CN109363800A - A kind of graphene nano electronic skin and preparation method thereof based on three-dimensional microstructures - Google Patents
A kind of graphene nano electronic skin and preparation method thereof based on three-dimensional microstructures Download PDFInfo
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- CN109363800A CN109363800A CN201811146065.1A CN201811146065A CN109363800A CN 109363800 A CN109363800 A CN 109363800A CN 201811146065 A CN201811146065 A CN 201811146065A CN 109363800 A CN109363800 A CN 109363800A
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
- A61F2/02—Prostheses implantable into the body
- A61F2/10—Hair or skin implants
- A61F2/105—Skin implants, e.g. artificial skin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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Abstract
A kind of graphene nano electronic skin and preparation method thereof based on three-dimensional microstructures, wherein, the preparation method of graphene nano electronic skin includes: that silicon wafer is introduced in quartz ampoule, and using plasma enhancing chemical vapour deposition technique provides the graphene nano of three-dimensional microstructures in silicon wafer growth under high temperature environment；After graphene nano growth shaping, the reaction gas mixtures being made of methane and hydrogen are introduced into quartz ampoule, so that graphene nano is rapidly decreased to room temperature；The dimethyl silicone polymer of molten condition is uniformly coated on silicon and is enveloped graphene nano, and is solidified into the laminated structure of soft and transparent；Dimethyl silicone polymer after solidification is removed from silicon wafer, and pastes top electrode on the edge of the dimethyl silicone polymer with laminated structure, to form graphene nano electronic skin.Graphene nano electronic skin of the invention has stretching outstanding and bending property, and makes simple, at low cost, high sensitivity.
Description
Technical field
The present invention relates to electronic skin sensor technical fields, and in particular to a kind of graphene based on three-dimensional microstructures is received
Rice electronic skin and preparation method thereof.
Background technique
Graphene (Graphene) be one kind by carbon atom with sp2Hybridized orbit forms the two dimension that hexangle type is in honeycomb lattice
Carbon nanomaterial.It is due to excellent optics, electricity, mechanical characteristic, in materialogy, micro-nano technology, the energy, biomedicine
It is with important application prospects with drug delivery etc., it is considered to be a kind of future revolutionary material.However, the prior art
In silicon graphene electronic skin there are many defects, on the one hand, silicon graphene is easy to be torn under very big tension
It splits, does not adapt to the immense pressure of mankind's activity, flexible, sensitive difference, on the other hand, in practical applications due to Graphene electrodes
It is not able to satisfy big extension requirement, so that its application is very limited.
Summary of the invention
The present invention in order to solve the above problems existing in the present technology, provides a kind of graphene based on three-dimensional microstructures
Nanoelectronic skin and preparation method thereof is easily torn with solving the poor biocompatibility of existing silicon graphene electronic skin
It splits, does not adapt to the technical problems such as the immense pressure of mankind's activity.
To achieve the above object, the graphene nano electronic skin based on three-dimensional microstructures that the present invention provides a kind of, packet
Dimethyl silicone polymer substrate, graphene nano layer and electrode are included, the dimethyl silicone polymer substrate is the piece of soft and transparent
Shape structure, the graphene nano layer is in three-dimensional microstructures and is equably embedded dimethyl silicone polymer substrate in laminated structure
In, the electrode is arranged on the edge of dimethyl silicone polymer substrate.
As present invention further optimization technical solution, the three-dimensional microstructures of the graphene nano layer are by several in battle array
The graphene nano cylinder composition of column distribution.
As present invention further optimization technical solution, the graphene nano cylinder is cylindrical body or tetragonal body.
As present invention further optimization technical solution, the electrode is silver electrode, and the silver electrode is using stickup
Mode is arranged on the edge of dimethyl silicone polymer substrate.
As another aspect of the present invention, the present invention also provides a kind of graphene nano electronics based on three-dimensional microstructures
The preparation method of skin, method includes the following steps:
S1, silicon wafer is introduced in quartz ampoule, using plasma enhances chemical vapor deposition under high temperature environment
Method provides the graphene nano of three-dimensional microstructures in silicon wafer growth；
S2, after graphene nano growth shaping, introduce the reaction gas mixtures that are made of methane and hydrogen to quartzy
Guan Zhong, so that graphene nano is rapidly decreased to room temperature；
S3, the dimethyl silicone polymer of molten condition is uniformly coated on silicon and is enveloped graphene nano, and
It is solidified into the laminated structure of soft and transparent；
S4, the dimethyl silicone polymer after solidification is removed from silicon wafer, and in the poly dimethyl with laminated structure
Top electrode is pasted on the edge of siloxanes, to form graphene nano electronic skin.
As present invention further optimization technical solution, in the step S1, silicon wafer is introduced in quartz ampoule,
Using plasma enhancing chemical vapour deposition technique provides the graphite of three-dimensional microstructures in silicon wafer growth under high temperature environment
Alkene nanometer specifically includes:
The quartz ampoule that silicon wafer is introduced in quartz ampoule, and will introduce silicon wafer heats in the environment of hydrogen, institute
Stating heating temperature is 750 degrees Celsius, and using plasma enhancing chemical vapour deposition technique is raw in silicon wafer while heating
Grow the graphene nano with three-dimensional microstructures.
As present invention further optimization technical solution, the reaction gas mixtures in the step S2 are in the following proportions
Flow is introduced into quartz ampoule:
Methane: hydrogen=8: 8SCCM.
As present invention further optimization technical solution, in the step S3, by the polydimethylsiloxanes of molten condition
Alkane is uniformly coated on silicon and envelopes graphene nano, and the laminated structure for being solidified into soft and transparent specifically includes:
The dimethyl silicone polymer of molten condition is uniformly coated on silicon and is coated using injection or injection-moulding device
Firmly graphene nano；
The silicon wafer for being coated with dimethyl silicone polymer is put into vacuum oven, hot setting 1h is to obtain cured poly- diformazan
Radical siloxane.
Graphene nano electronic skin based on three-dimensional microstructures of the invention and preparation method thereof can achieve to be had as follows
Beneficial effect:
Graphene nano electronic skin based on three-dimensional microstructures of the invention, by including that dimethyl silicone polymer serves as a contrast
Bottom, graphene nano layer and electrode, the dimethyl silicone polymer substrate are the laminated structure of soft and transparent, and the graphene is received
Rice layer is in three-dimensional microstructures and is equably embedded in the dimethyl silicone polymer substrate of laminated structure, and the electrode setting is poly-
On the edge of dimethyl siloxane substrate, protruded so that having the present invention is based on the graphene nano electronic skin of three-dimensional microstructures
Stretching and bending property, and make simple, at low cost, high sensitivity, to solve existing electronic skin biocompatibility
The technical issues of, moreover, the graphene nano electronic skin the present invention is based on three-dimensional microstructures adapts to the huge of mankind's activity
Pressure, to be widely used in electronic skin field.
The preparation method of graphene nano electronic skin based on three-dimensional microstructures of the invention, by including following step
It is rapid: S1, silicon wafer to be introduced in quartz ampoule, using plasma enhances chemical vapour deposition technique in silicon under high temperature environment
Chip grows the graphene nano with three-dimensional microstructures；S2, after graphene nano growth shaping, introduce by methane and hydrogen
The reaction gas mixtures of gas composition are into quartz ampoule, so that graphene nano is rapidly decreased to room temperature；S3, by molten condition
Dimethyl silicone polymer is uniformly coated on silicon and envelopes graphene nano, and is solidified into the sheet knot of soft and transparent
Structure；S4, the dimethyl silicone polymer after solidification is removed from silicon wafer, and in the dimethyl silicone polymer with laminated structure
Edge on paste top electrode, to form graphene nano electronic skin so that through the invention be based on three-dimensional microstructures
Graphene nano electronic skin preparation method be prepared based on three-dimensional microstructures graphene nano electronic skin tool
There are stretching outstanding and bending property, and make simple, at low cost, high sensitivity, to solve existing electronic skin biology
The technical issues of compatibility, moreover, the graphene nano electronic skin based on three-dimensional microstructures that the present invention is prepared can fit
The immense pressure of mankind's activity is answered, to be widely used in electronic skin field.
Detailed description of the invention
The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments.
Fig. 1 is the structural representation of the example provided the present invention is based on the graphene nano electronic skin of three-dimensional microstructures
Figure；
In figure: 1, dimethyl silicone polymer substrate, 2, graphene nano layer, 3, electrode.
Fig. 2 is the example provided the present invention is based on the preparation method of the graphene nano electronic skin of three-dimensional microstructures
Method flow diagram；
Fig. 3 is the example provided the present invention is based on the preparation process of the graphene nano electronic skin of three-dimensional microstructures
Preparation flow schematic diagram.
The object of the invention is realized, the embodiments will be further described with reference to the accompanying drawings for functional characteristics and advantage.
Specific embodiment
Below in conjunction with attached drawing and specific embodiment, the present invention is described further.Drawn in preferred embodiment
Such as "upper", "lower", "left", "right", " centre " and " one " term, only being illustrated convenient for narration, rather than to limit
The enforceable range of the present invention, relativeness are altered or modified, under the content of no substantial changes in technology, when being also considered as this hair
Bright enforceable scope.
As shown in Figure 1, the graphene nano electronic skin based on three-dimensional microstructures include dimethyl silicone polymer substrate 1,
Graphene nano layer 2 and electrode 3, the dimethyl silicone polymer substrate 1 are the laminated structure of soft and transparent, and the graphene is received
Rice layer 2 is in three-dimensional microstructures and is equably embedded in the dimethyl silicone polymer substrate 1 of laminated structure, and the electrode 3 is arranged
On the edge of dimethyl silicone polymer substrate.
In specific implementation, the three-dimensional microstructures of the graphene nano layer 2 are received by several graphenes in array distribution
Meter Zhu Ti composition, and it is further preferred that the graphene nano cylinder is cylindrical body or tetragonal body, certainly, the graphene
Nanometer cylinder can also be other shapes of column structure, such as triangle, star, not enumerate herein.
In specific implementation, the electrode 3 is silver electrode, and the silver electrode is adopted is arranged in poly dimethyl silicon in the method for paste
On the edge of oxygen alkane substrate 1.
The preparation method for the graphene nano electronic skin based on three-dimensional microstructures that the present invention also provides a kind of, above-mentioned
The graphene nano electronic skin (including embodiment corresponding to Fig. 1) based on three-dimensional microstructures of one embodiment can be by this
Preparation method is prepared, as shown in Fig. 2, the preparation method the following steps are included:
Step S1, silicon wafer is introduced in quartz ampoule, using plasma enhances chemical gaseous phase under high temperature environment
Sedimentation provides the graphene nano of three-dimensional microstructures in silicon wafer growth；
Step S2, after graphene nano growth shaping, introduce the reaction gas mixtures that are made of methane and hydrogen to
In quartz ampoule, so that graphene nano is rapidly decreased to room temperature；
Step S3, the dimethyl silicone polymer of molten condition is uniformly coated on silicon and envelopes graphene and received
Rice, and it is solidified into the laminated structure of soft and transparent；
Step S4, the dimethyl silicone polymer after solidification is removed from silicon wafer, and in poly- two with laminated structure
Top electrode is pasted on the edge of methylsiloxane, to form graphene nano electronic skin.
Preferably, in the step S1, silicon wafer is introduced in quartz ampoule, under high temperature environment using plasma
Enhancing chemical vapour deposition technique is specifically included in the graphene nano that silicon wafer growth provides three-dimensional microstructures:
The quartz ampoule that silicon wafer is introduced in quartz ampoule, and will introduce silicon wafer heats in the environment of hydrogen, institute
Stating heating temperature is 750 degrees Celsius, and using plasma enhancing chemical vapour deposition technique is raw in silicon wafer while heating
The graphene nano with three-dimensional microstructures is grown, wherein using plasma is to enhance the condition of chemical vapour deposition technique.
Preferably, flow is introduced into quartz ampoule the reaction gas mixtures in the step S2 in the following proportions:
Methane: hydrogen=8: 8SCCM (SCCM is meant that standard milliliters are per minute), the ratio are to test to measure more to close
The ratio of reason in actual production process, can adjust reaction gas mixing according to the practical cooling rate of graphene nano certainly
The introducing flow of object.
Preferably, in the step S3, the dimethyl silicone polymer of molten condition is uniformly coated on silicon and is wrapped
Graphene nano is covered, and the laminated structure for being solidified into soft and transparent specifically includes:
The dimethyl silicone polymer of molten condition is uniformly coated on silicon and is coated using injection or injection-moulding device
Firmly graphene nano；
The silicon wafer for being coated with dimethyl silicone polymer is put into vacuum oven, hot setting 1h is to obtain cured poly- diformazan
Radical siloxane.
Herein it should be noted that, although giving the preferred embodiment of step S1, step S2 and each step of step S3 above,
It but is not to be limited the scope of the invention with this, i.e., step S1- step S4 of the invention, each step can also use
Other specific technical solutions are realized, can only meet its application practical the technical issues of solving, i.e., so that passing through this hair
The graphite based on three-dimensional microstructures that the preparation method of the bright graphene nano electronic skin based on three-dimensional microstructures is prepared
Alkene nanoelectronic skin has stretching outstanding and bending property, and makes simple, at low cost, high sensitivity.
It is detailed below with reference to Fig. 3 in order to allow those skilled in the art to more fully understand and realize technical solution of the present invention
It is thin to illustrate that the present invention is based on the specific preparation flows of the graphene nano electronic skin of three-dimensional microstructures:
A: preparing the silicon wafer of the square of sheet, using the substrate grown as graphene nano；
B: using plasma enhancing chemical vapour deposition technique provides the graphene of three-dimensional microstructures in silicon wafer growth
Nanometer；
C: the dimethyl silicone polymer of molten condition is uniformly coated on silicon and is enveloped graphene nano, and solid
It is melted into piece；
D: the dimethyl silicone polymer with laminated structure after solidification is removed from silicon wafer.
Pass through the graphene nano based on three-dimensional microstructures prepared to above method employed in the embodiment of the present application
Electronic skin carries out sensitivity, stability, using the test of duration and flexibility etc., obtains that following test result is as follows:
(1) optimum growh time test
Recovery characteristics with test sample are tested to stretching, extract 4 samples, graphene nano growth time
Respectively 15 minutes, 30 minutes, 60 minutes and 120 minutes, test condition are the constant voltage that electrochemical workstation maintains 5V.
Analysis result obtains, and in 120 minutes growth times, the graphene nano electronic skin based on three-dimensional microstructures has optimal
Reactivity worth is stretched, and electronic skin is showed in stretching and bending application and protruded the most.
(2) sensitivity to stretching is tested
The resistance variations with electronic skin in recovery process are being stretched, maximum tension rate reaches and extends in close to 100%
The breakthrough limit of dimethyl silicone polymer.Test structure shows in this case still there is the response of current signal.It is hindered
Power changes the approximate exponential function for being reflected as draw ratio, there is shown to the highly sensitive of stretching.
(3) stability test
After 100 times stretch and restore, similar to original state to the resistance of stretching, this shows in big stretching shape
There is good stability under state.
Therefore, by above-mentioned test result it is found that the graphene nano electronics skin based on three-dimensional microstructures through the invention
The graphene nano electronic skin based on three-dimensional microstructures that the preparation method of skin is prepared has stretching outstanding and bending
Performance, and the technical issues of make simple, at low cost, high sensitivity, not only solve existing electronic skin biocompatibility, and
And it can be well adapted for the immense pressure of mankind's activity, to be widely applied in electronic skin field.
Although specific embodiments of the present invention have been described above, those skilled in the art should be appreciated that this
It is merely illustrative of, various changes or modifications can be made to present embodiment, without departing from the principle and substance of the present invention,
Protection scope of the present invention is only limited by the claims that follow.
Claims (8)
1. a kind of graphene nano electronic skin based on three-dimensional microstructures, which is characterized in that served as a contrast including dimethyl silicone polymer
Bottom, graphene nano layer and electrode, the dimethyl silicone polymer substrate are the laminated structure of soft and transparent, and the graphene is received
Rice layer is in three-dimensional microstructures and is equably embedded in the dimethyl silicone polymer substrate of laminated structure, and the electrode setting is poly-
On the edge of dimethyl siloxane substrate.
2. the graphene nano electronic skin according to claim 1 based on three-dimensional microstructures, which is characterized in that the stone
The three-dimensional microstructures of black alkene nanometer layer are made of several graphene nano cylinders in array distribution.
3. the graphene nano electronic skin based on three-dimensional microstructures stated according to claim 2, which is characterized in that the graphite
Alkene nanometer cylinder is cylindrical body or tetragonal body.
4. the graphene nano electronic skin based on three-dimensional microstructures stated according to claim 3, which is characterized in that the electrode
For silver electrode, the silver electrode, which is adopted, to be arranged in the method for paste on the edge of dimethyl silicone polymer substrate.
5. a kind of preparation side of the described in any item graphene nano electronic skins based on three-dimensional microstructures of Claims 1-4
Method, which is characterized in that method includes the following steps:
S1, silicon wafer is introduced in quartz ampoule, using plasma enhancing chemical vapour deposition technique exists under high temperature environment
Silicon wafer growth provides the graphene nano of three-dimensional microstructures；
S2, after graphene nano growth shaping, be introduced into the reaction gas mixtures being made of methane and hydrogen into quartz ampoule,
So that graphene nano is rapidly decreased to room temperature；
S3, the dimethyl silicone polymer of molten condition is uniformly coated on silicon and is enveloped graphene nano, and solidify
At the laminated structure of soft and transparent；
S4, the dimethyl silicone polymer after solidification is removed from silicon wafer, and in the polydimethylsiloxanes with laminated structure
Top electrode is pasted on the edge of alkane, to form graphene nano electronic skin.
6. the preparation method of the graphene nano electronic skin according to claim 5 based on three-dimensional microstructures, feature
It is, in the step S1, silicon wafer is introduced in quartz ampoule, using plasma enhances chemical gas under high temperature environment
Phase sedimentation is specifically included in the graphene nano that silicon wafer growth provides three-dimensional microstructures:
The quartz ampoule that silicon wafer is introduced in quartz ampoule, and will introduce silicon wafer heats in the environment of hydrogen, described to add
Hot temperature is 750 degrees Celsius, and using plasma enhancing chemical vapour deposition technique goes out in silicon wafer growth while heating
Graphene nano with three-dimensional microstructures.
7. the graphene nano electronic skin and preparation method thereof according to claim 6 based on three-dimensional microstructures, special
Sign is that flow is introduced into quartz ampoule the reaction gas mixtures in the step S2 in the following proportions:
Methane: hydrogen=8: 8 SCCM.
8. according to the described in any item graphene nano electronic skins and its preparation based on three-dimensional microstructures of claim 5 to 7
Method, which is characterized in that in the step S3, the dimethyl silicone polymer of molten condition is uniformly coated on silicon and is wrapped
Graphene nano is covered, and the laminated structure for being solidified into soft and transparent specifically includes:
The dimethyl silicone polymer of molten condition is uniformly coated on silicon using injection or injection-moulding device and envelopes stone
Black alkene nanometer；
The silicon wafer for being coated with dimethyl silicone polymer is put into vacuum oven, hot setting 1h is to obtain cured poly dimethyl silicon
Oxygen alkane.
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| CN112964282A (en) * | 2019-12-13 | 2021-06-15 | 北京联合大学 | Intelligent graphene flexible electronic skin and preparation method thereof |
| CN114046913A (en) * | 2021-11-17 | 2022-02-15 | 燕山大学 | Flexible graphene pressure sensor and preparation method thereof |
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