WO2021080334A1 - Compound for organic electronic element, organic electronic element using same, and electronic device thereof - Google Patents

Abstract

The present invention relates to a compound for an organic electronic element, an organic electronic element using same, and an electronic device comprising the organic electronic element. According to the present invention, an organic electronic element having high luminous efficiency, low driving voltage, and high thermal resistance can be provided, and the color purity and lifespan of the organic electronic element can be improved.

Description

Compound for organic electric device, organic electric device using same, and 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 electric 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, power consumption that is greater 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 optimum combination of the energy level and T1 value between each organic material layer and the intrinsic properties of the material (mobility, interfacial properties, etc.) is achieved.

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 the material used for the hole transport layer, since it must have a low HOMO value, most have a low T1 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 interface. Light emission in the light emitting layer or charge unbalance in the light emitting layer is caused 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 has a suitable driving voltage range (within the range of the driving voltage of the blue device of the full device). Mobility) is urgently 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 is reported to have a great effect 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, and a light-emitting auxiliary layer material should be supported by a stable and efficient material. In particular, development of materials used for the light-emitting auxiliary layer and the light-emitting layer is urgently required.

An object of the present invention is to provide a compound having high heat resistance, lowering the driving voltage of the device, and improving the luminous efficiency, color purity, and lifetime of the device, an organic electric device using the same, and an electronic device including the organic electric device It is done.

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

<Formula 1>

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 the present invention, high luminous efficiency, low driving voltage, and high heat resistance of the device can be achieved, and color purity and lifespan of the device can be improved.

1 to 3 schematically illustrate organic electric devices according to embodiments of the present invention.

4 shows a chemical formula according to an aspect of the present invention.

The present invention provides a compound represented by the following formula.

<Formula 1>

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

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

In order to describe the present embodiments, in adding reference numerals to elements in 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 the drawings referred to below, the accumulation ratio is not applied.

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.

Terms used in the present specification and appended claims are as follows, unless otherwise stated, without departing from the spirit of the present invention.

The term "halo" or "halogen" as used in this application includes fluorine (F), chlorine (Cl), bromine (Br), and iodine (I) unless otherwise specified.

The term "alkyl" or "alkyl group" as used in the present application has 1 to 60 carbons connected by a single bond, unless otherwise stated, a straight-chain alkyl group, a branched-chain alkyl group, a cycloalkyl (alicyclic) group, an alkyl-substituted It means a radical of a saturated aliphatic functional group including a cycloalkyl group and a cycloalkyl-substituted alkyl group.

The term "haloalkyl group" or "halogenalkyl group" as used in the present application means an alkyl group in which halogen is substituted unless otherwise specified.

The terms "alkenyl" or "alkynyl" as used in the present application each have a double bond or a triple bond, unless otherwise specified, include a straight or branched chain group, and have a carbon number of 2 to 60, but are limited thereto. It does not become.

The term "cycloalkyl" as used in the present application means an alkyl forming a ring having 3 to 60 carbon atoms unless otherwise specified, and is not limited thereto.

The term "alkoxy group" or "alkyloxy group" used in the present application refers to an alkyl group to which an oxygen radical is bonded, and has a carbon number of 1 to 60 unless otherwise specified, but is not limited thereto.

The terms "alkenyl group", "alkenoxy group", "alkenyloxy group", or "alkenyloxy group" as used in the present application mean an alkenyl group to which an oxygen radical is attached, and unless otherwise specified, 2 to 60 It has a carbon number of, but is not limited thereto.

The terms "aryl group" and "arylene group" used in the present application each have 6 to 60 carbon atoms, but are not limited thereto. In the present application, the aryl group or the arylene group includes a single cyclic type, a group of rings, and several cyclic compounds conjugated. For example, the aryl group may include a phenyl group, a biphenyl monovalent functional group, a naphthalene monovalent functional group, a fluorenyl group, a substituted fluorenyl group, and the arylene group may include a fluorenylene group, a substituted fluorenylene group It may contain a group.

The term "ring assemblies" as used herein refers to two or more ring systems (single ring or fused ring system) being directly connected to each other through a single bond or a double bond, and between such rings It means that the number of direct linkages is one less than the total number of ring systems in the compound. In the ring aggregate, the same or different ring systems may be directly linked to each other through a single bond or a double bond.

In the present application, since the aryl group includes a ring aggregate, the aryl group includes biphenyl and terphenyl in which a benzene ring, which is a single aromatic ring, is connected by a single bond. In addition, the aryl group also includes a compound in which an aromatic ring system conjugated with an aromatic single ring is connected by a single bond, for example, a compound in which fluorene, an aromatic ring system conjugated with an aromatic single ring benzene ring, is connected by a single bond. do.

The term "conjugated multiple ring systems" as used in the present application refers to a fused ring form sharing at least two atoms, and includes a form in which two or more hydrocarbon ring systems are fused and at least one heteroatom And the like in which at least one heterocyclic system is conjugated. Several such fused ring systems may be an aromatic ring, a heteroaromatic ring, an aliphatic ring, or a combination of these rings. For example, the aryl group may be a naphthalenyl group, a phenanthrenyl group, or a fluorenyl group, but is not limited thereto.

The term "spyro compound" as used in the present application has a'spiro union', and the spiro linkage refers to a connection 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 terms "fluorenyl group", "fluorenylene group", and "fluorentriyl group" as used in the present application are all hydrogen in the following structures, unless otherwise specified. It means a monovalent, divalent or trivalent functional group, and "substituted fluorenyl group", "substituted fluorenylene group" or "substituted fluorentriyl group" is a substituent R, R', R", R' It means that at least one of "is a substituent other than hydrogen, and includes a case in which 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 valence such as monovalent, divalent, or trivalent.

In addition, the R, R', R" and R'" are each independently an alkyl group having a carbon number of 1 to 20, an alkenyl group having a carbon number of 1 to 20, an aryl group having a carbon number of 6 to 30, 3 to It may be a heterocyclic group having 30 carbon atoms, for example, the aryl group may be phenyl, biphenyl, naphthalene, anthracene or phenanthrene, and the heterocyclic group may be pyrrole, furan, thiophene, pyrazole, imidazole, Triazole, pyridine, pyrimidine, pyridazine, pyrazine, triazine, indole, benzofuran, quinazoline or quinoxaline. For example, the substituted fluorenyl group and fluorenylene group are monovalent of 9,9-dimethylfluorene, 9,9-diphenylfluorene and 9,9'-spirobi[9H-fluorene], respectively. It may be a functional group or a divalent functional group.

The term "heterocyclic group" used in the present application 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" used in the present application represents N, O, S, P, or Si unless otherwise specified, and the heterocyclic group is a monocyclic type containing a heteroatom, a ring aggregate, a conjugated ring system, spy It means a compound and the like.

For example, the “heterocyclic group” may also include a compound including a heteroatom group such as _{SO 2} , P=O, and the like, as in the following compounds instead of carbon forming a ring.

The term "ring" as used in the present application includes monocyclic and polycyclic rings, including hydrocarbon rings as well as heterocycles including at least one heteroatom, and includes aromatic and non-aromatic rings.

The term "polycyclic" used in the present application includes ring assemblies such as biphenyl, terphenyl, etc., several fused ring systems and spiro compounds, and includes not only aromatic but also non-aromatic, hydrocarbon Rings of course include heterocycles containing at least one heteroatom.

The term "aliphatic ring group" as used in the present application refers to cyclic hydrocarbons excluding aromatic hydrocarbons, and includes monocyclic types, cyclic aggregates, conjugated cyclic systems, spiro compounds, etc., unless otherwise stated, It means 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 corresponds to an aliphatic ring.

In addition, when prefixes are named consecutively, it means that substituents are listed in the order described first. For example, in the case of an arylalkoxy group, it means an alkoxy group substituted with an aryl group, in the case of an alkoxycarbonyl group, it means a carbonyl group substituted with an alkoxy group, and in the case of an arylcarbonylalkenyl group, it means an alkenyl group substituted with an arylcarbonyl group, where The arylcarbonyl group is a carbonyl group substituted with an aryl group.

In addition, unless expressly stated otherwise, the term "substituted or unsubstituted" used in the present application "substituted" refers to deuterium, halogen, amino group, nitrile group, nitro group, C ₁ -C ₂₀ alkyl group, C ₁ -C ₂₀ alkoxy group, C ₁ -C ₂₀ alkylamine group, C ₁ -C ₂₀ alkylthiophene group, C ₆ -C ₂₀ arylthiophene group, C ₂ -C ₂₀ alkenyl group, C ₂ -C ₂₀ alkynyl, C ₃ -C ₂₀ cycloalkyl group of, C ₆ -C ₂₀ aryl group, of a C ₆ -C ₂₀ aryl group substituted with a heavy hydrogen, C ₈ -C ₂₀ aryl alkenyl group, a silane group, a boron It means substituted with one or more substituents selected from the group consisting of _{a C 2} -C ₂₀ heterocyclic group including a group, a germanium group, and at least one heteroatom selected from the group consisting of O, N, S, Si and P And, it is not limited to these substituents.

In the present application, the'functional 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 functional group reflecting the number', but it is described as the'parent compound name' You may. For example, in the case of'phenanthrene', which is a kind of aryl group, the monovalent'group' is'phenanthryl (group)', and the divalent group is named by dividing the valences such as'phenanthrylene (group)', etc. Although it may be described, it can also be described as'phenanthrene', which is the name of the parent compound regardless of the valence.

Similarly, even in the case of pyrimidine, it is described as'pyrimidine' regardless of the valence, or in the case of monovalent, it is referred to as pyrimidinyl (group), and in the case of divalent, the'group of the corresponding valency, such as It can also be written as'the name of'. Accordingly, in the present application, when the type of the substituent is described as the name of the parent compound, it may mean an n-valent'group' formed by desorption of a hydrogen atom bonded to a carbon atom and/or a heteroatom of the parent compound.

In addition, in the present specification, when describing the compound name 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 description, the formula used in this application is applied in the same way as the definition of the substituent group defined by the index definition 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 chemical 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.

Unless otherwise stated in the present application, to form a ring means that adjacent groups are bonded to each other to form a single ring or several conjugated rings, and a single ring and a plurality of conjugated rings formed are hydrocarbon rings as well as at least one It includes a heterocycle including a heteroatom, and may include aromatic and non-aromatic rings.

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, etc., can be expressed as a 3-condensed ring.

Meanwhile, the term "bridged bicyclic compound" as used in the present application refers to a compound in which two rings share three or more atoms to form a ring unless otherwise specified. At this time, the shared atoms may include carbon or heteroatoms.

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

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). An organic material layer including the compound according to the present invention is included between the second electrodes 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 capping layer 180 may be formed on one surface of the first electrode 110 or the second electrode 170 that is not in contact with the organic material layer, and when the capping layer 180 is formed, organic electricity The light efficiency of the device can be improved.

For example, the capping layer 180 may be formed on the second electrode 170. In the case of a top emission organic light emitting device, the capping layer 180 is formed so that the capping layer 180 is formed on 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 capping layer 180 can function as a buffer for the second electrode 170 .

Meanwhile, a buffer layer 210 or an 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. It may include 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, and a capping layer 180 is formed on the second electrode. I can.

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 plurality of stacks including a hole transport layer, a light emitting layer, and an electron transport layer. 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 organic material layers.

Specifically, the organic electric device according to an 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 capping 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).

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 is a material doped with a greenish yellow dopant and a red dopant in a green host. May be included, but the materials of the first emission layer 340 and the second emission layer 440 according to the exemplary embodiment of the present invention are not limited thereto.

In this case, the second hole transport layer 430 includes a second stack ST2 in which the energy level is set higher than the triplet excitation energy level of the second emission layer 440.

Since the energy level of the second hole transport layer 430 is higher than that of the second light emitting layer 440, the triplet exciton of the second light emitting layer 440 passes to the second hole transport layer 430, resulting in lower luminous efficiency. Can be prevented. That is, the second hole transport layer 430 may function as an exciton blocking layer that prevents tripping of triplet excitons while transporting holes from the inherent second emission layer 440. .

In addition, the first hole transport layer 330 may also be set to an energy level higher than the triplet excitation energy level of the first emission layer 340 for the function of the exciton blocking layer. In addition, the first electron transport layer 350 is also set to an energy level higher than the energy level of the triplet excited state of the first emission layer 340, and the second electron transport layer 450 is also triplet excitation of the second emission layer 440. It is preferable to set the energy level higher than the energy level of the state.

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 of the capping layer 180, but preferably, the hole transport layer 130, 330, 430, the light emission auxiliary layer 220 ), the light emitting layers 140, 340, and 440, and/or the capping layer 180 may be used as a material.

The organic electric device according to FIGS. 1 to 3 may further include a protective layer (not shown) and an encapsulation layer (not shown). The protective layer may be located on the capping layer, the encapsulation layer is located on the capping layer, and at least one side portion of the first electrode, the second electrode, and the organic material layer to protect the first electrode, the second electrode, and the organic material layer It can be formed to cover.

The protective layer may provide a flattened surface so that the encapsulation layer can be uniformly formed, and may serve to protect the first electrode, the second electrode, and the organic material layer in the manufacturing process of the encapsulation layer.

The encapsulation layer may play a role of preventing external oxygen and moisture from penetrating into the organic electric device.

On the other hand, even with the same and similar core, the band gap, electrical characteristics, and interface characteristics may vary depending on which substituent is bonded to a certain position, so the selection of the core and the combination of the sub-substituents bonded thereto may vary. In particular, long life and high efficiency can be achieved at the same time when the optimum combination of the energy level and T1 value between each organic material layer and the intrinsic properties of the material (mobility, interfacial properties, etc.) is achieved.

Therefore, in the present invention, by using the compound represented by Chemical Formula 1 as a material for the auxiliary light emitting layer 220, the light emitting layers 140, 340, and 440, and/or the capping layer 180, the energy level and the T1 value between each organic material layer, By optimizing the intrinsic properties of the material (mobility, interfacial properties, etc.), it was possible to simultaneously improve the lifespan and efficiency of the organic electric device.

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, the anode 110 is formed by depositing a metal or a conductive metal oxide or an alloy thereof on a substrate, and a hole injection layer 120 thereon. 320, 420), hole transport layers (130, 330, 430), light emitting layers (140, 340, 440), electron transport layers (150, 350, 450), and after forming an organic material layer including the electron injection layer 160, It can be manufactured by depositing a material that can be used as the cathode 170 thereon. In addition, a light emission auxiliary layer 220 between the hole transport layers 130, 330, and 430 and the emission layers 140, 340, and 440, and an electron transport auxiliary layer between the emission layer 140 and the electron transport layer 150 (not shown). May be further formed or may be formed in a stack structure as described above.

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 forming method.

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.

The organic electric device according to an embodiment of the present invention may include 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> <Formula 1-1>

In Formula 1,

1) X is O or S,

2) Ar ¹ , Ar ² , Ar ³ and Ar ⁴ 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; A fused ring group of an aliphatic ring of C ₃ to C _{60 and an aromatic ring of C 6} to C _60; A C ₁ to C ₅₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; Alkynyl group of C ₂ ~ C _20; An alkoxyl group of C ₁ to C _30; C ₆ ~ C ₃₀ aryloxy group; Or Formula 1-1; Or a combination thereof; Or neighboring groups can be bonded to each other to form a ring,

3) Y ₁ and Y ₂ are each independently O or S,

4) L ₁ and L ₂ are each independently a single bond; C ₆ ~ C ₆₀ arylene group; Fluorenylene group; A fused ring group of an aliphatic ring of C ₃ to C _{60 and an aromatic ring of C 6} to C _60; O, N, S, Si, and C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of P; And it is selected from the group consisting of a combination thereof,

5) R ¹ , R ² , R ³ and R ⁴ are each independently hydrogen; heavy hydrogen; halogen; 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; A fused ring group of an aliphatic ring of C ₃ to C _{60 and an aromatic ring of C 6} to C _60; A C ₁ to C ₅₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; Alkynyl group of C ₂ ~ C _20; An alkoxyl group of C ₁ to C _30; C ₆ ~ C ₃₀ is selected from the group consisting of aryloxy group; Alternatively, a plurality of R ¹ , R ² , R ³ , and R ⁴ may be bonded to each other to form a ring,

6) a is an integer of 0-2; c is an integer from 0 to 3; b and d are each independently an integer of 0-4,

7) Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , L ₁ , L ₂ , R ¹ , R ² , R ³ , R ⁴ and neighboring groups bonded to each other to form a ring formed by 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;} 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 arylalkoxy group; C6-C20 aryloxy group; C6-C20 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; _{A C 6} -C ₂₀ aryl group unsubstituted or substituted with deuterium; 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; C ₈ -C ₂₀ arylalkenyl group; And it may be further substituted with one or more substituents selected from the group consisting of a combination thereof.

In the above, when Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , R ¹ , R ² , R ³ or R ⁴ is an aryl group, preferably an aryl group _{of C 6} to C _{30 , more preferably C 6} to It may be a C ₁₈ aryl group, such as phenyl, biphenyl, naphthyl, terphenyl, and the like.

When the Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , R ¹ , R ² , R ³ or R ⁴ is a heterocyclic group, Preferably a C ₂ to C ₃₀ heterocyclic group, more preferably a C ₂ to C ₁₈ heterocyclic group, such as dibenzofuran, dibenzothiophene, naphthobenzothiophene, naphthobenzofuran, and the like. .

When the Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , R ¹ , R ² , R ³ or R ⁴ is a fluorenyl group, preferably 9,9-dimethyl-9H-fluorene, 9,9- It may be a diphenyl-9H-fluorenyl group, 9,9'-spirobifluorene, and the like.

The L ₁ and L ₂ In the case of an arylene group, preferably a C ₆ to C ₃₀ arylene group, more preferably a C ₆ to C ₁₈ arylene group, such as phenyl, biphenyl, naphthyl, terphenyl, and the like.

When the Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , R ¹ , R ² , R ³ or R ⁴ is an alkyl group, it may be preferably a C ₁ to C ₁₀ alkyl group, such as methyl, t-butyl, etc. I can.

When the Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , R ¹ , R ² , R ³ or R ⁴ is an alkoxyl group, preferably an alkoxyl group of C ₁ to C ₂₀ , more preferably C ₁ to C ₁₀ alkoxyl groups, such as methoxy, t-butoxy, and the like.

The ring formed by bonding adjacent groups of ^{Ar 1} , Ar ² , Ar ³ , Ar ⁴ , L ₁ , L ₂ , R ¹ , R ² , R ³ or R ⁴ 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; Or it _{may be an aliphatic ring group of C 3} ~ C ₆₀ , for example, when adjacent groups are bonded to each other to form an aromatic ring, preferably an aromatic ring of C ₆ ~ C ₂₀ , more preferably C ₆ ~ C ₁₄ Aromatic rings, such as benzene, naphthalene, phenanthrene, and the like can be formed.

Preferably, Formula 1 may be represented by any one of the following Formulas 2 to 6, but is not limited thereto.

<Formula 2> <Formula 3>

<Formula 4> <Formula 5>

<Formula 6>

In Formulas 2 to 6,

1) X, Y ₁ , Y ₂ , Ar ² , Ar ³ , Ar ⁴ , R ¹ , R ² , R ³ , R ⁴ , a, b, c, d, L ₁ and L ₂ are defined in Formula 1 above As has been done,

2) Y ₃ ~ Y ₈ are each independently O or S,

3) R ⁵ to R ¹⁰ are each independently deuterium; halogen; 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; A fused ring group of an aliphatic ring of C ₃ to C _{60 and an aromatic ring of C 6} to C _60; A C ₁ to C ₅₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; Alkynyl group of C ₂ ~ C _20; An alkoxyl group of C ₁ to C _30; C ₆ ~ C ₃₀ is selected from the group consisting of aryloxy group; Or, a plurality of R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , or R ¹⁰ may be bonded to each other to form a ring,

4) e, g and i are each independently an integer of 0-3; f, h, and j are each independently an integer of 0-4.

More preferably, Formula 1 may be represented by any one of Formulas 7 to 9 below, but is not limited thereto.

<Formula 7> <Formula 8>

<Formula 9>

In Chemical Formulas 7 to 9,

The X, Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , R ¹ , a, L ₁ and L ₂ are as defined in Formula 1 above.

Meanwhile, the compound represented by Formula 1 may be one of the following P-1 to P-139, but is not limited thereto.

In another embodiment of the present invention, the present invention provides a first electrode; A second electrode; And an organic material layer formed between the first electrode and the second electrode, wherein the organic material layer includes a compound represented by Formula 1 alone or in combination.

As another embodiment of the present invention, the present invention provides a first electrode; A second electrode; An organic material layer formed between the first electrode and the second electrode; And a capping layer, wherein the capping layer is formed on one side of both surfaces of the first electrode and the second electrode that is not in contact with the organic material layer, and the organic material layer or the capping layer is represented by Formula 1 The compound to be used alone or as a mixture is included.

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. That is, 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 included in the organic material layer may include a compound represented by Formula (1). .

Preferably, the organic material layer includes at least one of the hole transport layer, an emission auxiliary layer, and an emission layer. That is, the compound may be included in at least one of the hole transport layer, the light emitting auxiliary layer, and the light emitting 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.

Preferably, the organic material layer further includes a charge generation layer formed between the two or more stacks.

As another specific embodiment of the present invention, the present invention is to provide an electronic device including a display device including an organic electric device including a compound represented by Formula 1 and a control unit for driving the display device.

In an embodiment of the present invention, the compound of Formula 1 may be included alone, the compound may be included in a combination of two or more different from each other, or the compound may be included in a combination of two or more with another compound.

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 final product represented by Formula 1 according to the present invention may be synthesized as shown in Scheme 1 below, but is not limited thereto.

<Reaction Scheme 1>

I. Synthesis of Sub A

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

<Reaction Scheme 2>

Synthesis examples of specific compounds belonging to Sub A are as follows.

1. Sub A-4 Synthesis Example

(1) Sub A-4-a synthesis

N-phenyldibenzo[b,e][1,4]dioxin-2-amine (8.30 g, 30.15 mmol) in 4-bromo-1-chloronaphtho[2,3-b]benzofuran (10 g, 30.15 mmol), Pd ₂ (dba) ₃ (0.82 g, 0.90 mmol), P(t-Bu) ₃ (0.61 g, 3.01 mmol), NaOt-Bu (5.79 g, 60.30 mmol) and toluene (100 mL) were added and reacted. When the reaction was completed, the organic layer was extracted with water, dried over MgSO ₄ and concentrated, and the resulting compound was recrystallized using a silica gel column to obtain a product Sub A-4-a (13.16 g, yield: 83%).

(2) Sub A-4-b synthesis

Sub A-4-a (13.16 g, 25.02 mmol) to Bis(pinacolato)diboron (7.62 g, 30.02 mmol), Pd ₂ (dba) ₃ (1.14 g, 1.25 mmol), X-Phos (5.96 g, 12.51 mmol) ), KOAc (4.91 g, 50.04 mmol) and toluene (100 mL) were added and reacted. When the reaction was completed, the organic layer was extracted with water, dried over MgSO ₄ and concentrated, and the resulting compound was recrystallized using a silica gel column to obtain a product Sub A-4-b (12.36 g, yield: 80%).

(3) Sub A-4 synthesis

1-bromo-4-chlorobenzene (3.00 g, 15.66 mmol), Sub A-4-b (11.61 g, 18.80 mmol), Pd(PPh ₃ ) ₄ (0.54 g, 0.47 mmol) and K ₂ CO ₃ (6.49 g , 46.98 mmol) was added THF (45 mL) and H ₂ O (15 mL) and reacted. When the reaction was completed, the organic layer was extracted with water, dried over MgSO ₄ and concentrated, and the resulting compound was recrystallized using a silica gel column to obtain a product Sub A-4 (6.41 g, yield: 68%).

2. Sub A-17 synthesis example

(1) Sub A-17-a synthesis

4,4,5,5-tetramethyl-2-(1-(methylsulfinyl)naphthalen-2-yl)-1,3,2-dioxaborolane (60 g, 189.74 mmol), 4-bromo-1-chloro-2- _{THF (450 mL) and H 2} O (150 mL) were added to iodobenzene (50.17 g, 158.11 mmol), Pd(PPh ₃ ) ₄ (5.48 g, 4.74 mmol) and NaOH (18.96 g, 474.33 mmol) and reacted. . When the reaction was completed, the organic layer was extracted with water, dried over MgSO ₄ and concentrated, and the resulting compound was recrystallized using a silica gel column to obtain a product Sub A-17-a (40.82 g, yield: 68%).

(2) Sub A-17-b synthesis

Sulfuric acid (250 mL) was added to Sub A-17-a (40.82 g, 107.50 mmol) and stirred for 6 hours. It is recrystallized using toluene. The product Sub A-17-b (25.41 g, yield: 68%) was obtained.

(3) Sub A-17 synthesis

Sub A-17-b (25.41 g, 73.10 mmol) diphenylamine (12.37 g, 73.10 mmol), Pd ₂ (dba) ₃ (2.00 g, 2.19 mmol), P(t-Bu) ₃ (1.47 g, 7.31 mmol) ), NaOt-Bu (14.05 g, 146.2 mmol) and toluene (250 mL) were added and reacted. When the reaction was completed, the organic layer was extracted with water, dried over MgSO ₄ and concentrated, and the resulting compound was recrystallized using a silica gel column to obtain a product Sub A-17 (29.94 g, yield: 80%).

3. Sub A-33 Synthesis Example

1-bromo-3-chlorodibenzo[b,d]thiophene (10 g, 33.60 mmol) in N-phenyldibenzo[b,e][1,4]dioxin-2-amine (9.25 g, 33.60 mmol), Pd ₂ ( dba) ₃ (0.92 g, 1.00 mmol), P(t-Bu) ₃ (0.67 g, 3.36 mmol), NaOt-Bu (6.45 g, 67.20 mmol) and toluene (100 mL) were added and reacted. When the reaction was completed, the organic layer was extracted with water, dried over MgSO ₄ and concentrated, and the resulting compound was recrystallized using a silica gel column to obtain a product, Sub A-33 (12.72 g, yield: 77%).

4. Sub A-43 Synthesis Example

2-bromo-4-chlorodibenzo[b,d]thiophene (10 g, 33.60 mmol) in N-(thianthren-2-yl)spiro[fluorene-9,9'-xanthen]-2'-amine (18.87 g, 33.60 mmol), Pd ₂ (dba) ₃ (0.92 g, 1.00 mmol), P(t-Bu) ₃ (0.67 g, 3.36 mmol), NaOt-Bu (6.45 g, 67.20 mmol) and toluene (100 mL) were added. And reacted. When the reaction was completed, the organic layer was extracted with water, dried over MgSO ₄ and concentrated, and the resulting compound was recrystallized using a silica gel column to obtain a product Sub A-43 (20.66 g, yield: 79%).

5. Sub A-88 synthesis example

N-(9,9-dimethyl-9H-fluoren-3-yl)thianthren-2-amine (14.23 g, 33.60 mmol) in 1-bromo-4-chlorodibenzo[b,d]thiophene (10 g, 33.60 mmol) , Pd ₂ (dba) ₃ (0.92 g, 1.00 mmol), P(t-Bu) ₃ (0.67 g, 3.36 mmol), NaOt-Bu (6.45 g, 67.20 mmol) and toluene (100 mL) were added and reacted. . When the reaction was completed, the organic layer was extracted with water, dried over MgSO ₄ and concentrated, and the resulting compound was recrystallized using a silica gel column to obtain a product Sub A-88 (16.13 g, yield: 75%).

Meanwhile, the compound belonging to Sub A may be the following compound, but is not limited thereto.

compound	FD-MS	compound	FD-MS
Sub A-1	m/z=567.11 (C 36 H 22 ClNO 2 S=568.09)	Sub A-51	m/z= 647.10 (C 40 H 22 ClNO 4 S=648.13)
Sub A-2	m/z= 567.11 (C 36 H 22 ClNO 2 S= 568.09)	Sub A-52	m/z= 657.13 (C 42 H 24 ClNO 5 =658.11)
Sub A-3	m/z= 567.11 (C 36 H 22 ClNO 2 S= 568.09)	Sub A-53	m/z= 673.11 (C 42 H 24 ClNO 4 S=674.17)
Sub A-4	m/z= 601.14 (C 40 H 24 ClNO 3 = 602.09)	Sub A-54	m/z= 737.02 (C 42 H 24 ClNS 5 =738.41)
Sub A-5	m/z= 599.06 (C 36 H 22 ClNS 3 =600.21)	Sub A-55	m/z= 660.99 (C 36 H 20 ClNS 5 =662.31)
Sub A-6	m/z= 627.16 (C 42 H 26 ClNO 3 =628.12)	Sub A-56	m/z= 689.09 (C 42 H 24 ClNO 3 S 2 =690.23)
Sub A-7	m/z= 583.08 (C 36 H 22 ClNOS 2 =584.15)	Sub A-57	m/z= 629.03 (C 36 H 20 ClNO 2 S 3 =630.19)
Sub A-8	m/z= 567.11 (C 36 H 22 ClNO 2 S=568.09)	Sub A-58	m/z= 673.11 (C 42 H 24 ClNO 4 S=674.17)
Sub A-9	m/z= 567.11 (C 36 H 22 ClNO 2 S=568.09)	Sub A-59	m/z= 707.15 (C 46 H 26 ClNO 5 =708.17)
Sub A-10	m/z= 491.07 (C 30 H 18 ClNO 2 S=491.99)	Sub A-60	m/z= 645.01 (C 36 H 20 ClNOS 4 =646.25)
Sub A-11	m/z= 617.12 (C 40 H 24 ClNO 2 S=618.15)	Sub A-61	m/z= 737.02 (C 42 H 24 ClNS 5 =738.41)
Sub A-12	m/z= 551.13 (C 36 H 22 ClNO 3 =552.03)	Sub A-62	m/z= 581.10 (C 36 H 20 ClNO 5 =582.01)
Sub A-13	m/z= 599.06 (C 36 H 22 ClNS 3 =600.21)	Sub A-63	m/z= 711.00 (C 40 H 22 ClNS 5 =712.37)
Sub A-14	m/z= 597.06 (C 36 H 20 ClNO 2 S 2 =598.13)	Sub A-64	m/z= 689.09 (C 42 H 24 ClNO 3 S 2 =690.23)
Sub A-15	m/z= 541.09 (C 34 H 20 ClNO 2 S=542.05)	Sub A-65	m/z= 561.13 (C 38 H 24 ClNS=562.13)
Sub A-16	m/z= 567.11 (C 36 H 22 ClNO 2 S=568.09)	Sub A-66	m/z= 610.18 (C 42 H 27 ClN 2 O=611.14)
Sub A-17	m/z= 511.12 (C 34 H 22 ClNS=512.07)	Sub A-67	m/z= 625.16 (C 43 H 28 ClNS=626.21)
Sub A-18	m/z= 551.11 (C 36 H 22 ClNOS=552.09)	Sub A-68	m/z= 701.19 (C 49 H 32 ClNS=702.31)
Sub A-19	m/z= 475.08 (C 30 H 18 ClNOS=475.99)	Sub A-69	m/z= 485.10 (C 32 H 20 ClNS=486.03)
Sub A-20	m/z= 551.11 (C 36 H 22 ClNOS=552.09)	Sub A-70	m/z= 615.03 (C 36 H 22 ClNSSe=615.05)
Sub A-21	m/z= 525.10 (C 34 H 20 ClNOS=526.05)	Sub A-71	m/z= 601.13 (C 40 H 24 ClNOS=602.15)
Sub A-22	m/z= 617.10 (C 40 H 24 ClNS 2 =618.21)	Sub A-72	m/z= 541.07 (C 34 H 20 ClNS 2 =542.11)
Sub A-23	m/z= 585.15 (C 40 H 24 ClNO 2 =586.09)	Sub A-73	m/z= 599.06 (C 36 H 22 ClNS 3 =600.21)
Sub A-24	m/z= 649.07 (C 40 H 24 ClNOSe=649.05)	Sub A-74	m/z= 567.11 (C 36 H 22 ClNO 2 S=568.09)
Sub A-25	m/z= 567.11 (C 36 H 22 ClNO 2 S= 568.09)	Sub A-75	m/z= 629.02 (C 36 H 20 ClNS 4 =630.25)
Sub A-26	m/z= 567.11 (C 36 H 22 ClNO 2 S= 568.09)	Sub A-76	m/z= 675.09 (C 42 H 26 ClNS 3 =676.31)
Sub A-27	m/z= 523.03 (C 30 H 18 ClNS 3 =524.11)	Sub A-77	m/z= 673.11 (C 42 H 24 ClNO 4 S=674.17)
Sub A-28	m/z= 739.09 (C 46 H 26 ClNOS 3 =740.35)	Sub A-78	m/z= 737.02 (C 42 H 24 ClNS 5 =738.41)
Sub A-29	m/z= 599.06 (C 36 H 22 ClNS 3 =600.21)	Sub A-79	m/z= 629.03 (C 36 H 20 ClNO 2 S 3 =630.19)
Sub A-30	m/z= 567.11 (C 36 H 22 ClNO 2 S= 568.09)	Sub A-80	m/z= 689.09 (C 42 H 24 ClNO 3 S 2 =690.23)
Sub A-31	m/z= 523.03 (C 30 H 18 ClNS 3 =524.11)	Sub A-81	m/z= 629.03 (C 36 H 20 ClNO 2 S 3 =630.19)
Sub A-32	m/z= 583.08 (C 36 H 22 ClNOS 2 =584.15)	Sub A-82	m/z= 673.11 (C 42 H 24 ClNO 4 S=674.17)
Sub A-33	m/z= 491.07 (C 30 H 18 ClNO 2 S=491.99)	Sub A-83	m/z= 707.15 (C 46 H 26 ClNO 5 =708.17)
Sub A-34	m/z= 567.11 (C 36 H 22 ClNO 2 S= 568.09)	Sub A-84	m/z= 645.01 (C 36 H 20 ClNOS 4 =646.25)
Sub A-35	m/z= 601.14 (C 40 H 24 ClNO 3 = 602.09)	Sub A-85	m/z= 601.14 (C 40 H 24 ClNO 3 = 602.09)
Sub A-36	m/z= 507.05 (C 30 H 18 ClNOS 2 =508.05)	Sub A-86	m/z= 640.16 (C 42 H 25 ClN 2 O 3 =641.12)
Sub A-37	m/z= 683.17 (C 45 H 30 ClNO 2 S=684.25)	Sub A-87	m/z= 581.09 (C 36 H 20 ClNO 3 S=582.07)
Sub A-38	m/z= 567.11 (C 36 H 22 ClNO 2 S= 568.09)	Sub A-88	m/z= 639.09 (C 39 H 26 ClNS 3 =640.27)
Sub A-39	m/z= 541.09 (C 34 H 20 ClNO 2 S=542.05)	Sub A-89	m/z= 599.06 (C 36 H 22 ClNS 3 =600.21)
Sub A-40	m/z= 617.12 (C 40 H 24 ClNO 2 S=618.15)	Sub A-90	m/z= 649.08 (C 40 H 24 ClNS 3 =650.27)
Sub A-41	m/z= 673.09 (C 42 H 24 ClNO 2 S 2 =674.23)	Sub A-91	m/z= 537.04 (C 31 H 20 ClNS 3 =538.14)
Sub A-42	m/z= 643.14 (C 42 H 26 ClNO 2 S=644.19)	Sub A-92	m/z= 551.13 (C 36 H 22 ClNO 3 =552.03)
Sub A-43	m/z= 777.10 (C 49 H 28 ClNOS 3 =778.40)	Sub A-93	m/z= 521.07 (C 31 H 20 ClNOS 2 =522.08)
Sub A-44	m/z= 583.08 (C 36 H 22 ClNOS 2 =584.15)	Sub A-94	m/z= 643.14 (C 42 H 26 ClNO 2 S=644.19)
Sub A-45	m/z= 541.09 (C 34 H 20 ClNO 2 S=542.05)	Sub A-95	m/z= 583.08 (C 36 H 22 ClNOS 2 =584.15)
Sub A-46	m/z= 643.14 (C 42 H 26 ClNO 2 S=644.19)	Sub A-96	m/z= 557.07 (C 34 H 20 ClNOS 2 =558.11)
Sub A-47	m/z= 601.14 (C 40 H 24 ClNO 3 = 602.09)	Sub A-97	m/z= 721.04 (C 42 H 24 ClNOS 4 =722.35)
Sub A-48	m/z= 607.08 (C 38 H 22 ClNOS 2 =608.17)	Sub A-98	m/z= 613.06 (C 36 H 20 ClNO 3 S 2 =614.13)
Sub A-49	m/z= 705.07 (C 42 H 24 ClNO 2 S 3 =706.29)	Sub A-99	m/z= 645.01 (C 36 H 20 ClNOS 4 =646.25)
Sub A-50	m/z= 613.06 (C 36 H 20 ClNO 3 S 2 =614.13)	Sub A-100	m/z= 689.09 (C 42 H 24 ClNO 3 S 2 =690.23)

II. Synthesis of Sub B

Sub B of Scheme 1 may be synthesized as follows, but is not limited thereto.

1. Sub B-1 synthesis example

Bromobenzene (50 g, 318.45 mmol) in aniline (29.65 g, 318.45 mmol), Pd ₂ (dba) ₃ (8.74 g, 9.55 mmol), P(t-Bu)3 (6.44 g, 31.84 mmol), NaOt-Bu (61.20 g, 636.9 mmol) and toluene (900 mL) were added and reacted for 2 hours. When the reaction was completed, the organic layer was extracted with water, dried over MgSO ₄ and concentrated, and the resulting compound was recrystallized through a silica gel column to obtain a product Sub B-1 (40.41 g, yield: 75%).

2. Sub B-6 Synthesis Example

2-bromodibenzo[b,d]furan (50 g, 202.35 mmol) aniline (18.84 g, 202.35 mmol), Pd ₂ (dba) ₃ (5.55 g, 6.07 mmol), P(t-Bu) ₃ (4.09 g , 20.23 mmol), NaOt-Bu (38.89 g, 404.7 mmol) and toluene (600 mL) were added and reacted for 2 hours. When the reaction was completed, the organic layer was extracted with water, dried over MgSO ₄ and concentrated, and the resulting compound was recrystallized using a silica gel column to obtain a product Sub B-6 (41.97 g, yield: 80%).

3. Sub B-10 Synthesis Example

(1) Sub B-10-a synthesis

_{After dissolving in 500ml of CH 2} Cl _{2 in} dibenzo[b,e][1,4]dioxine (50 g, 271.45mmol), it was stirred at 0°C for 30 minutes. Br2 (43.16 g, 271.45mmol) was slowly added dropwise, and the reaction solution was stirred at room temperature for 6 hours. When the reaction was completed, extraction with water, the organic layer _{was dried over MgSO 4} and concentrated, and the resulting compound was recrystallized through a silica gel column to obtain a product Sub B-10-a (64.27 g, yield: 90%).

(2) Sub B-10 synthesis

Sub B-10-a (50 g, 190.04 mmol) aniline (17.69 g, 190.04 mmol), Pd ₂ (dba) ₃ (5.22 g, 5.70 mmol), P(t-Bu) ₃ (3.84 g, 19.00 mmol) ), NaOt-Bu (36.52 g, 380.08 mmol) and toluene (600 mL) were added and reacted for 2 hours. When the reaction was completed, the organic layer was extracted with water, dried over MgSO ₄ and concentrated, and the resulting compound was recrystallized using a silica gel column to obtain a product Sub B-10 (41.33 g, yield: 79%).

4. Sub B-17 synthesis example

(1) Sub B-17-a synthesis

naphthalene-2,3-diol (100 g, 624.33 mmol) in 4-chloro-1,2-difluorobenzene (92.73 g, 624.33 mmol), CuI (5.94 g, 31.21 mmol), K ₂ CO ₃ (129.42 g, 936.49 mmol) and DMF (3000mL) were added and reacted for 24 hours. When the reaction was completed, the organic layer was extracted with water, dried over MgSO ₄ and concentrated, and the resulting compound was recrystallized using a silica gel column to obtain a product Sub B-17-a (109.04 g, yield: 65%).

(2) Sub B-17 synthesis

Sub B-17-a (100 g, 372.16 mmol) aniline (41.59 g, 446.59 mmol), Pd ₂ (dba) ₃ (10.22 g, 11.16 mmol), P(t-Bu) ₃ (7.53 g, 37.21 mmol) ), NaOt-Bu (71.53 g, 744.32 mmol) and toluene (1000 mL) were added and reacted for 2 hours. When the reaction was completed, the organic layer was extracted with water, dried over MgSO ₄ and concentrated, and the resulting compound was recrystallized using a silica gel column to obtain a product Sub B-17 (89.60 g, yield: 74%).

5. Sub B-31 Synthesis Example

2-bromo-9,9-dimethyl-9H-fluorene (50 g, 183.03 mmol) in [1,1'-biphenyl]-4-amine (37.17 g, 219.63 mmol), Pd ₂ (dba) ₃ (5.02 g , 5.49 mmol), P(t-Bu) ₃ (3.70 g, 18.30 mmol), NaOt-Bu (35.18 g, 366.06 mmol) and toluene (500 mL) were added and reacted for 2 hours. When the reaction was completed, the organic layer was extracted with water, dried over MgSO ₄ and concentrated, and the resulting compound was recrystallized using a silica gel column to obtain a product Sub B-31 (49.62 g, yield: 75%).

Meanwhile, examples of the compounds belonging to Sub B are as follows, but are not limited thereto.

Table 2 below shows FD-MS (Field Desorption-Mass Spectrometry) values of some compounds belonging to Sub B.

compound	FD-MS	compound	FD-MS
Sub B-1	m/z= 169.09 (C 12 H 11 N= 169.23)	Sub B-19	m/z= 309.12 (C 22 H 15 NO= 309.37)
Sub B-2	m/z= 245.12 (C 18 H 15 N= 245.33)	Sub B-20	m/z= 375.11 (C 26 H 17 NS= 375.49)
Sub B-3	m/z= 275.08 (C 18 H 13 NS= 275.37)	Sub B-21	m/z= 325.09 (C 22 H 15 NS= 325.43)
Sub B-4	m/z= 351.11 (C 24 H 17 NS= 351.47)	Sub B-22	m/z= 385.15 (C 28 H 19 NO= 385.47)
Sub B-5	m/z= 351.11 (C 24 H 17 NS= 351.47)	Sub B-23	m/z= 325.09 (C 22 H 15 NS= 325.43)
Sub B-6	m/z= 259.10 (C 18 H 13 NO= 259.31)	Sub B-24	m/z= 457.11 (C 30 H 19 NO 2 S= 457.55)
Sub B-7	m/z= 335.13 (C 24 H 17 NO= 335.41)	Sub B-25	m/z= 351.13 (C 24 H 17 NO 2 = 351.41)
Sub B-8	m/z= 307.05 (C 18 H 13 NS 2 = 307.43)	Sub B-26	m/z= 440.15 (C 30 H 20 N 2 O 2 = 440.50)
Sub B-9	m/z= 383.08 (C 24 H 17 NS 2 = 383.53)	Sub B-27	m/z= 383.08 (C 24 H 17 NS 2 = 383.53)
Sub B-10	m/z= 275.09 (C 18 H 13 NO 2 = 275.31)	Sub B-28	m/z= 383.08 (C 24 H 17 NS 2 = 383.53)
Sub B-11	m/z= 351.13 (C 24 H 17 NO 2 = 351.41)	Sub B-29	m/z= 413.05 (C 24 H 15 NO 2 S 2 = 413.51)
Sub B-12	m/z= 323.02 (C 18 H 13 NSe= 322.27)	Sub B-30	m/z= 357.06 (C 22 H 15 NS 2 = 357.49)
Sub B-13	m/z= 381.10 (C 24 H 15 NO 4 = 381.39)	Sub B-31	m/z= 361.18 (C 27 H 23 N= 361.49)
Sub B-14	m/z= 413.05 (C 24 H 15 NO 2 S 2 = 413.51)	Sub B-32	m/z= 561.12 (C 37 H 23 NOS 2 = 561.72)
Sub B-15	m/z= 413.05 (C 24 H 15 NO 2 S 2 = 413.51)	Sub B-33	m/z= 335.17 (C 25 H 21 N= 335.45)
Sub B-16	m/z= 381.08 (C 24 H 15 NO 2 S= 381.45)	Sub B-34	m/z= 409.18 (C 31 H 23 N= 409.53)
Sub B-17	m/z= 325.11 (C 22 H 15 NO 2 = 325.37)	Sub B-35	m/z= 490.17 (C 34 H 22 N 2 O 2 = 490.56)
Sub B-18	m/z= 334.15 (C 24 H 18 N 2 = 334.42)	Sub B-36	m/z= 451.19 (C 33 H 25 NO= 451.57)

III. Synthesis example of final products

1. Synthesis Example of P-3

Sub A-3 (10 g, 17.60 mmol) to Sub B-1 (2.98 g, 17.60 mmol), Pd ₂ (dba) ₃ (0.48 g, 0.53 mmol), P(t-Bu) ₃ (0.36 g, 1.76 mmol), NaOt-Bu (3.38 g, 35.21 mmol) and toluene (60 mL) were added and reacted for 2 hours. When the reaction was completed, the organic layer was extracted with water, dried over MgSO ₄ and concentrated, and the resulting compound was recrystallized using a silica gel column to obtain a product P-3 (9.38 g, yield: 76%).

2. Synthesis Example of P-11

Sub A-3 (10 g, 17.60 mmol) to Sub B-6 (4.56 g, 17.60 mmol), Pd ₂ (dba) ₃ (0.48 g, 0.53 mmol), P(t-Bu) ₃ (0.36 g, 1.76 mmol), NaOt-Bu (3.38 g, 35.21 mmol) and toluene (60 mL) were added and reacted for 2 hours. When the reaction was completed, the organic layer was extracted with water, dried over MgSO ₄ and concentrated, and the resulting compound was recrystallized using a silica gel column to obtain a product P-11 (11.00 g, yield: 79%).

3. Synthesis Example of P-17

Sub A-17 (10 g, 19.53 mmol) to Sub B-10 (5.38 g, 19.53 mmol), Pd ₂ (dba) ₃ (0.54 g, 0.59 mmol), P(t-Bu) ₃ (0.40 g, 1.95 mmol), NaOt-Bu (3.75 g, 39.06 mmol) and toluene (60 mL) were added and reacted for 2 hours. When the reaction was completed, the organic layer was extracted with water, dried over MgSO ₄ and concentrated, and the resulting compound was recrystallized using a silica gel column to obtain a product P-17 (11.29 g, yield: 77%).

4. Synthesis Example of P-43

Sub A-43 (10 g, 12.85 mmol) to Sub B-8 (3.95 g, 12.85 mmol), Pd ₂ (dba) ₃ (0.35 g, 0.39 mmol), P(t-Bu) ₃ (0.26 g, 1.28 mmol), NaOt-Bu (2.47 g, 25.69 mmol) and toluene (50 mL) were added and reacted for 2 hours. When the reaction was completed, the organic layer was extracted with water, dried over MgSO ₄ and concentrated, and the resulting compound was recrystallized using a silica gel column to obtain a product P-43 (10.52 g, yield: 78%).

5. Synthesis Example of P-50

Sub A-50 (10 g, 16.28 mmol) to Sub B-33 (5.46 g, 16.28 mmol), Pd ₂ (dba) ₃ (0.45 g, 0.49 mmol), P(t-Bu) ₃ (0.33 g, 1.63 mmol), NaOt-Bu (3.13 g, 32.57 mmol) and toluene (50 mL) were added and reacted for 2 hours. When the reaction was completed, the organic layer was extracted with water, dried over MgSO ₄ and concentrated, and the resulting compound was recrystallized using a silica gel column to obtain a product P-50 (11.30 g, yield: 76%).

On the other hand, FD-MS (Field Desorption-Mass Spectrometry) values of the compounds P-1 to P-139 of the present invention prepared according to the synthesis example as described above are shown in Table 3 below.

compound	FD-MS	compound	FD-MS
P-1	m/z= 700.22 (C 48 H 32 N 2 O 2 S= 700.86)	P-71	m/z= 978.20 (C 64 H 38 N 2 O 3 S 3 =979.20)
P-2	m/z= 882.24 (C 60 H 38 N 2 O 2 S 2 = 883.10)	P-72	m/z= 918.15 (C 58 H 34 N 2 O 2 S 4 =919.16)
P-3	m/z= 700.22 (C 48 H 32 N 2 O 2 S= 700.86)	P-73	m/z= 976.14 (C 60 H 36 N 2 O 2 S 5 =977.26)
P-4	m/z= 926.35 (C 67 H 46 N 2 O 3 = 927.12)	P-74	m/z= 944.18 (C 60 H 36 N 2 O 4 S 3 =945.14)
P-5	m/z= 822.18 (C 54 H 34 N 2 OS 3 = 823.06)	P-75	m/z=1024.16 (C 64 H 36 N 2 O 4 S 4 =1025.24)
P-6	m/z= 760.27 (C 54 H 36 N 2 O 3 = 760.89)	P-76	m/z=1020.22 (C 66 H 40 N 2 O 4 S 3 =1021.24)
P-7	m/z= 822.18 (C 54 H 34 N 2 OS 3 = 823.06)	P-77	m/z= 928.21 (C 60 H 36 N 2 O 5 S 2 =929.08)
P-8	m/z= 892.31 (C 63 H 44 N 2 O 2 S= 893.12)	P-78	m/z= 1008.09 (C 60 H 36 N 2 S 7 =1009.38)
P-9	m/z= 806.21 (C 54 H 34 N 2 O 2 S 2 = 807.00)	P-79	m/z= 900.11 (C 54 H 32 N 2 O 2 S 5 =901.16)
P-10	m/z= 789.24 (C 54 H 35 N 3 O 2 S= 789.95)	P-80	m/z= 928.21 (C 60 H 36 N 2 O 5 S 2 =929.08)
P-11	m/z= 790.23 (C 54 H 34 N 2 O 3 S= 790.94)	P-81	m/z= 900.11 (C 54 H 32 N 2 O 2 S 5 =901.16)
P-12	m/z= 938.31 (C 67 H 42 N 2 O 4 = 939.08)	P-82	m/z= 944.18 (C 60 H 36 N 2 O 4 S 3 =945.14)
P-13	m/z= 732.17 (C 48 H 32 N 2 S 3 = 732.98)	P-83	m/z= 978.22 (C 64 H 38 N 2 O 5 S 2 =979.14)
P-14	m/z= 882.24 (C 60 H 38 N 2 O 2 S 2 = 883.10)	P-84	m/z= 916.08 (C 54 H 32 N 2 OS 6 =917.22)
P-15	m/z= 780.19 (C 52 H 32 N 2 O 2 S 2 = 780.96)	P-85	m/z= 946.27 (C 64 H 38 N 2 O 7 =947.02)
P-16	m/z= 866.26 (C 60 H 38 N 2 O 3 S= 867.04)	P-86	m/z= 1017.23 (C 66 H 39 N 3 O 5 S 2 =1018.17)
P-17	m/z= 750.23 (C 52 H 34 N 2 O 2 S= 750.92)	P-87	m/z= 990.12 (C 60 H 34 N 2 O 3 S 5 =991.24)
P-18	m/z= 790.23 (C 54 H 34 N 2 O 3 S= 790.94)	P-88	m/z= 984.22 (C 63 H 40 N 2 O 4 S 3 =985.20)
P-19	m/z= 746.15 (C 48 H 30 N 2 OS 3 = 746.96)	P-89	m/z= 944.18 (C 60 H 36 N 2 O 4 S 3 =945.14)
P-20	m/z= 822.18 (C 54 H 34 N 2 OS 3 = 823.06)	P-90	m/z= 1058.11 (C 64 H 38 N 2 S 7 =1059.44)
P-21	m/z= 796.17 (C 52 H 32 N 2 OS 3 = 797.02)	P-91	m/z= 882.17 (C 55 H 34 N 2 O 4 S 3 =883.07)
P-22	m/z= 856.22 (C 58 H 36 N 2 O 2 S 2 = 857.06)	P-92	m/z= 928.21 (C 60 H 36 N 2 O 5 S 2 =929.08)
P-23	m/z= 874.28 (C 62 H 38 N 2 O 4 = 875.00)	P-93	m/z= 898.15 (C 55 H 34 N 2 O 3 S 4 =899.13)
P-24	m/z= 920.14 (C 58 H 36 N 2 OS 2 Se= 920.02)	P-94	m/z= 988.26 (C 66 H 40 N 2 O 6 S=989.11)
P-25	m/z= 806.22 (C 54 H 34 N 2 O 4 S= 806.94)	P-95	m/z= 992.12 (C 60 H 36 N 2 OS 6 =993.32)
P-26	m/z= 912.21 (C 60 H 36 N 2 O 4 S 2 = 913.08)	P-96	m/z= 902.19 (C 58 H 34 N 2 O 5 S 2 =903.04)
P-27	m/z= 812.16 (C 52 H 32 N 2 O 2 S 3 = 813.02)	P-97	m/z= 1082.14 (C 66 H 38 N 2 O 4 S 5 =1083.34)
P-28	m/z= 978.20 (C 64 H 38 N 2 O 3 S 3 = 979.20)	P-98	m/z= 990.14 (C 60 H 3 4 N 2 O 5 S 4 =991.18)
P-29	m/z= 838.18 (C 54 H 34 N 2 O 2 S 3 = 839.06)	P-99	m/z= 1040.15 (C 64 H 36 N 2 O 5 S 4 =1041.24)
P-30	m/z= 806.22 (C 54 H 34 N 2 O 4 S= 806.94)	P-100	m/z= 1034.21 (C 66 H 38 N 2 O 7 S 2 =1035.16)
P-31	m/z= 794.10 (C 48 H 30 N 2 S 5 = 795.08)	P-101	m/z= 1050.19 (C 66 H 38 N 2 O 6 S 3 =1051.22)
P-32	m/z= 854.16 (C 54 H 34 N 2 OS 4 = 855.12)	P-102	m/z= 1098.12 (C 66 H 38 N 2 O 3 S 6 =1099.40)
P-33	m/z= 780.21 (C 52 H 32 N 2 O 4 S= 780.90)	P-103	m/z= 1054.04 (C 60 H 34 N 2 OS 8 =1055.43)
P-34	m/z= 888.19 (C 58 H 36 N 2 O 2 S 3 = 889.12)	P-104	m/z= 1034.21 (C 66 H 38 N 2 O 7 S 2 =1035.16)
P-35	m/z= 872.22 (C 58 H 36 N 2 O 3 S 2 = 873.06)	P-105	m/z= 990.14 (C 60 H 3 4 N 2 O 5 S 4 =991.18)
P-36	m/z= 778.12 (C 48 H 30 N 2 OS 4 = 779.02)	P-106	m/z= 1066.17 (C 66 H 38 N 2 O 5 S 4 =1067.28)
P-37	m/z= 922.29 (C 63 H 42 N 2 O 4 S= 923.10)	P-107	m/z= 1084.23 (C 70 H 40 N 2 O 7 S 2 =1085.22)
P-38	m/z= 971.28 (C 66 H 41 N 3 O 4 S= 972.13)	P-108	m/z= 990.14 (C 60 H 3 4 N 2 O 5 S 4 =991.18)
P-39	m/z= 812.16 (C 52 H 32 N 2 O 2 S 3 = 813.02)	P-109	m/z= 1132.16 (C 70 H 40 N 2 O 4 S 5 =1133.40)
P-40	m/z= 888.19 (C 58 H 36 N 2 O 2 S 3 = 889.12)	P-110	m/z= 1040.15 (C 64 H 36 N 2 O 5 S 4 =1041.24)
P-41	m/z= 912.21 (C 60 H 36 N 2 O 4 S 2 = 913.08)	P-111	m/z= 990.14 (C 60 H 3 4 N 2 O 5 S 4 =991.18)
P-42	m/z= 882.26 (C 60 H 38 N 2 O 4 S= 883.03)	P-112	m/z= 990.14 (C 60 H 3 4 N 2 O 5 S 4 =991.18)
P-43	m/z= 1048.17 (C 67 H 40 N 2 OS 5 = 1049.37)	P-113	m/z= 1052.27 (C 70 H 40 N 2 O 9 = 1053.10)
P-44	m/z= 854.16 (C 54 H 34 N 2 OS 4 = 855.12)	P-114	m/z= 1098.12 (C 66 H 38 N 2 O 3 S 6 = 1099.40)
P-45	m/z= 830.22 (C 56 H 34 N 2 O 4 S= 830.96)	P-115	m/z= 1104.06 (C 64 H 36 N 2 OS 8 = 1105.49)
P-46	m/z= 914.21 (C 60 H 38 N 2 O 2 S 3 = 915.16)	P-116	m/z= 1006.11 (C 60 H 34 N 2 O 4 S 5 = 1007.24)
P-47	m/z= 872.22 (C 58 H 36 N 2 O 3 S 2 = 873.06)	P-117	m/z= 990.14 (C 60 H 3 4 N 2 O 5 S 4 =991.18)
P-48	m/z= 878.16 (C 56 H 34 N 2 OS 4 = 879.14)	P-118	m/z=1066.17 (C 66 H 38 N 2 O 5 S 4 =1067.28)
P-49	m/z= 838.18 (C 54 H 34 N 2 O 2 S 3 = 839.06)	P-119	m/z=1066.17 (C 66 H 38 N 2 O 5 S 4 =1067.28)
P-50	m/z= 912.25 (C 61 H 40 N 2 O 3 S 2 = 913.12)	P-120	m/z= 990.14 (C 60 H 3 4 N 2 O 5 S 4 =991.18)
P-51	m/z= 886.20 (C 58 H 34 N 2 O 4 S 2 = 887.04)	P-121	m/z= 700.22 (C 48 H 32 N 2 O 2 S= 700.86)
P-52	m/z= 956.29 (C 66 H 40 N 2 O 6 = 957.05)	P-122	m/z= 898.21 (C 60 H 38 N 2 OS 3 = 899.16)
P-53	m/z= 806.22 (C 54 H 34 N 2 O 4 S= 806.94)	P-123	m/z= 624.19 (C 42 H 28 N 2 O 2 S= 624.76)
P-54	m/z= 976.12 (C 60 H 36 N 2 S 6 = 977.32)	P-124	m/z= 850.32 (C 61 H 42 N 2 O 3 = 851.02)
P-55	m/z= 884.11 (C 54 H 32 N 2 OS 5 = 885.16)	P-125	m/z= 700.22 (C 48 H 32 N 2 O 2 S=700.86)
P-56	m/z= 928.19 (C 60 H 36 N 2 O 3 S 3 = 929.14)	P-126	m/z= 700.22 (C 48 H 32 N 2 O 2 S=700.86)
P-57	m/z= 902.17 (C 58 H 34 N 2 O 3 S 3 = 903.10)	P-127	m/z= 700.22 (C 48 H 32 N 2 O 2 S=700.86)
P-58	m/z= 962.23 (C 64 H 38 N 2 O 4 S 2 = 963.14)	P-128	m/z= 700.22 (C 48 H 32 N 2 O 2 S=700.86)
P-59	m/z= 930.27 (C 64 H 38 N 2 O 6 = 931.02)	P-129	m/z=951.3 (C 64 H 33 D 5 N 2 O 7 =952.05)
P-60	m/z= 884.11 (C 54 H 32 N 2 OS 5 = 885.16)	P-130	m/z=808.22 (C 54 H 33 FN 2 O 3 S=808.93)
P-61	m/z= 960.14 (C 60 H 36 N 2 OS 5 =961.26)	P-131	m/z=771.15 (C 49 H 29 N 3 OS 3 =771.97)
P-62	m/z= 830.28 (C 57 H 38 N 2 O 5 =830.94)	P-132	m/z=730.23 (C 49 H 34 N 2 O 3 S=730.88)
P-63	m/z= 950.10 (C 58 H 34 N 2 S 6 =951.28)	P-133	m/z=788.24 (C 52 H 40 N 2 S 3 =789.09)
P-64	m/z= 912.21 (C 60 H 36 N 2 O 4 S 2 =913.08)	P-134	m/z=1049.31 (C 72 H 47 N 3 O 2 S 2 =1050.31)
P-65	m/z= 938.21 (C 62 H 38 N 2 O 2 S 3 =939.18)	P-135	m/z=856.22 (C 58 H 36 N 2 O 2 S 2 =857.06)
P-66	m/z= 955.30 (C 66 H 41 N 3 O 5 =956.07)	P-136	m/z=840.24 (C 58 H 36 N 2 O 3 S=841)
P-67	m/z= 1034.20 (C 67 H 42 N 2 S 5 =1035.39)	P-137	m/z=941.31 (C 66 H 43 N 3 O 2 S=942.15)
P-68	m/z= 1046.32 (C 73 H 46 N 2 O 4 S=1047.24)	P-138	m/z=865.28 (C 60 H 39 N 3 O 2 S=866.05)
P-69	m/z= 862.18 (C 56 H 34 N 2 O 2 S 3 =863.08)	P-139	m/z=916.28 (C 64 H 40 N 2 O 3 S=917.1)
P-70	m/z= 960.16 (C 60 H 36 N 2 O 4 SSe=959.98)

Manufacturing evaluation of organic electric devices

(Example 1) Red organic electroluminescent device (light emission auxiliary layer)

An organic electroluminescent device was manufactured according to a conventional method using the compound of the present invention as a light emitting auxiliary layer material.

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

Subsequently, after vacuum deposition of the compound P-7 of the present invention to a thickness of 40 nm on the hole transport layer to form a light emission auxiliary layer, 4,4'-N,N'-dicarbazole-biphenyl on the light emission auxiliary layer (hereinafter , CBP) as a host material, bis-(1-phenylisoquinolyl)iridium(III)acetylacetonate (hereinafter, (piq) ₂ Ir(acac)) as a dopant material, by doping at a weight ratio of 95:5. A light-emitting layer was formed by vacuum deposition to a thickness of 30 nm on the light-emitting auxiliary layer.

Next, (1,1'-biphenyl-4-olato)bis(2-methyl-8-quinolinolato)aluminum (hereinafter, BAlq) was vacuum deposited to a thickness of 5 nm on the emission layer to form a hole blocking layer, An electron transport layer was formed by vacuum depositing bis(10-hydroxybenzo[h]quinolinato)beryllium (hereinafter, BeBq _{2) to a thickness of 40 nm on the hole blocking layer.}

Thereafter, the electron injection layer is formed by depositing LiF, which is an alkali metal halide, to a thickness of 0.2 nm on the electron transport layer, and then Al is deposited on the electron injection layer to a thickness of 150 nm to form a cathode, thereby forming an organic electroluminescent device. Was prepared.

(Example 2) to (Example 16)

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-7 of the present invention as the light emitting auxiliary layer material of Example 1. .

(Comparative Example 1)

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

(Comparative Example 2)

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that the following Comparative Compound A was used instead of the compound P-7 of the present invention as the light emitting auxiliary layer material of Example 1.

<Comparative compound A>

Electroluminescence (EL) characteristics were measured with a PR-650 of photoresearch by applying a forward bias DC voltage to the organic electroluminescent devices manufactured according to Examples 1 to 16 and Comparative Examples 1 to 2, and the measurement As a result, the T95 life was measured using a life measurement equipment manufactured by McScience at a reference luminance of 2500 cd/m ^2. Table 4 below shows the results of device fabrication and evaluation.

	compound	Driving Voltage (V)	Current density (mA/cm 2 )	Luminance (cd/m 2 )	efficiency (cd/A)	T(95)	CIE
							x	y
Comparative Example (1)	-	6.5	35.2	2500	7.1	73.4	0.64	0.30
Comparative Example (2)	Comparative compound A	5.3	14.5	2500	17.3	85.2	0.62	0.30
Example (1)	P-7	4.9	10.8	2500	23.1	108.4	0.62	0.31
Example (2)	P-48	5.1	12.1	2500	20.6	106.7	0.60	0.35
Example (3)	P-49	5.0	11.8	2500	21.2	107.6	0.65	0.33
Example (4)	P-54	5.0	11.5	2500	21.8	108.3	0.61	0.32
Example (5)	P-59	4.9	11.3	2500	22.1	108.9	0.62	0.33
Example (6)	P-89	5.0	10.9	2500	22.9	103.7	0.60	0.35
Example (7)	P-91	5.1	11.1	2500	22.5	103.1	0.63	0.31
Example (8)	P-94	5.2	11.6	2500	21.6	101.7	0.62	0.34
Example (9)	P-95	5.1	11.4	2500	22.0	102.6	0.65	0.34
Example (10)	P-116	4.7	12.1	2500	20.7	100.4	0.62	0.31
Example (11)	P-117	4.7	11.8	2500	21.1	101.6	0.63	0.31
Example (12)	P-118	4.8	12.4	2500	20.2	99.5	0.64	0.31
Example (13)	P-119	4.9	12.7	2500	19.7	98.8	0.62	0.33
Example (14)	P-126	4.9	11.2	2500	22.3	107.8	0.65	0.33
Example (15)	P-127	4.8	10.4	2500	24.0	110.5	0.61	0.32
Example (16)	P-128	4.8	10.6	2500	23.7	109.2	0.62	0.31

As can be seen from the results of Table 4, when a red organic electroluminescent device was manufactured using the material for an organic electroluminescent device of the present invention as a light emitting auxiliary layer material, Comparative Example 1 and Comparative Compound without using the light emitting auxiliary layer Compared to Comparative Example 2 in which A was used as the light emitting auxiliary layer material, the driving voltage of the organic electroluminescent device could be lowered, and the luminous efficiency and lifespan were significantly improved.

In more detail, the device result of Comparative Example 2 using Comparative Compound A having a similar constituent to the compound of the present invention was improved than Comparative Example 1 in which the light-emitting auxiliary layer material was not used.

On the other hand, compared to Comparative Compound A, the compound of the present invention is the same in that dibenzo[b,d]thiophene is substituted with two amino groups and dibenzo[b,e][1,4]dioxine is substituted on the amino group. In the compound A, the amino group is substituted on both benzene rings of dibenzo[b,d]thiophene, and the compound of the present invention has two amino groups on one benzene ring of dibenzo[b,d]thiophene or dibenzo[b,d]furan. There is a difference in that they are all replaced.

Accordingly, looking at the device results of the Comparative Examples and Examples, it can be seen that even though Comparative Compound A and the compounds of the present invention are made of similar components, the physical properties of the compound are significantly different depending on the substitution position of the amino group. Likewise, by substituting two amino groups in one benzene ring of dibenzo[b,d]thiophene or dibenzo[b,d]furan, hole characteristics, light efficiency characteristics, energy level (LUMO, HOMO level, T1 level), hole The physical properties of the compound such as hole injection & mobility characteristics and electron blocking characteristics became more suitable for the red light-emitting auxiliary layer, and accordingly, Examples 1 to 1, which were significantly improved than the device characteristics of Comparative Example 2. It can be seen that the device result of Example 16 can be derived.

In addition, in the evaluation results of the above-described device fabrication, the device characteristics in which the compound of the present invention was applied to the light emitting auxiliary layer were described, but the compound of the present invention can be applied to one or more of the light emitting layer, the hole transport layer, the light emitting auxiliary layer, and the capping layer. have.

The above description is only illustrative of the present invention, and those of ordinary skill in the art to which the present invention pertains can include various methods for improving performance including other compounds within the range not departing from the essential characteristics of the present invention. Transformation will be possible.

Accordingly, the embodiments disclosed in the present specification are not intended to limit the present invention, but to describe the present invention, and the scope of the spirit 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.

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

Claims (12)

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

   <Formula 1> <Formula 1-1>

   

   

   In Formula 1,

   1) X is O or S,

   2) Ar ¹ , Ar ² , Ar ³ and Ar ⁴ 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; A fused ring group of an aliphatic ring of C ₃ to C _{60 and an aromatic ring of C 6} to C _60; A C ₁ to C ₅₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; Alkynyl group of C ₂ ~ C _20; An alkoxyl group of C ₁ to C _30; C ₆ ~ C ₃₀ aryloxy group; Or Formula 1-1; Or a combination thereof; Or neighboring groups can be bonded to each other to form a ring,

   3) Y ₁ and Y ₂ are each independently O or S,

   4) L ₁ and L ₂ are each independently a single bond; C ₆ ~ C ₆₀ arylene group; Fluorenylene group; A fused ring group of an aliphatic ring of C ₃ to C _{60 and an aromatic ring of C 6} to C _60; O, N, S, Si, and C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of P; And it is selected from the group consisting of a combination thereof,

   5) R ¹ , R ² , R ³ and R ⁴ are each independently hydrogen; heavy hydrogen; halogen; 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; A fused ring group of an aliphatic ring of C ₃ to C _{60 and an aromatic ring of C 6} to C _60; A C ₁ to C ₅₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; Alkynyl group of C ₂ ~ C _20; An alkoxyl group of C ₁ to C _30; C ₆ ~ C ₃₀ is selected from the group consisting of aryloxy group; Alternatively, a plurality of R ¹ , R ² , R ³ , and R ⁴ may be bonded to each other to form a ring,

   6) a is an integer of 0-2; c is an integer from 0 to 3; b and d are each independently an integer of 0-4,

   7) Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , L ₁ , L ₂ , R ¹ , R ² , R ³ , R ⁴ and neighboring groups bonded to each other to form a ring formed by 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;} 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 arylalkoxy group; C6-C20 aryloxy group; C6-C20 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; _{A C 6} -C ₂₀ aryl group unsubstituted or substituted with deuterium; 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; C ₈ -C ₂₀ arylalkenyl group; And it may be further substituted with one or more substituents selected from the group consisting of a combination thereof.
2. The compound according to claim 1, wherein the formula 1 is represented by any one of the following formulas 2 to 6:

   <Formula 2> <Formula 3>

   

   <Formula 4> <Formula 5>

   

   <Formula 6>

   

   In Formulas 2 to 6,

   1) X, Y ₁ , Y ₂ , Ar ² , Ar ³ , Ar ⁴ , R ¹ , R ² , R ³ , R ⁴ , a, b, c, d, L ₁ and L ₂ are defined in claim 1 above As it has been,

   2) Y ₃ ~ Y ₈ are each independently O or S,

   3) R ⁵ to R ¹⁰ are each independently deuterium; halogen; 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; A fused ring group of an aliphatic ring of C ₃ to C _{60 and an aromatic ring of C 6} to C _60; A C ₁ to C ₅₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; Alkynyl group of C ₂ ~ C _20; An alkoxyl group of C ₁ to C _30; C ₆ ~ C ₃₀ is selected from the group consisting of aryloxy group; Or, a plurality of R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , or R ¹⁰ may be bonded to each other to form a ring,

   4) e, g and i are each independently an integer of 0-3; f, h, and j are each independently an integer of 0-4.
3. The compound according to claim 1, wherein Formula 1 is represented by any one of Formulas 7 to 9 below:

   <Formula 7> <Formula 8>

   

   <Formula 9>

   

   In Chemical Formulas 7 to 9,

   The X, Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , R ¹ , a, L ₁ and L ₂ are as defined in claim 1.
4. The compound of claim 1, wherein the compound represented by Formula 1 is any one of the following P-1 to P-139:

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   
5. A first electrode; A second electrode; And an organic material layer formed between the first electrode and the second electrode,

   The organic material layer is an organic electric device comprising a compound represented by the formula (1) of claim 1 alone or in combination.
6. A first electrode; A second electrode; An organic material layer formed between the first electrode and the second electrode; And in the organic electric device comprising a capping layer,

   The capping layer is formed on one surface of both surfaces of the first electrode and the second electrode that is not in contact with the organic material layer,

   The organic material layer or the capping layer is an organic electric device comprising a compound represented by the formula (1) alone or in combination.
7. The method of claim 5 or 6,

   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 organic material layer is an organic electric device comprising at least one of the hole transport layer, the light emitting auxiliary layer and the light emitting layer.
9. The method of claim 5 or 6,

   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 or 6; And 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.

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