CN100586243C - A kind of red organic electroluminescence device and preparation method thereof - Google Patents
A kind of red organic electroluminescence device and preparation method thereof Download PDFInfo
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- CN100586243C CN100586243C CN200810050767A CN200810050767A CN100586243C CN 100586243 C CN100586243 C CN 100586243C CN 200810050767 A CN200810050767 A CN 200810050767A CN 200810050767 A CN200810050767 A CN 200810050767A CN 100586243 C CN100586243 C CN 100586243C
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- 238000005401 electroluminescence Methods 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims abstract description 89
- 239000000463 material Substances 0.000 claims abstract description 34
- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 claims abstract description 30
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052693 Europium Inorganic materials 0.000 claims abstract description 20
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000004411 aluminium Substances 0.000 claims abstract description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 11
- 235000010290 biphenyl Nutrition 0.000 claims abstract description 9
- 239000004305 biphenyl Substances 0.000 claims abstract description 9
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims abstract description 9
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 claims abstract description 8
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical group [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims abstract description 6
- UJOBWOGCFQCDNV-UHFFFAOYSA-N Carbazole Natural products C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims abstract description 5
- GJEKHPKMWRRWIC-UHFFFAOYSA-N CC(=O)C.FC(C(=O)C=1SC=CC1)(F)F Chemical compound CC(=O)C.FC(C(=O)C=1SC=CC1)(F)F GJEKHPKMWRRWIC-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000006267 biphenyl group Chemical group 0.000 claims abstract description 4
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 claims abstract description 3
- 238000001704 evaporation Methods 0.000 claims description 92
- 230000008020 evaporation Effects 0.000 claims description 90
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 15
- 239000011521 glass Substances 0.000 claims description 15
- 229910052760 oxygen Inorganic materials 0.000 claims description 15
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- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 abstract 1
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Abstract
The invention belongs to a kind of red organic electroluminescence device and preparation method thereof.Adopt vacuum evaporation process, preparing structure is indium tin oxide/4,4 '-two [N-(right-tolyl)-N-phenyl-amino] diphenyl or N, N '-two (1-naphthyl)-N, N '-diphenyl-1,1 '-diphenyl-4,4 '-diamines/oxine aluminium: with trifluoroacetyl thiophene acetone and Phen is the classical trivalent europium complex Eu (TTA) of first and second parts
3Phen: material of main part 4,4 '-N, N '-two carbazole diphenyl/2,9-dimethyl-4,7-diphenyl-1, the red organic electroluminescence device of 10-phenanthroline/oxine aluminium/lithium fluoride/metallic aluminium.The maximum electroluminescence current efficiency of device is 6.1cd/A, and maximum power efficiency is 3.5lm/W; High-high brightness is 2451.69cd/m
2
Description
Technical field
The present invention relates to a kind of red organic electroluminescence device and preparation method thereof.
Background technology
Compare with other plane Display Techniques such as LCD, plasma display device, Field Emission Display, ORGANIC ELECTROLUMINESCENCE DISPLAYS has a series of excellent specific properties, such as: glow color is adjustable, active illuminating, high brightness, high efficiency, wide visual angle, low energy consumption, preparation technology simple, can prepare crooked flexible display screen etc., in dull and stereotyped full-color display field, big plane, have broad application prospects, generally believed it is the most competitive Display Technique of new generation.At present, performance green and blue organic electroluminescent device is significantly improved, and has few products to come out.Yet as one of requisite three primary colors of ORGANIC ELECTROLUMINESCENCE DISPLAYS, red organic electroluminescence device still is faced with stern challenge, has mainly that luminous efficiency is low, efficient improves problems such as decay rapidly and brightness is low with current density.Therefore, how designing advanced luminescent material and optimised devices structure, to obtain high efficiency, high brightness red organic electroluminescence device be one of the research emphasis in this field at present.
In 10 years of past, the researcher develops many kinds of polymer or organic molecule red electroluminescent materials, its middle rare earth trivalent europium complex is because its pure ruddiness and narrow emission spectrum have caused extensive studies interest in the organic electroluminescent field.In order to improve the performance of rare earth trivalent europium complex electroluminescent device, the researcher has done a lot of work in the design of the optimization of rare earth trivalent europium complex and device architecture.As 2000, the people such as S.R.Forrest of Princeton university were with 4,4 '-N, and N '-two carbazole diphenyl (CBP) is a material of main part, will be respectively the classical trivalent europium complex Eu (TTA) of first and second parts with TTA and Phen (phen)
3Phen is entrained among the CBP as guest materials, has obtained showing the red electroluminescent device of pure trivalent europium ion feature emission, but the maximum external quantum efficiency of this device but has only 1.4% (0.4mA/cm
2), far below the theoretical limit 6% of this device external quantum efficiency.2003, people such as Ma Dongge reported with 3,4,7 that on Applied Physics Letters 8-tetramethyl-Phen (Tmphen) is as the rare-earth europium complex Eu (TTA) of second part
3Tmphen mixes it among material of main part CBP as guest materials and to have made red organic electroluminescence device, though maximum current efficient reaches 4.7cd/A, its high-high brightness has only 800cd/m
22005, people such as Zhang Hongjie delivered with 4,4,5,5,6,6 at Inorganic Chemistry, and 6-seven fluoro-1-(2-naphthyl) hexane-beta diketones (HFNH) are as the rare-earth europium complex Eu (HFNH) of first part
3Phen is doped to it and has prepared pure red electroluminescent device among CBP as guest materials, maximum current efficient is up to 4.14cd/A, but its high-high brightness also has only 957cd/m
2This shows, the method as luminescent layer can better must solve poor, the inefficient problem of device color color purity in the broad-band gap material of main part though the trivalent europium complex is mixed in utilization, and the problem that brightness is low, the device luminous efficiency decays does not rapidly still obtain substantive the improvement.
Causing the main cause of trivalent europium complex electroluminescent device efficient decay is that the central ion lifetime of excited state is longer, causes device serious triplet cancellation to occur under the high current density situation.And many trivalent europium complexes only fetter a kind of charge carrier (electronics or hole) in the organic electroluminescence device that mixes, and another charge carrier then mainly is distributed on the material of main part molecule.2007, people such as Zhang Hongjie proved (Journal of Applied Physics) by experiment: at Eu (TTA)
3In the CBP system that phen mixes, Eu (TTA)
3A phen molecule bound electron, most of holes then are distributed on the CBP molecule.Along with the raising of current density, the leading luminescence mechanism of device changes the Foster energy delivery into from carrier capture gradually.On the other hand, most of trivalent europium complex only absorbs the light of ultraviolet region, therefore causes the energy delivery from material of main part to the trivalent europium complex incomplete easily, obviously is unfavorable for the raising of device luminous efficiency and brightness.So, how to solve above problem and be raising trivalent europium complex electroluminescent device performance, show the task of top priority of its potential advantages in organic electroluminescent is used by design new device structure and optimised devices manufacture craft.
Summary of the invention
One of purpose of the present invention provides a kind of red organic electroluminescence device.
Another object of the present invention provides the preparation method of this red organic electroluminescence device.
As shown in Figure 1, red organic electroluminescence device provided by the invention is by substrate 1, anode layer 2, hole transmission layer 3, luminescent layer 4, hole blocking layer 5, electron transfer layer 6, resilient coating 7 and metallic cathode 8, by what connect and compose successively;
Wherein the red organic dyestuff of Can Zaing is: be the trivalent europium complex Eu (TTA) of first and second parts with trifluoroacetyl thiophene acetone (TTA) and Phen (phen)
3Phen, its molecular structure is as follows:
Wherein organic sensitizing dyestuff of Can Zaing is: oxine aluminium (being called for short AlQ), and its molecular structure is as follows:
The main body organic molecule material is: 4, and 4 '-N, N '-two carbazole diphenyl (being called for short CBP), its molecular structure is as follows:
In the described organic mixed material, the red organic dyestuff of doping and the weight ratio of main body organic molecule material are 2%-5%, and the organic sensitizing dyestuff of doping and the weight ratio of main body organic molecule material are 0.1%-0.6%;
That resilient coating 7 adopts is lithium fluoride (LiF);
That metallic cathode 8 adopts is metallic aluminium (Al);
Described anode and negative electrode intersect to form the luminous zone of device mutually, and area is 10 square millimeters; The thickness of hole transmission layer 3 is 30 to 60 nanometers, the thickness of luminescent layer 4 is 30 to 50 nanometers, and the thickness of hole blocking layer 5 is 15 to 30 nanometers, and the thickness of electron transfer layer 6 is 20 to 40 nanometers, the thickness of resilient coating 7 is 0.4 to 1.8 nanometer, and the thickness of metallic cathode 8 is 60 to 120 nanometers.
When applying forward voltage between two electrodes, this device will send the ruddiness that main peak is positioned at 612 nanometers.
The preparation method of red organic electroluminescence device provided by the invention is as follows:
Wherein, anode and negative electrode intersect to form the luminous zone of device mutually, and area is 10 square millimeters; The thickness of hole transmission layer 3 is 30 to 60 nanometers, the thickness of luminescent layer 4 is 30 to 50 nanometers, and the thickness of hole blocking layer 5 is 15 to 30 nanometers, and the thickness of electron transfer layer 6 is 20 to 40 nanometers, the thickness of resilient coating 7 is 0.4 to 1.8 nanometer, and the thickness of metallic cathode 8 is 60 to 120 nanometers; The evaporation rate of TPD (or NPB), CBP, BCP and AlQ is controlled at the 0.05-0.1 nm/sec in hole transmission layer 3, luminescent layer 4, hole blocking layer 5 and the electron transfer layer 6, the evaporation rate of red organic dyestuff is controlled at the 0.001-0.005 nm/sec, the evaporation rate of organic sensitizing dyestuff is controlled at the 0.00005-0.0006 nm/sec, the evaporation rate of LiF is controlled at the 0.005-0.015 nm/sec in the resilient coating 7, and the evaporation rate of Al is controlled at the 0.5-1.5 nm/sec in the metallic cathode 8; During evaporation luminescent layer 4, red organic dyestuff in the organic mixed material, organic sensitizing dyestuff and main body organic molecule material be evaporation simultaneously in different evaporation sources, make the red organic dyestuff of doping and the weight ratio of main body organic molecule material be controlled between the 2%-5% by the evaporation rate of regulating and control three kinds of materials, the weight ratio of organic sensitizing dyestuff and material of main part is controlled between the 0.1%-0.6%.
The invention has the beneficial effects as follows: organic sensitizing dyestuff AlQ by will having superior electron transport ability and trivalent europium complex with the special ratios codope in the material of main part CBP of wide energy gap, can improve the transmittability of electronics between the luminous zone, help widening between the luminous zone of device and weaken exciton concentration, thereby delay the decay that the device electroluminescent efficiency improves with current density.In addition, the mixing of AlQ molecule helps promoting in the luminescent layer balanced distribution of electronics and hole on the trivalent europium complex molecule, thereby further improves the efficient of device.
Another advantage of the present invention is: by ito anode being carried out accurate Low Pressure Oxygen plasma treatment, improved the hole injectability of device greatly, reduced the operating voltage of device; Simultaneously, adopt the suitable cathode layer of thickness, control the injection of electronics effectively, help between the luminous zone, causing an amount of hole accumulation, thereby help the distribution of electronics and hole on the balance trivalent europium complex molecule, and then the charge carrier recombination probability of raising device, finally improve the device electroluminescent efficiency.The maximum electroluminescence current efficiency of obtained device is 6.1cd/A, and maximum power efficiency is 3.5lm/W, and maximum external quantum efficiency is 3.3%, and the maximum recombination probability of corresponding device is 54.9%; The high-high brightness of obtained device is 2451.69cd/m
2
Description of drawings
Fig. 1 is the structural representation of red organic electroluminescence device provided by the invention.Among the figure, the 1st, glass substrate, the 2nd, anode layer, the 3rd, hole transmission layer, the 4th, luminescent layer, the 5th, hole blocking layer, the 6th, electron transfer layer, the 7th, resilient coating, the 8th, metallic cathode.Fig. 1 also is the accompanying drawing that the present invention makes a summary.
Fig. 2 is voltage-to-current density-luminosity response of red organic electroluminescence device embodiment 4 provided by the invention.The brightness of device raises along with the rising of current density and driving voltage, and the bright voltage that rises of device is 5.4 volts, is that 17.5 volts, current density are 464.19 milliamperes of every square centimeter of (mA/cm at voltage
2) time device obtain every square metre of (cd/m of high-high brightness 2110.2 candelas
2).
Fig. 3 is current density-power efficiency-current efficiency characteristic curve of red organic electroluminescence device embodiment 4 provided by the invention.The maximum current efficient of device is every ampere of 6.1 candela (cd/A), and maximum power efficiency is every watt of 3.5 lumen (1m/W).
Fig. 4 is voltage-to-current density-luminosity response of red organic electroluminescence device embodiment 6 provided by the invention.The brightness of device raises along with the rising of current density and driving voltage, and the bright voltage that rises of device is 5.4 volts, is that 18.0 volts, current density are 468.69mA/cm at voltage
2The time device obtain high-high brightness 2073.8cd/m
2
Fig. 5 is current density-power efficiency-current efficiency characteristic curve of red organic electroluminescence device embodiment 6 provided by the invention.The maximum current efficient of device is 5.99cd/A, and maximum power efficiency is 3.46lm/W.
Fig. 6 is the spectrogram of red organic electroluminescence device embodiment 4 provided by the invention, and spectrum all derives from the feature emission of trivalent europium ion, and main peak is positioned at 612 nanometers.
Embodiment
The invention will be further described below in conjunction with drawings and Examples.
Embodiment 1:
Earlier the ito anode stratification on the ito glass is corroded into the strip shaped electric poles of 10 mm wides, 30 millimeters long, then successively with cleaning fluid, deionized water ultrasonic cleaning 15 minutes and put into oven for drying.Then dried substrate being put into the preliminary treatment vacuum chamber, is ito anode to be carried out after 10 minutes the Low Pressure Oxygen plasma treatment it is transferred to the organic vapor deposition chamber with 250 volts voltage under the atmosphere of 10 handkerchiefs in vacuum degree.In vacuum degree is 1-5 * 10
-5In the organic vapor deposition chamber of handkerchief, the Eu (TTA) of the TPD hole transmission layer of evaporation 50 nanometer thickness, 45 nanometer thickness successively on the ITO layer
3Phen and AlQ mix the luminescent layer of CBP, the BCP hole blocking layer of 20 nanometer thickness and the AlQ electron transfer layer of 30 nanometer thickness altogether.Next, uncompleted device is transferred to the metal evaporation chamber, in 5-8 * 10
-5The LiF resilient coating of evaporation 1.0 nanometer thickness successively under the vacuum of handkerchief, at last by the metal A l electrode of special mask evaporation 100 nanometer thickness on LiF, being prepared into structure is ITO/TPD/AlQ (0.2%): Eu (TTA)
3Phen (3%): the organic electroluminescence device of CBP/BCP/AlQ/LiF/Al.The light-emitting area of this device is 10 square millimeters.The evaporation rate of TPD, CBP, BCP and AlQ (electron transfer layer) is controlled at 0.05 nm/sec, AlQ and Eu (TTA) in the luminescent layer
3The evaporation rate of phen is controlled at 0.0001 nm/sec and 0.0015 nm/sec, and the evaporation rate of LiF is controlled at 0.005 nm/sec, and the evaporation rate of Al is controlled at 0.5 nm/sec.Obtained device shows Eu (TTA) under direct voltage drive
3The emitting red light of phen, main peak are positioned at 612 nanometers.A bright voltage of device is 5.5 volts, and the high-high brightness of device is 2035.34cd/m
2The maximum current efficient of device is 5.25cd/A, and maximum power efficiency is 3.02lm/W.In addition, the maximum external quantum efficiency of device is 2.84%, and corresponding charge carrier recombination probability is 47.3%.
Embodiment 2:
Earlier the ito anode stratification on the ito glass is corroded into the strip shaped electric poles of 10 mm wides, 30 millimeters long, then successively with cleaning fluid, deionized water ultrasonic cleaning 15 minutes and put into oven for drying.Then dried substrate being put into the preliminary treatment vacuum chamber, is ito anode to be carried out after 10 minutes the Low Pressure Oxygen plasma treatment it is transferred to the organic vapor deposition chamber with 250 volts voltage under the atmosphere of 10 handkerchiefs in vacuum degree.In vacuum degree is 1-5 * 10
-5In the organic vapor deposition chamber of handkerchief, the Eu (TTA) of the TPD hole transmission layer of evaporation 50 nanometer thickness, 45 nanometer thickness successively on the ITO layer
3Phen and AlQ mix the luminescent layer of CBP, the BCP hole blocking layer of 20 nanometer thickness and the AlQ electron transfer layer of 30 nanometer thickness altogether.Next, uncompleted device is transferred to the metal evaporation chamber, in 5-8 * 10
-5The LiF resilient coating of evaporation 1.0 nanometer thickness successively under the vacuum of handkerchief, at last by the metal A l electrode of special mask evaporation 100 nanometer thickness on LiF, being prepared into structure is ITO/TPD/AlQ (0.3%): Eu (TTA)
3Phen (3%): the organic electroluminescence device of CBP/BCP/AlQ/LiF/Al.The light-emitting area of this device is 10 square millimeters.The evaporation rate of TPD, CBP, BCP and AlQ (electron transfer layer) is controlled at 0.05 nm/sec, AlQ and Eu (TTA) in the luminescent layer
3The evaporation rate of phen is controlled at 0.00015 nm/sec and 0.0015 nm/sec, and the evaporation rate of LiF is controlled at 0.005 nm/sec, and the evaporation rate of Al is controlled at 0.5 nm/sec.Obtained device shows Eu (TTA) under direct voltage drive
3The emitting red light of phen, main peak are positioned at 612 nanometers.A bright voltage of device is 5.3 volts, and the high-high brightness of device is 2394.58cd/m
2The maximum current efficient of device is 5.60cd/A, and maximum power efficiency is 3.32lm/W.In addition, the maximum external quantum efficiency of device is 3.02%, and corresponding charge carrier recombination probability is 50.4%.
Embodiment 3:
Earlier the ito anode stratification on the ito glass is corroded into the strip shaped electric poles of 10 mm wides, 30 millimeters long, then successively with cleaning fluid, deionized water ultrasonic cleaning 15 minutes and put into oven for drying.Then dried substrate being put into the preliminary treatment vacuum chamber, is ito anode to be carried out after 10 minutes the Low Pressure Oxygen plasma treatment it is transferred to the organic vapor deposition chamber with 250 volts voltage under the atmosphere of 10 handkerchiefs in vacuum degree.In vacuum degree is 1-5 * 10
-5In the organic vapor deposition chamber of handkerchief, the Eu (TTA) of the TPD hole transmission layer of evaporation 50 nanometer thickness, 45 nanometer thickness successively on the ITO layer
3Phen and AlQ mix the luminescent layer of CBP, the BCP hole blocking layer of 20 nanometer thickness and the AlQ electron transfer layer of 30 nanometer thickness altogether.Next, uncompleted device is transferred to the metal evaporation chamber, in 5-8 * 10
-5The LiF resilient coating of evaporation 1.0 nanometer thickness successively under the vacuum of handkerchief, at last by the metal A l electrode of special mask evaporation 100 nanometer thickness on LiF, being prepared into structure is ITO/TPD/AlQ (0.4%): Eu (TTA)
3Phen (3%): the organic electroluminescence device of CBP/BCP/AlQ/LiF/Al.The light-emitting area of this device is 10 square millimeters.The evaporation rate of TPD, CBP, BCP and AlQ (electron transfer layer) is controlled at 0.05 nm/sec, AlQ and Eu (TTA) in the luminescent layer
3The evaporation rate of phen is controlled at 0.0002 nm/sec and 0.0015 nm/sec, and the evaporation rate of LiF is controlled at 0.005 nm/sec, and the evaporation rate of Al is controlled at 0.5 nm/sec.Obtained device shows Eu (TTA) under direct voltage drive
3The emitting red light of phen, main peak are positioned at 612 nanometers.A bright voltage of device is 5.3 volts, and the high-high brightness of device is 2199.09cd/m
2The maximum current efficient of device is 5.24cd/A, and maximum power efficiency is 3.05lm/W.In addition, the maximum external quantum efficiency of device is 2.83%, and corresponding charge carrier recombination probability is 47.2%.
Embodiment 4:
Earlier the ito anode stratification on the ito glass is corroded into the strip shaped electric poles of 10 mm wides, 30 millimeters long, then successively with cleaning fluid, deionized water ultrasonic cleaning 15 minutes and put into oven for drying.Then dried substrate being put into the preliminary treatment vacuum chamber, is ito anode to be carried out after 10 minutes the Low Pressure Oxygen plasma treatment it is transferred to the organic vapor deposition chamber with 250 volts voltage under the atmosphere of 10 handkerchiefs in vacuum degree.In vacuum degree is 1-5 * 10
-5In the organic vapor deposition chamber of handkerchief, the Eu (TTA) of the TPD hole transmission layer of evaporation 50 nanometer thickness, 45 nanometer thickness successively on the ITO layer
3Phen and AlQ mix the luminescent layer of CBP, the BCP hole blocking layer of 20 nanometer thickness and the AlQ electron transfer layer of 30 nanometer thickness altogether.Next, uncompleted device is transferred to the metal evaporation chamber, in 5-8 * 10
-5The LiF resilient coating of evaporation 1.2 nanometer thickness successively under the vacuum of handkerchief, at last by the metal A l electrode of special mask evaporation 100 nanometer thickness on LiF, being prepared into structure is ITO/TPD/AlQ (0.3%): Eu (TTA)
3Phen (3%): the organic electroluminescence device of CBP/BCP/AlQ/LiF/Al.The light-emitting area of this device is 10 square millimeters.The evaporation rate of TPD, CBP, BCP and AlQ (electron transfer layer) is controlled at 0.05 nm/sec, AlQ and Eu (TTA) in the luminescent layer
3The evaporation rate of phen is controlled at 0.00015 nm/sec and 0.0015 nm/sec, and the evaporation rate of LiF is controlled at 0.005 nm/sec, and the evaporation rate of Al is controlled at 0.5 nm/sec.Obtained device shows Eu (TTA) under direct voltage drive
3The emitting red light of phen, main peak are positioned at 612 nanometers.A bright voltage of device is 5.4 volts, and the high-high brightness of device is 2110.23cd/m
2The maximum current efficient of device is 6.1cd/A, and maximum power efficiency is 3.5lm/W.In addition, the maximum external quantum efficiency of device is 3.29%, and corresponding charge carrier recombination probability is 54.9%.
Embodiment 5:
Earlier the ito anode stratification on the ito glass is corroded into the strip shaped electric poles of 10 mm wides, 30 millimeters long, then successively with cleaning fluid, deionized water ultrasonic cleaning 15 minutes and put into oven for drying.Then dried substrate being put into the preliminary treatment vacuum chamber, is ito anode to be carried out after 10 minutes the Low Pressure Oxygen plasma treatment it is transferred to the organic vapor deposition chamber with 250 volts voltage under the atmosphere of 10 handkerchiefs in vacuum degree.In vacuum degree is 1-5 * 10
-5In the organic vapor deposition chamber of handkerchief, the Eu (TTA) of the TPD hole transmission layer of evaporation 50 nanometer thickness, 45 nanometer thickness successively on the ITO layer
3Phen and AlQ mix the luminescent layer of CBP, the BCP hole blocking layer of 20 nanometer thickness and the AlQ electron transfer layer of 30 nanometer thickness altogether.Next, uncompleted device is transferred to the metal evaporation chamber, in 5-8 * 10
-5The LiF resilient coating of evaporation 1.2 nanometer thickness successively under the vacuum of handkerchief, at last by the metal A l electrode of special mask evaporation 80 nanometer thickness on LiF, being prepared into structure is ITO/TPD/AlQ (0.3%): Eu (TTA)
3Phen (3%): the organic electroluminescence device of CBP/BCP/AlQ/LiF/Al.The light-emitting area of this device is 10 square millimeters.The evaporation rate of TPD, CBP, BCP and AlQ (electron transfer layer) is controlled at 0.05 nm/sec, AlQ and Eu (TTA) in the luminescent layer
3The evaporation rate of phen is controlled at 0.00015 nm/sec and 0.0015 nm/sec, and the evaporation rate of LiF is controlled at 0.005 nm/sec, and the evaporation rate of Al is controlled at 0.5 nm/sec.Obtained device shows Eu (TTA) under direct voltage drive
3The emitting red light of phen, main peak are positioned at 612 nanometers.A bright voltage of device is 5.4 volts, and the high-high brightness of device is 2122.55cd/m
2The maximum current efficient of device is 5.45cd/A, and maximum power efficiency is 3.12lm/W.In addition, the maximum external quantum efficiency of device is 2.94%, and corresponding charge carrier recombination probability is 49.1%.
Embodiment 6:
Earlier the ito anode stratification on the ito glass is corroded into the strip shaped electric poles of 10 mm wides, 30 millimeters long, then successively with cleaning fluid, deionized water ultrasonic cleaning 15 minutes and put into oven for drying.Then dried substrate being put into the preliminary treatment vacuum chamber, is ito anode to be carried out after 10 minutes the Low Pressure Oxygen plasma treatment it is transferred to the organic vapor deposition chamber with 250 volts voltage under the atmosphere of 10 handkerchiefs in vacuum degree.In vacuum degree is 1-5 * 10
-5In the organic vapor deposition chamber of handkerchief, the Eu (TTA) of the TPD hole transmission layer of evaporation 50 nanometer thickness, 45 nanometer thickness successively on the ITO layer
3Phen and AlQ mix the luminescent layer of CBP, the BCP hole blocking layer of 20 nanometer thickness and the AlQ electron transfer layer of 30 nanometer thickness altogether.Next, uncompleted device is transferred to the metal evaporation chamber, in 5-8 * 10
-5The LiF resilient coating of evaporation 1.0 nanometer thickness successively under the vacuum of handkerchief, at last by the metal A l electrode of special mask evaporation 80 nanometer thickness on LiF, being prepared into structure is ITO/TPD/AlQ (0.3%): Eu (TTA)
3Phen (3%): the organic electroluminescence device of CBP/BCP/AlQ/LiF/Al.The light-emitting area of this device is 10 square millimeters.The evaporation rate of TPD, CBP, BCP and AlQ (electron transfer layer) is controlled at 0.05 nm/sec, AlQ and Eu (TTA) in the luminescent layer
3The evaporation rate of phen is controlled at 0.00015 nm/sec and 0.0015 nm/sec, and the evaporation rate of LiF is controlled at 0.005 nm/sec, and the evaporation rate of Al is controlled at 0.5 nm/sec.Obtained device shows Eu (TTA) under direct voltage drive
3The emitting red light of phen, main peak are positioned at 612 nanometers.A bright voltage of device is 5.4 volts, and the high-high brightness of device is 2073.80cd/m
2The maximum current efficient of device is 5.99cd/A, and maximum power efficiency is 3.46lm/W.In addition, the maximum external quantum efficiency of device is 3.23%, and corresponding charge carrier recombination probability is 53.9%.
Embodiment 7:
Earlier the ito anode stratification on the ito glass is corroded into the strip shaped electric poles of 10 mm wides, 30 millimeters long, then successively with cleaning fluid, deionized water ultrasonic cleaning 15 minutes and put into oven for drying.Then dried substrate being put into the preliminary treatment vacuum chamber, is ito anode to be carried out after 10 minutes the Low Pressure Oxygen plasma treatment it is transferred to the organic vapor deposition chamber with 250 volts voltage under the atmosphere of 10 handkerchiefs in vacuum degree.In vacuum degree is 1-5 * 10
-5In the organic vapor deposition chamber of handkerchief, the Eu (TTA) of the NPB hole transmission layer of evaporation 50 nanometer thickness, 45 nanometer thickness successively on the ITO layer
3Phen and AlQ mix the luminescent layer of CBP, the BCP hole blocking layer of 20 nanometer thickness and the AlQ electron transfer layer of 30 nanometer thickness altogether.Next, uncompleted device is transferred to the metal evaporation chamber, in 5-8 * 10
-5The LiF resilient coating of evaporation 1.2 nanometer thickness successively under the vacuum of handkerchief, at last by the metal A l electrode of special mask evaporation 80 nanometer thickness on LiF, being prepared into structure is ITO/NPB/AlQ (0.3%): Eu (TTA)
3Phen (3%): the organic electroluminescence device of CBP/BCP/AlQ/LiF/Al.The light-emitting area of this device is 10 square millimeters.The evaporation rate of NPB, CBP, BCP and AlQ (electron transfer layer) is controlled at 0.05 nm/sec, AlQ and Eu (TTA) in the luminescent layer
3The evaporation rate of phen is controlled at 0.00015 nm/sec and 0.0015 nm/sec, and the evaporation rate of LiF is controlled at 0.005 nm/sec, and the evaporation rate of Al is controlled at 0.5 nm/sec.Obtained device shows Eu (TTA) under direct voltage drive
3The emitting red light of phen, main peak are positioned at 612 nanometers.A bright voltage of device is 6.0 volts, and the high-high brightness of device is 2006.15cd/m
2The maximum current efficient of device is 5.71cd/A, and maximum power efficiency is 3.04lm/W.In addition, the maximum external quantum efficiency of device is 3.08%, and corresponding charge carrier recombination probability is 51.4%.
Embodiment 8:
Earlier the ito anode stratification on the ito glass is corroded into the strip shaped electric poles of 10 mm wides, 30 millimeters long, then successively with cleaning fluid, deionized water ultrasonic cleaning 15 minutes and put into oven for drying.Then dried substrate being put into the preliminary treatment vacuum chamber, is ito anode to be carried out after 10 minutes the Low Pressure Oxygen plasma treatment it is transferred to the organic vapor deposition chamber with 250 volts voltage under the atmosphere of 10 handkerchiefs in vacuum degree.In vacuum degree is 1-5 * 10
-5In the organic vapor deposition chamber of handkerchief, the Eu (TTA) of the NPB hole transmission layer of evaporation 50 nanometer thickness, 45 nanometer thickness successively on the ITO layer
3Phen and AlQ mix the luminescent layer of CBP, the BCP hole blocking layer of 20 nanometer thickness and the AlQ electron transfer layer of 30 nanometer thickness altogether.Next, uncompleted device is transferred to the metal evaporation chamber, in 5-8 * 10
-5The LiF resilient coating of evaporation 1.2 nanometer thickness successively under the vacuum of handkerchief, at last by the metal A l electrode of special mask evaporation 100 nanometer thickness on LiF, being prepared into structure is ITO/NPB/AlQ (0.3%): Eu (TTA)
3Phen (3%): the organic electroluminescence device of CBP/BCP/AlQ/LiF/Al.The light-emitting area of this device is 10 square millimeters.The evaporation rate of NPB, CBP, BCP and AlQ (electron transfer layer) is controlled at 0.05 nm/sec, AlQ and Eu (TTA) in the luminescent layer
3The evaporation rate of phen is controlled at 0.00015 nm/sec and 0.0015 nm/sec, and the evaporation rate of LiF is controlled at 0.005 nm/sec, and the evaporation rate of Al is controlled at 0.5 nm/sec.Obtained device shows Eu (TTA) under direct voltage drive
3The emitting red light of phen, main peak are positioned at 612 nanometers.A bright voltage of device is 5.9 volts, and the high-high brightness of device is 2002.98cd/m
2The maximum current efficient of device is 5.60cd/A, and maximum power efficiency is 3.02lm/W.In addition, the maximum external quantum efficiency of device is 3.02%, and corresponding charge carrier recombination probability is 50.4%.
Embodiment 9:
Earlier the ito anode stratification on the ito glass is corroded into the strip shaped electric poles of 10 mm wides, 30 millimeters long, then successively with cleaning fluid, deionized water ultrasonic cleaning 15 minutes and put into oven for drying.Then dried substrate being put into the preliminary treatment vacuum chamber, is ito anode to be carried out after 10 minutes the Low Pressure Oxygen plasma treatment it is transferred to the organic vapor deposition chamber with 250 volts voltage under the atmosphere of 10 handkerchiefs in vacuum degree.In vacuum degree is 1-5 * 10
-5In the organic vapor deposition chamber of handkerchief, the Eu (TTA) of the TPD hole transmission layer of evaporation 50 nanometer thickness, 45 nanometer thickness successively on the ITO layer
3Phen and AlQ mix the luminescent layer of CBP, the BCP hole blocking layer of 20 nanometer thickness and the AlQ electron transfer layer of 30 nanometer thickness altogether.Next, uncompleted device is transferred to the metal evaporation chamber, in 5-8 * 10
-5The LiF resilient coating of evaporation 1.2 nanometer thickness successively under the vacuum of handkerchief, at last by the metal A l electrode of special mask evaporation 100 nanometer thickness on LiF, being prepared into structure is ITO/TPD/AlQ (0.3%): Eu (TTA)
3Phen (4%): the organic electroluminescence device of CBP/BCP/AlQ/LiF/Al.The light-emitting area of this device is 10 square millimeters.The evaporation rate of TPD, CBP, BCP and AlQ (electron transfer layer) is controlled at 0.05 nm/sec, AlQ and Eu (TTA) in the luminescent layer
3The evaporation rate of phen is controlled at 0.00015 nm/sec and 0.002 nm/sec, and the evaporation rate of LiF is controlled at 0.005 nm/sec, and the evaporation rate of Al is controlled at 0.5 nm/sec.Obtained device shows Eu (TTA) under direct voltage drive
3The emitting red light of phen, main peak are positioned at 612 nanometers.A bright voltage of device is 5.4 volts, and the high-high brightness of device is 2451.69cd/m
2The maximum current efficient of device is 5.98cd/A, and maximum power efficiency is 3.45lm/W.In addition, the maximum external quantum efficiency of device is 3.23%, and corresponding charge carrier recombination probability is 53.8%.
Embodiment 10:
Earlier the ito anode stratification on the ito glass is corroded into the strip shaped electric poles of 10 mm wides, 30 millimeters long, then successively with cleaning fluid, deionized water ultrasonic cleaning 15 minutes and put into oven for drying.Then dried substrate being put into the preliminary treatment vacuum chamber, is ito anode to be carried out after 10 minutes the Low Pressure Oxygen plasma treatment it is transferred to the organic vapor deposition chamber with 250 volts voltage under the atmosphere of 10 handkerchiefs in vacuum degree.In vacuum degree is 1-5 * 10
-5In the organic vapor deposition chamber of handkerchief, the Eu (TTA) of the TPD hole transmission layer of evaporation 50 nanometer thickness, 45 nanometer thickness successively on the ITO layer
3Phen and AlQ mix the luminescent layer of CBP, the BCP hole blocking layer of 20 nanometer thickness and the AlQ electron transfer layer of 30 nanometer thickness altogether.Next, uncompleted device is transferred to the metal evaporation chamber, in 5-8 * 10
-5The LiF resilient coating of evaporation 0.8 nanometer thickness successively under the vacuum of handkerchief, at last by the metal A l electrode of special mask evaporation 100 nanometer thickness on LiF, being prepared into structure is ITO/TPD/AlQ (0.3%): Eu (TTA)
3Phen (4%): the organic electroluminescence device of CBP/BCP/AlQ/LiF/Al.The light-emitting area of this device is 10 square millimeters.The evaporation rate of TPD, CBP, BCP and AlQ (electron transfer layer) is controlled at 0.05 nm/sec, AlQ and Eu (TTA) in the luminescent layer
3The evaporation rate of phen is controlled at 0.00015 nm/sec and 0.002 nm/sec, and the evaporation rate of LiF is controlled at 0.005 nm/sec, and the evaporation rate of Al is controlled at 0.5 nm/sec.Obtained device shows Eu (TTA) under direct voltage drive
3The emitting red light of phen, main peak are positioned at 612 nanometers.A bright voltage of device is 5.4 volts, and the high-high brightness of device is 1995.05cd/m
2The maximum current efficient of device is 5.93cd/A, and maximum power efficiency is 3.46lm/W.In addition, the maximum external quantum efficiency of device is 3.20%, and corresponding charge carrier recombination probability is 53.4%.
Claims (6)
1, a kind of red organic electroluminescence device is by substrate (1), anode layer (2), hole transmission layer (3), luminescent layer (4), hole blocking layer (5), electron transfer layer (6), resilient coating (7) and metallic cathode (8), by connecting and composing in turn; Described substrate (1) is a glass substrate; Anode layer (2) adopts: indium tin oxide; Resilient coating (7) adopts: lithium fluoride; Metallic cathode (8) adopts: metallic aluminium; It is characterized in that:
Described hole transmission layer (3) adopts: 4,4 '-two [N-(right-tolyl)-N-phenyl-amino] diphenyl or N, N '-two (1-naphthyl)-N, N '-diphenyl-1,1 '-diphenyl-4,4 '-diamines; Their molecular structure is as follows:
Described luminescent layer (4) adopts: the organic mixed material of main body organic molecule material is gone in red organic dyestuff and organic sensitizing dyestuff codope; Wherein the red organic dyestuff of Can Zaing is to be the trivalent europium complex Eu (TTA) of first and second parts with trifluoroacetyl thiophene acetone and Phen
3Phen, its molecular structure is as follows:
Organic sensitizing dyestuff of described doping is an oxine aluminium, and its molecular structure is as follows:
Described main body organic molecule material is 4,4 '-N, and N '-two carbazole diphenyl, its molecular structure is as follows:
In the described organic mixed material, the red organic dyestuff of doping and the weight ratio of main body organic molecule material are 2%-5%, and the organic sensitizing dyestuff of doping and the weight ratio of main body organic molecule material are 0.1%-0.6%;
Described hole blocking layer (5) adopts: 2, and 9-dimethyl-4,7-diphenyl-1, the 10-phenanthroline, its molecular structure is as follows:
Described electron transfer layer (6) adopts: oxine aluminium.
2, a kind of red organic electroluminescence device as claimed in claim 1 is characterized in that the face resistance of the indium tin oxide layer of described anode layer (2) is 10-25 ohm.
3, a kind of red organic electroluminescence device as claimed in claim 1 or 2, the indium tin oxide layer that it is characterized in that described anode layer (2) is what handled by the Low Pressure Oxygen plasma.
4, a kind of red organic electroluminescence device as claimed in claim 1 or 2 is characterized in that described anode layer (2) and metallic cathode (8) intersect to form the luminous zone of device mutually, and area is 10 square millimeters; The thickness of hole transmission layer (3) is 30 to 60 nanometers, the thickness of luminescent layer (4) is 30 to 50 nanometers, the thickness of hole blocking layer (5) is 15 to 30 nanometers, the thickness of electron transfer layer (6) is 20 to 40 nanometers, the thickness of resilient coating (7) is 0.4 to 1.8 nanometer, and the thickness of metallic cathode (8) is 60 to 120 nanometers.
5, a kind of red organic electroluminescence device as claimed in claim 3 is characterized in that described anode layer (2) and metallic cathode (8) intersect to form the luminous zone of device mutually, and area is 10 square millimeters; The thickness of hole transmission layer (3) is 30 to 60 nanometers, the thickness of luminescent layer (4) is 30 to 50 nanometers, the thickness of hole blocking layer (5) is 15 to 30 nanometers, the thickness of electron transfer layer (6) is 20 to 40 nanometers, the thickness of resilient coating (7) is 0.4 to 1.8 nanometer, and the thickness of metallic cathode (8) is 60 to 120 nanometers.
6, the preparation method of a kind of red organic electroluminescence device as claimed in claim 1, it is characterized in that step is as follows with condition: the electrode that earlier ITO layer (2) chemical corrosion on the ito glass substrate (1) is become fine strip shape, use cleaning fluid then successively, deionized water ultrasonic cleaning 10-20 minute is also put into oven for drying, then dried substrate is put into the preliminary treatment vacuum chamber, be with the voltage of 200-350 volt it to be carried out after 5-15 minute the Low Pressure Oxygen plasma treatment it being transferred to the organic vapor deposition chamber under the atmosphere of 8-15 handkerchief in vacuum degree, treat that vacuum degree reaches 1-5 * 10
-5During handkerchief, go up evaporation hole transmission layer (3), luminescent layer (4), hole blocking layer (5) and electron transfer layer (6) at ITO layer (2) successively, next, uncompleted device is transferred to the metal evaporation chamber, in 5-8 * 10
-5Evaporation resilient coating (7) and metallic cathode (8) successively under the vacuum of handkerchief;
In hole transmission layer (3), luminescent layer (4), the hole blocking layer (5) 4,4 '-two [N-(right-tolyl)-N-phenyl-amino] diphenyl, 4,4 '-N, N '-two carbazole diphenyl, 2,9-dimethyl-4,7-diphenyl-1, the evaporation rate of the oxine aluminium of 10-phenanthroline and electron transfer layer (6) is controlled at the 0.05-0.1 nm/sec, is the trivalent europium complex Eu (TTA) of first and second parts with trifluoroacetyl thiophene acetone and Phen in the luminescent layer (4)
3The evaporation rate of phen is controlled at the 0.001-0.005 nm/sec, the evaporation rate of organic sensitizing dyestuff oxine aluminium is controlled at the 0.00005-0.0006 nm/sec, the evaporation rate of lithium fluoride is controlled at the 0.005-0.015 nm/sec in the resilient coating (7), and the evaporation rate of metallic aluminium is controlled at the 0.5-1.5 nm/sec in the metallic cathode (8); During evaporation luminescent layer (4), organic dyestuff, organic sensitizing dyestuff and the main body organic molecule material that organic mixed material mixes be evaporation simultaneously in different evaporation sources, make the red organic dyestuff of doping and the weight ratio of main body organic molecule material be controlled between the 2%-5% by the evaporation rate of regulating and control three kinds of materials, the weight ratio of organic sensitizing dyestuff and main body organic molecule material is controlled between the 0.1%-0.6%.
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