CN115159448A - Regular micro-nano cone array structure conductive film, and preparation method and application thereof - Google Patents
Regular micro-nano cone array structure conductive film, and preparation method and application thereof Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
- B81C1/00—Manufacture or treatment of devices or systems in or on a substrate
- B81C1/00015—Manufacture or treatment of devices or systems in or on a substrate for manufacturing microsystems
- B81C1/00134—Manufacture or treatment of devices or systems in or on a substrate for manufacturing microsystems comprising flexible or deformable structures
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/024—Anodisation under pulsed or modulated current or potential
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/045—Anodisation of aluminium or alloys based thereon for forming AAO templates
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
- C25D11/08—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing inorganic acids
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
- C25D11/10—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing organic acids
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/02—Electrolytic coating other than with metals with organic materials
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01L—MEASURING FORCE, STRESS, TORQUE, WORK, MECHANICAL POWER, MECHANICAL EFFICIENCY, OR FLUID PRESSURE
- G01L1/00—Measuring force or stress, in general
- G01L1/20—Measuring force or stress, in general by measuring variations in ohmic resistance of solid materials or of electrically-conductive fluids; by making use of electrokinetic cells, i.e. liquid-containing cells wherein an electrical potential is produced or varied upon the application of stress
- G01L1/22—Measuring force or stress, in general by measuring variations in ohmic resistance of solid materials or of electrically-conductive fluids; by making use of electrokinetic cells, i.e. liquid-containing cells wherein an electrical potential is produced or varied upon the application of stress using resistance strain gauges
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
- H01B13/0026—Apparatus for manufacturing conducting or semi-conducting layers, e.g. deposition of metal
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- General Physics & Mathematics (AREA)
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- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
Abstract
The invention discloses a regular micro-nano cone array structure conductive film, a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) Preparing a conical anodic aluminum oxide template by an anodic oxidation method; (2) Polymerizing monomers of a conductive polymer onto the hole wall of the conical anodic aluminum oxide template in the step (1) by adopting a chemical in-situ polymerization method; (3) Spin-coating a solution of a flexible high polymer on the conical alumina template obtained in the step (2), and placing the template in a vacuum drying oven for high-temperature treatment; (4) Putting the tapered alumina template subjected to vacuum high-temperature treatment into a mixed solution of hydrochloric acid and copper chloride to remove an aluminum substrate; (5) And (5) placing the template obtained in the step (4) in a phosphoric acid aqueous solution to remove the tapered anodic alumina template. The conductive film prepared by the method has the conductivity of the conductive polymer and the flexibility of the flexible polymer, and the prepared interlocking piezoresistive sensor has high sensitivity and large measuring range.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a regular micro-nano cone array structure conductive film, and a preparation method and application thereof.
Background
Bio-inspired micro-nanostructured films are considered to be one of the promising materials for the fabrication of high-sensitivity sensors. The bionic structure mainly comprises an interlocking structure, a crack structure, a whisker structure, a human skin structure and a fingerprint structure. The micro-nano interlocking sensor attracts the research and attention of many scholars due to the combination of the microstructure and the interlocking structure. Cheng et al prepared a sensitivity of 10.41kPa by coating graphene onto a PDMS array using microfabrication and micromanipulation techniques -1 The interlocking pressure sensor of (Cheng L, qian W, et al.J.Mater.chem.C,2020,8 (33): 11525-11531). Ha et al prepared flexible piezoresistive sensor with PDMS micro-column coated with ZnO nanowire, and the sensitivity of the sensor was 6.8kPa -1 (Ha M, lim S, et al. Advanced Functional Materials,2015, 25. Park et al designed an interlocking microsphere structure that mimics human skin, thereby producing a sensitivity of 15.1kPa -1 The sensors of (Park J, lee Y, et al. ACS Nano,2014,8 (5): 4689-4697).
However, the current molds for preparing microstructures mainly comprise silicon dioxide [ Lee Y, park J, ACS Nano,2018,12 (4): 4045-4054] and natural biomaterials [ Wan Y, qiu Z, small,2018,14 (35): 1-8], and the preparation of the silicon dioxide template needs to adopt the traditional photoetching technology, so that the preparation process is complex, the equipment dependence is strong, and the manufacturing cost is high. The dimension of the geometric microstructure of the natural biomaterial is not adjustable due to the inherent property of the microstructure, and the microstructure of the conductive film prepared by using the mold is mostly in the micron grade.
Disclosure of Invention
The invention aims to provide a preparation method of a regular micro-nano cone array structure conductive film;
the invention also aims to provide a method for preparing the interlocking piezoresistive sensor by using the conductive film prepared by the method.
Therefore, the invention adopts the following technical scheme:
a preparation method of a structured micro-nano cone array structure conductive film comprises the following steps:
(1) Preparing a single-layer or double-layer conical anodic aluminum oxide template on an aluminum substrate by adopting an anodic oxidation method;
(2) Polymerizing a monomer of a conductive polymer on the hole wall of the single-layer or double-layer conical anodic aluminum oxide template obtained in the step (1) by adopting a chemical in-situ polymerization method, wherein the monomer of the conductive polymer is pyrrole, aniline or thiophene;
(3) Spin-coating a solution of a flexible high polymer on the single-layer or double-layer conical alumina template which is attached with the conductive polymer on the surface and obtained in the step (2) by adopting a spin-coating method, then placing the template in a vacuum drying oven, and carrying out high-temperature treatment under a vacuum condition, wherein the flexible high polymer is polymethyl methacrylate, polystyrene, polyurethane or polyacrylonitrile;
(4) Placing the single-layer or double-layer conical anodic alumina template which is provided with the aluminum substrate and is provided with the conductive high polymer and flexible high polymer composite coating on the surface after vacuum high-temperature treatment into mixed solution of hydrochloric acid and copper chloride to remove the aluminum substrate;
(5) And (3) placing the single-layer or double-layer conical anodic aluminum oxide template with the conductive polymer and flexible polymer composite coating attached to the surface obtained in the step (4) into a phosphoric acid aqueous solution to remove the conical anodic aluminum oxide template, so as to obtain the single-layer or double-layer regular micro-nano cone array structure conductive film.
Wherein, when the single-layered tapered alumina template is prepared in the step (1), the reaction solution is 1wt% 3 PO 4 And the concentration of C is 0.03-0.3M 2 H 2 O 4 Mixed liquid, oxidation voltageRespectively 200V,190V,180V,170V,150V and 130V are decreased in turn, and the corresponding C 2 H 2 O 4 The concentrations are respectively 0.03M,0.05M,0.07M,0.1M,0.2M and 0.3M, and the reaction time is 10-40min; the method for preparing the double-layer conical aluminum oxide template comprises the step of anodizing the single-layer conical anodized aluminum template in 0.1-0.4M oxalic acid solution for 0.5-30min at the reaction temperature of 0-3 ℃.
The specific method of the step (2) is as follows: immersing the aluminum substrate with the surface attached with the conical anodic aluminum oxide into an aqueous solution of a conductive polymer monomer with the concentration of 0.2-0.4M, magnetically stirring for 20-35min, then adding a mixed aqueous solution containing 0.3-0.7M of p-toluenesulfonic acid and 0.3-0.6M of ferric trichloride in the same volume, and polymerizing for 40-80min under the condition of magnetic stirring.
Preferably, in the step (3), the solvent of the solution of the flexible high polymer is N, N-dimethylformamide, the mass fraction of the solute is 10-25wt%, the rotation speed of a spin coater is 500-4000r/min, and the spin coating time is 10-30s; the temperature of the vacuum drying oven is 80-160 ℃, and the time is 1-3.5h.
Preferably, in the step (4), the concentration of hydrochloric acid in the mixed solution of hydrochloric acid and copper chloride is 5 to 25wt%, and the concentration of copper chloride is 0.05 to 0.15mol/L.
Preferably, in the step (5), the mass fraction of the phosphoric acid aqueous solution is 10 to 30wt%, and the reaction temperature is 20 to 60 ℃.
The structured micro-nano cone array structure conductive film prepared by the preparation method has the advantages that the diameter of the micro-nano cone of the single-layer structured micro-nano cone array structure conductive film is 50nm-500nm, and the height of the micro-nano cone is 100nm-20 microns; in the double-layer regular micro-nano cone array structure conductive film, the diameter of the bottom layer nano column is 50nm-500nm, the height of the bottom layer nano column is 100nm-20 mu m, and the diameter of the top layer nano column is 50nm-100nm, and the height of the top layer nano column is 10nm-1000nm.
Firstly, taking two regular micro-nano cone array structure conductive films, respectively sticking a strip-shaped conductive electrode by conductive silver adhesive at the edge of the same side of one surface of the two conductive films, which is provided with a nano cone, and naturally drying the conductive films at room temperature; and placing the nano conical surfaces of the two conductive films face to face, extending the two strip electrodes in the same direction, and packaging to obtain the interlocking piezoresistive sensor.
Preferably, the size of the regular micro-nano cone array structure conducting film is (1-2) cm by (1-2) cm; the strip-shaped conductive electrode is a copper sheet, a gold sheet, a titanium sheet or a platinum sheet, or a magnetron sputtering copper, platinum, titanium or composite coating electrode thereof.
The packaging method comprises the step of packaging by using a flexible adhesive tape, wherein the flexible adhesive tape is a polyvinyl chloride adhesive tape or a polyurethane adhesive tape. The invention takes conical anodic alumina as a template, adopts an in-situ polymerization method and a high polymer spin coating method, and prepares a regular micro-nano cone array structure conductive film by dissolving the conical anodic alumina in a phosphoric acid aqueous solution, and further adopts an interlocking structure to package as an interlocking piezoresistive sensor.
The invention has the following beneficial effects:
(1) The single-layer or double-layer anodic alumina template adopted by the invention is a hexagonal continuous structure with holes vertical to the aluminum substrate and arranged in parallel, has the characteristics of ordered structure height, large specific surface area and the like, and can be adjusted in the size within the nanometer range, so that the diameter of the nanocone in the prepared single-layer conductive film is 50-500nm, and the height is adjustable within the range of 100nm-20 mu m; the diameter of the bottom layer nano column in the double-layer hierarchical structure conductive film can be 50nm-500nm, the height is 100nm-20 μm, and the diameter of the top layer nano column can be 50nm-100nm, and the height is 0nm-1000nm;
(2) The regular micro-nano cone array structure conducting film structure prepared by the invention is in a cone array structure taking a flexible high polymer as a core and a conductive high polymer as a shell, and has both the conductivity of the conductive polymer and the flexibility of the flexible high polymer, so that the conducting film structure can be used for preparing a flexible pressure sensor;
(3) The regular micro-nano cone array structure conductive film prepared by the embodiment of the invention has the size of 1cm x 1cm and the thickness of 1460nm (embodiment 1), and provides a basis for preparing a miniaturized sensor; the regular nano cone structure is more sensitive to tiny weak pressure due to the nano size and the large specific surface area, so that the prepared sensor has ultrahigh sensitivity;
(4) The interlocking piezoresistive sensor prepared by the interlocking packaging structure has the advantages that the nano cones and the nano cone surfaces are in face-to-face contact through interlocking, the contact area between the nano cones is effectively increased, the sensitivity of the sensor is further increased, and the interlocking piezoresistive sensor has the advantages of low voltage, high sensitivity, high precision and miniaturization.
(5) The invention combines the conductive high polymer and the flexible polymer by adopting a template method, the method is simple and feasible, the prepared film is highly regular, the flexible polymer is taken as a core, the conductive high polymer is taken as a shell, the conductive film is in a conical array structure, the conductive film has the conductivity of the conductive high polymer and the flexibility of the flexible polymer, and the structure of the film is stable.
Drawings
Fig. 1a is an SEM image of a single-layer micro-nano cone array structure conductive film prepared in example 1 of the present invention;
fig. 1b is an SEM image of the conductive film with a double micro-nano cone array structure prepared in embodiment 3 of the present invention;
fig. 2a is a real object diagram of a single-layer micro-nano cone array structure PPy thin film prepared in embodiment 1 of the present invention;
FIG. 2b is a diagram of a single layer nanocone array flexible conductive polymer PPy @ PMMA film prepared in example 1 of the present invention;
FIG. 3 is a schematic diagram of an exploded view of an interlocking piezoresistive sensor fabricated in example 1 of the present invention;
FIG. 4 is a schematic structural diagram of an interlocking piezoresistive sensor fabricated in example 1 of the present invention;
fig. 5 is a compression schematic diagram of the interlocking structure of the single-layer micro-nano cone array conductive film prepared in this embodiment 1;
fig. 6 is a compression schematic diagram of the double-layer micro-nano cone array conductive film interlocking structure with small hole pitch prepared in this embodiment 2;
fig. 7 is a compression schematic diagram of the large-pore-spacing double-layer micro-nano cone array conductive film interlocking structure prepared in this embodiment 3;
FIG. 8a is a piezoresistive test pattern for a sample prepared according to example 1 of the present invention;
FIG. 8b is a piezoresistive test pattern of a sample prepared in example 2 of the present invention;
FIG. 8c is a piezoresistive test pattern of a sample prepared in example 3 of the present invention;
in the figure:
1. polyvinyl chloride adhesive tape 2, strip-shaped electrode 3 and regular micro-nano cone array structure conducting film
Detailed Description
The process of the present invention will be described in detail with reference to specific examples.
Before the following examples are carried out, an aluminum sheet is pretreated and pre-oxidized, and the specific method comprises the following steps:
ultrasonically cleaning a high-purity aluminum sheet with the purity of 99.999 percent in acetone for 15min to remove grease on the surface, then cleaning the aluminum sheet with deionized water, then placing the aluminum sheet in a 1mol/L NaOH solution for 10min to remove a natural oxidation layer on the surface, and finally cleaning and drying the aluminum sheet with deionized water; taking a dried aluminum sheet as an anode and a titanium sheet as a cathode, and mixing the aluminum sheet and the titanium sheet in a solution volume ratio of 1:4, performing electrochemical polishing for 5min in a mixed solution of perchloric acid and absolute ethyl alcohol at the voltage of 21V and the temperature of 0-5 ℃ to obtain the aluminum sheet with a smooth surface.
Taking a pretreated aluminum sheet as an anode, a titanium sheet as a cathode, and taking a mixed solution containing 0.03M oxalic acid and 1wt% of phosphoric acid (namely, the concentrations of the oxalic acid and the phosphoric acid in the mixed solution are respectively 0.03M and 1wt%, the same applies below) as an electrolyte to carry out first anodic oxidation, wherein the oxidation voltage is 200V, the temperature is 0-3 ℃, and the oxidation time is 4 hours; placing the alumina film with the aluminum substrate after the first oxidation on a CrO containing 18g/L 3 And 6 wt.% of H 3 PO 4 The reaction temperature in the mixed solution is 60 ℃, and the generated alumina is removed to obtain the aluminum sheet with regular pits.
The solutions described in the following examples are aqueous solutions unless otherwise specified.
The technical solution of the invention is further illustrated by the following specific examples.
Example 1
A preparation method of a conducting film with a single-layer regular micro-nano cone array structure comprises the following steps of:
(1) Carrying out second anodic oxidation on the aluminum sheet with the regular pits under the condition that the conditions of the first anodic oxidation are the same, carrying out chemical corrosion for 45min in a 5wt% phosphoric acid solution after oxidizing for 2min, carrying out anodic oxidation for 2min again after chemical corrosion, carrying out chemical corrosion for 45min in the 5wt% phosphoric acid solution, and finally carrying out anodic oxidation for 2min again, carrying out chemical corrosion for 90min in the 5wt% phosphoric acid solution, thus obtaining a highly ordered single-layer conical Anodic Alumina (AAO) template;
(2) Soaking the AAO template prepared in the step (1) in a pyrrole aqueous solution with the volume of 10ml and the concentration of 0.3M, and magnetically stirring for 30min (using a beaker with the volume of 25 ml) to ensure that the pyrrole aqueous solution can fully enter holes of the AAO template; then adding 10ml of mixed aqueous solution containing 0.5M doping agent p-toluenesulfonic acid and 0.45M oxidant ferric trichloride, polymerizing for 60min, wherein the process is also carried out under the condition of magnetic stirring; then taking out the conical anodic alumina template plated with polypyrrole, and naturally drying;
(3) Dripping 20wt% of polymethyl methacrylate solution on the conical anodic alumina template with polypyrrole, which is obtained in the step (2), wherein the rotating speed of a spin coater is 800/min, and the spin coating time is 30s; after spin coating, placing the mixture into a vacuum drying oven, setting the temperature at 150 ℃ in a vacuum state, keeping the temperature for 2 hours, and then naturally cooling the mixture to room temperature;
(4) Removing the aluminum substrate from the single-layer conical anodic alumina template (with the conductive polymer and flexible polymer composite coating attached to the surface) with the aluminum substrate obtained in the step (3) in a mixed solution containing 10% hydrochloric acid and 0.1mol/L copper chloride;
(5) And (3) reacting the anodic alumina template obtained in the step (4) in a phosphoric acid solution with the temperature of 30 ℃ and the weight of 20w% to remove the conical anodic alumina template, so as to obtain the conductive film with the single-layer regular micro-nano cone array structure.
FESEM picture of the conducting film with the single-layer regular micro-nano cone array structure is shown in figure 1a, and the height of the nano cone is 1460nm. The cross section shows that the diameter of the nanocone gradually increases from top to bottom. The height and the diameter of the nano-cone structure can be continuously adjusted within the range of 50-500nm in diameter and 100nm-20 mu m in height by changing the size of the AAO template. The corresponding relation between the oxidation time and the height of the nano-cone is regulated and controlled by changing the second oxidation time in the step (1), the second oxidation time in the step (1) is 2min and is oxidized for 3 times, the corresponding height of the nano-cone is 1460nm, and specific parameters for regulating and controlling the height of the nano-cone by changing the oxidation time are shown in table 1.
TABLE 1 time for the second oxidation and the height of the corresponding nanocones prepared
Example 2
A preparation method of a double-layer micro-nano cone array structure conductive film comprises the following steps of sequentially carrying out:
(1) Carrying out second anodic oxidation on the aluminum sheet with the regular pits under the condition that the condition of the first anodic oxidation is the same, carrying out chemical corrosion for 15min in a 5wt% phosphoric acid solution after oxidizing for 2min, carrying out anodic oxidation for 2min again after the chemical corrosion, carrying out chemical corrosion for 15min in the 5wt% phosphoric acid solution, and carrying out oxidation and hole expansion for 4 times alternately, wherein the second oxidation is finished;
(2) Placing the aluminum sheet after the secondary oxidation in 0.15M oxalic acid solution, wherein the oxidation voltage is 100V and the oxidation time is 140s, and then performing chemical corrosion in 5wt% phosphoric acid solution for 30min to obtain a double-layer conical Anodic Aluminum Oxide (AAO) template;
(3) Soaking the prepared AAO template in a pyrrole aqueous solution with the volume of 10ml and the concentration of 0.3M, and magnetically stirring for 30min (using a beaker with the volume of 25 ml) to ensure that the pyrrole aqueous solution can fully enter the holes of the AAO template; then adding 10ml of mixed aqueous solution containing 0.5M doping agent p-toluenesulfonic acid and 0.45M oxidant ferric trichloride, polymerizing for 60min, wherein the process is also carried out under the condition of magnetic stirring; then taking out the conical anodic alumina template plated with polypyrrole, and naturally drying;
(4) Dripping 20wt% of polymethyl methacrylate solution on the conical anodic alumina template with polypyrrole, which is obtained in the step (2), wherein the rotating speed of a spin coater is 800/min, and the spin coating time is 30s; after spin coating, placing the mixture into a vacuum drying oven, setting the temperature at 150 ℃ in a vacuum state, keeping the temperature for 2 hours, and then naturally cooling the mixture to room temperature;
(5) Removing unreacted aluminum matrix from a conical anodic aluminum oxide template with an aluminum substrate in a mixed solution containing 10 percent hydrochloric acid and 0.1mol/L copper chloride,
(6) And (3) reacting in a 20w% phosphoric acid solution at 30 ℃ to remove the conical anodic aluminum oxide template, thereby obtaining the double-layer regular micro-nano cone array structure conductive film.
The flexible conductive high polymer film of the nanocone array is of a hierarchical structure, and on the basis of the nanocones at the bottom, 3-4 top-layer nanocones are grown, the diameter of the nanocones at the bottom is 215nm, and the cross interlocking of the hierarchical nanocones can be realized. The diameter of the bottom layer nanocone in the micropore interval hierarchical micro-nano cone is 50-250nm, and the height is adjustable within the range of 100nm-20 mu m; the diameter of the top layer nano-column can be continuously adjustable within 50nm-100nm and the height thereof is continuously adjustable within 0nm-1000nm.
Example 3
A preparation method of a double-layer regular micro-nano cone array structure conductive film with large pore space comprises the following steps in sequence:
(1) Carrying out second anodic oxidation on the aluminum sheet with the regular pits under the condition that the condition of the first anodic oxidation is the same, carrying out chemical corrosion for 37.5min in 5wt% phosphoric acid solution after oxidizing for 2min, carrying out anodic oxidation for 2min again after the chemical corrosion, carrying out chemical corrosion for 37.5min in 5wt% phosphoric acid solution, and carrying out oxidation and hole expansion for 4 times alternately, wherein the second oxidation is finished;
(2) Placing the aluminum sheet after secondary oxidation in 0.15M oxalic acid solution, wherein the oxidation voltage is 100V and the oxidation time is 140s, and then performing chemical corrosion in 5wt% phosphoric acid solution for 30min to obtain a large-pore-spacing hierarchical structure AAO template;
(3) Soaking the prepared AAO template in pyrrole aqueous solution with the volume of 10ml and the concentration of 0.3M, and magnetically stirring for 30min (using a beaker with the volume of 25 ml) to ensure that the pyrrole aqueous solution can fully enter the holes of the AAO template; then adding 10ml of mixed aqueous solution containing 0.5M doping agent p-toluenesulfonic acid and 0.45M oxidant ferric trichloride, polymerizing for 60min, wherein the process is also carried out under the condition of magnetic stirring; then taking out the conical anodic alumina template plated with polypyrrole, and naturally drying;
(4) Dripping 20wt% of polymethyl methacrylate solution on the conical anodic alumina template with polypyrrole, which is obtained in the step (2), wherein the rotating speed of a spin coater is 800/min, and the spin coating time is 30s; after spin coating, placing the mixture into a vacuum drying oven, setting the temperature at 150 ℃ in a vacuum state, keeping the temperature for 2 hours, and then naturally cooling the mixture to room temperature;
(5) Removing unreacted aluminum matrix in a mixed solution containing 10% hydrochloric acid and 0.1mol/L copper chloride,
(6) And (3) reacting in a 20w% phosphoric acid solution at 30 ℃ to remove the conical anodic aluminum oxide template, thereby obtaining the double-layer regular micro-nano cone array structure conductive film with the large pore space.
The FESEM picture of the flexible conductive high polymer film of the nanocone array is shown in figure 1b, a hierarchical structure is presented, about 3-4 small nanocones are grown on the basis of a large nanocone, the length of the nanocone at the bottom layer is about 1.67um, and the length of the nanocone at the top layer with the diameter of about 325nm is about 264nm. The diameter of the bottom layer nanocone in the macro-pore spacing hierarchical micro-nano cone is 250-500nm, and the height is adjustable within the range of 100nm-20 mu m; the diameter of the top layer nano column can be continuously adjusted within 50nm-100nm, and the height thereof can be continuously adjusted within 0nm-1000nm.
In the above 3 embodiments, besides polypyrrole, polyaniline or polythiophene may be used as the conductive polymer; the flexible polymer may also be polyurethane, polystyrene, or polyacrylonitrile.
Analysis of nano-cone array conductive polymer material object diagram
Fig. 2a is a physical diagram of a conductive polymer thin film of a nanocone array PPy, and it can be seen that there are many cracks on the surface of the conductive polymer thin film of a nanocone array PPy, which results in that a complete conductive network cannot be formed, and furthermore, due to poor mechanical properties, the PPy thin film cannot return to its original shape after being compressed.
In contrast, referring to a physical diagram of the nanocone array flexible conductive polymer ppy @ pmma prepared in example 1 of the present invention shown in fig. 2b, it can be seen from the figure that the film is an intact conductive film, no cracks appear on the surface, and the diagram shows that ppy @ pmma has good flexibility and can be freely bent, which provides a good basis for preparing a flexible sensor. Therefore, the introduction of the PMMA layer improves the flexibility of the PPy film, so that the PPy film has elastic recovery performance, and therefore, the PPy film can be used for manufacturing flexible pressure sensors.
EXAMPLE 4 preparation of interlocking piezoresistive Sensors
Referring to fig. 3, firstly, a strip-shaped electrode 2 is bonded with one side of the nano conical surface of the regular micro-nano cone array structure conductive film 2 by using conductive silver adhesive, and the regular micro-nano cone array structure conductive film is naturally dried at room temperature (the time is about 12 hours), wherein the size of the regular micro-nano cone array structure conductive film is 1cm by 1cm, and the size of the copper sheet electrode is 50mm by 2mm; and then placing the nanometer conical surfaces of the two regular micro-nano cone array structure conductive films bonded with the copper sheet electrodes face to face, and then packaging with a polyvinyl chloride tape 1 to obtain the interlocking piezoresistive sensor, wherein the size of the polyvinyl chloride tape is 1.5cm x 1.5cm. The prepared interlocking piezoresistive sensor is shown in fig. 4.
Analysis of compression mechanism
Referring to fig. 5, in the interlocking piezoresistive sensor manufactured by using the conductive film with the single-layer micro-nano cone array structure manufactured in embodiment 1, when no pressure is applied, the single-layer micro-nano cones are in cross contact with each other in an interlocking structure, and along with the increase of the pressure, the micro-nano cones are displaced in the first stage, so that the contact area is increased; and the second stage is compression deformation of the micro-nano cone.
Referring to fig. 6, in the interlocking sensor assembled by using the conductive film with the double-layer micro-nano cone structure with small hole pitch prepared in embodiment 2, when no pressure is applied, the double-layer micro-nano cones are in cross contact with each other in the interlocking structure, and along with the increase of the pressure, in the first stage, the double-layer micro-nano cones are displaced, and the contact area of the bottom micro-nano cone is increased; the second stage is extrusion deformation of the top micro-nano cone, and the contact area is further increased; the third stage is compression deformation of the double-layer micro-nano cone.
Referring to fig. 7, in the interlocking sensor assembled by the conductive film with the double-layer micro-nano cone structure and large pore space prepared in embodiment 2, when no pressure is applied, the top micro-nano cones are in cross contact with each other in the interlocking structure, and along with the increase of the pressure, the first stage is extrusion deformation of the top micro-nano cones, so that the contact area is increased; the second stage is compression deformation of the top micro-nano cone; the third stage is compression deformation of the bottom micro-nano cone.
Interlocking piezoresistive sensor sensitivity analysis
Figures 8a-c are piezoresistive test patterns of interlocking piezoresistive sensors fabricated from the nanocone array flexible conductive polymer films fabricated in examples 1-3, respectively, showing that the rate of resistance change increases with increasing pressure. The sensitivity calculation formula is as follows:
where S is the sensitivity and P is the pressure.
And then the sensitivity is calculated according to a sensitivity calculation formula.
FIG. 8a shows that when the pressure is 0.5kPa, the sensitivity of the interlocking piezoresistive sensor assembled by the nano-cone array PPy @ PMMA conductive film prepared in example 1 is 100.86kPa -1 The range of the measuring range is 0-5kPa, and the sensitivity value is far larger than the sensitivity value of the sensor reported in the prior research;
FIG. 8b shows that, when the pressure is 0.5kPa, the sensitivity of the interlocking piezoresistive sensor assembled by the nano-cone array PPy @ PMMA conductive film prepared in example 2 is 58.52kPa -1 The range of measurement is 0-12kPa, and the sensitivity value is larger than the sensitivity value of the sensor reported in the prior research;
FIG. 8c shows that, when the pressure is 0.5kPa, the sensitivity of the interlocking piezoresistive sensor assembled by the nano-cone array PPy @ PMMA conductive film prepared in example 3 is 43.39kPa -1 The sensitivity value is larger than the sensitivity value of the sensor reported in the prior research, and the measuring range is 0-21kPa, the effective range of the sensor is far larger than that of the same-scale micro-nano structure sensor.
Claims (10)
1. A preparation method of a structured micro-nano cone array structure conductive film comprises the following steps:
(1) Preparing a single-layer or double-layer conical anodic aluminum oxide template on an aluminum substrate by adopting an anodic oxidation method;
(2) Polymerizing a monomer of a conductive polymer on the hole wall of the single-layer or double-layer conical anodic aluminum oxide template obtained in the step (1) by adopting a chemical in-situ polymerization method, wherein the monomer of the conductive polymer is pyrrole, aniline or thiophene;
(3) Spin-coating a solution of a flexible high polymer on the single-layer or double-layer conical alumina template which is attached with the conductive polymer on the surface and obtained in the step (2) by adopting a spin-coating method, then placing the template in a vacuum drying oven, and carrying out high-temperature treatment under a vacuum condition, wherein the flexible high polymer is polymethyl methacrylate, polystyrene, polyurethane or polyacrylonitrile;
(4) Placing the single-layer or double-layer conical anodic aluminum oxide template which is provided with the aluminum substrate and is attached with the conductive polymer and flexible polymer composite coating on the surface after vacuum high-temperature treatment into a mixed solution of hydrochloric acid and copper chloride to remove the aluminum substrate;
(5) And (5) placing the single-layer or double-layer conical anodic aluminum oxide template with the conductive polymer and flexible polymer composite coating attached to the surface, which is obtained in the step (4), in a phosphoric acid aqueous solution to remove the conical anodic aluminum oxide template, so as to obtain the single-layer or double-layer regular micro-nano cone array structure conductive film.
2. The production method according to claim 1, wherein, when the single-layered tapered alumina template is produced in the step (1), the reaction solution is 1wt% as follows 3 PO 4 And a concentration of 0.03-0.3M C 2 H 2 O 4 The oxidation voltage of the mixed solution is respectively 200V,190V,180V,170V,150V and 130V and is decreased in turn, and the corresponding C is 2 H 2 O 4 The concentrations are respectively 0.03M,0.05M,0.07M,0.1M,0.2M and 0.3M, and the reaction time is 10-40min; preparation of double-layer conical alumina moldThe method of the plate is to anodize the single-layer conical anodized aluminum template for 0.5 to 30min in 0.1 to 0.4M oxalic acid solution, and the reaction temperature is 0 to 3 ℃.
3. The preparation method according to claim 1, wherein the specific method of step (2) is: immersing the aluminum substrate with the cone-shaped anodic aluminum oxide attached on the surface into aqueous solution of conductive polymer monomer with the concentration of 0.2-0.4M, magnetically stirring for 20-35min, then adding mixed aqueous solution containing 0.3-0.7M of p-toluenesulfonic acid and 0.3-0.6M of ferric trichloride with the same volume, and polymerizing for 40-80min under the condition of magnetic stirring.
4. The method of claim 1, wherein: in the step (3), the solvent of the solution of the flexible high polymer is N, N-dimethylformamide, the mass fraction of the solute is 10-25wt%, the rotating speed of a spin coater is 500-4000r/min, and the spin coating time is 10-30s; the temperature of the vacuum drying oven is 80-160 ℃, and the time is 1-3.5h.
5. The production method according to claim 1, wherein in the step (4), the concentration of hydrochloric acid in the mixed solution of hydrochloric acid and copper chloride is 5 to 25wt%, and the concentration of copper chloride is 0.05 to 0.15mol/L.
6. The production method according to claim 1, wherein in the step (5), the mass fraction of the phosphoric acid aqueous solution is 10 to 30wt%, and the reaction temperature is 20 to 60 ℃.
7. A structured micro-nano cone array structure conductive film prepared by the preparation method of any one of claims 1 to 6, which is characterized in that: the diameter of the micro-nano cone of the conducting film with the single-layer regular micro-nano cone array structure is 50nm-500nm, and the height of the micro-nano cone is 100nm-20 mu m; in the double-layer regular micro-nano cone array structure conductive film, the diameter of the bottom layer nano column is 50nm-500nm, the height of the bottom layer nano column is 100nm-20 mu m, and the diameter of the top layer nano column is 50nm-100nm, and the height of the top layer nano column is 10nm-1000nm.
8. An application of the structured micro-nano cone array structure conductive film of claim 7 in the preparation of interlocking piezoresistive sensors is characterized in that:
firstly, taking two regular micro-nano cone array structure conductive films, respectively sticking a strip-shaped conductive electrode on the same side edge of one surface of each conductive film with a nano cone by using conductive silver adhesive, and naturally drying at room temperature; and then placing the nano conical surfaces of the two conductive films face to face, extending the two strip electrodes in the same direction, and then packaging to obtain the interlocking piezoresistive sensor.
9. Use according to claim 8, characterized in that: the size of the regular micro-nano cone array structure conductive film is (1-2) cm; the strip-shaped conductive electrode is a copper sheet, a gold sheet, a titanium sheet or a platinum sheet, or is a magnetron sputtering copper, platinum, titanium or composite coating electrode thereof.
10. Use according to claim 8, wherein the packaging method is packaging with a flexible tape, which is a polyvinyl chloride tape or a polyurethane tape.
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