CN104078164A - Manufacturing method of copper nano wire network wrapped by graphene carbon film - Google Patents
Manufacturing method of copper nano wire network wrapped by graphene carbon film Download PDFInfo
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Abstract
The invention relates to manufacturing of metal transparent film electrodes, in particular to a manufacturing method of a copper nano wire network wrapped by a graphene carbon film. According to the manufacturing method of the copper nano wire network wrapped by the graphene carbon film, oxidation resistance and the optical-electrical characteristic of copper nano wire electrodes can be effectively improved. The manufacturing method includes the steps that the copper nano wire film electrodes are manufactured; graphene is grown on copper foil at low temperature; the vacuum melting point of copper nano wires is regulated and controlled; the copper nano wire network is wrapped by the graphene carbon film. The sample is sealed through a copper foil capsule, by using the method of strictly controlling the curing time and the reaction time of the sample through a magnetic force rod, the profile of the copper nano wires at high temperature can be kept stable, rapid cooling and annealing treatment after the graphene carbon film is wrapped can be finished, and therefore the surfaces of the whole side walls of the copper nano wires can be evenly wrapped by the graphene carbon film within the effective time to form a coaxial wrapped structure.
Description
Technical field
The present invention relates to the preparation of metal transparent membrane electrode, particularly relate to a kind of preparation method of Cu nanowire network of Graphene carbon film parcel.
Background technology
In the conductive layer of the equipment such as flat panel display, touch-screen, OLED, LED, smart window and solar cell, there is application widely in transparency electrode.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, will grow with each passing day future to the demand of transparency conductive electrode.And, because people have proposed certain requirement to the flexible characteristic of device, make researchers 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, the transparent conductive film that for example Cu nano wire and Ag nano wire form by stamped method has excellent performance, can be comparable with ITO.
In the stability study of Cu nano wire, it is found that it has good mechanical stability, bend constant (the A.R.Rathmell et al. of retention still above 1000 times, Adv.Mater.23,4798 (2011)), but be placed on and in air, be easy to oxidation and make resistance become large (H.Z.Guo et al., Sci.Rep.3,2323 (2013)).Thereby the oxidizable problem of Cu nano wire is needed solution badly.In order to reach antioxidant effect, some seminar attempts at Cu nano wire coated outside Ni, although the Cu nano wire electrical stability and the antioxygenic property that wrap after Ni get 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 exist for existing Cu nano wire the problems such as oxidation, and raising can effectively improve the preparation method of the Cu nanowire network of the non-oxidizability of Cu nano wire electrode and a kind of Graphene carbon film parcel of photoelectric characteristic.
The present invention includes following steps:
1) make Cu nano wire membrane electrode: be dispersed in n-hexane ultrasonic Cu nano wire synthetic chemical method, by vacuum filtration, Cu nanowire deposition is formed to film on nitrocellulose filter, the nitrocellulose filter that deposits 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 to 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, pass into H
2, carry out, after surperficial deoxidation compound processing, passing into H simultaneously
2and CH
4react, reaction finishes rear taking-up Cu paper tinsel, and light microscope and SEM test are carried out in Cu paper tinsel surface, can observe the Graphene thin layer being grown on Cu paper tinsel;
3) the vacuum fusing point of regulation and control Cu nano wire: the Si sheet that is pressed with Cu nano wire is put into quartz boat, seal with Copper Foil capsule, push again the low-temperature space of CVD reaction chamber, vacuumize, in the time that Heating Zone Temperature arrives 200 DEG C, sample is pushed to the thermal treatment zone, carry out low-temperature setting, then pull out sample to low-temperature space, when district to be heated temperature continues to be increased to 400～900 DEG C, then sample is pushed to thermal treatment zone reaction;
4) on Cu nano wire network, wrap up Graphene carbon film: in the time that Heating Zone Temperature arrives 200 DEG C, sample is pushed to the thermal treatment zone, carry out low-temperature setting, then pull out sample to low-temperature space, in the time that temperature arrives 700 DEG C, then sample is pushed to 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, and cooling annealing in process, 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: by vacuum filtration device, the Cu nano wire being scattered in n-hexane solvent is deposited on filter membrane equably, exert 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 μ m; The described time of exerting pressure can be 15～30s; Described substrate can adopt the one in Si sheet, sheet glass, PET plastic sheet, polyimide film etc.
In step 2) in, described CVD reaction chamber internal gas pressure is vacuumized and can adopt mechanical pump and molecular pump that CVD reaction chamber internal gas pressure is evacuated to 10
-3torr left and right; Described heating can adopt diamond heating; The time of described surperficial deoxidation compound processing can be 10～15min; The described H that simultaneously passes into
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 23 DEG C of left and right; Described vacuumizing can utilize mechanical pump and molecular pump that vacuum is evacuated to 9 × 10
-3below torr; Describedly sample is pushed to the thermal treatment zone can adopt magnetic rod that sample is pushed to the thermal treatment zone; The time of described low-temperature setting can be 15～20min; Describedly sample is pushed to thermal treatment zone reaction can adopt magnetic rod that sample is pushed to thermal treatment zone reaction; Sample is pushed after the reaction of the thermal treatment zone, and the Cu nano wire that can be observed Copper Foil capsule encapsulation process can the highlyest still keep insoluble and not reunite at 700 DEG C ± 30 DEG C, coincide with Graphene growth temperature.
In step 4) in, describedly sample is pushed to the thermal treatment zone can adopt magnetic rod that sample is pushed to the thermal treatment zone; The time of described low-temperature setting can be 15～20min; The described thermal treatment zone that again sample pushed can adopt magnetic rod that sample is pushed to the thermal treatment zone; The time of described reaction can be 5～10min.
Key of the present invention is: adopt Copper Foil capsule that sample is sealed, and utilize the method in curing time and the reaction time of the strict Quality control of magnetic rod, can make Cu nano wire keep stable appearance under middle high-temperature, and complete the rapid cooling annealing in process 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.Low-pressure chemical vapor deposition method for the present invention (LPCVD), grows Graphene at a lower temperature, and Graphene direct growth is wrapped in to Cu nano wire surface, instead of existing Graphene is transferred on Cu nano wire network.
In order to overcome better the oxidation of Cu nano wire, can further promote its conductive characteristic simultaneously, the present invention proposes that Carbon material (such as Graphene, carbon nano-tube) is replaced to Ni and is wrapped on Cu nano wire, there is the advantages such as non-oxidizability, high conductivity, high-transmission rate due to Graphene simultaneously, the conductance property that can significantly promote metal nanometer line, obtains high-quality transparency conductive electrode.From application point, on the opto-electronic device such as LED, solar cell, apply this Cu nano wire transparency electrode of having wrapped up Graphene, can improve its light output, efficiency of light absorption, and then improve its external quantum efficiency, can also extend life-span and the job stability of LED.
Brief description of the drawings
Fig. 1 is Cu nano wire membrane electrode stamping technique flow process.
Fig. 2 is the SEM figure of the Graphene of growing on Cu paper tinsel at 1000 DEG C.
Fig. 3 is the SEM figure of the Graphene of growing on Cu paper tinsel after optimizing at 700 DEG C.
Fig. 4 is the Copper Foil capsule of realizing Cu nano wire Graphene carbon film parcel.
Fig. 5 is the reaction unit schematic diagram of 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 figure.
Fig. 7 is unreacted Cu nano wire SEM figure.
Fig. 8 has been the Si substrate Raman spectrum of the sample of Graphene carbon film parcel.
Fig. 9 has been the Raman spectrum of Cu nano wire on the sample of Graphene carbon film parcel, proves that carbon film can well be wrapped in Cu nano wire surface.
Embodiment
First, adopt suction filtration stamping technique to make Cu nano wire membrane electrode.
1) get 50mg Cu nano wire, be dispersed in 10ml n-hexane through sonic oscillation 20min, therefrom get 0.5ml, be diluted to 30ml, sonic oscillation 20min with n-hexane.Therefrom measuring 10ml solution drops in the container on nitrocellulose filter again.Utilize vacuum filtration device (as shown in the first step in Fig. 1), open vacuum mechanical pump 3s, by logical n-hexane solvent suction filtration nitrocellulose filter, form the uniform Cu nano wire film of certain humidity.This technical essential is, must accurately control concentration and the volume of solution, and accurately control the vacuum filtration time (volume of this time and solution is proportional), after suction filtration, make Cu nano wire film still keep certain humidity, so that the impression of subsequent step is smooth.
2) uniform fold is had to the filter membrane of Cu nano wire film, take off from suction filtration head, and place and dry 5s in air, as shown in second step in Fig. 1.Impress to applicable by the humidity of drying further adjustment Cu nano wire film.
3) by the filter membrane of Cu nano wire film moderate 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 15s left and right, the solvent limit of further volatilizing is dry during this period, slowly throws off afterwards filter membrane, and Cu nano wire film can successfully be transferred in target substrate.
Then, low-temperature epitaxy Graphene on Cu paper tinsel.
In order to prove at 700 DEG C the Graphene formation of can growing on Cu surface, first 2cm × 2cm Cu paper tinsel is made to 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 air pressure is evacuated to lower than 10 with molecular pump
-3torr left and right, then heats reaction chamber.In the time that reaching 700 DEG C, temperature passes into H
2and CH
4reaction, reaction finishes rear taking-up Cu paper tinsel.Respectively to carrying out SEM test on the Cu paper tinsel of the Graphene of growth at 1000 DEG C and 700 DEG C, as shown in Figures 2 and 3.Result proves at 700 DEG C, and Cu surface still can nucleation growing graphene crystal grain.
Then, the vacuum fusing point of regulation and control Cu nano wire.
1) method of utilization Copper Foil capsule: the Si sheet that is printed on Cu nano wire is placed in quartz boat, then by Copper Foil capsule sealing for quartz boat surrounding, the about 0.025mm of copper thickness, 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 2mm left and right.As shown in Figure 4.Copper Foil capsule forms Cu atom atmosphere, contributes to improve the saturated vapor pressure on Cu nano wire surface, and its fusing point raises; Cu is to CH simultaneously
4pyrolysis there is certain catalytic action, can promote capsule CH
4decomposition efficiency.
2) utilize the method for magnetic rod: by tight the Copper Foil capsule one end magnetic rod hook that is pressed with Cu nano wire film Si sample, magnetic rod is slowly pushed to quartz ampoule reaction chamber, and make Copper Foil capsule in low-temperature space (23 DEG C of left and right) position.By cavity cushion rubber flange seal, start cavity to vacuumize, first adopt mechanical oil pump, reach 2 × 10 to vacuum degree
-2when Torr, open molecular pump, to low vacuum in 9 × 10
-3when Torr, start heating warm area to heat.
3) in the time that Heating Zone Temperature arrives 200 DEG C, utilize magnetic rod that sample is pushed to the thermal treatment zone, carry out low-temperature setting 15～20min, pull out thereafter sample to low-temperature space.When district to be heated temperature continues to be increased to design temperature (as 700 DEG C), re-use magnetic rod sample is pushed to 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, controls magnetic rod.Hold strong magnetic load push-pull and slowly control the magnetic rod of quartz ampoule inside, Copper Foil capsule is pushed to the thermal treatment zone (approximately 10min).After question response finishes, 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 the 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 is almost excellent, and Cu nano wire Stability Analysis of Structures is described under this design temperature.
4) method of utilization low-temperature setting: use the method for magnetic rod that sample is slowly pushed after 15min is solidified in the thermal treatment zone and pulled out in the time that Heating Zone Temperature reaches 200 DEG C.Solidify and can play two aspects, one, welds the contact of Cu nano wire network effectively, contributes to the conduction of Cu nano wire network; Its two, can carry out low-temperature setting processing 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 reformed at low temperatures, it is smooth and firm that surface can become.
Finally, at Cu nano wire surface parcel Graphene carbon film.
Use and at high temperature pass into H simultaneously
2and CH
4method Cu nano wire network is carried out to Graphene carbon film parcel: in the time that temperature reaches design temperature (700 DEG C), utilize magnetic rod to push reaction zone in Cu nano wire network sample, pass into 2sccm H simultaneously
2with 20sccm CH
4, CH
4enter Copper Foil capsule, under the catalytic action of Copper Foil inner surface, issue estranged splitting with high temperature, produce a large amount of C atoms, C atom dissolves and Cu nano wire surface, and forms Graphene carbon film, and Cu nano wire is formed to tight parcel.After reacting about 10min, pull out, now gas keeps the state of passing into, to protect Graphene carbon film the stablizing in temperature-fall period of parcel.H
2can reduction remove the oxide layer on Cu surface, this likely makes Cu nano wire more easily melt, but H
2be conducive to the growth of Graphene, thus consider, only in the time of 700 DEG C of growing graphenes by H
2with CH
4pass into simultaneously.
Above-mentioned sample is done respectively to Raman spectrum test without blank surface [Fig. 8] and the reacted sample [Fig. 9] of nano wire, 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 occurs that the relevant peak position of stronger Graphene C element occurs, as shown in Figure 9.The stable Graphene carbon film that wrapped up of reacted Cu nano wire is described.
The present invention utilizes low-pressure chemical vapor deposition method (LPCVD), wraps up Graphene carbon film on Cu nanowire network, effectively strengthens the antioxygenic property of Cu nanowire, to obtain good transparent electrode material.It is by adopting the technology of Copper Foil capsule and vacuum chamber operated by magnetic force bar, at 700 DEG C ± 30 DEG C of lower temperatures, grow Graphene, and improve the fusing point of Cu nanowire, make Cu nanowire under middle high-temperature, keep stablizing physical property, thereby 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 characteristic of Graphene to improve the quality of Cu nanowire transparency electrode.
Claims (10)
1. a preparation method for the Cu nanowire network of Graphene carbon film parcel, is characterized in that comprising the following steps:
1) make Cu nano wire membrane electrode: be dispersed in n-hexane ultrasonic Cu nano wire synthetic chemical method, by vacuum filtration, Cu nanowire deposition is formed to film on nitrocellulose filter, the nitrocellulose filter that deposits 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 to 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, pass into H
2, carry out, after surperficial deoxidation compound processing, passing into H simultaneously
2and CH
4react, reaction finishes rear taking-up Cu paper tinsel, and light microscope and SEM test are carried out in Cu paper tinsel surface, can observe the Graphene thin layer being grown on Cu paper tinsel;
3) the vacuum fusing point of regulation and control Cu nano wire: the Si sheet that is pressed with Cu nano wire is put into quartz boat, seal with Copper Foil capsule, push again the low-temperature space of CVD reaction chamber, vacuumize, in the time that Heating Zone Temperature arrives 200 DEG C, sample is pushed to the thermal treatment zone, carry out low-temperature setting, then pull out sample to low-temperature space, when district to be heated temperature continues to be increased to 400～900 DEG C, then sample is pushed to thermal treatment zone reaction;
4) on Cu nano wire network, wrap up Graphene carbon film: in the time that Heating Zone Temperature arrives 200 DEG C, sample is pushed to the thermal treatment zone, carry out low-temperature setting, then pull out sample to low-temperature space, in the time that temperature arrives 700 DEG C, then sample is pushed to 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, and cooling annealing in process, 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 that a kind of Graphene carbon film wraps up 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: by vacuum filtration device, the Cu nano wire being scattered in n-hexane solvent is deposited on filter membrane equably, exert 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 that a kind of Graphene carbon film wraps up as claimed in claim 2, is characterized in that described filter membrane adopts Merlon miillpore filter, and the aperture of filter membrane can be 0.2～12 μ m; The described time of exerting pressure can be 15～30s.
4. the preparation method of the Cu nanowire network that a kind of Graphene carbon film wraps up as claimed in claim 1, is characterized in that in step 1) in, described substrate adopts the one in Si sheet, sheet glass, PET plastic sheet, polyimide film.
5. the preparation method of the Cu nanowire network that a kind of Graphene carbon film wraps up as claimed in claim 1, is characterized in that in step 2) in, described CVD reaction chamber internal gas pressure is vacuumized is to adopt mechanical pump and molecular pump that CVD reaction chamber internal gas pressure is evacuated to 10
-3torr; Described heating can adopt diamond heating.
6. the preparation method of the Cu nanowire network that a kind of Graphene carbon film wraps up as claimed in claim 1, is characterized in that in step 2) in, the time of described surperficial deoxidation compound processing is 10～15min; The described H that simultaneously passes into
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.
7. 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 can utilize mechanical pump and molecular pump that vacuum is evacuated to 9 × 10
-3below torr; Describedly sample is pushed to the thermal treatment zone can adopt magnetic rod that sample is pushed to the thermal treatment zone.
8. the preparation method of the Cu nanowire network that a kind of Graphene carbon film wraps up as claimed in claim 1, is characterized in that in step 3) in, the time of described low-temperature setting is 15～20min; Describedly sample is pushed to thermal treatment zone reaction can adopt magnetic rod that sample is pushed to thermal treatment zone reaction.
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 4) in, it is described that sample is pushed to the thermal treatment zone is to adopt magnetic rod that sample is pushed to the thermal treatment zone; The described thermal treatment zone that again sample pushed can adopt magnetic rod that sample is pushed to the thermal treatment zone.
10. the preparation method of the Cu nanowire network that a kind of Graphene carbon film wraps up 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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| CN106654285A (en) * | 2016-11-18 | 2017-05-10 | 浙江大学 | Flexible current collector for lithium battery and preparation method thereof |
| CN106594678A (en) * | 2016-12-25 | 2017-04-26 | 厦门大学 | Preparation method of transparent film LED light modulator of metal nanowire |
| 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 |
| CN110484893A (en) * | 2019-08-01 | 2019-11-22 | 厦门大学 | A kind of preparation method of metal nanometer line 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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