CN112939484A - Preparation method of cobalt-doped bismuth ferrite system film material - Google Patents
Preparation method of cobalt-doped bismuth ferrite system film material Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 9
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 9
- 229910000859 α-Fe Inorganic materials 0.000 title abstract description 3
- 239000000843 powder Substances 0.000 claims abstract description 69
- 239000000758 substrate Substances 0.000 claims abstract description 52
- 238000000151 deposition Methods 0.000 claims abstract description 51
- 239000013077 target material Substances 0.000 claims abstract description 50
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000003980 solgel method Methods 0.000 claims abstract description 16
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 75
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 52
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 36
- 238000002156 mixing Methods 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 230000008021 deposition Effects 0.000 claims description 29
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 27
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 27
- 229910052760 oxygen Inorganic materials 0.000 claims description 27
- 239000001301 oxygen Substances 0.000 claims description 27
- 238000000137 annealing Methods 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 19
- 229910021641 deionized water Inorganic materials 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 18
- 238000005303 weighing Methods 0.000 claims description 18
- 239000011240 wet gel Substances 0.000 claims description 18
- 238000001354 calcination Methods 0.000 claims description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- 239000008139 complexing agent Substances 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 238000004090 dissolution Methods 0.000 claims description 9
- 239000000499 gel Substances 0.000 claims description 9
- 239000011521 glass Substances 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 9
- 230000003301 hydrolyzing effect Effects 0.000 claims description 9
- 238000011065 in-situ storage Methods 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 238000003825 pressing Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 6
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000005416 organic matter Substances 0.000 claims description 3
- 230000005291 magnetic effect Effects 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 3
- 239000010408 film Substances 0.000 description 62
- 239000000126 substance Substances 0.000 description 14
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 10
- 229940078494 nickel acetate Drugs 0.000 description 10
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 5
- 238000011160 research Methods 0.000 description 4
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 229910002902 BiFeO3 Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000005294 ferromagnetic effect Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000004549 pulsed laser deposition Methods 0.000 description 2
- 230000009897 systematic effect Effects 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 230000005290 antiferromagnetic effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- PPNKDDZCLDMRHS-UHFFFAOYSA-N dinitrooxybismuthanyl nitrate Chemical compound [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007777 multifunctional material Substances 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
- C03C17/3417—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials all coatings being oxide coatings
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/70—Properties of coatings
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/15—Deposition methods from the vapour phase
- C03C2218/152—Deposition methods from the vapour phase by cvd
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Abstract
The invention discloses a preparation method of a cobalt-doped bismuth ferrite system film material, wherein x is 0, 0.02, 0.04, 0.06, 0.08 and 0.10). Firstly, preparing BiFe by adopting a sol-gel method1‑ xCoxO3A system powder sample is obtained, then the powder sample of the material is dried and made into a block target material, and finally the block target material is deposited on an FTO substrate by a pulse laser deposition method to prepare the BiFe1‑ xCoxO3And (5) a system film. The method of the invention can ensure that the film has good quality, high phase purity, stable element proportion of the film, good adhesion between the film and the substrate, high success rate of pure-phase film preparation, good repeatability and BiFe1‑xCoxO3Obvious magnetic, ferroelectric and photovoltaic effects are observed in the system film sample.
Description
Technical Field
The invention relates to a preparation method of a ferroelectric film material, in particular to BiFe1-xCoxO3A preparation method of a system film material (wherein x is 0, 0.02, 0.04, 0.06, 0.08 and 0.10).
Background
Multiferroic materials refer to material systems that have spontaneous polarization of more than one of ferroelectric, ferromagnetic (antiferromagnetic), and ferroelastic properties at the same time. In the material, electric, magnetic and elastic sequence parameters coexist and form a series of interesting physical phenomena such as magnetoelectric coupling. The idea of ferroelectric, ferromagnetic coexistence and magnetoelectric coupling was basically derived from 19 th century french scientist Pierre Curie, but ferroelectric was not in hydrogen bonding class (KH) until the last 30 th century2PO4) Thus making the physical concept multiferroic a possibility to be experimentally realized. Materials with such properties are considered to have potential application values in the fields of future information technology, sensing, spintronic devices and the like. BiFeO3The material is one of the most representative multiferroic materials, and as a material with important application value in the future, with the development of multiferroic materials, the material is also a ferroelectric photovoltaic material with abnormal photovoltaic effect and gradually becomes a research hotspot of people, so that the finding of a substrate which can be simultaneously used for a magnetoelectric coupling device and a photovoltaic device and is suitable for a high-temperature environment in the film preparation process is also important. Doping modification and preparation of thin films thereof in inorganic material research are important basic research processes, so that BiFe1-xCoxO3The preparation method of the system film material is the basis of the research in the field of multifunctional materials.
Disclosure of Invention
The invention aims to overcome the defects of the prior BiFe1-xCoxO3The defects of low phase forming rate and insufficient film compactness of the system film preparation process are overcome, and the BiFe is provided1-xCoxO3A method of making a system film material, wherein x is 0, 0.02, 0.04, 0.06, 0.08, 0.10.
The technical scheme adopted by the invention is as follows:
BiFe1-xCoxO3A method for preparing a systematic film material (wherein x is 0, 0.02, 0.04, 0.06, 0.08, 0.10), comprising the steps of:
1. BiFe is prepared by adopting sol-gel method1-xCoxO3The powder is prepared by mixing the raw materials,
2. mixing BiFe1-xCoxO3Calcining the powder at high temperature to prepare a block target material,
3. depositing the bulk target on the FTO substrate by Pulsed Laser Deposition (PLD) to obtain BiFe1-xCoxO3And (5) a system film.
Further, the BiFe is prepared by the sol-gel method1-xCoxO3The materials used in the powder process comprise a bismuth source material, an iron source material, a cobalt source material, a solvent A, a solvent B and a complexing agent, wherein the bismuth source material, the iron source material and the cobalt source material are respectively bismuth nitrate, ferric nitrate, cobalt nitrate, deionized water, ethylene glycol and citric acid.
Further, the BiFe is prepared by the sol-gel method1-xCoxO3The powder sample specifically comprises the following steps:
1. accurately weighing bismuth nitrate, ferric nitrate and cobalt nitrate according to the mass ratio of 1:1-x: x, and sequentially adding a proper amount of ethylene glycol to completely dissolve to obtain a solution A;
2. citric acid is added according to the { mCitric acid＝nBiFe1-xCoxO3×[3+3×(1-x)+2×x]/2×MCitric acidAccurately weighing (wherein m is mass, n is amount of substance, and x is 0, 0.02, 0.04, 0.06, 0.08, 0.10), and adding into deionized water to completely dissolve to obtain solution B;
3. slowly adding the solution A into the solution B (the sequence can not be changed, so that the citric acid solution is in an excessive state in the system in the whole operation process), fully and uniformly mixing to obtain a solution C, and placing the solution C into a 75-85 ℃ water bath kettle for water bath stirring to make the solution become viscous and yellow to obtain wet gel;
4. placing the wet gel in a blast drying box, slowly hydrolyzing and drying for 4-5 days at the temperature of 95-105 ℃ to form dry gel, removing the organic matter at the temperature of 380-420 ℃, and annealing at the temperature of 640-660 ℃ to obtain BiFe1-xCoxO3Powder A.
Further, the ethylene glycol is based on a bismuth source material, an iron source material, a cobalt source materialThe amount of the bismuth nitrate is determined by the dissolution of the material, but the concentration of the bismuth nitrate cannot be lower than 1mol/L, i.e. cBismuth nitrate≥1mol/L。
Further, the dosage of the deionized water is determined according to the dissolution condition of the complexing agent.
Further, the BiFe1-xCoxO3Calcining the powder A at a high temperature to prepare a block target material, and specifically comprising the following steps of:
1. subjecting the dried BiFe1-xCoxO3Grinding powder A into fine powder B;
2. placing the fine powder B in a crucible, and calcining the fine powder B in a muffle furnace at the high temperature of 600-700 ℃ for 2-2.5 hours to obtain brownish black BiFe1-xCoxO3Powder C;
3. pressing the powder C into a cylindrical target material with the diameter of 30mm and the thickness of 2-3 mm by using a metal die, wherein the pressure intensity is 25 MPa;
4. placing the cylindrical target material in a muffle furnace at 600-700 ℃ for rapid annealing for 7-8min to obtain BiFe1-xCoxO3A target material.
Further, the pulse laser deposition method is used for depositing BiFe1-xCoxO3The deposition of the bulk target on the FTO substrate specifically comprises the following steps:
1. subjecting said BiFe to1-xCoxO3Respectively placing the block target material and the FTO substrate at proper positions of a target position and a lining disc, fixing, closing the vacuum cavity, and sequentially starting a mechanical pump and a molecular pump to vacuumize the vacuum cavity;
2. when the vacuum degree of the vacuum cavity reaches 5 multiplied by 10-4When Pa is needed, the molecular pump is closed, the oxygen valve is opened, and the oxygen pressure of the vacuum cavity is adjusted to 9 Pa;
3. setting the temperature of an FTO substrate in a vacuum chamber to be 650 ℃, and covering the FTO substrate by using a baffle;
4. setting the voltage of a pulse laser to be 19kV, setting the frequency to be 1Hz, and pre-striking for a time determined according to the actual surface condition of the target;
5. setting the energy of a pulsed laserAt the frequency of 4Hz and 350mJ, removing the baffle, starting deposition, introducing oxygen of 0.8atm after the deposition is finished, preserving the temperature for 1h in situ, and cooling to room temperature to obtain the BiFe1-xCoxO3A film.
Further, the BiFe is prepared1-xCoxO3The deposition time of the film is adjusted according to the thickness of the film to be prepared, and the growth rate of the film is about 95-105nm/h (different preparation environments are changed).
Furthermore, the FTO substrate belongs to conductive glass, the softening temperature is not lower than 700 ℃, and the reduction rate of the conductivity of the conductive layer is not higher than 50% at the temperature of 650 +/-10 ℃ and at the normal temperature.
The BiFe is prepared by adopting the technical scheme1-xCoxO3Systematic thin film (wherein x is 0, 0.02, 0.04, 0.06, 0.08, 0.10), using physical property comprehensive measurement system (PPMS), ferroelectric comprehensive test system and photovoltaic measurement system to said BiFe1-xCoxO3The system film is tested for magnetic, ferroelectric and photovoltaic performances, and the saturated magnetic field is extremely large and can reach 8T in a 10K environment, so that a necessary material foundation is laid for the research and development of novel multifunctional devices such as a micro magnetic sensor and the like in the future; because the sol-gel method is adopted to prepare the BiFe1-xCoxO3System powder, BiFe obtained1-xCoxO3The system powder has small grain diameter and high uniformity, and the sol-gel method has the characteristics of simple principle, low preparation requirement, easily controlled element proportion and the like; BiFe deposited by pulse laser deposition1-xCoxO3The film obtained by the method has the characteristics of good quality, high density, high uniformity, stable material components, good synchronism with target components and the like, and the BiFe prepared by adopting the FTO substrate with the temperature and the electric conductivity required by annealing is adopted1-xCoxO3The system film structure is more stable. And in BiFe1-xCoxO3Obvious magnetic, ferroelectric and photovoltaic effects are observed in the system film sample. The method of the invention can ensure that the film has good quality, high phase purity, stable element proportion of the film, and good film qualityThe substrate adhesion is good, and the success rate of pure phase film preparation is high, and the repeatability is good.
Drawings
The invention is described in further detail below with reference to the accompanying drawings and the detailed description;
FIG. 1 shows BiFe of the present invention1-xCoxO3The flow diagram of the preparation method of the system film material;
FIG. 2 shows BiFe of the present invention0.9Co0.1O3XRD pattern of the film;
FIG. 3 shows BiFe of the present invention0.9Co0.1O3Hysteresis loops of the film material at different temperatures;
FIG. 4 shows BiFe of the present invention0.9Co0.1O3Electric hysteresis loops of the film material under different electric fields;
FIG. 5 shows BiFe of the present invention0.9Co0.1O3I-V characteristic curve of the film material.
Detailed Description
As shown in one of figures 1-5, the invention discloses a BiFe1-xCoxO3A method for preparing a systematic film material (wherein x is 0, 0.02, 0.04, 0.06, 0.08, 0.10), comprising the steps of:
1: BiFe is prepared by adopting sol-gel method1-xCoxO3Powder samples.
1-1: accurately weighing bismuth nitrate, ferric nitrate and cobalt nitrate according to the mass ratio of 1:1-x: x, and sequentially adding a proper amount of ethylene glycol to completely dissolve to obtain a solution A;
1-2: citric acid is added according to the { mCitric acid＝nBiFe1-xCoxO3×[3+3×(1-x)+2×x]/2×MCitric acidAccurately weighing (wherein m is mass, n is amount of substance, and x is 0, 0.02, 0.04, 0.06, 0.08, 0.10), and adding into deionized water to completely dissolve to obtain solution B;
1-3: slowly adding the solution A into the solution B (the sequence can not be changed, so that the citric acid solution is in an excessive state in the system in the whole operation process), fully and uniformly mixing to obtain a solution C, and placing the solution C into a 75-85 ℃ water bath kettle for water bath stirring to make the solution become viscous and yellow to obtain wet gel;
1-4: placing the wet gel in a blast drying box, slowly hydrolyzing and drying for 4-5 days at the temperature of 95-105 ℃ to form dry gel, removing the organic matter at the temperature of 380-420 ℃, and annealing at the temperature of 640-660 ℃ to obtain BiFe1-xCoxO3Powder A;
2: mixing BiFe1-xCoxO3And calcining the powder at high temperature to prepare the block target material.
2-1: subjecting the dried BiFe1-xCoxO3Grinding powder A into fine powder B;
2-2: the fine powder B is placed in a crucible and is calcined for 2 hours at the high temperature of 600-700 ℃ in a muffle furnace to obtain brownish black BiFe1-xCoxO3Powder C;
2-3: pressing the powder C into a cylindrical target material with the diameter of 30mm and the thickness of 2-3 mm by using a metal die, wherein the pressure intensity is 25 MPa;
2-4: placing the cylindrical target material in a muffle furnace at 600-700 ℃ for rapid annealing for 7-8min to obtain BiFe1- xCoxO3A target material.
3: depositing the bulk target on an FTO substrate by a pulse laser deposition method to obtain BiFe1-xCoxO3A film.
3-1: subjecting said BiFe to1-xCoxO3Respectively placing the block target material and the FTO substrate at proper positions of a target position and a lining disc, fixing, closing the vacuum cavity, and sequentially starting a mechanical pump and a molecular pump to vacuumize the vacuum cavity;
3-2: when the vacuum degree of the vacuum cavity reaches 5 multiplied by 10-4When Pa is needed, the molecular pump is closed, the oxygen valve is opened, and the oxygen pressure of the vacuum cavity is adjusted to 9 Pa;
3-3: setting the temperature of an FTO substrate in a vacuum chamber to be 650 ℃, and covering the FTO substrate by using a baffle;
3-4: setting the voltage of a pulse laser to be 19kV, setting the frequency to be 1Hz, and pre-striking for a time determined according to the actual surface condition of the target;
3-5: setting the energy of a pulse laser at 350mJ and the frequency of 4Hz, removing the baffle, starting deposition, introducing 0.8atm oxygen after the deposition is finished, preserving the heat in situ for 1h, and cooling to room temperature to obtain the BiFe1-xCoxO3A film.
In the above steps, the deposition time is adjusted according to the thickness of the film to be prepared, and the growth rate of the film is 95-105 nm/h;
the FTO substrate belongs to conductive glass, the softening temperature is not lower than 700 ℃, and the conductivity of the conductive layer is not higher than 50% at the temperature of 650 ℃ and at the normal temperature.
Example 1
BiFe1-xCoxO3Preparation method of system film material (wherein x is 0, namely BiFeO3) The method comprises the following steps:
1: BiFe is prepared by adopting sol-gel method1-xCoxO3Powder samples.
1-1: accurately weighing bismuth nitrate and ferric nitrate according to the mass ratio of 1:1, and sequentially adding a proper amount of glycol to completely dissolve to obtain a solution A; the using amount of the ethylene glycol is determined according to the dissolving conditions of the bismuth nitrate and the ferric nitrate, wherein the mass concentration of the bismuth nitrate is not lower than 1 mol/L;
1-2: mixing citric acid according to mCitric acid＝nBiFe1-xCoxO3×[3+3×(1-0)+2×0]/2×MCitric acidAccurately weighing, wherein m is mass and n is amount of the substance, and adding a proper amount of deionized water to completely dissolve the substance to obtain a solution B; the deionized water is used for determining the dosage according to the dissolving condition of the complexing agent;
1-3: slowly adding the solution A into the solution B, mixing thoroughly to obtain solution C, placing into 75 deg.C water bath, stirring to make it viscous and yellow to obtain wet gel;
1-4: placing the wet gel in a blast drying oven, slowly hydrolyzing at 95 ℃, drying for 5 days to form dry gel, removing organic matters at 380 ℃, and annealing at 650 ℃ to obtain BiFe1-xCoxO3Powder A.
2: mixing BiFe1-xCoxO3And calcining the powder A at a high temperature to prepare the block target material.
2-1: the BiFe obtained in the step 1 is added1-xCoxO3Grinding powder A into fine powder B;
2-2: the fine powder B is placed in a crucible and calcined in a muffle furnace at the high temperature of 650 ℃ for 2.5 hours to obtain brownish black BiFe1-xCoxO3Powder C;
2-3: pressing the powder C into a cylindrical target material with the diameter of 30mm and the thickness of 2-3 mm by using a metal die, wherein the pressure intensity is 25 MPa;
2-4: placing the cylindrical target material in a muffle furnace at 650 ℃ for rapid annealing for 8min to obtain BiFe1-xCoxO3A target material.
3: depositing the bulk target on an FTO substrate by a pulse laser deposition method to obtain BiFe1-xCoxO3A film.
3-1: mixing BiFe1-xCoxO3The target material and the FTO substrate are respectively placed at proper positions of the target position and the lining disc and fixed, the vacuum cavity is closed, and the mechanical pump and the molecular pump are started in sequence to vacuumize the vacuum cavity;
3-2: when the vacuum degree of the vacuum cavity reaches 5 multiplied by 10-4When Pa is needed, the molecular pump is closed, the oxygen valve is opened, and the oxygen pressure of the vacuum cavity is adjusted to 9 Pa;
3-3: setting the temperature of an FTO substrate in a vacuum chamber to be 650 ℃, and covering the FTO substrate by using a baffle;
3-4: setting the voltage of a pulse laser to be 19kV, setting the frequency to be 1Hz, and pre-striking for a time determined according to the actual surface condition of the target;
3-5: setting the energy of a pulse laser at 350mJ and the frequency of 4Hz, removing the baffle, starting deposition for 1.5h, introducing 0.8atm oxygen after the deposition is finished, preserving the temperature for 1h in situ, and cooling to room temperature to obtain the BiFe1-xCoxO3A film;
in the above steps, the deposition time is adjusted according to the thickness of the film to be prepared, and the growth rate of the film is about 100 nm/h; the FTO substrate belongs to conductive glass, the softening temperature is 700 ℃, and the conductivity of the conductive layer is reduced by 50% at the temperature of about 650 ℃ and at normal temperature.
Example 2
BiFe1-xCoxO3Preparation method of system film material (wherein x is 0.02, namely BiFe)0.98Co0.02O3) The method comprises the following steps:
1: BiFe is prepared by adopting sol-gel method1-xCoxO3Powder samples.
1-1: accurately weighing bismuth nitrate, ferric nitrate and nickel acetate according to the mass ratio of 1:0.98:0.02, and sequentially adding a proper amount of glycol to completely dissolve to obtain a solution A; the dosage of the ethylene glycol is determined according to the dissolution conditions of the bismuth nitrate, the ferric nitrate and the nickel acetate, wherein the mass concentration of the bismuth nitrate is not lower than 1 mol/L.
1-2: mixing citric acid according to mCitric acid＝nBiFe1-xCoxO3×[3+3×(1-0.02)+2×0.02]/2×MCitric acidAccurately weighing, wherein m is mass and n is amount of the substance, and adding a proper amount of deionized water to completely dissolve the substance to obtain a solution B; the deionized water is used for determining the dosage according to the dissolving condition of the complexing agent;
1-3: slowly adding the solution A into the solution B, mixing thoroughly to obtain solution C, placing into 80 deg.C water bath, stirring to make it viscous and yellow to obtain wet gel;
1-4: placing the wet gel in a blast drying oven, slowly hydrolyzing at 100 ℃, drying for 5 days to form dry gel, removing organic matters at 400 ℃, and annealing at 650 ℃ to obtain BiFe1-xCoxO3Powder A.
2: mixing BiFe1-xCoxO3And calcining the powder A at a high temperature to prepare the block target material.
2-1: the BiFe obtained in the step 1 is added1-xCoxO3Grinding powder A into fine powder B;
2-2: placing the fine powder B in a crucible, and calcining the fine powder B in a muffle furnace at 675 ℃ for 2 hours to obtain brownish black BiFe1-xCoxO3Powder C;
2-3: pressing the powder C into a cylindrical target material with the diameter of 30mm and the thickness of 2-3 mm by using a metal die, wherein the pressure intensity is 25 MPa;
2-4: placing the cylindrical target material in a muffle furnace at 650 ℃ for rapid annealing for 8min to obtain BiFe1-xCoxO3A target material.
3: depositing the bulk target on an FTO substrate by a pulse laser deposition method to obtain BiFe1-xCoxO3A film.
3-1: mixing BiFe1-xCoxO3The target material and the FTO substrate are respectively placed at proper positions of the target position and the lining disc and fixed, the vacuum cavity is closed, and the mechanical pump and the molecular pump are started in sequence to vacuumize the vacuum cavity;
3-2: when the vacuum degree of the vacuum cavity reaches 5 multiplied by 10-4When Pa is needed, the molecular pump is closed, the oxygen valve is opened, and the oxygen pressure of the vacuum cavity is adjusted to 9 Pa;
3-3: setting the temperature of an FTO substrate in a vacuum chamber to be 650-680 ℃, and covering the FTO substrate by a baffle;
3-4: setting the voltage of a pulse laser to be 20kV, setting the frequency to be 1Hz, and pre-striking for a period of time according to the actual surface condition of the target;
3-5: setting the energy of a pulse laser at 350mJ and the frequency of 4Hz, removing the baffle, starting deposition for 1.5h, introducing 0.8atm oxygen after the deposition is finished, preserving the temperature for 1.2h in situ, and cooling to room temperature to obtain the BiFe1-xCoxO3A film;
in the above steps, the deposition time is adjusted according to the thickness of the film to be prepared, and the growth rate of the film is 95-105 nm/h; the FTO substrate belongs to conductive glass, the softening temperature is 720 ℃, and the conductivity of the conductive layer is reduced by 48% at the temperature of 650 ℃ and normal temperature.
Example 3
BiFe1-xCoxO3Preparation method of system film material (wherein x is 0.04, namely BiFe)0.96Co0.04O3) The method comprises the following steps:
1: BiFe is prepared by adopting sol-gel method1-xCoxO3Powder samples.
1-1: accurately weighing bismuth nitrate, ferric nitrate and nickel acetate according to the mass ratio of 1:0.96:0.04, and sequentially adding a proper amount of glycol to completely dissolve to obtain a solution A; the dosage of the ethylene glycol is determined according to the dissolution conditions of the bismuth nitrate, the ferric nitrate and the nickel acetate, wherein the mass concentration of the bismuth nitrate is not lower than 1 mol/L.
1-2: mixing citric acid according to mCitric acid＝nBiFe1-xCoxO3×[3+3×(1-0.04)+2×0.04]/2×MCitric acidAccurately weighing, wherein m is mass and n is amount of the substance, and adding a proper amount of deionized water to completely dissolve the substance to obtain a solution B; the deionized water is used for determining the dosage according to the dissolving condition of the complexing agent;
1-3: slowly adding the solution A into the solution B, mixing thoroughly to obtain solution C, placing into 85 deg.C water bath, stirring to make it viscous and yellow to obtain wet gel;
1-4: placing the wet gel in a blast drying oven, slowly hydrolyzing at 105 ℃, drying for 4 days to form dry gel, removing organic matters at 420 ℃, and annealing at 670 ℃ to obtain BiFe1-xCoxO3Powder A.
2: mixing BiFe1-xCoxO3And calcining the powder A at a high temperature to prepare the block target material.
2-1: the BiFe obtained in the step 1 is added1-xCoxO3Grinding powder A into fine powder B;
2-2: the fine powder B is placed in a crucible and calcined in a muffle furnace at the high temperature of 700 ℃ for 2 hours to obtain brownish black BiFe1-xCoxO3Powder C;
2-3: pressing the powder C into a cylindrical target material with the diameter of 30mm and the thickness of 2-3 mm by using a metal die, wherein the pressure intensity is 25 MPa;
2-4: placing the cylindrical target material in a muffle furnace at 650 ℃ for rapid annealing for 8min to obtain BiFe1-xCoxO3A target material.
3: depositing the bulk target on an FTO substrate by a pulse laser deposition method to obtain BiFe1-xCoxO3A film.
3-1: mixing BiFe1-xCoxO3The target material and the FTO substrate are respectively placed at proper positions of the target position and the lining disc and fixed, the vacuum cavity is closed, and the mechanical pump and the molecular pump are started in sequence to vacuumize the vacuum cavity;
3-2: when the vacuum degree of the vacuum cavity reaches 5 multiplied by 10-4When Pa is needed, the molecular pump is closed, the oxygen valve is opened, and the oxygen pressure of the vacuum cavity is adjusted to 9 Pa;
3-3: setting the temperature of an FTO substrate in a vacuum chamber to be 680 ℃, and covering the FTO substrate by using a baffle;
3-4: setting the voltage of a pulse laser to be 19kV, setting the frequency to be 1Hz, and pre-striking for a time determined according to the actual surface condition of the target;
3-5: setting the energy of a pulse laser at 350mJ and the frequency of 4Hz, removing the baffle, starting deposition for 1.5h, introducing 0.8atm oxygen after the deposition is finished, preserving the temperature for 1h in situ, and cooling to room temperature to obtain the BiFe1-xCoxO3A film;
in the above steps, the deposition time is adjusted according to the thickness of the film to be prepared, and the growth rate of the film is about 100 nm/h; the FTO substrate belongs to conductive glass, the softening temperature is not lower than 700 ℃, and the conductivity of the conductive layer is not higher than 50% at the temperature of 650 ℃ and at the normal temperature.
Example 4
BiFe1-xCoxO3Preparation method of system film material (wherein x is 0.06, namely BiFe)0.94Co0.06O3) The method comprises the following steps:
1: BiFe is prepared by adopting sol-gel method1-xCoxO3Powder samples.
1-1: accurately weighing bismuth nitrate, ferric nitrate and nickel acetate according to the mass ratio of 1:0.94:0.06, and sequentially adding a proper amount of glycol to completely dissolve to obtain a solution A; the dosage of the ethylene glycol is determined according to the dissolution conditions of the bismuth nitrate, the ferric nitrate and the nickel acetate, wherein the mass concentration of the bismuth nitrate is not lower than 1 mol/L.
1-2: mixing citric acid according to mCitric acid＝nBiFe1-xCoxO3×[3+3×(1-0.06)+2×0.06]/2×MCitric acidAccurately weighing, wherein m is mass and n is amount of the substance, and adding a proper amount of deionized water to completely dissolve the substance to obtain a solution B; the deionized water is used for determining the dosage according to the dissolving condition of the complexing agent;
1-3: slowly adding the solution A into the solution B, mixing thoroughly to obtain solution C, placing into 80 deg.C water bath, stirring to make it viscous and yellow to obtain wet gel;
1-4: placing the wet gel in a blast drying oven, slowly hydrolyzing and drying for 5 days at 100 ℃ to form dry gel, removing organic matters at 380-420 ℃, and annealing at 650 ℃ to obtain BiFe1-xCoxO3Powder A.
2: mixing BiFe1-xCoxO3And calcining the powder A at a high temperature to prepare the block target material.
2-1: the BiFe obtained in the step 1 is added1-xCoxO3Grinding powder A into fine powder B;
2-2: the fine powder B is placed in a crucible and is calcined in a muffle furnace at the high temperature of 650 ℃ for 2-hours to obtain brownish black BiFe1-xCoxO3Powder C;
2-3: pressing the powder C into a cylindrical target material with the diameter of 30mm and the thickness of 2-3 mm by using a metal die, wherein the pressure intensity is 25 MPa;
2-4: placing the cylindrical target material in a muffle furnace at 650 ℃ for rapid annealing for 8min to obtain BiFe1-xCoxO3A target material.
3: depositing the bulk target on an FTO substrate by a pulse laser deposition method to obtain BiFe1-xCoxO3A film.
3-1: mixing BiFe1-xCoxO3The target material and the FTO substrate are respectively placed at the proper positions of the target position and the lining disc and fixed, the vacuum cavity is closed, and the mechanical pump and the molecular pump are started in sequence to carry out vacuum cavity alignmentVacuumizing;
3-2: when the vacuum degree of the vacuum cavity reaches 5 multiplied by 10-4When Pa is needed, the molecular pump is closed, the oxygen valve is opened, and the oxygen pressure of the vacuum cavity is adjusted to 9 Pa;
3-3: setting the temperature of an FTO substrate in a vacuum chamber to be 650 ℃, and covering the FTO substrate by using a baffle;
3-4: setting the voltage of a pulse laser to be 19kV, setting the frequency to be 1Hz, and pre-striking for a time determined according to the actual surface condition of the target;
3-5: setting the energy of a pulse laser at 350mJ and the frequency of 4Hz, removing the baffle, starting deposition for 1.5h, introducing 0.8atm oxygen after the deposition is finished, preserving the temperature for 1h in situ, and cooling to room temperature to obtain the BiFe1-xCoxO3A film;
in the above steps, the deposition time is adjusted according to the thickness of the film to be prepared, and the growth rate of the film is 95-105 nm/h; the FTO substrate belongs to conductive glass, the softening temperature is not lower than 700 ℃, and the conductivity of the conductive layer is not higher than 50% at the temperature of 650 ℃ and at the normal temperature.
Example 5
BiFe1-xCoxO3Preparation method of system film material (wherein x is 0.08, namely BiFe)0.92Co0.08O3) The method comprises the following steps:
1: BiFe is prepared by adopting sol-gel method1-xCoxO3Powder samples.
1-1: accurately weighing bismuth nitrate, ferric nitrate and nickel acetate according to the mass ratio of 1:0.92:0.08, and sequentially adding a proper amount of glycol to completely dissolve to obtain a solution A; the dosage of the ethylene glycol is determined according to the dissolution conditions of the bismuth nitrate, the ferric nitrate and the nickel acetate, wherein the mass concentration of the bismuth nitrate is not lower than 1 mol/L.
1-2: mixing citric acid according to mCitric acid＝nBiFe1-xCoxO3×[3+3×(1-0.08)+2×0.08]/2×MCitric acidAccurately weighing, wherein m is mass and n is amount of the substance, and adding a proper amount of deionized water to completely dissolve the substance to obtain a solution B; deionized water according to the formulaThe dosage of the mixture is determined by the dissolution condition of the mixture;
1-3: slowly adding the solution A into the solution B, mixing thoroughly to obtain solution C, placing into 80 deg.C water bath, stirring to make it viscous and yellow to obtain wet gel;
1-4: placing the wet gel in a blast drying oven, slowly hydrolyzing at 100 ℃, drying for 5 days to form dry gel, removing organic matters at 400 ℃, and annealing at 650 ℃ to obtain BiFe1-xCoxO3Powder A.
2: mixing BiFe1-xCoxO3And calcining the powder A at a high temperature to prepare the block target material.
2-1: the BiFe obtained in the step 1 is added1-xCoxO3Grinding powder A into fine powder B;
2-2: the fine powder B is placed in a crucible and calcined in a muffle furnace at a high temperature of 650 ℃ for 2 hours to obtain brownish black BiFe1-xCoxO3Powder C;
2-3: pressing the powder C into a cylindrical target material with the diameter of 30mm and the thickness of 2-3 mm by using a metal die, wherein the pressure intensity is 25 MPa;
2-4: placing the cylindrical target material in a muffle furnace at 650 ℃ for rapid annealing for 8min to obtain BiFe1-xCoxO3A target material.
3: depositing the bulk target on an FTO substrate by a pulse laser deposition method to obtain BiFe1-xCoxO3A film.
3-1: mixing BiFe1-xCoxO3The target material and the FTO substrate are respectively placed at proper positions of the target position and the lining disc and fixed, the vacuum cavity is closed, and the mechanical pump and the molecular pump are started in sequence to vacuumize the vacuum cavity;
3-2: when the vacuum degree of the vacuum cavity reaches 5 multiplied by 10-4When Pa is needed, the molecular pump is closed, the oxygen valve is opened, and the oxygen pressure of the vacuum cavity is adjusted to 9 Pa;
3-3: setting the temperature of an FTO substrate in a vacuum chamber to be 650 ℃, and covering the FTO substrate by using a baffle;
3-4: setting the voltage of a pulse laser to be 19kV, setting the frequency to be 1Hz, and pre-striking for a time determined according to the actual surface condition of the target;
3-5: setting the energy of a pulse laser at 350mJ and the frequency of 4Hz, removing the baffle, starting deposition for 1.5h, introducing 0.8atm oxygen after the deposition is finished, preserving the temperature in situ for 1-1.2h, and cooling to room temperature to obtain the BiFe1-xCoxO3A film;
in the above steps, the deposition time is adjusted according to the thickness of the film to be prepared, and the growth rate of the film is about 100 nm/h; the FTO substrate belongs to conductive glass, the softening temperature is not lower than 700 ℃, and the conductivity of the conductive layer is not higher than 50% at the temperature of 650 ℃ and at the normal temperature.
Example 6
BiFe1-xCoxO3Preparation method of system film material (wherein x is 0.10, namely BiFe)0.9Co0.1O3) The method comprises the following steps:
1: BiFe is prepared by adopting sol-gel method1-xCoxO3Powder samples.
1-1: accurately weighing bismuth nitrate, ferric nitrate and nickel acetate according to the mass ratio of 1:0.9:0.1, and sequentially adding a proper amount of ethylene glycol to completely dissolve to obtain a solution A; the dosage of the ethylene glycol is determined according to the dissolution conditions of the bismuth nitrate, the ferric nitrate and the nickel acetate, wherein the mass concentration of the bismuth nitrate is not lower than 1 mol/L.
1-2: mixing citric acid according to mCitric acid＝nBiFe1-xCoxO3×[3+3×(1-0.9)+2×0.1]/2×MCitric acidAccurately weighing, wherein m is mass and n is amount of the substance, and adding a proper amount of deionized water to completely dissolve the substance to obtain a solution B; the deionized water is used for determining the dosage according to the dissolving condition of the complexing agent;
1-3: slowly adding the solution A into the solution B, mixing thoroughly to obtain solution C, placing into 80 deg.C water bath, stirring to make it viscous and yellow to obtain wet gel;
1-4: placing the wet gel in a forced air drying oven, slowly hydrolyzing at 100 deg.C, oven drying for 5 days to form dry gel, and drying at 4 deg.CRemoving organic matters at the temperature of 00 ℃, and annealing at the temperature of 650 ℃ to obtain BiFe1-xCoxO3Powder A.
2: mixing BiFe1-xCoxO3And calcining the powder A at a high temperature to prepare the block target material.
2-1: the BiFe obtained in the step 1 is added1-xCoxO3Grinding powder A into fine powder B;
2-2: the fine powder B is placed in a crucible and calcined in a muffle furnace at a high temperature of 650 ℃ for 2 hours to obtain brownish black BiFe1-xCoxO3Powder C;
2-3: pressing the powder C into a cylindrical target material with the diameter of 30mm and the thickness of 2-3 mm by using a metal die, wherein the pressure intensity is 25 MPa;
2-4: placing the cylindrical target material in a muffle furnace at 650 ℃ for rapid annealing for 8min to obtain BiFe1-xCoxO3A target material.
3: depositing the bulk target on an FTO substrate by a pulse laser deposition method to obtain BiFe1-xCoxO3A film.
3-1: mixing BiFe1-xCoxO3The target material and the FTO substrate are respectively placed at proper positions of the target position and the lining disc and fixed, the vacuum cavity is closed, and the mechanical pump and the molecular pump are started in sequence to vacuumize the vacuum cavity;
3-2: when the vacuum degree of the vacuum cavity reaches 5 multiplied by 10-4When Pa is needed, the molecular pump is closed, the oxygen valve is opened, and the oxygen pressure of the vacuum cavity is adjusted to 9 Pa;
3-3: setting the temperature of an FTO substrate in a vacuum chamber to be 650 ℃, and covering the FTO substrate by using a baffle;
3-4: setting the voltage of a pulse laser to be 19kV, setting the frequency to be 1Hz, and pre-striking for a time determined according to the actual surface condition of the target;
3-5: setting the energy of a pulse laser at 350mJ and the frequency of 4Hz, removing the baffle, starting deposition for 1.5h, introducing 0.8atm oxygen after the deposition is finished, preserving the temperature in situ for 1-1.2h, and cooling to room temperature to obtain the BiFe1-xCoxO3A film;
in the above steps, the deposition time is adjusted according to the thickness of the film to be prepared, and the growth rate of the film is 95-105 nm/h; the FTO substrate belongs to conductive glass, the softening temperature is not lower than 700 ℃, and the conductivity of the conductive layer is not higher than 50% at the temperature of 650 ℃ and at the normal temperature.
Claims (10)
1. BiFe1-xCoxO3The preparation method of the system film material is characterized by comprising the following steps: which comprises the following steps:
1: BiFe is prepared by adopting sol-gel method1-xCoxO3Powder;
2: mixing BiFe1-xCoxO3Calcining the powder at high temperature to prepare a block target material;
3: depositing the bulk target on an FTO substrate by a pulse laser deposition method to obtain BiFe1-xCoxO3And (5) a system film.
2. A BiFe according to claim 11-xCoxO3The preparation method of the system film material is characterized by comprising the following steps: x is 0, 0.02, 0.04, 0.06, 0.08 or 0.10.
3. A BiFe according to claim 11-xCoxO3The preparation method of the system film material is characterized by comprising the following steps: BiFe is prepared by adopting sol-gel method1-xCoxO3The materials used in the powder process comprise a bismuth source material, an iron source material, a cobalt source material, a solvent A, a solvent B and a complexing agent, wherein the bismuth source material, the iron source material and the cobalt source material, the solvent A and the solvent B are respectively bismuth nitrate, ferric nitrate, cobalt nitrate, deionized water, ethylene glycol and citric acid.
4. A BiFe according to claim 31-xCoxO3The preparation method of the system film material is characterized by comprising the following steps: step 1, adopting a sol-gel method to prepare BiFe1-xCoxO3The powder specifically comprises the following steps:
1-1, accurately weighing bismuth nitrate, ferric nitrate and cobalt nitrate according to the mass ratio of 1:1-x: x, and sequentially adding the bismuth nitrate, the ferric nitrate and the cobalt nitrate into ethylene glycol to be completely dissolved to obtain a solution A;
1-2, will be according to citric acid { mCitric acid＝nBiFe1-xCoxO3×[3+3×(1-x)+2×x]/2×MCitric acidAccurately weighing, and adding the weighed materials into deionized water to be completely dissolved to obtain a solution B;
1-3, slowly adding the solution A into the solution B, fully and uniformly mixing to obtain a solution C, and stirring in a water bath kettle at a temperature of 75-85 ℃ in a water bath manner to obtain wet gel;
1-4, placing the wet gel in a drying box, slowly hydrolyzing and drying for 4-5 days at the temperature of 95-105 ℃ to form dry gel, removing the organic matter at the temperature of 380-420 ℃, and annealing at the temperature of 640-660 ℃ to obtain the BiFe1-xCoxO3Powder;
5. a BiFe according to claim 41-xCoxO3The preparation method of the system film material is characterized by comprising the following steps: the ethylene glycol in the step 1-1 is determined according to the dissolution conditions of the bismuth source material, the iron source material and the cobalt source material, but the mass concentration of the bismuth nitrate cannot be lower than 1 mol/L.
6. A BiFe according to claim 41-xCoxO3The preparation method of the system film material is characterized by comprising the following steps: the deionized water in the step 1-2 is used for determining the dosage according to the dissolving condition of the complexing agent.
7. A BiFe according to claim 11-xCoxO3The preparation method of the system film material is characterized by comprising the following steps: step 2 is to mix BiFe1-xCoxO3Calcining the powder at high temperature to prepare the block target material, and specifically comprising the following steps of:
2-1, drying the BiFe1-xCoxO3Grinding the powder into fine powder B;
2-2, placing the fine powder B in a crucible, and calcining the fine powder B in a muffle furnace at the high temperature of 600-700 ℃ for 2-2.5 hours to obtain brownish black BiFe1-xCoxO3Powder C;
2-3, pressing the powder C into a cylindrical target material with the diameter of 30mm and the thickness of 2-3 mm by using a metal mold, wherein the pressure intensity is 25 MPa;
2-4, placing the cylindrical target material in a muffle furnace at the temperature of 600-700 ℃ for rapid annealing for 7-8min to obtain BiFe1-xCoxO3A target material.
8. A BiFe according to claim 11-xCoxO3The preparation method of the system film material is characterized by comprising the following steps: step 3, using a pulse laser deposition method to deposit BiFe1-xCoxO3The deposition of the bulk target on the FTO substrate specifically comprises the following steps:
3-1, mixing BiFe1-xCoxO3Respectively placing the block target material and the FTO substrate at proper positions of a target position and a lining disc, fixing, closing the vacuum cavity, and sequentially starting a mechanical pump and a molecular pump to vacuumize the vacuum cavity;
3-2, when the vacuum degree of the vacuum cavity reaches 5 x 10-4When Pa is needed, the molecular pump is closed, the oxygen valve is opened, and the oxygen pressure of the vacuum cavity is adjusted to 9 Pa;
3-3, setting the temperature of the FTO substrate in the vacuum chamber to be 650 ℃, and covering the FTO substrate by using a baffle;
3-4, setting the voltage of a pulse laser to be 19kV, setting the frequency to be 1Hz, and performing pre-striking according to the actual surface condition of the target material;
3-5, setting the energy of a pulse laser at 350mJ and the frequency at 4Hz, removing the baffle, starting deposition for 1.5h, introducing 0.8atm oxygen after the deposition is finished, preserving the heat in situ for 1h, and cooling to room temperature to obtain the BiFe1-xCoxO3And (5) a system film.
9. A BiFe according to claim 81-xCoxO3Film materialThe preparation method is characterized by comprising the following steps: to prepare BiFe1-xCoxO3The deposition time of the system film is adjusted according to the thickness of the film to be prepared, and the growth rate of the film is about 95-105 nm/h.
10. A BiFe according to claim 11-xCoxO3The preparation method of the system film material is characterized by comprising the following steps: the FTO substrate belongs to conductive glass, the softening temperature is not lower than 700 ℃, and the conductivity of the conductive layer is not higher than 50% at 650 +/-10 ℃ and at normal temperature.
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| 关晓英等: "《Co掺杂BiFeO3薄膜的溶胶凝胶法制备及性能研究》" * |
| 凌飞等: "铁酸铋薄膜的掺杂改性与光伏效应研究进展" * |
| 张晖等: "《Co掺杂BiFeO3的第一性原理研究》" * |
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