CN106232768B

CN106232768B - Organic photoelectric element and display element

Info

Publication number: CN106232768B
Application number: CN201580020568.2A
Authority: CN
Inventors: 金勋; 金昌佑; 柳银善; 郑成显; 郑镐国; 姜基煜; 姜义洙; 金伦焕; 柳东完; 朴宰汉; 郑又硕; 赵平锡
Original assignee: Samsung SDI Co Ltd
Current assignee: Samsung SDI Co Ltd
Priority date: 2014-05-30
Filing date: 2015-04-28
Publication date: 2019-12-10
Anticipated expiration: 2035-04-28
Also published as: KR101878398B1; KR20150138000A; TWI643837B; CN106232768A; TW201602060A; KR20180035196A

Abstract

The present invention relates to an organic photoelectric element and a display element, the organic photoelectric element includes: an anode and a cathode facing each other; an emissive layer between the anode and the cathode; a hole transport layer between the anode and the emissive layer; and a hole transport assisting layer between the hole transport layer and the emission layer, wherein the hole transport assisting layer includes 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. The organic photoelectric element of the invention can realize high efficiency and long service life. The explanations of chemical formulas 1 to 4 are the same as described in the specification.

Description

Organic photoelectric element and display element

Technical Field

The present invention relates to an organic photoelectric element and a display element.

Background

the organic photoelectric element is an element that converts electric energy into optical energy, and is also an element that converts optical energy into electric energy.

The organic photoelectric element can be classified as follows according to its driving principle.

One is a photovoltaic element in which excitons are generated by light energy, separated into electrons and holes and transferred to different electrodes to generate electrical energy; and the other is a light emitting element in which voltage or current is applied to an electrode to generate light energy from electric energy.

Examples of the organic photoelectric element may be an organic photoelectric element, an organic light emitting diode, an organic solar cell, and an organic photoconductor drum.

among them, Organic Light Emitting Diodes (OLEDs) have recently received attention due to the increasing demand for flat panel displays. The organic light emitting diode converts electric energy into light by applying current to an organic light emitting material.

The organic light emitting diode has a structure in which an organic layer is interposed between an anode and a cathode.

Disclosure of Invention

Technical problem

An embodiment provides an organic photoelectric element capable of realizing high efficiency and long life.

Another embodiment provides a display element including an organic photoelectric element.

technical solution

According to one embodiment, an organic photoelectric element includes an anode and a cathode facing each other; an emissive layer between the anode and the cathode; a hole transport layer between the anode and the emissive layer; and a hole transport assisting layer between the hole transport layer and the emission layer, wherein the hole transport assisting layer includes 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.

[ chemical formula 1]

In the chemical formula 1, the first and second,

L ¹ to L ³ are each independently a single bond, a substituted or unsubstituted C6 to C30 arylene, substituted or unsubstituted C3 to C30 cycloalkylene, a substituted or unsubstituted C2 to C30 divalent heterocyclic group, a combination thereof, or a fused ring of a combination thereof,

Ar ¹ -Ar ³ are each independently a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C3-C30 heterocyclic group, a combination thereof, or a fused ring of a combination thereof, and

At least one of Ar ¹ through Ar ³ is one of a group represented by formula A, a group represented by a combination of formula B and formula C, or a group represented by a combination of formula B and formula D,

Wherein, in the chemical formulas A to D,

X and Z are O, S or CR ^a R ^b,

two adjacent ones of formula B are fused to two adjacent ones of formula C or formula D,

Each of the unfused of formulae B and C is CR ^c,

R ¹ to R ⁴, R ^a to R ^c are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C3 to C20 cycloalkoxy group, a substituted or unsubstituted C1 to C20 alkylthio group, a substituted or unsubstituted C6 to C30 aralkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C6 to C30 aryloxy group, a substituted or unsubstituted C6 to C30 arylthio group, a substituted or unsubstituted C2 to C30 heterocyclic group, a substituted or unsubstituted C2 to C30 amino group, a substituted or unsubstituted C3 to C30 silyl group, a halogen, a cyano group, a nitro group, a hydroxyl group, a carboxyl group, a combination thereof, a L ¹ to ³ bond of a fused ring of formula L ¹,

R ¹ and R ² each independently exist or are condensed with each other to form a condensed ring, an

R ³ and R ⁴ each independently exist or are fused with each other to form a condensed ring,

Wherein, in chemical formulas 2 to 4,

Y ¹, 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 alkenylene group, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C2 to C30 divalent heterocyclic group, a combination thereof or a fused ring of a combination thereof,

ar ⁴, Ar ^4a and Ar ^4b are each independently a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heterocyclic group, or a combination thereof,

Adjacent two of chemical formula 3 are fused with adjacent two of chemical formula 4,

The two unfused groups of formula 3 are each CR ⁵ and CR ⁶,

R ⁵ to R ¹⁰ are independently hydrogen, deuterium, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C6 to C50 aryl, substituted or unsubstituted C2 to C50 heterocyclic group, or a combination thereof,

R ⁵ and R ⁶ each independently exist or are linked to each other to form a condensed ring,

R ⁷ and R ⁸ each independently exist or are linked to each other to form a condensed ring,

R ⁹ and R ¹⁰ each independently exist or are linked to each other to form a condensed ring,

At least one of R ⁵ to R ⁸ and Ar ⁴ of chemical formula 2 comprises a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted triphenylene group, or a substituted or unsubstituted carbazolyl group, and

at least one of R ⁵ to R ¹⁰, Ar ^4a, and Ar ^4b of chemical formula 3 or chemical formula 4 includes a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted biphenylene group, or a substituted or unsubstituted carbazolyl group.

According to another embodiment, a display element including an organic photoelectric element is provided.

Advantageous effects

An organic photoelectric element having high efficiency and long service life can be realized.

Drawings

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

Detailed Description

hereinafter, embodiments of the present invention are described in detail. However, these embodiments are exemplary, the invention is not limited thereto and the invention is defined by the scope of the claims.

In the present specification, when a definition is not otherwise provided, the term "substituted" refers to one substituted by a substituent selected from among the following, instead of the substituent or at least one hydrogen of the compound: deuterium, halogen, hydroxyl, amine, substituted or unsubstituted C1 to C30 amine, nitro, substituted or unsubstituted C1 to C40 silyl, C1 to C30 alkyl, C1 to C10 alkylsilyl, C3 to C30 cycloalkyl, C3 to C30 heterocycloalkyl, C6 to C30 aryl, C6 to C30 heterocyclyl, C1 to C20 alkoxy, fluoro, C1 to C10 trifluoroalkyl (such as trifluoromethyl) or cyano.

In addition, two adjacent substituents of substituted halogen, hydroxyl, amine, substituted or unsubstituted C1 to C20 amine, nitro, substituted or unsubstituted C3 to C40 silyl, C1 to C30 alkyl, C1 to C10 alkylsilyl, C3 to C30 cycloalkyl, C3 to C30 heterocycloalkyl, C6 to C30 aryl, C6 to C30 heterocyclic, C1 to C20 alkoxy, fluoro, C1 to C10 trifluoroalkyl (such as trifluoromethyl and the like) or cyano may be fused to each other to form a ring. For example, a substituted C6 to C30 aryl group may be fused with another adjacent substituted C6 to C30 aryl group to form a substituted or unsubstituted fluorene ring.

In the present specification, when a specific definition is not otherwise provided, the term "hetero" means one containing 1 to 3 hetero atoms selected from N, O, S, P and Si and the remaining carbon in one compound or substituent.

In the present specification, "aryl group" refers to a group having at least one hydrocarbon aromatic moiety and substantially hydrocarbon aromatic moieties linked by a single bond and a non-aromatic fused ring comprising directly or indirectly fused hydrocarbon aromatic moieties. Aryl groups can be monocyclic, polycyclic, or fused-ring polycyclic (i.e., rings that share adjacent pairs of carbon atoms) functional groups.

In the present specification, "heterocyclic group" includes heteroaryl and cyclic groups including at least one heteroatom selected from N, O, S, P and Si, other than carbon (C) of a cyclic compound, such as aryl, cycloalkyl, a fused ring, or a combination thereof. When the heterocyclyl is a fused ring, each or all of the rings of the heterocyclyl may contain at least one heteroatom.

More precisely, substituted or unsubstituted C6 to C30 aryl and/or substituted or unsubstituted C2 to C30 heteroaryl means substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthryl, substituted or unsubstituted phenanthryl, substituted or unsubstituted condensed tetraphenyl, substituted or unsubstituted pyrenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted p-terphenyl, substituted or unsubstituted m-terphenyl, substituted or unsubstituted chrysyl, substituted or unsubstituted terphenylene, substituted or unsubstituted perylene, substituted or unsubstituted indenyl, substituted or unsubstituted furyl, substituted or unsubstituted thienyl, substituted or unsubstituted pyrrolyl, substituted or unsubstituted pyrazolyl, 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 pyrimidyl, substituted or unsubstituted pyrazinyl, substituted or unsubstituted triazinyl, substituted or unsubstituted benzofuranyl, substituted or unsubstituted benzothiophenyl, substituted or unsubstituted benzimidazolyl, substituted or unsubstituted indolyl, substituted or unsubstituted quinolyl, substituted or unsubstituted isoquinolyl, substituted or unsubstituted quinazolinyl, substituted or unsubstituted quinolyl, substituted or unsubstituted naphthyridinyl, Substituted or unsubstituted benzoxazinyl, substituted or unsubstituted benzothiazinyl, substituted or unsubstituted acridinyl, substituted or unsubstituted phenazinyl, substituted or unsubstituted phenothiazinyl, substituted or unsubstituted phenazinyl, substituted or unsubstituted fluorene, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted carbazolyl, combinations thereof or fused rings of combinations of the foregoing, but are not limited thereto.

In the present specification, substituted or unsubstituted arylene, substituted or unsubstituted heteroarylene or substituted or unsubstituted divalent heterocyclic radical means a substituted or unsubstituted aryl or substituted or unsubstituted heterocyclic radical as defined above and having two linking groups, for example a substituted or unsubstituted phenylene, substituted or unsubstituted naphthyl, substituted or unsubstituted anthrylene, substituted or unsubstituted phenanthrylene, substituted or unsubstituted picrylene, substituted or unsubstituted pyrenylene, substituted or unsubstituted biphenylene, substituted or unsubstituted paracyclophenylene, substituted or unsubstituted tetraphenylene, substituted or unsubstituted biphenylene, substituted or unsubstituted peryleneene, peryleneene, Substituted or unsubstituted indenyl, substituted or unsubstituted furanylene, substituted or unsubstituted thienyl, substituted or unsubstituted pyrrolylene, substituted or unsubstituted pyrazolyl, substituted or unsubstituted imidazolyl, substituted or unsubstituted triazolylene, substituted or unsubstituted oxazolylene, substituted or unsubstituted thiazolyl, substituted or unsubstituted oxadiazolyl, substituted or unsubstituted thiadiazolyl, substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidinylene, substituted or unsubstituted pyrazinylene, substituted or unsubstituted triazinylene, substituted or unsubstituted benzofuranylene, substituted or unsubstituted benzothiophenyl, substituted or unsubstituted benzimidazolylene, A fused ring of a substituted or unsubstituted indolylenylene group, a substituted or unsubstituted quinolylene group, a substituted or unsubstituted isoquinolylene group, a substituted or unsubstituted quinazolinylene group, a substituted or unsubstituted quinolylene group, a substituted or unsubstituted naphthyrylene group, a substituted or unsubstituted benzoxazinyl group, a substituted or unsubstituted benzothiazinyl group, a substituted or unsubstituted acridine group, a substituted or unsubstituted phenazinylene group, a substituted or unsubstituted phenothiazinyl group, a substituted or unsubstituted phenoxazinyl group, a substituted or unsubstituted oxadiazinyl group, a substituted or unsubstituted fluorenylene group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted carbazolyl group, a combination thereof or a combination thereof, but not limited thereto.

In the present specification, the hole characteristics refer to characteristics capable of supplying electrons when an electric field (electric field) is applied and holes formed in the anode are easily injected into and transported in the emission layer due to a conductive characteristic according to a Highest Occupied Molecular Orbital (HOMO) level.

In addition, the electron characteristics refer to characteristics that are capable of accepting electrons when an electric field is applied and electrons formed in the cathode are easily injected into and transported in the emission layer due to conductive characteristics according to the Lowest Unoccupied Molecular Orbital (LUMO) level.

Hereinafter, an organic photoelectric element according to an embodiment is described.

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

Herein, the organic light emitting diode is described as one example of the organic photoelectric element (but the present invention is not limited thereto), and may be applied to other organic photoelectric elements in the same manner.

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

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 300 according to an embodiment includes an anode 110 and a cathode 120 facing each other; and an organic layer 105 interposed between the anode 110 and the cathode 120, wherein the organic layer 105 includes an emission layer 130, a hole transport auxiliary layer 142, and a hole transport layer 141.

The anode 110 may be made of a conductor having a high work function to assist hole injection, such as a metal, a metal oxide and/or a conductive polymer, the anode 110 may be, for example, a metal such as nickel, platinum, vanadium, chromium, copper, zinc, gold or an alloy thereof, a metal oxide such as zinc 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 is not limited thereto.

The cathode 120 may be made of a conductor having a low work function to facilitate electron injection, and may be, for example, a metal oxide, and/or a conductive polymer, the cathode 120 may be, for example, a metal or an alloy thereof, such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, lead, cesium, and barium, a multi-layered structure material, such as LiF/Al, LiO ₂/Al, LiF/Ca, LiF/Al, and BaF ₂/Ca, but is not limited thereto.

The emission layer 130 is interposed between the anode 110 and the cathode 120, and includes at least one host (host) and at least one dopant (dopant).

The dopant is a material that is mixed with the host in a small amount to generate light emission, and it may be an organic compound or a metal complex (metal complex), such as Al that emits fluorescence by singlet excitation; or a material such as a metal complex (metal complex) that emits light by multiple excitation (multiple excitation) into a triplet state or more 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 species thereof may be used.

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

[ chemical formula Z ]

L₂MX

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

M can be, for example, Ir, Pt, Os, Ti, Zr, Hf, Eu, Tb, Tm, Fe, Co, Ni, Ru, Rh, Pd, or combinations thereof, and L and X can be, for example, bidentate ligands.

The hole transport layer 141 is disposed between the anode 110 and the emission layer 130, and easily transports holes from the anode 110 to the emission layer 130. For example, the hole transport layer 141 may include a material having a HOMO energy level between a work function (work function) of a conductor forming the anode 110 and a HOMO energy level of a material forming the emission layer 130.

hole transport assist layer 142 is disposed between hole transport layer 141 and emissive layer 130, and in particular contacts emissive layer 130. The hole transport auxiliary layer 142 is disposed to contact the emission layer 130, and thus, hole transfer on the interface of the emission layer 130 and the hole transport layer 141 may be precisely controlled. The hole transport assist layer 142 may comprise more than one layer.

the hole transport assist layer 142 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 may have a relatively high HOMO energy level, while another of the compounds may have a relatively low HOMO energy level. Herein, a higher HOMO energy level indicates a higher absolute value when the vacuum energy level (vacuum level) is set at "0 electron volts", and a lower HOMO energy level indicates a lower absolute value when the vacuum energy level is set at "0 electron volts".

In addition, a compound having a relatively higher HOMO level and a compound having a relatively lower HOMO level should be regarded as being relative to each other, and herein, the former compound, that is, the compound having a relatively higher HOMO level, is a material having a relatively larger HOMO level difference with a material forming the hole transport layer 141 among materials having a higher HOMO level than the material forming the hole transport layer 141, and the latter compound, that is, the compound having a relatively lower HOMO level is a material having a relatively smaller HOMO level difference with the material forming the hole transport layer 141.

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

For example, an organic photoelectric element manufactured by using a plurality of compounds each having a different HOMO level may increase hole transfer by reducing a HOMO level difference between the hole transport layer 141 and the emission layer 130, and thus, prevent holes from accumulating on an interface of the hole transport layer 141 and the hole transport auxiliary layer 142 or the hole transport auxiliary layer 142 and the emission layer 130, and as a result, reduce a quenching (quenching) phenomenon in which holes are combined with excitons and disappear on each layer interface. Accordingly, the organic photoelectric element can be suppressed or prevented from being degraded and thus stabilized, and can also exhibit a much slower initial efficiency drop compared to an organic photoelectric element not using the hole transport assist layer 142, and thus improve efficiency and lifetime at the same time.

As described above, the hole transport assist layer 142 may include a plurality of compounds having different energy levels in one layer and, for example, a first compound and a second compound having different HOMO energy levels in one layer. The first compound and the second compound may be used in a uniform mixing ratio in the thickness direction of the hole transport assistance layer 142.

The HOMO levels of the first compound and the second compound can be represented by the following relational formula 1.

[ relational expression 1]

|E^H _p1|≠|E^H _p2|

in relation 1, E ^H _p1 indicates the HOMO energy level of the first compound, and E ^H _p2 indicates the HOMO energy level of the second compound.

One of the first compound and the second compound may have a relatively high HOMO energy level, and the other may have a relatively low HOMO energy level.

The first compound and the second compound can, for example, have a HOMO energy step greater than or equal to about 0.01 electron volts, specifically greater than or equal to about 0.02 electron volts, more specifically greater than or equal to about 0.03 electron volts, and even more specifically greater than or equal to about 0.05 electron volts. Herein, the first compound and the second compound may have HOMO levels represented by at least one of the following relational formulae 1a to 1 d.

[ relational expression 1a ]

E ^H _p1 -E ^H _p2 | ≧ 0.01 electron volt

[ relational expression 1b ]

e ^H _p1 -E ^H _p2 | ≧ 0.02 electron volt

[ relational expression 1c ]

E ^H _p1 -E ^H _p2 | ≧ 0.03 electron volt

[ relational expression 1d ]

E ^H _p1 -E ^H _p2 | ≧ 0.05 electron volt

The first compound and the second compound may have a HOMO level difference in a range of less than or equal to about 0.5 ev. The first compound and the second compound have HOMO energy level differences within the range, and thus may facilitate substantial injection of holes from the anode 110 into the emissive layer 130. Within this range, the first compound and the second compound may, for example, have HOMO levels less than or equal to about 0.4 electron volts, and more specifically less than or equal to about 0.3 electron volts.

Herein, the first compound and the second compound may have HOMO levels represented by at least one of the following relations 2a to 2 c.

[ relational expression 2a ]

Less than or equal to 0.5 electron volt | E ^H _p1 -E ^H _p2 |, and

[ relational expression 2b ]

Less than or equal to 0.4 electron volt | E ^H _p1 -E ^H _p2 |, and

[ relational expression 2c ]

Less than or equal to 0.3 electron volt | E ^H _p1 -E ^H _p2 |, and

For example, the first compound and the second compound may have HOMO levels represented by at least one of the following relations 3a to 5 e.

[ relational expression 3a ]

0 electron volt < | E ^H _p1 -E ^H _p2 | is less than or equal to 0.5 electron volt

[ relational expression 3b ]

E ^H _p1 -E ^H _p2 | is less than or equal to 0.01 electron volt and is less than or equal to 0.5 electron volt

[ relational expression 3c ]

E ^H _p1 -E ^H _p2 | is less than or equal to 0.02 electron volt and is less than or equal to 0.5 electron volt

[ relational expression 3d ]

E ^H _p1 -E ^H _p2 | is less than or equal to 0.03 electron volt and is less than or equal to 0.5 electron volt

[ relational expression 3e ]

e ^H _p1 -E ^H _p2 | is less than or equal to 0.05 electron volt and is less than or equal to 0.5 electron volt

[ relational expression 4a ]

0 electron volt < | E ^H _p1 -E ^H _p2 | is less than or equal to 0.4 electron volt

[ relational expression 4b ]

E ^H _p1 -E ^H _p2 | is less than or equal to 0.01 electron volt and is less than or equal to 0.4 electron volt

[ relational expression 4c ]

E ^H _p1 -E ^H _p2 | is less than or equal to 0.02 electron volt and is less than or equal to 0.4 electron volt

[ relational expression 4d ]

E ^H _p1 -E ^H _p2 | is less than or equal to 0.03 electron volt and is less than or equal to 0.4 electron volt

[ relational expression 4e ]

E ^H _p1 -E ^H _p2 | is less than or equal to 0.05 electron volt and is less than or equal to 0.4 electron volt

[ relational expression 5a ]

0 electron volt < | E ^H _p1 -E ^H _p2 | is less than or equal to 0.3 electron volt

[ relational expression 5b ]

E ^H _p1 -E ^H _p2 | is less than or equal to 0.01 electron volt and is less than or equal to 0.3 electron volt

[ relational expression 5c ]

E ^H _p1 -E ^H _p2 | is less than or equal to 0.02 electron volt and is less than or equal to 0.3 electron volt

[ relational expression 5d ]

e ^H _p1 -E ^H _p2 | is less than or equal to 0.03 electron volt and is less than or equal to 0.3 electron volt

[ relational expression 5e ]

E ^H _p1 -E ^H _p2 | is less than or equal to 0.05 electron volt and is less than or equal to 0.3 electron volt

The hole transport assisting layer 142 may be more than one layer, and herein, in the hole transport assisting layer 142, the first compound and the second compound may be included in a layer contacting the emission layer 130.

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

on the other hand, the hole transport assist layer 142 is disposed between the emission layer 130 and the hole transport layer 141, and may block transfer of electrons from the emission layer 130 to the hole transport layer 141. Accordingly, since the emission layer 130 may effectively define electrons, excitons may be more generated in the emission layer 130, while excitons may be prevented from being generated on the interface of the emission layer 130 and the hole transport layer 141. 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 LUMO energy levels further satisfying the following relations 6 to 9, for example.

[ relational expression 6]

|E^L _p1|<|E^L _{Main body}|

[ relational expression 7]

|E^L _p1|<|E^L _{dopant agent}|

[ relational expression 8]

|E^L _p2|<|E^L _{Main body}|

[ relational expression 9]

|E^L _p2|<|E^L _{Dopant agent}|

in the relations 6 to 9,

E^L _p1Indicating the LUMO energy level of the first compound, E^L _p2indicating the LUMO energy level, E, of the second compound^L _{Main body}indicating the LUMO level of the host of the emissive layer, and E^L _{Dopant agent}indicating the LUMO energy level of the dopant of the emissive layer.

The hole transport assisting layer 142 includes the first compound and the second compound satisfying the relations 6 to 9, and can effectively block the transfer of electrons from the emission layer 130 and improve efficiency.

The first compound and the second compound may each have, for example, a LUMO energy level in a range from about-2.10 electron volts to about-2.50 electron volts and one satisfying the relationship in that range.

On the other hand, the hole transport auxiliary layer 142 is disposed between the emission layer 130 and the hole transport layer 141, and may block transfer of excitons from the emission layer 130 to the hole transport layer 141. Accordingly, since the emission layer 130 may effectively hold excitons, light emission efficiency may be improved in the emission layer 130 while exciton loss may be reduced. As a result, 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 triplet energy level further satisfying the following relations 10 to 13.

[ relational expression 10]

|E^T _{Main body}|<|E^T _p1|

[ relational expression 11]

|E^T _{Main body}|<|E^T _p2|

[ relational expression 12]

|E^T _{dopant agent}|<|E^T _p1|

[ relational expression 13]

|E^T _{dopant agent}|<|E^T _p2|

in the relation 10 to the relation 13,

E^T _p1Is the triplet energy order of the first compound, E^T _p2Is the triplet energy order of the second compound, E^T _{Main body}Is the triplet energy level of the host of the emissive layer, and E^T _{Dopant agent}Is the triplet energy level of the dopant of the emissive layer.

The hole transport auxiliary layer 142 includes first and second compounds satisfying relational expressions 10 to 13, and thus effectively blocks exciton transfer from the emission layer 130 and improves efficiency.

The first compound and the second compound may, for example, have a triplet energy order in a range of about 2.35 electron volts to about 2.80 electron volts and satisfy the relationship within the range.

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.

[ chemical formula 1]

In the chemical formula 1, the first and second,

ar ¹ through Ar ³ are each independently a fused ring of a substituted or unsubstituted C6 through C30 aryl group, a substituted or unsubstituted C3 through C30 heterocyclic group, a combination thereof, or a combination thereof,

In the chemical formulae a to D,

X and Z are O, S or CR ^a R ^b,

Each of the unfused of formulae B and C is CR ^c,

Wherein, in chemical formulas 2 to 4,

the two unfused groups of formula 3 are each CR ⁵ and CR ⁶,

the compound represented by chemical formula 1 is an amine compound substituted with a condensed ring, and may satisfy the energy order described above.

In chemical formula 1, Ar ¹ to Ar ³ may be the same, at least one of Ar ¹ to Ar ³ is one of a group represented by chemical formula a, a group represented by a combination of chemical formula B and chemical formula C, or a group represented by a combination of chemical formula B and chemical formula D, and for example, in chemical formula 1,1 to 3 groups represented by chemical formula a, a group represented by a combination of chemical formula B and chemical formula C, and/or a group represented by a combination of chemical formula B and chemical formula D may be included.

For example, when the number of the group represented by formula a, the group represented by the combination of formula B and formula C, and/or the group represented by the combination of formula B and formula D is 1 to 3, at least one of X may be O or S.

in Ar ¹ to Ar ³ of chemical formula 1, other groups than the group represented by chemical formula a, the group represented by a combination of chemical formula B and chemical formula C, and/or the group represented by a combination of chemical formula B and chemical formula D may each independently be a fused ring of a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C3 to C30 heterocyclic group, a combination thereof, or a combination thereof.

For example, in Ar ¹ to Ar ³, the other groups than the group represented by formula a, the group represented by the combination of formula B and formula C, and/or the group represented by the combination of formula B and formula D may each independently be one of the groups listed in group 1, but are not limited thereto.

[ group 1]

In the population 1, the population is selected from,

R ⁷⁵ to R ¹¹⁷ are independently hydrogen, deuterium, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C2 to C30 heterocyclic, substituted or unsubstituted C1 to C30 alkoxy, substituted or unsubstituted C6 to C30 aralkyl, substituted or unsubstituted C5 to C30 aryloxy, substituted or unsubstituted C5 to C30 arylthio, substituted or unsubstituted C1 to C30 alkoxycarbonyl, carboxyl, halogen, cyano, nitro, hydroxyl, or a combination thereof.

Chemical formula 1 may be, for example, a compound represented by one of chemical formulas 1-I to 1-VIII, depending on the number and type of the group represented by chemical formula a, the group represented by the combination of chemical formula B and chemical formula C, and/or the group represented by the combination of chemical formula B and chemical formula D.

In chemical formulas 1-I to 1-VIII,

Ar ² and Ar ³ are independently substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C3 to C30 heterocyclic, combinations thereof or fused rings of combinations thereof,

X ^a to X ^c are each independently O, S or CR ^a R ^b,

R ^1b, R ^1b to R ^1b, R ^1b and R ^1b are each independently hydrogen, deuterium, substituted or unsubstituted C ^1b to C ^1b alkyl, substituted or unsubstituted C ^1b to C ^1b cycloalkyl, substituted or unsubstituted C ^1b to C ^1b alkoxy, substituted or unsubstituted C ^1b to C ^1b cycloalkoxy, substituted or unsubstituted C ^1b to C ^1b alkylthio, substituted or unsubstituted C ^1b to C ^1b aralkyl, substituted or unsubstituted C ^1b to C ^1b aryl, substituted or unsubstituted C ^1b to C ^1b aryloxy, substituted or unsubstituted C ^1b to C ^1b arylthio, substituted or unsubstituted C ^1b to C ^1b heterocyclyl, substituted or unsubstituted C ^1b to C ^1b amino, substituted or unsubstituted C ^1b to C ^1b arylthio, substituted or unsubstituted C ^1b to C ^1b, carboxyl, hydroxyl, nitro, a combination thereof.

For example, in chemical formulas 1-I to 1-VIII, at least one of X ^a to X ^c may each independently be O or S.

the second compound is a compound that has a relationship with the first compound and satisfies an energy order, 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 formulas 2-I to 2-IV.

In chemical formulas 2-I to 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 alkenylene group, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C2 to C30 divalent heterocyclic group, a combination thereof or a fused ring of a combination thereof,

Ar ⁴ and Ar ⁵ are each independently substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C2 to C30 heterocyclic, or a combination thereof,

Ar ^4a is each independently a substituted or unsubstituted C6 to C30 aryl group, and

R ⁵ to R ²⁰ are independently hydrogen, deuterium, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C6 to C50 aryl, substituted or unsubstituted C2 to C50 heterocyclic, 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 formulas 3-I to 3-VII.

In chemical formulas 3-I to 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 alkenylene group, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C2 to C30 divalent heterocyclic group, a combination thereof, or a fused ring of a combination thereof,

Ar ^4a and Ar ^4b are each independently substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C2 to C30 heterocyclic, or a combination thereof,

R ⁵ to R ¹⁰, 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 C2 to C50 heterocyclic group or a combination thereof,

R ^d and R ^e each independently exist or are linked to each other to form a condensed ring, an

At least one of R ⁵ to R ¹⁰, Ar ^4a, and Ar ^4b comprises a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted triphenylene, or a substituted or unsubstituted carbazolyl group.

The first compound may be, for example, one of compounds of formula F-1 to formula F-184, formula G-1 to formula G-184, formula H-1 to formula H-204, formula I-1 to formula I-65, but is not limited thereto.

The second compound may be, for example, one of the compounds represented by the following B-10 to B-132, C-10 to C-33, or D-10 to D-31, but is not limited thereto. Examples thereof are as follows.

The hole transport layer 141 is not particularly limited thereto, and may include, for example, a compound represented by chemical formula 5.

[ chemical formula 5]

In the chemical formula 5, the first and second organic solvents,

r ¹¹⁸ to R ¹²¹ are independently hydrogen, deuterium, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C2 to C30 heterocyclic group, or a combination thereof,

R ¹¹⁸ and R ¹¹⁹ each independently exist or are fused with each other to form a condensed ring,

R ¹²⁰ and R ¹²¹ independently exist or form a condensed ring,

Ar ⁶ -Ar ⁸ are independently substituted or unsubstituted C6-C30 aryl or substituted or unsubstituted C2-C30 heterocyclic group, and

l ⁴ to L ⁷ are independently a single bond, substituted or unsubstituted C2 to C10 alkylene, substituted or unsubstituted C2 to C10 alkenylene, substituted or unsubstituted C2 to C10 alkynylene, substituted or unsubstituted C6 to C30 arylene, divalent substituted or unsubstituted C2 to C30 heterocyclic group, or a combination thereof.

For example, Ar ⁶ of chemical formula 5 may be a substituted or unsubstituted phenyl group or a substituted or unsubstituted biphenyl group, and Ar ⁷ and Ar ⁸ of chemical formula 5 may be independently one of a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted fluorene group, a substituted or unsubstituted bisfluorene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted anthryl group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted dibenzothiophenyl group.

The compound represented by chemical formula 5 may be, for example, one of the compounds represented by the following J-1 to J-144, but is not limited thereto.

in fig. 1, the organic layer 105 may further include a hole injection layer, an electron blocking layer, an electron transport layer, an electron injection layer, and/or a hole blocking layer in addition to the emission layer 130, the hole transport auxiliary layer 142, and the hole transport layer 141.

The organic light emitting diode 300 may be manufactured by forming an anode or a cathode on a substrate, forming an organic layer according to a dry coating method such as evaporation (evaporation), sputtering (sputtering), plasma plating, and ion plating or a solution process such as inkjet printing, spin coating, slit coating, bar coating, and/or dip coating, and forming the cathode or the anode thereon.

The organic light emitting diode may be applied to an Organic Light Emitting Diode (OLED) display.

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

Synthetic intermediates

Synthesis of intermediate M-1

[ reaction scheme 1]

20 g (94.3 mmol) of 4-dibenzofuranboronic acid and 26.7 g (94.3 mmol) of 1-bromo-4-iodobenzene were placed in a round-bottom flask, 313 ml of toluene was added thereto to dissolve it, 117 ml of an aqueous solution obtained by dissolving 19.5 g (141.5 mmol) of potassium carbonate was added thereto, and the mixture was stirred. Subsequently, 1.09 g (0.94 mmol) of tetrakistriphenylphosphine palladium was added thereto, and the obtained mixture was refluxed and stirred under a nitrogen atmosphere for 12 hours. When the reaction was completed, the resultant was extracted with ethyl acetate, the extracted solution was dried with magnesium sulfate and filtered, and the filtered solution was concentrated under reduced pressure. Subsequently, the product obtained therefrom was purified by silica gel column chromatography using n-hexane/dichloromethane (9:1 v/v) to obtain 27 g of intermediate M-1 as a white solid (yield 89%).

LC-Mass (calculated: 322.00 g/mol, measured: M + ═ 322.09 g/mol, M +2 ═ 324.04 g/mol)

synthesis of intermediate M-2

[ reaction scheme 2]

38 g (154.90 mmol) of N, 4-diphenylaniline was placed in a round-bottom flask, 620 ml of methylene chloride was added thereto to dissolve it, 41.5 g (232.35 mmol) of N-bromosuccinimide were slowly added thereto at room temperature, and the mixture was stirred under a nitrogen atmosphere for 4 hours. When the reaction was complete, the resultant was diluted with dichloromethane and filtered over silica gel, and the filtered solution was concentrated under reduced pressure. Subsequently, the product obtained therefrom was purified by silica gel column chromatography using n-hexane/dichloromethane (7:3 v/v) to obtain 31.1 g of intermediate M-2 (yield 62%).

LC-Mass (calculated: 323.03 g/mol, measured: M + ═ 323.12 g/mol, M +2 ═ 325.11 g/mol)

Synthesis of intermediate M-3

[ reaction scheme 3]

31 g (95.62 mmol) of M-2 and 24.7 g (143.43 mmol) of naphthalen-1-ylboronic acid were placed in a round-bottom flask, 400 ml of toluene was added thereto to dissolve it, 250 ml of an aqueous solution obtained by dissolving 39.65 g (286.85 mmol) of potassium carbonate was added thereto, and the mixture was stirred. Subsequently, 2.21 g (1.91 mmol) of tetrakistriphenylphosphine palladium was added thereto, and the obtained mixture was refluxed and stirred under a nitrogen atmosphere for 12 hours. When the reaction was completed, the resultant was extracted with dichloromethane and distilled water, the extracted solution was dried over magnesium sulfate and filtered, and the filtered solution was concentrated under reduced pressure. Subsequently, the product obtained therefrom was purified by silica gel column chromatography using n-hexane/dichloromethane (7:3 v/v) to obtain 31.3 g of intermediate M-3 (yield 88%).

LC-Mass (calculated: 371.17 g/mol, measured: M + ═ 371.11 g/mol)

Synthesis of intermediate K-1

[ reaction scheme 4]

53.15 g (250.61 mmol) of 4-dibenzofuranboronic acid, 50 g (227.83 mmol) of 2-bromo-5-chloro-benzaldehyde, 62.98 g (455.66 mmol) of potassium carbonate and 7.89 g (6.84 mmol) of palladium tetrakistriphenylphosphine (Pd (PPh ₃) ₄) are in a round-bottom flask and then suspended in 1000 ml of toluene and 500 ml of distilled water, and then the suspension solution is refluxed under a nitrogen atmosphere and stirred for 12 hours.

LC-Mass (calculated: 306.74 g/mol, measured: M + ═ 306.79 g/mol)

Synthesis of intermediate K-2

[ reaction scheme 5]

64.64 g (210.73 mmol) of intermediate K-1 and 79.46 g (231.80 mmol) of (methoxymethyl) triphenylphosphonium chloride are suspended in 600 ml of tetrahydrofuran in a round-bottomed flask and maintained at 0 ℃. Subsequently, 28.38 g (252.87 mmol) of potassium tert-butoxide was slowly added thereto at 0 ℃ and the mixture was stirred at room temperature for 12 hours. When the reaction was completed, 600 ml of distilled water was added thereto for extraction, and the extracted solution was concentrated, suspended in 500 ml of dichloromethane, dried over magnesium sulfate, filtered with silica gel, and then concentrated again. The concentrated solution was dissolved in 400 ml of dichloromethane, 20 g of methanesulfonic acid was slowly added thereto, and the mixture was stirred at room temperature for 12 hours. When the reaction was completed, the solid produced therein was filtered, washed with 200 ml of distilled water and 200 ml of methanol and dried to obtain 48.4 g of intermediate K-2 (yield 76%).

LC-Mass (calculated: 302.75 g/mol, measured: M + ═ 303.84 g/mol)

Synthesis of intermediate K-3

[ reaction scheme 6]

11 g (36.33 mmol) of intermediate K-2, 1.25 g (2.18 mmol) Pd (dba)2, 10.7 g (109.00 mmol) KOAc, 2.45 g (8.72 mmol) P (Cy)3 and 11.07 g (43.60 mmol) bis (pinacolato) diboron were suspended in 150 ml DMF in a round-bottomed flask and then refluxed and stirred for 12 hours. When the reaction was completed, the resultant was allowed to cool to room temperature, 300 ml of distilled water was added thereto, and the mixture was stirred for one hour. Subsequently, the solid generated during agitation was filtered, washed with methanol, heated and dissolved in 300 ml of toluene, and then, filtered with silica gel, and the filtered solution was concentrated and recrystallized with toluene to obtain 9.05 g of intermediate K-3 (yield 63%).

Synthesis of intermediate K-4

[ reaction scheme 7]

15.0 g (65.77 mmol) of 4-dibenzothiopheneboronic acid and 20.47 g (72.35 mmol) of 1-bromo-3-iodobenzene were placed in a round-bottom flask, 300 ml of toluene was added thereto to dissolve it, 95 ml of an aqueous solution obtained by dissolving 19.1 g (138.12 mmol) of potassium carbonate was added thereto, and the mixture was stirred, then, 0.76 g (0.66 mmol) of tetrakistriphenylphosphine palladium (Pd (PPh ₃) ₄) was added thereto, and the mixture was refluxed and stirred under a nitrogen atmosphere for 12 hours.

Synthesis of intermediate K-5

[ reaction scheme 8]

21 g (64.7 mmol) of intermediate M-1, 1.74 g (29.4 mmol) of acetamide, and 17.3 g (117.0 mmol) of potassium carbonate were placed in a round-bottom flask, and 130 ml of xylene was added thereto to dissolve it. Subsequently, 1.12 g (5.88 mmol) of copper (I) iodide and 1.04 g (11.8 mmol) of N, N-dimethylethylenediamine were sequentially added thereto, and the mixture was refluxed and stirred under a nitrogen atmosphere for 48 hours. When the reaction was completed, the resultant was extracted with toluene and distilled water, an organic layer obtained therefrom was dried over magnesium sulfate and filtered, and the filtered solution was concentrated under reduced pressure. Subsequently, the product obtained therefrom was purified by silica gel column chromatography using n-hexane/ethyl acetate (5:5 vol%) to obtain 15 g of intermediate K-5 (yield 94%).

Synthesis of intermediate K-5-1

[ reaction scheme 9]

13.7 g (25.2 mmol) of intermediate K-5 and 4.2 g (75.6 mmol) of potassium hydroxide were placed in a round-bottom flask, and 80 ml of Tetrahydrofuran (THF) and 80 ml of ethanol were added thereto to dissolve it. The solution was refluxed and stirred for 12 hours under nitrogen atmosphere. When the reaction was completed, the resultant was concentrated under reduced pressure and extracted with dichloromethane and distilled water, an organic layer obtained therefrom was dried over magnesium sulfate and filtered, and the filtered solution was concentrated under reduced pressure. Subsequently, the product obtained therefrom was purified by silica gel column chromatography using n-hexane/dichloromethane (7:3 volume ratio) to obtain 11.4 g of intermediate K-5-1 (yield 90%).

Synthesis of intermediate K-6

[ reaction scheme 10]

In a round-bottom flask, 20 g (476.41 mmol) of N- (4-bromophenyl) -N, N-bis (1,1' -biphenyl-4-yl) amine, 1.03 g (1.26 mmol) of pd (dppf) Cl2, 12.8 g (50.38 mmol) of bis (pinacolato) diboron and 12.36 g (125.94 mmol) of potassium acetate were suspended in 210 ml of toluene, and then refluxed and stirred for 12 hours. When the reaction was complete, the resultant was cooled to room temperature and filtered, and the filtered solution was filtered over silica gel and concentrated. Subsequently, the concentrated solution was recrystallized from acetone to obtain 17 g of intermediate K-6 (yield 77%).

Synthesis of intermediate K-7

[ reaction scheme 11]

In a round-bottom flask, 20 g (49.96 mmol) of N- (4-bromophenyl) -N-phenylbiphenyl-4-amine, 1.22 g (1.50 mmol) of pd (dppf) Cl2, 15.22 g (59.95 mmol) of bis (pinacolato) diboron and 14.71 g (149.88 mmol) of potassium acetate were suspended in 250 ml of toluene and then refluxed and stirred for 12 hours. When the reaction was complete, the resultant was allowed to cool to room temperature and then filtered, and the filtered solution was filtered over silica gel and concentrated. The concentrated solution was recrystallized from acetone to obtain 18 g of intermediate K-7 (yield 81%).

Synthesis of intermediate K-8

[ reaction scheme 12]

22.96 g (71.43 mmol) of N- (biphenyl-3-yl) biphenyl-4-amine, 1.23 g (2.14 mmol) of Pd (dba)2, 0.43 g (2.14 mmol) of P (t-Bu)3 and 10.29 g (107.15 mmol) of NaO (t-Bu) are suspended in 500 ml of toluene in a round-bottom flask and subsequently stirred at 60 ℃ for 12 hours. When the reaction was completed, distilled water was added thereto, the mixture was stirred for 30 minutes and extracted, and the organic layer obtained therefrom was subjected to column chromatography via a silica gel column (hexane/dichloromethane ═ 9:1 (volume/volume)) to obtain 24 g of intermediate K-8 (yield 78%).

Synthesis of intermediate K-9

[ reaction scheme 13]

14.5 g (40.94 mmol) of triphenyleneboronic acid, 11.08 g (45.03 mmol) of 3-bromo-9H-carbazole, 11.32 g (81.88 mmol) of potassium carbonate, and 1.42 g (1.23 mmol) of tetrakis- (triphenylphosphine) palladium (0) (Pd (PPh ₃) ₄) were suspended in 180 ml of Tetrahydrofuran (THF) and 75 ml of distilled water in a round-bottom flask, and then refluxed and stirred for 12 hours, then the resultant was extracted with dichloromethane and distilled water, and the organic layer obtained therefrom was filtered with silica gel, then the solid product obtained therefrom after removing the organic solution was recrystallized with dichloromethane and n-hexane to obtain 14.66 g of intermediate K-9 (yield 91%).

Synthesis of intermediate K-10

[ reaction scheme 14]

16.0 g (49.66 mmol) of phenylcarbazolyl bromide, 11.53 g (54.62 mmol) of carbazolylboronic acid, 20.59 g (148.98 mmol) of potassium carbonate and 1.72 g (1.49 mmol) of tetrakis- (triphenylphosphine) palladium (0) (Pd (PPh ₃) ₄) were suspended in 150 ml of toluene and 65 ml of distilled water in a round-bottom flask, and then refluxed and stirred for 12 hours, then the resultant was extracted with dichloromethane and distilled water, and the organic layer obtained therefrom was filtered with silica gel after removing the organic solution therefrom, the solid product obtained therefrom was recrystallized with dichloromethane and n-hexane to obtain 18.26 g of intermediate K-10 (yield 90%).

Synthesis of intermediate K-11

[ reaction scheme 15]

19.2 g (59.08 mmol) of 3, 6-dibromo-9H-carbazole, 25.73 g (129.97 mmol) of [1,1' -biphenyl ] -4-ylboronic acid, 20.41 g (147.69 mmol) of potassium carbonate, and 2.05 g (1.77 mmol) of tetrakis- (triphenylphosphine) palladium (0) (Pd (PPh ₃) ₄) were suspended in 300 ml of toluene and 100 ml of distilled water in a round-bottom flask, and then refluxed and stirred for 12 hours, then the resultant was extracted and extracted with dichloromethane and distilled water, and then the organic layer obtained therefrom was filtered with silica gel, after removing the organic solution therefrom, the solid product obtained therefrom was recrystallized with dichloromethane and n-hexane to obtain 22.29 g of intermediate K-11 (yield 80%).

Synthesis of intermediate K-12

[ reaction scheme 16]

19.2 g (59.08 mmol) of 3, 6-dibromo-9H-carbazole, 25.73 g (129.97 mmol) of [1,1' -biphenyl ] -3-ylboronic acid, 20.41 g (147.69 mmol) of potassium carbonate, and 2.05 g (1.77 mmol) of tetrakis- (triphenylphosphine) palladium (0) (Pd (PPh ₃) ₄) were suspended in 300 ml of toluene and 100 ml of distilled water in a round-bottom flask, and then refluxed and stirred for 12 hours, then the resultant was extracted with dichloromethane and distilled water, and the organic layer obtained therefrom was filtered with silica gel, after removing the organic solution therefrom, the solid product obtained therefrom was recrystallized with dichloromethane and n-hexane to obtain 21.73 g of intermediate K-12 (yield 78%).

Synthesis of the final Compound

Synthesis example 1: synthesis of Compound I-61

[ reaction scheme 17]

15 g (46.4 mmol) of intermediate M-1, 4.9 g (23.2 mmol) of 9, 9-dimethyl-9H-fluoren-2-amine and 6.7 g (69.6 mmol) of sodium third butoxide (NaOt-Bu) were placed in a round-bottom flask and 160 ml of toluene was added thereto to dissolve it, then, 0.85 g (0.928 mmol) of Pd (dba) ₂ and 0.45 g (1.86 mmol) of tri-tert-butylphosphine (P (t-Bu) ₃ were sequentially added thereto, and the mixture was refluxed under nitrogen atmosphere and stirred for 4 hours, when the reaction was completed, the resultant was extracted with toluene and distilled water, the organic layer obtained therefrom was dried over magnesium sulfate and filtered, and the filtered solution was concentrated under reduced pressure, then, the product obtained therefrom was purified with n-hexane/dichloromethane (8:2 volume ratio) via column chromatography to obtain 27.4 g of silica gel compound I-61% (yield 85%).

LC-Mass (calculated: 693.27 g/mol, measured: M + ═ 693.51 g/mol)

Synthesis example 2: synthesis of Compound C-10

[ reaction scheme 18]

10 g (34.83 mmol) of phenylcarbazolylboronic acid and 11.77 g (38.31 mmol) of 2-bromotriphenylene were placed in a round-bottom flask, 140 ml of toluene was added thereto to dissolve it, 87 ml of an aqueous solution obtained by dissolving 14.44 g (104.49 mmol) of potassium carbonate was added thereto, and the mixture was stirred, then, 0.80 g (0.7 mmol) of tetrakistriphenylphosphine palladium (Pd (PPh ₃) ₄) was added thereto, and the mixture was refluxed under a nitrogen atmosphere and stirred for 12 hours.

LC-Mass (calculated: 469.18 g/mol, measured: M + ═ 469.10 g/mol)

Synthesis example 3: synthesis of Compound I-57

[ reaction scheme 19]

20.9 g (73.42 mmol) of Compound A, 30 g (80.76 mmol) of intermediate M-3 and 10.58 g (110.13 mmol) of sodium third butoxide are placed in a round-bottomed flask, and 700 ml of toluene is added thereto to dissolve it, then, 0.67 g (0.734 mmol) of Pd (dba) ₂ and 0.45 g (2.20 mmol) of tri-third butylphosphine are added thereto in this order, and the mixture is refluxed under a nitrogen atmosphere and stirred for 4 hours.

LC-Mass (calculated: 653.27 g/mol, measured: M + ═ 653.33 g/mol)

Synthesis example 4: synthesis of Compound B-43

[ reaction scheme 20]

12.33 g (30.95 mmol) of biphenylcarbazolyl bromide, 12.37 g (34.05 mmol) of biphenylcarbazolyl boronic acid, 12.83 g (92.86 mmol) of potassium carbonate and 1.07 g (0.93 mmol) of tetrakis- (triphenylphosphine) palladium (0) (Pd (PPh ₃) ₄) were suspended in 120 ml of toluene and 50 ml of distilled water in a round-bottom flask, and then the resultant was refluxed and stirred for 12 hours.

LC-Mass (calculated: 636.26 g/mol, measured: M + ═ 636 g/mol)

Synthesis example 5: synthesis of Compound B-114

[ reaction scheme 21]

80 g (547.23 mmol) of α -tetralone, 129.46 g (895.30 mmol) of phenylhydrazine hydrochloride and a small amount of acetic acid were added to 1800 ml of ethanol, and the mixture was refluxed and stirred under a nitrogen stream for 24 hours. When the reaction was complete, the resultant was cooled to room temperature, and the product obtained therefrom was filtered, basified with a small amount of aqueous NaHCO3 solution and recrystallized from ethanol to obtain 73.0 g of intermediate a (yield: 60%).

Subsequently, 74.0 g (337.47 mmol) of intermediate A and 116.17 g (427.46 mmol) of tetrachloro1, 4-benzoquinone are refluxed under a stream of nitrogen in 1200 ml of xylene and stirred for 4 hours. When the reaction was completed, an aqueous NaOH (10%) solution was added thereto, the mixture was extracted with dichloromethane, and the organic layer obtained therefrom was filtered with silica gel. After removing the organic solution therefrom, the solid product obtained therefrom was subjected to silica gel column chromatography with hexane, dichloromethane ═ 7:3 (v/v) and recrystallized with dichloromethane and hexane to obtain 31.0 g of intermediate B (yield: 42%).

Subsequently, 31.0 g (142.68 mmol) of intermediate B, 33.60 g (214.02 mmol) of bromobenzene, 285.36 g (27.42 mmol) of NaO (t-Bu) and 7.84 g (8.56 mmol) of Pd2(dba)3 were suspended in 500 ml of toluene, 41.54 ml (85.61 mmol) of P (t-Bu)3 was added thereto, and the mixture was refluxed and stirred under a nitrogen flow for 24 hours. The resultant was extracted with dichloromethane and distilled water, and the organic layer obtained therefrom was filtered with a silica gel filter. After removing the organic solution therefrom, the solid product was subjected to silica gel column chromatography with hexane, dichloromethane 7:3 (v/v) and recrystallized with dichloromethane and n-hexane to obtain 39.0 g of intermediate C (yield: 95%).

Subsequently, 39.0 g (132.94 mmol) of intermediate C and 26.03 g (146.24 mmol) of NBS were suspended in 460 ml of chloroform, and then refluxed and agitated under a stream of nitrogen for 4 hours. After the resultant was extracted with dichloromethane and distilled water, the organic layer obtained therefrom was filtered with silica gel, and the product obtained after removing the organic solution therefrom was recrystallized with dichloromethane and ethanol to obtain 45.51 g of intermediate D (yield: 92%).

subsequently, 22.5 g (60.44 mmol) of intermediate D, 19.95 g (78.57 mmol) of bis (pinacolato) diboron, 0.99 g (1.20 mmol) of PdCl2(dppf) and 17.79 g (181.32 mmol) of KOAc were suspended in 210 ml of toluene, and then refluxed and stirred under a nitrogen stream for 24 hours. The resultant was extracted with dichloromethane and distilled water, and the organic layer obtained therefrom was filtered with silica gel. After removing the organic solution therefrom, the solid product was subjected to silica gel column chromatography with hexane, dichloromethane ═ 7:3 (v/v) and recrystallized with dichloromethane and n-hexane to obtain 17.0 g of intermediate E (yield: 67%).

10.7 g (25.52 mmol) of intermediate E, 6.19 g (30.62 mmol) of 2-bromonitrobenzene, 7.05 g (51.04 mmol) of K ₂ CO ₃ and 0.59 g (0.51 mmol) of Pd (PPh ₃) ₄ were suspended in 150 ml of toluene and 75 ml of distilled water, and then refluxed and stirred under a nitrogen stream for 24 hours, when the reaction was completed, the reaction solution was extracted with dichloromethane, filtered with silica gel, distilled under reduced pressure, subjected to silica column chromatography with hexane: dichloromethane 7:3 (v/v), and then recrystallized with dichloromethane and n-hexane to obtain 8.1 g of intermediate F (yield: 77%).

subsequently, 8.1 g (19.54 mmol) of intermediate F and 17.0 ml (97.72 mmol) of triethyl phosphate were refluxed under a stream of nitrogen and stirred for 4 hours. When the reaction was completed, after removing the reaction solvent therefrom, the resultant was subjected to silica column chromatography with hexane: dichloromethane ═ 7:3 (v/v), to obtain 6.2G of intermediate G (yield: 83%).

Subsequently, 6.2G (16.21 mmol) of intermediate G, 6.01G (19.45 mmol) of bromo-3, 5-terphenyl, 4.67G (48.63 mmol) of NaO (t-Bu), and 0.59G (0.65 mmol) of Pd2(dba)3 were suspended in 500 ml of toluene, 0.39 ml (1.62 mmol) of P (t-Bu)3 was added thereto, and the mixture was refluxed and stirred under a nitrogen stream for 24 hours. Subsequently, the resultant was extracted with dichloromethane and distilled water, and the organic layer obtained therefrom was filtered with silica gel. After removing the organic solution therefrom, the solid product was subjected to silica gel column chromatography with hexane, dichloromethane 7:3 (v/v) and recrystallized with dichloromethane and n-hexane to obtain 8.6 g of compound B-114 (yield: 87%).

LC-Mass (calculated: 610.74 g/mol, measured: M +1 ═ 611 g/mol)

synthesis example 6: synthesis of Compound B-115

[ reaction scheme 22]

15.5 g (38.92 mmol) of biphenylcarbazolyl bromide, 12.29 g (42.81 mmol) of phenylcarbazolylboronic acid (phenylcarbazolyl bromide), 16.14 g (116.75 mmol) of potassium carbonate and 1.35 g (1.17 mmol) of tetrakis- (triphenylphosphine) palladium (0) (Pd (PPh ₃) ₄) were suspended in 150 ml of toluene and 70 ml of distilled water in a round-bottom flask, and then the resultant was refluxed and stirred for 12 hours.

LC-Mass (calculated: 560.69 g/mol, measured: M + ═ 560.22 g/mol)

Synthesis example 7: synthesis of Compound B-116

[ reaction scheme 23]

13.1 g (32.89 mmol) of biphenylcarbazolyl bromide, 13.14 g (36.18 mmol) of m-biphenylcarbazolylboronic acid (m-biphenylcarbazolylbolylbolyside), 13.64 g (98.676 mmol) of potassium carbonate and 1.14 g (0.99 mmol) of tetrakis- (triphenylphosphine) palladium (0) (Pd (PPh ₃) ₄) were suspended in 130 ml of toluene and 55 ml of distilled water in a round-bottom flask, and then the resultant was refluxed and stirred for 12 hours, then the resultant was extracted with dichloromethane and distilled water, and the organic layer was filtered with silica gel after removing the organic solution therefrom, the solid product was recrystallized with dichloromethane and n-hexane to obtain 19.27 g of compound B-116 (yield 92%).

LC-Mass (calculated: 636.26 g/mol, measured: M + ═ 636.11 g/mol)

Synthesis example 8: synthesis of Compound B-117

[ reaction scheme 24]

11.2 g (27.42 mmol) of intermediate K-10, 8.86 g (27.42 mmol) of intermediate M-1, 0.25 g (0.274 mmol) of Pd2(dba)3, 0.133 g (0.274 mmol) of P (t-Bu)3 and 3.95 g (41.13 mmol) of NaO (t-Bu) were suspended in 300 ml of toluene in a round-bottomed flask and subsequently stirred at 60 ℃ for 12 hours. When the reaction was completed, distilled water was added thereto, and the mixture was stirred for 30 minutes and extracted, and the organic layer obtained therefrom was subjected to column chromatography using silica gel (hexane/dichloromethane ═ 9:1 (volume/volume)) to obtain 19.5 g of intermediate B-117 (yield 88%).

LC-Mass (calculated: 650.76 g/mol, measured: M + ═ 650.71 g/mol)

Synthesis example 9: synthesis of Compound B-118

[ reaction scheme 25]

12.0 g (29.38 mmol) of intermediate K-10, 9.97 g (29.38 mmol) of intermediate K-4, 0.27 g (0.294 mmol) of Pd2(dba)3, 0.143 g (0.588 mmol) of P (t-Bu)3 and 4.24 g (44.06 mmol) of NaO (t-Bu) are suspended in 310 ml of toluene in a round-bottomed flask and stirred at 60 ℃ for 12 hours. When the reaction was completed, distilled water was added thereto, and the mixture was stirred for 30 minutes and extracted, and the organic layer obtained therefrom was subjected to silica gel column chromatography (hexane/dichloromethane ═ 9:1 (volume/volume)) to obtain 17.63 g of compound B-118 (yield 90%).

LC-Mass (calculated: 666.83 g/mol, measured: M + ═ 666.7 g/mol)

Synthesis example 10: synthesis of Compound C-23

[ reaction scheme 26]

14.6 g (37.1 mmol) of intermediate K-9, 12.62 g (40.82 mmol) of 5 '-bromo-1, 1':3', 1' -terphenyl, 1.70 g (1.86 mmol) of Pd2(dba)3, 3.53 g (7.42 mmol) of P (t-Bu)3 and 7.132 g (74.21 mmol) of NaO (t-Bu) were suspended in 280 ml of toluene in a round-bottomed flask and subsequently stirred at 60 ℃ for 12 hours. When the reaction was completed, distilled water was added thereto, the mixture was stirred for 30 minutes and extracted, and the organic layer obtained therefrom was subjected to silica gel column chromatography (hexane/dichloromethane ═ 9:1 (volume/volume)) to obtain 16.15 g of compound C-23 (yield 70%).

LC-Mass (calculated: 621.77 g/mol, measured: M + ═ 621.71 g/mol)

Synthesis example 11: synthesis of Compound D-30

[ reaction scheme 27]

20.0 g (42.41 mmol) of intermediate K-11, 11.88 g (42.41 mmol) of 4-iodo-1, 1' -biphenyl (Sigma-Aldrich Co., Ltd.), 0.388 g (0.424 mmol) of Pd2(dba)3, 0.206 g (0.848 mmol) of P (t-Bu)3 and 6.11 g (63.61 mmol) of NaO (t-Bu) were suspended in 420 ml of toluene in a round-bottomed flask and then stirred at 60 ℃ for 12 hours. When the reaction was completed, distilled water was added thereto, the mixture was stirred for 30 minutes and extracted, and the organic layer was subjected to silica gel column chromatography (hexane/dichloromethane ═ 9:1 (v/v)) to obtain 23.02 g of compound D-30 (yield 87%).

LC-Mass (calculated: 623.78 g/mol, measured: M + ═ 623.25 g/mol)

Synthesis example 12: synthesis of Compound D-31

[ reaction scheme 28]

20.0 g (42.41 mmol) of intermediate K-12, 11.88 g (42.41 mmol) of 4-iodo-1, 1' -biphenyl (Sigma-Aldrich Co., Ltd.), 0.388 g (0.424 mmol) of Pd2(dba)3, 0.206 g (0.848 mmol) of P (t-Bu)3 and 6.11 g (63.61 mmol) of NaO (t-Bu) were suspended in 420 ml of toluene in a round-bottomed flask and then stirred at 60 ℃ for 12 hours. When the reaction was completed, distilled water was added thereto, the mixture was stirred for 30 minutes and extracted, and the organic layer obtained therefrom was subjected to silica gel column chromatography (hexane/dichloromethane ═ 9:1 (volume/volume)) to obtain 22.49 g of compound D-31 (yield 85%).

LC-Mass (calculated: 623.78 g/mol, measured: M + ═ 623.21 g/mol)

Synthesis example 13: synthesis of Compound H-204

[ reaction scheme 29]

17.9 g (63.07 mmol) of 1- (4-bromophenyl) naphthalene, 6.0 g (28.67 mmol) of 2-amino-9, 9-dimethyl-9H-fluorene and 8.3 g (86.01 mmol) of sodium third butoxide are placed in a round-bottomed flask and 200 ml of toluene are added thereto to dissolve it, then, 0.165 g (0.287 mmol) of Pd (dba)2 and 0.145 g (0.72 mmol) of tri-third butylphosphine (P (t-Bu) ₃ are sequentially added thereto, and the mixture is refluxed under nitrogen atmosphere and stirred for 4 hours when the reaction is completed, the resultant is extracted with toluene and distilled water, the organic layer is dried over magnesium sulfate and filtered, and the filtered solution is concentrated under reduced pressure, then, the product is purified with n-hexane/dichloromethane (7:3 volume ratio) through a silica gel tube to obtain 15.3 g of light beige solid compound H-204 (yield 87%).

LC-Mass (calculated: 613.28 g/mol, measured: M + ═ 613.16 g/mol)

synthesis example 14: synthesis of Compound I-62

[ reaction scheme 30]

9.6 g (30.9 mmol) of 4-bromobiphenyl, 15.4 g (30.8 mmol) of intermediate K-5-1 and 5.35 g (55.6 mmol) of sodium tert-butoxide are placed in a round-bottom flask and 155 ml of toluene are added thereto to dissolve it, then 0.178 g (0.31 mmol) of Pd (dba)2 and 0.125 g (0.62 mmol) of tri-tert-butylphosphine (P (t-Bu) ₃ are added thereto in this order, and the mixture is refluxed and stirred for 4 hours under nitrogen atmosphere.

LC-Mass (calculated: 729.27 g/mol, measured: M + ═ 729.12 g/mol)

Synthesis example 15: synthesis of Compound I-63

[ reaction scheme 31]

15 g (49.55 mmol) of intermediate K-2, 27.2 g (52.02 mmol) of intermediate K-6 and 32.3 g (99.09 mmol) of cesium carbonate (Cs ₂ CO ₃) were placed in a round-bottom flask, and 250 ml of 1, 4-dioxolane was added thereto to dissolve it, then, 0.85 g (1.49 mmol) of Pd (dba) ₂ and 0.7 g (3.47 mmol) of tri-tert-butylphosphine (P (t-Bu) ₃ were sequentially added thereto, and the mixture was refluxed under a nitrogen atmosphere and agitated for 12 hours, when the reaction was completed, the resultant was cooled to room temperature, water was added thereto, the mixture was agitated for 30 minutes, and the solid produced therein was filtered, and washed with 200 ml of distilled water and 200 ml of methanol, respectively, the solid was heated and dissolved in 300 ml of Dichlorobenzene (DCB), and filtered with silica gel, 300 h was added thereto, and the mixture was filtered, wherein the solid produced was filtered, and the acetone was then, and the yield was obtained (I) was 2.17 ml acetone).

LC-Mass (calculated: 663.8 g/mol, measured: M + ═ 663.4 g/mol)

Synthesis example 16: synthesis of Compound I-64

[ reaction scheme 32]

10 g (33.03 mmol) of intermediate K-2, 14.77 g (33.03 mmol) of intermediate K-7 and 21.52 g (66.06 mmol) of cesium carbonate (Cs ₂ CO ₃) were placed in a round-bottom flask, and 200 ml of 1, 4-dioxolane was added thereto to dissolve it, then, 0.57 g (0.99 mmol) of Pd (dba) ₂ and 0.4 g (1.98 mmol) of tri-tert-butylphosphine (P (t-Bu) ₃ were sequentially added thereto, and the mixture was refluxed and agitated for 12 hours under a nitrogen atmosphere when the reaction was completed, the resultant was cooled to room temperature, water was added thereto, the mixture was agitated for 30 minutes, and the solid generated therein was filtered, and then washed with 200 ml of distilled water and 200 ml of methanol, respectively, the solid was heated and dissolved in 300 ml of DCtoluene (B), filtered and recrystallized from silica gel to obtain a yield of 10.9 g-64% of the compound.

LC-Mass (calculated: 587.7 g/mol, measured: M + ═ 587.4 g/mol)

Synthesis example 17: synthesis of Compound I-65

[ reaction scheme 33]

9.27 g (23.51 mmol) of intermediate K-3 and 10.16 g (23.51 mmol) of intermediate K-8 and 15.32 g (47.02 mmol) of cesium carbonate (Cs ₂ CO ₃) were placed in a round-bottom flask, and 150 ml of 1, 4-dioxyland was added thereto to dissolve it, then, 0.41 g (0.71 mmol) of Pd (dba) ₂ and 0.33 g (1.65 mmol) of tri-tributylphosphine (P (t-Bu) ₃ were sequentially added thereto, and the mixture was refluxed under a nitrogen atmosphere and stirred for 12 hours, when the reaction was completed, the resultant was allowed to cool to room temperature, water was added thereto, the mixture was stirred for 30 minutes, and the resulting solid was filtered, and washed with 200 ml of distilled water and 200 ml of methanol, respectively, the solid was heated and dissolved in 300 ml of toluene (DCB), column chromatography was performed using silica gel to obtain 8.65 g (I-52%) of compound.

LC-Mass (calculated: 663.8 g/mol, measured: M + ═ 663.2 g/mol)

Evaluation 1

The energy level of the main compound according to the synthesis example was measured.

After each compound was diluted to a concentration of 1 × 10 ^-5 moles with CHCl ₃, the HOMO energy level was calculated by measuring the UV absorption spectrum with Shimadzu UV-350Spectrometer (Shimadzu UV-350Spectrometer) at room temperature and then using the optical band gap (Eg) from the edge of the absorption spectrum (edge).

The LUMO energy level was calculated from the reduction initiation (reduction set) of the potential (V) -current (A) ampere graph of each compound obtained by using Cyclic Voltammetry (CV) (electrolyte: 0.1 mol Bu ₄ NClO ₄/solvent: CH ₂ Cl ₂/electrode: 3 electrode systems (working electrode: GC, reference electrode: Ag/AgCl, auxiliary electrode: Pt)).

The T1 energy level is calculated by: a mixture of MTHF (methyltetrahydrofu) and each compound (1 mg of each compound was dissolved in 3 cubic centimeters of MTHF) was placed in a quartz cell, the quartz cell was placed in liquid nitrogen (77 kelvin), its photoluminescence spectrum was measured with a photoluminescence measuring element, and it was compared with a general photoluminescence spectrum observed at room temperature to analyze only one peak observed at low temperature.

The results are provided in table 1.

(Table 1)

Manufacture of organic light-emitting diode

Example 1

A glass substrate coated with 1500 angstroms thick Indium Tin Oxide (ITO) was ultrasonically cleaned with distilled water. Subsequently, the glass substrate was ultrasonically washed with a solvent (such as isopropyl alcohol, acetone, methanol, and the like), moved into a plasma cleaner, cleaned for 5 minutes by using an oxygen plasma, and then moved into a vacuum depositor. The ITO transparent electrode thus obtained was used as an anode, and N- ([1,1' -biphenyl ] -4-yl) -9, 9-dimethyl-N- (4- (9-phenyl-9H-carbazol-3-yl) phenyl) -9H-fluorene-2-amine was vacuum deposited on an ITO substrate to form a hole injection layer 1400 a thick. I-61 obtained in Synthesis example 1 and C-10 obtained in Synthesis example 2 were simultaneously deposited on the hole transport layer at a 1:1 ratio to form a 50 Angstrom thick hole transport assist layer. BH113 (made of SFC) as a host doped with 5 wt% BD370 (made of SFC) was vacuum deposited on the hole transport assist layer to form a 250 angstrom thick emissive layer. 8- (4- (4, 6-bis (naphthalen-2-yl) -1,3, 5-triazin-2-yl) phenyl) quinolone was vacuum deposited onto the emissive layer to form a 250 angstrom thick electron transport layer. LiF (10 angstroms) and Al (1000 angstroms) were sequentially vacuum-deposited on the electron transport layer to form a cathode, thereby fabricating an organic light emitting diode.

Example 2

An organic light emitting diode was manufactured according to the same method as example 1, except that I-61 obtained in Synthesis example 1 and C-10 obtained in Synthesis example 2 were used in a ratio of 3:7 (weight/weight).

example 3

An organic light emitting diode was manufactured according to the same method as example 1, except that I-61 obtained in Synthesis example 1 and C-10 obtained in Synthesis example 2 were used in a ratio of 7:3 (weight/weight).

Example 4

An organic light emitting diode was manufactured according to the same method as example 1, except that B-117 obtained in Synthesis example 8 was used instead of C-10 obtained in Synthesis example 2.

Example 5

An organic light emitting diode was fabricated according to the same method as in example 1, except that B-115 obtained in Synthesis example 6 was used instead of C-10 obtained in Synthesis example 2.

Example 6

An organic light emitting diode was fabricated according to the same method as in example 1, except that H-204 obtained in Synthesis example 13 was used instead of I-61 obtained in Synthesis example 1.

Example 7

An organic light-emitting diode was fabricated according to the same method as in example 1, except that I-64 obtained in Synthesis example 16 was used instead of I-61 obtained in Synthesis example 1.

example 8

an organic light emitting diode was fabricated according to the same method as in example 1, except that D-30 obtained in Synthesis example 11 was used instead of C-10 obtained in Synthesis example 2.

example 9

An organic light emitting diode was fabricated according to the same method as in example 1, except that B-43 obtained in Synthesis example 4 was used instead of C-10 obtained in Synthesis example 2.

Example 10

An organic light emitting diode was fabricated according to the same method as in example 1, except that D-31 obtained in Synthesis example 12 was used instead of C-10 obtained in Synthesis example 2.

Example 11

An organic light emitting diode was fabricated according to the same method as in example 1, except that B-114 obtained in Synthesis example 5 was used instead of C-10 obtained in Synthesis example 2.

Example 12

An organic light-emitting diode was fabricated according to the same method as in example 1, except that I-62 obtained in Synthesis example 14 was used instead of I-61 obtained in Synthesis example 1, and B-116 obtained in Synthesis example 7 was used instead of C-10 obtained in Synthesis example 2.

Example 13

An organic light-emitting diode was manufactured according to the same method as in example 1, except that the ratio of 7:3 (weight/weight) of I-62 obtained in synthesis example 14 was changed instead of I-61 obtained in synthesis example 1, and B-116 obtained in synthesis example 7 was changed instead of C-10 obtained in synthesis example 2.

Example 14

An organic light-emitting diode was fabricated according to the same method as in example 1, except that I-63 obtained in Synthesis example 15 was used instead of I-61 obtained in Synthesis example 1, and B-118 obtained in Synthesis example 9 was used instead of C-10 obtained in Synthesis example 2.

example 15

An organic light-emitting diode was manufactured according to the same method as in example 1, except that the ratio of 3:1 (weight/weight) of I-63 obtained in Synthesis example 15 was changed instead of I-61 obtained in Synthesis example 1, and B-118 obtained in Synthesis example 9 was changed instead of C-10 obtained in Synthesis example 2.

Example 16

An organic light-emitting diode was fabricated according to the same method as in example 1, except that I-64 obtained in Synthesis example 16 was used instead of I-61 obtained in Synthesis example 1, and C-23 obtained in Synthesis example 10 was used instead of C-10 obtained in Synthesis example 2.

Example 17

An organic light-emitting diode was fabricated according to the same method as in example 1, except that I-64 obtained in Synthesis example 16 was used instead of I-61 obtained in Synthesis example 1, and B-116 obtained in Synthesis example 7 was used instead of C-10 obtained in Synthesis example 2.

example 18

An organic light-emitting diode was fabricated according to the same method as in example 1, except that I-65 obtained in Synthesis example 17 was used instead of I-61 obtained in Synthesis example 1, and B-43 obtained in Synthesis example 4 was used instead of C-10 obtained in Synthesis example 2.

Comparative example 1

An organic light emitting diode was manufactured according to the same method as example 1, but in which the hole transport auxiliary layer was not formed.

Comparative example 2

An organic light-emitting diode was manufactured according to the same method as example 1, but in which only I-61 obtained in synthesis example 1 was used instead of I-61 obtained in synthesis example 1 and C-10 obtained in synthesis example 2 to form a hole transport auxiliary layer.

Comparative example 3

An organic light emitting diode was manufactured according to the same method as example 1, but in which only the C-10 obtained in synthesis example 2 was used instead of the I-61 obtained in synthesis example 1 and the C-10 obtained in synthesis example 2 to form a hole transport auxiliary layer.

Comparative example 4

An organic light-emitting diode was manufactured according to the same method as example 4, but in which only B-117 obtained in synthesis example 8 was used instead of I-61 obtained in synthesis example 1 and B-117 obtained in synthesis example 8 to form a hole transport auxiliary layer.

Comparative example 5

An organic light-emitting diode was manufactured according to the same method as in example 12, but in which only I-62 obtained in synthesis example 14 was used instead of I-62 obtained in synthesis example 14 and B-116 obtained in synthesis example 7 to form a hole transport auxiliary layer.

Comparative example 6

an organic light-emitting diode was manufactured according to the same method as example 6, but in which only H-204 obtained in synthesis example 13 was used instead of H-204 obtained in synthesis example 13 and C-10 obtained in synthesis example 2 to form a hole transport auxiliary layer.

Comparative example 7

An organic light-emitting diode was manufactured according to the same method as in example 14, but in which only I-63 obtained in synthesis example 15 was used instead of I-63 obtained in synthesis example 15 and B-118 obtained in synthesis example 9 to form a hole transport auxiliary layer.

Comparative example 8

an organic light-emitting diode was manufactured according to the same method as in example 14, but in which only B-118 obtained in synthesis example 9 was used instead of I-63 obtained in synthesis example 15 and B-118 obtained in synthesis example 9 to form a hole transport auxiliary layer.

Comparative example 9

An organic light-emitting diode was manufactured according to the same method as example 7, but in which only I-64 obtained in synthesis example 16 was used instead of I-64 obtained in synthesis example 16 and C-10 obtained in synthesis example 2 to form a hole transport auxiliary layer.

Comparative example 10

An organic light-emitting diode was manufactured according to the same method as in example 18, but in which only I-65 obtained in synthesis example 17 was used instead of I-65 obtained in synthesis example 14 and B-43 obtained in synthesis example 4 to form a hole transport auxiliary layer.

Evaluation 2

The driving voltage and efficiency characteristics of the organic light emitting diode according to the example and the comparative example corresponding thereto were evaluated.

specific measurement methods are as follows, and the results are provided in table 2.

(1) Measuring the driving voltage

The driving voltage of the organic light emitting diode was measured at the same luminance (750 candelas per square meter) by increasing its voltage from 0 to 10 volts and using a current-voltage meter (Keithley 2400).

(2) Measuring change in brightness as a function of voltage change

The current value flowing in the unit cell of the organic light emitting diode obtained when the voltage was increased from 0 v to 10 v was measured using a current-voltage meter (gishili 2400), and the measured current value was divided by the area to obtain the result.

(3) Measuring change in brightness as a function of voltage change

When the voltage of the organic light emitting diode was increased from 0 v to 10 v, the luminance was measured by using a luminance meter (Minolta) Cs-1000A).

(4) Measuring luminous efficiency

The current efficiency (candela/ampere) at the same current density (10 milliamps/square centimeter) was calculated by using the luminance, current density, and voltage (volts) of items (2) and (3).

(Table 2)

referring to table 2, the organic light emitting diode according to the example shows significantly improved driving voltage and efficiency characteristics, compared to the organic light emitting diode according to comparative example 1, in which the hole transport auxiliary layer is not used, and the organic light emitting diode according to each comparative example, which includes a single compound.

Evaluation 3

Life characteristics of the organic light emitting diodes according to the examples and the comparative examples corresponding thereto were evaluated.

The lifetime characteristics were evaluated by maintaining a brightness of 6000 candelas per square meter (candelas per square meter) and measuring the time spent until the current efficiency (candelas per ampere) decreased to 97%.

The results are provided in table 3.

[ Table 3]

Referring to table 3, the organic light emitting diode according to the example exhibited significantly improved life span characteristics, compared to the organic light emitting diodes according to the comparative examples, each including a single compound.

While the invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not to be limited to the disclosed embodiments, but on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims. The foregoing embodiments are therefore to be considered illustrative of, but not limiting of, the invention in any way.

Claims

1. An organic photoelectric element, comprising:

An anode and a cathode facing each other,

An emissive layer between the anode and the cathode,

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

a hole transport auxiliary layer between the hole transport layer and the emissive layer,

Wherein the hole transport assisting layer comprises:

a first compound represented by one of chemical formulas 1-I to 1-III and 1-VI

A second compound represented by one of chemical formulas 2-I to 2-IV and 3-II:

[ chemical formula 1-I ] [ chemical formula 1-II ]

[ chemical formulas 1-III ] [ chemical formulas 1-VI ]

Wherein, in chemical formulas 1-I to 1-III and 1-VI,

L ¹ to L ³ are each independently a single bond or a substituted or unsubstituted C6 to C30 arylene,

Ar ² and Ar ³ are independently groups listed in group 1,

[ group 1]

、、、、、、、、、

In the population 1, the population is selected from,

R ⁷⁵ to R ¹¹⁷ are independently hydrogen, deuterium, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C1 to C30 alkoxy, carboxyl, halogen, cyano, nitro, hydroxyl, or a combination thereof,

X ^a in chemical formula 1-I is CR ^a R ^b, X ^a in chemical formula 1-VI is O, X ^a to X ^c in chemical formula 1-II and chemical formula 1-III are each independently O or CR ^a R ^b,

R ^1b, R ^2a to R ^2c, R ^3a to R ^3c, R ^4a to R ^4c, R ^a, and R ^b are each independently a fused ring of hydrogen, deuterium, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C1 to C20 alkoxy, halogen, cyano, nitro, hydroxyl, carboxyl, a combination thereof, or a combination thereof,

[ chemical formula 2-I ] [ chemical formula 2-II ]

[ chemical formula 2-III ] [ chemical formula 2-IV ]

Wherein, in chemical formulas 2-I to 2-IV,

Y ¹ to Y ³ are independently a single bond or a substituted or unsubstituted C6 to C30 arylene,

R ⁵ to R ²⁰ are each independently hydrogen, deuterium, or substituted or unsubstituted C1 to C20 alkyl, or a combination thereof,

[ chemical formula 3-II ]

Wherein, in chemical formula 3-II,

Y ^1a and Y ^1b are each independently a single bond or a substituted or unsubstituted C6 to C30 arylene,

ar ^4a and Ar ^4b are each independently substituted or unsubstituted C6 to C30 aryl,

R ⁷ to R ¹⁰, R ^d and R ^e are each independently hydrogen, deuterium, substituted or unsubstituted C1 to C20 alkyl, or a combination thereof,

R ⁷ and R ⁸ are each independently present,

r ⁹ and R ¹⁰ are each independently present,

R ^d and R ^e each independently exist, an

At least one of R ⁷ to R ¹⁰, Ar ^4a, and Ar ^4b comprises a substituted or unsubstituted C6 to C30 aryl group.

2. the organic optoelectronic element according to claim 1, wherein the first compound is one of compounds of group 2:

[ group 2]

[H-204]

[I-1]

[I-31]

[I-61] [I-62] [I-63] [I-64]

[I-65]

。

3. The organic optoelectronic element according to claim 1, wherein the second compound is one of the compounds of group 3:

[ group 3]

。

4. The organic photoelectric element according to claim 1, wherein the hole transport auxiliary layer contacts the emission layer.

5. The organic optoelectronic element of claim 1, wherein the hole transport assist layer comprises a plurality of layers, an

In the plurality of layers, the first compound and the second compound are included in a layer contacting the emission layer.

6. The organic photoelectric element according to claim 1, wherein a HOMO level difference between the first compound and the second compound is 0.01 electron volt to 0.5 electron volt.

7. The organic optoelectronic element of claim 1, wherein the emissive layer comprises a host and a dopant, an

The first compound and the second compound satisfy the following relational expressions 6 to 9:

[ relational expression 6]

|E^L _p1| < |E^L _{Main body}|

[ relational expression 7]

|E^L _p1| < |E^L _{Dopant agent}|

[ relational expression 8]

|E^L _p2| < |E^L _{Main body}|

[ relational expression 9]

|E^L _p2| < |E^L _{Dopant agent}|

Wherein, in the relational expressions 6 to 9,

E^L _p1Is the LUMO energy level of the first compound, E^L _p2Is the LUMO energy level of the second compound, E^L _{Main body}Is the LUMO energy level of the host of the emissive layer, and E^L _{Dopant agent}is the LUMO energy level of the dopant of the emissive layer.

8. The organic optoelectronic element of claim 1, wherein the emissive layer comprises a host and a dopant, an

the first compound and the second compound satisfy the following relational expressions 10 to 13:

[ relational expression 10]

|E^T _{main body}| < |E^T _p1|

[ relational expression 11]

|E^T _{Main body}| < |E^T _p2|

[ relational expression 12]

|E^T _{dopant agent}| < |E^T _p1|

[ relational expression 13]

|E^T _{Dopant agent}| < |E^T _p2|

Wherein, in the relation 10 to the relation 13,

9. The organic photoelectric element according to claim 1, wherein the first compound and the second compound have a uniform mixing ratio in a thickness direction of the hole-transport assisting layer.

10. The organic photoelectric element according to claim 1, wherein the hole transport layer comprises a compound represented by chemical formula 3:

[ chemical formula 3]

Wherein, in chemical formula 3,

R ¹²⁰ and R ¹²¹ independently exist or form a condensed ring,

L ⁴ to L ⁷ are independently a single bond, substituted or unsubstituted C2 to C10 alkylene, substituted or unsubstituted C2 to C10 alkenylene, substituted or unsubstituted C2 to C10 alkynylene, substituted or unsubstituted C6 to C30 arylene, substituted or unsubstituted C2 to C30 divalent heterocyclic group, or a combination thereof.

11. the organic photoelectric element according to claim 10, wherein Ar ⁶ of chemical formula 3 is a substituted or unsubstituted phenyl group or a substituted or unsubstituted biphenyl group, and

ar ⁷ and Ar ⁸ of formula 3 are independently one of substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted bisfluorenyl, substituted or unsubstituted terphenylene, substituted or unsubstituted anthryl, substituted or unsubstituted terphenylene, substituted or unsubstituted dibenzofuranyl, or substituted or unsubstituted dibenzothiophenyl.

12. A display element comprising the organic photoelectric element according to any one of claims 1 to 11.