KR102473369B1 - Compound for organic electronic element, organic electronic element comprising the same, and electronic device thereof - Google Patents

Abstract

Disclosed are an organic electric device including a compound represented by Chemical Formula 1, a first electrode, a second electrode, and an organic material layer between the first electrode and the second electrode, and an electronic device including the organic electric device. By including the compound represented by Chemical Formula 1 in the organic material layer, the driving voltage of the organic electric element can be lowered and the luminous efficiency and lifetime can be improved.

Description

Compound for organic electric element, organic electric element using the same, and electronic device thereof

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

In general, the organic light emitting phenomenon refers to a phenomenon in which electrical energy is converted into light energy using an organic material. An organic electric device using an organic light emitting phenomenon usually has a structure including an anode, a cathode, and an organic material layer therebetween. Here, the organic material layer is often composed of a multi-layer structure composed of different materials in order to increase the efficiency and stability of the organic electric device, and may include, 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 electric devices may be classified into light emitting materials and charge transport materials, such as hole injection materials, hole transport materials, electron transport materials, and electron injection materials, according to their functions. In addition, the light emitting material can be classified into a high molecular weight type and a low molecular weight type according to molecular weight, and can be classified into a fluorescent material derived from a singlet excited state of electrons and a phosphorescent material derived from a triplet excited state of electrons according to a light emitting mechanism. can In addition, light emitting materials may be classified into blue, green, and red light emitting materials and yellow and orange light emitting materials required to realize better natural colors according to the light emitting color.

On the other hand, when only one material is used as a light emitting material, the maximum emission wavelength moves to a longer wavelength due to intermolecular interactions, and the color purity decreases or the efficiency of the device decreases due to the emission attenuation effect. Therefore, color purity increases and energy transfer A host/dopant system may be used as a light emitting material in order to increase luminous efficiency. 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 to emit light with high efficiency. At this time, since the wavelength of the host moves to the wavelength range of the dopant, light of a desired wavelength can be obtained according to the type of dopant used.

Currently, the size of the portable display market tends to increase with large-area displays, and as a result, power consumption greater than that required for existing portable displays is required. Therefore, power consumption has become a very important factor for portable displays that have a limited power supply source such as a battery, and efficiency and lifespan problems must also be solved.

Efficiency, lifespan, driving voltage, etc. are related to each other, and as efficiency increases, driving voltage relatively decreases. indicates a tendency to increase life expectancy. However, efficiency cannot be maximized by simply improving the organic layer. This is because long life and high efficiency can be achieved at the same time when the optimal combination of the energy level and T ₁ value between each organic material layer and the intrinsic properties of the material (mobility, interfacial property, etc.) is achieved. .

Therefore, it is necessary to develop a light emitting material that has high thermal stability and can efficiently balance charge in the light emitting layer. That is, in order to fully exhibit the excellent characteristics of organic electric devices, materials constituting the organic layer in the device, such as hole injection materials, hole transport materials, light emitting materials, electron transport materials, electron injection materials, etc. are supported by stable and efficient materials. This should be preceded, but in particular, development of a host material and an electron transport layer of 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 the device and improving the luminous efficiency and lifetime 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 formula below.

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 and lifespan of the device can be remarkably improved.

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

In the present specification, the 'group name' corresponding to an aryl group, an arylene group, a heterocyclic group, etc. exemplified as examples of each symbol and its substituent may be described as a 'name of a group reflecting a valence', but described as a 'parent compound name' You may. For example, in the case of 'phenanthrene', which is a kind of aryl group, the name of the group may be described by dividing the valence, such as 'phenanthryl' for a monovalent group and 'phenanthrylene' for a divalent group, but the valence and Regardless, it can also be described as 'phenanthrene', which is the name of the parent compound. Similarly, in the case of pyrimidine, it can also be described as 'pyrimidine' regardless of the valence, or as the 'name of the group' of the corresponding valence, such as a pyrimidinyl group in the case of monovalent, or pyrimidinylene in the case of divalent. have.

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 structure, respectively, unless otherwise specified, " Substituted fluorenyl group" or "substituted fluorenyl group" means that at least one of the substituents R, R', R" is a substituent other than hydrogen, and R and R' are bonded to each other to form a This includes cases where they form a spy compound together.

As used herein, the term "spiro compound" has a 'spiro union', which means a connection formed by two rings sharing only one atom. At this time, the atoms shared by the two rings are called 'spiro atoms', and according to the number of spiro atoms in a compound, they are called 'monospiro-', 'dispiro-', and 'trispiro-', respectively. ' It's called a compound.

As used herein, the term "heterocyclic group" refers to a ring containing heteroatoms such as N, O, S, P or Si instead of carbon forming a ring, and is referred to as a "heteroaryl group" or "heteroarylene group". It includes not only an aromatic ring but also a non-aromatic ring, such as the following compound instead of carbon forming a ring, SO ₂ , and a compound containing a heteroatom group such as P=O may also be included.

In addition, unless explicitly stated otherwise, the chemical formula used in the present invention applies the same as the substituent definition by the exponent definition of the following formula.

Here, when a is an integer of 0, substituent R ¹ does not exist, and when a is an integer of 1, one substituent R ¹ is bonded to any one of the carbon atoms forming the benzene ring, and when a is an integer of 2 or 3 Each is combined as follows, wherein R ¹ may be the same or different from each other, and when a is an integer of 4 to 6, it is bonded to the carbon of the benzene ring in a similar manner, while the hydrogen bonded to the carbon forming the benzene ring is omit

Hereinafter, a layered structure of an organic electric element including the compound of the present invention will be described with reference to FIG. 1 .

1 is a diagram illustrating a stacked structure of an organic electric element according to an embodiment of the present invention.

Referring to FIG. 1, an organic electric element 100 according to the present invention includes a first electrode 120, a second electrode 180, and a first electrode 110 and a second electrode 180 formed on a substrate 110. ) is provided with an organic material layer containing the compound according to the present invention. In this case, the first electrode 120 may be an anode (anode), and the second electrode 180 may be a cathode (negative electrode), 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 a hole blocking layer, an electron blocking layer, a light emitting auxiliary layer 151, a buffer layer 141, and the like may be further included, and the electron transport layer 160 and the like may serve as the hole blocking layer. Maybe.

In addition, although not shown, the organic electric element according to the present invention may further include a protective layer or a capping layer formed on a surface opposite to the organic material layer among at least one surface of the first electrode and the second electrode.

The compound according to the present invention applied to the organic layer is a hole injection layer 130, a hole transport layer 140, an electron transport layer 160, an electron injection layer 170, a light emitting layer 150, a light efficiency improving layer, a light emitting auxiliary layer, etc. can be used as a material for For example, the compound of the present invention may be used as a material of the light emitting layer 150, preferably a host material of the light emitting layer. In addition, the compound of the present invention may be used as a material for an electron transport auxiliary layer or an electron transport layer.

An organic light emitting 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, depositing a metal or a metal oxide having conductivity or an alloy thereof on a substrate to form an anode 120, and a hole injection layer 130 thereon , After forming an organic material layer including a hole transport layer 140, a light emitting layer 150, an electron transport layer 160 and an electron injection layer 170, it can be manufactured by depositing a material that can be used as the cathode 180 thereon. have. In addition, an auxiliary light emitting layer 151 may be additionally formed between the hole transport layer 140 and the light emitting layer 150 .

In addition, the organic layer may be formed by a solution process or a solvent process 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, a doctor blading process, It can be manufactured with fewer layers by a method such as a screen printing process or a thermal transfer method. Since the organic layer according to the present invention can be formed in various ways, the scope of the present invention is not limited by the forming method.

The organic electric device according to the present invention may be one of an organic light emitting device (OLED), an organic solar cell, an organic photoconductor (OPC), an organic transistor (organic TFT), a device for monochromatic or white lighting, and a device for quantum dot display.

Another embodiment of the present invention may include an electronic device including a display device including the above-described organic electric element of the present invention and a control unit controlling the display device. At this time, 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 device, a game machine, various TVs, and various computers. The display device may include an organic light emitting display, a quantum dot display, and the like.

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

A compound according to one aspect of the present invention is represented by Formula 1 below.

<Formula 1>

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

R ₁ and R ₂ are each independently hydrogen; heavy hydrogen; halogen; cyano group; C ₆ ~ C ₆₀ aryl group; fluorenyl group; A C ₂ ~C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si, and P; C ₃ ~ C ₆₀ aliphatic ring group; C ₃ ~ C ₆₀ aliphatic ring and C ₆ ~ C ₆₀ aromatic ring fused ring group; C ₁ ~ C ₅₀ Alkyl group; A C ₂ ~C ₂₀ alkenyl group; A C ₂ ~C ₂₀ alkynyl group; C ₁ ~ C ₃₀ alkoxyl group; C ₆ ~ C ₃₀ aryloxy group; And -L'-N (R _a ) (R _b ); may be selected from the group consisting of.

n is an integer of 0 to 2, and when n is 2, a plurality of R _{1 '} s are the same as or different from each other.

m is an integer of 0 to 4, and when m is an integer of 2 or more, a plurality of R ₂ are the same or different, and adjacent R ₂ are bonded to each other to form C ₆ ~ C ₆₀ aromatic hydrocarbons, C ₂ ~ C ₆₀ A ring selected from the group consisting of a heterocyclic ring, a C ₃ ~C ₆₀ aliphatic ring, and a combination thereof may be formed.

When R ₁ and R ₂ are aryl groups, preferably C ₆ -C ₃₀ aryl groups, more preferably C ₆ -C ₁₈ aryl groups such as phenyl, biphenyl, naphthyl, pyrene, triphenylene , terphenyl, phenanthrene and the like. When R ₁ and R ₂ are heterocyclic groups, it is preferably a C ₂ ~ C ₃₀ heterocyclic group, more preferably a C ₂ ~ C ₂₄ heterocyclic group, still more preferably a C ₂ ~ C ₂₂ heterocyclic group. groups such as pyridine, pyrimidine, triazine, quinoline, quinazoline, carbazole, phenylcarbazole, dibenzothiophene, dibenzofuran, benzonaphthofuran, benzonaphthothiophene, benzothienopyrimidine, 14H-benzo[c]benzofuro[2,3-a]carbazole, 14H-benzo[c]benzothieno[2,3-a]carbazole, 1H-benzo[c]naphtho[2' ,3 ': 4,5] thieno [2,3-a] carbazole, dibenzobenzothienocarbazole, tribenzobenzothienocarbazole, indolocarbazole, indolophenylcarbazole, indolobiphenylcarbazole, benzoindolocarbazole, pyridoindole, pyridophenylindole, and the like. When R ₁ and R ₂ are fluorenyl groups, they may be dimethylfluorene, diphenylfluorene and the like.

When adjacent R ₂ bonds to each other to form an aromatic ring, preferably C ₆ ~ C ₃₀ aromatic hydrocarbons, more preferably C ₆ ~ C ₁₄ aromatic hydrocarbons, still more preferably C ₆ ~ C ₁₀ aromatic hydrocarbons such as benzene, naphthalene, phenanthrene and the like.

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

When L ₁ and L ₂ 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, naphthyl, and biphenyl. When L ₁ and L ₂ are heterocyclic groups, preferably C ₂ ~ C ₃₀ heterocyclic groups, more preferably C ₂ ~ C ₂₂ heterocyclic groups such as pyridine, pyrimidine, triazine, quinazoline, dibenzothiophene, pyridoindole, pyridophenylindole, carbazole, indolocarbazole, indolobenzocarbazole, dibenzofuran, and the like.

Ar ₁ and Ar ₂ are each independently a C ₆ ~ C ₆₀ aryl group; fluorenyl group; A C ₂ ~C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si, and P; C ₃ ~ C ₆₀ aliphatic ring group; C ₃ ~ C ₆₀ aliphatic ring and C ₆ ~ C ₆₀ aromatic ring fused ring group; C ₁ ~ C ₅₀ Alkyl group; A C ₂ ~C ₂₀ alkenyl group; A C ₂ ~C ₂₀ alkynyl group; C ₁ ~ C ₃₀ alkoxyl group; C ₆ ~ C ₃₀ aryloxy group; A silane group unsubstituted or substituted with a C ₁ -C ₂₀ alkyl group or a C ₆ -C ₂₀ aryl group; And -L'-N (R _a ) (R _b ) It may be selected from the group consisting of.

When Ar ₁ and Ar ₂ are aryl groups, preferably C ₆ -C ₃₀ aryl groups, more preferably C ₆ -C ₁₈ aryl groups such as phenyl, biphenyl, terphenyl, naphthyl, pyrene, triphenylene, phenanthrene and the like. When Ar ₁ and Ar ₂ are heterocyclic groups, it is preferably a C ₂ to C ₃₀ heterocyclic group, more preferably a C ₂ to C ₂₄ heterocyclic group, still more preferably a C ₂ to C ₂₂ heterocyclic group. Groups such as pyridine, pyrimidine, triazine, quinoline, quinazoline, benzoquinazoline, pyridoindole, pyridophenylindole, carbazole, phenylcarbazole, indolocarbazole, indolophenylcarbazole, indolodi Phenylcarbazole, 14H-benzo[c]benzofuro[2,3-a]carbazole, 14H-benzo[c]benzothieno[2,3-a]carbazole, 1H-benzo[c]naf To[2',3':4,5]thieno[2,3-a]carbazole, dibenzobenzothienocarbazole, tribenzobenzothienocarbazole, indolobenzocarbazole, dibenzocarbazole Benzothiophene, dibenzofuran, benzonaphthofuran, benzonaphthothiophene, benzothienopyrimidine, benzofuropyrimidine, 5a,10a-dihydrobenzo[4,5]imidazo[1,2-a] [1,3,5] triazine and the like. When Ar ₁ and Ar ₂ are alkyl groups, they are preferably C ₁ to C ₁₀ alkyl groups, more preferably C ₁ to C ₄ alkyl groups, such as methyl and t-butyl. When Ar ₁ and Ar ₂ are alkenyl groups, they are preferably C ₂ to C ₁₀ alkenyl groups, more preferably C ₂ to C ₄ alkenyl groups, such as entene, propene, and butene. When Ar ₁ and Ar ₂ are fluorenyl groups, they may be dimethylfluorene, diphenylfluorene or the like. Also, Ar ₁ and Ar ₂ may be trimethylsilane, methoxy, or the like.

o1 and o2 are integers of 0 or 1, respectively, and o1+o2 is an integer of 1 or greater.

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

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

R ₁ , R ₂ , a ring formed by connecting adjacent R ₂ , L ₁ , L ₂ , Ar ₁ , Ar ₂ , L', R _a and R _b are each deuterium; halogen; A silane group unsubstituted or substituted with a C ₁ -C ₂₀ alkyl group or a C ₆ -C ₂₀ aryl group; Siloxane group; boron group; Germanium group; cyano group; nitro group; A phosphine oxide group unsubstituted or substituted with a C ₁ -C ₂₀ alkyl group or a C ₆ -C ₂₀ aryl group; C ₁ -C ₂₀ Alkylthio group; C ₁ -C ₂₀ 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 deuterium-substituted C ₆ -C ₂₀ aryl group; 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; C ₃ -C ₂₀ aliphatic ring group; C ₇ -C ₂₀ arylalkyl group; C ₈ -C ₂₀ arylalkenyl group; And it may be further substituted with one or more substituents selected from the group consisting of combinations thereof.

Preferably, at least one of Ar ₁ and Ar ₂ is a heterocyclic group.

Also, preferably, at least one of Ar ₁ and Ar ₂ may be represented by Formula A-1 or A-2.

<Formula A-1> <Formula A-2>

In Formulas A-1 and A-2, each symbol may be defined as follows.

Q ¹ to Q ⁹ are each independently N or C(R ^e ). At this time, R ^e is hydrogen; heavy hydrogen; halogen; A silane group unsubstituted or substituted with a C ₁ -C ₂₀ alkyl group or a C ₆ -C ₂₀ aryl group; Siloxane group; boron group; Germanium group; cyano group; nitro group; C ₁ -C ₂₀ Alkylthio group; C ₁ -C ₂₀ 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 deuterium-substituted C ₆ -C ₂₀ aryl group; 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; C ₃ -C ₂₀ aliphatic ring group; C ₇ -C ₂₀ arylalkyl group; C ₈ -C ₂₀ arylalkenyl group; And it may be selected from the group consisting of combinations thereof, and adjacent R ^e may be bonded to each other to form a ring. The ring formed by bonding adjacent R ^e to each other may be selected from the group consisting of C ₆ ~ C ₂₀ aromatic hydrocarbons, C ₂ ~ C ₂₀ heterocycles, C ₃ ~ C ₂₀ aliphatic rings, and combinations thereof.

Z may be selected from the group represented by the formula below.

"*" in the formula of Z represents a site bonded to a ring containing Q ¹ to Q ⁴ .

V is independently of each other N or C(R ^h ).

W ¹ and W ² are each independently a single bond, -N-(L ¹ -Ar ¹ ), S, O, or C(R ^f )(R ^g )c.

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

Ar ¹ , R ^f , R ^g and R ^h 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; Siloxane group; boron group; cyano group; nitro group; C ₁ -C ₂₀ Alkylthio group; C ₁ -C ₂₀ 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 deuterium-substituted C ₆ -C ₂₀ aryl group; 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; C ₃ -C ₂₀ aliphatic ring group; And it is selected from the group consisting of combinations thereof, and R ^f and R ^g may be bonded to each other to form a ring. R ^f and R ^g may combine with each other to form a ring selected from the group consisting of C ₆ ~ C ₂₀ aromatic hydrocarbons, C ₂ ~ C ₂₀ heterocycles, C ₃ ~ C ₂₀ aliphatic rings, and combinations thereof. .

Also, preferably, Ar ₁ and Ar ₂ may be represented by one of the following formulas B-1 to B-3.

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

In Formulas B-1 to B-3, each symbol may be defined as follows.

X and Y are each independently O, S, or N-(L ₃ -Ar ₃ ), a and b are each an integer of 0 or 1, and a+b is an integer of 1 or greater.

R ₃ to R ₅ 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; Siloxane group; boron group; cyano group; nitro group; C ₁ -C ₂₀ Alkylthio group; C ₁ -C ₂₀ 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 deuterium-substituted C ₆ -C ₂₀ aryl group; 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; C ₃ -C ₂₀ aliphatic ring group; C ₇ -C ₂₀ arylalkyl group; C ₈ -C ₂₀ arylalkenyl group; And it is selected from the group consisting of combinations thereof, and adjacent groups, that is, adjacent R ₃ , adjacent R ₄ , or adjacent R ₅ may bond to each other to form a ring. The ring formed at this time may be selected from the group consisting of C ₆ ~ C ₂₀ aromatic hydrocarbons, C ₂ ~ C ₂₀ heterocycles, C ₃ ~ C ₃₀ aliphatic rings, and combinations thereof.

q and s are each an integer of 0 to 4, r is an integer of 0 to 2, when q is an integer of 2 or more, a plurality of R ₃ are the same as or different from each other, and when s is an integer of 2 or more, a plurality of R ₅ are mutually the same or different, and when r is 2, a plurality of R ₄ are the same as or different from each other.

When an aromatic hydrocarbon is formed by combining adjacent R ₃ , R ₄ , or R ₅ adjacent to each other, preferably a C ₆ to C ₁₄ aromatic hydrocarbon, more preferably a C ₆ to C ₁₀ aromatic hydrocarbons such as benzene, naphthalene, phenanthrene and the like. Preferably, adjacent R ₄ may be bonded to each other to form a benzene ring.

L ₃ is a single bond; C ₆ -C ₂₀ aryl group; A deuterium-substituted C ₆ -C ₂₀ aryl group; 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; C ₃ -C ₂₀ aliphatic ring group; And selected from the group consisting of combinations thereof,

Ar ₃ 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; cyano group; nitro group; C ₁ -C ₂₀ Alkylthio group; C ₁ -C ₂₀ 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 deuterium-substituted C ₆ -C ₂₀ aryl group; 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; C ₃ -C ₂₀ aliphatic ring group; C ₇ -C ₂₀ arylalkyl group; C ₈ -C ₂₀ arylalkenyl group; and combinations thereof.

When Ar ₃ is an aryl group, it is preferably a C ₆ -C ₁₈ aryl group, more preferably a C ₆ -C ₁₂ aryl group, such as phenyl, naphthyl, biphenyl and the like.

Specifically, the compound represented by Formula 1 may be one of the following compounds.

.

.

In another embodiment of the present invention, the present invention provides an organic electric device including a first electrode, a second electrode, and an organic material layer formed between the first electrode and the second electrode, wherein the organic material layer is represented by Chemical Formula 1 above. It includes one single compound or two or more compounds represented by

The organic material 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 preferably, the compound is a light emitting layer, an electron transport auxiliary layer, or an electron injection layer. included in the transport layer.

As another embodiment of the present invention, an electronic device including a display device including the organic electronic element and a control unit driving the display device is provided.

Hereinafter, a synthesis example of a compound represented by the chemical formula according to the present invention and a manufacturing example of an organic electric device will be described in detail with examples, but the present invention is not limited to the following examples.

synthesis example

The compound represented by Formula 1 according to the present invention (final products) may be synthesized by reacting sub 1 and sub 2 as shown in Scheme 1 below, but is not limited thereto.

<Scheme 1> (In Sub 1 and Sub 2, either G is Pinacolatoborane and the other is Hal, and Hal is Br or Cl)

I. Synthesis of Sub 1

A compound belonging to sub 1 of Reaction Scheme 1 may be synthesized by Reaction Scheme 2 below, but is not limited thereto.

<Scheme 2>

1. Sub 1-1 synthesis example

Sub 1-I-1 synthesis method

5-bromobenzo[ b ]naphtha[1,2- d ]thiophene (50 g, 155 mmol), bis(pinacolato)diboron (43.4 g, 171 mmol), KOAc (46 g, 466 mmol), PdCl ₂ (dppf) (3.8 g, 4.7 mmol) was dissolved in a solvent of DMF (980 mL), and then refluxed at 120° C. for 12 hours. When the reaction was completed, the reactant was cooled to room temperature, extracted with CH ₂ Cl ₂ and washed with water. After drying the organic layer with MgSO ₄ and concentrating, the resulting organic material was recrystallized using CH ₂ Cl ₂ and methanol as a solvent to obtain Sub 1-I-1 (45 g, 80%).

Sub 1-II-1 synthesis method

Sub 1-I-1 (40 g, 111 mmol), bromo-2-nitrobenzene (26.91 g, 133 mmol), K ₂ CO ₃ (46.03 g, 333 mmol), Pd(PPh ₃ ) ₄ (7.7 g, 6.66 mmol) in a round bottom flask, dissolved in THF (490 mL) and water (245 mL), and then refluxed at 80 °C for 12 hours. When the reaction was completed, the reactant was cooled to room temperature, extracted with CH ₂ Cl ₂ , and washed with water. After drying the organic layer with MgSO ₄ and concentrating, the resulting organic material was separated using a silica gel column to obtain Sub 1-II-1 (27.6 g, 70%).

Sub 1-1 synthesis method

Sub 1-II-1 (20 g, 56.3 mmol) and triphenylphosphine (37 g, 141 mmol) were dissolved in o -dichlorobenzene (235 mL) and refluxed for 24 hours. After the reaction was completed, the solvent was removed using vacuum distillation, and the concentrated product was passed through a silica gel column and recrystallized to obtain Sub 1-1 (13.6 g, 75%).

2. Sub 1-9 synthesis example

Sub 1-9-I synthesis method

2-bromo-9-phenyl-9H-carbazole (50 g, 155 mmol), bis(pinacolato)diboron (50.0 g, 155.2 mmol), KOAc (45.69 g, 465.5 mmol), PdCl ₂ (dppf) (3.8 g, 4.7 mmol) and DMF (775 mL) to obtain Sub 1-9-I (48.7 g, 85%) in the same manner as in the synthesis of Sub 1-I-1.

Sub 1-9-II synthesis method

Sub 1-I-9 (48.7 g, 131.9 mmol), bromo-2-nitrobenzene (31.98 g, 158.3 mmol), K ₂ CO ₃ (54.69 g, 395.7 mmol), Pd(PPh ₃ ) ₄ (7.62 g, 6.6 mmol), THF (66 mL), and water (20 mL) were used to obtain Sub 1-9-II (41.26 g, 88%) in the same manner as in the synthesis of Sub 1-II-1.

Sub 1-9 synthesis method

Sub 1-9 ( 22.9 g, 61%) was obtained.

3. Sub 1-15 synthesis example

Synthesis of Sub 1-I-15

1-bromo-9-phenyl-9H-carbazole (96 g, 298 mmol), bis(pinacolato)diboron (83.23 g, 327.7 mmol), KOAc (87.72 g, 893.9 mmol), PdCl ₂ (dppf) (7.3 g, 8.9 mmol) and DMF (1489 mL), Sub 1-I-15 (89.12 g, 81%) was obtained in the same manner as in the synthesis of Sub 1-I-1.

Synthesis of Sub 1-II-15

Sub 1-I-14 (89.12 g, 241.3 mmol), bromo-2-nitrobenzene (58.51 g, 289.6 mmol), K ₂ CO ₃ (100 g, 724 mmol), Pd(PPh ₃ ) ₄ (13.94 g, 12.1 mmol), THF (121 mL), and water (40 mL) were used to obtain Sub 1-II-15 (70.34 g, 82%) in the same manner as in the synthesis of Sub 1-II-1.

Sub 1-15 synthesis method

Sub 1-15 ( 45.44 g, 71%) was obtained.

4. Sub 1-20 synthesis example

Sub 1-I-20 synthesis method

9-([1,1'-biphenyl]-3-yl)-4-bromo-9H-carbazole (72 g, 180.8 mmol), bis(pinacolato)diboron (50.49 g, 198.8 mmol), KOAc (53.22 g, 542.3 mmol), PdCl ₂ (dppf) (4.43 g, 5.4 mmol), and DMF (903 mL) were used to prepare Sub 1-I-20 (59.58 g, 74%) in the same manner as in the synthesis of Sub 1-I-1. got

Synthesis of Sub 1-II-20

Sub 1-I-20 (59.58 g, 133.8 mmol), bromo-2-nitrobenzene (32.43 g, 160.5 mmol), K ₂ CO ₃ (55.47 g, 401.3 mmol), Pd(PPh ₃ ) ₄ (7.73 g, 6.7 mmol), THF (67 mL), and water (20 mL), Sub 1-II-20 (42.43 g, 72%) was obtained in the same manner as in the synthesis of Sub 1-II-1.

Sub 1-20 synthesis method

Sub 1-20 ( 32.66 g, 83%) was obtained.

5. Sub 1-22 synthesis example

Sub 1-22 synthesis method

Sub 1-I-22 (17.0 g, 63.5 mmol), 1,3-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzene (16.77 g, 50.8 mmol) , K ₂ CO ₃ (26.33 g, 190.5 mmol) and Pd(PPh ₃ ) ₄ (3.67 g, 3.2 mmol) were put into a round bottom flask, dissolved in THF (190 mL) and water (95 mL), and then heated to 80 °C. was refluxed for 12 hours. When the reaction was completed, the reactant was cooled to room temperature, extracted with CH ₂ Cl ₂ , and washed with water. After drying the organic layer with MgSO ₄ and concentrating, the resulting organic material was separated using a silica gel column to obtain Sub 1-22 (23.5 g, 85%).

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

[Table 1]

II. Synthesis of Sub 2

Sub 2 of Reaction Scheme 1 may be synthesized by the reaction pathways of Reaction Schemes 3 to 6 below, but is not limited thereto.

<Scheme 3>

<Scheme 4>

<Scheme 5>

<Scheme 6>

1. Sub 2-1 synthesis example

Sub 2-I-1 synthesis method

Ethyl carbonochloridoimidate (59 g, 981.5 mmol) and TEA (11.92 g, 117.8 mmol) were dissolved in methylene chloride (300ml), cooled to 0 ° C, and benzoyl chloride (13.8 g, 98.1 mmol) was dissolved in methylene chloride (190 ml). After dissolving in , it is slowly added dropwise. After stirring for 2 hours while maintaining 0°C, the mixture was stirred at room temperature for 16 hours. After the reaction is completed, impurities are filtered out, and then the solvent is removed by distillation under reduced pressure. The concentrated product was passed through a silica gel column and recrystallized to obtain Sub 2-I-1 (58.06 g, 50%).

Sub 2-1 synthesis method

Sub2-I-1 (58.06 g, 274.3 mmol) and 1H-benzo[d]imidazol-2-amine (36.53 g, 274.3 mmol) were added and stirred at 170 °C for 2 hours. After the reaction was completed, the reactant was cooled to room temperature, passed through a silica gel column, and recrystallized to obtain Sub 2-1 (63.6 g, 82%).

2. Sub 2-2 synthesis example

Sub 2-I-2 synthesis method

After dissolving ethyl carbonochloridoimidate (37 g, 344.1 mmol) and TEA (4.18 g, 41.3 mmol) in methylene chloride (100ml), cool to 0℃. After dissolving [1,1'-biphenyl]-4-carbonyl chloride (7.45 g, 34.4 mmol) in methylene chloride (70 ml) and slowly adding dropwise, stirring for 2 hours while maintaining 0 ℃, and then at room temperature for 16 hours Stir. After the reaction is completed, impurities are filtered out, and then the solvent is removed by distillation under reduced pressure. The concentrated product was passed through a silica gel column and recrystallized to obtain Sub 2-I-2 (55.44 g, 56%).

Sub 2-2 synthesis method

Sub 2-2 (57.2 g , 79%) was obtained.

3. Sub 2-21 synthesis example

Sub 2-I-21 synthesis method

After dissolving ethyl carbonochloridoimidate (25 g, 232.5 mmol) and TEA (2.82 g, 27.9 mmol) in methylene chloride (60ml), cool to 0℃. Dibenzo[b,d]furan-4-carbonyl chloride (5.36 g, 23.2 mmol) was dissolved in methylene chloride (50 ml) and slowly added dropwise. After stirring for 2 hours while maintaining 0 ° C., stir at room temperature for 16 hours. After the reaction is completed, impurities are filtered out, and then the solvent is removed by distillation under reduced pressure. The concentrated product was passed through a silica gel column and recrystallized to obtain Sub 2-I-21 (43.49 g, 62%).

Sub 2-II-21 synthesis method

Sub 2-II-21 ( 40.19 g, 75%) was obtained.

Sub 2-21 synthesis method

Sub 2-II-21 (40.19 g, 108.1 mmol) (4'-chloro-[1,1'-biphenyl]-4-yl)boronic acid (20.1 g, 86.5 mmol), Pd(PPh ₃ ) ₄ (6.25 g, 5.4 mmol), K ₂ CO ₃ (44.82 g, 324.3 mmol), THF (162 ml), water (324 ml) was added and stirred at 80 °C. After 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. Then, the concentrate was passed through a silica gel column and recrystallized to obtain Sub 2-21 (45.97 g, 88%).

4.Sub 2-46 synthesis example

Sub 2-I-46 synthesis method

After dissolving ethyl benzimidate-2,3,4,5,6-d5 (41 g, 265.9 mmol) and TEA (3.23 g, 31.9 mmol) in methylene chloride (80ml), cool to 0℃. Dissolve phosgene (0.24 g, 26.6 mmol) in methylene chloride (50 ml) and add slowly dropwise. After stirring for 2 hours while maintaining 0 ° C., stir at room temperature for 16 hours. After the reaction is completed, impurities are filtered out, and then the solvent is removed by distillation under reduced pressure. The concentrated product was passed through a silica gel column and recrystallized to obtain Sub 2-I-46 (40.9 g, 71%).

Sub 2-II-46 synthesis method

Sub 2-II-46 ( 24.44 g, 45%) was obtained.

Sub 2-46 synthesis method

Sub 2-II-46 (24.44 g, 84.9 mmol) obtained above (4-chlorophenyl)boronic acid (10.63\2 g, 67.9 mmol), Pd (PPh ₃ ) ₄ (4.91 g, 4.2 mmol), K ₂ CO ₃ (35.22 g, 254.8 mmol), THF (127 ml), water (255 ml) was added and stirred at 80 °C. After 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. Then, the concentrate was passed through a silica gel column and recrystallized to obtain Sub 2-46 (21.94 g, 71%).

5.Sub 2-57 synthesis example

Sub 2-I-57 synthesis method

After dissolving ethyl formimidate (38 g, 519.8 mmol) and TEA (6.31 g, 62.4 mmol) in methylene chloride (180ml), cool to 0℃. Dibenzo[b,d]thiophene-4-carbaldehyde (11.03 g, 52.0 mmol) was dissolved in methylene chloride (70 ml) and slowly added dropwise. After stirring for 2 hours while maintaining 0 ° C., stir at room temperature for 16 hours. After the reaction is completed, impurities are filtered out, and then the solvent is removed by distillation under reduced pressure. The concentrated product was passed through a silica gel column and recrystallized to obtain Sub 2-I-57 (100.16 g, 68%).

Sub 2-57 synthesis method

Using Sub 2-I-57 (100.16 g, 353.5 mmol) and 7-chloro-1H-benzo[d]imidazol-2-amine (59.24 g, 353.5 mmol), Sub 2 was synthesized in the same manner as in Sub 2-1 synthesis. -57 (94.85 g, 69%) was obtained.

6. Sub 2-70 synthesis example

Sub 2-I-70 synthesis method

After dissolving ethyl isonicotinimidate (73 g, 486.1 mmol) and TEA (5.90 g, 58.3 mmol) in methylene chloride (180ml), cool to 0℃. Dissolve formyl chloride (3.13 g, 48.6 mmol) in methylene chloride (60 ml) and add slowly dropwise. After stirring for 2 hours while maintaining 0 ° C., stir at room temperature for 16 hours. After the reaction is completed, impurities are filtered out, and then the solvent is removed by distillation under reduced pressure. The concentrated product was passed through a silica gel column and recrystallized to obtain Sub 2-I-70 (83.72 g, 81%).

Sub 2-70 synthesis method

Using Sub 2-I-70 (83.72 g, 393.7 mmol) and 7-chloro-1H-benzo[d]imidazol-2-amine (65.99 g, 393.7 mmol), Sub 2 was synthesized in the same manner as in Sub 2-1 synthesis. -70 (81.55 g, 73%) was obtained.

7.Sub 2-84 synthesis example

Sub 2-I-84 synthesis method

After dissolving ethyl carbonochloridoimidate (44.0 g, 409.2 mmol) and TEA (4.97 g, 49.1 mmol) in methylene chloride (150ml), cool to 0℃. Dissolve 9-phenyldibenzo[b,d]furan-2-carbonyl chloride (12.55 g, 40.9 mmol) in methylene chloride (50 ml) and slowly add dropwise. After stirring for 2 hours while maintaining 0 ° C., stir at room temperature for 16 hours. After the reaction is completed, impurities are filtered out, and then the solvent is removed by distillation under reduced pressure. The concentrated product was passed through a silica gel column and recrystallized to obtain Sub 2-I-84 (102.03 g, 66%).

Sub 2-84 synthesis method

Sub 2-84 (69.10 g, 57%) was obtained.

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

[Table 2]

III. synthesis of the final compound

1. Synthesis of Product P-1

After dissolving Sub 1-1 (5.12 g, 15.8 mmol) in toluene (158 ml) in a round bottom flask, Sub 2-1 (4.48 g, 15.8 mmol), Pd ₂ (dba) ₃ (0.43 g, 0.5 mmol) , P( t -Bu) ₃ (0.26 g, 1.3 mmol), NaO t -Bu (4.56 g, 47.5 mmol) were added and stirred at 100 °C. After 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. Then, the concentrate was passed through a silica gel column and recrystallized to obtain P-1 (7.22 g, 80%).

2. Synthesis of Product P-16

Sub 1-1 (4.78 g, 14.8 mmol), toluene (148 ml), Sub 2-21 (7.73 g, 14.8 mmol), Pd ₂ (dba) ₃ (0.41 g, 0.4 mmol), P( t -Bu) ₃ (0.24 g, 1.2 mmol) and NaO t -Bu (4.26 g, 44.3 mmol) were used to obtain P-16 (10.18 g, 85%) in the same manner as in the synthesis of P-1.

3. Synthesis of Product P-46

Sub 1-1 (7.2 g, 22.3 mmol), toluene (223 ml), Sub 2-46 (8.06 g, 22.3 mmol), Pd ₂ (dba) ₃ (0.61 g, 0.7 mmol), P( t -Bu) ₃ (0.36 g, 1.8 mmol) and NaO t -Bu (6.42 g, 66.8 mmol) were used to obtain P-42 (10.69 g, 74%) in the same manner as in the synthesis of P-1.

4. Synthesis of Product P-78

Sub 1-9 (4.28 g, 12.9 mmol), toluene (129 ml), Sub 2-2 (4.62 g, 12.9 mmol), Pd ₂ (dba) ₃ (0.35 g, 0.4 mmol), P( t -Bu) ₃ (0.21 g, 1.0 mmol) and NaO t -Bu (3.71 g, 38.6 mmol) were used to obtain P-78 (5.99 g, 71%) in the same manner as in the synthesis of P-1.

5. Synthesis of Product P-120

Sub 1-9 (5.72 g, 17.2 mmol), toluene (172 ml), Sub 2-57 (6.66 g, 17.2 mmol), Pd ₂ (dba) ₃ (0.47 g, 0.5 mmol), P( t -Bu) ₃ (0.28 g, 1.4 mmol) and NaO t -Bu (4.96 g, 51.6 mmol) were used to obtain P-120 (8.11 g, 69%) in the same manner as in the synthesis of P-1.

6. Synthesis of Product P-140

Sub 1-15 (6.21 g, 18.7 mmol), toluene (187 ml), Sub 2-1 (5.28 g, 18.7 mmol), Pd ₂ (dba) ₃ (0.51 g, 0.6 mmol), P( t -Bu) ₃ (0.3 g, 1.5 mmol) and NaO t -Bu (5.39 g, 56.0 mmol) were used to obtain P-140 (8.43 g, 78%) in the same manner as in the synthesis of P-1.

7. Synthesis of Product P-149

Sub 1-20 (3.71 g, 9.1 mmol), toluene (91 ml), Sub 2-84 (4.06 g, 9.1 mmol), Pd ₂ (dba) ₃ (0.25 g, 0.3 mmol), P( t -Bu) ₃ (0.15 g, 0.7 mmol) and NaO t -Bu (2.62 g, 27.2 mmol) were used to obtain P-149 (6.4 g, 86%) in the same manner as in the synthesis of P-1.

8. Synthesis of Product P-28

Sub 1-22 (23.50 g, 54.0 mmol), Sub 2-86 (8.90 g, 43.20 mmol), K ₂ CO ₃ (22.38 g, 161.9 mmol), Pd(PPh ₃ ) ₄ (3.12 g, 2.7 mmol) After putting it in a round bottom flask, it was dissolved in THF (162 mL) and water (81 mL) and refluxed at 80 °C for 12 hours. When the reaction was completed, the reactant was cooled to room temperature, extracted with CH ₂ Cl ₂ , and washed with water. After drying and concentrating the organic layer with MgSO ₄ , the resulting organic material was separated using a silica gel column to obtain P-28 (19.06 g, 72%).

On the other hand, the FD-MS values of the compounds P-1 to P-160 of the present invention prepared according to the Synthesis Example as described above are shown in Table 3 below.

[Table 3]

Manufacturing evaluation of organic light emitting devices

[ Example One] Red organic light emitting device (Host)

N ¹ -(naphthalen-2-yl)-N ⁴ ,N ⁴ -bis(4-(naphthalen-2-yl(phenyl)amino)phenyl)-N ¹ -phenylbenzene on the ITO layer (anode) formed on the glass substrate -1,4-diamine (hereinafter abbreviated as "2-TNATA") was vacuum deposited to a thickness of 60 nm to form a hole injection layer, and then 4,4-bis[N-(1 -Naphthyl)-N-phenylamino]biphenyl (hereinafter abbreviated as "NPD") was vacuum deposited to a thickness of 60 nm to form a hole transport layer.

Thereafter, the present invention compound P-1 as a host material and bis-(1-phenylisoquinolyl)iridium(III)acetylacetonate (hereinafter abbreviated as “(piq) ₂ Ir(acac)”) as a dopant material on the hole transport layer However, a light emitting layer having a thickness of 30 nm was deposited by doping dopants such that the weight ratio was 95:5.

Next, (1,1'-biphenyl-4-olato)bis(2-methyl-8-quinolinolato)aluminum (hereinafter abbreviated as "BAlq") was vacuum-deposited to a thickness of 10 nm on the light emitting layer to form a hole blocking layer. was formed, and tris(8-quinolinol) aluminum (hereinafter abbreviated as Alq ₃ ) was deposited to a thickness of 40 nm on the hole blocking layer to form an electron transport layer. Thereafter, LiF was deposited on the electron transport layer to a thickness of 0.2 nm to form an electron injection layer, and Al was deposited on the electron injection layer to a thickness of 150 nm to form a cathode.

[ Example 2] to [ Example 35]

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

[ comparative example 1] and [ comparative example 2]

An organic light emitting device was manufactured in the same manner as in Example 1, except that Comparative Compound 1 and Comparative Compound 2 were used instead of Compound P-1 of the present invention as the host material of the light emitting layer.

<Comparative compound 1> <Comparative compound 2>

Electroluminescence (EL) characteristics with PR-650 of Photoresearch Co., Ltd. by applying a forward bias DC voltage to the organic electroluminescent devices prepared by Examples 1 to 35, Comparative Example 1 and Comparative Example 2 of the present invention was measured, and the results of measuring the life of T95 through McScience's life measurement equipment at 2500 cd / m ² standard luminance are shown in Table 4 below.

[Table 4]

As can be seen from the results of Table 4, the device using the compound according to an embodiment of the present invention as a phosphorescent host material of the light emitting layer has a driving voltage compared to Comparative Examples 1 and 2 using Comparative Compound 1 and Comparative Compound 2, Significantly improved in terms of luminous efficiency and lifetime.

Compared to the widely used CBP (Comparative Compound 1) used as a host material, when using Comparative Compound 2 of a polycyclic compound type and the compound of the present invention, the driving voltage, efficiency and lifetime of the organic electric device were improved. In addition, Comparative Compound 2 and the compounds used in Examples 1 to 4 and Examples 12 to 18 of the present invention have similar structures, but have different substituents bonded to N of carbazole. Due to these differences, the present invention In the case of, it can be confirmed that the electrical characteristics of the organic light emitting device are further improved.

This is because, as the compound of the present invention has a relatively lower LUMO level than Comparative Compound 1, injection of electrons from the ETL into the light emitting layer becomes easy, and the charge balance in the light emitting layer is improved, eventually improving the driving voltage and lifespan of the device. In addition, when a specific substituent is introduced as in the compound of the present invention, rather than when triazine is introduced into the N portion of carbazole as in Comparative Example 2, the conjugation length of the compound becomes longer, resulting in a dopant in the host. It is believed that the efficiency of the organic light emitting device is improved because the charge transfer to the furnace is facilitated.

[ Example 36] Green organic light emitting device ( electron transport layer )

After vacuum depositing 2-TNATA to a thickness of 60 nm on the ITO layer (anode) formed on the glass substrate to form a hole injection layer, NPD was vacuum deposited to a thickness of 60 nm on the hole injection layer to form a hole transport layer. Next, doping 4,4'-N,N'-dicarbazole-biphenyl (hereinafter abbreviated as CBP) as a host material and Ir(ppy) ₃ as a dopant material at a weight ratio of 95:5 on the hole transport layer A 30 nm thick light emitting layer was deposited. Subsequently, BAlq was vacuum deposited to a thickness of 10 nm on the light emitting layer to form a hole blocking layer, and the compound P-24 of the present invention was vacuum deposited to a thickness of 40 nm on the hole blocking layer to form an electron transport layer. Thereafter, LiF was deposited to a thickness of 0.2 nm on the electron transport layer to form an electron injection layer, and then Al was deposited to a thickness of 150 nm to form a cathode.

[ Example 37] to [ Example 54] Green organic light emitting device

An organic light emitting device was prepared in the same manner as in Example 36, except that the compound of the present invention shown in Table 5 was used instead of compound P-24 as the electron transport layer material.

[ comparative example 3]

An organic light emitting device was manufactured in the same manner as in Example 36, except that Comparative Compound 3 was used instead of the compound P-24 of the present invention as an electron transport layer material.

<Comparative compound 3>

A forward bias DC voltage was applied to the organic electroluminescent devices prepared in Examples 36 to 54 and Comparative Example 3 of the present invention to measure electroluminescence (EL) characteristics with a PR-650 from Photoresearch, The results of measuring the life of T95 through McScience's life measurement equipment at 5000 cd / m ² standard luminance are shown in Table 5 below.

[Table 5]

As can be seen from the results of Table 5, when the compound of the present invention was used as the electron transport layer material, the driving voltage of the device was lowered and the efficiency and lifetime were significantly improved compared to the case of using Comparative Compound 3 as the electron transport layer material. Comparative compound 3 is Alq ₃ widely used as an electron transport layer material.

This is because the compound according to one embodiment of the present invention has a significantly lower (deep) HOMO level value than Comparative Compound 3, effectively preventing holes from passing over from the light emitting layer, so that holes and electrons in the light emitting layer balance charge As a result, efficiency and lifespan seem to be improved because light is formed inside the light emitting layer rather than at the interface of the electron transport layer.

Although the case where the compound of the present invention is used in the light emitting layer and the electron transport layer has been described above, materials commonly used for the electron transport layer and the light emitting layer are organic materials of organic electric elements such as electron injection layers, hole injection layers, hole transport layers and light emitting auxiliary layers. Can be used alone or in combination with other materials. Therefore, for the reasons described above, the compound of the present invention may be used singly or in combination with other materials such as other organic material layers, such as an electron injection layer and a hole injection layer, a hole transport layer and a light emitting auxiliary layer, in addition to the electron transport layer and the light emitting layer.

The above description is merely illustrative of the present invention, and those skilled in the art will be able to make various modifications without departing from the essential characteristics of the present invention. Therefore, the embodiments disclosed in this specification are intended to explain, not 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 according to 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 element 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 (12)

delete delete A compound represented by Formula 1 below:
<Formula 1>

In Formula 1,
R ₁ and R ₂ are each independently hydrogen; heavy hydrogen; halogen; cyano group; C ₆ ~ C ₆₀ aryl group; fluorenyl group; A C ₂ ~C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si, and P; C ₃ ~ C ₆₀ aliphatic ring group; C ₃ ~ C ₆₀ aliphatic ring and C ₆ ~ C ₆₀ aromatic ring fused ring group; C ₁ ~ C ₅₀ Alkyl group; A C ₂ ~C ₂₀ alkenyl group; A C ₂ ~C ₂₀ alkynyl group; C ₁ ~ C ₃₀ alkoxyl group; C ₆ ~ C ₃₀ aryloxy group; And -L'-N (R _a ) (R _b ); is selected from the group consisting of,
n is an integer from 0 to 2, and when n is 2, a plurality of R ₁ are the same as or different from each other;
m is an integer of 0 to 4, and when m is an integer of 2 or more, a plurality of R ₂ are the same or different, and adjacent R ₂ are bonded to each other to form C ₆ ~ C ₆₀ aromatic hydrocarbons, C ₂ ~ C ₆₀ A ring selected from the group consisting of a heterocyclic ring, a C ₃ ~C ₆₀ aliphatic ring, and combinations thereof may be formed;
o1 and o2 are integers of 0 or 1, respectively, and o1+o2 is 1 or 2;
L ₁ and L ₂ are each independently a single bond; C ₆ ~ C ₆₀ arylene group; Fluorenylene group; A C ₂ ~C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si, and P; C ₃ ~ C ₆₀ aliphatic ring group; And it is selected from the group consisting of combinations thereof,
Ar ₁ and Ar ₂ are each independently a C ₆ ~ C ₆₀ aryl group; fluorenyl group; A C ₂ ~C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si, and P; C ₃ ~ C ₆₀ aliphatic ring group; C ₃ ~ C ₆₀ aliphatic ring and C ₆ ~ C ₆₀ aromatic ring fused ring group; C ₁ ~ C ₅₀ Alkyl group; A C ₂ ~C ₂₀ alkenyl group; A C ₂ ~C ₂₀ alkynyl group; C ₁ ~ C ₃₀ alkoxyl group; C ₆ ~ C ₃₀ aryloxy group; A silane group unsubstituted or substituted with a C ₁ -C ₂₀ alkyl group or a C ₆ -C ₂₀ aryl group; And -L'-N (R _a ) (R _b ) It is selected from the group consisting of,
At least one of Ar ₁ and Ar ₂ is Formula A-1 or Formula A-2 below, except when o2 is 0 and R ₁ is both hydrogen and Ar ₁ is Formula A-2 below;
<Formula A-1><FormulaA-2>

In Formula A-1 and Formula A-2,
Q ¹ to Q ⁹ are each independently N or C (R ^e ),
R ^e is hydrogen; heavy hydrogen; halogen; A silane group unsubstituted or substituted with a C ₁ -C ₂₀ alkyl group or a C ₆ -C ₂₀ aryl group; Siloxane group; boron group; Germanium group; cyano group; nitro group; C ₁ -C ₂₀ Alkylthio group; C ₁ -C ₂₀ 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 deuterium-substituted C ₆ -C ₂₀ aryl group; 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; C ₃ -C ₂₀ aliphatic ring group; C ₇ -C ₂₀ arylalkyl group; C ₈ -C ₂₀ arylalkenyl group; And it is selected from the group consisting of combinations thereof,
Z is selected from the group represented by the formula below,

In the formula of Z, "*" is a site bonded to a ring containing Q ¹ to Q ⁴ ,
V are independently of each other N or C(R ^h ), provided that Z is

, at least one of V is N,
W ¹ and W ² are each independently a single bond, -N-(L ¹ -Ar ¹ ), S, O or C(R ^f )(R ^g );
L ¹ is a single bond; C ₆ ~ C ₂₀ arylene group; Fluorenylene group; A C ₂ ~C ₂₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si, and P; C ₃ ~ C ₂₀ aliphatic ring group; And it is selected from the group consisting of combinations thereof,
Ar ¹ , R ^f , R ^g and R ^h 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; Siloxane group; boron group; cyano group; nitro group; C ₁ -C ₂₀ Alkylthio group; C ₁ -C ₂₀ 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 deuterium-substituted C ₆ -C ₂₀ aryl group; 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; C ₃ -C ₂₀ aliphatic ring group; And it is selected from the group consisting of combinations thereof, R ^f and R ^g may be bonded to each other to form a ring,
L' is a single bond; C ₆ ~ C ₆₀ arylene group; Fluorenylene group; A C ₂ ~C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si, and P; C ₃ ~ C ₆₀ aliphatic ring group; And it is selected from the group consisting of combinations thereof,
Wherein R _a and R _b are each independently hydrogen; C ₆ ~ C ₆₀ aryl group; fluorenyl group; A C ₂ ~C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si, and P; C ₃ ~ C ₆₀ aliphatic ring group; And it is selected from the group consisting of combinations thereof,
R ₁ , R ₂ , a ring formed by combining adjacent R ₂ , L ₁ , L ₂ , Ar ₁ , Ar ₂ , L', R _a and R _b are each deuterium; halogen; A silane group unsubstituted or substituted with a C ₁ -C ₂₀ alkyl group or a C ₆ -C ₂₀ aryl group; Siloxane group; boron group; Germanium group; cyano group; nitro group; A phosphine oxide group unsubstituted or substituted with a C ₁ -C ₂₀ alkyl group or a C ₆ -C ₂₀ aryl group; C ₁ -C ₂₀ Alkylthio group; C ₁ -C ₂₀ 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 deuterium-substituted C ₆ -C ₂₀ aryl group; 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; C ₃ -C ₂₀ aliphatic ring group; C ₇ -C ₂₀ arylalkyl group; C ₈ -C ₂₀ arylalkenyl group; And it may be further substituted with one or more substituents selected from the group consisting of combinations thereof. A compound represented by Formula 1 below:
<Formula 1>

In Formula 1,
R ₁ and R ₂ are each independently hydrogen; heavy hydrogen; halogen; cyano group; C ₆ ~ C ₆₀ aryl group; fluorenyl group; A C ₂ ~C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si, and P; C ₃ ~ C ₆₀ aliphatic ring group; C ₃ ~ C ₆₀ aliphatic ring and C ₆ ~ C ₆₀ aromatic ring fused ring group; C ₁ ~ C ₅₀ Alkyl group; A C ₂ ~C ₂₀ alkenyl group; A C ₂ ~C ₂₀ alkynyl group; C ₁ ~ C ₃₀ alkoxyl group; C ₆ ~ C ₃₀ aryloxy group; And -L'-N (R _a ) (R _b ); is selected from the group consisting of,
n is an integer from 0 to 2, and when n is 2, a plurality of R ₁ are the same as or different from each other;
m is an integer of 0 to 4, and when m is an integer of 2 or more, a plurality of R ₂ are the same or different, and adjacent R ₂ are bonded to each other to form C ₆ ~ C ₆₀ aromatic hydrocarbons, C ₂ ~ C ₆₀ A ring selected from the group consisting of a heterocyclic ring, a C ₃ ~C ₆₀ aliphatic ring, and combinations thereof may be formed;
L ₁ and L ₂ are each independently a single bond; C ₆ ~ C ₆₀ arylene group; Fluorenylene group; A C ₂ ~C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si, and P; C ₃ ~ C ₆₀ aliphatic ring group; And it is selected from the group consisting of combinations thereof,
o1 and o2 are integers of 0 or 1, respectively, and o1+o2 is 1 or 2;
Ar ₁ and Ar ₂ are each independently a C ₆ ~ C ₆₀ aryl group; fluorenyl group; A C ₂ ~C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si, and P; C ₃ ~ C ₆₀ aliphatic ring group; C ₃ ~ C ₆₀ aliphatic ring and C ₆ ~ C ₆₀ aromatic ring fused ring group; C ₁ ~ C ₅₀ Alkyl group; A C ₂ ~C ₂₀ alkenyl group; A C ₂ ~C ₂₀ alkynyl group; C ₁ ~ C ₃₀ alkoxyl group; C ₆ ~ C ₃₀ aryloxy group; A silane group unsubstituted or substituted with a C ₁ -C ₂₀ alkyl group or a C ₆ -C ₂₀ aryl group; And -L'-N (R _a ) (R _b ) It is selected from the group consisting of,
However, at least one of Ar ₁ and Ar ₂ is selected from the group consisting of the following formulas B-1 to B-3:
<Formula B-1><FormulaB-2><FormulaB-3>

In the above formulas B-1 to B-3,
X and Y are independently O, S or N-(L ₃ -Ar ₃ ), a and b are each an integer of 0 or 1, a+b is an integer of 1 or greater,
R ₃ to R ₅ 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; Siloxane group; boron group; cyano group; nitro group; C ₁ -C ₂₀ Alkylthio group; C ₁ -C ₂₀ 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 deuterium-substituted C ₆ -C ₂₀ aryl group; 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; C ₃ -C ₂₀ aliphatic ring group; C ₇ -C ₂₀ arylalkyl group; C ₈ -C ₂₀ arylalkenyl group; And selected from the group consisting of combinations thereof, adjacent groups may be bonded to each other to form a ring,
q and s are each an integer of 0 to 4, r is an integer of 0 to 2, when q is an integer of 2 or more, a plurality of R ₃ are the same as or different from each other, and when s is an integer of 2 or more, a plurality of R ₅ are mutually the same or different, and when r is 2, a plurality of R ₄ are the same as or different from each other,
L ₃ is a single bond; C ₆ -C ₂₀ aryl group; A deuterium-substituted C ₆ -C ₂₀ aryl group; 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; C ₃ -C ₂₀ aliphatic ring group; And selected from the group consisting of combinations thereof,
Ar ₃ 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; cyano group; nitro group; C ₁ -C ₂₀ Alkylthio group; C ₁ -C ₂₀ 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 deuterium-substituted C ₆ -C ₂₀ aryl group; 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; C ₃ -C ₂₀ aliphatic ring group; C ₇ -C ₂₀ arylalkyl group; C ₈ -C ₂₀ arylalkenyl group; And it is selected from the group consisting of combinations thereof,
L' is a single bond; C ₆ ~ C ₆₀ arylene group; Fluorenylene group; A C ₂ ~C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si, and P; C ₃ ~ C ₆₀ aliphatic ring group; And it is selected from the group consisting of combinations thereof,
Wherein R _a and R _b are each independently hydrogen; C ₆ ~ C ₆₀ aryl group; fluorenyl group; A C ₂ ~C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si, and P; C ₃ ~ C ₆₀ aliphatic ring group; And it is selected from the group consisting of combinations thereof,
R ₁ , R ₂ , a ring formed by combining adjacent R ₂ , L ₁ , L ₂ , Ar ₁ , Ar ₂ , L', R _a and R _b are each deuterium; halogen; A silane group unsubstituted or substituted with a C ₁ -C ₂₀ alkyl group or a C ₆ -C ₂₀ aryl group; Siloxane group; boron group; Germanium group; cyano group; nitro group; A phosphine oxide group unsubstituted or substituted with a C ₁ -C ₂₀ alkyl group or a C ₆ -C ₂₀ aryl group; C ₁ -C ₂₀ Alkylthio group; C ₁ -C ₂₀ 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 deuterium-substituted C ₆ -C ₂₀ aryl group; 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; C ₃ -C ₂₀ aliphatic ring group; C ₇ -C ₂₀ arylalkyl group; C ₈ -C ₂₀ arylalkenyl group; And it may be further substituted with one or more substituents selected from the group consisting of combinations thereof. A compound characterized in that it is one of the following compounds:

. In the organic electric device including a first electrode, a second electrode, and an organic material layer formed between the first electrode and the second electrode,
The organic material layer comprises an organic electric device comprising the compound of any one of claims 3 to 5. According to claim 6,
The organic material layer comprises at least one of a hole injection layer, a hole transport layer, a light emitting auxiliary layer, a light emitting layer, an electron transport supplement, an electron transport layer, and an electron injection layer. According to claim 7,
An organic electric device, characterized in that the compound is included in the light emitting layer. According to claim 7,
An organic electric device, characterized in that the compound is included in the electron transport auxiliary layer or the electron transport layer. According to claim 6,
The organic layer is 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 element of claim 6; and
An electronic device comprising a controller for driving the display device. According to claim 11,
The electronic device, characterized in that the organic electric device is selected from the group consisting of organic light emitting devices, organic solar cells, organic photoreceptors, organic transistors, devices for monochromatic lighting and devices for quantum dot displays.

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