KR20150066429A - Organic Compound and Organic Light Emitting Diode Devices using the same - Google Patents

Abstract

The present invention relates to an organic compound and an organic light emitting diode device using same. The organic compound is selected from an aromatic ring compound, which is represented by Chemical formula wherein R is a substituted or unsubsituted alkyl group having C_1 to C_12; and A and B are symmetrically or asymmetrically bound to a 2-position and a 7-position of a fullerene core and are independently substituted or unsubstituted, and a heterogeneous ring compound. According to the present invention, efficiency of the organic light diode device can be increased; and driving voltages for the organic light diode device can be reduced.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic light emitting diode (OLED)

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to an organic light emitting diode (OLED) device, and more particularly, to an organic compound capable of lowering a driving voltage and realizing a simple device structure, and an organic light emitting diode device using the organic compound.

The development of a flat panel display device has been attracting attention as the display field, which is a video display device, is rapidly developed as it comes to information age where a large amount of information is required.

Specific examples of such flat panel display devices include a liquid crystal display (LCD), a plasma display panel (PDP), an electroluminescence display (ELD), a field emission display : FED), and organic light emitting diode (OLED) devices. The OLED display is rapidly evolving in response to consumer expectations such as thinning, light weight, and low power consumption.

Particularly, organic light emitting diode devices can be formed on a flexible substrate such as a plastic substrate. Therefore, active research has been actively conducted as a next generation display device, and a low voltage (for example, a voltage lower than that of a plasma display panel or an electroluminescence display) And the power consumption is relatively small.

1 is a schematic cross-sectional view of a conventional organic light emitting diode device.

1, an organic light emitting diode device 20 is formed on a substrate 10 and includes a first electrode 21, a hole injection layer 22, A light emitting material layer 24, an electron transport layer 25, an electron injection layer 26 and a second electrode 27 serving as a cathode are laminated in this order.

Holes are formed from the first electrode 21 as an anode through the hole injection layer (HIL) 22 and the hole transport layer (HTL) 23, And electrons are transferred from the second electrode 27 as a cathode to the electron injection layer (EIL) 26 and the electron transport layer (ETL) 25 To the light emitting material layer (24).

The holes and electrons transferred to the light emitting material layer 24 combine to form an exciton, which excites into an unstable energy state, returns to a stable energy state, and emits light.

As described above, in order to improve the efficiency, the conventional organic light emitting diode device is formed by stacking a plurality of layers. In order to prevent the quenching of the excitons in which holes and electrons are coupled, an electron blocking layer ) And a hole blocking layer. Such a complicated structure leads to a rise in cost and a decrease in productivity.

In addition, even in the case of an organic light emitting diode device fabricated in a multilayer structure, there are still barriers between layers, and in particular, hole injection is difficult due to a hole injection barrier. On the other hand, It is faster than hole. Accordingly, the coupling region of the holes and electrons is not located at the center of the light emitting material layer but is located at the interlayer interface, that is, at the interface between the light emitting material layer (EML) and the hole transporting layer (HTL) .

In order to solve the above-mentioned problems, it is required to simplify the structure of the organic light emitting diode device, and at the same time, the mobility of electrons and holes must be balanced so that the coupling region of electrons and holes exists in the light emitting material layer (EML).

Particularly, blue light emission requires a material having a broader energy bandgap than green and red. Therefore, it is difficult to develop materials. However, such a wide energy band gap has an advantage that it can be commonly applied to green and red light emission. Therefore, it is required to develop a material which can be used as a host of a blue light emitting material layer and is suitable for a simple device structure.

Accordingly, the present invention provides a novel device structure by using an organic compound having a hole transporting property in a hole injecting layer, a hole transporting layer, and a light emitting material layer of an organic light emitting diode device, thereby reducing cost and productivity, To solve the problem of a decrease in luminous efficiency.

In order to solve the above problems, the present invention provides a process for producing a fullerene derivative represented by the following formula, wherein R is a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, A and B are asymmetric or asymmetric And each independently selected from substituted or unsubstituted aromatic ring compounds or ring-opened ring compounds.

In the organic compound of the present invention, A and B each independently represent a substituted or unsubstituted carbazole group, an a-carboline group, a beta-carboline group, A γ-carboline group, a dibenzofuran group, a dibenzothiophene group, an arylamine group, an arylsilane group, and a phenyl group .

In the organic compound of the present invention, A and B are each independently selected from the following compounds.

The organic compound of the present invention is selected from the following compounds.

In another aspect, the present invention provides an organic compound represented by the following formula: wherein X is selected from carbon, nitrogen, oxygen, sulfur, and Y is selected from aryl or arylamine.

In the organic compound of the present invention, Y is selected from phenyl, naphthyl, terphenyl, xylene, triphenylamine, diphenylamine, phenaphthrenamine and substituents thereof.

The organic compound of the present invention is characterized by being any one of the following compounds.

In another aspect, the present invention provides a liquid crystal display comprising: a first electrode; A second electrode facing the first electrode; A light emitting material layer disposed between the first electrode and the second electrode; And a hole injection layer disposed between the first electrode and the light emitting material layer; And a hole transport layer disposed between the hole injection layer and the light emitting material layer, wherein at least one of the hole injection layer, the hole transport layer, and the light emitting material layer includes the organic compound .

In the organic light emitting diode device of the present invention, the hole injection layer is formed by mixing a dopant material and the organic compound as a host.

The LUMO level of the dopant material is in the range of -4.5 eV to -6.0 eV.

In the organic light emitting diode device of the present invention, the dopant material may be HAT-CN (hexaazatriphenylene-hexacarbonitrile) represented by the following formula.

In the organic light emitting diode device of the present invention, the mixing ratio of the dopant material in the hole injection layer is 0.1 to 20% based on the total weight of the organic compound and the dopant material.

In the organic light emitting diode device of the present invention, the hole injection layer, the hole transport layer, and the light emitting material layer are all formed of the organic compound.

In the organic light emitting diode device of the present invention, the light emitting material layer includes the organic compound and emits blue light.

In another aspect, the present invention provides a liquid crystal display comprising: a first electrode; A second electrode facing the first electrode; A light emitting material layer disposed between the first electrode and the second electrode; A hole injection layer disposed between the first electrode and the light emitting material layer; And a hole transport layer disposed between the hole injection layer and the light emitting material layer, wherein at least two of the hole injection layer, the hole transport layer, and the light emitting material layer are made of the same host material Thereby providing a diode element.

In the organic light emitting diode device of the present invention, the compounds forming the hole injecting layer, the hole transporting layer, and the light emitting material layer are all made of the same host material.

In the organic light emitting diode device of the present invention, the hole injection layer may further include an organic compound having a LUMO level of -4.5 eV to -6.0 eV, and the light emitting material layer may further include a dopant.

In the organic light-emitting diode device of the present invention, the organic compound having the LUMO level of -4.5 eV to -6.0 eV is HAT-CN (Hexaazatriphenylene-hexacarbonitrile) of the following formula:

In the organic light emitting diode device of the present invention, the mixing ratio of the organic compound having the LUMO level of -4.5 eV to -6.0 eV of the hole injection layer may be such that the host material and the organic compound having the LUMO level of -4.5 eV to -6.0 eV And 0.1 to 20% of the total weight of the compound.

The energy barrier of the electrode and the hole injecting layer or between the hole injecting layer and the hole transporting layer is minimized by doping the organic compound of the present invention with a deep material having a value of LUMO of about -4.5 to -6.0 eV, Can be improved. That is, since the organic compound of the present invention has high hole transporting properties, it lowers the hole injection barrier and improves the luminous efficiency.

Further, since the organic compound of the present invention can be used as a host for a hole injection layer, a hole transport layer, and a light emitting material layer, cost reduction and productivity can be improved through a simple structure organic light emitting diode device, By lowering the voltage, the power consumption can be minimized.

1 is a schematic cross-sectional view illustrating a conventional organic light emitting diode device.
2 is a cross-sectional view schematically showing an organic light emitting diode device according to an embodiment of the present invention.
3 is a cross-sectional view schematically showing an organic light emitting diode device according to another embodiment of the present invention.
4 is a cross-sectional view schematically showing an organic light emitting diode device according to another embodiment of the present invention.
5 is a graph showing current density measured according to a driving voltage of an organic light emitting diode device manufactured according to Experimental Example 1 of the present invention.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.

2 is a cross-sectional view illustrating an organic light emitting diode device according to an embodiment of the present invention.

2, the organic light emitting diode device 200 according to an exemplary embodiment of the present invention is formed on a substrate 100 and includes a first electrode 210, a hole injection layer (HIL) Layer 230, a hole transport layer (HTL) 240, a light emitting material layer (EML) 250, an electron transport layer (ETL) 260, An EIL (Electron Injection Layer) 270, and a second electrode 280.

The first electrode 210 may be made of a material having a relatively high work function value such as indium-tin-oxide (ITO) or indium zinc oxide (IZO), but the present invention is not limited thereto.

The hole injection layer 230 is formed on the first electrode, which is an anode, and includes an organic compound represented by Formula 1 below. The organic compound represented by Formula 1 is included in the organic light emitting diode device 200 according to the present invention as an organic compound having hole transporting properties.

[Chemical Formula 1]

In Formula 1, R is a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, A and B may be symmetrically or asymmetrically substituted at positions 2 and 7 of the fullerene core, Aromatic ring compound or ring-form ring compound.

A and B each independently represent a substituted or unsubstituted carbazole group, an a-carboline group, a beta-carboline group, a gamma-carboline group, A dibenzofuran group, a dibenzothiophene group, an arylamine group, an arylsilane group, and a phenyl group.

Each of A and B is independently selected from among the compounds shown below.

The organic compound represented by Formula 1 includes various compounds such as the following formulas FL-1 to FL-26.

In particular, the hole injection layer 230 may be formed by injecting an organic compound 220 having a LUMO level of -4.5 eV to -6.0 eV, for example, an organic compound represented by the following Formula 2, But is not necessarily limited thereto. The doping amount of the organic compound 220 represented by the following Formula 2 may be 0.1 to 20% by weight with respect to the entire hole injection layer 230. The organic compound 220 having the LUMO level of -4.5 eV to -6.0 eV may be used as a hole injection layer in a conventional organic light emitting diode device structure. The organic light emitting diode device 200 of the present invention is formed by doping an organic compound having the hole transporting property represented by Formula 1 of the present invention without using the organic compound 220 separately.

(2)

Hereinafter, as an example, methods for synthesizing the compounds FL-1, FL-2, FL-3, and FL-4 will be described in order.

1. Synthesis of Formula FL-1 Compound

Scheme 1

10 g (28.403 mmol) of 2,7-dibromo-9,9-dimethyl-9H-fluorene, 9.5 g (56.806 mmol) of carbazole, 4.3 g (22.722 mmol) of copper iodide 36 g (170.418 mmol) of potassium (K3PO4) and 2.7 ml (22.722 mmol) of trans-1,2-cyclohexanediamine were dissolved in 1,4-dioxane and stirred under reflux for 12 hours . After completion of the reaction, the solvent was distilled off under reduced pressure, and the residue was subjected to column chromatography using a solvent mixture of n-hexane and methylene chloride in a ratio of 4: 1, and then toluene was added to a short column The solvent was distilled off under reduced pressure, and the residue was recrystallized in a solvent of methylene chloride and petroleum ether to obtain 4.0 g (yield: 67%) of compound FL-1.

2. Synthesis of Formula FL-2 Compound

Scheme 2

10 g (28.403 mmol) of 2,7-dibromo-9,9-dimethyl-9H-fluorene, 2.37 g of carbazole (14.20 mmol), copper iodine (CuI) 540 6.03 g (28.404 mmol) of potassium tertiary phosphate (K3PO4) and 0.34 mL (2.840 mmol) of trans-1,2-cyclohexanediamine were added to 1,4-dioxane After dissolving, the mixture was stirred under reflux for 12 hours. After completion of the reaction, the solvent was distilled off under reduced pressure, and the residue was subjected to column chromatography using a solvent mixture of n-hexane and methylene chloride in a ratio of 4: 1. The solution was distilled under reduced pressure, and methylene chloride And recrystallized in a petroleum ether solvent to obtain 4.17 g (yield 67%) of compound X1.

Scheme 3

As shown in Reaction Scheme 3 above, 49 g (0.207 mmol) of compound X1 (4.562 mmol), 701 mg (4.148 mmol) of diphenylamine and Tris- (t-butyl) -phosphine mmol) and 798 mg (8.296 mmol) of sodium tert-butoxide were dissolved in toluene, and the solution was stirred under a palladium (II) acetate (Pd (OAc) Lt; / RTI > After completion of the reaction, the solvent was distilled off under reduced pressure, and the residue was subjected to column chromatography using a solvent mixture of n-hexane and methylene chloride in a volume ratio of 3: 1. The solution was distilled under reduced pressure, and methylene chloride And recrystallized in a petroleum ether solvent to obtain 1.5 g (yield 69%) of the compound FL-2.

3. Synthesis of Formula FL-3 Compound

Scheme 4

As shown in Reaction Scheme 4 above, 24.9 mL (206.83 mmol) of 1,3-dibromobenzene, 10 g (59.095 mmol) of diphenylamine, 899 mg of tri-o-tolyphosphine mmol) and 11.4 g (118.19 mmol) of sodium tert-butoxide were dissolved in toluene followed by addition of tris (dibenzylideneacetone) dipalladium (0) : Pd2 (dba) 3] catalyst for 12 hours. After completion of the reaction, the solvent was distilled off under reduced pressure, and the residue was subjected to column chromatography with n-hexane. The solution was distilled under reduced pressure and recrystallized in a solvent of methylene chloride and petroleum ether to obtain 9.26 g of compound X1 Yield: 48%).

Scheme 5

As shown in Scheme 5 above, 8.9 g (27.451 mmol) of compound X2 is dissolved in tetrahydrofuran (THF). After lowering the temperature to -78 ° C, slowly add 14.3 mL of a 2.5 M solution of n-butyllithium (n-BuLi). The mixture is stirred at room temperature for 1 hour after dropwise addition. After lowering the temperature again to -78 ° C, add 7.0 mL (41.176 mmol) of triethyl borate slowly. The mixture is stirred at room temperature for 12 hours after dropwise addition. After 12 hours, add 50 mL of 5 N hydrochloric acid (HCl) solution, remove tetrahydrofuran (THF), and extract with distilled water and methylene chloride. The solvent was distilled off under reduced pressure, and the residue was subjected to column chromatography with methylene chloride. The solution was distilled under reduced pressure to obtain 4.75 g (yield: 60%) of compound X3.

Scheme 6

2.06 g (4.7 mmol) of compound X1, 1.63 g (5.64 mmol) of compound X3 and 1.30 mg (9.4 mmol) of potassium carbonate (K2CO3) were dissolved in toluene and distilled water The mixture was refluxed for 12 hours under a catalyst of 217 mg (0.19 mmol) of tetrakis (triphenylphosphine) palladium (0) [tetrakis (triphenylphosphine) palladium (0)]. After completion of the reaction, the solvent was distilled off under reduced pressure, and the residue was subjected to column chromatography using a solvent mixture of n-hexane and methylene chloride in a ratio of 4: 1. The solution was distilled under reduced pressure, and methylene chloride And recrystallized in a solvent of petroleum ether to obtain 0.74 g (yield: 26%) of compound FL-3.

4. Synthesis of Formula FL-4 Compound

Scheme 7

As shown in Scheme 7 above, 5.0 g (14.2 mmol) of 2,7-dibromo-9,9-dimethyl-9H-fluorene, 649 mg (3.41 mmol) of copper iodide (CuI) 8.5 g (56.804 mmol) of sodium (NaI) and 0.99 mL (6.25 mmol) of trans-1,2-diaminomethylamine were dissolved in 1,4-dioxane and the mixture was refluxed for 12 hours . After the completion of the reaction, the solvent was distilled off under reduced pressure to remove the solvent. The residue was subjected to column chromatography with n-hexane and the solution was distilled under reduced pressure and recrystallized in a solvent of methylene chloride and petroleum ether to obtain 4.17 g of compound X4 Yield: 65%).

Scheme 8

As shown in Scheme 8 above, 2.5 g (5.59 mmol) of compound X4, 2.07 g (12.307 mmol) of carboline, 852 mg (4.48 mmol) of copper iodide (CuI), and potassium triphosphate (K3PO4) g (33.57 mmol) of trans-1,2-cyclohexanediamine and 0.54 mL (4.48 mmol) of trans-1,2-cyclohexanediamine were dissolved in 1,4-dioxane and refluxed for 12 hours. After the completion of the reaction, the solvent was distilled off under reduced pressure, and the residue was subjected to column chromatography using a solvent mixture of n-hexane and ethyl acetate (3: 1), and the solution was distilled under reduced pressure to obtain methylene chloride and petroleum And recrystallized in a solvent of petroleum ether to obtain 1.08 g (yield: 37%) of the compound FL-4.

FL-1 to FL-4 compounds, FL-11, FL-12 and FL-15 compounds prepared by the above synthetic methods and NPB (N, N'-di (naphthalen- (HOMO) and LUMO (Lowest Unoccupied Molecular Orbital) values, including UV absorption and emission wavelength of diphenyl-benzidine, were measured and summarized in Table 1 below.

Referring to Table 1, it can be seen that the band gap energy of the FL-1 to FL-4, FL-11, FL-12 and FL-15 compounds of the present invention is larger than 3.0 of the comparative NPB. Therefore, it can be inferred that the compounds FL-1 to FL-4, FL-11, FL-12 and FL-15 of the present invention can be used not only as a hole injecting layer and a hole transporting layer but also as a host of a light emitting material layer.

The hole transport layer 240 may be formed on the hole injection layer 230 and may include NPB (N, N'-di (naphthalen-1-yl) -N, N'- -bis- (3-methylphenyl) -N, N'-bis- (phenyl) -benzidine), but the present invention is not limited thereto.

The light emitting material layer 250 is formed on the hole transporting layer 240, and a dopant may be added to the host material if necessary. In this case, the host material and the dopant material may be either fluorescent or phosphorescent materials, and may be selected from the group consisting of polymers, but are not limited thereto. For example, when the light emitting material layer 250 emits blue light, the light emitting material layer 250 may include an anthracene derivative, a pyrene derivative, and a perylene derivative. Group may be doped with at least one fluorescent host material selected from the group of fluorescent blue (B) dopants. In addition, when the light emitting material layer 250 emits green light, the light emitting material layer 250 may be formed by doping a phosphorescent green (G) dopant with a phosphorescent host material comprising a carbazole compound or a metal complex . In addition, when the light emitting material layer 250 emits red light, the light emitting material layer 250 may be formed by doping phosphorescent red (R) dopant into a phosphorescent host material comprising a carbazole compound or a metal complex .

The electron transport layer 260 is formed on the light emitting material layer 250 and may be formed of oxadiazole, triazole, phenanthroline, benzoxazole, or benzthiazole ), But the present invention is not limited thereto.

The electron injection layer 270 is formed on the electron transport layer 260 and may be formed of LIF or lithium quinolate (LiQ), but is not limited thereto.

The second electrode 280 is formed on the electron injection layer 270 and may include a metal having a low work function such as aluminum (Al), silver (Ag), magnesium (Mg), lithium (Li) Or calcium (Ca), but the present invention is not limited thereto.

3 is a cross-sectional view illustrating an organic light emitting diode device according to another embodiment of the present invention. The hole transport layer 240 'is formed of the same material as the hole injection layer 230, that is, an organic compound represented by the above- The organic light emitting diode device is the same as the organic light emitting diode device according to Fig. Therefore, the same reference numerals are assigned to the same components, and repetitive description of the same components will be omitted.

3, the organic light emitting diode device 200 according to another embodiment of the present invention includes a hole injection layer 230 and a hole transport layer 240 'formed of an organic compound represented by Formula 1 described above The hole injection layer 230 may be doped with the organic compound 220 having the LUMO level of -4.5 eV to -6.0 eV, for example, the organic compound represented by the formula 2, and the organic compound 220 ) Can be variously changed. Therefore, since there is no hole injection barrier between the hole injection layer 230 and the hole transport layer 240 ', the driving voltage of the device can be lowered. Further, by forming the hole injection layer 230 and the hole transport layer 240 'from the same host material, there are advantages such as cost reduction and productivity improvement. In the hole injection layer 230, the doping amount of the organic compound represented by Formula 2 may be 0.1 to 20% by weight with respect to the entire hole injection layer 230.

The organic compounds represented by the general formulas (1) and (2) are the same as those described above, and thus the repeated description thereof will be omitted.

4 is a cross-sectional view illustrating an organic light emitting diode device according to another embodiment of the present invention. The hole transport layer 240 'and the light emitting material layer 250' are the same as the hole injection layer 230, Is the same as the organic light emitting diode device according to the above-mentioned FIG. 2 except that it is made of the organic compound represented by the formula (1). Therefore, the same reference numerals are assigned to the same components, and repetitive description of the same components will be omitted.

4, the organic light emitting diode device 200 according to another embodiment of the present invention includes the hole injection layer 230, the hole transport layer 240 ', and the light emitting material layer 250' The organic compound 220 having the above-described LUMO level of -4.5 eV to -6.0 eV, for example, the organic compound represented by the above-mentioned formula (2), may be added to the hole injection layer 230, And the organic compound 220 may be variously modified. The doping amount of the organic compound represented by Formula 2 may be 0.1 to 20% by weight with respect to the entire hole injection layer 230.

Further, although not shown, the dopant described above may be added to the light emitting material layer 250 'in one embodiment of the present invention. That is, the organic compound represented by Formula 1 is used as a host, and the dopant material (not shown) may be formed of any one of the above-described fluorescent materials or phosphorescent materials, But is not limited thereto.

Therefore, since there is no hole injection barrier between the hole injection layer 230, the hole transport layer 240 ', and the light emitting material layer 250' using the same material, the driving voltage of the device can be lowered. Further, by forming the hole injection layer 230, the hole transport layer 240 ', and the light emitting material layer 250' from the same host material, cost reduction and productivity can be improved.

Hereinafter, the present invention will be described with reference to specific experimental examples.

One. Experimental Example 1

Experimental Example 1 of the present invention shows that when the organic compound 220 having the above-described LUMO level of -4.5 eV to -6.0 eV acts as a hole injection layer alone or as a dopant of a hole injection layer And the hole injecting ability between the above-mentioned FL-1 and FL-2 compounds and the comparative example materials.

Example  One

The ITO substrate was patterned to have a light emitting area of 3 mm x 3 mm and then cleaned. After washing with UV ozone, it was loaded into the evaporation system. The substrate was then transferred into a vacuum deposition chamber for deposition of all other layers on top of the substrate. The base pressure is about 10 -6 to 10-7 Torr. Then, HAT-CN dopant is doped to the host FL-1 compound as a hole injection layer on ITO as an anode at a doping concentration of 10% to form a film with a thickness of 50 Å NPB was formed to a thickness of 600 Å as a hole transport layer and MADN (2-methyl-9,10-bis (naphthalene-2-yl) anthracene) was formed as a light emitting material layer to a thickness of 250 Å. Was formed to a thickness of 100 angstroms, and Al, which was a cathode, was deposited to a thickness of 1500 angstroms. The device was then encapsulated using a UV cured epoxy and a water getter.

NPB

MADN

Example  2

Except that the FL-2 compound was used as a host in the hole injection layer under the same process conditions as in Example 1 described above.

Comparative Example  One

Under the same process conditions as in Example 1 described above, only HAT-CN having a thickness of 50 angstroms was formed in the hole injection layer without a host.

Comparative Example  2

The device was manufactured under the same process conditions as in Example 1 except that NPB was used as the host of the hole injection layer.

The current-voltage characteristics of the organic light emitting diode devices of Examples 1 and 2 and Comparative Examples 1 and 2 prepared according to Experimental Example 1 were measured, and the results are shown in FIG.

As can be seen from FIG. 5, in the case of Comparative Example 2 prepared by doping NPB with HAT-CN as a host of the hole injection layer, the driving voltage was decreased in comparison with Comparative Example 1 in which HAT-CN was used alone in the hole injection layer . Specifically, with respect to the driving voltage at 10 mA / cm 2, Comparative Example 1 showed 8.5 V and Comparative Example 2 showed 7.7 V.

In the case of Examples 1 to 2 prepared by doping HAT-CN using FL-1 and FL-2 made by the synthesis method of the present invention as a host of the hole injection layer, Comparative Examples 1 to 2 The driving voltage is further reduced. Specifically, with respect to the driving voltage at 10 mA / cm 2, Example 1 showed 7.3 V and Example 2 showed 6.3 V.

2. Experimental Example 2

Experimental Example 2 of the present invention shows that the compounds FL-1, FL-2, FL-11, FL-12 and FL-15 used in the hole injecting layer, the hole transporting layer and the light emitting material layer, And is an organic light emitting diode device manufactured to compare the device characteristics of the materials of the comparative example.

Example  One

The ITO substrate was patterned to have a light emitting area of 3 mm x 3 mm and then cleaned. After washing with UV ozone, it was loaded into the evaporation system. The substrate was then transferred into a vacuum deposition chamber for deposition of all other layers on top of the substrate. The dopant HAT-CN was doped to a doping concentration of 10% on the host FL-1 compound as a hole injecting layer, a hole transporting layer, and a light emitting material layer on ITO as an anode after the base pressure was about 10 -6 to 10-7 Torr. And FL-1 alone was deposited to a thickness of 300 ANGSTROM without HAT-CN, and a dopant DPVBi (4,48-bis (2,28-diphenylvinyl) -1,18-biphenyl Was doped with a doping concentration of 15% to form a film having a thickness of 400 ANGSTROM, an Alq3 film having a thickness of 200 ANGSTROM as an electron transporting layer, LiF as an electron injecting layer having a thickness of 10 ANGSTROM, Respectively. The device was then encapsulated using a UV cured epoxy and a water getter.

            DPVBi

Example  2

Except that the FL-2 compound was used as a host for the hole injecting layer, the hole transporting layer, and the light emitting material layer under the same process conditions as in Example 1 described above.

Example  3

Except that the FL-11 compound was used as a host for the hole injecting layer, the hole transporting layer, and the light emitting material layer under the same process conditions as in Example 1 described above.

Example  4

Except that the FL-12 compound was used as a host for the hole injecting layer, the hole transporting layer, and the light emitting material layer under the same process conditions as in Example 1 described above.

Example  5

Except that the FL-15 compound was used as a host for the hole injecting layer, the hole transporting layer, and the light emitting material layer under the same process conditions as in Example 1 described above.

Comparative Example

The device was fabricated under the same process conditions as in Example 1 except that NPB was used as a host for the hole injecting layer, the hole transporting layer, and the light emitting material layer.

The voltage, the luminous efficiency, the quantum efficiency and the color coordinates of the organic light emitting diode devices of Examples 1 to 5 and Comparative Examples prepared according to Experimental Example 2 were measured and shown in Table 2 below.

Referring to Table 2, the organic light emitting diode device manufactured according to Example 2 of the present invention has significantly improved luminous efficiency and quantum efficiency as compared with the comparative example, and the driving voltage is lowered.

As described above, according to the present invention, a hole transport material having a large band gap energy is manufactured, and simultaneously applied as a hole injection layer, a hole transport layer and a host of a light emitting material layer of an organic light emitting diode device, The problem of lowering the productivity is solved and there is an advantage that the luminescence efficiency can be improved and the driving voltage can be reduced through doping of the material having the deep LUMO.

The hole injection layer 230, the hole injection layer 230 and the hole transport layer 240 'of FIG. 2, the hole injection layer 230, the hole transport layer 240' and the light emitting material layer 250 ' ) May contain an organic compound of the following formula (3) in place of the organic compound of the above formula (1). The hole injection layer 230 may include HAT-CN in an amount of 0.1 to 20% by weight based on the total weight of the light emitting material layer 250. The light emitting material layer 250 'may include 0.1 to 30% Blue light can be emitted. The dopant may be N, N'-bis (2,4-diphenyl) -N, N'-bis (2-fluorophenyl) -pyrene-1,6-diamine.

At least one of the hole injecting layer, the hole transporting layer, and the light emitting material layer may be a hole transporting layer, a hole injection layer, a hole transporting layer, a light emitting material layer, and a second electrode, The organic EL device has an effect of improving the luminous efficiency and quantum efficiency and lowering the driving voltage. Particularly, since both the hole injecting layer, the hole transporting layer and the light emitting material layer contain an organic compound represented by the following formula (3), the device structure is simplified, and the problem of cost increase and productivity deterioration is solved.

Since the organic compound of Formula 3 has excellent hole transporting properties, the hole injecting layer, the hole transporting layer, and the light emitting material layer all contain an organic compound of Formula 3, The luminous efficiency is further improved. In other words, the hole injection barrier is lowered, and a coupling region of holes and electrons is formed at the central portion of the light emitting layer, so that the light emitting efficiency is improved.

(3)

In Formula 3, X may be selected from among carbon, nitrogen, oxygen, and sulfur, and Y may be selected from aryl or arylamine. For example, Y may be selected from phenyl, naphthyl, terphenyl, xylene, triphenylamine, diphenylamine, and phenathrenylamine.

Specifically, Y may be selected from the following compounds.

The organic compound of the present invention represented by Formula 3 may be a compound represented by the following Formulas AN-1 to AN-16.

Hereinafter, examples of the synthesis of the organic compound according to the present invention will be described with reference to the organic compounds represented by the above-mentioned formulas AN-1, AN-2, AN-3 and AN-4.

1. Synthesis of Compound of Formula AN-1

(1) Synthesis of 3- (10-phenylanthracen-9-yl) -9H-carbazole

Scheme 9

To a 250 mL 2-neck flask was added 3-bromocarbazole (2.54 g, 10.320 mmol), 9-phenyl-boronic acid (3.69 g, 12.384 mmol), Na2CO3 (2.2 g, 20.64 mmol), Pd (PPh3) mmol) were dissolved in toluene / EtOH / H2O, and the mixture was refluxed and stirred at 120 ° C for 12 hours. After completion of the reaction, the reaction mixture was extracted with methylenechloride / H2O and distilled under reduced pressure to remove the solvent. The residue was subjected to column chromatography using n-hexane and methylene chloride (4: 1), methylene chloride And petroleum ether solvent to obtain 2.60 g of a white solid compound. (Yield 60%)

(2) Synthesis of AN-1 compound

Scheme 10

To a 250 mL 2-neck flask was added 3- (10-phenylanthracen-9-yl) -9H-carbazole (1.68 g, 4.00 mmol), 4-bromo-triphenylamine (1.43 g, 4.401 mmol), Pd2 (dba) , Tris-t-butylphosphine (47 μl, 0.200 mmol) and sodium tert-butoxide (770 mg, 8.00 mmol) were dissolved in toluene and refluxed for 12 hours. After completion of the reaction, the solvent was distilled off under reduced pressure, and the residue was subjected to column chromatography using n-hexane and methylene chloride as a solvent (4: 1), and then methylene chloride and petroleum ether (Petroleum ether) to obtain 2.53 g of a white solid AN-1 compound. (Yield: 95%)

2. Synthesis of Compound of Formula AN-2

Scheme 11

To a 250 mL 2-neck flask was added 3- (10-phenylanthracen-9-yl) -9H-carbazole (1.59 g, 3.80 mmol) and N- (4- bromophenyl) -N- phenylnaphthalen- , Tris-t-butylphosphine (27 μl, 0.114 mmol) and sodium tert-butoxide (728 mg, 7.58 mmol) were dissolved in toluene and the mixture was stirred for 12 hours Lt; / RTI > After completion of the reaction, the solvent was distilled off under reduced pressure, and the residue was subjected to column chromatography using n-hexane and methylene chloride as a solvent (3: 1), then methylene chloride and petroleum ether (Petroleum ether to yield 1.64 g of AN-2 compound in the form of a greenish solid. (Yield: 61%)

3. Synthesis of Compound of Formula AN-3

(1) Synthesis of N-phenylphenanthren-9-amine

Scheme 12

To a 250 mL 2-neck flask was added 9-bromophenanthrene (7.00 g, 27.22 mmol), aniline (3.7 mL, 40.84 mmol), Pd2 (dba) 3 (499 mg, 0.544 mmol), tris- mmol) and sodium tert-butoxide (3.90 mg, 40.84 mmol) were dissolved in toluene, and the mixture was refluxed for 12 hours. After completion of the reaction, the mixture was extracted with DI water / methylene chloride and distilled under reduced pressure. The solvent was removed and the residue was recrystallized in a solvent of n-hexane and methylene chloride (3: 1) and recrystallized in a solvent of methylene chloride and petroleum ether to obtain a solid state Of compound (4.60 g). (Yield: 63%)

(2) Synthesis of N- (3-bromophenyl) -N-phenylphenanthren-9-amine

Scheme 13

N-phenylphenanthren-9-amine (4.51 g, 16.74 mmol), 1,3-dibromobenzene (6.05 mL, 50.23 mmol), Pd2 (dba) 3 (307 mg, 0.355 mmol), tris- o-tolyphosphine (0.255 mL, 0.837 mmol) and sodium tert-butoxide (3.2 g, 33.49 mmol) were dissolved in toluene and refluxed for 12 hours. After completion of the reaction, the mixture was extracted with DI water / methylene chloride and distilled under reduced pressure. After removal of the solvent, the column was subjected to column chromatography using n-hexane and methylene chloride (7: 1). The solution was distilled under reduced pressure and recrystallized to obtain 2.9 g of a waxy compound. (Yield: 41%)

(3) Synthesis of AN-3

Scheme 14

To a 250 mL 2-neck flask was added 3- (10-phenylanthracen-9-yl) -9H-carbazole (1.25 g, 2.98 mmol) and N- (3- bromophenyl) -N- phenylphenanthren- (55 mg, 0.060 mmol), tris-t-butylphosphine (0.014 mL, 0.060 mmol) and sodium tert-butoxide (572 mg, 5.96 mmol) were dissolved in toluene and refluxed for 12 hours Lt; / RTI > After completion of the reaction, the mixture was extracted with DI water / methylene chloride and distilled under reduced pressure. The solvent was removed and the residue was recrystallized in a solvent of n-hexane and methylene chloride (3: 1) and recrystallized in a solvent of methylene chloride and petroleum ether to obtain a solid To obtain 1.14 g of AN-3 compound. (Yield 50%)

4. Synthesis of Compound of Formula AN-4

(1) Synthesis of 6- (10-phenylanthracen-9-yl) -9H-pyrido [2,3-b] indole

Scheme 15

To a 250 mL 2-neck flask was added bromo-carboline (3.0 g, 12.14 mmol), 9-phenylboronic acid (3.98 g, 13.36 mmol), Na2CO3 (2.57 g, 24.28 mmol), Pd (PPh3) 1.21 mmol) were dissolved in toluene / EtOH / H2O, and the mixture was refluxed at 120 ° C for 12 hours. After completion of the reaction, the reaction mixture was extracted with methylenechloride / H2O and distilled under reduced pressure to remove the solvent. The residue was subjected to column chromatography using n-hexane and ethylene acetate solvent (3: 1) and recrystallized in a solvent of methylene chloride and petroleum ether to obtain 2.32 g of solid compound ≪ / RTI > (Yield: 45%)

(2) Synthesis of 9- (4-iodophenyl) -6- (10-phenylanthracen-9-yl) -9H-pyrido [2,3- b] indole

Scheme 16

9-pyrido [2,3-b] indole (1.76 g, 4.19 mmol), 1,4-diiodobenzene (2.76 g, 8.37 mmol) in a 250 mL 2-neck flask, 1,2-dicyclohexanediamine (0.2 mL, 1.67 mmol) was dissolved in 1,4-dioxane and the mixture was refluxed at 120 ° C. for 12 hours. Lt; / RTI > After completion of the reaction, the reaction mixture was extracted with methylenechloride / H2O and distilled under reduced pressure to remove the solvent. The residue was recrystallized from methylenechloride / PE ether in a solvent of methylene chloride and petroleum ether in a solvent of n-hexane and methylene chloride (1: 5) 1.67 g of a solid compound was obtained. (Yield 64%)

(3) Synthesis of AN-4 Compound

Scheme 17

Pyran [2,3-b] indole (1.58 g, 2.54 mmol), diphenylamine (430 mg, 2.54 mmol), Pd2 (dba) in a 250 mL 2-neck flask, Tris-t-butylphosphine (0.012 mL, 0.050 mmol) and sodium tert-butoxide (488 mg, 5.08 mmol) were dissolved in toluene and the mixture was refluxed for 12 hours at 120 ° C. After completion of the reaction, the reaction mixture was extracted with methylene chloride / H2O and distilled under reduced pressure to remove the solvent. The residue was recrystallized from methylenechloride / PE ether in a solvent of methylene chloride and petroleum ether in a solvent of n-hexane and methylene chloride (1: 5) 0.54 g of a solid AN-4 compound was obtained. (Yield 32%)

Properties of the host material (Host (ref.)) Represented by the compounds AN-1 to AN-4, AN-6, AN-8 and AN-11 and the following formula 4 were measured and are summarized in Table 3 below.

[Chemical Formula 4]

Hereinafter, the performance of the organic light emitting diode device using the organic compound of the present invention and the organic light emitting diode device using the comparative material of Formula 4 will be described.

Device fabrication

The ITO substrate was patterned to have a light emitting area of 3 mm x 3 mm and then cleaned. After washing with UV ozone, it was loaded into the evaporation system. Then, the substrate was transferred into a vacuum deposition chamber. (Host / HAT-CN (10%)), ii) a hole transport layer (300 Å) (host), and iii) a hole injection layer A luminescent material layer 700 Å (host / dopant 15%), iv) an electron transport layer 200 Å (Alq 3), v) an electron injecting layer 10 Å (LiF), and vi) a cathode 1000 Å (Al) The device was then encapsulated using a UV cured epoxy and a water getter. The dopant of the light emitting material layer is N, N'-bis (2,4-diphenyl) -N, N'-bis (2-fluorophenyl) -pyrene-1,6-diamine.

(1) Comparative Example (Ref.)

In the above-described device, the material of the above chemical formula 4 was used as a host for the hole injecting layer, the hole transporting layer, and the light emitting material layer.

(2) AN-1 element

In the above-described device, the material of the above-described formula AN-1 was used as a host for the hole injecting layer, the hole transporting layer, and the light emitting material layer.

(3) AN-3 element

In the above-described device, the material of the above-described formula AN-3 was used as a host for the hole injecting layer, the hole transporting layer, and the light emitting material layer.

(4) AN-6 element

In the above-described device, the material of the above-described formula AN-6 was used as a host for the hole injecting layer, the hole transporting layer and the light emitting material layer.

(5) AN-8 element

In the above-described device, the material of the above-described formula AN-8 was used as a host for the hole injecting layer, the hole transporting layer and the light emitting material layer.

(6) AN-11 element

In the above-described device, the substance of the above formula AN-11 was used as a host for the hole injecting layer, the hole transporting layer, and the light emitting material layer.

Except for the host of the hole injecting layer, the hole transporting layer, and the light emitting material layer, all of which were manufactured in the same manner. The characteristics of the device were measured and are summarized in Table 4 below.

As can be seen from Table 4, when the organic compounds (AN-1, AN-3, AN-6, AN-8 and AN-11) of the present invention are used in comparison with the comparative example (Ref. And the luminous efficiency is improved. Since the organic compound of the present invention has excellent hole characteristics, the combination of holes and electrons can be formed at the center of the light emitting material layer, thereby improving the light emitting efficiency.

That is, as shown in Table 3, the organic compound of the present invention and the host material of the comparative example have similar characteristics in LUMO, HOMO, and the like, but the host material of the comparative example further hinders the hole transport because of its strong electronic characteristics. However, since the organic compound of the present invention has a strong hole characteristic, the hole transporting property is improved, and the hole and electron are bonded at the center of the light emitting material layer, thereby improving the luminous efficiency.

Further, by forming the hole injection layer, the hole transport layer, and the light emitting material layer as one host, it is possible to provide an organic light emitting diode device having a simple structure and excellent characteristics.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the invention as defined in the appended claims. It can be understood that

100: substrate 200: organic light emitting diode element
210: anode 220: dopant of the hole injection layer
230: Hole injection layer 240, 240 ': Hole injection layer
250, 250 ': light emitting material layer 260: electron transporting layer
270: electron injection layer 280: cathode

Claims (18)

An organic compound represented by the following formula:

(Wherein R is a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, A and B are symmetrically or asymmetrically bonded to the 2 and 7 positions of the fullerene core, and each independently represents a substituted or unsubstituted aromatic ring compound or a variant Ring compound).
The method according to claim 1,
A and B each independently represent a substituted or unsubstituted carbazole group, an a-carboline group, a beta-carboline group, a gamma-carboline group, A dibenzofuran group, a dibenzothiophene group, an arylamine group, an arylsilane group, and a phenyl group.
The method according to claim 1,
Wherein A and B are each independently selected from the following compounds.

The method according to claim 1,
Wherein the organic compound is any one selected from the following compounds.

An organic compound represented by the following formula:

(X is selected from carbon, nitrogen, oxygen, sulfur, and Y is selected from aryl or arylamine.)
6. The method of claim 5,
And Y is selected from the group consisting of phenyl, naphthyl, terphenyl, xylene, triphenylamine, diphenylamine, phenanthrenylamine and substituents thereof.
6. The method of claim 5,
Wherein the organic compound is any one of the following compounds.

A first electrode;
A second electrode facing the first electrode;
A light emitting material layer disposed between the first electrode and the second electrode;
A hole injection layer disposed between the first electrode and the light emitting material layer;
And a hole transport layer positioned between the hole injection layer and the light emitting material layer,
Wherein at least one of the hole injection layer, the hole transport layer, and the light emitting material layer comprises an organic compound of any one of claims 1 to 7.
9. The method of claim 8,
Wherein the hole injection layer is formed by mixing a dopant material having a LUMO level of -4.5 eV to -6.0 eV and the organic compound.
10. The method of claim 9,
Wherein the dopant material is HAT-CN (Hexaazatriphenylene-hexacarbonitrile) having the following formula.

10. The method of claim 9,
Wherein a mixing ratio of the dopant material in the hole injection layer is 0.1 to 20% based on the total weight of the organic compound and the dopant material.
The method according to any one of claims 8 to 11,
Wherein the hole injection layer, the hole transport layer, and the light emitting material layer are all formed of the organic compound.
The method according to any one of claims 8 to 11,
Wherein the light emitting material layer includes the organic compound and emits blue light.
A first electrode;
A second electrode facing the first electrode;
A light emitting material layer disposed between the first electrode and the second electrode;
A hole injection layer disposed between the first electrode and the light emitting material layer;
And a hole transport layer positioned between the hole injection layer and the light emitting material layer,
Wherein at least two of the hole injecting layer, the hole transporting layer, and the light emitting material layer are made of the same host material.
15. The method of claim 14,
Wherein the hole injecting layer, the hole transporting layer, and the compound forming the light emitting material layer are all made of the same host material.
16. The method according to any one of claims 14 to 15,
Wherein the hole injection layer further comprises an organic compound having a LUMO level of -4.5 eV to -6.0 eV, and the light emitting material layer further comprises a dopant.
17. The method of claim 16,
Wherein the organic compound having the LUMO level of -4.5 eV to -6.0 eV is made of HAT-CN (Hexaazatriphenylene-hexacarbonitrile) represented by the following formula.

17. The method of claim 16,
The mixing ratio of the organic compound having the LUMO level of the hole injection layer of -4.5 eV to -6.0 eV is 0.1-20% based on the total weight of the organic compound having the LUMO level of -4.5 eV to -6.0 eV Characteristic organic light emitting diode device.

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