KR102366721B1 - Compound for organic electronic element, organic electronic element comprising the same, and electronic device thereof - Google Patents

Abstract

Disclosed are an organic electric device comprising a compound represented by Chemical Formula 1, a first electrode, a second electrode, and an organic material layer between the first and second electrodes, and an electronic device including the same, wherein the organic material layer is a compound represented by Chemical Formula 1 By including, it is possible to lower the driving voltage of the organic electric device, it is possible to improve the luminous efficiency and lifespan.

Description

A compound for an organic electric device, an organic electric device using the same, and an electronic device thereof

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

In general, the organic light emitting phenomenon refers to a phenomenon in which electric energy is converted into light energy using an organic material. An organic electric device using an organic light emitting phenomenon usually has a structure including an anode and a cathode and an organic material layer therebetween. Here, the organic layer is often formed of a multi-layered structure composed of different materials in order to increase the efficiency and stability of the organic electric device, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer.

A material used as an organic layer in an organic electric device may be classified into a light emitting material and a charge transport material, such as a hole injection material, a hole transport material, an electron transport material, an electron injection material, etc. according to their function.

In addition, the light emitting material can be classified into a high molecular type and a low molecular type according to the molecular weight, and can be classified into a fluorescent material derived from a singlet excited state of an electron and a phosphorescent material derived from a triplet excited state of an electron according to the light emission mechanism. can In addition, the light emitting material may be divided into blue, green, and red light emitting materials and yellow and orange light emitting materials necessary for realizing a better natural color according to the emission color.

On the other hand, when only one material is used as a light emitting material, the maximum emission wavelength is shifted to a longer wavelength due to intermolecular interaction, and there is a problem in that the color purity is lowered or the efficiency of the device is reduced due to the emission attenuation effect. A host/dopant system may be used as a light emitting material in order to increase the luminous efficiency through the The principle is that when a small amount of a dopant having a smaller energy band gap than that of the host forming the emission layer is mixed in the emission layer, excitons generated in the emission 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 band of the dopant, light having a desired wavelength can be obtained according to the type of dopant used.

Currently, the portable display market is a large-area display, and the size thereof is increasing, so that power consumption greater than the power consumption required for the existing portable display is required. Therefore, power consumption has become a very important factor for a portable display having a limited power supply such as a battery, and the problem of efficiency and lifespan must also be solved.

Efficiency, lifespan, and driving voltage are related to each other, and when the efficiency is increased, the driving voltage is relatively decreased. It shows a tendency to increase the lifespan. However, the efficiency cannot be maximized by simply improving the organic material layer. This is because, when the energy level between each organic material layer, the T ₁ value, and the intrinsic properties (mobility, interfacial properties, etc.) of the material are optimally combined, a long lifespan and high efficiency can be achieved at the same time. Therefore, 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 sufficiently exhibit the excellent characteristics of an organic electric device, the material constituting the organic material layer in the device, such as a hole injection material, a hole transport material, a light emitting material, an electron transport material, an electron injection material, etc., is supported by a stable and efficient material. However, the development of stable and efficient organic material for organic electric devices has not yet been sufficiently developed. Accordingly, the development of new materials is continuously required, and in particular, the development of a host material for the light emitting layer is urgently required.

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

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

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

By using the compound according to the embodiment of the present invention, the driving voltage of the device can be lowered, and the luminous efficiency, color purity, and lifespan of the device can be greatly improved.

1 is an exemplary view of an organic electroluminescent device according to the present invention.

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

In adding reference numerals to the components of each drawing, it should be noted that the same components are given the same reference numerals as much as possible even though 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 gist of the present invention, the detailed description thereof will be omitted.

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

Further, when a component, such as a layer, membrane, region, plate, etc., is said to be “on” or “on” another component, this means not only when it is “directly above” another component, but also when another component is in between. It should be understood that cases may be included. Conversely, when it is said that an element is "on top of" another part, it should be understood to mean that there is no other part in the middle.

As used in this specification and the appended claims, unless otherwise indicated, the following terms have the following meanings.

As used herein, the term “halo” or “halogen” refers to fluorine (F), bromine (Br), chlorine (Cl) or iodine (I), unless otherwise specified.

The term "alkyl" or "alkyl group" as used herein, unless otherwise specified, has a single bond of 1 to 60 carbon atoms, a straight chain alkyl group, a branched chain alkyl group, a cycloalkyl (alicyclic) group, an alkyl-substituted cyclo means a radical of saturated aliphatic functional groups including alkyl groups and cycloalkyl-substituted alkyl groups.

As used herein, the term “haloalkyl group” or “halogenalkyl group” refers to an alkyl group substituted with halogen unless otherwise specified.

The term "alkenyl group" or "alkynyl group" used in the present invention, unless otherwise specified, has a double or triple bond of 2 to 60 carbon atoms, respectively, and includes a straight or branched chain group, and is limited thereto it is not

As used herein, the term “cycloalkyl” refers to an alkyl forming a ring having 3 to 60 carbon atoms, unless otherwise specified, and is not limited thereto.

As used herein, the term "alkoxyl group", "alkoxy group", or "alkyloxy group" refers to an alkyl group to which an oxygen radical is attached, and has 1 to 60 carbon atoms unless otherwise specified, and is limited thereto. it is not

As used herein, the term “aryloxyl group” or “aryloxy group” refers to an aryl group to which an oxygen radical is attached, and has 6 to 60 carbon atoms unless otherwise specified, but is not limited thereto.

As used herein, the term "fluorenyl group" or "fluorenylene group" means a monovalent or divalent functional group in which R, R' and R" are all hydrogen in the following structures, respectively, unless otherwise specified, " A substituted fluorenyl group" or "substituted fluorenylene group" means that at least one of the substituents R, R', and R" is a substituent other than hydrogen, and R and R' are bonded to each other to It includes the case of forming a compound as a spy together.

The terms "aryl group" and "arylene group" used in the present invention have 6 to 60 carbon atoms, respectively, unless otherwise specified, and are not limited thereto. In the present invention, the aryl group or the arylene group includes a monocyclic type, a ring aggregate, a fused multiple ring system, a spiro compound, and the like.

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 specified, the number of carbon atoms each containing at least one heteroatom It means a ring of 2 to 60, but is not limited thereto. As used herein, the term "heteroatom" refers to N, O, S, P or Si, unless otherwise specified, and the heterocyclic group is a monocyclic group including a heteroatom, a ring aggregate, a fused multiple ring system, a spy means a compound or the like.

In addition, the "heterocyclic group" may include a ring containing SO ₂ instead of carbon forming the ring. For example, "heterocyclic group" includes the following compounds.

As used herein, the term "ring" includes monocyclic and polycyclic rings, and includes hydrocarbon rings as well as heterocycles containing at least one heteroatom, and includes aromatic and non-aromatic rings.

As used herein, the term "polycyclic" includes ring assemblies such as biphenyl, terphenyl, etc., fused multiple ring systems and spiro compounds, and includes aromatic as well as non-aromatic, hydrocarbon Rings include, of course, heterocycles containing at least one heteroatom.

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

As used herein, the term "fused multiple ring system" refers to a fused ring form shared by at least two atoms, and includes a fused ring system of two or more hydrocarbons and at least one heteroatom. and a form in which at least one heterocyclic system is fused. The fused multiple ring system may be an aromatic ring, a heteroaromatic ring, an aliphatic ring, or a combination of these rings.

The term "spiro compound" used in the present invention has a 'spiro union', and the spiro linkage means a connection formed by sharing only one atom in two rings. At this time, the atoms shared by the two rings are called 'spiro atoms', and they are respectively 'monospiro-', 'dispiro-', 'trispiro-', depending on the number of spiro atoms in a compound. ' It's called a compound.

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

In addition, unless otherwise explicitly stated, in the term "substituted or unsubstituted" as used herein, "substitution" means deuterium, halogen, amino group, nitrile group, nitro group, C ₁ -C ₂₀ alkyl group, C ₁ -C ₂₀ Alkoxy group, C ₁ -C ₂₀ Alkylamine group, C ₁ -C ₂₀ Alkylthiophene group, C ₆ -C ₂₀ Arylthiophene group, C ₂ -C ₂₀ Alkenyl group, C ₂ -C ₂₀ alkynyl group, C ₃ -C ₂₀ cycloalkyl group, C ₆ -C ₂₀ aryl group, C ₆ -C ₂₀ aryl group substituted with deuterium, C ₈ -C ₂₀ arylalkenyl group, silane group, boron group, germanium group, and O, N, S, Si and P containing at least one heteroatom selected from the group consisting of C ₂ -C ₂₀ heterocyclic group means substituted with one or more substituents selected from the group consisting of and is not limited to these substituents.

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 substituents may be described as 'the name of the group reflecting the valence', but is described as 'name of the parent compound' You may. For example, in the case of 'phenanthrene', which is a type of aryl group, the monovalent 'group' is 'phenanthryl' and the divalent group is 'phenanthrylene'. Regardless, it can also be described as the name of the parent compound, 'phenanthrene'. Similarly, in the case of pyrimidine, regardless of the valence, it can be described as 'pyrimidine' or as the 'name of the group' of the valence, such as a pyrimidinyl group in the case of monovalent or pyrimidinylene in the case of divalent. there is.

In addition, unless there is an explicit explanation, the formula used in the present invention applies the same as the definition of the substituent by the exponential definition of the following formula.

Here, when a is an integer of 0, the substituent R ¹ means that it does not exist, that is, when a is 0, it means that all hydrogens are bonded to the carbons forming the benzene ring. It 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 is bonded to any one carbon of the carbons forming the benzene ring, and when a is an integer of 2 or 3, it may be bonded as follows, for example, a is 4 to 6 Even if it is an integer of , it is bonded to the carbon of the benzene ring in a similar manner, and when a is an integer of 2 or more, R ¹ may be the same as or different from each other.

1 is an exemplary view 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 120 , a second electrode 180 , and a first electrode 120 formed on a substrate 110 , and the second electrode 120 . An organic material layer including the compound according to the present invention is provided between the two electrodes 180 . In this case, the first electrode 120 may be an anode (anode), the second electrode 180 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 sequentially include a hole injection layer 130 , a hole transport layer 140 , a light emitting layer 150 , an electron transport layer 160 , and an electron injection layer 170 on the first electrode 120 . At this time, at least one of these layers may be omitted, or may further include a hole blocking layer, an electron blocking layer, a light emission auxiliary layer 151, an electron transport auxiliary layer, a buffer layer 141, etc., and the electron transport layer 160, etc. It may also serve as a hole blocking layer.

In addition, although not shown, the organic electric device according to an embodiment of the present invention further includes a protective layer or a light efficiency improving layer (Capping layer) formed on at least one surface of the first electrode and the second electrode opposite to the organic material layer. can do.

The compound according to an embodiment of the present invention applied to the organic material layer is a hole injection layer 130, a hole transport layer 140, a light emitting auxiliary layer 151, an electron transport auxiliary layer, an electron transport layer 160, an electron injection layer ( 170) and the like, a host or dopant material of the light emitting layer 150, or a material of the light efficiency improving layer. For example, the compound of the present invention may be used as a material for the emission layer 150 , the hole transport layer 140 , and/or the emission auxiliary layer 151 , and preferably as a host material for the emission layer 150 .

On the other hand, even with the same core, the band gap, electrical properties, interface properties, etc. may vary depending on which position the substituent is bonded to, so the selection of the core and the combination of sub-substituents bonded thereto Research is required, and in particular, when the energy level and T ₁ value between each organic material layer, and the intrinsic properties of the material (mobility, interfacial properties, etc.) are optimally combined, a long lifespan and high efficiency can be achieved at the same time.

Therefore, in the present invention, by forming the light emitting layer 150 using the compound represented by Chemical Formula 1, the energy level and T ₁ value between each organic material layer, the intrinsic properties of the material (mobility, interfacial properties, etc.), etc. are optimized to make the organic electric device life and efficiency can be improved at the same time.

The organic electroluminescent device according to an embodiment of the present invention may be manufactured using various deposition methods. It can be manufactured using a deposition method such as PVD or CVD, for example, by depositing a metal or a metal oxide having conductivity or an alloy thereof on a substrate to form the anode 120, and the hole injection layer 130 thereon. , after forming an organic material layer including the hole transport layer 140, the light emitting layer 150, the electron transport layer 160, and the electron injection layer 170, it can be prepared by depositing a material that can be used as the cathode 180 thereon. there is. In addition, an auxiliary light emitting layer 151 may be further formed between the hole transport layer 140 and the light emitting layer 150 , and an electron transport auxiliary layer may be further formed between the light emitting layer 150 and the electron transport layer 160 .

In addition, the organic layer is a solution process or a solvent process rather than a 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, Dr. Blay It can be manufactured with a smaller number of 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 formation method.

The organic electric device according to an embodiment of the present invention may be a top emission type, a back emission type, or a double-sided emission type depending on a material used.

WOLED (White Organic Light Emitting Device) has the advantage of being easy to realize high resolution and excellent in processability, and can be manufactured using the existing color filter technology of LCD. Various structures for a white organic light emitting diode mainly used as a backlight device have been proposed and patented. Typically, a side-by-side method in which R (Red), G (Green), and B (Blue) light emitting units are mutually planar, and a stacking method in which R, G, and B light emitting layers are stacked up and down There is a color conversion material (CCM) method using electroluminescence by the blue (B) organic light emitting layer and photo-luminescence of an inorganic phosphor using the light therefrom. could also be applied to such WOLEDs.

In addition, the organic electric device according to an embodiment of the present invention may be one of an organic electroluminescent device, an organic solar cell, an organophotoreceptor, an organic transistor, and a device for single-color or white lighting.

Another embodiment of the present invention may include a display device including the organic electric device of the present invention described above, and an electronic device including a control unit for controlling the display device. In this case, the electronic device may be a current or future wired/wireless communication terminal, and includes all electronic devices such as a mobile communication terminal such as a mobile phone, a PDA, an electronic dictionary, a PMP, a remote control, a navigation system, a game machine, various TVs, and various computers.

Hereinafter, the compound according to one aspect of the present invention will be described.

The compound according to one aspect of the present invention is represented by the following formula (1).

<Formula 1>

In Formula 1, each symbol may be defined as follows.

R ¹ to R ¹² are each independently hydrogen; heavy hydrogen; halogen; C ₆ ~ C ₆₀ Aryl group; fluorenyl group; O, N, S, Si and P containing at least one heteroatom C ₂ ~ C ₆₀ A heterocyclic group; C ₃ ~ C ₆₀ A fused ring group of an aliphatic ring and a C ₆ ~ C ₆₀ aromatic ring; C ₁ ~ C ₅₀ Alkyl group; C ₂ ~ C ₂₀ Alkenyl group; C ₂ ~ C ₂₀ Alkynyl group; C ₁ ~ C ₃₀ An alkoxyl group; C ₆ ~ C ₃₀ Aryloxy group; and -L′-N(R _a )(R _b ); and adjacent groups may be bonded to each other to form a ring.

When R ¹ to R ¹² are an aryl group, preferably a C ₆ to C ₃₀ aryl group, more preferably a C ₆ to C ₁₄ aryl group, specifically, phenyl, biphenyl, naphthalene, phenanthrene, etc. may be . When R ¹ To R ¹² is a heterocyclic group, preferably a C ₂ ~ C ₃₀ heterocyclic group, more preferably a C ₂ ~ C ₁₂ heterocyclic group, specifically pyrimidine, triazine, carbazole, etc. may be there is.

A ring formed by bonding neighboring groups among R ¹ to R ¹² is a C ₂ ~ C ₆₀ hetero atom comprising at least one heteroatom among C ₆ ~ C ₆₀ aromatic hydrocarbons, O, N, S, Si and P It may be a ring or fluorene, and specifically benzene, naphthalene, phenanthrene, and the like.

Ring X is C ₆ ~ C ₆₀ Aromatic hydrocarbon; fluorene; O, N, S, Si and P containing at least one heteroatom C ₂ ~ C ₆₀ Heterocycle; and a C ₃ ~ C ₆₀ aliphatic ring and a C ₆ ~ C ₆₀ aromatic ring fused ring; is selected from the group consisting of.

When Ring X is an aromatic hydrocarbon, preferably C ₆ to C ₃₀ aromatic hydrocarbon, more preferably C ₆ to C ₁₈ aromatic hydrocarbon, specifically benzene, biphenyl, naphthalene, phenanthrene, triphenylene, pyrene , fluoranthene, and the like. When Ring X is a heterocyclic ring, preferably a C ₂ ~ C ₃₀ heterocycle, more preferably a C ₂ ~ C ₂₄ heterocycle, specifically pyridine, pyrimidine, pyrazine, pyridazine, quinoline, quinoxaline, quina Zoline, benzoquinazoline, dibenzoquinazoline, benzothiophene, benzofuran, indole, dibenzothiophene, benzonaphthothiophene, dibenzofuran, benzonaphthofuran, carbazole, benzothienopyrimidine, Benzofuropyrimidine, pyrimidoindole, 1,1-dimethyl-1H-indene, pyrimidodimethylindene, imidazopyridine, imidazoquinoline, dihydrodiphenylphenazine, dihydrodimethylphenylacridine , phenylphenoxazine, phenylphenothiazine, cyanthrene, dibenzodioxin, naphthyridine, benzopyridothiophene, benzothienoquinoxaline, benzofuroquinoxaline, and the like. When ring X is fluorene, it may be 9-diphenyl-9H-fluorene, 9,9'-spirobifluorene, or the like.

The L' is a single bond; C ₆ ~ C ₆₀ Arylene group; fluorenylene group; C ₃ ~ C ₆₀ A fused ring group of an aliphatic ring and a C ₆ ~ C ₆₀ aromatic ring; And C ₂ ~ C ₆₀ A heterocyclic group; may be selected from the group consisting of.

The R _a and R _b are each independently a C ₆ ~ C ₆₀ aryl group; fluorenyl group; C ₃ ~ C ₆₀ A fused ring group of an aliphatic ring and a C ₆ ~ C ₆₀ aromatic ring; And O, N, S, Si and P containing at least one heteroatom C ₂ ~ C ₆₀ A heterocyclic group; may be selected from the group consisting of.

The aryl group, arylene group, aromatic hydrocarbon, fluorenyl group, fluorenylene group, fluorene, heterocyclic group, heterocyclic group, fused ring group, fused ring, alkyl group, alkenyl group, alkynyl group, alkoxy group, aryloxy group , and a ring formed by bonding adjacent groups of R ¹ to R ¹² to each other is deuterium; halogen; a silane group unsubstituted or substituted with a C ₁ -C ₂₀ alkyl group or a C ₆ -C ₂₀ aryl group; siloxane group; boron group; germanium group; cyano group; nitro group; C ₁ -C ₂₀ Alkylthio group; C ₁ -C ₂₀ An alkoxyl group; C ₁ -C ₂₀ Alkyl group; C ₂ -C ₂₀ alkenyl group; C ₂ -C ₂₀ alkynyl group; C ₆ -C ₂₀ Aryl group; a C ₆ -C ₂₀ aryl group substituted with deuterium; fluorenyl group; C ₂ -C ₂₀ A heterocyclic group comprising at least one heteroatom selected from the group consisting of O, N, S, Si and P; C ₃ -C ₂₀ cycloalkyl group; C ₇ -C ₂₀ Arylalkyl group; C ₈ -C ₂₀ arylalkenyl group; -L'-N(R _a )(R _b ); And it may be further substituted with one or more substituents selected from the group consisting of combinations thereof, wherein L', R _a and R _b are as defined above.

Formula 1 may be represented by Formula 2 below.

<Formula 2>

In Formula 2, R ¹ to R ¹² are as defined in Formula 1, and X ¹ to X ⁴ are each independently N, C(R′), N(R′), S, O, or C(R′). )(R"), and m is 0 or 1.

R' and R" 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; a siloxane group; a boron group; a germanium group; cya No group; Nitro group; C ₁ -C ₂₀ Alkylthio group; C ₁ -C ₂₀ Alkoxy group; C ₁ -C ₂₀ alkyl group; C ₂ -C ₂₀ alkenyl group; C ₂ -C ₂₀ alkynyl group; C ₆ -C ₂₀ Aryl group; C ₆ -C ₂₀ Aryl group substituted with deuterium; Fluorenyl group; C ₂ containing at least one heteroatom selected from the group consisting of O, N, S, Si and P -C ₂₀ heterocyclic group; C ₃ -C ₂₀ cycloalkyl group; C ₇ -C ₂₀ arylalkyl group; C ₈ -C ₂₀ arylalkenyl group; -L′-N(R _a )(R _b ); And it is selected from the group consisting of combinations thereof, and adjacent R' may be bonded to each other to form a ring.

When R _a and R _b are an aryl group, preferably a C ₆ ~ C ₃₀ aryl group, more preferably a C ₆ ~ C ₁₄ aryl group, specifically, phenyl, biphenyl, naphthalene, phenanthrene, etc. may be . When R _a and R _b are a heterocyclic group, preferably a C ₂ ~ C ₃₀ heterocyclic group, more preferably a C ₂ ~ C ₁₂ heterocyclic group, specifically dibenzofuran, dibenzothiophene, etc. there is. When R _a and R _b are fluorenyl groups, they may be 9-dimethyl-9H-fluorene, 9-diphenyl-9H-fluorene, 9,9′-spirobifluorene, or the like.

Formula 2 may be represented by Formula 3 or Formula 4 below.

<Formula 3> <Formula 4>

In Formulas 3 and 4, R ¹ to R ¹² , and X ¹ to X ⁴ are as defined in Formula 2.

In addition, Chemical Formula 1 may be represented by one of Chemical Formulas 5 to 18 below.

<Formula 5> <Formula 6> <Formula 7>

<Formula 8> <Formula 9> <Formula 10>

<Formula 11> <Formula 12> <Formula 13>

<Formula 14> <Formula 15> <Formula 16>

<Formula 17> <Formula 18>

In Formulas 5 to 18, R ¹ to R ¹² , and X ¹ to X ⁴ are as defined in Formula 2.

X ⁵ to X ³³ are each independently N, C(R'), N(R'), S, O or C(R')(R"), and Y ¹ and Y ² are each independently N(R) '), S, O or C(R')(R"), wherein R' and R" are as defined in formula (2).

Specifically, Chemical Formula 1 may be one of the following compounds.

In another aspect of the present invention, the present invention provides an organic electric device including a first electrode, a second electrode, and an organic material layer positioned between the first electrode and the second electrode. In this case, the organic material layer includes the compound represented by Formula 1 above.

The organic layer includes at least one of a hole injection layer, a hole transport layer, a light emitting auxiliary layer, a light emitting layer, an electron transport auxiliary layer, an electron transport layer, and an electron injection layer, and the compound represented by Formula 1 is a hole injection layer, a hole transport layer, It may be included in at least one of a light emitting auxiliary layer, a light emitting layer, an electron transport auxiliary layer, an electron transport layer, and an electron injection layer, and preferably may be included in the light emitting layer. In this case, the compound may be included in the form of a single compound or a mixture of two or more, and preferably, the compound represented by Formula 1 may be used as a host material of the light emitting layer, in particular, a red phosphorescent host material.

Hereinafter, examples of the synthesis of the compound represented by Formula 1 and the preparation of an organic electric device according to the present invention will be described in detail with reference to examples, but the present invention is not limited to the following examples.

Synthesis example

Illustratively, the compound represented by Formula 1 according to the present invention (Final Products) may be prepared as in Scheme 1 or Scheme 2 below, but is not limited thereto.

<Scheme 1>

<Scheme 2>

Synthesis of Sub 1

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

<Scheme 3>

Synthesis of Sub 1-1

(1) Synthesis of Sub 1-I

The starting material, 2,7-dibromonaphthalene (40.0 g, 139.9 mmol) was placed in a round-bottom flask and dissolved in 700 mL of THF, (2-nitrophenyl)boronic acid (51.4 g, 307.7 mmol), Pd(PPh ₃ ) ₄ (4.9 g, 4.2 mmol), K ₂ CO ₃ (58.0 g, 419.6 mmol), 300 mL of water were added and stirred at 80°C. After completion of the reaction, extraction with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ , concentrated, and the resulting compound was recrystallized by silicagel column to obtain 42.2 g (yield: 84%) of the product.

(2) Synthesis of Sub 1-1

Sub 1-I (42.2 g, 113.9 mmol) obtained in the above synthesis was placed in a round-bottom flask and dissolved with 570 mL of DMF, followed by PPh ₃ (89.9 g, 341.8 mmol) was added and stirred at 165 °C. After completion of the reaction, the reaction was extracted with CH ₂ Cl ₂ and water, and the organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was recrystallized by silicagel column to obtain 25.5 g (yield: 73%) of the product.

Synthesis of Sub 1-7

(1) Synthesis of Sub 1-II-1

The starting materials, 2-bromo-9-iodophenanthrene (30.0 g, 78.3 mmol) and (10-nitrophenanthren-9-yl)boronic acid (23.01 g, 86.16 mmol), were synthesized using the method of Sub 1-I above to synthesize the product 30.1 g (Yield: 80%) was obtained.

(2) Synthesis of Sub 1-II

Sub 1-II-1 (30.0 g, 62.7 mmol) and (2-nitrophenyl) boronic acid (11.5 g, 69.0 mmol) were used for the synthesis of Sub 1-I to obtain 24.2 g (yield: 74 %) of the product. .

(3) Synthesis of Sub 1-7

Sub 1-II (24.0 g, 46.1 mmol) was obtained by using the above method for synthesizing Sub 1-1 to obtain 15.6 g (yield: 74 %) of the product.

Synthesis of Sub 1-11

(1) Synthesis of Sub 1-III-1

Sub 1-1 (20.0 g, 65.3 mmol) was dissolved in 350 mL of DMF in a round-bottom flask, NBS (N-bromosuccinimide (12.8 g, 71.8 mmol) was added and stirred at room temperature for 6 hours. When the reaction was completed, the organic layer After separation, the product was dried over MgSO ₄ and concentrated, and the resulting compound was recrystallized by silicagel column to obtain 19.8 g (yield: 79%) of the product.

(2) Synthesis of Sub 1-11

17.5 g (yield: 78%) of Sub 1-III-1 (18.0 g, 62.7 mmol) and phenanthren-3-ylboronic acid (11.4 g, 51.4 mmol) was obtained by using the above method for synthesizing Sub 1-I.

Synthesis of Sub 1-13

(1) Synthesis of Sub 1-IV-1

The starting materials, 2-bromo-7-iodonaphthalene (30.0 g, 90.1 mmol) and (4-chloro-2-nitrophenyl)boronic acid (20.0 g, 99.1 mmol), were synthesized using the method of Sub 1-I above to synthesize product 27.7 g (Yield: 85%) was obtained.

(2) Sub 1-IV-2 synthesis

Sub 1-IV-1 (25.0 g, 68.9 mmol) and (2-nitrophenyl)boronic acid (12.7 g, 75.8 mmol) were used for the synthesis of Sub 1-I to obtain 22.2 g (yield: 80 %) of the product. .

(3) Sub 1-IV-3 synthesis

Sub 1-IV-2 (20.0 g, 49.4 mmol) was obtained by using the method for synthesizing Sub 1-1 above to obtain 10.1 g (yield: 60 %) of the product.

(4) Sub 1-13 synthesis

Sub 1-IV-3 (10.0 g, 29.3 mmol) and (9-(4,6-diphenyl-1,3,5-triazin-2-yl)-9H-carbazol-2-yl)boronic acid (14.3 g , 32.3 mmol) was obtained by using the synthesis method of Sub 1-I above to obtain 15.5 g (yield: 75 %) of the product.

Examples of compounds included in Sub 1 are as follows, but are not limited thereto. Table 1 shows the values of FD-MS (Field Desorption-Mass Spectrometry) for the compounds included in Sub 1 exemplified below.

[Table 1]

Sub 2's Synthesis example

The compound belonging to Sub 2 of Scheme 1 may be synthesized by the following reaction route, but is not limited thereto.

Synthesis example of Sub 2-19

Put 2,3-dichloro-9H-carbazole (15.0 g, 63.5 mmol) in a round-bottom flask and dissolve it with toluene (300 mL), then 2-bromo-4-phenylquinazoline (23.5 g, 82.6 mmol), Pd ₂ (dba) ₃ (1.75 g, 1.9 mmol), P( t -Bu) ₃ (0.8 g, 3.8 mmol), and NaO t -Bu (18.3 g, 190.6 mmol) were added sequentially and stirred at 100°C. After the reaction was completed, the organic layer was extracted with ether and water, dried over MgSO ₄ , concentrated, and the resulting compound was recrystallized using silicagel column to obtain 21.5 g (yield: 77%) of the product.

Synthesis example of Sub 2-39

2,3-dichloro-1H-indole (14.0 g, 75.3 mmol) and 2-bromo-3-phenylquinoxaline (27.9 g, 97.8 mmol) were synthesized according to the method of Sub 2-19 above to 22.2 g of the product (yield: 76 %) ) was obtained.

Synthesis example of Sub 2-50

Triphenylen-2-ylboronic acid (13.3 g, 48.7 mmol) and 4-bromo-1,2-dichlorobenzene (10.0 g, 44.3 mmol) were synthesized by the method of Sub 1-I above to 11.9 g of the product (yield: 72 %) got

Synthesis example of Sub 2-66

7.2 g (yield: 74%) of bromobenzene (9.7 g, 61.7 mmol) and 3,4-dichloroaniline (5.0 g, 30.9 mmol) was obtained by using the synthesis method of Sub 2-19.

Examples of compounds included in Sub 2 are as follows, but are not limited thereto. Table 2 shows the values of FD-MS (Field Desorption-Mass Spectrometry) for the compounds included in Sub 2 exemplified below.

[Table 2]

of the final compound Synthesis example

P-3 Synthesis Example

Sub 1-1 (4.6 g, 15.0 mmol) was placed in a round-bottom flask and dissolved with toluene (100 mL), followed by Sub 2-3 [Cas. 2050-75-1] (3.0 g, 15.0 mmol), Pd ₂ (dba) ₃ (0.4 g, 0.5 mmol), P( t -Bu) ₃ (0.2 g, 0.9 mmol), NaO t -Bu (4.3 g) , 45.0 mmol) and stirred at 100 °C. Upon completion of the reaction, the mixture was extracted with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ , concentrated, and the resulting compound was recrystallized by silicagel column to obtain 3.5 g (yield: 54%) of the product.

P-19 Synthesis Example

Sub 1-1 and (5.5 g, 18.0 mmol) and Sub 2-19 (18.0 g, 7.9 mmol) were synthesized using the above P-3 synthesis method to obtain 7.2 g (yield: 60%) of the product.

P-26 Synthesis Example

Sub 1-1 and (4.8 g, 15.7 mmol) and Sub 2-26 [Cas No. 2213-63-0] (3.1 g, 15.7 mmol) was obtained by using the above synthesis method of P-3 to obtain 3.9 g (yield: 58 %) of the product.

P-27 Synthesis Example

Sub 1-1 and (4.1 g, 13.4 mmol) and Sub 2-27 [Cas No.26907-93-7] (3.3 g, 13.4 mmol) were synthesized by using the above P-3 synthesis method to obtain 3.5 g of the product (yield: 54%) was obtained.

P-39 Synthesis Example

Sub 1-1 and (4.6 g, 15.0 mmol) and Sub 2-39 (5.9 g, 15.0 mmol) were synthesized using the above P-3 synthesis method to obtain 6.5 g (yield: 69%) of the product.

P-46 synthesis example

Sub 1-7 and (5.5 g, 12.0 mmol) and Sub 2-45 [Cas No. 4926-53-8] (2.3 g, 12.0 mmol) was obtained by using the above synthesis method of P-3 to obtain 4.2 g (yield: 62 %) of the product.

P-50 synthesis example

Sub 1-11 and (5.6 g, 11.6 mmol) and Sub 2-1 [Cas No. 95-50-1] (1.7 g, 11.6 mmol) was obtained by using the above synthesis method of P-3 to obtain 4.2 g (yield: 66 %) of the product.

P-52 synthesis example

Sub 1-13 and (4.9 g, 7.0 mmol) and Sub 2-1 [Cas No. 95-50-1] (1.0 g, 7.0 mmol) was obtained by using the above synthesis method of P-3 to obtain 2.7 g (yield: 50 %) of the product.

P-58 synthesis example

Sub 1-1 and (6.6 g, 21.5 mmol) and Sub 2-50 (8.0 g, 21.5 mmol) were synthesized using the above P-3 method to obtain 8.2 g (yield: 63 %) of the product.

P-74 synthesis example

Sub 1-1 and (3.9 g, 12.7 mmol) and Sub 2-66 (4.0 g, 12.7 mmol) were synthesized using the above P-3 method to obtain 4.6 g (yield: 66 %) of the product.

P-83 synthesis example

Sub 1-1 and (4.4 g, 14.4 mmol) and Sub 2-75 [Cas No. 943611-33-4] (4.1 g, 14.4 mmol) was obtained by using the above synthesis method of P-3 to obtain 4.6 g (yield: 62 %) of the product.

P-94 Synthesis Example

Sub 1-1 and (5.5 g, 18.0 mmol) and Sub 2-86 [Cas No. 164471-02-7] (6.3 g, 18.0 mmol) was obtained by using the above synthesis method of P-3 to obtain 6.1 g (yield: 58 %) of the product.

Table 3 below shows the values of FD-MS (Field Desorption-Mass Spectrometry) of the final compound synthesized according to the above synthesis example.

[Table 3]

Manufacturing evaluation of organic electric devices

[ Example One] Red Organic electroluminescent device (phosphorescent host)

On the ITO layer (anode) formed on the glass substrate, a 4,4',4"-Tris[2-naphthyl(phenyl)amino]triphenylamine (hereinafter abbreviated as "2-TNATA") film was vacuum-deposited to form a 60 nm-thick hole After forming the injection layer, a 4,4'-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (hereinafter abbreviated as "NPD") film was vacuum-deposited to a thickness of 60 nm to form a hole transport layer. Then, on the hole transport layer, compound P-1 of the present invention as a host material and bis-(1-phenylisoquinolyl)iridium(III)acetylacetonate as a dopant material (hereinafter abbreviated as "(piq) ₂ Ir(acac)") A light emitting layer was deposited to a thickness of 30 nm by doping at a weight ratio of 95:5 using a (1,1'-biphenyl-4-olato)bis(2-methyl-8-quinolinolato )Aluminum (hereinafter abbreviated as “BAlq”) was vacuum-deposited to a thickness of 10 nm, and tris-(8-hydroxyquinoline)aluminum (hereinafter abbreviated as “Alq ₃ ”) was deposited at 40 nm as an electron transport layer on the hole blocking layer. Thereafter, LiF, which is an alkali metal halide, was deposited to a thickness of 0.2 nm as an electron injection layer, and then Al was deposited to a thickness of 150 nm to form a cathode, thereby manufacturing an organic electroluminescent device.

[ Example 2] to [ Example 34]

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

[ comparative example 1] and [ comparative example 2]

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that the following comparative compound A or comparative compound B was used instead of the compound P-1 of the present invention as the host material of the light emitting layer.

<Comparative compound A> <Comparative compound B>

Electroluminescence (EL) characteristics by applying a forward bias DC voltage to the organic electroluminescent devices manufactured by Examples 1 to 34, Comparative Examples 1 and 2 of the present invention, and PR-650 of Photoresearch Corporation was measured, and the T95 lifetime was measured using a lifetime measuring device manufactured by McScience at 2500 cd/m ² standard luminance, and the measurement results are shown in Table 4 below.

[Table 4]

As can be seen from the results of Table 4, the organic light emitting device using the material for the organic light emitting device of the present invention as a phosphorescent host has significantly improved luminous efficiency, lifespan and driving voltage. That is, when the compound of the present invention is used as a host material, compared to Comparative Compound A, which is CBP, which is mainly used as a host material, or Comparative Compound B, which has a structure similar to Chemical Formula 1, of the present invention is used as a host material, The luminous efficiency, lifespan and driving voltage are significantly improved.

This is believed to be because the compound of the present invention having a novel structure has appropriate HOMO and LUMO energy compared to the comparative compounds, and thus the charge balance of holes and electrons in the light emitting layer is increased.

The above description is merely illustrative of the present invention, and various modifications will be possible without departing from the essential characteristics of the present invention by those skilled in the art to which the present invention pertains. Accordingly, the embodiments disclosed in the present specification are intended to illustrate, not to limit the present invention, and the spirit and scope of the present invention are not limited by these embodiments. The protection scope of the present invention should be construed by the following claims, and all technologies within the scope equivalent thereto should be construed as being included in the scope of the present invention.

100: organic electric device 110: substrate
120: first electrode 130: hole injection layer
140: hole transport layer 141: buffer layer
150: light emitting layer 151: light emitting auxiliary layer
160: electron transport layer 170: electron injection layer
180: second electrode

Claims (11)

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

In Formula 1,
R ¹ to R ¹² are each independently hydrogen; heavy hydrogen; halogen; C ₆ ~ C ₃₀ Aryl group; fluorenyl group; O, N, S, Si and P containing at least one heteroatom C ₂ ~ C ₃₀ A heterocyclic group; And -L'-N(R _a ) (R _b ) is selected from the group consisting of, adjacent groups are bonded to each other to form a C ₆ ~ C ₁₈ aromatic hydrocarbon ring,
Ring X is a C ₆ ~ C ₁₈ aromatic hydrocarbon group; fluorenylene group; O, N, S, Si and P containing at least one heteroatom C ₂ ~ C ₂₄ A heterocyclic group; And C ₃ ~ C ₃₀ selected from the group consisting of an aliphatic ring and a C ₆ ~ C ₃₀ aromatic ring fused ring group,
Wherein L' is a single bond,
The R _a and R _b are each independently a C ₆ ~ C ₃₀ aryl group; fluorenyl group; And O, N, S, Si and P, including at least one heteroatom C ₂ ~ C ₃₀ It is selected from the group consisting of a heterocyclic group,
The aryl group, an arylene group, an aromatic hydrocarbon group, a fluorenyl group, a fluorenylene group, a heterocyclic group, a fused ring group, and a ring formed by bonding adjacent groups among R ¹ to R ¹² is deuterium; halogen; cyano group; C ₁ -C ₂₀ Alkyl group; C ₂ -C ₂₀ alkenyl group; C ₆ -C ₂₀ Aryl group; a C ₆ -C ₂₀ aryl group substituted with deuterium; fluorenyl group; C ₂ -C ₂₀ A heterocyclic group comprising at least one heteroatom selected from the group consisting of O, N, S, Si and P; And it may be further substituted with one or more substituents selected from the group consisting of -L'-N(R _a )(R _b ). The method of claim 1,
Formula 1 is a compound, characterized in that represented by the following formula 2:
<Formula 2>

In Formula 2, R ¹ To R ¹² Are the same as defined in claim 1,
X ¹ to X ⁴ are each independently N, C(R'), N(R'), S, O or C(R')(R"), m is 0 or 1,
R′ and R″ are each independently hydrogen; deuterium; halogen; cyano group; C ₁ -C ₂₀ alkyl group; C ₂ -C ₂₀ alkenyl group; C ₆ -C ₂₀ aryl group; C substituted with deuterium 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 -L'-N (R _a ) (R _b ) is selected from the group consisting of,
In C(R'), adjacent R's are bonded to each other to form a C ₆ ~ C ₁₄ aromatic hydrocarbon group; fluorenylene group; O, N, S, Si and P containing at least one heteroatom C ₂ ~ C ₂₀ A heterocyclic group; and a C ₃ ~ C ₂₀ aliphatic ring and a C ₆ ~ C ₂₀ aromatic ring fused ring group may form a ring selected from the group consisting of,
Wherein L', R _a and R _b are as defined in claim 1 . The method of claim 1,
Formula 1 is a compound, characterized in that represented by one of the following Formulas 3 to 18:
<Formula 3><Formula4>

<Formula 5><Formula6><Formula7>

<Formula 8><Formula9><Formula10>

<Formula 11><Formula12><Formula13>

<Formula 14><Formula15><Formula16>

<Formula 17><Formula18>

In Formulas 3 to 18,
R ¹ to R ¹² are as defined in claim 1,
X ¹ to X ³³ are each independently N, C(R'), N(R'), S, O or C(R')(R"),
Y ¹ and Y ² are each independently N(R'), S, O or C(R')(R"),
R′ and R″ are each independently hydrogen; deuterium; halogen; cyano group; C ₁ -C ₂₀ alkyl group; C ₂ -C ₂₀ alkenyl group; C ₆ -C ₂₀ aryl group; C substituted with deuterium 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 -L'-N (R _a ) (R _b ) is selected from the group consisting of,
In C(R'), adjacent R's are bonded to each other to form a C ₆ ~ C ₁₄ aromatic hydrocarbon group; fluorenylene group; O, N, S, Si and P containing at least one heteroatom C ₂ ~ C ₂₀ A heterocyclic group; and a C ₃ ~ C ₂₀ aliphatic ring and a C ₆ ~ C ₂₀ aromatic ring fused ring group may form a ring selected from the group consisting of,
Wherein L', R _a and R _b are as defined in claim 1 . The method of claim 1,
Formula 1 is a compound, characterized in that one of the following compounds:

. a first electrode; a second electrode; and an organic material layer formed between the first electrode and the second electrode,
The organic material layer is an organic electric device, characterized in that it contains the compound of any one of claims 1 to 4. 6. The method of claim 5,
The compound is an organic electric device, characterized in that it is included in the form of a single compound or a mixture of two or more. 6. The method of claim 5,
The organic material layer is an organic electric device comprising at least one of a hole injection layer, a hole transport layer, a light emitting auxiliary layer, a light emitting layer, an electron transport auxiliary layer, an electron transport layer, and an electron injection layer. 8. The method of claim 7,
The compound is an organic electric device, characterized in that used as a red phosphorescence host material of the light emitting layer. 6. The method of claim 5,
The organic material layer is an organic electric device, characterized in that formed by a spin coating process, a nozzle printing process, an inkjet printing process, a slot coating process, a dip coating process or a roll-to-roll process. A display device comprising the organic electric device of claim 5; and
An electronic device comprising a; a control unit for driving the display device. 11. The method of claim 10,
The organic electroluminescent device is an organic electroluminescent device, an organic solar cell, an organic photoreceptor, an organic transistor, and an electronic device, characterized in that one of a single color or white lighting device.

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