Uniformly polarized biological piezoelectric film, preparation method and application
By induced uniform arrangement of biopiezoelectric materials by using the substrate electric field during physical vapor deposition, the problems of low preparation efficiency and poor compatibility of biopiezoelectric materials in the prior art are solved, and efficient and convenient biopiezoelectric films are achieved. Preparation and performance improvement.
Patent Information
- Application Number
- CN202411286204.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-09-13
- Publication Date
- 2024-12-27
AI Technical Summary
It is difficult to prepare a film of biopiezoelectric material with uniform polarization in the prior art. The solution method is low in efficiency, the direct solidification method requires the introduction of additional materials and the product efficiency is low, the induction method is high, and the traditional piezoelectric material has poor compatibility with biological bodies.
During physical vapor deposition, the local electric field in the substrate area induced the uniform arrangement of biopiezoelectric materials molecules, and used conductive material substrates and biopiezoelectric materials such as glycine, peptides, proteins or cellulose to achieve efficient and convenient biopiezoelectric Films are prepared and polarization characteristics are adjusted by substrate electric field.
It realizes efficient, convenient, and directly integrated polarized uniform biopiezoelectric thin film preparation, improves the performance of piezoelectric energy harvester, is low cost and compatible with semiconductor processes, is biocompatible, and has performance improvement of more than 400%.
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Figure CN119212542A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of piezoelectric materials, and in particular to a biological piezoelectric film with uniform polarization, a preparation method and application thereof. Background Art
[0002] Piezoelectric materials have been widely used in energy harvesters, sensors, transformers, actuators, piezoelectric electronics, etc. Conventional materials, such as piezoelectric ceramics such as barium titanate, lead titanate, zinc oxide, and molybdenum disulfide, have been widely studied, but their brittleness and non-biological nature limit their application in biological systems.
[0003] The electrical stimulation signals generated by biomaterials under the action of external forces are extremely important for biological processes. For example, the piezoelectric effect of bones can promote bone growth, healing and remodeling. However, piezoelectric biomaterials with uniform polarization are very difficult to prepare. This is mainly because conventional strong electric field pre-polarization treatment methods are difficult to achieve uniformity of randomly arranged polarization directions in biomaterials. In addition, the final application of biopiezoelectric materials also requires a breakthrough in the technical bottleneck of device preparation, and existing technical means all have disadvantages. Existing technologies include the following types:
[0004] Solution method: Spin-coat a solution of biopiezoelectric material (mixed diphenylalanine and 1,1,1,3,3,3-hexafluoro-2-propanol) on the gold-plated Si substrate surface in advance. Since diphenylalanine molecules have spontaneous dipole moments, they can form an oriented seed crystal layer under an external electric field. Then, add a drop of pure diphenylalanine solution. After the solvent evaporates naturally, a biopiezoelectric material film with uniform polarization can be obtained [Reference 1: Nature Communications, 2016, 7: 13566].
[0005] Disadvantages of the solution method: (1) It is impossible to directly grow biological piezoelectric materials with consistent polarization directions, and a layer of seed grains must be prepared in advance on the substrate; (2) When the piezoelectric material continues to grow on the seed grains, the subsequent solution evaporation process is slow, requiring more than 6 hours, and is inefficient.
[0006] Direct coagulation method: a mixed aqueous solution of glycine and polyvinyl alcohol is obtained. Glycine forms hydrogen bonds with polyvinyl alcohol to achieve a polarization-consistent arrangement. Ultrasonic treatment is further used to reduce the nucleation barrier and prevent agglomeration. After evaporating the solvent, a glycine / polyvinyl alcohol composite film is obtained, which can be peeled off and transferred to any substrate [Document 2: A high-voltage γ-glycine / PVA film and its preparation and application, CN 117362715A].
[0007] Disadvantages of direct solidification method: (1) New materials (polyvinyl alcohol) need to be introduced to regulate the growth orientation. Its piezoelectricity originates from the oriented γ-glycine formed by hydrogen bonding with polyvinyl alcohol, and the polarization intensity varies with the mixing ratio of polyvinyl alcohol / glycine. (2) The product is a γ-glycine / polyvinyl alcohol composite film, which needs to be peeled off and then integrated onto the wafer, which is inefficient.
[0008] Induction method: In the highly chemically active Pt(111) / SiO 2 / Si substrate surface, as the solution evaporates, glycine crystals are precipitated. In this process, the chemical reaction between the Pt(111) crystal surface and glycine induces the polarization arrangement of glycine. [Document 3: A L-polylactic acid coated β-glycine composite fiber film and its preparation method and application, CN 118007314A]
[0009] Disadvantages of the induction method: It uses the precious metal Pt, and has requirements for exposed crystal surfaces, requires a Pt (111) active surface, and has a high cost. Summary of the invention
[0010] In order to overcome the defects of the above-mentioned prior art, the purpose of the present invention is to propose a bio-piezoelectric film with uniform polarization, a preparation method and an application. During the physical vapor deposition process, the local electric field in the substrate area is used to induce the deposited bio-piezoelectric material molecules to achieve uniform arrangement, thereby obtaining a bio-piezoelectric material film with high-voltage electrical response, and applying it in energy harvesting, which has the advantages of high efficiency, convenience, direct integration and uniform polarization.
[0011] To achieve the above object, the present invention provides the following technical solutions:
[0012] A biological piezoelectric film with uniform polarization includes a substrate layer and a deposited layer on its surface, wherein the substrate layer is made of conductive material, including low-resistance silicon, ITO conductive glass or Au / Si; the deposited layer is made of biological piezoelectric material, including glycine, polypeptide, protein or cellulose.
[0013] A method for preparing a biological piezoelectric film with uniform polarization comprises the following steps:
[0014] Step 1: wash the substrate with deionized water, anhydrous ethanol and acetone in sequence, and after drying, place the substrate in the substrate area of a physical vapor deposition device, with a parallel electrode plate pre-installed on the back of the substrate; then place the biopiezoelectric material to be deposited in a crucible, and close the cavity of the physical vapor deposition device;
[0015] Step 2, evacuating the physical vapor deposition equipment chamber to a preset vacuum degree, heating the substrate to a first preset temperature, setting the parallel electrode plate electric field on the back of the substrate to a preset voltage, and heating the crucible containing the bio-piezoelectric material to a second preset temperature;
[0016] Step 3: The deposition layer begins to grow on the substrate surface, and stops growing after the deposition layer reaches a preset thickness;
[0017] Step 4: turn off the electric field of the parallel electrode plate on the back of the substrate, cool the substrate and the crucible to room temperature, turn off the vacuum system of the physical vapor deposition equipment, wait for the cavity to return to normal pressure, open the cavity, and obtain a bio-piezoelectric material film.
[0018] In step 1, the substrate layer is made of conductive material, including low-resistance silicon, ITO conductive glass or Au / Si; the deposition layer is made of biological piezoelectric material, including glycine, peptide, protein or cellulose.
[0019] The preset vacuum degree of the physical vapor deposition equipment chamber in step 2 is 10 -3 ~10 -1 Pa.
[0020] In step 2, the first preset temperature of the substrate is 100-300°C.
[0021] In step 2, the preset voltage of the parallel electrode plate electric field is -10 to 10 kV.
[0022] The second preset temperature of the crucible in step 2 is 150-500°C.
[0023] The preset thickness of the deposited layer in step 3 is 1 to 30 μm.
[0024] A piezoelectric energy harvester comprises the uniformly polarized biological piezoelectric film as described in claim 1, and the uniformly polarized biological piezoelectric film prepared based on the above method.
[0025] The specific steps of the piezoelectric energy harvester and its manufacturing method are as follows:
[0026] Step 1) scraping up a corner of the uniformly polarized bio-piezoelectric material film to expose the substrate surface, and sticking the metal wire to the substrate surface with carbon tape to obtain a piezoelectric film with wires;
[0027] Step 2) Take another substrate that has been washed and dried with deionized water, anhydrous ethanol, and acetone in sequence, and use carbon tape to stick a metal wire to a corner of the substrate, and then cover it on the surface of the piezoelectric film with wire obtained in step 1), and use insulating tape to fix the substrate with the metal wire and the obtained piezoelectric film with wire together to obtain a piezoelectric energy harvester.
[0028] Compared with the prior art, the beneficial effects of the present invention are:
[0029] 1. The present invention realizes the preparation of a biological piezoelectric film with uniform polarization through the electric field in the substrate region. The physical vapor deposition technology adopted realizes the direct integration of the device, which is compatible with the existing semiconductor process. It is not only low-cost and high-efficiency, but also can adjust the polarization uniformity of the biological piezoelectric film through the electric field in the substrate region, thereby promoting the improvement of the performance of the biological piezoelectric device.
[0030] 2. Traditional piezoelectric materials are mostly piezoelectric ceramics such as barium titanate, lead titanate, zinc oxide, and molybdenum disulfide, and the compatibility of ceramic materials with organisms is average. The piezoelectric material proposed in the present invention is glycine, polypeptide, protein or cellulose, which are mostly components of organisms, so it has biocompatibility and will have broad application prospects in the biomedical field.
[0031] 3. The present invention adjusts the polarization uniformity of the biological piezoelectric film through the electric field, so that the performance of the piezoelectric energy harvester is improved by more than 400%.
[0032] In summary, the present invention has good biocompatibility and is compatible with existing semiconductor processes. The polarization uniformity characteristics of the biopiezoelectric film can be adjusted by the electric field in the substrate region, and the cost is low and the efficiency is high. BRIEF DESCRIPTION OF THE DRAWINGS
[0033] In order to more clearly illustrate the technical solutions in one or more embodiments of the present disclosure or related technologies, the following briefly introduces the drawings required for use in the embodiments or related technology descriptions. Obviously, the drawings described below are only some embodiments recorded in one or more embodiments of the present disclosure. For ordinary technicians in this field, other drawings can also be obtained based on these drawings without creative labor. By reading the detailed description of the non-limiting embodiments made with reference to the following drawings, other features, purposes and advantages of the present disclosure will become more obvious.
[0034] Figure 1 It is a flow chart of the preparation method of the present invention.
[0035] Figure 2 Schematic diagram of the physical vapor deposition device used in the present invention; the polarization direction of the bio-piezoelectric molecules with spontaneous dipole moment is adjusted by means of the electric field of the parallel electrode plates on the back of the substrate, thereby obtaining a bio-piezoelectric film with uniform polarization.
[0036] Figure 3 This is the XRD spectrum of the glycine / ITO film of the present invention. By comparing with the characteristic peaks of the bare substrate, the glycine film sample has four more characteristic peaks, which is consistent with the standard card PDF#06-0230. The above four characteristic peaks are (101), (102), (003), and (412) respectively. It can be determined that the film obtained on the surface of the ITO substrate is pure phase γ-glycine.
[0037] Figure 4 is a SEM photo of the glycine / ITO film of the present invention, wherein: Figure 4 (a) is the upper surface, showing that the surface of the glycine film is flat and dense. Figure 4 (b) is a cross section, from which it can be seen that the obtained amino acid film has a uniform thickness of about 5 μm, and the film is dense with few pores.
[0038] Figure 5 is a piezoelectric force microscope phase diagram of the glycine / ITO film of the present invention, wherein: Figure 5 (a) is the phase diagram with applied electric field (10 kV), Figure 5 (b) is the phase diagram of the glycine / ITO film obtained when no electric field is applied. It can be seen that after the electric field is applied, the surface polarization orientation of the glycine / ITO film is more consistent and uniform. The piezoelectric coefficient d 33 It is 18.0pm / V.
[0039] Figure 6 Schematic diagram and physical diagram of the ITO / glycine / ITO piezoelectric energy harvester of the present invention.
[0040] Figure 7 This is a performance diagram of the ITO / glycine / ITO piezoelectric energy harvester of the present invention. Under periodic external pressure, the open circuit voltage generated by the piezoelectric energy harvester is collected through the copper wire, where: Figure 7 (a) is the open circuit voltage diagram of the device when the applied electric field is 10 kV, and its maximum value is 0.25 V. Figure 7 (b) is the open circuit voltage diagram of the device without applying an electric field, and its maximum value is 0.06 V. This is mainly because the polarization of the prepared biopiezoelectric film is more uniform after applying an electric field, which helps to increase the collection efficiency of the biopiezoelectric energy harvester. DETAILED DESCRIPTION
[0041] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.
[0042] In the description of the embodiments of the present invention, unless otherwise specified, “plurality” means two or more than two.
[0043] Example 1
[0044] A biological piezoelectric film with uniform polarization comprises a substrate layer and a deposited layer on its surface, wherein the substrate layer is made of conductive material ITO conductive glass; and the deposited layer is made of biological piezoelectric material including glycine.
[0045] A method for preparing a biological piezoelectric film with uniform polarization, specifically comprising:
[0046] (1) The ITO substrate is cleaned with deionized water, anhydrous ethanol, and acetone in sequence, and after being blown dry with nitrogen, the substrate is placed in the substrate area of a physical vapor deposition device, and a parallel electrode plate is pre-installed on the back of the substrate; then, the biopiezoelectric material to be deposited is placed in a crucible, and the cavity of the physical vapor deposition device is closed;
[0047] (2) Evacuate the physical vapor deposition equipment chamber to a preset vacuum degree of 10 -3 Pa, heating the substrate to a first preset temperature of 100°C, setting the parallel electrode plate electric field behind the substrate region to a preset voltage of 10 kV, and heating the crucible containing glycine to a second preset temperature of 150°C;
[0048] (3) The deposition layer begins to grow on the substrate surface and stops growing when the deposition layer reaches a preset thickness of 5 μm;
[0049] (4) Turn off the parallel electrode plate electric field behind the substrate area, cool the substrate and crucible to room temperature, turn off the vacuum system of the physical vapor deposition equipment, wait for the cavity to return to normal pressure, open the cavity, and obtain the glycine / ITO film.
[0050] See also Figure 2 , which is a schematic diagram of the physical vapor deposition device used in the present invention. The gaseous molecules of the bio-piezoelectric material with spontaneous dipole moment evaporated from the crucible will be affected by the electric field of the parallel plate electrode on the back of the substrate when approaching the substrate, which causes the spontaneous dipole moment of the piezoelectric molecules to converge with the direction of the electric field, and finally deposit on the surface of the conductive substrate, thereby obtaining a bio-piezoelectric film with uniform polarization.
[0051] See also Figure 3 By comparing the characteristic peaks of the bare substrate, the glycine film sample has four more characteristic peaks, which are consistent with the standard card PDF#06-0230. The above four characteristic peaks are (101), (102), (003), and (412), respectively, confirming that the obtained film is pure phase γ-glycine.
[0052] See also Figure 4 ,Through the SEM photos of glycine / ITO films, it can be seen that the surface of the glycine film is smooth, the thickness of the amino acid film is uniform, about 5μm, the film is dense, and has few pores.
[0053] See also Figure 5The obtained film was scanned by piezoelectric force microscopy. It can be seen that the polarization orientation of the film surface is more consistent and uniform after the electric field is applied. The piezoelectric coefficient d 33 It is 18.0pm / V.
[0054] See also Figure 6 , a piezoelectric energy harvester, comprising the above-mentioned uniformly polarized biological piezoelectric film, and the uniformly polarized biological piezoelectric film prepared based on the above-mentioned method.
[0055] The specific steps of the method for making the piezoelectric energy harvester are:
[0056] Step 1) scraping up a corner of the uniformly polarized bio-piezoelectric material film to expose the substrate surface, and sticking the metal wire to the substrate surface with carbon tape to obtain a piezoelectric film with wires;
[0057] Step 2) Take another substrate that has been washed and dried with deionized water, anhydrous ethanol, and acetone in sequence, and use carbon tape to stick a metal wire to a corner of the substrate, and then cover it on the surface of the piezoelectric film with wire obtained in step 1), and use insulating tape to fix the substrate with the metal wire and the obtained piezoelectric film with wire together to obtain a piezoelectric energy harvester.
[0058] Example 2
[0059] A biological piezoelectric film with uniform polarization comprises a substrate layer and a deposited layer on its surface, wherein the substrate layer is made of conductive material ITO conductive glass; and the deposited layer is made of biological piezoelectric material including glycine.
[0060] A method for preparing a biological piezoelectric film with uniform polarization, specifically comprising the following steps:
[0061] (1) The ITO substrate is cleaned with deionized water, anhydrous ethanol, and acetone in sequence, and after being blown dry with nitrogen, the substrate is placed in the substrate area of a physical vapor deposition device, and a parallel electrode plate is pre-installed on the back of the substrate; then, the biopiezoelectric material to be deposited is placed in a crucible, and the cavity of the physical vapor deposition device is closed;
[0062] (2) Evacuate the physical vapor deposition equipment chamber to a preset vacuum degree of 10 -2 Pa, heating the substrate to a first preset temperature of 100°C, setting the parallel electrode plate electric field behind the substrate region to a preset voltage of -10 kV, and heating the crucible containing glycine to a second preset temperature of 150°C;
[0063] (3) The deposition layer begins to grow on the substrate surface and stops growing when the deposition layer reaches a preset thickness of 10 μm;
[0064] (4) Turn off the parallel electrode plate electric field behind the substrate area, cool the substrate and crucible to room temperature, turn off the vacuum system of the physical vapor deposition equipment, wait for the cavity to return to normal pressure, open the cavity, and obtain the glycine / ITO film.
[0065] A piezoelectric energy harvester comprises the above-mentioned uniformly polarized biological piezoelectric film and the uniformly polarized biological piezoelectric film prepared based on the above-mentioned method.
[0066] The specific steps of the method for making the piezoelectric energy harvester are:
[0067] Step 1) scraping up a corner of the uniformly polarized bio-piezoelectric material film to expose the substrate surface, and sticking the metal wire to the substrate surface with carbon tape to obtain a piezoelectric film with wires;
[0068] Step 2) Take another substrate that has been washed and dried with deionized water, anhydrous ethanol, and acetone in sequence, and use carbon tape to stick a metal wire to a corner of the substrate, and then cover it on the surface of the piezoelectric film with wire obtained in step 1), and use insulating tape to fix the substrate with the metal wire and the obtained piezoelectric film with wire together to obtain a piezoelectric energy harvester.
[0069] Example 3
[0070] A biological piezoelectric film with uniform polarization comprises a substrate layer and a deposited layer on its surface, wherein the substrate layer is made of conductive material ITO conductive glass; and the deposited layer is made of biological piezoelectric material including glycine.
[0071] A method for preparing a biological piezoelectric film with uniform polarization, specifically comprising the following steps:
[0072] (1) The ITO substrate is cleaned with deionized water, anhydrous ethanol, and acetone in sequence, and after being blown dry with nitrogen, the substrate is placed in the substrate area of a physical vapor deposition device, and a parallel electrode plate is pre-installed on the back of the substrate; then, the biopiezoelectric material to be deposited is placed in a crucible, and the cavity of the physical vapor deposition device is closed;
[0073] (2) Evacuate the physical vapor deposition equipment chamber to a preset vacuum degree of 10 -2 Pa, heating the substrate to a first preset temperature of 150°C, setting the parallel electrode plate electric field behind the substrate region to a preset voltage of 10 kV, and heating the crucible containing glycine to a second preset temperature of 200°C;
[0074] (3) The deposition layer begins to grow on the substrate surface and stops growing when the deposition layer reaches a preset thickness of 10 μm;
[0075] (4) Turn off the parallel electrode plate electric field behind the substrate area, cool the substrate and crucible to room temperature, turn off the vacuum system of the physical vapor deposition equipment, wait for the cavity to return to normal pressure, open the cavity, and obtain the glycine / ITO film.
[0076] A piezoelectric energy harvester comprises the above-mentioned uniformly polarized biological piezoelectric film and the uniformly polarized biological piezoelectric film prepared based on the above-mentioned method.
[0077] The specific steps of the method for making the piezoelectric energy harvester are:
[0078] Step 1) scraping up a corner of the uniformly polarized bio-piezoelectric material film to expose the substrate surface, and sticking the metal wire to the substrate surface with carbon tape to obtain a piezoelectric film with wires;
[0079] Step 2) Take another substrate that has been washed and dried with deionized water, anhydrous ethanol, and acetone in sequence, and use carbon tape to stick a metal wire to a corner of the substrate, and then cover it on the surface of the piezoelectric film with wire obtained in step 1), and use insulating tape to fix the substrate with the metal wire and the obtained piezoelectric film with wire together to obtain a piezoelectric energy harvester.
[0080] Example 4
[0081] A biological piezoelectric film with uniform polarization comprises a substrate layer and a deposited layer on its surface, wherein the substrate layer is made of conductive material, such as low-resistance silicon; and the deposited layer is made of biological piezoelectric material, such as polypeptide.
[0082] A method for preparing a biological piezoelectric film with uniform polarization, specifically comprising the following steps:
[0083] (1) The low-resistance silicon substrate is cleaned with deionized water, anhydrous ethanol, and acetone in sequence, blown dry with nitrogen, and placed in the substrate area of the physical vapor deposition equipment. A baffle is set in front of the substrate, and a parallel electrode plate is introduced on the back of the substrate. Then, the biopiezoelectric material to be deposited is placed in a crucible and the cavity is closed;
[0084] (2) Evacuate the physical vapor deposition equipment chamber to a preset vacuum degree of 10 -2 Pa, heating the substrate to a first preset temperature of 120°C, setting the parallel electrode plate electric field behind the substrate region to a preset voltage of 0 kV, and heating the crucible containing the polypeptide to a second preset temperature of 180°C;
[0085] (3) The deposition layer begins to grow on the substrate surface and stops growing when the deposition layer reaches a preset thickness of 5 μm;
[0086] (4) Turn off the parallel electrode plate electric field behind the substrate area, cool the substrate and crucible to room temperature, turn off the vacuum system of the physical vapor deposition equipment, wait for the cavity to return to normal pressure, open the cavity, and obtain the polypeptide / low-resistance silicon film.
[0087] A piezoelectric energy harvester comprises the above-mentioned uniformly polarized biological piezoelectric film and the uniformly polarized biological piezoelectric film prepared based on the above-mentioned method.
[0088] The specific steps of the method for making the piezoelectric energy harvester are:
[0089] Step 1) scraping up a corner of the uniformly polarized bio-piezoelectric material film to expose the substrate surface, and sticking the metal wire to the substrate surface with carbon tape to obtain a piezoelectric film with wires;
[0090] Step 2) Take another substrate that has been washed and dried with deionized water, anhydrous ethanol, and acetone in sequence, and use carbon tape to stick a metal wire to a corner of the substrate, and then cover it on the surface of the piezoelectric film with wire obtained in step 1), and use insulating tape to fix the substrate with the metal wire and the obtained piezoelectric film with wire together to obtain a piezoelectric energy harvester.
[0091] Example 5
[0092] A biological piezoelectric film with uniform polarization comprises a substrate layer and a deposited layer on its surface, wherein the substrate layer is made of conductive material, such as low-resistance silicon; and the deposited layer is made of biological piezoelectric material, such as glycine.
[0093] A method for preparing a biological piezoelectric film with uniform polarization, specifically comprising the following steps:
[0094] (1) The low-resistance silicon substrate is cleaned with deionized water, anhydrous ethanol, and acetone in sequence, blown dry with nitrogen, and placed in the substrate area of the physical vapor deposition equipment. A baffle is set in front of the substrate, and a parallel electrode plate is introduced on the back of the substrate. Then, the biopiezoelectric material to be deposited is placed in a crucible and the cavity is closed;
[0095] (2) Evacuate the physical vapor deposition equipment chamber to a preset vacuum degree of 10 -3 Pa, heating the substrate to a first preset temperature of 140°C, setting the parallel electrode plate electric field behind the substrate region to a preset voltage of 10 kV, and heating the crucible containing glycine to a second preset temperature of 200°C;
[0096] (3) The deposition layer begins to grow on the substrate surface and stops growing when the deposition layer reaches a preset thickness of 10 μm;
[0097] (4) Turn off the parallel electrode plate electric field behind the substrate area, cool the substrate and crucible to room temperature, turn off the vacuum system of the physical vapor deposition equipment, wait for the chamber to return to normal pressure, open the chamber, and obtain a glycine / low-resistance silicon film.
[0098] A piezoelectric energy harvester comprises the above-mentioned uniformly polarized biological piezoelectric film and the uniformly polarized biological piezoelectric film prepared based on the above-mentioned method.
[0099] The specific steps of the method for making the piezoelectric energy harvester are:
[0100] Step 1) scraping up a corner of the uniformly polarized bio-piezoelectric material film to expose the substrate surface, and sticking the metal wire to the substrate surface with carbon tape to obtain a piezoelectric film with wires;
[0101] Step 2) Take another substrate that has been washed and dried with deionized water, anhydrous ethanol, and acetone in sequence, and use carbon tape to stick a metal wire to a corner of the substrate, and then cover it on the surface of the piezoelectric film with wire obtained in step 1), and use insulating tape to fix the substrate with the metal wire and the obtained piezoelectric film with wire together to obtain a piezoelectric energy harvester.
[0102] Example 6
[0103] A biological piezoelectric film with uniform polarization comprises a substrate layer and a deposited layer on its surface, wherein the substrate layer is made of conductive material, such as low-resistance silicon; and the deposited layer is made of biological piezoelectric material, such as protein.
[0104] A method for preparing a biological piezoelectric film with uniform polarization, specifically comprising the following steps:
[0105] (1) The low-resistance silicon substrate is cleaned with deionized water, anhydrous ethanol, and acetone in sequence, blown dry with nitrogen, and placed in the substrate area of the physical vapor deposition equipment. A baffle is set in front of the substrate, and a parallel electrode plate is introduced on the back of the substrate. Then, the biopiezoelectric material to be deposited is placed in a crucible and the cavity is closed;
[0106] (2) Evacuate the physical vapor deposition equipment chamber to a preset vacuum degree of 10 -2 Pa, heating the substrate to a first preset temperature of 150°C, setting the parallel electrode plate electric field behind the substrate region to a preset voltage of 5 kV, and heating the crucible containing the protein to a second preset temperature of 200°C;
[0107] (3) The deposition layer begins to grow on the substrate surface and stops growing when the deposition layer reaches a preset thickness of 10 μm;
[0108] (4) Turn off the parallel electrode plate electric field behind the substrate area, cool the substrate and crucible to room temperature, turn off the vacuum system of the physical vapor deposition equipment, wait for the chamber to return to normal pressure, open the chamber, and obtain a low-resistance silicon / protein film.
[0109] A piezoelectric energy harvester comprises the above-mentioned uniformly polarized biological piezoelectric film and the uniformly polarized biological piezoelectric film prepared based on the above-mentioned method.
[0110] The specific steps of the method for making the piezoelectric energy harvester are:
[0111] Step 1) scraping up a corner of the uniformly polarized bio-piezoelectric material film to expose the substrate surface, and sticking the metal wire to the substrate surface with carbon tape to obtain a piezoelectric film with wires;
[0112] Step 2) Take another substrate that has been washed and dried with deionized water, anhydrous ethanol, and acetone in sequence, and use carbon tape to stick a metal wire to a corner of the substrate, and then cover it on the surface of the piezoelectric film with wire obtained in step 1), and use insulating tape to fix the substrate with the metal wire and the obtained piezoelectric film with wire together to obtain a piezoelectric energy harvester.
[0113] See also Figure 7 , which is the performance diagram of the obtained piezoelectric energy harvester. Under the action of periodic external pressure, the open circuit voltage generated by the piezoelectric energy harvester was collected through the copper wire. The open circuit voltage of the thin film device obtained without applying an electric field was 0.06V, and the open circuit voltage of the thin film device obtained after applying an electric field was 0.25V. The device performance was significantly improved by more than 400%. This is mainly because the polarization of the biological piezoelectric film prepared after applying an electric field is more uniform, which helps to increase the collection efficiency of the biological piezoelectric energy harvester.
[0114] In addition, it should be understood that although the present specification is described according to implementation modes, not every implementation mode contains only one independent technical solution. This description of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each embodiment may also be appropriately combined to form other implementation modes that can be understood by those skilled in the art.
Claims
1. A biological piezoelectric film with uniform polarization, comprising a substrate layer and a deposited layer on its surface, characterized in that: The substrate layer is made of conductive material, including low-resistance silicon, ITO conductive glass or Au / Si; the deposition layer is made of biological piezoelectric material, including glycine, polypeptide, protein or cellulose.
2. A method for preparing a biological piezoelectric film with uniform polarization, characterized in that: The specific steps include: Step 1, washing the substrate with deionized water, anhydrous ethanol and acetone in sequence, and after drying, placing the substrate in the substrate area of a physical vapor deposition device, with a parallel electrode plate pre-installed on the back of the substrate; Then, the biopiezoelectric material to be deposited is placed in a crucible, and the chamber of the physical vapor deposition device is closed; Step 2, evacuating the physical vapor deposition equipment chamber to a preset vacuum degree, heating the substrate to a first preset temperature, setting the parallel electrode plate electric field on the back of the substrate to a preset voltage, and heating the crucible containing the bio-piezoelectric material to a second preset temperature; Step 3: The deposition layer begins to grow on the substrate surface, and stops growing after the deposition layer reaches a preset thickness; Step 4: turn off the electric field of the parallel electrode plate on the back of the substrate, cool the substrate and the crucible to room temperature, turn off the vacuum system of the physical vapor deposition equipment, wait for the cavity to return to normal pressure, open the cavity, and obtain a bio-piezoelectric material film.
3. The method for preparing a biological piezoelectric film with uniform polarization according to claim 2, characterized in that: The substrate layer is made of conductive material, including low-resistance silicon, ITO conductive glass or Au / Si; the deposition layer is made of biological piezoelectric material, including glycine, polypeptide, protein or cellulose.
4. The method for preparing a biological piezoelectric film with uniform polarization according to claim 2, characterized in that: The preset vacuum degree of the physical vapor deposition equipment chamber in step 2 is 10 -3 ~10 -1 Pa.
5. The method for preparing a biological piezoelectric film with uniform polarization according to claim 2, characterized in that: In step 2, the first preset temperature of the substrate is 100-300°C.
6. The method for preparing a biological piezoelectric film with uniform polarization according to claim 2, characterized in that: In step 2, the preset voltage of the parallel electrode plate electric field is -10 to 10 kV.
7. The method for preparing a biological piezoelectric film with uniform polarization according to claim 2, characterized in that: The second preset temperature of the crucible in step 2 is 150-500°C.
8. The method for preparing a biological piezoelectric film with uniform polarization according to claim 2, characterized in that: The preset thickness of the deposited layer in step 3 is 1 to 30 μm.
9. A piezoelectric energy harvester, characterized in that: It includes the uniformly polarized biopiezoelectric film as described in claim 1, and the uniformly polarized biopiezoelectric film prepared by any method according to claims 2 to 8.
10. The piezoelectric energy harvester according to claim 9, characterized in that: The specific steps of its preparation method are: Step 1) scraping up a corner of the uniformly polarized bio-piezoelectric material film to expose the substrate surface, and sticking the metal wire to the substrate surface with carbon tape to obtain a piezoelectric film with wires; Step 2) Take another substrate that has been washed and dried with deionized water, anhydrous ethanol, and acetone in sequence, and use carbon tape to stick a metal wire to a corner of the substrate, and then cover it on the surface of the piezoelectric film with wire obtained in step 1), and use insulating tape to fix the substrate with the metal wire and the obtained piezoelectric film with wire together to obtain a piezoelectric energy harvester.
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