KR102122213B1 - organic light-emitting diode with High efficiency - Google Patents

Abstract

The present invention relates to an organic light emitting device having a high efficiency, in more detail the first electrode;
A second electrode opposed to the first electrode; An organic light emitting device comprising a hole injection layer or a hole transport layer interposed between the first electrode and the second electrode; and a light emitting layer, wherein the hole injection layer or the hole transport layer is represented by the following [Formula A] or [Formula B] At least one amine compound represented; The light emitting layer relates to an organic light emitting device comprising at least one compound represented by any one of the following [Formula D1] to [Formula D5], [Formula A], [Formula B] and [Formula D1] to [Formula D1] D5] is the same as described in the detailed description of the invention

Description

Organic light-emitting diode with high efficiency

The present invention relates to an organic light emitting device having high efficiency, and more specifically, a material having a specific structure is used as a hole injection layer material or a hole transport layer material in the organic light emitting device, and another specific structure material is used for the dopant in the light emitting layer. By including, it relates to an organic light emitting device exhibiting high efficiency.

An organic light emitting diode (OLED) is a display using a self-emission phenomenon, and has a large viewing angle and can be lighter and shorter than a liquid crystal display, and has advantages such as a fast response speed and is full-color. ) Application to display or lighting is expected.

In general, the organic light emitting phenomenon refers to a phenomenon that converts electrical energy into light energy using an organic material. An organic light emitting device using an organic light emitting phenomenon usually has a structure including an anode and a cathode and an organic material layer therebetween.

Here, in order to increase the efficiency and stability of the organic light emitting device, the organic material layer is often formed of a multi-layered structure composed of different materials, for example, may be formed of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like. When a voltage is applied between two electrodes in the structure of the organic light emitting device, holes are injected at the anode, and electrons are injected at the cathode, and an exciton is formed when the injected holes meet the electrons. When it falls to the ground again, it glows. It is known that such an organic light emitting device has characteristics such as self-luminescence, high luminance, high efficiency, low driving voltage, wide viewing angle, high contrast, and high-speed response.

Materials used as the organic material layer in the organic light emitting device may be classified into light emitting materials and charge transport materials, such as hole injection materials, hole transport materials, electron transport materials, electron injection materials, etc. Alternatively, a hole blocking layer or the like may be added.

As a prior art for such a hole transport layer, in Patent Registration No. 10-1074193 (announcement date: 2011.10.14), organic light emission using a compound having a core structure in which at least one benzene ring is condensed in a carbazole structure as a hole transport layer compound A device is disclosed, and in Patent Registration No. 10-1455156 (Announcement date: 2014.10.27), a light-emitting auxiliary layer having a HOMO level between the hole transport layer HOMO energy level and the HOMO energy level of the light-emitting layer between the hole transport layer and the emission layer A description is given of an organic light emitting device in which it is formed.

In addition, as a conventional technique for the dopant compound of the light emitting layer, Patent Publication No. 10-2008-0015865 (2008.02.20) discloses an organic light emitting device using an adenoamine-linked indenofluorene derivative or the like, and disclosed In Patent Publication No. 10-2012-0047706 (20012.05.14), a structure in which dibenzofuran or dibenzothiophene is present with fluorene or benzofuran or dibenzothiophene is present with carbazole in one molecule An organic light emitting device using a compound is disclosed.

However, in spite of various attempts to produce an organic light emitting device in the prior art including the above-mentioned literature, there is still a need for development of an organic light emitting device having improved luminous efficiency. to be.

Registered Patent Publication No. 10-1074193 (Announcement date: October 14, 2011)

Registered Patent Publication No. 10-1455156 (Notice: 2014.10.27)

Patent Publication No. 10-2008-0015865 (2008.02.20)

Patent Publication No. 10-2012-0047706 (2012.05.14)

Therefore, the technical problem to be achieved by the present invention includes a hole injection layer material having a specific structure or a hole transport layer material having a specific structure, and also includes a dopant material having a specific structure in the light emitting layer, thereby providing a novel organic light emitting device having high efficiency characteristics. (organic light emitting diode, OLED) to provide.

The present invention to achieve the above technical problems, the first electrode; A second electrode opposed to the first electrode; An organic light emitting device comprising a hole injection layer or a hole transport layer interposed between the first electrode and the second electrode; and a light emitting layer, wherein the hole injection layer or the hole transport layer is represented by the following [Formula A] or [Formula B] At least one amine compound represented; It provides an organic light emitting device wherein the light emitting layer comprises at least one compound represented by any one of the following [Formula D1] to [Formula D5].

[Formula A]

[Formula B]

In the above [Formula A] and [Formula B],

A1, A2, E and F are each the same or different from each other, and are each independently a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 50 carbon atoms, or a substituted or unsubstituted aromatic heterocycle having 2 to 40 carbon atoms;

Two carbon atoms adjacent to each other in the aromatic ring of A1 and two carbon atoms adjacent to each other in the aromatic ring of A2 form a condensed ring by forming a five-membered ring with carbon atoms connected to the substituents R1 and R2;

The linking groups L1 to L6 are the same as or different from each other, and independently of each other, a single bond, a substituted or unsubstituted alkylene group having 1 to 60 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 60 carbon atoms, a substituted or unsubstituted group, Alkynylene group having 2 to 60 carbon atoms, substituted or unsubstituted cycloalkylene group having 3 to 60 carbon atoms, substituted or unsubstituted heterocycloalkylene group having 2 to 60 carbon atoms, substituted or unsubstituted aryl having 6 to 60 carbon atoms A alkylene group or a substituted or unsubstituted heteroarylene group having 2 to 60 carbon atoms;

The M is any one selected from NR ₃ , CR ₄ R ₅ , SiR ₆ R ₇ , GeR ₈ R ₉ , O, S, Se;

The substituents R1 to R9, Ar1 to Ar4 are the same or different from each other, and independently of each other, hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, substituted Or an unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted cycloalke having 5 to 30 carbon atoms Nyl group, substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms, substituted or unsubstituted heterocycloalkyl group having 2 to 30 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, substituted or unsubstituted carbon number 6 Aryloxy group having 30 to 30, substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, substituted or unsubstituted arylthio group having 6 to 30 carbon atoms, substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, substituted Or an unsubstituted arylamine group having 6 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, a substituted or unsubstituted 1 to 30 carbon atoms An alkyl germanium group, a substituted or unsubstituted aryl germanium group having 1 to 30 carbon atoms, any one selected from a cyano group, a nitro group, and a halogen group,

The R1 and R2 may be connected to each other to form an alicyclic, aromatic monocyclic or polycyclic ring, and the carbon atoms of the formed alicyclic, aromatic monocyclic or polycyclic ring are N, O, P, Si, S, Ge , Se, Te may be substituted with any one or more heteroatoms selected from;

Wherein p1 and p2, r1 and r2, s1 and s2 are integers of 1 to 3, but when each of these is 2 or more, each of the linkers L1 to L6 is the same or different from each other,

Ar1 and Ar2 may be connected to each other to form a ring, and Ar3 and Ar4 may be connected to each other to form a ring;

Wherein x and y is an integer of 0 or 1, provided that x + y = 1,

In Formula A, two carbon atoms adjacent to each other in the A2 ring combine with * in the structural formula Q1 to form a condensed ring,

In Formula B, two carbon atoms adjacent to each other in the A1 ring are combined with * in the structural formula Q2 to form a condensed ring, and two carbon atoms adjacent to each other in the A2 ring are combined with * in the structural formula Q1 to form a condensed ring. To form.

[Formula D1]

In [Formula D1], A ₁₁ to A ₁₄ are the same as or different from each other, and are each independently a substituted or unsubstituted aryl group having 6 to 24 carbon atoms or a substituted or unsubstituted heteroaryl group having 2 to 24 carbon atoms. ,

R ₁₀ is hydrogen, deuterium, substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, substituted or unsubstituted A cycloalkenyl group having 5 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkylthioxy group having 1 to 30 carbon atoms, Substituted or unsubstituted arylthio group having 6 to 30 carbon atoms, substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, substituted or unsubstituted arylamine group having 6 to 30 carbon atoms, substituted or unsubstituted 6 to 6 carbon atoms Aryl group of 50, substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms having O, N or S as a hetero atom, substituted or unsubstituted silicone group, substituted or unsubstituted boron group, substituted or unsubstituted silane Any one selected from the group consisting of groups, carbonyl groups, phosphoryl groups, amino groups, nitrile groups, hydroxy groups, nitro groups, halogen groups, amide groups and ester groups,

n1 is an integer from 1 to 8, and when n1 is 2 or more, each R ₁₀ is the same or different from each other,

Carbon of the pyrene ring in which R10 is not substituted is bonded to hydrogen or deuterium.

[Formula D2]

In the above [Formula D2],

Z ₁ is any _{one selected} from substituted or unsubstituted aromatic hydrocarbon rings having 6 to 30 carbon atoms, substituted or unsubstituted aromatic hetero rings having 2, 20 carbon atoms having O, N or S as heteroatoms,

The substituents R ₁₁ to R ₁₆ are the same or different, and each independently hydrogen, deuterium, substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, substituted or unsubstituted aryl group having 6 to 50 carbon atoms, substituted or unsubstituted An alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted heteroatom selected from O, N, and S Heteroaryl group having 2 to 50 carbon atoms having any one or more, substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, substituted or unsubstituted 1 to 30 carbon atoms Alkyl thioxy group, substituted or unsubstituted arylthio group having 6 to 30 carbon atoms, substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, substituted or unsubstituted arylamine group having 6 to 30 carbon atoms, substituted or unsubstituted Any one selected from a substituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, a cyano group, a nitro group, a hydroxyl group and a halogen group, the substituents R ₁₃ to R Any one of ₁₆ is a single bond to be coupled to the linker L ₁₁ for connection with the structural formula Q ₃ ,

The structural formula Q3 connected to the Z1 ring and the structural formula Q3 connected to the 6-membered ring connected to the substituents R ₁₃ to R ₁₆ are the same or different, respectively.

The substituents R ₁₁ and R ₁₂ may be connected to each other to form a ring,

The substituents R ₁₃ to R ₁₆ may be connected to substituents adjacent to each other to form a substituted, aromatic monocyclic or polycyclic ring, and the formed alicyclic, aromatic monocyclic or polycyclic carbon atom may be N, S , It may be substituted with any one or more heteroatoms selected from O,

Two carbon atoms adjacent to each other in the Z1 form a condensed ring by forming a 5-membered ring with the carbon atoms connected to the substituents R11 and R12,

Carbon atom that does not form a 5-membered ring in the aromatic ring of Z1 and the linking group L11 in Q3 are bonded,

The linking group L11 is a single bond, a substituted or unsubstituted alkylene group having 1 to 60 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 60 carbon atoms, a substituted or unsubstituted alkynylene group having 2 to 60 carbon atoms, substituted Or an unsubstituted cycloalkylene group having 3 to 60 carbon atoms, a substituted or unsubstituted heterocycloalkylene group having 2 to 60 carbon atoms, a substituted or unsubstituted arylene group having 6 to 60 carbon atoms, or a substituted or unsubstituted 2 to 60 carbon atoms. Any one selected from heteroarylene groups;

n2 is an integer from 0 to 2, and when n2 is 2, each linker L11 is the same as or different from each other,

The substituents Ar ₁₁ and Ar ₁₂ are the same or different, and each independently substituted or unsubstituted aryl group having 6 to 40 carbon atoms, substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms, substituted or unsubstituted carbon number. It is any one selected from an alkyl group of 1 to 40, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms.

[Formula D3]

In the above [Formula D3],

X is a single bond, any one selected from CR ₁₈ R ₁₉ , NR ₂₈ , O, S and SiR ₂₉ R ₃₀ ,

Z ₂ and Z ₃ are the same or different, and each independently substituted or unsubstituted aromatic hydrocarbon ring having 6 to 30 carbon atoms, substituted or unsubstituted aromatic hetero atom having 2, 20 carbon atoms having O, N or S as a hetero atom. Any one selected from rings,

The two carbon atoms adjacent to each other in Z2 and the two carbon atoms adjacent to each other in Z3 form a 5-membered ring to form a condensed ring,

The substituents R ₁₈ to R ₃₀ are the same or different, and each independently hydrogen, deuterium, substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, substituted or unsubstituted aryl group having 6 to 50 carbon atoms, substituted or unsubstituted An alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted heteroatom selected from O, N, and S Heteroaryl group having 2 to 50 carbon atoms having any one or more, substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, substituted or unsubstituted 1 to 30 carbon atoms Alkyl thioxy group, substituted or unsubstituted arylthio group having 6 to 30 carbon atoms, substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, substituted or unsubstituted arylamine group having 6 to 30 carbon atoms, substituted or unsubstituted It is any one selected from substituted alkylsilyl groups having 1 to 30 carbon atoms, substituted or unsubstituted arylsilyl groups having 6 to 30 carbon atoms, cyano groups, nitro groups, hydroxyl groups, and halogen groups,

Each of the R ₂₀ to R ₂₇ may be connected to a substituent adjacent to each other to form a substituted, aromatic monocyclic or polycyclic ring, and the formed alicyclic, aromatic monocyclic or polycyclic carbon atom may be N, S, It may be substituted with any one or more heteroatoms selected from O,

The A21 and A22 are the same or different, and are independently represented by the following [Structural Q4],

[Structural Formula Q4]

In the above [Structural Formula Q4],

* Means a binding site to which the linking group L ₁₂ in Q4 is bonded to a carbon atom that does not form a 5-membered ring in the aromatic ring of Z2 or Z3 of the above [Formula D3],

The linking group L ₁₂ is a single bond, a substituted or unsubstituted alkylene group having 1 to 60 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 60 carbon atoms, a substituted or unsubstituted alkynylene group having 2 to 60 carbon atoms, Substituted or unsubstituted cycloalkylene group having 3 to 60 carbon atoms, substituted or unsubstituted heterocycloalkylene group having 2 to 60 carbon atoms, substituted or unsubstituted arylene group having 6 to 60 carbon atoms or substituted or unsubstituted carbon number 2 to Any one selected from 60 heteroarylene groups;

n3 is an integer from 0 to 2, and when n3 is 2, each linker L ₁₂ is the same or different from each other,

The substituents Ar ₁₃ and Ar ₁₄ are the same or different, and each independently substituted or unsubstituted aryl group having 6 to 40 carbon atoms, substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms, substituted or unsubstituted It is any one selected from an alkyl group having 1 to 40 carbon atoms, or a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms.

[Formula D4]

[Formula D5]

In [Formula D4] and [Formula D5], A ₃₁ , A ₃₂ , E1 and F1 are the same or different, and each independently substituted or unsubstituted aromatic hydrocarbon ring having 6 to 50 carbon atoms, or substituted or unsubstituted An aromatic heterocycle having 2 to 40 carbon atoms;

Two carbon atoms adjacent to each other in the aromatic ring of A ₃₁ and two carbon atoms adjacent to each other in the aromatic ring of A ₃₂ form a condensed ring by forming a five-membered ring with carbon atoms connected to the substituents R ₃₁ and R ₃₂ To form;

The linking groups L ₂₁ to L ₃₂ are the same or different, and each independently a single bond, a substituted or unsubstituted alkylene group having 1 to 60 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 60 carbon atoms, a substituted or unsubstituted group. A substituted alkynylene group having 2 to 60 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 60 carbon atoms, a substituted or unsubstituted heterocycloalkylene group having 2 to 60 carbon atoms, a substituted or unsubstituted 6 to 60 carbon atoms An arylene group or a substituted or unsubstituted heteroarylene group having 2 to 60 carbon atoms;

W is any one selected from NR ₃₃ , CR ₃₄ R ₃₅ , SiR ₃₆ R ₃₇ , GeR ₃₈ R ₃₉ , O, S, Se;

The substituents R ₃₁ to R ₃₉ , Ar ₂₁ to Ar ₂₈ are the same or different, and each independently hydrogen, deuterium, substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, substituted or unsubstituted aryl having 6 to 50 carbon atoms Group, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted 5 to 30 carbon atoms Cycloalkenyl group, substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms, substituted or unsubstituted heterocycloalkyl group having 2 to 30 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, substituted or unsubstituted Aryloxy group having 6 to 30 carbon atoms, substituted or unsubstituted alkylthioxy group having 1 to 30 carbon atoms, substituted or unsubstituted arylthiooxy group having 5 to 30 carbon atoms, substituted or unsubstituted alkylamine having 1 to 30 carbon atoms Group, a substituted or unsubstituted arylamine group having 5 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 5 to 30 carbon atoms, a substituted or unsubstituted carbon number 1 to 30 alkyl germanium group, a substituted or unsubstituted aryl germanium group having 1 to 30 carbon atoms, any one selected from a cyano group, a nitro group, a halogen group,

The R ₃₁ and R ₃₂ may be connected to each other to form an alicyclic, aromatic monocyclic or polycyclic ring, and the carbon atoms of the formed alicyclic, aromatic monocyclic or polycyclic ring are N, O, P, Si, S , Ge, Se, Te Can be substituted with any one or more heteroatoms;

Wherein p11 to p14, r11 to r14 and s11 to s14 are integers of 1 to 3, respectively, when each of them is 2 or more, each of the linking groups L ₂₁ to L ₃₂ is the same or different from each other,

X1 is an integer of 1 or 2, y1 and z1 are the same or different, respectively, and are integers of 0 to 3 independently of each other,

Ar ₂₁ and Ar ₂₂ , Ar ₂₃ and Ar ₂₄ , Ar ₂₅ and Ar _26, and Ar ₂₇ and Ar ₂₈ may be connected to each other to form a ring;

In Formula D4, two carbon atoms adjacent to each other in the A ₃₂ ring combine with * in the structural formula Q ₁₁ to form a condensed ring,

In Formula D5, two carbon atoms adjacent to each other in the A ₃₁ ring form a condensed ring by combining with * of the structural formula Q ₁₂ , and two carbon atoms adjacent to each other in the A ₃₂ ring are represented by * of the structural formula Q ₁₁ Can combine to form a condensed ring,

Here, the'substitution' in the'substituted or unsubstituted' in [Formula A], [Formula B], [Formula D1] to [Formula D5] is deuterium, cyano group, halogen group, hydroxy group, nitro group , An alkyl group having 1 to 24 carbon atoms, a halogenated alkyl group having 1 to 24 carbon atoms, an alkenyl group having 2 to 24 carbon atoms, an alkynyl group having 2 to 24 carbon atoms, a heteroalkyl group having 1 to 24 carbon atoms, an aryl group having 6 to 24 carbon atoms, a carbon number 7 to 24 arylalkyl groups, 2 to 24 heteroaryl groups or 2 to 24 heteroarylalkyl groups, 1 to 24 alkoxy groups, 1 to 24 alkylamino groups, 6 to 24 arylamino groups, carbon number It means that it is substituted with one or more substituents selected from the group consisting of a heteroaryl amino group having 1 to 24, an alkylsilyl group having 1 to 24 carbon atoms, an arylsilyl group having 6 to 24 carbon atoms, and an aryloxy group having 6 to 24 carbon atoms.

The organic light emitting device according to the present invention can exhibit more improved efficiency than the organic light emitting device according to the prior art.

1 is a schematic diagram of an organic light emitting device according to an embodiment of the present invention.

Hereinafter, the present invention will be described in more detail.

The organic light emitting device according to the present invention includes a first electrode; A second electrode opposed to the first electrode; An organic light emitting device comprising a hole injection layer or a hole transport layer interposed between the first electrode and the second electrode; and a light emitting layer, wherein the hole injection layer or the hole transport layer is represented by [Formula A] or [Formula B] At least one amine compound represented; It provides an organic light emitting device in which the light emitting layer includes at least one compound represented by any one of the above [Formula D1] to [Formula D5].

That is, the organic light emitting device according to the present invention uses the compound represented by any one of the formulas D1 to D5 as a light emitting layer material, and also uses the amine compound represented by the formula A or formula B as a hole injection layer material or holes When used as a transport layer material, it may have improved characteristics of high efficiency.

On the other hand, considering the range of the alkyl group or the aryl group in the "substituted or unsubstituted alkyl group having 1 to 24 carbon atoms", "substituted or unsubstituted aryl group having 6 to 24 carbon atoms", the carbon number of 1 to 24 The range of the carbon number of the alkyl group and the aryl group having 6 to 24 carbon atoms means the total number of carbon atoms constituting the alkyl portion or the aryl portion when the substituent is regarded as unsubstituted without considering the substituted portion. For example, the phenyl group substituted with a butyl group in the para position should be regarded as corresponding to an aryl group having 6 carbon atoms substituted with a butyl group having 4 carbon atoms.

The aryl group, which is a substituent used in the compound of the present invention, is an organic radical derived from an aromatic hydrocarbon by removal of one hydrogen. When the aryl group has a substituent, it is fused with adjacent substituents to each other to form a ring. Can be.

Specific examples of the aryl group include a phenyl group, o-biphenyl group, m-biphenyl group, p-biphenyl group, o-terphenyl group, m-terphenyl group, p-terphenyl group, naphthyl group, anthryl group, phenanthryl group, Aromatic groups such as pyrenyl group, indenyl, fluorenyl group, tetrahydronaphthyl group, peryleneyl, chrysenyl, naphthacenyl, fluoranthenyl, and the like, and at least one hydrogen atom of the aryl group is a deuterium atom, a halogen atom , Hydroxy group, nitro group, cyano group, silyl group, amino group (-NH ₂ , -NH(R), -N(R')(R''), R'and R" independently of each other have 1 to 10 carbon atoms. An alkyl group, in this case referred to as "alkylamino group"), amidino group, hydrazine group, hydrazone group, carboxyl group, sulfonic acid group, phosphoric acid group, alkyl group having 1 to 24 carbon atoms, halogenated alkyl group having 1 to 24 carbon atoms, 2 to 24 carbon atoms Alkenyl group of 2 to 24 carbon atoms, alkynyl group of 1 to 24 carbon atoms, aryl group of 6 to 24 carbon atoms, arylalkyl group of 6 to 24 carbon atoms, heteroaryl group of 2 to 24 carbon atoms or 2 to 24 carbon atoms It may be substituted with a heteroaryl alkyl group.

The heteroaryl group, which is a substituent used in the compound of the present invention, includes 1, 2 or 3 hetero atoms selected from N, O, P or S, and means a ring aromatic system having 2 to 24 carbon atoms, the remaining ring atoms being carbon, The rings can be fused to form a ring. And one or more hydrogen atoms of the heteroaryl group can be substituted with the same substituents as the aryl group.

Specific examples of the alkyl group that is a substituent used in the present invention include methyl, ethyl, propyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl, hexyl and the like, and at least one hydrogen atom in the alkyl group is The atom can be substituted with a substituent similar to that of the aryl group.

Specific examples of the alkoxy group which is a substituent used in the compound of the present invention include methoxy, ethoxy, propoxy, isobutyloxy, sec-butyloxy, pentyloxy, iso-amyloxy, hexyloxy, and the like. One or more hydrogen atoms of the alkoxy group can be substituted with the same substituents as the aryl group.

Specific examples of the silyl group which is a substituent used in the compound of the present invention include trimethylsilyl, triethylsilyl, triphenylsilyl, trimethoxysilyl, dimethoxyphenylsilyl, diphenylmethylsilyl, diphenylvinylsilyl, methylcyclobutylsilyl , Dimethylfurylsilyl, and the like, and one or more hydrogen atoms of the silyl group can be substituted with the same substituents as the aryl group.

On the other hand, in the organic light emitting device according to the present invention, the amine compound represented by Formula A or Formula B in the formula A in the A2 ring adjacent to each other two carbon atoms combine with * of the structural formula Q1 to form a condensed ring, In addition, in Formula B, two carbon atoms adjacent to each other in the A1 ring are combined with * in the structural formula Q2 to form a condensed ring, and two carbon atoms adjacent to each other in the A2 ring are combined with * in the structural formula Q1 It forms a condensed ring, characterized in that it has an amine group in only one of the A1 ring and A2 ring in the above formula A and formula B, these can be used in the hole injection layer or hole transport layer in the organic light emitting device, preferably Can be used for the hole transport layer.

Meanwhile, according to the present invention The light emitting layer in the organic light emitting device includes a host and a dopant, and the compound represented by any one of [Chemical Formula D1] to [Chemical Formula D5] may be used as a dopant.

In one embodiment, A1, A2, E, and F in Formula A or Formula B are the same or different, and may be independently substituted or unsubstituted aromatic hydrocarbon rings having 6 to 50 carbon atoms.

As described above, in the case where A1, A2, E, and F in Formula A or Formula B are the same or different, and each independently represents a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 50 carbon atoms, the substituted or The unsubstituted aromatic hydrocarbon ring having 6 to 50 carbon atoms may be the same or different, and independently selected from [Structural Formula 10] to [Structural Formula 21].

[Structural Formula 10] [Structural Formula 11] [Structural Formula 12]

[Structural Formula 13] [Structural Formula 14] [Structural Formula 15]

[Structural Formula 16] [Structural Formula 17] [Structural Formula 18]

[Structural Formula 19] [Structural Formula 20] [Structural Formula 21]

In [Structural Formulas 10] to [Structural Formula 21], “-*” is used to form a 5-membered ring containing carbon atoms connected to R1 and R2, or to form a 5-membered ring containing M in the structural formulas Q1 and Q2. Means a binding site,

When the aromatic hydrocarbon rings of [Structural Formulas 10] to [Structural Formula 21] correspond to the A1 ring or A2 ring, and when combined with Structural Formula Q1 or Structural Formula Q2, two adjacent carbon atoms among them combine with * of Structural Formula Q1 Or in combination with * in structural formula Q2 to form a condensed ring;

In [Formula 10] to [Formula 21], R is the same as R1 to R9 defined above, m is an integer of 1 to 8, and when m is 2 or more or when R is 2 or more, each R is the same as each other. Or it may be different.

In addition, as an embodiment according to the present invention, x in Formula A and Formula B may be 1, and y may be 0.

In addition, as an embodiment according to the present invention, in the formula A and formula B, the linking groups L1 to L6 are the same or different, and are each independently a single bond, or selected from the following [Structural Formulas 22] to [Structural Formula 30] Is any one, p1 and p2, r1 and r4, s1 and s2 may be 1 or 2, respectively.

[Structural Formula 22] [Structural Formula 23] [Structural Formula 24] [Structural Formula 25]

[Structural Formula 26] [Structural Formula 27] [Structural Formula 28] [Structural Formula 29]

[Structural Formula 30]

Carbon atoms of the aromatic ring in the linking group may be hydrogen or deuterium.

Meanwhile, Ar11, Ar12, Ar13, and Ar14 in Chemical Formula D2 and Chemical Formula D3 in the present invention are the same or different, and may be independently substituted or unsubstituted aryl groups having 6 to 30 carbon atoms.

In addition, according to an embodiment of the present invention, in the [Chemical Formula D2] and [Chemical Formula D3], Z1 to Z3 are the same or different, and may be independently substituted or unsubstituted aromatic hydrocarbon rings having 6 to 30 carbon atoms. have.

In addition, in the present invention, in Formula D2 and Formula D3, Z1 to Z3 are the same or different, and when each independently substituted or unsubstituted carbon number 6 to 30 carbon atoms, the substituted or unsubstituted aromatic group having 6 to 30 carbon atoms The hydrocarbon ring may be any one selected from the following [Structural Formula 10] to [Structural Formula 21].

[Structural Formula 10] [Structural Formula 11] [Structural Formula 12]

[Structural Formula 13] [Structural Formula 14] [Structural Formula 15]

[Structural Formula 16] [Structural Formula 17] [Structural Formula 18]

[Structural Formula 19] [Structural Formula 20] [Structural Formula 21]

"-*" in [Formula 10] to [Structural Formula 21] means a binding site of a carbon atom for forming a 5-membered ring in Z1, Z2 or Z3,

In [Structural Formula 10] to [Structural Formula 21], R is the same as R11 to R16 or R20 to R27 defined above,

m is an integer of 1 to 8, and when m is 2 or more, or when R is 2 or more, each R may be the same or different from each other.

In addition, according to an embodiment of the present invention, the linking groups L11 and L12 in the formulas D2 and D3 are the same or different, and are a single bond independently of each other, or selected from the above formulas 22 to 30 It can be one.

Meanwhile, A ₂₁ , A ₂₂ , E 1, and F 1 in Chemical Formulas D4 and D5 of the present invention may be the same or different, and may be independently substituted or unsubstituted aromatic hydrocarbon rings having 6 to 50 carbon atoms.

On the other hand, the preparation of the dopant compound represented by the above [Formula D4] and [Formula D5] in the present invention is WO/2015/174682 (International Publication Date: 2015.11.19, International Application Number: PCT/KR2015/004552) It can be prepared as described.

As described above, A ₃₁ , A ₃₂ , E 1, and F 1 in Formula D4 and Formula D5 are the same or different, and may be independently substituted or unsubstituted aromatic hydrocarbon rings having 6 to 50 carbon atoms.

Here, in the formulas D4 and D5, A ₃₁ , A ₃₂ , E1 and F1 are the same or different, and each independently substituted or unsubstituted aromatic hydrocarbon ring having 6 to 50 carbon atoms, the substitution Alternatively, the unsubstituted aromatic hydrocarbon ring having 6 to 50 carbon atoms may be the same or different, and may be any one selected from [Structural Formula 10] to [Structural Formula 21] independently of each other.

[Structural Formula 10] [Structural Formula 11] [Structural Formula 12]

[Structural Formula 13] [Structural Formula 14] [Structural Formula 15]

[Structural Formula 16] [Structural Formula 17] [Structural Formula 18]

[Structural Formula 19] [Structural Formula 20] [Structural Formula 21]

In [Formula 10] to [Formula 21], "-*" forms a 5-membered ring containing carbon atoms connected to R31 and R32 in Formulas D4 and D5, or W in the Formulas Q11 and Q12 Means a binding site for forming a 5-membered ring containing,

In addition, when the aromatic hydrocarbon ring of [Structural Formula 10] to [Structural Formula 21] corresponds to the A31 ring or A32 ring in Chemical Formulas D4 and D5 and combines with Chemical Formulas Q11 or Q12, two of them are adjacent to each other. The carbon atom is combined with * of the structural formula Q11 or * of the structural formula Q12 to form a condensed ring,

In [Formula 10] to [Formula 21], R is the same as R31 to R39, m is an integer of 1 to 8, and when m is 2 or more, or when R is 2 or more, each R is the same or Can be different.

In addition, in the present invention, the linking groups L21 to L32 in the formulas D4 and D5 are the same or different, and are each independently a single bond, or any one selected from the above structures 22 to 30, p11 to p14, r11 to r14, and s11 to s14 may be 1 or 2, respectively.

In addition, according to an embodiment of the present invention, x1 and y1 in Chemical Formula D4 and Chemical Formula D5 may be 1 and z1 may be 0, respectively.

Meanwhile, the amine compound represented by Formula A or Formula B in the present invention may be any one selected from the group represented by the following Formulas 1 to 165, but is not limited thereto.

<Formula 1> <Formula 2> <Formula 3>

<Formula 4> <Formula 5> <Formula 6>

<Formula 7> <Formula 8> <Formula 9>

<Formula 10> <Formula 11> <Formula 12>

<Formula 13> <Formula 14> <Formula 15>

<Formula 16> <Formula 17> <Formula 18>

<Formula 19> <Formula 20> <Formula 21>

<Formula 22> <Formula 23> <Formula 24>

<Formula 25> <Formula 26> <Formula 27>

<Formula 28> <Formula 29> <Formula 30>

<Formula 31> <Formula 32> <Formula 33>

<Formula 34> <Formula 35> <Formula 36>

<Formula 37> <Formula 38> <Formula 39>

<Formula 40> <Formula 41> <Formula 42>

<Formula 43> <Formula 44> <Formula 45>

<Formula 46> <Formula 47> <Formula 48>

<Formula 49> <Formula 50> <Formula 51>

<Formula 52> <Formula 53> <Formula 54>

<Formula 55> <Formula 56> <Formula 57>

<Formula 58> <Formula 59> <Formula 60>

<Formula 61> <Formula 62> <Formula 63>

<Formula 64> <Formula 65> <Formula 66>

<Formula 67> <Formula 68> <Formula 69>

<Formula 70> <Formula 71> <Formula 72>

<Formula 73> <Formula 74> <Formula 75>

<Formula 76> <Formula 77> <Formula 78>

<Formula 79> <Formula 80> <Formula 81>

<Formula 82> <Formula 83> <Formula 84>

<Formula 85> <Formula 86> <Formula 87>

<Formula 88> <Formula 89> <Formula 90>

<Formula 91> <Formula 92> <Formula 93>

<Formula 94> <Formula 95> <Formula 96>

<Formula 97> <Formula 98> <Formula 99>

<Formula 100> <Formula 101> <Formula 102>

<Formula 103> <Formula 104> <Formula 105>

<Formula 106> <Formula 107> <Formula 108>

<Formula 109> <Formula 110> <Formula 111>

<Formula 112> <Formula 113> <Formula 114>

<Formula 115> <Formula 116> <Formula 117>

<Formula 118> <Formula 119> <Formula 120>

<Formula 121> <Formula 122> <Formula 123>

<Formula 124> <Formula 125> <Formula 126>

<Formula 127> <Formula 128> <Formula 129>

<Formula 130> <Formula 131> <Formula 132>

<Formula 133> <Formula 134> <Formula 135>

<Formula 136> <Formula 137> <Formula 138>

<Formula 139> <Formula 140> <Formula 141>

<Formula 142> <Formula 143> <Formula 144>

<Formula 145> <Formula 146> <Formula 147>

<Formula 148> <Formula 149> <Formula 150>

<Formula 151> <Formula 152> <Formula 153>

<Formula 154> <Formula 155> <Formula 156>

<Formula 157> <Formula 158> <Formula 159>

<Formula 160> <Formula 161> <Formula 162>

<Formula 163> <Formula 164> <Formula 165>

Further, in the present invention, the compound represented by [Chemical Formula D1] may be any one compound selected from the group represented by the following [Compound 101] to [Compound 190], but is not limited thereto.

<Compound 101> <Compound 102> <Compound 103>

<Compound 104> <Compound 105> <Compound 106>

<Compound 107> <Compound 108> <Compound 109>

<Compound 110> <Compound 111> <Compound 112>

<Compound 113> <Compound 114> <Compound 115>

<Compound 116> <Compound 117> <Compound 118>

<Compound 119> <Compound 120> <Compound 121>

<Compound 122> <Compound 123> <Compound 124>

<Compound 125> <Compound 126> <Compound 127>

<Compound 128> <Compound 129> <Compound 130>

<Compound 131> <Compound 132> <Compound 133>

<Compound 134> <Compound 135> <Compound 136>

<Compound 137> <Compound 138> <Compound 139>

<Compound 140> <Compound 141> <Compound 142>

<Compound 143> <Compound 144> <Compound 145>

<Compound 146> <Compound 147> <Compound 148>

<Compound 149> <Compound 150> <Compound 151>

<Compound 152> <Compound 153> <Compound 154>

<Compound 155> <Compound 156> <Compound 157>

<Compound 158> <Compound 159> <Compound 160>

<Compound 161> <Compound 162> <Compound 163>

<Compound 164> <Compound 165> <Compound 166>

<Compound 167> <Compound 168> <Compound 169>

<Compound 170> <Compound 171> <Compound 172>

<Compound 173> <Compound 174> <Compound 175>

<Compound 176> <Compound 177> <Compound 178>

<Compound 179> <Compound 180> <Compound 181>

<Compound 182> <Compound 183> <Compound 184>

<Compound 185> <Compound 186> <Compound 187>

<Compound 188> <Compound 189> <Compound 190>

In addition, in the present invention, the compound represented by [Chemical Formula D2] may be any one compound selected from the following [Compound 201] to [Compound 260], but is not limited thereto.

<Compound 201> <Compound 202> <Compound 203>

<Compound 204> <Compound 205> <Compound 206>

<Compound 207> <Compound 208> <Compound 209>

<Compound 210> <Compound 211> <Compound 212>

<Compound 213> <Compound 214> <Compound 215>

<Compound 216> <Compound 217> <Compound 218>

<Compound 219> <Compound 220> <Compound 221>

<Compound 222> <Compound 223> <Compound 224>

<Compound 225> <Compound 226> <Compound 227>

<Compound 228> <Compound 229> <Compound 230>

<Compound 231> <Compound 232> <Compound 233>

<Compound 234> <Compound 235> <Compound 236>

<Compound 237> <Compound 238> <Compound 239>

<Compound 240> <Compound 241> <Compound 242>

<Compound 243> <Compound 244> <Compound 245>

<Compound 246> <Compound 247> <Compound 248>

<Compound 249> <Compound 250> <Compound 251>

<Compound 252> <Compound 253> <Compound 254>

<Compound 255> <Compound 256> <Compound 257>

<Compound 258> <Compound 259> <Compound 260>

In addition, in the present invention, the compound represented by [Chemical Formula D3] may be any one compound selected from the following [Compound 261] to [Compound 326], but is not limited thereto.

<Compound 261> <Compound 262> <Compound 263>

<Compound 264> <Compound 265> <Compound 266>

<Compound 267> <Compound 268> <Compound 269>

<Compound 270> <Compound 271> <Compound 272>

<Compound 273> <Compound 274> <Compound 275>

<Compound 276> <Compound 277> <Compound 278>

<Compound 279> <Compound 280> <Compound 281>

<Compound 282> <Compound 283> <Compound 284>

<Compound 285> <Compound 286> <Compound 287>

<Compound 288> <Compound 289> <Compound 290>

<Compound 291> <Compound 292> <Compound 293>

<Compound 294> <Compound 295> <Compound 296>

<Compound 297> <Compound 298> <Compound 299>

<Compound 300> <Compound 301> <Compound 302>

<Compound 303> <Compound 304> <Compound 305>

<Compound 306> <Compound 307> <Compound 308>

<Compound 309> <Compound 310> <Compound 311>

<Compound 312> <Compound 313> <Compound 314>

<Compound 315> <Compound 316> <Compound 317>

<Compound 318> <Compound 319> <Compound 320>

<Compound 321> <Compound 322> <Compound 323>

<Compound 324> <Compound 325> <Compound 326>

In addition, in the present invention, the compound represented by [Chemical Formula D4] or [Chemical Formula D5] may be any one compound selected from [Compound 401] to [Compound 639], but is not limited thereto.

<Compound 401> <Compound 402> <Compound 403>

<Compound 404> <Compound 405> <Compound 406>

<화합물 407><화합물 408><화합물 409>

<Compound 407><Compound408><Compound409>

<Compound 410> <Compound 411> <Compound 412>

<화합물 413><화합물 414><화합물 415>

<Compound 413><Compound414><Compound415>

<Compound 416> <Compound 417> <Compound 418>

<Compound 419> <Compound 420> <Compound 421>

<Compound 422> <Compound 423> <Compound 424>

<Compound 425> <Compound 426> <Compound 427>

<Compound 428> <Compound 429> <Compound 430>

<화합물 431><화합물 432><화합물 433>

<Compound 431><Compound432><Compound433>

<Compound 434> <Compound 435> <Compound 436>

<Compound 437> <Compound 438> <Compound 439>

<화합물 440><화합물 441><화합물 442>

<Compound 440><Compound441><Compound442>

<화합물 443><화합물 444><화합물 445>

<Compound 443><Compound444><Compound445>

<Compound 446> <Compound 447> <Compound 448>

<화합물 449><화합물 450><화합물 451>

<Compound 449><Compound450><Compound451>

<Compound 452> <Compound 453> <Compound 454>

<Compound 455> <Compound 456> <Compound 457>

<화합물 458><화합물 459><화합물 460>

<Compound 458><Compound459><Compound460>

<Compound 461> <Compound 462> <Compound 463>

<Compound 464> <Compound 465> <Compound 466>

<화합물 467><화합물 468><화합물 469>

<Compound 467><Compound468><Compound469>

<Compound 470> <Compound 471> <Compound 472>

<Compound 473> <Compound 474> <Compound 475>

<Compound 476> <Compound 477> <Compound 478>

<Compound 479> <Compound 480> <Compound 481>

<Compound 482> <Compound 483> <Compound 484>

<Compound 485> <Compound 486> <Compound 487>

<화합물 488><화합물 489><화합물 490>

<Compound 488><Compound489><Compound490>

<화합물 491><화합물 492><화합물 493>

<Compound 491><Compound492><Compound493>

<Compound 494> <Compound 495> <Compound 496>

<Compound 497> <Compound 498> <Compound 499>

<Compound 500> <Compound 501> <Compound 502>

<Compound 503> <Compound 504> <Compound 505>

<Compound 506> <Compound 507> <Compound 508>

<Compound 509> <Compound 510> <Compound 511>

<Compound 512> <Compound 513> <Compound 514>

<Compound 515> <Compound 516> <Compound 517>

<Compound 518> <Compound 519> <Compound 520>

<Compound 521> <Compound 522> <Compound 523>

<Compound 524> <Compound 525> <Compound 526>

<Compound 527> <Compound 528> <Compound 529>

<Compound 530> <Compound 531> <Compound 532>

<Compound 533> <Compound 534> <Compound 535>

<Compound 536> <Compound 537> <Compound 538>

<Compound 539> <Compound 540> <Compound 541>

<Compound 542> <Compound 543> <Compound 544>

<Compound 545> <Compound 546> <Compound 547>

<Compound 548> <Compound 549> <Compound 550>

<Compound 551> <Compound 552> <Compound 553>

<Compound 554> <Compound 555> <Compound 556>

<Compound 557> <Compound 558> <Compound 559>

<Compound 560> <Compound 561> <Compound 562>

<Compound 563> <Compound 564> <Compound 565>

<Compound 566> <Compound 567> <Compound 568>

<Compound 569> <Compound 570> <Compound 571>

<Compound 572> <Compound 573> <Compound 574>

<Compound 575> <Compound 576> <Compound 577>

<Compound 578> <Compound 579> <Compound 580>

<Compound 581> <Compound 582> <Compound 583>

<Compound 584> <Compound 585> <Compound 586>

<Compound 587> <Compound 588> <Compound 589>

<Compound 590> <Compound 591> <Compound 592>

<Compound 593> <Compound 594> <Compound 595>

<Compound 596> <Compound 597> <Compound 598>

<Compound 599> <Compound 600> <Compound 601>

<Compound 602> <Compound 603> <Compound 604>

<Compound 605> <Compound 606> <Compound 607>

<Compound 608> <Compound 609> <Compound 610>

<Compound 611> <Compound 612> <Compound 613>

<Compound 614> <Compound 615> <Compound 616>

<Compound 617> <Compound 618> <Compound 619>

<Compound 620> <Compound 621> <Compound 622>

<Compound 623> <Compound 624> <Compound 625>

<Compound 626> <Compound 627> <Compound 628>

<Compound 629> <Compound 630> <Compound 631>

<Compound 632> <Compound 633> <Compound 634>

<Compound 635> <Compound 636> <Compound 637>

<Compound 638> <Compound 639>

As a more preferred embodiment of the present invention, in the organic light emitting device, the first electrode is an anode, the second electrode is a cathode, and in addition to the light emitting layer, the hole injection layer and the hole transport layer, the organic light emitting device has an electron blocking layer, an electron transport layer, And an electron injection layer, and may include a hole injection layer between the anode and the hole transport layer, and may sequentially include an electron transport layer and an electron injection layer between the light emitting layer and the cathode.

More preferably, the organic light emitting device of the present invention includes a hole transport layer and a light emitting layer between the first electrode and the second electrode, and the hole transport layer includes at least one amine compound represented by Formula A or Formula B. Includes; The light emitting layer may include at least one compound represented by any one of formulas D1 to D5 as a dopant material.

At this time, in the present invention, "(organic layer) includes one or more organic compounds" means, "(organic layer) one or more organic compounds belonging to the scope of the present invention or two or more different kinds of organic compounds. It may include a compound.

In addition, as a preferred embodiment of the present invention, the organic light emitting device may include an electron blocking layer between the hole transport layer and the light emitting layer.

In addition, in the present invention, one or more layers selected from the hole injection layer, the hole transport layer, the light emitting layer, the electron transport layer and the electron injection layer may be formed by a deposition process or a solution process. Here, the deposition process means a method of forming a thin film by evaporating a material used as a material for forming the respective layers through heating or the like in a vacuum or a low pressure state, and the solution process forms the respective layers. It means a method of mixing a material used as a material for a solvent with a solvent and forming a thin film through methods such as inkjet printing, roll-to-roll coating, screen printing, spray coating, dip coating, spin coating, and the like.

In addition, the organic light emitting device in the present invention includes a flat panel display device; Flexible display devices; A monochromatic or white flat panel lighting device; And a monochromatic or white flexible lighting device.

In the present invention, as the material of the hole transport layer, other compounds other than the amine compound represented by Formula A or Formula B of the present invention may be used, and an electron donor molecule having a small ionization potential is usually used, mainly triphenylamine. Diamine, triamine, or tetraamine derivatives serving as the basic skeleton are often used. For example, N,N'-bis(3-methylphenyl)-N,N'-diphenyl-[1,1-biphenyl]- 4,4'-diamine (TPD) or N,N'-di(naphthalen-1-yl)-N,N'-diphenylbenzidine (a-NPD) or the like can be additionally used.

A hole injection layer (HIL, Hole Injecting Layer) may be additionally stacked on the lower portion of the hole transport layer, and the hole injection layer material is also used in the art in addition to the compound having an amine group represented by Formula A or Formula B of the present invention. As long as it is commonly used, it can be used without particular limitation, for example, CuPc (copperphthalocyanine) or starburst amines TCTA(4,4',4"-tri(N-carbazolyl)triphenyl-amine), m -MTDATA(4,4',4"-tris-(3-methylphenylphenyl amino)triphenylamine) may be additionally used.

Meanwhile, the host used for the light emitting layer in the present invention may include one or more compounds represented by the following [Formula H], and various other known dopant materials may be used.

[Formula H]

In the above [Formula H],

X ₁ to X ₁₀ are the same as or different from each other, and each independently a hydrogen atom, a deuterium atom, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, substituted or unsubstituted A cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted cycloalkenyl group having 5 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, Substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, substituted or unsubstituted arylthiooxy group having 5 to 30 carbon atoms, substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, substituted or unsubstituted 5 to 5 carbon atoms 30 arylamine group, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 50 carbon atoms having O, N or S, a substituted or unsubstituted silicon group, A substituted or unsubstituted boron group, a substituted or unsubstituted silane group, a carbonyl group, a phosphoryl group, an amino group, a nitrile group, a hydroxy group, a nitro group, a halogen group, an amide group and an ester group, and Adjacent groups can form condensed rings of aliphatic, aromatic, aliphatic heteroaromatics.

More specifically, the host may be represented by any one selected from the group represented by the following [Compound 701] to [Compound 896], but is not limited thereto.

[Compound 701] [Compound 702] [Compound 703] [Compound 704]

[Compound 705] [Compound 706] [Compound 707] [Compound 708]

[Compound 709] [Compound 710] [Compound 711] [Compound 712]

[Compound 713] [Compound 714] [Compound 715] [Compound 716]

[Compound 717] [Compound 718] [Compound 719] [Compound 720]

[Compound 721] [Compound 722] [Compound 723] [Compound 724]

[Compound 725] [Compound 726] [Compound 727] [Compound 728]

[Compound 729] [Compound 730] [Compound 731] [Compound 732]

[Compound 733] [Compound 734] [Compound 735] [Compound 736]

[Compound 737] [Compound 738] [Compound 739] [Compound 740]

[Compound 741] [Compound 742] [Compound 743] [Compound 744]

[Compound 745] [Compound 746] [Compound 747] [Compound 748]

[Compound 749] [Compound 750] [Compound 751] [Compound 752]

[Compound 753] [Compound 754] [Compound 755] [Compound 756]

[Compound 757] [Compound 758] [Compound 759] [Compound 760]

[Compound 761] [Compound 762] [Compound 763] [Compound 764]

[Compound 765] [Compound 766] [Compound 767] [Compound 768]

[Compound 769] [Compound 770] [Compound 771] [Compound 772]

[Compound 773] [Compound 774] [Compound 775] [Compound 776]

[Compound 777] [Compound 778] [Compound 779] [Compound 780]

[Compound 781] [Compound 782] [Compound 783] [Compound 784]

[Compound 785] [Compound 786] [Compound 787] [Compound 788]

[Compound 789] [Compound 790] [Compound 791] [Compound 792]

[Compound 793] [Compound 794] [Compound 795] [Compound 796]

[Compound 797] [Compound 798] [Compound 799] [Compound 800]

[Compound 801] [Compound 802] [Compound 803] [Compound 804]

[Compound 805] [Compound 806] [Compound 807] [Compound 808]

[Compound 809] [Compound 810] [Compound 811] [Compound 812]

[Compound 813] [Compound 814] [Compound 815] [Compound 816]

[Compound 817] [Compound 818] [Compound 819] [Compound 820]

[Compound 821] [Compound 822] [Compound 823] [Compound 824]

[Compound 825] [Compound 826] [Compound 827] [Compound 828]

[Compound 829] [Compound 830] [Compound 831] [Compound 832]

[Compound 833] [Compound 834] [Compound 835] [Compound 836]

[Compound 837] [Compound 838] [Compound 839] [Compound 840]

[Compound 841] [Compound 842] [Compound 843] [Compound 844]

[Compound 845] [Compound 846] [Compound 847] [Compound 848]

[Compound 849] [Compound 850] [Compound 851] [Compound 852]

[Compound 853] [Compound 854] [Compound 855] [Compound 856]

[Compound 857] [Compound 858] [Compound 859] [Compound 860]

[Compound 861] [Compound 862] [Compound 863] [Compound 864]

[Compound 865] [Compound 866] [Compound 867] [Compound 868]

[Compound 869] [Compound 870] [Compound 871] [Compound 872]

[Compound 873] [Compound 874] [Compound 875] [Compound 876]

[Compound 877] [Compound 878] [Compound 879] [Compound 880]

[Compound 881] [Compound 882] [Compound 883] [Compound 884]

[Compound 885] [Compound 886] [Compound 887] [Compound 888]

[Compound 889] [Compound 890] [Compound 891] [Compound 892]

[Compound 893] [Compound 894] [Compound 895] [Compound 896]

In addition, the light emitting layer may further include various host and various dopant materials in addition to the dopant and host.

On the other hand, when the light emitting layer according to the present invention includes a host and a dopant, the content of the dopant may be generally selected from about 0.01 to about 20 parts by weight based on about 100 parts by weight of the host, but is not limited thereto. .

Meanwhile, in the present invention, as the electron transport layer material, a known electron transport material may be used as a function of stably transporting electrons injected from the electron injection electrode (Cathode). Examples of known electron transport materials include quinoline derivatives, in particular tris(8-quinolinolate) aluminum (Alq3), Liq, TAZ, BAlq, beryllium bis (benzoquinolin-10-noate) (beryllium bis (benzoquinolin- 10-olate: Bebq2), compound 901, compound 902, BCP, oxadiazole derivatives such as PBD, BMD, BND, or the like may be used, but is not limited thereto.

TAZ BAlq

<Compound 901> <Compound 902> BCP

Further, in the electron transport layer used in the present invention, the organometallic compound represented by the following formula F may be used alone or in combination with the electron transport layer material.

[Formula F]

In the above [Formula F],

Y is a portion selected from C, N, O, and S directly bonded to M to form a single bond, and a portion selected from C, N, O, and S forming a coordination bond to M. And a ligand chelated by the single bond and coordination bond; The M is an alkali metal, alkaline earth metal, aluminum (Al) or boron (B) atom, the OA is a monovalent ligand capable of single bond or coordination with the M,

O is oxygen,

A is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted 2 to 20 carbon atoms Alkynyl group, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted cycloalkenyl group having 5 to 30 carbon atoms and a substituted or unsubstituted hetero 2 to 50 carbon atom having O, N or S Any one selected from aryl groups,

When M is one metal selected from alkali metals, m=1, n=0,

When M is one metal selected from alkaline earth metals, m=1, n=1, or m=2, n=0,

When M is boron or aluminum, m is any one of 1 to 3, and n is one of 0 to 2, and m + n = 3 is satisfied.

In the present invention, Y is the same or different, and may be any one selected from the following [Structural C1] to [Structural C39] independently of each other, but is not limited thereto.

[Structural Formula C1] [Structural Formula C2] [Structural Formula C3]

[Structural C4] [Structural C5] [Structural C6]

[Structural C7] [Structural C8] [Structural C9] [Structural C10]

[Structural C11] [Structural C12] [Structural C13]

[Structural Formula C14] [Structural Formula C15] [Structural Formula C16]

[Structural C17] [Structural C18] [Structural C19] [Structural C20]

[Structural C21] [Structural C22] [Structural C23]

[Structural C24] [Structural C25] [Structural C26]

[Structural C27] [Structural C28] [Structural C29] [Structural C30]

[Structural C31] [Structural C32] [Structural C33]

[Structural C34] [Structural C35] [Structural C36]

[Structural C37] [Structural C38] [Structural C39]

In the above [Structural Formula C1] to [Structural Formula C39],

R is the same or different from each other, and each independently hydrogen, deuterium, halogen, cyano group, substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, substituted or unsubstituted aryl group having 6 to 30 carbon atoms, substituted or unsubstituted Heteroaryl group having 3 to 30 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, substituted or Unsubstituted alkylamino group having 1 to 30 carbon atoms, substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, and substituted or unsubstituted arylsilyl having 6 to 30 carbon atoms. It is selected from groups, and may be connected to an adjacent substituent by alkylene or alkenylene to form a spiro ring or fused ring. However,'substituted' in the'substituted or unsubstituted' is deuterium, cyano group, halogen group, hydroxy group, nitro group, alkyl group, alkoxy group, alkylamino group, arylamino group, hetero arylamino group, alkylsilyl group, aryl It means substituted with one or more substituents selected from the group consisting of silyl group, aryloxy group, aryl group, heteroaryl group, germanium, phosphorus and boron.

On the other hand, an electron injection layer (EIL, Electron Injecting Layer), which facilitates the injection of electrons from the cathode and ultimately improves power efficiency, may be further stacked on the electron transport layer. It can also be used without particular limitation as long as it is commonly used in the art, for example, LiF, NaCl, CsF, Li ₂ O, BaO and the like can be used.

The electron injection layer may have a thickness of about 1 mm 2 to about 100 mm 2, and about 3 mm 2 to about 90 mm 2. When the thickness of the electron injection layer satisfies the above-described range, satisfactory electron injection characteristics can be obtained without a substantial increase in driving voltage.

Hereinafter, a method of manufacturing the organic light emitting device of the present invention will be described with reference to FIG. 1.

1 is a cross-sectional view showing the structure of an organic light-emitting device of the present invention. The organic light emitting device according to the present invention includes an anode 20, a hole transport layer 40, an organic light emitting layer 50, an electron transport layer 60 and a cathode 80, and a hole injection layer 30 and electrons as necessary The injection layer 70 may be further included, and it is also possible to further form an intermediate layer of one layer or two layers.

Looking at the manufacturing method of the organic light emitting device according to the present invention with reference to FIG.

First, an anode 20 is formed by coating a material for an anode electrode on the substrate 10. Here, as the substrate 10, a substrate used in a conventional organic EL device is used, but an organic substrate or a transparent plastic substrate having excellent transparency, surface smoothness, handling ease, and waterproofness is preferable. In addition, as the material for the anode electrode, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO ₂ ), and zinc oxide (ZnO), which are transparent and excellent in conductivity, are used.

A hole injection layer 30 is formed by vacuum thermal vapor deposition or spin coating a hole injection layer material on the anode 20 electrode. Next, a hole transport layer 40 is formed by vacuum thermal evaporation or spin coating of a hole transport layer material on the hole injection layer 30.

Subsequently, an electron blocking layer is selectively formed as necessary between the hole transport layer and the light emitting layer 50 to be formed thereafter, and then, an organic light emitting layer 50 is stacked on the hole transport layer 40, and the organic light emitting layer Optionally, a hole blocking layer (not shown) may be formed on the upper portion of the 50 as a vacuum deposition method or a spin coating method to form a thin film. The hole blocking layer is a hole When flowing through the organic light emitting layer and flowing into the cathode, the life and efficiency of the device are reduced, and thus, this problem is prevented by using a material having a very low level of HOMO (Highest Occupied Molecular Orbital). At this time, the hole-blocking material used is not particularly limited, but has an electron transporting ability and has a higher ionization potential than the light emitting compound, and typically BAlq, BCP, TPBI, etc. can be used.

After the electron transport layer 60 is deposited on the hole blocking layer through a vacuum deposition method or a spin coating method, an electron injection layer 70 is formed and a metal for forming a cathode is vacuum-coated on the electron injection layer 70. The organic EL device is completed by depositing to form the cathode 80 electrode. Here, the metal for forming the negative electrode is lithium (Li), magnesium (Mg), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver ( Mg-Ag) and the like, and a transmissive cathode using ITO and IZO may be used to obtain a front light emitting device.

Hereinafter, the present invention will be described in more detail with reference to preferred embodiments. However, these examples are intended to illustrate the present invention in more detail, it will be apparent to those skilled in the art that the scope of the present invention is not limited thereby.

(Example)

Preparation example of hole transport layer compound

Synthesis Example 1: Synthesis of Formula 13

Synthesis Example 1-(1): Synthesis of [Intermediate 1-a]

[Intermediate 1-a]

In a 500 mL round-bottom flask methyl 2-iodobenzoate (19.1 g, 73 mmol), 4-dibenzofuranboronic acid (18.7 g, 88 mmol), tetrakis(triphenylphosphine)palladium (1.7 g, 0.15 mmol), potassium carbonate (20.2 g, 146.7 mmol) was added, and 125 mL of toluene, 125 mL of tetrahydrofuran, and 50 mL of water were added. The temperature of the reactor was raised to 80° C. and stirred for 10 hours. When the reaction was completed, the temperature of the reactor was lowered to room temperature, extracted with ethyl acetate, and the organic layer was separated. The organic layer was concentrated under reduced pressure and separated by column chromatography to obtain [Intermediate 1-a]. (9.5 g, 43%)

Synthesis Example 1-(2): Synthesis of [Intermediate 1-b]

[Intermediate 1-b]

In a 2 L round-bottom flask, bromobenzene (13.2 g, 83.97 mmol) and tetrahydrofuran 250 ml were added and stirred in a low-temperature nitrogen environment. About 58 ml of n-butyl lithium was slowly added dropwise over 2 hours at -78°C, and [Intermediate 1-a] (9.4 g 31.1 mmol) was added. After completion of the reaction, 100 ml of water was added, stirred for 30 minutes, and then extracted to obtain [Intermediate 1-b]. (3.2 g, 24%)

Synthesis Example 1-(3): Synthesis of [Intermediate 1-c]

[Intermediate 1-c]

[Intermediate 1-b] (55.0 g, 129 mmol), 500 ml of acetic acid and 10 ml of sulfuric acid were added to a 2 L round-bottom flask and stirred at reflux for 5 hours. After the reaction was completed, it was cooled to room temperature, and the resulting solid was filtered. After washing with methanol, [Intermediate 1-c] was obtained. (50 g, 95%)

Synthesis Example 1-(4): Synthesis of [Intermediate 1-d]

[Intermediate 1-d]

In a 2 L round-bottom flask [Intermediate 1-c] (50 g, 122 mmol), dichloromethane 600 ml was added and stirred at room temperature. Bromine (13.7 ml, 85 mmol) was diluted with 50 ml of dichloromethane and added dropwise, followed by stirring for about 3 hours. Recrystallization with methanol gave [Intermediate 1-d]. (45 g, 76%)

Synthesis Example 1-(5): Synthesis of [Formula 13]

[Formula 13]

In a 250 ml round bottom flask [Intermediate 1-d] (4.3 g, 0.009 mol), bis-biphenyl-4-yl-amine (4.3 g, 0.013 mol), palladium(II) acetate (0.08 g, 0.4 mmol) , Sodium tertiary butoxide (3.4 g, 0.035 mol), triteryl butylphosphine (0.07 g, 0.4 mmol), and 60 ml of toluene were added and stirred at reflux for 2 hours. After the reaction was completed, it was cooled to room temperature. The reaction solution was extracted with dichloromethane and water. The organic layer was separated, anhydrous treated with magnesium sulfate, and concentrated under reduced pressure. After separation by column chromatography, recrystallization with dichloromethane and acetone gave [Formula 13]. (2.6 g, 40%)

MS (MALDI-TOF): m/z 727.29 [M ⁺ ]

Synthesis Example 2: Synthesis of Formula 40

Synthesis Example 2-(1): Synthesis of [Intermediate 2-a]

[Intermediate 2-a]

In a 1 L round-bottom flask, add 4-dibenzofuranboronic acid (85.0 g, 0.401 mol), bismuth(III) nitrate pentahydrate (99.2 g, 0.20 mol), toluene 400 ml, and in a nitrogen atmosphere at 70°C for 3 hours It was stirred. After completion of the reaction, the mixture was cooled to room temperature, and the resulting solid was filtered. After washing with toluene, [Intermediate 2-a] (61.5 g, 72%) was obtained.

Synthesis Example 2-(2): Synthesis of [Intermediate 2-b]

[Intermediate 2-b]

Ethyl cyanoacetate (202.9 g, 1.794 mol) and 500 ml of dimethylformamide were added to a 2 L round-bottom flask. Potassium hydroxide (67.10 g, 1.196 mol) and potassium cyanide (38.95 g, 0.598 mol) were added, 200 ml of dimethylformamide was added, and the mixture was stirred at room temperature. [Intermediate 2-a] (127.5 g, 0.737 mol) was added little by little to the reaction solution, followed by stirring at 50°C for 72 hours. After completion of the reaction, 200 ml of aqueous sodium hydroxide solution (25%) was added and stirred under reflux. After stirring for 3 hours, the mixture was cooled to room temperature, and extracted with ether acetate and water. The organic layer was separated, concentrated under reduced pressure, and separated by column chromatography to obtain [Intermediate 2-b] (20.0 g, 16%).

Synthesis Example 2-(3): Synthesis of [Intermediate 2-c]

[Intermediate 2-c]

In a 2 L round-bottom flask, [Intermediate 2-b] (20.0 g, 0.096 mol), ethanol 600 ml, and potassium hydroxide aqueous solution (142.26 g, 2.53 mol) were added and stirred at reflux for 12 hours. When the reaction was completed, it was cooled to room temperature. 400 ml of 6 N-hydrochloric acid was added to the reaction solution, acidified, and the resulting solid was stirred for 20 minutes and then filtered. After washing with ethanol, [Intermediate 2-c] (17.0 g, 88.5%) was obtained.

Synthesis Example 2-(4): Synthesis of [Intermediate 2-d]

[Intermediate 2-d]

[Intermediate 2-c] (17.0 g, 0.075 mol) and 15 ml of sulfuric acid were added to a 2 L round-bottom flask and refluxed for 72 hours. After the reaction was completed, the mixture was cooled to room temperature, and extracted with ethyl acetate and water. The organic layer was separated and washed with an aqueous sodium hydrogen carbonate solution. The organic layer was concentrated under reduced pressure, and methanol was added in excess, and the resulting solid was filtered to obtain [Intermediate 2??d] (14.0 g, 77.6%).

Synthesis Example 2-(5): Synthesis of [Intermediate 2-e]

[Intermediate 2-e]

In a 500 mL round-bottom flask, [Intermediate 2-d] (14.0 g, 0.058 mol), hydrochloric acid 20 ml and water 100 ml were added and cooled to 0° C. and stirred for 1 hour. At the same temperature, 50 ml of sodium nitrite (7.4 g, 0.116 mol) aqueous solution was added dropwise to the reaction solution, followed by stirring for 1 hour. When 100 ml of potassium iodide (30.0 g, 0.180 mol) aqueous solution was added dropwise, the temperature of the reaction solution was added dropwise while not exceeding 5°C. The mixture was stirred at room temperature for 5 hours, and after the reaction was completed, it was washed with an aqueous sodium cysulfate solution, and then extracted with ethyl acetate and water. The organic layer was concentrated under reduced pressure, and separated by column chromatography to obtain [Intermediate 2-e] (9.1 g, 48%).

Synthesis Example 2-(6): Synthesis of [Intermediate 2-f]

[Intermediate 2-f]

In a 250 mL round-bottom flask methyl5-bromo-2-iodobenzoate (9.3 g, 25 mmol), 4-dibenzoboronic acid (8.3 g, 28 mmol), tetrakis(triphenylphosphine)palladium ( 0.6 g, 0.05 mmol), potassium carbonate (6.7 g, 50 mmol) was added, 50 mL of toluene, 50 mL of tetrahydrofuran, and 20 mL of water were added. The temperature of the reactor was raised to 80° C. and stirred for 10 hours. When the reaction was completed, the temperature of the reactor was lowered to room temperature, extracted with ethyl acetate, and the organic layer was separated. The organic layer was concentrated under reduced pressure and separated by column chromatography to obtain [Intermediate 2-f] (5.3 g, 52.3%).

Synthesis Example 2-(7): Synthesis of [Intermediate 2-g]

[Intermediate 2-g]

In a 500 ml round bottom flask, bromobenzene (25.5 g, 0.163 mol) and tetrahydrofuran 170 ml were added and cooled to -78°C in a nitrogen atmosphere. To the reaction solution, n-butyllithium (1.6 M) (95.6 ml, 0.153 mol) was added dropwise. After stirring at the same temperature for 1 hour, [Intermediate 2-f] (20.0 g, 0.051 mol) was added, followed by stirring at room temperature for 3 hours. After the reaction was completed, 50 ml of water was added and stirred for 30 minutes. After extraction with ethyl acetate and water, the organic layer was separated and concentrated under reduced pressure. 200 ml of acetic acid and 1 ml of hydrochloric acid were added to the concentrated material, and the mixture was heated to 80° C. and stirred. After the reaction was completed, it was cooled to room temperature and the resulting solid was filtered. After washing with methanol, [Intermediate 2-g] (20.0 g, 78%) was obtained.

Synthesis Example 2-(8): Synthesis of [Intermediate 2-h]

[Intermediate 2-h]

[Intermediate 2-h] (20.0 g, 0.04 mol) was used instead of [Intermediate 1-c] in Synthesis Example 1-(4) to obtain [Intermediate 2-h] (13.1 g, 50%) in the same manner. .

Synthesis Example 2-(9): Synthesis of [Formula 40]

[Formula 40]

In the above Synthesis Example 1-(5), [Intermediate 2-h] was used instead of [Intermediate 1-d], and bis(4-tertiarybutylphenyl)amine was used instead of Bis-biphenyl-4-yl-amine. It was synthesized in the same manner except for [Formula 40]. (Yield 45%)

MS (MALDI-TOF): m/z 777.36 [M ⁺ ]

Synthesis Example 3: Synthesis of Formula 75

Synthesis Example 3-(1): Synthesis of [Intermediate 3-a]

[Intermediate 3-a]

After adding 25 g (80 mmol) of [Intermediate 1-a] to a round-bottom flask containing 250 ml of tetrahydrofuran, the temperature was lowered to -78 °C under nitrogen. After 30 minutes, 210 ml (240 mmol) of 1.0 M methyl magnesium bromide was slowly added dropwise. After dropping slowly after 1 hour, the temperature is raised to room temperature. After stirring at room temperature for about 2 hours, an aqueous ammonium chloride solution is added dropwise. After extraction, distillation under reduced pressure, and recrystallization with nucleic acids, 19.4 g of [Intermediate 3-a] was obtained (80% yield).

Synthesis Example 3-(2): Synthesis of [Intermediate 3-b]

[Intermediate 3-b]

20 g (66 mmol) of [Intermediate 3-a] was added to a round-bottom flask containing 300 ml of acetic acid and stirred at 0°C for 10 minutes. Add 350 mL of phosphoric acid and stir at room temperature for about 1 hour. After extraction by neutralization with aqueous sodium hydroxide solution, it is concentrated under reduced pressure. Separation by column chromatography gave [Intermediate 3-b] 13.7 g (yield 73%).

Synthesis Example 3-(3): Synthesis of [Intermediate 3-c]

[Intermediate 3-c]

[Intermediate 3-c] was obtained in the same manner using [Intermediate 3-b] instead of [Intermediate 1-c] used in Synthesis Example 1-(4). (Yield 45%)

Synthesis Example 3-(4): Synthesis of [Intermediate 3-d]

[Intermediate 3-d]

In a 500 ml round-bottom flask, 4-tertiarythylaniline (32.1 g, 215 mmol), 4-bromobiphenyl (50.1 g, 215 mmol), bis-dibenzylideneacetone dipalladium (3.9 g, 4 mmol), 2 ,2'-bis(diphenylphosphine)-1,1'-binaphthyl (1.2 g, 4 mmol), sodium tertiary butoxide (41.3 g, 43 mmol), toluene 200 ml was added and refluxed. After cooling to room temperature, washed with methanol and recrystallized from dichloromethane and methane to obtain [Intermediate 3-d]. (50.5 g, 78%)

Synthesis Example 3-(5): Synthesis of [Formula 75]

[Formula 75]

[Intermediate 3-c] was used instead of [Intermediate 1-d] used in Synthesis Example 1-(5), and [Intermediate 3-d] was used instead of bis-biphenyl-4-yl-amine. [Formula 75] was obtained. (Yield 67%)

MS (MALDI-TOF): m/z 583.29 [M ⁺ ]

Preparation example of dopant compound

Synthesis Example 4: Synthesis of Compound 169

Synthesis Example 4-(1): Synthesis of [Intermediate 4-a]

[Intermediate 4-a]

1-bromo-4-(trimethylsilyl)benzene (11.4 g, 0.050 mol), 2,6-dimethylaniline (6.2 g, 0.050 mol), palladium acetate (0.22 g, 1 mmol), 2,2'-bis (Diphenylphosphino)-1-1'-binaphthyl (1.3 g, 2 mmol), sodium utter review toxin (12.2 g, 0.120 mol) was added to 100 mL of toluene and refluxed for 12 hours. After cooling to room temperature, extraction was performed with ethyl acetate, followed by separation by column chromatography to obtain [Intermediate 4-a] (10.5 g, 78%).

Synthesis Example 4-(2): Synthesis of [Compound 169]

[Compound 169]

1,6-dibromopyrene (4 g, 0.011 mol), [Intermediate 4-a] (6.7 g, 0.025 mol), sodium tertivaloxide (5.3 g, 0.055 mol), palladium acetate (0.1 g, 0.44 mmol), tritertyl phosphine (0.36 g, 1.7 mmol) was added to 50 mL of toluene and refluxed for 24 hours. After lowering the temperature to room temperature, the mixture was extracted with ethyl acetate and separated by column chromatography to obtain [Compound 169] (5.7 g, 70%).

MS (MALDI-TOF): m/z 736.37 [M ⁺ ]

Synthesis Example 5: Synthesis of Compound 203

Synthesis Example 5-(1): Synthesis of [Compound 203]

[Compound 203]

In a round bottom flask 5,9-dibromo-7,7-dimethyl-7H-benzofluorene 10.7 g (26.7 mmol), 4-(phenylamino)benzonitrile 5.2 g (26.7 mmol), BINAP 0.7 g ( 1 mmol), disdibenzylidene acetone dipalladium 0.4 g (0.7 mmol), sodium utter review oxide 6.5 g (66.9 mmol), and 100 ml of toluene were added under nitrogen and refluxed for 12 hours. After completion of the reaction, the layers were separated, the organic layer was concentrated under reduced pressure, and separated by column chromatography to obtain [Compound 203] 12.9 g. (Yield 77%)

MS (MALDI-TOF): m/z 628.26 [M] ⁺

Synthesis Example 6: Synthesis of Compound 226

Synthesis Example 6-1. Synthesis of [Intermediate 6-a]

[Intermediate 6-a]

In a round-bottom flask, methyl 2-bromobenzoate 24 g (112 mmol), 9-phenanthrenboronic acid 34.7 g (0.156 mmol), tetrakistriphenylphosphine palladium 2.6 g (2 mmol), potassium carbonate 30.9 g ( 223 mmol), 50 mL of water, 125 mL of toluene and 125 mL of tetrahydrofuran were added and refluxed for 12 hours. After completion of the reaction, the reaction mixture was separated and the organic layer was concentrated under reduced pressure, and then separated by column chromatography to obtain [Intermediate 6-a] 25 g (yield 72%).

Synthesis Example 6-2. Synthesis of [Intermediate 6-b]

[Intermediate 6-b]

After adding 25 g (80 mmol) of [Intermediate 6-a] to a round-bottom flask containing 250 ml of tetrahydrofuran, lower the temperature to -78 °C under nitrogen. After 30 minutes, 210 ml (240 mmol) of 1.0 M methyl magnesium bromide was slowly added dropwise. After dropping slowly after 1 hour, the temperature is raised to room temperature. After stirring at room temperature for about 2 hours, an aqueous ammonium chloride solution is added dropwise. After extraction, distillation under reduced pressure, and recrystallization with nucleic acid, [Intermediate 6-b] 27 g (yield 82%) was obtained.

Synthesis Example 6-3. Synthesis of [Intermediate 6-c]

[Intermediate 6-c]

29 g (66 mmol) of [Intermediate 6-b] is added to a round bottom flask containing 290 ml of acetic acid. After raising the temperature to 80 ℃, add 1-2 drops of hydrochloric acid aqueous solution to the reaction solution. The reaction solution was refluxed for about 2 hours, the temperature was lowered to room temperature, and the produced solid was filtered to obtain 26 g (Intermediate 6-c) (yield 93%).

Synthesis Example 6-4. Synthesis of [Intermediate 6-d]

[Intermediate 6-d]

[Intermediate 6-c] (16.2 g, 0.055 mol) was added to 250 mL of dimethylformamide and stirred at 0°C. N-bromosuccinimide (21.5 g, 0.121 mol) was dissolved in 70 mL of dimethylformamide dropwise and stirred for 6 hours. The distilled water was filtered and washed with hexane. It was dissolved in dichloromethane, heated, and treated with acidic clay and activated carbon. Washed with dichloromethane and recrystallized from hexane to obtain 19.1 g of [Intermediate 6-d]. (Yield 77%)

Synthesis Example 6-5. Synthesis of [Compound 226]

[Intermediate 6-d] is used instead of 5,9-dibromo-7,7-dimethyl-7H-benzofluorene used in Synthesis Example 5-1, and N-phenyl is used instead of 4-(phenylamino)benzonitrile. It was synthesized by the same method except that -1-naphthylamine was used to obtain [Compound 226]. (Yield 70%)

MS (MALDI-TOF): m/z 728.32 [M] ⁺

Synthesis Example 7: Synthesis of Compound 264

Synthesis Example 7-1. Synthesis of [Intermediate 7-a]

[Intermediate 7-a]

1-(2-bromophenyl)naphthalene (3.5 g, 12.2 mmol) was added to 50 mL of tetrahydrofuran, n-butyllithium (5.8 mL, 14.6 mmol) was added dropwise at -78°C, and then stirred for about 1 hour. . A solution of 9-xanthone (2.1 g, 10.8 mmol) dissolved in 10 mL of tetrahydrofuran was slowly added dropwise at the same temperature, stirred for 2 hours, and then stirred at room temperature for 12 hours. After extraction with ethyl acetate, recrystallization with diethyl ether gave [Intermediate 7-a] 3.2 g (yield 75%).

Synthesis Example 7-2. Synthesis of [Intermediate 7-b]

[Intermediate 7-b]

[Intermediate 7-a] (26.5 g, 66.3 mmol) was added to 300 mL of acetic acid, the mixture was raised to 80° C., and 1 to 2 rooms of aqueous hydrochloric acid solution were added and refluxed for about 2 hours. After lowering the temperature to room temperature, it was filtered to obtain 22.8 g of [Intermediate 7-b] (yield 90%).

Synthesis Example 7-3. Synthesis of [Intermediate 7-c]

[Intermediate 7-c]

[Intermediate 7-b] (21 g, 0.055 mol) was added to 250 mL of dimethylformamide and stirred at 0°C. N-bromosuccinimide (21.5 g, 0.121 mol) was dissolved in 70 mL of dimethylformamide dropwise and stirred for 6 hours. The distilled water was filtered and washed with hexane. It was dissolved in dichloromethane, heated, and treated with acidic clay and activated carbon. Washed with dichloromethane and recrystallized from hexane to obtain 17.8 g of [Intermediate 7-c] (yield 60%).

Synthesis Example 7-4. Synthesis of [Compound 264]

[Intermediate 7-c] was used instead of 5,9-dibromo-7,7-dimethyl-7H-benzofluorene used in Synthesis Example 5-1, and N-phenyl was substituted for 4-(phenylamino)benzonitrile. It was synthesized by the same method except that -4-biphenylamine was used to obtain [Compound 264]. (Yield 70%)

MS (MALDI-TOF): m/z 868.35 [M] ⁺

Synthesis Example 8: Synthesis of Compound 281

Synthesis Example 8-1. Synthesis of [Intermediate 8-a]

[Intermediate 8-a]

9-Phenanthreneboronic acid (16.4 g, 0.073 mol), 1-bromo-2-iodobenzene (17.3 g, 0.061 mol), tetrakis(triphenylphosphine)palladium (3.62 g, 0.003 mol), carbonic acid Potassium (16.9 g, 0.122 mol) was added to 150 mL of 1,4-dioxane, 150 mL of toluene and 60 mL of distilled water and refluxed for 12 hours. After cooling to room temperature and extracting with ethyl acetate, it was separated by column chromatography to obtain [Intermediate 8-a] 16.7 g (yield 82%).

Synthesis Example 8-2. Synthesis of [Intermediate 8-b]

[Intermediate 8-b]

[Intermediate 8-b] was synthesized in the same manner as in Synthesis Examples 7-1 to 7-3 using [Intermediate 8-a] instead of 1-(2-bromophenyl)naphthalene used in Synthesis Example 7-1 to obtain [Intermediate 8-b]. . (Yield 52%)

Synthesis Example 8-3. Synthesis of [Compound 281]

[Intermediate 8-b] was used instead of 5,9-dibromo-7,7-dimethyl-7H-benzofluorene used in Synthesis Example 5-1, and 4-toucher was used instead of 4-(phenylamino)benzonitrile. Synthesis was performed in the same manner as that of using reviewsyldiphenylamine to obtain [Compound 281]. (Yield 70%)

MS (MALDI-TOF): m/z 878.42 [M] ⁺

Synthesis Example 9: Synthesis of Compound 498

Synthesis Example 9-(1): Synthesis of [Intermediate 9-a]

[Intermediate 9-a]

In a 1 L round-bottom flask, 4-dibenzofuranboronic acid (85.0 g, 0.401 mol), bismuth(III) nitrate pentahydrate (99.2 g, 0.200 mol), and 400 ml of toluene were added and stirred at 70°C for 3 hours. After completion of the reaction, the mixture was cooled to room temperature, and the resulting solid was filtered. After washing with toluene, [Intermediate 9-a] (61.5 g, 72%) was obtained.

Synthesis Example 9-(2): Synthesis of [Intermediate 9-b]

[Intermediate 9-b]

Ethyl cyanoacetate (202.9 g, 1.794 mol) and 500 ml of dimethylformamide were placed in a 2L round-bottom flask. Potassium hydroxide (67.1 g, 1.196 mol) and potassium cyanide (38.95 g, 0.598 mol) were added, 200 ml of dimethylformamide was added, and the mixture was stirred at room temperature. [Intermediate 9-a] (127.5 g, 0.737 mol) was added to the reaction solution little by little, followed by stirring at 50°C for 72 hours. After completion of the reaction, 200 ml of aqueous sodium hydroxide solution (25%) was added and stirred under reflux. After stirring for 3 hours, the mixture was cooled to room temperature, and extracted with ether acetate and water. The organic layer was separated, concentrated under reduced pressure, and separated by column chromatography to obtain [Intermediate 9-b] (20.0 g, 16%).

Synthesis Example 9-(3): Synthesis of [Intermediate 9-c]

[Intermediate 9-c]

In a 2 L round-bottom flask, [Intermediate 9-b] (20.0 g, 0.096 mol), ethanol 600 ml, and potassium hydroxide aqueous solution (142.26 g, 2.53 mol) were added and stirred at reflux for 12 hours. When the reaction was completed, it was cooled to room temperature. 400 ml of 6 N hydrochloric acid was added to the reaction solution, acidified, and the resulting solid was stirred for 20 minutes and filtered. The solid was washed with ethanol to obtain [Intermediate 9-c] (17.0 g, 88.5%).

Synthesis Example 9-(4): Synthesis of [Intermediate 9-d]

[Intermediate 9-d]

In a 2 L round-bottom flask, [Intermediate 9-c] (17.0 g, 0.075 mol) and 15 ml of sulfuric acid were added and stirred under reflux for 72 hours. After the reaction was completed, the mixture was cooled to room temperature, and extracted with ethyl acetate and water. The organic layer was separated and washed with an aqueous sodium hydrogen carbonate solution. The organic layer was added with an excess of methanol during concentration under reduced pressure, and the resulting solid was filtered to obtain [Intermediate 9-d] (14.0 g, 77.6%).

Synthesis Example 9-(5): Synthesis of [Intermediate 9-e]

[Intermediate 9-e]

In a 500 mL round-bottom flask, [Intermediate 9-d] (14.0 g, 0.058 mol), hydrochloric acid 20 ml and water 100 ml were added, cooled to 0° C., and stirred for 1 hour. At the same temperature, 50 ml of sodium nitrite (7.4 g, 0.116 mol) aqueous solution was added dropwise to the reaction solution, followed by stirring for 1 hour. When 100 ml of potassium iodide (30.0 g, 0.180 mol) aqueous solution was added dropwise, the temperature of the reaction solution was added dropwise while not exceeding 5°C. The mixture was stirred at room temperature for 5 hours, and after the reaction was completed, it was washed with an aqueous sodium cysulfate solution, and then extracted with ethyl acetate and water. The organic layer was concentrated under reduced pressure and separated by column chromatography to obtain [Intermediate 9-e] (9.1 g, 48%).

Synthesis Example 9-(6): Synthesis of [Intermediate 9-f]

[Intermediate 9-f]

In a 250 mL round-bottom flask [Intermediate 9-e] (9.3 g, 25 mmol), 1-dibenzofuranboronic acid (8.3 g, 28 mmol), tetrakis(triphenylphosphine)palladium (0.6 g, 0.05 mmol) ), potassium carbonate (6.7 g, 50 mmol) was added, 50 mL of toluene, 50 mL of tetrahydrofuran, and 20 mL of water were added. The temperature of the reactor was raised to 80° C. and stirred for 10 hours. When the reaction was completed, the temperature of the reactor was lowered to room temperature, extracted with ethyl acetate, and the organic layer was separated. The organic layer was concentrated under reduced pressure and separated by column chromatography to obtain [Intermediate 9-f] (5.3 g, 52.3%).

Synthesis Example 9-(7): Synthesis of [Intermediate 9-g]

[Intermediate 9-g]

[Intermediate 9-f] (5.3 g, 15 mmol), sodium hydroxide (0.7 g, 17 mmol) and 50 ml of ethanol were added to a 100 mL round-bottom flask and stirred at reflux for 48 hours. The resulting solid, which was acidified by adding 2-N hydrochloric acid to the solution cooled to room temperature, was stirred for 30 minutes and then filtered. Recrystallization with dichloromethane and hexane gave [Intermediate 9-g] (4.5 g, 88.0%).

Synthesis Example 9-(8): Synthesis of [Intermediate 9-h]

[Intermediate 9-h]

In a 100 ml round-bottom flask [Intermediate 9-g] (4.5 g, 12 mmol), 30 ml of methanesulfonic acid was added and heated to 80° C. and stirred for 3 hours. After cooling to room temperature, the reaction solution was slowly added dropwise to 50 ml of ice water and stirred for 30 minutes. The resulting solid was filtered and washed with water and methanol to obtain [Intermediate 9-h] (3.8 g, 88.8%).

Synthesis Example 9-(9): Synthesis of [Intermediate 9-i]

[Intermediate 9-i]

In a 100 mL round bottom flask [Intermediate 9-h] (3.8 g, 11 mmol), dichloromethane 40 ml was added and stirred at room temperature. Bromine (1.1 ml, 22 mmol) was added dropwise diluted in 10 ml of dichloromethane and stirred at room temperature for 8 hours. After completion of the reaction, 20 ml of acetone was added to the reaction vessel and stirred. The resulting solid was filtered and washed with acetone. The solid was recrystallized from monochlorobenzene to obtain [Intermediate 9-i] (3.0 g, 55%).

Synthesis Example 9-(10): Synthesis of [Intermediate 9-j]

[Intermediate 9-j]

In a 100 ml round-bottom flask, 2-bromobiphenyl (2.1 g, 0.009 mol) and 30 ml of tetrahydrofuran were added and cooled to -78 °C in a nitrogen atmosphere. Normal butyl lithium (4.8 ml, 0.008 mol) was added dropwise to the cooled reaction solution at the same temperature. The reaction solution was stirred for 2 hours [Intermediate 9-i] (3.0 g, 0.006 mol) was added little by little and stirred at room temperature. The reaction was terminated by adding 10 ml of H2O, and extracted with ethyl acetate and water. The organic layer was separated, concentrated under reduced pressure, and recrystallized with acetonitrile to obtain [Intermediate 9-j] (2.5 g, 64%).

Synthesis Example 9-(11): Synthesis of [Intermediate 9-k]

[Intermediate 9-k]

In a 100 ml round-bottom flask, [Intermediate 9-j] (2.5 g, 0.04 mol), acetic acid 25 ml, and sulfuric acid 0.5 ml were added and stirred at reflux for 5 hours. When a solid was formed, the reaction was confirmed by thin film chromatography, and then cooled to room temperature. The resulting solid was filtered, washed with H 2 O, methanol, dissolved in monochlorobenzene, filtered with silica gel, concentrated and cooled to room temperature to obtain [Intermediate 9-k] (2.2 g, 90%).

Synthesis Example 9-(12): Synthesis of [Compound 498]

[Compound 498]

In a 100 ml round bottom flask [Intermediate 9-k] (2.2 g, 0.003 mol), bis(4-tertiarybutylphenyl)amine (2.3 g, 0.008 mol), palladium(II)acetate (0.04 g, 0.2 mmol) , Sodium tertiary butoxide (1.6 g, 0.016 mol), triteryl butylphosphine (0.04 g, 0.2 mmol), and 30 ml of toluene were added and stirred at reflux for 2 hours. After the reaction was completed, it was cooled to room temperature. The reaction solution was extracted with dichloromethane and water. The organic layer was separated, anhydrous treated with magnesium sulfate, and concentrated under reduced pressure. After separation by column chromatography, recrystallization with dichloromethane and acetone gave [Compound 498] (1.4 g, 43%).

MS (MALDI-TOF): m/z 1054.54 [M ⁺ ]

Synthesis Example 10: Synthesis of Compound 631

Synthesis Example 10-(1): Synthesis of [Intermediate 10-a]

[Intermediate 10-a]

Bromobenzene (25.5 g, 0.163 mol) and tetrahydrofuran were added to a 500 ml round-bottom flask and cooled to -78 °C in a nitrogen atmosphere. Butyl lithium (1.6 M) (95.6 ml, 0.153 mol) was added dropwise to the cooled reaction solution. After stirring at the same temperature for 1 hour, [Intermediate 9-f] (20.0 g, 0.051 mol) was added, followed by stirring at room temperature for 3 hours. After the reaction was completed, 50 ml of water was added and stirred for 30 minutes. After extraction with ethyl acetate and water, the organic layer was separated and concentrated under reduced pressure. 200 ml of acetic acid and 1 ml of hydrochloric acid were added to the concentrated material, and the mixture was heated to 80°C and stirred. After completion of the reaction, it was filtered at room temperature and washed with methanol to obtain [Intermediate 10-a] (20.0 g, 78%).

Synthesis Example 10-(2): Synthesis of [Intermediate 10-b]

[Intermediate 10-b]

In a 100 mL round-bottom flask [Intermediate 10-a] (20 g, 58 mmol), dichloromethane 40 ml was added and stirred at room temperature. Bromine (5.8 ml, 116 mmol) was added dropwise diluted in 10 ml of dichloromethane and stirred at room temperature for 8 hours. After completion of the reaction, 20 ml of acetone was added to the reaction vessel and stirred. The resulting solid was filtered and washed with acetone. Recrystallization with monochlorobenzene gave [Intermediate 10-b] (15.8 g, 55%).

Synthesis Example 10-(3): Synthesis of [Compound 631]

[Compound 631]

In a 100 ml round-bottom flask [Intermediate 10-b] (4.0 g, 0.006 mol), di-p-tolylamine (3.2 g, 0.016 mol), palladium(II)acetate (0.08 g, 0.4 mmol), sodium tertiary Butoxide (3.2 g, 0.032 mol), tributylbutylphosphine (0.08 g, 0.4 mmol), and 50 ml of toluene were added and stirred at reflux for 2 hours. After the reaction was completed, it was cooled to room temperature. The reaction solution was extracted with dichloromethane and water. The organic layer was separated, anhydrous treated with magnesium sulfate, and concentrated under reduced pressure. After separation and purification by column chromatography, recrystallization with dichloromethane and acetone gave [Compound 631] (2.1 g, 41%).

MS (MALDI-TOF): m/z 888.37 [M ⁺ ]

Synthesis Example of Hole Transport Layer Compound

Synthesis Example 11: Synthesis of Formula 2

Synthesis Example 11-(1): Synthesis of [Intermediate 11-a]

[Intermediate 11-a]

Methyl 2-iodobenzoate (19.1 g, 73 mmol), 4-dibenzofuranboronic acid (18.7 g, 88 mmol), tetrakis(triphenylphosphine)palladium (1.7 g, 0.15) in a 500 mL round-bottom flask mmol), potassium carbonate (20.2 g, 146.7 mmol) was added, and 125 mL of toluene, 125 mL of tetrahydrofuran, and 50 mL of water were added. The temperature of the reactor was raised to 80° C. and stirred for 10 hours. When the reaction was completed, the temperature of the reactor was lowered to room temperature, extracted with ethyl acetate, and the organic layer was separated. The organic layer was concentrated under reduced pressure and separated by column chromatography to obtain [Intermediate 11-a]. (9.5 g, 43%)

Synthesis Example 11-(2): Synthesis of [Intermediate 11-b]

[Intermediate 11-b]

In a 500 mL round-bottom flask, [Intermediate 11-a] (13.6 g, 45 mmol), sodium hydroxide (2.14 g, 54 mmol) and ethanol 170 ml were added and stirred at reflux for 48 hours. After completion of the reaction by thin film chromatography, the mixture was cooled to room temperature. 2-Normal hydrochloric acid was added dropwise to the cooled solution, and the resulting solid was filtered after stirring for 30 minutes. Recrystallization with dichloromethane and normal hexane gave [Intermediate 11-b]. (11.4 g, 88%)

Synthesis Example 11-(3): Synthesis of [Intermediate 11-c]

[Intermediate 11-c]

In a 250 ml round-bottom flask [Intermediate 11-b] (11.2 g, 39 mmol), 145 ml of methanesulfonic acid was added, heated to 80° C. and stirred for 3 hours. After completion of the reaction by thin film chromatography, the mixture was cooled to room temperature. The reaction solution was slowly added dropwise to 150 ml of ice water and stirred for 30 minutes. The resulting solid was filtered and washed with water and methanol to obtain [Intermediate 11-c]. (8.7 g, 83%)

Synthesis Example 11-(4): Synthesis of [Intermediate 11-d]

[Intermediate 11-d]

In a 1 L round-bottom flask [Intermediate 11-c] (8.6 g, 32 mmol), dichloromethane 300 ml was added and stirred at room temperature. Bromine (3.4 ml, 66 mmol) was added dropwise diluted in 50 ml of dichloromethane and stirred at room temperature for 8 hours. After the reaction was completed, 100 ml of acetone was added to the reaction vessel and stirred. The resulting solid was filtered and washed with acetone. The solid was recrystallized from monochlorobenzene to obtain [Intermediate 11-d]. (8.7 g, 78%)

Synthesis Example 11-(5): Synthesis of [Intermediate 11-e]

[Intermediate 11-e]

In a 250 ml round-bottom flask, 2-bromobiphenyl (8.4 g, 0.036 mol) and tetrahydrofuran 110 ml were added and cooled to -78 °C in a nitrogen atmosphere. Normal butyl lithium (19.3 ml, 0.031 mol) was added dropwise to the cooled reaction solution at the same temperature. The reaction solution was stirred for 2 hours, and [Intermediate 11-d] (8.4 g, 0.024 mol) was added little by little and stirred at room temperature. When the color of the reaction solution changed, the completion of the reaction was confirmed by TLC. The reaction was terminated by adding 50 ml of water, and extracted with ethyl acetate and water. The organic layer was separated, concentrated under reduced pressure, and recrystallized with acetonitrile to obtain [Intermediate 11-e]. (9.9 g, 82%)

Synthesis Example 11-(6): Synthesis of [Intermediate 11-f]

[Intermediate 11-f]

In a 250 ml round-bottom flask, [Intermediate 11-e] (9.6 g, 0.019 mol), acetic acid 120 ml, and sulfuric acid 2 ml were added and stirred at reflux for 5 hours. When a solid was formed, the reaction was confirmed by thin film chromatography, and then cooled to room temperature. The resulting solid was filtered, washed with water and methanol, dissolved in monochlorobenzene, filtered through silica gel, concentrated and cooled to room temperature to obtain [Intermediate 11-f]. (8.3 g, 90%>

Synthesis Example 11-(7): Synthesis of [Formula 2]

[Intermediate 11-f] [Formula 2]

In a 250 ml round-bottom flask [Intermediate 11-f] (4.4 g, 0.009 mol), (4-tertiarybutylphenyl)-phenylamine (4.7 g, 0.021 mol), palladium(II) acetate (0.08 g, 0.4 mmol) ), sodium tertiary butoxide (3.4 g, 0.035 mol), tributyl phosphine (0.07 g, 0.4 mmol), and 60 ml of toluene were added and stirred at reflux for 2 hours. After the reaction was completed, it was cooled to room temperature. The reaction solution was extracted with dichloromethane and water. The organic layer was separated, anhydrous treated with magnesium sulfate, and concentrated under reduced pressure. After separation and purification by column chromatography, dichloromethane and acetone were recrystallized to obtain [Formula 2]. (3.3 g, 58%)

MS (MALDI-TOF): m/z 629.27 [M ⁺ ]

Synthesis Example 12: Synthesis of Formula 87

Synthesis Example 12-(1): Synthesis of [Intermediate 12-a]

[Intermediate 12-a]

Synthesis Example 11-(1), Synthesis Example 3, using (6-phenyldibenzo[b,d]furan-4-yl)boronic acid instead of 4-dibenzofuranboronic acid used in Synthesis Example 11-(1) It was synthesized in the same manner as -(1) to 3-(3) to obtain [Intermediate 12-a]. (Yield 48%)

Synthesis Example 12-(2). Synthesis of [Intermediate 12-b]

Synthesis was carried out in the same manner, except that aniline was used instead of 4-tertiarythyl aniline used in Synthesis Example 3-(4), and 2-bromo-9,9-dimethylfluorene was used instead of 4-bromobiphenyl. [Intermediate 12-b] was obtained. (Yield 75%)

Synthesis Example 12-(3). Synthesis of [Formula 87]

[Intermediate 12-a] was used instead of [Intermediate 1-d] used in Synthesis Example 1-(5), and [Intermediate 12-b] was used instead of bis-biphenyl-4-yl-amine. [Formula 87] was obtained. (Yield 69%)

MS (MALDI-TOF): m/z 643.29 [M ⁺ ]

Synthesis Example 13: Synthesis of Formula 146

Synthesis Example 13-(1): Synthesis of [Intermediate 13-a]

[Intermediate 13-a]

Using 4-dibenzothiophenboronic acid instead of 4-dibenzofuranboronic acid used in Synthesis Example 11-(1), Synthesis Examples 11-(1), Synthesis Examples 1-(1) to 1-(3) and It was synthesized in the same manner to obtain [Intermediate 13-a]. (Yield 68%)

Synthesis Example 13-(2): Synthesis of [Intermediate 13-b]

[Intermediate 13-b]

1-bromo-4-(2-naphthyl)benzene (10.0 g, 0.035 mol), 4-tertiarybutylaniline (5.8 g, 0.039 mol), tris(dibenzylideneacetone)di in a 250 ml round bottom flask Palladium(0) (0.65 g, 0.0007 mol), sodium tertiary butoxide (6.79 g, 0.0706 mol), 2,2'-bis(diphenylphosphino)-1,1'-binaphthalene (0.44 g, 0.0007 mol) 100 ml of toluene was added and stirred at reflux for 3 hours. After the reaction was completed, the mixture was cooled to room temperature, and extracted with ethyl acetate and water. The organic layer was separated, dried over magnesium sulfate, and concentrated under reduced pressure. Separated by column chromatography to obtain [Intermediate 13-b] (10 g, 80%).

Synthesis Example 13-(3): Synthesis of [Formula 146]

[Intermediate 13-a] was used instead of [Intermediate 1-d] used in Synthesis Example 1-(5), and [Intermediate 13-b] was used instead of bis-biphenyl-4-yl-amine. [Formula 146] was obtained. (Yield 48%)

MS (MALDI-TOF): m/z 773.31 [M ⁺ ]

Examples 1 to 24: Preparation of organic light emitting device

The ITO glass was patterned to have a light emitting area of 2 mm×2 mm, and then washed. After mounting the ITO glass in the vacuum chamber base pressure is 1 × 10 ^{- 6} torr and then so that the film formed by the ITO on DNTPD (700 Å), a compound (300 Å) shown in Table 1 in order. Then, the a light emitting layer as a host [BH] and a dopant to a mixture of compound 3 wt% in Table 1, the film formation (250Å) as in the following, the electron transport layer [Formula E-1] and [Chemical Formula E-2] An organic light emitting device was manufactured by depositing 300 로 at a ratio of 1:1 and 5 Å and Al (1000 Å) in the order of [Formula E-1] with an electron injection layer. The characteristics of the organic light emitting device were measured at 0.4 mA.

[DNTPD] [BH]

[Formula E-1] [Formula E-2]

Comparative Examples 1 to 8

Instead of the hole transport layer compound used in Examples 1 to 24, an organic light emitting device was manufactured in the same manner except that the following <HT>, which is used as a hole transport compound in the prior art, was produced, and the characteristics of the organic light emitting device were 0.4 mA. It was measured and shown in Table 1. The structure of <HT> is as follows.

[HT]

division Hole transport compound Dopant CIEx CIEy Cd/A λmax Example 1 Formula 13 Compound 161 0.1327 0.1189 11.09 459 Example 2 Compound 169 0.1327 0.1191 11.37 460 Example 3 Compound 203 0.1414 0.1195 10.04 450 Example 4 Compound 226 0.1415 0.1194 10.21 450 Example 5 Compound 264 0.1364 0.1292 10.83 457 Example 6 Compound 281 0.1365 0.1295 11.13 457 Example 7 Compound 498 0.1367 0.1117 10.58 456 Example 8 Compound 631 0.1361 0.1093 10.37 456 Example 9 Formula 40 Compound 161 0.1327 0.1189 10.98 459 Example 10 Compound 169 0.1326 0.1188 11.12 459 Example 11 Compound 203 0.1414 0.1196 9.98 450 Example 12 Compound 226 0.1413 0.1196 10.18 450 Example 13 Compound 264 0.1363 0.1294 10.76 457 Example 14 Compound 281 0.1365 0.1293 10.88 457 Example 15 Compound 498 0.1366 0.1114 10.46 456 Example 16 Compound 631 0.1361 0.1111 10.35 456 Example 17 Formula 75 Compound 161 0.1327 0.1190 11.18 459 Example 18 Compound 169 0.1326 0.1187 11.41 459 Example 19 Compound 203 0.1413 0.1194 10.14 450 Example 20 Compound 226 0.1412 0.1197 10.34 450 Example 21 Compound 264 0.1364 0.1294 11.08 457 Example 22 Compound 281 0.1364 0.1294 11.22 457 Example 23 Compound 498 0.1365 0.1116 10.95 456 Example 24 Compound 631 0.1361 0.1110 10.52 456 Comparative Example 1 HT Compound 161 0.1327 0.1188 9.78 459 Comparative Example 2 Compound 169 0.1326 0.1187 9.83 459 Comparative Example 3 Compound 203 0.1413 0.1195 8.99 450 Comparative Example 4 Compound 226 0.1413 0.1197 9.18 450 Comparative Example 5 Compound 264 0.1363 0.1294 9.99 457 Comparative Example 6 Compound 281 0.1364 0.1294 10.02 457 Comparative Example 7 Compound 498 0.1365 0.1118 9.21 456 Comparative Example 8 Compound 631 0.1358 0.1110 8.66 456

As shown in Table 1, the organic light emitting device according to the present invention shows high luminous efficiency compared to HT, which is commonly used as a hole transport layer material according to the prior art, and thus has applicability as an organic light emitting device having improved properties.

Claims (21)

A first electrode;
A second electrode opposed to the first electrode;
An organic light emitting device comprising a hole injection layer or a hole transport layer; and a light emitting layer interposed between the first electrode and the second electrode,
The hole injection layer or the hole transport layer contains at least one amine compound represented by the following [Formula A] or [Formula B]; The light emitting layer is an organic light emitting device comprising at least one compound represented by any one of the following [Formula D1] to [Formula D5].
[Formula A]

[Formula B]

In the above [Formula A] and [Formula B],
A1, A2, E and F are each the same or different from each other, and are each independently a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 50 carbon atoms;
Two carbon atoms adjacent to each other in the aromatic ring of A1 and two carbon atoms adjacent to each other in the aromatic ring of A2 form a condensed ring by forming a five-membered ring with carbon atoms connected to the substituents R1 and R2;
The linking groups L1 to L6 are the same as or different from each other, and are each independently a single bond, or a substituted or unsubstituted arylene group having 6 to 60 carbon atoms;
The M is any one selected from CR ₄ R ₅ , O, S;
The substituents R1 to R2, R4 to R5, Ar1 to Ar4 are the same as or different from each other, and independently of each other, hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, substituted or unsubstituted 6 to 50 carbon atoms An aryl group, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, a cyano group, a nitro group, Any one selected from halogen groups,
R1 and R2 may be connected to each other to form an alicyclic, aromatic monocyclic or polycyclic ring;
Wherein p1 and p2, r1 and r2, s1 and s2 are integers of 1 to 3, but when each of these is 2 or more, each of the linkers L1 to L6 is the same or different from each other,
Ar1 and Ar2 may be connected to each other to form a ring, and Ar3 and Ar4 may be connected to each other to form a ring;
X is 1,
y is 0,
In Formula A, two carbon atoms adjacent to each other in the A2 ring combine with * in the structural formula Q1 to form a condensed ring,
In Formula B, two carbon atoms adjacent to each other in the A1 ring combine with * in the structural formula Q2 to form a condensed ring, and two carbon atoms adjacent to each other in the A2 ring combine with * in the structural formula Q1 to form a condensed ring. To form.

[Formula D1]

In [Formula D1], A ₁₁ to A ₁₄ are the same as or different from each other, and are each independently a substituted or unsubstituted aryl group having 6 to 24 carbon atoms or a substituted or unsubstituted heteroaryl group having 2 to 24 carbon atoms. ,
R ₁₀ is hydrogen, deuterium, substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, substituted or unsubstituted aryl group having 6 to 50 carbon atoms, nitrile group, nitro group And it is any one selected from the group consisting of halogen groups,
n1 is an integer from 1 to 8, and when n1 is 2 or more, each R ₁₀ is the same or different from each other,
Carbon of the pyrene ring in which R10 is not substituted is bonded to hydrogen or deuterium.

[Formula D2]

In the above [Formula D2],
Z ₁ is any one selected from substituted or unsubstituted aromatic hydrocarbon rings having 6 to 30 carbon atoms,
The substituents R ₁₁ to R ₁₆ are the same or different, and each independently hydrogen, deuterium, substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, substituted or unsubstituted aryl group having 6 to 50 carbon atoms, substituted or unsubstituted Any one selected from an alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, a cyano group, a nitro group, and a halogen group, and any one of the substituents R ₁₃ to R ₁₆ Is a single bond to be coupled to the linker L ₁₁ for connection with the structural formula Q ₃ ,
The structural formula Q3 connected to the Z1 ring and the structural formula Q3 connected to the 6-membered ring connected to the substituents R ₁₃ to R ₁₆ are the same or different, respectively.
The substituents R ₁₁ and R ₁₂ may be connected to each other to form a ring,
The substituents R ₁₃ to R ₁₆ may be connected to substituents adjacent to each other to form a substituted or aromatic monocyclic or polycyclic ring,
Two carbon atoms adjacent to each other in the Z1 form a condensed ring by forming a 5-membered ring with the carbon atoms connected to the substituents R11 and R12,
Carbon atom that does not form a 5-membered ring in the aromatic ring of Z1 and the linking group L11 in Q3 are bonded,
The linking group L11 is any one selected from a single bond or a substituted or unsubstituted arylene group having 6 to 60 carbon atoms;
n2 is an integer from 0 to 2, and when n2 is 2, each linker L11 is the same as or different from each other,
The substituents Ar ₁₁ and Ar ₁₂ are the same or different, and each independently substituted or unsubstituted aryl group having 6 to 40 carbon atoms, substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms, substituted or unsubstituted carbon number. It is any one selected from an alkyl group of 1 to 40, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms.

[Formula D3]

In the above [Formula D3],
X is a single bond, any one selected from CR ₁₈ R ₁₉ , O and S,
Z ₂ and Z ₃ are the same or different, and are each independently a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 30 carbon atoms,
The two carbon atoms adjacent to each other in Z2 and the two carbon atoms adjacent to each other in Z3 form a 5-membered ring to form a condensed ring,
The substituents R ₁₈ to R ₂₇ are the same or different, and each independently hydrogen, deuterium, substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, substituted or unsubstituted aryl group having 6 to 50 carbon atoms, substituted or unsubstituted Any selected from 3 to 30 cycloalkyl groups, substituted or unsubstituted alkylsilyl groups with 1 to 30 carbon atoms, substituted or unsubstituted arylsilyl groups with 6 to 30 carbon atoms, cyano groups, nitro groups, and halogen groups One,
Each of R ₂₀ to R ₂₇ may be connected to a substituent adjacent to each other to form a substituted or aromatic monocyclic or polycyclic ring,
The A21 and A22 are the same or different, and are independently represented by the following [Structural Q4],
[Structural Formula Q4]

In the above [Structural Formula Q4],
* Means a binding site to which the linking group L ₁₂ in Q4 is bonded to a carbon atom that does not form a 5-membered ring in the aromatic ring of Z2 or Z3 of the above [Formula D3],
The linking group L ₁₂ is any one selected from a single bond or a substituted or unsubstituted arylene group having 6 to 60 carbon atoms;
n3 is an integer from 0 to 2, and when n3 is 2, each linker L ₁₂ is the same or different from each other,
The substituents Ar ₁₃ and Ar ₁₄ are the same or different, and each independently substituted or unsubstituted aryl group having 6 to 40 carbon atoms, substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms, substituted or unsubstituted It is any one selected from an alkyl group having 1 to 40 carbon atoms, or a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms.

[Formula D4]

[Formula D5]

In the above [Formula D4] and [Formula D5],
A ₃₁ , A ₃₂ , E1 and F1 are the same or different, and are each independently a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 50 carbon atoms;
Two carbon atoms adjacent to each other in the aromatic ring of A ₃₁ and two carbon atoms adjacent to each other in the aromatic ring of A ₃₂ form a condensed ring by forming a five-membered ring with carbon atoms connected to the substituents R ₃₁ and R ₃₂ To form;
The linking groups L ₂₁ to L ₃₂ are the same or different, and are each independently selected from a single bond or a substituted or unsubstituted arylene group having 6 to 60 carbon atoms;
W is any one selected from NR ₃₃ , CR ₃₄ R ₃₅ , O and S;
The substituents R ₃₁ to R ₃₅ are the same or different, and each independently hydrogen, deuterium, substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, substituted or unsubstituted aryl group having 6 to 50 carbon atoms, substituted or unsubstituted Any selected from 3 to 30 cycloalkyl groups, substituted or unsubstituted alkylsilyl groups with 1 to 30 carbon atoms, substituted or unsubstituted arylsilyl groups with 5 to 30 carbon atoms, cyano groups, nitro groups, halogen groups ego,
Ar ₂₁ to Ar ₂₈ are the same or different, and each independently hydrogen, deuterium, substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, substituted or unsubstituted aryl group having 6 to 50 carbon atoms, substituted or unsubstituted carbon number 3 to 30 cycloalkyl group, substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms, substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, substituted or unsubstituted arylsilyl group having 5 to 30 carbon atoms, cyan It can be any one selected from no, nitro, and halogen groups,
R ₃₁ and R ₃₂ may be connected to each other to form an alicyclic, aromatic monocyclic or polycyclic ring;
Wherein p11 to p14, r11 to r14 and s11 to s14 are integers of 1 to 3, respectively, when each of them is 2 or more, each of the linking groups L ₂₁ to L ₃₂ is the same or different from each other,
X1 is 1, y1 and z1 are the same or different, and are each independently an integer of 0 to 1,
Ar ₂₁ and Ar ₂₂ , Ar ₂₃ and Ar ₂₄ , Ar ₂₅ and Ar _26, and Ar ₂₇ and Ar ₂₈ may be connected to each other to form a ring;
In Formula D4, two carbon atoms adjacent to each other in the A ₃₂ ring combine with * in the structural formula Q ₁₁ to form a condensed ring,
In Formula D5, two carbon atoms adjacent to each other in the A ₃₁ ring form a condensed ring by combining with * of the structural formula Q ₁₂ , and two carbon atoms adjacent to each other in the A ₃₂ ring are represented by * of the structural formula Q ₁₁ Can combine to form a condensed ring,
Here, the'substitution' in the'substituted or unsubstituted' in [Formula A], [Formula B], [Formula D1] to [Formula D5] is deuterium, cyano group, halogen group, nitro group, carbon number The group consisting of an alkyl group of 1 to 24, a halogenated alkyl group of 1 to 24 carbon atoms, an aryl group of 6 to 24 carbon atoms, an arylalkyl group of 7 to 24 carbon atoms, an alkylsilyl group of 1 to 24 carbon atoms, and an arylsilyl group of 6 to 24 carbon atoms. It means that it is substituted with one or more substituents selected from. According to claim 1,
The light emitting layer includes a host and a dopant, and the compound represented by any one of [Formula D1] to [Formula D5] is an organic light emitting device, characterized in that used as a dopant. According to claim 1,
In Formula A and Formula B, A1, A2, E, and F are the same or different, and are independently substituted or unsubstituted aromatic hydrocarbon rings having 6 to 50 carbon atoms,
A ₃₁ , A ₃₂ , E1, and F1 in the formulas D4 and D5 are the same or different, and are organic light-emitting devices, characterized in that they are independently substituted or unsubstituted aromatic hydrocarbon rings having 6 to 50 carbon atoms. The method of claim 3,
In Formula A, Formula B, Formula D4 and Formula D5, the substituted or unsubstituted aromatic hydrocarbon ring having 6 to 50 carbon atoms is the same or different, and independently selected from [Structural Formula 10] to [Structural Formula 21] It characterized in that the organic light emitting device.
[Structural Formula 10] [Structural Formula 11] [Structural Formula 12]

[Structural Formula 13] [Structural Formula 14] [Structural Formula 15]

[Structural Formula 16] [Structural Formula 17] [Structural Formula 18]

[Structural Formula 19] [Structural Formula 20] [Structural Formula 21]

In the above [Formula 10] to [Structural Formula 21],
"-*" represents a binding site for forming a 5-membered ring containing carbon atoms linked to the R1 and R2 in the formulas A and B, or to forming a 5-membered ring containing M in the structural formulas Q1 and Q2. Mean;
In addition, it means a binding site for forming a 5-membered ring containing carbon atoms linked to the R31 and R32 in the formulas D4 and D5, or a 5-membered ring containing W in the structural formulas Q11 and Q12,
When the aromatic hydrocarbon rings of [Formula 10] to [Formula 21] correspond to the A1 ring or A2 ring in Formula A and Formula B, and when combined with Structural Formula Q1 or Structural Formula Q2, two adjacent carbon atoms Combining with * of the structural formula Q1 or * of the structural formula Q2 to form a condensed ring;
In addition, when the aromatic hydrocarbon ring of [Structural Formula 10] to [Structural Formula 21] corresponds to the A31 ring or A32 ring in Chemical Formulas D4 and D5 and combines with Chemical Formulas Q11 or Q12, two of them are adjacent to each other. The carbon atom is combined with * of the structural formula Q11 or * of the structural formula Q12 to form a condensed ring,
In [Structural Formulas 10] to [Structural Formula 21], R is the same as R1 to R9 or R31 to R39 defined in claim 1, m is an integer of 1 to 8, and m is 2 or more or R is 2 or more Each R may be the same or different from each other. delete According to claim 1,
In the formulas D4 and D5, x1 and y1 are 1 and z1 is 0, respectively. According to claim 1,
In Formula D2 and Formula D3, the Z1 to Z3 are the same or different, and the organic light-emitting device, characterized in that each independently substituted or unsubstituted aromatic hydrocarbon ring having 6 to 30 carbon atoms. The method of claim 7,
The substituted or unsubstituted aromatic hydrocarbon ring having 6 to 30 carbon atoms in Formula D2 and Formula D3 is any one selected from the following [Structural Formula 10] to [Structural Formula 21].
[Structural Formula 10] [Structural Formula 11] [Structural Formula 12]

[Structural Formula 13] [Structural Formula 14] [Structural Formula 15]

[Structural Formula 16] [Structural Formula 17] [Structural Formula 18]

[Structural Formula 19] [Structural Formula 20] [Structural Formula 21]

"-*" in [Formula 10] to [Structural Formula 21] means a binding site of a carbon atom for forming a 5-membered ring in Z1, Z2 or Z3,
In [Structural Formula 10] to [Structural Formula 21], R is the same as R11 to R16 or R20 to R27 defined in claim 1,
m is an integer of 1 to 8, and when m is 2 or more, or when R is 2 or more, each R may be the same or different from each other. According to claim 1,
Ar11, Ar12, Ar13, and Ar14 in Chemical Formulas D2 and D3 are the same or different, and are organic light-emitting devices, which are independently substituted or unsubstituted aryl groups having 6 to 30 carbon atoms. According to claim 1,
The linking groups L1 to L6 in Formula A and Formula B are the same or different, and are each independently a single bond, or [Structural Formula 22], [Structural Formula 23], [Structural Formula 25], [Structural Formula 27], [Structural Formula 28] ], [Structural Formula 30] is any one selected from,
p1 and p2, r1 and r4, s1 and s2 are organic light emitting devices, characterized in that 1 or 2, respectively.
[Structural Formula 22] [Structural Formula 23] [Structural Formula 25]

[Structural Formula 27] [Structural Formula 28] [Structural Formula 30]

Carbon atoms of the aromatic ring in the linking group may be hydrogen or deuterium. According to claim 1,
The linking groups L11 and L12 in the formulas D2 and D3 are the same or different, and are each independently a single bond, or the following [Structural Formula 22], [Structural Formula 23], [Structural Formula 25], [Structural Formula 27], [Structural Formula 28] ], [Structural Formula 30], characterized in that any one selected from the organic light emitting device.
[Structural Formula 22] [Structural Formula 23] [Structural Formula 25]

[Structural Formula 27] [Structural Formula 28] [Structural Formula 30]

Carbon atoms of the aromatic ring in the linking group may be hydrogen or deuterium. According to claim 1,
The linking groups L21 to L32 in Chemical Formula D4 and Chemical Formula D5 are the same or different, and are each independently a single bond, or [Structural Formula 22], [Structural Formula 23], [Structural Formula 25], [Structural Formula 27], [Structural Formula 28] ], [Structural Formula 30] is any one selected from,
p11 to p14, r11 to r14, s11 to s14 is an organic light emitting device, characterized in that 1 or 2, respectively.
[Structural Formula 22] [Structural Formula 23] [Structural Formula 25]

[Structural Formula 27] [Structural Formula 28] [Structural Formula 30]

Carbon atoms of the aromatic ring in the linking group may be hydrogen or deuterium. According to claim 1,
The amine compounds represented by Formula A or Formula B are represented by the following <Formula 1> to <Formula 3>, <Formula 5>, <Formula 7> to <Formula 9>, <Formula 11> to <Formula 14>, <Formula 21> to <Formula 24>, <Formula 27>, <Formula 29> to <Formula 34>, <Formula 37> to <Formula 44>, <Formula 55> to <Formula 57>, <Formula 61>, <Formula 61>63>,<Formula65>,<Formula66>,<Formula68>,<Formula70> to <Formula 90>, <Formula 92>, <Formula 94>, <Formula 97> to <Formula 104>, <Formula 106>, <formula 107>, <formula 109> to <formula 111>, <formula 114>, <formula 115> to <formula 117>, <formula 122> to <formula 124>, <formula 127> to <formula 132>, <Formula 134> to <Formula 144>, <Formula 146>, <Formula 148> to <Formula 165> organic light emitting device, characterized in that any one selected from the group.
<Formula 1><Formula2><Formula3>

<Formula 5>

<Formula 7><Formula8><Formula9>

<Formula 11><Formula12>

<Formula 13><Formula14>

<Formula 21>

<Formula 22><Formula23><Formula24>

<Formula 27>

<Formula 29><Formula30>

<Formula 31><Formula32><Formula33>

<Formula 34>

<Formula 37><Formula38><Formula39>

<Formula 40><Formula41><Formula42>

<Formula 43><Formula44>

<Formula 55><Formula56><Formula57>

<Formula 61><Formula63>

<Formula 65><Formula66>

<Formula 68>

<Formula 70><Formula71><Formula72>

<Formula 73><Formula74><Formula75>

<Formula 76><Formula77><Formula78>

<Formula 79><Formula80><Formula81>

<Formula 82><Formula83><Formula84>

<Formula 85><Formula86><Formula87>

<Formula 88><Formula89><Formula90>

<Formula 92><Formula94>

<Formula 97><Formula98><Formula99>

<Formula 100><Formula101><Formula102>

<Formula 103><Formula104>

<Formula 106><Formula107>

<Formula 109><Formula110><Formula111>

<Formula 114>

<Formula 115><Formula116><Formula117>

<Formula 122><Formula123>

<Formula 124>

<Formula 127><Formula128><Formula129>

<Formula 130><Formula131><Formula132>

<Formula 134><Formula135>

<Formula 136><Formula137><Formula138>

<Formula 139><Formula140><Formula141>

<Formula 142><Formula143><Formula144>

<Formula 146>

<Formula 148><Formula149><Formula150>

<Formula 151><Formula152><Formula153>

<Formula 154><Formula155><Formula156>

<Formula 157><Formula158><Formula159>

<Formula 160><Formula161><Formula162>

<Formula 163><Formula164><Formula165>

According to claim 1,
Compounds represented by Formula D1 are <Compound 101> to <Compound 107>, <Compound 109> to <Compound 116>, <Compound 118> to <Compound 180>, <Compound 182> to <Compound 186>, < Compound 188> to <Compound 190>, an organic light emitting device, characterized in that any one selected from the group.
<Compound 101><Compound102><Compound103>

<Compound 104><Compound105><Compound106>

<Compound 107><Compound109>

<Compound 110><Compound111><Compound112>

<Compound 113><Compound114><Compound115>

<Compound 116><Compound118>

<Compound 119><Compound120><Compound121>

<Compound 122><Compound123><Compound124>

<Compound 125><Compound126><Compound127>

<Compound 128><Compound129><Compound130>

<Compound 131><Compound132><Compound133>

<Compound 134><Compound135><Compound136>

<Compound 137><Compound138><Compound139>

<Compound 140><Compound141><Compound142>

<Compound 143><Compound144><Compound145>

<Compound 146><Compound147><Compound148>

<Compound 149><Compound150><Compound151>

<Compound 152><Compound153><Compound154>

<Compound 155><Compound156><Compound157>

<Compound 158><Compound159><Compound160>

<Compound 161><Compound162><Compound163>

<Compound 164><Compound165><Compound166>

<Compound 167><Compound168><Compound169>

<Compound 170><Compound171><Compound172>

<Compound 173><Compound174><Compound175>

<Compound 176><Compound177><Compound178>

<Compound 179><Compound180>

<Compound 182><Compound183><Compound184>

<Compound 185><Compound186>

<Compound 188><Compound189><Compound190>

According to claim 1,
The compound represented by the formula (D2) is an organic light emitting device, characterized in that any one selected from the group represented by the following compound 201 to compound 260.
<Compound 201><Compound202><Compound203>

<Compound 204><Compound205><Compound206>

<Compound 207><Compound208><Compound209>

<Compound 210><Compound211><Compound212>

<Compound 213><Compound214><Compound215>

<Compound 216><Compound217><Compound218>

<Compound 219><Compound220><Compound221>

<Compound 222><Compound223><Compound224>

<Compound 225><Compound226><Compound227>

<Compound 228><Compound229><Compound230>

<Compound 231><Compound232><Compound233>

<Compound 234><Compound235><Compound236>

<Compound 237><Compound238><Compound239>

<Compound 240><Compound241><Compound242>

<Compound 243><Compound244><Compound245>

<Compound 246><Compound247><Compound248>

<Compound 249><Compound250><Compound251>

<Compound 252><Compound253><Compound254>

<Compound 255><Compound256><Compound257>

<Compound 258><Compound259><Compound260>

According to claim 1,
The compound represented by the formula (D3) is characterized in that any one selected from the group represented by the following <Compound 261> to <Compound 289>, <Compound 291>, <Compound 292>, <Compound 294> to <Compound 326> Organic light emitting device.
<Compound 261><Compound262><Compound263>

<Compound 264><Compound265><Compound266>

<Compound 267><Compound268><Compound269>

<Compound 270><Compound271><Compound272>

<Compound 273><Compound274><Compound275>

<Compound 276><Compound277><Compound278>

<Compound 279><Compound280><Compound281>

<Compound 282><Compound283><Compound284>

<Compound 285><Compound286><Compound287>

<Compound 288><Compound289>

<Compound 291><Compound292>

<Compound 294><Compound295><Compound296>

<Compound 297><Compound298><Compound299>

<Compound 300><Compound301><Compound302>

<Compound 303><Compound304><Compound305>

<Compound 306><Compound307><Compound308>

<Compound 309><Compound310><Compound311>

<Compound 312><Compound313><Compound314>

<Compound 315><Compound316><Compound317>

<Compound 318><Compound319><Compound320>

<Compound 321><Compound322><Compound323>

<Compound 324><Compound325><Compound326>

According to claim 1,
The compounds represented by Chemical Formula D4 or Chemical Formula D5 are <Compound 401> to <Compound 421>, <Compound 423>, <Compound 424>, <Compound 428> to <Compound 440>, <Compound 445> to <Compound 488 >, <Compound 497> to <Compound 499>, <Compound 503> to <Compound 534>, <Compound 536>, <Compound 537>, <Compound 539> to <Compound 557>, <Compound 562>, <Compound 564 >, <Compound 565>, <Compound 567> to <Compound 637> organic light emitting device, characterized in that any one selected from the group.
<Compound 401><Compound402><Compound403>

<Compound 404><Compound405><Compound406>

<Compound 407><Compound408><Compound409>

<Compound 410><Compound411><Compound412>

<Compound 413><Compound414><Compound415>

<Compound 416><Compound417><Compound418>

<Compound 419><Compound420><Compound421>

<Compound 423><Compound424>

<Compound 428><Compound429><Compound430>

<Compound 431><Compound432><Compound433>

<Compound 434><Compound435><Compound436>

<Compound 437><Compound438><Compound439>

<Compound 440><Compound445>

<Compound 446><Compound447><Compound448>

<Compound 449><Compound450><Compound451>

<Compound 452><Compound453><Compound454>

<Compound 455><Compound456><Compound457>

<Compound 458><Compound459><Compound460>

<Compound 461><Compound462><Compound463>

<Compound 464><Compound465><Compound466>

<Compound 467><Compound468><Compound469>

<Compound 470><Compound471><Compound472>

<Compound 473><Compound474><Compound475>

<Compound 476><Compound477><Compound478>

<Compound 479><Compound480><Compound481>

<Compound 482><Compound483><Compound484>

<Compound 485><Compound486><Compound487>

<Compound 488>

<Compound 497><Compound498><Compound499>

<Compound 503><Compound504><Compound505>

<Compound 506><Compound507><Compound508>

<Compound 509><Compound510><Compound511>

<Compound 512><Compound513><Compound514>

<Compound 515><Compound516><Compound517>

<Compound 518><Compound519><Compound520>

<Compound 521><Compound522><Compound523>

<Compound 524><Compound525><Compound526>

<Compound 527><Compound528><Compound529>

<Compound 530><Compound531><Compound532>

<Compound 533><Compound534>

<Compound 536><Compound537>

<Compound 539><Compound540><Compound541>

<Compound 542><Compound543><Compound544>

<Compound 545><Compound546><Compound547>

<Compound 548><Compound549><Compound550>

<Compound 551><Compound552><Compound553>

<Compound 554><Compound555><Compound556>

<Compound 557><Compound562>

<Compound 564><Compound565>

<Compound 567><Compound568>

<Compound 569><Compound570><Compound571>

<Compound 572><Compound573><Compound574>

<Compound 575><Compound576><Compound577>

<Compound 578><Compound579><Compound580>

<Compound 581><Compound582><Compound583>

<Compound 584><Compound585><Compound586>

<Compound 587><Compound588><Compound589>

<Compound 590><Compound591><Compound592>

<Compound 593><Compound594><Compound595>

<Compound 596><Compound597><Compound598>

<Compound 599><Compound600><Compound601>

<Compound 602><Compound603><Compound604>

<Compound 605><Compound606><Compound607>

<Compound 608><Compound609><Compound610>

<Compound 611><Compound612><Compound613>

<Compound 614><Compound615><Compound616>

<Compound 617><Compound618><Compound619>

<Compound 620><Compound621><Compound622>

<Compound 623><Compound624><Compound625>

<Compound 626><Compound627><Compound628>

<Compound 629><Compound630><Compound631>

<Compound 632><Compound633><Compound634>

<Compound 635><Compound636><Compound637>

According to claim 1,
The organic light emitting device is an organic light emitting device, characterized in that it further comprises at least one of an electron blocking layer, an electron transport layer, and an electron injection layer. The method of claim 18,
At least one layer selected from each of the layers is an organic light emitting device, characterized in that formed by a deposition process or a solution process. The method of claim 18,
The organic light emitting device comprises an electron blocking layer between the hole transport layer and the light emitting layer. According to claim 1,
The organic light emitting device includes a flat panel display device; Flexible display devices; A monochromatic or white flat panel lighting device; And, Monochromatic or white flexible lighting device; Organic light-emitting device characterized in that it is used in any one device selected from.

Images