CN108198937A - A kind of graphene/fullerene/graphene all-carbon molecular device construction method - Google Patents
A kind of graphene/fullerene/graphene all-carbon molecular device construction method Download PDFInfo
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- CN108198937A CN108198937A CN201711461783.3A CN201711461783A CN108198937A CN 108198937 A CN108198937 A CN 108198937A CN 201711461783 A CN201711461783 A CN 201711461783A CN 108198937 A CN108198937 A CN 108198937A
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- H—ELECTRICITY
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- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/671—Organic radiation-sensitive molecular electronic devices
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/20—Carbon compounds, e.g. carbon nanotubes or fullerenes
- H10K85/211—Fullerenes, e.g. C60
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Abstract
The invention discloses a kind of graphene/fullerene/graphene all-carbon molecular device construction methods, include the following steps：1) MCBJ components are built, including two Graphene electrodes and liquid pool, described two Graphene electrodes are located in liquid pool；2) it draws fullerene molecule solution to add in liquid pool, Graphene electrodes is made to be immersed in the molecular solution；3) apply certain bias at electrode both ends, start the bending of top rod driving chip, generate graphene/fullerene/graphene all-carbon molecular device.The method of the present invention can successfully build graphene/fullerene/graphene all-carbon molecular device.
Description
Technical field
Invention is related to carbon based electron, full carbon molecules device and unimolecule electrical measurement technology.
Background technology
Electronics miniaturization is the trend of era development.Moore's Law is predicted：Every 18 of integrated circuit number on chip
The moon will double.The diminution for increasing the size for implying electronic device of integrated circuit number.But current silicon-based electronic device
Part miniaturization has tended to material and physics limit, carbon-based including zero dimension fullerene, one-dimensional carbon nanotube, two-dimensional graphene
Nano material is considered as to replace the optimal selection of silicon-based semiconductor.At the same time, two-dimensional graphene/one-dimensional carbon nanotube is compound
C-based nanomaterial is also because the good physical-chemical characteristic shown not available for single individual receives researcher
Extensive concern.Graphene/carbon nanotube composite material can be divided into two class of rich graphene hydridization and rich carbon nano-tube hybridization.Rich graphite
Alkene hydridization shows as the structure that carbon nanotube is horizontally or vertically distributed in large-area graphene piece interlayer, and carbon nanotube effectively inhibits
Graphene stacked in multi-layers phenomenon occurs, and increases empty quantity, which goes out compared to single graphene or carbon
The nanotube more preferably properties such as conduction, heat conduction, hydrogen storage.Rich carbon nano-tube hybridization shows as small pieces layer graphene and carbon nanotube
Internal layer or the structure that is connected of layer structure, small pieces layer graphene increase catalytic group, which can be used as good
Oxidation reduction catalyst.Graphene/carbon nanotube composite material synthetic technology is further ripe in recent years, and is successfully applied to energy
The fields such as storage, electrochemical sensor, photoelectric device.
Another member's fullerene of c-based nanomaterial family has excellent physico such as superconduction, high pressure resistant, ferromagnetism
Performance is learned, the molecular device based on fullerene also shows rectification behavior, negative differential resistance effect (Negative
Differential Resistance Effect, NDR) etc. unique physical phenomenon.Compared with carbon nanotube, fullerene has
The advantages such as zero-fault and stable structure, while the synthetic technologys of the full carbon molecules of a variety of caged is continued to optimize, to design dissimilarity
The providing more choices property of nano molecular device of energy.And graphene is expected to, by synergistic effect, construct electronics with fullerene
Transmission channel effectively reduces the low conductivity that graphene crystal boundary and imperfect tape come, two-dimensional graphene/zero dimension fulvene compounding material
Excellent physical and chemical performance is expected to have, but is still at present blank in this important directions research work.
Therefore, two-dimensional graphene/zero dimension fullerene composite nano materials are constructed, and is studied and is advanced to unimolecule ruler
Degree pushes carbon based electron and the further development of full carbon molecules device by great.
Invention content
It is an object of the invention to realize the structure in the full carbon molecules device of unimolecule scale two-dimensional graphene/zero dimension fullerene
It builds, this will be helpful to the full carbon molecules device physics chemical property of study two-dimensional graphene/zero dimension fullerene, contribute to full carbon electronics
The further development learned.
Technical scheme is as follows：
A kind of graphene/fullerene/graphene all-carbon molecular device construction method, includes the following steps：
1) MCBJ components are built, including two Graphene electrodes and liquid pool, described two Graphene electrodes are located at
In liquid pool；
2) it draws fullerene molecule solution to add in liquid pool, Graphene electrodes is made to be immersed in the molecular solution；
3) apply certain bias at electrode both ends, start the bending of top rod driving chip, generate graphene/fullerene/graphite
The full carbon molecules device of alkene.
In the present invention, in step 2), the solvent of fullerene molecule solution includes n-decane, n-hexane, hexamethylene, heptan
At least one of alkane, octane, isooctane.
In the present invention, the concentration range of fullerene molecule solution is preferably 0.01-0.1mg/ml.
In the present invention, the bias range is preferably 0.01-1.00V.
Present invention uses Mechanical controllables associated with a kind of stepper motor and piezoelectric ceramics to split knot (Mechanically
Controllable Break Junction, MCBJ) technology.At present, the molecular structure building method packet of unimolecule scale in the world
It includes scanning tunneling microscope and splits knot (Scanning Tunneling Microscope Break Junction, STM-BJ) technology
With MCBJ technologies.STM-BJ technologies are transformed using existing STM instruments, and costly, and the molecule knot constructed is easy for cost
It is influenced by extraneous vibration.In comparison, MCBJ can reach 10 based on its experimental principle3Attenuation coefficient (attenuation coefficient
It is defined as ratio of the mandril displacement distance with the electrode that it causes to displacement distance), i.e. the displacement of piezoelectric ceramics nanoscale,
Accurate control of the Graphene electrodes to micromicron grade scale displacement is can obtain, greatly reduces interference of the extraneous vibration to molecule knot,
The full carbon molecules device that can be achieved to stablize and repeat is constructed.
MCBJ technologies of the present invention use Graphene electrodes chip.Common graphene synthetic method includes oxygen reduction
Graphite, chemical vapor deposition (Chemical Vapor Deposition, CVD) method, wherein reduction-oxidation graphite method are grown
Graphene often with the shortcomings of defective larger, the number of plies is more, and CVD growth method can effectively solve the problems, such as these.The present invention
Using the graphene that CVD method is grown as electrode.
In the present invention, Graphene electrodes chip is installed in the MCBJ devices of 3 stress, with screw by chip two
End is fixed on MCBJ pedestals, and mandril is located at the underface at chip midpoint, and the motive force that mandril is moved upwardly or downwardly generation can
Realize chip bending, mandril is made of piezoelectric ceramics and stepper motor, and the step pitch of stepper motor is in micron dimension, and piezoelectric ceramics
Step pitch up to nanometer scale, but movement speed is slower.Fullerene solution is added dropwise in the liquid pool above chip, and in graphite
Alkene electrode both ends apply certain bias.When starting, the mandril of beneath chips is downward by the effect of stepper motor driving force
It is mobile, substrate is driven to be bent downwardly, driving Graphene electrodes form nano gap to side stretching inside, and two electrodes are to production
Raw tunnel electric current, the movement of mandril, which is converted to by piezoelectric ceramics, at this time controls.When Tunneling conductance reaches the setting upper limit 10-3G0(G0
For quantum conductance, equal to 2e2/ h, about 77.6 μ S), mandril converting motion direction moves up, and electrode constantly becomes larger to gap,
Tunnelling current also reduces therewith, and when electrode increases to gap the distance to match with fullerene molecule, Graphene electrodes are to logical
The active force for crossing π-π stacking captures fullerene molecule, constructs graphene/fullerene/graphene molecules knot, instrument is shown at this time
The conductance signal shown is to be summed it up by the conductance of molecule knot and Tunneling conductance, but predominantly molecule junction conduction determines, conductance-away from
From showing apparent step in single curve.Mandril continues to move up, the fracture of molecule knot, and tunnelling current is moved to less than instrument on mandril
Device detection limit is hereinafter, constantly repeat the above process so that graphene/fullerene/graphene molecules knot is connected and is broken repeatedly.
In addition, scheme proposed by the invention can carry out under the normal temperature and pressure conditions of Experiment of General Chemistry room, have good
Universality.
Description of the drawings
The invention will be further described with reference to the accompanying drawings and examples.
Fig. 1 is the MCBJ device positive structure diagrams of the embodiment of the present invention.
Fig. 2 is the MCBJ device overlooking the structure diagrams of the embodiment of the present invention.
Fig. 3 is the Graphene electrodes chip positive structure diagram of the embodiment of the present invention.
Fig. 4 is the Graphene electrodes chip overlooking the structure diagram of the embodiment of the present invention.
Fig. 5 is the structure diagram of the full carbon molecules device of the embodiment of the present invention.
Fig. 6 is the one-dimensional conductance statistical chart of graphene/fullerene/graphene all-carbon molecular device of the embodiment of the present invention.
In figure：Graphene chip 1；Liquid pool 2；Fixture 3；Pedestal 4；Stainless steel base 5；Resin 6；Graphene copper wire 7.
Specific embodiment
Following embodiment will the present invention is further illustrated with reference to attached drawing.
Embodiment 1MCBJ devices are built.
Referring to the CN201710461800.7 of Fig. 1 to Fig. 4 and applicant's earlier application, " one kind is used to controllably split knot skill
The Graphene electrodes chip of art " is incorporated herein by the part of the present invention.
1st, Graphene electrodes chip is prepared
Using long 30mm, width 10mm, thickness 0.2mm flexible stainless steel substrates as substrate, polished with sand paper, ring increased with this
Oxygen resin then is cleaned by ultrasonic using ethyl alcohol, ultra-pure water clean, is placed in 105 DEG C of baking ovens drying successively in the frictional force of substrate surface.
Weigh 9 catalyst of a certain amount of Stycast 2850FT types resin and Henkel Loctite Catalyst, resin and catalysis
Agent quality proportioning is 3.5%~4.0% (in the present embodiment, for 3.5%), uniform stirring 10min makes it react completely.It takes
A small amount of epoxy resin uniformly smears a circle in stainless steel substrates center line side about 1.0-1.5mm.It is a diameter of 22mm will to be about
One end bending camber of 0.3mm graphene copper wires.After epoxy resin slightly cures, the graphene copper wire of bending is positioned over
Epoxy resin center, is pressed lightly on tweezers, and epoxy resin is made to submerge graphene copper wire.The chip places 12h under room temperature
Curing.
Said chip is positioned on probe platform, blend compounds band fixes chip both sides, another doubling is bent
Graphene copper wire be fixed on the syringe needle of probe station, two graphene copper wire tip spacing are adjusted to using probe station and microscope
About 20 μm.Graphene copper wire is fixed on chip with the epoxy resin handled well.It is taken after curing about 12h on probe platform
Under, graphene chip is purged totally with small flow nitrogen.
2nd, liquid pool is cleaned
Liquid pool is impregnated with the Piranha washing lotion of the ︰ 3 of double oxygen water ︰ concentrated sulfuric acids=1, the Piranha outwelled after a few hours in beaker is molten
Liquid is rinsed repeatedly with ultra-pure water, is reused ultra-pure water heating and is boiled, repeats ultrapure water boiling part three times, be finally putting into
It is dried in 105 DEG C of baking ovens.
3rd, chip and liquid pool
Piezoelectric ceramics and fixture are fixed with screw first, then graphene chip is installed on above fixture, fixture and core
Piece distance is about 1.0~1.5mm.
Liquid pool is the apertured plate member that material is polytetrafluoroethylene (PTFE), and liquid pool bottom carries the groove to match with sealing ring.With
Tweezers press lightly on so that sealing ring is fixed on liquid pool, and the liquid pool with sealing ring is installed on above Graphene electrodes, use
Screw fixes liquid pool.The graphene copper wire that both sides are not covered with epoxy on chip is pierced by from liquid pool preformed hole, is used
Graphene copper wire is connect by crocodile clip with external circuit.Liquid pool and fixture are fixed with screw again.
Embodiment 2
Graphene/C60/ graphene all-carbon molecular devices are constructed, and carry out Electric transport properties characterization using MCBJ devices.
1st, molecular solution is configured
Take 0.05mg C60Molecule is placed in 2.5mL solvent bottles, and 1000 μ L n-decanes (Decane) are taken with 1000 μ L liquid-transfering guns
Solvent is dissolved in solvent bottle, and is made it completely dissolved with vortex oscillator.
2nd, molecular solution is added dropwise
Experimental group：20 μ L fullerene molecules solution are drawn with 100 μ L liquid-transfering guns to add in liquid pool, submerge Graphene electrodes
In molecular solution.
Blank group：20 μ L n-decanes are drawn with 100 μ L liquid-transfering guns to add in liquid pool, and Graphene electrodes is made to be immersed in the positive last of the ten Heavenly stems
Alkane.
6th, data acquire
After installing, apply certain bias (in the present embodiment, being 0.1V) at electrode both ends, start top rod driving core
Piece is bent, during mandril pumps, the formation and fracture of graphene/fullerene/graphene molecules knot repeatedly,
During this, electrical signal is acquired by externally measured circuit.
7. data process＆analysis
The data of acquisition are handled by big data, drafting obtains one-dimensional conductance statistical chart and two-dimentional conductance-distance statistics
Figure, the one-dimensional conductance statistical chart of experimental group is in the detectable range (logG/G of conductance0=-5.5~-3.5) occur in apparent
Conductance peak, two-dimentional conductance-distance statistics figure shows noticeable steps, and blank group occurs without conductance peak and conductance step, shows
Successfully construct graphene/C60/ graphene molecules device, and show excellent electronic transport performance.
The present invention has versatility, constructs different fullerene molecules and graphene composite material molecular device, it is only necessary to replace
Fullerene molecule solution.
Claims (8)
1. a kind of graphene/fullerene/graphene all-carbon molecular device construction method, includes the following steps：
1) MCBJ components are built, including two Graphene electrodes and liquid pool, described two Graphene electrodes are located at liquid pool
It is interior or below the liquid pool；
2) it draws fullerene molecule solution to add in liquid pool, Graphene electrodes is made to be immersed in the molecular solution；
3) apply certain bias at electrode both ends, start the bending of top rod driving chip, generation graphene/fullerene/graphene is complete
Carbon molecules device；The mandril of beneath chips is moved down by the effect of stepper motor driving force, and substrate is driven to be bent downwardly, and is driven
Dynamic Graphene electrodes form nano gap to side stretching inside, movement of two electrodes to generation tunnel electric current, at this time mandril
Conversion is extremely controlled by piezoelectric ceramics；When Tunneling conductance reaches the setting upper limit, mandril converting motion direction moves up, between electrode pair
Gap constantly becomes larger, and tunnelling current also reduces therewith, when electrode increases to gap in the distance to match with fullerene molecule, graphite
Alkene electrode constructs graphene/fullerene/graphene molecules knot to capturing fullerene molecule.
2. a kind of graphene/fullerene/graphene all-carbon molecular device construction method according to claim 1, feature
It is：In step 1), the MCBJ components have the mandril being made of piezoelectric ceramics and stepper motor.
3. a kind of graphene/fullerene/graphene all-carbon molecular device construction method according to claim 1, feature
It is：In step 1), the Graphene electrodes are using the graphene of CVD method growth as electrode.
4. a kind of graphene/fullerene/graphene all-carbon molecular device construction method according to claim 1, feature
It is：In step 2), the concentration range of fullerene molecule solution is 0.01-0.1mg/ml.
5. a kind of graphene/fullerene/graphene all-carbon molecular device construction method according to claim 1, feature
It is：In step 2), the solvent of fullerene molecule solution is included in n-decane, n-hexane, hexamethylene, heptane, octane, isooctane
At least one.
6. a kind of graphene/fullerene/graphene all-carbon molecular device construction method according to claim 1, feature
It is：In step 3), the bias range is 0.01-1.00V.
7. a kind of graphene/fullerene/graphene all-carbon molecular device construction method according to claim 1, feature
It is：The setting upper limit of the Tunneling conductance is 10-3G0。
8. a kind of graphene/fullerene/graphene all-carbon molecular device construction method according to claim 1, feature
It is：After step 3), mandril continues to move up, the fracture of molecule knot, tunnelling current is moved on mandril less than instrument detection limit hereinafter,
It constantly repeats the above process so that graphene/fullerene/graphene molecules knot is connected and is broken repeatedly.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115196626A (en) * | 2021-04-01 | 2022-10-18 | 格拉弗尔工业有限责任公司 | Columnar carbon and graphene plate lattice composite material |
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