KR101233379B1 - Compound for organic photoelectric device and organic photoelectric device comprising same - Google Patents

Abstract

The present invention relates to a novel compound for an organic photoelectric device and an organic photoelectric device including the same, wherein the compound is represented by the following Chemical Formula 1.

 [Formula 1]

In Formula 1, the definitions for Ar ₁ , L and Q ₁ to Q ₁₃ are as described in the detailed description of the invention.

Electron transport, hole transport, bipolar, organic photoelectric device, driving voltage, lifetime, efficiency

Description

COMPOUND FOR ORGANIC PHOTOELECTRIC DEVICE AND ORGANIC PHOTOELECTRIC DEVICE COMPRISING SAME

The present invention relates to a compound for an organic photoelectric device and an organic photoelectric device including the same.

A photoelectric device is a device that converts light energy into electrical energy or vice versa in a broad sense. Examples of such photoelectric devices include organic electroluminescent devices, solar cells, and transistors. have. Among these optoelectronic devices, organic light emitting diodes (OLEDs) are particularly attracting attention as the demand for flat panel displays increases.

An organic electroluminescent device is a device that converts electrical energy into light by applying an electric field to an organic light emitting material, and triphenyldiamine, a low molecular aromatic diamine derivative derived from CWTang of Eastman Kodak in 1987. Low voltage drive organic EL by a stacked element comprising a thin film of a derivative (hole transport layer) and a thin film of tris (8-hydroxy-quinolate) aluminum (Alq3) (electron transporting light emitting layer) Since devices (CWTang, SA Vanslyke, Applied Physics Letters, Vol. 51, pp. 913-915, 1987, etc.) have been reported, studies on organic EL devices using organic materials as constituent materials have been actively conducted.

In general, an organic EL device has a structure formed on a glass substrate in order of an anode made of a transparent electrode, an organic thin film layer including a light emitting region, and a cathode made of a metal electrode. The organic thin film layer may include a light emitting layer, a hole injection layer, a hole transport layer, an electron transport layer or an electron injection layer, and may further include an electron blocking layer or a hole blocking layer due to light emission characteristics of the light emitting layer. When an electric field is applied to the organic EL device having such a structure, holes are injected from the anode and electrons are injected from the cathode, and the respective holes and electrons move toward each other and then recombine to each other. Will form a high exciton. In this case, light having a specific wavelength is generated as the excitons move to the ground state.

In general, in order to obtain high luminous efficiency in organic EL devices, holes and electrons in the light emitting layer should be smoothly combined. However, since the electron mobility of the organic material is slower than the hole mobility, the hole and the electron in the light emitting layer cannot be efficiently bound. Therefore, there is a need for the development of a novel compound that can increase the electron injection and mobility from the cathode and block the movement of holes.

In addition, the life of the organic EL device can be shortened while the material is crystallized by Joule heat generated when the device is driven. In order to solve this problem, 2- (4-biphenylyl) -5- (4-t-butylphenyl) -1,3,4-oxadiazole (PBD) having high electron transfer speed (Jpn. Appl. Phys., 27, L269 (1988)) has been proposed, but there is a problem that the crystallization when driving the device due to the lack of thermal stability. In addition, studies on basocuproin (BCP) and aluminum mixed coordination complexes (BAlq, Bis (2-methyl-8-quinolinolate) -4- (phenylphenolate) aluminum) with excellent hole mobility characteristics have been actively conducted. . However, the materials have excellent characteristics of lowering hole mobility, low electron injection characteristics, and crystallization during device driving, and thus, did not show satisfactory device characteristics.

Therefore, in order to achieve high efficiency and long life of the organic light emitting diode, development of an organic compound having high thermal stability that is excellent in injection and mobility of electrons and can suppress crystallization during driving is required.

One embodiment of the present invention is to provide a compound for an organic photoelectric device which is excellent in electron injection and mobility, and has a high thermal stability that can suppress crystallization when driving the organic photoelectric device.

Another embodiment of the present invention is to provide an organic photoelectric device including the compound for an organic photoelectric device.

Another embodiment of the present invention is to provide a display device including the organic photoelectric device.

One embodiment of the present invention provides a compound for an organic photoelectric device represented by the following Chemical Formula 1.

[Formula 1]

(In the formula 1,

Ar ₁ is a group consisting of a substituted or unsubstituted aryl group, a substituted or unsubstituted arylamine group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted heteroarylamine group, a substituted or unsubstituted cycloalkyl group Selected from

L is a substituted or unsubstituted arylene group or a substituted or unsubstituted heteroarylene group,

Q ₁ to Q ₁₃ are the same as or different from each other, each independently N or selected from the group consisting of CR ₁ to CR ₁₃ corresponding to the subscripts of Q, respectively

R ₁ to R ₄ are the same as or different from each other, and each independently hydrogen, a substituted or unsubstituted aryl group, a substituted or unsubstituted arylamine group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted hetero An arylamine group and a substituted or unsubstituted cycloalkyl group, provided that R ₁ to R ₄ are not all hydrogen at the same time,

R ₅ to R ₁₃ are the same as or different from each other, and each independently hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, a substitution Or an unsubstituted arylamine group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted heteroarylamine group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted amino group, SiR '(R' is 1 carbon atom) To an alkyl group of 6 to 6) and B).

Another embodiment of the present invention includes an anode, a cathode, and an organic thin film layer interposed between the anode and the cathode and at least one layer including a light emitting layer, wherein at least one of the organic thin film layers is It provides an organic photoelectric device comprising a compound represented by the formula (1).

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 present invention has excellent electron injection and mobility, and has high thermal stability, thereby suppressing crystallization during driving of the organic photoelectric device. As a result, when the compound for an organic photoelectric device is applied to an organic photoelectric device, a driving voltage may be lowered and life and efficiency may be improved.

Hereinafter, embodiments of the present invention will be described in detail. However, it should be understood that the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.

In the present specification, "substituted", unless otherwise defined, halogen atom, hydroxy group, cyano group, nitro group, amide group, carboxyl group, alkyl group, alkenyl group, alkoxy group, arylamine group, aryl group, aralkyl group, Aralkenyl group, aryloxy group, arylthio group, alkoxycarbonyl group, heterocyclic group, amine group, and cycloalkyl group, BR ₆ R ₇ , and SiR ₆ R ₇ R ₈ (wherein R ₆ to R ₈ 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 30 carbon atoms, and a substituted or unsubstituted aryl group having 6 to 50 carbon atoms). .

In addition, in this specification, unless otherwise defined, "hetero" contains 1 to 3 heteroatoms selected from the group consisting of N, O, S, and P in one ring group, and the remainder is carbon. Do.

According to one embodiment of the present invention, a compound for an organic photoelectric device represented by Chemical Formula 1 is provided.

[Formula 1]

(In the formula 1,

Ar ₁ is a group consisting of a substituted or unsubstituted aryl group, a substituted or unsubstituted arylamine group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted heteroarylamine group, and a substituted or unsubstituted cycloalkyl group. Selected from

L is a substituted or unsubstituted arylene group or a substituted or unsubstituted heteroarylene group,

Q ₁ to Q ₁₃ are the same as or different from each other, each independently N or selected from the group consisting of CR ₁ to CR ₁₃ corresponding to the subscripts of Q, respectively

R ₁ to R ₄ are the same as or different from each other, and each independently hydrogen, a substituted or unsubstituted aryl group, a substituted or unsubstituted arylamine group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted hetero An arylamine group and a substituted or unsubstituted cycloalkyl group, provided that R ₁ to R ₄ are not all hydrogen at the same time,

R ₅ to R ₁₃ are the same as or different from each other, and each independently hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, a substitution Or an unsubstituted arylamine group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted heteroarylamine group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted amino group, SiR '(R' is 1 carbon atom) To an alkyl group of 6 to 6) and B).

Structural design is basically involved in synthesizing organic materials used in organic photoelectric devices and other industries. There are several elements required for structural design, the first of which is wavelength. The number of aromatic benzenes used in the material design, or the proper placement of the electron donor or electron acceptor material, changes the excitation wavelength of the material and determines the light emitting region that can be used. Second is molecular weight. Materials used as materials for organic photoelectric devices require an appropriate glass transition temperature when used for vacuum deposition. Higher molecular weights typically correlate with higher glass transition temperatures. Of course, the structure of the material is also affected, but in the molecular weight of 1,000 or less molecules, the glass transition temperature is determined by the high molecular weight. Third is the basic structure except the functional group. As the material used for the organic photoelectric device, a material having excellent hole transporting ability or excellent electron transporting capability, or an amphoteric ability containing both hole and electron transporting capability at the same time is used according to the characteristics of each layer. In each case it is easy to impart the desired capability by introducing an auxiliary functional group when the basic structure has an electron or hole transport capability.

In particular, derivatives such as pyridine, quinoline, triazine and benzimidazole have excellent electron transfer properties, and derivatives such as carbazole and arylamine have excellent hole transfer properties. Bi-polar materials that have both electron and hole transport properties can be used in materials that require both electron and hole transport properties.By introducing both derivatives with good hole transport properties and derivatives with good electron transport properties, Can be implemented.

In the present invention, by introducing a variety of aryl groups or heteroaryl groups in the basic structure having an electron or hole transfer ability, absorption and emission in the desired wavelength region can occur, a molecular weight having an appropriate glass transition temperature, electron transfer or hole transfer We wanted to synthesize materials that can give us the desired electrical properties.

Referring to the structure of Formula 1, the compound of Formula 1 according to the present invention is connected to the core portion and the core portion, including Q ₁ to Q ₁₃ , Ar ₁ , and R ₁ to R ₁₃ It can think by dividing into the functional substituent part containing.

Q ₁ to Q ₁₃ of the core part in Chemical Formula 1 are C (carbon) or N (nitrogen), arylbenzene having six carbons or heteroarylbenzene including N are adjacent to each other in the plane to form a wide Has an energy band gap. Accordingly, in particular, when any one or two or more of Q ₁ to Q ₁₃ in Chemical Formula 1 is N, the lower unoccupied molecular orbital (LUMO) energy level is lowered and the electron affinity of the molecule is increased to improve the electron injection and migration characteristics. Can be improved. Therefore, since the voltage required for driving the organic light emitting element can be reduced, the effect of increasing the power efficiency can be given.

In addition, the functional substituent moiety including Ar ₁ and R ₁ to R ₁₃ serves to enhance the intermolecular interaction by imparting a certain rigidity to the compound. Accordingly, the compound of Formula 1 has a high glass transition temperature, thereby improving thermal stability and lifespan of the organic light emitting device.

The functional substituent moiety may be a functional group having excellent electron injection characteristics, or composed of functional groups capable of increasing thermal stability. That is, a compound having an electron transporting ability can be provided by introducing a substituent having electron transporting properties into these functional substituent moieties, and a compound having a hole transporting ability can be provided by introducing a substituent having hole transporting properties, Moreover, the compound which has amphotericity can also be provided by introducing the substituent which has an electron transport characteristic, and the substituent which has a hole transport characteristic together. In addition, the hole injection / transfer capability and the electron injection / transfer capability may be selectively provided, thereby enabling efficient hole-electron coupling in the light emitting layer. For example, when one selected from Ar ₁ and R ₁ to R ₁₃ is an arylamine or heteroarylamine group, the compound may be usefully used as a hole injection layer and a hole transport layer material.

On the other hand, when any one selected from R ₁ to R ₄ in the formula (1) is a heterocyclic group such as heteroaryl group, heterocycloalkenyl group, or heterocycloalkynyl group excellent in electron affinity to enhance the electron injection or transport capacity It can be usefully used as an electron injection layer or an electron transport layer material.

These functional substituent moieties can also impart amorphous properties without glass transition temperatures by introducing different kinds of substituents. Accordingly, the lifespan characteristics of the organic light emitting device may be further improved by imparting properties having no crystallinity to improve thermal or electrical stability. Therefore, when at least one of said R <_1> -R <_4> and Ar <_1> is a heterocyclic group, it is preferable that the other is an aryl group, and when one is an aryl group, the other is a heterocyclic group. As such, when the heterocyclic group is introduced, the hole blocking ability is improved by providing a low homo energy level. Moreover, if at least one of said R <_1> -R <_4> and Ar <_1> is a heteroarylamine group, the other is an arylamine group, and if either is an arylamine group, it is preferable that the other is a heteroarylamine group. In the case of having such a structure, not only have the hole and electron transfer ability at the same time, but also have an asymmetric structure, which is preferable because it can increase the amorphousness.

Specifically, in Formula 1, Ar ₁ is a substituted or unsubstituted aryl group, a substituted or unsubstituted arylamine group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted heteroarylamine group and It is selected from the group consisting of a substituted or unsubstituted cycloalkyl group.

R ₁ to R ₄ are the same as or different from each other, and each independently hydrogen, a substituted or unsubstituted aryl group, a substituted or unsubstituted arylamine group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted hetero An arylamine group and a substituted or unsubstituted cycloalkyl group, provided that R ₁ to R ₄ are not all hydrogen at the same time,

R ₅ to R ₁₃ are the same as or different from each other, and each independently hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, a substitution Or an unsubstituted arylamine group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted heteroarylamine group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted amino group, SiR '(R' is 1 carbon atom) To an alkyl group of 6 to 6) and B.

It is more preferable that the said aryl group is a substituted or unsubstituted C6-C40, Preferably it is a substituted or unsubstituted C6-C30 aryl group. At this time, the aryl group is a monocyclic aryl group such as phenyl group, biphenyl group, terphenyl group, styrene; Or when using polycyclic aryl groups, such as a naphthyl group, anthracenyl group, a phenanthrene group, a pyrenyl group, and a perrylenyl group, since it can be usefully used as a light emitting layer, it is more preferable.

The arylamine 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 group, carbazole group, and triphenyl amine group What is chosen from the group which consists of can be used more preferably.

The heterocyclic group is a heteroaryl group having 5 to 50 carbon atoms containing a hetero atom, a heterocycloalkyl group having 5 to 50 carbon atoms, a heterocycloalkenyl group having 5 to 50 carbon atoms, and a heterocycloalkynyl group having 5 to 50 carbon atoms And it means that it is selected from the group consisting of the fused ring. The heterocyclic group preferably contains 1 to 20 hetero atoms, and more preferably 1 to 15 hetero atoms.

Examples of the heterocyclic group include pyrrolyl group, pyridinyl group, indolyl group, 1-isoindolyl group, 2-furyl group, benzofuranyl group, isobenzofuranyl group, quinolyl group, isoquinolyl group, quinoxalinyl group and carba Zolyl group, phenanthridine yl group, acridinyl group, 1,7-phenanthroline-2-yl group, phenazine yl group, phenoxyazine yl group, phenoxazine yl group, 2-oxazolyl group, 3-furazanyl group, 2-thienyl group, 2-methylpyrrole-1-yl group, 2-methyl-1-indolyl group, thiophene group, benzothiophene group, furan group, pyrrole group, imidazole group, thiazole group, oxazole group, oxa A diazole group, a thiadiazole group, a triazole group, a pyridinyl group, a pyrazine group, a quinolinyl group, an isoquinolinine group, an acridil group, an imidazopyridinyl group, an imidazopyrimidinyl group, etc. are mentioned. Among these, thiophene group, benzothiophene group, furan group, pyrrole group, imidazole group, thiazole group, oxazole group, oxadiazole group, thiadiazole group, triazole group, pyridinyl group, pyrazine group, quinolinyl group, What is selected from the group which consists of an isoquinolinin group, an acrydyl group, an imidazopyridinyl group, and an imidazopyrimidinyl group can be used more preferably. When the substituted or unsubstituted heterocyclic group is an imidazole group or a triazole group, the substituent bonded to the nitrogen (N) element of the imidazole group or the triazole group may be a substituted or unsubstituted methyl group, ethyl group, propyl group, isopropyl Alkyl groups such as groups, butyl groups, tertiary-butyl groups, pentyl groups, hexyl groups, heptyl groups and the like; Cycloalkyl groups such as substituted or unsubstituted cyclopentyl groups, cyclohexyl groups, and the like; Aryl groups such as substituted or unsubstituted phenyl group, biphenyl group, naphthyl group and the like; And it may be used more preferably selected from the group consisting of a substituted or unsubstituted heterocyclic group. In this case, the heterocyclic group is preferably a heteroaryl group such as a pyridyl group, bipyridyl group, quinolyl group, isoquinolyl group and the like.

The heteroarylamine group is a part of hydrogen in the amine group is substituted with a heteroaryl group, heteroaryl group is the same as described above.

The cycloalkyl group is preferably a substituted or unsubstituted cycloalkyl group having 3 to 50 carbon atoms, specifically, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, 4-methylcyclohexyl group, 1-a And a dandanyl group, 2-adamantyl group, 1-norbornyl group, 2-norbornyl group and the like.

The alkyl group is preferably selected from the group consisting of a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, more preferably may be selected from the group consisting of a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms. Specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, pentyl, iso-amyl, hexyl and the like.

The alkoxy group is a functional group represented by -OY, Y is hydrogen or an alkyl group, wherein the alkyl group is the same as described above.

The alkenyl group contains a carbon double bond in the middle or the end of the alkyl group, and examples thereof include vinyl, propenyl, butenyl and hexenyl. Wherein the alkyl group is the same as described above.

L, which serves as a linking group connecting the core and the functional substituent moiety, is a substituted or unsubstituted arylene group, or a substituted or unsubstituted heteroarylene group.

Specifically, the arylene group may include a phenylene group, a naphthylene group, an anthracene group, a phenanthrene group, and the like, and as a heteroarylene group, a 2,3-tetazole-diyl group, a 1,3-triazole-di Diary, 1, 5-benzimidazole-diyl group, 2,5-benzothiazole-diyl group, 2,5-pyrimidine-diyl group, 3-phenyl-2,5-tetrazol-diyl group, 2, 5-pyridine-diyl group, 2,4-furan-diyl group, 1,3-piperidine-diyl group, 2,4-morpholin-diyl group, 1,2-thiophene-diyl group, 1,4 -Thiophene-diyl group, quinoline-diyl group, isoquinoline-diyl group, etc. are mentioned.

Representative examples of the compound according to an embodiment of the present invention represented by Formula 1 include compounds represented by the following Formulas 1-1 to 1-38, the compound of the present invention is not limited thereto:

The compound for an organic photoelectric device according to the present invention may have an appropriate glass transition temperature by introducing various aryl groups or heteroaryl groups into a core having electron or hole transfer capability. In addition, by adjusting the number or type of the heteroaryl group, the energy level can be adjusted, thereby improving the electron injection ability or the hole injection ability. In addition, it is possible to impart the necessary properties for electron transfer, including a functional group capable of imparting planarity, it is possible to improve the thermal stability by controlling the molecular weight. In addition, by introducing different functional groups, it is possible to increase the amorphousness, thereby improving the life and efficiency when driving the optoelectronic device. It also has a wide energy bandgap and low homoenergy level to provide good hole blocking capability.

The compound for an organic photoelectric device including the compound as described above may play a role of hole injection, hole transport, light emission, or electron injection and / or transport, and may also serve as a light emitting host with an appropriate dopant. In the organic light emitting device, 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 the life characteristics, efficiency characteristics, electrochemical stability, and thermal stability of the organic light emitting diode, and lower driving voltage.

Accordingly, according to another embodiment of the present invention, an organic photoelectric device including the compound for an organic photoelectric device is provided. 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 the case of an organic solar cell, a compound for an organic photoelectric device according to an embodiment 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, or the like. have.

Hereinafter, the organic electroluminescent device will be described in detail. According to another embodiment of the present invention, a first electrode (anode), a second electrode (cathode) and at least one organic thin film layer disposed between the first electrode and the second electrode, the organic thin film layer An organic light emitting device including the compound for an organic photoelectric device is provided.

In addition, the organic thin film layer is a light emitting layer; And at least one layer selected from the group consisting of an electron transport layer, an electron injection layer, a hole transport layer, a hole injection layer, and a hole blocking layer (blocking layer), wherein at least one layer includes the compound for an organic photoelectric device. Include.

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

1 to 5, the organic light emitting diodes 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 an anode material, and a material having a large work function is preferable as the anode material so that hole injection can be smoothly performed into an 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, etc.), but is not limited thereto. Preferably, a transparent electrode including indium tin oxide (ITO) may be used as the anode.

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. , Multilayer structure materials such as LiO ₂ / Al, LiF / Ca, LiF / Al, and BaF ₂ / Ca, and the like, but are not limited thereto. Preferably, a metal electrode such as aluminum may be used as the cathode.

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 including an emission layer 230 and an hole transport layer 140 including an electron transport layer (not shown) as the organic thin film layer 105. As shown in FIG. 2, the organic thin film layer 105 may be a two-layer type including a light emitting 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 is a three-layered organic photoelectric device 300 having an electron transport layer 150, an emission layer 130, and a hole transport layer 140 as an organic thin film layer 105. ), The light emitting layer 130 is in an independent form, and has a form in which a film (electron transport layer 150 and hole transport layer 140) having excellent electron transport properties and hole transport properties is stacked in separate layers.

Referring to FIG. 4, FIG. 4 illustrates a four-layered organic photoelectric device 400 having an electron injection layer 160, a light emitting layer 130, a hole transport layer 140, and a hole injection layer 170 as an organic thin film layer 105. As shown in FIG. 3, the hole injection layer 170 is added to the three layered organic photoelectric device 300 in order to improve adhesion to ITO used as an anode.

Referring to FIG. 5, FIG. 5 shows different functions as the organic thin film layer 105 such as the electron injection layer 160, the electron transport layer 150, the light emitting layer 130, the hole transport layer 140, and the hole injection layer 170. The five-layer organic photoelectric device 500 in which five layers exist are shown, and the organic photoelectric device 500 is effective in lowering the voltage by separately forming the electron injection layer 160.

1 to 5, the light emitting layers 130 and 230 forming the organic thin film layer 105; And an electron transport layer 150, an electron injection layer 160, a hole transport layer 140, a hole injection layer 170, a hole blocking layer, and a combination thereof. Include. In this case, the compound for an organic photoelectric device may be included in the electron transporting layer 150 or the electron injection layer 160, and in particular, when included in the electron transporting layer, a hole blocking layer (not shown) does not need to be separately formed. It is preferable to provide an organic photoelectric device having a structure.

In addition, when the compound for an organic photoelectric device is included in the light emitting layers 130 and 230, the compound for an organic photoelectric device may be included as a phosphorescent or fluorescent host, or may be included as a fluorescent blue dopant.

The above-described organic light emitting device includes a dry film method such as evaporation, sputtering, plasma plating, and ion plating after forming an anode 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 only intended to illustrate or explain the present invention, and thus the present invention should not be limited thereto.

(abandonment Photoelectric  Synthesis of Compound for Device)

Example  1: Synthesis of Compound (1-15)

Compound (1-15), shown as a specific example of the compound for an organic photoelectric device of the present invention, was synthesized through a two-step route as shown in Scheme 1 below.

[Reaction Scheme 1]

A first step; Synthesis of intermediate product (A)

1-bromo-2-phenylethynyl-benzene 15.0 g (58.3 mmol), 2- (4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2- I) Suspension was prepared by suspending 21.2 g (64.2 mmol) of tetraphenyl-naphthalene and 4 g (3.5 mmol) of tetrakis- (triphenylphosphine) palladium in 250 ml of tetrahydrofuran to prepare 48.4 g (350 mmol) of potassium carbonate. A solution dissolved in 100 ml of water was added to this suspension, and the obtained mixture was heated to reflux for 18 hours. After the reaction fluid was separated into two layers, the organic layer was washed with saturated aqueous sodium chloride solution and dried over anhydrous sodium sulfate.

After distilling off the organic solvent under reduced pressure, the residue was recrystallized with toluene, and the precipitated crystals were separated by filtration and washed with toluene to obtain 19.2 g (yield: 86%) of the intermediate product (A). .

A second step; Synthesis of Intermediate Product (B)

15.0 g (39.4 mmol) of the intermediate product (A) prepared in the first step, and 78.8 ml (78.8 mmol) of iodine monochloride were added to 500 ml of dichloromethane at -78 ° C and stirred at -40 ° C for 30 minutes. After completion of the reaction with sodium thiosulfate solution, the organic layer was extracted with dichloromethane and dried over anhydrous sodium sulfate.

The organic solvent was distilled off under reduced pressure to give 13.3 g (yield 67%) of the intermediate product (B).

A third step; Synthesis of Compound (1-15)

3.0 g (5.92 mmol) of the intermediate product (B) prepared in the second step, 3- (4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2- (2) Suspension was prepared by suspending 2.16 g (6.52 mmol) of tetraphenyl-quinoline and 410 mg (0.36 mmol) of tetrakis- (triphenylphosphine) palladium in 100 ml of tetrahydrofuran, and 4.9 g (35.5 mmol) of potassium carbonate. The solution dissolved in 40 ml of water was added to this suspension, and the obtained mixture was heated to reflux for 18 hours. After the reaction fluid was separated into two layers, the organic layer was washed with saturated aqueous sodium chloride solution and dried over anhydrous sodium sulfate.

After distilling off the organic solvent under reduced pressure, the residue was recrystallized with toluene, and the precipitated crystals were separated by filtration and washed with toluene to obtain 3.1 g (yield: 89%) of compound (1-15). did.

Example  2: synthesis of compound (1-20)

Compound (1-20), given as a specific example of the compound for an organic photoelectric device of the present invention, was synthesized through a one-step route as shown in Scheme 2 below.

[Reaction Scheme 2]

3.0 g (5.92 mmol) of the intermediate product (B) prepared in the second step of Example 1, 4- (1-phenyl-1H-benzimidazol-2-yl)-(4,4,5,5- 2.58 g (6.52 mmol) of tetramethyl-1,3,2-dioxaborolan-2-yl) benzene and 0.41 mg (0.36 mmol) of tetrakis- (triphenylphosphine) palladium were added to 100 ml of tetrahydrofuran. The suspension was prepared by suspension, a solution of 4.91 g (35.5 mmol) of potassium carbonate dissolved in 40 ml of water was added to the suspension, and the obtained mixture was heated to reflux for 18 hours. After the reaction fluid was separated into two layers, the organic layer was washed with saturated aqueous sodium chloride solution and dried over anhydrous sodium sulfate.

After distilling off the organic solvent under reduced pressure, the residue was recrystallized from toluene, and the precipitated crystals were separated by filtration and washed with toluene to obtain 3.4 g (yield: 88%) of compound (1-20). did.

Example  3: Synthesis of Compound (1-24)

Compound (1-24), given as a specific example of the compound for an organic photoelectric device of the present invention, was synthesized through a one-step route as shown in Scheme 3 below.

Scheme 3

3.0 g (5.92 mmol) of intermediate product (B) prepared in the second step of Example 1, 1,3- (3,3-bis-quinolinyl)-(5- (4,4,5,5) 2.99 g (6.52 mmol) of tetramethyl-1,3,2-dioxaborolan-2-yl) benzene and 0.41 mg (0.36 mmol) of tetrakis- (triphenylphosphine) palladium 100 ml of tetrahydrofuran Suspension was prepared in suspension, a solution of 4.91 g (35.5 mmol) of potassium carbonate dissolved in 40 ml of water was added to the suspension, and the obtained mixture was heated to reflux for 18 hours.The reaction fluid was separated into two layers, and then the organic layer. Was washed with a saturated aqueous sodium chloride solution and dried over anhydrous sodium sulfate.

After distilling off the organic solvent under reduced pressure, the residue was recrystallized from toluene, and the precipitated crystals were separated by filtration and washed with toluene to obtain 3.9 g (yield: 93%) of compound (1-24). did.

Comparative example  One

As a comparative substance, tris (8-hydroxy-quinolate) aluminum: Alq3 was prepared.

Experimental Example  1: Fabrication of ionization energy measuring device

Corning's 15 Ω / cm ² (120 nm) ITO glass substrates were cut into 25 mm x 25 mm x 0.7 mm sizes, ultrasonically cleaned in isopropyl alcohol and pure water for 5 minutes each, and then UV and ozone for 30 minutes. Washed with.

The organic thin film having a thickness of 100 nm was formed by spin coating the compounds according to Examples 1 to 3 and Comparative Example 1 on the substrate. The formed substrate was used as a working electrode, Ag / AgCl as a reference electrode, and Pt as a counter electrode, and tetrabutylammonium perchlorate was added to acetonitrile at a concentration of 0.1 M. Oxidation potential was measured using the solution as an electrolyte. The measured potential was calculated by using the potential difference from the ferrocene (ferrocene) as a reference material.

(Physical measurement results and analysis)

1) Measurement of energy level

The energy levels of the compounds according to Examples 1 to 3 and Comparative Example 1 were measured and the results are shown in Table 1.

As shown in Table 1, it can be seen that the compounds of Examples 1 to 3 have very low LUMO energy levels. Through this, it can be seen that by effectively blocking the movement of holes when used in the electron transport layer, the combination of holes and electrons can effectively occur in the light emitting layer.

In addition, it can be confirmed that there is no absorption in the visible region by having a wide bandgap energy (bandgap energy). As a result, the loss of light formed in the light emitting layer may be reduced, and thus the efficiency may be increased when applied to the organic light emitting device.

(abandonment Photoelectric  Manufacture of devices)

Example  4

Corning Cut 15 Ω / cm ² (120 nm) ITO glass substrates to 50 mm x 50 mm x 0.7 mm, ultrasonically clean for 5 minutes each in isopropyl alcohol and pure water, and then UV, Ozone washed.

N ¹ , N ^{1 ′} -(biphenyl-4,4′-diyl) bis (N ^1- (naphthalen-2-yl) -N ⁴ , N ⁴ -diphenylbenzene-1,4-diamine) on the glass substrate ( 65 nm), N, N'-di (1-naphthyl) -N, N'-diphenylbenzidine (NPB) (40 nm), N, N, N ', N'-Tetrakis (3,4-dimethylphenyl ) chry-sene-6,12-diamine: 9- (3- (Naphthalen-1-yl) phenyl) -10- (naphthalen-2-yl) anthracene (fluorescence blue host from Idemitsu) 5% (25 nm) And Example 3 (35 nm) prepared in Example 3 was sequentially vacuum vacuum deposition to form a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer in sequence.

Lithium quinolate (Liq) was vacuum deposited to a thickness of 0.5 nm as an electron injection layer on the electron transport layer, and Al was vacuum deposited to a thickness of 100 nm to form a Liq / Al electrode. The structure of the manufactured organic photoelectric device is as shown in FIG. 5.

Comparative example  2: fabrication of ionization energy measuring device

Corning's 15 W / cm ² (120 nm) ITO glass substrates were cut into 25 mm x 25 mm x 0.7 mm sizes, ultrasonically cleaned in isopropyl alcohol and pure water for 5 minutes each, followed by UV and ozone for 30 minutes. Washed.

N ¹ , N ^{1 ′} -(biphenyl-4,4′-diyl) bis (N ^1- (naphthalen-2-yl) -N ⁴ , N ⁴ -diphenylbenzene-1,4-diamine) on the glass substrate ( 65 nm), N, N'-di (1-naphthyl) -N, N'-diphenylbenzidine (NPB) (40 nm), N, N, N ', N'-Tetrakis (3,4-dimethylphenyl chrysene-6,12-diamine: 9- (3- (Naphthalen-1-yl) phenyl) -10- (naphthalen-2-yl) anthracene (fluorescent blue host from Idemitsu) and 5% (25 nm) Tris (8-hydroxy-quinolate) aluminum (Alq3) (35 nm) was sequentially vacuum deposited to form a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer in this order. .

Liq as an electron injecting layer was vacuum deposited on the electron transporting layer to a thickness of 0.5 nm, and Al was vacuum-deposited to a thickness of 100 nm to form a Liq / Al electrode. The structure of the manufactured organic photoelectric device is as shown in FIG. 5.

Experimental Example  2: organic Photoelectric  Device performance measurement

For each organic photoelectric device manufactured in Example 4, the luminous efficiency according to the voltage was measured. The specific measuring method is as follows.

(1) Measurement of change in current density according to voltage change

For the organic photoelectric device manufactured in Example 4, a current value flowing through the unit device was measured by using a current-voltmeter (Keithley 2400) while increasing the voltage from 0 V to 14 V, and measuring the measured current value as the area. The current density was measured by dividing.

(2) Measurement of luminance change according to voltage change

For the organic photoelectric device manufactured in Example 4, the luminance was measured using a luminance meter (Minolta Cs-1000A) while increasing the voltage from 0 V to 14 V.

(3) measurement of power efficiency

Calculate the power efficiency using the luminance value, the current density, and the voltage (V) measured in the "(1) change of current density according to voltage change" and "(2) measurement of luminance change according to voltage change". It was. The results are summarized in Table 2 below.

As shown in Table 2, the organic photoelectric device of Example 4 in which the electron transport layer was formed using the compound for an organic photoelectric device according to the present invention exhibited excellent current efficiency and color characteristics, It can be seen that the compound can be usefully used as a compound for an organic photoelectric device.

The present invention is not limited to the above embodiments, but may be manufactured in various forms, and a person skilled in the art to which the present invention pertains has another specific form without changing the technical spirit or essential features of the present invention. It will be appreciated that the present invention may be practiced as. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.

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

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

100, 200, 300, 400, 500: 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

Claims (14)

Compound for an organic photoelectric device represented by the formula (1). [Formula 1]

(In the formula 1, Ar ₁ is a group consisting of a substituted or unsubstituted aryl group, a substituted or unsubstituted arylamine group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted heteroarylamine group, and a substituted or unsubstituted cycloalkyl group. Is selected from, L is a substituted or unsubstituted arylene group, or a substituted or unsubstituted heteroarylene group, Q ₁ to Q ₁₃ are the same as or different from each other, each independently N or selected from the group consisting of CR ₁ to CR ₁₃ corresponding to the subscripts of Q, respectively R ₁ to R ₄ are the same as or different from each other, and each independently hydrogen, a substituted or unsubstituted aryl group, a substituted or unsubstituted arylamine group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted hetero An arylamine group, and a substituted or unsubstituted cycloalkyl group, provided that R ₁ to R ₄ are not all hydrogen at the same time, R ₅ to R ₁₃ are the same as or different from each other, and each independently hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, a substitution Or an unsubstituted arylamine group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted heteroarylamine group, a substituted or unsubstituted cycloalkyl group, and a substituted or unsubstituted amino group.) The method of claim 1, At least one of the above R ₁ to R ₄ and Ar ₁ if one is a heterocyclic group, the other is an aryl group, if one is an aryl group, the other compound for an organic photoelectric device is a heterocyclic group. The method of claim 1, At least one of the above R ₁ to R ₄ and Ar ₁ if one is a heteroarylamine group, the other is an arylamine group, if one is an arylamine group, the other compound for an organic photoelectric device is a hetero arylamine group. . The method of claim 1, Compound of Formula 1 is a compound for an organic photoelectric device selected from the group consisting of the following compounds 1-1 to 1-38.

The method of claim 1, The compound for organic photoelectric elements which is an electron injection material or electron transport material for organic electroluminescent elements. The method of claim 1, The compound for organic photoelectric elements which is a light emitting material for organic electroluminescent elements. The method of claim 1, A compound for an organic photoelectric device, which is a phosphorescent or fluorescent host for an organic electroluminescent device. The method of claim 1, The compound for organic photoelectric elements which is contained the fluorescent blue dopant for organic electroluminescent elements. An anode, a cathode, and an organic thin film layer interposed between the anode and the cathode and comprising at least one layer or a plurality of layers including a light emitting layer, At least one layer of the said organic thin film layer contains the organic electroluminescent element compound of any one of Claims 1-8. 10. The method of claim 9, The organic thin film layer, An organic photoelectric device further comprising: a hole transport layer, a hole injection layer, an electron transport layer, an electron injection layer, a hole blocking layer, and a combination thereof. 10. The method of claim 9, The light emitting layer is an organic photoelectric device comprising the compound for an organic photoelectric device. 10. The method of claim 9, The organic thin film layer has an electron injection layer or an electron transport layer, and the electron injection layer or the electron transport layer contains the compound for an organic photoelectric device. 10. The method of claim 9, The organic photoelectric device is selected from the group consisting of an organic light emitting device, an organic solar cell, an organic transistor, an organic photosensitive drum, and an organic memory device. A display device comprising the organic photoelectric device of claim 9.

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