KR102826373B1 - 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 element including an anode, a cathode, and an organic layer between the anode and the cathode, and an electronic device including the organic electric element, wherein the organic layer includes a mixture of compounds represented by the chemical formulas 1 and 2 of the present invention, so that the driving voltage of the organic electric element can be lowered and the luminous efficiency and lifespan can be improved.

Description

Organic electronic element comprising a compound for an organic electronic element and an electronic device thereof {AN ORGANIC ELECTRONIC ELEMENT COMPRISING COMPOUND FOR ORGANIC ELECTRONIC ELEMENT AND AN ELECTRONIC DEVICE THEREOF}

The present invention relates to an organic electric device comprising a compound for an organic electric device and an electronic device thereof.

In general, the organic luminescence phenomenon refers to a phenomenon that converts electrical energy into light energy using organic materials. An organic electric device utilizing the organic luminescence phenomenon usually has a structure including an anode, a cathode, and an organic layer between them. Here, the organic layer is often composed of a multilayer structure composed of different materials in order to increase the efficiency and stability of the organic electric device, and can be composed 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 organic layers in organic electroluminescent devices 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, depending on their functions. In addition, the light-emitting materials can be classified into high molecular weight and low molecular weight types depending on their molecular weight, and can be classified into fluorescent materials derived from singlet excited states of electrons and phosphorescent materials derived from triplet excited states of electrons depending on their luminescence mechanisms. In addition, the light-emitting materials can be classified into blue, green, and red light-emitting materials and yellow and orange light-emitting materials required to realize better natural colors depending on their luminescence colors.

Meanwhile, when only one substance is used as a light-emitting material, the maximum light-emitting wavelength shifts to a longer wavelength due to intermolecular interaction, and the color purity decreases or the efficiency of the device decreases due to the light-emitting attenuation effect. Therefore, a host/dopant system can be used as a light-emitting material to increase the color purity and the light-emitting efficiency through energy transfer. The principle is that when a small amount of a dopant having a smaller energy band gap than the host forming the light-emitting layer is mixed into the light-emitting layer, excitons generated in the light-emitting layer are transported to the dopant, thereby emitting light with high efficiency. At this time, the wavelength of the host shifts to the wavelength of the dopant, so light of a desired wavelength can be obtained depending on the type of dopant used.

Currently, the portable display market is trending toward increasing in size with large-area displays, which requires greater power consumption than that required by existing portable displays. Therefore, power consumption has become a very important factor for portable displays that have a limited power supply source called a battery, and efficiency and lifespan issues must also be resolved.

Efficiency, lifespan, and driving voltage are interrelated. When efficiency increases, the driving voltage relatively decreases. As the driving voltage decreases, the crystallization of organic substances due to Joule heating generated during operation decreases, which tends to increase the lifespan. However, efficiency cannot be maximized simply by improving the organic layer. This is because long lifespan and high efficiency can be achieved simultaneously when the energy level and T ₁ value between each organic layer and the inherent properties of the material (mobility, interfacial properties, etc.) are optimally combined.

Therefore, there is a need for the development of a light-emitting material that has high thermal stability and can efficiently achieve charge balance within the light-emitting layer. In other words, in order to fully demonstrate the excellent characteristics of organic electric devices, it is necessary for the materials forming the organic layers within the devices, such as hole injection materials, hole transport materials, light-emitting materials, electron transport materials, and electron injection materials, to be supported by stable and efficient materials. However, stable and efficient organic layer materials for organic electric devices have not yet been sufficiently developed, and among these, the development of host materials for the light-emitting layer is particularly urgently required.

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

In one aspect, the present invention provides an organic electric device including compounds represented by the following chemical formulas 1 and 2 in a light-emitting layer.

<Chemical Formula 1> <Chemical Formula 2>

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

By using a mixture of a compound represented by chemical formula 1 of the present invention and a compound represented by chemical formula 2 as a material for a light-emitting layer, the driving voltage of the device can be lowered, and the light-emitting efficiency and lifespan of the device can be improved.

Figures 1 to 3 are exemplary diagrams of organic electroluminescent devices according to the present invention.

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

The terms "fluorenyl group", "fluorenylene group", and "fluorene triyl group" used in the present invention, unless otherwise stated, mean a monovalent, divalent, or trivalent functional group wherein R, R', and R" in the following structures are all hydrogen, and a "substituted fluorenyl group", a "substituted fluorenylene group", or a "substituted fluorene triyl group" mean that at least one of the substituents R, R', and R" is a substituent other than hydrogen, and includes a case where R and R' are bonded to each other to form a spiro compound together with the carbon to which they are bonded. In the present specification, regardless of valence, a fluorenyl group, a fluorenylene group, and a fluorene triyl group may all be referred to as a fluorene group.

The term "spiro compound" used in the present invention has a 'spiro linkage', and a spiro linkage means a link formed by two rings sharing only one atom. At this time, the atom shared between the two rings is called a 'spiro atom', and depending on the number of spiro atoms contained in a compound, they are called 'monospiro-', 'dicepiro-', and 'trispiro-' compounds, respectively.

The term "heterocyclic group" used in the present invention includes not only aromatic rings such as "heteroaryl group" or "heteroarylene group" but also non-aromatic rings, and unless otherwise stated means a ring having 2 to 60 carbon atoms each containing one or more heteroatoms, but is not limited thereto. The term "heteroatom" used herein represents N, O, S, P or Si unless otherwise stated, and a heterocyclic group means a single ring type, ring aggregate, fused multiple ring system, spiro compound, etc. containing a heteroatom.

The term "heterocyclic group" used in the present invention means a ring which contains a heteroatom such as N, O, S, P or Si instead of carbon forming the ring, and includes not only an aromatic ring such as a "heteroaryl group" or a "heteroarylene group" but also a non-aromatic ring, and may also include a compound which contains a heteroatom group such as SO ₂ , P = O instead of carbon forming the ring, as in the following compounds.

The term "aliphatic ring" used in the present invention means a cyclic hydrocarbon other than an aromatic hydrocarbon, and includes a single ring, a ring aggregate, a fused multiple ring system, a spiro compound, etc., and unless otherwise stated, means a ring having 3 to 60 carbon atoms, but is not limited thereto. For example, even if an aromatic ring, benzene, and a non-aromatic ring, cyclohexane, are fused, it is also considered an aliphatic ring.

In this specification, the 'group name' corresponding to the aryl group, arylene group, heterocyclic group, etc., which are exemplified as each symbol and its substituent, may be described as the 'group name reflecting the valence', or may be described as the 'parent compound name'. For example, in the case of 'phenanthrene', which is a type of aryl group, the name of the group may be described by distinguishing the valence, such as 'phenanthryl' for the monovalent 'group' and 'phenantrylene' for the divalent group, or it may be described as 'phenanthrene', the name of the parent compound, regardless of the valence. Similarly, in the case of pyrimidine, it may be described as 'pyrimidine' regardless of the valence, or it may be described as the 'group name' of the corresponding valence, such as pyrimidinyl group for monovalent and pyrimidinylene for divalent.

In addition, in this specification, numbers or alphabets indicating positions may be omitted when describing compound names or substituent names. For example, pyrido[4,3-d]pyrimidine may be described as pyridopyrimidine, benzofuro[2,3-d]pyrimidine may be described as benzofuropyrimidine, and 9,9-dimethyl-9H-fluorene may be described as dimethylfluorene. Accordingly, both benzo[g]quinoxaline and benzo[f]quinoxaline may be described as benzoquinoxaline.

In addition, unless explicitly stated otherwise, the chemical formulas used in the present invention are applied in the same manner as the substituent definitions by the index definitions of the chemical formulas below.

Here, when a is an integer of 0, the substituent R ¹ is absent, that is, when a is 0, it means that hydrogen is bonded to all the carbons forming the benzene ring. In this case, the indication of the hydrogen bonded to the carbon can be omitted and the chemical formula or compound can be described. In addition, when a is an integer of 1, one substituent R ¹ bonds to any one of the carbons forming the benzene ring, and when a is an integer of 2 or 3, it can bond as follows, for example, and when a is an integer of 4 to 6, it bonds to the carbon of the benzene ring in a similar manner, and when a is an integer of 2 or greater, R ¹ can be the same or different.

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

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

When adding reference signs to components of each drawing, it should be noted that identical components are given the same signs as much as possible even if they are shown on different drawings. In addition, when describing the present invention, if it is determined that a specific description of a related known configuration or function may obscure the gist of the present invention, the detailed description is omitted.

In describing components of the present invention, terms such as first, second, A, B, (a), (b), etc. may be used. These terms are only intended to distinguish the components from other components, and the nature, order, or sequence of the components are not limited by these terms. When it is described that a component is "connected," "coupled," or "connected" to another component, it should be understood that the component may be directly connected or connected to the other component, but another component may also be "connected," "coupled," or "connected" between each component.

Also, when it is said that a component such as a layer, film, region, or plate is "on" or "over" another component, it should be understood that this includes not only the case where it is "directly on" the other component, but also the case where there are other components in between. Conversely, when it is said that a component is "directly on" another part, it should be understood to mean that there are no other parts in between.

Figures 1 to 3 are exemplary diagrams of organic electric devices according to embodiments of the present invention.

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

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

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

Preferably, a light efficiency improvement layer (180) may be formed on one side of the first electrode (110) or the second electrode (170) that is not in contact with the organic layer, and when the light efficiency improvement layer (180) is formed, the light efficiency of the organic electric element may be improved.

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

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

Referring to FIG. 2, an organic electric element (200) according to another embodiment of the present invention may include a hole injection layer (120), a hole transport layer (130), a buffer layer (210), 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) sequentially formed on a first electrode (110), and a light efficiency improvement layer (180) may be formed on the second electrode.

Although not shown in FIG. 2, an electron transport auxiliary layer may be additionally 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 layer may be formed in a form in which a plurality of stacks including a hole transport layer, a light-emitting layer, and an electron transport layer are formed. This will be described with reference to FIG. 3.

Referring to FIG. 3, an organic electric element (300) according to another embodiment of the present invention may have two or more sets of stacks (ST1, ST2) of organic layers formed of multiple layers formed between a first electrode (110) and a second electrode (170), and a charge generation layer (CGL) may be formed between the stacks of organic layers.

Specifically, an organic electric device according to one embodiment of the present invention may include a first electrode (110), a first stack (ST1), a charge generation layer (CGL: Charge Generation Layer), a second stack (ST2), a second electrode (170), and a light efficiency improvement layer (180).

The first stack (ST1) is an organic layer formed on the first electrode (110), which may include a first hole injection layer (320), a first hole transport layer (330), a first light-emitting 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 light-emitting layer (440), and a second electron transport layer (450). In this way, the first stack and the second stack may be organic layers having the same stacked structure, but may also be organic layers having different stacked 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 light-emitting layer (340) and the second light-emitting layer (440) to increase current efficiency generated in each light-emitting layer and to smoothly distribute charges.

The first light-emitting layer (340) may include a light-emitting material including a blue fluorescent dopant in a blue host, and the second light-emitting layer (440) may include a material in which a greenish yellow dopant and a red dopant are doped together in a green host; however, the materials of the first light-emitting layer (340) and the second light-emitting layer (440) according to the embodiment of the present invention are not limited thereto.

In FIG. 3, n can be an integer from 1 to 5, and when n is 2, a charge generation layer (CGL) and a third stack can be additionally stacked on the second stack (ST2).

When a plurality of light-emitting layers are formed by a multilayer stack structure as in Fig. 3, not only can an organic light-emitting device be manufactured that emits white light by the mixing effect of the light emitted from each light-emitting layer, but an organic light-emitting device that emits light of various colors can also be manufactured.

The compound represented by the chemical formula 1 of the present invention can be used as a material for a hole injection layer (120, 320, 420), a hole transport layer (130, 330, 430), a buffer layer (210), a light-emitting auxiliary layer (220), an electron transport layer (150, 350, 450), an electron injection layer (160), a light-emitting layer (140, 340, 440), or a light efficiency improvement layer (180). However, preferably, a mixture of the compound represented by the chemical formula 1 of the present invention and the compound represented by the chemical formula 2 is used/is used as a host for the light-emitting layer (140, 340, 440), and the compound represented by the chemical formula 1 can be used as a material for a hole transport band layer such as the hole transport layer (130, 330, 430) and/or the light-emitting auxiliary layer (220).

Even if the core is identical or similar, the band gap, electrical properties, interface properties, etc. can vary depending on which substituent is bonded at which position. Therefore, research is needed on the selection of the core and the combination of sub-substituents bonded to it. In particular, when the energy level and _T1 value between each organic layer, and the intrinsic properties of the material (mobility, interface properties, etc.) are optimally combined, both a long lifespan and high efficiency can be achieved.

Therefore, in the present invention, by using a mixture of a compound represented by chemical formula 1 and a compound represented by chemical formula 2 as a host for a light-emitting layer (140, 340, 440) and/or using the compound represented by chemical formula 1 as a material for a hole transport band layer such as a hole transport layer (130, 330, 430) and/or a light-emitting auxiliary layer (220), the energy level and T ₁ value between each organic layer, the intrinsic properties of the material (mobility, interface properties, etc.), etc., can be optimized, thereby simultaneously improving the lifespan and efficiency of the organic electric device.

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

In addition, the organic layer can be manufactured with a smaller number of layers by using various polymer materials, rather than a deposition method, such as a solution process or a solvent process, 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, a doctor blading process, a screen printing process, or a thermal transfer method. Since the organic layer according to the present invention can be formed by various methods, the scope of the present invention is not limited by the formation method.

An organic electric device according to one embodiment of the present invention may be a front-emitting, back-emitting, or double-sided emitting type depending on the material used.

In addition, the organic electric device according to one embodiment of the present invention may be selected from the group consisting of an organic light-emitting device, an organic solar cell, an organic photoconductor, an organic transistor, a monochrome lighting device, and a quantum dot display device.

Another embodiment of the present invention may include a display device including the organic electric element 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 systems, game consoles, various TVs, and various computers.

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

An organic electric device according to one aspect of the present invention includes an anode, a cathode, and an organic layer formed between the anode and the cathode, wherein the organic layer includes a phosphorescent emitting layer, and a host of the phosphorescent emitting layer includes a first compound represented by the following chemical formula 1 and a second compound represented by the following chemical formula 2.

<Chemical Formula 1> <Chemical Formula 2>

First, chemical formula 1 is explained.

In the above chemical formula 1, each symbol can be defined as follows.

Ar ¹ to Ar ³ are each independently a C ₆ to C ₆₀ aryl group or a fluorenyl group, wherein the aryl group may be further substituted with a fluorenyl group, and the fluorenyl group may be further substituted with a C ₁ to C ₂₀ alkyl group or a C ₆ to C ₂₀ aryl group.

When Ar ¹ to Ar ³ are aryl groups, they are preferably C ₆ to C ₃₀ aryl groups, more preferably C ₆ to C ₁₈ aryl groups, such as phenyl, biphenyl, naphthyl, terphenyl, phenanthrene, etc.

When Ar ¹ to Ar ³ are fluorenyl groups, it can be 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 -fluorene, etc.

L ¹ to L ³ are each independently a single bond, a C ₆ to C ₆₀ arylene group or a fluorenylene group, wherein the arylene group may be further substituted with a fluorenyl group, and the fluorenylene group may be further substituted with a C ₁ to C ₂₀ alkyl group or a C ₆ to C ₂₀ aryl group.

When L ¹ to L ³ are arylene groups, they are preferably C ₆ to C ₃₀ arylene groups, more preferably C ₆ to C ₁₈ arylene groups, such as phenylene, biphenyl, naphthalene, terphenyl, and the like.

When L ¹ to L ³ are fluorenyl groups, they can be 9,9-dimethyl-9H-fluorene, 9,9-diphenyl-9H-fluorene, 9,9'-spirofluorene, etc.

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

Next, the following chemical formula 2 is explained.

<Chemical Formula 2>

In the above chemical formula 2, each symbol can be defined as follows.

X ₄ to X ₆ are N or C(L-Ar), and at least one of X ₄ to X ₆ is N. Therefore, a ring comprising X ₄ to X ₆ can be a pyridine derivative, a pyrimidine derivative, or a triazine derivative.

The above L is selected from the group consisting of a single bond; a C ₆ to C ₆₀ arylene group; a fluorenylene group; a C ₃ to C ₆₀ aliphatic ring group; and a C ₂ to C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P, and when L is plural, they are each the same or different.

The above Ar is selected from the group consisting of hydrogen; deuterium; halogen; cyano group; nitro group; _C6 ~ _C60 aryl group; fluorenyl group; _C2 ~ _C60 heterocyclic group containing at least one heteroatom of O, N, S, Si and P; _C3 ~ _C60 aliphatic ring group; _C1 ~ _C30 alkyl group; _C2 ~ _C30 alkenyl group; _C2 ~ _C30 alkynyl group; _C1 ~ _C30 alkoxyl group; _C6 ~ _C30 aryloxy group; and -L'-N(R _a )(R _b ), and when Ar is plural, they are each the same or different.

Ar ⁴ to Ar ⁶ can be independently selected from the group consisting of a C ₆ to C ₆₀ aryl group; a fluorenyl group; a C ₂ to C ₆₀ heterocyclic group including at least one heteroatom selected from O, N, S, Si and P; and a C ₃ to C ₆₀ aliphatic ring group.

When Ar ⁴ to Ar ⁶ are aryl groups, they are preferably C ₆ to C ₃₀ aryl groups, more preferably C ₆ to C ₁₈ aryl groups, such as phenyl, biphenyl, naphthyl, terphenyl, anthracene, pyrene, phenanthrene, triphenylene, and the like.

When Ar ⁴ to Ar ⁶ are a heterocyclic group, it is preferably a C ₂ to C ₃₀ heterocyclic group, more preferably a C ₂ to C ₂₁ heterocyclic group, for example, pyridine, dibenzothiophene, dibenzofuran, quinazoline, quinoxaline, quinoline, phenanthroline, imidazole, benzonaphthyridine, benzoquinoline, benzothiopyrimidine, benzofuropyrimidine, benzoacridine, dibenzoacridine, and the like.

When Ar ⁴ to Ar ⁶ are fluorenyl groups, they may be 9,9-dimethylfluorene, 9,9-diphenylfluorene, 9,9'-spirofluorene, etc.

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

When L ⁴ to L ⁶ are arylene groups, they are preferably C ₆ to C ₃₀ arylene groups, more preferably C ₆ to C ₁₈ arylene groups, such as phenyl, biphenyl, naphthyl, terphenyl, and the like.

When L ⁴ to L ⁶ are heterocyclic groups, they are preferably C ₂ to C ₃₀ heterocyclic groups, more preferably C ₂ to C ₁₂ heterocyclic groups, such as pyridine, quinazoline, benzoquinazoline, quinoxaline, dibenzothiophene, dibenzofuran, etc.

The above L' can be selected from the group consisting of a single bond; a C ₆ to C ₆₀ arylene group; a fluorenylene group; a C ₃ to C ₆₀ aliphatic ring group; and a C ₂ to C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P.

The above R _a and R _b can be independently selected from the group consisting of a C ₆ to C ₆₀ aryl group; a fluorenyl group; a C ₃ to C ₆₀ aliphatic ring group; and a C ₂ to C ₆₀ heterocyclic group including at least one heteroatom selected from O, N, S, Si and P.

The above Ar ⁴ to Ar ⁶ , Ar, L ⁴ to L ⁶ , L, R _a , R _b , L' are each independently 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; a germanium group; a cyano group; a nitro group; a C ₁ -C ₂₀ alkylthio group; a C ₁ -C ₂₀ alkoxy group; a C ₆ -C ₂₀ arylalkoxy group; a C ₁ -C ₂₀ alkyl group; a C ₂ -C ₂₀ alkenyl group; a C ₂ -C ₂₀ alkynyl group; a C ₆ -C ₂₀ aryl group; a fluorenyl group; A C ₂ -C ₂₀ heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si and P; a C ₃ -C ₂₀ aliphatic ring group; a C ₇ -C ₂₀ arylalkyl group; and a C ₈ -C ₂₀ arylalkenyl group.

Preferably, the chemical formula 2 can be represented by one of the following chemical formulas 2-A to 2-C.

<Chemical Formula 2-A> <Chemical Formula 2-B> <Chemical Formula 2-C>

In the above chemical formulas 2-A to 2-C, Ar ⁴ to Ar ⁶ and L ⁴ to L ⁶ are as defined in the above chemical formula 2.

In addition, preferably, the chemical formula 2 can be represented by one of the following chemical formulas 2-1 to 2-8.

<Chemical Formula 2-1> <Chemical Formula 2-2>

<Chemical Formula 2-3> <Chemical Formula 2-4>

<Chemical Formula 2-5> <Chemical Formula 2-6>

<Chemical Formula 2-7> <Chemical Formula 2-8>

In the above chemical formulas 2-1 to 2-8, Ar ⁵ , Ar ⁶ , L ⁴ to L ⁶ , X ₄ to X ₆ are as defined in chemical formula 2.

R ₁ is selected from the group consisting of hydrogen; deuterium; halogen; cyano group; nitro group; C ₆ to C ₂₀ aryl group; fluorenyl group; C ₂ to C ₂₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P; C ₃ to C ₂₀ aliphatic ring group; fused ring group of C ₃ to C ₂₀ aliphatic ring and C ₆ to C ₂₀ aromatic ring; C ₁ to C ₂₀ alkyl group; C ₂ to C ₂₀ alkenyl group; C _{2 to} C ₂₀ alkynyl group; C 1 to C ₂₀ alkoxy group; C ₆ to C ₂₀ aryloxy group; and -L ₃ -N(R ₅ )(R ₆ ), and adjacent groups can be bonded to each other to form a ring.

p is an integer from 0 to 4, q is an integer from 0 to 9, r is an integer from 0 to 5, and if p, q, or r is an integer greater than or equal to 2, then each of R ₁ is equal to or different from each other.

X ₇ and X ₈ independently represent a single bond, N-(L ₂ -Ar ₂ ), O, S or C(R ₂ )(R ₃ ), and at least one of X ₇ and X ₈ is not a single bond. That is, at least one of X ₇ and X ₈ is N-(L ₂ -Ar ₂ ), O, S or C(R ₂ )(R ₃ ).

Y ¹ to Y ³⁸ are each independently C, C(R ₄ ) or N, and adjacent R _{4 s} can combine with each other to form a ring.

The above R ₂ to R ₄ are each independently hydrogen; deuterium; halogen; cyano group; nitro group; C ₆ to C ₂₀ aryl group; fluorenyl group; C ₂ to C ₂₀ heterocyclic group including at least one heteroatom selected from O, N, S, Si and P; C ₃ to C ₂₀ aliphatic ring group; fused ring group of a C ₃ to C ₂₀ aliphatic ring and a C ₆ to C ₂₀ aromatic ring; C ₁ to C ₂₀ alkyl group; C ₂ to C ₂₀ alkenyl group; C ₂ to C ₂₀ alkynyl group; C ₁ to C ₂₀ alkoxy group; C ₆ to C ₂₀ aryloxy group; And -L ₃ -N(R ₅ )(R ₆ ) is selected from the group consisting of, R ₂ and R ₃ can combine with each other to form a ring, and adjacent R ₄ s can combine with each other to form a ring.

p is an integer from 0 to 4, q is an integer from 0 to 9, r is an integer from 0 to 5, and if p, q, or r is an integer greater than or equal to 2, then each of R ₁ is equal to or different from each other.

The above L ₂ and L ₃ can be independently selected from the group consisting of a single bond; a C ₆ to C ₂₀ arylene group; a fluorenylene group; a C ₂ to C ₂₀ heterocyclic group including at least one heteroatom selected from O, N, S, Si and P; a C ₃ to C ₂₀ aliphatic ring group; and combinations thereof.

The above Ar ₂ may be selected from the group consisting of a C ₆ to C ₂₀ aryl group; a fluorenyl group; a C ₂ to C ₂₀ heterocyclic group including at least one heteroatom selected from O, N, S, Si, and P; a C ₃ to C ₂₀ aliphatic ring group; and combinations thereof.

The above R ₅ and R ₆ can be independently selected from the group consisting of a C ₆ to C ₂₀ aryl group; a fluorenyl group; a C ₂ to C ₂₀ heterocyclic group including at least one heteroatom selected from O, N, S, Si and P; a C ₃ to C ₂₀ aliphatic ring group; and combinations thereof.

However, compounds represented by Chemical Formulas 3-3-1 to 3-3-4 in Chemical Formula 2-3 are excluded.

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

In the above chemical formulas 3-3-1 to 3-3-4, L ⁴ to L ⁶ , Ar ⁵ , and Ar ⁶ are as defined in chemical formula 2.

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

.

Preferably, in the chemical formula 1, L ¹ to L ³ may be independently selected from the group consisting of the following chemical formulas b-1 to b-12, and in the chemical formula 2, L ⁴ may be selected from the group consisting of the following chemical formulas b-1 to b-13.

<Chemical formula b-1> <Chemical formula b-2> <Chemical formula b-3> <Chemical formula b-4>

<Chemical formula b-5> <Chemical formula b-6> <Chemical formula b-7> <Chemical formula b-8>

<Chemical formula b-9> <Chemical formula b-10>

<chemical formula b-11> <chemical formula b-12> <chemical formula b-13>

In the above chemical formulas b-1 to b-13, each symbol can be defined as follows.

Y ¹ is N-(L ^a -Ar ^a ), O, S or C(R _d )(R _e ), and Z ¹ to Z ³ are each independently C, C(R _f ) or N, and at least one of Z ¹ to Z ³ is N. However, when L ¹ to L ³ are of the above chemical formula b-11 or b-12, Y ¹ is C(R _d )(R _e ).

R ⁵ to R ⁷ , R _d , R _e and R _f are each independently hydrogen; deuterium; halogen; cyano group; nitro group; C ₆ to C ₂₀ aryl group; fluorenyl group; C ₂ to C ₂₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P; C ₃ to C ₂₀ aliphatic ring group; fused ring group of C ₃ to C ₂₀ aliphatic ring and C ₆ to C ₂₀ aromatic ring; C ₁ to C ₂₀ alkyl group; C ₂ to C ₂₀ alkenyl group; C ₂ to C ₂₀ alkynyl group; C ₁ to C ₂₀ alkoxy group; And an aryloxy group of C ₆ to C ₃₀ ; is selected from the group consisting of, and adjacent groups can be bonded to each other to form a ring, R _d and R _e can be bonded to each other to form a ring, and adjacent R _f in C(R _f ) can be bonded to each other to form a ring. When R _d and R _e are bonded to each other to form a ring, a spiro compound can be formed together with the C to which they are bonded.

f is an integer from 0 to 6, e, g, h, i are each integers from 0 to 4, j, k are each integers from 0 to 3, l is each integer from 0 to 2, m is an integer from 0 to 3, and when each of these is an integer greater than or equal to 2, the plurality of R ^5s , the plurality of R ^6s , and the plurality of R ^7s are the same or different from each other.

The above Ar ^a can be selected from the group consisting of a C ₆ to C ₂₀ aryl group; a fluorenyl group; a C ₂ to C ₂₀ heterocyclic group including at least one heteroatom selected from O, N, S, Si, and P; a C ₃ to C ₂₀ aliphatic ring group; and combinations thereof.

The above L ^a may be independently selected from the group consisting of a single bond; a C ₆ to C ₂₀ arylene group; a fluorenylene group; a C ₂ to C ₂₀ heterocyclic group including at least one heteroatom selected from O, N, S, Si and P; a C ₃ to C ₂₀ aliphatic ring group; and combinations thereof.

In one embodiment of the present invention, it is preferable to use the compound represented by the chemical formula 1 and the compound represented by the chemical formula 2 as a host material by mixing them in a weight ratio of 2:8 to 8:2.

In another embodiment of the present invention, the organic layer further includes one or more hole transport band layers formed between the light-emitting layer and the anode, and the hole transport band layers include at least one layer of a hole transport layer and a light-emitting auxiliary layer, and include a compound represented by chemical formula 1.

Hereinafter, examples of synthesis of compounds represented by chemical formulas 1 and 2 according to the present invention and examples of manufacturing organic electric devices are described, but the present invention is not limited to the following examples.

Synthetic example

[ Synthetic example 1] Chemical formula 1

The compound represented by chemical formula 1 according to the present invention (Final product 1) can be synthesized by the reaction path of the following reaction scheme 1. The compound represented by chemical formula 1 was manufactured by the synthetic method disclosed in the applicant's Korean Patent Registration No. 10-1786749 (registration notice dated October 11, 2017), Korean Patent Application No. 2014-0152779 (filed on November 5, 2014), and Korean Patent Application No. 2014-0161275 (filed on November 19, 2014), etc.

<Reaction Formula 1>

I. Example of Sub 1

Compounds belonging to Sub 1 of the above reaction scheme 1 may be compounds as follows, but are not limited thereto, and Table 1 shows the FD-MS (Field Desorption-Mass Spectrometry) values of compounds belonging to Sub 1.

[Table 1]

Ⅱ. Synthesis example of Sub 2

Sub 2 of the above reaction scheme 1 can be synthesized by the reaction path of the following reaction scheme 2, but is not limited thereto.

<Reaction Formula 2>

Example of Sub 2-4

Aniline (15 g, 161.1 mmol), 1-bromonaphthalene (36.7 g, 177.2 mmol), Pd ₂ (dba) ₃ (7.37 g, 8.05 mmol), P(t-Bu) ₃ (3.26 g, 16.1 mmol), NaOt-Bu (51.08 g, 531.5 mmol), and toluene (1690 mL) were added to a round-bottomed flask and the reaction was carried out at 100 °C. When the reaction was completed, the mixture was extracted with CH ₂ Cl ₂ and water, and the organic layer was dried over MgSO ₄ and concentrated. The resulting organic matter was separated through a silica gel column and recrystallized to obtain 25.4 g of Sub 2-4. (Yield: 72%)

Example of Sub 2-27

[1,1'-biphenyl]-4-amine (15 g, 88.6 mmol), 2-(4-bromophenyl)-9,9-diphenyl-9H-fluorene (46.2 g, 97.5 mmol), Pd ₂ (dba) ₃ (4.06 g, 4.43 mmol), P(t-Bu) ₃ (1.8 g, 8.86 mmol), NaOt-Bu (28.1 g, 292.5 mmol), toluene (931 mL) were added to a round-bottom flask, and the reaction was carried out in the same manner as Sub 4-1 to obtain 34.9 g of Sub 2-27. (Yield: 70%)

Compounds belonging to Sub 2 may include, but are not limited to, the compounds below, and Table 2 shows the FD-MS values of the compounds below.

[Table 2]

III. Final compound Synthetic example

1-1 synthesis

Sub 1-1 (10 g, 42.9 mmol), Sub 2-1 (13.79 g, 42.9 mmol), Pd ₂ (dba) ₃ (1.18 g, 1.29 mmol), P(t-Bu) ₃ (8.68 g, 42.9 mmol), NaOt-Bu (8.25 g, 85.80 mmol), and toluene (429 mL) were added to a round-bottomed flask and the reaction was carried out at 100 °C. When the reaction was completed, the mixture was extracted with CH ₂ Cl ₂ and water, and the organic layer was dried over MgSO ₄ and concentrated. The resulting organic matter was separated through a silica gel column and recrystallized to obtain 15.6 g of compound 1-1. (Yield: 77%)

Synthesis of 1-4

Sub 1-2 (10 g, 35.3 mmol), Sub 2-2 (14.8 g, 35.31 mmol), Pd ₂ (dba) ₃ (0.97 g, 1.06 mmol), P(t-Bu) ₃ (7.14 g, 35.31 mmol), NaOt-Bu (6.79 g, 70.63 mmol), toluene (353 mL) were used in the same manner as in 1-1 to obtain 16.9 g of compound 1-4. (Yield: 78%)

Composite of 1-10

Using Sub 1-6 (10 g, 32.34 mmol), Sub 2-7 (12.86 g, 32.34 mmol), Pd ₂ (dba) ₃ (0.89 g, 0.97 mmol), P(t-Bu) ₃ (6.54 g, 32.34 mmol), NaOt-Bu (6.22 g, 64.68 mmol), toluene (323 mL), the same method as 1-1 was carried out to obtain 15.1 g of compound 1-10. (Yield: 75%)

Synthesis of 1-78

Using Sub 1-33 (10 g, 21.21 mmol), Sub 2-1 (5.20 g, 21.21 mmol), Pd ₂ (dba) ₃ (0.58 g, 0.64 mmol), P(t-Bu) ₃ (4.29 g, 21.21 mmol), NaOt-Bu (4.08 g, 42.43 mmol), toluene (212 mL), the same method as 1-1 was carried out to obtain 10.57 g of compound 1-87. (Yield: 70%)

Synthesis of 1-95

Using Sub 1-42 (10 g, 25.17 mmol), Sub 2-21 (9.10 g, 25.17 mmol), Pd ₂ (dba) ₃ (0.69 g, 0.76 mmol), P(t-Bu) ₃ (5.09 g, 25.17 mmol), NaOt-Bu (4.84 g, 50.34 mmol), toluene (252 mL), the same method as 1-1 was carried out to obtain 12.28 g of compound 1-95. (Yield: 72%)

The FD-MS values of compounds 1-1 to 1-97 of the present invention manufactured according to the above synthetic examples are as shown in Table 3 below.

[Table 3]

[ Synthetic example 2] Chemical formula 2

The compound represented by chemical formula 2 of the present invention (Final product 2) can be prepared as in the following reaction scheme 3, but is not limited thereto.

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

I. Sub 5 of Synthetic example

1. Sub 5-1 Synthetic 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) and 4-biphenylboronic acid (CAS Registry Number: 5122-94-1) (13.1 g, 66.19 mmol) are placed in a round-bottom flask and dissolved in THF (370 ml). Then, Pd(PPh ₃ ) ₄ (3.8 g, 3.31 mmol), K ₂ CO ₃ (27.4 g, 198.57 mmol), and water (165 ml) are added and the mixture is stirred and refluxed. After the reaction is complete, the mixture is extracted with ether and water, and the organic layer is concentrated. The concentrated organic layer was dried with MgSO ₄ and concentrated once more, separated with a silica gel column, and recrystallized to obtain 20.8 g of the product (yield 75%).

2. Sub 5-8 Synthetic example

Using 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 water, the same method as Sub 5-1 was carried out to obtain 20.3 g of the product. (Yield 71%)

3. Sub 5-19 Synthetic example

Using 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 equivalents), K ₂ CO ₃ (3 equivalents), anhydrous THF and water, the product 15.7 g was obtained. (Yield 69%)

4. Sub 5-19 Synthetic example

Using 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 ) ₄ (0.05 equivalents), K ₂ CO ₃ (3 equivalents), anhydrous THF and water, the same method as Sub 5-1 was carried out to obtain 30.8 g of the product. (Yield 65%)

Compounds belonging to Sub 5 may include, but are not limited to, the compounds below, and Table 4 shows the FD-MS values of the compounds below.

[Table 4]

II. Sub 6 Synthetic example

Sub 6 of the above reaction scheme 3 can be synthesized by the following reaction scheme 4, but is not limited thereto.

<Reaction Scheme 4> (Hal ³ is I, Br or Cl, L is L ⁵ or L ⁶ , and Ar is Ar ⁷ or Ar ⁸ )

1. Sub 6-2 Synthetic example

4-bromo-1,1'-biphenyl (5 g, 21.45 mmol) was dissolved in DMF (270 ml), and 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), DMF (270 ml) were added and stirred and refluxed at 120°C. When the reaction was complete, the temperature of the reaction product was cooled to room temperature, extracted with MC, and washed with water. The organic layer was dried over MgSO ₄ and concentrated. The concentrate was then separated through a silica gel column to obtain 3.4 g (80%) of the product.

2. Sub 6-37 Synthetic example

2-bromodibenzo[b,d]furan (10 g, 40.47 mmol) was dissolved in anhydrous DMF, and bis(pinacolato)diboron (13.3 g, 52.61 mmol), PdCl ₂ (dppf) _, (0.05 equivalent), KOAc (3 equivalent) were added, and the mixture was stirred and refluxed at 120°C. When the reaction was complete, the temperature of the reaction product was cooled to room temperature, extracted with MC, and washed with water. The organic layer was dried over MgSO ₄ and concentrated. The concentrate was then separated using a silica gel column to synthesize 7 g of the product. (Yield 82%)

Compounds belonging to Sub 6 may include, but are not limited to, the compounds below, and Table 5 shows the FD-MS values of the compounds below.

[Table 5]

III. Synthesis of the compound of chemical formula 3

1. Synthesis example of 3-15

In a round bottom flask, add Sub 5-1 (5 g, 11.91 mmol) and Sub 6-44 (4 g, 13.1 mmol) and dissolve in THF (70 ml). Then, add Pd(PPh ₃ ) ₄ (0.7 g, 0.6 mmol), K ₂ CO ₃ (5 g, 35.73 mmol) and water (30 ml) and reflux while stirring. When the reaction is complete, extract with ether and water, and concentrate the organic layer. Dry the concentrated organic layer with MgSO ₄ and concentrate once more. The final concentrate was separated using a silica gel column and recrystallized to obtain 5.4 g of the product. (Yield 71%)

2. Synthesis example of 3-55

Using Sub 5-29 (4 g, 14.94 mmol), Sub 6-45 (9.5 g, 16.43 mmol), Pd(PPh ₃ ) ₄ (0.05 equivalents), K ₂ CO ₃ (3 equivalents), anhydrous THF and water, the same method as in the synthesis method 3-15 was used to synthesize 8.8 g of the product. (Yield 77%)

3. Synthesis example of 3-96

Sub 5-29 (4 g, 14.94 mmol), Sub 6-47 (7 g, 16.43 mmol), Pd(PPh ₃ ) ₄ (0.05 equivalents), K ₂ CO ₃ (3 equivalents), anhydrous THF and water were used in the same manner as in the synthesis method 3-15 to synthesize 6 g of the product. (Yield 66%)

4. Synthesis example of 3-106

Using 2,4-dichloro-6-phenyl-1,3,5-triazine (7 g, 30.97 mmol), Sub 6-47 (13.1 g, 61.94 mmol), Pd(PPh ₃ ) ₄ (0.1 equivalent), K ₂ CO ₃ (6 equivalent), anhydrous THF and water, the same method as in the synthetic method 3-15 was used to synthesize 9.7 g of the product. (Yield 64%)

5. Synthesis example of 3-111

Sub 5-29 (4 g, 14.94 mmol), Sub 6-41 (7.3 g, 16.43 mmol), Pd(PPh ₃ ) ₄ (0.05 equivalents), K ₂ CO ₃ (3 equivalents), anhydrous THF and water were used in the same manner as in the synthesis method 3-15 to synthesize 7 g of the product. (Yield 75%)

6. Synthesis example of 3-138

Sub 5-54 (4 g, 12.59 mmol), Sub 6-59 (5.86 g, 15.10 mmol), Pd(PPh ₃ ) ₄ (0.05 equivalents), K ₂ CO ₃ (3 equivalents), anhydrous THF and water were used in the same manner as in the synthesis method 3-15 to synthesize 6 g of the product. (Yield 77%)

The FD-MS values of compounds 3-1 to 3-141 synthesized by the above synthetic method are as shown in Table 6 below.

[Table 6]

Manufacturing and Evaluation of Organic Electronics

[ Example 1] to [ Example 20] Red organic light-emitting diode ( luminescent layer mixed phosphorescent host)

A 4,4',4"-Tris[2-naphthyl(phenyl)amino]triphenylamine (hereinafter abbreviated as "2-TNATA") film was vacuum-deposited on an ITO layer (anode) formed on a glass substrate to form a 60 nm thick hole injection layer, and then a 4,4'-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (hereinafter abbreviated as "NPB") film was vacuum-deposited to a 60 nm thick to form a hole transport layer.

Next, a 30 nm thick light-emitting layer was formed on the hole transport layer, and at this time, as shown in Table 5 below, a mixture of a compound represented by Chemical Formula 1 of the present invention (first host) and a compound represented by Chemical Formula 2 of the present invention (second host) was mixed in a weight ratio of 3:7 as a host, and bis-(1-phenylisoquinolyl)iridium(Ⅲ)acetylacetonate (hereinafter abbreviated as "(piq) ₂ Ir(acac")) was used as a dopant, and the dopant was doped so that the host and dopant had a weight ratio of 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 light-emitting layer to form a hole-blocking layer.

Next, bis(10-hydroxybenzo[h]quinolinato)beryllium (hereinafter abbreviated as BeBq ₂ ) was deposited on the hole blocking layer to a thickness of 41 nm to form an electron transport layer. After that, LiF was deposited on the electron transport layer to a thickness of 0.2 nm, and then Al was deposited to a thickness of 150 nm to form a cathode, thereby manufacturing an organic light emitting device.

[ Comparative example 1] and [ Comparative example 2]

An organic light-emitting device was manufactured in the same manner as in Example 1, except that compound 1-1 or compound 3-140 was used alone as the host material of the light-emitting layer, as described in Table 7 below.

[ Comparative example 3] to [ Comparative example 8]

An organic light-emitting device was manufactured in the same manner as in Example 1, except that one of refs 1 to 3 was used as a first host and a mixture of compounds 3-140 or 3-141 was used as a second host as described in Table 7 below as the host material of the light-emitting layer.

<ref 1> <ref 2> <ref 3>

A forward bias DC voltage was applied to the organic electroluminescence devices manufactured by Examples 1 to 20 and Comparative Examples 1 to 8 of the present invention, and the electroluminescence (EL) characteristics were measured using PR-650 from Photoresearch. The T95 lifespan was measured using a lifespan measuring device from Maxscience at a reference luminance of 2500 cd/m ² . The measurement results are shown in Table 7 below.

[Table 7]

As can be seen from the results in Table 7 above, when the compounds for organic electroluminescence devices of the present invention represented by Chemical Formula 1 and Chemical Formula 2 are mixed and used as a phosphorescent host (Examples 1 to 20), the efficiency and lifespan are significantly improved compared to when the compound represented by Chemical Formula 1 or Chemical Formula 2 is used alone (Comparative Examples 1 to 2) or when one of ref 1 to ref 3 and the compound represented by Chemical Formula 2 of the present invention are mixed and used as a host (Comparative Examples 3 to 8).

That is, compared to Comparative Examples 1 and 2, which each used a compound of the present invention represented by Chemical Formula 1 or Chemical Formula 2 as a single host, in the case of the devices of Comparative Examples 3 to 8, which used a mixture of two compounds as a host, the device characteristics were further improved, and it could be confirmed that in the case of the present invention, which used a mixture of substances corresponding to Chemical Formula 1 and Chemical Formula 2 of the present invention as a host, the efficiency and lifespan were significantly improved compared to Comparative Examples 3 to 5.

Based on the above experimental results, the inventors determined that a mixture of the substance of Chemical Formula 1 and the substance of Chemical Formula 2 has novel properties other than the properties of each substance, and therefore measured the PL lifetime for each of the compound of Chemical Formula 1, the compound of Chemical Formula 2, and the mixture of them.

As a result, it was confirmed that a new PL wavelength was formed in the case of the mixture, unlike when it was a single compound, and it was confirmed that the decrease and disappearance time of the newly formed PL wavelength increased by about 60 to 360 times compared to when it was a single compound.

This is because, when a mixture is used as in the present invention, electrons and holes move not only through the energy levels of each substance, but also the efficiency and lifespan are increased due to electron and hole movement or energy transfer by a new region (exciplex) having a new energy level formed by the mixture. As a result, when a mixture of a compound represented by Chemical Formula 1 and a compound represented by Chemical Formula 2 is used as a host as in the present invention, it can be said that the mixed thin film is an important example showing exciplex energy transfer and light emission processes.

In particular, when a compound in which all aryl groups or fluorenyl groups are bonded as substituents of the amine group in the chemical formula 1 of the present invention is used as a component of the mixture, the compound represented by the chemical formula 1, which has stability against holes and rapid hole injection characteristics compared to compounds in which a heterocycle is substituted for the amine group as in ref 1 to ref 3, exhibits good electrochemical synergy with the compound represented by the chemical formula 2, which has strong electron characteristics, so it appears that the efficiency and lifespan of the device are maximized.

[ Example 21] to [ Example 24] By mixing ratio Red organic light-emitting diode

An organic light-emitting device was manufactured using the same method as in Example 1, except that the first host and the second host were mixed and used at a certain ratio as described in Table 8 below.

The electroluminescence (EL) characteristics were measured using PR-650 from Photoresearch by applying a forward bias DC voltage to the organic electroluminescence devices manufactured by Examples 21 to 24 of the present invention, and the T95 lifespan was measured using lifespan measuring equipment from Maxscience at a standard luminance of 2500 cd/m ² . The results are shown in Table 8 below.

[Table 8]

As shown in Table 8 above, devices were manufactured and measured by mixing the compounds of the present invention at different ratios (7:3, 5:5, 3:7). From Table 8 above, it can be seen that when the ratio of the first host to the second host is 3:7, the efficiency and lifespan are the best. In other words, as the ratio of the second host in the mixture increases, the efficiency and lifespan improve.

These results suggest that it is important to derive a mixing ratio that maximizes the charge balance within the light-emitting layer, because the amount of mixing ratio in the mixture affects the device characteristics.

The above description is merely an example of the present invention, and those skilled in the art will appreciate that various modifications may be made without departing from the essential characteristics of the present invention. Accordingly, the embodiments disclosed in this specification are not intended to limit the present invention, but rather to explain it, 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 following claims, and all techniques within the equivalent scope should be interpreted as being included in the scope of the rights of the present invention.

100, 200, 300: Organic electrochemical device 110: First electrode
120: Hole injection layer 130: Hole transport layer
140: Emitting layer 150: Electron transport layer
160: Electron injection layer 170: Second electrode
180: Light efficiency improvement layer 210: Buffer layer
220: Light-emitting auxiliary layer 320: First hole injection layer
330: First hole transport layer 340: First light emitting layer
350: 1st electron transport layer 360: 1st charge generation layer
361: Second charge generation layer 420: Second hole injection layer
430: Second hole transport layer 440: Second light emitting layer
450: Second electron transport layer CGL: Charge generation layer
ST1: 1st stack ST2: 2nd stack

Claims (13)

In an organic electric device including an anode, a cathode, and an organic layer formed between the anode and the cathode,
An organic electric device characterized in that the organic layer includes a phosphorescent emitting layer, and the host of the phosphorescent emitting layer includes a first compound represented by the following chemical formula 1 and a second compound represented by the following chemical formula 2:
<Chemical Formula 1><Chemical Formula 2>

In the above chemical formula 1,
Ar ¹ to Ar ³ are independently unsubstituted C ₆ to C ₆₀ aryl groups,
L ¹ to L ³ are independently a single bond or an unsubstituted C ₆ to C ₆₀ arylene group,
However, this does not apply to cases where the chemical formula 1 contains a fluorene moiety or a triphenylene moiety.
In the above chemical formula 2,
X ₄ to X ₆ are N or C(L-Ar), and at least one of X ₄ to X ₆ is N,
Ar ⁴ to Ar ⁶ are independently selected from the group consisting of a C ₆ to C ₆₀ aryl group; a fluorenyl group; a C ₂ to C ₆₀ heterocyclic group including at least one heteroatom selected from O, N, S, Si and P; and a C ₃ to C ₆₀ aliphatic ring group.
The above Ar is selected from the group consisting of hydrogen; deuterium; halogen; cyano group; C ₆ to C ₆₀ aryl group; fluorenyl group; C ₂ to C ₆₀ heterocyclic group including at least one heteroatom of O, N, S, Si and P; C ₃ to C ₆₀ aliphatic ring group; C ₁ to C ₃₀ alkyl group; C ₂ to C ₃₀ alkenyl group; C ₂ to C ₃₀ alkynyl group; C ₁ to C ₃₀ alkoxyl group; C ₆ to C ₃₀ aryloxy group; and -L'-N(R _a )(R _b ), and when Ar is plural, they are the same or different from each other,
L ⁴ to L ⁶ , L and L' are independently selected from the group consisting of a single bond; a C ₆ to C ₆₀ arylene group; a fluorenylene group; a C ₃ to C ₆₀ aliphatic ring group; and a C ₂ to C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P, and when L is plural, each L is the same or different from each other,
The above R _a and R _b are independently selected from the group consisting of a C ₆ to C ₆₀ aryl group; a fluorenyl group; a C ₃ to C ₆₀ aliphatic ring group; and a C ₂ to C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P.
However, this does not apply to cases where the chemical formula 2 contains a carbazole moiety.
The above Ar ⁴ to Ar ⁶ , Ar, L ⁴ to L ⁶ , L, L', R _a , and R _b are each independently deuterium; halogen; a silane group unsubstituted or substituted with a C ₁ -C ₂₀ alkyl group or a C ₆ -C ₂₀ aryl group; a cyano group; a C _{1 -C 20} alkylthio group; _a C ₁ -C ₂₀ alkoxy group; a C 1 -C 20 alkyl group; a C ₂ -C ₂₀ alkenyl group; a C ₂ -C ₂₀ alkynyl group; a C ₆ -C ₂₀ aryl group; a fluorenyl group; a C ₂ -C ₂₀ heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si, and P; and may be further substituted with one or more substituents selected from the group consisting of an aliphatic ring group of C ₃ -C ₂₀ . In paragraph 1,
An organic electric device characterized in that the above L ⁴ is independently selected from a group consisting of the following chemical formulas b-1 to b-13:
<Chemical formula b-1><Chemical formula b-2><Chemical formula b-3><Chemical formula b-4>

<Chemical formula b-5><Chemical formula b-6><Chemical formula b-7><Chemical formula b-8>

<Chemical formula b-9><Chemical formula b-10>

<chemical formula b-11><chemical formula b-12><chemical formula b-13>

In the chemical formulas b-1 to b-13 above,
Y ¹ is O, S or C(R')(R"),
Z ¹ to Z ³ are independently C, C(R _c ) or N, and at least one of Z ¹ to Z ³ is N,
R ⁵ to R ⁷ , R', R" and R _c are independently selected from the group consisting of hydrogen; deuterium; halogen; cyano group; C ₆ to C ₂₀ aryl group; fluorenyl group; C ₂ to C ₂₀ heterocyclic group including at least one heteroatom of O, N, S, Si and P; C ₃ to C ₂₀ aliphatic ring group; C ₁ to C ₂₀ alkyl group; C ₂ to C ₂₀ alkenyl group; C ₂ to C ₂₀ alkynyl group; and C ₁ to C ₂₀ alkoxy group, and adjacent groups may bond to each other to form a ring, R' and R" may bond to each other to form a ring, and adjacent R _c may bond to each other to form a ring,
f is an integer from 0 to 6, e, g, h, i are each integers from 0 to 4, j, k are each integers from 0 to 3, l is each integer from 0 to 2, m is an integer from 0 to 3, and when each of these is an integer greater than or equal to 2, the plurality of R ^5s , the plurality of R ^6s , and the plurality of R ^7s are the same or different from each other. In paragraph 1,
The above chemical formula 2 is an organic electric device characterized by being represented by one of the following chemical formulas 2-A to 2-C:
<Chemical Formula 2-A><Chemical Formula 2-B><Chemical Formula 2-C>

In the above chemical formulas 2-A to 2-C, Ar ⁴ to Ar ⁶ and L ⁴ to L ⁶ are as defined in the first term. In paragraph 1,
The above chemical formula 2 is an organic electric device characterized by being represented by one of the following chemical formulas 2-1 to 2-8:
<Chemical Formula 2-1><Chemical Formula 2-2>

<Chemical Formula 2-3><Chemical Formula 2-4>

<Chemical Formula 2-5><Chemical Formula 2-6>

<Chemical Formula 2-7><Chemical Formula 2-8>

In the chemical formulas 2-1 to 2-8 above, Ar ⁵ , Ar ⁶ , L ⁴ to L ⁶ , X ₄ to X ₆ are as defined in the first clause,
R ₁ is selected from the group consisting of hydrogen; deuterium; halogen; cyano group; C ₆ to C ₂₀ aryl group; fluorenyl group; C ₂ to C ₂₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P; C ₃ to C ₂₀ aliphatic ring group; C ₁ to C ₂₀ alkyl group; C ₂ to C ₂₀ alkenyl group; C ₂ to C ₂₀ alkynyl group; and C ₁ to C ₂₀ alkoxy group, and adjacent groups can be bonded to each other to form a ring,
p is an integer from 0 to 4, q is an integer from 0 to 9, r is an integer from 0 to 5, and if p, q or r is an integer greater than or equal to 2, then each of R ₁ is equal to or different from each other,
X ₇ and X ₈ are independently a single bond, N-(L ₂ -Ar ₂ ), O, S or C(R ₂ )(R ₃ ), and at least one of X ₇ and X ₈ is not a single bond,
Y ¹ to Y ³⁸ are each independently C, C(R ₄ ) or N, and adjacent R _{4 s} may combine with each other to form a ring,
The above R ₂ to R ₄ are independently selected from the group consisting of hydrogen; deuterium; halogen; cyano group; C ₆ to C ₂₀ aryl group; fluorenyl group; C ₂ to C ₂₀ heterocyclic group including at least one heteroatom of O, N, S, Si and P; C ₃ to C ₂₀ aliphatic ring group; C ₁ to C ₂₀ alkyl group; C ₂ to C ₂₀ alkenyl group; C ₂ to C ₂₀ alkynyl group; and C ₁ to C ₂₀ alkoxy group, and R ₂ and R ³ can be bonded to each other to form a ring, and adjacent R ₄ can be bonded to each other to form a ring,
The above L ₂ and L ₃ are independently selected from the group consisting of a single bond; a C ₆ to C ₂₀ arylene group; a fluorenylene group; a C ₂ to C ₂₀ heterocyclic group including at least one heteroatom among O, N, S, Si and P; a C ₃ to C ₂₀ aliphatic ring group; and combinations thereof.
The above Ar ₂ is selected from the group consisting of a C ₆ to C ₂₀ aryl group; a fluorenyl group; a C ₂ to C ₂₀ heterocyclic group including at least one heteroatom among O, N, S, Si and P; a C ₃ to C ₂₀ aliphatic ring group; and combinations thereof.
The above R ₅ and R ₆ can be independently selected from the group consisting of a C ₆ to C ₂₀ aryl group; a fluorenyl group; a C ₂ to C ₂₀ heterocyclic group including at least one heteroatom among O, N, S, Si and P; a C ₃ to C ₂₀ aliphatic ring group; and a combination thereof.
However, compounds represented by the following chemical formulas 3-3-1 to 3-3-4 in the above chemical formula 2-3 are excluded.
<Chemical Formula 3-3-1><Chemical Formula 3-3-2><Chemical Formula 3-3-3><Chemical Formula 3-3-4>

In the chemical formulas 3-3-1 to 3-3-4, L ⁴ to L ⁶ , Ar ⁵ and Ar ⁶ are as defined in the first paragraph. In paragraph 1,
An organic electric device characterized in that the compound represented by the chemical formula 1 is one of the following compounds:

. In paragraph 1,
An organic electric device characterized in that the compound represented by the chemical formula 2 is one of the following compounds:








. In paragraph 1,
An organic electric device characterized in that the host is a mixture in which the first compound and the second compound are mixed in a weight ratio of 2:8 to 8:2. In paragraph 1,
An organic electric device characterized in that the organic layer includes two or more stacks including a hole transport layer, a light-emitting layer, and an electron transport layer sequentially formed on the anode. In Article 8,
An organic electric device characterized in that the organic layer further includes a charge generation layer formed between two or more stacks. In paragraph 1,
The organic layer further includes one or more hole transport band layers formed between the light-emitting layer and the anode,
An organic electric device characterized in that the hole transport band layer comprises at least one layer of a hole transport layer and a light-emitting auxiliary layer, and comprises a compound represented by chemical formula 1. In paragraph 1,
An organic electric device characterized by further comprising a light efficiency improvement layer formed on a layer that does not come into contact with the organic layer among both surfaces of the anode or both surfaces of the cathode. A display device including the organic electric element of claim 1; and
An electronic device including a control unit that drives the display device. In Article 12,
An electronic device characterized in that the organic electroluminescent element is selected from the group consisting of an organic light-emitting element, an organic solar cell, an organic photoconductor, an organic transistor, a monochrome lighting element, and a quantum dot display element.