KR20090039598A - Novel compound and organic photoelectric device including the same - Google Patents

Abstract

A novel compound having electron injection property and electron transport characteristic is provided to improve the efficiency and longivity of an organic photoelectric device. An organic photoelectric device comprises: anode; cathode; and organic thin film layer inserted between the anode and cathode of least one layer. At least one layer of the organic thin film layer comprises the novel compound of the chemical formula 1. The organic thin film layer comprises a light-emitting layer and at least one layer selected among a hole-transport layer, a hole injection layer, an electron-transport layer and an electron injection layer.

Description

Novel compound and organic photoelectric device including the same {NOVEL COMPOUND AND ORGANIC PHOTOELECTRIC DEVICE INCLUDING THE SAME}

The present invention relates to a novel compound and organic photoelectric devices including the same, and more particularly to a novel compound and an organic photoelectric device comprising the same that can improve the efficiency characteristics and lifetime characteristics of the organic photoelectric device. will be.

An organic photoelectric device converts electrical energy into light energy by applying current to an organic material and has a structure in which a functional organic material layer is inserted between an anode and a cathode.

The electrical characteristics of organic photoelectric devices are similar to light emitting diodes (LEDs). After holes are injected from the anode and electrons are injected from the cathode, the holes and electrons move toward each other electrode. Recombination results in the formation of high energy excitons. In this case, light having a specific wavelength is generated as the excitons move to the ground state.

The organic light emission phenomenon was first discovered in the early 1960s using anthracene, but was not attracted much attention due to the high driving voltage. As it became possible, it attracted a lot of attention. Later, in the late 1990s, while developing a polymer light emitting device using poly (p-phenylenevinylene) (PPV) in Cambridge, research has been largely divided into a low molecular light emitting device (SMOLED) and a polymer organic light emitting device (PLED). .

The low molecular organic light emitting device is manufactured in the form of a thin film by vacuum deposition method, so the efficiency and lifespan performance is good, and the high molecular organic light emitting device uses the inkjet or spin coating method and the initial investment cost is small and the large area is large. Painter has an advantage.

Both low molecular weight organic light emitting diodes and high molecular weight organic light emitting diodes are attracting attention as next-generation displays because they have advantages such as self-luminous, high-speed response, wide viewing angle, ultra-thin, high-definition, durability, and wide driving temperature range. In particular, compared to conventional LCD (liquid crystal display) as a self-luminous type, even in a dark place or outside light is good cyanity, and no backlight is required, it can reduce the thickness and weight to 1/3 of the LCD.

In addition, the response speed is 1000 times faster than the LCD in microseconds, it is possible to implement a perfect video without afterimage. Therefore, it is expected to be spotlighted as an optimal display in line with the recent multimedia era. Based on these advantages, it has made rapid technological developments with efficiency of 80 times and lifespan over 100 times since its first development in the late 1980s. Increasingly, the inch organic light emitting device panel has been announced.

In order to increase the size, the luminous efficiency must be increased and the life of the device must be accompanied. In this case, the light emitting efficiency of the device should be smoothly coupled to the holes and electrons in the light emitting layer. However, since the electron mobility of the organic material is generally slower than the hole mobility, in order to efficiently combine holes and electrons in the light emitting layer, an efficient electron transport layer is used to increase the electron injection and mobility from the cathode, It should be able to block the movement of holes.

In addition, in order to improve the life, it is necessary to prevent the material from crystallizing due to Joule heat generated when the device is driven.

As a study to solve this problem, 2- (4-biphenylyl) -5- (4-t-butylphenyl) -1,3,4-oxadiazole (PBD) having high electron transfer speed (Jpn, J. Appl. Phys. 27, L269 (1988)) has been proposed, but it is easy to achieve crystallization when driving the device, and there is a problem that the thermal stability is insufficient. In addition, there have been proposals for basocuproin (BCP) and aluminum mixed coordination complex (BAlq; Bis (2-methyl-8-quinolinolate) -4- (phenylphenolate) aluminum) having excellent hole blocking properties. On the other hand, there is a problem that the electron injection characteristics are poor and easy to achieve crystallization, and did not show satisfactory device characteristics.

Therefore, there is an urgent need to develop an organic compound having excellent electron injection and mobility and high crystallinity that can prevent crystallization during driving.

The present invention is to provide a novel compound that can improve the efficiency characteristics and life characteristics of the organic photoelectric device.

The present invention also provides an organic photoelectric device comprising the novel compound.

However, technical problems to be achieved by the present invention are not limited to the above-mentioned problems, and other technical problems will be clearly understood by the average technician from the following description.

In order to achieve the above object, the present invention provides a novel compound represented by the following formula (1):

[Formula 1]

In Chemical Formula 1,

A ₁ to A ₃ , B, and D ₂ are the same or different, each independently selected from the group consisting of CR ₃ and N,

D ₁ is selected from the group consisting of O, S, Se, and NR ₄ ,

When D ₁ is NR ₄ , D ₂ is CR ₃ Or N,

When D ₁ is not NR ₄ , D ₂ is N,

E is hydrogen, substituted or unsubstituted alkyl group, nitrile group, fluoroalkyl group, cyano group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted heterocyclic group, nitro group, carbonyl group , An amide group, and SO ₂ R _{5 It} is selected from the group consisting of

R ₁ to R ₂ may not be hydrogen at the same time and are hydrogen; Halogen group; Nitrile group; Cyano group; Nitro group; Amide group; Carbonyl group; Ester group; Substituted or unsubstituted alkyl group; Substituted or unsubstituted alkoxy group; Substituted or unsubstituted alkenyl group; Substituted or unsubstituted aryl group; Substituted or unsubstituted arylamine group; Substituted or unsubstituted heteroarylamine group: Substituted or unsubstituted heterocyclic group; Substituted or unsubstituted amino group; A substituted or unsubstituted cycloalkyl group; BR ₆ R ₇ ; And SiR ₆ R ₇ R ₈ .

R ₃ is selected from the group consisting of hydrogen and a substituted or unsubstituted alkyl group,

R ₄ is a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a nitrile group, a cyano group, a nitro group, a carbonyl group, and an amide group Is selected from the group consisting of,

R ₅ is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted cycloalkyl group, a nitrile group, a cyano group, a nitro group, a carbonyl group, and an amide group Is selected from the group consisting of,

R ₆ to R ₈ are the same or different, and each independently selected from the group consisting of a substituted or unsubstituted alkyl group and a substituted or unsubstituted aryl group.

In addition, the present invention provides an organic photoelectric device including an organic thin film layer including the novel compound.

The novel compounds of the present invention have excellent electron injection characteristics and electron transport characteristics, and can improve efficiency characteristics and life characteristics of organic photoelectric devices.

Other specific details of embodiments of the present invention are included in the following detailed description.

Hereinafter, embodiments of the present invention will be described in detail. However, this is presented as an example, by which the present invention is not limited and the present invention is defined only by the scope of the claims to be described later.

Unless stated otherwise in the specification, "substituted" means that a hydrogen atom in a compound is a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted Arylamine group, substituted or unsubstituted aryl group, substituted or unsubstituted arylalkyl group, substituted or unsubstituted arylalkenyl group, substituted or unsubstituted heterocyclic group, nitrile group, cyano group, acetylene group, substituted or unsubstituted It means a substituted amine group, substituted or unsubstituted cycloalkyl group, nitro group, carbonyl group, amide group, BR ₆ R _7, and SiR ₆ R ₇ R _{8 It} is substituted with at least one member selected from the group consisting of.

Unless stated otherwise in the specification, an "alkyl group" means an alkyl group of C ₁ to C ₃₀ , more preferably an alkyl group of C ₁ to C ₂₀ , an "alkoxy group" means an alkoxy group of C ₁ to C ₃₀ , Preferably, alkoxy group of C ₁ to C ₂₀ , "alkenyl group" means C ₂ to C ₂₀ alkenyl group, more preferably C ₂ to C ₁₀ alkenyl group, "aryl group" means C ₆ To C ₄₀ aryl group, more preferably C ₆ To C ₃₀ aryl group, “heterocycle” means C ₂ To C ₂₀ heterocycle, more preferably C ₂ To C ₁₅ heterocycle, “cycloalkyl group” means C ₃ To C ₂₀ cycloalkyl group, more preferably C ₃ to C ₁₀ cycloalkyl group.

In addition, in the present invention, "heterocycle" means heteroaryl, heterocycloalkyl, heterocycloalkenyl, or a fusion ring thereof including a hetero atom, and a hetero atom means N, O, S or Si. In addition, the heterocycle means that it contains 1 to 20 heteroatoms, preferably 1 to 15 heteroatoms.

The novel compounds of the present invention can be represented by the following formula (1).

[Formula 1]

In Chemical Formula 1,

A ₁ to A ₃ , B, and D ₂ are the same or different, and each independently, may be selected from the group consisting of CR ₃ and N. Further, at least one of the A ₁ to A ₃ is more preferably N.

D ₁ may be selected from the group consisting of O, S, Se, and NR ₄ , and more preferably selected from the group consisting of O, S, and NR ₄ . In addition, when D ₁ is NR ₄ , D ₂ is CR ₃ Or a N, D ₂ is D ₁ is N, if the non-NR _4.

E is hydrogen, substituted or unsubstituted alkyl group, nitrile group, fluoroalkyl group, cyano group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted heterocyclic group, nitro group, carbonyl group , Amide group, and SO ₂ R ₅ It can be selected from the group consisting of.

R ₁ to R ₂ may not be hydrogen at the same time and are hydrogen; Halogen group; Nitrile group; Cyano group; Nitro group; Amide group; Carbonyl group; Ester group; Substituted or unsubstituted alkyl group; Substituted or unsubstituted alkoxy group; Substituted or unsubstituted alkenyl group; Substituted or unsubstituted aryl group; Substituted or unsubstituted arylamine group; Substituted or unsubstituted heteroarylamine group: Substituted or unsubstituted heterocyclic group; Substituted or unsubstituted amino group; A substituted or unsubstituted cycloalkyl group; BR ₆ R ₇ ; And SiR ₆ R ₇ R ₈ It can be selected from the group consisting of.

Moreover, it is more preferable that said R <_1> -R <_2> differs from each other. Further, preferably, R ₁ to R ₂ is a nitrile group, nitro group, amide group, carbonyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted aryl group, substituted or unsubstituted Arylamine group, heterocyclic group, substituted or unsubstituted cycloalkyl group, BR ₆ R ₇ , and SiR ₆ R ₇ R ₈ It can be selected from the group consisting of.

R ₃ may be selected from the group consisting of hydrogen and a substituted or unsubstituted alkyl group.

R ₄ is composed of a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a nitrile group, a cyano group, a nitro group, a carbonyl group, and an amide group Can be selected from the group.

R ₅ is composed of a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted cycloalkyl group, a nitrile group, a cyano group, a nitro group, a carbonyl group, and an amide group Can be selected from the group.

R ₆ to R ₈ are the same or different, and each independently selected from the group consisting of a substituted or unsubstituted alkyl group and a substituted or unsubstituted aryl group, preferably consisting of an alkyl group, an aryl group, and an alkyl substituted aryl group Can be selected from the group.

R ₁ of Chemical Formula ₁ In R to R ₂ , examples of the aryl group include monocyclic aromatics such as phenyl group, biphenyl group, terphenyl group and styrene; Or a polycyclic aromatic ring such as naphthyl group, anthracenyl group, phenanthrene group, pyrenyl group, and perrylenyl group, but is not limited thereto.

R ₁ of Chemical Formula ₁ In R to R ₂ , examples of the aryl amine group include diphenyl amine group, dinaphthyl amine group, dibiphenyl amine group, phenyl naphthyl amine group, phenyl diphenyl amine group, and totolyl. An amine group, a phenyl tolyl amine group, a carbazole group, a triphenyl amine group, etc. are mentioned, but it is not limited to this.

R ₁ of Chemical Formula ₁ In R to R ₂ , examples of the heterocyclic group include a thiophene group, a furan group, a pyrrole group, an imidazolyl group, a thiazolyl group, an oxazolyl group, an oxadiazolyl group, a triazolyl group, a pyridinyl group, a pyrazine group , Quinolinyl group, isoquinolinine group, acridil group, imidazopyridinyl group, imidazopyrimidinyl group and the like, but is not limited thereto.

Substituents bonded to N of the imidazole group and the triazole group may include a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heterocyclic group. It is preferable that the heterocyclic group is a heteroaryl group. When the substituent bonded to N of the imidazole group and the triazole group is an alkyl group, typical examples thereof include methyl group, ethyl group, propyl group, isopropyl group, butyl group, tertiary-butyl group, pentyl group, hexyl group, or heptyl group And the like; In the case of a cycloalkyl group, a typical example is a cyclopentyl group or a cyclohexyl group; In the case of an aryl group, a phenyl group, a biphenyl group, a naphthyl group, etc. are mentioned; In the case of a hetero aryl group, there may be mentioned a pyridyl group, a bipyridyl group, a quinolyl group, an isoquinolyl group, and the like, but is not limited thereto.

The various substituents described above may be substituted with the novel compound represented by Chemical Formula 1, and do not change the fundamental physical properties of the novel compound.

Representative examples of R ₁ in the formula (1), to which a compound represented by the formula 2 to 22, but the R ₁ is not limited thereto.

[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]

Representative examples of R ₂ in Formula 1 include compounds represented by Formulas 2 to 22 or compounds represented by Formulas 23 to 64, and R ₂ is not limited thereto.

[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]

Representative examples of Formula 1 include compounds represented by the following Formulas 65 to 127, and the compound of Formula 1 is not limited thereto.

[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]

Such novel compounds can be used in the manufacture of organic photoelectric devices.

In this case, the organic photoelectric device refers to an organic light emitting device, an organic solar cell, an organic transistor, and an organic memory device.

In the organic light emitting device, the novel compound of the present invention may be used in the organic thin film layer to improve efficiency and lifespan characteristics of the organic light emitting device.

In addition, in the case of an organic solar cell, the novel compound of the present invention is included in an electrode or an electrode buffer layer to increase quantum efficiency, and in the case of an organic transistor, it may be used as an electrode material in a gate, a source-drain electrode, and the like.

Hereinafter, the organic light emitting device will be described in detail. According to another embodiment of the present invention, a first electrode, a second electrode, and at least one organic thin film layer disposed between the first electrode and the second electrode, the organic thin film layer is a novel An organic light emitting device comprising a compound is provided.

In addition, the organic thin film layer may include a light emitting layer, an electron transport layer, an electron injection layer, a hole transport layer, a hole injection layer, a hole blocking layer, and at least one of these layers includes the novel compound of Chemical Formula 1 above.

The novel compound of the formula (1) can be thought of as divided into a core moiety containing A ₁ to A ₃ and a functional substituent moiety containing R ₁ and R ₂ , and a pentagonal ring. Looking at this structure, the core portion is more preferably composed of three substituents that are not identical to each other to form an asymmetric core structure. In the asymmetric core structure, the amorphous property can be enhanced to suppress crystallization, so that the lifespan characteristic can be improved when driving the organic light emitting device. On the contrary, in the case of a compound having the same substituent and achieving symmetry, it is easy to achieve crystallization, which may be a cause of shortening the lifespan characteristics of the organic light emitting device when driven.

In addition, when at least one of A ₁ to A ₃ is nitrogen, the LUMO energy level may be lowered to improve electron injection and movement characteristics, thereby reducing the voltage required for driving the organic light emitting device, thereby increasing power efficiency. There is.

In addition, R ₁ and R ₂ are functional groups having excellent electron injection characteristics, or functional groups capable of increasing thermal stability. The R ₁ and R ₂ may not be hydrogen at the same time, preferably when the R ₁ and R ₂ are not the same, the amorphous properties can be further increased, The hole injection / transfer capability and the electron injection / transfer capability can be selectively provided, thereby enabling efficient hole-electron coupling in the light emitting layer.

In addition, when R ₁ to R ₂ are an alkyl group containing an amine group, a cycloalkyl group containing an amine group, an aryl group containing an amine group, a heterocyclic group containing an amine group, and the like, the novel compound of the formula (1) may be a hole injection layer and a hole transport layer. Various materials can be used. In this case, the heterocyclic group containing the amine group is more preferably a heteroaryl group containing an amine group.

In addition, when R ₁ to R ₂ is a material having excellent electron affinity such as heterocyclic group, nitrile group, nitro group, carbonyl group, amide group, etc., the novel compound of Formula 1 may be used as an electron injection layer or electron transport layer material. . In this case, the heterocyclic group is more preferably a heteroaryl group.

In addition, when R ₁ to R ₂ are an anthracene, an aryl group in the form of perylene, pyrene and stilbene, the novel compound of Formula 1 may be used in the light emitting layer.

In addition, one of R ₁ to R ₂ is a substituent such as an alkyl group containing an amine group, a cycloalkyl group containing an amine group, an aryl group containing an amine group, a heterocyclic group containing an amine group, and the other is a heterocyclic group, In the case of substituents, such as a nitrile group, a nitro group, a carbonyl group, and an amide group, the novel compound of the said Formula (1) has amphoteric property, and is more preferable. In this case, the heterocyclic ring containing the amine group is preferably a heteroaryl group containing an amine group, and the heterocyclic group is preferably a heteroaryl group.

In addition, “D ₁ ” of the functional substituent moiety including the pentagonal ring may be present as O, S, Se, or NR ₄ , which imparts thermal stability to the novel compound of Formula 1.

Substituents such as E or R ₄ of NR ₄ (D ₁ ) each include an alkyl group containing an amine group, a cycloalkyl group containing an amine group, an aryl group containing an amine group, and a heterocyclic group containing an amine group; And a substituent including a heterocyclic group, a nitrile group, a nitro group, a carbonyl group, an amide group, and the like, it is possible to enhance amorphous properties and to fine-tune hole and electron transfer properties. In this case, the heterocyclic ring containing the amine group is preferably a heteroaryl group containing an amine group, and the heterocyclic group is preferably a heteroaryl group.

In addition, E, or NR ₄ (D ₁₎ of R ₄ from an E the substituent of the alkyl group, and a heterocyclic group containing an aryl group, an amine group-containing cycloalkyl group, an amine containing an amine containing an amino group, R _{In the} case of a substituent such as a _tetravalent heterocyclic group, a nitrile group, a nitro group, a carbonyl group, an amide group, or vice versa, amorphous properties can be enhanced and fine control of hole and electron transfer properties can be performed. In this case, the heterocyclic ring containing the amine group is preferably a heteroaryl group containing an amine group, and the heterocyclic group is preferably a heteroaryl group.

The organic light emitting device according to the embodiment of the present invention, by introducing a variety of substituents in R ₁ and R ₂ of Formula 1 to form a compound having a variety of energy band gap, a hole injection layer, a hole transport layer, a light emitting layer, electron It includes a novel compound that can satisfy various conditions required for the injection layer, the delivery layer and the like. Therefore, a device having a low driving voltage and high luminous efficiency can be realized.

1 to 5 are cross-sectional views of an organic light emitting device using the novel compound of Formula 1 prepared according to one embodiment of the present invention.

1 to 5, an organic light emitting diode according to an embodiment of the present invention includes an anode 10, a cathode 20, and at least one organic thin film layer 30 disposed between the anode and the cathode. It has a structure to include.

The anode includes a cathode material, and a material having a large work function is preferable as the anode material so that hole injection can be smoothly performed into the organic thin film layer. Specific examples of the positive electrode material that can be used in the present invention include metals such as nickel, platinum, vanadium, chromium, copper, zinc, gold and alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO); Combinations of metals and oxides such as ZnO and Al or SnO ₂ and Sb; Conductive polymers such as poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (polyehtylenedioxythiophene: PEDT), polypyrrole and polyaniline, and the like. It is not.

The negative electrode includes a negative electrode material, and the negative electrode material is generally a material having a small work function to facilitate electron injection into the organic thin film layer. Specific examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, lead, cesium, barium, and alloys thereof; Multi-layered materials such as LiF / Al, LiO ₂ / Al, LiF / Ca, LiF / Al, and BaF ₂ / Ca may be used, but are not limited thereto.

Referring to FIG. 1, the organic thin film layer 30 may exist only as the light emitting layer 31.

Referring to FIG. 2, the organic thin film layer 30 may be a two-layer type including a light emitting layer 31 and a hole transport layer 32. In this case, the light emitting layer 31 functions as an electron transport layer and the hole transport layer 32. Silver improves the bonding property and hole transport property with an electrode.

Referring to FIG. 3, the organic thin film layer 30 may exist in a three-layer type including an electron transport layer 33 having excellent electron transport property, a light emitting layer 31, and a hole transport layer 32 having excellent hole transport property.

Referring to FIG. 4, the organic thin film layer 30 may be a four-layer type including an electron transport layer 33, a light emitting layer 31, a hole transport layer 32, and a hole injection layer 34, and a three-layer organic light emitting device. A hole injection layer may be added to the anode to increase the adhesion with the anode.

Referring to FIG. 5, the organic thin film layer may be a five-layer type including an electron injection layer 35, an electron transport layer 33, a light emitting layer 31, a hole transport layer 32, and a hole injection layer 34. The effect can be increased by lowering the voltage.

The organic light emitting device described above may be formed by forming an anode on a substrate, and then using a dry film method such as evaporation, sputtering, plasma plating, and ion plating, or spin coating or dipping. ) And a wet film forming method such as a flow coating method, and the like, and then an anode may be formed on the organic thin film layer.

Hereinafter, the present invention will be described in more detail with reference to the following examples, but the following examples are only preferred embodiments of the present invention, and the present invention is not limited to the following examples.

Synthesis Example  1: 3- (anthracene-9-yl) -5- (pyridin-3-yl) Benzaldehyde (3- ( anthracen -9-yl) -5- (pyridin-3-yl) benzaldehyde)

3- (anthracen-9-yl) -5-bromobenzaldehyde (3- (anthracen-9-yl) -5-bromobenzaldehyde) 7.9 g (21.9 mmol), pyridine-3- boronic acid neopentyl glycol ester (pyridine-3-boronic acid neopentylglycol ester) 5 g (24.4 mmol), tetrakis (triphenylphosphine) palladium (0)) 0.85 g (3 mol%), and sodium carbonate ) 5.17 g (48.8 mmol) was dissolved in 90 ml of tetrahydrofuran / water (volume ratio of tetrahydrofuran / H ₂ O = 2/1), and reacted at 80 ° C. for 12 hours. The obtained reaction was extracted with ethyl acetate, the solvent was removed under reduced pressure, separated by column and dried to give 7.24 g (Y = 91%) of a white solid.

Synthesis Example  2: 3- (anthracene-9-yl) -5- (3,5-di (pyridin-3-yl)) Benzaldehyde Synthesis of (3- (anthracen-9-yl) -5- (3,5-di (pyridin-3-yl)) benzaldehyde)

3- (anthracen-9-yl) -5-bromobenzaldehyde (3- (anthracen-9-yl) -5-bromobenzaldehyde) 3.61 g (10 mmol), 3- (3- (4,4,5,5 -Tetramethyl-1,3,2-dioxaborolan-2-yl) -5- (pyridine-3-yl) phenyl) pyridine (3- (3- (4,4,5,5-tetramethyl-1 (3,2-dioxaborolan-2-yl) -5- (pyridin-3-yl) phenyl) pyridine) 3.94 g (11 mmol), tetrakis (triphenylphosphine) palladium (0) 0)) 0.35 g (3 mol%) and 2.2 g (43.2 mmol) of sodium carbonate were dissolved in 90 ml of tetrahydrofuran / water (volume ratio of tetrahydrofuran / H ₂ O = 2/1), and the reaction was carried out at 80 ° C. for 12 hours. The obtained reaction was extracted with ethyl acetate, the solvent was removed under reduced pressure, separated by column, and dried to obtain 3.9 g (Y = 76%) of a white solid.

Synthesis Example  3: 2- (4- (4,4,5,5,- Tetramethyl -1,3,2- Dioxaboloran -2 days) Phenyl ) -5- Fe Neyl-1,3,4-oxadiazole (2- (4- (4,4,5,5- tetramethyl -1,3,2- dioxaborolan -2-yl) phenyl) -5-phenyl-1,3,4-oxadiazole)

5 g (16.6 mmol) of 2- (4-bromophenyl) -5-phenyl-1,3,4-oxadiazole (2- (4-bromophenyl) -5-phenyl-1,3,4-oxadiazole), 5.1 g (19.9 mmol) of bis (pinacolato) diboron, a complex of [1,1'-bis (diphenylphosphino) ferrocene] dichloro-palladium (II) and dichloromethane (a 0.41 g (3 mol%) of complex [1,1'-Bis (diphenylphosphino) ferrocene] dichloro-palladium (II) with dichloromethane, 4.9 g (49.8 mmol) of potassium acetate was added to dimethylformaimde: After dissolving in 100 ml and reacted at 80 ℃ for 12 hours. The reaction product was extracted with ethyl acetate, the solvent was removed under reduced pressure, separated by column, and dried to yield 3.1 g (Y = 53%) of a pale yellow solid.

Synthesis Example  4: 2- (3- (anthracene-9-yl) -5- Bromophenyl ) Benzo [d] Oxazole Synthesis of (2- (3- (anthracen-9-yl) -5-bromophenyl) benzo [d] oxazole

10 g (27.7 mmol) of 3- (anthracen-9-yl) -5-bromobenzaldehyde) and 3.6 g (2-aminophenol) 2- (3-aminoanthene-9-yl) -5-bromobenzaldehyde mmol) was dissolved in 100 ml of acetic acid and stirred at room temperature for 30 minutes. 14.7 g (33.2 mmol) of lead (IV) acetate was added thereto, followed by stirring at 50 ° C. for 1 hour. The reaction product was poured into water, extracted with ethyl acetate, the solvent was removed under reduced pressure, separated by column and dried to obtain 4.5 g (Y = 33%) of white solid.

Example  1: Synthesis of Compound of Formula 67

3 g of 3- (anthracene-9-yl) -5- (pyridin-3-yl) benzaldehyde (3- (anthracen-9-yl) -5- (pyridin-3-yl) benzaldehyde) prepared in Synthesis Example 1 (8.3 mmol) and 0.91 g (8.3 mmol) of 2-aminophenol were dissolved in 80 ml of acetic acid and stirred at room temperature for 30 minutes. 4.4 g (9.96 mmol) of lead (IV) acetate was added thereto, followed by stirring at 50 ° C. for 1 hour. The obtained reaction was poured into water, extracted with ethyl acetate, the solvent was removed under reduced pressure, separated by column and dried to give 2.17 g (Y = 58%) of white solid.

Example  2: synthesis of a compound of formula 70

3 g of 3- (anthracene-9-yl) -5- (pyridin-3-yl) benzaldehyde (3- (anthracen-9-yl) -5- (pyridin-3-yl) benzaldehyde) prepared in Synthesis Example 1 (8.3 mmol) and 1.25 g (10 mmol) of 2-aminophenol (2-aminothiophenol) were dissolved in 40 ml of acetic acid and stirred at room temperature for 30 minutes. 4.4 g (9.96 mmol) of lead (IV) acetate was added thereto, followed by stirring at 50 ° C. for 1 hour. The reaction product was poured into water, extracted with ethyl acetate, the solvent was removed under reduced pressure, separated by column and dried to give 2.74 g (Y = 71%) of white solid.

Example  3: Synthesis of Compound of Formula 73

3- (anthracen-9-yl) -5- (pyridin-3-yl) benzaldehyde (3- (anthracen-9-yl) -5- (pyridin-3-yl) benzaldehyde) 0.36 prepared in Synthesis Example 1 g (1 mmol) and 0.22 g (1.2 mmol) of N-phenyl-o-phenylenediamine were dissolved in 30 ml of acetic acid and stirred at room temperature for 30 minutes. 0.53 g (1.2 mmol) of lead (IV) acetate was added thereto, followed by stirring at 50 ° C. for 1 hour. The obtained reaction was poured into water, extracted with ethyl acetate, the solvent was removed under reduced pressure, separated by column and dried to obtain 0.27 g (Y = 51%) of white solid.

Example  4: Synthesis of Compound of Formula 96

3- (anthracene-9-yl) -5- (3,5-di (pyridin-3-yl)) benzaldehyde (3- (anthracen-9-yl) -5- (3, prepared in Synthesis Example 2) 2 g (3.9 mmol) of 5-di (pyridin-3-yl)) benzaldehyde) and 0.51 g (4.7 mmol) of 2-aminophenol (2-aminophenol) were dissolved in 200 ml of acetic acid and stirred at room temperature for 30 minutes. 2.1 g (4.7 mmol) of lead (IV) acetate was added thereto, followed by stirring at 50 ° C. for 1 hour. The reaction product was poured into water, extracted with ethyl acetate, the solvent was removed under reduced pressure, separated by column and dried to obtain 1.2 g (Y = 51%) of white solid.

Example  5: synthesis of a compound of Formula 119

2- (4- (4,4,5,5-tetramethyl-1,3,2-dioxabobolan-2-yl) phenyl) -5-phenyl-1,3,4 prepared in Synthesis Example 3 Oxadiazole (2- (4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) -5-phenyl-1,3,4-oxadiazole) (6.7 mmol), 2- (3- (anthracen-9-yl) -5-bromophenyl) benzo [d] oxazole (2- (3- (anthracen-9-yl)-, prepared in Synthesis Example 4) 5-bromophenyl) benzo [d] oxazole) 2.5g (5.5mmol), tetrakis (triphenylphosphine) palladium (0)) 0.19g (3mol%), and sodium carbonate carbonate) 1.2 g (11.1 mmol) was dissolved in 90 ml of tetrahydrofuran / water (volume ratio of tetrahydrofuran / H ₂ O = 2/1), and then reacted at 80 ° C. for 12 hours. The obtained reaction was extracted with ethyl acetate, the solvent was removed under reduced pressure, separated by column and dried to give 2.6 g (Y = 79%) of white solid.

Example  6: Fabrication of Organic Light Emitting Device

Corning's 15 Ω / cm ² (1200 Å) ITO glass substrates were cut to 25 mm x 25 mm x 0.7 mm, ultrasonically cleaned in isopropyl alcohol and pure water for 5 minutes, and then UV and ozone for 30 minutes. Washed with.

N, N'-di (1-naphthyl) -N, N'-diphenylbenzidine (NPD) was vacuum deposited on the substrate to form a hole transport layer having a thickness of 40 nm.

4,4'-bis (carbazol-9-yl) biphenyl (CBP: 4,4'-Bis (carbazol-9-yl) biphenyl) as a phosphorescent host on the hole transport layer and tris (phenylpyridine) as a phosphorescent dopant Iridium (tris (phenylpyridine) Iridium) was vacuum deposited at a weight ratio of 90:10 to form a light emitting layer having a thickness of 30 nm.

BAlq was vacuum deposited on the emission layer to form a hole blocking layer having a thickness of 5 nm.

A compound of Formula 67 was vacuum deposited on the hole blocking layer to form an electron transport layer having a thickness of 20 nm.

LiF 5nm / Al 100nm were sequentially vacuum deposited on the electron transport layer to form a cathode formed of LiF / Al to prepare an organic light emitting device of Example 1.

Example  7: Fabrication of Organic Light Emitting Device

An organic light-emitting device was manufactured in the same manner as in Example 6, except that the compound of Chemical Formula 70 prepared in Example 2 was used as the electron transport layer.

Example  8: Fabrication of Organic Light Emitting Device

An organic light-emitting device was manufactured in the same manner as in Example 6, except that the compound of Formula 96 prepared in Example 4 was used as the electron transport layer.

Example  9: Fabrication of Organic Light Emitting Device

An organic light-emitting device was manufactured in the same manner as in Example 6, except that the compound of Formula 119 prepared in Example 5 of the present invention was used as the electron transporting layer.

Comparative example  1: Fabrication of Organic Light Emitting Device

An organic light-emitting device was manufactured in the same manner as in Example 6, except that Alq3, which is an electron transport material, was used as the electron transport layer.

Property measurement results and analysis

One) ^One H NMR  analysis

The compounds of Chemical Formulas 67, 70, 73, 96, and 119 synthesized in Examples 1 to 5 are analyzed by nuclear magnetic resonance spectroscopy ( ¹ H NMR (nuclear magnetic resonance spectroscopy)), respectively. It was.

2) Measurement of driving voltage, brightness, current efficiency, and power efficiency

The driving voltage (Vd) and turn-on voltage (Von) required to give brightness of 1000 nits for the organic light emitting diodes of Examples 6 to 9 and Comparative Example 1 were measured and shown in Table 1 below. Referring to Table 1 below, the organic light emitting device of Examples 6 to 9 it can be seen that the driving voltage and turn-on voltage is significantly lower than the organic light emitting device of Comparative Example 1.

Device characteristic measurement result at 1000nit  Turn-on voltage (Von, V) Drive voltage (Vd, V) Comparative Example 1 8.00 3.40 Example 6 7.40 3.00 Example 7 6.60 3.00 Example 8 6.40 3.20 Example 9 7.00 3.00

The current efficiency (cd / A) and power efficiency (Im / W) of the organic light emitting diodes of Examples 6 to 9 and Comparative Example 1 were measured, and the results of Examples 6, 8, and Comparative Example 1 are shown in the table. 2 and FIG. 11. Referring to Table 2 and FIG. 11, while the driving voltage and the turn-on voltage of the organic light emitting diodes of Examples 6 and 8 are significantly lower than those of Comparative Example 1, it was confirmed that the current efficiency and the power efficiency were significantly higher. Moreover, about Example 7 and 9, the current efficiency and the power efficiency which are equivalent to Example 6 and 8 were confirmed.

Device characteristic measurement result at 1000 nit Max Current Efficiency (cd / A) Power Efficiency (Im / W) Current Efficiency (cd / A) Power Efficiency (Im / W) Comparative Example 1 21.60 8.48 22.92 8.60 Example 6 29.80 12.60 29.93 16.89 Example 8 25.14 12.34 25.80 12.85

In addition, the current density characteristics of the organic light emitting diodes of Examples 6 to 9 and Comparative Example 1 were measured and shown in FIG. 12. Referring to FIG. 12, it was confirmed that the organic light emitting diodes of Examples 6 to 9 were much better in current density characteristics than in Comparative Example 1.

These results indicate that the bonding of holes and electrons in the light emitting layer is balanced, and Examples 6 to 9 were found to balance the bonding of holes and electrons in the light emitting layer, and the compounds used in Examples 6 to 9 Compared with Alq3, which is a general electron transport material, it was confirmed that it had excellent electron injection characteristics and electron transport characteristics.

3) thermal property measurement

The compounds obtained in Examples 1 to 5 were first analyzed by differential scanning calorimetry (DSC), and were analyzed secondarily with the compounds that had completed the first analysis. Among these, the analytical results of the compound of Example 1 are shown in FIG. 13. Referring to FIG. 13, the compound of Example 1 showed a melting point peak in the first analysis, but did not show a melting point peak in the second analysis. From this, it was confirmed that the compound of Example 1 was present in a stable amorphous state.

In addition, it was confirmed that the compounds of Examples 2 to 5 exist in an amorphous state in the same manner. Therefore, the organic light emitting device including the compound of Examples 1 to 5 is not affected by Joule heat during driving, it can be expected to show improved life characteristics compared to the conventional organic light emitting device.

All simple modifications or changes of the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.

1 to 5 are cross-sectional views showing various embodiments of the organic photoelectric device according to the present invention.

6 shows a ¹ H NMR spectrum of a compound of Formula 67 prepared according to Example 1 of the present invention.

FIG. 7 shows a ¹ H NMR spectrum of a compound of Formula 70 prepared according to Example 2 of the present invention.

8 shows a ¹ H NMR spectrum of a compound of Formula 73 prepared according to Example 3 of the present invention.

9 shows a ¹ H NMR spectrum of a compound of Formula 96 prepared according to Example 4 of the present invention.

10 is a ¹ H NMR spectrum of the compound of Formula 119 prepared according to Example 5 of the present invention.

11 is a graph measuring power efficiency of organic light emitting diodes manufactured according to Examples 6, 8, and Comparative Example 1 of the present invention.

12 is a graph measuring current density characteristics of organic light emitting diodes manufactured according to Examples 6 to 9 and Comparative Example 1 of the present invention.

13 is a graph showing the thermal properties of the compound of formula 67 prepared according to Example 1 of the present invention.

<Explanation of symbols for the main parts of the drawings>

10: anode 20: cathode

30: organic thin film layer 31: light emitting layer

32: hole transport layer 33: electron transport layer

34: hole injection layer 35: electron injection layer

Claims (10)

Compound represented by the following formula (1): [Formula 1]

In Chemical Formula 1, A ₁ to A ₃ , B, and D _{2 are the} same as or different from each other, and are each independently selected from the group consisting of CR ₃ or N, D ₁ is selected from the group consisting of O, S, Se, and NR ₄ , When D ₁ is NR ₄ , D ₂ is CR ₃ or N, If D ₁ is not NR ₄ , then D ₂ is N, E is hydrogen, substituted or unsubstituted alkyl group, nitrile group, fluoroalkyl group, cyano group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted heterocyclic group, nitro group, carbonyl group , An amide group, and SO ₂ R _{5 It} is selected from the group consisting of R ₁ to R ₂ may not be hydrogen at the same time, hydrogen; Halogen group; Nitrile group; Cyano group; Nitro group; Amide group; Carbonyl group; Ester group; Substituted or unsubstituted alkyl group; Substituted or unsubstituted alkoxy group; Substituted or unsubstituted alkenyl group; Substituted or unsubstituted aryl group; Substituted or unsubstituted arylamine group; Substituted or unsubstituted heteroarylamine group: Substituted or unsubstituted heterocyclic group; Substituted or unsubstituted amino group; A substituted or unsubstituted cycloalkyl group; BR ₆ R ₇ ; And SiR ₆ R ₇ R _{8 It} is selected from the group consisting of, R ₃ is selected from the group consisting of hydrogen and a substituted or unsubstituted alkyl group, R ₄ is a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a nitrile group, a cyano group, a nitro group, a carbonyl group, and an amide group Is selected from the group consisting of, R ₅ is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted cycloalkyl group, a nitrile group, a cyano group, a nitro group, a carbonyl group, and an amide group Is selected from the group consisting of, R ₆ to R ₈ are the same or different, and each independently selected from the group consisting of a substituted or unsubstituted alkyl group and a substituted or unsubstituted aryl group.  The method of claim 1, R ₁ and R ₂ are different from each other. The method of claim 1, Substituted alkyl group, substituted alkoxy group, substituted alkenyl group, substituted aryl group, substituted arylamine group, substituted heteroarylamine group, substituted heterocyclic group, substituted amino group, and substituted cycloalkyl group are halogen Groups, substituted or unsubstituted alkyl groups, substituted or unsubstituted alkenyl groups, substituted or unsubstituted alkoxy groups, substituted or unsubstituted arylamine groups, substituted or unsubstituted aryl groups, substituted or unsubstituted arylalkyl groups, Substituted or unsubstituted aryl alkenyl group, substituted or unsubstituted heterocyclic group, nitrile group, cyano group, acetylene group, substituted or unsubstituted amine group, substituted or unsubstituted cycloalkyl group, nitro group, carbonyl group, amide group , BR ₆ R ₇ , and SiR ₆ R _{7 A} compound which is substituted with one or more selected from the group consisting of R ₈ . The method of claim 1, In R ₁ to R ₂ of Formula 1, wherein the aryl group is a monocyclic aromatic or polycyclic aromatic. The method of claim 1, In R ₁ to R ₂ of Formula 1, the aryl amine group is a diphenyl amine group, dinaphthyl amine group, dibiphenyl amine group, phenyl naphthyl amine group, phenyl diphenyl amine group, ditolyl amine group, phenyl tolyl amine A group, a carbazole group, and a triphenyl amine group. The method of claim 1, In R ₁ to R ₂ of Formula 1, the heterocyclic group is a thiophene group, furan group, pyrrole group, imidazole group, thiazolyl group, oxazolyl group, oxadiazolyl group, triazolyl group, pyridinyl group, A compound selected from the group consisting of pyridazine group, quinolinyl group, isoquinolinin group, acridil group, imidazopyridinyl group, and imidazopyrimidinyl group. The method of claim 5, The substituent bonded to the nitrogen of the imidazole group and the triazole group is selected from the group consisting of a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heterocyclic group. The compound selected. The method of claim 1, R ₁ to R ₂ of Formula 1 One is a substituent selected from the group consisting of an alkyl group containing an amine group, a cycloalkyl group containing an amine group, an aryl group containing an amine group, and a heterocyclic group containing an amine group, and the other is a heterocyclic group, a nitrile group, Compound which is a substituent selected from the group consisting of a nitro group, a carbonyl group, and an amide group. anode; cathode; And at least one organic thin film layer disposed between the anode and the cathode, wherein at least one of the organic thin film layers comprises a novel compound of formula (1). The method of claim 9, The organic thin film layer, Light emitting layer; And An organic photoelectric device comprising at least one layer selected from the group consisting of a hole transport layer, a hole injection layer, an electron transport layer, and an electron injection layer.

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