CN104078164B - A kind of preparation method of Cu nanowire network of Graphene carbon film parcel - Google Patents
A kind of preparation method of Cu nanowire network of Graphene carbon film parcel Download PDFInfo
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Abstract
A preparation method for the Cu nanowire network of Graphene carbon film parcel, relates to the preparation of metallic transparent membrane electrode.The preparation method of the Cu nanowire network of a kind of Graphene carbon film parcel of non-oxidizability and the photoelectric characteristic effectively can improving Cu nano wire electrode is provided.Make Cu nano wire membrane electrode; Low-temperature epitaxy Graphene on Cu paper tinsel; The vacuum fusing point of regulation and control Cu nano wire; Cu nano wire network wraps up Graphene carbon film.Copper Foil capsule is adopted to be sealed by sample, utilize the curing time of the strict Quality control of magnetic rod and the method in reaction time, Cu nano wire can be made under middle high-temperature to keep stable appearance, and the rapid cooling annealing in process completed after parcel Graphene carbon film, make Graphene carbon film be able to evenly be wrapped in the whole sidewall surfaces of Cu nano wire within effective time, form the package structure of coaxial type.
Description
Technical field
The present invention relates to the preparation of metallic transparent membrane electrode, particularly relate to the preparation method of the Cu nanowire network of a kind of Graphene carbon film parcel.
Background technology
Transparency electrode exists in the conductive layer of the equipment such as flat panel display, touch-screen, OLED, LED, smart window and solar cell to be applied widely.Traditional transparency electrode generally adopts ITO, AZO etc., and these electrode materials are often due to complex manufacturing technology, and condition is harsh and expensive.Along with the development of electronic technology, future will grow with each passing day to the demand of transparency conductive electrode.Further, because the flexible characteristic of people to device proposes certain requirement, researchers are made to start gradually to probe into some new materials, such as carbon nano-tube, Graphene etc.But the transparent conductive film that these materials are made generally has higher sheet resistance and light transmittance ratio, is not therefore also suitable for most practical application.In the recent period, it is found that metal nanometer line, such as Cu nano wire and Ag nano wire have excellent performance by the transparent conductive film that stamped method is formed, can be comparable with ITO.
In the stability study of Cu nano wire, it is found that it has good mechanical stability, bend more than the 1000 times still constant (A.R.Rathmelletal. of retention, Adv.Mater.23,4798 (2011)), but put and be easy to oxidation in atmosphere resistance is become large (H.Z.Guoetal., Sci.Rep.3,2323 (2013)).Thus the oxidizable problem of Cu nano wire needs solution badly.In order to reach antioxidant effect, some seminar attempts wrapping up Ni outside Cu nano wire, although wrap the Cu nano wire electrical stability after Ni and antioxygenic property gets a promotion, along with the concentration of the parcel of Ni raises, the resistance of Cu nano wire is also increasing.
Summary of the invention
Object of the present invention is intended to there is the problems such as oxidation for existing Cu nano wire, improves the preparation method of the Cu nanowire network of a kind of Graphene carbon film parcel of non-oxidizability and the photoelectric characteristic effectively can improving Cu nano wire electrode.
The present invention includes following steps:
1) Cu nano wire membrane electrode is made: the Cu nano wire ultrasonic disperse synthesized by chemical method is in n-hexane, by vacuum filtration, Cu nanowire deposition is formed film on nitrocellulose filter, the nitrocellulose filter depositing Cu nano wire film is covered in substrate;
2) low temperature (700 DEG C ± 30 DEG C) growing graphene on Cu paper tinsel: Cu paper tinsel folding is inserted quartz boat, then push CVD reaction chamber heating warm area, CVD reaction chamber internal gas pressure is vacuumized, then to the heating of quartz reaction chamber, passes into H
2, after carrying out the process of surperficial deoxidation compound, pass into H simultaneously
2and CH
4react, reaction terminates rear taking-up Cu paper tinsel, carries out light microscope and SEM test, can observe the Graphene thin layer of growth on Cu paper tinsel to Cu paper tinsel surface;
3) the vacuum fusing point of Cu nano wire is regulated and controled: the Si sheet being pressed with Cu nano wire is put into quartz boat, seal with Copper Foil capsule, push the low-temperature space of CVD reaction chamber again, vacuumize, when Heating Zone Temperature arrives 200 DEG C, sample is pushed the thermal treatment zone, carry out low-temperature setting, then pull out sample to low-temperature space, when hot zone temperature to be added continues to be increased to 400 ~ 900 DEG C, then sample is pushed thermal treatment zone reaction;
4) on Cu nano wire network, Graphene carbon film is wrapped up: when Heating Zone Temperature arrives 200 DEG C, sample is pushed the thermal treatment zone, carry out low-temperature setting, then sample is pulled out to low-temperature space, when temperature arrives 700 DEG C, then sample is pushed the thermal treatment zone, pass into CH simultaneously
4and H
2reaction, with at Cu nano wire surface parcel Graphene carbon film, after completion of the reaction, pulls out sample to low-temperature space, cooling annealing in process, namely at Cu nano wire surface parcel Graphene carbon film, obtains the Cu nanowire network of Graphene carbon film parcel.
In step 1) in, described making Cu nano wire membrane electrode can adopt suction filtration stamping technique to make Cu nano wire membrane electrode, concrete steps are: pass through Vacuum filtration device, the Cu nano wire be scattered in n-hexane solvent is deposited on filter membrane equably, apply pressure from the back side of filter membrane, Cu nano wire network thin-film is transferred in substrate; Described filter membrane can adopt Merlon miillpore filter, and the aperture of filter membrane can be 0.2 ~ 12 μm; Describedly execute the stressed time and can be 15 ~ 30s; Described substrate can adopt the one in Si sheet, sheet glass, PET sheet, polyimide film etc.
In step 2) in, described being vacuumized by CVD reaction chamber internal gas pressure can adopt mechanical pump and molecular pump that CVD reaction chamber internal gas pressure is evacuated to 10
-3about torr; Described heating can adopt diamond heating; The time of described surperficial deoxidation compound process can be 10 ~ 15min; Describedly pass into H simultaneously
2and CH
4in H
2can be 2 ~ 5sccm, CH
4can be 20 ~ 60sccm; The temperature of described reaction can be 600 ~ 1000 DEG C, preferably 670 ~ 730 DEG C.
In step 3) in, described in push the low-temperature space of CVD reaction chamber temperature can be about 23 DEG C; Described vacuumizing can utilize mechanical pump and molecular pump that vacuum is evacuated to 9 × 10
-3below torr; The described thermal treatment zone that pushed by sample can adopt magnetic rod that sample is pushed the thermal treatment zone; The time of described low-temperature setting can be 15 ~ 20min; Described sample is pushed the thermal treatment zone reaction can adopt magnetic rod sample is pushed the thermal treatment zone reaction; After sample being pushed thermal treatment zone reaction, the Cu nano wire that can be observed Copper Foil capsule encapsulation process the highlyest can still keep insoluble and not reunite at 700 DEG C ± 30 DEG C, coincide with graphene growth temperature.
In step 4) in, the described thermal treatment zone that pushed by sample can adopt magnetic rod that sample is pushed the thermal treatment zone; The time of described low-temperature setting can be 15 ~ 20min; The described thermal treatment zone that pushed by sample again can adopt magnetic rod that sample is pushed the thermal treatment zone; The time of described reaction can be 5 ~ 10min.
Key of the present invention is: adopt Copper Foil capsule to be sealed by sample, and utilize the curing time of the strict Quality control of magnetic rod and the method in reaction time, Cu nano wire can be made under middle high-temperature to keep stable appearance, and the rapid cooling annealing in process completed after parcel Graphene carbon film, make Graphene carbon film be able to evenly be wrapped in the whole sidewall surfaces of Cu nano wire within effective time, form the package structure of coaxial type.The present invention, with low-pressure chemical vapor deposition method (LPCVD), grows Graphene at a lower temperature, and Graphene direct growth is wrapped in Cu nano wire surface, instead of is transferred on Cu nano wire network by existing Graphene.
In order to overcome the oxidation of Cu nano wire better, its conductive characteristic can be promoted further simultaneously, the present invention proposes that Carbon material (such as Graphene, carbon nano-tube) is replaced Ni and is wrapped on Cu nano wire, there is due to Graphene the advantages such as non-oxidizability, high conductivity, high-transmission rate simultaneously, significantly can promote the conductance property of metal nanometer line, obtain high-quality transparency conductive electrode.From application point, the opto-electronic device such as LED, solar cell is applied this Cu nano wire transparency electrode of having wrapped up Graphene, its light output, efficiency of light absorption can be improved, and then improve its external quantum efficiency, life-span and the job stability of LED can also be extended.
Accompanying drawing explanation
Fig. 1 is Cu nano wire membrane electrode stamping technique flow process.
Fig. 2 is the SEM figure of the Graphene grown on Cu paper tinsel at 1000 DEG C.
Fig. 3 is the SEM figure of the Graphene grown on Cu paper tinsel after optimizing at 700 DEG C.
Fig. 4 is the Copper Foil capsule realizing Cu nano wire Graphene carbon film parcel.
Fig. 5 is the reaction unit schematic diagram realizing Cu nano wire Graphene carbon film parcel
Fig. 6 passes into CH after optimizing at 700 DEG C
4and H
2reacted Cu nano wire SEM schemes.
Fig. 7 is that unreacted Cu nano wire SEM schemes.
Fig. 8 has been the Si substrate Raman spectrum of the sample of Graphene carbon film parcel.
Fig. 9 be Graphene carbon film parcel sample on the Raman spectrum of Cu nano wire, proves that carbon film can well be wrapped in Cu nano wire surperficial.
Embodiment
First, suction filtration stamping technique is adopted to make Cu nano wire membrane electrode.
1) get 50mgCu nano wire, be dispersed in 10ml n-hexane through sonic oscillation 20min, therefrom get 0.5ml, be diluted to 30ml with n-hexane, sonic oscillation 20min.Therefrom measure again in the container that 10ml solution drops on nitrocellulose filter.Utilize Vacuum filtration device (as shown in the first step in Fig. 1), open vacuum mechanical pump 3s, n-hexane solvent suction filtration is led to nitrocellulose filter, forms the uniform Cu nano wire film of certain humidity.This technical essential is, accurately must control concentration and the volume of solution, and accurately control the vacuum filtration time (volume of this time and solution is proportional), make Cu nano wire film still keep certain humidity after suction filtration, so that the impression of subsequent step is smooth.
2) uniform fold is had the filter membrane of Cu nano wire film, take off from suction filtration head, and placement dries 5s, as shown in second step in Fig. 1 in atmosphere.By drying the humidity of adjustment Cu nano wire film further to being applicable to impression.
3) by the filter membrane of Cu nano wire film moderate for humidity, face down is transferred to (as Si sheet) in target substrate, and utilize pouring weight to apply certain pressure (as shown in the 3rd step Fig. 1) from the back side simultaneously, Cu nano wire film and substrate surface good contact, keep impression about 15s, during this period solvent volatilize further limit do, slowly throw off filter membrane afterwards, Cu nano wire film can successfully be transferred in target substrate.
Then, low-temperature epitaxy Graphene on Cu paper tinsel.
In order to Graphene at proving 700 DEG C can be formed at Cu surface-borne, first 2cm × 2cmCu paper tinsel is made capsule form, keep Cu paper tinsel upper and lower surface not contact, put into quartz boat, push reaction chamber, first with mechanical pump, chamber internal gas pressure is evacuated to lower than 10
-2torr, then with molecular pump, air pressure is evacuated to lower than 10
-3about torr, then heats reaction chamber.H is passed into when temperature reaches 700 DEG C
2and CH
4reaction, reaction terminates rear taking-up Cu paper tinsel.SEM test is carried out respectively, as shown in Figures 2 and 3 on the Cu paper tinsel of the Graphene of growth at 1000 DEG C and 700 DEG C.Result proves at 700 DEG C, and Cu surface still can nucleation growing graphene crystal grain.
Then, the vacuum fusing point of Cu nano wire is regulated and controled.
1) use the method for Copper Foil capsule: the Si sheet being printed on Cu nano wire is placed in quartz boat, then by the Copper Foil capsule sealing of quartz boat surrounding, copper thickness is about 0.025mm, capsule sealing part adopts the sealing of clamp method.Capsule encapsulation process ensures that the upper surface of Si sample does not contact with Copper Foil capsule inner surface, and distance is probably about 2mm.As shown in Figure 4.Copper Foil capsule forms Cu atom atmosphere, contributes to the saturated vapor pressure improving Cu nano wire surface, raises its fusing point; Cu is to CH simultaneously
4pyrolysis there is certain catalytic action, can capsule CH be promoted
4decomposition efficiency.
2) method of magnetic rod is utilized: by tight for the Copper Foil capsule one end magnetic rod hook being pressed with Cu nano wire film Si sample, magnetic rod slowly pushed quartz ampoule reaction chamber, and makes Copper Foil capsule be in low-temperature space (about 23 DEG C) position.Cavity is used cushion rubber flange seal, start to vacuumize cavity, first adopt mechanical oil pump, reach 2 × 10 to vacuum degree
-2during Torr, open molecular pump, to low vacuum in 9 × 10
-3start during Torr to heat heating warm area.
3) when Heating Zone Temperature arrives 200 DEG C, utilize magnetic rod that sample is pushed the thermal treatment zone, carry out low-temperature setting 15 ~ 20min, pull out thereafter sample to low-temperature space.When hot zone temperature to be added continues to be increased to design temperature (as 700 DEG C), re-use magnetic rod and sample is pushed thermal treatment zone reaction.As shown in Figure 5, the rear end of bar is added with built-in strong magnet to magnetic rod structural representation, can utilize manual strong magnetic load push-pull, across quartzy vacuum chamber tube wall, control magnetic rod.Hold the magnetic rod that strong magnetic load push-pull slowly controls quartz ampoule inside, Copper Foil capsule is pushed to the thermal treatment zone (about 10min).After question response terminates, pull strong magnetic load push-pull by magnetic rod and Copper Foil capsule La Hui normal temperature district.Use magnetic rod can shorten the heating time of Cu nano wire in temperature-rise period, and accurately control high temperature heating time, very important for realization of the present invention.Cu nano wire after 700 DEG C of high-temperature heatings, as shown in Figure 6, contrast does not add the Cu nano wire before thermal response, and as shown in Figure 7, Cu nano wire form almost stands intact, and under this design temperature is described, Cu nanoscale wire structures is stablized.
4) method of low-temperature setting is used: pull out use the method for magnetic rod sample slowly to be pushed thermal treatment zone solidification 15min when Heating Zone Temperature reaches 200 DEG C after.Solidification can play two aspects, one, effectively welds the contact of Cu nano wire network, contributes to the conduction of Cu nano wire network; Its two, can carry out low-temperature setting process to Cu nano wire surface, first remove a small amount of n-hexane residual solvent and the chloride ion of adsorption, then surface C u atom is reformed at low temperatures, surface can become smooth and firm.
Finally, at Cu nano wire surface parcel Graphene carbon film.
Use and at high temperature pass into H simultaneously
2and CH
4method Graphene carbon film parcel is carried out to Cu nano wire network: when temperature reaches design temperature (700 DEG C), utilize magnetic rod to push reaction zone in Cu nano wire network sample, pass into 2sccmH simultaneously
2and 20sccmCH
4, CH
4enter Copper Foil capsule, issue estranged splitting, produce a large amount of C atom under the catalytic action of Copper Foil inner surface with high temperature, C atom dissolves and Cu nano wire surface, and forms Graphene carbon film, forms tight parcel to Cu nano wire.Pull out after reacting about 10min, now gas keeps the state of passing into, to protect the Graphene carbon film of parcel stablizing in temperature-fall period.H
2the oxide layer on Cu surface is removed in energy reduction, and this likely makes Cu nano wire more easily melt, but H
2be conducive to the growth of Graphene, so consider, only when 700 DEG C of growing graphenes by H
2with CH
4pass into simultaneously.
Above-mentioned sample is done Raman spectrum test respectively without the blank surface [Fig. 8] of nano wire and reacted sample [Fig. 9], found that at 1500cm
-1place occurs without any other peak position, as shown in Figure 8, illustrates that the growth response of Graphene or any carbon form does not occur substrate surface.And carry out the Cu nano wire network after Graphene carbon film encapsulation reaction, at 1580cm
-1place occur stronger Graphene C element be correlated with peak position occur, as shown in Figure 9.Illustrate that reacted Cu nano wire is stable and wrapped up Graphene carbon film.
The present invention utilizes low-pressure chemical vapor deposition method (LPCVD), and Cu nanowire network wraps up Graphene carbon film, effectively strengthens the antioxygenic property of Cu nanowire, to obtain excellent transparent electrode material.It is by adopting the technology of Copper Foil capsule and vacuum chamber operated by magnetic force bar, Graphene is grown at lower temperature 700 DEG C ± 30 DEG C, and improve the fusing point of Cu nanowire, make Cu nanowire keep stablizing physical property under middle high-temperature, thus realize the parcel of Graphene carbon film on Cu nanowire.Use the method effectively to overcome the oxidizable problem of Cu nanowire, and utilize the superior electrical characteristics of Graphene to improve the quality of Cu nanowire transparency electrode.
Claims (13)
1. a preparation method for the Cu nanowire network of Graphene carbon film parcel, is characterized in that comprising the following steps:
1) Cu nano wire membrane electrode is made: the Cu nano wire ultrasonic disperse synthesized by chemical method is in n-hexane, by vacuum filtration, Cu nanowire deposition is formed film on nitrocellulose filter, the nitrocellulose filter depositing Cu nano wire film is covered in substrate;
2) on Cu paper tinsel at temperature 700 DEG C ± 30 DEG C growing graphene: by Cu paper tinsel folding insert quartz boat, then push CVD reaction chamber heating warm area, CVD reaction chamber internal gas pressure is vacuumized, then to quartz reaction chamber heating, pass into H
2, after carrying out the process of surperficial deoxidation compound, pass into H simultaneously
2and CH
4react, reaction terminates rear taking-up Cu paper tinsel, carries out light microscope and SEM test, can observe the Graphene thin layer of growth on Cu paper tinsel to Cu paper tinsel surface;
3) the vacuum fusing point of Cu nano wire is regulated and controled: the Si sheet being pressed with Cu nano wire is put into quartz boat, seal with Copper Foil capsule, push the low-temperature space of CVD reaction chamber again, vacuumize, when Heating Zone Temperature arrives 200 DEG C, sample is pushed the thermal treatment zone, carry out low-temperature setting, then pull out sample to low-temperature space, when hot zone temperature to be added continues to be increased to 400 ~ 900 DEG C, then sample is pushed thermal treatment zone reaction;
4) on Cu nano wire network, Graphene carbon film is wrapped up: when Heating Zone Temperature arrives 200 DEG C, sample is pushed the thermal treatment zone, carry out low-temperature setting, then sample is pulled out to low-temperature space, when temperature arrives 700 DEG C, then sample is pushed the thermal treatment zone, pass into CH simultaneously
4and H
2reaction, with at Cu nano wire surface parcel Graphene carbon film, after completion of the reaction, pulls out sample to low-temperature space, cooling annealing in process, namely at Cu nano wire surface parcel Graphene carbon film, obtains the Cu nanowire network of Graphene carbon film parcel.
2. the preparation method of the Cu nanowire network of a kind of Graphene carbon film parcel as claimed in claim 1, it is characterized in that in step 1) in, described making Cu nano wire membrane electrode adopts suction filtration stamping technique to make Cu nano wire membrane electrode, concrete steps are: pass through Vacuum filtration device, the Cu nano wire be scattered in n-hexane solvent is deposited on filter membrane equably, apply pressure from the back side of filter membrane, Cu nano wire network thin-film is transferred in substrate.
3. the preparation method of the Cu nanowire network of a kind of Graphene carbon film parcel as claimed in claim 2, it is characterized in that described filter membrane adopts Merlon miillpore filter, the aperture of filter membrane is 0.2 ~ 12 μm; It is described that to execute the stressed time be 15 ~ 30s.
4. the preparation method of the Cu nanowire network of a kind of Graphene carbon film parcel as claimed in claim 1, is characterized in that in step 1) in, described substrate adopts the one in Si sheet, sheet glass, PET sheet, polyimide film.
5. the preparation method of the Cu nanowire network of a kind of Graphene carbon film parcel as claimed in claim 1, is characterized in that in step 2) in, described being vacuumized by CVD reaction chamber internal gas pressure adopts mechanical pump and molecular pump that CVD reaction chamber internal gas pressure is evacuated to 10
-3torr; Described heating adopts diamond heating.
6. the preparation method of the Cu nanowire network of a kind of Graphene carbon film parcel as claimed in claim 1, is characterized in that in step 2) in, the time of described surperficial deoxidation compound process is 10 ~ 15min; Describedly pass into H simultaneously
2and CH
4in H
2be 2 ~ 5sccm, CH
4be 20 ~ 60sccm; The temperature of described reaction is 600 ~ 1000 DEG C.
7. the preparation method of the Cu nanowire network of a kind of Graphene carbon film parcel as claimed in claim 6, is characterized in that the temperature of described reaction is 670 ~ 730 DEG C.
8. the preparation method of the Cu nanowire network of a kind of Graphene carbon film parcel as claimed in claim 1, is characterized in that in step 3) in, described in push the low-temperature space of CVD reaction chamber temperature be 23 DEG C; Described vacuumizing utilizes mechanical pump and molecular pump that vacuum is evacuated to 9 × 10
-3below torr.
9. the preparation method of the Cu nanowire network of a kind of Graphene carbon film parcel as claimed in claim 1, is characterized in that in step 3) in, the described thermal treatment zone that pushed by sample adopts magnetic rod that sample is pushed the thermal treatment zone.
10. the preparation method of the Cu nanowire network of a kind of Graphene carbon film parcel as claimed in claim 1, is characterized in that in step 3) in, the time of described low-temperature setting is 15 ~ 20min.
The preparation method of the 11. Cu nanowire networks of a kind of Graphene carbon film parcel as claimed in claim 1, is characterized in that in step 3) in, describedly sample is pushed thermal treatment zone reaction and adopt magnetic rod sample to be pushed thermal treatment zone reaction.
The preparation method of the 12. Cu nanowire networks of a kind of Graphene carbon film parcel as claimed in claim 1, is characterized in that in step 4) in, the described thermal treatment zone that pushed by sample adopts magnetic rod that sample is pushed the thermal treatment zone; The described thermal treatment zone that pushed by sample again adopts magnetic rod that sample is pushed the thermal treatment zone.
The preparation method of the 13. Cu nanowire networks of a kind of Graphene carbon film parcel as claimed in claim 1, is characterized in that in step 4) in, the time of described low-temperature setting is 15 ~ 20min; The time of described reaction is 5 ~ 10min.
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| CN104569052B (en) * | 2014-12-17 | 2017-02-22 | 东南大学 | Method for preparing graphene oxide sensor |
| CN104934108B (en) * | 2014-12-31 | 2017-07-21 | 重庆元石石墨烯技术开发有限责任公司 | Metal nanometer line-graphene portal structure composite and preparation method thereof |
| CN106205768B (en) * | 2015-01-13 | 2017-11-07 | 浙江大学 | The compound conductive material of a kind of graphene film and metal Nano structure and preparation method |
| CN104942455B (en) * | 2015-05-14 | 2017-02-22 | 西安交通大学 | Low-temperature self-welding method of carbon-coating copper nanowires |
| CN106006585B (en) * | 2016-05-19 | 2018-04-24 | 东南大学 | A kind of method using dimethyl silicone polymer fast transfer boron nitride pellicle |
| CN106521455B (en) * | 2016-09-21 | 2019-10-18 | 见嘉环境科技（苏州）有限公司 | The preparation method of single-layer graphene package copper nano-particle is grown on porous carbon materials |
| CN106654285B (en) * | 2016-11-18 | 2021-03-05 | 浙江大学 | Flexible current collector for lithium battery and preparation method thereof |
| CN106594678B (en) * | 2016-12-25 | 2019-03-05 | 厦门大学 | A kind of transparent membrane LED dimmer preparation method of metal nanometer line |
| CN109468612A (en) * | 2019-01-07 | 2019-03-15 | 中国科学院兰州化学物理研究所 | Mechanical toughening carbon-based solid composite lubricating film and its preparation method and application |
| CN110484893B (en) * | 2019-08-01 | 2020-09-04 | 厦门大学 | Preparation method of metal nanowire core-shell structure |
| CN110666158A (en) * | 2019-09-29 | 2020-01-10 | 深圳第三代半导体研究院 | Method for coating nano copper with graphene |
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