KR20070108667A - New organometallic complex compound and organic electroluminescence device using the same - Google Patents

Abstract

New organometallic complex compounds are provided to improve energy potential, electrochemical and thermal stability, and serve crystalline or noncrystalline properties according to substituents or thin layer forming methods, thereby being used in an organic electroluminescence device. New organometallic complex compounds represented by the formula(1) are provided, wherein X and Y are each independently O, S, Se, Te, As, NR, PR, CR'R", SiR'R" or GeR'R" in which R' and R" are each independently hydrogen, oxygen, C1-C20 alkyl group, C6-C30 aryl group or C4-C30 hetero ring group; M is Li, Na, K, Cs, Rb, Be, Mg, Ca, Zn, Al, Ga, In, Cu, Fe, Mn, Zr, Bi, Mn, Co or Ni; n is an integer from 1 to 3; R1 to R4 are each independently selected from hydrogen, halogen group, hydroxy group, C1-C20 linear or branched alkyl group, C1-C20 linear or branched alkoxy group, C1-C20 linear or branched thioalkoxy group, optionally substituted C2-C20 linear or branched alkenyl group, optionally substituted C2-C20 linear or branched alkynyl group, C6-C30 aryl group, C6-C30 aryl amine group, C4-C30 hetero ring group, amino group, nitrile group, nitro group, sulfonyl group, amide group, imide group and ester group.

Description

New organometallic complex compound and organic electroluminescence device using the same

FIG. 1 shows an example of an organic light emitting device comprising a substrate 1, an anode 2, a hole injection layer 3, a hole transport layer 4, a light emitting layer 5, an electron injection layer 6, and a cathode 7. The figure shown.

2 illustrates a bottom contact type organic thin film transistor device including a substrate 8, an insulating layer 9, a gate electrode 10, a source electrode 11, a drain electrode 12, and an organic material layer 13. Is an example of an example.

3 illustrates a top contact type organic thin film transistor device including a substrate 8, an insulating layer 9, a gate electrode 10, a source electrode 11, a drain electrode 12, and an organic material layer 13. Is an example of an example.

4 is a diagram illustrating an example of an organic solar cell including a substrate 14, an anode 15, an electron donor layer 16, an electron acceptor layer 17, and a cathode 18.

The present invention relates to a novel organometallic complex and an organic electronic device using the same.

The present society, called an information society, was made by the discovery of inorganic semiconductors represented by Si and the development of various electronic devices using them. However, electronic devices using inorganic materials have to invest a lot of equipment because they have to go through high temperature or vacuum process during manufacturing, and they have properties that are difficult to apply to flexible displays, which are currently being spotlighted as next generation displays.

In order to overcome the above problems, organic semiconductor materials have recently been spotlighted as semiconductor materials having various physical properties. The organic semiconductor material may be applied to various electronic devices in which inorganic semiconductor materials have been used. Representative electronic devices using organic semiconductor materials include organic light emitting devices, organic solar cells, organic thin film transistors, and the like.

An organic electronic device such as an organic solar cell, an organic light emitting device, or an organic transistor is an electronic device using semiconductor properties of an organic semiconductor material, and typically includes two or more electrodes and an organic material layer interposed between two electrodes. For example, solar cells generate electricity by using electrons and holes separated from excitons (exitons) generated in the organic material layer by solar energy. The organic light emitting device converts current into visible light by injecting electrons and holes into the organic material layer from two electrodes. The organic transistor transports holes or electrons formed in the organic material layer between the source electrode and the drain electrode by the voltage applied to the gate. Such electronic devices may further include an electron / hole injection layer, an electron / hole extraction layer, or an electron / hole transport layer to improve performance.

Organic semiconductor materials for use in the electronic devices should have good hole or electron mobility. In order to satisfy this, most organic semiconductor materials have a conjugated structure.

In addition, the organic semiconductor materials used in the respective electronic devices have different preferred morphology forms depending on the characteristics required by the devices.

For example, when forming a thin film using an organic semiconductor material, it is preferable that the thin film has an amorphous property in an organic light emitting device, while in the organic thin film transistor, it is preferable that the thin film has a crystalline property. Do.

That is, when the organic thin film has a crystalline property in the organic light emitting device, this may result in a decrease in luminous efficiency, an increase in the quenching site in the charge transport, an increase in the leakage current, and the like, and may inhibit device performance.

On the other hand, in the organic transistor, the larger the charge mobility of the organic layer is, the better. Therefore, it is preferable that the intermolecular packing occurs well and the organic thin film has crystallinity. It is particularly preferable that such a crystalline organic film form a single crystal, and in the case of forming a polycrystalline form, it is preferable that the size of each crystal domain is large and these domains are well connected to each other.

In order to satisfy the above requirements, in the organic light emitting device, NPB (4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl), Alq ₃ ( Non-planar materials such as aluminum tris (8-hydroxyquinoline) are mainly used, and in organic transistors, such as pentacene and polythiophene to facilitate intermolecular packing Substances having a plate-like structure, such as a rodlike structure or a phthalocyanine derivative, are mainly used.

However, the morphology or crystallinity varies greatly depending on the shape of the molecular structure as well as the conditions for forming the thin film. In other words, when a thin film is formed on a low temperature substrate at a high speed, an amorphous thin film is formed. However, when a thin film is slowly formed on a substrate maintaining a specific temperature, a thin film having relatively high crystallinity can be formed. In addition, the degree of crystallinity or morphology may also be changed by heat treatment after forming a thin film.

Meanwhile, the organic electronic device may be manufactured to include two or more organic material layers by laminating two or more organic semiconductor materials having different uses for improving performance of the device.

For example, the organic light emitting device may further include a hole injection layer, a hole transport layer, an electron transport layer, and an electron injection layer, thereby increasing the performance of the device by smoothly injecting and transporting holes or electrons from the anode or the cathode.

In the case of the organic thin film transistor, in order to reduce the contact resistance between the semiconductor layer and the electrode, a method of introducing an auxiliary semiconductor made of an organic semiconductor or processing a SAM with an organic material has been introduced. By processing, the method of improving the contact characteristic with a semiconductor is used.

In addition, the organic semiconductor material used in the organic electronic device preferably has thermal stability against Joule heat generated during the movement of charges in the device, and suitable band gap and HOMO or LUMO energy level for smooth injection or transport of charges. It is preferable to have. In addition, the organic semiconductor material should be excellent in chemical stability, interfacial characteristics with an electrode or an adjacent layer, and should be excellent in stability to moisture or oxygen.

In the art, it is required to develop an organic material that satisfies the characteristics required individually in accordance with the characteristics commonly required for the organic electronic device as described above or the type of the electronic device, and is more suitable for a specific use if necessary.

Accordingly, the present inventors have synthesized a novel organometallic complex, and the requirements for the organometallic complex to be used in organic electronic devices such as organic light emitting devices, organic transistors and organic solar cells, such as appropriate energy level, electrochemical stability and thermal The stability and the like can be satisfied, and depending on the substituent or the method of forming a thin film, it can have amorphous or crystalline properties, so that it can satisfy the requirements required for each device individually, and complete the present invention. It was.

The present invention seeks to provide novel organometallic complexes.

In addition, the present invention is to provide an organic electronic device using the organometallic complex compound.

The present invention provides an organometallic complex represented by the following formula (1).

In Chemical Formula 1,

X and Y are, independently from each other, O, S, Se, Te, As, NR, PR, CR'R ", SiR'R" or GeR'R ",

Herein, R ′ and R ″ are each independently a hydrogen atom, an oxygen atom, an alkyl group of C ₁ to C ₂₀ , an aryl group of C ₆ to C ₃₀ , or a heterocyclic group of C ₄ to C ₃₀ ,

M is a metal atom capable of 1 to trivalent bonding, Li, Na, K, Cs, Rb, Be, Mg, Ca, Zn, Al, Ga, In, Cu, Fe, Mn, Zr, Bi, Mn, Co or Ni,

n is an integer of 1 to 3,

R1 to R4 are each independently a hydrogen atom, a halogen group, a hydroxy group, a C ₁ ~ C ₂₀ linear or branched alkyl group, C ₁ ~ C ₂₀ linear or branched alkoxy group, C ₁ ~ C ₂₀ Or branched thioalkoxy group, substituted or unsubstituted C ₂ to C ₂₀ straight or branched alkenyl group, substituted or unsubstituted C ₂ to C ₂₀ straight or branched alkynyl group, C ₆ to C ₃₀ aryl group, C ₆ ~ C ₃₀ aryl amine group, C ₄ ~ C ₃₀ hetero ring group, amino group, nitrile group, nitro group, sulfonyl group, amide group, imide group, ester group , Where they can form condensed rings of aliphatic, aromatic, aliphatic or aromatic hetero groups with groups adjacent to each other or form spiro bonds.

Preferably, in Formula 1, R1 to R4 independently from each other, form a condensed ring of the aliphatic, aromatic, aliphatic hetero or aromatic hetero and the groups adjacent to each other or form a spiro bond.

In addition, preferably in Chemical Formula 1,

X is O, S, Se, Si, CH ₂ , C- (CH ₃ ) ₂ , C- (C ₆ H ₅ ) ₂ , N-CH ₃ , NC ₆ H ₅ , Si- (CH ₃ ) ₂ or Si -(C ₆ H ₅ ) ₂ ,

Y is O, S, Se, N-CH ₃ or NC ₆ H ₅ ego,

M is Zn, Al or Be,

n is an integer of 2 or 3.

In particular, the organometallic complex of Chemical Formula 1 may be represented by the following Chemical Formula 2 or Chemical Formula 3.

In Chemical Formula 2,

X, Y, M and n are as defined in Formula 1,

R5 to R12 are the same as defined in the formula (1) R1 to R4.

In Chemical Formula 3,

X, Y, M and n are as defined in Formula 1,

R5 to R8, R13 and R14 are the same as the definition of R1 to R4 in Formula 1,

z is O, S, Se, NR 'or PR',

Wherein R 'is as defined in the formula (1).

Most preferably, the organometallic complex compound of Formula 1 may be represented by the following formula (4).

In Formula 4, R5 to R12 are the same as the definition of R1 to R4 in the formula (1).

In Chemical Formulas 1 to 4, when R1 to R14 are an aryl group or a heterocyclic group, they may be exemplified below, but the scope of the present invention is not limited thereto.

Wherein R is a hydrogen atom, a C ₁ to C ₂₀ straight or branched alkyl group, C ₁ to C ₂₀ straight or branched alkoxy group, C ₁ to C ₂₀ straight or branched thioalkoxy group, An aryl group of C ₆ -C ₃₀ or a heterocyclic group of C ₄ -C ₃₀ .

Specific examples of the compound represented by Formula 1 according to the present invention are shown below, but are not limited thereto.

The present invention also provides an organic electronic device comprising two or more electrodes and one or more organic material layers disposed between two electrodes, wherein one or more layers of the organic material layers include the compound of Formula 1.

The compound represented by Formula 1 according to the present invention is an organometallic complex in which an organic ligand and a metal are complexed, and a material having various bandgaps from blue to red may be prepared by the kind of atoms constituting X, Y, and M. Can be. In addition, the band gap can be further controlled by the substituents substituted for R1 to R14, and the properties can also be changed.

In particular, in the compound of the present invention, the characteristics of the entire compound can be greatly changed by the kind of the atoms forming Y and X. For example, when oxygen or a substituted nitrogen atom is selected, a compound having a wavelength of blue to green can be prepared by weakening the intermolecular packing, and selecting an atom having a large intermolecular interaction such as a sulfur atom. In this case, the packing may be maximized by the action of these atoms to produce a material having a yellow-red band gap.

As described in the prior art, in the organic light emitting device, a material having various wavelengths from blue to red is required, and as the organometallic complex of Chemical Formula 1, a material having such various wavelengths can be obtained.

In addition, when the organic light emitting device emits green or red light, a doping method may be used. In this case, a dopant having a high emission efficiency having a green wavelength may be doped to a host having a blue band gap. In the case of a dopant emitting a red light emission wavelength, it is known that the dopant is mainly doped with a green or yellow band gap. In other words, it is known that the energy transfer from the host to the dopant occurs well when the band gap difference between the host and the dopant is not large.

Therefore, it can be seen that the organometallic complexes according to the present invention can be used in the blue light emitting layer, and particularly have properties suitable for use as a host when doping red or green.

In addition, in the case of the organic thin film transistor, it is preferable that the band gap is relatively small, and it is preferable that the packing between molecules is maximized. Therefore, in the case of a substance into which a sulfur atom is introduced among the derivatives of the present invention, the transistor can be used as a semiconductor material. This is because the emission wavelength of the material in the solid phase significantly shifts to a long wavelength, it can be seen that the packing and interaction between the molecules is large. This property can also maximize the effect by introducing a substituent that can further increase the conjugation at the position of R1 ~ R14.

In addition, the compounds of the present invention can change the spatial properties of the material by the type of metal. For example, when the center metal is made of a divalent metal such as zinc, the two ligands have a tetrahedron structure around the zinc metal, whereas when the center metal is made of a trivalent metal such as aluminum, it has a spherical spatial structure. do. In addition, in the case of a copper metal, the ligand may have a planar structure to facilitate intermolecular packing.

In other words, it is possible to control the intermolecular interaction by determining the three-dimensional structure of the entire molecule by the coordination ability of each metal.

On the other hand, when the organic electronic device according to the present invention is an organic light emitting device, it may have a structure including a form in which the first electrode, at least one organic material layer and the second electrode are sequentially stacked. The organic material layer may be a multilayer structure including two or more layers selected from a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer, but is not limited thereto and may have a single layer structure. One example of the organic light emitting device according to the present invention is shown in FIG. 1. For example, the organic light emitting device according to the present invention uses a physical vapor deposition (PVD) method, such as sputtering or electron beam evaporation, to deposit a metal or conductive metal oxide or an alloy thereof on the substrate 1 to form an anode (2). Can be prepared by forming an organic material layer such as a hole injection layer 3, a hole transport layer 4, a light emitting layer 5 or an electron transport layer 6 thereon, and then depositing a cathode 7 thereon. have. In addition to the above method, an organic light emitting device may be manufactured by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate.

When the organic electronic device according to the present invention is an organic transistor, the structure may be the structure of FIG. 2 or 3. That is, the organic transistor according to the present invention may have a structure including an insulating layer 9, a gate electrode 10, a source electrode 11, a drain electrode 12, and an organic material layer 13.

When the organic electronic device according to the present invention is an organic solar cell, its structure may be the structure of FIG. 4. That is, the organic solar cell according to the present invention may have a structure including a cathode 15, an electron donor layer 16, an electron acceptor layer 17, and an anode 18 sequentially stacked.

Hereinafter, preferred examples are provided to aid in understanding the present invention. However, the following examples are merely provided to more easily understand the present invention, and the contents of the present invention are not limited thereto.

Production Example  :

In order to synthesize the organometallic complex represented by Formula 1, the following Compounds A to F may be used as starting materials.

Production Example  One  Preparation of Compound A

Dissolve 10.7 ml (0.1 mmol) of 2-aminothiophenol in 500 ml ethyl acetate and 8 ml of 2-chloroacetyl chloride dissolved in 10 ml ethyl acetate at 3-6 ° C. 0.1 mol) was slowly added dropwise. At the same temperature, 14 ml (0.1 mmol) of triethylamine dissolved in 10 ml of ethyl acetate were slowly added dropwise. After stirring for 4 hours at 10 ° C. or less, water was added, the organic layer was separated, water was removed with anhydrous magnesium sulfate, and the solvent was removed by distillation under reduced pressure. Ethyl acetate was added to the mixture, and the resulting solid was filtered off. The filtrate was collected, and the resultant was column separated using ethyl acetate / hexane (EA / n-HEX) = 1/9 as a developing solvent, thereby obtaining Compound A (10.5 g, 57.2%).

NMR (CDCl ₃ , ppm): 8.0 (d, 1H), 7.87 (d, 1H), 7.48 (t, 1H), 7.42 (t, 1H), 4.92 (s, 2H)

Production Example  2  : Preparation of Compound B

10.9 g (0.1 mmol) of 2-aminophenol was dissolved in 500 ml of ethyl acetate, and then 14 ml (0.1 mol) of triethylamine were added thereto. After cooling with ice water, 8 ml (0.1 mol) of 2-chloroacetyl chloride diluted with 10 ml of ethyl acetate was slowly added dropwise. After stirring at the same temperature for 1 hour, water was added, extraction was performed with ethyl acetate, water was removed with anhydrous magnesium sulfate, and distilled under reduced pressure to obtain 12.85 g (76.7%) of a pale yellow solid. 5 g (26.9 mmol) was taken and dissolved in 50 ml toluene, and 1 g of p-toluenesulfonic acid was added thereto, and the mixture was refluxed with water for one day. The product was extracted with ethyl acetate and water, the organic layer was taken, water was removed with anhydrous magnesium sulfate, and the solvent was removed under reduced pressure. The resulting solid was separated by column separation with ethyl acetate / hexane (EA / n-HEX) = 1/4 as a developing solvent to obtain compound B (3.5 g, 77.46%).

NMR (CDCl ₃ , ppm): 7.7 (m, 1H), 7.5 (m, 1H), 7.3 (m, 2H), 4.7 (s, 2H)

Production Example  3  : Preparation of Compound C

3.68 g (20 mmol) of N-Phenyl-1,2-phenylenediamine is completely dissolved in 130 ml of ethyl acetate, and then 1.6 ml (20 mmol) at 0 to 10 ° C. 2-chloroacetyl chloride was added slowly. After addition, 2.8 ml (20 mmol) of triethylamine was added slowly. After stirring at the same temperature for 1 hour, the mixture was stirred at room temperature for one day. Water was added to terminate the reaction, followed by extraction with ethyl acetate and distillation under reduced pressure to obtain a solid. 100 ml of 4N HCl was added to the solid and refluxed for 4 hours. After cooling to room temperature, neutralized with saturated aqueous sodium bicarbonate (NaHCO ₃ ), extracted with ethyl acetate, passed through silica gel and distilled under reduced pressure to obtain a brown compound C (4.1 g, 84%).

NMR (DMSO-d ₆ ): 7.7 (m, 1H, b), 7.7-7.5 (m, 5H), 7.3-7.2 (m, 2H), 7.1 (m, 1H, b), 4.8 (s, 2H)

Production Example  4  : Preparation of Compound D

3.36 g (20 mmol) of methyl thiosalicylate and 3.67 g (20 mmol) of 2-chloromethylbenzthiazole were dissolved in 60 ml of ethanol, followed by potassium carbonate (K ₂ CO ₃ ). 8.29 g (60 mmol) was added and refluxed for 4 hours. After cooling to room temperature, 2N HCl was added thereto, stirred for 30 minutes, filtered, washed with distilled water, and dried in vacuo. It was stirred while boiling with ethanol and filtered to give a yellow compound D (4.98 g, 87.8%).

NMR (CDCl ₃ , ppm): 7.99-7.74 (m, 2H), 7.88-7.85 (d, 1H), 7.76-7.73 (d, 1H), 7.52-7.42 (m, 3H), 7.38-7.33 (t, 1H)

MS: [M + H] ⁺ = 284

Production Example  5  : Preparation of Compound E

1.68 g (10 mmol) of methyl thiosalicylate and 1.68 g (10 mmol) of 2-chloromethyl benzoxazole are dissolved in 60 ml of ethanol, followed by potassium carbonate (K ₂ CO ₃ ). 4.15 g (30 mmol) was added and stirred for one day. After cooling to room temperature, 2N HCl aqueous solution was added, and the resulting solid was filtered and washed with clean water. Acetone was added and stirred for 30 minutes, followed by filtration and vacuum drying to yield a pale yellow compound E (1.19 g, 44.6%) having blue fluorescence.

NMR (CDCl ₃ , ppm): 8.01 ~ 7.98 (d, 1H), 7.80 ~ 7.78 (d, 1H), 7.70 ~ 7.68 (d, 1H), 7.59 ~ 7.56 (d, 1H), 7.50 ~ 7.40 (m, 2H), 7.39 ~ 7.30 (m, 2H)

MS: [M + H] ⁺ = 268

Production Example  6  : Preparation of Compound F

After dissolving 1.21 g (5 mmol) of 2-chloromethyl-N-phenylbenzimidazole and 0.84 g (5 mmol) of methyl thiosalicylate in 100 ml of ethanol, carbonic acid was completely dissolved. 2.07 g (15 mmol) of potassium (K ₂ CO ₃ ) was added and refluxed for 4 hours. After cooling to room temperature, 2N HCl aqueous solution was added and extracted with ethyl acetate. After removing the remaining water with anhydrous magnesium sulfate, the solvent was distilled under reduced pressure. Ethanol was added to the resulting solid, stirred for 3 hours while boiling, and the solid obtained by filtration was dried in vacuo to give Compound F (1.3 g, 76%).

NMR (DMSO-d ₆ ); 7.8 (m, 1H), 7.8 to 7.6 (m, 8H), 7.4 (m, 2H), 7.3 (t, 1H), 7.2 (t, 1H), 7.0 (d, 1H)

MS: [M + H] ⁺ = 343

Example  One  : Preparation of Compound 17

0.5 g (1.87 mmol) of 3-Hydroxy-2- (benzoxazolyl) benzthiophene was completely dissolved in 350 ml of ethanol, followed by zinc acetate dihydrate. 0.205 g (0.94 mmol) was added. After stirring for 4 hours at 50 ~ 60 ℃ filtered, washed with clean ethanol and dried under vacuum to obtain compound 17 (0.48 g). This material was purified by sublimation.

m.p = 435.9 ° C.,

MS: [M + H] ⁺ = 597

Example  2  : Preparation of Compound 18

3 g (10.6 mmol) of 3-hydroxy-2- (2-benzthiazolyl) benzthiophene (3-Hydroxy-2- (2-benzthiazolyl) benzthiophene) was dissolved in 1.2 L of ethanol and completely dissolved. 1.16 g (5.3 mmol) of zinc acetate dihydrate dissolved in ethanol was added thereto, stirred at 50˜60 ° C. for 4 hours, and then cooled to room temperature. Filtration, washing with clean ethanol and drying in vacuo afforded compound 18 (2.8 g). This material was purified by sublimation.

m.p = 410 ° C.,

MS: [M + H] ⁺ = 629

Example  3  : Preparation of Compound 19

1 g (2.92 mmol) of 3-hydroxy- (2- (N-phenylbenzimidazolyl) benzthiophene (3-Hydroxy-2- (N-phenylbenzimidazolyl) benzthiophene) was dissolved in 500 ml of ethanol, followed by zinc acetate. 0.32 g (1.46 mmol) of dihydrate were added, stirred at 60 ° C. for 4 hours, cooled to room temperature, filtered and washed with clean ethanol Compound 19 (1.09 g, 96.7%) was dried under vacuum. This material was purified by sublimation.

m.p = 342 ° C.,

MS: [M + H] ⁺ = 747

Example  4  : Preparation of Compound 39

0.5 g (1.87 mmol) of 3-hydroxy-2- (benzoxazolyl) benzthiophene was completely dissolved in 100 ml of ethanol, followed by addition of 0.025 g (0.125 mmol) of aluminum isopropoxide. After stirring for one day at 60 ~ 70 ℃, cooled to room temperature, filtered, washed with clean ethanol and dried in vacuo to give compound 39. This material was purified by sublimation.

m.p = 435.9 ° C.,

MS: [M + H] ⁺ = 597

Experimental Example  One  :

A glass substrate coated with a thin film of ITO (indium tin oxide) at a thickness of 1500 Å was placed in distilled water in which detergent was dissolved and ultrasonically cleaned. The detergent used was a product of Fischer Co. and Millipore Co. Secondly filtered distilled water was used as a product filter. After ITO was washed for 30 minutes, ultrasonic washing was performed twice with distilled water for 10 minutes. After the distilled water was washed, ultrasonic cleaning with a solvent such as isopropyl alcohol, acetone, methanol, dried and then transferred to a plasma cleaner. The substrate was cleaned for 5 minutes using oxygen plasma and then transferred to a vacuum evaporator.

Hexanitrile hexaazatriphenylene was thermally vacuum deposited to a thickness of 500 kPa on the prepared ITO transparent electrode to form an anode having an ITO conductive layer and an n-type organic material. NPB (600 kPa), which is a material for transferring holes, was vacuum deposited thereon, and then Compound 18 prepared in Example 2 serving as a light emitting layer was vacuum deposited to a thickness of 200 kPa. Alq ₃ was vacuum deposited to a thickness of 300 kPa on the light emitting layer to form a thin film of the organic material layer. Alq ₃ Lithium fluoride (LiF) and 2500 μm thick aluminum were sequentially deposited on the substrate to form a cathode. In the above process, the deposition rate of the organic material was maintained at 1 Å / sec, the lithium fluoride was 0.2 Å / sec, and the aluminum was maintained at the deposition rate of 3-7 Å / sec.

As a result of applying a forward electric field of 4.06 V to the fabricated electroluminescent device, a green spectrum of 95 nit brightness corresponding to x = 0.34 and y = 0.55 was observed based on 1931 CIE color coordinate at a current density of 10 mA / cm 2. .

The device maintained a luminance of 58.4% of the initial luminance after 550.3 hours at 50 mA.

Experimental Example  2  :

A glass substrate coated with a thin film of ITO (indium tin oxide) at a thickness of 1500 Å was placed in distilled water in which detergent was dissolved and ultrasonically cleaned. The detergent used was a product of Fischer Co. and Millipore Co. Secondly filtered distilled water was used as a product filter. After ITO was washed for 30 minutes, ultrasonic washing was performed twice with distilled water for 10 minutes. After the distilled water was washed, ultrasonic cleaning with a solvent such as isopropyl alcohol, acetone, methanol, dried and then transferred to a plasma cleaner. The substrate was cleaned for 5 minutes using oxygen plasma and then transferred to a vacuum evaporator.

Hexonitrile hexaazatriphenylene was thermally vacuum deposited to a thickness of 500 kPa on the thus prepared ITO transparent electrode to form an anode having an ITO conductive layer and an n-type organic material. NPB (600 kW), which is a material for transporting holes, was vacuum deposited on the same, and Compound 18 and DCJTB prepared in Example 2 serving as a light emitting layer were vacuum deposited to a thickness of 200 kW at a ratio of 100: 2. Alq ₃ was vacuum deposited to a thickness of 300 kPa on the light emitting layer to form a thin film of the organic material layer. Lithium fluoride (LiF) and aluminum having a thickness of 2500 mW were deposited on the Alq ₃ sequentially to form a cathode. In the above process, the deposition rate of the organic material was maintained at 1 Å / sec, the lithium fluoride was 0.2 Å / sec, and the aluminum was maintained at the deposition rate of 3-7 Å / sec.

As a result of applying a forward electric field of 4.4 V to the fabricated electroluminescent device, a green spectrum of 2795 nit brightness corresponding to x = 0.63 and y = 0.36 was observed based on 1931 CIE color coordinate at a current density of 10 mA / cm 2. .

The device maintained a luminance of 73% of the initial luminance after 288 hours at 50 mA.

Experimental Example  3  :

An n-doped low-resistance silicon wafer was used as the gate electrode, and a SiO ₂ gate insulating film having a thickness of 3000 Å was formed thereon by thermal oxidation. Subsequently, gold was deposited by photolithography to form a source-drain electrode having a channel length of 10 μm and a channel width of 300 μm. The substrate having the structure thus obtained was subjected to UV-ozone plasma treatment, spin-coated HMDS (hexamethyldisilasane) at 3000 rpm for 30 seconds, and then heat-treated at 120 ° C. for 2 minutes. It was observed that Compound 18 prepared in Example 2 was vacuum deposited to operate as an organic thin film transistor.

The organometallic complex according to the present invention can satisfy the requirements for use in organic electronic devices such as organic light emitting devices, organic transistors and organic solar cells, such as suitable energy level, electrochemical stability and thermal stability, depending on the substituent Alternatively, according to the method of forming a thin film, it may have an amorphous or crystalline property to satisfy the requirements required for each device individually. Therefore, the organometallic complex according to the present invention may play various roles in the organic electronic device as described above. It can improve the service life characteristics. In addition, organic transistors having high charge mobility and improved thermal stability can be obtained by using properties of good intermolecular packing.

Claims (12)

An organometallic complex represented by the following formula (1). <Formula 1>

In Chemical Formula 1, X and Y are, independently from each other, O, S, Se, Te, As, NR, PR, CR'R ", SiR'R" or GeR'R ", Herein, R ′ and R ″ are each independently a hydrogen atom, an oxygen atom, an alkyl group of C ₁ to C ₂₀ , an aryl group of C ₆ to C ₃₀ , or a heterocyclic group of C ₄ to C ₃₀ , M is a metal atom capable of 1 to trivalent bonding, Li, Na, K, Cs, Rb, Be, Mg, Ca, Zn, Al, Ga, In, Cu, Fe, Mn, Zr, Bi, Mn, Co or Ni, n is an integer of 1 to 3, R1 to R4 are each independently a hydrogen atom, a halogen group, a hydroxy group, a C ₁ ~ C ₂₀ linear or branched alkyl group, C ₁ ~ C ₂₀ linear or branched alkoxy group, C ₁ ~ C ₂₀ Or branched thioalkoxy group, substituted or unsubstituted C ₂ to C ₂₀ straight or branched alkenyl group, substituted or unsubstituted C ₂ to C ₂₀ straight or branched alkynyl group, C ₆ to C ₃₀ aryl group, C ₆ ~ C ₃₀ aryl amine group, C ₄ ~ C ₃₀ hetero ring group, amino group, nitrile group, nitro group, sulfonyl group, amide group, imide group, ester group Here they can form a condensed ring of aliphatic, aromatic, aliphatic or aromatic hetero with groups adjacent to each other or form spiro bonds. The organometallic complex of claim 1, wherein in Formula 1, R1 to R4 form, independently of each other, a condensed ring of an aliphatic, aromatic, aliphatic hetero or aromatic hetero group with an adjacent group and form a spiro bond. According to claim 1, in the formula 1, X is O, S, Se, Si, CH ₂ , C- (CH ₃ ) ₂ , C- (C ₆ H ₅ ) ₂ , N-CH ₃ , NC ₆ H ₅ , Si- (CH ₃ ) ₂ or Si -(C ₆ H ₅ ) ₂ , Y is O, S, Se, N-CH ₃ or NC ₆ H ₅ ego, M is Zn, Al or Be, n is an integer of 2 or 3, wherein the organometallic complex. The organometallic complex of claim 1, wherein the organometallic complex of Formula 1 is represented by Formula 2 below. <Formula 2>

In Chemical Formula 2, X, Y, M and n are as defined in Formula 1, R5 to R12 are the same as defined in the formula (1) R1 to R4. The organometallic complex of claim 1, wherein the organometallic complex of Formula 1 is represented by the following Formula 3. <Formula 3>

In Chemical Formula 3, X, Y, M and n are as defined in Formula 1, R5 to R8, R13 and R14 are the same as the definition of R1 to R4 in Formula 1, z is O, S, Se, NR 'or PR', Wherein R 'is as defined in the formula (1). The organometallic complex of claim 1, wherein the organometallic complex of Formula 1 is represented by the following Formula 4. <Formula 4>

In Formula 4, R5 to R12 are the same as the definition of R1 to R4 in the formula (1). The compound of any one of claims 1, 2 and 4 to 6, wherein in the formulas (1) to (4), when R1 to R14 is an aryl group or a heterocyclic group, they are selected from the group consisting of An organometallic complex characterized by the above-mentioned.

Wherein R is a hydrogen atom, a C ₁ to C ₂₀ straight or branched alkyl group, C ₁ to C ₂₀ straight or branched alkoxy group, C ₁ to C ₂₀ straight or branched thioalkoxy group, An aryl group of C ₆ -C ₃₀ or a heterocyclic group of C ₄ -C ₃₀ . The organometallic complex of claim 1, wherein the compound of Formula 1 is selected from the group consisting of the following structural formulas.

An organic electronic device comprising at least two electrodes and at least one organic layer disposed between two electrodes, wherein at least one of the organic layers comprises the compound of claim 1. The organic electronic device of claim 9, wherein the organic electronic device is an organic light emitting device, and has a structure in which a first electrode, one or more organic material layers, and a second electrode are sequentially stacked, and at least one of the organic material layers is a first layer. An organic electronic device comprising the compound of claim. 10. The organic electronic device of claim 9, wherein the organic electronic device is an organic transistor, and has a structure including a gate electrode, an insulating layer, one or more organic material layers, a source electrode, and a drain electrode. An organic electronic device comprising a compound. The organic electronic device of claim 9, wherein the organic electronic device is an organic solar cell, and has a structure including an anode, an electron donor layer, an electron acceptor layer, and a cathode sequentially stacked, and the electron donor layer or the electron acceptor layer. The organic electronic device comprising the compound of claim 1.

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