ₁₀ , C ₁ to C ₄ , C ₁ , C ₂ , C ₃ , C _4, etc. It may be an alkyl group.

At least one of the aryl group, arylene group, aromatic ring group, fluorenyl group, fluorenylene group, heterocyclic group, and alicyclic group is substituted with an alkoxyl group, and the alkoxyl group is C ₁ ~ C ₂₀ , C ₁ It may be an alkoxyl group such as ~C ₁₀ , C ₁ ~C ₄ , C ₁ , C ₂ , C ₃ , C _4.

Formula 1 may be represented by one of Formulas 2 to 7 below.

<Formula 2> <Formula 3>

<Formula 4> <Formula 5>

<Formula 6> <Formula 7>

In Chemical Formulas 2 to 7, Z ₁ , Z ₃ , Z ₄ , L _a -L _c , Ar _a , Ar _b are the same as defined in Chemical Formula 1.

In addition, Formula 1 may be represented by one of Formulas 8 to 13 below.

<Formula 8> <Formula 9>

<Formula 10> <Formula 11>

<Formula 12> <Formula 13>

In Formulas 8 to 13, Z ₁ and Z ₂ are each independently O, S or C(R')(R"), and R', R", Z ₃ , Z ₄ , L _a to L _c , Ar _a and Ar _b are the same as defined in Formula 1,

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 emission layer, an electron transport auxiliary layer, an electron transport layer and an electron injection layer, and preferably the compound may be included in the emission auxiliary layer.

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 a and Sub b as shown in Scheme 1 below, but is not limited thereto.

<Reaction Scheme 1>

Sub a of Synthesis example

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

<Reaction Scheme 2>

1.Sub a-1 Synthesis example

8-bromobenzo[b]naphtho[2,1-d]thiophene (30 g, 95.78 mmol), aniline (8.92 g, 95.78 mmol), Pd ₂ (dba) ₃ (0.03 equivalent), (t-Bu)3P (0.06 equivalent), and NaOt-Bu (3 equivalent) were dissolved in anhydrous toluene, and then refluxed for 3 hours. When the reaction was completed, the temperature of the reaction product was cooled to room temperature _{, extracted with CH 2} Cl ₂ , and washed with water. A small amount of water _{was removed with anhydrous MgSO 4} , filtered under reduced pressure, and concentrated. Thereafter, the concentrate was separated by a silica gel column and recrystallized to obtain 26.5 g of a product. (Yield: 85%)

2.Sub a-11 Synthesis example

10-bromobenzo[b]naphtho[1,2-d]thiophene (50 g, 159.64 mmol), 9,9-diphenyl-9H-fluoren-2-amine (53.23 g, 159.64 mmol), Pd ₂ (dba) ₃ (0.03 equivalents), (t-Bu)3P (0.06 equivalents), and NaOt-Bu (3 equivalents) were dissolved in anhydrous toluene, and then proceeded in the same manner as the synthesis method of Sub a-1 to obtain 73.2 g of the product. (Yield: 81%)

3.Sub a-15 Synthesis example

3-bromo-9-phenyl-9H-carbazole (40 g, 124.14 mmol), dibenzo[b,d]thiophen-2-amine (23.74 g, 124.14 mmol), Pd ₂ (dba) ₃ (0.03 equivalents), (t-Bu) ₃ P (0.06 equivalents), and NaOt-Bu (3 equivalents) were dissolved in anhydrous toluene, and then proceeded in the same manner as the synthesis method of Sub a-1 to obtain 44.85 g of the product. (Yield: 82%)

4.Sub a-26 Synthesis example

2-bromo-11,11-dimethyl-11H-benzo[b]fluorene (35 g, 108.28 mmol), 9,9-dimethyl-9H-fluoren-2-amine (22.66 g, 108.28 mmol), Pd ₂ (dba ) ₃ (0.03 equivalents), (t-Bu) ₃ P (0.06 equivalents), and NaOt-Bu (3 equivalents) were dissolved in anhydrous toluene, and then proceeded in the same manner as the synthesis method of Sub a-1 to obtain 48.90 g of a product. (Yield: 80%)

5.Sub a-75 Synthesis example

(1) Synthesis of Sub a-75A

2-bromodibenzo[b,d]thiophene (50 g, 190.00 mmol), (2-chlorophenyl)boronic acid (29.7 g, 190.00 mmol), Pd(PPh ₃ ) ₄ (0.03 eq), NaOH (3 eq.) After dissolving in THF and a small amount of water, it was refluxed for 24 hours. Thereafter, it proceeded in the same manner as the synthesis method of Sub a-1 to obtain 46.5 g of the product. (Yield: 83%)

(2) Synthesis of Sub a-75

Sub a-75A (40 g, 135.69 mmol), aniline (12.64 g, 135.69 mmol), Pd ₂ (dba) ₃ (0.03 equivalents), (t-Bu) ₃ P (0.06 equivalents), and NaOt-Bu (3 equivalents) were dissolved in anhydrous toluene, and then proceeded as in the synthesis method of Sub a-1 to obtain 47.7 g of the product. (Yield: 80%)

6.Sub a-94 Synthesis example

1-bromobenzo[b]naphtho[2,3-e][1,4]dioxine (15 g, 47.9 mmol), [1,1'-biphenyl]-4-amine (8.5 g, 50.3 mmol), Pd ₂ (dba) ₃ (0.03 equivalents), (t-Bu)3P (0.06 equivalents), and NaOt-Bu (3 equivalents) were dissolved in anhydrous toluene, and then proceeded in the same manner as the synthesis method of Sub a-1 to obtain 14.62 g of the product. (Yield: 76%)

7.Sub a-99 Synthesis example

10-bromo-12,12-dimethyl-12H-benzo[a]thioxanthene (17 g, 47.8 mmol), [1,1'-biphenyl]-4-amine (8.5 g, 50.2 mmol), Pd ₂ (dba) ₃ (0.03 equivalents), (t-Bu)3P (0.06 equivalents), and NaOt-Bu (3 equivalents) were dissolved in anhydrous toluene, and then proceeded in the same manner as the synthesis method of Sub a-1 to obtain 15.7 g of the product. (Yield: 74%)

8.Sub a-104 Synthesis example

(1) Synthesis of Sub a-104A

9-bromo-11-phenylbenzo[a]phenoxathiine (14 g, 34.5 mmol), (2-chlorophenyl)boronic acid (5.4 g, 34.5 mmol), Pd(PPh3)4 (0.03 eq), NaOH (3 eq) After dissolving in anhydrous THF and a small amount of water, it was refluxed for 24 hours. Thereafter, it proceeded in the same manner as the synthesis method of Sub a-1 to obtain 10.2 g of the product. (Yield: 68%)

(2) Synthesis of Sub a-104

Sub a-104A (40 g, 135.69 mmol), aniline (12.64 g, 135.69 mmol), Pd2(dba)3 (0.03 equivalent), (t-Bu)3P (0.06 equivalent), NaOt-Bu (3 equivalent) dissolved in anhydrous toluene After that, it proceeded in the same manner as the synthesis method of Sub a-1 to obtain 47.7 g of the product. (Yield: 65%)

9.Sub a-106 Synthesis example

(1) Synthesis of Sub a-106A

2-bromophenoxathiine (17 g, 60.9 mmol), (4-chlorophenyl)boronic acid (9.5 g, 60.9 mmol), Pd(PPh ₃ ) ₄ (0.03 eq), NaOH (3 eq) in anhydrous THF and a small amount of water After dissolving and refluxing for 24 hours, the product 13.6 g was obtained by proceeding in the same manner as for the synthesis of Sub a-1. (Yield: 69%)

(2) Synthesis of Sub a-106

Sub a-106A (13.0 g, 42.0 mmol), 3-(9-methyl-9H-fluoren-9-yl)aniline (11.9 g, 44.1 mmol), Pd ₂ (dba) ₃ (0.03 equivalents), (t-Bu) ₃ P (0.06 equivalents), and NaOt-Bu (3 equivalents) were dissolved in anhydrous toluene, and then proceeded as in the synthesis method of Sub a-1 to obtain 15.3 g of the product. (Yield: 67%)

The compounds belonging to Sub a 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]

Sub b synthesis method

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

<Reaction Scheme 3>

1.Sub b-1 Synthesis example

After dissolving 1-bromo-4-chlorodibenzo[b,d]furan (30 g, 106.56 mmol) in THF (600ml), phenylboronic acid (13 g, 106.56 mmol), Pd(PPh ₃ ) ₄ (0.03 equivalent), K ₂ CO ₃ (3 eq) and water (150 ml) were added and stirred 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 23.2 g (yield: 78%) of the product.

2. Sub b-4 Synthesis example

After dissolving 4-bromo-1-chlorodibenzo[b,d]thiophene (30 g, 100.81 mmol) with THF (600ml), dibenzo[b,d]furan-2-ylboronic acid (21.4 g, 106.56 mmol), Pd (PPh ₃ ) ₄ (0.03 equivalents), K ₂ CO ₃ (3 equivalents), and water (150 ml) were added and proceeded in the same manner as in the synthesis method of Sub b-1 to obtain 31.0 g (yield: 80%) of the product. .

3.Sub b-18 Synthesis example

(1) Synthesis of Sub b-18A

After dissolving 4-bromo-1-iododibenzo[b,d]furan (30 g, 80.43 mmol) with THF (600ml), phenylboronic acid (9.8 g, 80.43 mmol), Pd(PPh ₃ ) ₄ (0.03 equivalent), K ₂ CO ₃ (3 equivalents) and water (150 ml) were added, followed by the same method as for the synthesis of Sub b-1 to obtain 19.5 g (yield: 75%) of the product.

(2) Synthesis of Sub b-18

After dissolving Sub b-18A (19 g, 58.79 mmol) in THF (600ml), (3-chlorophenyl)boronic acid (9.2 g, 58.79 mmol), Pd(PPh ₃ ) ₄ (0.03 equivalent), K ₂ CO ₃ (3 equivalents) and water (150ml) were added and proceeded in the same manner as for the synthesis of Sub b-1 to obtain 18.2 g (yield: 87%) of the product.

4.Sub b-36 Synthesis example

After dissolving 10-bromo-7-chlorobenzo[b]naphtho[2,1-d]thiophene (30 g, 86.29 mmol) with THF (600ml), dibenzo[b,d]thiophen-2-ylboronic acid (19.7 g , 86.29 mmol), Pd(PPh ₃ ) ₄ (0.03 equivalents), K ₂ CO ₃ (3 equivalents), and water (150 ml) were added and proceeded in the same manner as for the synthesis of Sub b-1, and the product 32.7 g (yield : 84%) was obtained.

5.Sub b-50 Synthesis example

After dissolving 1-bromo-4-chlorobenzo[b]naphtho[2,3-e][1,4]dioxine (25 g, 71.92 mmol) with THF (240 ml), phenylboronic acid (8.7 g, 71.92 mmol), and Pd(PPh ₃ ) ₄ (0.03 equivalents), K ₂ CO ₃ (3 equivalents), and water (120 ml) were added and proceeded in the same manner as for the synthesis of Sub b-1 to obtain 19.84 g (yield: 80%) of the product. Got it.

6.Sub b-52 Synthesis example

After dissolving 11-bromo-8-chlorobenzo[a]thianthrene (22 g, 57.94 mmol) in THF (193ml), phenylboronic acid (7.0 g, 57.94 mmol), Pd(PPh ₃ ) ₄ (0.03 equivalent), K ₂ CO ₃ (3 equivalents) and water (97 ml) were added, followed by the same method as for the synthesis of Sub b-1 to obtain 16.82 g (yield: 77%) of the product.

7.Sub b-54 Synthesis example

(1) Synthesis of Sub b-54A

After dissolving 1-bromo-4-iododibenzo[b,e][1,4]dioxine (20 g, 51.42 mmol) in THF (171 ml), phenylboronic acid (6.2 g, 51.42 mmol), Pd(PPh ₃ ) ₄ (0.03 equivalents), K ₂ CO ₃ (3 equivalents), and water (150 ml) were added and proceeded in the same manner as for the synthesis of Sub b-1 to obtain 12.56 g (yield: 72%) of the product.

(2) Synthesis of Sub b-54

After dissolving Sub b-54A (12.56 g, 37.03 mmol) in THF (123ml), (2-chlorophenyl)boronic acid (5.7 g, 37.03 mmol), Pd(PPh ₃ ) ₄ (0.03 equivalent), K ₂ CO ₃ (3 equivalents) and water (62ml) were added, followed by the same method as for the synthesis of Sub b-1, to obtain 10.3 g (yield: 75%) of the product.

8.Sub b-59 Synthesis example

(1) Synthesis of Sub b-59A

After dissolving 1-bromo-4-iodo-9,9,10,10-tetramethyl-9,10-dihydroanthracene (26 g, 58.94 mmol) with THF (196 ml), phenylboronic acid (7.19 g, 58.94 mmol), Pd (PPh ₃ ) ₄ (0.03 equivalents), K ₂ CO ₃ (3 equivalents), and water (98 ml) were added and proceeded in the same manner as for the synthesis of Sub b-1 to obtain 17.9 g (yield: 78%) of the product. .

(2) Synthesis of Sub b-59

After dissolving Sub b-59A (17.9 g, 45.97 mmol) in THF (153ml), (5-chloropyridin-2-yl)boronic acid (7.2 g, 45.9 mmol), Pd(PPh ₃ ) ₄ (0.03 eq), K ₂ CO ₃ (3 equivalents) and water (77 ml) were added, followed by the same method as for the synthesis of Sub b-1 to obtain 15.4 g (yield: 79%) of the product.

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

[Table 2]

Of the final compound Synthesis example

1.P-1 Synthesis example

Sub a-1 (10 g, 30.73 mmol), Sub b-1 (8.57 g, 30.73 mmol), Pd ₂ (dba) ₃ (0.03 equivalent), (t-Bu) ₃ P (0.06 equivalent), and NaOt-Bu (3 equivalent) were dissolved in anhydrous toluene, followed by refluxing for 3 hours. 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 14.8 g (yield: 82%) of the product.

2. P-10 Synthesis example

Sub a-10 (10 g, 24.90 mmol), Sub b-7 (8.59 g, 24.90 mmol), Pd ₂ (dba) ₃ (0.03 equivalent), (t-Bu) ₃ P (0.06 equivalent), NaOt-Bu (3 equivalent) was dissolved in anhydrous toluene and then proceeded in the same manner as the synthesis method of P-1, and the product 14.1 g (yield: 80% ).

3. P-26 Synthesis example

Sub a-26 (10 g, 22.14 mmol), Sub b-15 (11.5 g, 22.14 mmol), Pd ₂ (dba) ₃ (0.03 equivalent), (t-Bu) ₃ P (0.06 equivalent), NaOt-Bu (3 equivalent) was dissolved in anhydrous toluene and then proceeded in the same manner as the synthesis method of P-1, and the product 16.9 g (yield: 82% ).

4. P-42 Synthesis example

Sub a-42 (10 g, 32.32 mmol), Sub b-22 (14.4 g, 32.32 mmol), Pd ₂ (dba) ₃ (0.03 equivalents), (t-Bu) ₃ P (0.06 equivalents), NaOt-Bu (3 equivalents) were dissolved in anhydrous toluene and then proceeded in the same manner as the synthesis method of P-1, and the product 20.0 g (yield: 86%) ).

5. P-66 Synthesis example

Sub a-66 (10 g, 29.81 mmol), Sub b-29 (14.8 g, 29.81 mmol), Pd ₂ (dba) ₃ (0.03 equivalents), (t-Bu) ₃ P (0.06 equivalents), and NaOt-Bu (3 equivalents) were dissolved in anhydrous toluene, and then refluxed for 3 hours. When the reaction was completed, the product was _{extracted with CH 2} Cl ₂ and water, and the organic layer _{was dried over MgSO 4} and concentrated, and the resulting compound was recrystallized with a silicagel column to obtain 19.2 g (yield: 81%) of the product.

6. P-99 Synthesis example

Sub a-91 (16 g, 39.85 mmol), Sub b-21 (12.7 g, 41.8 mmol), Pd ₂ (dba) ₃ (0.03 equivalent), (t-Bu) ₃ P (0.06 equivalent), NaOt-Bu (3 equivalent) was dissolved in anhydrous toluene and then proceeded in the same manner as the synthesis method of P-1, and the product 19.4 g (yield: 73% ).

7. P-104 Synthesis example

Sub a-91 (19 g, 47.3 mmol), Sub b-54 (18.4 g, 49.6 mmol), Pd ₂ (dba) ₃ (0.03 equivalent), (t-Bu) ₃ P (0.06 equivalent), NaOt-Bu (3 equivalent) was dissolved in anhydrous toluene and then proceeded in the same manner as the synthesis method of P-1, and the product 28.2 g (yield: 81%) ).

8. P-107 Synthesis example

Sub a-98 (14 g, 30.6 mmol), Sub b-56 (13.5 g, 32.1 mmol), Pd ₂ (dba) ₃ (0.03 equivalents), (t-Bu) ₃ P (0.06 equivalents), NaOt-Bu (3 equivalents) were dissolved in anhydrous toluene and then proceeded in the same manner as the synthesis method of P-1, and the product 18.2 g (yield: 78%) ).

9. P-110 Synthesis example

Sub a-101 (17 g, 36.2 mmol), Sub b-56 (16 g, 38.0 mmol), Pd ₂ (dba) ₃ (0.03 equivalents), (t-Bu) ₃ P (0.06 equivalents), NaOt-Bu (3 equivalents) were dissolved in anhydrous toluene and then proceeded in the same manner as the synthesis method of P-1, and the product 23.8 g (yield: 77%) ).

10. P-116 Synthesis example

Sub a-107 (11 g, 42.4 mmol), Sub b-49 (15.3 g, 44.5 mmol), Pd ₂ (dba) ₃ (0.03 equivalent), (t-Bu) ₃ P (0.06 equivalent), NaOt-Bu (3 equivalent) was dissolved in anhydrous toluene and then proceeded in the same manner as the synthesis method of P-1, and the product 19.9 g (yield: 83% ).

The FD-MS values of the compounds P-1 to P-116 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 One] Red organic electroluminescent device ( Light-emitting auxiliary layer )

Hole injection by vacuum deposition of 4,4',4''-Tris[2-naphthyl(phenyl)amino]triphenylamine (hereinafter abbreviated as 2-TNATA) to a thickness of 60 nm on the ITO layer (anode) formed on the glass substrate After forming a layer, on the hole injection layer N,N'-bis(1-naphthalenyl)-N,N'-bis-phenyl-(1,1'-biphenyl)-4,4'-diamine (hereinafter , Abbreviated as NPB) was vacuum deposited to a thickness of 60 nm to form a hole transport layer.

Subsequently, after vacuum-depositing the compound P-1 of the present invention to a thickness of 20 nm on the hole transport layer to form a light emission auxiliary layer, 4,4'-N,N'-dicarbazole-biphenyl ( Hereinafter, abbreviated as CBP) as a host material and bis-(1-phenylisoquinolyl)iridium(III)acetylacetonate (hereinafter, _{abbreviated as (piq) 2} Ir(acac)) as a dopant material in a 95:5 weight ratio Dopant was doped so as to be vacuum deposited to a thickness of 30 nm to form a light emitting layer.

Subsequently, (1,1'-biphenyl-4-olato)bis(2-methyl-8-quinolinolato)aluminum (hereinafter, abbreviated as BAlq) was vacuum deposited to a thickness of 5 nm on the emission layer to form a hole blocking layer. Then, bis(10-hydroxybenzo[h]quinolinato)beryllium (hereinafter, BeBq ₂ ) was vacuum 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 to form an electron injection layer, and then Al was deposited to a thickness of 150 nm to form a cathode, thereby manufacturing an organic electroluminescent device.

[ Example 2] to [ Example 36]

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 below was used instead of the compound P-1 of the present invention as the light emitting auxiliary layer material.

[ Comparative example One]

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

[ Comparative example 2] and [ Comparative example 3]

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that Comparative Compound 1 and Comparative Compound 2 were respectively used as the light emitting auxiliary layer material.

<Comparative compound 1> <Comparative compound 2>

By applying a forward bias DC voltage to the organic electroluminescent devices manufactured according to Examples 1 to 36 and Comparative Examples 1 to 3 of the present invention, electroluminescence (EL) characteristics were obtained with PR-650 of photoresearch. It was measured, and the 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 material for a light emission auxiliary layer, a light emission auxiliary layer is not formed (Comparative Example 1), or when Comparative Compound 1 or Comparative Compound 2 is used (Comparative Example 2 and Compared to Comparative Example 3), the driving voltage of the device was lowered, and both efficiency and life were improved.

The compound of the present invention has a structure similar to that of Comparative Compound 1, but differs in that at least one of the rings A to D is an aromatic ring _{of C 10.} For example, the compound of the present invention corresponding to Comparative Compound 1 is in a form in which one more benzene is condensed on the benzene ring of the fluorene moiety or one more benzene ring is condensed on the benzene ring of the dibenzothiophene moiety. There is a difference.

Comparative Compound 2 is similar to the present invention in that it contains a naphthobenzodioxin moiety, but differs in that it is a compound containing two amine groups.

Therefore, depending on the number of amine groups contained in the compound and the form of fusion, the properties of the compound such as hole characteristics, light efficiency characteristics, energy level (LUMO, HOMO level, T1 level), hole injection & mobility characteristics, electron blocking characteristics, etc. It can be seen that the device result may be different due to the difference in physical properties.

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 scope of the present invention is 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.

CROSS-REFERENCE TO RELATED APPLICATION

This patent application is for patent application No. 10-2019-0118044 filed in Korea on September 25, 2019 and Patent Application No. 10-2020-0020129 filed in Korea on February 19, 2020. Priority is claimed in accordance with Articles 119 to 121 and 365 (35 USC Articles 119 to §121 and §365), all of which are incorporated by reference into this patent application. In addition, if this patent application claims priority for countries other than the United States for the same reason as above, all the contents are incorporated into this patent application as references.

Claims (12)

1. Compound represented by the following formula (1):

   <Formula 1>

   

   In Formula 1,

   Z ₁ to Z ₄ are each independently a single bond, O, S, or C(R')(R"),

   A ring, B ring, C ring, and D ring are independently of each other C ₆ ~ C _{60 aromatic ring group or C 2} ~ C ₆₀ heterocycle containing at least one heteroatom of O, N, S, Si and P Group, and at least one of the A ring, B ring, C ring and D ring is a C ₁₀ aromatic ring group,

   L _a , L _b and L _c 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 _a and Ar _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′ and R” are independently of each other hydrogen; deuterium; halogen; cyano group; nitro group; C ₆ ~ C ₆₀ aryl group; fluorenyl group; O, N, S, Si and P C ₂ ~ C ₆₀ heterocyclic group; C ₃ ~ C ₆₀ aliphatic ring group; C ₁ ~ C ₃₀ alkyl group; C ₂ ~ C ₃₀ alkenyl group; C ₂ ~ C ₃₀ alkynyl group; C ₁ ~ C ₃₀ alkoxyl group; And C ₆ ~ C ₃₀ is selected from the group consisting of aryloxy group, R'and R" may be bonded to each other to form a ring,

   The aryl group, arylene group, aromatic ring group, fluorenyl group, fluorenylene group, heterocyclic group, aliphatic ring group, alkyl group, alkenyl group, alkynyl group, alkoxyl group, aryloxy group, and R'and R" are Each of the rings formed by bonding to each other is 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 siloxane group; a cyano group; a nitro group; C ₁ -C ₂₀ Alkylthio group of; C ₁ -C ₂₀ alkoxy group; C ₆ -C ₂₀ aryloxy group; C ₆ -C ₂₀ arylthio group; C ₁ -C ₂₀ alkyl group unsubstituted or substituted with halogen; C ₂ -C ₂₀ alkenyl group; C ₂ -C ₂₀ alkynyl group; C ₆ -C ₂₀ aryl group; fluorenyl group; At least one heteroatom selected from the group consisting of O, N, S, Si and P C ₂ -C ₂₀ heterocyclic group; C ₃ -C ₂₀ aliphatic ring group; C ₇ -C ₂₀ arylalkyl group; And C ₈ -C ₂₀ with one or more substituents selected from the group consisting of arylalkenyl group Can be substituted.
2. The method of claim 1,

   Formula 1 is a compound characterized in that represented by one of the following formulas 2 to 7:

   <Formula 2> <Formula 3>

   

   <Formula 4> <Formula 5>

   

   <Formula 6> <Formula 7>

   

   In Chemical Formulas 2 to 7, Z ₁ , Z ₃ , Z ₄ , L _a -L _c , Ar _a , Ar _b are as defined in claim 1.
3. The method of claim 1,

   Formula 1 is a compound characterized in that represented by one of the following Formulas 8 to 13:

   <Formula 8> <Formula 9>

   

   <Formula 10> <Formula 11>

   

   <Formula 12> <Formula 13>

   

   In Formulas 8 to 13, Z ₁ and Z ₂ are each independently O, S or C(R')(R"), and R', R", Z ₃ , Z ₄ , L _a to L _c , Ar _a and Ar _b are as defined in claim 1.
4. The method of claim 1,

   The compound represented by Formula 1 is a compound characterized in that one of the following compounds:

   

   

   

   

   

   .
5. 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 the compound represented by the formula (1) of claim 1.
6. The method of claim 5,

   Further comprising a light efficiency improvement layer formed on one side of the anode or the cathode that is not in contact with the organic material layer,

   The light efficiency improvement layer is an organic electric device, characterized in that it comprises a compound represented by the formula (1) of claim 1.
7. The method of claim 5,

   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.
8. The method of claim 7,

   The compound is an organic electric device, characterized in that included in the light emission auxiliary layer.
9. The method of claim 5,

   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.
10. The method of claim 9,

    The organic material layer further comprises a charge generation layer formed between the two or more stacks.
11. A display device comprising the organic electric device of claim 5; And

    Electronic device comprising a; a control unit for driving the display device.
12. The method of claim 11,

    The organic electroluminescent 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.

Images