WO2019185058A1 - Organic electroluminescent component and display component - Google Patents

Abstract

The present invention relates to an organic electroluminescent component and a display component. The organic electroluminescent component comprises: an anode, a cathode, a light-emitting layer between the anode and the cathode; a hole injection transport layer between the anode and the light-emitting layer; and a hole transport auxiliary layer between the hole transport layer and the light-emitting layer, where the hole transport auxiliary layer comprises a first compound expressed by chemical formula 1 and a second compound expressed by chemical formula 2 or by the combination of chemical formula 3 and chemical formula 4. The explanations for chemical formula 1 to chemical formula 4 are same as described in the description. The present invention implements the organic electroluminescent component having high efficiency and an extended service life.

Description

Organic electroluminescent device and display element Technical field

The present invention relates to the field of semiconductor technology, and more particularly to an organic electroluminescent device and a display device including the same.

Background technique

The organic electroluminescent device technology can be used for manufacturing new display products as well as for preparing new lighting products, and is expected to replace the existing liquid crystal display and fluorescent lighting, and has a wide application prospect. An organic electroluminescent device is used as a current device. When a voltage is applied to electrodes at both ends thereof and an electric field acts on the positive and negative charges in the organic layer functional material film layer, the positive and negative charges are further recombined in the organic light-emitting layer, that is, Electroluminescence.

Organic electroluminescent devices are generally multilayer in structure, and various auxiliary functional layers other than the luminescent layer also play a vital role in device performance. Reasonable device structure can effectively improve the performance of the device. Electron injection layer, electron transport layer, hole blocking layer, luminescent layer, hole transport auxiliary layer, hole transport layer and hole injection layer are widely used to improve device performance. .

At present, research on improving the performance of organic electroluminescent devices includes: reducing the driving voltage of the device, improving the luminous efficiency of the device, and improving the service life of the device. In order to realize the continuous improvement of the performance of organic electroluminescent devices, not only the innovation of the structure and preparation process of organic electroluminescent devices, but also the continuous research and innovation of organic electroluminescent functional materials are required to produce higher performance organic electroluminescence. Luminous functional material.

The carriers (holes and electrons) in the organic electroluminescent device are respectively injected into the device by the two electrodes of the device under the driving of the electric field, and are combined to emit light in the luminescent layer. Hole transport auxiliary layer materials used in existing organic electroluminescent devices are known, for example

Etc., there are HOMO energy levels and the HOMO energy level difference of the host material of the light-emitting layer is large, and it is easy to form an accumulated charge at the material interface, which affects the lifetime of the OLED device.

In addition, in organic electroluminescent devices, not all of the energy levels of the materials are well matched, and the barrier between them severely hinders the effective injection of holes. A reasonable energy level structure facilitates the formation of a step barrier for the energy levels in each layer of the device, reduces the potential barrier of hole injection, and reduces the driving voltage of the device, thereby improving the luminous efficiency and lifetime of the device.

Therefore, there is an ongoing need to develop organic electroluminescent devices having excellent luminous efficiency and longevity.

Summary of the invention

The present invention is directed to an organic electroluminescent device having improved luminous efficiency, heat resistance and service life, and a display element including the same.

An object of the present invention is achieved by providing an organic electroluminescent device comprising an anode and a cathode facing each other; a light-emitting layer between the anode and the cathode; and an anode and a light-emitting layer a hole transporting layer; and a hole transporting auxiliary layer between the hole transporting layer and the light emitting layer, wherein the hole transporting auxiliary layer comprises the first compound represented by Chemical Formula 1 and the chemical formula 2 or Chemical Formula 3 and the chemical formula A combination of 4 represents the second compound.

In Chemical Formula 1,

Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ , Ar ₅ and Ar ₆ are each independently represented by a C1 to C10 linear or branched alkyl substituted or unsubstituted phenyl group, a C1 to C10 linear or branched alkyl group. a substituted or unsubstituted biphenyl group, a C1-C10 linear or branched alkyl substituted or unsubstituted naphthyl group;

Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ , Ar ₅ , and Ar ₆ may also be represented by the structure represented by Chemical Formula A.

[Chemical Formula A]

In Chemical Formula A, any one of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ is represented as a single bond which is bonded to N in Chemical Formula 1, and the remaining R _n are independently independent. Expressed as a hydrogen atom, a C1-C10 linear or branched alkyl group, and n is represented by 1 to 8;

X represents an O, S, C1 to C10 linear or branched alkyl substituted methylene group, a C6 to C15 aryl substituted methylene group, and a C6 to C15 aryl substituted imido group.

Wherein, in Chemical Formula 1 to Chemical Formula 4,

Y ₁ , Y _1a and Y _1b are each independently a single bond, a substituted or unsubstituted C 1 -C 20 alkylene group, a substituted or unsubstituted C 2 -C 20 alkenylene group, substituted or unsubstituted a fused ring of a C6-C30 arylene group, a substituted or unsubstituted C2 to C30 divalent heterocyclic group, a combination thereof, or a combination thereof,

Ar ₇ , Ar _7a and Ar _7b are each independently a substituted or unsubstituted C 6 -C 30 aryl group, a substituted or unsubstituted C 2 -C 30 heterocyclic group, or a combination thereof.

The adjacent two * of Chemical Formula 3 are fused with the adjacent two * of Chemical Formula 4,

The unfused * of Chemical Formula 3 are each CR ₉ and CR ₁₀ ,

R ₉ to R _{14 are} independently hydrogen, deuterium, substituted or unsubstituted C 1 -C 20 alkyl, substituted or unsubstituted C 6 -C 50 aryl, substituted or unsubstituted C 2 -C 50 heterocyclic ring Base or combination thereof,

R ₉ and R ₁₀ are each independently present or linked to each other to form a fused ring,

R ₁₁ and R ₁₂ are each independently present or connected to each other to form a fused ring,

R ₁₃ and R ₁₄ are each independently present or linked to each other to form a fused ring,

At least one of R ₉ to R ₁₂ and Ar ₇ of Chemical Formula 2 contains a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted bistriphenylene group or a substituted or unsubstituted hydrazine. Azolyl, and

At least one of R ₉ to R ₁₄ , Ar _7a and Ar _7b of the compound 3 or the compound 4 contains a substituted or unsubstituted C 6 -C 30 aryl group, a substituted or unsubstituted biphenylene group or a substituted group. Or unsubstituted carbazolyl.

The invention has the beneficial effects that an organic electroluminescent device having high efficiency and long service life can be realized. In an organic electroluminescent device comprising a hole transporting auxiliary layer comprising the first and second organic materials of the present invention, a HOMO of the first and second organic materials is defined, the level matching of the anode and the luminescence The barrier between the layer interfaces is reduced, which facilitates the injection of holes from the anode into the light-emitting layer, improves the hole injection efficiency, reduces the driving voltage of the device, reduces the accumulated charge at the interface contact, and improves the stability of the device. And the lifetime of the hole transport auxiliary layer material, the higher triplet excitation level can block the excitons generated in the light-emitting layer in the light-emitting layer, thereby improving the luminous efficiency of the device. In addition, the higher glass transition temperature of the hole transporting auxiliary layer material of the present invention improves the heat resistance of the device. And the organic film layer composed of two different materials can effectively improve the molecular arrangement and the intermolecular interaction force, so that the film layer has higher stability, reduces the leakage current of the device, and improves the service life of the device.

DRAWINGS

FIG. 1 is a cross-sectional view showing an organic light emitting diode according to an embodiment.

Figure 2 shows the current efficiency as a function of temperature.

3 is a graph showing a leakage current test of a reverse voltage of a device fabricated in Device Example 1 and Device Comparative Example 1 of the present invention.

detailed description

Hereinafter, embodiments of the invention are described in detail. However, the embodiments are illustrative, the invention is not limited thereto and the invention is defined by the specifications of the claims.

In the present specification, when a definition is not otherwise provided, the term "substituted" means one substituted with a substituent selected from each of the following: instead of a substituent or at least one hydrogen substituted by a compound: an anthracene, a halogen, a hydroxyl group, Amine, substituted or unsubstituted C1-C30 amine group, nitro group, substituted or unsubstituted C1-C40 silane group, C1-C30 alkyl group, C1-C10 alkyl silane group, C3~C30 ring Alkyl, C3-C30 heterocycloalkyl, C6-C30 aryl, C6-C30 heterocyclic, C1-C20 alkoxy, fluoro, C1-C10 trifluoroalkyl (such as trifluoromethyl) or cyanide base.

Further, substituted halogen, hydroxy, amine, substituted or unsubstituted C1 to C20 amine, nitro, substituted or unsubstituted C3 to C40 silane, C1 to C30 alkyl, C1 to C10 Alkylsilyl group, C3-C30 cycloalkyl group, C3-C30 heterocycloalkyl group, C6-C30 aryl group, C6-C30 heterocyclic group, C1-C20 alkoxy group, fluorine group, C1-C10 trifluoroalkyl group Two adjacent substituents (such as a trifluoromethyl group and the like) or a cyano group may be fused to each other to form a ring. For example, a substituted C6-C30 aryl group can be fused to another adjacent substituted C6-C30 aryl group to form a substituted or unsubstituted anthracene ring.

In the present specification, the term "hetero" means that one or three hetero atoms selected from N, O, S, P, and Si are contained in one compound or substituent, and the remainder is not specifically provided. One of the carbon.

In the present specification, "aryl group" means a non-aromatic thickened portion having at least one hydrocarbon aromatic moiety and a substantially aromatic hydrocarbon moiety passing through a single bond and containing a hydrocarbon aromatic moiety directly or indirectly fused. Ring-linked groups. The aryl group can be a monocyclic, polycyclic or fused ring polycyclic (ie, a ring that shares an adjacent pair of carbon atoms) functional groups.

In the present specification, the "heterocyclic group" includes a heteroaryl group and a ring of carbon (C) containing at least one hetero atom selected from N, O, S and Si instead of a cyclic compound. A group such as an aryl group, a cycloalkyl group, a fused ring or a combination thereof. When the heterocyclic group is a fused ring, each ring or all of the rings of the heterocyclic group may contain at least one hetero atom.

More specifically, a substituted or unsubstituted C6-C30 aryl group and/or a substituted or unsubstituted C2-C30 heteroaryl group means a substituted or unsubstituted phenyl group, substituted or unsubstituted. Substituted naphthyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted fused tetraphenyl, substituted or unsubstituted fluorenyl, substituted or Unsubstituted biphenyl, substituted or unsubstituted tert-triphenyl, substituted or unsubstituted triphenyl, substituted or unsubstituted thio, substituted or unsubstituted Biphenylene, substituted or unsubstituted fluorenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted furyl, substituted or unsubstituted thiophenyl, substituted or not Substituted pyrrolyl, substituted or unsubstituted pyrazolyl, substituted or unsubstituted imidazolyl, substituted or unsubstituted triazolyl, substituted or unsubstituted oxazolyl, Substituted or unsubstituted thiazolyl, substituted or unsubstituted oxadiazolyl, substituted or unsubstituted Thiadiazolyl, substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted pyrazinyl, substituted or unsubstituted triazinyl, substituted or Unsubstituted benzofuranyl, substituted or unsubstituted benzothienyl, substituted or unsubstituted benzimidazolyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted Quinolinyl, substituted or unsubstituted isoquinolinyl, substituted or unsubstituted quinazolinyl, substituted or unsubstituted quinoxalinyl, substituted or unsubstituted naphthyridine a substituted or unsubstituted benzoxazinyl group, a substituted or unsubstituted benzothiazinyl group, a substituted or unsubstituted acridine group, a substituted or unsubstituted phenazine group, Substituted or unsubstituted phenothiazine, substituted or unsubstituted phenoxazinyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted dibenzofuranyl, substituted or substituted Unsubstituted dibenzothiophenyl, substituted or unsubstituted carbazolyl, combinations thereof or the aforementioned groups Bonded fused rings, but is not limited thereto.

In the present specification, a substituted or unsubstituted arylene group, a substituted or unsubstituted heteroarylene group or a substituted or unsubstituted divalent heterocyclic group means as defined above and has two a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group of a linking group, such as a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, Substituted or unsubstituted fluorenylene, substituted or unsubstituted phenanthrylene, substituted or unsubstituted fused tetraphenyl, substituted or unsubstituted fluorenylene, substituted or unsubstituted Substituted biphenylene, substituted or unsubstituted sub-p-triphenyl, substituted or unsubstituted inter-s-triphenyl, substituted or unsubstituted decyl, substituted or unsubstituted Substituted triphenylene, substituted or unsubstituted anthracenylene, substituted or unsubstituted anthracenylene, substituted or unsubstituted furanyl, substituted or unsubstituted sub Thienyl, substituted or unsubstituted pyrrolyl, substituted or unsubstituted pyrazolyl, substituted Or unsubstituted imidazolyl, substituted or unsubstituted tributazolyl, substituted or unsubstituted oxazolyl, substituted or unsubstituted thiazolyl, substituted or unsubstituted A oxadiazolyl group, a substituted or unsubstituted thiadiazole group, a substituted or unsubstituted pyridylene group, a substituted or unsubstituted pyrimidinyl group, a substituted or unsubstituted sub Pyrazinyl, substituted or unsubstituted triazinyl, substituted or unsubstituted benzofuranyl, substituted or unsubstituted benzothiophenyl, substituted or unsubstituted sub Benzimidazolyl, substituted or unsubstituted fluorenylene, substituted or unsubstituted quinolinyl, substituted or unsubstituted isoisoquinolyl, substituted or unsubstituted sub Quinazolinyl, substituted or unsubstituted quinoxalinyl, substituted or unsubstituted naphthyridinyl, substituted or unsubstituted benzoxazinyl, substituted or unsubstituted Benzothiazinyl, substituted or unsubstituted acridinyl, substituted or unsubstituted phenylpyrazine Substituted or unsubstituted morphine thiazinyl, substituted or unsubstituted phenylpyrazine, substituted or unsubstituted fluorenylene, substituted or unsubstituted bisbenzofuranyl A substituted or unsubstituted bis(dibenzothiophenyl) group, a substituted or unsubstituted oxazolyl group, a combination thereof or a fused ring of the foregoing groups, but is not limited thereto.

In the present specification, the hole characteristic means that electrons can be supplied when an electric field is applied and due to a conductive characteristic according to the highest occupied molecular orbital (HOMO) level, holes formed in the anode are easily injected into the light-emitting layer. And features transmitted in the luminescent layer.

In addition, the electronic feature refers to a feature capable of accepting electrons when an electric field is applied and due to a conductive feature according to a lowest unoccupied molecular orbital (LUMO) level, electrons formed in the cathode are easily injected into the light-emitting layer and transmitted in the light-emitting layer. .

Hereinafter, an organic electroluminescent device according to one embodiment will be described.

The organic electroluminescence device may be any element that converts electrical energy into light energy and converts light energy into electric energy without particular limitation, and may be, for example, an organic electroluminescence device, an organic light emitting diode, an organic solar cell, and an organic photoconductor drum.

Herein, the organic light emitting diode is described as an example of the organic electroluminescent device (but the invention is not limited thereto), and can be applied to other organic electroluminescent devices in the same manner.

In the figures, the thickness of layers, films, panels, regions, etc. are exaggerated for clarity. Throughout the specification, the same reference numerals indicate the same elements. It will be understood that when an element such as a layer, a film, a region or a substrate is referred to as "on" another element, it may be directly on the other element or the intervening element may be present. In contrast, when an element is referred to as being "directly on" another element, there is no intervening element.

FIG. 1 is a schematic cross-sectional view of an organic light emitting diode according to an embodiment.

Referring to FIG. 1, an organic light emitting diode (20) according to an embodiment includes an anode (5) and a cathode (1) facing each other; and an organic layer (10) interposed between the anode (5) and the cathode (1). The organic layer (10) comprises a light-emitting layer (2), a hole transport auxiliary layer (3), and a hole transport layer (4).

The anode (5) may be made of a conductor having a higher work function to aid in hole injection, such as a metal, a metal oxide, and/or a conductive polymer. The anode (5) may be, for example, a metal such as nickel, platinum vanadium, chromium, copper, zinc, gold or alloys thereof; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO). a combination of a metal and an oxide such as ZnO and Al or SnO ₂ and Sb; a conductive polymer such as poly(3-methylthiophene), poly(3,4-(ethylene-1,2-dioxy)thiophene (poly(3,4-(ethylene-1,2-dioxy)thiophene); PEDOT), polypyrrole, and polyaniline, but are not limited thereto.

The cathode (1) may be made of a conductor having a lower work function to aid electron injection, and may be, for example, a metal, a metal oxide, and/or a conductive polymer. The cathode (1) may be, for example, a metal or an alloy thereof such as magnesium, calcium, sodium, potassium, titanium, indium, lanthanum, lithium, lanthanum, aluminum, silver, tin, lead, lanthanum and cerium; a multilayer structural material such as LiF /Al, LiO ₂ /Al, LiF/Ca, LiF/Al, and BaF ₂ /Ca, but are not limited thereto.

The luminescent layer (2) is interposed between the anode (5) and the cathode (1) and comprises at least one host and at least one dopant.

The dopant is a material that is mixed with a host in a small amount to generate light emission, and may be an organic compound or a metal complex such as Al that emits fluorescence by singlet excitation; or such as by multi-state excitation (multiple excitation) A material of a metal complex that emits light in a triplet state or greater than a triplet state. The dopant may be, for example, an inorganic compound, an organic compound or an organic/inorganic compound, and one or more kinds thereof may be used.

An example of the dopant may be an organometallic compound containing Ir, Pt, Os, Ti, Zr, Hf, Eu, Tb, Tm, Fe, Co, Ni, Ru, Rh, Pd, or a combination thereof. The dopant may be, for example, a compound represented by the following chemical formula Z, but is not limited thereto.

[Chemical Formula Z]

L ₂ MX

In the chemical formula Z, M is a metal and L is the same as or different from X, and is a ligand which forms a complex with M.

M may be, for example, Ir, Pt, Os, Ti, Zr, Hf, Eu, Tb, Tm, Fe, Co, Ni, Ru, Rh, Pd, or a combination thereof, and L and X may be, for example, a bidentate ligand.

The hole transport layer (4) is disposed between the anode (5) and the light-emitting layer (2), and is easy to transport holes from the anode (5) to the light-emitting layer (2). For example, the hole transport layer (4) may comprise a material having a HOMO energy level between a work function of a conductor forming the anode (5) and a HOMO energy level of a material forming the light-emitting layer (2).

The hole transport auxiliary layer (3) is disposed between the hole transport layer (4) and the light-emitting layer (2), and particularly in contact with the light-emitting layer (2). The hole transport auxiliary layer (3) is disposed to contact the light-emitting layer (2), and therefore, hole transfer at the interface between the light-emitting layer (2) and the hole transport layer (4) can be precisely controlled. The hole transport assisting layer (3) may comprise a plurality of compounds having different energy levels, such as different HOMO energy levels associated with hole transport.

For example, one of the compounds has a relatively high HOMO level, while the other of the compounds can have a relatively low HOMO level. Herein, the higher HOMO level indicates a higher absolute value when the vacuum leve is set at "0 eV", while the lower HOMO level is set at "0 eV" at the vacuum level. Lower indicates the lower absolute value.

In addition, compounds having relatively high HOMO levels and compounds having relatively low HOMO levels should be considered relative to each other, and herein, the former compound, ie, a compound having a relatively high HOMO level, has Among the materials having a higher HOMO level than the material forming the hole transport layer (4), the material forming the hole transport layer (4) has a relatively large HOMO level difference material, and the latter compound, that is, has a relative The compound of the lower HOMO level is a material having a relatively small HOMO level difference from the material forming the hole transport layer (4).

In this way, a plurality of compounds having different HOMO levels are used in common, and thus, the respective advantages of the compounds having higher HOMO levels and lower HOMO levels, respectively, can simultaneously improve efficiency and lifetime.

For example, an organic electroluminescent device fabricated by using a plurality of compounds each having a different HOMO level can increase hole transfer by reducing a HOMO level difference between a hole transport layer (4) and a light-emitting layer (2). And, therefore, preventing holes from accumulating at the interface of the hole transport layer (4) and the hole transport auxiliary layer (3) or the hole transport auxiliary layer (3) and the light-emitting layer (2), and as a result, reducing voids A quenching phenomenon in which excitons are combined and disappear at the interface of each layer. Therefore, the organic electroluminescent device can be suppressed or prevented from degrading, and thus stabilized, and the initial efficiency drop much slower than that of the organic electroluminescent device not using the hole transport auxiliary layer (3) can be exhibited, And at the same time improve efficiency and longevity.

As described above, the hole transporting auxiliary layer (3) may comprise a plurality of compounds having different energy levels in one layer and, for example, a first compound and a second compound having different HOMO levels in one layer. Further, the first compound and the second compound may be used in a uniform mixing ratio along the thickness direction of the hole transporting auxiliary layer (3).

One of the first compound and the second compound may have a relatively high HOMO energy level while the other may have a relatively low HOMO energy level. The first compound and the second compound have a HOMO energy level difference within the range, and thus can promote the substantial injection of holes from the anode (5) into the light-emitting layer (2). The HOMO energy levels of the first compound and the second compound can be represented by the following relation 1 and relation 2.

[Relationship 1]

∣E ^H _{first compound-} E ^H _{second compound} ∣≥0.1 eV

[Relationship 2]

∣E ^H _{first compound-} E ^H _{second compound} ∣≤0.3 eV

E ^H is the HOMO level of the compound, that is, the HOMO level difference between the first compound and the second compound is from 0.1 eV to 0.3 eV.

The hole transport auxiliary layer (3) may be more than one layer, and herein, in the hole transport auxiliary layer (3), the first compound and the second compound may be included in the layer contacting the light-emitting layer (2).

The first compound and the second compound may each have a HOMO level in the range of, for example, about - 5.45 electron volts to about - 5.80 electron volts and satisfying the relationship within the range.

On the other hand, the hole transporting auxiliary layer (3) is disposed between the light emitting layer (2) and the hole transporting layer (4), and can block the electron self-emitting layer (2) from being transferred to the hole transporting layer (4). Therefore, since the light-emitting layer (2) can effectively define electrons, excitons can be more generated in the light-emitting layer (2) while preventing interface between the light-emitting layer (2) and the hole transport layer (4). Generate excitons. Therefore, efficiency can be improved.

For example, when the hole transport auxiliary layer (142) includes the first compound and the second compound, the first compound and the second compound may have, for example, a LUMO energy level that further satisfies the following relation 3 to relation 6.

[Relationship 3]

∣E ^L _{first compound} ∣<∣E ^L _host ∣

[Relationship 4]

∣E ^L _{first compound} ∣<∣E ^L _dopant ∣

[Relationship 5]

∣E ^L _{second compound} ∣<∣E ^L _host ∣

[Relationship 6]

∣E ^L _{second compound} ∣<∣E ^L _dopant ∣

In relation 3 to relation 6,

E ^L is the LUMO level of the compound.

The hole transport assisting layer (3) contains the first compound and the second compound satisfying the relationship of Equation 3 to Equation 6, and can effectively block electron transfer from the light-emitting layer (2) and improve efficiency.

The first compound and the second compound may each have, for example, a LUMO energy level in the range of from about -2.00 electron volts to about -2.50 electron volts and one that satisfies the relationship within the range.

On the other hand, the hole transporting auxiliary layer (3) is disposed between the light emitting layer (2) and the hole transporting layer (4), and can block the transfer of excitons from the light emitting layer (2) to the hole transporting layer (4). . Therefore, since the light-emitting layer (2) can effectively maintain the excitons, the light-emitting efficiency can be improved in the light-emitting layer (2) while the exciton loss can be reduced. As a result, efficiency can be improved. The triplet level of the first compound is T1 > 2.6 ev.

T1 is the triplet level of the compound.

The first compound and the second compound may be selected from compounds satisfying the energy level, for example, the first compound may be represented by Chemical Formula 1, and the second compound may be represented by Chemical Formula 2 or a combination of Chemical Formula 3 and Chemical Formula 4.

Wherein, in Chemical Formula 1,

Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ , Ar ₅ and Ar ₆ are each independently represented by a C1 to C10 linear or branched alkyl substituted or unsubstituted phenyl group, a C1 to C10 linear or branched alkyl group. a substituted or unsubstituted biphenyl group, a C1-C10 linear or branched alkyl substituted or unsubstituted naphthyl group;

Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ , Ar ₅ , and Ar ₆ may also be represented by the structure represented by Chemical Formula A.

In Chemical Formula A, any one of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ is represented as a single bond which is bonded to N in Chemical Formula 1, and the remaining R _n are independently independent. Expressed as a hydrogen atom, a C1-C10 linear or branched alkyl group, and n is represented by 1 to 8;

X represents an O, S, C1 to C10 linear or branched alkyl substituted methylene group, a C6 to C15 aryl substituted methylene group, and a C6 to C15 aryl substituted imido group.

Wherein, in Chemical Formula 1 to Chemical Formula 4,

Y ₁ , Y _1a and Y _1b are each independently a single bond, a substituted or unsubstituted C 1 -C 20 alkylene group, a substituted or unsubstituted C 2 -C 20 alkenylene group, substituted or unsubstituted a fused ring of a C6-C30 arylene group, a substituted or unsubstituted C2 to C30 divalent heterocyclic group, a combination thereof, or a combination thereof,

Ar ₇ , Ar _7a and Ar _7b are each independently a substituted or unsubstituted C 6 -C 30 aryl group, a substituted or unsubstituted C 2 -C 30 heterocyclic group, or a combination thereof.

The adjacent two * of Chemical Formula 3 are fused with the adjacent two * of Chemical Formula 4,

The unfused * of Chemical Formula 3 are each CR ₉ and CR ₁₀ ,

R ₉ to R _{14 are} independently hydrogen, deuterium, substituted or unsubstituted C 1 -C 20 alkyl, substituted or unsubstituted C 6 -C 50 aryl, substituted or unsubstituted C 2 -C 50 heterocyclic ring Base or combination thereof,

R ₉ and R ₁₀ are each independently present or linked to each other to form a fused ring,

R ₁₁ and R ₁₂ are each independently present or connected to each other to form a fused ring,

R ₁₃ and R ₁₄ are each independently present or linked to each other to form a fused ring,

At least one of R ₉ to R ₁₂ and Ar ₇ of Chemical Formula 2 contains a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted bistriphenylene group or a substituted or unsubstituted hydrazine. Azolyl, and

At least one of R ₉ to R ₁₄ , Ar _7a and Ar _7b of the compound 3 or the compound 4 contains a substituted or unsubstituted C 6 -C 30 aryl group, a substituted or unsubstituted biphenylene group or a substituted group. Or unsubstituted carbazolyl.

In Chemical Formula 1, when Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ , Ar ₅ and Ar _{6 are} represented by a C1 to C10 linear or branched alkyl substituted or unsubstituted phenyl group, a C1 to C10 straight chain or a branched chain When an alkyl-substituted or unsubstituted biphenyl group or a C1-C10 linear or branched alkyl group is substituted or unsubstituted naphthyl group, at least Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ , Ar ₅ , and Ar ₆ are at least There are two biphenyl groups which are represented by C1 to C10 linear or branched alkyl substituted or unsubstituted, and at least one C1 to C10 linear or branched alkyl substituted or unsubstituted biphenyl is adjacent or inter a positional connection; when at least one of Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ , Ar ₅ , Ar ₆ is represented by the structure of the chemical formula A, and X represents a C1-C10 linear or branched alkyl-substituted methylene group At the time of the base, at least one of Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ , Ar ₅ and Ar ₆ is represented by a C1 to C10 linear or branched alkyl substituted or unsubstituted biphenyl group, and C1 to C10 are straight. A chain or branched alkyl substituted or unsubstituted biphenyl group is an ortho or meta linkage.

The chemical formula 1 may be, for example, a compound represented by one of Chemical Formula 1-I to Chemical Formula 1-III, according to the group represented by Chemical Formula A.

Wherein, in Chemical Formula 1-I,

Ar ₁ ', Ar ₂ ', Ar ₃ ', Ar ₄ ', Ar ₅ ', and Ar ₆ ' are each independently represented by a C1 to C10 linear or branched alkyl substituted or unsubstituted phenyl group, C1 to C10 straight. a substituted or unsubstituted biphenyl group, a C1-C10 linear or branched alkyl substituted or unsubstituted naphthyl group; and Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ , Ar ₅ , At least two of Ar ₆ are represented by a C1 to C10 linear or branched alkyl substituted or unsubstituted biphenyl group, and at least one C1 to C10 linear or branched alkyl substituted or unsubstituted biphenyl group. Connected to a neighbor or meta position;

In Chemical Formula 1-II to Chemical Formula 1-III,

Ar ₁ ', Ar ₂ ', Ar ₃ ', Ar ₄ ', Ar ₅ ', and Ar ₆ ' are each independently represented by a C1 to C10 linear or branched alkyl substituted or unsubstituted phenyl group, C1 to C10 straight. a substituted or unsubstituted biphenyl group, a C1 to C10 linear or branched alkyl substituted or unsubstituted naphthyl group; when X is represented by a C1 to C10 linear or branched alkyl group; In the case of a methylene group, one or two of Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ , Ar ₅ , and Ar ₆ are represented by a C1-C10 linear or branched alkyl substituted or unsubstituted biphenyl group, and The C1-C10 linear or branched alkyl substituted or unsubstituted biphenyl group is an ortho or meta linkage.

The second compound is a compound having a relationship with the first compound and satisfying the energy level, and is a carbazole compound substituted with an aryl group, a biphenylene group or a carbazolyl group.

The compound represented by Chemical Formula 2 may be, for example, one of the compounds represented by Chemical Formula 2-I to Chemical Formula 2-IV.

Wherein, in Chemical Formula 2-I to Chemical Formula 2-IV,

Y ₁ to Y _{3 are} independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C2 to C20 alkylene group, a substituted or unsubstituted C6 to C30 subunit. a fused ring of an aryl group, a substituted or unsubstituted C2 to C30 divalent heterocyclic group, a combination thereof, or a combination thereof,

Ar ₇ and Ar ₈ are each independently a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C2-C30 heterocyclic group, or a combination thereof.

Ar _7a is a substituted or unsubstituted C6-C30 aryl group, and

R ₉ to R ₂₄ are each independently hydrogen, deuterium, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C6 to C50 aryl, substituted or unsubstituted C2 to C50 Ring group or a combination thereof.

The compound represented by the combination of Chemical Formula 3 and Chemical Formula 4 may be, for example, one of the compounds represented by Chemical Formula 3-I to Chemical Formula 3-VII.

Wherein, in Chemical Formula 3-I to Chemical Formula 3-VII,

Y _1a and Y _1b are each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C2 to C20 alkylene group, a substituted or unsubstituted C6 to C30. a fused ring of an arylene group, a substituted or unsubstituted C2 to C30 divalent heterocyclic group, a combination thereof, or a combination thereof,

Ar _7a and Ar _7b are each independently a substituted or unsubstituted C 6 -C 30 aryl group, a substituted or unsubstituted C 2 -C 30 heterocyclic group, or a combination thereof.

R ₉ to R ₁₄ , R _d and R _e are each independently hydrogen, deuterium, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C6 to C50 aryl, substituted or unsubstituted Substituted C2-C50 heterocyclic group or a combination thereof,

R ₉ and R ₁₀ are each independently present or linked to each other to form a fused ring,

R ₁₁ and R ₁₂ are each independently present or connected to each other to form a fused ring,

R ₁₃ and R ₁₄ are each independently present or linked to each other to form a fused ring,

R _d and R _e are each independently present or linked to each other to form a fused ring, and

At least one of R ₉ to R ₁₄ , Ar _7a and Ar _7b comprises a substituted or unsubstituted C 6 -C 30 aryl group, a substituted or unsubstituted biphenylene group or a substituted or unsubstituted anthracene Azolyl.

The first compound may be, for example, one of the compounds of Chemical Formulas I-1 to I-141 in Group 1, but is not limited thereto.

The second compound may be, for example, one of the compounds of Chemical Formulas II-1 to II-45 in Group 2, but is not limited thereto.

The hole transport layer (4) is not subject to its particular limitation.

In FIG. 1, in addition to the light-emitting layer (2), the hole transport auxiliary layer (3), and the hole transport layer (4), the organic layer (10) may further include a hole injection layer, an electron blocking layer, and an electron transport layer. , an electron injecting layer and/or a hole blocking layer.

The organic light emitting diode (20) can be formed by forming an anode or a cathode on a substrate, according to a dry coating method such as evaporation, sputtering, plasma plating, and ion plating, or such as inkjet printing, spin coating. The solution process of slit coating, bar coating, and/or dip coating forms an organic layer, and a cathode or an anode is formed thereon to be fabricated.

The organic light emitting diode can be applied to an organic light emitting diode (OLED) display.

Hereinafter, the embodiments will be described in more detail with reference to examples. However, these examples are not to be construed as limiting the scope of the invention in any sense.

Example 1:

Synthesis of intermediate N

Weighing the raw material I and the raw material II with toluene, and then adding Pd ₂ (dba) ₃ , triphenylphosphine and potassium t-butoxide; and mixing the above reactants at a reaction temperature of 90-110 ° C under an inert atmosphere The reaction is carried out for 10-24 hours, the reaction solution is cooled and filtered, and the filtrate is rotary-screwed and passed through a silica gel column to obtain the target compound; the molar ratio of the starting material I to the starting material II is 1: (1.0-1.5); Pd ₂ (dba) ₃ and The molar ratio of the starting material I is (0.006-0.02): 1, the molar ratio of sodium t-butoxide to the starting material I is (2.0-3.0): 1; the molar ratio of triphenylphosphine to the starting material I is (2.0-3.0): 1; 1 g of starting material I was added to 50-100 mL of toluene.

Take the synthesis of intermediate N-1 as an example:

A 250 ml three-necked flask was charged with 0.01 mol of 1-aniline, 0.012 mol of 2-bromobiphenyl, 0.03 mol of potassium t-butoxide, and 1 × 10 ^-4 mol of Pd ₂ (dba) ₃ ,1 under a nitrogen atmosphere. ×10 ^-4 mol of tri-tert-butylphosphine, 150 ml of toluene, heating under reflux for 12 hours, sampling the plate, the reaction is complete; natural cooling, filtration, rotary distillation of the filtrate, passing through a silica gel column to obtain intermediate N-1; elemental analysis structure ( Molecular formula C ₁₈ H ₁₅ N): calcd for C, 88.13; H, 6.16; N, 5.71; ESI-MS (m/z) (M ⁺ ): Found: 245.

Preparation of intermediate N-2, intermediate N-3, intermediate N-4, intermediate N-5, intermediate N-6 and intermediate N-7 according to the procedure for the preparation of intermediate N-1 in Example 1. The corresponding replacement of the raw materials is shown in Table 1 below:

Table 1

Intermediates Ar1 and Ar2 were prepared according to the method for preparing intermediate N.

Synthesis of intermediate M

Weighing raw material III and intermediate Ar1 are dissolved in toluene, and then Pd ₂ (dba) ₃ , triphenylphosphine and potassium t-butoxide are added; the mixed solution of the above reactants is reacted at a reaction temperature of 90-110 ° C under an inert atmosphere. The reaction is carried out for 10-24 hours, the reaction solution is cooled and filtered, and the filtrate is rotary-screwed and passed through a silica gel column to obtain Intermediate A; the molar ratio of the starting material III to the intermediate Ar1 is 1: (1.0-1.5); Pd ₂ (dba) The molar ratio of ₃ to the raw material III is (0.006-0.02): 1, the molar ratio of sodium t-butoxide to the raw material III is (2.0-3.0): 1; the molar ratio of triphenylphosphine to the raw material III is (2.0- 3.0): 1; 1 g of starting material III was added to 50-100 mL of toluene.

The intermediate A and the intermediate Ar2 are weighed and dissolved in toluene, and then Pd ₂ (dba) ₃ , triphenylphosphine and potassium t-butoxide are added; and the mixed solution of the above reactants is reacted at a reaction temperature of 90-110 under an inert atmosphere. The reaction is carried out at ° C for 10-24 hours, the reaction solution is cooled and filtered, and the filtrate is rotary-screwed and passed through a silica gel column to obtain intermediate M; the molar ratio of the intermediate A to the intermediate Ar2 is 1: (1.0-1.5); Pd ₂ The molar ratio of (dba) ₃ to intermediate A is (0.006-0.02): 1, the molar ratio of sodium t-butoxide to intermediate A is (2.0-3.0): 1; the molar ratio of triphenylphosphine to intermediate A The ratio was (2.0-3.0): 1; 1 g of Intermediate A was added to 50-100 mL of toluene.

Take the synthesis of intermediate M-1 as an example:

A 250 ml three-necked flask was charged with 0.01 mol of the starting material III, 0.012 mol of the intermediate Ar1-1, 0.03 mol of potassium t-butoxide, 1 × 10 ^-4 mol of Pd ₂ (dba) ₃ , 1 × under a nitrogen atmosphere. 10 ^-4 mol of tri-tert-butylphosphine, 150 ml of toluene, heated to reflux for 12 hours, sampling the plate, the reaction is complete; naturally cooled, filtered, the filtrate is steamed, passed through a silica gel column to obtain intermediate A-1; elemental analysis structure (molecular formula) C ₁₈ H ₁₃ Br ₂ N): calcd for C,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, ESI-MS (m/z) (M ⁺ ): calcd.

A 250 ml three-necked flask was charged with 0.01 mol of Intermediate A-1, 0.012 mol of Intermediate Ar2-1, 0.03 mol of potassium t-butoxide, and 1 × 10 ^-4 mol of Pd ₂ (dba) ₃ under a nitrogen atmosphere. , 1 × 10 ^-4 mol of tri-tert-butylphosphine, 150 ml of toluene, heated under reflux for 12 hours, sampling the plate, the reaction is complete; naturally cooled, filtered, the filtrate is steamed, passed through a silica gel column to obtain intermediate M-1; elemental analysis The structure (molecular formula C ₃₆ H ₂₇ BrN ₂ ): calcd. C, 76.19; H, 4.48; s, s, s, s, s, s, s, s, s, s, s, s, s, s. ESI-MS (m/z) (M ⁺ ): 553.

Intermediate M-2, intermediate M-3, intermediate M-4, intermediate M-5, intermediate M-6, intermediate M-7 and intermediate were prepared according to the above method for the preparation of intermediate M-1. Body M-8, the raw material corresponding replacement is shown in Table 2 below:

Table 2

Example 2: Synthesis of Compound I-6:

A 250 ml three-necked flask was charged with 0.01 mol of intermediate M-1, 0.012 mol of intermediate N-1, 0.03 mol of potassium t-butoxide, and 1 × 10 ^-4 mol of Pd ₂ (dba) ₃ under a nitrogen atmosphere. , 1 × 10 ^-4 mol of tri-tert-butylphosphine, 150 ml of toluene, heated under reflux for 12 hours, sampling the plate, the reaction is complete; naturally cooled, filtered, the filtrate is steamed, passed through a silica gel column to obtain compound 9; elemental analysis structure (molecular formula) C ₅₄ H ₄₁ N ₃ ): calcd for C,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, ESI-MS (m/z) (M ⁺ ): Theory: 731.33.

Example 3: Synthesis of Compound I-18:

The preparation method of the compound 18 was the same as that of Example 2 except that the intermediate M-1 was replaced with the intermediate M-2, and the intermediate N-2 was substituted for the intermediate N-1; the elemental analysis structure (the molecular formula C ₆₆ H ₄₉ N _{3 )} The theoretical value is C, 89.66; H, 5.59; N, 4.75; C, 89.67; H, 5.59; N, 4.74. ESI-MS (m/z) (M ⁺ ): calc.

Example 4: Synthesis of Compound I-27:

Compound 27 was prepared in the same manner as in Example 2 except that intermediate M-2 was used to replace intermediate M-1, intermediate N-3 was substituted for intermediate N-1; and elemental analysis structure (Molecular Formula C ₅₈ H ₄₃ N _{3 )} The theoretical value is C, 89.08; H, 5.54; N, 5.37; Test value: C, 89.07; H, 5.54; N, 5.38. ESI-MS (m/z) (M ⁺ ): Found: 78.

Example 5: Synthesis of Compound I-40:

The preparation method of the compound 40 was the same as that of Example 2 except that the intermediate M-1 was replaced with the intermediate M-3, and the intermediate N-4 was replaced with the intermediate N-1; the elemental analysis structure (the molecular formula C ₆₃ H ₄₉ N _{3 )} Calcd, C, 89.23; H, 5.82; N, 4.95. ESI-MS (m/z) (M ⁺ ): calc.

Example 6: Synthesis of Compound I-54:

Compound 54 was prepared in the same manner as in Example 2 except that intermediate M-4 was used to replace intermediate M-1, intermediate N-5 was substituted for intermediate N-1; and elemental analysis structure (molecular formula C ₆₆ H ₅₃ N _{3 )} The theoretical value is C, 89.25; H, 6.02; N, 4.73; C, 89.24; H, 6.02; N, 4.74. ESI-MS (m/z) (M ⁺ ): calc.

Example 7: Synthesis of Compound I-72:

Compound 72 was prepared in the same manner as in Example 2 except that intermediate M-5 was substituted for intermediate M-1, intermediate N-5 was substituted for intermediate N-1; and elemental analysis structure (Molecular Formula C ₆₁ H ₄₇ N _{3 )} The theoretical value is C, 89.13; H, 5.76; N, 5.11; Test value: C, 89.12; H, 5.76; N, 5.12. ESI-MS (m/z) (M ⁺ ): calc.

Example 8: Synthesis of Compound I-90:

Compound 90 was prepared in the same manner as in Example 2 except that intermediate M-6 was substituted for intermediate M-1, intermediate N-5 was substituted for intermediate N-1; and elemental analysis structure (molecular formula C ₇₀ H ₅₅ N _{3 )} The theoretical value is C, 89.61; H, 5.91; N, 4.48; C, 89.62; H, 5.91; N, 4.47. ESI-MS (m/z) (M ⁺ ): calc.

Example 9: Synthesis of Compound I-111:

The compound 111 was prepared in the same manner as in Example 2 except that the intermediate M-1 was replaced with the intermediate M-7, and the intermediate N-6 was substituted for the intermediate N-1; the elemental analysis structure (Molecular Formula C ₆₃ H ₄₇ N _3O) The theoretical value is C, 87.77; H, 5.50; N, 4.87; O, 1.86; </ RTI></RTI></RTI><RTIgt; ESI-MS (m/z) (M ⁺ ): calc. 861.

Example 10: Synthesis of Compound I-136:

Compound 136 was prepared in the same manner as in Example 2 except that the intermediate M-1 was replaced with the intermediate M-8 and the intermediate N-1 was replaced with the intermediate N-1; the elemental analysis structure (Molecular Formula C ₆₄ H ₅₇ N _{3 )} The theoretical value is C, 88.54; H, 6.62; N, 4.84; Test value: C, 88.55; H, 6.62; N, 4.83. ESI-MS (m/z) (M ⁺ ): calc. 867.

The organic compound of the present invention is used in a light-emitting device and can be used as a hole transport auxiliary layer material. For the compounds of the present invention, I-6, I-18, I-27, I-40, I-54, I-72, I-90, I-111, I-136, I-156, I-162, I- 171, I-180, I-201, I-233, I-252, II-24, II-26, II-37, and II-45 perform T1 energy level, thermal performance, HOMO energy level, and LUMO energy level, respectively. Test, the test results are shown in Table 3.

table 3

Compound	T1(ev)	Tg (°C)	HOMO energy level (ev)	LUMO energy level (ev)
Compound I-6	2.68	130	-5.57	-2.46
Compound I-18	2.66	134	-5.60	-2.32
Compound I-27	2.67	148	-5.58	-2.35
Compound I-40	2.68	145	-5.62	-2.40

Compound I-54	2.70	147	-5.58	-2.28
Compound I-72	2.71	140	-5.53	-2.34
Compound I-90	2.68	145	-5.61	-2.35
Compound I-111	2.69	138	-5.60	-2.40
Compound I-136	2.71	142	-5.62	-2.35
Compound I-156	2.70	148	-5.58	-2.36
Compound I-162	2.68	147	-5.59	-2.32
Compound I-171	2.69	144	-5.60	-2.35
Compound I-180	2.68	144	-5.57	-2.32
Compound I-201	2.67	138	-5.56	-2.38
Compound I-233	2.69	146	-5.59	-2.36
Compound I-252	2.70	146	-5.60	-2.37
Compound II-21	2.72	145	-5.70	-2.44
Compound II-26	2.70	142	-5.72	-2.42
Compound II-37	2.57	139	-5.76	-2.30
Compound II-45	2.73	134	-5.80	-2.32

Note: The triplet energy level T1 is tested by Hitachi's F4600 fluorescence spectrometer. The test conditions of the material are 2*10 ^-5 toluene solution; the glass transition temperature Tg is by differential scanning calorimetry (DSC, Germany Benz DSC204F1 differential scanning) Calorimeter), the heating rate is 10 °C / min; the highest occupied molecular orbital HOMO level is tested by the ionization energy test system (IPS3), the test is atmospheric; the lowest unoccupied molecular orbital LUMO energy level is by cyclic voltammetry (CV) test and calculate the income.

It can be seen from the above table data that the organic compound of the present invention has suitable HOMO and LUMO energy levels, can be applied to the hole transport auxiliary layer, and has a high triplet energy level and a high glass transition temperature, so that The efficiency and lifetime of the fabricated OLED device containing the organic compound of the present invention are improved.

Manufacturing organic light emitting diodes

Device Embodiment 1

The device example uses ITO as an anode, Al as a cathode, CBP and Ir(ppy) ₃ as a light-emitting layer material by weight ratio of 90:10, HAT-CN as a hole injection layer material, and NPB as a hole transport layer material. The compound I-6 prepared in the examples of the present invention and the commercially available compound II-24 were simultaneously used as a hole transport auxiliary layer at a ratio of 1:1, TPBI was used as an electron transport layer material, and LiF was used as an electron injection layer material. The specific production steps are as follows:

The ITO anode layer on the transparent substrate layer was cleaned, ultrasonically cleaned with deionized water, acetone, and ethanol for 15 minutes, respectively, and then treated in a plasma cleaner for 2 minutes; on the ITO anode layer, vacuum-deposited by vacuum evaporation The hole injection layer material HAT-CN has a thickness of 10 nm, and this layer serves as a hole injection layer; on the hole injection layer, the compound I prepared in the embodiment of the present invention is simultaneously deposited by vacuum evaporation at a ratio of 1:1. 6 and the obtained compound II-21 as a hole transport auxiliary layer having a thickness of 20 nm; vapor-depositing the light-emitting layer on the hole transport auxiliary layer, the host material is CBP, and the doping material is Ir(ppy) ₃ , CBP and Ir (ppy) _{3 has} a mass ratio of 9:1 and a thickness of 30 nm; on the luminescent layer, a hole blocking/electron transport material TPBI is deposited by vacuum evaporation to a thickness of 40 nm, and this layer of organic material acts as a hole block / Electron transport layer used; above the hole blocking / electron transport layer, vacuum evaporation of the electron injection layer LiF, the thickness of 1nm, the layer is an electron injection layer; above the electron injection layer, vacuum evaporation of the cathode Al (100nm ), the layer is a cathode reflective electrode layer.

After completing the fabrication of the electroluminescent device according to the above steps, the IVL data and light decay lifetime of the device were measured, and the results are shown in Table 5. The molecular structure of the relevant material is as follows:

Device Examples 2-16 and Comparative Example 1

The devices of Examples 2-16 and Comparative Examples 1, 2 and Device Example 1 were fabricated in exactly the same manner, and the same substrate material and electrode material were used, and the film thickness of the electrode material was also kept the same, except that The materials used for the hole transport/electron blocking layer are different. See Table 4 for specific data.

Table 4

The efficiency and lifetime data of the devices of the respective examples and comparative examples are shown in Table 5.

table 5

It can be seen from the device data results of Table 5 that the organic light-emitting device of the present invention achieves a large improvement in efficiency and lifetime relative to OLED devices of known materials.

In order to compare the efficiency degradation of different devices at high current densities, a definition of the efficiency attenuation coefficient φ is shown, which represents the difference between the maximum efficiency μ100 of the device and the maximum efficiency μm of the device at a driving current of 100 mA/cm ² and the maximum efficiency. The ratio, the larger the value of φ, indicates that the efficiency of the device is more severely rolled off. Conversely, the problem that the device decays rapidly at high current density is controlled. The device attenuation efficiency φ was measured for each of the device examples 1-16 and the comparative examples 1 and 2. The detection results are shown in Table 6:

Table 6

Device code	Efficiency attenuation coefficient φ
Device Embodiment 1	0.22
Device Embodiment 2	0.25
Device Embodiment 3	0.23
Device Embodiment 4	0.24
Device Example 5	0.24
Device Example 6	0.26
Device Example 7	0.21
Device Embodiment 8	0.21
Device Example 9	0.22
Device Embodiment 10	0.21

Device Example 11	0.24
Device Embodiment 12	0.23
Device Embodiment 13	0.23
Device Embodiment 14	0.24
Device Example 15	0.24
Device Embodiment 16	0.22
Comparative example 1	0.40
Comparative example 2	0.35

From the data of Table 6, it can be seen from the comparison of the efficiency decay coefficients of the examples and the comparative examples that the organic light-emitting device of the present invention can effectively reduce the efficiency roll-off.

Further, the OLED device prepared by the material of the invention is more stable when operating at a low temperature, and the device examples 1, 4, and 8 and the device comparison examples 1 and 2 are tested in the range of -10 to 80 ° C, and the results are shown in the table. 7 and Figure 2.

Table 7

As can be seen from the data in Table 7 and FIG. 2, device embodiments 1, 4, and 8 are device structures in which the materials of the present invention and known materials are matched, and compared with the comparative examples 1 and 2 of the device, not only the low temperature efficiency but also the temperature rise. In the high process, the efficiency rises steadily.

In order to further test the beneficial effects produced by the compound of the present invention, the devices fabricated in Device Example 1 and Device Comparative Example 1 of the present invention were subjected to a reverse voltage leakage current test, and the test data is shown in FIG. 3, which is available from FIG. It is known that the device of the present invention and the device of the comparative example 1 have a small leakage current and a stable current curve. Therefore, the material of the present invention has a long service life after being fabricated.

Although the present invention has been described in connection with what is presently considered as a practical example embodiment, it is understood that the invention is not limited to the disclosed embodiments. Rather, the invention is intended to cover various modifications and equivalents of the embodiments Therefore, the foregoing embodiments are to be considered as illustrative and not restrictive.

Symbol Description

20: Organic light emitting diode

5: anode

1: cathode

2: luminescent layer

4: hole transport layer

3: hole transport auxiliary layer

10: organic layer

Claims (12)

1. An organic electroluminescent device, characterized in that it comprises at least:

   Anode and cathode,

   a luminescent layer between the anode and the cathode,

   a hole transport layer between the anode and the luminescent layer, and

   a hole transport auxiliary layer between the hole transport layer and the light emitting layer,

   Wherein the hole transport auxiliary layer comprises:

   a first compound represented by Chemical Formula 1 and

   A second compound represented by Chemical Formula 2 or a combination of Chemical Formula 3 and Chemical Formula 4:

   

   Wherein, in Chemical Formula 1,

   Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ , Ar ₅ and Ar ₆ are each independently represented by a C1 to C10 linear or branched alkyl substituted or unsubstituted phenyl group, a C1 to C10 linear or branched alkyl group. a substituted or unsubstituted biphenyl group, a C1-C10 linear or branched alkyl substituted or unsubstituted naphthyl group;

   Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ , Ar ₅ , and Ar ₆ may also be represented by the structure represented by Chemical Formula A.

   

   In Chemical Formula A, any one of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ is represented as a single bond which is bonded to N in Chemical Formula 1, and the remaining R _n are independently independent. Expressed as a hydrogen atom, a C1-C10 linear or branched alkyl group, and n is represented by 1 to 8;

   X represents an O, S, C1 to C10 linear or branched alkyl substituted methylene group, a C6 to C15 aryl substituted methylene group, and a C6 to C15 aryl substituted imido group.

   

   Wherein, in Chemical Formula 2 to Chemical Formula 4,

   Y ₁ , Y _1a and Y _1b are each independently a single bond, a substituted or unsubstituted C 1 -C 20 alkylene group, a substituted or unsubstituted C 2 -C 20 alkenylene group, substituted or unsubstituted a fused ring of a C6-C30 arylene group, a substituted or unsubstituted C2 to C30 divalent heterocyclic group, a combination thereof, or a combination thereof,

   Ar ₇ , Ar _7a and Ar _7b are each independently a substituted or unsubstituted C 6 -C 30 aryl group, a substituted or unsubstituted C 2 -C 30 heterocyclic group, or a combination thereof.

   The adjacent two * of Chemical Formula 3 are fused with the adjacent two * of Chemical Formula 4,

   The unfused * of Chemical Formula 3 are each CR ₉ and CR ₁₀ ,

   R ₉ to R _{14 are} independently hydrogen, deuterium, substituted or unsubstituted C 1 -C 20 alkyl, substituted or unsubstituted C 6 -C 50 aryl, substituted or unsubstituted C 2 -C 50 heterocyclic ring Base or combination thereof,

   R ₉ and R ₁₀ are each independently present or linked to each other to form a fused ring,

   R ₁₁ and R ₁₂ are each independently present or connected to each other to form a fused ring,

   R ₁₃ and R ₁₄ are each independently present or linked to each other to form a fused ring,

   At least one of R ₉ to R ₁₂ and Ar ₇ of Chemical Formula 2 contains a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted bistriphenylene group or a substituted or unsubstituted hydrazine. Azolyl, and

   At least one of R ₉ to R ₁₄ , Ar _7a and Ar _7b of the compound 3 or the compound 4 contains a substituted or unsubstituted C 6 -C 30 aryl group, a substituted or unsubstituted biphenylene group or a substituted group. Or unsubstituted carbazolyl.
2. The organic electroluminescent device according to claim 1, wherein, in Chemical Formula 1, when Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ , Ar ₅ , and Ar ₆ are each represented as a C1 to C10 straight chain or a branched chain. Alkyl substituted or unsubstituted phenyl, C1-C10 straight or branched alkyl substituted or unsubstituted biphenyl, C1-C10 straight or branched alkyl substituted or unsubstituted naphthyl, Ar ₁ At least two of Ar ₂ , Ar ₃ , Ar ₄ , Ar ₅ , and Ar ₆ are represented by a C1 to C10 linear or branched alkyl substituted or unsubstituted biphenyl group, and at least one C1 to C10 linear chain Or a branched alkyl substituted or unsubstituted biphenyl group is an ortho or meta linkage; when one or two of Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ , Ar ₅ , and Ar ₆ are represented by the chemical formula A structure And X represents a C1-C10 linear or branched alkyl-substituted methylene group, and at least one of Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ , Ar ₅ , and Ar ₆ is represented by a C1 to C10 linear chain. Or a branched alkyl substituted or unsubstituted biphenyl group, and a C1-C10 linear or branched alkyl substituted or unsubstituted biphenyl group is an ortho or meta linkage.
3. The organic electroluminescent device according to claim 1, wherein the first compound is represented by one of Chemical Formula 1-I to Chemical Formula 1-III:

   

   Wherein, in Chemical Formula 1-I,

   Ar ₁ ', Ar ₂ ', Ar ₃ ', Ar ₄ ', Ar ₅ ', and Ar ₆ ' are each independently represented by a C1 to C10 linear or branched alkyl substituted or unsubstituted phenyl group, C1 to C10 straight. a substituted or unsubstituted biphenyl group, a C1-C10 linear or branched alkyl substituted or unsubstituted naphthyl group; and Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ , Ar ₅ , At least two of Ar ₆ are represented by a C1 to C10 linear or branched alkyl substituted or unsubstituted biphenyl group, and at least one C1 to C10 linear or branched alkyl substituted or unsubstituted biphenyl group. Connected to a neighbor or meta position;

   In Chemical Formula 1-II to Chemical Formula 1-III,

   Ar ₁ ', Ar ₂ ', Ar ₃ ', Ar ₄ ', Ar ₅ ', and Ar ₆ ' are each independently represented by a C1 to C10 linear or branched alkyl substituted or unsubstituted phenyl group, C1 to C10 straight. a substituted or unsubstituted biphenyl group, a C1 to C10 linear or branched alkyl substituted or unsubstituted naphthyl group; when X is represented by a C1 to C10 linear or branched alkyl group; In the case of a methylene group, at least one of Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ , Ar ₅ and Ar ₆ is represented by a C1 to C10 linear or branched alkyl substituted or unsubstituted biphenyl group, and C1 to A C10 linear or branched alkyl substituted or unsubstituted biphenyl group is an ortho or meta linkage.
4. The organic electroluminescent device according to claim 1, wherein the second compound is represented by one of Chemical Formula 2-I to Chemical Formula 2-IV:

   

   

   Wherein, in Chemical Formula 2-I to Chemical Formula 2-IV,

   Y ₁ to Y _{3 are} independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C2 to C20 alkylene group, a substituted or unsubstituted C6 to C30 subunit. a fused ring of an aryl group, a substituted or unsubstituted C2 to C30 divalent heterocyclic group, a combination thereof, or a combination thereof,

   Ar ₇ and Ar ₈ are each independently a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C2-C30 heterocyclic group, or a combination thereof.

   Ar _7a is a substituted or unsubstituted C6-C30 aryl group, and

   R ₉ to R ₂₄ are each independently hydrogen, deuterium, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C6 to C50 aryl, substituted or unsubstituted C2 to C50 Ring group or a combination thereof.
5. The organic electroluminescent device according to claim 1, wherein the second compound is represented by one of Chemical Formula 3-I to Chemical Formula 3-VII:

   

   

   Wherein, in Chemical Formula 3-I to Chemical Formula 3-VII,

   Y _1a and Y _1b are each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C2 to C20 alkylene group, a substituted or unsubstituted C6 to C30. a fused ring of an arylene group, a substituted or unsubstituted C2 to C30 divalent heterocyclic group, a combination thereof, or a combination thereof,

   Ar _7a and Ar _7b are each independently a substituted or unsubstituted C 6 -C 30 aryl group, a substituted or unsubstituted C 2 -C 30 heterocyclic group, or a combination thereof.

   R ₉ to R ₁₄ , R _d and R _e are each independently hydrogen, deuterium, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C6 to C50 aryl, substituted or unsubstituted Substituted C2-C50 heterocyclic group or a combination thereof,

   R ₉ and R ₁₀ are each independently present or linked to each other to form a fused ring,

   R ₁₁ and R ₁₂ are each independently present or connected to each other to form a fused ring,

   R ₁₃ and R ₁₄ are each independently present or linked to each other to form a fused ring,

   R _d and R _e are each independently present or linked to each other to form a fused ring, and

   At least one of R ₉ to R ₁₄ , Ar _7a and Ar _7b comprises a substituted or unsubstituted C 6 -C 30 aryl group, a substituted or unsubstituted biphenylene group or a substituted or unsubstituted anthracene Azolyl.
6. The organic electroluminescent device according to claim 1, wherein the first compound is any one of the following compounds:

   

   

   

   

   

   

   

   

   

   
7. The organic electroluminescent device according to claim 1, wherein the second compound is any one of the following compounds:

   

   
8. The organic electroluminescent device according to claim 1, wherein the hole transporting auxiliary layer contacts the light emitting layer.
9. The organic electroluminescent device according to claim 1, wherein a HOMO level difference between the first compound and the second compound is from 0.1 eV to 0.3 eV.
10. The organic electroluminescent device according to claim 1, wherein the first compound has a triplet level T1 > 2.6 ev.
11. A display element comprising the organic electroluminescent device according to any one of claims 1 to 10.
12. A method for producing a compound, characterized in that the compound has the structure of Chemical Formula 1.

    

    Wherein, in Chemical Formula 1,

    Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ , Ar ₅ and Ar ₆ are each independently represented by a C1 to C10 linear or branched alkyl substituted or unsubstituted phenyl group, a C1 to C10 linear or branched alkyl group. a substituted or unsubstituted biphenyl group, a C1-C10 linear or branched alkyl substituted or unsubstituted naphthyl group;

    Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ , Ar ₅ , and Ar ₆ may also be represented by the structure represented by Chemical Formula A.

    

    In Chemical Formula A, any one of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ is represented as a single bond which is bonded to N in Chemical Formula 1, and the remaining R _n are independently independent. Expressed as a hydrogen atom, a C1-C10 linear or branched alkyl group, and n is represented by 1 to 8;

    X represents an O, S, C1 to C10 linear or branched alkyl substituted methylene group, a C6 to C15 aryl substituted methylene group, and a C6 to C15 aryl substituted imido group.

    The reaction equation is:

    

    The specific preparation method is as follows:

    The intermediate M and the intermediate N are weighed and dissolved in toluene, and then Pd ₂ (dba) ₃ , triphenylphosphine and potassium t-butoxide are added; and the mixed solution of the above reactants is reacted at a reaction temperature of 90-110 under an inert atmosphere. The reaction is carried out at ° C for 10-24 hours, the reaction solution is cooled and filtered, and the filtrate is rotary-screwed and passed through a silica gel column to obtain the target compound; the amount of the toluene is 30-50 mL of toluene per gram of the intermediate M; The molar ratio of the body M is 1: (1.0-1.5); the molar ratio of the Pd ₂ (dba) ₃ to the intermediate M is (0.006-0.02): 1, the molar ratio of the sodium t-butoxide to the intermediate M The ratio is (2.0-3.0): 1; the molar ratio of the triphenylphosphine to the intermediate M is (2.0-3.0):1.

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