KR20170064181A - Low molecular luminous compound enabled solution process, organic light emiting didoe and display devie having the compound - Google Patents
Low molecular luminous compound enabled solution process, organic light emiting didoe and display devie having the compound Download PDFInfo
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Abstract
The present invention relates to an organic light emitting diode device and an organic light emitting diode (OLED) display device in which a low molecular weight luminescent compound capable of solution process and a luminescent compound are applied to an organic material layer of the device. The luminescent compound according to the present invention can be applied not only to a device through a solution process but also to a deep blue device with improved color purity and excellent luminescent characteristics such as luminescent efficiency.
Description
More particularly, the present invention relates to a blue light emitting compound capable of a solution process, a light emitting diode including the organic compound layer in the organic compound layer, and a display device.
Recently, as the size of display devices has been increased, the demand for flat display devices with less space occupation is increasing. The technology of an organic light emitting diode device, also called an organic electroluminescent device (OELD) .
When an electric charge is injected into a light emitting material layer formed between an electron injection electrode (cathode) and a hole injection electrode (anode), the organic light emitting diode device emits light while paired with electrons. The device can be formed on a flexible transparent substrate such as a plastic substrate and can be driven at a lower voltage (10 V or less) than a plasma display panel or an inorganic electroluminescence (EL) It also has a relatively low power consumption and excellent color purity. In addition, organic light emitting diode devices are capable of displaying three colors of green, blue, and red, making them a next-generation rich color display device and attracting many people's attention. Here, the process of fabricating the organic light emitting diode device will be briefly described.
(1) First, a material such as indium tin oxide (ITO) is deposited on a transparent substrate to form an anode.
(2) A hole injecting layer (HIL) is formed on the anode.
(3) Next, a hole transporting layer (HTL) is formed on the hole injection layer. If necessary, an electron blocking layer (EBL) may be formed to confine the excitons in the light emitting material layer.
(4) Next, an emitting material layer (EML) is formed on the hole transport layer. At this time, a dopant is added as needed.
(5) Next, an electron transporting layer (ETL) and an electron injecting layer (EIL) are formed on the light emitting material layer. Alternatively, a hole blocking layer (HBL) may be formed to a thickness of 5 to 10 nm in order to confine the exciton in the light emitting material layer.
(6) Next, a cathode is formed on the electron injection layer, and a protective film is formed on the cathode.
As described above, in order to improve the efficiency, the organic light emitting diode device has a structure in which a hole injecting layer, a hole transporting layer, a light emitting material layer, an electron transporting layer, and an electron injecting layer are laminated between an anode and a cathode. In addition, an electron blocking layer (EBL) and a hole blocking layer (HBL) may be additionally included to prevent quenching of the exciton. Such a complicated structure increases the cost and the productivity.
In addition, in the conventional organic light emitting diode device, efficient hole injection is difficult due to a hole injection barrier, while electron injection and delivery speed is relatively fast. Therefore, the coupling region of holes and electrons is not located in the light emitting material layer but is located between the layer and the layer, that is, between the light emitting material layer and the hole transporting layer, thereby reducing the luminous efficiency. In order to solve the above-mentioned problem, it is necessary 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.
Particularly, blue light emission requires a material having a broad energy bandgap compared to green and red, which makes it difficult to develop materials. However, since the blue luminescent material has a large energy gap, there is a common applicability for green and red luminescence.
With respect to the blue light emitting material, U.S. Patent No. 6,455,720 discloses a 2,2- (diaryl) vinylphosphine compound, and US Patent Publication No. 2007-0292714 discloses a Discloses a blue light emitting compound having a pyrene structure and having a diphenylamino group substituted at the terminal thereof. Korean Patent Publication No. 2002-0070333 discloses a blue light emitting compound having a diphenyl anthracene structure and an aryl group substituted at the center thereof. Korean Patent Publication No. 2007-0023335 discloses a blue light emitting compound having a dipyrene- A blue light-emitting compound is disclosed. However, the light emitting materials disclosed in these patents have insufficient lifetime, luminous efficiency, and brightness, and have low color purity, making it difficult to implement deep blue, which poses a problem in realizing full-color displays of full color.
Meanwhile, a conventional vacuum deposition process is used to dope a light emitting material into an organic material layer constituting the organic light emitting diode, for example, a hole injection layer, a hole transport layer, and a light emitting material layer. However, in recent years, attempts have been made to apply a solution process instead of a vacuum deposition method. The combination of the solution process and the printing process makes it possible to print the organic material solution only in a desired place when OLED pixels are manufactured, so that consumption of the organic material is reduced as compared with the vacuum deposition method of vaporizing the organic material in the entire vacuum chamber , The use efficiency of the organic material increases.
In addition, since the solution process is relatively less expensive than the vacuum deposition, it is cost competitive. In order to realize a full-color display, the three primary colors of red-green-blue are respectively patterned to form unit pixels. In the vacuum deposition method, only the specific region opened through a fine metal mask (FMM) . However, as the size of the substrate increases and the required resolution increases, there is a restriction on the process conditions that can be implemented by the FMM method. The solution process has advantages in cost competitiveness, fairness, enlargement and high resolution compared with the conventional vacuum deposition process.
Conventionally, a light emitting compound developed by a solution process is mostly a polymer compound, and a film can be formed by a simple method such as spin coating. However, the polymer compound has a relatively low luminous efficiency as compared with the low molecular materials produced by the vapor deposition process. In particular, since the color luminescent material used in the conventional solution process has a color coordinate of 0.13 or more, it is troublesome to fabricate a device using a hard cavity or a soft cavity on a lower substrate for application to a display device.
Due to these problems, a hybrid structure was adopted in which a solution process was applied to the red region and the green region among the three pigments, and a deposition process was applied to the blue region. However, in this case, it is difficult to form a uniform charge balance due to the interface difference between the HTL applying the solution process and the BCL (blue common layer) applying the deposition process. Therefore, charges are accumulated in a specific region in the light emitting diode, charge balance is lowered, and holes and electrons are not combined in EML such as BCL, and are coupled between HTL and EML to emit light. Therefore, there is a problem in that the color characteristics of the blue device are deteriorated, and the efficiency and the life are deteriorated.
It is an object of the present invention to provide a low-molecular light-emitting compound capable of solution processing and a light-emitting diode and a display device to which the compound is applied to an organic material layer.
Another object of the present invention is to provide a low molecular weight luminescent compound having excellent color purity, low driving voltage, high efficiency and long lifetime, and a light emitting diode and a display device using the compound.
Another object of the present invention is to provide a light emitting compound which can improve cost competitiveness and fairness, and can realize a large size and high resolution, and a light emitting diode and a display device to which the compound is applied.
According to an aspect of the present invention, there is provided a low molecular weight blue light emitting compound capable of performing a solution process and satisfying excellent color purity, low driving voltage, high luminous efficiency and long lifetime.
According to another aspect of the present invention, there is provided a light emitting device comprising the above-described light emitting compound in at least one layer of an organic material layer, for example, a light emitting material layer, a hole injecting layer and a hole transporting layer, Lt; / RTI >
According to another aspect of the present invention, there is provided a display device in which the above-mentioned blue light emitting compound has a light emitting diode applied to at least one of organic layers.
The low molecular weight luminescent compound synthesized according to the present invention is implemented so that a solution process is possible. Therefore, unlike the deposition process, doping can be performed through a solution process only in a region requiring a light emitting compound, thereby achieving the efficiency of the organic material.
In addition, the luminescent compound of the present invention has excellent color purity, low driving voltage, high efficiency and long lifetime, and can realize a large-sized and high-resolution display by applying a solution process.
1 is a schematic cross-sectional view of an organic light emitting diode according to an exemplary embodiment of the present invention.
2 is a schematic cross-sectional view of an organic light emitting diode display device according to an exemplary embodiment of the present invention.
3 is a graph showing the TGA analysis results of measuring the thermal stability of the synthesized luminescent compound according to an exemplary embodiment of the present invention.
4A and 4B are graphs showing the results of measurement of ultraviolet spectrum and PL spectrum of the synthesized luminescent compound according to an exemplary embodiment of the present invention, respectively. FIG. 4A shows a luminescent compound dissolved in an organic solvent, and FIG. 4B shows a luminescent compound in a thin film state.
5 is a graph showing the results of measurement of the voltage-current of the synthesized luminescent compound according to an exemplary embodiment of the present invention.
FIG. 6 is a schematic cross-sectional view of a light emitting diode device manufactured according to an exemplary embodiment of the present invention, in which energy levels are indicated.
FIG. 7 is a graph illustrating a current density and a light emission characteristic according to a driving voltage of a light emitting diode device manufactured according to an exemplary embodiment of the present invention.
8 is a graph showing EL intensity of a light emitting diode device manufactured according to an exemplary embodiment of the present invention.
FIG. 9 is a graph illustrating an external quantum efficiency (EQE) of a light emitting diode device manufactured according to an exemplary embodiment of the present invention.
10 is a graph illustrating luminous efficiency and voltage efficiency of a light emitting diode device manufactured according to an exemplary embodiment of the present invention.
According to an aspect of the present invention, there is provided a luminescent compound capable of being subjected to a solution process represented by the following general formula (1).
(R 1 and R 2 are each independently a hydrogen atom or a C 1 -C 20 alkyl group in the formula (1); or R 3 to R 5 are each independently hydrogen, C 1 -C 20 alkyl group, substituted or not heavy hydrogen, C 1 - C 10 alkyl group, C 1 -C 10 alkylsilyl group, C 1 -C 10 alkyl halide, nitro, -CN, a homo or hetero-aryl group substituted with at least one functional group selected from a group consisting of a halogen and a phenyl group)
For example, a luminescent compound that can be subjected to the solution process of
(2)
(Wherein R 1 to R 5 are the same as defined in formula (1)
In one specific embodiment, R 1 and R 2 are each a C 1 -C 10 alkyl group, R 3 and R 4 are each a C 1 -C 10 alkyl group, R 5 is unsubstituted or substituted with deuterium, C 1 -C 10 alkylsilyl group, C 1 -C 10 alkyl halide, nitro, -CN, and may be a homo-date aryl substituted with at least one functional group selected from the group consisting of halogen.
According to another aspect of the present invention, there is provided a plasma display panel comprising: a first electrode; A second electrode facing the first electrode; And at least one organic compound layer disposed between the first electrode and the second electrode, wherein the organic compound layer includes a light emitting compound capable of performing the solution process described above.
In one exemplary embodiment, the organic layer may include a layer of a light emitting material.
In an alternative embodiment, the light-emitting compound capable of being subjected to the solution process may be included in at least one organic material layer between the first electrode and the light-emitting material layer and between the hole injection layer and the hole transport layer.
According to another aspect of the present invention, there is provided a plasma display panel comprising: a first substrate; A driving thin film transistor located on the first substrate; A light emitting diode disposed on the first substrate and connected to the driving thin film transistor, the light emitting diode including a light emitting compound capable of performing the solution process described above in at least one organic layer; And a second substrate covering the light emitting diode and being attached to the first substrate.
Hereinafter, the present invention will be described in more detail with reference to the accompanying drawings where necessary.
[Luminescent compound]
The present invention relates to a low-molecular blue light-emitting compound capable of being subjected to a solution process represented by, for example, the following formula (1).
(R 1 and R 2 are each independently a hydrogen atom or a C 1 -C 20 alkyl group in the formula (1); or R 3 to R 5 are each independently hydrogen, C 1 -C 20 alkyl group, substituted or not heavy hydrogen, C 1 - C 10 alkyl group, C 1 -C 10 alkylsilyl group, C 1 -C 10 alkyl halide, nitro, -CN, a homo or hetero-aryl group substituted with at least one functional group selected from a group consisting of a halogen and a phenyl group)
That is, the low-molecular blue light-emitting compound of the present invention is an acridine derivative, which is directly connected to the acridine derivative, and has a strong hole property of a fluorene structure which can be substituted with various substituents, The balance between electrons and holes can be improved. In addition, the solution process can be applied by using various substituents on the acridine derivative and fluorene constituting the core.
In one preferred embodiment, the C 1 -C 20 alkyl group constituting R 1 and R 2 is a C 1 -C 10 alkyl group, more preferably methyl, ethyl, n-propyl, i-propyl, n-butyl, can be a C 1 -C 6 alkyl group, such as i- butyl, t- butyl, but the present invention is not limited to this.
Further, the aryl group constituting R 3 to R 5 constituting the formula (1) may be, for example, a C 5 -C 30 unsubstituted or substituted homo or heteroaryl group, or a homo or heteroarylene group.
More specifically, the homoaryl group constituting R 3 to R 5 of the general formula (1) is not substituted or is a group selected from the group consisting of deuterium, a C 1 -C 10 alkyl group, a C 1 -C 10 alkylsilyl group, a C 1 -C 10 alkyl halide, A phenyl group substituted with at least one functional group selected from the group consisting of -CN, halogen and a phenyl group, naphthyl, indenyl, anthracenyl, fluorenyl, and may be selected from the group consisting of phenalenyl, phenanthrenyl, pyrenyl, tetraphenyl, biphenyl, terphenyl and spiro-fluorenyl. But the present invention is not limited thereto.
The heteroaryl group constituting R 3 to R 5 of formula (1) may be unsubstituted or substituted with at least one substituent selected from the group consisting of deuterium, a C 1 -C 10 alkyl group, a C 1 -C 10 alkylsilyl group, a C 1 -C 10 alkyl halide, a nitro group, Carbazole, pyridazine, pyrazine, imidazole, pyrazole, oxadiazole substituted with at least one functional group selected from the group consisting of CN, halogen and phenyl groups, Oxadiazole, triazole, furan, pyrimidine, oxazole, pyrrole, pyridine, triazine, thiazole, thiazole, Thiophene, and N-substituted spiro-fluorenyl, but the present invention is not limited thereto.
In one exemplary embodiment, the C 1 -C 10 alkyl group in the substituent of the aryl group constituting R 3 to R 5 in the general formula (1) is methyl, ethyl, n-propyl, i-propyl, , and C 1 -C 6 alkyl group, such as t- butyl, C 1 -C 10 alkyl silyl group is a silyl C 1 -C 6 alkyl, such as trimethylsilyl group, C 1 -C 10 alkyl halides such as trifluoromethyl C 1 -C 6 alkyl halide, and the halogen may be fluorine.
According to one exemplary embodiment, R < 5 > constituting the formula (1) may be substituted on the opposite side of the acridine derivative. In this case, the dissolution characteristics of the blue light emitting compound with respect to the organic solvent can be improved, and the electrical characteristics and luminescence characteristics can be improved. For example, the low molecular weight blue fluorescent compound capable of the solution process of the present invention may include a compound represented by the following formula (2).
(2)
(Wherein R 1 to R 5 are the same as defined in formula (1)
In one specific embodiment, R 1 and R 2 are each a C 1 -C 10 alkyl group, R 3 and R 4 are each a C 1 -C 10 alkyl group, R 5 is unsubstituted or substituted by deuterium, C 1 -C 10 alkylsilyl group, C 1 -C 10 alkyl halide, nitro, -CN, and may be a homo-date aryl substituted with at least one functional group selected from the group consisting of halogen.
Specific examples of the blue light emitting compound that can be subjected to the solution process according to the present invention include (10- (7- (anthracen-9-yl) -9,9-dioctyl-9H-fluoren- 2- 9,9-dimethyl-9,10-dihydroacridine (hereinafter referred to as AFAN), (10- (7- (9,9'-spirobi [fluorene] -2- -9,9-dioctyl-9H-fluoren-2-yl) -9,9-dimethyl-9,10-dihydroacridine (hereinafter referred to as AFSBF) (9,9-dimethylacridin-10 (9H) -yl) -9,9-dioctyl-9H-fluoren-2-yl) -9,9'-spirobi [fluorene] AFSBFN " herein), but the present invention is not limited thereto.
(3)
Formula 4
Formula 5
[Light Emitting Diodes and Display Devices]
For example, a luminescent compound capable of being subjected to a solution process represented by the general formulas (1) to (5) shows excellent thermal stability (see FIG. 3) and has excellent PL characteristics dissolved in an organic solvent as well as a thin film state See FIG. 4B), and may be doped into one or more organic layers constituting the light emitting diode through a solution process. Therefore, solution and printing processes such as spin coating, blade coating and roll-slot coating can be applied. Since a liquid material is used, the process is simple, low-cost equipment can be utilized, and doping can be performed only on a desired pixel region, thereby improving the use efficiency of the material.
In addition, since these luminescent compounds can emit blue wavelength light, they can be used not only as a blue dopant for a luminescent material layer but also for a triplet energy value (see Fig. 6) Layer bipolar host for the phosphorescent material.
Furthermore, since the compound of the present invention has a wide energy band gap (see Table 1) and exhibits an excellent current density at a low driving voltage (see FIG. 7), the hole transporting property can be improved. Accordingly, the luminescent compound of the present invention can be used as another organic layer such as a hole injecting layer and a hole transporting layer in green (G) and red (R) pixel regions in an organic light emitting diode device.
An embodiment of an organic light emitting diode device to which the blue fluorescent compound of the present invention is applied is shown in Fig. 2) formed between the first substrate 101 (see FIG. 2) and the second substrate 102 (see FIG. 2) facing each other and the light emitting diodes E ).
The light emitting diode E includes a
The
On the other hand, the organic
At least one organic layer of the
In another alternative embodiment, a compound other than the luminescent compound of the present invention may be used in the
In one exemplary embodiment, when the light emitting compound of the present invention is used as a host material for the light emitting
On the other hand, the
In addition, the
The light emitting diode manufactured according to the exemplary embodiment of the present invention has excellent current density and light emission characteristics and is driven at a low voltage (FIG. 7), EL intensity (FIG. 8), external quantum efficiency (EQE The efficiency and the voltage efficiency are excellent (see FIG. 10). Therefore, the present invention can be applied to a display device such as an organic light emitting diode display device by adopting the light emitting diode of the present invention. 2 is a schematic cross-sectional view of a display device according to an exemplary embodiment of the present invention.
2, in the
The
Specifically, the
A
A
An interlayer insulating
The
A
The
The
Alternatively, the driving thin film transistor DTr may have an inverted staggered structure in which a gate electrode is positioned below the semiconductor layer and a source electrode and a drain electrode are located above the semiconductor layer. In this case, the semiconductor layer may be made of amorphous silicon.
Further, a switching thin film transistor (not shown) having substantially the same structure as the driving thin film transistor DTr is further formed on the
A
The light emitting diode E constituting the light emitting
As described above, the
The
In addition, a second substrate, that is, an
Hereinafter, the present invention will be described in more detail with reference to the following Examples. However, the present invention is not limited to the technical ideas described in the following Examples.
Synthetic example 1: Methyl 2- ( phenylamino ) benzoate (2)
2- (phenylamino) benzoic acid (10 g, 46.8 mmol) was dissolved in methanol (200 mL) and SOCl 2 (8.5 mL, 117.2 mmol) was slowly added to the 100 mL three-necked flask at 0 ° C. After the reaction mixture was refluxed for 12 hours, the reaction was terminated and the reaction mixture was poured into cold water to give a solid which was washed with water. The resulting solid was dissolved again in methylene chloride (MC), washed with NaHCO 3 aqueous solution, dried over anhydrous Na 2 SO 4 and the solvent was removed by vacuum distillation to obtain a yellow product liquid (yield: 9.6 g, 90%).
1 H NMR (300 MHz, CDCl 3 ,?): 9.48 (s, 1H), 7.99-7.95 (m, 1H), 7.37-7.24 (m, 6H), 7.12-7.07 (m, 1 H), 3.90 (s, 3 H).
Synthetic example 2: 2- (2- ( Phenylamino ) phenyl) propane -2- be (3) Synthesis of
Methyl 2- (phenylamino) benzoate (5.0 g, 22.0 mmol) synthesized in Synthesis Example 1 was dissolved in THF (75 mL) and then CH 3 MgBr (3.0 M in ether) (33.7 mL, 101.2 mmol) Is added slowly at -78 [deg.] C, the reaction mixture turns orange to brown and finally shows yellow color. The reaction mixture was kept at room temperature for 12 hours and poured into cold water to terminate the reaction. After separating the organic layer with ethyl acetate (EA), the organic layer is washed again with water and brine solution. Finally, the organic layer is washed with anhydrous Na 2 SO 4 and the organic solvent is vacuum distilled to obtain a brown colored liquid product (Yield 4.85 g, 97%).
1 H NMR (300 MHz, DMSO -d 6, δ): 8.47 (s, 1H), 7.22-7.12 (m, 5H), 6.97 (d, J = 6.6 Hz, 2H), 6.84-6.79 (m, 2H ), 5.78 (s, 1 H), 1.49 (s, 6 H).
Synthetic example 3: 9,9- Dimethyl -9,10- 다 디아라디드ine ( DMACR ) Synthesis of
Polyphosphoric acid (PPA, 60 mL) was added to a 2- (2- (phenylamino) phenyl) propan-2-ol (3.0 g, 13.2 mmol) synthesized in Synthesis Example 2, Lt; / RTI > To terminate the reaction, the reaction mixture was poured into water and neutralized to give a solid. After filtration, it was dissolved again in MC, neutralized with NaHCO 3 aqueous solution and washed with water and brine solution. Finally, after removing water with anhydrous Na 2 SO 4 , the product is formed by vacuum distillation, and a white solid product can be obtained by column chromatography using EA / hexane (0.5: 9.5) as a developing solvent (Yield 2.70 g, 98%).
1 H NMR (300 MHz, CDCl 3, δ): 7.40 (d, J = 9.0 Hz, 2H), 7.12 (t, J = 9 Hz, 2H), 6.94 (t, J = 9 Hz, 2H), 6.70 (d, J = 9.0 Hz, 2H), 6.14 (bs, 1H), 1.60 (s, 6H).
Synthetic example 4: 10- (7- Bromo -9,9- diothyl -9H- fluoren -2- yl ) -9,9- dimethyl -9,10-dihydroacridine (5)
9,9-dimethyl-9,10-dihydroacridine (DMACR, 1.00 g, 4.78 mmol) synthesized in Synthesis Example 3 was dissolved in toluene (20 mL), and sodium tert-butoxide (1.14 g, 11.95 mmol ) And 2,7-dibromo-9,9-dioctyl-9H-fluorene compound (6.5 g, 11.95 mmol). The reaction mixture was refluxed in an argon atmosphere for about 30 minutes and then treated with tris (dibenzylideneacetone) dipalladium (0) (Pd 2 (dba) 3 , 88 mg, 0.095 mmol) and 1,1'-bis (diphenylphosphino) ferrocene 106 mg, 0.191 mmol) was added thereto, and the mixture was refluxed at 110 DEG C for 12 hours. To terminate the reaction, the reaction mixture was diluted with EA and water. The organic layer was separated and washed with water and brine solution. The organic solution was separated by vacuum distilled water and then separated by column chromatography using EA / hexane (1: 9) as eluent to obtain a white solid compound 5 (yield: 1.80 g, 56%).
1 H NMR (300 MHz, CDCl 3, δ): 7.91 (d, J = 8.1 Hz, 1H), 7.63 (d, J = 9.0 Hz, 1H), 7.53-7.47 (m, 4H), 7.30-7.25 ( m, 2H), 6.95-6.92 (m, 4H), 6.31-6.28 (m, 2H), 1.95 (q, J = 8.1 Hz, 4H) , 0.82 (t, J = 6.3 Hz, 6H), 0.693 (m, 4H).
Synthetic example 5: 10- (9,9- Dioctyl -7- (4,4,5,5- tetramethyl -1,3,2- dioxaborolan -2-yl) -9H- fluoren -2- yl ) - 9,9- dimethyl -9,10- 다 디아라디드ine (6) Synthesis of
To a 150 mL three-necked flask was added 10- (7-bromo-9,9-dioctyl-9H-fluoren-2-yl) -9,9-dimethyl-9,10- dihydroacridine (1.00 g, 1.47 mmol ) Was dissolved in 1,4-dioxane (20 mL), bis (pinacolato) diboron (445 mg, 1.76 mmol) and potassium acetate (360 mg, 3.67 mmol) were added. The reaction mixture was refluxed in an argon atmosphere for 30 minutes, PdCl 2 (dppf) (53 mg, 0.073 mmol) was added, and the mixture was stirred at 100 ° C for 12 hours. After confirming the progress of the reaction, 1,4-dioxane was removed under reduced pressure, EA and water were added, the organic layer was separated, washed with water and brine solution, and water was removed with anhydrous Na 2 SO 4 . The solvent was removed under reduced pressure, and the resulting compound was separated by column chromatography using EA / hexane (0.5: 9.5) as eluent to give the product 6 as a white solid (yield: 1.00 g, 94%).
1 H NMR (300 MHz, CDCl 3, δ): 7.96 (dd, J = 7.5 Hz, J = 1.8 Hz, 1H), 7.88-7.85 (m, 1H), 7.79-7.75 (m, 2H), 7.49- 2H), 7.47 (m, 2H), 7.30-7.25 (m, 2H), 6.97-6.90 (m, 4H), 6.34-6.30 1.41 (s, 12H), 1.20-1.04 (m, 20H), 0.83-0.78 (m, 6H), 0.66 (m, 4H).
Synthetic example 6: AFAN , AFSBF , AFSBFN Synthesis of
AFAN, AFSBF and AFSBFN can be synthesized in the following way.
100 mL compound in a three-necked flask 6 (0.10 g, 0.138 mmol) , 9-bromoanthracene or Br-SBF (bromo-spirobifulorene) or Br-SBFN (bromo-spirobifluorene cyanide ) (0.151 mmol) and 2M K 2 CO 3 (3.0 mL ) aqueous solution and 1,4-dioxane (stirring for 30 minutes after addition of 8.0 mL) and Pd (PPh 3) 4 (9 mg, 0.007 mmol) was added. The reaction mixture was refluxed at 100 ° C for 12 hours under a nitrogen atmosphere. After the reaction was completed, the organic layer was separated, washed with brine aqueous solution (2 x 50 mL), and then dehydrated with anhydrous Na 2 SO 4 . After removing the organic solvent from the vacuum decompression, the product was separated by column chromatography using EA / hexane (0.5: 9.5 or 1: 9) as developing solvent and then recrystallized in ethanol. The final compounds AFAN, AFSBF and AFSBFN can be obtained at 55%, 60% and 58%, respectively.
AFAN: white solid, 1 H NMR (300 MHz,
AFSBF: white solid, 1 H NMR (300 MHz,
AFSBFN: Pale Green Solid, 1 H NMR (300 MHz,
Example One: AFAN , AFSBF , AFSBFN Thermal stability
TGA analysis was performed to examine the thermal stability of the blue fluorescent compounds AFAN, AFSBF, and AFSBFN synthesized in the synthesis examples of the present invention. The results are shown in FIG. The temperature at which 5% decomposition proceeds is 423 ° C, 435 ° C and 439 ° C for AFAN, AFSBF and AFSBFN, respectively, which are very thermally stable compounds.
Example 2: AFAN , AFSBF , AFSBFN Of UV-visible and Photoluminescence ( PL ) Spectrum and current measurement
UV-visible absorption spectra were measured using a Shimadzu UV-3100 spectrometer in a state in which AFAN, AFSBF, and AFSBFN synthesized in the synthesis examples of the present invention were dissolved in chloroform and in a thin film state. 4A and 4B are graphs showing the UV-visible absorption spectrum and the PL measurement results of the blue fluorescent compound synthesized in the present invention. In AFAN, AFSBF and AFSBFN, the maximum absorption peaks were measured at 280 nm, 332 nm and 346 nm . PL was measured with Hitachi F-4500 in the state of AFAN, AFSBF, AFSBFN dissolved in chloroform and in the state of thin film. PL was measured with the excitation wavelength at the UV maximum absorption wavelength measured in each blue fluorescent compound. As shown in FIGS. 4A and 4B, the blue fluorescence compounds AFAN, AFSBF, and AFSBFN synthesized in the present invention exhibited a maximum emission peak at 417 nm, 437 nm, and 470 nm, respectively, Able to know. In addition, the current-voltage of the blue fluorescent compound synthesized according to the present invention was measured. The measurement results are shown in Fig. As shown, the compounds of the present invention showed good current characteristics at low voltages. Table 1 below shows optical, electrochemical and thermal properties of AFAN, AFSBF, and AFSBFN, the blue fluorescent compounds synthesized in the present invention.
Example 3: Blue fluorescence Substance AFAN , AFSBF , AFSBFN Using Organic field Fabrication of light emitting device
An organic electroluminescent device was fabricated according to a conventional method using AFAN, AFBSF, and AFBSFN, which are blue fluorescent compounds synthesized in the synthesis examples of the present invention, as a light emitting material of the light emitting layer. In order to fabricate an organic electroluminescent device, a transparent electrode substrate coated with ITO on a glass substrate was thoroughly cleaned, an anode was formed using a photosensitive resin and an etching solution, and then cleaned again. A thin film was formed by spin coating at a thickness of about 40 nm of PEDOT: PSS as a hole injection layer. AFAN, AFSBF, and ASFBFN, which are blue fluorescent compounds synthesized in the examples of the present invention, were used as a light emitting material of the light emitting layer, and a light emitting layer was formed with a thickness of 50 nm by spin coating. TPBi was vacuum deposited to a thickness of 20 nm as an electron transport layer. Then, a thin film was sequentially formed by vacuum evaporation of LiF, which is an electron injection layer, and an Al electrode as a cathode was formed to fabricate an organic electroluminescent device. The vacuum for the vacuum deposition was maintained at 4 × 10 -6 torr or less while the thin film was formed by vapor deposition. The film thickness and film growth rate were controlled by using a crystal sensor. The emission area was 4 ㎟ and the driving voltage was a DC voltage and a forward bias voltage was used. 6 shows the structure of the organic electroluminescent device applied to the present invention and the energy levels of the hole injecting layer, the hole transporting layer, the light emitting layer, and the electron transporting layer.
Example 4: Measurement of luminescence characteristics of light-emitting diodes
In this embodiment, the luminescent characteristics of the organic EL device fabricated in Example 3 were measured using a conventional method. FIG. 8 shows the electroluminescence (EL) intensity, FIG. 9 shows the external quantum efficiency (EQE), FIG. 10 shows the results of measuring the luminous efficiency and the voltage efficiency Respectively. As shown, the device fabricated according to the present invention exhibited the maximum electroluminescence spectrum in the pure blue wavelength region from 421 nm to 436 nm and exhibited typical diode characteristics in which the luminescence brightness increased with increasing current density. For AFSBF and AFSBFN, the maximum emission luminance was 300 cd / m 2 and the maximum external quantum efficiency was 2.47%. Especially, AFSBF and AFSBFN exhibited pure blue luminescent color with improved color purity which was significantly blue-shifted than the known blue luminescence in terms of color coordinates (0.156, 0.052) and (0.165, 0.122). Table 2 summarizes the physical properties of the light emitting diode devices measured according to this embodiment.
Although the present invention has been described based on the exemplary embodiments and examples of the present invention, the present invention is not limited to the technical ideas described in the above-described embodiments and examples. On the contrary, those skilled in the art can easily make various modifications and alterations based on the above-described embodiments and embodiments. It will be apparent, however, that such modifications and variations are all within the scope of the present invention.
100: display device 101: first substrate (base substrate)
102: second substrate (encapsulation substrate)
110: first electrode 120: organic light emitting layer
121: Hole injection layer 122: Hole transport layer
123: luminescent material layer 124: electron transport layer
125: electron injection layer 130: second electrode
DTr: driving thin film transistor E: organic light emitting diode
Claims (7)
Formula 1
(R 1 and R 2 are each independently a hydrogen atom or a C 1 -C 20 alkyl group in the formula (1); or R 3 to R 5 are each independently hydrogen, C 1 -C 20 alkyl group, substituted or not heavy hydrogen, C 1 - C 10 alkyl group, C 1 -C 10 alkylsilyl group, C 1 -C 10 alkyl halide, nitro, -CN, a homo or hetero-aryl group substituted with at least one functional group selected from a group consisting of a halogen and a phenyl group)
The luminescent compound capable of being subjected to the solution process of the above formula (1) is a solution process comprising a compound represented by the following formula (2).
(2)
(Wherein R 1 to R 5 are the same as defined in formula (1)
And R 1 and R 2 are C 1 -C 10 alkyl group in the above formula 1, R 3 and R 4 is an alkyl group of C 1 -C 10, respectively, R 5 is unsubstituted or substituted with heavy hydrogen, C 1 -C 10 alkylsilyl group, C 1 -C 10 alkyl halide, nitro, -CN, and the aryl group Homo solution process the light-emitting compound is substituted by at least one functional group selected from the group consisting of halogen.
A second electrode facing the first electrode;
At least one organic compound layer disposed between the first electrode and the second electrode, wherein the organic compound layer includes a light-emitting compound capable of performing a solution process as recited in any one of claims 1 to 3,
.
A driving thin film transistor located on the first substrate;
A light emitting diode disposed on the first substrate and connected to the driving thin film transistor, the light emitting diode including a light emitting compound capable of performing a solution process according to any one of claims 1 to 3 in at least one organic layer;
A second substrate covering the light emitting diode and being attached to the first substrate,
.
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