CN103924194A - Conductive thin film, preparation method and application thereof - Google Patents
Conductive thin film, preparation method and application thereof Download PDFInfo
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- CN103924194A CN103924194A CN201310008603.1A CN201310008603A CN103924194A CN 103924194 A CN103924194 A CN 103924194A CN 201310008603 A CN201310008603 A CN 201310008603A CN 103924194 A CN103924194 A CN 103924194A
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Abstract
A conductive thin film including a silver layer and a tungsten trioxide layer which are arranged in a manner of lamination. The silver layer and the tungsten trioxide layer are in nanowire structures. The conductive thin film has a high light-transmittance and a low electrical resistance. The thin film is manufactured into an integration of nanowires. Compared with a common transparent conductive thin film, the thin film increases light extraction efficiency of an organic electroluminescent device. The conductive thin film is prepared in a manner of depositing the tungsten trioxide layer onto the surface of the silver layer to form a double-layer conductive thin film. The thin film is high in surface work function, can reduce a starting voltage of a device and improve luminous efficiency of the device. The invention also provides a preparation method and an application of the conductive thin film.
Description
Technical field
The present invention relates to photoelectric semiconductor material, particularly relate to conductive film, its preparation method, use substrate, its preparation method and the organic electroluminescence device of the organic electroluminescence device of this conductive film.
Background technology
Conductive film electrode is the basic component of organic electroluminescence device (OLED), and the quality of its performance directly affects the luminous efficiency of whole device.Wherein, transparent conductive film is optical clear performance and conductivity to be compounded in to the photoelectric material of one, because it has excellent photoelectric characteristic, become study hotspot and advanced subject in recent years, can be widely used in solar cell, LED, TFT, the screen display fields such as LCD and touch-screen.The raising requiring along with device performance, also improves requiring for the performance of the nesa coating as device anode.For the needs of device light extraction efficiency, a lot of research institutions are all managing to insert scattering layer between anode and substrate.
High performance device, also requires anode to have higher surface work function, and the energy level of itself and other functional layer is matched, and reduces potential barrier, improves Carrier Injection Efficiency, finally reaches high electrical efficiency.
Summary of the invention
Based on this, be necessary conductive film, its preparation method that provides a kind of work function higher, the substrate that uses the organic electroluminescence device of this conductive film, its preparation method and organic electroluminescence device.
A conductive film, comprises stacked silver layer and tungstic oxide layer, and wherein, described silver layer and tungstic oxide layer are nano thread structure, and the nanowire diameter of described silver layer is 50nm～500nm, and the nanowire diameter of described tungstic oxide layer is 8nm～80nm.
In an embodiment, the thickness of described silver layer is 30nm ~ 400nm therein, and the thickness of described tungstic oxide layer is 6nm ~ 70nm.
A preparation method for conductive film, comprises the following steps:
Substrate, by acid treatment, then with acetone and ethanol ultrasonic cleaning, after oven dry is put into described substrate to the silica tube of tube furnace;
The vacuum tightness that the silica tube of tube furnace is set is 10
2pa ~ 10
3pa, temperature is 350 ℃ ~ 700 ℃, then in the silica tube of tube furnace, passes into rare gas element, the flow velocity of described rare gas element is 50cm
3/ min～180cm
3/ min;
First silver powder is placed in boat, described boat is placed in the silica tube of tube furnace; The evaporation time of described silver powder is 10 minutes～40 minutes, at described substrate surface, forms silver layer, stops silver layer described in evaporation;
Then anhydrous wolframic acid powder is placed in boat, described boat is placed in the silica tube of tube furnace; The evaporation time of anhydrous wolframic acid powder is 3 minutes～20 minutes, at described silver layer surface, forms described tungstic oxide layer, stops tungstic oxide layer described in evaporation, continues to pass into rare gas element cool to room temperature; And
Peel off described substrate, obtain described stacked silver layer and tungstic oxide layer conductive film.
In an embodiment, described silver layer and tungstic oxide layer are nano thread structure therein, and the nanowire diameter of described silver layer is 50nm～500nm, and the nanowire diameter of tungstic oxide layer is 8nm～80nm.
In an embodiment, the thickness of described silver layer is 30nm ~ 400nm therein, and the thickness of described tungstic oxide layer is 6nm ~ 70nm.
A kind of substrate of organic electroluminescence device, comprise the substrate, silver layer and the tungstic oxide layer that stack gradually, wherein, described silver layer and tungstic oxide layer are nano thread structure, the nanowire diameter of described silver layer is 50nm～500nm, and the nanowire diameter of tungstic oxide layer is 8nm～80nm.
In an embodiment, the thickness of described silver layer is 30nm ~ 400nm therein, and the thickness of described tungstic oxide layer is 6nm ~ 70nm.
A preparation method for the substrate of organic electroluminescence device, comprises the following steps:
Substrate, by acid treatment, is then used to acetone and ethanol ultrasonic cleaning, after oven dry, described substrate is put into the silica tube of tube furnace;
The vacuum tightness that the silica tube of tube furnace is set is 10
2pa ~ 10
3pa, temperature is 350 ℃ ~ 700 ℃, then in the silica tube of tube furnace, passes into rare gas element, the flow velocity of described rare gas element is 50cm
3/ min～180cm
3/ min;
First silver powder is placed in boat, described boat is placed in the silica tube of tube furnace; The evaporation time of described silver powder is 10 minutes～40 minutes, at described substrate surface, forms silver layer, stops silver layer described in evaporation;
Then tungstic oxide is placed in boat, described boat is placed in the silica tube of tube furnace; The evaporation time of tungsten trioxide powder is 3 minutes～20 minutes, at described silver layer surface, forms described tungstic oxide layer, stops tungstic oxide layer described in evaporation, continues to pass into rare gas element cool to room temperature.
Therein in an embodiment, described silver layer and tungstic oxide layer are nano thread structure, and the nanowire diameter of described silver layer is 50nm～500nm, and the nanowire diameter of tungstic oxide layer is 8nm～80nm, the thickness of described silver layer is 30nm ~ 400nm, and the thickness of described tungstic oxide layer is 6nm ~ 70nm.
A kind of organic electroluminescence device, comprise the anode, luminescent layer and the negative electrode that stack gradually, described anode comprises substrate, silver layer and the tungstic oxide layer stacking gradually, wherein, described silver layer and tungstic oxide layer are nano thread structure, the nanowire diameter of described silver layer is 50nm～500nm, and the nanowire diameter of tungstic oxide layer is 8nm～80nm.
Above-mentioned conductive film is prepared double-deck conductive film by the surface deposition WO 3 film at silver layer, conductive film is made the set of nano wire, there is higher surface work function, can guarantee high printing opacity again, the light extraction efficiency that is conducive to device improves, conductive film is at the long scope visible light transmissivity 88% ~ 90% of 470 ~ 790nm, square resistance scope 15 ~ 85 Ω/, surface work function 4.8 ~ 5.1eV; The preparation method of above-mentioned conductive film, adopts the mode of hot evaporation to prepare silver layer and tungstic oxide layer, and technique is low compared with cost, easily operation and the high advantage of repetition rate; Use this conductive film as the anode of organic electroluminescence device, between the surface work function of conductive film and the HOMO energy level of general organic luminous layer, gap is less, has reduced the injection barrier of current carrier, can improve significantly luminous efficiency.
Accompanying drawing explanation
Fig. 1 is the structural representation of the conductive film of an embodiment;
Fig. 2 is the structural representation of substrate of the organic electroluminescence device of an embodiment;
Fig. 3 is the structural representation of the organic electroluminescence device of an embodiment;
Fig. 4 is the equipment schematic diagram of the method for the present invention's hot evaporation of preparing conductive film and electrically-conductive backing plate;
Fig. 5 is the transmitted light spectrogram of the conductive film of embodiment 1 preparation;
Fig. 6 is the electron-microscope scanning figure of the conductive film of embodiment 1 preparation;
Fig. 7 is the electroluminescent device of embodiment 1 preparation and brightness and the voltage curve of comparative example comparison.
Embodiment
Below in conjunction with the drawings and specific embodiments, conductive film, its preparation method, the substrate that uses the organic electroluminescence device of this conductive film, its preparation method and organic electroluminescence device are further illustrated.
Refer to Fig. 1, the conductive film 100 of an embodiment comprises stacked silver layer 30 and tungstic oxide layer 10.
Silver layer 30 is nano thread structure, and silver layer 30 nanowire diameter are 50nm～500nm.
The thickness of silver layer 30 is 30nm ~ 400nm, is preferably 200nm.
Tungstic oxide layer 10 is nano thread structure, and tungstic oxide layer 10 nanowire diameter are 8nm～80nm.
The thickness of tungstic oxide layer 10 is 6nm ~ 70nm, is preferably 35nm.
Above-mentioned conductive film 100 is by the double-deck conductive film of surface deposition tungstic oxide layer 10 film preparation at silver layer 30, the double-deck conductive film of preparation can keep good conductivity like this, make again the work function of conductive film 100 obtain significant raising, conductive film 100 is at 470 ~ 790nm wavelength region visible light transmissivity 88% ~ 90%, square resistance scope 15 Ω/ ~ 85 Ω/, surface work function 4.8eV ~ 5.1eV.
The preparation method of above-mentioned conductive film 100, comprises the following steps:
S110, by substrate by acid treatment, then with acetone and ethanol ultrasonic cleaning, after oven dry, described substrate is put into the silica tube of tube furnace;
The vacuum tightness that tube furnace is set is 10
2pa ~ 10
3pa, temperature is 350 ℃ ~ 700 ℃, then in the silica tube of tube furnace, passes into rare gas element, the flow velocity of described rare gas element is 50cm
3/ min～180cm
3/ min;
Substrate is glass substrate;
Rare gas element comprises nitrogen, helium and argon gas.
In present embodiment, the vacuum tightness of vacuum cavity is preferably 3 * 10
2pa.
Step S120, first silver powder is placed in boat, described boat is placed in the silica tube of tube furnace; The evaporation time of described silver powder is 10 minutes～40 minutes, at described substrate surface, forms silver layer, stops silver layer described in evaporation.
Preferably, silver layer 30 is nano thread structure, and silver layer 30 nanowire diameter are 50nm～500nm.
The thickness of silver layer 30 is 30nm ~ 400nm, is preferably 200nm.
Step S130, then tungstic oxide is placed in boat, described boat is placed in the silica tube of tube furnace; The evaporation time of tungsten trioxide powder is 3 minutes～20 minutes, at described silver layer surface, forms described tungstic oxide layer, stops tungstic oxide layer described in evaporation, continues to pass into rare gas element cool to room temperature.
Preferably, tungstic oxide layer 10 is nano thread structure, and tungstic oxide layer 10 nanowire diameter are 8nm～80nm.
The thickness of tungstic oxide layer 10 is 6nm ~ 70nm, is preferably 35nm.
Step S140, peel off described substrate, obtain described stacked silver layer 30 and tungstic oxide layer 10 conductive film 100.
The preparation method of above-mentioned conductive film, adopts the mode of hot evaporation to prepare silver layer 30 and tungstic oxide layer 10, and technique is low compared with cost, and easily operation and repetition rate are high.
Refer to Fig. 2, the substrate 200 of the organic electroluminescence device of an embodiment, comprises stacked substrate 201, silver layer 202 and tungstic oxide layer 203.
Substrate 201 is glass substrate;
Rare gas element comprises nitrogen, helium and argon gas.
Silver layer 30 is nano thread structure, and silver layer 30 nanowire diameter are 50nm～500nm.
The thickness of silver layer 30 is 30nm ~ 400nm, is preferably 200nm.
Tungstic oxide layer 10 is nano thread structure, and tungstic oxide layer 10 nanowire diameter are 8nm～80nm.
The thickness of tungstic oxide layer 10 is 6nm ~ 70nm, is preferably 35nm.
The substrate 200 of above-mentioned organic electroluminescence device, by the surface deposition tungstic oxide layer 203 at silver layer 202, can keep good conductivity, makes again the work function of the substrate 200 of organic electroluminescence device obtain significant raising.
The preparation method of the substrate 200 of above-mentioned organic electroluminescence device, comprises the following steps:
S210, by substrate by acid treatment, then with acetone and ethanol ultrasonic cleaning, after oven dry, described substrate is put into the silica tube of tube furnace;
The vacuum tightness that the silica tube of tube furnace is set is 10
2pa ~ 10
3pa, temperature is 350 ℃ ~ 700 ℃, then in the silica tube of tube furnace, passes into rare gas element, the flow velocity of described rare gas element is 50cm
3/ min～180cm
3/ min;
Substrate is glass substrate;
Rare gas element comprises nitrogen, helium and argon gas.
In present embodiment, the vacuum tightness of vacuum cavity is preferably 3 * 10
2pa.
Step S220, first silver powder is placed in boat, described boat is placed in the silica tube of tube furnace; The evaporation time of described silver powder is 10 minutes～40 minutes, at described substrate surface, forms silver layer, stops silver layer described in evaporation.
Preferably, silver layer 30 is nano thread structure, and silver layer 30 nanowire diameter are 50nm～500nm.
The thickness of silver layer 30 is 30nm ~ 400nm, is preferably 200nm.
Step S230, then tungstic oxide is placed in boat, described boat is placed in the silica tube of tube furnace; The evaporation time of tungsten trioxide powder is 3 minutes～20 minutes, at described silver layer surface, forms described tungstic oxide layer, stops tungstic oxide layer described in evaporation, continues to pass into rare gas element cool to room temperature.
Preferably, tungstic oxide layer 10 is nano thread structure, and tungstic oxide layer 10 nanowire diameter are 8nm～80nm.
The thickness of tungstic oxide layer 10 is 6nm ~ 70nm, is preferably 35nm.
The preparation method of the substrate 200 of above-mentioned organic electroluminescence device, adopts the mode of hot evaporation to prepare silver layer 202 and tungstic oxide layer 203, and technique is low compared with cost, and easily operation and repetition rate are high.
Refer to Fig. 3, the organic electroluminescence device 300 of an embodiment comprises substrate 301, anode 302, luminescent layer 303 and the negative electrode 304 stacking gradually.
Anode 302 is made by conductive film 100, comprise the silver layer 30 and the tungstic oxide layer 10 that stack gradually, wherein, described silver layer and tungstic oxide layer are nano thread structure, the nanowire diameter of described silver layer is 50nm～500nm, and the nanowire diameter of described tungstic oxide layer is 8nm～80nm.
Substrate 301 is glass substrate, is appreciated that, according to the difference of organic electroluminescence device 300 concrete structures, substrate 301 can omit.Luminescent layer 303 materials are Alq
3and the material of negative electrode 304 is silver, gold, aluminium, platinum and magnalium etc.
The thickness of silver layer is 30nm ~ 400nm, and preferred, the thickness of silver layer is 200nm, and the thickness of described tungstic oxide layer is 6nm ~ 70nm, and preferred, the thickness of tungstic oxide layer is 35nm.
Be appreciated that above-mentioned organic electroluminescence device 300 also can arrange other functional layers according to user demand.
Above-mentioned organic electroluminescence device 300, use conductive film 100 as the anode of organic electroluminescence device, surface work function 4.8 ~ the 5.1eV of conductive film, and between the HOMO energy level (being typically 5.7～6.3eV) of general organic luminous layer, gap is less, reduce the injection barrier of current carrier, can improve luminous efficiency.
Fig. 4 is the equipment schematic diagram of the method for the present invention's hot evaporation of preparing above-mentioned conductive film and electrically-conductive backing plate, comprise gas output device 430, the silica tube 410 of tube furnace, be arranged on the resistance wire 420 of the silica tube indirect heating of tube furnace, mode is at boat 440 and the substrate 450 of silica tube 410 inside of tube furnace, the pore space structure 452 forming by acid corrosion on the surface of described substrate 450, the method of this hot evaporation adopts substrate 450 and boat 440 is placed in same level, by gas output device 430 input rare gas elementes, under vacuum high-pressure condition, evaporation source is constantly evaporated, because having coarse pore space structure 452, substrate surface can promote evaporation source to grow to equidirectional, and can not form film at substrate surface, and then formation nano thread structure.
Be specific embodiment below.
Embodiment 1
Substrate, by hydrofluoric acid treatment, then with acetone and ethanol ultrasonic cleaning, after oven dry is put into described substrate to the silica tube of tube furnace; The vacuum tightness that the silica tube of tube furnace is set is 3.0 * 10
2pa, temperature is 500 ℃, then in the silica tube of tube furnace, passes into argon gas, the flow velocity of argon gas is 120cm
3/ min; First silver powder is placed in boat, boat is placed in the silica tube of tube furnace; The evaporation time of silver powder is 25 minutes, at substrate surface, forms silver layer, stops silver layer described in evaporation; Then tungstic oxide is placed in boat, boat is placed in the silica tube of tube furnace; The evaporation time of tungsten trioxide powder is 10 minutes, at silver layer surface, form tungstic oxide layer, stop evaporation tungstic oxide layer, continue to pass into argon gas cool to room temperature and peel off described substrate, obtain stacked silver layer and tungstic oxide layer conductive film, the thickness of silver layer is 200nm, and the thickness of tungstic oxide layer is 35nm, conductive film is as the anode of organic semiconductor device, and luminescent layer adopts Alq
3, negative electrode adopts Ag.
Test result: adopt four point probe resistance meter to record square resistance scope 15 Ω/, surface work function tester records surface work function 5.1eV.
Refer to Fig. 5, Figure 5 shows that the transmitted spectrum of the transparent conductive film obtaining, use ultraviolet-visible pectrophotometer test, test wavelength is 300 ~ 800nm.Film average transmittances in visible ray 470nm ~ 790nm wavelength region has reached 90% as seen from Figure 5.
Refer to Fig. 6, Fig. 6 is the electron-microscope scanning figure of the conductive film of embodiment 1 preparation, the vertical substrates of nano wire growth as seen from the figure, and silver layer and tungstic oxide layer are nano thread structure, nanowire diameter 50nm～the 500nm of silver layer is main, and the nano wire 8nm～80nm of tungstic oxide layer is main.
Refer to Fig. 7, Fig. 7 is the electroluminescent device of embodiment 1 preparation and brightness and the voltage curve of comparative example comparison, curve 1 is membrane electro luminescent device voltage and the brightness relationship curve of embodiment 1 preparation as seen from Figure 7, curve 2 is membrane electro luminescent device voltage and brightness relationship curves prepared by comparative example, can find out: nanometer wire sample reduces from 5.5 to 5.0V the trigger voltage of device, and brightness improves from 450 to 600cd/m
2.
Comparative example
By acetone and ethanol ultrasonic cleaning for substrate, after oven dry, described substrate is put into vapor deposition apparatus; The vacuum tightness that vapor deposition apparatus is set is 3.0 * 10
2pa, temperature is 500 ℃, first silver powder is placed in boat, at substrate surface, forms indium layer, stops indium layer described in evaporation; Obtain silver layer conductive film, thickness is 200nm, then at silver layer surface evaporation tungstic oxide layer, the thickness of tungstic oxide layer is 35nm, obtains the double-deck conductive film of silver layer and tungstic oxide layer as the anode of organic semiconductor device, and luminescent layer adopts Alq
3, negative electrode adopts Ag.
Embodiment 2
Substrate, by hydrofluoric acid treatment, then with acetone and ethanol ultrasonic cleaning, after oven dry is put into described substrate to the silica tube of tube furnace; The vacuum tightness that the silica tube of tube furnace is set is 1.0 * 10
3pa, temperature is 500 ℃, then in the silica tube of tube furnace, passes into argon gas, the flow velocity of argon gas is 180cm
3/ min; First silver powder is placed in boat, boat is placed in the silica tube of tube furnace; The evaporation time of silver powder is 40 minutes, at substrate surface, forms silver layer, stops silver layer described in evaporation; Then tungstic oxide is placed in boat, boat is placed in the silica tube of tube furnace; The evaporation time of tungsten trioxide powder is 20 minutes, at silver layer surface, form tungstic oxide layer, stop evaporation tungstic oxide layer, at the bottom of continuing to pass into argon gas cool to room temperature peeling liner, obtain stacked silver layer and tungstic oxide layer conductive film, the thickness of silver layer is 30nm, and the thickness of tungstic oxide layer is 10nm, conductive film is as the anode of organic semiconductor device, and luminescent layer adopts Alq
3, negative electrode adopts Ag.
Test result: adopt four point probe resistance meter to record square resistance scope 85 Ω/, surface work function 5.0eV, the test of use ultraviolet-visible pectrophotometer, test wavelength is that 300 ~ 800nm film average transmittances in visible ray 470nm ~ 790nm wavelength region has reached 88%.
Embodiment 3
Substrate, by hydrofluoric acid treatment, then with acetone and ethanol ultrasonic cleaning, after oven dry is put into described substrate to the silica tube of tube furnace; The vacuum tightness that the silica tube of tube furnace is set is 1.0 * 10
2pa, temperature is 500 ℃, then in the silica tube of tube furnace, passes into nitrogen, the flow velocity of nitrogen is 50cm
3/ min; First silver powder is placed in boat, boat is placed in the silica tube of tube furnace; The evaporation time of silver powder is 10 minutes, at substrate surface, forms silver layer, stops silver layer described in evaporation; Then tungstic oxide is placed in boat, boat is placed in the silica tube of tube furnace; The evaporation time of tungsten trioxide powder is 3 minutes, at silver layer surface, form tungstic oxide layer, stop evaporation tungstic oxide layer, at the bottom of continuing to pass into nitrogen cool to room temperature peeling liner, obtain stacked silver layer and tungstic oxide layer conductive film, the thickness of silver layer is 400nm, and the thickness of tungstic oxide layer is 60nm, conductive film is as the anode of organic semiconductor device, and luminescent layer adopts Alq
3, negative electrode adopts Ag.
Test result: adopt four point probe resistance meter to record square resistance scope 37 Ω/, surface work function 4.8eV, the test of use ultraviolet-visible pectrophotometer, test wavelength is that 300 ~ 800nm film average transmittances in visible ray 470nm ~ 790nm wavelength region has reached 90%.
Embodiment 4
Substrate, by hydrofluoric acid treatment, then with acetone and ethanol ultrasonic cleaning, after oven dry is put into described substrate to the silica tube of tube furnace; The vacuum tightness that the silica tube of tube furnace is set is 7.0 * 10
2pa, temperature is 500 ℃, then in the silica tube of tube furnace, passes into nitrogen, the flow velocity of nitrogen is 120cm
3/ min; First silver powder is placed in boat, boat is placed in the silica tube of tube furnace; The evaporation time of silver powder is 30 minutes, at substrate surface, forms silver layer, stops silver layer described in evaporation; Then tungstic oxide is placed in boat, boat is placed in the silica tube of tube furnace; The evaporation time of tungsten trioxide powder is 7 minutes, at silver layer surface, form tungstic oxide layer, stop evaporation tungstic oxide layer, at the bottom of continuing to pass into nitrogen cool to room temperature peeling liner, obtain stacked silver layer and tungstic oxide layer conductive film, the thickness of silver layer is 300nm, and the thickness of tungstic oxide layer is 6nm, conductive film is as the anode of organic semiconductor device, and luminescent layer adopts Alq
3, negative electrode adopts Ag.
Test result: adopt four point probe resistance meter to record square resistance scope 75 Ω/, surface work function 4.9eV, the test of use ultraviolet-visible pectrophotometer, test wavelength is that 300 ~ 800nm film average transmittances in visible ray 470nm ~ 790nm wavelength region has reached 90%.
Embodiment 5
Substrate, by hydrofluoric acid treatment, then with acetone and ethanol ultrasonic cleaning, after oven dry is put into described substrate to the silica tube of tube furnace; The vacuum tightness that the silica tube of tube furnace is set is 2.0 * 10
2pa, temperature is 500 ℃, then in the silica tube of tube furnace, passes into nitrogen, the flow velocity of nitrogen is 70cm
3/ min; First silver powder is placed in boat, boat is placed in the silica tube of tube furnace; The evaporation time of silver powder is 35 minutes, at substrate surface, forms silver layer, stops silver layer described in evaporation; Then tungstic oxide is placed in boat, boat is placed in the silica tube of tube furnace; The evaporation time of tungsten trioxide powder is 15 minutes, at silver layer surface, form tungstic oxide layer, stop evaporation tungstic oxide layer, at the bottom of continuing to pass into nitrogen cool to room temperature peeling liner, obtain stacked silver layer and tungstic oxide layer conductive film, the thickness of silver layer is 350nm, and the thickness of tungstic oxide layer is 7nm, conductive film is as the anode of organic semiconductor device, and luminescent layer adopts Alq
3, negative electrode adopts Ag.
Test result: adopt four point probe resistance meter to record square resistance scope 42 Ω/, surface work function 5.0eV, the test of use ultraviolet-visible pectrophotometer, test wavelength is that 300 ~ 800nm film average transmittances in visible ray 470nm ~ 790nm wavelength region has reached 89%.
The above embodiment has only expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (10)
1. a conductive film, is characterized in that, described conductive film comprises stacked silver layer and tungstic oxide layer, wherein, described silver layer and tungstic oxide layer are nano thread structure, and the nanowire diameter of described silver layer is 50nm～500nm, and the nanowire diameter of described tungstic oxide layer is 8nm～80nm.
2. conductive film according to claim 1, is characterized in that, the thickness of described silver layer is 30nm ~ 400nm, and the thickness of described tungstic oxide layer is 6nm ~ 70nm.
3. a preparation method for conductive film, is characterized in that, comprises the following steps:
Substrate, by acid treatment, then with acetone and ethanol ultrasonic cleaning, after oven dry is put into described substrate to the silica tube of tube furnace;
The vacuum tightness that the silica tube of tube furnace is set is 10
2pa ~ 10
3pa, temperature is 350 ℃ ~ 700 ℃, then in the silica tube of tube furnace, passes into rare gas element, the flow velocity of described rare gas element is 50cm
3/ min～180cm
3/ min;
First silver powder is placed in boat, described boat is placed in the silica tube of tube furnace; The evaporation time of described silver powder is 10 minutes～40 minutes, at described substrate surface, forms silver layer, stops silver layer described in evaporation;
Then anhydrous wolframic acid powder is placed in boat, described boat is placed in the silica tube of tube furnace; The evaporation time of anhydrous wolframic acid powder is 3 minutes～20 minutes, at described silver layer surface, forms described tungstic oxide layer, stops tungstic oxide layer described in evaporation, continues to pass into rare gas element cool to room temperature; And
Peel off described substrate, obtain described stacked silver layer and tungstic oxide layer conductive film.
4. the preparation method of conductive film according to claim 3, is characterized in that, described silver layer and tungstic oxide layer are nano thread structure, and the nanowire diameter of described silver layer is 50nm～500nm, and the nanowire diameter of tungstic oxide layer is 8nm～80nm.
5. the preparation method of conductive film according to claim 3, is characterized in that, the thickness of described silver layer is 30nm ~ 400nm, and the thickness of described tungstic oxide layer is 6nm ~ 70nm.
6. the substrate of an organic electroluminescence device, it is characterized in that, comprise the substrate, silver layer and the tungstic oxide layer that stack gradually, wherein, described silver layer and tungstic oxide layer are nano thread structure, the nanowire diameter of described silver layer is 50nm～500nm, and the nanowire diameter of tungstic oxide layer is 8nm～80nm.
7. the substrate of organic electroluminescence device according to claim 6, is characterized in that, the thickness of described silver layer is 30nm ~ 400nm, and the thickness of described tungstic oxide layer is 6nm ~ 70nm.
8. a preparation method for the substrate of organic electroluminescence device, is characterized in that, comprises the following steps:
Substrate, by acid treatment, is then used to acetone and ethanol ultrasonic cleaning, after oven dry, described substrate is put into the silica tube of tube furnace;
The vacuum tightness that the silica tube of tube furnace is set is 10
2pa ~ 10
3pa, temperature is 350 ℃ ~ 700 ℃, then in the silica tube of tube furnace, passes into rare gas element, the flow velocity of described rare gas element is 50cm
3/ min～180cm
3/ min;
First silver powder is placed in boat, described boat is placed in the silica tube of tube furnace; The evaporation time of described silver powder is 10 minutes～40 minutes, at described substrate surface, forms silver layer, stops silver layer described in evaporation;
Then anhydrous wolframic acid powder is placed in boat, described boat is placed in the silica tube of tube furnace; The evaporation time of anhydrous wolframic acid powder is 3 minutes～20 minutes, at described silver layer surface, forms described tungstic oxide layer, stops tungstic oxide layer described in evaporation, continues to pass into rare gas element cool to room temperature.
9. the preparation method of the substrate of organic electroluminescence device according to claim 8, it is characterized in that, described silver layer and tungstic oxide layer are nano thread structure, the nanowire diameter of described silver layer is 50nm～500nm, the nanowire diameter of tungstic oxide layer is 8nm～80nm, the thickness of described silver layer is 30nm ~ 400nm, and the thickness of described tungstic oxide layer is 6nm ~ 70nm.
10. an organic electroluminescence device, comprise the anode, luminescent layer and the negative electrode that stack gradually, it is characterized in that, described anode comprises substrate, silver layer and the tungstic oxide layer stacking gradually, wherein, described silver layer and tungstic oxide layer are nano thread structure, and the nanowire diameter of described silver layer is 50nm～500nm, and the nanowire diameter of tungstic oxide layer is 8nm ~ 80nm.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016011794A1 (en) * | 2014-07-25 | 2016-01-28 | 京东方科技集团股份有限公司 | Transparent conductive electrode and preparation method therefor and oled display device |
| CN110517808A (en) * | 2019-08-05 | 2019-11-29 | 中国民用航空飞行学院 | A kind of composite conductive thin film and preparation method thereof based on silver nanowires |
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