CN112939484B - Preparation method of cobalt-doped bismuth ferrite system film material - Google Patents
Preparation method of cobalt-doped bismuth ferrite system film material Download PDFInfo
- Publication number
- CN112939484B CN112939484B CN202110121396.5A CN202110121396A CN112939484B CN 112939484 B CN112939484 B CN 112939484B CN 202110121396 A CN202110121396 A CN 202110121396A CN 112939484 B CN112939484 B CN 112939484B
- Authority
- CN
- China
- Prior art keywords
- bife
- preparation
- powder
- steps
- system film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000463 material Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 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 73
- 239000013077 target material Substances 0.000 claims abstract description 73
- 239000000758 substrate Substances 0.000 claims abstract description 59
- 238000000151 deposition Methods 0.000 claims abstract description 50
- 238000003980 solgel method Methods 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 11
- 230000005291 magnetic effect Effects 0.000 claims abstract description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 87
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- 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
- 230000008021 deposition Effects 0.000 claims description 29
- 238000004090 dissolution Methods 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
- 239000000126 substance Substances 0.000 claims description 20
- 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
- 238000001354 calcination Methods 0.000 claims description 18
- 238000005303 weighing Methods 0.000 claims description 18
- 239000011240 wet gel Substances 0.000 claims description 18
- 239000008139 complexing agent Substances 0.000 claims description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- 238000010009 beating Methods 0.000 claims description 9
- 238000001816 cooling Methods 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
- 238000002156 mixing Methods 0.000 claims description 9
- 238000000643 oven drying Methods 0.000 claims description 9
- 238000003825 pressing Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 230000001105 regulatory effect Effects 0.000 claims description 8
- 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
- 239000010941 cobalt Substances 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 3
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Natural products OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims 4
- 230000005621 ferroelectricity Effects 0.000 claims 1
- 230000005307 ferromagnetism Effects 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 3
- 239000010408 film Substances 0.000 description 63
- 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
- 238000007605 air drying Methods 0.000 description 8
- 238000004321 preservation Methods 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
- 230000005294 ferromagnetic effect Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000004549 pulsed laser deposition Methods 0.000 description 2
- 244000248349 Citrus limon Species 0.000 description 1
- 235000005979 Citrus limon Nutrition 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000005290 antiferromagnetic effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 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
- 239000002245 particle Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a preparation method of a cobalt-doped bismuth ferrite system film material, wherein x=0, 0.02, 0.04, 0.06, 0.08 and 0.10). Firstly, preparing BiFe by adopting a sol-gel method 1‑ x Co x O 3 The system powder sample is dried to prepare a block target material, and finally the block target material is deposited on an FTO substrate by a pulse laser deposition method to prepare BiFe 1‑ x Co x O 3 A system film. The method of the invention can ensure that the film has good quality, high phase purity, stable film element proportion, good film and substrate adhesion, high success rate of pure-phase film preparation, good repeatability and BiFe 1‑x Co x O 3 Obvious magnetic, ferroelectric and photovoltaic effects are observed in the system film samples.
Description
Technical Field
The invention relates to a preparation method of ferroelectric film material, in particular to BiFe 1-x Co x O 3 A method for preparing a system film material (wherein x=0, 0.02, 0.04, 0.06, 0.08 and 0.10).
Background
Multiferroic materials refer to material systems that have more than one spontaneous polarization in combination of ferroelectric, ferromagnetic (antiferromagnetic), and ferroelastic. In such materials, electrical, magnetic, and elastic order parameters coexist and form an interesting series of physical phenomena such as magneto-electric coupling. The idea of ferroelectric, ferromagnetic coexistence and magneto-electric coupling is basically derived from the 19 th century french scientist Pierre Curie, but does not exist in hydrogen bonding materials (KH 2 PO 4 ) Thereby leading toThe physical concept of multiferroics has the potential to be realized experimentally. Materials with such properties are considered to have potential application values in the fields of future information technology, sensing, spintronics devices and the like. BiFeO 3 As one of the most representative multiferroic materials, the material has important application value in the future, along with the development of multiferroic materials, the material is also a ferroelectric photovoltaic material with abnormal photovoltaic effect and gradually becomes a research hot spot of people, so that the search of a substrate which can be simultaneously used for a magneto-electric 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 are important basic research processes in inorganic material research, so BiFe 1-x Co x O 3 The 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 prior BiFe 1-x Co x O 3 The system film preparation process has the defects of low phase formation rate and insufficient film compactness, and provides BiFe 1-x Co x O 3 A method for preparing a system film material, wherein x=0, 0.02, 0.04, 0.06, 0.08, 0.10.
The technical scheme adopted by the invention is as follows:
BiFe (BiFe) 1-x Co x O 3 A method for preparing a system film material (wherein x=0, 0.02, 0.04, 0.06, 0.08, 0.10), comprising the steps of:
1. BiFe preparation by sol-gel method 1-x Co x O 3 The powder is mixed with the powder,
2. BiFe is prepared 1-x Co x O 3 Calcining the powder at high temperature to prepare a block target material,
3. depositing a bulk target material on the FTO substrate by a pulse laser deposition method (Pulsed Laser Deposition, PLD) to obtain BiFe 1-x Co x O 3 A system film.
Further, the sol-gel method is used for preparing BiFe 1-x Co x O 3 The material used in the powder comprises bismuth source materialThe bismuth source material, the iron source material and the cobalt source material are respectively bismuth nitrate, ferric nitrate, cobalt nitrate, deionized water, glycol and citric acid.
Further, the sol-gel method is used for preparing BiFe 1-x Co x O 3 The 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 { m } Citric acid ＝n BiFe1-xCoxO3 ×[3+3×(1-x)+2×x]/2×M Citric acid Accurately weighing (wherein m is mass, n is the amount of substance, x=0, 0.02, 0.04, 0.06, 0.08, 0.10), and adding proper amount of deionized water for complete dissolution to obtain solution B;
3. slowly adding the solution A into the solution B (the sequence is not changeable so as to keep the citric acid solution 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 water bath of a water bath kettle at 75-85 ℃ to stir so as to enable the solution C to be sticky and yellow, thus obtaining wet gel;
4. placing wet gel in a forced air drying oven, slowly hydrolyzing at 95-105deg.C, oven drying for 4-5 days to form xerogel, removing organic substances at 380-420 deg.C, and annealing at 640-660 deg.C to obtain BiFe 1-x Co x O 3 Powder a.
Further, the amount of the ethylene glycol is determined according to the dissolution conditions of the bismuth source material, the iron source material and the cobalt source material, but the concentration of the bismuth nitrate substance is not lower than 1mol/L, namely c Bismuth nitrate ≥1mol/L。
Further, the deionized water is used in an amount determined according to the dissolution of the complexing agent.
Further, the BiFe 1-x Co x O 3 The powder A is calcined at high temperature and is made into a block target material, which comprises the following steps:
1. drying the BiFe 1-x Co x O 3 Grinding the powder A into fine powder B;
2. placing the fine powder B in a crucible, and calcining at 600-700 ℃ for 2-2.5 hours in a muffle furnace to obtain brown black BiFe 1-x Co x O 3 Powder 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 25MPa;
4. the cylindrical target material is placed in a muffle furnace at 600-700 ℃ for rapid annealing for 7-8min, and BiFe is obtained 1-x Co x O 3 And (3) a target material.
Further, the pulse laser deposition method is to deposit BiFe 1-x Co x O 3 The bulk target material deposition on the FTO substrate specifically comprises the following steps:
1. the BiFe is subjected to 1-x Co x O 3 The block target material and the FTO substrate are respectively placed at proper positions of the target position and the lining disc and are fixed, the vacuum cavity is closed, and the mechanical pump and the molecular pump are sequentially started to vacuumize the vacuum cavity;
2. when the vacuum degree of the vacuum cavity reaches 5 multiplied by 10 -4 When Pa, closing the molecular pump, opening the oxygen valve, and adjusting the oxygen pressure of the vacuum cavity to 9Pa;
3. setting the temperature of an FTO substrate of a vacuum chamber to 650 ℃, wherein the FTO substrate is covered by a baffle plate;
4. setting the voltage of a pulse laser to be 19kV, and pre-beating the target material at the frequency of 1Hz, wherein the time is determined according to the actual surface condition of the target material;
5. setting the energy of a pulse laser to 350mJ and the frequency to 4Hz, removing the baffle plate, starting deposition, introducing oxygen of 0.8atm after the deposition is finished, and cooling to room temperature after in-situ heat preservation for 1h to obtain BiFe 1-x Co x O 3 A film.
Further, the BiFe is prepared 1-x Co x O 3 The 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 (the different preparation environments are changed).
Further, 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+/-10 ℃ and the normal temperature.
The invention adopts the technical proposal to prepare BiFe 1-x Co x O 3 System film (wherein x=0, 0.02, 0.04, 0.06, 0.08, 0.10) for said BiFe using physical property integrated measurement System (PPMS), ferroelectric integrated test System and photovoltaic measurement System 1-x Co x O 3 The system film is tested for magnetic, ferroelectric and photovoltaic properties, 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 miniature magneto-sensitive sensors in the future; because the method adopts the sol-gel method to prepare the BiFe 1-x Co x O 3 System powder, biFe produced 1-x Co x O 3 The system powder has the characteristics of small particle size, high uniformity, simple principle, low preparation requirement, easy control of element proportion and the like; finally, biFe deposited by pulse laser deposition method 1-x Co x O 3 The system film has the characteristics of good quality, high density, high uniformity, stable material components, good synchronization with target components and the like, and is prepared from the BiFe by adopting the FTO substrate with the temperature required in annealing resistance and conductivity 1-x Co x O 3 The architecture of the system film is more stable. And in BiFe 1-x Co x O 3 Obvious magnetic, ferroelectric and photovoltaic effects are observed in the system film samples. The method can ensure that the film has good quality, high phase purity, stable film element proportion, good film and substrate adhesion, high success rate of pure-phase film preparation and good repeatability.
Drawings
The invention is described in further detail below with reference to the drawings and detailed description;
FIG. 1 shows BiFe of the present invention 1-x Co x O 3 A flow diagram of a preparation method of the system film material;
FIG. 2 shows BiFe of the present invention 0.9 Co 0.1 O 3 Film and method for producing the sameAn XRD pattern of (b);
FIG. 3 shows BiFe of the present invention 0.9 Co 0.1 O 3 Hysteresis loops of the film material at different temperatures;
FIG. 4 shows BiFe of the present invention 0.9 Co 0.1 O 3 Electric hysteresis loops of the film material under different electric fields;
FIG. 5 shows BiFe of the present invention 0.9 Co 0.1 O 3 I-V characteristic curve of the film material.
Detailed Description
As shown in one of FIGS. 1-5, the present invention discloses a BiFe 1-x Co x O 3 A method for preparing a system film material (wherein x=0, 0.02, 0.04, 0.06, 0.08, 0.10), comprising the steps of:
1: biFe preparation by sol-gel method 1-x Co x O 3 Powder 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 { m } Citric acid ＝n BiFe1-xCoxO3 ×[3+3×(1-x)+2×x]/2×M Citric acid Accurately weighing (wherein m is mass, n is the amount of substance, x=0, 0.02, 0.04, 0.06, 0.08, 0.10), and adding proper amount of deionized water for complete dissolution to obtain solution B;
1-3: slowly adding the solution A into the solution B (the sequence is not changeable so as to keep the citric acid solution 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 water bath of a water bath kettle at 75-85 ℃ to stir so as to cause the solution C to be sticky and yellow, thus obtaining wet gel;
1-4: placing wet gel in a forced air drying oven, slowly hydrolyzing at 95-105deg.C, oven drying for 4-5 days to form xerogel, removing organic substances at 380-420 deg.C, and annealing at 640-660 deg.C to obtain BiFe 1-x Co x O 3 Powder A;
2: biFe is prepared 1-x Co x O 3 Calcining the powder at high temperature to prepare the block target material.
2-1: drying the BiFe 1-x Co x O 3 Grinding the powder A into fine powder B;
2-2: placing the fine powder B in a crucible, and calcining at 600-700 ℃ in a muffle furnace for 2 hours to obtain brown black BiFe 1-x Co x O 3 Powder 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 25MPa;
2-4: the cylindrical target material is placed in a muffle furnace at 600-700 ℃ for rapid annealing for 7-8min, and BiFe is obtained 1- x Co x O 3 And (3) a target material.
3: depositing a block target material on the FTO substrate by using a pulse laser deposition method to obtain BiFe 1-x Co x O 3 A film.
3-1: the BiFe is subjected to 1-x Co x O 3 The block target material and the FTO substrate are respectively placed at proper positions of the target position and the lining disc and are fixed, the vacuum cavity is closed, and the mechanical pump and the molecular pump are sequentially started to vacuumize the vacuum cavity;
3-2: when the vacuum degree of the vacuum cavity reaches 5 multiplied by 10 -4 When Pa, closing the molecular pump, opening the oxygen valve, and adjusting the oxygen pressure of the vacuum cavity to 9Pa;
3-3: setting the temperature of an FTO substrate of a vacuum chamber to 650 ℃, wherein the FTO substrate is covered by a baffle plate;
3-4: setting the voltage of a pulse laser to be 19kV, and pre-beating the target material at the frequency of 1Hz, wherein the time is determined according to the actual surface condition of the target material;
3-5: setting the energy of a pulse laser to 350mJ and the frequency to 4Hz, removing the baffle plate, starting deposition, introducing oxygen of 0.8atm after the deposition is finished, and cooling to room temperature after in-situ heat preservation for 1h to obtain BiFe 1-x Co x O 3 A film.
In the steps, the deposition time is regulated according to the thickness of the film to be prepared, and the film growth rate is 95-105nm/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 ℃ or the normal temperature.
Example 1
BiFe (BiFe) 1-x Co x O 3 Preparation method of system film material (wherein x=0, i.e. BiFeO 3 ) Comprising the following steps:
1: biFe preparation by sol-gel method 1-x Co x O 3 Powder 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 ethylene glycol to completely dissolve to obtain a solution A; the dosage of the ethylene glycol is determined according to the dissolution conditions of bismuth nitrate and ferric nitrate, wherein the concentration of bismuth nitrate substances is not lower than 1mol/L;
1-2: citric acid according to m Citric acid ＝n BiFe1-xCoxO3 ×[3+3×(1-0)+2×0]/2×M Citric acid Accurately weighing, wherein m is mass, n is the amount of a substance, and adding a proper amount of deionized water for complete dissolution to obtain a solution B; the deionized water determines the dosage of the complexing agent according to the dissolution condition of the complexing agent;
1-3: slowly adding the solution A into the solution B, fully and uniformly mixing to obtain a solution C, and placing the solution C into a water bath kettle at the temperature of 75 ℃ for water bath stirring to enable the solution A to be sticky and yellow to obtain wet gel;
1-4: placing wet gel in a forced air drying oven, slowly hydrolyzing at 95deg.C, oven drying for 5 days to form xerogel, removing organic substances at 380deg.C, and annealing at 650deg.C to obtain BiFe 1-x Co x O 3 Powder a.
2: biFe is prepared 1-x Co x O 3 And calcining the powder A at high temperature to prepare the block target material.
2-1: the BiFe obtained in the step 1 is processed 1-x Co x O 3 Grinding the powder A into fine powder B;
2-2: placing the fine powder B in a crucible, and calcining at 650 ℃ in a muffle furnace for 2.5 hours to obtain brown black BiFe 1-x Co x O 3 Powder 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 25MPa;
2-4: the cylindrical target material is placed in a muffle furnace at 650 ℃ for rapid annealing for 8min, and BiFe is obtained 1-x Co x O 3 And (3) a target material.
3: depositing a block target material on the FTO substrate by using a pulse laser deposition method to obtain BiFe 1-x Co x O 3 A film.
3-1: biFe is prepared 1-x Co x O 3 The target material and the FTO substrate are respectively placed at proper positions of the target position and the substrate disc and are fixed, the vacuum cavity is closed, and the mechanical pump and the molecular pump are sequentially started to vacuumize the vacuum cavity;
3-2: when the vacuum degree of the vacuum cavity reaches 5 multiplied by 10 -4 When Pa, closing the molecular pump, opening the oxygen valve, and adjusting the oxygen pressure of the vacuum cavity to 9Pa;
3-3: setting the temperature of an FTO substrate of a vacuum chamber to 650 ℃, wherein the FTO substrate is covered by a baffle plate;
3-4: setting the voltage of a pulse laser to be 19kV, and pre-beating the target material at the frequency of 1Hz, wherein the time is determined according to the actual surface condition of the target material;
3-5: setting the energy of a pulse laser to 350mJ and the frequency to 4Hz, removing the baffle plate, starting deposition for 1.5h, introducing 0.8atm oxygen after the deposition is finished, and cooling to room temperature after in-situ heat preservation for 1h to obtain BiFe 1-x Co x O 3 A film;
in the steps, the deposition time is regulated 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 a conductive layer is reduced by 50% at the temperature of 650 ℃ or the normal temperature.
Example 2
BiFe (BiFe) 1-x Co x O 3 Preparation method of system film material (wherein x=0.02, namely BiFe 0.98 Co 0.02 O 3 ) Comprising the following steps:
1: biFe preparation by sol-gel method 1-x Co x O 3 Powder 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 ethylene glycol for complete dissolution to obtain a solution A; wherein the dosage of the ethylene glycol is determined according to the dissolution condition of bismuth nitrate, ferric nitrate and nickel acetate, and the concentration of bismuth nitrate is not lower than 1mol/L.
1-2: citric acid according to m Citric acid ＝n BiFe1-xCoxO3 ×[3+3×(1-0.02)+2×0.02]/2×M Citric acid Accurately weighing, wherein m is mass, n is the amount of a substance, and adding a proper amount of deionized water for complete dissolution to obtain a solution B; the deionized water determines the dosage of the complexing agent according to the dissolution condition of the complexing agent;
1-3: slowly adding the solution A into the solution B, fully and uniformly mixing to obtain a solution C, and placing the solution C into a water bath of an 80 ℃ water bath kettle to stir so as to cause the solution A to be sticky and yellow, thus obtaining wet gel;
1-4: placing wet gel in a forced air drying oven, slowly hydrolyzing at 100deg.C, oven drying for 5 days to form xerogel, removing organic substances at 400deg.C, and annealing at 650deg.C to obtain BiFe 1-x Co x O 3 Powder a.
2: biFe is prepared 1-x Co x O 3 And calcining the powder A at high temperature to prepare the block target material.
2-1: the BiFe obtained in the step 1 is processed 1-x Co x O 3 Grinding the powder A into fine powder B;
2-2: placing the fine powder B in a crucible, and calcining at 675 ℃ in a muffle furnace for 2 hours to obtain brown-black BiFe 1-x Co x O 3 Powder 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 25MPa;
2-4: the cylindrical target material is placed in a muffle furnace at 650 ℃ for rapid annealing for 8min, and BiFe is obtained 1-x Co x O 3 And (3) a target material.
3: depositing a block target material on the FTO substrate by using a pulse laser deposition method to obtain BiFe 1-x Co x O 3 A film.
3-1: biFe is prepared 1-x Co x O 3 The target material and the FTO substrate are respectively placed at proper positions of the target position and the substrate disc and are fixed, the vacuum cavity is closed, and the mechanical pump and the molecular pump are sequentially started to vacuumize the vacuum cavity;
3-2: when the vacuum degree of the vacuum cavity reaches 5 multiplied by 10 -4 When Pa, closing the molecular pump, opening the oxygen valve, and adjusting the oxygen pressure of the vacuum cavity to 9Pa;
3-3: setting the temperature of an FTO substrate of a vacuum chamber to 650-680 ℃, wherein the FTO substrate is covered by a baffle plate;
3-4: setting the voltage of a pulse laser to be 20kV, and pre-beating the target material at the frequency of 1Hz, wherein the time is determined according to the actual surface condition of the target material;
3-5: setting the energy of a pulse laser to 350mJ and the frequency to 4Hz, removing the baffle plate, starting deposition for 1.5h, introducing 0.8atm oxygen after the deposition is finished, preserving heat in situ for 1.2h, and cooling to room temperature to obtain BiFe 1-x Co x O 3 A film;
in the steps, the deposition time is regulated according to the thickness of the film to be prepared, and the film growth rate is 95-105nm/h; the FTO substrate belongs to conductive glass, the softening temperature is 720 ℃, and the conductivity of a conductive layer is reduced by 48% at the temperature of 650 ℃ or at normal temperature.
Example 3
BiFe (BiFe) 1-x Co x O 3 Preparation method of system film material (wherein x=0.04, i.e. BiFe 0.96 Co 0.04 O 3 ) Comprising the following steps:
1: biFe preparation by sol-gel method 1-x Co x O 3 Powder 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 ethylene glycol for complete dissolution to obtain a solution A; wherein the dosage of the ethylene glycol is determined according to the dissolution condition of bismuth nitrate, ferric nitrate and nickel acetate, and the concentration of bismuth nitrate is not lower than 1mol/L.
1-2: lemon will be usedCitric acid according to m Citric acid ＝n BiFe1-xCoxO3 ×[3+3×(1-0.04)+2×0.04]/2×M Citric acid Accurately weighing, wherein m is mass, n is the amount of a substance, and adding a proper amount of deionized water for complete dissolution to obtain a solution B; the deionized water determines the dosage of the complexing agent according to the dissolution condition of the complexing agent;
1-3: slowly adding the solution A into the solution B, fully and uniformly mixing to obtain a solution C, and placing the solution C into a water bath of a water bath kettle at 85 ℃ to stir so as to be sticky and yellow to obtain wet gel;
1-4: placing wet gel in a forced air drying oven, slowly hydrolyzing at 105deg.C, oven drying for 4 days to form xerogel, removing organic substances at 420 deg.C, and annealing at 670 deg.C to obtain BiFe 1-x Co x O 3 Powder a.
2: biFe is prepared 1-x Co x O 3 And calcining the powder A at high temperature to prepare the block target material.
2-1: the BiFe obtained in the step 1 is processed 1-x Co x O 3 Grinding the powder A into fine powder B;
2-2: placing the fine powder B in a crucible, and calcining at 700 ℃ in a muffle furnace for 2 hours to obtain brown-black BiFe 1-x Co x O 3 Powder 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 25MPa;
2-4: the cylindrical target material is placed in a muffle furnace at 650 ℃ for rapid annealing for 8min, and BiFe is obtained 1-x Co x O 3 And (3) a target material.
3: depositing a block target material on the FTO substrate by using a pulse laser deposition method to obtain BiFe 1-x Co x O 3 A film.
3-1: biFe is prepared 1-x Co x O 3 The target material and the FTO substrate are respectively placed at proper positions of the target position and the substrate disc and are fixed, the vacuum cavity is closed, and the mechanical pump and the molecular pump are sequentially started to vacuumize the vacuum cavity;
3-2: when the vacuum degree of the vacuum cavity reaches 5 multiplied by 10 -4 At Pa, the molecule is turned offThe pump is used for opening an oxygen valve and adjusting the oxygen pressure of the vacuum cavity to 9Pa;
3-3: setting the temperature of an FTO substrate of a vacuum chamber to 680 ℃, wherein the FTO substrate is covered by a baffle plate;
3-4: setting the voltage of a pulse laser to be 19kV, and pre-beating the target material at the frequency of 1Hz, wherein the time is determined according to the actual surface condition of the target material;
3-5: setting the energy of a pulse laser to 350mJ and the frequency to 4Hz, removing the baffle plate, starting deposition for 1.5h, introducing 0.8atm oxygen after the deposition is finished, and cooling to room temperature after in-situ heat preservation for 1h to obtain BiFe 1-x Co x O 3 A film;
in the steps, the deposition time is regulated 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 ℃ or the normal temperature.
Example 4
BiFe (BiFe) 1-x Co x O 3 Preparation method of system film material (wherein x=0.06, i.e. BiFe 0.94 Co 0.06 O 3 ) Comprising the following steps:
1: biFe preparation by sol-gel method 1-x Co x O 3 Powder 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 ethylene glycol for complete dissolution to obtain a solution A; wherein the dosage of the ethylene glycol is determined according to the dissolution condition of bismuth nitrate, ferric nitrate and nickel acetate, and the concentration of bismuth nitrate is not lower than 1mol/L.
1-2: citric acid according to m Citric acid ＝n BiFe1-xCoxO3 ×[3+3×(1-0.06)+2×0.06]/2×M Citric acid Accurately weighing, wherein m is mass, n is the amount of a substance, and adding a proper amount of deionized water for complete dissolution to obtain a solution B; the deionized water determines the dosage of the complexing agent according to the dissolution condition of the complexing agent;
1-3: slowly adding the solution A into the solution B, fully and uniformly mixing to obtain a solution C, and placing the solution C into a water bath of an 80 ℃ water bath kettle to stir so as to cause the solution A to be sticky and yellow, thus obtaining wet gel;
1-4: placing wet gel in a forced air drying oven, slowly hydrolyzing at 100deg.C, oven drying for 5 days to form xerogel, removing organic substances at 380-420 deg.C, and annealing at 650deg.C to obtain BiFe 1-x Co x O 3 Powder a.
2: biFe is prepared 1-x Co x O 3 And calcining the powder A at high temperature to prepare the block target material.
2-1: the BiFe obtained in the step 1 is processed 1-x Co x O 3 Grinding the powder A into fine powder B;
2-2: placing the fine powder B in a crucible, and calcining at 650 ℃ in a muffle furnace for 2-hours to obtain brown-black BiFe 1-x Co x O 3 Powder 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 25MPa;
2-4: the cylindrical target material is placed in a muffle furnace at 650 ℃ for rapid annealing for 8min, and BiFe is obtained 1-x Co x O 3 And (3) a target material.
3: depositing a block target material on the FTO substrate by using a pulse laser deposition method to obtain BiFe 1-x Co x O 3 A film.
3-1: biFe is prepared 1-x Co x O 3 The target material and the FTO substrate are respectively placed at proper positions of the target position and the substrate disc and are fixed, the vacuum cavity is closed, and the mechanical pump and the molecular pump are sequentially started to vacuumize the vacuum cavity;
3-2: when the vacuum degree of the vacuum cavity reaches 5 multiplied by 10 -4 When Pa, closing the molecular pump, opening the oxygen valve, and adjusting the oxygen pressure of the vacuum cavity to 9Pa;
3-3: setting the temperature of an FTO substrate of a vacuum chamber to 650 ℃, wherein the FTO substrate is covered by a baffle plate;
3-4: setting the voltage of a pulse laser to be 19kV, and pre-beating the target material at the frequency of 1Hz, wherein the time is determined according to the actual surface condition of the target material;
3-5: setting the energy of a pulse laser to 350mJ and the frequency to 4Hz, removing the baffle plate, starting deposition for 1.5h, introducing 0.8atm oxygen after the deposition is finished, and cooling to room temperature after in-situ heat preservation for 1h to obtain BiFe 1-x Co x O 3 A film;
in the steps, the deposition time is regulated according to the thickness of the film to be prepared, and the film growth rate is 95-105nm/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 ℃ or the normal temperature.
Example 5
BiFe (BiFe) 1-x Co x O 3 Preparation method of system film material (wherein x=0.08, i.e. BiFe 0.92 Co 0.08 O 3 ) Comprising the following steps:
1: biFe preparation by sol-gel method 1-x Co x O 3 Powder 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 ethylene glycol for complete dissolution to obtain a solution A; wherein the dosage of the ethylene glycol is determined according to the dissolution condition of bismuth nitrate, ferric nitrate and nickel acetate, and the concentration of bismuth nitrate is not lower than 1mol/L.
1-2: citric acid according to m Citric acid ＝n BiFe1-xCoxO3 ×[3+3×(1-0.08)+2×0.08]/2×M Citric acid Accurately weighing, wherein m is mass, n is the amount of a substance, and adding a proper amount of deionized water for complete dissolution to obtain a solution B; the deionized water determines the dosage of the complexing agent according to the dissolution condition of the complexing agent;
1-3: slowly adding the solution A into the solution B, fully and uniformly mixing to obtain a solution C, and placing the solution C into a water bath of an 80 ℃ water bath kettle to stir so as to cause the solution A to be sticky and yellow, thus obtaining wet gel;
1-4: placing wet gel in a forced air drying oven, slowly hydrolyzing at 100deg.C, oven drying for 5 days to form xerogel, removing organic substances at 400deg.C, and annealing at 650deg.C to obtain BiFe 1-x Co x O 3 Powder a.
2: biFe is prepared 1-x Co x O 3 And calcining the powder A at high temperature to prepare the block target material.
2-1: the BiFe obtained in the step 1 is processed 1-x Co x O 3 Grinding the powder A into fine powder B;
2-2: placing the fine powder B in a crucible, and calcining at 650 ℃ in a muffle furnace for 2 hours to obtain brown-black BiFe 1-x Co x O 3 Powder 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 25MPa;
2-4: the cylindrical target material is placed in a muffle furnace at 650 ℃ for rapid annealing for 8min, and BiFe is obtained 1-x Co x O 3 And (3) a target material.
3: depositing a block target material on the FTO substrate by using a pulse laser deposition method to obtain BiFe 1-x Co x O 3 A film.
3-1: biFe is prepared 1-x Co x O 3 The target material and the FTO substrate are respectively placed at proper positions of the target position and the substrate disc and are fixed, the vacuum cavity is closed, and the mechanical pump and the molecular pump are sequentially started to vacuumize the vacuum cavity;
3-2: when the vacuum degree of the vacuum cavity reaches 5 multiplied by 10 -4 When Pa, closing the molecular pump, opening the oxygen valve, and adjusting the oxygen pressure of the vacuum cavity to 9Pa;
3-3: setting the temperature of an FTO substrate of a vacuum chamber to 650 ℃, wherein the FTO substrate is covered by a baffle plate;
3-4: setting the voltage of a pulse laser to be 19kV, and pre-beating the target material at the frequency of 1Hz, wherein the time is determined according to the actual surface condition of the target material;
3-5: setting the energy of a pulse laser to 350mJ and the frequency to 4Hz, removing the baffle plate, starting deposition for 1.5h, introducing 0.8atm oxygen after the deposition is finished, preserving heat in situ for 1-1.2h, and cooling to room temperature to obtain BiFe 1-x Co x O 3 A film;
in the steps, the deposition time is regulated 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 ℃ or the normal temperature.
Example 6
BiFe (BiFe) 1-x Co x O 3 Preparation method of system film material (wherein x=0.10, namely BiFe 0.9 Co 0.1 O 3 ) Comprising the following steps:
1: biFe preparation by sol-gel method 1-x Co x O 3 Powder 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 for complete dissolution to obtain a solution A; wherein the dosage of the ethylene glycol is determined according to the dissolution condition of bismuth nitrate, ferric nitrate and nickel acetate, and the concentration of bismuth nitrate is not lower than 1mol/L.
1-2: citric acid according to m Citric acid ＝n BiFe1-xCoxO3 ×[3+3×(1-0.9)+2×0.1]/2×M Citric acid Accurately weighing, wherein m is mass, n is the amount of a substance, and adding a proper amount of deionized water for complete dissolution to obtain a solution B; the deionized water determines the dosage of the complexing agent according to the dissolution condition of the complexing agent;
1-3: slowly adding the solution A into the solution B, fully and uniformly mixing to obtain a solution C, and placing the solution C into a water bath of an 80 ℃ water bath kettle to stir so as to cause the solution A to be sticky and yellow, thus obtaining wet gel;
1-4: placing wet gel in a forced air drying oven, slowly hydrolyzing at 100deg.C, oven drying for 5 days to form xerogel, removing organic substances at 400deg.C, and annealing at 650deg.C to obtain BiFe 1-x Co x O 3 Powder a.
2: biFe is prepared 1-x Co x O 3 And calcining the powder A at high temperature to prepare the block target material.
2-1: the BiFe obtained in the step 1 is processed 1-x Co x O 3 Grinding the powder A into fine powder B;
2-2: placing the fine powder B in a crucible, and calcining at 650 ℃ in a muffle furnace for 2 small piecesAt the time, brown-black BiFe is obtained 1-x Co x O 3 Powder 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 25MPa;
2-4: the cylindrical target material is placed in a muffle furnace at 650 ℃ for rapid annealing for 8min, and BiFe is obtained 1-x Co x O 3 And (3) a target material.
3: depositing a block target material on the FTO substrate by using a pulse laser deposition method to obtain BiFe 1-x Co x O 3 A film.
3-1: biFe is prepared 1-x Co x O 3 The target material and the FTO substrate are respectively placed at proper positions of the target position and the substrate disc and are fixed, the vacuum cavity is closed, and the mechanical pump and the molecular pump are sequentially started to vacuumize the vacuum cavity;
3-2: when the vacuum degree of the vacuum cavity reaches 5 multiplied by 10 -4 When Pa, closing the molecular pump, opening the oxygen valve, and adjusting the oxygen pressure of the vacuum cavity to 9Pa;
3-3: setting the temperature of an FTO substrate of a vacuum chamber to 650 ℃, wherein the FTO substrate is covered by a baffle plate;
3-4: setting the voltage of a pulse laser to be 19kV, and pre-beating the target material at the frequency of 1Hz, wherein the time is determined according to the actual surface condition of the target material;
3-5: setting the energy of a pulse laser to 350mJ and the frequency to 4Hz, removing the baffle plate, starting deposition for 1.5h, introducing 0.8atm oxygen after the deposition is finished, preserving heat in situ for 1-1.2h, and cooling to room temperature to obtain BiFe 1-x Co x O 3 A film;
in the steps, the deposition time is regulated according to the thickness of the film to be prepared, and the film growth rate is 95-105nm/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 ℃ or the normal temperature.
Claims (9)
1. BiFe (BiFe) 0.9 Co 0.1 O 3 The preparation method of the system film material is characterized by comprising the following steps: the saidThe preparation method of the material comprises the following steps:
1: biFe preparation by sol-gel method 0.9 Co 0.1 O 3 A powder;
2: biFe is prepared 0.9 Co 0.1 O 3 Calcining the powder at high temperature to prepare a block target;
3: depositing a block target material on the FTO substrate by using a pulse laser deposition method to obtain BiFe 0.9 Co 0.1 O 3 A system film material;
the BiFe 0.9 Co 0.1 O 3 The system film material has ferromagnetism, ferroelectricity and photovoltaic property, and the saturated magnetic field can reach 8T in 10K environment.
2. A BiFe according to claim 1 0.9 Co 0.1 O 3 The preparation method of the system film material is characterized by comprising the following steps: biFe preparation by sol-gel method 0.9 Co 0.1 O 3 The materials used in the powder process comprise bismuth source materials, iron source materials, cobalt source materials, a solvent A, a solvent B and a complexing agent, wherein the bismuth source materials, the iron source materials, the cobalt source materials, the solvent A, the solvent B and the complexing agent are bismuth nitrate, ferric nitrate, cobalt nitrate, deionized water, glycol and citric acid respectively.
3. A BiFe according to claim 2 0.9 Co 0.1 O 3 The preparation method of the system film material is characterized by comprising the following steps: in the step 1, a sol-gel method is adopted to prepare BiFe 0.9 Co 0.1 O 3 The powder specifically comprises the following steps:
1-1, accurately weighing bismuth nitrate, ferric nitrate and cobalt nitrate according to the mass ratio of 1:0.9:0.1, 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 in accordance with citric acid { m } Citric acid =n BiFe0.9Co0.1O3 ×[3＋3×(0.9)＋2×0.1]/2×M Citric acid Accurately weighing, and adding the solution into deionized water to be completely dissolved to obtain solution B;
1-3, slowly adding the solution A into the solution B, fully and uniformly mixing to obtain a solution C, and placing the solution C into a water bath kettle at 75-85 ℃ for water bath stirring to obtain wet gel;
1-4, placing wet gel in a drying oven, slowly hydrolyzing at 95-105deg.C, oven drying for 4-5 days to form xerogel, removing organic substances at 380-420 deg.C, and annealing at 640-660 deg.C to obtain BiFe 0.9 Co 0.1 O 3 And (3) powder.
4. A BiFe according to claim 3 0.9 Co 0.1 O 3 The preparation method of the system film material is characterized by comprising the following steps: the amount of 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 concentration of the bismuth nitrate substance cannot be lower than 1mol/L.
5. A BiFe according to claim 3 0.9 Co 0.1 O 3 The preparation method of the system film material is characterized by comprising the following steps: the deionized water in the step 1-2 is used in a certain amount according to the dissolution condition of the complexing agent.
6. A BiFe according to claim 1 0.9 Co 0.1 O 3 The preparation method of the system film material is characterized by comprising the following steps: in step 2, biFe 0.9 Co 0.1 O 3 The powder is calcined at high temperature and is made into a block target material, which comprises the following steps:
2-1, dried BiFe 0.9 Co 0.1 O 3 Grinding the powder into fine powder B;
2-2, placing the fine powder B in a crucible, and calcining at 600-700 ℃ for 2-2.5 hours in a muffle furnace to obtain brown black BiFe 0.9 Co 0.1 O 3 Powder C;
2-3, pressing the powder C into a cylindrical target with the diameter of 30mm and the thickness of 2-3 mm by using a metal die, wherein the pressure is 25MPa;
2-4, placing the cylindrical target material in a muffle furnace at 600-700 ℃ for rapid annealing for 7-8min to obtain BiFe 0.9 Co 0.1 O 3 And (3) a target material.
7. A BiFe according to claim 1 0.9 Co 0.1 O 3 The preparation method of the system film material is characterized by comprising the following steps: in the step 3, biFe is deposited by pulse laser 0.9 Co 0.1 O 3 The bulk target material deposition on the FTO substrate specifically comprises the following steps:
3-1, biFe 0.9 Co 0.1 O 3 The block target and the FTO substrate are respectively placed at proper positions of the target position and the substrate disc and are fixed, the vacuum cavity is closed, and the mechanical pump and the molecular pump are sequentially started to vacuumize the vacuum cavity;
3-2, when the vacuum degree of the vacuum cavity reaches 5 multiplied by 10 -4 Closing a molecular pump, opening an oxygen valve and adjusting the oxygen pressure of the vacuum cavity to 9Pa when Pa;
3-3, setting the temperature of the FTO substrate of the vacuum chamber to 650 ℃, wherein the FTO substrate is covered by a baffle plate;
3-4, setting the voltage of the pulse laser as 19kV and the frequency as 1Hz for pre-beating, wherein the time is determined according to the actual surface condition of the target;
3-5, setting the energy of the pulse laser to 350mJ with the frequency of 4Hz, removing the baffle, starting deposition for 1.5h, introducing oxygen of 0.8atm after deposition, preserving heat in situ for 1h, and cooling to room temperature to obtain BiFe 0.9 Co 0.1 O 3 A system film.
8. A BiFe according to claim 7 0.9 Co 0.1 O 3 The preparation method of the film material is characterized by comprising the following steps: preparation of BiFe 0.9 Co 0.1 O 3 The deposition time of the system film is regulated according to the thickness of the film to be prepared, and the film growth rate is 95-105 nm/h.
9. A BiFe according to claim 1 0.9 Co 0.1 O 3 The preparation method of the system film material is characterized by comprising the following steps: the FTO substrate belongs to conductive glass, and is softenedThe 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110121396.5A CN112939484B (en) | 2021-01-28 | 2021-01-28 | Preparation method of cobalt-doped bismuth ferrite system film material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110121396.5A CN112939484B (en) | 2021-01-28 | 2021-01-28 | Preparation method of cobalt-doped bismuth ferrite system film material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112939484A CN112939484A (en) | 2021-06-11 |
| CN112939484B true CN112939484B (en) | 2024-01-23 |
Family
ID=76239050
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110121396.5A Active CN112939484B (en) | 2021-01-28 | 2021-01-28 | Preparation method of cobalt-doped bismuth ferrite system film material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112939484B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110791732A (en) * | 2019-11-15 | 2020-02-14 | 福建师范大学 | Preparation method of nickel-doped bismuth ferrite film system material |
-
2021
- 2021-01-28 CN CN202110121396.5A patent/CN112939484B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110791732A (en) * | 2019-11-15 | 2020-02-14 | 福建师范大学 | Preparation method of nickel-doped bismuth ferrite film system material |
Non-Patent Citations (4)
| Title |
|---|
| 关晓英等.《Co掺杂BiFeO3薄膜的溶胶凝胶法制备及性能研究》.《新疆师范大学学报》（自然科学版）.2015,第34卷(第3期),第33-38页. * |
| 凌飞等.铁酸铋薄膜的掺杂改性与光伏效应研究进展.《硅酸盐通报》.2015,第34卷第262-268页. * |
| 张晖等.《Co掺杂BiFeO3的第一性原理研究》.《物理学报》.2009,第58卷(第58期),7141-7146. * |
| 雷天宇等.《铁酸铋薄膜的溶胶-凝胶法制备及电性能研究进展》.《表面技术》.2014,第43卷(第3期),第129-136页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112939484A (en) | 2021-06-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110791732B (en) | Preparation method of nickel-doped bismuth ferrite film system material | |
| Metz | Electrical properties of NTC thermistors made of manganite ceramics of general spinel structure: Mn3− x− x′ M x N x′ O4 (0≤ x+ x′≤ 1; M and N being Ni, Co or Cu). Aging phenomenon study | |
| CN109709192B (en) | Gas-sensitive nanomaterial based on tungsten oxide/tin oxide core-shell nanosheet structure, preparation process and application thereof | |
| Trukhanov et al. | Magnetic properties of anion-deficient La 1− x Ba x MnO 3− x/2 (0≤ x≤ 0.30) manganites | |
| CN109182981B (en) | Preparation method of strontium cobaltate film material | |
| CN104193316B (en) | Yttrium iron garnet film and preparation method thereof | |
| CN114150375A (en) | Method for preparing Fe-Sn-Se-Te quaternary film by magnetron co-sputtering | |
| CN110498681B (en) | Relaxor ferroelectric ceramic with high electrocaloric effect at room temperature, preparation method and application thereof | |
| CN112939484B (en) | Preparation method of cobalt-doped bismuth ferrite system film material | |
| CN113185267B (en) | Cobalt-doped perovskite ceramic and preparation method thereof | |
| CN104362250A (en) | Heterojunction with exchange bias effect and electricity resulted resistance change effect and preparation method thereof | |
| CN111525021B (en) | Bismuth sodium titanate-based film with positive and negative electric clamping effect and preparation method thereof | |
| CN109867304B (en) | Vanadium dioxide metal insulation phase change regulation and control method and application | |
| CN114560698B (en) | Method for enhancing performance of calcium bismuth niobate high-temperature piezoelectric ceramic by inducing texture through oxide sintering aid | |
| CN106987811B (en) | A kind of temperature magnetic field film-sensing material and preparation method thereof | |
| CN110937925A (en) | Bismuth ferrite-based thin film with high polarization strength and large strain characteristic and preparation method thereof | |
| CN115159974A (en) | SrFeO 3-x Reactive flash firing preparation method of ceramic | |
| CN102503376A (en) | Preparation method of manganese cobalt nickel thermosensitive ceramic material | |
| CN113680311B (en) | Preparation method of zinc-based composite metal oxide | |
| CN107056271B (en) | GaFeO3Ceramic target material and preparation method of nano film | |
| CN106756787B (en) | A kind of magneto-optic memory technique and preparation method thereof of controllable magneto-spectroscopy | |
| CN107140968B (en) | High-temperature lead-free piezoelectric ceramic and preparation method thereof | |
| CN114182211B (en) | Preparation method of super tetragonal phase bismuth ferrite film material with bottom electrode | |
| CN114974341A (en) | Four-state memory based on barium-doped bismuth ferrite system film and preparation method thereof | |
| CN113235159B (en) | Method for preparing single crystal nickel ferrite film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |