CN103083007A - Piezoresistive electronic skin and preparation method thereof - Google Patents
Piezoresistive electronic skin and preparation method thereof Download PDFInfo
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- CN103083007A CN103083007A CN2013100344781A CN201310034478A CN103083007A CN 103083007 A CN103083007 A CN 103083007A CN 2013100344781 A CN2013100344781 A CN 2013100344781A CN 201310034478 A CN201310034478 A CN 201310034478A CN 103083007 A CN103083007 A CN 103083007A
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Abstract
The invention provides piezoresistive electronic skin and a preparation method thereof. According to the piezoresistive electronic skin, carbon nano tube films are adopted to serve as conductive layers, polydimethylsiloxane, polyethylene terephthalate, polyvinyl alcohol, polyvinyl formal, polyethylene and other materials provided with micronano patterns serves as substrates, and therefore the substrate has the advantages of being high in flexibility, prone to bending and the like, is low in operating voltage, little in power, high in sensitivity, and short in response time. More importantly, the patterning flexible substrates are adopted to serve as a base body, and sensitivity of the electronic skin to external tiny applied force is greatly improved.
Description
Technical field
The present invention relates to sensor field, relate in particular to a kind of pressure resistance type electronics skin and preparation method thereof.
Background technology
Robot as artificial intelligence's automation devices, more and more is dissolved into the mankind's daily life, and is replacing the mankind and carrying out related work such as high temperature, high pressure, the dangerous industry such as explosive.Present robot system has been passed through the integrated of various kinds of sensors, has realized many visions such as the mankind, audition and olfactory function.But, how as the mankind, have responsive feeling function, be also one of challenge of facing of robot system all the time.The birth of electronics skin will bring huge variation to robot system, make robot to obtain more information from external environment.
Although since two thousand four, the part Study group of Japan and the U.S. has been reported the electronics skin based on organic field effect tube type, condenser type and pressure resistance type, but cut both ways, for example, complicated processing technique and device architecture, larger driving voltage, lower sensitivity, the use of rigidity silica-base material makes device have the scope of application that the characteristics such as nontransparent and inflexibility have also limited device.
Therefore, necessary a kind of simple in structure, high sensitivity, pinpoint accuracy and the durable artificial electronics skin of providing.
Summary of the invention
The purpose of this invention is to provide a kind of pressure resistance type electronics skin based on carbon nano-tube film of brand new, it has the advantages such as low cost, low driving voltage, high sensitivity, fast-response time, high stability.
In order to achieve the above object, the invention provides a kind of pressure resistance type electronics skin, it comprises:
Two flexible substrate;
Two conductive layers are coated in respectively on two flexible substrate, and two conductive layers are in contact with one another;
Two conductive electrode contact with two conductive layers respectively.
Preferably, described at least one flexible substrate adopts the polydimethylsiloxane thin film.
Preferably, at least one mask of described polydimethylsiloxane thin film has pattern, and the size of described pattern is between 0.1-500 μ m.
Preferably, described conductive layer comprises carbon nano-tube film, and described carbon nano-tube film mainly is comprised of the network that CNT interweaves.
Preferably, the light transmittance of described carbon nano-tube film is 50-97%, and sheet resistance is 100-10
7Ω/sq.
Preferably, the thickness of described carbon nano-tube film is generally in the 10nm-500nm left and right, by one or more compound formed in SWCN, double-walled carbon nano-tube and multi-walled carbon nano-tubes, wherein, described SWCN is metallic single-wall carbon nano-tube or the mixing SWCN that contains simultaneously metallicity and semiconductive carbon nano tube.
Preferably, described conductive layer can be one or two or more kinds combination of any conducting metal in copper, silver and gold or semi-conducting material.
Preferably, described conductive electrode be adopt in gold, platinum, nickel, silver, indium, copper, CNT and Graphene any one material or more than two kinds the combination of material make.
In order to achieve the above object, the present invention also provides a kind of preparation method of pressure resistance type electronics skin, and step is as follows:
The flexible substrate of S1, preparation two patternings, wherein one deck is the polydimethylsiloxane thin film at least;
S2, preparation carbon nano-tube solution, and be coated to respectively two flexible substrate band patterned surfaces, forming carbon nano-tube film, opposite, the side assembling with figuratum carbon nano-tube film forms the thin-film device that carbon nano-tube film is in contact with one another;
S3, use conductive material form respectively upper and lower conductive electrode on two carbon nano-tube films, and draw wire from conductive electrode, obtain pressure resistance type electronics skin.
Preferably, the polydimethylsiloxane thin film in described S1 prepares by the following method:
S11, polydimethylsiloxane was degassed 1-30 minute in a vacuum, and pour at one and establish on figuratum template, the thickness of polydimethylsiloxane is between 0.1-3mm, afterwards at the curing molding more than 0.5 hour of heating at the temperature of 50-100 ℃;
Polydimethylsiloxane after S12, curing molding took off from template after organic solvent for ultrasonic 5-30 minute.
Preferably, described template can be silicon substrate, metal substrate, cloth, the silk fabrics with micro structure or the organism organ with micro structure; Described organic solvent can be methanol, ethanol or ethylene glycol.
Preferably, described step S2 specifically can comprise:
S21, the CNT of single wall and/or double-walled, Shao Bi, many walls is added the aqueous solution of the surfactant that contains 1wt%-10wt%, until CNT concentration is 0.01-50mg/ml, then, with the ultrasonic pre-dispersed 1min-10h of this mixed solution, form carbon nano tube dispersion liquid;
S22, to more than the speed centrifugal treating 0.1h of this carbon nano tube dispersion liquid with 1000-20000rpm, get supernatant as film forming before solution;
S23, adopt deionized water with film forming before solution dilution 1-100 doubly, then, use airbrush to be sprayed into equably two flexible substrate band patterned surfaces the carbon nano-tube solution of dilution, form carbon nano-tube film, opposite, a side assembling with figuratum carbon nano-tube film forms the thin-film device that carbon nano-tube film is in contact with one another.
Preferably, in described step S23 before being assembled into thin-film device, adopt deionized water repeatedly to soak the thin film that there is carbon nano-tube film on described surface, in order to removing surfactant, the described carbon nano-tube film 0.1-24h of the strong acid treatment take concentration as 3-8M again after drying.
Compared with prior art, good effect of the present invention is: it is that the materials such as conductive layer and polydimethylsiloxane, polyphenyl dioctyl phthalate second diester, polyvinyl alcohol, polyvinyl formal, polyethylene are flexible substrate that this pressure resistance type electronics skin adopts carbon nano-tube film, make substrate have the advantages such as high flexibility is flexible, and its running voltage is low, power consumption is little, and is highly sensitive, response time is short.What is more important adopts the flexible substrate of patterning as matrix in the present invention, increased the quantity of contact resistance, has improved greatly the sensitivity of micro force to external world of electronics skin.Simultaneously, the selected template of its patterning process is to need not the soft template such as the little course of processing of any complexity, extremely easy to obtain and cheap cloth or silk.
Description of drawings
Fig. 1 is the structural representation of a preferred embodiment of the present invention;
Fig. 2 is the SEM picture with polydimethylsiloxane thin film of little pattern;
Fig. 3 is the SEM picture of single wall carbon nano-tube film;
Fig. 4 is the pressure of the embodiment of the present invention and the schematic diagram of resistance variations;
Fig. 5 is the flow chart of preparation method of the present invention.
The specific embodiment
Below in conjunction with accompanying drawing and specific embodiment, the present invention is described in further detail.
Please refer to Fig. 1, this embodiment has disclosed a kind of pressure resistance type electronics skin, and it comprises:
Two flexible substrate 11,12;
Two conductive layers 21,22 are coated in respectively on two flexible substrate 11,12, and two conductive layers 21,22 are in contact with one another;
Two conductive electrode 31,32 contact with two conductive layers 21,22 respectively.
Described at least one flexible substrate adopts the polydimethylsiloxane thin film, and at least one mask of described polydimethylsiloxane thin film has micro-nano pattern, and the size of described pattern is between 0.1-500 μ m.
Described conductive layer 21,22 comprises carbon nano-tube film, and described carbon nano-tube film mainly is comprised of the network that CNT interweaves.The light transmittance of described carbon nano-tube film is 50-97%, and sheet resistance is 100-10
7Ω/sq.The thickness of described carbon nano-tube film is generally in the 10nm-500nm left and right, by one or more compound formed in SWCN, double-walled carbon nano-tube and multi-walled carbon nano-tubes, wherein, described SWCN is metallic single-wall carbon nano-tube or the mixing SWCN that contains simultaneously metallicity and semiconductive carbon nano tube.Described carbon nano-tube film can be also the carbon nano-tube film that mixes or modify through nitrogen or boron, noble metal, metal, surfactant and organic high molecular compound etc.Described CNT can adopt by hydroxyl (OH), carboxyl (COOH), amino (NH
2) CNT of functionalization, the CNT of high molecular polymer functionalization, the CNT of metal nanoparticle functionalization, the CNT of metal oxide functional and the CNT of biomolecule functionalization.Described conductive layer 21,22 can also be one or two or more kinds combination of any conducting metal in copper, silver and gold or semi-conducting material.
Specifically with reference to the embodiment of Fig. 1, conductive electrode 31 is be connected with conductive layer 21 and be not connected connection with conductive layer, conductive electrode 32 is be connected with conductive layer 22 and be not connected connection with conductive layer, and the carbon pipe thin film with micro-nano pattern can only be connected with one of them conductive electrode respectively.In addition, described conductive electrode 31, the 32nd adopts any one material in gold, platinum, nickel, silver, indium, copper, CNT and Graphene or more than two kinds, the combination of material is made.
Please refer to Fig. 5, the present invention also provides a kind of preparation method of pressure resistance type electronics skin, and step is as follows:
The flexible substrate of S1, preparation two patternings, wherein one deck is the polydimethylsiloxane thin film at least;
In S1, described polydimethylsiloxane thin film prepares by the following method:
S11, polydimethylsiloxane was degassed 1-30 minute in a vacuum, and pour at one and establish on figuratum template, the thickness of polydimethylsiloxane is between 0.1-3mm, afterwards at the curing molding more than 0.5 hour of heating at the temperature of 50-100 ℃;
Polydimethylsiloxane after S12, curing molding took off from template after organic solvent for ultrasonic 5-30 minute.
Described template can be silicon substrate, metal substrate, cloth, the silk fabrics with micro structure or the organism organ with micro structure; Described organic solvent can be methanol, ethanol or ethylene glycol.The one side of the described polydimethylsiloxane thin film that makes or two sides are positioned under the oxygen plasma condition, act on 1-60 minute.Described polydimethylsiloxane thin film can also be macromolecular material, can be selected from but be not limited to any one or the combination more than two kinds in polyphenyl dioctyl phthalate second diester, polyvinyl alcohol, polyvinyl formal and polyethylene.
Please refer to Fig. 2, scanning electron microscope (SEM) photo for prepared polydimethylsiloxane thin film with micro-nano pattern illustrates and has constructed the pattern with periodic micro structure on the polydimethylsiloxane thin film.
S2, preparation carbon nano-tube solution, and be coated to respectively two flexible substrate band patterned surfaces, forming carbon nano-tube film, opposite, the side assembling with figuratum carbon nano-tube film forms the thin-film device that carbon nano-tube film is in contact with one another;
In S2, described step S2 specifically can comprise:
S21, the CNT of single wall and/or double-walled, Shao Bi, many walls is added the aqueous solution of the surfactant that contains 1wt%-10wt%, until CNT concentration is 0.01-50mg/ml, then, with the ultrasonic pre-dispersed 1min-10h of this mixed solution, form carbon nano tube dispersion liquid; In present embodiment, described surfactant can adopt common ion-type or nonionic surfactant, the preferred ionic surfactant that adopts, the present invention especially preferably adopts but is not limited to dodecyl sodium sulfate and dodecylbenzene sodium sulfonate etc., and its concentration is preferably 1-10wt%.
S22, to more than the speed centrifugal treating 0.1h of this carbon nano tube dispersion liquid with 1000-20000rpm, get supernatant as film forming before solution;
S23, adopt deionized water with film forming before solution dilution 1-100 doubly, then, use airbrush to be sprayed into equably two flexible substrate band patterned surfaces the carbon nano-tube solution of dilution, form carbon nano-tube film, opposite, a side assembling with figuratum carbon nano-tube film forms the thin-film device that carbon nano-tube film is in contact with one another.Need to prove, the time that the thickness of this carbon nano-tube film and conductivity can be sprayed by the amount of institute's carbon nanotubes is decided.The higher spray time of the consumption of CNT is longer, and its intensity is larger, and electric conductivity is better.In present embodiment, described film formation process can adopt the conventional thin film-forming methods such as vacuum filtration or spin coating, spraying, printing.For example, if adopt the spraying thin film-forming method, its scheme is specially: the carbon nano tube dispersion liquid of getting after dilution is sprayed on the figuratum polydimethylsiloxane thin film of tool with airbrush with the pressure of 0.1-1psi, then thin film is placed on heating furnace, be heated to 80-120 ℃, accelerate the moisture evaporation, then use the residual surfactant in the washed with de-ionized water carbon nano-tube film, just can make the carbon nano-tube film that is attached to figuratum polydimethylsiloxane thin film.If adopt the thin film-forming methods such as printing, coating, its scheme is specially: the carbon nano tube dispersion liquid after the modes such as employing spin coating, spraying will be diluted is film forming on the material that has glass, Muscovitum, silicon chip etc. and have flat surface.Accordingly, the better method of removing this substrate is: the aqueous solution that adopts water or contain acid, alkali, salt etc. floods to carbon nano-tube film from substrate and comes off, and then this carbon nano-tube film is transferred on the polydimethylsiloxane thin film of patterning.
In addition, in described step S23 before being assembled into thin-film device, adopt deionized water repeatedly to soak the thin film that there is carbon nano-tube film on described surface, in order to removing surfactant, the described carbon nano-tube film 0.1-24h of the strong acid treatment take concentration as 3-8M again after drying.In present embodiment, strong acid can be in nitric acid, hydrochloric acid any one or mix.
Please refer to Fig. 3, for SWCN adhere to the polydimethylsiloxane thin film on after the SEM photo, the instruction book wall carbon nano tube is interweaved, and well adheres to the polydimethylsiloxane film surface.
S3, use conductive material form respectively upper and lower conductive electrode on two carbon nano-tube films, and draw wire from conductive electrode, obtain pressure resistance type electronics skin.
In S3, conductive material as electrode, is generally silver slurry or elargol, can be also the gas electrode of doing by methods such as steaming degree or ion sputterings, as gold, and silver, copper, aluminum etc.
Please refer to Fig. 4, under the running voltage of 1V, in air atmosphere, the resistance value of measuring this resistance sensor is 110-120k Ω, on the time point of 30 seconds, 60 seconds, 90 seconds, after correspondence applied the pressure of 60Pa, 120Pa, 180Pa respectively, the resistance value fast-descending was for example after the pressure that applies 60Pa, the resistance value fast-descending is to 95-105k Ω, and result shows that this resistance sensor has high sensitivity and very short response time.
Compared with prior art, good effect of the present invention is: it is that the materials such as conductive layer and polydimethylsiloxane, polyphenyl dioctyl phthalate second diester, polyvinyl alcohol, polyvinyl formal, polyethylene are flexible substrate that this pressure resistance type electronics skin adopts carbon nano-tube film, make substrate have the advantages such as high flexibility is flexible, and its running voltage is low, power consumption is little, and is highly sensitive, response time is short.What is more important adopts the flexible substrate of patterning as matrix in the present invention, increased the quantity of contact resistance, has improved greatly the sensitivity of micro force to external world of electronics skin.Simultaneously, the selected template of its patterning process is to need not the soft template such as the little course of processing of any complexity, extremely easy to obtain and cheap cloth or silk.
Electronics skin of the present invention can be used for the detection to physiology signal, comprises that human pulse is beated, heartbeat, eyeball pressure, speak throat's muscle group vibrations of causing and the motion of other position muscle of kinetic health and epidermis.For instance, when the detection that is used for human body wrist position beat pulse, can accurately differentiate P peak in pulse, T peak and D peak, and described human pulse is beated and is comprised due to tremulous pulse the beating of each position of human body of causing of beating.
Be understandable that, for the person of ordinary skill of the art, can make other various corresponding changes and distortion by technical conceive according to the present invention, and all these change and distortion all should belong to the protection domain of claim of the present invention.
Claims (13)
1. a pressure resistance type electronics skin, is characterized in that, comprising:
Two flexible substrate;
Two conductive layers are coated in respectively on two flexible substrate, and two conductive layers are in contact with one another;
Two conductive electrode contact with two conductive layers respectively.
2. pressure resistance type electronics skin according to claim 1, is characterized in that: described at least one flexible substrate employing polydimethylsiloxane thin film.
3. pressure resistance type electronics skin according to claim 2, it is characterized in that: at least one mask of described polydimethylsiloxane thin film has pattern, and the size of described pattern is between 0.1-500 μ m.
4. pressure resistance type electronics skin according to claim 1, it is characterized in that: described conductive layer comprises carbon nano-tube film, described carbon nano-tube film mainly is comprised of the network that CNT interweaves.
5. pressure resistance type electronics skin according to claim 4, it is characterized in that: the light transmittance of described carbon nano-tube film is 50-97%, sheet resistance is 100-10
7Ω/sq.
6. pressure resistance type electronics skin according to claim 4, it is characterized in that: the thickness of described carbon nano-tube film is generally between 10nm-500nm, by one or more compound formed in SWCN, double-walled carbon nano-tube and multi-walled carbon nano-tubes, wherein, described SWCN is metallic single-wall carbon nano-tube or the mixing SWCN that contains simultaneously metallicity and semiconductive carbon nano tube.
7. pressure resistance type electronics skin according to claim 1 is characterized in that: described conductive layer can be one or two or more kinds combination of any conducting metal in copper, silver and gold or semi-conducting material.
8. pressure resistance type electronics skin according to claim 1 is characterized in that: described conductive electrode be adopt in gold, platinum, nickel, silver, indium, copper, CNT and Graphene any one material or more than two kinds the combination of material make.
9. the preparation method of a pressure resistance type electronics skin, is characterized in that, step is as follows:
The flexible substrate of S1, preparation two patternings, wherein one deck is the polydimethylsiloxane thin film at least;
S2, preparation carbon nano-tube solution, and be coated to respectively two flexible substrate band patterned surfaces, forming carbon nano-tube film, opposite, the side assembling with figuratum carbon nano-tube film forms the thin-film device that carbon nano-tube film is in contact with one another;
S3, use conductive material form respectively upper and lower conductive electrode on two carbon nano-tube films, and draw wire from conductive electrode, obtain pressure resistance type electronics skin.
10. the preparation method of pressure resistance type electronics skin according to claim 9, it is characterized in that: the polydimethylsiloxane thin film in described S1 prepares by the following method:
S11, polydimethylsiloxane was degassed 1-30 minute in a vacuum, and pour at one and establish on figuratum template, the thickness of polydimethylsiloxane is between 0.1-3mm, afterwards at the curing molding more than 0.5 hour of heating at the temperature of 50-100 ℃;
Polydimethylsiloxane after S12, curing molding took off from template after organic solvent for ultrasonic 5-30 minute.
11. the preparation method of pressure resistance type electronics skin according to claim 10 is characterized in that: described template can be silicon substrate, metal substrate, cloth, the silk fabrics with micro structure or the organism organ with micro structure; Described organic solvent can be methanol, ethanol or ethylene glycol.
12. the preparation method of pressure resistance type electronics skin according to claim 9 is characterized in that: described step S2 specifically can comprise:
S21, the CNT of single wall and/or double-walled, Shao Bi, many walls is added the aqueous solution of the surfactant that contains 1wt%-10wt%, until CNT concentration is 0.01-50mg/ml, then, with the ultrasonic pre-dispersed 1min-10h of this mixed solution, form carbon nano tube dispersion liquid;
S22, to more than the speed centrifugal treating 0.1h of this carbon nano tube dispersion liquid with 1000-20000rpm, get supernatant as film forming before solution;
S23, adopt deionized water with film forming before solution dilution 1-100 doubly, then, use airbrush to be sprayed into equably two flexible substrate band patterned surfaces the carbon nano-tube solution of dilution, form carbon nano-tube film, opposite, a side assembling with figuratum carbon nano-tube film forms the thin-film device that carbon nano-tube film is in contact with one another.
13. the preparation method of pressure resistance type electronics skin according to claim 12, it is characterized in that: in described step S23 before being assembled into thin-film device, adopt deionized water repeatedly to soak the thin film that there is carbon nano-tube film on described surface, in order to removing surfactant, the described carbon nano-tube film 0.1-24h of the strong acid treatment take concentration as 3-8M again after drying.
Priority Applications (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013100344781A CN103083007A (en) | 2013-01-29 | 2013-01-29 | Piezoresistive electronic skin and preparation method thereof |
| CN201310396009.4A CN103961073B (en) | 2013-01-29 | 2013-09-04 | Piezoresistive electronic skin and preparation method thereof |
| AU2014211862A AU2014211862B2 (en) | 2013-01-29 | 2014-01-28 | Electronic skin, preparation method and use thereof |
| JP2015554045A JP6180547B2 (en) | 2013-01-29 | 2014-01-28 | Electronic skin and its manufacturing method and use |
| EP14746641.1A EP2953012B1 (en) | 2013-01-29 | 2014-01-28 | Electronic skin, preparation method and use thereof |
| US14/764,165 US9816882B2 (en) | 2013-01-29 | 2014-01-28 | Electronic skin, preparation method and use thereof |
| KR1020157022839A KR101877108B1 (en) | 2013-01-29 | 2014-01-28 | Electronic skin, preparation method and use thereof |
| CA2899676A CA2899676C (en) | 2013-01-29 | 2014-01-28 | Electronic skin, preparation method and use thereof |
| PCT/CN2014/071631 WO2014117724A1 (en) | 2013-01-29 | 2014-01-28 | Electronic skin, preparation method and use thereof |
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