CN102881841A - Semiconductor photoelectric device using copper/graphene composite electrode as anode - Google Patents
Semiconductor photoelectric device using copper/graphene composite electrode as anode Download PDFInfo
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Abstract
The invention discloses a semiconductor photoelectric device using a copper/graphene composite electrode as an anode. A graphene film is grown on a copper foil by a chemical vapor deposition (CVD) method, and the obtained copper/graphene composite material is used as the anode of the semiconductor photoelectric device such as a top emitting organic light emitting diode (OLED), so that the process can be simplified, the light emitting efficiency of the device is improved, and the stability of the device is increased.
Description
Technical field
The present invention relates to semiconductor photoelectric device, be specifically related to anode material and the preparation thereof of semiconductor photoelectric device.
Background technology
In recent years, organic electroluminescent LED (OLED) is because the advantage such as its high brightness, low driving voltage, high-quantum efficiency and more and more get more and more people's extensive concerning and be applied to the demonstration field such as mobile phone.Usually, major applications is 2.5-3.5eV in the lumo energy of the organic material of OLED, and its HOMO energy level is 5-6eV.Thereby reach effectively the purpose of injecting electronics and hole in the organic material for the injection barrier that overcomes electrode and organic layer interface, negative electrode adopts the metal of low work function usually, and anode then adopts the material of high work function to cooperate.At present, tin indium oxide (ITO) is used as the anode material of OLED widely.Ito thin film has advantages of good conductivity (minimum 10 Ω/), the work function (4.8eV) that light transmittance is high and higher of reaching, but the shortcoming that also exists some to be difficult to overcome: phosphide element is rare on the earth, ITO is easily crisp and be difficult to be applied to flexible optoelectronic and learn, and the diffusion of indium in the organic layer of OLED is so that device stability reduction etc.In order to overcome above-mentioned shortcoming, people wish to search out a kind of anode material that can substitute ito thin film.The discovery of Graphene in 2004 provides a kind of new thinking to people.
Graphene is a kind of carbon atom monolayer material of two dimension, all has high light transmittance (can reach 97%) at visible light and infrared band, suitable work function (approximately 4.6eV), and have great carrier mobility, have great application potential in the optoelectronics field in future.2010, several seminar comprised our seminar in the world, realized Graphene is applied to OLED as anode material, but the efficient of device were all generally lower.As everyone knows, affect a series resistance that very important factor is device of efficient.In all large tracts of land graphene preparation methods, the square resistance of the Graphene that chemical gas-phase deposition method obtains is minimum, about hundreds of Ω/, and it compares still very high with ito thin film, must lose like this luminous efficiency of device.The people such as Han have adopted nitric acid and chlorogold solution that Graphene is carried out the P type and have mixed, minimum being down to about 30 Ω/ of square resistance of 4 layer graphenes of chemical vapor deposition acquisition, close with ito thin film, realized the end bright dipping light emission (Han TH et al.Nature Photon.6,105 (2012)) of greater efficiency.But also there are some shortcomings in this approach: at first, the chemical vapor deposition growing graphene carries out at catalytic metal substrate (such as copper, nickel etc.), in device fabrication processes, usually metal substrate need to be eroded, transfer on the target substrate by the wet method shifting process of complexity again, so not only cause the waste of catalytic metal, and whole technological process and difficulty are increased greatly; Secondly, shifting process and solute doping bring all can for the Graphene surface and stain, and cause the surface undulation degree to increase, and easily cause the electric leakage of OLED, reduce stability and the life-span of device; Again, top emission OLED is owing to having large aperture opening ratio, high-resolution and long-life, present main flow OLED, if Graphene is applied among the top emission OLED, usually need to be at the high metal of back side evaporation reflectivity of the target substrate of having Graphene, propagation loses in the target substrate owing to Multi reflection is limited in thereby therefore have quite a few light; At last, the heat that distributes of device work also might make the Graphene as anode be destroyed.
Summary of the invention
The object of the present invention is to provide a kind of anode material for semiconductor photoelectric device, the particularly anode material of organic electroluminescence device, with simplification of flowsheet, improve the light extraction efficiency of device, increase the stability of device.
The anode of semiconductor photoelectric device of the present invention is copper/graphene combination electrode, comprises Copper Foil and the graphene film that is grown on the Copper Foil.
Above-mentioned Copper Foil is the catalytic metal substrate that utilizes the chemical gas-phase deposition method growing graphene, also is the part of described combination electrode simultaneously.Usually, the thickness of described Copper Foil is 10 microns～100 microns, the single or multiple lift of chemical vapor deposition growth thereon Graphene, and the two consists of the composite anode of photoelectric device simultaneously.
Copper/graphene combination electrode of the present invention can be applicable to semiconductor photoelectric device and comprises the aspects such as organic electroluminescent LED, solar cell and Organic Electricity memory device, for example as the anode of top radiation organic EL diode, and for example as anode of organic solar batteries etc.
Copper/graphene combination electrode of the present invention utilizes the chemical gas-phase deposition method growing graphene and makes at Copper Foil, and concrete preparation method comprises the steps:
1) Copper Foil is cleaned up, then vacuumize under the protection of hydrogen Copper Foil is carried out annealing in process;
2) pass into methane and hydrogen, at pressure 0.4 ~ 0.6Torr, under the condition that temperature is 950 ~ 1000 ℃, then growing graphene is cooled to room temperature to desired thickness on the Copper Foil after step 1) is processed.
Above-mentioned steps 1) uses successively acetone, ethanol, deionized water ultrasonic cleaning Copper Foil, then vacuumize, pass into 10 ~ 20SCCM hydrogen, keep pressure 0.1 ~ 0.3Torr, in 30 ~ 60 minutes, rise to 950 ~ 1000 ℃, cycle annealing 20 ~ 30 minutes.
Above-mentioned steps 2) pass into 20 ~ 30SCCM methane and 10 ~ 20SCCM hydrogen, keep pressure at 0.4 ~ 0.6Torr, 950 ~ 1000 ℃ of temperature kept 20 ~ 30 minutes, and obtaining growing on the Copper Foil has the combination electrode material of Graphene.
At present, the main method for preparing in the world the Graphene of large-area high-quality is chemical vapor deposition.And the catalytic substrate material of the chemical vapor deposition metal such as nickel, copper normally.Especially the low copper of carbon atom solubility is used to the even high-quality Graphene of growing large-area especially widely.The present invention adopts the way of chemical vapor deposition to prepare metallic copper/graphene combination electrode, and is applied to the anode of the photoelectric devices such as OLED, organic solar batteries.At first, the series resistance that it can the decrease device, and do not need the method for mixing by to Graphene.Secondly, it can avoid the shortcoming of conventional Graphene anode effectively: the first, and metallic copper/graphene combination electrode has been avoided the shifting process of Graphene as anode material, simplified greatly technological process and avoided the waste of catalytic metal; The second, owing to not needing shifting process and to the solute doping of Graphene, can realize that zero stains, increased the stability of device; The 3rd, copper itself is a kind of preferably reflective metals, be applied to push up emission OLED and be conducive to improve the light extraction efficiency of top emission, and copper/Graphene composite anode can effectively be avoided the propagation loss of light in the target substrate (such as glass) that the transfer Graphene arrives; The 4th, copper is fabulous heat dissipation conductor, can help the heat radiation of device.
Description of drawings
Fig. 1 is the structural representation that OLED is launched on embodiment 1 prepared top.
Fig. 2 is the current efficiency-voltage relationship figure of the prepared OLED take copper/graphene combination electrode as anode of embodiment 1 and ITO comparative device.
Fig. 3 is the power efficiency-voltage relationship figure of the prepared OLED take copper/graphene combination electrode as anode of embodiment 1 and ITO comparative device.
Embodiment
The present invention is described in further detail by the following examples, its to scope of the present invention without any restriction.Those skilled in the art may find apparent realization other substitute technology means of the present invention for them under Spirit Essence of the present invention instructs, all should think that these substitute technology means are included in the scope of the present invention.
By the OLED of following step preparation take copper/graphene combination electrode as anode:
1, chemical gas-phase deposition method prepares copper/graphene combination electrode
(1) preparation of samples: with 100 microns Copper Foils (1cm * 1cm) with acetone, ethanol, deionized water ultrasonic cleaning, put into the tube furnace flat-temperature zone.Be evacuated to about 0.01Torr.
(2) heat up: pass into the hydrogen of 20SCCM in tube furnace, pressure is stabilized in 0.3Torr.Set the temperature control program, in 60 minutes, rise to 1000 ℃.
(3) cycle annealing: kept 30 minutes at 1000 ℃ of constant temperature.
(4) Graphene growth: pass into 25SCCM methane and 12SCCM hydrogen, keep the interior pressure of stove about 0.5Torr, kept 30 minutes.
(5) cooling: the flow of keeping methane and hydrogen is constant, and body of heater is down to room temperature with 50 ℃/minute.
2, the little Molecule OLEDs preparation take copper/graphene combination electrode as anode
(1) copper/graphene combination electrode is put into the OLED evaporated device, be evacuated to 5.0 * 10
-4Below the Pa.
(2) evaporation deposition V successively on copper/graphene combination electrode
2O
5, NPB, Alq
3: C545T, Alq
3, Bphen:Cs
2CO
3Deng organic material.Evaporation rate is controlled at 0.1nm/s.
(3) add mask plate, evaporate successively Sm, Au as semitransparent cathode.
The structural representation of the OLED of said method preparation as shown in Figure 1, take ITO as anode material, the OLED of preparation same structure is device as a comparison, after testing, this copper/graphene combination electrode is that the luminous efficiency (maximum current efficient 6.1cd/A and maximum power efficiency 7.6lm/W) of the OLED of anode is that the luminous efficiency of OLED of anode is high than Graphene obviously, and has surpassed the comparative device (the highest 3.0cd/A and 5.1lm/W) (seeing Fig. 2 and Fig. 3) of ITO.
Claims (9)
1. a semiconductor photoelectric device is characterized in that, its anode is copper/graphene combination electrode, and this combination electrode comprises Copper Foil and the graphene film that is grown on the Copper Foil.
2. semiconductor photoelectric device as claimed in claim 1 is characterized in that, described semiconductor photoelectric device is organic electroluminescent LED.
3. semiconductor photoelectric device as claimed in claim 1 or 2 is characterized in that, the thickness of described Copper Foil is 10 microns ~ 100 microns.
4. semiconductor photoelectric device as claimed in claim 1 or 2 is characterized in that, described graphene film is to be grown in single or multiple lift Graphene on the described Copper Foil by chemical gas-phase deposition method.
5. the preparation method of the described semiconductor photoelectric device of claim 1, utilize chemical gas-phase deposition method growing graphene film at Copper Foil, then the composite material that forms with this Copper Foil and graphene film is finished the making of whole device as the anode of semiconductor photoelectric device.
6. preparation method as claimed in claim 5 is characterized in that, described semiconductor photoelectric device is organic electroluminescent LED.
7. the preparation method shown in claim 5 or 6 is characterized in that, the preparation process of wherein said anode is as follows:
1) Copper Foil is cleaned up, then vacuumize, under the protection of hydrogen, Copper Foil is carried out annealing in process;
2) pass into methane and hydrogen, at pressure 0.4 ~ 0.6Torr, under the condition that temperature is 950 ~ 1000 ℃, then growing graphene is cooled to room temperature to desired thickness on the Copper Foil after step 1) is processed.
8. preparation method as claimed in claim 7, it is characterized in that, described step 1) is used acetone, ethanol, deionized water ultrasonic cleaning Copper Foil successively, then vacuumize, pass into 10 ~ 20SCCM hydrogen, keep pressure 0.1 ~ 0.3Torr, in 30 ~ 60 minutes, rise to 950 ~ 1000 ℃, cycle annealing 20 ~ 30 minutes.
9. preparation method as claimed in claim 7 is characterized in that, described step 2) pass into 20 ~ 30SCCM methane and 10 ~ 20SCCM hydrogen, keep pressure about 0.4 ~ 0.6Torr, 950 ~ 1000 ℃ of temperature kept 20 ~ 30 minutes.
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Cited By (7)
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| CN103280541A (en) * | 2013-05-23 | 2013-09-04 | 北京工业大学 | Process method for preparing soft element and soft substrate on CVD (chemical vapor deposition) graphene |
| CN103343328A (en) * | 2013-07-10 | 2013-10-09 | 合肥微晶材料科技有限公司 | Method for synthesizing graphene under positive pressure condition |
| CN103943654A (en) * | 2014-03-05 | 2014-07-23 | 上海天马有机发光显示技术有限公司 | OLED array substrate, manufacturing method thereof, display panel and display device |
| CN105529410A (en) * | 2016-01-31 | 2016-04-27 | 南京邮电大学 | Manufacturing method of grapheme organic electroluminescent device |
| CN108321212A (en) * | 2017-12-21 | 2018-07-24 | 秦皇岛京河科学技术研究院有限公司 | The preparation method and its structure of SiC Schottky diode |
| CN108321080A (en) * | 2017-12-21 | 2018-07-24 | 秦皇岛京河科学技术研究院有限公司 | The preparation method and its structure of the SiC MOSFET elements of high reliability |
| CN108321213A (en) * | 2017-12-21 | 2018-07-24 | 秦皇岛京河科学技术研究院有限公司 | The preparation method and its structure of SiC power diode devices |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103280541A (en) * | 2013-05-23 | 2013-09-04 | 北京工业大学 | Process method for preparing soft element and soft substrate on CVD (chemical vapor deposition) graphene |
| CN103280541B (en) * | 2013-05-23 | 2016-02-17 | 北京工业大学 | A kind of process preparing flexible device and flexible substrate on CVD Graphene |
| CN103343328A (en) * | 2013-07-10 | 2013-10-09 | 合肥微晶材料科技有限公司 | Method for synthesizing graphene under positive pressure condition |
| CN103943654A (en) * | 2014-03-05 | 2014-07-23 | 上海天马有机发光显示技术有限公司 | OLED array substrate, manufacturing method thereof, display panel and display device |
| CN103943654B (en) * | 2014-03-05 | 2017-02-01 | 上海天马有机发光显示技术有限公司 | OLED array substrate, manufacturing method thereof, display panel and display device |
| CN105529410A (en) * | 2016-01-31 | 2016-04-27 | 南京邮电大学 | Manufacturing method of grapheme organic electroluminescent device |
| CN105529410B (en) * | 2016-01-31 | 2017-05-17 | 南京邮电大学 | Manufacturing method of grapheme organic electroluminescent device |
| CN108321212A (en) * | 2017-12-21 | 2018-07-24 | 秦皇岛京河科学技术研究院有限公司 | The preparation method and its structure of SiC Schottky diode |
| CN108321080A (en) * | 2017-12-21 | 2018-07-24 | 秦皇岛京河科学技术研究院有限公司 | The preparation method and its structure of the SiC MOSFET elements of high reliability |
| CN108321213A (en) * | 2017-12-21 | 2018-07-24 | 秦皇岛京河科学技术研究院有限公司 | The preparation method and its structure of SiC power diode devices |
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