KR101233369B1 - Novel compound for organic photoelectric device and organic photoelectric device including the same - Google Patents

Abstract

The present invention can provide a compound for an organic photoelectric device represented by the following formula 1 to 3 excellent in the transport capacity and thermal stability of holes and electrons.

[Formula 1]

 [Formula 2]

(3)

In Formulas 1 to 3, the definitions of Ar ₁ , Ar ₂ , R ₁ to R ₁₀ , and R ′ ₁ to R ′ ₃ are as described in the specification.

In addition, the compound for an organic photoelectric device according to the present invention may provide an organic photoelectric device having excellent life and efficiency characteristics.

Organic photoelectric devices, holes, electrons, transport capacity, thermal stability, lifetime, efficiency

Description

Novel compound for organic photoelectric device and organic photoelectric device including the same}

The present invention relates to a novel compound for an organic photoelectric device and an organic photoelectric device including the same, and more particularly, to a compound for an organic photoelectric device having excellent transport ability and thermal stability of holes and electrons. The present invention relates to a compound for an organic photoelectric device capable of providing an excellent organic photoelectric device and an organic photoelectric device including the same.

An organic photoelectric device means a device that converts light energy into electrical energy in a broad sense, or vice versa. Among such organic photoelectric devices, organic light emitting diodes (OLEDs), in particular, have attracted attention as the demand for flat panel displays increases.

The organic electroluminescent device has a structure in which a functional organic thin film layer is inserted between an anode and a cathode. In this case, the organic thin film layer may include a light emitting layer, a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer and the like, and may further include an electron blocking layer or a hole blocking layer due to the light emission characteristics of the light emitting layer.

In 1987, Eastman Kodak Co., Ltd. laminated a hole transport layer of a diamine derivative and an electron transporting layer of tris (8-hydroxy-quinolate) aluminum (Alq ₃ ) as an organic thin film layer. The first development of an organic electroluminescent device using a structure, and in 1987 CW Tang et al. Reported the first organic electroluminescent device with practical performance (Appl. Phys. Lett., Vol. 51 (12), 913, 1987 ). However, the organic electroluminescent device has been required to improve electrical characteristics and lifetime characteristics.

In the organic electroluminescent device, when holes are injected from the anode and electrons are injected from the cathode, the holes and the electrons move toward each other and then recombine to form excitons having high energy. At this time, light having a specific wavelength is generated as the excitons move to the ground state. Such light emission may be divided into fluorescence using excitons in singlet state and phosphorescence using excitons in triplet state. Recently, it is known that phosphorescence as well as fluorescence may be used as light emission of an organic electroluminescent device (Appl. Phys. Lett., 74 (3), 442, 1999; Appl. Phys. Lett., 75 (1), 4). , 1999).

In the phosphorescent material using such phosphorescence, electrons transfer from the ground state to the excited state, and then the singlet excitons are non-luminescently transferred to the triplet excitons through intersystem crossing, and then the triplet excitons are transferred to the ground state. Light emission is achieved. In this case, the phosphorescent light emitting material is more likely than the fluorescent light emitting material because the spin forbidden is not directly transferred to the ground state during the transition of the triplet excitons. There is an advantage that the emission duration is long.

In addition, when the light emitting excitons are formed by recombination of holes and electrons, triplet light emitting excitons are generated about three times more than singlet light emitting excitons. Therefore, there is a limit of luminous efficiency in the case of fluorescent light emitting materials using singlet excitons. On the other hand, when the phosphorescent material is used, both excitons of the triplet and singlet states can be used, and theoretically, the internal quantum efficiency can be up to 100%. Therefore, in the case of using the phosphorescent material, there is an advantage that can achieve a light emission efficiency about four times higher than the fluorescent material.

Meanwhile, the efficiency and performance of the light emitting device may vary depending on the host material used for the light emitting layer. In addition, a dopant may be added to the emission layer together with the host material in order to increase efficiency and stability of the emission state. In particular, 4,4-N, N-dicarbazolebiphenyl (CBP) was mainly used as the host material, but the compound has a disadvantage of very low thermal stability. In addition, the symmetry of the compound is high and easy to crystallize, there is a disadvantage that a short circuit or a pixel defect may occur when the temperature of the device rises. In addition, the compound has a problem that the light emission efficiency of the device is reduced because the excitation is not formed effectively in the light emitting layer because the movement of the hole is faster than the movement of the electron.

Therefore, in order to implement an organic photoelectric device having excellent efficiency and lifespan, development of a phosphorescent host material and a charge transporting material having excellent bipolar characteristics that can transfer both holes and electrons well is excellent. It is true.

One embodiment of the present invention provides a compound for an organic photoelectric device excellent in the ability to transport holes and electrons.

Another embodiment of the present invention provides an organic photoelectric device having excellent life and efficiency characteristics, including the compound for an organic photoelectric device.

Technical problems to be achieved by the present invention are not limited to the technical problems mentioned above, and other technical problems not mentioned will be clearly understood by those skilled in the art from the following description.

The technical problems to be achieved by the present invention are not limited to the technical problems mentioned above.

One embodiment of the present invention provides a compound for an organic photoelectric device represented by the following formula (1).

[Formula 1]

(In the formula 1,

Ar ₁ is a substituted or unsubstituted arylene group having 6 to 20 carbon atoms,

Ar ₂ is a substituted or unsubstituted alkyl group having 1 to 40 carbon atoms, a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, a substituted or unsubstituted arylamine group having 6 to 40 carbon atoms, and a substituted or unsubstituted carbon atom 2 It is selected from the group consisting of to 40 heteroaryl groups,

R ₁ to R ₉ are the same as or different from each other, and each independently, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms, a substituted or unsubstituted carbon group having 1 to 30 carbon atoms An alkenyl group, a substituted or unsubstituted alkenylene group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms, However, two adjacent to each other selected from R ₁ to R ₅ may form a fusion ring, two adjacent to each other selected from R ₆ to R ₉ may form a fusion ring,

R ' ₁ to R' ₃ are the same as or different from each other, each independently selected from the group consisting of a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, and a substituted or unsubstituted aryl group having 6 to 20 carbon atoms.)

Another embodiment of the present invention provides a compound for an organic photoelectric device represented by Formula 2 below.

[Formula 2]

(In Formula 2,

Ar ₁ is a substituted or unsubstituted arylene group having 6 to 20 carbon atoms,

Ar ₂ is a substituted or unsubstituted alkyl group having 1 to 40 carbon atoms, a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, a substituted or unsubstituted arylamine group having 6 to 40 carbon atoms, and a substituted or unsubstituted carbon atom 2 It is selected from the group consisting of to 40 heteroaryl groups,

R ₁ to R ₉ are the same as or different from each other, and each independently, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms, a substituted or unsubstituted carbon group having 1 to 30 carbon atoms An alkenyl group, a substituted or unsubstituted alkenylene group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms, However, two adjacent to each other selected from R ₁ to R ₅ may form a fusion ring, two adjacent to each other selected from R ₆ to R ₉ may form a fusion ring,

R ' ₁ to R' ₃ are the same as or different from each other, each independently selected from the group consisting of a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, and a substituted or unsubstituted aryl group having 6 to 20 carbon atoms.)

Another embodiment of the present invention provides a compound for an organic photoelectric device represented by the following formula (3).

(3)

(3)

Ar ₁ is a single bond or a substituted or unsubstituted arylene group having 6 to 20 carbon atoms,

Ar ₂ is a substituted or unsubstituted alkyl group having 1 to 40 carbon atoms, a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, a substituted or unsubstituted arylamine group having 6 to 40 carbon atoms, and a substituted or unsubstituted carbon atom 2 It is selected from the group consisting of to 40 heteroaryl groups,

R ₁ to R ₁₀ are the same as or different from each other, and each independently, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms, a substituted or unsubstituted carbon group having 1 to 30 carbon atoms An alkenyl group, a substituted or unsubstituted alkenylene group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms, However, two adjacent to each other selected from R ₁ to R ₅ may form a fusion ring, two adjacent to each other selected from R ₆ to R ₁₀ may form a fusion ring,

R ' ₁ to R' ₃ are the same as or different from each other, each independently selected from the group consisting of a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, and a substituted or unsubstituted aryl group having 6 to 20 carbon atoms.)

Another embodiment of the present invention is an organic photoelectric device comprising an anode, a cathode and at least one organic thin film layer interposed between the anode and the cathode, at least one of the organic thin film layer is one of the present invention It provides an organic photoelectric device comprising a compound for an organic photoelectric device according to the embodiment.

Another embodiment of the present invention provides a display device including the organic photoelectric device.

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

The compound for an organic photoelectric device according to the embodiment of the present invention utilizes phosphorescent light emission, and has excellent thermal stability such that the glass transition temperature (T _g ) and the thermal decomposition temperature (T _d ) are 110 ° C. or higher and 400 ° C. or higher, respectively. . In addition, the compound for an organic photoelectric device has a bipolar (bipolar) characteristic that can transfer both holes and electrons well. Thus, another embodiment of the present invention can provide an organic photoelectric device including the compound for an organic photoelectric device, excellent in life characteristics, and having a high luminous efficiency even at a low driving voltage.

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.

In the present specification, "substituted" means a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 1 to 10 carbon atoms, a substituted or unsubstituted carbon group having 6 to 20 unless otherwise defined. It means substituted with a substituent selected from the group consisting of an aryl group, a substituted or unsubstituted arylamine group having 6 to 20 carbon atoms, and a substituted or unsubstituted heteroaryl group having 2 to 20 carbon atoms.

In addition, in this specification, "hetero" means containing one to three heteroatoms of N, O, S, or P in one ring unless otherwise defined, and the remainder is carbon.

The compound for an organic photoelectric device according to the embodiment of the present invention simultaneously includes a benzimidazole having excellent electron transfer characteristics and an indolo [2,3, c] carbazole group having excellent hole transfer characteristics, and various substituents. It is substituted by, and has a bipolar (bipolar) property that can transfer both holes and electrons well.

Hereinafter, a compound for an organic photoelectric device according to an embodiment of the present invention will be described in more detail.

One embodiment of the present invention provides a compound for an organic photoelectric device represented by the following formula (1).

[Formula 1]

(In the formula 1,

Ar ₁ is a substituted or unsubstituted arylene group having 6 to 20 carbon atoms,

Ar ₂ is a substituted or unsubstituted alkyl group having 1 to 40 carbon atoms, a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, a substituted or unsubstituted arylamine group having 6 to 40 carbon atoms, and a substituted or unsubstituted carbon atom 2 It is selected from the group consisting of to 40 heteroaryl groups,

R ₁ to R ₉ are the same as or different from each other, and each independently, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms, a substituted or unsubstituted carbon group having 1 to 30 carbon atoms An alkenyl group, a substituted or unsubstituted alkenylene group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms, However, two adjacent to each other selected from R ₁ to R ₅ may form a fusion ring, two adjacent to each other selected from R ₆ to R ₉ may form a fusion ring,

R ' ₁ to R' ₃ are the same as or different from each other, each independently selected from the group consisting of a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, and a substituted or unsubstituted aryl group having 6 to 20 carbon atoms.)

In addition, another embodiment of the present invention provides a compound for an organic photoelectric device represented by the following formula (2).

[Formula 2]

(In Formula 2,

Ar ₁ is a substituted or unsubstituted arylene group having 6 to 20 carbon atoms,

Ar ₂ is a substituted or unsubstituted alkyl group having 1 to 40 carbon atoms, a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, a substituted or unsubstituted arylamine group having 6 to 40 carbon atoms, and a substituted or unsubstituted carbon atom 2 It is selected from the group consisting of to 40 heteroaryl groups,

R ₁ to R ₉ are the same as or different from each other, and each independently, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms, a substituted or unsubstituted carbon group having 1 to 30 carbon atoms An alkenyl group, a substituted or unsubstituted alkenylene group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms, However, two adjacent to each other selected from R ₁ to R ₅ may form a fusion ring, two adjacent to each other selected from R ₆ to R ₉ may form a fusion ring,

R ' ₁ to R' ₃ are the same as or different from each other, each independently selected from the group consisting of a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, and a substituted or unsubstituted aryl group having 6 to 20 carbon atoms.)

In addition, another embodiment of the present invention provides a compound for an organic photoelectric device represented by the following formula (3).

(3)

(3)

Ar ₁ is a single bond or a substituted or unsubstituted arylene group having 6 to 20 carbon atoms,

Ar ₂ is a substituted or unsubstituted alkyl group having 1 to 40 carbon atoms, a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, a substituted or unsubstituted arylamine group having 6 to 40 carbon atoms, and a substituted or unsubstituted carbon atom 2 It is selected from the group consisting of to 40 heteroaryl groups,

R ₁ to R ₁₀ are the same as or different from each other, and each independently, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms, a substituted or unsubstituted carbon group having 1 to 30 carbon atoms An alkenyl group, a substituted or unsubstituted alkenylene group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms, However, two adjacent to each other selected from R ₁ to R ₅ may form a fusion ring, two adjacent to each other selected from R ₆ to R ₁₀ may form a fusion ring,

R ' ₁ to R' ₃ are the same as or different from each other, each independently selected from the group consisting of a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, and a substituted or unsubstituted aryl group having 6 to 20 carbon atoms.)

In Chemical Formulas 1 to 3, the arylene group of Ar ₁ may be a monocyclic arylene group such as a phenylene group, a biphenylene group, and a terphenylene group; Alternatively, polycyclic arylene groups such as naphthylene group, anthracenylene group, phenanthrenylene group, pyrenylene group, perylenylene group, and pyrenylene group may be used as a light emitting layer of an organic photoelectric device.

In Formulas 1 to 3, when Ar ₂ is a derivative of a substituent selected from the group consisting of an aryl group, a carbazole group, an arylamine group, and a fluorene group, it may provide not only electrical properties but also improved thermal stability. have.

More specifically, Ar ₂ may be selected from the group consisting of substituents represented by the following Chemical Formulas 4 to 12.

[Formula 4] [Formula 5] [Formula 6]

[Formula 7] [Formula 8] [Formula 9]

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

(In Chemical Formulas 4 to 12,

R ″ ₁ to R ″ ₉ are the same as or different from each other, and are each independently selected from the group consisting of an unsubstituted alkyl group having 1 to 10 carbon atoms, and an unsubstituted aryl group having 6 to 12 carbon atoms,

a, c, e, g, h, j, and l are the same or different from each other and are each independently 1 or 2,

b, d, f, i, and k are the same or different from each other and independently of each other, 0 or an integer between 1 and 2.)

In addition, when Ar ₂ is an unsubstituted alkyl group, the Ar ₂ may be more easily applied when forming a film by a wet film method.

The compound for an organic photoelectric device represented by Chemical Formula 1 may be more specifically represented by the following Chemical Formulas 13 to 74. However, the following compounds are only specific examples of the present invention, and the present invention is not limited by the following compounds.

[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]

In addition, as the compound for an organic photoelectric device represented by Formula 2, those represented by the following Formulas 75 to 78 may be used. However, the following compounds are only specific examples of the present invention, and the present invention is not limited by the following compounds.

[Formula 75] [Formula 76]

[Formula 77] [Formula 78]

In addition, as the compound for an organic photoelectric device represented by Formula 3, those represented by the following Formulas 79 to 82 may be used. However, the following compounds are only specific examples of the present invention, and the present invention is not limited by the following compounds.

[Formula 79] [Formula 80]

[Formula 81] [Formula 82]

The compound for an organic photoelectric device according to the embodiment of the present invention may be used as a host material alone or in combination with a dopant. A dopant is a compound having a high luminous ability per se, and is also called a guest because it is mixed with the host material in a small amount. The dopant is generally used in the art and is not particularly limited. More specifically, the dopant may be a fluorescent or phosphorescent dopant having high luminous quantum efficiency, poor aggregation, and which may be uniformly distributed in the host material. have.

In particular, the dopant may be a phosphorescent dopant material selected from the group consisting of red, green, blue, and white, such as a metal complex capable of emitting light by multiplet excitaion of a triplet state or more. Good to do. More specifically, the phosphorescent dopant may be an organometallic compound including an element selected from the group consisting of Ir, Pt, Os, Ti, Zr, Hf, Eu, Tb, Tm, and combinations thereof. More specifically, as the red phosphorescent dopant, platinum-octaethylporphyrin complex (PtOEP), Ir (Piq) ₂ (acac), Ir (Piq) ₃ , RD 61 manufactured by UDC, etc. may be used, and as the green phosphorescent dopant, Ir (PPy) ₂ (acac), Ir (PPy) ₃ , GD48 from UDC, Inc. may be used, and (4,6-F ₂ PPy) ₂ Irpic may be used as the blue phosphorescent dopant. At this time, Piq means 1-phenylisoquinoline (1-phenylisoquinoline), acac means acetylacetonate, F ₂ PPy means 2- (difluorophenyl) pyridinato, pic is Refers to picolinate, PPy means 2-phenylpyridine.

The compound for an organic photoelectric device according to the exemplary embodiment of the present invention has a glass transition temperature (T _g ) of 110 ° C. or more and a thermal decomposition temperature (T _d ) of 400 ° C. or more. More specifically, the glass transition temperature (T _g ) is in the range of 110 to 200 ° C, and the pyrolysis temperature (T _d ) is in the range of 400 to 600 ° C. Thus, it can be used as a host material or charge transport material having thermal stability and electrochemical stability. In particular, the thermal decomposition temperature (T _d ) may be 430 ℃ or more.

The compound for an organic photoelectric device according to the exemplary embodiment of the present invention may be used in an organic thin film layer to improve efficiency characteristics of the organic photoelectric device and to lower driving voltage. In addition, the life characteristics can be improved.

Accordingly, one embodiment of the present invention provides an organic photoelectric device comprising the compound for an organic photoelectric device. In this case, the organic photoelectric device means an organic light emitting device, an organic solar cell, an organic transistor, an organic photosensitive drum, or an organic memory device. In particular, in the case of an organic solar cell, a compound for an organic photoelectric device according to an exemplary embodiment of the present invention is included in an electrode or an electrode buffer layer to increase quantum efficiency. Can be used.

Hereinafter, an organic photoelectric device will be described in detail.

Another embodiment of the present invention is an organic photoelectric device comprising an anode, a cathode and at least one organic thin film layer interposed between the anode and the cathode, at least one of the organic thin film layer is an embodiment of the present invention It provides an organic photoelectric device comprising a compound for an organic photoelectric device according to.

The compound for an organic photoelectric device may be used as a host material or a charge transport material.

Therefore, the organic thin film layer which may include the compound for an organic photoelectric device may include a light emitting layer, a hole transport layer, a hole injection layer, a hole blocking layer, an electron transport layer, an electron injection layer, an electron blocking layer, or any one or more layers thereof. It may include. At least one of these layers includes a compound for an organic photoelectric device according to the present invention. In particular, the compound for an organic photoelectric device according to an embodiment of the present invention may be included in a layer selected from the group consisting of a light emitting layer, a hole transport layer, a hole injection layer, an electron transport layer, an electron injection layer, and combinations thereof.

1 to 5 are cross-sectional views of an organic photoelectric device including the compound for an organic photoelectric device according to an embodiment of the present invention.

1 to 5, an organic photoelectric device 100, 200, 300, 400, and 500 according to an embodiment of the present invention may include an anode 120, a cathode 110, and a gap between the anode and the cathode. It has a structure including at least one organic thin film layer 105 interposed therebetween.

The anode 120 includes a cathode material. As the anode material, a material having a large work function is preferably used to facilitate injection of holes into the organic thin film layer. Specific examples of the positive electrode material include metals such as nickel, platinum, vanadium, chromium, copper, zinc, and gold or alloys thereof, and include zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO). And metal oxides such as ZnO and Al, or combinations of metals and oxides such as SnO ₂ and Sb, and poly (3-methylthiophene), poly [3,4- (ethylene-1, 2-dioxy) thiophene] (conductive polymers such as polyehtylenedioxythiophene (PEDT), polypyrrole and polyaniline). However, the positive electrode material is not limited to these compounds. In particular, it is preferable to use a transparent electrode containing ITO as the anode material.

The negative electrode 110 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, or alloys thereof, and LiF / Al. And multilayered structure materials such as LiO ₂ / Al, LiF / Ca, LiF / Al, and BaF ₂ / Ca. However, the negative electrode material is not limited to these compounds. In particular, it is preferable to use a metal electrode such as aluminum as the cathode material.

First, referring to FIG. 1, FIG. 1 illustrates an organic photoelectric device 100 in which only a light emitting layer 130 exists as an organic thin film layer 105. The organic thin film layer 105 may exist only as a light emitting layer 130.

Referring to FIG. 2, FIG. 2 illustrates a two-layered organic photoelectric device 200 in which an emission layer 230 including an electron transport layer and a hole transport layer 140 exist as an organic thin film layer 105, and an organic thin film layer 105. The silver may have a two-layer type including an emission layer 230 and a hole transport layer 140. In this case, the light emitting layer 130 functions as an electron transporting layer, and the hole transporting layer 140 functions to improve the bonding property with a transparent electrode such as ITO and the hole transporting property.

Referring to FIG. 3, FIG. 3 illustrates a three-layered organic photoelectric device 300 having an electron transport layer 150, a light emitting layer 130, and a hole transport layer 140 as an organic thin film layer 105. In 105, the light emitting layer 130 is in an independent form, and has a form in which layers (electron transport layer 150 and hole transport layer 140) having excellent electron transport properties and hole transport properties are stacked in separate layers.

Referring to FIG. 4, FIG. 4 illustrates a four-layered organic photoelectric device 400 in which an electron injection layer 160, an emission layer 130, a hole transport layer 140, and a hole injection layer 170 exist as an organic thin film layer 105. ), The hole injection layer 170 may improve the adhesion to ITO used as an anode.

Referring to FIG. 5, FIG. 5 is an organic thin film layer 105, which is different from an electron injection layer 160, an electron transport layer 150, an emission layer 130, a hole transport layer 140, and a hole injection layer 170. As a five-layered organic photoelectric device 500 having five layers serving as a function, the organic photoelectric device 500 is effective in lowering voltage by separately forming an electron injection layer 160.

1 to 5, the electron transport layer 150, the electron injection layer 160, the light emitting layers 130 and 230, the hole transport layer 140, and the hole injection layer 170 forming the organic thin film layer 105, or these Combination of the above includes a compound for an organic photoelectric device. In this case, the compound for an organic photoelectric device may be used in the electron transport layer 150 including the electron transport layer 150 or the electron injection layer 160, and the hole blocking layer (not shown) when included in the electron transport layer It is effective to provide an organic photoelectric device having a more simplified structure because there is no need to form a) separately.

The above-described organic photoelectric device includes a dry film method such as vacuum deposition, sputtering, plasma plating, and ion plating after an anode is formed on a substrate; Alternatively, the organic thin film layer may be formed by a wet film method such as spin coating, dipping, flow coating, or the like, followed by forming a cathode thereon.

According to another embodiment of the present invention, a display device including the organic photoelectric device is provided.

Hereinafter, specific embodiments of the present invention will be described. However, the embodiments described below are merely for illustrating or explaining the present invention in detail, and thus the present invention is not limited thereto.

Synthesis of Compound for Organic Photoelectric Device

Example 1 Synthesis of Compound of Formula 13

The compound of Formula 13, which is presented as a specific example of the compound for an organic photoelectric device of the present invention, was synthesized through the same route as in Schemes 1 and 2.

[Reaction Scheme 1]

A first step; Synthesis of intermediate product (A)

In a 2-liter round bottom flask equipped with a reflux condenser and a stirrer, 20.0 g (60.6 mmol) of 1,2-diiodobenzene and 31.7 g (127.3 mmol) of 2-nitrophenylboronic acid-pinacholate were diluted with dimethylformamide and distilled water. After dissolving in a 4: 1 volume ratio, 40.2 g (127.3 mmol) of barium hydroxide and octahydrate and 0.57 g of [1,1 '-(diphenylphosphino) ferrocene] dichloropalladium (PdCl ₂ (dppf)) 7.0 mmol) was added dropwise and stirred for 8 hours at 60 ° C. The reaction was filtered through a reduced pressure filter and extracted using ethyl acetate, the solvent was removed, and the compound was purified using chromatography (column: silica gel). Isolation yielded the intermediate product A. Elemental analysis of the obtained compound (EA) was as follows: C, 67.50; H, 3.78; N, 8.75; O, 19.98

A second step; Synthesis of Intermediate Product (B) (Indolo [2,3, c] carbazole)

In a 1 liter round bottom flask equipped with a reflux condenser and a stirrer, 33.0 g (100.3 mmol) of the intermediate product (A) prepared in step 1 and 135.0 g (515.0 mmol) of triphenylphosphine (PPh ₃ ) were used as a solvent. It was dissolved in dichlorobenzene and stirred at 180 ° C for 24 hours. The o-dichlorobenzene was removed by distillation under reduced pressure, and then the compound was separated using chromatography (column: silica gel) to obtain an intermediate product (B) (indolo [2,3, c] carbazole). Elemental analysis (EA) of the obtained compound was as follows: C, 85.02; H, 3.96; N, 11.02

[Reaction Scheme 2]

A third step; Synthesis of intermediate product (C)

10.0 g (39.0 mmol) of intermediate product (B) prepared in step 2 and 13.62 g (39.0 mmol) of 2- (4-bromophenyl) -1-phenyl-benzimidazole were dissolved in dimethyl sulfoxide (DMSO). Then, 0.77 g (7.8 mmol) of copper chloride (I), 8.08 g (58.5 mmol) of potassium carbonate and 1.4 g (7.8 mmol) of 1,10-phenanthroline were added dropwise, followed by heating and stirring at 150 ° C. for 12 hours. It was. After the reaction was completed, the solution was poured into distilled water to crystallize, and the reaction product was filtered through a reduced pressure filter to obtain a solid product. The solid product was dissolved in methylene chloride and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the compound was separated using chromatography (column: silica gel) to obtain an intermediate product (C). Elemental analysis (EA) of the obtained compound was as follows: C, 84.71; H, 4.61; N, 10.68

Step 4; Synthesis of Compound of Formula 13

5.0 g (9.53 mmol) of the intermediate product (C) prepared in step 3 and 2.14 g (10.5 mmol) of iodobenzene were dissolved in dimethyl sulfoxide (DMSO), and then 0.19 g (1.9 mmol) of copper chloride (I), 1.98 g (14.3 mmol) of potassium carbonate and 0.34 g (1.9 mmol) of 1,10-phenanthroline were added dropwise, followed by heating and stirring at 150 ° C. for 12 hours. After the reaction was completed, the solution was poured into distilled water to crystallize, and the reaction product was filtered through a reduced pressure filter to obtain a solid product. The solid product was dissolved in methylene chloride and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the compound was separated by chromatography (column: silica gel) to obtain a compound of formula (13). Elemental analysis (EA) of the obtained compound was as follows: C, 85.98; H, 4.70; N, 9.33

Example 2: Synthesis of Compound of Formula 14

Compound of Formula 14 presented as a specific example of the compound for an organic photoelectric device of the present invention was synthesized through the same path as Scheme 3 below.

Scheme 3

A first step; Synthesis of Compound of Formula 14

2.5 g (4.77 mmol) of the intermediate product (C) prepared in Step 3 of Example 1 and 1.71 g (5.3 mmol) of 3-bromo-9-phenyl-9H-carbazole were dissolved in dimethyl sulfoxide (DMSO). Then 0.1 g (0.95 mmol) of copper (I), 1.0 g (7.2 mmol) of potassium carbonate and 0.17 g (0.95 mmol) of 1,10-phenanthroline were added dropwise, followed by heating and stirring at 150 ° C. for 12 hours. It was. After the reaction was completed, the solution was poured into distilled water to crystallize, and the reaction product was filtered through a reduced pressure filter to obtain a solid product. The solid product was dissolved in methylene chloride and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the compound was separated by chromatography (column: silica gel) to obtain a compound of formula (14). Elemental analysis (EA) of the obtained compound was as follows: C, 86.25; H, 4.61; N, 9.14

Example 3: Compound Synthesis of Formula 48

The compound of Chemical Formula 48, presented as a specific example of the compound for an organic photoelectric device of the present invention, was synthesized through the same path as in Scheme 4 below.

[Reaction Scheme 4]

A first step; Synthesis of intermediate product (D)

10.0 g (39.0 mmol) of intermediate product (B) prepared in step 2 of Example 1 and 13.62 g (39.0 mmol) of 2- (3-bromophenyl) -1-phenyl-benzimidazole were prepared by dimethyl sulfoxide ( DMSO), 0.77 g (7.8 mmol) of copper chloride (I), 8.08 g (58.5 mmol) of potassium carbonate and 1.4 g (7.8 mmol) of 1,10-phenanthroline were added dropwise, followed by 12 hours at 150 ° C. Heated and stirred. After the reaction was completed, the solution was poured into distilled water to crystallize, and the reaction product was filtered through a reduced pressure filter to obtain a solid product. The solid product was dissolved in methylene chloride and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the compound was separated using chromatography (column: silica gel) to obtain an intermediate product (D). Elemental analysis (EA) of the obtained compound was as follows: C, 84.71; H, 4.61; N, 10.68

A second step; Synthesis of Compound of Formula 48

2.5 g (4.77 mmol) of the intermediate product (D) prepared in step 1 and 1.72 g (5.3 mmol) of (4-bromophenyl) -diphenylamine were dissolved in dimethyl sulfoxide, and then copper (I) 0.1. g (0.95 mmol), 1.0 g (7.2 mmol) of potassium carbonate and 0.17 g (0.95 mmol) of 1,10-phenanthroline were added dropwise, followed by heating and stirring at 150 ° C. for 12 hours. After the reaction was completed, the solution was poured into distilled water to crystallize, and the reaction product was filtered through a reduced pressure filter to obtain a solid product. The solid product was dissolved in methylene chloride and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the compound was separated by chromatography (column: silica gel) to obtain a compound of formula 48. Elemental analysis (EA) of the obtained compound was as follows: C, 86.02; H, 4.86; N, 9.12

Example 4: Synthesis of Compound of Formula 49

Compound of formula 49 presented as a specific example of the compound for an organic photoelectric device of the present invention was synthesized through the same path as Scheme 5 below.

Scheme 5

A first step; Synthesis of Compound of Formula 49

2.5 g (4.77 mmol) of the intermediate product (D) prepared in step 1 of Example 3, and 1.71 g (5.3 mmol) of 9- (3-bromophenyl) -9H-carbazole were added to dimethyl sulfoxide (DMSO). After melting, 0.1 g (0.95 mmol) of copper (I), 1.0 g (7.2 mmol) of potassium carbonate and 0.17 g (0.95 mmol) of 1,10-phenanthroline were added dropwise, followed by heating at 150 ° C. for 12 hours and Stirred. After the reaction was completed, the solution was poured into distilled water to crystallize, and the reaction product was filtered through a reduced pressure filter to obtain a solid product. The solid product was dissolved in methylene chloride and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the compound was separated by chromatography (column: silica gel) to obtain a compound of formula 49. Elemental analysis (EA) of the obtained compound was as follows: C, 86.25; H, 4.61; N, 9.14

Experimental Example 1: Evaluation of the thermal stability of the compound for an organic photoelectric device

The glass ion temperature (T _g ) and the thermal decomposition temperature (T _d ) of the compound for an organic photoelectric device synthesized in Examples 1 to 4 were measured by differential scanning calorimetry (DSC) and thermogravimetry (TGA). Was measured.

Manufacture of organic light emitting device

Examples 5 to 8

An organic electroluminescent device having the following structure was prepared using the compound for an organic photoelectric device synthesized in Examples 1 to 4 as a host and Ir (PPy) ₃ as a dopant.

ITO was used as a cathode of 1000 kPa, and aluminum (Al) was used as a cathode of 1000 kPa.

The organic electroluminescent device has a five-layer structure, and specifically, NPD (400 kW) / Compound for organic photoelectric device + Ir (PPy) ₃ (10 wt%, 300 kW) / BAlq (50 kW) / Alq3 (200 kW) / LiF ( It was prepared in the 5-layered structure of 5).

Specifically, the method of manufacturing the organic electroluminescent device, the anode is cut into ITO glass substrate having a sheet resistance value of 15 Ω / cm ² to 50mm × 50mm × 0.7mm size in each of acetone, isopropyl alcohol and pure water Ultrasonic cleaning for 15 minutes was followed by UV ozone cleaning for 30 minutes.

NPD was deposited on the substrate at a vacuum degree of 650 × 10 ⁻⁷ Pa and a deposition rate of 0.1 to 0.3 nm / s to form a hole transport layer having a film thickness of 400 μs.

Subsequently, a light emitting layer having a thickness of 300 μs was formed using the compound for an organic photoelectric device synthesized in Examples 1 to 4 under the same vacuum deposition conditions. At this time, phosphorescent dopant Ir (PPy) ₃ was simultaneously deposited.

At this time, by adjusting the deposition rate of the phosphorescent dopant, when the total amount of the light emitting layer is 100% by weight, the compounding amount of the phosphorescent dopant was deposited to 10% by weight.

BAlq was deposited on the light emitting layer using the same vacuum deposition conditions to form a hole blocking layer having a thickness of 50 kHz. Subsequently, Alq ₃ was deposited under the same vacuum deposition conditions to form an electron transport layer having a film thickness of 200 μs. LiF and Al were sequentially deposited on the electron transport layer to complete the organic electroluminescent device.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

1 to 5 are cross-sectional views illustrating various embodiments of an organic photoelectric device that may be manufactured including a compound for an organic photoelectric device according to an embodiment of the present invention.

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

100: organic photoelectric device 110: cathode

120: anode 105: organic thin film layer

130: light emitting layer 140: hole transport layer

150: electron transport layer 160: electron injection layer

170: hole injection layer 230: light emitting layer + electron transport layer

Claims (11)

A compound for an organic photoelectric device represented by Formula 1 below: [Formula 1]

(In the formula 1, Ar ₁ is a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, Ar ₂ is a substituted or unsubstituted alkyl group having 1 to 40 carbon atoms, a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, a substituted or unsubstituted arylamine group having 6 to 40 carbon atoms, and a substituted or unsubstituted carbon atom 2 It is selected from the group consisting of to 40 heteroaryl groups, R ₁ to R ₉ are the same as or different from each other, and each independently, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 1 to 30 carbon atoms, a substituted or unsubstituted carbon group having 6 to 30 carbon atoms An aryl group and a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms, provided that two adjacent ones selected from R ₁ to R ₅ may form a fusion ring, and R ₆ to Two adjacent to each other selected from R ₉ may form a fusion ring, R ' ₁ to R' ₃ are the same as or different from each other, each independently selected from the group consisting of a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, and a substituted or unsubstituted aryl group having 6 to 20 carbon atoms.) delete delete The method of claim 1, Ar ₂ is an organic photoelectric device compound selected from the group consisting of substituents represented by the following Chemical Formulas 4 to 12: [Formula 4] [Formula 5] [Formula 6]

[Formula 7] [Formula 8] [Formula 9]

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

(In Chemical Formulas 4 to 12, R ″ ₁ to R ″ ₉ are the same as or different from each other, and are each independently selected from the group consisting of an unsubstituted alkyl group having 1 to 10 carbon atoms, and an unsubstituted aryl group having 6 to 12 carbon atoms, a, c, e, g, h, j, and l are the same or different from each other and are each independently 1 or 2, b, d, f, i, and k are the same or different from each other and independently of each other, 0 or an integer between 1 and 2.) The method of claim 1, The compound for an organic photoelectric device is a compound for an organic photoelectric device that is used as a host material alone or in combination with a dopant. The method of claim 5, The dopant is a phosphorescent dopant selected from the group consisting of red, green, blue, and white compound for an organic photoelectric device. The method of claim 1, The compound for an organic photoelectric device is a compound for an organic photoelectric device that the glass transition temperature (T _g ) is 110 ℃ or more, the thermal decomposition temperature (T _d ) is 400 ℃ or more. In an organic photoelectric device comprising an anode, a cathode and at least one organic thin film layer interposed between the anode and the cathode, At least one of the organic thin film layer is an organic photoelectric device comprising the compound for an organic photoelectric device according to claim 1. 9. The method of claim 8, The organic photoelectric device compound is used as a host material or charge transport material. 9. The method of claim 8, The organic thin film layer is an organic photoelectric device that is selected from the group consisting of a light emitting layer, a hole transport layer, a hole injection layer, an electron transport layer, an electron injection layer, and combinations thereof. A display device comprising the organic photoelectric device of claim 8.

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