WO2021177616A1 - Organic electronic device comprising capping layer, and electronic apparatus comprising same - Google Patents

Abstract

The present invention relates to an organic electronic device comprising a capping layer, and an electronic apparatus comprising same, and the capping layer is formed with a compound represented by chemical formula 1, of the present invention, and thus the efficiency and color purity of an organic electronic device can be improved.

Description

Organic electric device including light efficiency improving layer and electronic device including same

The present invention relates to an organic electric device including a light efficiency improving layer and an electronic device including the same.

The organic light emitting device is a self-luminous device, and has a wide viewing angle and excellent contrast, as well as a fast response time, excellent luminance, driving voltage and response speed characteristics, and multicolorization is possible.

Such an organic light emitting device has a structure in which a first electrode (anode), a hole transport region, a light emitting layer, an electron transport region, and a second electrode (cathode) are sequentially formed on a substrate. Holes injected from the first electrode move to the emission layer via the hole transport region, and electrons injected from the second electrode move to the emission layer via the electron transport region. Carriers such as holes and electrons recombine in the emission layer region to generate excitons, and light is generated as the excitons change from an excited state to a ground state.

The luminous efficiency of the organic light emitting diode can be generally divided into internal luminescent efficiency and external liminescent efficiency.

The internal luminous efficiency is related to how efficiently excitons are generated and light conversion is performed in the organic layer interposed between the first and second electrodes (that is, between the anode and the cathode), such as a hole transport layer, a light emitting layer, and an electron transport layer, etc. External luminous efficiency (hereinafter also referred to as “light coupling efficiency”) refers to the efficiency at which light generated in the organic layer is extracted to the outside of the organic light emitting device, and even if high light conversion efficiency is achieved in the organic layer (that is, , even if the internal luminous efficiency is high), if the external luminous efficiency is low, the overall luminous efficiency of the organic light emitting diode is inevitably reduced.

Recently, in addition to research on improving device characteristics by changing the performance of each material, technology for improving color purity and increasing efficiency by optimized optical thickness between an anode and a cathode in a top device with a resonance structure has been developed. It is one of the important factors to improve performance. Compared with the bottom device structure of the non-resonant structure, the top device structure has a large optical energy loss due to surface plasmon polariton (SPP) because the formed light is reflected by the anode, which is a reflective film, and emitted toward the cathode.

Accordingly, one of the important methods for improving the shape and efficiency of the EL spectrum is a method of applying a capping layer to a top cathode type.

In general, metals such as Al, Pt, Ag, and Au are mainly used as cathode electrodes, and SSP is generated on the surface of these metal electrodes. For example, when the cathode is used as Ag, the light emitted by the Ag of the cathode is quenched by the SPP (light energy loss due to Ag) and the efficiency is reduced.

However, when the light efficiency improvement layer is used, SPP occurs at the interface between the MgAg electrode and the high refractive organic material, and among them, transverse electric (TE) polarized light is annihilated in the vertical direction by the evanescent wave. , TM (transverse magnetic) polarized light traveling along the cathode and the capping layer has a wavelength amplification phenomenon due to surface plasma resonance. As a result, the intensity of the peak increases, so that high efficiency and effective color purity control are possible.

Therefore, there is a need for research and development on the material of the light efficiency improving layer capable of improving the color purity while improving the overall efficiency of the organic electric device.

Accordingly, an object of the present invention is to provide an organic electric device having significantly improved luminous efficiency and color purity by forming a light efficiency improving layer with a specific compound, and an electronic device including the same.

In one aspect, the present invention provides an organic electric device comprising a compound represented by the following formula in a light efficiency improving layer and an electronic device thereof.

By using the compound according to the present invention as a material for the light efficiency improvement layer, the luminous efficiency and color purity of the organic electric device can be improved.

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

[Explanation of code]

100, 200, 300: organic electric device 110: first electrode

120: hole injection layer 130: hole transport layer

140: light emitting layer 150: electron transport layer

160: electron injection layer 170: second electrode

180: light efficiency improvement layer 210: buffer layer

220: light emitting auxiliary layer 320: first hole injection layer

330: first hole transport layer 340: first light emitting layer

350: first electron transport layer 360: first charge generation layer

361: second charge generation layer 420: second hole injection layer

430: second hole transport layer 440: second light emitting layer

450: second electron transport layer CGL: charge generation layer

ST1: first stack ST2: second stack

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

As used herein, the term "fluorenyl group" refers to a substituted or unsubstituted fluorenyl group, "fluorenylene group" refers to a substituted or unsubstituted fluorenyl group, and as used in the present invention, the fluorenyl group or The fluorenylene group includes a case in which R and R' are bonded to each other in the following structure to form a spiro compound together with the carbon to which they are bonded.

"Substituted fluorenyl group", "substituted fluorenylene group" means that at least one of R, R', R" in the following structure is a substituent other than hydrogen, and in the present specification, regardless of the valence, a fluorenyl group , a fluorenylene group, a fluorentriyl group, etc. may all be called a fluorene group.

As used herein, the term "spiro compound" has a 'spiro linkage', and the spiro linkage means a linkage formed by sharing only one atom between 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.

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, a compound including a heteroatom group such as SO 2} , P=O, etc. may be included in the heterocyclic group, such as the following compounds instead of carbon forming a ring.

The term "aliphatic ring group" used in the present invention refers to a cyclic hydrocarbon other than an aromatic hydrocarbon, and includes a monocyclic type, a ring aggregate, a fused multiple ring system, a spiro compound, etc., unless otherwise specified, the number of carbon atoms It means a ring of 3 to 60, but is not limited thereto. For example, even when benzene, which is an aromatic ring, and cyclohexane, which is a non-aromatic ring, are fused, it corresponds to an aliphatic ring.

In the present specification, the 'group name' corresponding to the aryl group, arylene group, heterocyclic group, etc. exemplified as examples of each symbol and its 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 in the case of monovalent, as a pyrimidinyl group, in the case of divalent, as the 'name of the group' of the corresponding valence, such as pyrimidinylene. have.

In addition, in the present specification, in describing the compound name or the substituent name, numbers or alphabets indicating positions may be omitted. For example, pyrido[4,3-d]pyrimidine to pyridopyrimidine, benzofuro[2,3-d]pyrimidine to benzofuropyrimidine, 9,9-dimethyl-9H-flu Orene can be described as dimethylfluorene and the like. Therefore, both benzo[g]quinoxaline and benzo[f]quinoxaline can be described as benzoquinoxaline.

In addition, unless there is an explicit explanation, the formula used in the present invention is 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, and in this case, the indication of hydrogen bonded to carbon is shown. 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 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.

In addition, unless otherwise specified in the present specification, when representing a condensed ring, the number in 'number-condensed ring' indicates the number of rings to be condensed. For example, a form in which three rings are condensed with each other, such as anthracene, phenanthrene, benzoquinazoline, etc., may be expressed as a 3-condensed ring.

In addition, unless otherwise specified in the present specification, when a ring is expressed in the form of a 'numeric atom' such as a 5-membered ring, a 6-membered ring, etc., the number in 'number-atom' indicates the number of elements forming the ring. For example, thiophene or furan may correspond to a 5-membered ring, and benzene or pyridine may correspond to a 6-membered ring.

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

At this time, unless otherwise specified in the present specification, 'neighboring groups' refers to each other when describing the following chemical formula as an example, R ₁ and R _{2 each other} , R ₂ and R _{3 each other} , R ₃ and R _{4 each other} , Not only R ₅ and R _{6 but also R 7} and R ₈ sharing one carbon are included, and not immediately adjacent, such as _{R 1} and R ₇ , R ₁ and R _{8 ,} or R ₄ and R _{5 , etc.} Substituents bonded to ring constituents (such as carbon or nitrogen) may also be included. That is, if there is a substituent on a ring constituent element such as carbon or nitrogen immediately adjacent to it, they may be a neighboring group, but if no substituent is bonded to a ring constituent element at the immediately adjacent position, it is bonded to the next ring constituent element It can be a group adjacent to the substituent group, and also the substituents bonded to the same ring constituent carbon can be said to be adjacent groups.

_{When substituents bonded to the same carbon as R 7} and R ₈ in the following formula combine with each other to form a ring, a compound including a spiro moiety may be formed.

,

In addition, in the present specification, the expression 'neighboring groups may combine with each other to form a ring' is used in the same meaning as 'neighboring groups combine with each other to selectively form a ring', and at least one pair of It means a case where adjacent groups are bonded to each other to form a ring.

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

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

Referring to FIG. 1 , an organic electric device 100 according to an embodiment of the present invention includes a first electrode 110 , a second electrode 170 , and a first electrode 110 formed on a substrate (not shown). and an organic material layer formed between the second electrode 170 and the light efficiency improving layer 180 formed on the first electrode 170 .

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

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

The light efficiency improving layer 180 is formed on one side of the second electrode 170 that is not in contact with the organic material layer.

The thickness of the light efficiency improving layer may be 30 ~ 120nm. The lower limit of the thickness of the light efficiency improving layer may be, for example, 40 nm or more, 50 nm or more, or 55 nm or more. The upper limit of the thickness of the light efficiency improving layer may be, for example, 100 nm or less, 80 nm or less, or 65 nm or less. When the thickness of the light efficiency improving layer is adjusted within the above-described range, it is possible to provide an organic electric device having high light efficiency and color purity due to surface plasma resonance.

The light efficiency improving layer may have a refractive index of 1.85 or more for light having a wavelength of 450 to 750 nm. The upper limit of the refractive index of the light efficiency improving layer is not particularly limited, but may be, for example, 3.0 or less or 2.5 or less. When the refractive index of the light efficiency improving layer is adjusted within the above-described range, an organic electric device having high light efficiency and color purity by surface plasma resonance can be provided.

1 illustrates a case in which the light efficiency improving layer 180 is formed on the second electrode 170 in the top emission method, the light efficiency improving layer is also on one side of both surfaces of the first electrode 110 that is not in contact with the organic material layer. can be formed.

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

Referring to FIG. 2 , the organic electric device 200 according to another embodiment of the present invention includes a hole injection layer 120 , a hole transport layer 130 , a buffer layer 210 sequentially formed on the first electrode 110 , It may include a light emitting auxiliary layer 220 , a light emitting layer 140 , an electron transport layer 150 , an electron injection layer 160 , and a second electrode 170 , and a light efficiency improving layer 180 is formed on the second electrode. can be

Although not shown in FIG. 2 , an electron transport auxiliary layer may be further formed between the light emitting layer 140 and the electron transport layer 150 .

In addition, according to another embodiment of the present invention, the organic material layer may have a form in which a plurality of stacks including a hole transport layer, a light emitting layer, and an electron transport layer are formed. This will be described with reference to FIG. 3 .

Referring to FIG. 3 , an organic electric device 300 according to another embodiment of the present invention includes two stacks ST1 and ST2 of an organic material layer formed of a multilayer between the first electrode 110 and the second electrode 170 . More than one set may be formed, and a charge generating layer (CGL) may be formed between stacks of organic material layers.

Specifically, the organic electric device according to an embodiment of the present invention includes a first electrode 110 , a first stack ST1 , a charge generation layer (CGL), a second stack ST2, and a second electrode. 170 and the light efficiency improving layer 180 may be included.

The first stack ST1 is an organic material layer formed on the first electrode 110 , which is a first hole injection layer 320 , a first hole transport layer 330 , a first emission layer 340 , and a first electron transport layer 350 . ), and the second stack ST2 may include a second hole injection layer 420 , a second hole transport layer 430 , a second emission layer 440 , and a second electron transport layer 450 . . As such, the first stack and the second stack may be organic material layers having the same stacked structure or organic material layers having different stacked structures.

A charge generation layer CGL may be formed between the first stack ST1 and the second stack ST2 . The charge generation layer CGL may include a first charge generation layer 360 and a second charge generation layer 361 . The charge generating layer CGL is formed between the first light emitting layer 340 and the second light emitting layer 440 to increase the efficiency of current generated in each light emitting layer and smoothly distribute charges.

The first light-emitting layer 340 may include a light-emitting material including a blue fluorescent dopant in a blue host, and the second light-emitting layer 440 includes a material in which a green host is doped with a greenish yellow dopant and a red dopant. may be included, but is not limited thereto.

In FIG. 3 , n may be an integer of 1 to 5. When n is 2, the charge generation layer CGL and the third stack may be additionally stacked on the second stack ST2 .

When a plurality of light emitting layers are formed by the multilayer stack structure method as shown in FIG. 3 , an organic electroluminescent device that emits white light by the mixing effect of light emitted from each light emitting layer can be manufactured as well as light of various colors. It is also possible to manufacture an organic electroluminescent device that emits light.

According to an embodiment of the present invention, by using the compound represented by Formula 1 of the present invention as a material for the light efficiency improving layer 180, it is possible to significantly improve the luminous efficiency and color purity while improving the lifespan of the organic electric device.

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 110, and the hole injection layer 120 thereon , after forming an organic material layer including the hole transport layer 130 , the light emitting layer 140 , the electron transport layer 150 and the electron injection layer 160 , a material that can be used as the cathode 170 is deposited on the organic material layer, and then It may be manufactured by forming the light efficiency improving layer 180 on the cathode 170 .

In addition, an auxiliary light emitting layer 220 may be formed between the hole transport layer 130 and the light emitting layer 140 , and an electron transport auxiliary layer (not shown) may be further formed between the light emitting layer 140 and the electron transport layer 150 . It can also be formed in a stack structure as shown.

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 the material used.

In addition, the organic electric device according to an embodiment of the present invention may be selected from the group consisting of an organic electroluminescent device, an organic solar cell, an organic photoreceptor, an organic transistor, a device for monochromatic lighting, and a device for a quantum dot display.

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

An organic electric device according to an aspect of the present invention includes a first electrode; a second electrode; at least one organic material layer formed between the first electrode and the second electrode; and a light efficiency improving layer formed on one surface of both surfaces of the first electrode not in contact with the organic material layer or on one surface of both surfaces of the second electrode not in contact with the organic material layer, wherein the light efficiency improving layer is represented by the following formula (1) compounds.

<Formula 1>

<Formula 1-1>

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

X and Z independently of one another are O or S, and Y is N(R), C(R')(R"), O or S.

Ar ^{1 To} Ar ^{4 Are} each independently a 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 aliphatic group; -L'-N(R _a )(R _b ); and Formula 1-1, and ^{at least one of Ar 1} to Ar ⁴ is represented by Formula 1-1.

L ^{1 To} L ^{7 Are} each independently a single bond; C ₆ ~ C ₆₀ Arylene group; fluorenylene group; O, N, S, Si and P containing at least one heteroatom C ₂ ~ C ₆₀ A heterocyclic group; And C ₃ ~ C _{60 It} is selected from the group consisting of an aliphatic cyclic group.

R ¹ to R ³ are each independently hydrogen; heavy hydrogen; halogen; cyano group; nitro group; 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 aliphatic group; C ₁ ~ C ₃₀ Alkyl group; C ₂ ~ C ₃₀ Alkenyl group; C ₂ ~ C ₃₀ 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.

n and p are each an integer of 0-4, m is an integer of 0-2, and when each of these is an integer of 2 or more, each of R ^{1 ,} each of R ^{2 , and} each of R ³ are the same as or different from each other.

o is an integer of 0 to 2, and when o is 2, ^{each of L 1 ,} each of L ^{2 ,} each of L ^{3 ,} each of Ar ^{1 , and} each of Ar ² are the same as or different from each other.

The L' is a single bond; C ₆ ~ C ₆₀ Arylene group; fluorenylene group; O, N, S, Si and P containing at least one heteroatom C ₂ ~ C ₆₀ A heterocyclic group; And C ₃ ~ C _{60 It} is selected from the group consisting of an aliphatic cyclic group.

The R, R _a and R _b are each independently a 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; And C ₃ ~ C _{60 It} is selected from the group consisting of an aliphatic cyclic group.

Wherein R' and R" are each independently hydrogen; deuterium; halogen; cyano group; nitro group; C ₆ ~ C ₆₀ aryl group; fluorenyl group; O, N, S, at least one heteroatom of S, Si and P Containing C ₂ ~ C ₆₀ Heterocyclic group; C ₃ ~ C ₆₀ Aliphatic ring group; C ₁ ~ C ₃₀ Alkyl group; C ₂ ~ C ₃₀ Alkenyl group; C ₂ ~ C ₃₀ Alkynyl group; C ₁ ~ C ₃₀ An alkoxyl group; And C ₆ ~ C _{30 It} is selected from the group consisting of an aryloxy group, R' and R" may be bonded to each other to form a ring. When R' and R" combine with each other to form a ring, a spiro compound may be formed.

When ^{at least one of Ar 1} to Ar ⁴ , R ¹ to R ³ , R, R _a , R _b , R′, and R" is an aryl group, the aryl group is, for example, C ₆ to C ₃₀ , C ₆ to C ₂₅ , C ₆ ~C ₂₀ , C ₆ ~C ₁₈ , C ₆ ~C ₁₆ , C ₆ ~C ₁₄ , C ₆ ~C ₁₂ , C ₆ ~C ₁₀ , C ₆ , C ₁₀ , C ₁₂ , C ₁₃ , C ₁₄ , C ₁₆ , _{may be an aryl group such as C 18} , and specifically, phenyl, biphenyl, naphthyl, terphenyl, phenanthrene, and the like.

When ^{at least one of L 1} to L ⁷ and L' is an arylene group, the arylene group is, for example, C ₆ to C ₃₀ , C ₆ to C ₂₅ , C ₆ to C ₂₀ , C ₆ to C ₁₈ , C ₆ ~C ₁₆ , C ₆ ~C ₁₄ , C ₆ ~ C ₁₂ , C ₆ ~C ₁₀ , C ₆ , C ₁₀ , C ₁₂ , C ₁₃ , C ₁₄ , C ₁₆ , C ₁₈ may be an arylene group, Specifically, it may be phenylene, biphenyl, naphthylene, terphenyl, and the like.

When at least ^{one of} Ar 1 to Ar ⁴ , R ¹ to R ³ , R, R _a , R _b , R′, R″, L ¹ to L ⁷ , and L′ is a heterocyclic group, the heterocyclic group is, for example, C ₂ ~C ₃₀ , C ₂ ~C ₂₄ , C ₂ ~C ₂₀ , C ₂ ~C ₁₈ , C ₂ ~C ₁₆ , C ₂ ~C ₁₂ , C ₂ ~C ₈ , C ₃ , C ₄ , C ₅ , C ₇ , C ₈ , C ₁₂ , C ₁₃ , C ₁₆ , _{may be a heterocyclic group such as C 18} , and specifically, pyridine, pyrimidine, pyrazine, pyridazine, triazine, furan, pyrrole, silol, indene, Indole, phenyl-indole, benzoindole, phenyl-benzoindole, pyrazinoindole, quinoline, isoquinoline, benzoquinoline, pyridoquinoline, quinazoline, benzoquinazoline, dibenzoquinazoline, phenanthroquinazoline, quinoxaline, Benzoquinoxaline, dibenzoquinoxaline, benzofuran, naphthobenzofuran, dibenzofuran, phenanthrobenzofuran, dinaphthofuran, thiophene, benzothiophene, dibenzothiophene, naphthobenzothiophene, phenanthro Benzothiophene, dinaphthothiophene, carbazole, phenyl-carbazole, benzocarbazole, phenyl-benzocarbazole, naphthyl-benzocarbazole, dibenzocarbazole, indolocarbazole, benzofuropyridine, benzo thienopyridine, benzofuropyridine, benzothienopyrimidine, benzofuropyrimidine, benzothienopyrazine, benzofuropyrazine, benzoimidazole, benzothiazole, benzoxazole, benzosilol, phenan Troline, dihydro-phenylphenazine, 10-phenyl-10H-phenoxazine, phenoxazine, phenothiazine, dibenzodioxin, benzodibenzodioxin, cyanthrene, 9,9-dimethyl-9H-xanthrene , 9,9-dimethyl-9H-thioxanthrene, dihydrodimethylphenylacridine, spiro[fluorene-9,9'-xanthene], and the like.

When ^{at least one of R 1} to R ³ , R', and R" is an alkyl group, the alkyl group is, for example, C ₁ to C ₂₀ , C ₁ to C ₁₀ , C ₁ to C ₄ , C ₁ , C ₂ , C ₃ , _{may be an alkyl group such as C 4} , specifically methyl, ethyl, propyl, t-butyl, and the like.

The aryl group, an arylene group, a fluorenyl group, a fluorenylene group, a heterocyclic group, an aliphatic ring group, an alkyl group, an alkenyl group, an alkynyl group, an alkoxyl group, an aryloxy group, a ring formed by bonding adjacent groups to each other, and A ring formed by combining R′ and R″ is deuterium; halogen; a silane group unsubstituted or substituted with a _{C 1} -C ₂₀ alkyl group or C ₆ -C _{20 aryl group; C 1} -C ₂₀ alkyl group or C ₆ -C ₂₀ Phosphine oxide unsubstituted or substituted with an aryl group; Siloxane group; Cyano group; Nitro group; C ₁ -C ₂₀ Alkylthio group; C ₁ -C _{20 Alkoxy group; C 6} -C ₂₀ Aryloxy group; C ₆ -C ₂₀ Arylthio 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; Flu _{Orenyl group; C 2} -C ₂₀ heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si and P; And C ₃ -C ₂₀ One selected from the group consisting of an aliphatic ring group It may be substituted with more than one substituent.

Among the rings formed by bonding the aryl group, fluorenyl group, heterocyclic group, aliphatic ring group, alkyl group, alkenyl group, alkynyl group, alkoxy group, aryloxy group, arylene group, fluorenylene group, and neighboring groups to each other When at least one is substituted with an aryl group, the aryl group is, for example, C ₆ -C ₂₀ , C ₆ -C ₁₈ , C ₆ -C ₁₆ , C ₆ -C ₁₄ , C ₆ -C ₁₂ , C ₆ -C ₁₀ , C _It may be an aryl group such as 6 , C ₁₀ , C ₁₂ , C ₁₃ , C ₁₄ , C ₁₆ , C _{18 .}

Among the rings formed by bonding the aryl group, fluorenyl group, heterocyclic group, aliphatic ring group, alkyl group, alkenyl group, alkynyl group, alkoxy group, aryloxy group, arylene group, fluorenylene group, and neighboring groups to each other When at least one is substituted with a heterocyclic group, the heterocyclic group is, for example, C ₂ ~ C ₂₀ , C ₂ ~ C ₁₈ , C ₂ ~ C ₁₆ , C ₂ ~ C ₁₂ , C ₂ ~ C ₈ , C ₃ , C ₄ , C ₅ , C ₇ , C ₈ , C ₁₂ , C ₁₃ , C ₁₆ , C ₁₈ may be a heterocyclic group.

Among the rings formed by bonding the aryl group, fluorenyl group, heterocyclic group, aliphatic ring group, alkyl group, alkenyl group, alkynyl group, alkoxy group, aryloxy group, arylene group, fluorenylene group, and neighboring groups to each other When at least one is substituted with an alkyl group, the alkyl group may be, for example, an alkyl group such as C ₁ to C ₂₀ , C ₁ to C ₁₀ , C ₁ to C ₄ , C ₁ , C ₂ , C ₃ , C ₄ .

Formula 1 may be represented by Formula 2 or Formula 3 below.

<Formula 2> <Formula 3>

In Formulas 2 and 3, X, Y, Ar ¹ to Ar ⁴ , L ¹ to L ⁶ , R ¹ , R ² , m, and n are the same as defined in Formula 1 above.

Formula 1 may be represented by one of Formulas 4 to 7 below.

<Formula 4> <Formula 5>

<Formula 6> <Formula 7>

In Formulas 4 to 7, X, Ar ¹ to Ar ⁴ , L ¹ to L ⁶ , R ¹ , R ² , R, R′, R″, m, n, o are the same as defined in Formula 1.

The Chemical Formula 1-1 may be represented by the following Chemical Formula 1-1A.

<Formula 1-1A>

In Formula 1-1A, Z, L ⁷ , R ³ , and p are the same as defined in Formula 1.

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

.

Hereinafter, a synthesis example of the compound represented by Formula 1 according to the present invention and a manufacturing example of an organic electric device will be described in detail with reference to 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 product) may be prepared by reacting Core 1 and Sub1 as shown in Scheme 1 below, but is not limited thereto.

<Scheme 1>

(Hal ¹ and Hal ² are each I, Br or Cl, L′ is L ² or L ⁵ , L″ is L ³ or L ⁶ , Ar′ is Ar ¹ or Ar ³ , Ar″ is Ar ² or Ar ⁴ Lim)

I. Synthesis example of Core1

Core 1 of Scheme 1 may be synthesized by the reaction routes of Schemes 2 to 5, but is not limited thereto. Hal ³ is halogen.

<Scheme 2> (when Y=S)

<Scheme 3> (When Y=O)

<Scheme 4> (when Y=NR)

<Scheme 5> (When Y=C(R')(R"))

(R ⁶ is R', R")

(1) Synthesis example of Core1-1

Synthesis of Core1-1b

After dissolving 5-bromo-2-(4-chlorophenyl)benzo[d]oxazole (20 g, 65.82 mmol) in THF (216 mL), (2-nitrophenyl)boronic acid (10.82 g, 64.82 mmol), Pd ( PPh ₃ ) ₄ (1.50 g, 1.30 mmol), K ₂ CO ₃ (17.91 g, 129.63 mmol), water (44 mL) were added and stirred at 80° C. Upon completion of the reaction _{, 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 separated by a silica gel column and recrystallized to obtain 17.28 g of a product (yield: 76%).

Synthesis of Core1-1a

To Core1-1b (17.28 g, 49.26 mmol) was added triphenylphosphine (38.76 g, 147.79 mmol) and stirred at 220°C. Upon completion of the reaction _{, the mixture was extracted with CH 2} Cl ₂ and water, and the organic layer was dried over _{MgSO 4 and concentrated.} Thereafter, the concentrate was separated by a silica gel column and recrystallized to obtain 12.56 g (yield: 80%) of the product.

Synthesis of Core1-1

After dissolving Core1-1a (12.56 g, 39.40 mmol) in DCB (56 mL), iodobenzene (8.84 g, 43.34 mmol), copper (0.25 g, 3.94 mmol), K ₂ CO ₃ (16.34 g, 118.21 mmol), 18-crown-6 (20.83 g, 78.81 mmol) was added and stirred at 150°C. Upon completion of the reaction _{, the mixture was extracted with CH 2} Cl ₂ and water, and the organic layer was dried over _{MgSO 4 and concentrated.} Thereafter, the concentrate was separated by a silica gel column and recrystallized to obtain 11.36 g of a product (yield: 73%).

(2) Synthesis example of Core1-19

Synthesis of Core1-19a

After dissolving 5-bromo-2-(4-chlorophenyl)benzo[d]thiazole (20 g, 61.61 mmol) in DMF (88 mL), 2-chlorophenol (7.92g, 61.61mmol), copper (0.39 g, 6.16) mmol), K ₂ CO ₃ (25.54 g, 184.83 mmol), and 18-crown-6 (32.57 g, 123.22 mmol) were added and refluxed. Upon completion of the reaction _{, the mixture was extracted with CH 2} Cl ₂ and water, and the organic layer was dried over _{MgSO 4 and concentrated.} Thereafter, the concentrate was separated by a silica gel column and recrystallized to obtain 17.43 g of a product (yield: 76%).

Synthesis of Core1-19

After Core1-19a (17.43 g, 46.82 mmol) was dissolved in AcOH (156 mL), Pd(OAc) ₂ (0.21 g, 0.94 mmol), K ₂ CO ₃ (19.41 g, 140.47 mmol) was added and refluxed. Upon completion of the reaction _{, the mixture was extracted with CH 2} Cl ₂ and water, and the organic layer was dried over _{MgSO 4 and concentrated.} Thereafter, the concentrate was separated by a silica gel column and recrystallized to obtain 10.22 g (yield: 65%) of the product.

(3) Synthesis example of Core1-24

Synthesis of Core1-24a

After dissolving 7-bromo-2-(4-chlorophenyl)-4-phenylbenzo[d]thiazole (20 g, 49.91 mmol) in DMF (71 mL) in a round-bottom flask, 3-chlorophenol (7.06 g, 54.90 mmol) , copper (0.32 g, 4.99 mmol), K ₂ CO ₃ (20.69 g, 149.73 mmol), 18-crown-6 (26.38 g, 149.32 mmol) was put and refluxed. Upon completion of the reaction _{, 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 separated by a silica gel column and recrystallized to obtain 14.05 g of a product (yield: 68%).

Synthesis of Core1-24

After Core1-24a (14.05 g, 46.82 mmol) was dissolved in AcOH (160 mL) in a round-bottom flask, Pd(OAc) ₂ (0.15 g, 0.68 mmol), K ₂ CO ₃ (14.07 g, 101.83 mmol) was added. refluxed. Upon completion of the reaction _{, the mixture was extracted with CH 2} Cl ₂ and water, and the organic layer was dried over _{MgSO 4 and concentrated.} Thereafter, the concentrate was separated by a silica gel column and recrystallized to obtain 8.81 g (yield: 63%) of the product.

(4) Synthesis example of Core 1-43

Synthesis of Core 1-43b

After dissolving 2-(4-bromophenyl)-6-iodobenzo[d]oxazole (20 g, 50.00 mmol) in THF (167 mL), (2-chloro-6-(methylthio)phenyl)boronic acid (7.09 g, 35.00 mmol) ), Pd(PPh ₃ ) ₄ (1.16 g, 1.00 mmol), K ₂ CO ₃ (13.82 g, 99.99 mmol) were added and stirred at 85°C. When the reaction was completed, the solvent was removed, _{extracted with CH 2} Cl ₂ and water, and the organic layer was dried over _{MgSO 4 and concentrated.} Thereafter, the concentrate was separated by a silica gel column and recrystallized to obtain 16.80 g (yield: 78%) of the product.

Synthesis of Core 1-43a

_{AcOH (130 mL), H 2} O ₂ (1.46 g, 42.90 mmol) was added to Core1-43b (16.80 g, 39.00 mmol) and stirred at room temperature. After the reaction was completed, the solvent was removed, neutralized with 1M NaOH, and extracted with ethyl acetate and water. Then, the organic layer _{was dried over MgSO 4} , concentrated and recrystallized to obtain 13.24 g of a product (yield: 76%).

Synthesis of Core 1-43

Core1-43a (13.24 g, 29.64 mmol) was placed in H ₂ SO ₄ (99 ml) and stirred at 65°C. When the reaction was completed, the mixture was neutralized using an aqueous NaOH solution, followed by _{extraction with CH 2} Cl ₂ and water. Thereafter, the organic layer _{was dried over MgSO 4} and concentrated, and the concentrate was separated by a silica gel column and recrystallized to obtain 8.97 g (yield: 73%) of the product.

(5) Synthesis example of Core1-58

Synthesis of Core1-58b

After dissolving 2-chlorobenzo[d]thiazol-6-yl)boronic acid (20 g, 93.70 mmole) in THF (312mL), 1-bromo-2-(iodomethyl)benzene (27.82 g, 93.70 mmol), Pd(PPh) ₃ ) ₄ (2.17 g, 1.87 mmol), K ₂ CO ₃ (25.90 g, 187.41 mmol) was added and stirred at 85 °C. When the reaction was completed, the solvent was removed, _{extracted with CH 2} Cl ₂ and water, and the organic layer was dried over _{MgSO 4 and concentrated.} Then, the concentrate was separated by a silica gel column to obtain 26.34 g of a product (yield: 83%).

Synthesis of Core1-58a

After dissolving Core1-58b (26.34 g, 77.77 mmol) in THF (259 mL), NH ₄ Cl (8.32 g, 155.53 mmol), Caesium pivalate (1.09 g 4.67 mmol), Pd(OAc) ₂ (0.35 g, 1.56 mmol) ) and stirred at 90 °C. When the reaction was completed, the solvent was removed, _{extracted with CH 2} Cl ₂ and water, and the organic layer was dried over _{MgSO 4 and concentrated.} Then, the concentrate was separated by a silica gel column to obtain 14.23 g of a product (yield: 71%).

Synthesis of Core1-58

After dissolving Core1-58a (12.39 g, 48.07 mmol) in toluene (160 mL), MethylIodide (17.06 g, 120.18 mol), NaH ₂ PO ₄ (12.69 g, 119.98 mol), Potassium bis(trimethylsilyl)amide (31.65 g 158.64) mmol) and stirred at 130 °C. Upon completion of the reaction _{, 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 separated by a silica gel column to obtain 8.52 g of a product (yield: 62%).

The compound belonging to Core1 may be a compound as follows, but is not limited thereto, and Table 1 shows FD-MS (Field Desorption-Mass Spectrometry) values of the following compounds.

[Table 1]

II. Synthesis of Sub 1

Sub1 of Scheme 1 may be synthesized by the reaction route of Scheme 6 below, but is not limited thereto.

<Scheme 6>

(1) Sub1-1 synthesis example

4-(benzo[d]oxazol-2-yl)aniline (20 g, 95.13 mmol) to 2-(4-bromophenyl)benzo[d]oxazole (20.86 g, 76.10 mmol), Pd ₂ (dba) ₃ (0.75 g, 0.82 mmol), 50% P( t- Bu) ₃ (0.75 g, 0.82 mmol), NaO t- Bu (7.87 g, 81.87 mmol), toluene (136 ml) were added and stirred at 80°C. Upon completion of the reaction _{, 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 separated by a silica gel column and recrystallized to obtain 23.73 g (yield: 62%) of the product.

(2) Sub1-2 Synthesis Example

4-(benzo[d]oxazol-2-yl)aniline (20 g, 95.13 mmol) to 2-(4-bromophenyl)benzo[d]thiazole (22.08 g, 76.10 mmol), Pd ₂ (dba) ₃ (0.75) g, 0.82 mmol), 50% P( t- Bu) ₃ (0.75 g, 0.82 mmol), NaO t- Bu (7.87 g, 81.87 mmol), toluene (136 ml) were added and stirred at 80°C. Upon completion of the reaction _{, 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 separated by a silica gel column and recrystallized to obtain 26.34 g (yield: 66%) of the product.

(3) Sub1-33 synthesis example

4-(benzo[d]oxazol-2-yl)aniline (20 g, 95.13 mmol) to 2-bromobenzo[d]thiazole (16.29 g, 76.10 mmol), Pd ₂ (dba) ₃ (0.75 g, 0.82 mmol) , 50% P( t -Bu) ₃ (0.75 g, 0.82 mmol), NaO t -Bu (7.87 g, 81.87 mmol), toluene (136 ml) were added and stirred at 80°C. Upon completion of the reaction _{, the mixture was extracted with CH 2} Cl ₂ and water, and the organic layer was dried over _{MgSO 4 and concentrated.} Thereafter, the concentrate was separated by a silica gel column and recrystallized to obtain 19.93 g (yield: 61%) of the product.

(4) Sub1-56 synthesis example

4-(benzo[d]thiazol-2-yl)aniline (20 g, 88.38 mmol) to 2-(1-chlorodibenzo[b,d]furan-4-yl)benzo[d]oxazole (22.61 g, 70.70 mmol) ), Pd ₂ (dba) ₃ (0.75 g, 0.82 mmol), 50% P( t- Bu) ₃ (0.75 g, 0.82 mmol), NaO t- Bu (7.87 g, 81.87 mmol), toluene (136 ml) was added and stirred at 130 °C. Upon completion of the reaction _{, 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 separated by a silica gel column and recrystallized to obtain 26.12 g (yield: 58%) of the product.

(5) Sub1-62 synthesis example

4-(benzo[d]oxazol-2-yl)aniline (20 g, 95.13 mmol) to 2-(9-chlorodibenzo[b,d]thiophen-2-yl)benzo[d]thiazole (26.78 g, 76.10 mmol) ), Pd ₂ (dba) ₃ (0.75 g, 0.82 mmol), 50% P( t- Bu) ₃ (0.75 g, 0.82 mmol), NaO t- Bu (7.87 g, 81.87 mmol), toluene (136 ml) was added and stirred at 130 °C. Upon completion of the reaction _{, the mixture was extracted with CH 2} Cl ₂ and water, and the organic layer was dried over _{MgSO 4 and concentrated.} Thereafter, the concentrate was separated by a silica gel column and recrystallized to obtain 30.00 g of a product (yield: 60%).

The compound belonging to Sub1 may be a compound as follows, but is not limited thereto, and Table 2 shows FD-MS (Field Desorption-Mass Spectrometry) values of the following compounds.

[Table 2]

III. Synthesis example of final compound

P-1 Synthesis Example

Core1-1 (20 g, 50.65 mmol) to Sub1-1 (20.43 g, 50.65 mmol), Pd ₂ (dba) ₃ (0.75 g, 0.82 mmol), 50% P( t- Bu) ₃ (0.75 g, 0.82) mmol), NaO t -Bu (7.87 g, 81.87 mmol), and toluene (169 ml) were added and stirred at 130°C. Upon completion of the reaction _{, 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 separated by a silica gel column and recrystallized to obtain 22.90 g (yield: 86%) of the product.

P-7 Synthesis Example

Sub1-2 (16.24 g, 38.71 mmol), Pd ₂ (dba) ₃ (0.71 g, 0.77 mol), P(t-Bu) ₃ (0.31 g, 1.55 mmol) in Core1-8 (13 g, 38.71 mmol) , NaOt-Bu (7.44 g, 77.42 mmol) was added, and the same method was followed for the synthesis of P-1 to obtain 23.63 g (yield 85%) of the product.

P-12 Synthesis Example

Sub1-1 (14.21 g, 35.22 mmol), Pd ₂ (dba) ₃ (0.65 g, 0.70 mol), P(t-Bu) ₃ (0.29 g, 1.41 mmol) in Core1-12 (15 g, 35.22 mmol) , NaOt-Bu (6.77 g, 70.44 mmol) was added, followed by the same method as in the synthesis of P-1 to obtain 20.66 g (yield 74%) of the product.

P-52 Synthesis Example

Core1-29 (13 g, 31.56 mmol) to Sub1-1 (12.73 g, 31.56 mmol), Pd ₂ (dba) ₃ (0.58 g, 0.63 mol), P(t-Bu) ₃ (0.26 g, 1.26 mmol) , NaOt-Bu (6.07 g, 63.12 mmol) was added, and the same method was followed for the synthesis of P-1 to obtain 16.72 g (yield 68%) of the product.

P-92 Synthesis Example

(1) Synthesis example of Inter-92

Core1-63 (15 g, 29.02 mmol) in Sub1-46 (3.93 g, 23.22 mmol), Pd ₂ (dba) ₃ (0.53 g, 0.58 mmol), 50% P( t- Bu) ₃ (0.23 g, 1.16) mmol), NaO t -Bu (5.58 g, 58.04 mmol) and toluene (97 ml) were added and stirred at 65°C. Upon completion of the reaction _{, the mixture was extracted with CH 2} Cl ₂ and water, and the organic layer was dried over _{MgSO 4 and concentrated.} Thereafter, the concentrate was separated by a silica gel column and recrystallized to obtain 13.70 g of a product (yield: 78%).

(2) Synthesis example of P-92

Inter-92 (13.70 g, 22.64 mmol) in Sub1-26 (8.88 g, 22.64 mmol), Pd ₂ (dba) ₃ (0.41 g, 0.45 mmol), 50% P( t- Bu) ₃ (0.18 g, 0.91) mmol), NaO t -Bu (4.35 g, 45.27 mmol) and toluene (75 ml) were added and stirred at 130°C. Upon completion of the reaction _{, the mixture was extracted with CH 2} Cl ₂ and water, and the organic layer was dried over _{MgSO 4 and concentrated.} Thereafter, the concentrate was separated by a silica gel column and recrystallized to obtain 18.28 g (yield: 84%) of the product.

P-99 Synthesis Example

(1) Synthesis example of Inter-99

Core1-10 (14 g, 35.12 mmol) in Sub1-26 (14.03 g, 24.58 mmol), Pd ₂ (dba) ₃ (0.64 g, 0.70 mmol), 50% P( t- Bu) ₃ (0.28 g, 1.40) mmol), NaO t -Bu (6.75 g, 70.24 mmol) and toluene (117 ml) were added and stirred at 65°C. Upon completion of the reaction _{, 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 separated by a silica gel column and recrystallized to obtain 19.34 g of a product (yield: 62%).

(2) Synthesis example of P-99

Inter-99 (19.34 g, 21.77 mmol) in Sub1-46 (3.68 g, 21.77 mmol), Pd ₂ (dba) ₃ (0.40 g, 0.44 mmol), 50% P( t- Bu) ₃ (0.18 g, 0.87) mmol), NaO t -Bu (4.18 g, 43.54 mmol), and toluene (73 ml) were added and stirred at 130°C. Upon completion of the reaction _{, the mixture was extracted with CH 2} Cl ₂ and water, and the organic layer was dried over _{MgSO 4 and concentrated.} Thereafter, the concentrate was separated by a silica gel column and recrystallized to obtain 16.23 g of a product (yield: 73%).

FD-MS values of compounds P-1 to P-124 of the present invention prepared according to the above synthesis examples are shown in Table 3 below.

[Table 3]

Manufacturing evaluation of organic electric devices

[Example 1] Blue organic light emitting device (light efficiency improvement layer)

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

Thereafter, 9,10-di(naphthalen-2-yl)anthracene as a host and BD-052X (Idemitsu kosan) as a dopant were used on the hole transport layer, but doped with dopants so that these weight ratios were 93:7 A light emitting layer was formed.

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 on the hole blocking layer to a thickness of 40 nm to form an electron transport layer.

Thereafter, LiF was deposited to a thickness of 0.2 nm on the electron transport layer to form an electron injection layer, and Al was deposited on the electron injection layer to a thickness of 150 nm to form a cathode, and then the compound P-1 of the present invention was A film was formed to a thickness of 60 nm to form a light efficiency improving layer.

[Example 2] to [Example 16]

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 a material for the light efficiency improvement layer.

[Comparative Example 1]

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that the light efficiency improving layer was not formed.

[Comparative Example 2]

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that the following comparative compound A was used instead of the compound P-1 of the present invention as a material for the light efficiency improvement layer.

<Comparative compound A>

By applying a forward bias DC voltage to the organic electroluminescent devices manufactured by Examples 1 to 16, Comparative Examples 1 and 2 of the present invention, the electroluminescence (EL) characteristics were obtained with PR-650 of Photoresearch. was measured, and the T95 lifespan was measured using the life measuring equipment of McScience at ^{500cd/m 2 standard luminance.} The measurement results are shown in Table 4 below.

[Table 4]

[Example 17] to [Example 32] Green organic light emitting device

4,4'-N,N'-dicarbazole-biphenyl (hereinafter referred to as CBP) as a host and tris(2-phenylpyridine)-iridium (hereinafter referred to as Ir(ppy) ₃ ) as a dopant were used, but these weight ratios were 95 : An organic electroluminescent device was manufactured in the same manner as in Example 1, except that the dopant was doped to a ratio of 5 and the compound shown in Table 5 was used as the light efficiency improving layer.

[Comparative Example 3]

An organic electroluminescent device was manufactured in the same manner as in Example 17, except that the light efficiency improving layer was not formed.

[Comparative Example 4]

An organic electroluminescent device was manufactured in the same manner as in Example 17, except that Comparative Compound A was used as a material for the light efficiency improving layer.

By applying a forward bias DC voltage to the organic electroluminescent devices manufactured by Examples 17 to 32, Comparative Examples 3 and 4 of the present invention, the electroluminescence (EL) characteristics were measured with PR-650 of Photoresearch. was measured, and the T95 lifetime was measured using a life measuring device of McScience at ^{5000 cd/m 2 standard luminance.} The measurement results are shown in Table 5 below.

[Table 5]

[Example 33] to [Example 48] Red organic light emitting device

bis-(1-phenylisoquinolyl)iridium(III)acetylacetonate (hereinafter referred to as (piq) ₂ Ir(acac)) as the dopant, and the compound shown in Table 6 below as the light efficiency improving layer. An organic electroluminescent device was manufactured in the same manner as in Example 17.

[Comparative Example 5]

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

[Comparative Example 6]

An organic electroluminescent device was manufactured in the same manner as in Example 33, except that Comparative Compound A was used as a material for the light efficiency improving layer.

By applying a forward bias DC voltage to the organic electroluminescent devices manufactured by Examples 33 to 48, Comparative Examples 5 and 6 of the present invention, the electroluminescence (EL) characteristics were measured with PR-650 of Photoresearch. was measured, and the T95 lifetime was measured using a life measuring device of McScience at ^{2500 cd/m 2 standard luminance.} The measurement results are shown in Table 6 below.

[Table 6]

As can be seen from Tables 4 to 6, when the compound represented by Formula 1 of the present invention is used as a material for the light efficiency improving layer, the lifespan is increased compared to the case where the light efficiency improving layer is not formed or when the comparative compound A is used, but the efficiency and Color purity is significantly improved.

When the light efficiency improvement layer is formed, SPPs (Surface plasmon polaritons) are generated at the interface between the Al electrode (cathode) and the high refractive organic material. Among them, TE (transverse electric) polarized light improves light efficiency by evanescent wave TM (transverse magnetic) polarized light that is dissipated in the vertical direction in the layer and moves along the cathode and the light efficiency improvement layer is amplified by surface plasma resonance. As a result, the efficiency and color purity seem to be improved.

The compound of the present invention has a tetracyclic core in which oxazole and thiazole moieties having a high refractive index in the visible wavelength band (range of 430 nm to 780 nm) are fused, and at least one amino group is bonded to this core, It has a structure in which a substituent such as benzoxazole and benzothiazole, which can increase the refractive index, is also bonded to the amino group.

Therefore, the compound of the present invention has a higher refractive index than the comparative compound A due to synergy due to the combination of the core and the substituent, and as a result, the light generated in the organic layer is extracted to the outside of the organic light emitting device by the principle of constructive interference. As this increases, the overall light efficiency of the organic light emitting diode is improved.

The above description is merely illustrative of the present invention, and those of ordinary skill in the art to which the present invention pertains will be able to make various modifications without departing from the essential characteristics of the present invention. Accordingly, the embodiments disclosed herein are for illustrative purposes rather than limiting the present invention, and the scope of the present invention is 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.

CROSS-REFERENCE TO RELATED APPLICATION

This patent application is based on U.S. Patent Law Articles 119 to 121 and 365 (35 USC §119 to §121, §365 Articles) with respect to Patent Application No. 10-2020-0026915 filed in Korea on March 04, 2020. ), and all contents are incorporated into this patent application by reference. In addition, if this patent application claims priority to countries other than the United States for the same reason as above, all contents thereof are incorporated into this patent application by reference.

Claims (10)

1. a first electrode; a second electrode; at least one organic material layer formed between the first electrode and the second electrode; and a light efficiency improving layer formed on one surface of both surfaces of the first electrode not in contact with the organic material layer or on one surface of both surfaces of the second electrode not in contact with the organic material layer,

   The light efficiency improving layer is an organic electric device comprising a compound represented by the following formula (1):

   <Formula 1>

   

   <Formula 1-1>

   

   In Formula 1,

   X and Z are each independently O or S,

   Y is N(R), C(R')(R"), O or S;

   Ar ^{1 To} Ar ^{4 Are} each independently a 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 aliphatic group; and -L'-N(R _a )(R _b ), wherein at least one of ^{Ar 1} to Ar ^{4 is represented by Formula 1-1,}

   L ^{1 To} L ^{7 Are} each independently a single bond; C ₆ ~ C ₆₀ Arylene group; fluorenylene group; O, N, S, Si and P containing at least one heteroatom C ₂ ~ C ₆₀ A heterocyclic group; And C ₃ ~ C _{60 It} is selected from the group consisting of an aliphatic cyclic group,

   R ¹ to R ³ are each independently hydrogen; heavy hydrogen; halogen; cyano group; nitro group; 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 aliphatic group; C ₁ ~ C ₃₀ Alkyl group; C ₂ ~ C ₃₀ Alkenyl group; C ₂ ~ C ₃₀ Alkynyl group; C ₁ ~ C ₃₀ An alkoxyl group; C ₆ ~ C ₃₀ Aryloxy group; And -L'-N(R _a ) (R _b ) is selected from the group consisting of, adjacent groups may combine with each other to form a ring,

   n and p are each an integer of 0-4, m is an integer of 0-2, and when each of these is an integer of 2 or more, each of R ^{1 ,} each of R ^{2 , and} each of R ³ are the same as or different from each other,

   o is an integer of 0 to 2, and when o is 2, ^{each of L 1 ,} each of L ^{2 ,} each of L ^{3 ,} each of Ar ^{1 ,} each of Ar ² are the same as or different from each other,

   The L' is a single bond; C ₆ ~ C ₆₀ Arylene group; fluorenylene group; O, N, S, Si and P containing at least one heteroatom C ₂ ~ C ₆₀ A heterocyclic group; And C ₃ ~ C _{60 It} is selected from the group consisting of an aliphatic cyclic group,

   The R, R _a and R _b are each independently a 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; And C ₃ ~ C _{60 It} is selected from the group consisting of an aliphatic cyclic group,

   Wherein R' and R" are each independently hydrogen; deuterium; halogen; cyano group; nitro group; C ₆ ~ C ₆₀ aryl group; fluorenyl group; O, N, S, at least one heteroatom of S, Si and P Containing C ₂ ~ C ₆₀ Heterocyclic group; C ₃ ~ C ₆₀ Aliphatic ring group; C ₁ ~ C ₃₀ Alkyl group; C ₂ ~ C ₃₀ Alkenyl group; C ₂ ~ C ₃₀ Alkynyl group; C ₁ ~ C ₃₀ An alkoxyl group; And C ₆ ~ C ₃₀ selected from the group consisting of an aryloxy group, R' and R" may be bonded to each other to form a ring,

   The aryl group, an arylene group, a fluorenyl group, a fluorenylene group, a heterocyclic group, an aliphatic ring group, an alkyl group, an alkenyl group, an alkynyl group, an alkoxyl group, an aryloxy group, a ring formed by bonding adjacent groups to each other, and A ring formed by combining R′ and R″ 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; a C 1} -C ₂₀ alkyl group or C ₆ -C ₂₀ Phosphine oxide unsubstituted or substituted with an aryl group; Siloxane group; Cyano group; Nitro group; C ₁ -C ₂₀ Alkylthio group; C ₁ -C _{20 Alkoxy group; C 6} -C ₂₀ Aryloxy group; C ₆ -C ₂₀ Arylthio 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; Flu _{Orenyl group; C 2} -C ₂₀ heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si and P; And one selected from the group consisting of _{C 3} -C _{20 aliphatic ring group} It may be substituted with more than one substituent.
2. The method of claim 1,

   Formula 1 is an organic electric device, characterized in that represented by Formula 2 or Formula 3:

   <Formula 2> <Formula 3>

   

   In Formulas 2 and 3, X, Y, Ar ¹ to Ar ⁴ , L ¹ to L ⁶ , R ¹ , R ² , m, and n are the same as defined in claim 1.
3. The method of claim 1,

   Formula 1 is an organic electric device, characterized in that represented by one of the following Formulas 4 to 7:

   <Formula 4> <Formula 5>

   

   <Formula 6> <Formula 7>

   

   In Formulas 4 to 7, X, Ar ¹ to Ar ⁴ , L ¹ to L ⁶ , R ¹ , R ² , R, R′, R″, m, n, o are the same as defined in claim 1.
4. The method of claim 1,

   The formula 1-1 is an organic electric device, characterized in that represented by the following formula 1-1A:

   <Formula 1-1A>

   

   In Formula 1-1A, Z, L ⁷ , R ³ , and p are as defined in claim 1.
5. The method of claim 1,

   The compound represented by Formula 1 is an organic electric device, characterized in that one of the following compounds:

   

   

   

   

   

   

   .
6. The method of claim 1,

   The organic material layer is an organic electric device comprising a hole transport layer, a light emitting layer and an electron transport layer.
7. According to claim 6,

   The organic layer comprises at least two stacks including the hole transport layer, the light emitting layer and the electron transport layer.
8. 8. The method of claim 7,

   The organic material layer is an organic electric device, characterized in that it further comprises a charge generation layer formed between the two or more stacks.
9. A display device comprising the organic electric device of claim 1; and

   An electronic device comprising a; a control unit for driving the display device.
10. 10. The method of claim 9,

    The organic electric device is an electronic device, characterized in that selected from the group consisting of an organic electroluminescent device, an organic solar cell, an organic photoreceptor, an organic transistor, a device for monochromatic lighting, and a device for a quantum dot display.

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