CN101562232A - Color-adjustable organic electroluminescent device and preparation method thereof - Google Patents
Color-adjustable organic electroluminescent device and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to a color-adjustable organic electroluminescent device and a preparation method thereof. The preparation method adopts a vacuum evaporation plating process and balances the capability of carrier injection by incorporating organic electron transport materials, thereby increasing the recombination probability of the device. In addition, the incorporation of the organic electron transport materials can widen luminescent intervals, weaken exciton quenching and then ease the attenuation of the luminescent efficiency of the device. The luminescent color of the device is adjusted by adjusting the concentration of the organic electron transport materials in a luminescent layer, wherein the organic electroluminescent device displays blue luminescence when the weight ratio of the organic electron transport materials to a main organic blue luminescent material is controlled to be between 0.1 and 0.3 percent, and the device displays aquamarine blue luminescence when the weight ratio of the organic electron transport materials to a main organic blue luminescent material is between 0.4 and 0.8 percent. The device has the maximum current efficiency of 4.77 cd/A, the maximum power efficiency of 3.35 lm / W and the maximum brightness of 22,420 cd/m<2>.
Description
Technical field
The present invention relates to a kind of color-adjustable organic electroluminescent device and preparation method thereof.
Background technology
ORGANIC ELECTROLUMINESCENCE DISPLAYS is a kind of novel Display Technique that progressively tends to ripe in the present photoelectric device field and huge practical prospect is arranged.Compare with other plane Display Techniques such as LCD, plasma display device, Field Emission Display, ORGANIC ELECTROLUMINESCENCE DISPLAYS has that glow color is adjustable, active illuminating, high brightness, high efficiency, wide visual angle, low energy consumption, preparation technology are simple, can prepare a series of excellent specific properties such as crooked flexible display screen, and 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.Therefore, the research of ORGANIC ELECTROLUMINESCENCE DISPLAYS has attracted the extensive concern of scientific circles and industrial quarters and has played an active part in, and makes the performance of organic electroluminescence device obtain development rapidly in more than ten years in the past.At present, performance green and red organic electroluminescence device is significantly improved, and overall performance satisfies practical needs substantially.Yet as one of requisite three primary colors of ORGANIC ELECTROLUMINESCENCE DISPLAYS, blue organic electroluminescent device still is faced with stern challenge, has mainly that device efficiency is low, brightness is low and problem such as operating voltage height.In addition, because of its potential application in white light parts, the blue-green Study on Organic Light-Emitting Devices is becoming new focus.Though the researcher has done a large amount of theories and experiment work, the performance of blue-green organic electroluminescence device does not still satisfy practical requirement.Therefore, how designing blueness, the blue-green organic electroluminescence device that advanced luminescent material and optimised devices structure obtain high efficiency, high brightness, low-work voltage is one of the research emphasis in this field at present.
In 10 years of past, the researcher develops blueness, the blue-green electroluminescent material that many kinds comprise organic molecule and polymer, and the design and optimization of device architecture has also caused extensive studies interest in blue, blue-green organic electroluminescent field.As 2006, people such as Meng-Huan Ho have reported on Applied Physics Letters with 2-methyl-9,10-two (1-naphthalene) anthracene (α, α-MADN) is a material of main part, with styrylamine (BD-1) is the navy blue organic electroluminescence device of guest materials, but this device maximum current efficient and power efficiency have only 3.3cd/A and 1.3lm/W.2006, people such as Wang Lixiang have reported poly-(9 on Applied PhysicsLetters, the blue organic electroluminescent device of 9-two (6 '-diethoxy phosphinylidyne hexyl) fluorenes (PF-EP), the maximal efficiency of this device is 4.0cd/A, its high-high brightness is less than 4000cd/m
22008, people such as horse what light have delivered with 2 on Journal of Physical Chemistry C, 5,2 ', 5 '-tetraphenyl ethylene base biphenyl (TSB) is material of main part, with 1,4-two (4 '-N, N diphenylamines styryl) benzene (DPA-DSB) is the blue organic electroluminescent device of guest materials, though the maximum current efficient of device up to 12.2cd/A, its high-high brightness also has only 17350cd/m
2This shows that though alleviated poor, the inefficient problem of device color color purity to a certain extent through effort for many years, the problem that device brightness is low, operating voltage is high does not still obtain substantive the improvement.
Cause blueness, blue-green organic electroluminescence device device brightness is low and a basic reason of problem such as operating voltage height is that blueness, blue-green luminous organic material have higher energy gap.Usually, high energy gap is accompanied by and higher is not minimumly occupied molecular orbit or lower highest occupied molecular orbital, thereby causes device electronics injection barrier or hole injection barrier too high, and then causes between the luminous zone electronics to inject deficiency or the hole is injected not enough.As a result, unbalanced charge carrier injects and has caused the lower recombination probability of device, finally influences the luminous efficiency of device.On the other hand, unbalanced charge carrier injects often contiguous organic layer interface between the luminous zone that causes device, and very narrow.Cause exciton concentration excessive and produce serious cancellation between narrow luminous zone, and then cause the decay rapidly of device luminous efficiency with the raising of current density; As a result, blue, blue-green organic electroluminescence device has very low efficient usually when high current density, further limited the raising of device brightness.In addition, too high electronics injection barrier or hole injection barrier will improve the operating voltage of device and reduce the current density of device, thereby the decay of acceleration efficiency and device is aging, this also be cause blueness, the brightness of blue-green organic electroluminescence device is low and the major reason of problem such as operating voltage height.So how to solve above problem by design new device structure and optimised devices manufacture craft is the task of top priority that improves blueness and blue-green organic electroluminescence device performance, shows its potential advantages in the organic electroluminescent application.
Summary of the invention
One of purpose of the present invention provides a kind of color-adjustable organic electroluminescent device.
Another object of the present invention provides a kind of preparation method of color-adjustable organic electroluminescent device.
As shown in Figure 1, color-adjustable organic electroluminescent device provided by the invention is connected and composed successively by substrate 1, anode layer 2, hole transmission layer/luminescent layer 3, hole blocking layer 4, electron transfer layer 5, resilient coating 6 and metallic cathode 7;
Hole transmission layer/luminescent layer 3 adopts: the weight ratio of organic electronic transferring material and the organic blue emitting material of main body is the organic mixed material of 0.1%-0.8%;
Wherein the organic electronic transferring material of Can Zaing is: oxine aluminium (being called for short AlQ),
Its molecular structure is as follows:
Wherein the organic blue emitting material of the main body of Can Zaing is: 4,4 '-two [N-(right-tolyl)-N-phenyl-amino] diphenyl (being called for short TPD), N, N '-two (1-naphthyl)-N, N '-diphenyl-1,1 '-diphenyl-4,4 '-diamines (being called for short NPB), perhaps 4,4 '-N, its molecular structure of N '-two carbazole diphenyl (being called for short CBP) is as follows:
Hole blocking layer 4 adopts: 2, and 9-dimethyl-4,7-diphenyl-1,10-phenanthroline (being called for short BCP), its molecular structure is as follows:
Electron transfer layer 5 adopts: oxine aluminium (being called for short AlQ);
That resilient coating 6 adopts is lithium fluoride (LiF);
That metallic cathode 7 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/luminescent layer 3 is 40 to 60 nanometers, and the thickness of hole blocking layer 4 is 20 to 40 nanometers, and the thickness of electron transfer layer 5 is 20 to 40 nanometers, and the thickness of resilient coating 6 is 0.8 to 1.2 nanometer, and the thickness of metallic cathode 7 is 90 to 120 nanometers.
When applying forward voltage between two electrodes, this device will send main peak and be positioned at the blue light about 447 nanometers or be positioned at the blue green light that the blue light of 435 nanometers and green glow that main peak is positioned at 515 nanometers mix by main peak.
The preparation method of blue organic electroluminescent device provided by the invention is as follows:
Earlier ITO layer 2 chemical corrosion on the ito glass substrate 1 are become the electrode of fine strip shape, then successively with cleaning fluid, deionized water ultrasonic cleaning and put into oven for drying, then dried substrate is put into the preliminary treatment vacuum chamber, in vacuum degree is that the voltage that lies prostrate with 350-450 under the atmosphere of 8-15 handkerchief carries out 5-15 minute Low Pressure Oxygen plasma treatment to it, then, it is transferred to the organic vapor deposition chamber, treat that vacuum degree reaches 1-5 * 10
-5During handkerchief, evaporation hole transmission layer/luminescent layer 3, hole blocking layer 4 and electron transfer layer 5 on ITO layer 2 successively, next, uncompleted device is transferred to the metal evaporation chamber, in 5-8 * 10
-5Evaporation resilient coating 6 and metallic cathode 7 successively under the vacuum of handkerchief;
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/luminescent layer 3 is 40 to 60 nanometers, and the thickness of hole blocking layer 4 is 20 to 40 nanometers, and the thickness of electron transfer layer 5 is 20 to 40 nanometers, and the thickness of resilient coating 6 is 0.8 to 1.2 nanometer, and the thickness of metallic cathode 7 is 90 to 120 nanometers; The evaporation rate of NPB in hole transmission layer/luminescent layer 3, hole blocking layer 4 and the electron transfer layer 5 (or TPD and CBP), BCP and AlQ is controlled at the 0.05-0.1 nm/sec, the evaporation rate of organic electronic transferring material AlQ is controlled at the 0.00005-0.0008 nm/sec in hole transmission layer/luminescent layer 3, the evaporation rate of LiF is controlled at the 0.005-0.015 nm/sec in the resilient coating 6, and the evaporation rate of Al is controlled at the 0.5-1.5 nm/sec in the metallic cathode 7; During evaporation luminescent layer 3, organic electronic transferring material and the organic blue emitting material of main body be evaporation simultaneously in different evaporation sources, makes the organic electronic transferring material of doping and the weight ratio of material of main part be controlled between the 0.1%-0.8% by the evaporation rate of regulating and control two kinds of materials.When the weight ratio of electron transport material and material of main part was between 0.1%-0.3%, device showed blue-light-emitting; When the weight ratio of electron transport material and material of main part was between 0.4%-0.8%, device showed that blue-green is luminous.
Beneficial effect: be doped to by the organic electronic transferring material AlQ that will have superior electron transport ability among main body blue emitting material NPB, the TPD or CBP of wide energy gap, can improve the ability between electronics injection luminous zone, help the distribution of electronics and hole between the balance luminous zone, finally improve the recombination probability and the efficient of device.Simultaneously, mixing of AlQ also improved the transmittability of electronics in luminescent layer, help widening between the luminous zone of device and weaken exciton concentration, thereby delay the device electroluminescent efficiency, finally improve the brightness of device and reduce the operating voltage of device with the decay that current density improves.
Another advantage of the present invention is: can artificially regulate the relative distribution on NPB and AlQ molecule of electronics and hole by the concentration of organic electronic transferring material AlQ in the control luminescent layer, thereby regulate the luminous ratio of NPB and two kinds of materials of AlQ, finally realize accurate adjustable in the device glow color is from the navy blue to the bluish-green colour range.Make the organic electronic transferring material of doping and the weight ratio of material of main part be controlled between the 0.1%-0.8% by the evaporation rate of regulating and control two kinds of materials.When the weight ratio of electron transport material and material of main part was between 0.1%-0.3%, device showed blue-light-emitting; When the weight ratio of electron transport material and material of main part was between 0.4%-0.8%, device showed that blue-green is luminous.
The maximum current efficient of obtained device is 4.77cd/A, and maximum power efficiency is 3.35lm/W, and high-high brightness is 22420cd/m
2
Description of drawings
Fig. 1 is the structural representation of color-adjustable organic electroluminescent device provided by the invention.Among the figure, the 1st, glass substrate, the 2nd, anode layer, the 3rd, hole transmission layer/luminescent layer, the 4th, hole blocking layer, the 5th, electron transfer layer, the 6th, resilient coating, the 7th, 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 color-adjustable organic electroluminescent 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 3.4 volts, is that 14.4 volts, current density are 650.96 milliamperes of every square centimeter of (mA/cm at voltage
2) time device obtain every square metre of (cd/m of high-high brightness 20020 candelas
2).
Fig. 3 is current density-power efficiency-current efficiency characteristic curve of color-adjustable organic electroluminescent device embodiment 4 provided by the invention.The maximum current efficient of device is every ampere of 4.20 candela (cd/A), and maximum power efficiency is every watt of 2.49 lumen (lm/W).
Fig. 4 is the spectrogram of color-adjustable organic electroluminescent device embodiment 4 provided by the invention, and spectrum derives from the blue emission of NPB, and main peak is positioned at 447 nanometers.
Fig. 5 is voltage-to-current density-luminosity response of color-adjustable organic electroluminescent device embodiment 10 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 3.6 volts, is that 14.9 volts, current density are 797.30mA/cm at voltage
2The time device obtain high-high brightness 22420cd/m
2
Fig. 6 is current density-power efficiency-current efficiency characteristic curve of color-adjustable organic electroluminescent device embodiment 10 provided by the invention.The maximum current efficient of device is 4.77cd/A, and maximum power efficiency is 2.91lm/W.
Fig. 7 is the spectrogram of color-adjustable organic electroluminescent device embodiment 10 provided by the invention, and spectrum derives from the blue emission of NPB and the green emission of AlQ, and main peak is positioned at 454 nanometers, and acromion is positioned at 491 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 400 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 BCP hole blocking layer of hole transmission layer/luminescent layer of the AlQ doping NPB of evaporation 50 nanometer thickness, 30 nanometer thickness and the AlQ electron transfer layer of 30 nanometer thickness successively on the ITO layer.Next, uncompleted device is transferred to the metal evaporation chamber, in 5-8 * 10
-5The LiF resilient coating of evaporation 1.0 nanometer thickness under the vacuum of handkerchief, by the metal A l electrode of special mask evaporation 100 nanometer thickness on the LiF resilient coating, being prepared into structure is ITO/AlQ (0.1%): the organic electroluminescence device of NPB/BCP/AlQ/LiF/Al at last.The light-emitting area of this device is 10 square millimeters.The evaporation rate of NPB, BCP and AlQ (electron transfer layer) is controlled at 0.05 nm/sec, and the evaporation rate of AlQ is controlled at 0.00005 nm/sec in the luminescent layer, 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 demonstrates blue-light-emitting under 3.5 to 11.4 volts direct voltage drive, main peak is positioned at 447 nanometers.The high-high brightness of device is 16274cd/m
2, maximum current efficient is 2.48cd/A, maximum power efficiency is 2.17lm/W.
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 400 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 BCP hole blocking layer of hole transmission layer/luminescent layer of the AlQ doping NPB of evaporation 40 nanometer thickness, 30 nanometer thickness and the AlQ electron transfer layer of 30 nanometer thickness successively on the ITO layer.Next, uncompleted device is transferred to the metal evaporation chamber, in 5-8 * 10
-5The LiF resilient coating of evaporation 1.0 nanometer thickness under the vacuum of handkerchief, by the metal A l electrode of special mask evaporation 100 nanometer thickness on the LiF resilient coating, being prepared into structure is ITO/AlQ (0.2%): the organic electroluminescence device of NPB/BCP/AlQ/LiF/Al at last.The light-emitting area of this device is 10 square millimeters.The evaporation rate of NPB, BCP and AlQ (electron transfer layer) is controlled at 0.05 nm/sec, and the evaporation rate of AlQ is controlled at 0.0001 nm/sec in the luminescent layer, 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 demonstrates blue-light-emitting under 3.5 to 12.6 volts direct voltage drive, main peak is positioned at 449 nanometers.The high-high brightness of device is 19843cd/m
2, maximum current efficient is 3.33cd/A, maximum power efficiency is 2.41lm/W.
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 400 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 BCP hole blocking layer of hole transmission layer/luminescent layer of the AlQ doping NPB of evaporation 50 nanometer thickness, 30 nanometer thickness and the AlQ electron transfer layer of 30 nanometer thickness successively on the ITO layer.Next, uncompleted device is transferred to the metal evaporation chamber, in 5-8 * 10
-5The LiF resilient coating of evaporation 1.0 nanometer thickness under the vacuum of handkerchief, by the metal A l electrode of special mask evaporation 100 nanometer thickness on the LiF resilient coating, being prepared into structure is ITO/AlQ (0.2%): the organic electroluminescence device of NPB/BCP/AlQ/LiF/Al at last.The light-emitting area of this device is 10 square millimeters.The evaporation rate of NPB, BCP and AlQ (electron transfer layer) is controlled at 0.05 nm/sec, and the evaporation rate of AlQ is controlled at 0.0001 nm/sec in the luminescent layer, 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 demonstrates blue-light-emitting under 3.5 to 12.6 volts direct voltage drive, main peak is positioned at 448 nanometers.The high-high brightness of device is 20086cd/m
2, maximum current efficient is 3.90cd/A, maximum power efficiency is 1.92lm/W.
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 400 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 BCP hole blocking layer of hole transmission layer/luminescent layer of the AlQ doping NPB of evaporation 60 nanometer thickness, 30 nanometer thickness and the AlQ electron transfer layer of 30 nanometer thickness successively on the ITO layer.Next, uncompleted device is transferred to the metal evaporation chamber, in 5-8 * 10
-5The LiF resilient coating of evaporation 1.0 nanometer thickness under the vacuum of handkerchief, by the metal A l electrode of special mask evaporation 100 nanometer thickness on the LiF resilient coating, being prepared into structure is ITO/AlQ (0.2%): the organic electroluminescence device of NPB/BCP/AlQ/LiF/Al at last.The light-emitting area of this device is 10 square millimeters.The evaporation rate of NPB, BCP and AlQ (electron transfer layer) is controlled at 0.05 nm/sec, and the evaporation rate of AlQ is controlled at 0.0001 nm/sec in the luminescent layer, 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 demonstrates blue-light-emitting under 3.4 to 14.4 volts direct voltage drive, main peak is positioned at 447 nanometers.The high-high brightness of device is 20020cd/m
2, maximum current efficient is 4.20cd/A, maximum power efficiency is 2.49lm/W.
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 400 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 BCP hole blocking layer of hole transmission layer/luminescent layer of the AlQ doping NPB of evaporation 60 nanometer thickness, 20 nanometer thickness and the AlQ electron transfer layer of 30 nanometer thickness successively on the ITO layer.Next, uncompleted device is transferred to the metal evaporation chamber, in 5-8 * 10
-5The LiF resilient coating of evaporation 1.0 nanometer thickness under the vacuum of handkerchief, by the metal A l electrode of special mask evaporation 100 nanometer thickness on the LiF resilient coating, being prepared into structure is ITO/AlQ (0.2%): the organic electroluminescence device of NPB/BCP/AlQ/LiF/Al at last.The light-emitting area of this device is 10 square millimeters.The evaporation rate of NPB, BCP and AlQ (electron transfer layer) is controlled at 0.05 nm/sec, and the evaporation rate of AlQ is controlled at 0.0001 nm/sec in the luminescent layer, 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 demonstrates blue-light-emitting under 4.1 to 14.6 volts direct voltage drive, main peak is positioned at 446 nanometers.The high-high brightness of device is 20746cd/m
2, maximum current efficient is 4.51cd/A, maximum power efficiency is 2.48lm/W.
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 400 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 BCP hole blocking layer of hole transmission layer/luminescent layer of the AlQ doping NPB of evaporation 50 nanometer thickness, 30 nanometer thickness and the AlQ electron transfer layer of 30 nanometer thickness successively on the ITO layer.Next, uncompleted device is transferred to the metal evaporation chamber, in 5-8 * 10
-5The LiF resilient coating of evaporation 1.0 nanometer thickness under the vacuum of handkerchief, by the metal A l electrode of special mask evaporation 100 nanometer thickness on the LiF resilient coating, being prepared into structure is ITO/AlQ (0.4%): the organic electroluminescence device of NPB/BCP/AlQ/LiF/Al at last.The light-emitting area of this device is 10 square millimeters.The evaporation rate of NPB, BCP and AlQ (electron transfer layer) is controlled at 0.05 nm/sec, and the evaporation rate of AlQ is controlled at 0.0002 nm/sec in the luminescent layer, 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 is under 3.4 to 12.0 volts direct voltage drive, and it is luminous to demonstrate blue-green, and main peak is positioned at 455 nanometers, and acromion is positioned at 492 nanometers.The high-high brightness of device is 20829cd/m
2, maximum current efficient is 3.51cd/A, maximum power efficiency is 3.35lm/W.
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 400 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 BCP hole blocking layer of hole transmission layer/luminescent layer of the AlQ doping NPB of evaporation 50 nanometer thickness, 30 nanometer thickness and the AlQ electron transfer layer of 30 nanometer thickness successively on the ITO layer.Next, uncompleted device is transferred to the metal evaporation chamber, in 5-8 * 10
-5The LiF resilient coating of evaporation 1.0 nanometer thickness under the vacuum of handkerchief, by the metal A l electrode of special mask evaporation 100 nanometer thickness on the LiF resilient coating, being prepared into structure is ITO/AlQ (0.5%): the organic electroluminescence device of NPB/BCP/AlQ/LiF/Al at last.The light-emitting area of this device is 10 square millimeters.The evaporation rate of NPB, BCP and AlQ (electron transfer layer) is controlled at 0.05 nm/sec, and the evaporation rate of AlQ is controlled at 0.00025 nm/sec in the luminescent layer, 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 is under 3.3 to 12.6 volts direct voltage drive, and it is luminous to demonstrate blue-green, and main peak is positioned at 494 nanometers, and acromion is positioned at 446 nanometers.The high-high brightness of device is 21278cd/m
2, maximum current efficient is 3.83cd/A, maximum power efficiency is 3.04lm/W.
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 400 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 BCP hole blocking layer of hole transmission layer/luminescent layer of the AlQ doping NPB of evaporation 40 nanometer thickness, 30 nanometer thickness and the AlQ electron transfer layer of 30 nanometer thickness successively on the ITO layer.Next, uncompleted device is transferred to the metal evaporation chamber, in 5-8 * 10
-5The LiF resilient coating of evaporation 1.0 nanometer thickness under the vacuum of handkerchief, by the metal A l electrode of special mask evaporation 100 nanometer thickness on the LiF resilient coating, being prepared into structure is ITO/AlQ (0.6%): the organic electroluminescence device of NPB/BCP/AlQ/LiF/Al at last.The light-emitting area of this device is 10 square millimeters.The evaporation rate of NPB, BCP and AlQ (electron transfer layer) is controlled at 0.05 nm/sec, and the evaporation rate of AlQ is controlled at 0.0003 nm/sec in the luminescent layer, 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 is under 3.5 to 11.4 volts direct voltage drive, and it is luminous to demonstrate blue-green, and main peak is positioned at 503 nanometers, and acromion is positioned at 456 nanometers.The high-high brightness of device is 20719cd/m
2, maximum current efficient is 3.72cd/A, maximum power efficiency is 3.14lm/W.
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 400 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 BCP hole blocking layer of hole transmission layer/luminescent layer of the AlQ doping NPB of evaporation 50 nanometer thickness, 30 nanometer thickness and the AlQ electron transfer layer of 30 nanometer thickness successively on the ITO layer.Next, uncompleted device is transferred to the metal evaporation chamber, in 5-8 * 10
-5The LiF resilient coating of evaporation 1.0 nanometer thickness under the vacuum of handkerchief, by the metal A l electrode of special mask evaporation 100 nanometer thickness on the LiF resilient coating, being prepared into structure is ITO/AlQ (0.6%): the organic electroluminescence device of NPB/BCP/AlQ/LiF/Al at last.The light-emitting area of this device is 10 square millimeters.The evaporation rate of NPB, BCP and AlQ (electron transfer layer) is controlled at 0.05 nm/sec, and the evaporation rate of AlQ is controlled at 0.0003 nm/sec in the luminescent layer, 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 is under 3.5 to 12.6 volts direct voltage drive, and it is luminous to demonstrate blue-green, and main peak is positioned at 501 nanometers, and acromion is positioned at 456 nanometers.The high-high brightness of device is 20329cd/m
2, maximum current efficient is 4.22cd/A, maximum power efficiency is 2.63lm/W.
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 400 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 BCP hole blocking layer of hole transmission layer/luminescent layer of the AlQ doping NPB of evaporation 60 nanometer thickness, 30 nanometer thickness and the AlQ electron transfer layer of 30 nanometer thickness successively on the ITO layer.Next, uncompleted device is transferred to the metal evaporation chamber, in 5-8 * 10
-5The LiF resilient coating of evaporation 1.0 nanometer thickness under the vacuum of handkerchief, by the metal A l electrode of special mask evaporation 100 nanometer thickness on the LiF resilient coating, being prepared into structure is ITO/AlQ (0.6%): the organic electroluminescence device of NPB/BCP/AlQ/LiF/Al at last.The light-emitting area of this device is 10 square millimeters.The evaporation rate of NPB, BCP and AlQ (electron transfer layer) is controlled at 0.05 nm/sec, and the evaporation rate of AlQ is controlled at 0.0003 nm/sec in the luminescent layer, 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 is under 3.6 to 14.9 volts direct voltage drive, and it is luminous to demonstrate blue-green, and main peak is positioned at 454 nanometers, and acromion is positioned at 491 nanometers.The high-high brightness of device is 22420cd/m
2, maximum current efficient is 4.77cd/A, maximum power efficiency is 2.91lm/W.
Embodiment 11:
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 400 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 BCP hole blocking layer of hole transmission layer/luminescent layer of the AlQ doping NPB of evaporation 60 nanometer thickness, 20 nanometer thickness and the AlQ electron transfer layer of 30 nanometer thickness successively on the ITO layer.Next, uncompleted device is transferred to the metal evaporation chamber, in 5-8 * 10
-5The LiF resilient coating of evaporation 1.0 nanometer thickness under the vacuum of handkerchief, by the metal A l electrode of special mask evaporation 100 nanometer thickness on the LiF resilient coating, being prepared into structure is ITO/AlQ (0.6%): the organic electroluminescence device of NPB/BCP/AlQ/LiF/Al at last.The light-emitting area of this device is 10 square millimeters.The evaporation rate of NPB, BCP and AlQ (electron transfer layer) is controlled at 0.05 nm/sec, and the evaporation rate of AlQ is controlled at 0.0003 nm/sec in the luminescent layer, 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 is under 3.3 to 13.7 volts direct voltage drive, and it is luminous to demonstrate blue-green, and main peak is positioned at 495 nanometers, and acromion is positioned at 459 nanometers.The high-high brightness of device is 21901cd/m
2, maximum current efficient is 4.02cd/A, maximum power efficiency is 2.61lm/W.
Embodiment 12:
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 400 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 BCP hole blocking layer of hole transmission layer/luminescent layer of the AlQ doping NPB of evaporation 50 nanometer thickness, 30 nanometer thickness and the AlQ electron transfer layer of 30 nanometer thickness successively on the ITO layer.Next, uncompleted device is transferred to the metal evaporation chamber, in 5-8 * 10
-5The LiF resilient coating of evaporation 1.0 nanometer thickness under the vacuum of handkerchief, by the metal A l electrode of special mask evaporation 100 nanometer thickness on the LiF resilient coating, being prepared into structure is ITO/AlQ (0.8%): the organic electroluminescence device of NPB/BCP/AlQ/LiF/Al at last.The light-emitting area of this device is 10 square millimeters.The evaporation rate of NPB, BCP and AlQ (electron transfer layer) is controlled at 0.05 nm/sec, and the evaporation rate of AlQ is controlled at 0.0004 nm/sec in the luminescent layer, 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 is under 3.6 to 13.7 volts direct voltage drive, and it is luminous to demonstrate blue-green, and main peak is positioned at 504 nanometers, and acromion is positioned at 455 nanometers.The high-high brightness of device is 21229cd/m
2, maximum current efficient is 4.38cd/A, maximum power efficiency is 2.68lm/W.
Claims (3)
1, a kind of color-adjustable organic electroluminescent device, it is characterized in that it is connected and composed in turn by substrate (1), anode layer (2), hole transmission layer/luminescent layer (3), hole blocking layer (4), electron transfer layer (5), resilient coating (6) and metallic cathode (7);
Described substrate (1) is a glass substrate; Anode layer (2) adopts indium tin oxide; It is the organic mixed material of 0.1%-0.8% that hole transmission layer/luminescent layer (3) adopts the weight ratio of organic electronic transferring material and the organic blue emitting material of main body;
Wherein the organic electronic transferring material of Can Zaing is an oxine aluminium, and its molecular structure is as follows:
The organic blue emitting material of main body is 4,4 '-two [N-(right-tolyl)-N-phenyl-amino] diphenyl, perhaps N, N '-two (1-naphthyl)-N, N '-diphenyl-1,1 '-diphenyl-4,4 '-diamines, perhaps 4,4 '-N, N '-two carbazole diphenyl, their molecular structure is as follows:
Hole blocking layer (4) adopts 2,9-dimethyl-4, and 7-diphenyl-1, the 10-phenanthroline, its molecular structure is as follows:
Electron transfer layer (5) adopts oxine aluminium;
What resilient coating (6) adopted is lithium fluoride;
What metallic cathode (7) adopted is metallic aluminium;
Described anode layer (2) and metallic cathode (7) intersect to form the luminous zone of device mutually, and area is 10 square millimeters; The thickness of hole transmission layer/luminescent layer (3) is 40 to 60 nanometers, the thickness of hole blocking layer (4) is 20 to 40 nanometers, the thickness of electron transfer layer (5) is 20 to 40 nanometers, and the thickness of resilient coating (6) is 0.8 to 1.2 nanometer, and the thickness of metallic cathode (7) is 90 to 120 nanometers.
2, a kind of color-adjustable organic electroluminescent device as claimed in claim 1, it is characterized in that, described hole transmission layer/luminescent layer (3), make the organic electronic transferring material of doping and the weight ratio of material of main part be controlled between the 0.1%-0.3% by the evaporation rate of controlling described organic electronic transferring material and the organic blue emitting material of main body, resulting organic electroluminescence device shows blue-light-emitting; By control described organic electronic transferring material and the organic blue emitting material of main body weight ratio between 0.4%-0.8%, device shows that blue-green is luminous.
3, the preparation method of a kind of color-adjustable organic electroluminescent 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 350-450 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/luminescent layer (3), hole blocking layer (4) and electron transfer layer (5) at ITO layer (2) successively, next, uncompleted device is transferred to the metal evaporation chamber, in 5-8 * 10
-5Evaporation resilient coating (6) and metallic cathode (7) successively under the vacuum of handkerchief;
Hole transmission layer/luminescent layer (3), in hole blocking layer (4) and the electron transfer layer (5) 4,4 '-two [N-(right-tolyl)-N-phenyl-amino] diphenyl, N, N '-two (1-naphthyl)-N, N '-diphenyl-1,1 '-diphenyl-4,4 '-diamines, 4,4 '-N, N '-two carbazole diphenyl, 2,9-dimethyl-4,7-diphenyl-1, the evaporation rate of 10-phenanthroline and oxine aluminium is controlled at the 0.05-0.1 nm/sec, the evaporation rate of organic electronic transferring material oxine aluminium is controlled at the 0.00005-0.0008 nm/sec in hole transmission layer/luminescent layer (3), and the evaporation rate of lithium fluoride is controlled at the 0.005-0.015 nm/sec in the resilient coating (6), and the evaporation rate of metallic aluminium is controlled at the 0.5-1.5 nm/sec in the metallic cathode (7); During evaporation hole transmission layer/luminescent layer (3), organic electronic transferring material that organic mixed material mixes and main body blue organic luminous material be evaporation simultaneously in different evaporation sources, makes the organic electronic transferring material of doping and the weight ratio of the organic blue emitting material of main body be controlled between the 0.1%-0.8% by the evaporation rate of regulating and control two kinds of materials; When the weight ratio of electron transport material and material of main part between 0.1%-0.3%, device shows blue-light-emitting; When the weight ratio of electron transport material and material of main part between 0.4%-0.8%, device shows that blue-green is luminous.
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| CN101728491B (en) * | 2009-12-21 | 2012-09-05 | 中国科学院长春应用化学研究所 | White organic luminescent element and preparation method thereof |
| US10115909B2 (en) | 2015-04-16 | 2018-10-30 | Boe Technology Group Co., Ltd. | Organic electroluminescent device, manufacturing method thereof and electronic equipment |
| CN112510161A (en) * | 2020-12-02 | 2021-03-16 | 吉林大学 | Color-adjustable organic electroluminescent device and preparation method thereof |
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| CN1446031A (en) * | 2002-03-20 | 2003-10-01 | 铼宝科技股份有限公司 | Illuminator with adjustable colors |
| CN100466332C (en) * | 2006-01-18 | 2009-03-04 | 中国科学院化学研究所 | Method for preparing organic ELD capable of regulating light emitting colors |
| CN101123298A (en) * | 2007-09-11 | 2008-02-13 | 电子科技大学 | A structure-optimized white light organic EL part |
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| CN101728491B (en) * | 2009-12-21 | 2012-09-05 | 中国科学院长春应用化学研究所 | White organic luminescent element and preparation method thereof |
| US10115909B2 (en) | 2015-04-16 | 2018-10-30 | Boe Technology Group Co., Ltd. | Organic electroluminescent device, manufacturing method thereof and electronic equipment |
| CN112510161A (en) * | 2020-12-02 | 2021-03-16 | 吉林大学 | Color-adjustable organic electroluminescent device and preparation method thereof |
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