A method for preparing a wearable ferroelectric photovoltaic film
The flexible NBT-SCO film is prepared by the sol-gel method and magnetron sputtering technology, which solves the problems of high cost and lack of bendability of existing ferroelectric photovoltaic films, and realizes efficient photoelectric conversion and wide application.
Patent Information
- Application Number
- CN202210739413.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2022-06-28
- Publication Date
- 2025-10-17
- Estimated Expiration
- 2042-06-28
AI Technical Summary
Existing methods for preparing ferroelectric photovoltaic films are costly, have stringent equipment requirements, and lack film bendability, limiting their application scenarios. The open-circuit voltage of traditional photovoltaic materials is limited by the band gap, making it difficult to improve photoelectric conversion efficiency.
NBT-SCO thin films were prepared using the sol-gel method. By combining magnetron sputtering and mechanical exfoliation techniques with a flexible substrate, the photoelectric conversion and bendability of the thin films were achieved by controlling the ligand field and oxygen vacancy concentration.
The preparation of bendable ferroelectric photovoltaic films improves photovoltaic performance and is suitable for more application scenarios, including wearable devices, smart electronic devices and medical devices, achieving efficient conversion of solar energy into electrical energy output.
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Figure CN115117257B_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The application belongs to the field of photovoltaic materials and technology, and particularly relates to a preparation method of a wearable ferroelectric photovoltaic film. BACKGROUND
[0002] In the face of the dual challenges of current energy consumption and environmental pollution, the use of clean renewable energy has become a problem to be solved. With the gradual development of photoelectric conversion technology, photovoltaic effect has shown obvious advantages in modern industry. It can convert solar energy into electrical energy to alleviate the energy crisis. The traditional semiconductor photovoltaic effect is based on PN junction to realize the photoelectric conversion process, and uses the space charge region to separate the photo-generated carriers, which limits the open-circuit voltage to the band gap, making it difficult to further improve the photoelectric conversion efficiency. Ferroelectric photovoltaic materials have the advantages of not being limited by the band gap and being green and non-toxic, and are widely used due to their excellent photovoltaic performance. Nowadays, with the continuous development of electronic device integration, people have higher requirements for its portability, bendability and lightness, so the research and use of flexible electronic devices have gained great recognition and development prospects. Therefore, flexible photovoltaic devices show great application potential in wearable devices, smart electronic devices and medical devices. However, due to the limitation of the Fermi level difference between P-type and N-type semiconductors, the open-circuit voltage is always limited by the band gap of the material. And the existing ferroelectric photovoltaic film material does not have the characteristics of thin film bending, which greatly limits its application scene range.
[0003] The existing ferroelectric photovoltaic film preparation method, such as pulsed laser deposition (PLD), requires a vacuum environment for the preparation process, high working conditions, high cost of instruments and equipment, slow deposition speed, and a deposition thickness of about several hundred nanometers to 1 micron per hour. At present, it can only be used for scientific research and is not suitable for production. In addition, the widely used magnetron sputtering technology has the problem of instability and abnormal production behavior of metals due to the high activity of oxygen atoms during oxide film deposition. Moreover, due to the influence of reaction sputtering hysteresis effect, the stoichiometric ratio of the prepared film appears to be different, which is not suitable for the preparation of flexible NBT-SCO((Na 0.5 Bi 0.5 TiO3)-SrCoO3) materials. SCO is dissolved into NBT to form a solid solution, which means that a certain amount of SCO components is added to the NBT structure according to the corresponding site while maintaining the original NBT structure. In simple terms, Sr ions and Co ions replace Na, Bi ions and Ti ions in the original structure to form a structure. SUMMARY
[0004] To solve the above technical problems, the application provides a preparation method of a flexible wearable ferroelectric photovoltaic film.
[0005] Specifically, the application provides a preparation method of a wearable ferroelectric photovoltaic film, and a wearable NBT-SCO film is prepared by using a sol-gel method.Under the condition of light, the electrons in the valence band in the film are excited to jump to the conduction band by photons, the photo-generated carriers are separated and directionally moved to form a current under the action of depolarization field, and the photoelectric conversion process is realized.In addition, the photovoltaic performance of the film can be improved by controlling the ligand field and oxygen vacancy concentration.The prepared wearable film can be applied to various wearable devices, intelligent electronic devices and biomedical fields.
[0006] The application provides a preparation method of a wearable ferroelectric photovoltaic film, and the features include the following steps:
[0007] 1) First, configure NBT-SCO sol and place it in a dry environment for aging for 8-10 days;
[0008] 1) Prepare a flexible substrate, use a pipette to suck the sol in step 1) and drop it on the flexible substrate, and then use a spin coater to spin the sol on the flexible substrate, the rotation speed is set to 500 rpm and 5500 rpm respectively, and the spinning time is 15 s and 30 s respectively;
[0009] 3) Finally, bake on a baking table at 250-280 DEG C for 3 minutes, and then put it into a rapid annealing furnace and sinter at 600 DEG C for 5 minutes;
[0010] 4) Repeat the above operation 8 to 10 times, and then perform final annealing for 15 minutes, and naturally cool to obtain a film; then cover a mask plate on the film, and deposit a top Au electrode with a diameter of 0.1 mm on the film by using a magnetron sputtering technology;
[0011] 5) The film prepared in step 4) is mechanically peeled to obtain a wearable ferroelectric photovoltaic film NBT-SCO.
[0012] Preferably, the NBT-SCO sol in step 1) is prepared by the following steps: Bi (NO3) 3·5H2O, CH3COONa, Sr (C2H3O2) 2, Co (NO3) 2·6H2O, (C4H9O) 4Ti are added to the solvent of ethylene glycol dimethyl ether in stoichiometric ratio of 399-679:399-679:42:42:798-1358, and an appropriate amount of acetylacetone is added to prepare a sol with a concentration of 0.4 mol / L. The acetylacetone is used to inhibit the hydrolysis of tetrabutyl titanate.
[0013] Preferably, the preparation of the flexible substrate in step (2) is as follows: a Pt layer is deposited on the fluorine crystal mica substrate as a bottom electrode and buffer layer by using a magnetron sputtering technique.
[0014] Preferably, the annealing process in steps 3) and 4) is carried out in an oxygen atmosphere. Because the thin film will cause the surface of the prepared thin film to be rough if it lacks an oxygen environment during the annealing process, the annealing process needs to be carried out in an oxygen atmosphere.
[0015] Preferably, the mechanical peeling method used in step (5) is a scalpel mechanical peeling method.
[0016] In the preparation of the NBT-SCO sol in step 1), the environmental aging time plays an important role in obtaining a clear NBT-SCO sol. If the aging time is too short, the series of chemical reactions such as hydrolysis and condensation in the sol are not sufficient, and if the aging time is too long, a stable sol cannot be formed, and the sol is prone to deterioration and is not easy to spin-coat. Figure 2 As shown in (b) of the above table, when the aging time is 11 days, the gel produces delamination, causing the sol preparation to fail, and when the aging time is 10 days in (a) of the above table, the sol solution is uniform and transparent, indicating that the sol preparation is successful. Figure 2
[0017] The rotation speed of the spin coater in step 2) is higher than 5500 r / min, which will cause the sol to be unable to be uniformly spin-coated, and lower than 500 r / min, which will cause each layer of sol to be too thick, and the sol is prone to cracking after baking. The two-step rotation in step 2) is to prepare the optimal thin film. The small rotation speed in the first step is to coat the sol on the entire thin film and to shake off the excess sol, and the time of 15 seconds can meet this requirement. The high rotation speed in the second step is to uniformly spin-coat the sol on the thin film, and the slightly longer time of 30 seconds can ensure the uniformity of spin-coating.
[0018] The baking temperature in the step 3) is too low to completely volatilize the organic solvent and causes the baking time to be prolonged, and the baking temperature is too high to cause cracks on the surface of the thin film in the process of rapid temperature rising. Therefore, through repeated experiments, it is determined that the baking temperature in the step 3) is preferably within 250-280 DEG C.
[0019] Compared with the prior art, the present application has the following beneficial effects:
[0020] 1) By using the flexible substrate to replace the rigid substrate, a flexible wearable ferroelectric photovoltaic thin film is obtained, and compared with other preparation methods of flexible photovoltaic thin films, the present application has the advantages of simple operation, stable process and high success rate; the present application fills the blank of the method for preparing the ferroelectric photovoltaic thin film material without the thin film bendability, and compared with the pulse laser deposition method and the magnetron sputtering technology, the present application does not need to use special and expensive equipment and harsh vacuum environment, the stoichiometric ratio of the prepared thin film composition has little loss difference with the original material ratio, and the disadvantages of the magnetron sputtering technology are avoided.
[0021] 2) By adjusting the solid solution ratio to 0.03-0.05, the ligand field and the oxygen vacancy concentration can be controlled, and the photovoltaic performance of the thin film is improved. Experimental results show that when the solid solution ratio is greater than 0.05, the photovoltaic performance of the thin film will be obviously decreased, and when the solid solution ratio is 0.05, the photovoltaic performance is optimal.
[0022] 3) By using the two-step rotation, the uniformity of the spin coating is ensured, and the prepared thin film has excellent uniformity.
[0023] 4) A wearable ferroelectric photovoltaic thin film NBT-SCO is prepared by using the sol-gel method, and the solar energy can be converted into electric energy output. The wearable thin film prepared by the present application can meet more demands and application scenarios. Specifically, the wearable thin film can be applied to solar energy transportation, such as solar energy vehicles, solar energy sailboats and even solar energy airplanes, and daily intelligent electronic and communication equipment, such as solar energy backpacks, solar energy tents, solar energy flashlights and the like. In addition, an important application field of the flexible solar energy photovoltaic thin film is the building integrated photovoltaic, and the high flexibility and light weight make it can be integrated on the window, roof, outer wall or inner wall. In the medical instrument field, the wearable thin film prepared by the present application can be in contact with the skin and human tissues, and can accurately monitor physiological signals and related medical indicators, such as body temperature, respiration, blood pressure, electrocardio and the like, so as to provide real-time basic data for big data medical treatment. BRIEF DESCRIPTION OF DRAWINGS
[0024] Figure 1 The morphology of the NBT-SCO wearable thin film prepared in Example 1 in the natural state (in the a of FIG. 6) and the bending state (in the b of FIG. 6) is shown in FIG. 6. Figure 1 The morphology of the NBT-SCO wearable thin film prepared in Example 1 in the natural state (in the a of FIG. 6) and the bending state (in the b of FIG. 6) is shown in FIG. 6.Figure 1 of b).
[0025] Figure 2 The sols were prepared in the same way as in Example 1, step 1) except that the aging time was 10 days (a) and 11 days (b) respectively. Figure 2 Figure 2 The sols prepared in the same way as in Example 1, step 1) except that the aging time was 10 days (a) and 11 days (b) respectively.
[0026] Figure 3 The morphology of the thin films prepared in the same way as in Example 1 (a), Comparative Example 1 (b) and Comparative Example 2 (c). Figure 3 Figure 3 Figure 3 The XRD patterns of the NBT-SCO wearable thin films prepared in the same way as in Example 1 (a) and Example 2 (b).
[0027] Figure 4 The XPS spectra of the NBT-SCO wearable thin films prepared in the same way as in Example 1 and Example 2.
[0028] Figure 5 The J-V curves of the NBT-SCO wearable thin films prepared in the same way as in Example 1 and Example 2.
[0029] Figure 6 The photoelectric current as a function of time of the NBT-SCO wearable thin films prepared in the same way as in Example 1 (a) and Example 2 (b) and Comparative Example 3 (c).
[0030] Figure 7 DETAILED DESCRIPTION
[0031] The specific embodiments and effects of the present application will be illustrated by the following examples, but the scope of the present application is not limited thereto.
[0032] Preparation of NBT-0.03SCO with a solid solution ratio of 0.03 for wearable ferroelectric photovoltaic thin films in Example 1
[0033] A specific method for preparing wearable ferroelectric photovoltaic thin films NBT-0.03SCO:
[0034] 1) According to 0.97(Na 0.5 Bi 0.5 TiO3)-0.03SrCoO3 stoichiometric ratio of pure Bi (NO3)3·5H2O bismuth nitrate pentahydrate 2.5664g, CH3COONa sodium acetate 0.434g, Sr(C2H3O2)2 strontium acetate 0.0621g, Co(NO3)2·6H2O cobalt nitrate hexahydrate 0.0881g, (C4H9O)4Ti titanium tetrabutoxide 3.368g (i.e. the molar ratio of each substance is 679:679:42:42:1358) are added to 25mL of ethylene glycol methyl ether solvent, wherein 8% excess is weighed to compensate for the volatilization of Bi and Na elements. After the sol is stirred uniformly, 0.5mL of acetylacetone is added to prepare a sol with a concentration of 0.4mol / L, and is aged for 10 days;
[0035] 2) The fluorine crystal mica substrate is cleaned in deionized water and dried, a Pt layer is deposited on the cleaned fluorine crystal mica substrate as a bottom electrode and buffer layer by using a magnetron sputtering technology, a pipette is used to drop the sol in step 1) on a flexible substrate, and a spin coater is used to spin uniformly, the rotation speed is set to 500rpm and 5500rpm respectively, and the spinning time is set to 15s and 30s respectively, to obtain a wet film after spinning;
[0036] 3) The wet film after spinning is immediately placed on a baking table at 280℃ and baked for 3 minutes, and then placed in an RTP rapid annealing furnace and sintered at 600℃ for 5 minutes, and the whole annealing process is carried out in an oxygen atmosphere;
[0037] 4) The above operation is repeated 8 times, and finally a terminal annealing is performed for 15 minutes, and the film is naturally cooled, a mask plate is covered on the film, and a top Au electrode with a diameter of 0.1mm is deposited on the film by using a magnetron sputtering technology;
[0038] 5) The film with a top electrode prepared is mechanically peeled off by a scalpel to obtain a bendable wearable ferroelectric photovoltaic film NBT-0.03SCO.
[0039] Preparation of wearable ferroelectric photovoltaic film NBT-0.05SCO of example 2
[0040] A specific method for preparing wearable ferroelectric photovoltaic film NBT-0.05SCO
[0041] 1) According to 0.95(Na 0.5 Bi 0.5The stoichiometric ratio of TiO3)-0.05SrCoO3 is weighed with Bi(NO3)3.5H2O 2.513g, CH3COONa 0.424g, Sr(C2H3O2)2 0.1037g, Co(NO3)2.6H2O 0.1468g, (C4H9O)4Ti 3.2992g (i.e. the molar ratio of each substance is 399:399:42:42:798) of which the purity is analytically pure, and which is added to 25mL of ethylene glycol methyl ether solvent. In order to compensate for the volatilization of Bi and Na elements, 8% excess is weighed. After the sol is stirred uniformly, 0.5mL of acetylacetone is added to prepare a sol with a concentration of 0.4mol / L, and is aged for 10 days.
[0042] 2) The fluorine crystal mica substrate is cleaned in deionized water and dried, a Pt layer is deposited on the cleaned fluorine crystal mica substrate as a bottom electrode and buffer layer by using a magnetron sputtering technology, the sol in step 1) is sucked by a pipette and dropped on a flexible substrate, and the wet film is obtained by spin coating with a spin coater at a speed of 500rpm and 5500rpm for 15s and 30s respectively.
[0043] 3) The wet film is immediately placed on a baking table at 280℃ and baked for 3 minutes, and then placed in an RTP rapid annealing furnace and sintered at 600℃ for 5 minutes. The whole annealing process is carried out in an oxygen atmosphere.
[0044] 4) The above operation is repeated 8 times, and finally, the terminal annealing is carried out for 15 minutes, and the film is naturally cooled. A mask plate is covered on the film, and a top Au electrode with a diameter of 0.1mm is deposited on the film by using a magnetron sputtering technology.
[0045] 5) The film with the prepared top electrode is mechanically peeled off by a scalpel to obtain a bendable wearable ferroelectric photovoltaic film NBT-0.05SCO.
[0046] Preparation of wearable ferroelectric photovoltaic film NBT-0.05SCO of example 3
[0047] A specific method for preparing wearable ferroelectric photovoltaic film NBT-0.05SCO
[0048] 1) According to 0.95(Na 0.5 Bi 0.5The stoichiometric ratio of TiO3)-0.05SrCoO3 is weighed with Bi(NO3)3.5H2O 2.513g, CH3COONa 0.424g, Sr(C2H3O2)2 0.1037g, Co(NO3)2.6H2O 0.1468g, (C4H9O)4Ti 3.2992g (i.e. the molar ratio of each substance is 399:399:42:42:798), which are all of analytical purity, and added to 25mL of ethylene glycol methyl ether solvent. In order to compensate for the volatilization of Bi and Na elements, 8% excess is weighed. After the sol is stirred uniformly, 0.5mL of acetylacetone is added to prepare a sol with a concentration of 0.4mol / L, and aged for 10 days;
[0049] 2) The fluorine crystal mica substrate is cleaned in deionized water and dried, a Pt layer is deposited on the cleaned fluorine crystal mica substrate as a bottom electrode and buffer layer by using a magnetron sputtering technology, the sol in 1) is sucked with a pipette and dropped on a flexible substrate, and the wet film is obtained by spin coating with a spin coater at a speed of 500rpm and 5500rpm for 15s and 30s respectively.
[0050] 3) The spin-coated wet film is immediately placed on a baking table at 280℃ for 3 minutes, and then placed in an RTP rapid annealing furnace for sintering at 600℃ for 5 minutes. The whole annealing process is carried out in an oxygen atmosphere.
[0051] 4) The above operation is repeated 10 times, and finally a terminal annealing is performed for 15 minutes, and the film is naturally cooled. A mask plate is covered on the film, and a top Au electrode with a diameter of 0.1mm is deposited on the film by using a magnetron sputtering technology.
[0052] 5) The film with the prepared top electrode is mechanically peeled off by a scalpel to obtain a bendable wearable ferroelectric photovoltaic film NBT-0.05SCO.
[0053] Preparation of wearable ferroelectric photovoltaic film NBT-0.05SCO of example 4
[0054] A specific method for preparing wearable ferroelectric photovoltaic film NBT-0.05SCO
[0055] 1) The stoichiometric ratio of 0.95(Na 0.5 Bi 0.5The stoichiometric ratio of Bi(NO3)3·5H2O (5H2O bismuth nitrate) 2.513 g, CH3COONa (sodium acetate) 0.424 g, Sr(C2H3O2)2 (strontium acetate) 0.1037 g, Co(NO3)2·6H2O (6H2O cobalt nitrate) 0.1468 g, (C4H9O)4Ti (titanium tetrabutoxide) 3.2992 g (i.e. the molar ratio of each substance is 399:399:42:42:798) of analytical pure Bi(NO3)3·5H2O five water bismuth nitrate, CH3COONa sodium acetate, Sr(C2H3O2)2 strontium acetate, Co(NO3)2·6H2O six water cobalt nitrate, (C4H9O)4Ti titanium tetrabutoxide) is weighed into 25 mL of ethylene glycol methyl ether solvent, and 8% excess is added to compensate for the volatilization of Bi and Na elements. After the sol is stirred uniformly, 0.5 mL of acetylacetone is added to prepare a sol with a concentration of 0.4 mol / L, and it is aged for 10 days at room temperature;
[0056] 2) The fluorine crystal mica substrate is cleaned in deionized water and dried, a Pt layer is deposited on the cleaned fluorine crystal mica substrate as a bottom electrode and buffer layer by using a magnetron sputtering technology, the sol in 1) is sucked by a pipette and dropped on a flexible substrate, and the sol is uniformly spin-coated by using a spin coater, the rotation speed is set to 500 rpm and 5500 rpm respectively, and the spin-coating time is set to 15 s and 30 s respectively, to obtain a wet film after spin-coating;
[0057] 3) The wet film after spin-coating is immediately placed on a baking table at 250℃ and baked for 3 minutes, and then placed in an RTP rapid annealing furnace and sintered at 600℃ for 5 minutes, and the whole annealing process is carried out in an oxygen atmosphere.
[0058] 4) The above operation is repeated 10 times, and finally, a terminal annealing is performed for 15 minutes, and the film is naturally cooled, a mask plate is covered on the film, and a top Au electrode with a diameter of 0.1 mm is deposited on the film by using a magnetron sputtering technology;
[0059] 5) The film with the prepared top electrode is mechanically peeled off by a scalpel to obtain a bendable wearable ferroelectric photovoltaic film NBT-0.05SCO.
[0060] Comparative Example 1, Comparative Example 2, Comparative Example 3 (solid solution ratio 0.07)
[0061] Compared with Example 1, the high rotation speed condition in step 2) of Comparative Example 1 is selected to be 5600 rpm, and the baking temperature in step 3) of Comparative Example 2 is 300℃. It can be seen from Figure 3 that Figure 3 b (Comparative Example 1) and Figure 3 c (Comparative Example 2) are compared with Figure 3 a (Example 1), the film obtained in Comparative Example 1 is thin in the center and the thickness is uneven, and the film obtained in Comparative Example 2 has cracks, which shows that the spin-coating rate and the baking temperature are important factors affecting the success of film preparation.
[0062] Comparative Example 3 differs from Example 1 in that the solid solution ratio is different, i.e. the stoichiometric ratio of the substances used in step 1) is as follows: according to 0.93(Na 0.5 Bi 0.5 TiO3)-0.07SrCoO3, 2.4605 g of Bi(NO3)3·5H2O, bismuth nitrate pentahydrate with a purity of analytical grade, 0.416 g of CH3COONa, sodium acetate, 0.1453 g of Sr(C2H3O2)2, strontium acetate, 0.2057 g of Co(NO3)2·6H2O, cobalt nitrate hexahydrate, and 3.2297 g of (C4H9O)4Ti, titanium tetrabutoxide, i.e. the molar ratio of the substances is 297:297:42:42:558, are weighed into 25 mL of ethylene glycol methyl ether as a solvent, wherein 8% excess is weighed to compensate for the volatilization of Bi and Na elements. After the sol is stirred uniformly, 0.5 mL of acetylacetone is added to prepare a sol with a concentration of 0.4 mol / L, and the sol is aged for 10 days. The other preparation steps are the same as in Example 1.
[0063] Measurement of thin film performance parameters
[0064] 1. XRD measurement of NBT-SCO wearable thin film
[0065] The XRD pattern is scanned and tested using a PANalytical-Empyrea X-ray scanner, and a Cu target is used in the testing process, with a wavelength λ value of The test range is set to 20-60°, and the X-ray diffraction pattern of the sample to be tested is obtained by the diffraction of X-rays in the crystal. Figure 4 The test results of Examples 1 and 2 are consistent with the standard card of the crystal library, indicating that the NBT-SCO flexible thin film prepared in Examples 1 and 2 is very successful.
[0066] 2. XPS pattern measurement of NBT-SCO wearable thin film
[0067] The Co element of the thin film sample is tested by XPS using a Kratos Amicus testing system, and the results are as follows: Figure 5 It can be seen that, with the increase of the solid solution ratio (0.05 (Example 2) compared with 0.03 (Example 1)), the Co 3+ content in the thin film gradually increases, and the oxygen vacancy concentration also gradually increases. It is shown that, by increasing the SCO solid solution ratio, the oxygen vacancy and crystal structure can be controlled.
[0068] 3. J-V relationship curve of NBT-SCO wearable thin film
[0069] The system for testing the J-V relationship curve is self-made in the laboratory, including a dark box and a power of 50 mW / cm2 Xenon lamp light source, chopper, movable probe station and external Keithley-2400 source meter, etc. During the test, the light source is vertically hit on the sample surface, and the source meter is used to detect the current on the sample surface by applying voltage, and the J-V curve under light and no light is drawn, as shown in Figure 6 It can be seen that with the increase of the SCO solid solution ratio (0.03 (Example 1) and 0.05 (Example 2)), the open circuit voltage and short circuit current of the thin film are increasing, indicating the enhancement of the photovoltaic performance.
[0070] 4. The photoelectric current of the NBT-SCO wearable thin film with time under light
[0071] The device used for testing the light response is the same as that for testing the J-V curve. During the test, a periodic light-no light environment is applied to the thin film, and the photoelectric current of the thin film is received. The thin film has a switching effect, indicating that the thin film has good photovoltaic performance. Figure 7 The light response of the thin film with a solid solution ratio of 0.03 (Example 1), 0.05 (Example 2) and 0.07 (Comparative Example 3) is shown in the table. It can be seen that when the solid solution ratio increases from 0.03 to 0.05, the switching response of the thin film is enhanced, and when the solid solution ratio is 0.07, the switching response of the thin film is weakened, which indicates that the thin film with a solid solution ratio of 0.05 has the best photovoltaic response. By comparing the performance parameters of the thin film, it can be found that the ferroelectric photovoltaic thin film prepared by the present application has performance parameters that meet the performance needs of wearable photovoltaic thin films when the solid solution ratio is in the range of 0.03-0.05, and when the solid solution ratio is greater than 0.05, it is difficult to meet the performance needs of photovoltaic thin films. Considering the J-V curve and the light response graph, the present application protects the preparation method of the wearable thin film with a solid solution ratio of 0.03-0.05.
[0072] The preparation method provided by the present application can convert solar energy into electrical energy output under the condition of light, and can improve the photovoltaic performance of the wearable thin film by adjusting the ligand field and the oxygen vacancy concentration. The bendable characteristic of the thin film also meets more social needs, and provides great guidance for the research and application of wearable photovoltaic devices.
[0073] It should be understood that although the present specification is described in terms of embodiments, the description of the specification is only for the sake of clarity, and the specification should be considered as a whole by those skilled in the art, and other embodiments that can be understood by those skilled in the art should also belong to the protection scope of the present application.
Claims
1. A method for preparing a wearable ferroelectric photovoltaic film, characterized in that: 1) Bi(NO3)3·5H2O bismuth nitrate pentahydrate, CH3COONa sodium acetate, Sr(C2H3O2)2 strontium acetate, Co(NO3)2·6H2O cobalt nitrate hexahydrate, and (C4H9O)4Ti tetrabutyl titanate are added to an ethylene glycol methyl ether solvent in a stoichiometric ratio of 399-679:399-679:42:42:798-1358, and an appropriate amount of acetylacetone is added to prepare an NBT-SCO sol with a concentration of 0.4 mol / L, which is then aged in a dry environment for 8-10 days; 2) using magnetron sputtering technology, depositing a Pt layer on a fluorophlogopite substrate as a bottom electrode and a buffer layer to obtain a flexible substrate, using a pipette to draw the aged sol in step 1) and drop it onto the flexible substrate, and then using a spin coater to spin-coat the sol onto the flexible substrate, with the rotation speed set to 500 rpm and 5500 rpm, respectively, for 15 s and 30 s, respectively; 3) Finally, bake on a baking table at 250-280°C for 3 minutes, and then place in a rapid annealing furnace and sinter at 600°C for 5 minutes; 4) Repeat the above steps 8 to 10 times, perform a final annealing for 15 minutes, and cool naturally to obtain a thin film; then, cover the thin film with a mask and deposit a top Au electrode with a diameter of 0.1 mm on the thin film using magnetron sputtering technology; 5) Mechanically peeling the thin film with the top Au electrode prepared in step 4) to obtain the wearable ferroelectric photovoltaic thin film NBT-SCO.
2. The method for preparing a wearable ferroelectric photovoltaic thin film according to claim 1, wherein: The annealing process in step 3) and step 4) is performed in an oxygen atmosphere.
3. The method for preparing a wearable ferroelectric photovoltaic thin film according to claim 1, wherein: The mechanical stripping method used in step 5) is mechanical stripping with a scalpel.