Piezoelectric nanogenerator and preparation method and application thereof

Abstract

The application belongs to the technical field of electronic devices, and provides a piezoelectric nanogenerator and a preparation method and application thereof.The piezoelectric nanogenerator provided by the application comprises a flexible substrate, a bottom electrode layer, a zinc oxide nanowire array piezoelectric layer, an organic piezoelectric film layer and a top electrode layer which are arranged in layers;the material of the organic piezoelectric film layer comprises 4-(4-dimethylaminostyryl)methylpyridine p-toluenesulfonate and polydimethylsiloxane.The piezoelectric nanogenerator of the application uses 4-(4-dimethylaminostyryl)methylpyridine p-toluenesulfonate (DAST) and polydimethylsiloxane as the organic piezoelectric film layer;since DAST has excellent piezoelectric characteristics and flexibility, the piezoelectric nanogenerator composed of DAST is more flexible and more likely to be elastically deformed, thereby solving the shortcomings of the piezoelectric nanogenerator based on pure zinc oxide nanowire array, i.e., low flexibility and weak piezoelectric output characteristics.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of electronic devices, in particular to a piezoelectric nanogenerator and a preparation method and application thereof. BACKGROUND

[0002] With the development of the times, miniaturization and portability of electronic devices have become a trend. Nanoelectronic devices such as nanorobots and nanoprobes have been applied in various fields such as national defense, medical treatment, energy, chemical industry, and electric power. Therefore, providing continuous and controllable electric energy for these nanoelectronic devices has become a new goal for researchers, and the concept of nanogenerator has emerged as the times require. The nanogenerator based on piezoelectric effect can convert the small and difficult-to-utilize mechanical energy in the environment into the electric energy required by nanoelectronic devices. Such nanogenerator has the advantages of small size, high sensitivity, and low price, and is an excellent choice for realizing self-powered nanoelectronic devices. Therefore, in recent years, it has been favored by scholars all over the world.

[0003] Due to the semiconductor and piezoelectric coupling characteristics of zinc oxide nanowire array, it has always been a popular material for manufacturing piezoelectric nanogenerator. However, the piezoelectric nanogenerator based on zinc oxide nanowire array also has defects such as low stability, poor flexibility, and weak piezoelectric output. SUMMARY

[0004] Therefore, the purpose of the present application is to provide a piezoelectric nanogenerator and a preparation method and application thereof. The piezoelectric nanogenerator provided by the present application has high stability, good flexibility, and strong piezoelectric output.

[0005] In order to achieve the above-mentioned purpose of the application, the present application provides the following technical solutions:

[0006] The present application provides a piezoelectric nanogenerator, which comprises a flexible substrate, a bottom electrode layer, a zinc oxide nanowire array piezoelectric layer, an organic piezoelectric film layer, and a top electrode layer which are stacked.

[0007] The material of the organic piezoelectric film layer comprises 4-(4-dimethylaminostyryl) methylpyridine p-toluenesulfonate and polydimethylsiloxane.

[0008] Preferably, the material of the flexible substrate comprises polyethylene terephthalate, polycarbonate, polypropylene, polyimide, or polymethyl methacrylate.

[0009] Preferably, the material of the bottom electrode layer and the top electrode layer is independently ITO, copper, gold, silver, platinum, palladium, or iridium; and the thickness of the bottom electrode layer and the top electrode layer is independently 50-100 nm.

[0010] Preferably, the zinc oxide in the zinc oxide nanowire array piezoelectric layer is nanorod zinc oxide; the diameter of the nanorod zinc oxide is 60-150 nm; and the thickness of the zinc oxide nanowire array piezoelectric layer is 2-5 μm.

[0011] Preferably, the thickness of the organic piezoelectric film layer is 5-10 μm; and the mass percentage of 4-(4-dimethylaminostyryl)methylpyridinium p-toluenesulfonate in the organic piezoelectric film layer is 1-20%.

[0012] The present application also provides a preparation method of the piezoelectric nanogenerator as described above, comprising the following steps:

[0013] preparing a bottom electrode layer on a flexible substrate;

[0014] after preparing a zinc oxide seed layer on the bottom electrode layer, preparing a zinc oxide nanowire array piezoelectric layer based on the zinc oxide seed layer by a hydrothermal method;

[0015] preparing an organic piezoelectric film layer on the zinc oxide nanowire array piezoelectric layer;

[0016] preparing a top electrode layer on the organic piezoelectric film layer to obtain the piezoelectric nanogenerator.

[0017] Preferably, the thickness of the zinc oxide seed layer is 10-20 nm; the preparation method of the zinc oxide seed layer is magnetron sputtering; and the parameters of the magnetron sputtering include: radio frequency power of 140-180 W, argon flow rate of 50-65 mL / min, and time of 10-20 min.

[0018] Preferably, the precursor solution of the hydrothermal method is a zinc acetate dihydrate-urotropin solution; and the molar ratio of zinc acetate dihydrate to urotropin in the zinc acetate dihydrate-urotropin solution is 1:1-2.

[0019] Preferably, the temperature of the hydrothermal method is 60-100℃, and the time is 60-360 min.

[0020] The present application also provides an application of the piezoelectric nanogenerator as described above or the piezoelectric nanogenerator obtained by the preparation method as described above in a nanoelectronic device.

[0021] The application provides a piezoelectric nanogenerator, which comprises a flexible substrate, a bottom electrode layer, a zinc oxide nanowire array piezoelectric layer, an organic piezoelectric film layer and a top electrode layer which are stacked. The pure zinc oxide nanowire array is prone to be damaged in the experimental pressing process, the piezoelectric nanogenerator of the application is stacked with 4-(4-dimethylaminostyryl) methyl pyridine p-toluene sulfonate (DAST) and polydimethylsiloxane as the organic piezoelectric film layer on the zinc oxide nanowire array piezoelectric layer, since the DAST has excellent flexibility, the zinc oxide nanowire array can be effectively protected, the piezoelectric nanogenerator composed of the zinc oxide nanowire array is more flexible and more prone to elastic deformation, and the defect of low flexibility of the piezoelectric nanogenerator based on the pure zinc oxide nanowire array is solved.

[0022] The application further provides a preparation method of the piezoelectric nanogenerator, which comprises the following steps: preparing the bottom electrode layer on the flexible substrate; preparing the zinc oxide seed crystal layer on the bottom electrode layer, and then preparing the zinc oxide nanowire array piezoelectric layer by using the hydrothermal method based on the zinc oxide seed crystal layer; preparing the organic piezoelectric film layer on the zinc oxide nanowire array piezoelectric layer; and preparing the top electrode layer on the organic piezoelectric film layer to obtain the piezoelectric nanogenerator.

[0023] The application further provides an application of the piezoelectric nanogenerator in a nanoelectronic device. BRIEF DESCRIPTION OF DRAWINGS

[0024] Figure 1 The piezoelectric nanogenerator provided for the embodiment 1 of the application is shown in the structure schematic view. DETAILED DESCRIPTION

[0025] The application provides a piezoelectric nanogenerator, which comprises a flexible substrate, a bottom electrode layer, a zinc oxide nanowire array piezoelectric layer, an organic piezoelectric film layer and a top electrode layer which are stacked.

[0026] The material of the organic piezoelectric film layer comprises 4-(4-dimethylaminostyryl) methyl pyridine p-toluene sulfonate and polydimethylsiloxane.

[0027] In the present application, the raw materials used in the present application are preferably commercially available products, unless otherwise specified.

[0028] The piezoelectric nanogenerator provided by the present application comprises a flexible substrate. In the present application, the material of the flexible substrate preferably comprises polyethylene terephthalate (PET), polycarbonate (PC), polypropylene (PP), polyimide (PI) or polymethyl methacrylate (PMMA), and is further preferably polyethylene terephthalate (PET).

[0029] The piezoelectric nanogenerator provided by the present application comprises a bottom electrode layer stacked on the flexible substrate. In the present application, the material of the bottom electrode layer is preferably ITO, copper, gold, silver, platinum, palladium or iridium, and is further preferably ITO. In the present application, the thickness of the bottom electrode layer is preferably 50-100 nm.

[0030] The piezoelectric nanogenerator provided by the present application comprises a zinc oxide nanowire array piezoelectric layer stacked on the bottom electrode layer. In the present application, the thickness of the zinc oxide nanowire array piezoelectric layer is preferably 2-5 μm, and is further preferably 3-4 μm. In the present application, the zinc oxide in the zinc oxide nanowire array piezoelectric layer is preferably nanorod zinc oxide; the diameter of the nanorod zinc oxide is preferably 60-150 nm.

[0031] The piezoelectric nanogenerator provided by the present application comprises an organic piezoelectric film layer stacked on the zinc oxide nanowire array piezoelectric layer. In the present application, the material of the organic piezoelectric film layer comprises 4-(4-dimethylaminostyryl) methylpyridine p-toluenesulfonate (DAST) and polydimethylsiloxane (PDMS). In the present application, the mass percentage of 4-(4-dimethylaminostyryl) methylpyridine p-toluenesulfonate in the organic piezoelectric film layer is preferably 1-20%. In the present application, the thickness of the organic piezoelectric film layer is 5-10 μm.

[0032] The piezoelectric nanogenerator provided by the present application comprises a top electrode layer stacked on the organic piezoelectric film layer. In the present application, the material of the top electrode layer is preferably ITO, copper, gold, silver, platinum, palladium or iridium. In the present application, the thickness of the top electrode layer is preferably 50-100 nm.

[0033] The piezoelectric nanogenerator provided by the present application preferably further comprises a protective layer stacked on the top electrode layer. In the present application, the material of the protective layer preferably comprises polyethylene terephthalate (PET), polycarbonate (PC), polypropylene (PP), polyimide (PI) or polymethyl methacrylate (PMMA), and is further preferably polyethylene terephthalate (PET). In the present application, the thickness of the protective layer is preferably 0.05 mm-0.2 mm.

[0034] The application further provides a preparation method of the piezoelectric nanogenerator.

[0035] The bottom electrode layer is prepared on a flexible substrate.

[0036] After the zinc oxide seed layer is prepared on the bottom electrode layer, a zinc oxide nanowire array piezoelectric layer is prepared by using a hydrothermal method based on the zinc oxide seed layer.

[0037] An organic piezoelectric film layer is prepared on the zinc oxide nanowire array piezoelectric layer.

[0038] A top electrode layer is prepared on the organic piezoelectric film layer to obtain the piezoelectric nanogenerator.

[0039] The bottom electrode layer is prepared on a flexible substrate. In the application, the flexible substrate is preferably pretreated before the bottom electrode layer is prepared, and the pretreatment preferably comprises sequentially performing acetone ultrasonic washing, anhydrous ethanol ultrasonic washing, deionized water washing and drying; the time of the acetone ultrasonic washing, the anhydrous ethanol ultrasonic washing and the deionized water washing is independently preferably 10-20 min. In the application, the preparation method of the bottom electrode layer is preferably sputtering or evaporation, and the application does not make specific limitation on the parameters of the sputtering or evaporation as long as the bottom electrode layer with a target thickness can be obtained.

[0040] After the bottom electrode layer is prepared, the application preferably further comprises: taking out the obtained sample, repeatedly washing with deionized water and drying to prepare the zinc oxide seed layer subsequently.

[0041] After the bottom electrode layer is prepared, the application prepares a zinc oxide seed layer on the bottom electrode layer. In the application, the thickness of the zinc oxide seed layer is preferably 10-20 nm. In the application, the preparation method of the zinc oxide seed layer is preferably magnetron sputtering; the parameters of the magnetron sputtering include: the radio frequency power is preferably 140-180 W, further preferably 150-170 W, and more preferably 160 W; the argon flow rate is preferably 50-65 mL / min, and further preferably 55-60 mL / min; and the time is preferably 10-20 min.

[0042] After the preparation of the zinc oxide seed layer, the present application uses a hydrothermal method to prepare a zinc oxide nanowire array piezoelectric layer based on the zinc oxide seed layer. In the present application, the precursor solution of the hydrothermal method is preferably a zinc acetate dihydrate-urotropin solution; the molar ratio of zinc acetate dihydrate to urotropin in the zinc acetate dihydrate-urotropin solution is preferably 1:1-2, further preferably 1:1.2-1.8, and more preferably 1:1.4-1.6. In the present application, the solvent of the zinc acetate dihydrate-urotropin solution is preferably water. In the present application, the temperature of the hydrothermal method is preferably 60-100℃; the time is preferably 60-360 min. In the present application, the hydrothermal method preferably includes the following steps: immersing the flexible substrate on which the bottom electrode layer and the zinc oxide seed layer are laminated into the precursor solution to prepare the zinc oxide nanowire array piezoelectric layer by the hydrothermal method. In the present application, the hydrothermal method is preferably carried out in a sealed high-pressure reaction kettle.

[0043] After the preparation of the zinc oxide nanowire array piezoelectric layer, the present application preferably further includes: taking out the obtained sample, repeatedly rinsing with deionized water, and drying; to prepare a subsequent organic piezoelectric film layer.

[0044] After the preparation of the zinc oxide nanowire array piezoelectric layer, the present application prepares an organic piezoelectric film layer on the zinc oxide nanowire array piezoelectric layer. In the present application, the preparation method of the organic piezoelectric film layer is preferably a spin coating method. In the present application, the steps of the spin coating method preferably include: mixing 4-(4-dimethylaminostyryl)methylpyridinium p-toluenesulfonate and a polydimethylsiloxane mixture, spin coating onto the zinc oxide nanowire array piezoelectric layer, and sequentially performing vacuum debubbling and curing. The present application does not make specific limitations on the operation of the vacuum debubbling, as long as the bubbles can be completely removed. In the present application, the temperature of the curing is preferably 70℃, and the time is preferably 2 h.

[0045] After the preparation of the organic piezoelectric film layer, the present application prepares a top electrode layer on the organic piezoelectric film layer to obtain the piezoelectric nanogenerator. In the present application, the preparation method of the top electrode layer is preferably sputtering or evaporation, and the present application does not make specific limitations on the parameters of the sputtering or evaporation, as long as the top electrode layer with the target thickness can be obtained.

[0046] The present application also provides the piezoelectric nanogenerator prepared by the preparation method of the above technical solution or the piezoelectric nanogenerator in the above technical solution in the application of nanoelectronic devices. The present application does not make specific limitations on the application mode of the piezoelectric nanogenerator in the nanoelectronic devices, and the application mode well known to those skilled in the art can be used.

[0047] The piezoelectric nanogenerator and the preparation method thereof provided by the present application will be described in detail below in conjunction with examples, but they should not be understood as limitations on the protection scope of the present application.

[0048] Embodiment

[0049] Zinc acetate and hexamethylenetetramine (Urotropine) powder were weighed with a molar ratio of 1:1, and then equal molar zinc acetate and hexamethylenetetramine were fully dissolved and mixed with deionized water, and stirred uniformly for 15 min to prepare a precursor solution with a volume of 50 mL and a total concentration of zinc acetate and hexamethylenetetramine of 30 mM for standby.

[0050] A commercially available flexible PET / ITO was used as a flexible substrate and a bottom electrode layer; the commercially available flexible PET / ITO was cut into a square sheet with a size of 2 cm x 2 cm. Then the cut flexible PET / ITO was placed in a clean beaker, and was sequentially subjected to ultrasonic washing with acetone for 10 min and ultrasonic washing with ethanol for 10 min, and then was repeatedly washed with deionized water. Finally, the cleaned flexible PET / ITO was placed in an oven and dried at 80°C for 1 h for standby.

[0051] A dense and continuous ZnO seed layer with a thickness of 16 nm was grown on the ITO of the cleaned flexible PET / ITO by radio frequency magnetron sputtering, and the radio frequency magnetron sputtering conditions were as follows: argon flow rate was 65 mL / min, radio frequency power was 180 W, temperature of the flexible PET / ITO was room temperature, and time was 20 min.

[0052] The flexible PET / ITO with the ZnO seed layer was vertically placed in a high-pressure reaction kettle containing the precursor solution, the high-pressure reaction kettle was strictly sealed, and was placed in an oven for hydrothermal growth to obtain a zinc oxide nanowire array piezoelectric layer with a thickness of 3 μm; the hydrothermal growth was carried out in a closed high-pressure environment at a temperature of 95°C for 3 h. After the hydrothermal growth was completed, the high-pressure reaction kettle was taken out of the oven and was cooled to room temperature, and then the sample was taken out, repeatedly washed with deionized water, and dried.

[0053] First, the DAST powder was repeatedly ground, and then the ground DAST powder was filtered with a 900-mesh screen to obtain small-size DAST particles; the small-size DAST particles were mixed with PDMS in a certain proportion, and were mechanically stirred for 1 h to obtain a uniformly mixed DAST-PDMS material; in the DAST-PDMS material, the mass percentage of DAST was 1%, 5%, 10%, 15%, and 20%, respectively; and the obtained piezoelectric nanogenerators were named as piezoelectric nanogenerator-1, piezoelectric nanogenerator-5, piezoelectric nanogenerator-10, piezoelectric nanogenerator-15, and piezoelectric nanogenerator-20, respectively.

[0054] Different DAST-PDMS materials were spin-coated on the piezoelectric layer of the zinc oxide nanowire array at 60 s, 500 rpm, and then vacuumized for 30 min to remove bubbles in the film. The DAST-PDMS was cured by heating in an oven at 70 ℃ for 2 h to obtain an organic piezoelectric film layer with a thickness of 10 μm.

[0055] The top electrode layer (PET / ITO, ITO in contact with the organic piezoelectric film layer) was pressed on the organic piezoelectric film layer and connected with the upper and lower bottom electrodes and the top electrode by copper wires, and the piezoelectric nanogenerator was completed. Figure 1 The piezoelectric nanogenerator obtained in this embodiment is shown in the structure diagram.

[0056] The stability of the piezoelectric nanogenerator was determined by the number of bending and compression failures, and the results are shown in Table 1.

[0057] The flexibility of the piezoelectric nanogenerator was determined by the bending deformation rate, and the results are shown in Table 1.

[0058] The piezoelectric output of the piezoelectric nanogenerator was determined by a digital multimeter, and the results are shown in Table 1.

[0059] Table 1 shows the performance test results of the piezoelectric nanogenerator.

[0060]

[0061] The above only describes the preferred embodiments of the present application, and it should be noted that those skilled in the art can make several improvements and refinements without departing from the principles of the present application, and these improvements and refinements should also be considered within the scope of protection of the present application.

Claims

1. A piezoelectric nanogenerator, characterized by, The piezoelectric nanogenerator comprises a flexible substrate, a bottom electrode layer, a zinc oxide nanowire array piezoelectric layer, an organic piezoelectric film layer and a top electrode layer arranged in layers. The material of the organic piezoelectric film layer comprises 4-(4-dimethylaminostyryl) methylpyridine p-toluenesulfonate and polydimethylsiloxane. The mass percentage of 4-(4-dimethylaminostyryl) methylpyridine p-toluenesulfonate in the organic piezoelectric film layer is 1-20%.

2. The piezoelectric nanogenerator of claim 1, wherein, The material of the flexible substrate comprises polyethylene terephthalate, polycarbonate, polypropylene, polyimide or polymethyl methacrylate.

3. The piezoelectric nanogenerator of claim 1, wherein, The material of the bottom electrode layer and the top electrode layer is independently ITO, copper, gold, silver, platinum, palladium or iridium; the thickness of the bottom electrode layer and the top electrode layer is independently 50-100 nm.

4. The piezoelectric nanogenerator of claim 1, wherein, The zinc oxide in the zinc oxide nanowire array piezoelectric layer is nanorod zinc oxide; the diameter of the nanorod zinc oxide is 60-150 nm; the thickness of the zinc oxide nanowire array piezoelectric layer is 2-5 μm.

5. The piezoelectric nanogenerator of claim 1, wherein, The thickness of the organic piezoelectric film layer is 5-10 μm.

6. The method of claim 1 to 5, wherein the piezoelectric nanogenerator is prepared by the steps of: The piezoelectric nanogenerator comprises the following steps: Preparation of a bottom electrode layer on a flexible substrate; Preparation of a zinc oxide seed layer on the bottom electrode layer, and preparation of a zinc oxide nanowire array piezoelectric layer based on the zinc oxide seed layer by a hydrothermal method; Preparation of an organic piezoelectric film layer on the zinc oxide nanowire array piezoelectric layer; Preparation of a top electrode layer on the organic piezoelectric film layer to obtain the piezoelectric nanogenerator.

7. The preparation method according to claim 6, characterized in that, The thickness of the zinc oxide seed layer is 10-20 nm; the preparation method of the zinc oxide seed layer is magnetron sputtering; the parameters of the magnetron sputtering include: radio frequency power of 140-180 W, argon flow rate of 50-65 mL / min, and time of 10-20 min.

8. The preparation method according to claim 6, characterized in that, The temperature of the hydrothermal method is 60-100 ℃, and the time is 60-360 min.

9. The production method according to claim 6 or 8, characterized by, 10. Use of the piezoelectric nanogenerator of any one of claims 1-5 or the piezoelectric nanogenerator obtained by the preparation method of any one of claims 6-9 in a nano-electronic device. ​

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