CN1142708C - Single layer organic electroluminescent device and its preparation method - Google Patents
Single layer organic electroluminescent device and its preparation method Download PDFInfo
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- CN1142708C CN1142708C CNB011155639A CN01115563A CN1142708C CN 1142708 C CN1142708 C CN 1142708C CN B011155639 A CNB011155639 A CN B011155639A CN 01115563 A CN01115563 A CN 01115563A CN 1142708 C CN1142708 C CN 1142708C
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- organic electroluminescent
- electroluminescent device
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Abstract
The present invention relates to a single-layer organic electroluminescent device and a preparing method thereof. The device comprises a single luminous layer and a buffering layer, wherein the luminous layer is clamped between two electrode layers to transmit electrons; the buffering layer is clamped between a first electrode and the organic luminous layer. The device has the preparing method that an organic material film is vaporized and plated on the first electrode to serve as the buffering layer. The organic material is preferably polytetrafluoroethene. After the device is manufactured, a postprocessing process is needed. The buffering layer film is prepared on the film surface by a special method, and has a nanometer structure with uniform distribution. Thus, the high-efficiency injection of cavities is realized, and the luminous efficiency and the stability of the device are enhanced.
Description
Technical field
The present invention relates to a kind of single layer organic electroluminescent device, in particular, the present invention relates to the single layer organic electroluminescent device of a kind of luminous efficiency height, good stability, also relate to this preparation of devices method.
Background technology
1987, people such as the C.W.TANG (C.W.Tang of U.S. Kodak company, S.A.Slyke, Appl.Phys.Lett.51,913 (1987)) adopt double-decker first, with the aromatic diamines analog derivative as hole mobile material, with a kind of fluorescence efficiency very high and can make with Vacuum Coating method the high-quality thin film of even compact organic small molecule material---three (oxine) aluminium is (hereinafter to be referred as Alq
3) as the luminescent layer material, prepare higher quantum efficiency (1%), high-luminous-efficiency (＞1.5lm/W), high brightness (＞1000cd/m
2) and low driving voltage (＜10V) organic electroluminescence device (hereinafter to be referred as OLED) makes the research work in this field enter a brand-new era.Nineteen ninety, Britain Cambridge university Cavan enlightening is permitted breadboard Burroughes and his colleague finds that polymeric material also has good electroluminescent properties, and this important discovery is arrived polymer arts with the research promotion of electroluminescent organic material.Over year, people constantly improve the preparation technology of organic electroluminescence device surplus in the of ten, and its correlation technique development rapidly.
At present, in technical field of organic electroluminescence, one of effective ways that improve the device luminous efficiency are to regulate and control the balance of carrier electrons and hole concentration by adjusting device architecture.In the device of present sandwich construction, hole mobile material is compared with electron transport material, because its vitrification point is lower, so its stability is very poor, improving hole material glass temperature is an important channel of improving OLED stability.
In recent years, in order to simplify device preparation technology, people have proposed the idea of preparation single layer device.Adopt the device of single layer structure, not only can simplify the preparation technology of electroluminescent device, thereby further reduce the cost of electroluminescent display, also can reduce the light loss that the device inner membrance causes because of scattering and refraction at the interface simultaneously.
U.S. Pat 5,853,905 (day for announcing: on December 29th, 1998) disclose a kind of structure of single layer organic electroluminescent device, it has adopted one deck or two layers of insulation material resilient coating.This resilient coating is enough thin, so that charge carrier can tunnelling enter organic luminous layer.The subject matter that above-mentioned patent exists is that the charge carrier injection efficiency of the resilient coating that is made of insulating material is not high enough, and is seriously uneven in device inside electronics, hole, thereby make the luminous efficiency of prepared single layer device very low, and less stable.
Summary of the invention
The purpose of this invention is to provide a kind of single layer organic electroluminescent device that can make the efficient injection in hole.
Another object of the present invention provides a kind of preparation method of single layer organic electroluminescent device.
For achieving the above object, a technical scheme of the present invention provides a kind of single layer organic electroluminescent device, this device comprises first electrode layer and the second electrode lay, and be clipped in described first electrode layer, but the luminescent layer of the individual layer transmission electronic between the second electrode lay, it is characterized in that: but also comprise one deck resilient coating between the luminescent layer that is clipped in described first electrode layer and individual layer transmission electronic, this resilient coating is prepared on the film surface through the vacuum thermal evaporation method has equally distributed nanostructure, cushioning layer material is polytetrafluoroethylene (hereinafter to be referred as Teflon), and thickness is less than 10nm.
The organic electroluminescence device that the present invention proposes has the following advantages:
(1) owing to do not have hole transmission layer in the device architecture, promptly do not adopt the low hole mobile material of vitrification point, so the stability of device is improved;
(2) comprise in the device architecture through the vacuum thermal evaporation method and be prepared into the resilient coating that has even distribution nanostructure on the film surface, thereby realized the efficient injection in hole, improved the luminous efficiency of device.
Another technical scheme of the present invention provides a kind of preparation method of single layer organic electroluminescent device, and this method may further comprise the steps:
(1) utilize washing agent to boil with the ultrasonic method of deionized water transparent conduction base sheet is cleaned, dried, wherein the conducting film above the conductive substrate is as first electrode layer of device;
(2) conductive substrate behind the above-mentioned cleaning, drying being placed pressure is 1 * 10
-5～1 * 10
-3In the vacuum chamber of Pa, evaporation one deck organic material film is as resilient coating on above-mentioned conducting film to utilize the vacuum thermal evaporation method, and organic material is a polytetrafluoroethylene, and film vapor deposition speed is 0.01～0.04nm/s, and film thickness is less than 10nm;
(3) in above-mentioned vacuum chamber, keep-up pressure constant, but on above-mentioned buffer layer thin film, continue the luminescent layer of evaporation individual layer transmission electronic, but the luminescent layer of transmission electronic is made up of luminous organic material;
(4) in above-mentioned vacuum chamber, keep-up pressure constantly, on above-mentioned luminescent layer, continue the second electrode lay of evaporated metal layer as device;
It is characterized in that also comprising the steps:
(5) post-processing step after (1) to (4) step makes device, adds a forward dc voltage to device, the electric current of device rises greatly and with voltage, and this moment, device was not luminous, after voltage reaches certain value, the electric current of device sharply descends suddenly, meanwhile device begins luminously, and post-processing step finishes, after the said method reprocessing, add forward voltage to device, the electric current of device reduces greatly, increases with voltage, and device brightness is along with increase.
Another technical scheme of the present invention provides a kind of single layer organic electroluminescent device according to method for preparing, it is characterized in that: the buffer layer thin film of this device is prepared on the film surface through the vacuum thermal evaporation method has equally distributed nanostructure.This buffer layer thin film is preferably the Teflon film, and this material is prepared on the film surface through the vacuum thermal evaporation method has equally distributed nanostructure (as shown in Figure 2), and thickness is less than 10nm.
Single layer organic electroluminescent device provided by the invention can be realized the efficient injection in hole.When adopting Alq
3But during as the luminescent layer of transmission electronic, can obtain the green emitting of high brightness.Prepared device has and opens that bright voltage is low, brightness is high, the characteristics of good stability; And compare with other multilayer device, can operate as normal under high voltage, luminous efficiency does not obviously reduce.Use the current density-voltage curve after brightness-voltage curve, efficient-voltage curve and the reprocessing of single layer organic electroluminescent device of preparation method of the present invention preparation to see Fig. 3, Fig. 4 and Fig. 6 respectively.
Description of drawings
Fig. 1 is the structural representation of the single layer organic electroluminescent device that proposes of the present invention, and wherein 1 is transparent substrate, and 2 is first electrode layers, the 3rd, and resilient coating, the 4th, but the luminescent layer of individual layer transmission electronic, the 5th, the second electrode lay, the 6th, power supply.
Fig. 2 is atomic force microscope (AFM) figure that utilization preparation method of the present invention prepares the Teflon film.
Fig. 3 is that (structure is ITO/Teflon (xnm)/Alq to the single layer organic electroluminescent device that uses preparation method of the present invention to prepare
3/ Ca/Ag) brightness-voltage curve.
Fig. 4 is that (structure is ITO/Teflon (xnm)/Alq to the single layer organic electroluminescent device that uses preparation method of the present invention to prepare
3/ Ca/Ag) efficient-voltage curve.
Fig. 5 is that (structure is ITO/Teflon (xnm)/Alq to the single layer organic electroluminescent device that uses preparation method of the present invention to prepare
3Current density-voltage curve in/Ca/Ag) the last handling process.
Fig. 6 is that (structure is ITO/Teflon (xnm)/Alq to the single layer organic electroluminescent device that uses preparation method of the present invention to prepare
3/ Ca/Ag) current density-the voltage curve after the reprocessing.
Elaborate content of the present invention below in conjunction with drawings and Examples.
Embodiment
The single layer organic electroluminescent device structure that the present invention proposes as shown in Figure 1, wherein: 1 is transparent substrate, can be glass or plastics; 2 is first electrode layer (anode layer) of conductive film as device, first electrode layer material is generally the higher metals of work function such as metal oxides such as tin indium oxide (hereinafter to be referred as ITO), zinc oxide, zinc tin oxide or gold, copper, silver, the optimized ITO that is chosen as; 3 is the resilient coating of insulating barrier as device, and its thickness is less than 10nm, and cushioning layer material is generally polymethyl methacrylate, polyimides, fluoropolymer, perhaps LiF, AlF
3, CaF
2, MgF
2, SiO
2, MgO, Al
2O
3With inorganic matters such as diamonds, the present invention is preferably Teflon; The 4th, but the luminescent layer of individual layer transmission electronic, but the luminescent layer of transmission electronic form by luminous organic material, as Alq
3, N, N '-two-(1-naphthyl)-N, N '-diphenyl-1,1-xenyl-4,4-diamines (hereinafter to be referred as NPB), N, N '-diphenyl-N, N '-two (aminomethyl phenyl)-1,1 '-xenyl-4,4 '-diamines (hereinafter to be referred as TPD), 4-hydroxy-acridine zinc are (hereinafter to be referred as Zn (Ac)
2) etc.; 5 is the second electrode lay (cathode layer) of metal level as device, and the second electrode lay material is generally the alloy of the lower metal of work functions such as lithium, magnesium, calcium, strontium, aluminium, indium or they and copper, gold, silver.
Embodiment one:
Utilize washing agent boil with the ultrasonic method of deionized water be that the ito glass of 60 Ω cleans, dries to square resistance, wherein the thickness of ITO is 180nm.It is 1 * 10 that ito glass after cleaning is placed pressure
-4Utilize hot evaporation coating method evaporation Teflon buffer thin film on the ITO film in the vacuum chamber of Pa, evaporation speed is 0.02nm/s, and film thickness is 8nm.In vacuum chamber, continue evaporation organic layer Alq
3, evaporation speed is 0.1nm/s, thickness is 60nm.Continue evaporated metal layer in vacuum chamber, metal level is made up of Ca and Ag successively, and the evaporation speed of Ca, Ag is 0.6nm/s, and thickness is respectively 35nm and 130nm.The device of preparation uses direct voltage to carry out reprocessing, and at the 23V place, electric current sharply reduces suddenly, and last handling process finishes.It is 4V that device opens bright voltage, and brightness was 2500cd/m when voltage was 24V
2
Embodiment two:
Utilize washing agent boil with the ultrasonic method of deionized water be that the ito glass of 70 Ω cleans, dries to square resistance, wherein the thickness of ITO is 100nm.It is 1 * 10 that ito glass after cleaning is placed pressure
-3Utilize hot evaporation coating method evaporation Teflon buffer thin film on the ITO film in the vacuum chamber of Pa, evaporation speed is 0.04nm/s, and film thickness is 10nm.Continue evaporation organic layer TPD in vacuum chamber, evaporation speed is 0.4nm/s, and thickness is 70nm.Continue evaporated metal layer in vacuum chamber, metal level is made up of Mg-Ag alloy and Ag successively, and the total evaporation speed of Mg-Ag is 1.5nm/s, and the ratio of Mg and Ag evaporation speed is 4: 1, and thickness is 100nm, and the evaporation speed of Ag is 0.3nm/s, and evaporation thickness is 130nm.The device of preparation uses direct voltage to carry out reprocessing, and at the 30V place, electric current sharply reduces suddenly, and last handling process finishes.It is 3.5V that device opens bright voltage, and brightness was 600cd/m when voltage was 24V
2
Embodiment three:
Utilize washing agent boil with the ultrasonic method of deionized water be that the ito glass of 30 Ω cleans, dries to square resistance, wherein the thickness of ITO is 240nm.It is 1 * 10 that ito glass after cleaning is placed pressure
-5Utilize hot evaporation coating method evaporation Teflon buffer thin film on the ITO film in the vacuum chamber of Pa, evaporation speed is 0.01nm/s, and film thickness is 6nm.In vacuum chamber, continue evaporation organic layer Zn (Ac)
2, evaporation speed is 0.2nm/s, thickness is 40nm.Continue evaporated metal layer in vacuum chamber, metal level is made up of Ca and Ag successively, and the evaporation speed of Ca, Ag is respectively 0.3nm/s and 0.2nm/s, and thickness is respectively 25nm and 150nm.The device of preparation uses direct voltage to carry out reprocessing, and at the 18V place, electric current sharply reduces suddenly, and last handling process finishes.It is 4.5V that device opens bright voltage, and brightness was 500cd/m when voltage was 24V
2
Although describe the present invention in conjunction with the preferred embodiments, but the present invention is not limited to the foregoing description, should be appreciated that under the guiding of the present invention's design, those skilled in the art can carry out various modifications and improvement, and claims have been summarized scope of the present invention.
Claims (7)
1. single layer organic electroluminescent device, this device comprises first electrode layer and the second electrode lay, but and the luminescent layer that is clipped in the individual layer transmission electronic between described first electrode layer, the second electrode lay, it is characterized in that: but also comprise one deck resilient coating between the luminescent layer that is clipped in described first electrode layer and individual layer transmission electronic, this resilient coating is prepared on the film surface through the vacuum thermal evaporation method has equally distributed nanostructure, cushioning layer material is a polytetrafluoroethylene, and thickness is less than 10nm.
2. single layer organic electroluminescent device as claimed in claim 1 is characterized in that: described first electrode layer material is tin indium oxide, zinc oxide, zinc tin oxide, gold, copper or silver.
3. single layer organic electroluminescent device as claimed in claim 1 or 2 is characterized in that: described first electrode layer material is a tin indium oxide.
4. single layer organic electroluminescent device as claimed in claim 1, it is characterized in that: but the luminescent layer material of described individual layer transmission electronic is three (oxine) aluminium, N, N '-two-(1-naphthyl)-N, N '-diphenyl-1,1-xenyl-4,4-diamines, N, N '-diphenyl-N, N '-two (aminomethyl phenyl)-1,1 '-xenyl-4,4 '-diamines or 4-hydroxy-acridine zinc.
5. single layer organic electroluminescent device as claimed in claim 1 is characterized in that wherein said the second electrode lay material is followed successively by Mg-Ag alloy and Ag, or is followed successively by Ca and Ag.
6. method for preparing the described single layer organic electroluminescent device of claim 1, this method may further comprise the steps:
(1) utilize washing agent to boil with the ultrasonic method of deionized water transparent conduction base sheet is cleaned, dried, wherein the conducting film above the conductive substrate is as first electrode layer of device;
(2) conductive substrate behind the above-mentioned cleaning, drying being placed pressure is 1 * 10
-5～1 * 10
-3In the vacuum chamber of Pa, evaporation one deck organic material film is as resilient coating on above-mentioned conducting film to utilize the vacuum thermal evaporation method, and organic material is a polytetrafluoroethylene, and film vapor deposition speed is 0.01～0.04nm/s, and film thickness is less than 10nm;
(3) in above-mentioned vacuum chamber, keep-up pressure constant, but on above-mentioned buffer layer thin film, continue the luminescent layer of evaporation individual layer transmission electronic, but the luminescent layer of transmission electronic is made up of luminous organic material;
(4) in above-mentioned vacuum chamber, keep-up pressure constantly, on above-mentioned luminescent layer, continue the second electrode lay of evaporated metal layer as device;
It is characterized in that also comprising the steps:
(5) post-processing step after (1) to (4) step makes device, adds a forward dc voltage to device, the electric current of device rises greatly and with voltage, and this moment, device was not luminous, after voltage reaches certain value, the electric current of device sharply descends suddenly, meanwhile device begins luminously, and post-processing step finishes, after the said method reprocessing, add forward voltage to device, the electric current of device reduces greatly, increases with voltage, and device brightness is along with increase.
7. the preparation method of single layer organic electroluminescent device as claimed in claim 6, it is characterized in that: described transparent conduction base sheet is an indium oxide tin glass.
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| WO2006125735A1 (en) * | 2005-05-23 | 2006-11-30 | Thomson Licensing | Light-emitting panel for illuminating or displaying images provided with a composite transparent upper electrode |
| CN100464834C (en) * | 2005-11-08 | 2009-03-04 | 华南师范大学 | Preparation method of organic nano-particle |
| CN105651737A (en) * | 2015-12-24 | 2016-06-08 | 江苏双仪光学器材有限公司 | Metal laminated medium sub-wavelength grating-based biological sensing chip |
| CN106803546A (en) * | 2017-02-20 | 2017-06-06 | 厦门世纳芯科技有限公司 | A kind of light emitting diode with quantum dots and preparation method thereof |
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