KR20200134877A - An organic electronic element comprising compound for organic electronic element and an electronic device thereof - Google Patents

Abstract

The present invention provides an organic electric device including an anode, a cathode, and an organic material layer between the anode and the cathode, and an electronic device including the organic electric device. By including a mixture of compounds represented by chemical formulas 1, 2 and 3 of the present invention in the organic material layer, it is possible to lower the driving voltage of the organic electric device and improve the luminous efficiency and lifespan of the organic electric device.

Description

An organic electric device including a compound for an organic electric device, and an electronic device therefor

The present invention relates to an organic electric device including a compound for an organic electric device 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 electronic device, and may be formed of, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer.

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 to realize better natural colors 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 in the existing portable display is required. Therefore, power consumption has become a very important factor for portable displays that have a limited power supply source such as a battery, and efficiency and life issues must also 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, the crystallization of organic substances caused by Joule heating during driving decreases. It shows a tendency to increase the lifespan. However, simply improving the organic material layer cannot maximize the efficiency. This is because 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 materials (mobility, interfacial properties, etc.) are optimally combined. .

Accordingly, there is a need to develop a light emitting material that has high thermal stability and can efficiently achieve charge balance in the light emitting layer. In other words, in order to fully exhibit the excellent characteristics of organic electronic devices, materials that make up the organic material layer in the device, such as hole injection materials, hole transport materials, luminescent materials, electron transport materials, electron injection materials, etc., are supported by stable and efficient materials. Although this should be preceded, development of a stable and efficient organic material layer material for an organic electric device has not been sufficiently developed, and among them, development of a host material for a light emitting layer is urgently required.

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

In one aspect, the present invention provides an organic electric device including each compound represented by the following Chemical Formulas 1 to 3 in an emission layer.

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

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 a mixture of the compounds represented by Chemical Formulas 1 to 3 of the present invention as a material for a light emitting layer, the driving voltage of the device can be lowered, and the luminous efficiency and lifespan of the device can be improved.

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

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 multiple 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" as used in the present invention has a'spyro linkage', and the spyro linkage refers to a linkage made by two rings sharing only one atom. At this time, the atoms shared in the two rings are referred to as'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 means a ring of 2 to 60, but is not limited thereto. The term "heteroatom" as used herein refers to N, O, S, P, or Si unless otherwise specified, and the heterocyclic group is a monocyclic type containing a heteroatom, a ring aggregate, a conjugated ring system, spy It means a compound and the like.

The term "heterocyclic group" as used herein 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 means 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, it may be described as the parent compound name'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 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 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, the substituent R ¹ means that the substituent R ¹ does not exist, 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 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 a C ₆ ~ C ₆₀ aromatic ring group; Fluorenyl group; O, N, S, Si, and C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of P; And C ₃ ~ C ₆₀ aliphatic ring group; may be selected from the group consisting of.

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 should 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 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 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 emission layers are formed by the multilayer 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 emission layer, 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), electron injection layer 160, light emitting layer (140, 340, 440), or may be used as a material for the light efficiency improvement layer 180, but preferably, each compound represented by Formulas 1 to 3 of the present invention is mixed One mixture is used as a host of the emission layers 140, 340, and 440, and the compound represented by Formula 1 is a hole transport band layer such as the hole transport layer 130, 330, 430 and/or the light emission auxiliary layer 220 It can 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 materials (mobility, interfacial properties, etc.) are optimally combined.

Therefore, a mixture of the compounds represented by Chemical Formulas 1 to 3 of the present invention is used as a host of the emission layers 140, 340, and 440, and/or the compound represented by Chemical Formula 1 is used in the hole transport layers 130, 330, 430) and/or the light-emitting auxiliary layer 220, by optimizing the energy level and T ₁ value between each organic material layer, and the intrinsic properties of the material (mobility, interfacial properties, etc.) It is possible to improve the life and efficiency of the electric device at the same time.

The organic electroluminescent device according to an embodiment of the present invention may be manufactured using various deposition methods. It can be manufactured using a deposition method such as PVD or CVD. For example, 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 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 printing 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.

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

In an organic electric device comprising an organic electroluminescent device anode, a cathode, and an organic material layer formed between the anode and the cathode according to an aspect of the present invention, the organic material layer includes a phosphorescent emission layer, and the host of the phosphorescent emission layer is represented by the following formula The first compound represented by 1, the second compound represented by the following formula (2), and the third compound represented by the following formula (3) are included.

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

First, Formula 1 will be described.

Each symbol in Formula 1 may be defined as follows.

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; And C ₃ ~ C ₆₀ It may be selected from the group consisting of an aliphatic ring group.

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, biphenyl, naphthyl, terphenyl, phenanthrene , Anthracene, triphenylene, pyrene, chrysene, and the like.

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 ₂₆ heterocyclic group such as pyridine, pyrimidine, pyrazine, pyridazine, Triazine, furan, thiophene, pyrrole, silol, indene, benzofuran, benzothiophene, benzoimidazole, benzothiazole, benzoxazole, benzosilol, dibenzofuran, dibenzothiophene, carbazole, quinoline, Isoquinoline, quinoxaline, quinazoline, phenanthroline, benzonaphthothiophene, benzonaphthofuran, phenylcarbazole, benzocarbazole, phenyl-benzocarbazole, dibenzocarbazole, benzofuropyridine, benzothy Enopyridine, indolocarbazole, 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.

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

When L ¹ to L ³ 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, biphenyl, naphthalene, terphenyl, etc. have.

When L ¹ to L 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 dibenzothiophene, dibenzofuran, carba Sol, phenylcarbazole, and the like.

When L ¹ to L ³ are fluorenyl groups, they may be 9,9-dimethyl-9H-fluorene, 9,9-diphenyl-9H-fluorene, 9,9'-spirofluorene, and the like.

The Ar ¹ ~Ar ³ and L ¹ ~L ³ are each deuterium; 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; 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 containing 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 arylalkenyl group; It may be further substituted with one or more substituents selected from the group consisting of.

Formula 1 may be represented by one of the following Formulas 1-A to 1-I.

<Formula 1-A> <Formula 1-B> <Formula 1-C>

<Formula 1-D> <Formula 1-E> <Formula 1-F>

<Formula 1-G> <Formula 1-H> <Formula 1-I>

In Formulas 1-A to 1-I, each symbol may be defined as follows.

L ¹ to L ³ , Ar ² , Ar ³ are the same as defined in Chemical Formula 1.

A ring, B ring, C ring, D ring, E ring and F ring are independently of each other C ₆ ~ C ₂₀ aromatic ring group, or C containing at least one heteroatom of O, N, S, Si and P _It is a heterocyclic group of ₃ to C ₂₀ , and rings A to F may be further substituted with one or more R ₂ which are the same as or different from each other.

X ⁹ , X ¹⁰ and X ¹¹ are each independently O, S, N(L ₁ -Ar ₁ ) or C(R')(R").

R ³ , R ⁴ , R ₂ , R', R" and Ar ₁ are each independently hydrogen; deuterium; halogen; a silane group unsubstituted or substituted with a C ₁ -C ₂₀ alkyl group or a C ₆ -C ₂₀ aryl group ; Cyano group; Nitro group; C ₁ -C ₂₀ alkoxy group; C ₆ -C ₂₀ aryloxy group; C ₁ -C ₂₀ alkyl group; C ₂ -C ₂₀ alkenyl group; C ₂ -C ₂₀ alkyne Diary; C ₆ -C ₂₀ Aryl group; Fluorenyl group; C ₂ -C ₂₀ heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; And C ₃ -C ₂₀ aliphatic ring group; selected from the group consisting of, 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.

Here, the term "adjacent groups among" may be a neighbor to each other by R ^3, between the adjacent R ³ and R ^4, adjacent to each other a group or R 'and R "the ring formed by bonding to each other, is C ₆ ~ C ₂₀ It may be a C ₃ ~ C ₂₀ heterocyclic group including at least one heteroatom of an aromatic ring group, a fluorene group, O, N, S, Si and P, or an aliphatic ring group of C ₃ -C ₂₀ .

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

L ⁷ 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 ₁ is a single bond; C ₆ ~ C ₂₀ arylene group; Fluorenylene group; C ₃ ~ C ₂₀ aliphatic ring group; And O, N, S, Si and P may be selected from the group consisting of a heterocyclic group of C ₂ ~ C ₂₀ containing at least one heteroatom.

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

Next, the following Chemical Formula 2 will be described.

Each symbol in Formula 2 may be defined as follows.

Ar ⁴ to Ar ⁶ 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; And it may be selected from the group consisting of an aliphatic ring group of C ₃ ~ C ₆₀ , Ar ⁴ ~ Ar ⁶ At least one is a C ₂ ~ C ₆₀ heterocyclic group including a 5-membered ring.

When Ar ⁴ to Ar ⁶ is 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, biphenyl, naphthyl, terphenyl, phenanthrene , Triphenylene, and the like.

When Ar ⁴ to Ar ⁶ is a heterocyclic group, preferably a C ₂ to C ₃₀ heterocyclic group, more preferably a C ₂ to C ₂₂ heterocyclic group such as pyridine, pyrimidine, triazine, quinoline, iso Quinoline, quinazoline, quinoxaline, naphthyridine, acridine, benzoxazole, phenanthroline, dibenzothiophene, dibenzofuran, carbazole, benzocarbazole, phenyl-benzocarbazole, benzonaphthofuran, Benzonaphthothiophene, benzophenanthrofuran, benzophenanthrothiophene, benzoquinoline, benzimidazole, benzothienopyrimidine, benzofuropyrimidine, and the like.

When Ar ⁴ to Ar ⁶ are fluorenyl groups, it may be 9,9-dimethyl-9H-fluorene, 9,9-diphenyl-9H-fluorene, 9,9'-spirofluorene, and the like.

L ⁴ to L ⁶ are each independently a single bond; C ₆ ~ C ₆₀ arylene group; Fluorenylene group; C ₃ ~ C ₆₀ aliphatic ring group; And O, N, S, Si, and a C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of P; It may be selected from the group consisting of.

When L ⁴ to L ⁶ are an arylene group, preferably a C ₆ to C ₃₀ aryl group, more preferably a C ₆ to C ₁₈ aryl group, such as phenylene, biphenyl, naphthalene, terphenyl, etc. have.

When L ⁴ to L ⁶ are heterocyclic groups, preferably a C ₂ to C ₃₀ heterocyclic group, more preferably a C ₂ to C ₁₆ heterocyclic group such as pyridine, pyrimidine, triazine, quinoxaline, Benzimidazole, benzofuropypyrazine, benzothienopyrazine, carbazole, phenyl-carbazole, benzocarbazole, dibenzofuran, dibenzothiophene, and the like.

X ¹ to X ³ are each independently C(R ₁ ) or N, and at least one of X ¹ to X ³ is N. Accordingly, the ring containing X ¹ to X ³ may be pyridine, pyrimidine, triazine or a derivative thereof.

R ₁ is 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 ; And it is selected from the group consisting of aryloxy group of C ₆ ~ C ₃₀ , neighboring groups may be bonded to each other to form a ring. When R ₁ is plural, each of R ₁ may be the same as or different from each other.

However, except for the case of including triphenylene in Ar ⁴ to Ar ⁶ , preferably (L ⁴ -Ar ⁴ ) to (L ⁶ -Ar ⁶ ) except for the case of including triphenylene, further Preferably, the case including triphenylene in Formula 2 is excluded.

The Ar ⁴ ~Ar ⁶ , L ⁴ ~L ⁶ , and R ₁ are each deuterium; 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; 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 containing 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 arylalkenyl group; It may be further substituted with one or more substituents selected from the group consisting of.

Preferably, Formula 2 may be represented by one of Formulas 2-1 to 2-3 below.

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

In Formulas 2-1 to 2-3, L ⁴ to L ⁶ and Ar ⁴ to Ar ⁶ are the same as defined in Formula 2.

Preferably, in Formula 2, at least one of Ar ⁴ to Ar ⁶ may be selected from the group consisting of the following Formulas a-1 to a-5.

<Formula a-1> <Formula a-2>

<Formula a-3> <Formula a-4> <Formula a-5>

In Formulas a-1 to a-5, each symbol may be defined as follows.

X ¹² and X ¹³ are independently of each other N, N(L ₂ -Ar ₂ ), O, S, C(R ₃ ) or C(R ₄ )(R ₅ ), and Y ¹ to Y ¹⁸ are independently of each other N, C or C(R ₆ ). If R ₃ is plural, each of R ₃ is the same or different, and if R ₄ is plural, each of R ₄ is the same or different, and if R ₅ is plural, each of R ₅ is the same or different from each other, and R ₆ In the case of a plurality of these, each of R ₆ is the same as or different from each other.

In formulas a-1, a-2 and a-5, if X ¹² is N or C(R ₃ ), X ¹² is combined with L ⁴ to L ⁵ , so Y ⁹ to Y ¹⁸ is N or C(R ₆ ) If one of Y ⁹ ~ Y ¹⁸ is C, it is combined with L ⁴ ~ L ⁵ , so X ¹² can be N(L ₂ -Ar ₂ ), O, S or C(R ₄ )(R ₅ ) have. That is, X ¹² must be N or C (R ₃ ) or one of Y ⁹ to Y ¹⁸ must be C.

Similarly, in formula a-3, X ¹² is N or C (R ₃ ) or one of Y ¹ to Y ⁸ must be C, and in formula a-4, X ¹² or X ¹³ is N or C (R ₃ ) or Y ^{One of 1} to Y ⁸ must be C.

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

Ar ₂ are each independently a C ₆ -C ₂₀ aryl group; Fluorenyl group; O, N, S, Si, and C ₂ -C ₂₀ heterocyclic group containing at least one heteroatom 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.

R ₃ to R ₆ are each independently hydrogen; heavy hydrogen; halogen; A silane group unsubstituted or substituted with a C ₁ -C ₂₀ alkyl group or a C ₆ -C ₂₀ aryl group; Cyano group; Nitro group; C ₁ -C ₂₀ alkoxy group; A C ₆ -C ₂₀ aryloxy group; A C ₁ -C ₂₀ alkyl group; An alkenyl group of C ₂ -C ₂₀ ; Alkynyl group of C ₂ -C ₂₀ ; C ₆ -C ₂₀ aryl group; Fluorenyl group; O, N, S, Si, and C ₂ -C ₂₀ heterocyclic group containing at least one heteroatom selected from the group consisting of P; And C ₃ -C ₂₀ may be selected from the group consisting of aliphatic ring groups, neighboring groups may be bonded to each other to form a ring, and R ₄ and R ₅ may be bonded to each other to form a ring. Here, the neighboring group may be a neighboring R ₆ .

Specifically, the compound represented by Formula 2 may be one of the following compounds, but is not limited thereto.

.

.

Preferably, the L ¹ to L ⁶ may be each independently selected from the group consisting of the following Formulas b-1 to b-13.

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

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

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

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

In Formulas b-1 to b-13, each symbol may be defined as follows.

Z is O, S, N(L ₃ -Ar ₃ ) or C(R _a )(R _b ).

Z ⁴⁹ , Z ⁵⁰ and Z ⁵¹ are each independently C, C (R _c ) or N, and at least one of Z ⁴⁹ , Z ⁵⁰ and Z ⁵¹ is N.

R ⁸ to R ¹⁰ , and R _a to R _c are each independently hydrogen; heavy hydrogen; halogen; A silane group unsubstituted or substituted with a C ₁ -C ₂₀ alkyl group or a C ₆ -C ₂₀ aryl group; Cyano group; Nitro group; C ₁ -C ₂₀ alkoxy group; A C ₆ -C ₂₀ aryloxy group; A C ₁ -C ₂₀ alkyl group; An alkenyl group of C ₂ -C ₂₀ ; Alkynyl group of C ₂ -C ₂₀ ; C ₆ -C ₂₀ aryl group; Fluorenyl group; O, N, S, Si, and C ₂ -C ₂₀ heterocyclic group containing 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, and neighboring groups may be bonded to each other to form a ring.

a", c", d" and e" are each an integer of 0 to 4, b" is an integer of 0 to 6, f" and g" are each an integer of 0 to 3, and h" is 0 to 2 Is an integer of, i" is an integer of 0 to 3, when each of them is an integer of 2 or more, each of R ^8, each of R ^{9, and} each of R ¹⁰ are the same or different from each other, and when R _c is plural, each of R _c is each Same or different

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

Ar ₃ are each independently a C ₆ -C ₂₀ aryl group; Fluorenyl group; O, N, S, Si, and C ₂ -C ₂₀ heterocyclic group containing at least one heteroatom selected from the group consisting of P; And C ₃ -C ₂₀ is selected from the group consisting of an aliphatic ring group.

Next, the following Chemical Formula 3 will be described.

<Formula 3>

In Formula 3, each symbol may be defined as follows.

X ⁴ to X ⁸ are each independently C(R ₁ ) or N. Accordingly, the ring containing X ⁴ to X ⁸ may be an aromatic ring or a hetero ring containing N.

For example, when the ring containing X ⁴ to X ⁸ is an aromatic ring, it may be preferably an aromatic ring of C ₆ to C ₃₀ , more preferably an aromatic ring of C ₆ to C ₁₈ , and containing N In the case of a heterocyclic group, it may be preferably a C ₂ ~ C ₃₀ heterocyclic group, more preferably a C ₂ ~ C ₁₈ heterocyclic group. For example, the ring containing X ⁴ to X ⁸ is phenyl, naphthalene, triphenylene, phenanthrene, triazine, pyrimidine, pyridine, quinoline, quinazoline, quinoxaline, carbazole, phenylcarbazole, benzoquinoxaline, It may be benzoquinazoline, benzofuroquinazoline, and the like.

R ¹ , R ² and R ₁ 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 ; And it is selected from the group consisting of aryloxy group of C ₆ ~ C ₃₀ , neighboring groups may be bonded to each other to form a ring.

Ring group of a neighboring each other R ^1, is formed in combination with each other between the adjacent R ^2, or adjacent to each other a ring R ₁ is C ₆ ~ C _60; Fluorenyl group; O, N, S, Si, and C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of P; Alternatively, it may be a C ₃ ~ C ₆₀ aliphatic ring group.

When adjacent R ¹ or adjacent R ² are bonded to each other to form an aromatic ring, preferably an aromatic ring group of C ₆ to C ₃₀ , more preferably an aromatic ring group of C ₆ to C ₁₂ , such as, Can form a ring such as benzene, naphthalene, etc., when forming a heterocycle, preferably a C ₂ ~ C ₃₀ heterocyclic group, more preferably a C ₂ ~ C ₁₀ heterocyclic group, such as thiophene , Benzothiophene, furan, benzofuran, pyrrole, phenylpyrrole, indole, phenylindole, etc. can be formed, and when forming an aliphatic ring, preferably C ₃ ~ C ₃₀ aliphatic ring, more preferably C ₃ to C ₁₁ aliphatic rings such as 5,5-dimethylcyclopenta-1,3-diene, dimethylindene, and the like can be formed.

In addition, when adjacent R _1s are bonded to each other to form an aromatic ring, preferably an aromatic ring group of C ₆ to C ₃₀ , more preferably an aromatic ring group of C ₆ to C ₁₄ such as benzene, naphthalene, A ring such as phenanthrene can be formed, and when forming a hetero ring, preferably a C ₂ to C ₃₀ heterocyclic group, more preferably a C ₂ to C ₁₀ heterocyclic group, such as thiophene, Benzothiophene, furan, benzofuran, pyrrole, phenylpyrrole, indole, phenylindole, and the like can be formed.

a is an integer of 0 to 4, when a is an integer of 2 or more, each of R ¹ is the same as 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, When R ₁ is plural, each of R ₁ is the same as or different from each other.

When R ¹ and R ² are an aryl group, preferably a C ₆ to C ₃₀ aryl group, more preferably a C ₆ to C ₁₈ aryl group, such as phenyl, naphthyl, biphenyl, terphenyl, etc. .

When R ¹ and R ² are heterocyclic groups, preferably a C ₂ to C ₃₀ heterocyclic group, more preferably a C ₂ to C ₂₈ heterocyclic group such as carbazole, phenylcarbazole, naphthylcarba Sol, terphenylcarbazole, benzocarbazole, benzocarbazole substituted with biphenyl, dibenzothiophene, benzonaphthothiophene, dibenzofuran, benzonaphthofuran, benzothienocarbazole, benzofuro It may be carbazole and the like.

When R ¹ and R ² are alkyl groups, preferably a C ₁ to C ₁₀ alkyl group, more preferably a C ₁ to C ₄ alkyl group, such as methyl, t-butyl, etc., R ³⁰ and R ³¹ may be In the case of a fluorenyl group, it may be 9,9-dimethylfluorene, 9,9-diphenylfluorene, 9,9'-spirofluorene, and the like.

The rings formed by bonding of R ¹ , R ² , R ₁ , and neighboring 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 arylalkoxy 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 containing 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 arylalkenyl group; It may be further substituted with one or more substituents selected from the group consisting of.

Preferably, Chemical Formula 3 may be represented by Chemical Formula 3-1 below.

<Formula 3-1>

In Formula 3-1, v and w are each an integer of 0 to 2, v+w is an integer of 1 or more, and X ⁴ to X ⁸ are the same as defined in Formula 3 above.

Preferably, Formula 3 may be represented by the following Formula 3-2 or Formula 3-3.

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

In Formula 3-2 or Formula 3-3, X ⁴ to X ⁸ , R ¹ , R ² , and a are the same as defined in Formula 3.

L ⁹ is a single bond; C ₆ ~ C ₆₀ arylene group; Fluorenylene group; O, N, S, Si, and C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of P; And C ₃ ~ C ₆₀ It may be selected from the group consisting of an aliphatic ring group.

X ¹⁴ is N, N(L-Ar), O, S, C(R _d ) or C(R _e )(R _f ).

R ¹² , R ¹³ , and R _d to R _f are each independently hydrogen; heavy hydrogen; halogen; Cyano group; Nitro group; C ₆ ~ C ₂₀ aryl group; Fluorenyl group; O, N, S, Si, and C ₂ ~ C ₂₀ heterocyclic group containing at least one heteroatom of P; C ₃ ~ C ₂₀ aliphatic ring group; C ₁ ~ C ₂₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; Alkynyl group of C ₂ ~ C ₂₀ ; C ₁ ~ C ₂₀ alkoxy group; And C ₆ ~ C ₃₀ is selected from the group consisting of aryloxy groups, neighboring groups may be bonded to each other to form a ring, and R _e and R _f may be bonded to each other to form a ring.

d and f are an integer of 0 to 3, e is an integer of 0 to 5, g is an integer of 0 to 4, when d is an integer of 2 or more, each of R ² is the same as or different from each other, and e and f are an integer of 2 or more. When each of R ¹² is the same or different from each other, when g is an integer of 2 or more, each of R ¹³ is the same or different from each other.

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

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

Preferably, Chemical Formula 3 may be represented by one of Chemical Formulas 3-4 to 3-7 below.

<Formula 3-4> <Formula 3-5> <Formula 3-6> <Formula 3-7>

In Formulas 3-4 to 3-7, X ⁴ to X ⁸ , R ¹ , R ² , b are the same as defined in Formula 3, h is an integer of 0 to 6, and i is of 0 to 8 Is an integer, and when each of these is an integer of 2 or more, each of R ¹ is the same as or different from each other.

Preferably, Formula 3-3 may be represented by one of Formulas 3-8 to 3-17.

<Formula 3-8> <Formula 3-9> <Formula 3-10>

<Formula 3-11> <Formula 3-12> <Formula 3-13>

<Formula 3-14> <Formula 3-15> <Formula 3-16>

<Formula 3-17>

In Formulas 3-8 to 3-17, X ⁴ to X ⁸ , R ¹ , R ² , R ¹² , R ¹³ , L, Ar, a, g are the same as defined in Formula 3-3, and c And n is an integer of 0-3, respectively.

Specifically, the compound represented by Formula 3 may be one of the following compounds, but is not limited thereto.

.

.

In one embodiment of the present invention, the host of the light emitting layer is a mixture of 10 to 70% by weight of the first compound, 10 to 60% by weight of the second compound, and 10 to 50% by weight of the third compound, preferably Preferably, the first compound is 30 to 60% by weight, the second compound is a mixture of 20 to 40% by weight, and the third compound is a mixture of 20 to 40% by weight.

In another embodiment of the present invention, the organic material layer may include two or more stacks including a hole transport layer, a light emitting layer, and an electron transport layer sequentially formed on the anode, and the organic material layer is a charge generation layer formed between the two or more stacks. It may further include.

In another embodiment of the present invention, the organic material layer further includes at least one hole transport band layer formed between the light emitting layer and the anode, and the hole transport band layer includes at least one of a hole transport layer and a light emission auxiliary layer. And includes a compound represented by Formula 1.

Hereinafter, examples for synthesizing the compounds represented by Formulas 1 to 3 according to the present invention and examples for preparing an organic electric device will be described with reference to examples, but the present invention is not limited to the following examples.

Synthesis example

[Synthesis Example 1] Chemical Formula 1

The compound represented by Formula 1 according to the present invention (Final product 1) can be synthesized by the reaction route of Reaction Scheme 1 below. The compound represented by Formula 1 is the applicant's Korean Patent Registration No. 10-1786749 (registered on Oct. 11, 2017), Korean Patent Application No. 2014-0152779 (filed on Nov. 5, 2014), and Korean Patent Application No. 2014-0161275 (2014.11. .19 filed) and the like.

<Scheme 1> (Hal ¹ is I, Br or Cl)

I. Synthesis of Sub1-1

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

<Scheme 2> (Hal is I, Br or Cl)

1. Sub 1-1-76 synthesis example

In a round bottom flask, Aniline (50 g, 536.9 mmol), 3-bromonaphtho[2,3-b]benzofuran (158.9 g, 536.9 mmol), Pd ₂ (dba) ₃ (14.75 g, 16.1 mmol), P(t- Bu) ₃ (6.52 g, 32.2 mmol), NaOt-Bu (103.2 g, 1073.8 mmol), and toluene (2684 mL) were added, followed by reaction at 100 °C. When the reaction is complete, the mixture is extracted with CH ₂ Cl ₂ and water, and the organic layer is dried over MgSO ₄ and concentrated. Thereafter, the concentrate was separated by a silica gel column and recrystallized to obtain 129.5 g of a product. (Yield: 78%)

2. Sub 1-1-110 synthesis example

In a round bottom flask, [1,1'-biphenyl]-4-amine (50 g, 295.5 mmol), 2-bromo-11,11-dimethyl-11H-benzo[b]fluorene (95.5 g, 295.5 mmol), Pd ₂ (dba) ₃ (8.12 g, 8.9 mmol), P(t-Bu) ₃ (3.59 g, 17.7 mmol), NaOt-Bu (56.8 g, 590.9 mmol), toluene (1477 mL) was added and the Sub 1- It proceeded in the same manner as in 1-76 to obtain 87.5 g of a product. (Yield: 72%)

II. Synthesis of Sub 1-2

Sub 1-2 of Scheme 1 may be synthesized according to Scheme 3 below, but is not limited thereto.

<Scheme 3> (Hal ¹ and Hal ² are each independently I, Br or Cl)

III. Synthesis of final compound (final product 1)

1. Synthesis of 1-76

In a round bottom flask, Sub 1-2-76 (142.0 g, 418.6 mmol), Sub 1-1-76 (129.5 g, 418.6 mmol), Pd ₂ (dba) ₃ (11.5 g, 12.6 mmol), P(t- After adding Bu) ₃ (5.1 g, 25.1 mmol), NaOt-Bu (80.5 g, 837.2 mmol), and toluene (2093 mL), the reaction proceeds at 100°C. When the reaction is complete, the mixture is extracted with CH ₂ Cl ₂ and water, and the organic layer is dried over MgSO ₄ and concentrated. Thereafter, the concentrate was separated by a silica gel column and recrystallized to obtain 173.5 g of a product. (Yield: 73%)

2. Synthesis of 1-110

In a round bottom flask, Sub 1-2-110 (52.5 g, 212.6 mmol), Sub 1-1-110 (87.5 g, 212.6 mmol), Pd ₂ (dba) ₃ (5.8 g, 6.4 mmol), P(t- Bu) ₃ (2.6 g, 12.8 mmol), NaOt-Bu (40.9 g, 425.2 mmol), and toluene (1063 mL) were added and proceeded in the same manner as in 1-76 to obtain 92.1 g of the product. (Yield: 75%)

FD-MS (Field Desorption-Mass Spectrometry) values of the compounds 1-1 to 1-130 of the present invention prepared according to the synthesis example as described above are shown in Table 1 below.

[Table 1]

[Synthesis Example 2] Chemical Formula 2

The compound represented by Formula 2 may be synthesized by reacting Sub 3 and Sub 4 as shown in Scheme 4 below, but is not limited thereto.

<Scheme 4> (Hal ³ and Hal ⁴ are I, Br or Cl, G ¹ is L ⁵ or L ⁶ , G ² is Ar ⁵ or Ar ⁶ )

I. Synthesis example of Sub 3

1. Sub 3-1 synthesis example

2-([1,1'-biphenyl]-4-yl)-4,6-dichloro-1,3,5-triazine (CAS Registry Number: 10202-45-6) (20 g, 66.19 mmol), 4 -biphenylboronic acid (CAS Registry Number: 5122-94-1) (13.1 g, 66.19 mmol) is dissolved in THF (370 ml), Pd(PPh ₃ ) ₄ (3.8 g, 3.31 mmol), K ₂ CO ₃ (27.4 g, 198.57 mmol) and water (165 ml) were added and stirred under reflux. When the reaction is complete, the organic layer is concentrated after extraction with ether and water. The concentrated organic layer was dried over MgSO ₄ and concentrated once more. The final concentrate was separated by a silica gel column and recrystallized to obtain 20.8 g of a product. (Yield 75%)

2. Sub 3-8 Synthesis Example

2,4-dichloro-6-(naphthalen-2-yl)-1,3,5-triazine (20 g, 72.43 mmol), (3-(pyridin-2-yl)phenyl)boronic acid (14.3 g, 72.43 mmol), Pd(PPh ₃ ) ₄ (0.05 equivalents), K ₂ CO ₃ (3 equivalents), anhydrous THF and a small amount of water were used in the same manner as the Sub 3-1 synthesis method to synthesize 20.3 g of the product. . (Yield 71%)

3. Sub 3-19 Synthesis Example

2-([1,1'-biphenyl]-4-yl)-4,6-dichloro-1,3,5-triazine (15 g, 49.64 mmol), (9,9-dimethyl-9H-fluoren-3 -yl)boronic acid (11.8 g, 49.64 mmol), Pd(PPh ₃ ) ₄ (0.05 eq), K ₂ CO ₃ (3 eq), anhydrous THF and a small amount of water, the same as the above Sub 3-1 synthesis method 15.7 g of the product was synthesized by proceeding with the method. (Yield 69%)

4.Sub 3-35 Synthesis example

2,4-dichloro-6-phenyl-1,3,5-triazine (30 g, 132.71 mmol), dibenzo[b,d]furan-2-ylboronic acid (28.1 g, 132.71 mmol), Pd(PPh ₃ ) _{Using 4} (0.05 equivalents), K ₂ CO ₃ (3 equivalents), anhydrous THF and a small amount of water, 30.8 g of the product was synthesized by proceeding in the same manner as in the above Sub 3-1 synthesis method. (Yield 65%)

The compound belonging to Sub 3 may be the following compound, but is not limited thereto, and Table 2 shows the FD-MS (Field Desorption-Mass Spectrometry) values of the following compounds.

[Table 2]

II. Synthesis example of Sub 4

Sub 4 of Scheme 4 may be synthesized by the reaction route of Scheme 5 below, but is not limited thereto.

<Scheme 5> (Hal ⁵ is I, Br and Cl)

1. Sub 4-2 Synthesis Example

4-bromo-1,1'-biphenyl (5 g, 21.45 mmol) bis(pinacolato)diboron (7.1 g, 27.89 mmol), PdCl ₂ (dppf) _, (0.78 g, 1.07 mmol), KOAc (6.3 g, 64.35 mmol) and DMF (270 ml) were added and stirred at 120° C. to reflux. When the reaction is finished, the temperature of the reactant is cooled to room temperature, extracted with MC, and washed with 1N HCl. The organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was separated by a silica gel column to obtain 3.4 g (80%) of Sub 4-2.

2. Sub 4-37 Synthesis Example

2-bromodibenzo[b,d]furan (10 g, 40.47 mmol) to bis(pinacolato)diboron (13.3 g, 52.61 mmol), PdCl ₂ (dppf) _, (0.05 eq), KOAc (3 eq), anhydrous DMF After addition, 7 g of the product was synthesized by proceeding in the same manner as in the above Sub 4-2 synthesis method. (Yield 82%)

The compound belonging to Sub 4 may be the following compound, but is not limited thereto, and Table 3 shows the FD-MS (Field Desorption-Mass Spectrometry) values of the following compounds.

[Table 3]

III. Synthesis example of final compound (final product 2)

1. Synthesis example of 2-9

Sub 4-36 (2.8 g, 13.1 mmol) in Sub 3-1 (5 g, 11.91 mmol) and dissolved in THF (70 ml), Pd(PPh ₃ ) ₄ (0.7 g, 0.6 mmol), K ₂ CO ₃ (5 g, 35.73 mmol), and water (30 ml) were added and stirred under reflux. When the reaction is complete, the organic layer is concentrated after extraction with ether and water. The concentrated organic layer was dried over MgSO ₄ and concentrated once more. The final concentrate was separated by a silica gel column and recrystallized to obtain 5.4 g of the product. (Yield 71%)

2. Synthesis example of 2-29

Sub 3-39 (4 g, 14.94 mmol) to Sub 4-47 (6.2 g, 16.43 mmol), Pd(PPh ₃ ) ₄ (0.05 eq), K ₂ CO ₃ (3 eq), anhydrous THF and a small amount of water Was added and proceeded in the same manner as in the above synthesis method 2-9 to synthesize 8.1 g of the product. (Yield 84%)

3. Synthesis example of 2-62

Sub 3-33 (4 g, 10.7 mmol) to Sub 4-32 (2.7 g, 11.8 mmol), Pd(PPh ₃ ) ₄ (0.05 eq), K ₂ CO ₃ (3 eq), anhydrous THF and a small amount of water Was added and proceeded in the same manner as in the above synthesis method 2-9 to synthesize 4.4 g of the product. (Yield 80%)

4. Synthesis example of 2-115

Sub 3-41 (10 g, 37.35 mmol) to Sub 4-48 (4.7 g, 18.5 mmol), Pd(PPh ₃ ) ₄ (0.1 eq), K ₂ CO ₃ (6 eq), anhydrous THF and a small amount of water And 9.1 g of the product was synthesized by proceeding in the same manner as in the above synthesis method 2-9. (Yield 78%)

The FD-MS values of the compounds 2-1 to 2-116 of the present invention prepared according to the synthesis example as described above are shown in Table 4 below.

[Table 4]

[ Synthesis example 3] Formula 3

The compound represented by Formula 3 according to the present invention (final product 3) may be synthesized by reacting Sub 5 and Sub 6 as shown in Scheme 6 below, but is not limited thereto.

<Scheme 6> (Hal ⁷ is I, Br or Cl)

I. Sub 5 Synthesis example

Sub 5 of Scheme 6 may be synthesized by the reaction route of Scheme 7 below, but is not limited thereto.

<Scheme 7> (Hal ⁸ And Hal ⁹ is I, Br or Cl)

1. Sub 5-7 synthesis example

(1) Synthesis of Sub5-a-1

After dissolving 3-bromo-9-phenyl-9H-carbazole (50.0 g, 155 mmol) in DMF, bis(pinacolato)diboron (43.3 g, 171 mmol), PdCl ₂ (dppf) (3.40 g, 4.65 mmol), KOAc (64.3 g, 465 mmol) was added and stirred at 90°C. When the reaction was completed, DMF was removed through distillation, and extraction was performed with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ , concentrated, and the resulting compound was separated by a silica gel column and recrystallized to obtain 41.8 g (yield: 73%) of the product.

(2) Synthesis of Sub5-7

After dissolving Sub5-a-1 (41.8 g, 113 mmol) in THF, 3-bromo-9H-carbazole (27.8 g, 113 mmol), Pd(PPh ₃ ) ₄ (7.83 g, 6.78 mmol), K ₂ CO ₃ (2.74 g, 13.6 mmol), water was added and stirred at 80°C. When the reaction was completed, the resultant was extracted with CH ₂ Cl ₂ and water, and the organic layer was dried over MgSO ₄ and concentrated. The resulting compound was separated by a silica gel column and recrystallized to obtain 37.9 g (yield: 82%) of the product.

2. Sub 5-16 Synthesis Example

(1) Synthesis of Sub5-a-2

Naphthalen-1-ylboronic acid (30.0 g, 174 mmol), 4-bromo-2-iodo-1-nitrobenzene (57.2 g, 174 mmol), Pd(PPh ₃ ) ₄ (12.1 g, 10.5 mmol), K ₂ CO ₃ (72.3 g, 523 mmol) was used and proceeded in the same manner as for the synthesis of Sub5-7 to obtain 44.6 g (yield: 78%) of the product.

(2) Synthesis of Sub5-a-3

Sub5-a-2 (44.6 g, 136 mmol) was dissolved in o- dichlorobenzene (350 mL), triphenylphosphine (89.2 g, 340 mmol) was added, followed by stirring at 200°C. When the reaction was completed, o- dichlorobenzene was removed through distillation, and extracted with CH ₂ Cl ₂ and water. Thereafter, the organic layer was dried over MgSO ₄ , concentrated, and the resulting compound was separated by a silica gel column and recrystallized to obtain 33.4 g (yield: 83%) of the product.

(3) Synthesis of Sub5-16

Sub5-a-3 (33.4 g, 113 mmol), Sub5-a-1 (41.7 g, 113 mmol), Pd(PPh ₃ ) ₄ (7.83 g, 6.78 mmol), K ₂ CO ₃ (46.8 g, 339 mmol) ) To obtain 40.9 g (yield: 79%) of the product by proceeding in the same manner as the synthesis method of Sub5-7.

3. Sub 5-26 Synthesis Example

(1) Synthesis of Sub5-a-4

2-bromodibenzo[b,d]thiophene (50.0 g, 190 mmol), Bis(pinacolato)diboron (53.7 g, 209 mmol), PdCl ₂ (dppf) (4.17 g, 5.70 mmol), KOAc (55.9 g, 570 mmol) ) To obtain 41.8 g (yield: 71%) of the product by proceeding in the same manner as the synthesis method of Sub5-a-1.

(2) Synthesis of Sub5-26

Sub5-a-4 (41.8 g, 135 mmol), Sub5-a-3 (40.0 g, 135 mmol), Pd(PPh ₃ ) ₄ (9.36 g, 8.10mmol), K ₂ CO ₃ (56.0 g, 405 mmol) ) To obtain 44.2 g (yield: 82%) of the product by proceeding in the same manner as for the synthesis of Sub5-7.

4. Sub 5-33 Synthesis Example

(1) Synthesis of Sub5-a-5

2-bromodibenzo[b,d]thiophene (60.0 g, 228 mmol), (2-nitrophenyl)boronic acid (38.1 g, 228 mmol), Pd(PPh ₃ ) ₄ (15.8 g, 13.7 mmol), K ₂ CO ₃ (94.5 g, 684 mmol) was used in the same manner as for the synthesis of Sub5-7 to obtain 58.5 g of a product (yield: 84%).

(2) Synthesis of Sub5-a-6

Sub5-a-5 (58.5 g, 192 mmol) and triphenylphosphine (126 g, 479 mmol) were used in the same manner as for the synthesis of Sub5-a-3 to obtain 45.0 g of a product (yield: 86%).

(3) Synthesis of Sub5-a-7

In a round bottom flask, add Sub 5-a-6 (45.0 g, 165 mmol), N-Bromosuccinimide (29.3 g, 165 mmol), and Methylene chloride (350 mL), and stir at room temperature for 4 hours. When the reaction is complete, distilled water is added, followed by extraction with methylene chloride and water. Thereafter, the organic layer was dried over MgSO ₄ , concentrated, and the resulting compound was recrystallized with methylene chloride and hexane to obtain 41.8 g (yield: 72%) of the product.

(4) Sub5 Synthesis of -33

Sub5-a-1 (43.8 g, 119 mmol), Sub5-a-7 (41.8 g, 119 mmol), Pd(PPh ₃ ) ₄ (8.22 g, 7.12 mmol), K ₂ CO ₃ (49.2 g, 356 mmol) ) To obtain 50.0 g (yield: 82%) of the product by proceeding in the same manner as the synthesis method of Sub5-7.

5.Sub 5-36 Synthesis example

(One) Sub5 -a-8 synthesis

After dissolving 1,4-dibromo-9-phenyl-9H-carbazole (50.0 g, 125 mmol) with toluene (500 mL), 2-chloroaniline (15.9 g, 125 mmol), Pd ₂ (dba) ₃ (3.42 g , 3.74 mmol), P( t -Bu) ₃ (1.51 g, 7.48 mmol), NaO t -Bu (24.0 g, 249 mmol) were added and stirred at 120°C. When the reaction is complete, the mixture is extracted with CH ₂ Cl ₂ and water, and the organic layer is dried over MgSO ₄ and concentrated. Thereafter, the concentrate was separated by a silica gel column and recrystallized to obtain 43.0 g (yield: 77%) of the product.

(2) Sub5 Synthesis of -a-9

Sub5-a-8 (43.0 g, 96.0 mmol) and triphenylphosphine (62.9 g, 240 mmol) were used in the same manner as for the synthesis of Sub5-a-3 to obtain 32.0 g (yield: 81%) of the product.

(3) Sub5 Synthesis of -36

Sub5-a-9 (32.0 g, 77.7 mmol), Sub5-a-10 (28.7 g, 77.7 mmol), Pd(PPh ₃ ) ₄ (5.39 g, 4.66 mmol), K ₂ CO ₃ (32.2 g, 233 mmol) ) To obtain 33.4 g (yield: 75%) of the product by proceeding in the same manner as the synthesis method of Sub5-7.

6. Sub 5-40 Synthesis Example

(1) Synthesis of Sub5-a-11

Dibenzo[b,d]thiophen-3-ylboronic acid (50.0 g, 219 mmol), 4-bromo-2-iodo-1-nitrobenzene (71.9 g, 219 mmol), Pd(PPh ₃ ) ₄ (15.2g, 13.2 mmol), K ₂ CO ₃ (90.8 g, 657 mmol) was used to obtain 64.0 g (yield: 76%) of the product by proceeding in the same manner as for the synthesis of Sub5-7.

(2) Synthesis of Sub5-a-12

Sub5-a-11 (64.0 g, 166 mmol) and triphenylphosphine (10.9 g, 416 mmol) were used in the same manner as for the synthesis of Sub5-a-3 to obtain 46.9 g of a product (yield: 80%).

(3) Synthesis of Sub5-40

Sub5-a-12 (46.9 g, 133 mmol), Sub5-a-10 (49.3 g, 133 mmol), Pd(PPh ₃ ) ₄ (9.25 g, 8.01 mmol), K ₂ CO ₃ (55.3 g, 400 mmol) ) To obtain 58.4 g (yield 85%) of the product by proceeding in the same manner as the synthesis method of Sub5-7.

7. Sub 5-74 Synthesis Example

(One) Sub5 Synthesis of -a-13

Naphthalene-1-ylboronic acid (34.0 g, 198 mmol), 1-bromo-2-nitronaphthalene (49.8g, 198 mmol), Pd(PPh ₃ ) ₄ (1.37 g, 11.9 mmol), K ₂ CO ₃ (82.0 g , 593 mmol) was used in the same manner as for the synthesis of Sub5-7 to obtain 51.0 g (yield: 86%) of the product.

(2) Synthesis of Sub5-74

Sub5-a-13 (51.0 g, 170 mmol) and triphenylphosphine (111 g, 425 mmol) were used in the same manner as for the synthesis of Sub5-a-3 to obtain 31.8 g (yield: 70%) of the product.

The compound belonging to Sub 5 may be the following compound, but is not limited thereto, and Table 5 shows the FD-MS (Field Desorption-Mass Spectrometry) values of the following compounds.

[Table 5]

Ⅱ. Synthesis example of Sub 6

The compound belonging to Sub 6 may be the following compound, but is not limited thereto, and Table 6 shows the FD-MS (Field Desorption-Mass Spectrometry) value of the compound belonging to Sub 6.

[Table 6]

III. Synthesis of final compound (final product 3)

1. 3-30 Synthesis Example

After dissolving Sub 5-7 (37.9 g, 92.8 mmol) with Toluene (400ml), Sub 6-2 (21.6 g, 92.8 mmol), Pd ₂ (dba) ₃ (2.55 g, 2.78 mmol), P( t- Bu) ₃ (1.13 g, 5.57 mmol), NaO t -Bu (17.8 g, 186 mmol) was added and stirred at 100°C. When the reaction is complete, the mixture is extracted with CH ₂ Cl ₂ and water, and the organic layer is dried over MgSO ₄ and concentrated. Thereafter, the concentrate was separated by a silica gel column and recrystallized to obtain 45.8 g (yield: 88%) of the product.

2. 3-49 Synthesis Example

Sub5-16 (40.9 g, 89.2 mmol), Sub6-2 (20.8 g, 89.2 mmol), Pd ₂ (dba) ₃ (2.45 g, 2.68 mmol), P( t -Bu) ₃ (1.08 g, 5.35 mmol) , NaO t -Bu (17.1 g, 178 mmol) was used in the same manner as in the synthesis method of 3-30 to obtain 45.8 g (yield: 84%) of the product.

3. 3-59 Synthesis Example

Sub5-26 (44.2 g, 111 mmol), Sub6-3 (25.8 g, 111 mmol), Pd ₂ (dba) ₃ (3.04 g, 3.32 mmol), P( t -Bu) ₃ (1.34 g, 6.64 mmol) , NaO t -Bu (21.3 g, 221 mmol) was used in the same manner as in the synthesis method of 3-30 to obtain 52.5 g (yield: 86%) of the product.

4. 3-108 Synthesis Example

Sub5-74 (31.8 g, 119 mmol), Sub6-23 (36.8 g, 119 mmol), Pd ₂ (dba) ₃ (3.27 g, 3.57 mmol), P( t- Bu) ₃ (1.44 g, 7.14mmol) , NaO t -Bu (22.9 g, 238 mmol) was used in the same manner as in the synthesis method of 3-30 to obtain 53.1 g (yield 90%) of the product.

The FD-MS values of the compounds 3-1 to 3-135 of the present invention prepared according to the synthesis example as described above are shown in Table 7 below.

[Table 7]

Manufacturing evaluation of organic electric devices

[ Example 1] to [ Example 36] Green organic electroluminescent device ( Emitting layer Mixed phosphorescent host)

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

Next, a light emitting layer having a thickness of 30 nm was formed on the hole transport layer, in which case the first compound (first host) represented by Chemical Formula 1 of the present invention, and the second compound represented by Chemical Formula 2 of the present invention, as shown in Table 8 below. A mixture obtained by mixing a compound (second host) and a compound (third host) represented by Chemical Formula 3 of the present invention in a weight ratio of 1:5:4 as a host, tris(2-phenylpyridine)-iridium (hereinafter "Ir ( ppy) ₃ ") was used as a dopant, but the dopant was doped so that the weight ratio of the host and the dopant 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. Formed.

Thereafter, 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, and then Al was deposited to a thickness of 150 nm to form a cathode, thereby manufacturing an organic electroluminescent device.

[ Example 37] and [ Example 38]

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that the first compound, the second compound, and the third compound were mixed at 5:2:3 as the host material of the emission layer.

[ Comparative example 1] to [ Comparative example 3]

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that Compound 2-13, Compound 2-45, and ref 1 below were used alone as host materials for the emission layer.

[Comparative Example 4]

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that compounds 2-45 and 3-36 were mixed at 5:5 as a host material for the emission layer.

[Comparative Example 5]

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that ref 1 and Compound 3-36 were mixed at 5:5 as a host material for the emission layer.

[Comparative Example 6]

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that Compound 1-21, Ref 1, and Compound 3-34 were mixed and used as a host material of the emission layer.

[ Comparative example 7]

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that Compound 1-21, Compound 3-34, and ref 2 were mixed and used as host materials for the emission layer.

<ref 1> <ref 2>

By applying a forward bias DC voltage to the organic electroluminescent devices prepared according to Examples 1 to 38 and Comparative Examples 1 to 7 of the present invention, electroluminescence (EL) characteristics were obtained with PR-650 of photoresearch. It was measured, and the T95 life was measured through a life measurement equipment of McScience at 5000 cd/m ² reference brightness, and the measurement results are shown in Table 8 below.

[Table 8]

As can be seen from the results of Table 8, when the compound for an organic electroluminescent device of the present invention represented by Chemical Formula 1, Chemical Formula 2, and Chemical Formula 3 is mixed and used as a phosphorescent host (Examples 1 to 38), a single material was used. Devices (Comparative Examples 1 to 3), devices using a mixture of two types of compounds (Comparative Examples 4 and 5), and a mixture of each compound represented by Formulas 1 and 3 and 3 types of compounds ref 1 or ref 2 It can be seen that the driving voltage, efficiency, and lifespan are significantly improved compared to the devices used (Comparative Examples 6 and 7).

Looking at the comparative example, compared to the case of using one type of compound, when two types of compounds are mixed and used, the lifespan and efficiency are improved, and when three types of compounds are mixed and used (Comparative Examples 6 and 7), the most efficient It can be confirmed that it is excellent.

However, compared to Comparative Examples 6 and 7, in the case of the present invention in which three compounds represented by the respective formulas of the present invention were mixed, the driving voltage was lowered and the lifespan and efficiency were significantly improved.

When the compounds represented by Formulas 1 to 3 are mixed as in the present invention, the reason for the excellent characteristics of the device is that the hole transport material and the HOMO energy level difference are minimized by using the amine compound represented by Formula 1 as a host. Hole transport from the transport layer to the light emitting layer is facilitated, so that holes can be provided to the light emitting layer more quickly, and the compound of Formula 2 of the present invention having a limited substituent has a deep LUMO energy level, thus minimizing the difference between the electron transport material and the LUMO energy level. It is more suitable for electron transfer, because the compound represented by Formula 3 has an appropriate energy band and high T1.

Therefore, when the compounds of Formulas 1 to 3 are mixed, the ability to inject and transport holes and electrons toward the light emitting layer is improved, and stability is increased. As a result, driving of the entire device is improved, and the charge balance of holes and electrons in the light emitting layer is increased, so that light emission is well performed inside the light emitting layer rather than the hole transport layer interface, thereby increasing the efficiency. Seems to have maximized the lifespan of In conclusion, the combination of Formula 1, Formula 2, and Formula 3 electrochemically synergistically improves the performance of the device as a whole.

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 is in the scope of the following claims. It should be interpreted by, and all technologies within the scope equivalent thereto should be interpreted 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 (20)

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 includes a phosphorescent emission layer, and the host of the phosphorescent emission layer includes a first compound represented by the following formula (1), a second compound represented by the following formula (2), and a third compound represented by the following formula (3). Organic electric devices characterized by:
<Formula 1><Formula2><Formula3>

In Formulas 1 to 3,
Ar ¹ to Ar ⁶ 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; And C ₃ to C ₆₀ is selected from the group consisting of an aliphatic ring group, and at least one of Ar ⁴ to Ar ⁶ is a C ₂ to C ₆₀ heterocyclic group including a 5-membered ring, and triphenyl from Ar ⁴ to Ar ⁶ Except for Ren,
L ¹ to L ⁶ are each independently a single bond; C ₆ ~ C ₆₀ arylene group; Fluorenylene group; C ₃ ~ C ₆₀ aliphatic ring group; And O, N, S, Si and P containing at least one heteroatom C ₂ ~ C ₆₀ heterocyclic group; is selected from the group consisting of,
X ¹ to X ⁸ are each independently C(R ₁ ) or N, and at least one of X ¹ to X ³ is N,
R ¹ , R ² and R ₁ 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 ; And C ₆ ~ C ₃₀ is selected from the group consisting of aryloxy group, neighboring groups can be bonded to each other to form a ring,
a is an integer of 0 to 4, and when a is an integer of 2 or more, each of R ¹ is the same as 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 as or different from each other,
When R ₁ is plural, each of R ₁ is the same as or different from each other,
The Ar ¹ to Ar ⁶ , L ¹ to L ⁶ , R ¹ , R ² , R ₁ , 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 arylalkoxy 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 containing 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,
Formula 1 is an organic electric device, characterized in that represented by one of the following formula 1-A to formula 1-I:
<Formula 1-A><Formula1-B><Formula1-C>

<Formula 1-D><Formula1-E><Formula1-F>

<Formula 1-G><Formula1-H><Formula1-I>

In Formula 1-A to Formula 1-I, L ¹ to L ³ , Ar ² , Ar ³ are the same as defined in claim 1,
A ring, B ring, C ring, D ring, E ring and F ring are independently of each other C ₆ ~ C ₂₀ aromatic ring group, or C containing at least one heteroatom of O, N, S, Si and P _It is a heterocyclic group of ₃ to C ₂₀ , and rings A to F may be further substituted with one or more R ₂ which are the same as or different from each other,
X ⁹ , X ¹⁰ and X ¹¹ are each independently O, S, N(L ₁ -Ar ₁ ) or C(R')(R"),
R ³ , R ⁴ , R ₂ , R', R" and Ar ₁ are each independently hydrogen; deuterium; halogen; a silane group unsubstituted or substituted with a C ₁ -C ₂₀ alkyl group or a C ₆ -C ₂₀ aryl group ; Cyano group; Nitro group; C ₁ -C ₂₀ alkoxy group; C ₆ -C ₂₀ aryloxy group; C ₁ -C ₂₀ alkyl group; C ₂ -C ₂₀ alkenyl group; C ₂ -C ₂₀ alkyne Diary; C ₆ -C ₂₀ Aryl group; Fluorenyl group; C ₂ -C ₂₀ heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; And C ₃ -C ₂₀ aliphatic ring group; selected from the group consisting of, adjacent 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,
c is an integer of 0-4, and when c is an integer of 2 or more, each of R ³ is the same as or different from each other,
L ⁷ 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 ₁ is a single bond; C ₆ ~ C ₂₀ arylene group; Fluorenylene group; C ₃ ~ C ₂₀ aliphatic ring group; And O, N, S, Si and P is selected from the group consisting of a C ₂ ~ C ₂₀ heterocyclic group containing at least one heteroatom. The method of claim 1,
Formula 2 is an organic electric device, characterized in that represented by one of the following Formulas 2-1 to 2-3:
<Formula 2-1><Formula2-2><Formula2-3>

In Formulas 2-1 to 2-3, L ⁴ to L ⁶ and Ar ⁴ to Ar ⁶ are the same as defined in claim 1. The method of claim 1,
At least one of the Ar ⁴ to Ar ⁶ is an organic electric device, characterized in that selected from the group consisting of the following formulas a-1 to a-5:
<Formula a-1><Formulaa-2>

<Formula a-3><Formulaa-4><Formulaa-5>

In Formulas a-1 to a-5,
X ¹² and X ¹³ are independently of each other N, N(L ₂ -Ar ₂ ), O, S, C(R ₃ ) or C(R ₄ )(R ₅ ), and Y ¹ to Y ¹⁸ are independently of each other N, C or C (R ₆ ),
L ₂ is each independently a single bond; C ₆ ~ C ₂₀ arylene group; Fluorenylene group; C ₃ ~ C ₂₀ aliphatic ring group; And O, N, S, Si and P is selected from the group consisting of a heterocyclic group of C ₂ ~ C ₂₀ containing at least one heteroatom,
Ar ₂ are each independently a C ₆ -C ₂₀ aryl group; Fluorenyl group; O, N, S, Si, and C ₂ -C ₂₀ heterocyclic group containing at least one heteroatom selected from the group consisting of P; And C ₃ -C ₂₀ is selected from the group consisting of an aliphatic ring group,
R ₃ to R ₆ are each independently hydrogen; heavy hydrogen; halogen; A silane group unsubstituted or substituted with a C ₁ -C ₂₀ alkyl group or a C ₆ -C ₂₀ aryl group; Cyano group; Nitro group; C ₁ -C ₂₀ alkoxy group; A C ₆ -C ₂₀ aryloxy group; A C ₁ -C ₂₀ alkyl group; An alkenyl group of C ₂ -C ₂₀ ; Alkynyl group of C ₂ -C ₂₀ ; C ₆ -C ₂₀ aryl group; Fluorenyl group; O, N, S, Si, and C ₂ -C ₂₀ heterocyclic group containing at least one heteroatom selected from the group consisting of P; And C ₃ -C ₂₀ may be selected from the group consisting of aliphatic ring groups, neighboring groups may be bonded to each other to form a ring, and R ₄ and R ₅ may be bonded to each other to form a ring. The method of claim 1,
The L ¹ to L ⁶ are each independently an organic electric device, characterized in that selected from the group consisting of the following formulas b-1 to b-13:
<Formula b-1><Formulab-2><Formulab-3>

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

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

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

In Formulas b-1 to b-13,
Z is O, S, N(L ₃ -Ar ₃ ) or C(R _a )(R _b ),
Z ⁴⁹ , Z ⁵⁰ and Z ⁵¹ are each independently C, C (R _c ) or N, and at least one of Z ⁴⁹ , Z ⁵⁰ and Z ⁵¹ is N,
R ⁸ to R ¹⁰ , and R _a to R _c are each independently hydrogen; heavy hydrogen; halogen; A silane group unsubstituted or substituted with a C ₁ -C ₂₀ alkyl group or a C ₆ -C ₂₀ aryl group; Cyano group; Nitro group; C ₁ -C ₂₀ alkoxy group; A C ₆ -C ₂₀ aryloxy group; A C ₁ -C ₂₀ alkyl group; An alkenyl group of C ₂ -C ₂₀ ; Alkynyl group of C ₂ -C ₂₀ ; C ₆ -C ₂₀ aryl group; Fluorenyl group; O, N, S, Si, and C ₂ -C ₂₀ heterocyclic group containing 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, and adjacent groups may be bonded to each other to form a ring,
a", c", d" and e" are each an integer of 0 to 4, b" is an integer of 0 to 6, f" and g" are each an integer of 0 to 3, and h" is 0 to 2 Is an integer of, i" is an integer of 0 to 3, and when each of them is an integer of 2 or more, each of R ^8, each of R ^{9, and} each of R ¹⁰ are the same or different, and when R _c is plural, each of R _c The same or different,
L ₃ is each independently a single bond; C ₆ ~ C ₂₀ arylene group; Fluorenylene group; C ₃ ~ C ₂₀ aliphatic ring group; And O, N, S, Si and P is selected from the group consisting of a heterocyclic group of C ₂ ~ C ₂₀ containing at least one heteroatom,
Ar ₃ are each independently a C ₆ -C ₂₀ aryl group; Fluorenyl group; O, N, S, Si, and C ₂ -C ₂₀ heterocyclic group containing at least one heteroatom selected from the group consisting of P; And C ₃ -C ₂₀ is selected from the group consisting of an aliphatic ring group. The method of claim 1,
Formula 3 is an organic electric device, characterized in that represented by the following formula 3-1:
<Formula 3-1>

In Formula 3-1, v and w are each an integer of 0 to 2, v+w is an integer of 1 or more, and X ⁴ to X ⁸ are as defined in claim 1. The method of claim 1,
Formula 3 is an organic electric device, characterized in that represented by the following formula 3-2 or formula 3-3:
<Formula 3-2><Formula3-3>

In Formula 3-2 or Formula 3-3, X ⁴ ~X ⁸ , R ¹ , R ² , a are the same as defined in claim 1,
L ⁹ is a single bond; C ₆ ~ C ₆₀ arylene group; Fluorenylene group; O, N, S, Si, and C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of P; And C ₃ ~ C ₆₀ is selected from the group consisting of an aliphatic ring group,
X ¹⁴ is N, N(L-Ar), O, S, C(R _d ) or C(R _e )(R _f ),
R ¹² , R ¹³ , and R _d to R _f are each independently hydrogen; heavy hydrogen; halogen; Cyano group; Nitro group; C ₆ ~ C ₂₀ aryl group; Fluorenyl group; O, N, S, Si, and C ₂ ~ C ₂₀ heterocyclic group containing at least one heteroatom of P; C ₃ ~ C ₂₀ aliphatic ring group; C ₁ ~ C ₂₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; Alkynyl group of C ₂ ~ C ₂₀ ; C ₁ ~ C ₂₀ alkoxy group; And C ₆ ~ C ₃₀ is selected from the group consisting of aryloxy groups, neighboring groups may be bonded to each other to form a ring, and R _e and R _f may be bonded to each other to form a ring,
d and f are an integer of 0 to 3, e is an integer of 0 to 5, g is an integer of 0 to 4,
When d is an integer of 2 or more, each of R ² is the same as or different from each other,
When e and f are integers of 2 or more, each of R ¹² is the same as or different from each other,
When g is an integer of 2 or more, each of R ¹³ is the same as or different from each other,
L is a single bond; C ₆ ~ C ₂₀ arylene group; Fluorenylene group; O, N, S, Si, and C ₂ ~ C ₂₀ heterocyclic group containing at least one heteroatom of P; And C ₃ ~ C ₂₀ is selected from the group consisting of an aliphatic ring group,
Ar is a C ₆ ~ C ₂₀ aryl group; Fluorenyl group; O, N, S, Si, and C ₂ ~ C ₂₀ heterocyclic group containing at least one heteroatom of P; And C ₃ ~ C ₂₀ is selected from the group consisting of an aliphatic ring group. The method of claim 1,
Formula 3 is an organic electric device, characterized in that represented by one of the following formulas 3-4 to 3-7:
<Formula 3-4><Formula3-5><Formula3-6><Formula3-7>

In Formulas 3-4 to 3-7, X ⁴ to X ⁸ , R ¹ , R ² , b are the same as defined in claim 1, h is an integer of 0 to 6, and i is of 0 to 8 Is an integer, and when each of these is an integer of 2 or more, each of R ¹ is the same as or different from each other. The method of claim 7,
Formula 3-3 is an organic electric device, characterized in that represented by one of the following Formulas 3-8 to 3-17:
<Formula 3-8><Formula3-9><Formula3-10>

<Formula 3-11><Formula3-12><Formula3-13>

<Formula 3-14><Formula3-15><Formula3-16>

<Formula 3-17>

In Formulas 3-8 to 3-17, X ⁴ to X ⁸ , R ¹ , R ² , R ¹² , R ¹³ , L, Ar, a, g are the same as defined in Formula 3-3, and c And n is an integer of 0-3, respectively. The method of claim 1,
An organic electric device, characterized in that the compound represented by Formula 1 is one of the following compounds:

. The method of claim 1,
An organic electric device, characterized in that the compound represented by Formula 2 is one of the following compounds:

. The method of claim 1,
An organic electric device, characterized in that the compound represented by Formula 3 is one of the following compounds:

. The method of claim 1,
The host is an organic electric device, characterized in that a mixture of 10 to 70% by weight of the first compound, 10 to 60% by weight of the second compound, and 10 to 50% by weight of the third compound. The method of claim 13,
The host is an organic electric device, characterized in that a mixture of 30 to 60% by weight of the first compound, 20 to 40% by weight of the second compound, and 20 to 40% by weight of the third compound. The method of claim 1,
The organic material layer comprises at least two stacks including a hole transport layer, an emission layer, and an electron transport layer sequentially formed on the anode. The method of claim 15,
The organic material layer further comprises a charge generation layer formed between the two or more stacks. The method of claim 1,
The organic material layer further includes at least one hole transport band layer formed between the light emitting layer and the anode,
The hole transport band layer includes at least one of a hole transport layer and an emission auxiliary layer, and includes a compound represented by Chemical Formula 1. The method of claim 1,
An organic electric device comprising: a light efficiency improving layer formed on a layer not in contact with the organic material layer on both sides of the anode or on both sides of the cathode. A display device comprising the organic electric device of claim 1; And
Electronic device comprising a; a control unit for driving the display device. The method of claim 19,
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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