CN109748264A - A kind of method of preparing graphene at normal temperature flexible electrode - Google Patents
A kind of method of preparing graphene at normal temperature flexible electrode Download PDFInfo
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- CN109748264A CN109748264A CN201910071882.3A CN201910071882A CN109748264A CN 109748264 A CN109748264 A CN 109748264A CN 201910071882 A CN201910071882 A CN 201910071882A CN 109748264 A CN109748264 A CN 109748264A
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Abstract
The present invention relates to a kind of methods of preparing graphene at normal temperature flexible electrode, pattern needed for pasting in smooth substrate, and the certain thickness reducing material of magnetron sputtering in substrate, realize the method that in-situ reducing graphene oxide obtains particular graphite alkene flexible electrode film.In the present invention, pass through the exposure mask of electrode pattern needed for pasting, the reducing material of the reduced graphene of certain shapes is sputtered, and then obtain the Graphene electrodes film of specific shape, without being further cut into electrode shape, it can effectively ensure that the integrality of graphene film can also reduce the waste of raw material.Furthermore in the present invention, alternative target range is wide, and the film flatness sputtered is high, and the thickness of sputtered film is controllable, and thickness is controllable and uniform graphene film convenient for obtaining, convenient for directly being shifted with adhesive tape.
Description
Technical field
The present invention relates to a kind of methods of preparing graphene at normal temperature flexible electrode, needed for pasting specifically in smooth substrate
The pattern of electrode, and certain thickness reducing material is obtained in substrate by the methods of sputtering, evaporation, deposition, and further
The substrate room temperature is put into graphene oxide solution, and then realizes that in-situ reducing graphene oxide obtains patterned Graphene electricity
A kind of method of very thin films.
Background technique
With the improvement of living standards, people increasingly pay attention to guarding health, flexible electronic and wearable electronic device
Part has many advantages, such as that light and portable, comfort is good and timely feedbacks to get more and more people's extensive concerning due to it.Various flexible materials,
Such as metal nano material, conducting polymer, various carbon materials (carbon nanotube, graphene, natural biologic material) are
It is widely used in wearable electronic.Wherein carbon material due to conducting electricity very well, chemical thermal stability is high, inherent structure spirit
The features such as living, light-weight and friendly to the mankind is the ideal material of flexible wearable electronic device.
Nanoscale or micron-sized graphene film have good flexible and electric conductivity, can pass through between human skin
Van der Waals force forms good contact, and grapheme material has high conductivity, and noninvasive, real-time, comfortable monitoring may be implemented
The important vital signs of human body.In existing research, Graphene electrodes film can be prepared by chemical vapour deposition technique, but
It is at high cost, it is not easy to be mass produced, the graphene of growth such as needs to shift, is cut into corresponding pattern at multiple steps, increases
The cost of preparation, the yield for reducing product.
A kind of method that the present invention proposes directly preparation patterned Graphene electrodes film, without carrying out pattern-cut, and
And have many advantages, such as that reduction effect is good, electrical signal is high, prepare it is simple, at low cost, can mass production.
Summary of the invention
The purpose of the present invention is to provide a kind of room temperature that in-situ reducing graphene oxide prepares specific pattern to prepare graphite
The method of alkene flexible electrode.
Graphene preparation method provided by the invention, the advantage compared with other prepare the method for oxidation graphene film
Be: reducing material and preparation method range are wide, and can be by controlling the thickness of reducing material film, to effectively realize also
The control of former graphene oxide film thickness, this method have easy to operate, low in cost, safety non-pollution, high efficiency etc.
Advantage.
A kind of method of preparing graphene at normal temperature flexible electrode proposed by the present invention, the specific steps are as follows:
(1) substrate and glass container are cleaned, i.e., first sufficiently cleans substrate and glass container with acetone, then by substrate and glass
Container is respectively put into deionized water, by ultrasonic sufficiently cleaning, removes the impurity and inorganic pollution on their surfaces, then base
Bottom and glass container are respectively with being dried with nitrogen；
(2) taking finely dispersed concentration is that the graphene oxide solution of 0.1~5 mg/mL is added to the glass that step (1) obtains
In container；
(3) the hollow out exposure mask of required electrode shape is attached in substrate obtained by step (1)；
(4) since the connectivity between some metals and substrate is poor, in order to guarantee to restore obtained graphene film
One layer of adhesive layer is first formed on the substrate using sputtering method for integrality, then sputters redox graphene institute on it again
Material；
(5) it after step (4) sputtering is completed, puts it into rapidly in step (2) prepared graphene oxide solution, 50~
1~3 h is reacted in 100 DEG C of thermal station, obtains the Graphene electrodes grown in substrate surface；
(6) it takes out, uses from graphene oxide solution in the Graphene electrodes of substrate surface growth by what step (5) reaction was completed
Deionized water cleans the Graphene electrodes of growth several times, then the Graphene electrodes grown in substrate surface is immersed in extremely dilute
Hydrochloric acid in 10~30 min；
(7) product that step (6) obtains is cleaned several times with deionized water, removes the Graphene electrodes grown in substrate surface
Extremely dilute hydrochloric acid of surface adhesion is put into 50~80 DEG C of thermal station dry 10~30 min, patterned graphene can be obtained
Electrode.
In the present invention, the partial size of graphene oxide described in step (2) is 1~15 μm.
In the present invention, glass container used in step (1) is 100~250 mL.
In the present invention, substrate used in step (1) is the various materials for possessing flat surface such as silicon wafer or glass plate.
In the present invention, adhesive layer used in step (4) includes: any in chromium or titanium.
In the present invention, it includes: the high-purities such as copper, iron or nickel that material used in redox graphene is prepared in step (4)
Metal and other materials with reproducibility in it is any.
In the present invention, extremely dilute hydrochloric acid described in step (6), concentration is 1.0 × 10-9~1.0 × 10-4 mol/L。
The present invention has the advantages that compared with existing preparation Graphene electrodes film process
(1) in this method, alternative target range is wide, nearly all metal, alloy and with reproducibility other are solid
Body material, such as silicon etc., and obtained film flatness height is sputtered, convenient for obtaining graphene film in homogeneous thickness；
(2) this method can accurately control sputtering by parameters such as control sputtering power, sputtering time or inert gas flows
The thickness of film is conducive to control reduction and obtains the thickness of graphene film；
(3) this method can time by reduction and temperature, effectively control reduction obtains the thickness of graphene film；
(4) this method has been sputtered the thin of the reduced graphene of certain shapes by the exposure mask of electrode pattern needed for pasting
Membrane material, and then the Graphene electrodes film of specific shape is obtained, without being further cut into electrode shape；
(5) this method is not necessarily to large scale equipment, easy to operate, at low cost, without heating in reaction process, can carry out at room temperature
Reduction reaction, it is safer, high-efficient；
(6) graphene film thickness made from this method is moderate, convenient for directly being shifted with adhesive tape, and can effectively ensure that graphite
The integrality of alkene film.
Detailed description of the invention
Fig. 1 a is image mask used in the present invention, and Fig. 1 b is the net of the pierced pattern of specific shape provided by the invention
The structural schematic diagram of version.
Fig. 2 a and Fig. 2 b point are comparison diagrams before and after magnetron sputtering copper reduction graphene oxide on a silicon substrate.
Fig. 3 is magnetron sputtering copper on the surface of the obtained graphene sample of 0.5 mg/mL graphene oxide solution reductase 12 h
And the SEM figure in section, it is exterior view in Fig. 3 a, Fig. 3 b is sectional view.
Fig. 4 is the graphene that the graphene oxide used in embodiment 1 and magnetron sputtering copper reduction graphene oxide obtain
XPS spectrum figure, Fig. 4 a is the XPS of graphene oxide, the XPS for the graphene film that Fig. 4 b is.
Fig. 5 is to react 1h in embodiment 3 to obtain the human skin impedance under the different frequency that Graphene electrodes film is measured
Value.
Fig. 6 is to react 1h in embodiment 3 to obtain the human body electrocardio figure that Graphene electrodes film is measured.
Specific embodiment
Above scheme is described further below in conjunction with specific embodiment.It should be understood that these embodiments are for illustrating
The present invention and be not limited to limit the scope of the invention.Implementation condition used in the examples can be done according to the condition of specific producer
Further adjustment, the implementation condition being not specified is usually the condition in routine experiment.
Below with reference to embodiment, the present invention will be described in detail, it should be understood that citing described herein is only used to explain this
Invention, is not intended to limit the present invention.
Embodiment 1
(1) substrate and glass container are cleaned, i.e., first with the abundant cleaning silicon chip substrate of acetone and glass container, then by silicon wafer substrate
It is respectively put into deionized water with glass container, by ultrasonic sufficiently cleaning, removes the impurity and inorganic pollution on their surfaces
Afterwards, respectively with being dried with nitrogen；
(2) graphene oxide solution of finely dispersed 0.5 mg/mL of concentration is taken to be added to the glass container that step (1) obtains
In；
(3) the hollow out exposure mask of specific electrode shape is attached in the silicon wafer substrate that step (1) obtains；
It (4) is that 50 sccm sputter the chromium of 3 min, then identical sputtering item under the conditions of sputtering power is 150 W in argon stream
Under part, the copper of 20min is sputtered；
(5) it after sputtering is completed, puts it into rapidly in step (2) prepared graphene oxide solution, in 65 DEG C of thermal station
2 h of reaction are stood, the Graphene electrodes grown in substrate surface are obtained；
(6) step (5) reaction is completed in the careful slave graphene oxide of the obtained Graphene electrodes in substrate surface growth
It takes out, is carefully cleaned 3 times with Graphene electrodes film of the deionized water to growth, then sample is immersed in 1.0 × 10-7 mol/L
Hydrochloric acid in 25 min；
(7) Graphene electrodes for obtaining step (6) remove sample surfaces adherency again with careful cleaning 3 times of deionized water
Dilute hydrochloric acid is put into 60 DEG C of thermal station dry 20 min, patterned Graphene electrodes can be obtained.
Embodiment 2: it is same as Example 1, but graphene oxide solution concentration changes 0.1 mg/mL, 0.2 mg/ into respectively
ML and 1 mg/mL.
Embodiment 3: it is same as Example 1, but the reaction time is respectively 0.5 h, 1 h and 3h.
Embodiment 4: it is same as Example 1, but reaction temperature is respectively 50 DEG C, 80 DEG C and 100 DEG C.
Embodiment 5: it is same as Example 1, but the sputtering time of metallic copper is respectively 10 min and 30 min.
Embodiment 6: it is same as Example 1, but substrate is supported with bracket in reduction process, and increase below substrate
Magneton is added to stir.
Fig. 1 a is image mask used in the present invention, and Fig. 1 b is the net of the pierced pattern of specific shape provided by the invention
The structural schematic diagram of version, it is identical with Graphene electrodes shape made from reality.Fig. 2 a and Fig. 2 b point are magnetic on a silicon substrate
Comparison diagram before and after control sputtering copper reduction graphene oxide, can prepare multiple electrodes in same substrate as we can see from the figure, greatly
Preparation efficiency is improved greatly, the electrode of required shape can also be obtained by changing the mask pattern of hollow out.Fig. 3 is scanning electron microscope
The exterior view (Fig. 3 a) and sectional view (Fig. 3 b) for shooting Graphene electrodes film made from embodiment (1), can be with from sectional view
Clearly find out that graphene film has the structure of stacked in layers, from exterior view it can be seen that graphene film obtained has very
High integrality and planarization.Fig. 4 is the XPS spectrum of the graphene oxide used in embodiment 1 and the graphene obtained after reduction
Figure, Fig. 4 a are the XPS of graphene oxide, the XPS for the graphene film that Fig. 4 b is, the stone obtained after as can be seen from the figure restoring
Oxygen content substantially reduces in black alkene, illustrates that this method can effective redox graphene.Under the different frequency shown from Fig. 5
The test result of human skin impedance it can be seen that with frequency raising, impedance significantly reduces, and illustrates the stone of invention preparation
Black alkene electrode and being bonded for skin are close, by the high reliablity for the electrobiology signal that the electrode acquires.From fig. 6, it can be seen that
Stable electrocardiosignal can be obtained by Graphene electrodes prepared by the present invention, and the peak of feature electrocardiogram is high-visible.
The above embodiments merely illustrate the technical concept and features of the present invention, and its object is to allow person skilled in the art
It cans understand the content of the present invention and implement it accordingly, it is not intended to limit the scope of the present invention.It is all smart according to the present invention
The equivalent transformation or modification that refreshing essence is done, should be covered by the protection scope of the present invention.
Claims (7)
1. a kind of method of preparing graphene at normal temperature flexible electrode, it is characterised in that specific step is as follows:
(1) substrate and glass container are cleaned, i.e., first sufficiently cleans substrate and glass container with acetone, then by substrate and glass
Container is respectively put into deionized water, by ultrasonic sufficiently cleaning, removes the impurity and inorganic pollution on their surfaces, then base
Bottom and glass container are respectively with being dried with nitrogen；
(2) taking finely dispersed concentration is that the graphene oxide solution of 0.1~5 mg/mL is added to the glass that step (1) obtains
In container；
(3) the hollow out exposure mask of required electrode shape is attached in substrate obtained by step (1)；
(4) since the connectivity between some metals and substrate is poor, in order to guarantee to restore obtained graphene film
One layer of adhesive layer is first formed on the substrate using sputtering method for integrality, then sputters redox graphene institute on it again
Material；
(5) it after step (4) sputtering is completed, puts it into rapidly in step (2) prepared graphene oxide solution, 50~
1~3 h is reacted in 100 DEG C of thermal station, obtains the Graphene electrodes grown in substrate surface；
(6) by step (5) reaction complete substrate surface growth Graphene electrodes taken out from graphene oxide, spend from
Sub- water cleans the Graphene electrodes of growth several times, then the Graphene electrodes grown in substrate surface is immersed in extremely dilute salt
10~30 min in acid；
(7) product that step (6) obtains is cleaned several times with deionized water, removes the Graphene electrodes grown in substrate surface
Extremely dilute hydrochloric acid of surface adhesion is put into 50~80 DEG C of thermal station dry 10~30 min, patterned graphene can be obtained
Electrode.
2. the method for preparing graphene at normal temperature flexible electrode according to claim 1, it is characterised in that described in step (2)
The partial size of graphene oxide is 1~15 μm.
3. the method for preparing graphene at normal temperature flexible electrode according to claim 1, it is characterised in that used in step (1)
Glass container be 100~250 mL.
4. the method for preparing graphene at normal temperature flexible electrode according to claim 1, it is characterised in that used in step (1)
Substrate be the various materials for possessing flat surface such as silicon wafer or glass plate.
5. the method for preparing graphene at normal temperature flexible electrode according to claim 1, it is characterised in that used in step (4)
Adhesive layer include: any in chromium or titanium.
6. the method for preparing graphene at normal temperature flexible electrode according to claim 1, it is characterised in that preparation in step (4)
Material used in redox graphene includes: in the metal and other materials with reproducibility of the high-purities such as copper, iron or nickel
It is any.
7. the method for preparing graphene at normal temperature flexible electrode according to claim 1, it is characterised in that described in step (6)
Extremely dilute hydrochloric acid, concentration are 1.0 × 10-9~1.0 × 10-4 mol/L。
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20150079533A (en) * | 2015-06-19 | 2015-07-08 | 서울대학교산학협력단 | Preparing method of reduced graphene oxide film, reduced graphene oxide film prepared by the same, and graphene electrode including the reduced graphene oxide film |
| CN106486344A (en) * | 2016-12-01 | 2017-03-08 | 无锡格菲电子薄膜科技有限公司 | A kind of preparation method of the graphene film of patterning |
| CN106629675A (en) * | 2016-09-28 | 2017-05-10 | 上海理工大学 | Preparation method of high-heat-conduction flexible graphene film |
| CN107697906A (en) * | 2017-08-21 | 2018-02-16 | 上海理工大学 | A kind of preparation method of copper/graphene composite material |
| CN107887076A (en) * | 2017-10-27 | 2018-04-06 | 成都天航智虹知识产权运营管理有限公司 | A kind of preparation method of graphene conductive film |
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- 2019-01-25 CN CN201910071882.3A patent/CN109748264A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20150079533A (en) * | 2015-06-19 | 2015-07-08 | 서울대학교산학협력단 | Preparing method of reduced graphene oxide film, reduced graphene oxide film prepared by the same, and graphene electrode including the reduced graphene oxide film |
| CN106629675A (en) * | 2016-09-28 | 2017-05-10 | 上海理工大学 | Preparation method of high-heat-conduction flexible graphene film |
| CN106486344A (en) * | 2016-12-01 | 2017-03-08 | 无锡格菲电子薄膜科技有限公司 | A kind of preparation method of the graphene film of patterning |
| CN107697906A (en) * | 2017-08-21 | 2018-02-16 | 上海理工大学 | A kind of preparation method of copper/graphene composite material |
| CN107887076A (en) * | 2017-10-27 | 2018-04-06 | 成都天航智虹知识产权运营管理有限公司 | A kind of preparation method of graphene conductive film |
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