CN108911730A - B doping bismuth ferrite solid solution membranes and its preparation method and application - Google Patents
B doping bismuth ferrite solid solution membranes and its preparation method and application Download PDFInfo
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- 229910000859 α-Fe Inorganic materials 0.000 title claims abstract description 51
- 239000006104 solid solution Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 31
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 239000012528 membrane Substances 0.000 title abstract 2
- 239000010408 film Substances 0.000 claims abstract description 114
- 239000000758 substrate Substances 0.000 claims abstract description 68
- 238000000034 method Methods 0.000 claims abstract description 54
- 230000008569 process Effects 0.000 claims abstract description 29
- 238000000576 coating method Methods 0.000 claims abstract description 26
- 238000000137 annealing Methods 0.000 claims abstract description 25
- 239000011248 coating agent Substances 0.000 claims abstract description 25
- 239000010409 thin film Substances 0.000 claims abstract description 24
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 9
- 238000004528 spin coating Methods 0.000 claims description 24
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 10
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 9
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 4
- 239000002738 chelating agent Substances 0.000 claims description 2
- 239000012024 dehydrating agents Substances 0.000 claims description 2
- 229910002075 lanthanum strontium manganite Inorganic materials 0.000 claims 1
- 239000013078 crystal Substances 0.000 abstract description 19
- 239000000463 material Substances 0.000 abstract description 17
- 230000000694 effects Effects 0.000 abstract description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052742 iron Inorganic materials 0.000 abstract description 3
- 238000012545 processing Methods 0.000 abstract description 3
- 238000010583 slow cooling Methods 0.000 abstract description 2
- AOWKSNWVBZGMTJ-UHFFFAOYSA-N calcium titanate Chemical compound [Ca+2].[O-][Ti]([O-])=O AOWKSNWVBZGMTJ-UHFFFAOYSA-N 0.000 abstract 1
- 230000001737 promoting effect Effects 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 description 24
- 238000002156 mixing Methods 0.000 description 13
- 238000003756 stirring Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 238000004140 cleaning Methods 0.000 description 7
- 230000005291 magnetic effect Effects 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 230000005621 ferroelectricity Effects 0.000 description 5
- 230000005307 ferromagnetism Effects 0.000 description 5
- 230000008878 coupling Effects 0.000 description 4
- 238000010168 coupling process Methods 0.000 description 4
- 238000005859 coupling reaction Methods 0.000 description 4
- 230000005294 ferromagnetic effect Effects 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 230000035882 stress Effects 0.000 description 4
- 230000010287 polarization Effects 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 238000004549 pulsed laser deposition Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 238000000231 atomic layer deposition Methods 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- WEUCVIBPSSMHJG-UHFFFAOYSA-N calcium titanate Chemical compound [O-2].[O-2].[O-2].[Ca+2].[Ti+4] WEUCVIBPSSMHJG-UHFFFAOYSA-N 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000407 epitaxy Methods 0.000 description 2
- 238000009396 hybridization Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 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 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229910002902 BiFeO3 Inorganic materials 0.000 description 1
- YMVZSICZWDQCMV-UHFFFAOYSA-N [O-2].[Mn+2].[Sr+2].[La+3] Chemical compound [O-2].[Mn+2].[Sr+2].[La+3] YMVZSICZWDQCMV-UHFFFAOYSA-N 0.000 description 1
- ODQMZRPRPNZQNC-UHFFFAOYSA-N [Tb+3].[Tb+3].[O-][Mn]([O-])(=O)=O.[O-][Mn]([O-])(=O)=O.[O-][Mn]([O-])(=O)=O Chemical compound [Tb+3].[Tb+3].[O-][Mn]([O-])(=O)=O.[O-][Mn]([O-])(=O)=O.[O-][Mn]([O-])(=O)=O ODQMZRPRPNZQNC-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000005290 antiferromagnetic effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 description 1
- XQKKWWCELHKGKB-UHFFFAOYSA-L calcium acetate monohydrate Chemical compound O.[Ca+2].CC([O-])=O.CC([O-])=O XQKKWWCELHKGKB-UHFFFAOYSA-L 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
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- 230000018109 developmental process Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- -1 lanthanum aluminate Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- MFUVDXOKPBAHMC-UHFFFAOYSA-N magnesium;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MFUVDXOKPBAHMC-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/26—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on ferrites
- C04B35/2691—Other ferrites containing alkaline metals
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/624—Sol-gel processing
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3232—Titanium oxides or titanates, e.g. rutile or anatase
- C04B2235/3234—Titanates, not containing zirconia
- C04B2235/3236—Alkaline earth titanates
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
- C04B2235/443—Nitrates or nitrites
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- C—CHEMISTRY; METALLURGY
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
- C04B2235/449—Organic acids, e.g. EDTA, citrate, acetate, oxalate
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
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- Dispersion Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Compounds Of Iron (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a kind of B doping bismuth ferrite solid solution membranes and preparation method and application, preparation method to include：Prepare B doping bismuth ferrite solid solution colloidal sols；Solid solution colloidal sol is formed into collosol coating in coating on substrate；Collosol coating on substrate is subjected to thermosetting processing；By thermosetting, treated that collosol coating makes annealing treatment；Wherein, the flatness of film surface, control and the crystallinity for promoting material are promoted by keeping after being rapidly heated in annealing；Then slow cooling promotes the outer single domain of film forming face again.Above method of the invention improves traditional bismuth ferrite collosol and gel preparation thin film technique, is adulterated by B, the piezoelectricity enhancement effect for obtaining quasi- homotype phase boundary is mixed with calcium titanate；By adjusting annealing process, the more iron thin films of high quality extension room temperature of preparation have good high pressure electrical property, room temperature multiferroic and single crystal epitaxial.
Description
Technical Field
The invention relates to the technical field of preparation of magnetoelectric coupling materials, in particular to a B-site bismuth-doped ferrite solid solution film and a preparation method and application thereof.
Background
The multiferroic material has ferroelectricity and ferromagnetism, is a multifunctional magnetoelectric composite material, not only has various single ferroelectricity (such as ferroelectricity and ferromagnetism), but also can control electric polarization through a magnetic field or control a magnetic pole through an electric field through the coupling composite synergistic effect of the ferroelectricity; and is therefore the technical core of many electronic devices and sensors. The common multiferroic materials such as TMO (TbMnO3, terbium manganate) and BFO (BiFeO3, bismuth ferrite) have very excellent performance. Meanwhile, the disadvantages of the two exist; for example, the temperature of the magnetoelectric coupling phenomenon in the TMO system is far lower than room temperature, and the novel ferroelectricity thereof can be rarely achieved in strength; BFOs are not in a ferromagnetic state but in an antiferromagnetic state at room temperature and do not meet the reading requirements of information storage materials.
Based on the above, (1-x) BiTi hybridized with B site in perovskite structure(1-y)/2FeyMg(1-y)/2O3-xCaTiO3The coexistence of room temperature ferroelectric and ferromagnetic properties is successfully realized in the solid solution ceramic material, and simultaneously, due to the complexity of doping, a new challenge is also provided for the development from a ceramic system to a high-quality thin film system and the related process for preparing a miniature electronic device. Therefore, a hybrid mode can be correspondingly adopted in the preparation of the BFO thin film material to realize the coexistence of the room-temperature ferroelectric and ferromagnetic properties.
At present, the preparation of the bismuth ferrite film adopts a plurality of preparation methods such as laser pulse deposition (PLD), Atomic Layer Deposition (ALD), Chemical Vapor Deposition (CVD) and the like, is very sensitive to experimental conditions such as temperature and oxygen pressure and depends on epitaxial stress provided by a high-quality single crystal substrate, and some methods also need expensive Pulsed Laser Deposition (PLD) equipment; the finally prepared BFO material has defects in out-of-plane direction single domain structure and room temperature ferromagnetism. Compared with the method, the method for preparing the BFO film by the sol-gel method is a more suitable mode, and has the obvious advantages of capability of performing multi-element doping, flexibility and accuracy in doping, strong controllability and capability of realizing industrial large-scale production; and in the preparation of high-quality thin film materials of ferroelectric and ferromagnetic room-temperature multiferroic materials, B bit element hybridization can be flexibly prepared, and the influence of the B bit element hybridization on the Curie temperature, the ferromagnetism and the room-temperature magnetoelectric coupling strength of the materials can be researched. However, the current sol-gel preparation method of the room-temperature multiferroic film is adopted, the prepared film is a bismuth ferrite polycrystalline film, the piezoelectric enhancement effect caused by the chemical proportion of the morphotropic phase boundary is not available, the substrate ductility is not available, or the surface can not achieve the crystal boundary-free and high flatness.
Disclosure of Invention
The invention mainly aims to provide a preparation method of a B-site doped bismuth ferrite solid solution film, aiming at improving multiferroic and single crystal epitaxial properties of the prepared bismuth ferrite solid solution film at room temperature and enabling the bismuth ferrite solid solution film to have good high-voltage performance.
In order to achieve the purpose, the preparation method of the B-site bismuth-doped ferrite solid solution film is characterized by comprising the following steps of:
preparing B-site bismuth-doped ferrite solid solution sol;
coating the solid solution sol on a substrate to form a sol coating;
carrying out thermosetting treatment on the sol coating on the substrate;
annealing the sol coating after the thermosetting treatment; wherein the temperature of the annealing treatment is 700-900 ℃, and the cooling rate in the cooling process of the annealing treatment is 0.5-1 ℃/s.
The invention further provides the B-site bismuth-doped ferrite solid solution film directly prepared by the method. And the application of the B-site bismuth-doped ferrite solid solution film in a sensor or a driver.
The method improves the traditional bismuth ferrite sol-gel film preparation technology, and obtains the piezoelectric enhancement effect of the morphotropic phase boundary by mixing B-site doping and calcium titanate; by finely adjusting annealing parameters, the prepared high-quality epitaxial room-temperature multiferroic film has good high-voltage electrical property, room-temperature multiferroic property and single crystal epitaxy property.
Drawings
FIG. 1 is a schematic illustration of surface voltage writing to a prepared film sample according to one embodiment of the present invention;
FIG. 2 is a graph showing the results of profile measurements on a prepared film sample according to one embodiment of the present invention;
FIG. 3 is a graph of the results of an amplitude test on a prepared film sample according to one embodiment of the present invention;
FIG. 4 is a graph showing the results of phase testing on prepared film samples according to one embodiment of the present invention;
FIG. 5 is an XRD diffractogram of a thin film sample prepared in accordance with one embodiment of the present invention;
FIG. 6 is a graph of magnetic moment versus temperature for a prepared film sample in accordance with an embodiment of the present invention;
FIG. 7 is a schematic illustration of surface voltage writing to a prepared film sample according to yet another embodiment of the present invention;
FIG. 8 is a graph showing the results of profile measurements on a prepared film sample according to still another embodiment of the present invention;
FIG. 9 is a graph showing the results of an amplitude test on a prepared film sample according to still another embodiment of the present invention;
FIG. 10 is a graph showing the results of a phase test on a prepared film sample according to still another embodiment of the present invention;
fig. 11 is an XRD diffractogram of a thin film sample prepared according to still another embodiment of the present invention.
Detailed Description
The implementation, functional features and advantages of the objects of the present invention will be further explained with reference to the accompanying drawings. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention provides a preparation method of a B-site bismuth-doped ferrite solid solution film, which is improved on the basis of the traditional method for preparing the film by bismuth ferrite sol-gel, and comprises the following steps:
s10, preparing B-site bismuth-doped ferrite solid solution sol;
s20, coating the bismuth ferrite solid solution sol obtained in the step S10 on a substrate to form a sol coating;
s30, carrying out thermosetting treatment on the sol coating;
s40, annealing the sol coating after thermosetting treatment; wherein, the quality of the film is controlled by adopting rapid heating and slow cooling in the annealing treatment process;
s50, peeling the substrate to obtain the B-site bismuth-doped ferrite solid solution film prepared by the invention.
In the implementation of the above steps of the invention, firstly, the piezoelectric enhancement effect of the morphotropic phase boundary is obtained by B-site doping, specifically, in step S10, B-site bismuth-doped ferrite solid solution sol is adopted as a material for preparing the film, and specifically, the B-site bismuth-doped ferrite is (1-x) BiTi(1-y)/2FeyMg(1-y)/2O3-xCaTiO3Wherein the doping amount x is 0.1-0.2, and y is 0.7-0.95. Meanwhile, in order to further reduce the influence on the quality of subsequent film voids and the like caused by the volatility, the compatibility and the like of the solvent, the dehydrating agent propionic anhydride is added in the preparation of the sol gel, so that the condensation polymerization reaction among the components can be promoted, and the property of the sol can be improved. The addition amount of the propionic anhydride is 0.5-2 times of the solvent amount according to the requirement of conventional implementation. Meanwhile, the preparation is carried out by adopting a metal organic system in the preparation of the sol, preferably glycol monomethyl ether is adopted as a solvent, and a chelating agent citric acid is added into the sol. For a specific sol preparation process, reference may be made to (1-x) BiTi described in other papers or patents(1-y)/2FeyMg(1-y)/2O3-xCaTiO3The preparation method of the bismuth-doped ferrite solid solution sol is carried out, or the sol with the doping amount of x being 0.15 and y being 0.8 is prepared by adopting the following detailed implementation steps:
s11, calculating according to the preparation amount of the sol of 0.3 mol/L100 mL, obtaining the raw materials by adopting the following table:
s12, dissolving Bi, Fe, Mg and Ca salts in 50mL of ethylene glycol monomethyl ether in sequence, and fully mixing and stirring until the salts are dissolved to obtain a first solution A;
s13, dissolving titanium tetraisopropoxide in 30mL of ethylene glycol monomethyl ether, and fully mixing and stirring to obtain a second solution B;
s14, adding the second solution B into the first solution A, and fully mixing and stirring to obtain a mixed solution C;
s15, adding 0.03mol of citric acid into the mixed solution C, and fully mixing, stirring and uniformly mixing; continuously stirring for 12 hours under the normal temperature and pressure environment to obtain 0.3mol/L sol;
s16, taking 20mL of the 0.3mol/L sol prepared in the step S15, adding 20mL of ethylene glycol monomethyl ether for dilution, then adding 10mL of propionic anhydride, and mixing and stirring uniformly;
and S17, finally transferring the film to a conical flask for sealed storage, standing and aging for 72 hours, and then preparing the film.
Further, after the preparation of the sol is completed, step S20 is performed by coating the sol of step S10 on a substrate, wherein the substrate of the present invention provides an epitaxial stress based on a single crystal substrate having a lattice constant equivalent to that of the prepared bismuth ferrite, and a single crystal substrate having a lattice constant controlled in a range of 3.85 a to 3.95 a is used to reduce the stress of the thin film suitable for the extension of the bismuth ferrite. In practice, one of NbSTO substrate (Nb-doped Strontium Titanate (STO) single crystal substrate), LSMO (lanthanum strontium manganese oxide), LAO (lanthanum aluminate) may be preferably used; wherein the doping concentration of Nb in the NbSTO substrate is 0.5%, and the substrate crystal orientation is in the [001] direction. The size of the substrate may be determined by selecting appropriate specifications according to the size of a film to be produced.
Meanwhile, in step S20, the sol is coated on the substrate, preferably by spin coating; compared with a coating mode such as blade coating, the method can avoid the reduction of the uniformity and the regularity of the film caused by the size error of the scraper. Of course, other similar coating methods may be used when the quality requirements for film-forming quality are met. Meanwhile, based on the requirements on the quality of the film preparation, the film coating is carried out under the vacuum condition, and the spin coating process comprises a slow process and a fast process; the sol is firstly rotated slowly and then rotated rapidly under the vacuum condition, so that on one hand, the dispersion stability of the sol in the high-speed rotation process can be ensured, and the influence on the spin coating effect caused by the centrifugal action of the substrate and the liquid sol is prevented; on the other hand, the environment is well isolated, and the interference of other particles on the preparation process can be avoided; the uniformity of components in the film can be improved on the whole, the existence of micron particles in the film is avoided, and the thickness of the film is uniform and controllable.
In the implementation, the spin coating process of step S20 is performed by using a vacuum spin coater, and the rotation speed control in the specific operation may be performed by using the following parameters:
| step (ii) of | Rotational speed r/min | Time/second | Acceleration of a vehicle |
| Slow speed process | 600±20 | 7±2 | 600 |
| Quickly pass throughProgram for programming | 5000±100 | 15±2 | 1200 |
Meanwhile, to further prevent and remove the influence of other particles on the film formation before spin coating, the Nb-doped Strontium Titanate (STO) single crystal substrate NbSTO was subjected to a cleaning treatment with oxygen plasma before spin coating. On one hand, the oxygen plasma can be used for bombardment and oxidation elimination of pollutants on the surface of the substrate through various active particles and the substrate; on the other hand, the surface of the substrate can be subjected to micro-processing, so that the surface crystal grains are smooth crystal grains, and the subsequent improvement of the quality of the film is facilitated. Controlling the time of the oxygen plasma cleaning treatment for 90-100 s; the processing process is controlled within a proper time to avoid the generation of atomic holes and surface damage on the surface of the substrate, which affects the quality of the subsequent film preparation.
After the spin coating at step S20, step S30 further thermally cures the substrate coated with the sol, and primarily dries and cures the sol by heating; on one hand, volatile components in the sol can quickly and uniformly escape, and the influence on the film forming quality caused by the reduction of the uniformity of film components due to different escape speeds of steam is prevented; on the other hand, the film material can be well combined with the substrate through heating treatment without falling off, and micron cracks are avoided, so that the performance of the prepared film is ensured. In addition, the heating process in the implementation comprises two stages of preheating and drying firstly and then heating and maintaining; in the specific implementation, the sample is placed close to a heating table and preheated and dried at 180 ℃ for a moment, the surface is uniformly discolored, and then the temperature of the heating table is adjusted to 400 ℃ and kept for 30 +/-2 minutes. According to the invention, preheating and drying are carried out for a moment, and then heating is carried out, so that the problems of crystallization caused by temperature jump or non-uniform dispersion caused by excessively viscous sol liquid of the film raw material can be well avoided, the substrate and the film raw material are promoted to be better combined, and the quality of the prepared film can be further improved.
On the other hand, in actual use, there may be different film thicknesses according to different needs, so when a film with a thicker thickness is required, the steps S20 (sol dropping-spin coating) to S30 (heat curing) may be repeated by dropping a new sol again after each thermosetting, and new film layers formed on the surface of the cured film layers may be gradually increased until the thickness of the film reaches the required thickness.
After step S30, step S40 anneals the cured spin-on coating. In the annealing process of the annealing process, the flatness of the surface of the sample is improved through rapid temperature rise; keeping the temperature within the range of 700-900 ℃ of the highest crystallization temperature, and controlling and improving the crystallinity of the material; when the number of layers of the film is increased in the temperature range, the film can be implemented by properly adopting a higher range of temperature according to the quality requirement of preparation; and finally, slowly cooling (the cooling rate is about 0.5-1 ℃/s) to promote the film to form an out-of-plane single domain. The temperature control of the various stages of the complete annealing process in the implementation of specific details employs the following parameters:
| sequence of stages | Target temperature | Rise/fall time | Time of heat preservation |
| 1 | 100±5℃ | 80±5s | 30±5s |
| 2 | 450±10℃ | 70±5s | 300±5s |
| 3 | 700～900℃ | 70±5s | 600±10s |
| 4 | At room temperature | 700～1800s | 10±2s |
As can be seen from the temperature change parameter setting in the annealing process, the main annealing process of the invention adopts the steps of firstly heating (pre-annealing) for several times and then slowly cooling to room temperature, the cooling time is relatively long, the rate is controlled to be about 0.5-1 ℃/s, and the film is promoted to form an out-of-plane single domain.
The preparation method of the B-site doped bismuth ferrite solid solution film is adopted to improve the traditional film preparation technology of bismuth ferrite sol-gel, and the B-site doping is mixed with calcium titanate to obtain the piezoelectric enhancement effect of the morphotropic phase boundary; providing epitaxial stress for thin film growth by using a substrate; by finely adjusting annealing parameters, the prepared high-quality epitaxial room-temperature multiferroic film has good high-voltage electrical property, room-temperature multiferroic property and single crystal epitaxy property.
On the basis of the method, the invention further provides a B-site bismuth-doped ferrite solid solution film material prepared by the method; has good high-voltage electrical property, room temperature multiferroic property and single crystal ductility.
The invention further provides application of the B-site bismuth-doped ferrite solid solution film material prepared in the above way in sensors and drivers.
In order to make the details of the preparation method of the B-site doped bismuth ferrite solid solution thin film of the present invention more beneficial to understanding and implementation of those skilled in the art, and to verify the progressive effect of the thin film material prepared by the present invention, the above contents of the present invention are exemplified by the following specific examples.
Example 1
In this example 1, the film preparation was carried out using the following detailed procedure:
s11, 100mL (1-x) BiTi according to 0.3mol/L(1-y)/2FeyMg(1-y)/2O3-xCaTiO3Calculated for the amount of sol prepared (x ═ 0.15 and y ═ 0.8), the starting materials were obtained using the following table:
| name of medicine | Molecular weight | Purity of the drug | Experimental proportions | Stoichiometric number | Weighing mass |
| Bismuth nitrate (pentahydrate) | 485.07 | 0.98 | 1.1 | 0.85 | 13.8839g |
| Ferric nitrate (nine water) | 404.02 | 0.985 | 1 | 0.544 | 8.3675g |
| Magnesium nitrate (hexahydrate) | 256.41 | 0.99 | 1 | 0.085 | 0.6605g |
| Calcium acetate (monohydrate) | 176.18 | 0.99 | 1 | 0.15 | 0.8008g |
| Titanium tetraisopropoxide | 340.32 | 0.99 | 1 | 0.235 | 2.4235g |
| Citric acid (Yishui) | 210.14 | 0.995 | 1 | 1 | 6.3359g |
| Ethylene glycol methyl ether | 76.09 | >0.99 | - | - | - |
| Propionic anhydride | 130.14 | >0.985 | - | - | - |
S12, dissolving Bi, Fe, Mg and Ca salts in 50mL of ethylene glycol monomethyl ether in sequence, and fully mixing and stirring until the salts are dissolved to obtain a first solution A;
s13, dissolving titanium tetraisopropoxide in 30mL of ethylene glycol monomethyl ether, and fully mixing and stirring to obtain a second solution B;
s14, adding the second solution B into the first solution A, and fully mixing and stirring to obtain a mixed solution C;
s15, adding 0.03mol of citric acid into the mixed solution C, and fully mixing, stirring and uniformly mixing; continuously stirring for 12 hours under the normal temperature and pressure environment to obtain 0.3mol/L sol;
s16, taking 20mL of the 0.3mol/L sol prepared in the step S15, adding 20mL of ethylene glycol monomethyl ether for dilution, then adding 10mL of propionic anhydride, and mixing and stirring uniformly;
and S17, finally transferring the film to a conical flask for sealed storage, standing and aging for 72 hours, and then preparing the film.
S21, selecting a Nb-doped Strontium Titanate (STO) single crystal substrate, wherein the crystal orientation is in the [001] direction, the doping concentration is 0.5%, and the size of the substrate is 5 x 1 mm;
s22, cleaning the substrate of the step S21 in an oxygen plasma cleaner for 100S;
s23, placing the substrate cleaned in the step S22 on a spin coater, and then vacuumizing to fix the substrate;
s24, adding the sol prepared in the step S17 onto a substrate in a static dropping mode;
s25, pressing down a program start key of the spin coater, and starting spin coating; the spin coating process was set as follows:
and S26, after the spin-coating process of the spin-coating machine is stopped, removing the vacuum, and taking down the sample.
S31, transferring the substrate sample coated with the sol in the step S26 to a constant temperature heating table, drying the substrate sample close to the heating table (at 180 ℃) for a moment, and placing the substrate sample in the center of the heating table after the surface is uniformly discolored;
s32, the temperature of the heating stage was further adjusted to 400 ℃, and heating was continued for 30 minutes.
The steps S24-S32 are cured to form a single coating, and the thickness of the single film layer formed after the dropwise adding sol is generally controlled, spin-coated and cured is about tens of nanometers; therefore, according to the film thickness requirement of different products, technicians can repeat the steps from S24 to S32 in the implementation process to form a multilayer film, and the multilayer film can be stopped until the thickness of the film reaches the required thickness; in the embodiment 1, the above steps are repeated until the thickness of the film layer is about 10 μm, and then the process is stopped;
s40, annealing the substrate coated and cured with the multi-layer film layer, wherein the annealing parameters are as follows:
| sequence of stages | Target temperature | Rise/fall time | Time of heat preservation |
| 1 | 100℃ | 80s | 30s |
| 2 | 450℃ | 70s | 300s |
| 3 | 800℃ | 70s | 600s |
| 4 | 30℃ | 1600s | 10s |
S50, taking out the film sample annealed in step S40, and then peeling off the substrate, i.e. the B-site bismuth-doped ferrite solid solution film prepared in this embodiment 1.
Example 2
In this example 2 the film preparation was carried out using the following detailed procedure:
s10, according to (1-x) BiTi(1-y)/2FeyMg(1-y)/2O3-xCaTiO3After the amounts of the respective materials were calculated to be 0.1 for x and 0.7 for y, a 100mL sol of 0.3mol/L was prepared according to the same procedure as in example 2.
S21, selecting an LSMO substrate with the size of 5 × 1 mm;
s22, cleaning the substrate of the step S21 in an oxygen plasma cleaning machine for 90S;
s23, placing the substrate cleaned in the step S22 on a spin coater, and then vacuumizing to fix the substrate;
s24, adding the sol prepared in the step S10 onto a substrate in a static dropping mode;
s25, pressing down a program start key of the spin coater, and starting spin coating; the spin coating process was set as follows:
and S26, after the spin-coating process of the spin-coating machine is stopped, removing the vacuum, and taking down the sample.
S31, transferring the substrate sample coated with the sol in the step S26 to a constant temperature heating table, drying the substrate sample close to the heating table (at 180 ℃) for a moment, and placing the substrate sample in the center of the heating table after the surface is uniformly discolored;
s32, the temperature of the heating stage was further adjusted to 400 ℃ and the heating was continued for 28 minutes.
The steps S24-S32 are cured to form a single coating, and the thickness of the single film layer formed after the dropwise adding sol is generally controlled, spin-coated and cured is about tens of nanometers; therefore, according to the film thickness requirement of different products, technicians can repeat the steps from S24 to S32 in the implementation process to form a multilayer film, and the multilayer film can be stopped until the thickness of the film reaches the required thickness; in the embodiment 1, the above steps are repeated until the thickness of the film layer is about 10 μm, and then the process is stopped;
s40, annealing the substrate coated and cured with the multi-layer film layer, wherein the annealing parameters are as follows:
| sequence of stages | Target temperature | Rise/fall time | Time of heat preservation |
| 1 | 95℃ | 75s | 25s |
| 2 | 440℃ | 65s | 295s |
| 3 | 700℃ | 65s | 590s |
| 4 | 28℃ | 1570s | 8s |
S50, taking out the film sample annealed in step S40, and then peeling off the substrate, i.e., the B-site bismuth-doped ferrite solid solution film prepared in this embodiment 2.
Example 3
In this example 3 the film preparation was carried out using the following detailed procedure:
s10, according to (1-x) BiTi(1-y)/2FeyMg(1-y)/2O3-xCaTiO3After the amounts of the respective materials were calculated to be 0.2 and 0.95, a sol of 0.3mol/L and 100mL was prepared according to the same procedure as in example 3.
S21, selecting a LAO substrate, wherein the size of the substrate is 5 × 1 mm;
s22, cleaning the substrate of the step S21 in an oxygen plasma cleaning machine for 95S;
s23, placing the substrate cleaned in the step S22 on a spin coater, and then vacuumizing to fix the substrate;
s24, adding the sol prepared in the step S17 onto a substrate in a static dropping mode;
s25, pressing down a program start key of the spin coater, and starting spin coating; the spin coating process was set as follows:
and S26, after the spin-coating process of the spin-coating machine is stopped, removing the vacuum, and taking down the sample.
S31, transferring the substrate sample coated with the sol in the step S26 to a constant temperature heating table, drying the substrate sample close to the heating table (at 180 ℃) for a moment, and placing the substrate sample in the center of the heating table after the surface is uniformly discolored;
s32, the temperature of the heating stage was further adjusted to 400 ℃, and the heating was continued for 32 minutes.
The steps S24-S32 are cured to form a single coating, and the thickness of the single film layer formed after the dropwise adding sol is generally controlled, spin-coated and cured is about tens of nanometers; therefore, according to the film thickness requirement of different products, technicians can repeat the steps from S24 to S32 in the implementation process to form a multilayer film, and the multilayer film can be stopped until the thickness of the film reaches the required thickness; in the embodiment 1, the above steps are repeated until the thickness of the film layer is about 10 μm, and then the process is stopped;
s40, annealing the substrate coated and cured with the multi-layer film layer, wherein the annealing parameters are as follows:
| sequence of stages | Target temperature | Rise/fall time | Time of heat preservation |
| 1 | 105℃ | 85s | 35s |
| 2 | 460℃ | 75s | 305s |
| 3 | 810℃ | 75s | 610s |
| 4 | 32℃ | 1630s | 12s |
S50, taking out the film sample annealed in step S40, and then peeling off the substrate, i.e., the B-site bismuth-doped ferrite solid solution film prepared in this embodiment 3.
Further, the film prepared in the example of the present invention, in order to verify the properties of the film, the film prepared in example 1 was tested, including:
(1) the voltage writing shown in fig. 1 is performed in a 4-micron area on the surface of the film sample, and then the piezoelectric force PFM scanning is performed in a 5-micron area, and the detected film morphology result is shown in fig. 2, the amplitude is shown in fig. 3, and the phase is shown in fig. 4. From the basic performance tests shown in fig. 2 to 4, it can be seen that the phase of the thin film prepared in example 1 after negative voltage writing is substantially the same as the original phase of the thin film in the unwritten area, which indicates that the original thin film has a single polarization direction.
(2) The XRD diffraction of the prepared film sample is carried out, the result is shown in figure 5, and as can be seen from figure 5, the sample and the substrate only have 001 and 002 diffraction peaks and no other impurity peaks, which indicates that the sample is a 001 oriented single crystal epitaxial film.
(3) The relationship between the magnetic moment of the film and the temperature was further measured, and the results are shown in fig. 6, FC and ZFC are respectively the curves of the variation of the magnetic moment of the sample with the temperature measured under the conditions of cooling with a magnetic field (6000 Oe) and cooling without a magnetic field (0 Oe) and adding 200 Oe during the temperature rise. It can be seen that FC and ZFC coincide above 380K, indicating that the curie temperature of the sample is 380K, i.e. the sample has room temperature ferromagnetism.
Also, the test was performed with a thin film prepared with an LSMO substrate of decimation example 2, comprising:
(1) the voltage writing shown in fig. 7 is performed in a 4-micron area on the surface of the film sample, and then the piezoelectric force PFM scanning is performed in a 5-micron area, and the detected film morphology result is shown in fig. 8, the amplitude is shown in fig. 9, and the phase is shown in fig. 10. From the basic performance tests of fig. 8-10, it can be seen that the phase of the thin film prepared in example 2 after negative voltage writing is substantially the same as the original phase of the thin film in the unwritten area, indicating that the original thin film has a single polarization direction.
(2) The result of XRD diffraction of the thin film sample prepared in example 2 is shown in FIG. 11, and it can be seen from FIG. 11 that both the sample and the substrate have only 001 and 002 diffraction peaks and no other impurity peaks, indicating that the sample is a 001 oriented single crystal epitaxial thin film.
From the results of the above tests, it can be seen that the thin film prepared by the present invention has multiferroic and single crystal epitaxial properties at room temperature and gives it good high piezoelectric properties; compared with the existing sol-gel preparation method of the room-temperature multiferroic film, the method has obvious progress.
The above description is only a preferred embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes, which are made by using the contents of the present specification and the accompanying drawings, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (10)
1. A preparation method of a B-site bismuth-doped ferrite solid solution film is characterized by comprising the following steps:
preparing B-site bismuth-doped ferrite solid solution sol;
coating the solid solution sol on a substrate to form a sol coating;
carrying out thermosetting treatment on the sol coating on the substrate;
annealing the sol coating after the thermosetting treatment; wherein the temperature of the annealing treatment is 700-900 ℃, and the cooling rate in the cooling process of the annealing treatment is 0.5-1 ℃/s.
2. The method for preparing the B-site doped bismuth ferrite solid solution film according to claim 1, wherein the B-site doped bismuth ferrite solid solution sol is
(1-x)BiTi(1-y)/2FeyMg(1-y)/2O3-xCaTiO3Wherein x is 0.1 to 0.2 and y is 0.7 to 0.95.
3. The method for preparing a B-site doped bismuth ferrite solid solution thin film according to claim 1 or 2, wherein the lattice constant of the substrate is 3.85 to 3.95 angstroms.
4. The method of claim 3, wherein the substrate is one of NbSTO, LSMO or LAO.
5. The method of preparing a B-site doped bismuth ferrite solid solution film as claimed in claim 2, wherein in the step of preparing the B-site doped bismuth ferrite solid solution sol,
and a dehydrating agent propionic anhydride is added into the B-site bismuth-doped ferrite solid solution sol.
6. The method for preparing a B-site doped bismuth ferrite solid solution film as claimed in claim 2 or 5, wherein the solvent of the B-site doped bismuth ferrite solid solution sol is ethylene glycol monomethyl ether.
7. The method for preparing a B-site doped bismuth ferrite solid solution film as claimed in claim 2 or 5, wherein a chelating agent citric acid is added to the B-site doped bismuth ferrite solid solution sol.
8. The method for preparing the B-site doped bismuth ferrite solid solution thin film according to claim 1 or 2, wherein the step of coating the solid solution sol on a substrate to form a sol coating is carried out by spin coating, and the spin coating comprises the following steps:
firstly, spin-coating at a first rotating speed, and then spin-coating at a second rotating speed; wherein,
the first rotating speed is 580-620 r/min, and the second rotating speed is 4900-5100 r/min.
9. A B-site bismuth-doped ferrite solid solution film, which is prepared by the method for preparing the B-site bismuth-doped ferrite solid solution film according to any one of claims 1 to 8.
10. Use of the B-site doped bismuth ferrite solid solution thin film of claim 9 in a sensor or actuator.
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| CN109761596A (en) * | 2019-03-15 | 2019-05-17 | 中南大学 | A kind of La, Zn codope bismuth ferrite thin film and its preparation method and application |
| WO2020010870A1 (en) * | 2018-07-12 | 2020-01-16 | 深圳先进技术研究院 | B-site doped bismuth ferrite solid solution thin film, and preparation method therefor and application thereof |
| WO2022032584A1 (en) * | 2020-08-13 | 2022-02-17 | 深圳先进技术研究院 | Solid solution multiferroic thin film and preparation method, and electronic device applied to 5g storage technology |
| WO2024016379A1 (en) * | 2022-07-19 | 2024-01-25 | 深圳先进技术研究院 | Multiferroic thin film precursor and preparation method therefor, and prepared flexible multiferroic thin film |
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| AU2012307082A1 (en) * | 2011-09-09 | 2014-04-17 | Panorama Synergy Ltd | Method of crystallising thin films |
| CN102586747B (en) * | 2012-03-13 | 2016-06-22 | 浙江理工大学 | A kind of (BiFeO3)m/(La0.7Sr0.3MnO3) preparation method of n plural layers |
| CN103839928B (en) * | 2014-03-05 | 2016-07-13 | 欧阳俊 | A kind of high pressure, Low dark curient, high polarization intensity bismuth ferrite thin film and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2020010870A1 (en) * | 2018-07-12 | 2020-01-16 | 深圳先进技术研究院 | B-site doped bismuth ferrite solid solution thin film, and preparation method therefor and application thereof |
| CN109761596A (en) * | 2019-03-15 | 2019-05-17 | 中南大学 | A kind of La, Zn codope bismuth ferrite thin film and its preparation method and application |
| CN109761596B (en) * | 2019-03-15 | 2021-09-14 | 中南大学 | La and Zn co-doped bismuth ferrite film and preparation method and application thereof |
| WO2022032584A1 (en) * | 2020-08-13 | 2022-02-17 | 深圳先进技术研究院 | Solid solution multiferroic thin film and preparation method, and electronic device applied to 5g storage technology |
| WO2024016379A1 (en) * | 2022-07-19 | 2024-01-25 | 深圳先进技术研究院 | Multiferroic thin film precursor and preparation method therefor, and prepared flexible multiferroic thin film |
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