CN114409395A - Ferroelectric photovoltaic film with adjustable polarization and band gap and preparation method thereof - Google Patents
Ferroelectric photovoltaic film with adjustable polarization and band gap and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of functional thin films and energy storage information, and relates to a ferroelectric photovoltaic thin film with adjustable polarization and band gap and a preparation method thereof. The ferroelectric photovoltaic film is a homogeneous sandwich structure with a ferroelectric polarization layer, a light absorption layer and a ferroelectric polarization layer which are alternated, wherein the ferroelectric layer and the light absorption layer are homogeneous components Bi x1‑ Re x FeO3A base film, wherein,Rethe preparation method adopts a chemical solution-spin coating method to synthesize the ferroelectric multifunctional film with the structure. Preparing a precursor solution with the molar concentration of 0.1-0.4MAnd finally annealing for 20-30 min in a heating furnace at 550-750 ℃ through spin coating and pyrolysis, and obtaining the ferroelectric and band gap controllable film through optimization of co-annealing. The invention adopts the structural design of the device and the sol-gel synthesis method to develop a new structure ferroelectric film, the components of the precursor are accurate and controllable, the synthesis condition is simple, and finally, the high-quality ferroelectric film with excellent performance is obtained.
Description
Technical Field
The invention belongs to the technical field of condensed state physics, functional films and energy storage information, and particularly relates to a ferroelectric photovoltaic film with adjustable polarization and band gap and a preparation method thereof.
Background
Whether ferroelectric materials can have photovoltaic performance while having high polarization is always a scientific issue of great concern. The photovoltaic effect refers to a process in which photo-generated carriers absorb light energy through irradiation of sunlight, are separated, and are converted from light energy to electric energy. Compared with the traditional photovoltaic device based on the P-N junction, the ferroelectric photovoltaic effect (FE-PV) has the unique advantages of high output voltage, controllable photovoltaic response and the like, is expected to become a new generation photovoltaic device, has an internal mechanism different from that of the traditional P-N junction, and is generally classified into a 1. photovoltaic effect; 2. a depolarizing field effect; 3. a schottky characteristic; 4. domain wall effects, etc.
Photovoltaic research based on Transition Metal Oxides (TMOs) has been developed vigorously recently, and since TMOs has abundant physical properties such as ferroelectricity, magnetism and photovoltaic properties while having chemical stability, it provides new ideas for heterojunction photovoltaic devices such as photo-controlled resistive switching and electrical switching PV effect.
In 1956, Chynoweth, A in the ferroelectric BaTiO3The PV effect was first observed, and stable photocurrent was also observed at temperatures above the curie temperature. [ Chynoweth A G. Surface spaces-Charge Layers in titanium Titanate [ J ]]. Physical Review, 1956, 102(3):705-714.]In recent decades, Pb (Zr, Ti) O has been studied3The FE-PV effect is found in (PZT) perovskite oxide systems, but the current density of these materials is small (about 10)-9A/m2) And the forbidden band width is very large (generally 3.5 eV), so that the high photoelectric efficiency cannot be achieved.
Among the reported TMOs with PV properties, BiFeO3(BFO) is a single-phase multiferroic material at room temperature, has a perovskite structure and belongs to R3c space group. Due to its relatively small bandgap (<2.8 eV) and large polarizationPeople are interested in the method. The ferroelectric polarization of BFO is derived from Bi3+When Bi is in the a-position3+Ion presentation 6s26p0In valence electron configuration of (B), Bi3+6s of ion2Lone electron and Bi3+Ionic vacancy 6p02p of orbital and O6The electrons hybridize. Ions form Bi-O covalent bonds, resulting in structural distortion and thus ferroelectric polarization. Although much work has been done on the BFO ferroelectric photovoltaic effect, it is difficult to specify which mechanism is particularly important. Various mechanisms in different structures often act together, the situation is more complicated, but documents prove that when the thickness of a film is larger, the photovoltaic effect and the domain wall effect have larger photovoltaic influence on the material. For its photovoltaic effect, it can be considered that the photonically excited electron-hole (e-h) pair is separated by a depolarization field due to uncompensated Ferroelectric (FE) polarization and a stable photocurrent is generated, and the sign of the photovoltaic output can be switched by reversing the polarization by an external electric field. The FePV effect, which has a large photocurrent, photovoltage and Power Conversion Efficiency (PCE) simultaneously in BFO, is greatly hindered due to its relatively low operational absorption coefficient and large optical bandgap. By adding Bi3+The appropriate substitution of some lanthanide rare earth metal ions attempts to alter the structure of BFO. Rare earth ion in Bi3+The substitution of the sites stabilizes the perovskite structure, maintains non-centrosymmetry, and suppresses Bi3+And (4) volatilizing. In addition, the BFO generates structural distortion due to internal chemical pressure caused by rare earth ion doping, and the BFO is converted from a rhombohedral phase to a pseudo-cubic phase, so that the optical band gap is reduced. Adding Co into B position of BFO3+Bi can also be controlled3+The volatility of the ions reduces the formation of oxygen vacancies. 2014, R, Nechache and researchers in the group add Cr to BFO film3+The element makes the PCE of the BFO reach 8.1% of the original record. And Cr3+The doping can reduce the band gap from 2.7eV to 1.5 eV, thereby greatly improving the visible light absorption and reducing the light charge recombination rate. [ Nechache R, Harnagea C, Li S, et al, Bandgap tuning of a multiferroic oxide solar cells [ J]. Nature Photonics, 2014, 9(1):61-67.]In the same year, Prakash Chandra Sati et al found that the Eu concentration was variedIncreasing, the optical bandgap decreases from 2.25 eV to 2.16 eV. And can effectively improve the magnetic and dielectric properties, wherein the residual magnetization is increased from 0.0003 emu/g to 0.087 emu/g. [ Chhoker S, Kumar M, Sati P C, et al. infection of Eu customization on Structure, magnetic, optical and dielectric Properties of BiFeO3 multiferroic ceramics[J]. Ceramics International, 2015, 41(2):2389-2398.]
In summary, the BFO film has the problems of large leakage current, small generated photo-generated current, etc., and is always limited in application, and the replacement with appropriate a/B sites can effectively improve the leakage current of BFO, increase polarization, and effectively reduce the band gap, so we have designed a structure that enables the BFO film to realize appreciable photovoltaic effect while maintaining high residual polarization, and realize the controllability of polarization and band gap, and at the same time, the preparation thereof by a simple method is especially important for the photovoltaic era.
The sol-gel method (sol-gel) for preparing the film is one of solution deposition methods (CSD), and because the components of the precursor liquid are controllable, the film is easy to be doped and modified by A or B site replacement, in addition, the film synthesized by the sol-gel method has uniform components, can also be used for preparing a multilayer composite film, and has controllable thickness; the film making equipment is simple, the vacuum condition is not needed, the raw material source is wide, and the cost is low; the chemical reaction is easy to carry out, and the synthesis temperature is low; and the uniformity of molecular level can be realized in the precursor liquid at the initial stage of the film preparation so as to obtain the fine structure of target micrometer and even nanometer scale.
Disclosure of Invention
The invention discloses a ferroelectric photovoltaic thin film with adjustable polarization and photovoltaic and a preparation method thereof, which aim to solve any one of the above and other potential problems in the prior art.
The technical scheme of the invention is as follows: a ferroelectric photovoltaic film with adjustable polarization and band gap and a preparation method thereof are disclosed, wherein the film consists of an upper ferroelectric polarization layer, a light absorption layer and a lower ferroelectric polarization layer and is of a sandwich homogeneous structure; the ferroelectric layer and the light-absorbing layer are homogeneous component Bi x1- Re x FeO3A base film, wherein,Relanthanide salts, 0% or lessxLess than or equal to 50 percent; adjusting the content of rare earth metal elements to realize a high-polarization ferroelectric layer (less than or equal to 0 percent)xLess than or equal to 15 percent) and a light-absorbing layer with low band gap (less than or equal to 15 percent)x≤50 %）。
Another object of the present invention is to provide a process for preparing the above ferroelectric photovoltaic thin film with adjustable polarization and band gap, which specifically comprises the following steps:
s1) preparing precursor solutions of the ferroelectric polarization layer and the light absorption layer;
s2) spin-coating the precursor solution obtained in S1) on a substrate to obtain an amorphous film structure;
s3) annealing the amorphous film structure obtained in S2), and cooling the amorphous film structure to room temperature in air to obtain the ferroelectric photovoltaic film with adjustable polarization and band gap and target thickness.
Further, the specific steps of S1) are:
s1.1) adding bismuth salt into a solvent, and uniformly stirring to obtain a bismuth-containing salt solution;
s1.2) adding rare earth metal salt into a bismuth-containing salt solution, and uniformly stirring to obtain a mixed solution;
s1.3) adding iron salt into the mixed solution obtained in S1.2), uniformly stirring, adding a chelating agent to obtain a precursor solution with the molar concentration of 0.1-0.4M, standing for more than 24 hours, and fully hydrolyzing and polycondensing to respectively obtain a precursor solution of the ferroelectric polarization layer and a precursor solution of the light absorption layer.
S1.4) adding a small amount of transition metal such as cobalt salt into the mixed solution obtained in the step S1.3), adding and stirring uniformly, adding a chelating agent to obtain a precursor solution with the molar concentration of 0.1-0.4M, standing for more than 24 hours, and performing sufficient hydrolysis and polycondensation to obtain the ferroelectric photovoltaic film with adjustable polarization and band gap.
Further, the specific process of S2) is as follows:
s2.1) filtering the precursor solution of the ferroelectric polarization layer and the light absorption layer obtained in the S1.3) to remove large particles for later use;
s2.2) selecting an FTO substrate, cleaning, and placing on a spin coater;
s2.3) uniformly spin-coating the precursor solution processed by the S2.1) on the substrate processed by the S2.2), then pyrolyzing and cooling on a heating table to obtain an amorphous film structure attached on the substrate.
Further, the specific steps of S3) are:
s3.1) putting the substrate which is obtained in the step S2.3) and is attached to the substrate and is obtained after spin coating of the amorphous film structure with the specific thickness into an annealing furnace with the temperature of 550-750 ℃ for heat preservation for 20-30 min, cooling the substrate to the room temperature in the air,
s3.2) the annealing process described in S3.1) above may employ two annealing modes, which are the same composition annealing mode or the same thickness annealing mode, respectively.
Further, the rare earth metal is lanthanide salt, and the addition amount is as follows: the molar ratio of the rare earth metal salt to the bismuth salt is in the range of 0 to 1.
Further, a small amount of transition metal such as Co salt is added into the S1.4), and the addition amount is as follows: the molar ratio of transition metal salt to iron salt is in the range of 0 to 0.1.
Rare earth metal salt is used for replacing A-site Bi in BFO3+Ions, not only can inhibit Bi3+Volatilizing; substitution of B-site Co in BFO with transition metal salts3+Ions can reduce the formation of Bi vacancies and O vacancies, reduce leakage current and increase polarization;
further, the diameter of the filter head for filtering in S2.1) is 0.20-0.25 μm;
the rotation speed of the spin coating in the S2.2) is 500-4000rpm, and the spin coating time is 25-35S;
the pyrolysis temperature is 250 ℃ and 400 ℃, and the pyrolysis time is 5-15 min.
Further, the annealing mode with the same composition in S3.2) means that films with the same chemical composition are annealed at the same time, and the annealing mode with the same thickness means that annealing is performed with a fixed thickness.
Further, the thickness of the ferroelectric photovoltaic film with adjustable polarization and band gap is 300-60 nm; the polarization can reach 70 mu C/cm2The band gap can be as low as 2.2-2.4 eV. This is comparable to other classical ferroelectric photovoltaic thin film properties.
The invention has the beneficial technical effects that: due to the adoption of the technical scheme, the preparation method provided by the invention comprises the following steps: the components of the precursor liquid are accurate and controllable, the uniformity of the molecular level is realized, and the components of the film are uniform and have high quality; the film making equipment is simple, the vacuum condition is not needed, the cost is lower, and the film thickness and the preparation temperature are controllable; a series of new-structure films with various different components can be realized by changing the A-site rare earth metal ion components. And excellent multifunctionality such as ferroelectric photovoltaics.
Drawings
The invention is further illustrated with reference to the following figures and examples.
FIG. 1 is a schematic structural diagram of a ferroelectric photovoltaic thin film with adjustable polarization and band gap according to the present invention.
FIG. 2 is an XRD pattern, ferroelectric diagram and bandgap diagram of the coating 8 film 10% -50% Eu.
Fig. 3 is an XRD pattern, ferroelectric pattern and bandgap pattern of a co-thickness annealed and co-composition annealed film coated with only one light absorbing layer.
FIG. 4 is an XRD pattern, ferroelectric pattern and band gap pattern of the 9-layer film which is compositionally annealed and has the number of light absorption layers of 0, 1, 2 and 3.
In the figure:
the manufacturing method comprises the following steps of 1, an FTO substrate, 2, an upper iron polarization layer, 3, a light absorption layer, 4, a lower iron polarization layer and 5, a Pt electrode.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
On the contrary, the invention is intended to cover alternatives, modifications, equivalents and alternatives which may be included within the spirit and scope of the invention as defined by the appended claims. Furthermore, in the following detailed description of the present invention, certain specific details are set forth in order to provide a better understanding of the present invention. It will be apparent to one skilled in the art that the present invention may be practiced without these specific details.
As shown in fig. 1, the present invention provides a polarization and bandgap tunable ferroelectric photovoltaic thin film, the structure of which comprises: an upper iron polarizing layer, a light absorbing layer, and a lower iron polarizing layer;
wherein the light absorption layer is arranged between the upper iron polarization layer and the lower iron polarization layer and is constructed into a sandwich homogeneous structure;
the thicknesses of the upper iron polarization layer, the light absorption layer and the lower iron polarization layer are all 50-200 nm.
The thin film structure is a three-side phase-pseudo cubic phase-orthogonal phase composite perovskite structure.
The upper iron polarization layer, the light absorption layer and the lower iron polarization layer are all homogeneous components Bi x1- Re x FeO3A base film ofReIs lanthanide series salt.
Wherein in the upper and lower iron polarization layersxThe value of (A) is not more than 0%xLess than or equal to 50 percent; in the light absorbing layerxThe value of (A) is less than or equal to 15%x≤50 %。
A method for preparing the ferroelectric photovoltaic thin film with adjustable polarization and band gap comprises the following specific processes:
s1) preparing a precursor solution of the ferroelectric polarization layer and a precursor solution of the light absorption layer;
s2) spin-coating the precursor solution obtained in S1) on a substrate to obtain an amorphous film structure;
s3) annealing the amorphous film structure obtained in S2), and cooling the amorphous film structure to room temperature in air to obtain the ferroelectric photovoltaic film with adjustable polarization and band gap and target thickness.
The S1) comprises the following specific steps:
s1.1) adding bismuth salt into a solvent, and uniformly stirring to obtain a bismuth-containing salt solution;
s1.2) adding rare earth metal salt into a bismuth-containing salt solution, and uniformly stirring to obtain a mixed solution;
s1.3) adding iron salt into the mixed solution obtained in S1.2), uniformly stirring, adding a chelating agent to obtain a precursor solution with the molar concentration of 0.1-0.4M, standing for more than 24 hours, and fully hydrolyzing and polycondensing to respectively obtain a precursor solution of the ferroelectric polarization layer and a precursor solution of the light absorption layer.
Said S1.3) may also be added small amounts of transition metal salts such as Co salts.
The S2) comprises the following specific steps:
s2.1) filtering the precursor solution of the ferroelectric polarization layer and the precursor solution of the light absorption layer obtained in the S1.3) by using a filter head with the diameter of 0.20-0.25 mu m to remove large particles for later use;
s2.2) selecting an FTO substrate, cleaning, and placing on a spin coater;
s2.3) according to the rotation speed of 500-4000rpm of spin coating and the spin coating time of 25-35S, respectively and uniformly spin-coating the precursor solution of the ferroelectric polarization layer obtained in the S2.2) and the precursor solution of the light absorption layer on the substrate treated in the S2.2), and then pyrolyzing the substrate on a heating table at the temperature of 250-400 ℃ for 5-15min for cooling, thereby obtaining the amorphous film structure attached on the substrate.
The S3) comprises the following specific steps:
and (3) putting the substrate which is obtained in the step (S2.3) and is attached to the substrate and is obtained after spin coating of the amorphous film structure with the specific thickness into an annealing furnace with the temperature of 550-750 ℃ for heat preservation for 20-30 min, and cooling the substrate to the room temperature in the air.
The annealing mode of the annealing process is the same component annealing mode or the same thickness annealing mode.
The thickness of the ferroelectric photovoltaic film with adjustable polarization and band gap is 300-600 nm; the polarization can reach 70 mu C/cm at most2The band gap can be as low as 2.2-2.4 eV.
The ferroelectric photovoltaic thin film with adjustable polarization and band gap is prepared by the method of any one of claims 5 to 9.
The principle of the invention is as follows:
proper replacement of A-site Bi in BFO by rare earth metal salt3+Ions can stabilize the structure of perovskite, maintain the non-central symmetry of crystal structure and inhibit Bi3+Volatilizing; proper substitution of B-site Co in BFO with transition metal salts3+Ions, also inhibit Bi3+Volatilization of Bi and O vacancies is reduced, the leakage current is reduced, and polarization is increased; combines the component point with better A/B position substituted BFO ferroelectric polarization and the component point with better light absorption performance,and designing a proper structure and an annealing process to finally obtain the ferroelectric photovoltaic film with adjustable polarization and band gap.
Example 1
In bismuth nitrate pentahydrate (Bi (NO)3)3·5H2O) and europium nitrate hexahydrate (Eu (NO)3)3·6H2O) 4.8mL Ethylene Glycol Methyl Ether (EGME) was added. Then adding cobalt nitrate hexahydrate (Co (NO) into the mixed solution3)3·6H2O) and iron nitrate nonahydrate (Fe (NO)3)3·9H2O). The chemical formula of the preparation is Bi1.06Fe0.95Co0.05O3、Bi0.96Eu0.1Fe0.95Co0.05O3、Bi0.86Eu0.2Fe0.95Co0.05O3、Bi0.76Eu0.3Fe0.95Co0.05O3、Bi0.66Eu0.4Fe0.95Co0.05O3And Bi0.56Eu0.5Fe0.95Co0.05O3And 5mL of the precursor solution with the molar concentration of 0.2M. Spin-coating a film on an FTO substrate, sucking a proper amount of precursor liquid by using a liquid-transferring gun, dropwise adding the precursor liquid on the substrate to fully cover the surface of the substrate, firstly using 500rpm to spin slowly for 15s, and then using 4000rpm to spin quickly for 20 s; moving the substrate to a heating plate at 350 ℃ for pyrolysis for 10min, air-cooling to room temperature, and repeating for 4 layers; and finally, moving the film into an annealing furnace to rapidly heat up, annealing at 650 ℃ for 30min, cooling the film to room temperature in the air, and repeating the annealing for 2 times to obtain 8 layers of ferroelectric films with different components.
XRD analysis is carried out on the prepared film to obtain an image as shown in figure 2, and all the films are shown as pure phases in the XRD spectrum; from the ferroelectric and bandgap diagrams, the ferroelectric performance is best when the doping content of Eu is 10%; when the doping content of Eu is 20%, the Eu has considerable light absorption performance.
Example 2
In bismuth nitrate pentahydrate (Bi (NO)3)3·5H2O) and europium nitrate hexahydrate (Eu (NO)3)3·6H2O) 4.8mL of ethylene glycol A was addedEther (EGME). Then adding cobalt nitrate hexahydrate (Co (NO) into the mixed solution3)3·6H2O) and iron nitrate nonahydrate (Fe (NO)3)3·9H2O). The chemical formula of the preparation is Bi0.96Eu0.1Fe0.95Co0.05O3And Bi0.86Eu0.2Fe0.95Co0.05O3And 5mL of the precursor solution with the molar concentration of 0.2M. Spin-coating a film on an FTO substrate, and absorbing a proper amount of Bi by using a liquid-transferring gun0.96Eu0.1Fe0.95Co0.05O3Dropwise adding the mixture on a substrate, fully covering the surface of the substrate, and slowly spin-coating at 500rpm for 15s and then quickly spin-coating at 4000rpm for 20 s; moving the substrate to a heating plate at 350 ℃ for pyrolysis for 10min, air-cooling to room temperature, and repeating for 3 layers; then moving the mixture into an annealing furnace to rapidly raise the temperature, and annealing the mixture for 30min at 650 ℃; cooling to room temperature in air. Then using a liquid-transfering gun to suck a proper amount of Bi0.86Eu0.2Fe0.95Co0.05O3Dropwise adding the mixture on a substrate, fully covering the surface of the substrate, and slowly spin-coating at 500rpm for 15s and then quickly spin-coating at 4000rpm for 20 s; moving the substrate to a heating plate at 350 ℃ for pyrolysis for 10min to obtain a light absorption layer;
group a (anneal with same composition): moving the mixture into an annealing furnace to rapidly heat up, and annealing for 30min at 650 ℃; cooling to room temperature in air, and spin-coating 5 layers of Bi0.96Eu0.1Fe0.95Co0.05O3Placing into an annealing furnace, rapidly heating, and annealing at 650 deg.C for 30 min; and cooling to room temperature in the air to obtain the component a annealed ferroelectric film.
Group B (same thickness anneal): spin-coating with 2 layers of Bi0.96Eu0.1Fe0.95Co0.05O3Putting the pyrolyzed material into an annealing furnace to be rapidly heated, and annealing for 30min at 650 ℃; cooling to room temperature in the air to obtain a light absorption layer; spin-coating 3 layers of Bi0.96Eu0.1Fe0.95Co0.05O3Then the mixture is put into an annealing furnace to be rapidly heated and annealed at 650 ℃ for 30 min; and cooling to room temperature in air, and air-cooling to room temperature to obtain the co-annealed ferroelectric film.
XRD analysis is carried out on the prepared film to obtain an image as shown in figure 3, and all the films are shown as pure phases in the XRD spectrum; from the ferroelectric and bandgap plots, the ferroelectric properties and bandgap of group B (co-annealing) are best.
Example 3
In bismuth nitrate pentahydrate (Bi (NO)3)3·5H2O) and europium nitrate hexahydrate (Eu (NO)3)3·6H2O) 4.8mL Ethylene Glycol Methyl Ether (EGME) was added. Then adding cobalt nitrate hexahydrate (Co (NO) into the mixed solution3)3·6H2O) and iron nitrate nonahydrate (Fe (NO)3)3·9H2O). The chemical formula of the preparation is Bi0.96Eu0.1Fe0.95Co0.05O3And Bi0.86Eu0.2Fe0.95Co0.05O3And 5mL of the precursor solution with the molar concentration of 0.2M. Spin-coating a film on an FTO substrate, and absorbing a proper amount of Bi by using a liquid-transferring gun0.96Eu0.1Fe0.95Co0.05O3Dropwise adding the mixture on a substrate, fully covering the surface of the substrate, and slowly spin-coating at 500rpm for 15s and then quickly spin-coating at 4000rpm for 20 s; moving the substrate to a heating plate at 350 ℃ for pyrolysis for 10 min; air cooling to room temperature, repeating 3 layers, transferring into an annealing furnace, rapidly heating, and annealing at 650 deg.C for 30 min; cooling to room temperature in air to obtain the ferroelectric polarization layer. Then using a liquid-transfering gun to suck a proper amount of Bi0.86Eu0.2Fe0.95Co0.05O3Dropwise adding the mixture on a substrate, fully covering the surface of the substrate, and slowly spin-coating at 500rpm for 15s and then quickly spin-coating at 4000rpm for 20 s; moving the substrate to a heating plate at 350 ℃ for pyrolysis for 10 min; repeat 0, 1, 2, 3 times respectively. Respectively correspondingly spin- coating 3, 2, 1 and 0 layers of Bi0.96Eu0.1Fe0.95Co0.05O3Keeping the thickness of the middle layer consistent before annealing, putting the middle layer into an annealing furnace after pyrolysis, quickly heating, and annealing for 30min at 650 ℃; cooling to room temperature in the air to obtain a light absorption layer; spin-coating 3 layers of Bi0.96Eu0.1Fe0.95Co0.05O3Then the mixture is put into an annealing furnace to be rapidly heated and annealed at 650 ℃ for 30 min; cooling to room temperature in air, and air cooling to room temperatureAnd obtaining the co-annealed ferroelectric film.
XRD analysis is carried out on the prepared film to obtain an image as shown in figure 4, and all the films are shown as pure phases in the XRD spectrum; as can be seen from the ferroelectric and bandgap diagrams, the films with a co-annealed interlayer have the best ferroelectric properties.
The ferroelectric photovoltaic thin film with adjustable polarization and band gap and the preparation method thereof provided by the embodiment of the application are described in detail above. The above description of the embodiments is only for the purpose of helping to understand the method of the present application and its core ideas; meanwhile, for a person skilled in the art, according to the idea of the present application, there may be variations in the specific embodiments and the application scope, and in summary, the content of the present specification should not be construed as a limitation to the present application.
As used in the specification and claims, certain terms are used to refer to particular components. As one skilled in the art will appreciate, manufacturers may refer to a component by different names. This specification and claims do not intend to distinguish between components that differ in name but not function. In the following description and in the claims, the terms "include" and "comprise" are used in an open-ended fashion, and thus should be interpreted to mean "include, but not limited to. "substantially" means within an acceptable error range, and a person skilled in the art can solve the technical problem within a certain error range to substantially achieve the technical effect. The description which follows is a preferred embodiment of the present application, but is made for the purpose of illustrating the general principles of the application and not for the purpose of limiting the scope of the application. The protection scope of the present application shall be subject to the definitions of the appended claims.
It is also noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a good or system that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such good or system. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other like elements in a commodity or system that includes the element.
It should be understood that the term "and/or" as used herein is merely one type of association that describes an associated object, meaning that three relationships may exist, e.g., a and/or B may mean: a exists alone, A and B exist simultaneously, and B exists alone. In addition, the character "/" herein generally indicates that the former and latter related objects are in an "or" relationship.
The foregoing description shows and describes several preferred embodiments of the present application, but as aforementioned, it is to be understood that the application is not limited to the forms disclosed herein, but is not to be construed as excluding other embodiments and is capable of use in various other combinations, modifications, and environments and is capable of changes within the scope of the application as described herein, commensurate with the above teachings, or the skill or knowledge of the relevant art. And that modifications and variations may be effected by those skilled in the art without departing from the spirit and scope of the application, which is to be protected by the claims appended hereto.
Claims (10)
1. A polarization and bandgap tunable ferroelectric photovoltaic thin film, the polarization and bandgap tunable ferroelectric photovoltaic thin film structure comprising: an upper iron polarizing layer, a light absorbing layer, and a lower iron polarizing layer;
wherein the light absorption layer is arranged between the upper iron polarization layer and the lower iron polarization layer and is constructed into a sandwich homogeneous structure;
the thicknesses of the upper iron polarization layer, the light absorption layer and the lower iron polarization layer are all 50-200 nm.
2. A polarization and bandgap tunable ferroelectric photovoltaic thin film as in claim 1, wherein the thin film structure is a tripartite phase-pseudo-cubic phase-orthorhombic phase composite perovskite structure.
3. The polarization and bandgap tunable of claim 1The ferroelectric photovoltaic film is characterized in that the upper ferroelectric polarization layer, the light absorption layer and the lower ferroelectric polarization layer are all homogeneous Bi x1- Re x FeO3A base film which is a film of a base material,
wherein in the upper and lower iron polarization layersxThe value of (A) is not more than 0%xLess than or equal to 50 percent; in the light absorbing layerxThe value of (A) is less than or equal to 15%x≤50 %。
4. The polarization and bandgap tunable ferroelectric photovoltaic thin film as claimed in claim 3, wherein the polarization and bandgap tunable ferroelectric photovoltaic thin film is a single layer or a multilayerReIs lanthanide series salt.
5. A method for preparing a polarization and bandgap tunable ferroelectric photovoltaic thin film according to any one of claims 1-4, wherein the method comprises the following specific processes:
s1) preparing a precursor solution of the ferroelectric polarization layer and a precursor solution of the light absorption layer;
s2) spin-coating the precursor solution obtained in S1) on a substrate to obtain an amorphous film structure;
s3) annealing the amorphous film structure obtained in S2), and cooling the amorphous film structure to room temperature in air to obtain the ferroelectric photovoltaic film with adjustable polarization and band gap and target thickness.
6. The method as claimed in claim 5, wherein the specific steps of S1) are as follows:
s1.1) adding bismuth salt into a solvent, and uniformly stirring to obtain a bismuth-containing salt solution;
s1.2) adding rare earth metal salt into a bismuth-containing salt solution, and uniformly stirring to obtain a mixed solution;
s1.3) adding iron salt into the mixed solution obtained in S1.2), uniformly stirring, adding a chelating agent to obtain a precursor solution with the molar concentration of 0.1-0.4M, standing for more than 24 hours, and fully hydrolyzing and polycondensing to respectively obtain a precursor solution of the ferroelectric polarization layer and a precursor solution of the light absorption layer.
7. The method as claimed in claim 6, wherein the specific steps of S2) are as follows:
s2.1) filtering the precursor solution of the ferroelectric polarization layer and the precursor solution of the light absorption layer obtained in the S1.3) by using a filter head with the diameter of 0.20-0.25 mu m for later use;
s2.2) selecting an FTO substrate, cleaning, and placing on a spin coater;
s2.3) according to the rotation speed of 500-4000rpm of spin coating and the spin coating time of 25-35S, respectively and uniformly spin-coating the precursor solution of the ferroelectric polarization layer obtained in the S2.2) and the precursor solution of the light absorption layer on the substrate treated in the S2.2), and then pyrolyzing the substrate on a heating table at the temperature of 250-400 ℃ for 5-15min for cooling, thereby obtaining the amorphous film structure attached on the substrate.
8. The method as claimed in claim 7, wherein the specific steps of S3) are:
and (3) annealing the substrate attached with the amorphous film structure spin with the specific thickness obtained in the step (S2.3) according to a certain annealing mode, and cooling the substrate to room temperature in the air to obtain the ferroelectric photovoltaic film with adjustable polarization and band gap.
9. The method according to claim 8, wherein the annealing mode in the annealing process is a same-component annealing mode or a same-thickness annealing mode, and the annealing process is carried out by keeping the temperature of an annealing furnace at 550-750 ℃ for 20-30 min.
10. The method as claimed in claim 5, wherein the thickness of the polarization and bandgap tunable ferroelectric photovoltaic thin film is 300-600 nm; the polarization can reach 70 mu C/cm at most2The band gap can be as low as 2.2-2.4 eV.
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