CN112945428A - Micro-scale grid-shaped dielectric layer and preparation method and application thereof - Google Patents
Micro-scale grid-shaped dielectric layer and preparation method and application thereof Download PDFInfo
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- CN112945428A CN112945428A CN201911262590.4A CN201911262590A CN112945428A CN 112945428 A CN112945428 A CN 112945428A CN 201911262590 A CN201911262590 A CN 201911262590A CN 112945428 A CN112945428 A CN 112945428A
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- G01L1/14—Measuring force or stress, in general by measuring variations in capacitance or inductance of electrical elements, e.g. by measuring variations of frequency of electrical oscillators
Abstract
The invention discloses a preparation method of a micro-scale grid-shaped dielectric layer, which takes a PDMS film as a substrate and carries out 3D printing on ionic gel to obtain the micro-scale grid-shaped dielectric layer. The micro-nano 3D printing technology is used, a complex photoetching process is not needed, the experiment steps are simple, the operation is easy, and the cost is low. The experiment can be completed in a common experiment environment without an ultra-clean environment in the process of printing the ionic gel to prepare the dielectric layer, and the requirement on the operation environment is low. The resulting dielectric layer is sandwiched between two electrodes to form a flexible sensor having a microstructure different from that of usual in<The sensitivity can reach 65.71Kpa in the range of 0.4kPa‑1The sensitivity is higher.
Description
Technical Field
The invention relates to the technical field of flexible electronic materials, in particular to a micro-scale grid-shaped dielectric layer and a preparation method and application thereof.
Background
In recent years, the field of flexible electronics has evolved over the years. Flexible sensors are becoming important applications in future robotics, in vitro diagnostics and energy harvesting. According to recent advances in robotic systems, prostheses, and wearable medical devices, efforts to implement high-sensitivity flexible sensors with simple methods have become a research focus for experimenters.
The dielectric layer or electrode prepared from the PDMS material is required to be added with different microstructures on the PDMS film according to the working principle of the capacitive sensor to improve the sensitivity of the sensor. The microstructures prepared by the template method comprise pyramid-shaped, semicircular, cylindrical, folded, nanoneedle, hole, random microstructures and the like. The process for preparing the microstructures by utilizing the template method is complex and has high requirements on experimental environment. Therefore, it is a problem to be solved to prepare a new microstructure by a simple process.
Disclosure of Invention
The invention aims to provide a method for preparing a micro-scale grid-shaped dielectric layer aiming at the defect that the micro-structure dielectric layer prepared by a template method in the prior art has high requirements on experimental environment.
The invention also aims to provide the micro-scale grid-shaped dielectric layer prepared by the preparation method.
The technical scheme adopted for realizing the purpose of the invention is as follows:
a preparation method of a micro-scale grid-shaped dielectric layer comprises the following steps:
step 1: preparing a PDMS film;
step 2: uniformly stirring P (VDF-HFP) and acetone, adding ionic liquid, heating in water bath to obtain ionic gel, and standing;
and step 3: filling the obtained ionic gel into a needle tube, and carrying out latticed 3D printing by taking the PDMS film obtained in the step (1) as a substrate;
and 4, step 4: and drying and curing the 3D printed ionic gel and peeling the ionic gel from the substrate to obtain the latticed ionic gel film.
In the above technical scheme, in the step 1, the preparation method of the PDMS film comprises the steps of uniformly coating PDMS and a curing agent thereof on a glass slide, and drying and curing to obtain the PDMS film.
In the above technical scheme, the mass ratio of the PDMS to the curing agent thereof is (8-12): 1, the drying and curing conditions are that the temperature is 70-90 ℃ and the time is 4-5 h.
In the above technical scheme, in step 2, the ionic liquid is 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide.
In the technical scheme, the mass ratio of P (VDF-HFP) to acetone is 1 (10-15); the mass ratio of P (VDF-HFP) to the ionic liquid is (5-5.5): (4.5-5).
In the technical scheme, the water bath heating temperature is 60-80 ℃.
In the above technical solution, the grid-like 3D printing in step 3 includes a program 01 and a program 02;
setting the size of the micro-scale grid-shaped dielectric layer to be printed as a, and the grid size as b;
the program 01: the lead screw moves a along the X-axis direction in sequence at the speed of 1 cm/s; b, moving along the Y-axis direction; moving along the X-axis direction, moving a along the Y-axis direction, and moving b; circulating for a/b times in sequence;
the program 02: the lead screw moves a along the Y-axis direction in sequence at the speed of 1 cm/s; b, moving along the X-axis direction; moving along the Y-axis direction by-a; b, moving along the X-axis direction; and circulating for a/b times in sequence.
In the technical scheme, in the step 4, the drying and curing conditions are that the temperature is 70-90 ℃ and the time is 4-5 h.
In one aspect of the present invention, the micro-scale grid-like dielectric layer prepared by the above preparation method has a size of (18-21) mm x (18-21) mm and a grid size of (0.9-1.1) mm x (0.9-1.1) mm.
In one aspect of the invention, the use of a micro-scale grid-like dielectric layer in a flexible sensor.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the preparation method of the micro-scale grid-shaped dielectric layer, provided by the invention, PDMS is used as a substrate, a micro-nano 3D printing technology is used, a complex photoetching process is not required, the experiment steps are simple, the operation is easy, and the cost is low. The experiment can be completed in a common experiment environment without an ultra-clean environment in the process of printing the ionic gel to prepare the dielectric layer, and the requirement on the operation environment is low.
2. The flexible sensor prepared by the micro-scale grid-shaped dielectric layer senses the change of pressure through an electric double layer formed by ionic gel, the sensitivity of the sensor can reach 65.71Kpa-1 within the range of less than 0.4kPa, the repeatability can reach 7200 times at least, the minimum pressure can be detected to be 1.5pa, the quick response time is 43ms, and the sensitivity of the flexible capacitance sensor is greatly improved.
Drawings
FIG. 1 is a schematic flow chart of a method for preparing a dielectric layer in example 1;
FIG. 2 is a flow chart of ionic gel preparation in step 2 of example 1;
FIG. 3 is a schematic structural diagram of a micro-nano 3D printing platform;
FIG. 4 is a schematic structural view of a flexible sensor according to embodiment 2;
fig. 5 is a graph of sensitivity data for the flexible sensor of example 2.
In the figure: 1-a plastic substrate, 2-z-axis moving platform, 3-Y-axis moving lead screw I, 4-Y-axis moving lead screw belt, 5-Y-axis moving lead screw II, 6-X-axis moving lead screw and 7-an injection pump; 8-needle tube, 9-first bayonet, 10-second bayonet, 11 screw control system, 12-first wire, 13 injection pump control system, 14-second wire, 15- (P (VDF-HFP), 16-acetone, 17-P (VDF-HFP) and acetone mixed reagent, 18-ionic liquid, 19-water, 20-ionic gel, 21-glass slide, 26-PDMS, 22-grid ionic gel film, 23-upper electrode, 24-lower electrode, 25-magnetic stirring bead and 26-PDMS.
Detailed Description
The present invention will be described in further detail with reference to specific examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
A method for preparing a micro-scale grid-shaped dielectric layer, as shown in fig. 1, comprises the following steps:
step 1: uniformly mixing PDMS26 and a curing agent thereof in a mass ratio of 10:1, coating the mixture on a glass slide 21, and drying and curing the mixture at 80 ℃ for 4 hours to obtain a PDMS film;
step 2: as shown in FIG. 2, 1.18g of structural polymer P (VDF-HFP) (1,1, 1-trifluoro-N- [ (trifluoromethyl) sulfonyl) methanesulfonamide ] lithium salt) (manufacturer Sigma-Aldrich)15 was mixed in a 1:15 ratio with 17.7g of acetone 16 into a small beaker and sealed with tinfoil, and stirred on a magnetic stirrer at 600rpm for one hour. After stirring was complete, a large beaker was prepared and 1/5 of tap water 19 was poured in, which was placed on a magnetic stirrer and allowed to heat to 70 ℃. After completion of heating, the mixture was heated in accordance with the formula P (VDF-HFP): ionic liquid 5.5:4.5 0.965g of ionic liquid 18 (i.e. 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide, abbreviated as EMIM (TFSI), source leaf biotechnology limited) was weighed into a small beaker with the mixed liquid and immediately sealed with tinfoil. And (3) placing the small beaker into the heated large beaker, adjusting the stirring speed of a magnetic stirrer to 600rpm, keeping the temperature unchanged at 70 ℃, and starting water bath heating to prepare the ionic gel 20 with certain viscosity. Stopping the magnetic stirring instrument after 10 minutes, taking out the small beaker, and standing for 10-15 minutes at room temperature;
and step 3: after the ionogel in the small beaker had cooled down and became viscous, 0.3mL of ionogel 20 was aspirated through a previously prepared 1mL needle 8, and a 110 μm needle was attached. A small amount 502 of glue may be applied to the needle tube during needle installation to prevent the needle from being pushed off during printing. Moreover, after the needle tube absorbs the ionic gel, the small beaker needs to be sealed and placed in a room temperature environment again;
and 4, step 4: taking the PDMS film obtained in the step 1 as a substrate, and carrying out latticed 3D printing; and (3) printing by taking the PDMS film obtained in the step (1) as a substrate, so that a sample is clean and the printed ionic gel is not easy to collapse.
The microscale, reticulated dielectric layers of the present invention were prepared and exhibited substantially the same performance as example 1, with process parameter adjustments made in accordance with the teachings of the present invention.
Example 2
This embodiment describes the 3D printing process in detail.
As shown in fig. 3, in the micro-nano 3D printing platform, 1 is a plastic substrate, 2 is a z-axis moving platform, 3 is a Y-axis moving lead screw one, 4 is a Y-axis moving lead screw belt, 5 is a Y-axis moving lead screw two, 6 is an X-axis moving lead screw, and 7 is an injection pump; 8 is a needle tube (the volume is 1mL, the inner diameter of the needle head is 110 μm), 9 is a first bayonet (used for pushing the needle tube), 10 is a second bayonet (used for fixing the needle tube), 11 is a lead screw control system, 12 is a first electric wire (connecting the lead screw and the lead screw control system), 13 is an injection pump control system, and 14 is a second electric wire (connecting the injection pump and the injection pump control system);
electrifying the micro-nano 3D printing platform, and starting the screw control system 11 and the injection pump control system 13. The adjustment screw control system 11 adjusts the syringe pump 7 to the home position. And (3) placing the PDMS film obtained in the step (1) on a z-axis moving platform 2, installing a needle tube 8 filled with the ionic gel 20 on an injection pump 7, and adjusting the height of the z-axis moving platform 2 and the placing position of the PDMS film according to the position of the needle tube 8. According to the size of the grid-shaped dielectric layer designed previously, the screw control system 11 and the injection pump control system 13 are debugged, and a motion program is input into the screw control system 11:
the dimensions of the dielectric layer according to the printing are 20mm by 20mm, and the grid size is 1mm by 1 mm. The setting is performed according to the following program data.
Procedure 01: the lead screw moves 20mm along the X-axis direction at the speed of 1cm/s and does not move along the Y-axis; the screw rod moves 1.0mm along the Y-axis direction at the speed of 1cm/s and does not move along the X-axis; the screw rod moves by-20 mm along the X-axis direction at the speed of 1cm/s and does not move along the Y-axis; the screw rod moves 1.0mm along the Y-axis direction at the speed of 1cm/s and does not move along the X-axis; and circulating 20 times in sequence.
Procedure 02: the lead screw moves 20mm along the Y-axis direction at the speed of 1cm/s and does not move along the X-axis; the screw rod moves 1.0mm along the X-axis direction at the speed of 1cm/s and does not move along the Y-axis; the screw rod moves by-20 mm along the Y-axis direction at the speed of 1cm/s and does not move along the X-axis; the screw rod moves 1.0mm along the X-axis direction at the speed of 1cm/s and does not move along the Y-axis; and circulating 20 times in sequence.
After the process 01 is finished, i.e. after the first layer of ion gel folding line printing is finished, the syringe pump returns to the initial position, and the process 02 is started to print the second layer of ion gel folding line on the basis of the first layer.
And after printing is finished, closing the lead screw control system 11 and the injection pump control system 13, stripping the printed latticed ionic gel film from the PDMS film, drying and curing at 80 ℃ for 5 hours, and finishing the preparation of the dielectric layer of the sensor.
The micro-scale grid-shaped dielectric layer of the present embodiment can be prepared by adjusting the process parameters according to the content of the present embodiment, and exhibits the performance substantially consistent with that of embodiment 2.
Example 3
A flexible sensor, as shown in fig. 4, comprises an upper electrode 23, a lower electrode 24, and a micro-scale grid-like dielectric layer 22 prepared in example 1 interposed between the upper electrode 23 and the lower electrode 24.
The preparation method of the electrode comprises the following steps: taking 200uL of silver nanowire solution (AgNWs for short) (the concentration is 10mg/ml, the diameter of the silver nanowire is 90nm, and the length is 40-60um) by using a liquid transfer machine, and placing the silver nanowire solution on a vortex oscillator to oscillate for 1-2min so as to uniformly disperse the silver nanowire in the reagent. The purchased transparent CPI film (25um thick) was cut to 10X 10cm2Sized and placed on a relatively flat laboratory bench. And (4) cleaning the coating rod, dripping the AgNWs solvent which is uniformly dispersed on the upper end of the CPI film after the coating rod is dried, and immediately rolling and coating downwards by using the coating rod. And finally, putting the CPI film coated with AgNWs on the rod into a drying box, and drying for 30min at 80 ℃.
Two sections of conductive adhesive with the length of 10cm are cut, one end of the conductive adhesive is fixed on an upper electrode and a lower electrode of the flexible sensor respectively, and the other end of the conductive adhesive is used for being connected with an Agilent LCR meter capable of measuring the capacitance value of the sensor and used for measuring the performance of the capacitive sensor. As shown in FIG. 5, the sensor has a sensitivity of 65.71Kpa-1 in the range of <0.4kPa, repeatability of at least 7200 times, a detectable minimum pressure of 1.5pa and a fast response time of 43 ms.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of a micro-scale grid-shaped dielectric layer is characterized by comprising the following steps:
step 1: preparing a PDMS film;
step 2: uniformly stirring P (VDF-HFP) and acetone, adding ionic liquid, heating in water bath to obtain ionic gel, and standing;
and step 3: filling the obtained ionic gel into a needle tube, and carrying out latticed 3D printing by taking the PDMS film obtained in the step (1) as a substrate;
and 4, step 4: and drying and curing the 3D printed ionic gel and peeling the ionic gel from the substrate to obtain the latticed ionic gel film.
2. The method of claim 1, wherein the PDMS film is prepared by uniformly coating PDMS and a curing agent on a glass slide, drying and curing to obtain the PDMS film in step 1.
3. The method according to claim 2, wherein the mass ratio of the PDMS to the curing agent is (8-12): 1, the drying and curing conditions are that the temperature is 70-90 ℃ and the time is 4-5 h.
4. The method according to claim 1, wherein in step 2, the ionic liquid is 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide.
5. The method according to claim 4, wherein the mass ratio of P (VDF-HFP) to acetone is 1 (10-15); the mass ratio of P (VDF-HFP) to the ionic liquid is (5-5.5): (4.5-5).
6. The method of claim 5, wherein the water bath heating temperature is 60-80 ℃.
7. The production method according to claim 1, wherein the mesh-like 3D printing in step 3 includes a program 01 and a program 02;
setting the size of the micro-scale grid-shaped dielectric layer to be printed as a, and the grid size as b;
the program 01: the lead screw moves a along the X-axis direction in sequence at the speed of 1 cm/s; b, moving along the Y-axis direction; moving along the X-axis direction, moving a along the Y-axis direction, and moving b; circulating for a/b times in sequence;
the program 02: the lead screw moves a along the Y-axis direction in sequence at the speed of 1 cm/s; b, moving along the X-axis direction; moving along the Y-axis direction by-a; b, moving along the X-axis direction; and circulating for a/b times in sequence.
8. The method according to claim 1, wherein in step 4, the drying and curing conditions are 70-90 ℃ for 4-5 h.
9. The micro-scale grid-like dielectric layer prepared by the preparation method of claim 7, wherein the micro-scale grid-like dielectric layer has a size of (18-21) mm x (18-21) mm and a grid size of (0.9-1.1) mm x (0.9-1.1) mm.
10. Use of the micro-scale grid-like dielectric layer of claim 9 in a flexible sensor.
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| CN114295255A (en) * | 2021-12-29 | 2022-04-08 | 金陵科技学院 | Flexible pressure sensor based on 3D prints |
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Application publication date: 20210611 |