KR20210001061A - Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof - Google Patents

Abstract

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

Description

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

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

In general, the organic light emission phenomenon refers to a phenomenon in which electrical energy is converted into light energy using an organic material. An organic electric device using an 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 electric 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.

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. In addition, the light-emitting material may be classified into a high molecular type and a low molecular type according to its molecular weight, and according to a light emitting mechanism, it may 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 for realizing 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 emission wavelength shifts to a long wavelength due to intermolecular interactions, and the color purity decreases or the efficiency of the device decreases due to the emission attenuation effect.Therefore, the increase in color purity and energy transfer A host/dopant system may be used as a light emitting material in order to increase the luminous efficiency through. The principle is that when a small amount of a dopant having an energy band gap smaller than that of the host forming the light emitting layer is mixed in the light emitting layer, excitons generated in the light emitting layer are transported to the dopant to emit light with high efficiency. At this time, since the wavelength of the host moves to the wavelength of the dopant, light having a desired wavelength can be obtained according to the type of dopant used.

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

Efficiency, lifespan, and driving voltage are related to each other, and when the efficiency is increased, 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 efficiency. 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 recent years, in order to solve the problem of light emission in the hole transport layer in 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, and desired according to each light emitting layer (R, G, B). 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, thereby generating excitons through 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 T ₁ value, and as a result, excitons generated in the light-emitting layer pass to the hole transport layer interface or the hole transport layer, resulting in the hole transport layer. Light emission at the interface 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 electronic 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 driving voltage range of the blue device of the full device). There is an urgent need to develop a light-emitting auxiliary layer having mobility).

However, this cannot be achieved simply with the structural characteristics of the core of the light-emitting auxiliary layer material, and the characteristics of the core and sub-substituents of the light-emitting auxiliary layer material, and the proper 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 long-life device can be implemented.

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

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

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

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

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

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

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

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

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

The term "spyro compound" used in the present invention has a'spyro linkage', and a 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'spiro atoms', and these are respectively referred to as'monospiro-','dispiro-', and'trispyro-' depending on the number of spiro atoms in a compound. 'It is called a compound.

The term "heterocyclic group" as 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 refers to 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 containing a heteroatom, a ring aggregate, a conjugated ring system, spy Means a compound, etc.

The term "heterocyclic group" as used in the present invention refers to a ring in which a heteroatom such as N, O, S, P or Si is included instead of carbon forming the ring, and "heteroaryl group" or "heteroarylene group" A non-aromatic ring is included as well as an aromatic ring such as, and a compound including a heteroatom group such as SO ₂ , P=O and the like may be included instead of carbon forming the ring.

The term "aliphatic ring group" 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, benzene as an aromatic ring and cyclohexane, a non-aromatic ring, are fused to 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 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' and the divalent group can be labeled with the valence by dividing the valency such as'phenanthrylene'. Regardless of the parent compound, it may be described as'phenanthrene'. Similarly, even 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 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 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, it 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, etc., 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 or a six-membered ring, the number in'number-atomic' 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 specification, the ring formed by bonding of adjacent groups to each other is an aromatic ring group of C ₆ ~ C ₆₀ ; Fluorenyl group; O, N, S, Si, and C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of P; And C ₃ ~ C ₆₀ aliphatic ring group; may be selected from the group consisting of.

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 can 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 adjacent 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 containing 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 neighbors It refers to a case where one group is 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, if 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 only used to distinguish the component from other components, and the nature, order, or order of the component 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".

In addition, 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, as well as another component 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, the first electrode may be a cathode and the 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, the hole injection layer 120, the hole transport layer 130, the light emitting layer 140, the electron transport layer 150, and the 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 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 SPPs (surface plasmon polaritons) 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 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 formed 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 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 1-5. 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 that emits white light by the mixing effect of light emitted from each light-emitting layer, as well as light of various colors. An organic electroluminescent device that emits light can also be manufactured.

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 the light efficiency improvement layer 180 may be used as a material, but preferably, the light emitting auxiliary layer 220, the light emitting layers 140, 340, 440 ) And/or the light efficiency improvement layer 180 may be used as a material.

Since the band gap, electrical properties, and interfacial properties may vary depending on which substituent is bonded to any position of 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, the light emission layers 140, 340, and 440, and/or the light efficiency improvement layer 180, the energy level and T ₁ between each organic material layer By optimizing the value and intrinsic properties of the material (mobility, interfacial properties, etc.), it is possible to simultaneously improve the life and efficiency of organic electric devices.

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, a metal or a conductive metal oxide or an alloy thereof is deposited 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 spin coating process, nozzle printing process, inkjet printing process, slot coating process, dip coating process, roll-to-roll process, doctor blaze. It can be manufactured with fewer layers by a method such as a printing process, a screen printing process, or a thermal transfer method. Since the organic material layer according to the present invention may 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 of a top emission type, a bottom emission type, or a double side 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. At this time, 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.

X is O or S.

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

When neighboring groups are bonded to each other to form an aromatic ring, preferably a C ₆ ~ C ₂₀ aromatic ring, more preferably a C ₆ ~ C ₁₄ aromatic ring, such as benzene, naphthalene, phenanthrene, etc. I can.

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

When R ¹ to R ⁴ are an aryl group, preferably a C ₆ to C ₃₀ aryl group, more preferably a C ₆ to C ₁₈ aryl group such as phenyl, naphthyl, biphenyl, terphenyl, phenanthrene, etc. I can.

When R ¹ to R ⁴ are heterocyclic groups, preferably a C ₂ to C ₃₀ heterocyclic group, more preferably a C ₂ to C ₁₈ heterocyclic group such as pyridine, pyrimidine, triazine, pyridazine, Quinoline, isoquinoline, quinazoline, benzoquinazoline, dibenzoquinazoline, quinoxaline, benzoquinoxaline, benzothienopyrimidine, benzofuropyrimidine, pyridopyrazine, benzothienopyrazine, dibenzothio Offene, dibenzofuran, carbazole, phenylcarbazole, and the like.

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

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

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

When L ¹ and L ² are heterocyclic groups, preferably a C ₂ to C ₃₀ heterocyclic group, more preferably a C ₂ to C ₁₈ heterocyclic group such as pyridine, pyrimidine, triazine, quinazoline , Benzoquinazoline, benzothienopyrimidine, benzofuropyrimidine, benzoquinoxaline, pyridopyrazine, benzothienopyrazine, quinoline, carbazole, phenylcarbazole, and the like.

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

When Ar ¹ to Ar ³ are an aryl group, preferably a C ₆ to C ₃₀ aryl group, more preferably a C ₆ to C ₁₈ aryl group such as phenyl, naphthyl, biphenyl, terphenyl, phenanthrene, Triphenylene and the like.

When Ar ¹ to Ar ³ are fluorenyl groups, 9,9-dimethyl-9H-fluorene, 9,9-diphenyl-9H-fluorene, 9,9'-spirofluorene, spiro[benzo [ b ]fluorene-11,9'-fluorene], benzo[ b ]fluorene, 11,11-diphenyl-11 H -benzo[ b ]fluorene, 9-(naphthalen-2-yl)9- phenyl -9 H - may be a fluorene.

When Ar ¹ to Ar ³ 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 pyridine, pyrazine, triazine, dibenzothiophene , Quinoxaline, benzothienopyrimidine, dibenzofuran, benzonaphthothiophene, benzonaphthofuran, carbazole, phenylcarbazole, and the like.

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

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

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

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

When R _a and R _b are fluorenyl groups, it may be 9,9-dimethyl-9H-fluorene, 9,9-diphenyl-9H-fluorene, 9,9'-spirofluorene, and the like.

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

Preferably, the R ¹ to R ⁴ at least one of the -L ¹ -Ar ¹ may il, R ¹ to R ⁴ is one or -L ¹ -Ar to the case where ¹ is the general formula (1) in the formula 1-1 To 1-4.

<Formula 1-1> <Formula 1-2> <Formula 1-3> <Formula 1-4>

In Formulas 1-1 to 1-4, R ¹ to R ⁴ , a to d, X, L ¹ and Ar ¹ are the same as defined in Formula 1 above.

In addition, preferably, at least one of the R ¹ to R ⁴ may be -L ² -N(Ar ² )(Ar ³ ), wherein one of R ¹ to R ⁴ is -L ² -N(Ar ² ) In the case of (Ar ³ ), Formula 1 may be represented by Formulas 1-5 to 1-8 below.

<Formula 1-5> <Formula 1-6> <Formula 1-7> <Formula 1-8>

In Formulas 1-5 to 1-8, R ¹ to R ⁴ , a to d, X, L ² , Ar ² and Ar ³ are the same as defined in Formula 1 above.

Preferably, Ar ¹ may include a compound represented by the following Formula 2 or Formula 3, and more preferably, Ar ¹ may be represented by the following Formula 2 or Formula 3.

<Formula 2> <Formula 3>

In Formulas 2 and 3, each symbol may be defined as follows.

Z ¹ to Z ⁸ are each independently N or C(R ₁ ), at least one of Z ¹ to Z ⁵ is N, and at least one of Z ⁶ to Z ⁸ is N.

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

C ring is a C ₆ ~ C ₆₀ aromatic ring group; Or O, N, S, Si, and P is a C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom. The C ring may be further substituted with one or more R ₁ of the same or different.

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

Preferably, Formula 3 includes a compound represented by one of the following Formulas 3-1 to 3-6, and more preferably, Formula 3 may be represented by one of the following Formulas 3-1 to 3-6. have.

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

<Formula 3-4> <Formula 3-5> <Formula 3-6>

In Formulas 3-1 to 3-6, Z ⁶ to Z ⁸ , R ₁ , L ₁ are the same as defined in Formula 3, o is an integer of 0 to 4, p is an integer of 0 to 6, q Is an integer of 0 to 8, and when each of them is an integer of 2 or more, each of R ₁ is the same as or different from each other, X ¹ and X ² are each independently O or S, and e and f are each an integer of 0 or 1 At least one of e and f is 1.

Preferably, at least one of Ar ² and Ar ³ includes a compound represented by the following Formula 4, and more preferably, at least one of Ar ² and Ar ³ may be represented by the following Formula 4.

<Formula 4>

In Chemical Formula 4, each symbol may be defined as follows.

Y is O, S, N(R ₄ ) or C(R')(R").

R ₂ , R ₃ , R'and R" are independently of each other hydrogen; deuterium; halogen; a silane group unsubstituted or substituted with a C ₁ -C ₂₀ alkyl group or a C ₆ -C ₂₀ aryl group; a siloxane group; a boron group ; germanium group; a cyano group; a nitro group; a C ₁ -C ₂₀ come alkylthio; C ₁ -C ₂₀ alkoxy group; Im coming aryl of C ₆ -C _20;; C ₆ -C ₂₀ aryloxy C ₁ -C ₂₀ alkyl group; C ₂ -C ₂₀ alkenyl group; C ₂ -C ₂₀ alkynyl group; C ₆ -C ₂₀ aryl group; fluorenyl group; O, N, S, Si and P group consisting of C ₂ -C ₂₀ heterocyclic group containing at least one heteroatom selected from; C ₃ -C ₂₀ aliphatic ring group; C ₇ -C ₂₀ arylalkyl group; And C ₈ -C ₂₀ arylalkenyl group It is selected from the group consisting of yiru, and neighboring groups may be bonded to each other to form a ring, and R′ and R” may be bonded to each other to form a ring.

R ₄ is a C ₆ -C ₂₀ aryl group; Fluorenyl group; O, N, S, Si, and C ₂ -C ₂₀ heterocyclic group including at least one heteroatom selected from the group consisting of P; And C ₃ -C ₂₀ It may be selected from the group consisting of an aliphatic ring group.

i is an integer of 0 to 4, when i is an integer of 2 or more, each of R ₂ is the same or different from each other, j is an integer of 0 to 3, and when j is an integer of 2 or more, each of R ₃ is the same or different from each other.

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 electrical 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 yet 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 yet another aspect of the present invention, the present invention provides an electronic device including a display device including an organic electric element 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 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 is synthesized by reacting Sub 1 and Sub 2 as shown in Scheme 1 below, but is not limited thereto.

<Reaction Scheme 1>

I. Synthesis Example of Sub 1

Sub1 of Scheme 1 may be synthesized by the reaction paths of Schemes 2-1 to 2-4 below, but is not limited thereto.

<Reaction Scheme 2-1>

<Reaction Scheme 2-2>

<Reaction Scheme 2-3>

<Reaction Scheme 2-4>

One. Sub1 -One Synthesis example

(1) Sub1-1b synthesis

Sub1-1a (40 g, 0.15 mol), 2-chloroaniline (19.4 g, 0.15 mol), Pd ₂ (dba) ₃ (4.2 g, 0.005 mol), 50% P( t -Bu) ₃ (3.7 g, 0.009 mol), NaO t -Bu (44 g, 0.46 mol) was added to toluene (310ml) and stirred at 90°C. When the reaction is finished, the temperature of the reactant is cooled to room temperature, toluene is removed, and then extracted with MC and washed with water. Thereafter, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was separated using a silica gel column to obtain 40 g (85%) of the product.

(2) Sub1-1c synthesis

Sub1-1b (40 g, 0.13 mol) Pd(OAc) ₂ (0.9 g, 0.004 mol), P(t-Bu) ₃ (3.1 g, 0.008 mol), K ₂ CO ₃ (53.5 g, 0.40 mol) , DMA (260 ml) was added and refluxed at 170° C. for 12 hours. When the reaction is finished, the temperature of the reactant is cooled to room temperature, toluene is removed, and then extracted with MC and washed with water. Thereafter, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was separated using a silica gel column to obtain 30 g (85.1%) of the product.

(3) Sub1-1d synthesis

Sub1-1c (30 g, 0.11 mol), 1-bromo-4-chloro-2-iodobenzene (35 g, 0.11 mol), Pd ₂ (dba) ₃ (3 g, 0.003 mol), 50% P( t- Bu) ₃ (2.7 g, 0.006 mol), NaO t -Bu (31.7 g, 0.33 mol), toluene (220 ml), proceed in the same manner as the synthesis method of Sub1-1b to obtain 41 g (80.6%) of the product Got it.

(4) Sub1-1 synthesis

Sub1-1d (40 g, 0.09 mol), Pd(OAc) ₂ (0.6 g, 0.003 mol), P(t-Bu) ₃ (2.1 g, 0.005 mol), K ₂ CO ₃ (35.8 g, 0.26 mol) , DMA (180 ml) was carried out in the same manner as for the synthesis of Sub1-1c to obtain 27 g (81.8%) of the product.

2. Sub1 -6 Synthesis example

(1) Sub1-6b synthesis

Sub1-6a (40 g, 0.15 mol), 2,4-dichloroaniline (24.6 g, 0.15 mol), Pd ₂ (dba) ₃ (4.2 g, 0.005 mol), 50% P( t -Bu) ₃ (3.7 g , 0.009 mol), NaO t -Bu (44 g, 0.46 mol), and toluene (310 ml) were used in the same manner as the synthesis method of Sub1-1b to obtain 44 g (84%) of the product.

(2) Sub1-6c synthesis

Sub1-6b (44 g, 0.13 mol), Pd(OAc) ₂ (0.9 g, 0.004 mol), P(t-Bu) ₃ (3.1 g, 0.008 mol), K ₂ CO ₃ (53.5 g, 0.40 mol) , DMA (260 ml) was carried out in the same manner as for the synthesis of Sub1-1c to obtain 34 g (86.4%) of the product.

(3) Sub1-6d synthesis

Sub1-6c (34 g, 0.11 mol), 1-bromo-2-iodobenzene (31 g, 0.11 mol), Pd ₂ (dba) ₃ (3 g, 0.003 mol), 50% P( t -Bu) ₃ ( 2.7 g, 0.006 mol), NaO t -Bu (31.7 g, 0.33 mol), and toluene (220 ml) were used in the same manner as the synthesis method of Sub1-1b to obtain 45 g (88.1%) of the product.

(4) Sub1-6 synthesis

Sub1-6d (45 g, 0.10 mol), Pd(OAc) ₂ (0.7 g, 0.003 mol), P(t-Bu) ₃ (2.4 g, 0.006 mol), K ₂ CO ₃ (35.8 g, 0.26 mol) , DMA (180 ml) was carried out in the same manner as for the synthesis of Sub1-1c to obtain 32 g (86.2%) of the product.

3. Sub1 -16 Synthesis example

(1) Sub1-16b synthesis

Sub1-16a (48 g, 0.15 mol), 2,4-dichloroaniline (24.6 g, 0.15 mol), Pd ₂ (dba) ₃ (4.2 g, 0.005 mol), 50% P( t -Bu) ₃ (3.7 g , 0.009 mol), NaO t -Bu (44 g, 0.46 mol), and toluene (310 ml) were used in the same manner as the synthesis method of Sub1-1b to obtain 45 g (85%) of the product.

(2) Sub1-16c synthesis

Sub1-16b (45 g, 0.13 mol), Pd(OAc) ₂ (0.9 g, 0.004 mol), P(t-Bu) ₃ (3.1 g, 0.008 mol), K ₂ CO ₃ (53.5 g, 0.40 mol) , DMA (260 ml) was carried out in the same manner as for the synthesis of Sub1-1c to obtain 39 g (83.4%) of the product.

(3) Sub1-16d synthesis

Sub1-16c (39 g, 0.11 mol), 1-bromo-2-iodobenzene (31 g, 0.11 mol), Pd ₂ (dba) ₃ (3 g, 0.003 mol), 50% P( t -Bu) ₃ ( 2.7 g, 0.006 mol), NaO t -Bu (31.7 g, 0.33 mol), and toluene (220 ml) were used in the same manner as the synthesis method of Sub1-1b to obtain 48 g (85.9%) of the product.

(4) Sub1-16 synthesis

Sub1-16d (48 g, 0.09 mol), Pd(OAc) ₂ (0.6 g, 0.003 mol), P(t-Bu) ₃ (2.3 g, 0.006 mol), K ₂ CO ₃ (38.8 g, 0.28 mol) , DMA (187 ml) was carried out in the same manner as for the synthesis of Sub1-1c to obtain 37 g (91.5%) of the product.

4. Sub1 -23 Synthesis example

(1) Sub1-23b synthesis

Sub1-23a (45 g, 0.10 mol), 2,5-dichloroaniline (16.9 g, 0.10 mol), Pd ₂ (dba) ₃ (2.9 g, 0.003 mol), 50% P( t -Bu) ₃ (2.5 g , 0.006 mol), NaO t -Bu (30 g, 0.31 mol), and toluene (209ml) were used in the same manner as for the synthesis of Sub1-1b to obtain 43 g (80.4%) of the product.

(2) Sub1-23c synthesis

Sub1-23b (43 g, 0.08 mol), Pd(OAc) ₂ (0.6 g, 0.003 mol), P(t-Bu) ₃ (2 g, 0.006 mol), K ₂ CO ₃ (34.9 g, 0.25 mol) , DMA (170 ml) was carried out in the same manner as for the synthesis of Sub1-1c to obtain 33 g (82.6%) of the product.

(3) Sub1-23d synthesis

Sub1-23c (33 g, 0.07 mol), 1-bromo-2-iodobenzene (19.6 g, 0.07 mol), Pd ₂ (dba) ₃ (1.9 g, 0.002 mol), 50% P( t -Bu) ₃ ( 1.7 g, 0.004 mol), NaO t -Bu (20 g, 0.21 mol), and toluene (140 ml) were used in the same manner as the synthesis method of Sub1-1b to obtain 40 g (91.4%) of the product.

(4) Sub1-23 synthesis

Sub1-23d (40 g, 0.06 mol), Pd(OAc) ₂ (0.4 g, 0.002 mol), P(t-Bu) ₃ (1.5 g, 0.004 mol), K ₂ CO ₃ (26.3 g, 0.19 mol) , DMA (127 ml) was carried out in the same manner as for the synthesis of Sub1-1c to obtain 30 g (86.1%) of the product.

5. Sub1 -30 Synthesis example

(1) Sub1-30b synthesis

Sub1-30a (42 g, 0.15 mol), 2-chloroaniline (18.9 g, 0.15 mol), Pd ₂ (dba) ₃ (4.1 g, 0.005 mol), 50% P( t- Bu) ₃ (3.6 g, 0.009 mol), NaO t -Bu (43 g, 0.45 mol), and toluene (300ml) were carried out in the same manner as in the synthesis method of Sub1-1b to obtain 40 g (81.7%) of the product.

(2) Sub1-30c synthesis

Sub1-30b (40 g, 0.12 mol), Pd(OAc) ₂ (0.82 g, 0.004 mol), P(t-Bu) ₃ (3 g, 0.007 mol), K ₂ CO ₃ (50 g, 0.37 mol) , DMA (245 ml) was carried out in the same manner as for the synthesis of Sub1-1c to obtain 30 g (84.6%) of the product.

(3) Sub1-30d synthesis

Sub1-30c (30 g, 0.10 mol), 1-bromo-2-iodobenzene (29.1 g, 0.10 mol), Pd ₂ (dba) ₃ (2.8 g, 0.003 mol), 50% P( t -Bu) ₃ ( 2.5 g, 0.006 mol), NaO t -Bu (29.7 g, 0.31 mol), and toluene (200 ml) were used in the same manner as the synthesis method of Sub1-1b to obtain 37 g (80.5%) of the product.

(4) Sub1-30 synthesis

Sub1-30d (37 g, 0.08 mol), Pd(OAc) ₂ (0.6 g, 0.002 mol), P(t-Bu) ₃ (2 g, 0.005 mol), K ₂ CO ₃ (34.4 g, 0.25 mol) , DMA (166 ml) was carried out in the same manner as for the synthesis of Sub1-1c to obtain 24 g (79.1%) of the product.

6. Sub1 -36 Synthesis example

(1) Sub1-36b synthesis

Sub1-36a (48 g, 0.15 mol), 2-chloroaniline (18.9 g, 0.15 mol), Pd ₂ (dba) ₃ (4.1 g, 0.005 mol), 50% P( t- Bu) ₃ (3.6 g, 0.009 mol), NaO t -Bu (43 g, 0.45 mol), and toluene (300ml) were used in the same manner as the synthesis method of Sub1-1b to obtain 47 g (85.6%) of the product.

(2) Sub1-36c synthesis

Sub1-36b (47 g, 0.13 mol), Pd(OAc) ₂ (0.85 g, 0.004 mol), P(t-Bu) ₃ (3.1 g, 0.008 mol), K ₂ CO ₃ (52 g, 0.38 mol), Using DMA (255 ml), it proceeded in the same manner as the synthesis method of Sub1-1c to obtain 35 g (82.6%) of the product.

(3) Sub1-36d synthesis

Sub1-36c (35 g, 0.10 mol), 2-bromo-4-chloro-1-iodobenzene (33.2 g, 0.10 mol), Pd ₂ (dba) ₃ (2.8 g, 0.003 mol), 50% P( t- Bu) ₃ (2.5 g, 0.006 mol), NaO t -Bu (29.7 g, 0.31 mol), toluene (210 ml), proceed in the same manner as the synthesis method of Sub1-1b to obtain a product 44 g (80.2%) Got it.

(4) Sub1-36 synthesis

Sub1-36d (44 g, 0.08 mol), Pd(OAc) ₂ (0.6 g, 0.002 mol), P(t-Bu) ₃ (2 g, 0.005 mol), K ₂ CO ₃ (34.4 g, 0.25 mol) , DMA (168 ml) was carried out in the same manner as for the synthesis of Sub1-1c to obtain 27 g (72.6%) of the product.

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

[Table 1]

II. Exemplary compound of Sub 2

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

[Table 2]

Ⅲ. Of the final compound Synthesis example

1.P-3 synthesis

Sub1-5 (10 g, 0.03 mol) to Sub2-12 (9.4 g, 0.03 mol), Pd(PPh ₃ ) ₄ (0.9 g, 0.001 mol), NaOH (3.1 g, 0.08 mol), THF (52 mL), It was added to water (15 mL) and allowed to react for 6 hours. After the reaction was completed, the temperature of the reactant was cooled to room temperature, THF and H ₂ O were removed, followed by extraction with MC and washing with water. Thereafter, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was separated by a silica gel column and recrystallized to obtain 12 g (79.2%) of the product.

2. P-20 synthesis

Sub1-7 (10 g, 0.03 mol), Sub2-24 (10.7 g, 0.03 mol), Pd(PPh ₃ ) ₄ (0.9 g, 0.001 mol), NaOH (3.1 g, 0.08 mol), THF (52 mL), Using water (15 mL), it proceeded in the same manner as in the synthesis method of P-3 to obtain 14 g (85.2%) of the product.

3. P-22 synthesis

Sub1-26 (20 g, 0.05 mol), Sub2-17 (20.6 g, 0.05 mol), Pd(PPh ₃ ) ₄ (1.8 g, 0.002 mol), NaOH (6 g, 0.16 mol), THF (110 mL), Using water (35 mL), it proceeded in the same manner as in the synthesis method of P-3 to obtain 28 g (88.2%) of the product.

4. Synthesis Example of P-33

Sub1-3 (10 g, 0.03 mol), Sub2-26 (8.7 g, 0.03 mol), Pd(PPh ₃ ) ₄ (0.7 g, 0.001 mol), NaOH (3.1 g, 0.08 mol), THF (60 mL), Using water (20 mL), it proceeded in the same manner as in the synthesis method of P-3 to obtain 9 g (62.2%) of the product.

5. Synthesis Example of P-44

Sub1-6 (15 g, 0.04 mol), Sub2-43 (14.5 g, 0.04 mol), Pd(PPh ₃ ) ₄ (1.4 g, 0.002 mol), NaOH (4.7 g, 0.12 mol), THF (80 mL), Using water (23 mL), it proceeded in the same manner as for the synthesis of P-3, to obtain 19 g (82.1%) of the product.

6. Synthesis Example of P-56

Sub1-7 (30 g, 0.08 mol) to Sub2-54 (25.3 g, 0.08 mol), Pd ₂ (dba) ₃ (2.1 g, 0.002 mol), 50% P( t- Bu) ₃ (1.9 g, 0.004) mol), NaO t -Bu (23.4 g, 0.24 mol), and toluene (160ml) were added and stirred at 90°C. After the reaction was completed, the temperature of the reaction product was cooled to room temperature, toluene was removed, extracted with MC, and the organic layer was concentrated. Then, the resulting organic material was separated by a silica gel column and recrystallized to obtain 45 g (85.7%) of the product.

7. P-81 Synthesis example

Sub1-6 (30 g, 0.08 mol) to Sub2-80 (22 g, 0.08 mol), Pd(PPh ₃ ) ₄ (2.7 g, 0.002 mol), NaOH (9.4 g, 0.24 mol), THF (160 mL), Using water (40 mL), the product was proceeded in the same manner as for the synthesis of P-3 to obtain 30 g (76.4%) of the product.

The FD-MS values of the compounds P-1 to P-90 of the present invention prepared according to the synthesis example as described above are shown in Table 3 below.

[Table 3]

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

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

Then, on the hole transport layer, compound P-3 of the present invention as a host material, bis-(1-phenylisoquinolyl)iridium(III)acetylacetonate (hereinafter, abbreviated as "(piq) ₂ Ir(acac)") as a dopant Although used as a material, a light emitting layer having a thickness of 30 nm was deposited by doping with a dopant so that the weight ratio was 95:5.

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

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

[ Example 2] to [ Example 32]

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that the compound of the present invention described in Table 4 was used instead of the compound P-3 of the present invention as a host material.

[ Comparative example 1] and [ Comparative example 2]

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that Comparative Compound A or Comparative Compound B was used as a host material.

<Comparative Compound A> <Comparative Compound B>

Electroluminescence (EL) characteristics were measured with PR-650 of Photoresearch by applying a forward bias DC voltage to the organic electroluminescent devices manufactured according to Examples 1 to 32 and Comparative Examples 1 and 2 of the invention. And, the T95 life was measured through the life measurement equipment of McScience at the standard 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 the light emitting layer material, the driving voltage is lowered and the efficiency and lifespan are lower than when Comparative Compound A or Comparative Compound B is used (Comparative Examples 1 to 2). It can be seen that there is a significant improvement.

That is, when Comparative Compound B having a similar basic skeleton to Formula 1 of the present invention is used as a host material (Comparative Example 2), driving voltage, efficiency, and lifespan are higher than when Comparative Compound A is used as a host material (Comparative Example 1). All were improved, and compared to Comparative Example 2, when the compound of the present invention was used as a host material, all of the driving voltage, efficiency and life were significantly improved.

In more detail, the compound of the present invention includes a heteroatom such as S or O in the ring of the structure of Formula 1, so that it has a higher refractive index and a higher Tg value compared to the comparative compound, and the energy transfer effect is maximized. do. As a result, the luminous efficiency is greatly improved and the lifespan is also significantly improved due to high thermal stability.

In addition, the compound of the present invention containing the element S or O has an increased planarity compared to the comparative compound B containing the element N, and as a result, the packing density is improved, thereby improving the performance of the device. .

These results show that even with similar compounds, the energy level or thin film characteristics of the compound are significantly different depending on the type of hetero element or specific substituent, and this difference is a major factor in improving device performance during device deposition (e.g. energy balance, stability, etc.) This suggests that the device result may be different.

[ Example 33] Red organic electroluminescent device ( Light-emitting auxiliary layer )

A 2-TNATA film was vacuum-deposited on the ITO layer (anode) formed on the glass substrate to form a hole injection layer with a thickness of 60 nm, and then NPB was vacuum evaporated to form a hole transport layer having a thickness of 60 nm. Subsequently, the compound P-44 of the present invention was vacuum deposited to a thickness of 20 nm on the hole transport layer to form a light emission auxiliary layer.

Thereafter, on the light-emitting auxiliary layer, 4,4'-N,N'-dicarbazole-biphenyl (hereinafter referred to as "CBP") as a host material, and (piq) ₂ Ir (acac) as a dopant material are used. Dopant was doped so that the weight ratio was 95:5 to form a light emitting layer having a thickness of 30 nm.

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

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

[ Example 34] to [ Example 57 ]

An organic electroluminescent device was manufactured in the same manner as in Example 33, except that the compound of the present invention described in Table 5 was used instead of the compound P-44 of the present invention as a light emitting auxiliary layer material.

[Comparative Example 3]

An organic electroluminescent device was manufactured in the same manner as in Example 33, except that the light emission auxiliary layer was not formed.

[Comparative Example 4] and [Comparative Example 5]

An organic electroluminescent device was manufactured in the same manner as in Example 33, except that Comparative Compound C or Comparative Compound D below was used instead of Compound P-44 of the present invention as a material for the auxiliary layer.

<Comparative Compound C> <Comparative Compound D>

Electroluminescence (EL) characteristics were measured with PR-650 of photoresearch company by applying a forward bias DC voltage to organic electric devices manufactured according to Examples 33 to 57 and Comparative Examples 3 to 5 of the present invention. In addition, the T95 life was measured using a life measurement equipment of McScience at a standard luminance of 2500 cd/m ² . The measurement results are shown in Table 5 below.

[Table 5]

As can be seen from the results of Table 5, when the compound of the present invention is used as a material for the light-emitting auxiliary layer, the driving of the device is compared to Comparative Examples 3 to 5 in which the light-emitting auxiliary layer was not formed or Comparative Compound C or Comparative Compound D was used. It can be seen that the voltage is lowered and the efficiency and lifespan are significantly improved.

Comparing Comparative Examples 3 to 5, the device results were superior in the case of using Comparative Compound C or Comparative Compound D (Comparative Examples 4 to 5) than the case in which the light emission auxiliary layer was not used (Comparative Example 3). And, compared to Comparative Examples 4 to 5, the device result was better when the compound of the present invention, which has a structure similar to that of the comparative compound, but contains heteroatoms such as S and O in the polycyclic group core, is used as a light emitting auxiliary layer material. I did.

Comparing the results of Comparative Example 4, Comparative Example 5, and Examples 33 to 57, since S and O were included in the polycyclic group core, they had a higher refractive index and a higher Tg value than that of the cyclic compound containing N. And it seems that the lifespan is increased due to improved thermal safety. In addition, by using the compound of the present invention as a light emitting auxiliary layer, the HOMO or LUMO energy level of the compound of the present invention has an appropriate value between the hole transport layer and the light emitting layer, and thus, the charge balance between holes and electrons. ) And light emission occurs inside the light-emitting layer rather than the hole transport layer interface, so it seems that the efficiency and lifespan are maximized.

Meanwhile, when a compound containing a substituent of dibenzothiophene or dibenzofuran is used as the light emitting auxiliary layer material among the embodiments of the present invention, compared to the case where a compound having a substituent of a simple aryl is used as the light emitting auxiliary layer material , Efficiency, etc. have been improved. This is due to the difference in hole mobility in the light emitting auxiliary layer, which is considered to affect the overall device characteristics.

In the case of the light-emitting auxiliary layer, it is necessary to grasp the correlation between the hole transport layer and the light-emitting layer (host). Even if a similar core is used, even a skilled person infers the characteristics of the light-emitting auxiliary layer in which the compound of the present invention is used. It will be very difficult.

The above description is only illustrative of the present invention, and those of ordinary skill in the art to which the present invention pertains will be able to make various modifications without departing from the essential characteristics of the present invention. Accordingly, the embodiments disclosed in the present specification are not intended to limit the present invention, but to explain the present invention, and the spirit and scope of the present invention are not limited by these embodiments. The scope of protection of the present invention should be interpreted by the claims below, and all technologies within the scope equivalent thereto should be construed as being included in the scope of the present invention.

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

Claims (16)

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

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

In Formulas 1-1 to 1-4, R ¹ to R ⁴ , a to d, X, L ¹ and Ar ¹ are as defined in claim ¹ . The method of claim 1,
Formula 1 is a compound characterized in that represented by one of the formulas 1-5 to 1-8:
<Formula 1-5><Formula1-6><Formula1-7><Formula1-8>

In Formulas 1-5 to 1-8, R ¹ to R ⁴ , a to d, X, L ² , Ar ² and Ar ³ are as defined in claim 1. The method of claim 1,
Ar ¹ is an organic electric device, characterized in that it comprises a compound represented by the formula (2) or (3):
<Formula 2><Formula3>

In Formula 2 and Formula 3,
Z ¹ to Z ⁸ are each independently N or C (R ₁ ), at least one of Z ¹ to Z ⁵ is N, and at least one of Z ⁶ to Z ⁸ is N,
L ₁ is 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,
C ring is a C ₆ ~ C ₆₀ aromatic ring group; Or O, N, S, Si and P is a heterocyclic group of C ₂ ~ C ₆₀ containing at least one heteroatom, the C ring may be further substituted with one or more of the same or different R ₁ ,
R ₁ is hydrogen; heavy hydrogen; halogen; A silane group unsubstituted or substituted with a C ₁ -C ₂₀ alkyl group or a C ₆ -C ₂₀ aryl group; Siloxane group; Boron group; Germanium group; Cyano group; Nitro group; C ₁ -C ₂₀ alkylthio group; C ₁ -C ₂₀ alkoxy group; A C ₆ -C ₂₀ aryloxy group; C ₆ -C ₂₀ arylthio group; A C ₁ -C ₂₀ alkyl group; An alkenyl group of C ₂ -C ₂₀ ; Alkynyl group of C ₂ -C ₂₀ ; C ₆ -C ₂₀ aryl group; Fluorenyl group; O, N, S, Si, and C ₂ -C ₂₀ heterocyclic group including at least one heteroatom selected from the group consisting of P; C ₃ -C ₂₀ aliphatic ring group; A C ₇ -C ₂₀ arylalkyl group; And C ₈ -C ₂₀ is selected from the group consisting of an arylalkenyl group, and neighboring groups may be bonded to each other to form a ring. The method of claim 5,
Formula 3 is a compound, characterized in that selected from the group consisting of the following formulas 3-1 to 3-6:
<Formula 3-1><Formula3-2><Formula3-3>

<Formula 3-4><Formula3-5><Formula3-6>

In Formulas 3-1 to 3-6, Z ⁶ to Z ⁸ , R ₁ , L ₁ are the same as defined in claim 5, o is an integer of 0 to 4, p is an integer of 0 to 6, q Is an integer of 0 to 8, and when each of them is an integer of 2 or more, each of R ₁ is the same as or different from each other, X ¹ and X ² are each independently O or S, and e and f are each an integer of 0 or 1 At least one of e and f is 1. The method of claim 1,
At least one of the Ar ² and Ar ³ is a compound characterized in that it comprises a compound represented by the following formula (4):
<Formula 4>

In Chemical Formula 4,
Y is O, S, N(R ₄ ) or C(R')(R"),
R ₂ , R ₃ , R'and R" are independently of each other hydrogen; deuterium; halogen; a silane group unsubstituted or substituted with a C ₁ -C ₂₀ alkyl group or a C ₆ -C ₂₀ aryl group; a siloxane group; a boron group ; germanium group; a cyano group; a nitro group; a C ₁ -C ₂₀ come alkylthio; C ₁ -C ₂₀ alkoxy group; Im coming aryl of C ₆ -C _20;; C ₆ -C ₂₀ aryloxy C ₁ -C ₂₀ alkyl group; C ₂ -C ₂₀ alkenyl group; C ₂ -C ₂₀ alkynyl group; C ₆ -C ₂₀ aryl group; fluorenyl group; O, N, S, Si and P group consisting of C ₂ -C ₂₀ heterocyclic group containing at least one heteroatom selected from; C ₃ -C ₂₀ aliphatic ring group; C ₇ -C ₂₀ arylalkyl group; And C ₈ -C ₂₀ arylalkenyl group It is selected from the group consisting of irru, and neighboring groups can be bonded to each other to form a ring, and R'and R" can be bonded to each other to form a ring,
R ₄ is a C ₆ -C ₂₀ aryl group; Fluorenyl group; O, N, S, Si, and C ₂ -C ₂₀ heterocyclic group including at least one heteroatom selected from the group consisting of P; And C ₃ -C ₂₀ is selected from the group consisting of an aliphatic ring group,
i is an integer of 0-4, and when i is an integer of 2 or more, each of R ₂ is the same as or different from each other,
j is an integer of 0 to 3, and when j is an integer of 2 or more, each of R ₃ is the same or different from each other. The method of claim 1,
The compound represented by Formula 1 is a compound characterized in that one of the following compounds:

. In an organic electric device comprising an anode, a cathode, and an organic material layer formed between the anode and the cathode,
The organic material layer is an organic electric device, characterized in that it contains a single compound or two or more compounds represented by the formula (1) of claim 1. In an organic electric device comprising an anode, a cathode, an organic material layer formed between the anode and the cathode, and a light efficiency improvement layer,
The light efficiency improvement layer is formed on one side of both sides of the anode or the cathode that is not in contact with the organic material layer,
An organic electric device, characterized in that the organic material layer or the light efficiency improvement layer comprises a compound represented by Formula 1 of claim 1. The method of claim 9 or 10,
The organic material layer comprises at least one of a hole injection layer, a hole transport layer, a light emission auxiliary layer, a light emission layer, an electron transport auxiliary layer, an electron transport layer and an electron injection layer. The method of claim 11,
The compound is an organic electric device, characterized in that contained in at least one of the light emitting layer and the light emitting auxiliary layer. The method of claim 9 or 10,
The organic material layer comprises two or more stacks including a hole transport layer, an emission layer, and an electron transport layer sequentially formed on the anode. The method of claim 13,
The organic material layer further comprises a charge generation layer formed between the two or more stacks. A display device comprising the organic electric device of claim 9 or 10; And
Electronic device comprising a; a control unit for driving the display device. The method of claim 15,
The organic electric device is an electronic device, characterized in that selected from the group consisting of an organic electroluminescent device, an organic solar cell, an organic photoreceptor, an organic transistor, a monochromatic lighting device, and a quantum dot display device.

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