CN107117830A - A kind of LaSrMnCo is co-doped with many iron thin films of bismuth ferrite and preparation method thereof - Google Patents
A kind of LaSrMnCo is co-doped with many iron thin films of bismuth ferrite and preparation method thereof Download PDFInfo
- Publication number
- CN107117830A CN107117830A CN201710254704.5A CN201710254704A CN107117830A CN 107117830 A CN107117830 A CN 107117830A CN 201710254704 A CN201710254704 A CN 201710254704A CN 107117830 A CN107117830 A CN 107117830A
- Authority
- CN
- China
- Prior art keywords
- lasrmnco
- thin films
- doped
- many iron
- iron thin
- 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.)
- Granted
Links
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 159
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 68
- 239000010409 thin film Substances 0.000 title claims abstract description 66
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 61
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 229910000859 α-Fe Inorganic materials 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000010408 film Substances 0.000 claims abstract description 77
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000011572 manganese Substances 0.000 claims abstract description 25
- 238000004528 spin coating Methods 0.000 claims abstract description 25
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 claims abstract description 20
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims abstract description 18
- 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 abstract description 17
- 230000010287 polarization Effects 0.000 claims abstract description 13
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims abstract description 10
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229940071125 manganese acetate Drugs 0.000 claims abstract description 10
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims abstract description 10
- 238000000137 annealing Methods 0.000 claims abstract description 3
- 239000011521 glass Substances 0.000 claims description 37
- 239000000758 substrate Substances 0.000 claims description 37
- 239000007788 liquid Substances 0.000 claims description 27
- 239000002243 precursor Substances 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 16
- 230000003749 cleanliness Effects 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 230000005684 electric field Effects 0.000 claims description 8
- 229910021645 metal ion Inorganic materials 0.000 claims description 8
- 239000013078 crystal Substances 0.000 claims description 7
- LITYQKYYGUGQLY-UHFFFAOYSA-N iron nitric acid Chemical compound [Fe].O[N+]([O-])=O LITYQKYYGUGQLY-UHFFFAOYSA-N 0.000 claims 1
- 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 abstract description 18
- 238000000034 method Methods 0.000 abstract description 11
- 229910002902 BiFeO3 Inorganic materials 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 9
- 230000005621 ferroelectricity Effects 0.000 abstract description 7
- 238000002474 experimental method Methods 0.000 abstract description 3
- 239000000470 constituent Substances 0.000 abstract description 2
- 230000001788 irregular Effects 0.000 abstract description 2
- 238000003980 solgel method Methods 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000003599 detergent Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 230000005855 radiation Effects 0.000 description 6
- 230000006641 stabilisation Effects 0.000 description 6
- 238000011105 stabilization Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000012535 impurity Substances 0.000 description 4
- 230000005291 magnetic effect Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 2
- 230000005307 ferromagnetism Effects 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 230000005290 antiferromagnetic effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 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
- 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
- C04B35/2608—Compositions containing one or more ferrites of the group comprising manganese, zinc, nickel, copper or cobalt and one or more ferrites of the group comprising rare earth metals, alkali metals, alkaline earth metals or lead
- C04B35/2633—Compositions containing one or more ferrites of the group comprising manganese, zinc, nickel, copper or cobalt and one or more ferrites of the group comprising rare earth metals, alkali metals, alkaline earth metals or lead containing barium, strontium or calcium
-
- 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
- C04B35/2641—Compositions containing one or more ferrites of the group comprising rare earth metals and one or more ferrites of the group comprising alkali metals, alkaline earth metals or lead
-
- 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
- C04B35/62222—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining ceramic 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
- C03C2217/90—Other aspects of coatings
- C03C2217/94—Transparent conductive oxide layers [TCO] being part of a multilayer coating
-
- 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
- C03C2218/11—Deposition methods from solutions or suspensions
- C03C2218/116—Deposition methods from solutions or suspensions by spin-coating, centrifugation
-
- 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
- C03C2218/30—Aspects of methods for coating glass not covered above
- C03C2218/32—After-treatment
-
- 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
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
-
- 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
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/74—Physical characteristics
- C04B2235/76—Crystal structural characteristics, e.g. symmetry
- C04B2235/768—Perovskite structure ABO3
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Structural Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Magnetic Ceramics (AREA)
- Inorganic Insulating Materials (AREA)
Abstract
Many iron thin films of bismuth ferrite and preparation method thereof are co-doped with the invention provides a kind of LaSrMnCo, using bismuth nitrate, lanthanum nitrate, strontium nitrate, ferric nitrate, manganese acetate and cobalt nitrate as raw material (bismuth nitrate excessive 5%), using ethylene glycol monomethyl ether and acetic anhydride as solvent, the technique annealed with spin-coating method and layer by layer is prepared for Bi0.97‑ xLaxSr0.03Fe0.94Mn0.04Co0.02O3Many iron thin films, i.e. LaSrMnCo are co-doped with many iron thin films of bismuth ferrite.The present invention uses sol gel process, and uses spin coating and layer by layer annealing method, and equipment requirement is simple, and experiment condition is easily achieved, and film, and chemical constituent controllable precise are suitably prepared on big surface and surface in irregular shape, can improve BiFeO3The multi-ferrum property of film, obtained LaSrMnCo is co-doped with many iron thin film uniformities of bismuth ferrite preferably, is many iron thin films of high residual polarization value and low coercive field, effectively enhances the ferroelectricity and dielectric properties of film.
Description
Technical field
The invention belongs to field of functional materials, the FTO/glass substrate surfaces being related in functionalization prepare LaSrMnCo and are total to
Mix many iron thin films of bismuth ferrite, specially Bi0.97-xLaxSr0.03Fe0.94Mn0.04Co0.02O3Many iron thin films, x=0.03~0.18.
Background technology
Multi-iron material refers in certain temperature range while having in ferroelectricity, ferromagnetism or ferroelasticity two kinds or two kinds
Material above.BiFeO3(BFO) it is one of a small number of single phase multi-iron materials, the perovskite structure with distortion (belongs to R3c points
Group), a kind of oblique hexagonal structure for deviateing preferable perovskite structure as formed by cubic structure is stretched along (111) direction, in room
Temperature is lower to have ferroelectric order and antiferromagnetic order simultaneously, due to higher ferroelectric transition temperature (Tc=1103K) and magnetic phase
Temperature (TN=643K), in magnetoelectric transducer, spin electric device has wide practical use and obtained in terms of memory
Concern.
Currently used for preparation BiFeO3The method of film has a lot, but BiFeO3In film bismuth element volatile and
Part Fe3+To Fe2+Transformation, make to produce more Lacking oxygen in film, so as to cause BiFeO3Film has serious leakage
Electrical phenomena and larger coercive field, magnetic are weaker, it is difficult to polarize, it is difficult to obtain higher residual polarization value, therefore actually should
It is restricted in.In addition, BiFeO3There is weak ferromagnetism in film, make it be difficult to meet memory device of new generation and other many
It is eager to excel needed for function element magneto-electric coupled.To improve BiFeO3The multi-ferrum property of film, most commonly seen method is exactly that ion is mixed
It is miscellaneous.
At present, also not on Bi0.97-xLaxSr0.03Fe0.94Mn0.04Co0.02O3The phase of many iron thin films and preparation method thereof
Close report.
The content of the invention
Many iron thin films of bismuth ferrite and preparation method thereof, this method are co-doped with it is an object of the invention to provide a kind of LaSrMnCo
Equipment requirement is simple, and experiment condition is easily reached, doping is easily controlled, and obtained LaSrMnCo is co-doped with many iron thin films of bismuth ferrite
For Bi0.97-xLaxSr0.03Fe0.94Mn0.04Co0.02O3Many iron thin films, can improve BiFeO3The multi-ferrum property of base film.
To achieve these goals, the present invention is adopted the following technical scheme that：
A kind of LaSrMnCo is co-doped with many iron thin films of bismuth ferrite, and the LaSrMnCo is co-doped with many iron thin films of bismuth ferrite for Bi0.97- xLaxSr0.03Fe0.94Mn0.04Co0.02O3Film, x=0.03~0.18, its structure is trigonal crystal structure, and space group is R3c:H and
R3m:R coexists.
The LaSrMnCo is co-doped with residual polarization value of many iron thin films of bismuth ferrite under 700kV/cm electric fields for 191~230 μ
C/cm2, coercive field is 222~274kV/cm.
It is 488~774 that the LaSrMnCo, which is co-doped with dielectric constant of many iron thin films of bismuth ferrite under 1kHz frequencies,.
Described LaSrMnCo is co-doped with the preparation method of many iron thin films of bismuth ferrite, comprises the following steps：
Step 1：It is in molar ratio (1.02-x):x:0.03:0.94:0.04:0.02 by bismuth nitrate, lanthanum nitrate, strontium nitrate,
Ferric nitrate, manganese acetate and cobalt nitrate are dissolved in ethylene glycol monomethyl ether, are stirring evenly and then adding into acetic anhydride, are continued to stir, are obtained
Precursor liquid；Wherein x=0.03~0.15；
Step 2：Precursor liquid is spin-coated on FTO/glass substrates, wet film is obtained, wet film is after spin coating at 190~210 DEG C
Under toast to obtain dry film, annealed in atmosphere at 540~550 DEG C, obtain crystalline state Bi0.97- xLaxSr0.03Fe0.94Mn0.04Co0.02O3Film；
Step 3：By crystalline state Bi0.97-xLaxSr0.03Fe0.94Mn0.04Co0.02O3Film cooling to room temperature, repeat step 2 until
Required thickness is reached, that is, obtains LaSrMnCo and is co-doped with many iron thin films of bismuth ferrite.
The total concentration of metal ion is 0.2~0.4mol/L in precursor liquid in the step 1.
Ethylene glycol monomethyl ether and the volume ratio of acetic anhydride are (2.5~3.5) in the precursor liquid:1.
The step 2 first cleans up FTO/glass substrates before carrying out, and then irradiates under ultraviolet light, makes FTO/
Glass substrate surfaces reach atomic cleanliness degree.
Spin coating rotating speed in the step 2 during spin coating is 3600~4200r/min, and spin coating time is 12~18s.
Baking time in the step 2 after spin coating is 6~8min.
Annealing time in the step 2 is 20~25min.
Relative to prior art, the invention has the advantages that：
The LaSrMnCo that the present invention is provided is co-doped with the preparation method of many iron thin films of bismuth ferrite, using sol-gel process, with nitre
Sour bismuth, lanthanum nitrate, strontium nitrate, ferric nitrate, manganese acetate and cobalt nitrate are raw material (bismuth nitrate excessive 5%), with ethylene glycol monomethyl ether and
Acetic anhydride is solvent, prepares precursor liquid, then the technique annealed with spin-coating method and layer by layer is prepared for Bi0.97- xLaxSr0.03Fe0.94Mn0.04Co0.02O3Film, i.e. LaSrMnCo are co-doped with many iron thin films of bismuth ferrite.Present invention selection rare earth element
La and alkaline-earth metal Sr adulterates A, and transient metal Mn and Co adulterate B, by way of A, B codopes, have film
Good dielectric and ferroelectric properties.Rare earth doped element can suppress Bi volatilization on A positions, reduce Lacking oxygen, and then reduce
Leakage current, effectively improves the ferroelectric properties of film；Divalence alkali metal ion can compensate the charge unbalance that Lacking oxygen is caused, and have
Effect ground suppresses Fe3+The valence state fluctuation of ion；Containing transition metal ion can suppress Fe on B positions3+To Fe2+Conversion, reduces oxygen
The generation in room, the doping of magnetic ion can improve the magnetic property of film.It can effectively suppress Bi by A, B codopes
Volatilization, reduce film in Fe2+, Lacking oxygen content and defect generation so that polarization of the enhanced film under extra electric field
Intensity, effectively improves the ferroelectric properties of film.The present invention uses sol-gel technology, and the side of film is prepared compared to other
Method, this method equipment requirement is simple, and experiment condition is easily achieved, with low cost, and reaction is easily carried out, and technical process temperature is low,
Preparation process and doping are easily controlled, chemical constituent controllable precise, suitably on big surface and surface in irregular shape
Prepare film, it is easy to mix some trace elements equal and quantitative, atom or molecular level can be obtained in a short time
Uniformity, the LaSrMnCo for preparing of the present invention is co-doped with many iron thin film uniformities of bismuth ferrite preferably, with high residual polarization value, low rectifys
Stupid field and high-k, are effectively improved the ferroelectricity and dielectric properties of film.
LaSrMnCo produced by the present invention is co-doped with the consistency height of many iron thin films of bismuth ferrite, even grain size, its chemistry
Structural formula is Bi0.97-xLaxSr0.03Fe0.94Mn0.04Co0.02O3, x=0.03~0.18, the film belongs to trigonal crystal structure, space group
For R3c:H (23.34%~72.74%) and R3m:R (27.26%~76.66%) coexists, and the film has high residual polarization
Value, low coercive field and high-k, can improve BiFeO3The multi-ferrum property of base film.
Further, it is that 700kV/cm, La contain that LaSrMnCo produced by the present invention, which is co-doped with many iron thin films of bismuth ferrite in electric field,
When amount x is respectively 0.03,0.06,0.09,0.18, its remanent polarization is followed successively by 230 μ C/cm2、209μC/cm2、215μC/
cm2、191μC/cm2, coercive field is followed successively by 274kV/cm, 271kV/cm, 265kV/cm, 222kV/cm, is high residual polarization value
(191~230 μ C/cm2) and low coercive field (222~274kV/cm) many iron thin films.And LaSrMnCo produced by the present invention
The many iron thin films of bismuth ferrite are co-doped with when it is 0.03,0.06,0.09,0.18 that frequency, which is 1kHz, La doping x, its dielectric constant point
Not Wei 488,689,653,774, be many iron thin films of high-k.
Brief description of the drawings
Fig. 1 is the XRD refine figures that LaSrMnCo prepared by the present invention is co-doped with many iron thin films of bismuth ferrite；
Fig. 2 is dielectric constant and dielectric loss and the test that LaSrMnCo prepared by the present invention is co-doped with many iron thin films of bismuth ferrite
The graph of a relation of frequency；
Fig. 3 is the ferroelectric hysteresis loop that LaSrMnCo prepared by the present invention is co-doped with many iron thin films of bismuth ferrite.
Embodiment
The present invention is described further with currently preferred specific embodiment below in conjunction with the accompanying drawings, raw material is analysis
It is pure.
Embodiment 1
Step 1：FTO/glass substrates are totally sealed up for safekeeping in absolute ethyl alcohol with liquid detergent, acetone, washes of absolute alcohol respectively
In it is standby；
Step 2：By raw material of bismuth nitrate, lanthanum nitrate, strontium nitrate, ferric nitrate, manganese acetate and cobalt nitrate, (bismuth nitrate is excessive
5%) it is in molar ratio, 0.99:0.03:0.03:0.94:0.04:0.02 (x=0.03) is dissolved in ethylene glycol monomethyl ether, stirring
30min, adds acetic anhydride, stirs 90min, obtains the precursor liquid for the stabilization that metal ion total concentration is 0.3mol/L；Wherein
Ethylene glycol monomethyl ether and the volume ratio of acetic anhydride are 3:1；
Step 3：N is used after FTO/glass substrates are washed with deionized water only2Drying, then irradiate clean with ultraviolet radiation instrument
Net FTO/glass substrate 40min, make FTO/glass substrate surfaces reach atomic cleanliness degree, are then spin-coated on precursor liquid
On FTO/glass substrates, its spin coating rotating speed is 3700r/min, and spin coating time is 16s, obtains wet film, and wet film dries at 200 DEG C
Roasting 7min obtains dry film, then the 21min that anneals in atmosphere at 545 DEG C, produces crystalline state
Bi0.94La0.03Sr0.03Fe0.94Mn0.04Co0.02O3Film；
Step 4：By crystalline state Bi0.94La0.03Sr0.03Fe0.94Mn0.04Co0.02O3Film cooling is to room temperature, and repeat step 2 is straight
Required thickness is reached, that is, obtains LaSrMnCo and is co-doped with many iron thin films of bismuth ferrite.
LaSrMnCo made from XRD determining embodiment 1 is co-doped with the thing phase composition structure of many iron thin films of bismuth ferrite, such as Fig. 1 institutes
Show, the film belongs to trigonal crystal structure, space group is R3c:H and R3m:R coexists, the appearance without impurity.SEM determines embodiment 1
Obtained LaSrMnCo is co-doped with the microscopic appearance of many iron thin films of bismuth ferrite.Surveyed with Radiant Multiferroic ferroelectricities analyzer
LaSrMnCo made from examination embodiment 1 is co-doped with the ferroelectric properties of many iron thin films of bismuth ferrite, as shown in Fig. 2 frequency is 1kHz, electric field
During for 700kV/cm, the residual polarization value of the film is 230 μ C/cm2, coercive field is 274kV/cm.Use Agilent E4980A
LaSrMnCo made from accurate LCR tables testing example 1 is co-doped with the dielectric properties of many iron thin films of bismuth ferrite, as shown in figure 3, frequency
During for 1kHz, the dielectric constant of the film is 488.
Embodiment 2
Step 1：FTO/glass substrates are totally sealed up for safekeeping in absolute ethyl alcohol with liquid detergent, acetone, washes of absolute alcohol respectively
In it is standby；
Step 2：By raw material of bismuth nitrate, lanthanum nitrate, strontium nitrate, ferric nitrate, manganese acetate and cobalt nitrate, (bismuth nitrate is excessive
5%) it is in molar ratio, 0.96:0.06:0.03:0.94:0.04:0.02 (x=0.06) is dissolved in ethylene glycol monomethyl ether, stirring
30min, adds acetic anhydride, stirs 90min, obtains the precursor liquid for the stabilization that metal ion total concentration is 0.3mol/L；Wherein
Ethylene glycol monomethyl ether and the volume ratio of acetic anhydride are 3:1；
Step 3：N is used after FTO/glass substrates are washed with deionized water only2Drying, then irradiate clean with ultraviolet radiation instrument
Net FTO/glass substrate 40min, make FTO/glass substrate surfaces reach atomic cleanliness degree, are then spin-coated on precursor liquid
On FTO/glass substrates, its spin coating rotating speed is 3900r/min, and spin coating time is 15s, obtains wet film, and wet film dries at 200 DEG C
Roasting 6.5min obtains dry film, then the 24min that anneals in atmosphere at 545 DEG C, produces crystalline state
Bi0.91La0.06Sr0.03Fe0.94Mn0.04Co0.02O3Film；
Step 4：By crystalline state Bi0.91La0.06Sr0.03Fe0.94Mn0.04Co0.02O3Film cooling is to room temperature, and repeat step 2 is straight
Required thickness is reached, that is, obtains LaSrMnCo and is co-doped with many iron thin films of bismuth ferrite.
LaSrMnCo made from XRD determining embodiment 2 is co-doped with the thing phase composition structure of many iron thin films of bismuth ferrite, such as Fig. 1 institutes
Show, the film belongs to trigonal crystal structure, space group is R3c:H and R3m:R coexists, the appearance without impurity.SEM determines embodiment 2
Obtained LaSrMnCo is co-doped with the microscopic appearance of many iron thin films of bismuth ferrite.Surveyed with Radiant Multiferroic ferroelectricities analyzer
LaSrMnCo made from examination embodiment 2 is co-doped with the ferroelectric properties of many iron thin films of bismuth ferrite, as shown in Fig. 2 frequency is 1kHz, electric field
During for 700kV/cm, the residual polarization value of the film is 209 μ C/cm2, coercive field is 271kV/cm.Use Agilent E4980A
LaSrMnCo made from accurate LCR tables testing example 2 is co-doped with the dielectric properties of many iron thin films of bismuth ferrite, as shown in figure 3, frequency
During for 1kHz, the dielectric constant of the film is 689.
Embodiment 3
Step 1：FTO/glass substrates are totally sealed up for safekeeping in absolute ethyl alcohol with liquid detergent, acetone, washes of absolute alcohol respectively
In it is standby；
Step 2：By raw material of bismuth nitrate, lanthanum nitrate, strontium nitrate, ferric nitrate, manganese acetate and cobalt nitrate, (bismuth nitrate is excessive
5%) it is in molar ratio, 0.93:0.09:0.03:0.94:0.04:0.02 (x=0.0.09) is dissolved in ethylene glycol monomethyl ether, stirring
30min, adds acetic anhydride, stirs 90min, obtains the precursor liquid for the stabilization that metal ion total concentration is 0.3mol/L；Wherein
Ethylene glycol monomethyl ether and the volume ratio of acetic anhydride are 3:1；
Step 3：N is used after FTO/glass substrates are washed with deionized water only2Drying, then irradiate clean with ultraviolet radiation instrument
Net FTO/glass substrate 40min, make FTO/glass substrate surfaces reach atomic cleanliness degree, are then spin-coated on precursor liquid
On FTO/glass substrates, its spin coating rotating speed is 3800r/min, and spin coating time is 15s, obtains wet film, and wet film dries at 200 DEG C
Roasting 7.5min obtains dry film, then the 23min that anneals in atmosphere at 545 DEG C, produces crystalline state
Bi0.88La0.09Sr0.03Fe0.94Mn0.04Co0.02O3Film；
Step 4：By crystalline state Bi0.88La0.09Sr0.03Fe0.94Mn0.04Co0.02O3Film cooling is to room temperature, and repeat step 2 is straight
Required thickness is reached, that is, obtains LaSrMnCo and is co-doped with many iron thin films of bismuth ferrite.
LaSrMnCo made from XRD determining embodiment 3 is co-doped with the thing phase composition structure of many iron thin films of bismuth ferrite, such as Fig. 1 institutes
Show, the film belongs to trigonal crystal structure, space group is R3c:H and R3m:R coexists, the appearance without impurity.SEM determines embodiment 3
Obtained LaSrMnCo is co-doped with the microscopic appearance of many iron thin films of bismuth ferrite.Surveyed with Radiant Multiferroic ferroelectricities analyzer
LaSrMnCo made from examination embodiment 3 is co-doped with the ferroelectric properties of many iron thin films of bismuth ferrite, as shown in Fig. 2 frequency is 1kHz, electric field
During for 700kV/cm, the residual polarization value of the film is 215 μ C/cm2, coercive field is 265kV/cm.Use Agilent E4980A
LaSrMnCo made from accurate LCR tables testing example 3 is co-doped with the dielectric properties of many iron thin films of bismuth ferrite, as shown in figure 3, frequency
During for 1kHz, the dielectric constant of the film is 653.
Embodiment 4
Step 1：FTO/glass substrates are totally sealed up for safekeeping in absolute ethyl alcohol with liquid detergent, acetone, washes of absolute alcohol respectively
In it is standby；
Step 2：By raw material of bismuth nitrate, lanthanum nitrate, strontium nitrate, ferric nitrate, manganese acetate and cobalt nitrate, (bismuth nitrate is excessive
5%) it is in molar ratio, 0.90:0.12:0.03:0.94:0.04:0.02 (x=0.12) is dissolved in ethylene glycol monomethyl ether, stirring
30min, adds acetic anhydride, stirs 90min, obtains the precursor liquid for the stabilization that metal ion total concentration is 0.2mol/L；Wherein
Ethylene glycol monomethyl ether and the volume ratio of acetic anhydride are 2.5:1；
Step 3：N is used after FTO/glass substrates are washed with deionized water only2Drying, then irradiate clean with ultraviolet radiation instrument
Net FTO/glass substrate 35min, make FTO/glass substrate surfaces reach atomic cleanliness degree, are then spin-coated on precursor liquid
On FTO/glass substrates, its spin coating rotating speed is 3600r/min, and spin coating time is 18s, obtains wet film, and wet film dries at 190 DEG C
Roasting 8min obtains dry film, then the 25min that anneals in atmosphere at 540 DEG C, produces crystalline state
Bi0.85La0.12Sr0.03Fe0.94Mn0.04Co0.02O3Film；
Step 4：By crystalline state Bi0.85La0.12Sr0.03Fe0.94Mn0.04Co0.02O3Film cooling is to room temperature, and repeat step 2 is straight
Required thickness is reached, that is, obtains LaSrMnCo and is co-doped with many iron thin films of bismuth ferrite.
Embodiment 5
Step 1：FTO/glass substrates are totally sealed up for safekeeping in absolute ethyl alcohol with liquid detergent, acetone, washes of absolute alcohol respectively
In it is standby；
Step 2：By raw material of bismuth nitrate, lanthanum nitrate, strontium nitrate, ferric nitrate, manganese acetate and cobalt nitrate, (bismuth nitrate is excessive
5%) it is in molar ratio, 0.87:0.15:0.03:0.94:0.04:0.02 (x=0.15) is dissolved in ethylene glycol monomethyl ether, stirring
30min, adds acetic anhydride, stirs 90min, obtains the precursor liquid for the stabilization that metal ion total concentration is 0.4mol/L；Wherein
Ethylene glycol monomethyl ether and the volume ratio of acetic anhydride are 3.5:1；
Step 3：N is used after FTO/glass substrates are washed with deionized water only2Drying, then irradiate clean with ultraviolet radiation instrument
Net FTO/glass substrate 45min, make FTO/glass substrate surfaces reach atomic cleanliness degree, are then spin-coated on precursor liquid
On FTO/glass substrates, its spin coating rotating speed is 4200r/min, and spin coating time is 12s, obtains wet film, and wet film dries at 210 DEG C
Roasting 6min obtains dry film, then the 20min that anneals in atmosphere at 550 DEG C, produces crystalline state
Bi0.82La0.15Sr0.03Fe0.94Mn0.04Co0.02O3Film；
Step 4：By crystalline state Bi0.82La0.15Sr0.03Fe0.94Mn0.04Co0.02O3Film cooling is to room temperature, and repeat step 2 is straight
Required thickness is reached, that is, obtains LaSrMnCo and is co-doped with many iron thin films of bismuth ferrite.
Embodiment 6
Step 1：FTO/glass substrates are totally sealed up for safekeeping in absolute ethyl alcohol with liquid detergent, acetone, washes of absolute alcohol respectively
In it is standby；
Step 2：By raw material of bismuth nitrate, lanthanum nitrate, strontium nitrate, ferric nitrate, manganese acetate and cobalt nitrate, (bismuth nitrate is excessive
5%) it is in molar ratio, 0.84:0.18:0.03:0.94:0.04:0.02 (x=0.18) is dissolved in ethylene glycol monomethyl ether, stirring
30min, adds acetic anhydride, stirs 90min, obtains the precursor liquid for the stabilization that metal ion total concentration is 0.3mol/L；Wherein
Ethylene glycol monomethyl ether and the volume ratio of acetic anhydride are 3:1；
Step 3：N is used after FTO/glass substrates are washed with deionized water only2Drying, then irradiate clean with ultraviolet radiation instrument
Net FTO/glass substrate 40min, make FTO/glass substrate surfaces reach atomic cleanliness degree, are then spin-coated on precursor liquid
On FTO/glass substrates, its spin coating rotating speed is 4000r/min, and spin coating time is 14s, obtains wet film, and wet film dries at 200 DEG C
Roasting 7min obtains dry film, then the 22min that anneals in atmosphere at 545 DEG C, produces crystalline state
Bi0.79La0.18Sr0.03Fe0.94Mn0.04Co0.02O3Film；
Step 4：By crystalline state Bi0.79La0.18Sr0.03Fe0.94Mn0.04Co0.02O3Film cooling is to room temperature, and repeat step 2 is straight
Required thickness is reached, that is, obtains LaSrMnCo and is co-doped with many iron thin films of bismuth ferrite.
LaSrMnCo made from XRD determining embodiment 6 is co-doped with the thing phase composition structure of many iron thin films of bismuth ferrite, such as Fig. 1 institutes
Show, the film belongs to trigonal crystal structure, space group is R3c:H and R3m:R coexists, the appearance without impurity.SEM determines embodiment 6
Obtained LaSrMnCo is co-doped with the microscopic appearance of many iron thin films of bismuth ferrite.Surveyed with Radiant Multiferroic ferroelectricities analyzer
LaSrMnCo made from examination embodiment 6 is co-doped with the ferroelectric properties of many iron thin films of bismuth ferrite, as shown in Fig. 2 frequency is 1kHz, electric field
During for 700kV/cm, the residual polarization value of the film is 191 μ C/cm2, coercive field is 222kV/cm.Use Agilent E4980A
LaSrMnCo made from accurate LCR tables testing example 6 is co-doped with the dielectric properties of many iron thin films of bismuth ferrite, as shown in figure 3, frequency
During for 1kHz, the dielectric constant of the film is 774.
Above said content is to combine specific preferred embodiment further description made for the present invention, is not
Whole or unique embodiment, those of ordinary skill in the art are by reading description of the invention to technical solution of the present invention
Any equivalent conversion taken, is that claim of the invention is covered.
Claims (10)
1. a kind of LaSrMnCo is co-doped with many iron thin films of bismuth ferrite, it is characterised in that it is thin that the LaSrMnCo is co-doped with many iron of bismuth ferrite
Film is Bi0.97-xLaxSr0.03Fe0.94Mn0.04Co0.02O3Film, x=0.03~0.18, its structure is trigonal crystal structure, and space group is
R3c:H and R3m:R coexists.
2. LaSrMnCo according to claim 1 is co-doped with many iron thin films of bismuth ferrite, it is characterised in that the LaSrMnCo is total to
Residual polarization value of many iron thin films of bismuth ferrite under 700kV/cm electric fields is mixed for 191~230 μ C/cm2, coercive field be 222~
274kV/cm。
3. LaSrMnCo according to claim 1 is co-doped with many iron thin films of bismuth ferrite, it is characterised in that the LaSrMnCo is total to
It is 488~774 to mix dielectric constant of many iron thin films of bismuth ferrite under 1kHz frequencies.
4. the LaSrMnCo in claim 1-3 described in any one is co-doped with the preparation method of many iron thin films of bismuth ferrite, its feature
It is, comprises the following steps：
Step 1：It is in molar ratio (1.02-x):x:0.03:0.94:0.04:0.02 by bismuth nitrate, lanthanum nitrate, strontium nitrate, nitric acid
Iron, manganese acetate and cobalt nitrate are dissolved in ethylene glycol monomethyl ether, are stirring evenly and then adding into acetic anhydride, are continued to stir, are obtained forerunner
Liquid；Wherein x=0.03~0.18；
Step 2：Precursor liquid is spin-coated on FTO/glass substrates, wet film is obtained, wet film dries after spin coating at 190~210 DEG C
Dry film is baked to obtain, is annealed in atmosphere at 540~550 DEG C, obtains crystalline state Bi0.97-xLaxSr0.03Fe0.94Mn0.04Co0.02O3It is thin
Film；
Step 3：By crystalline state Bi0.97-xLaxSr0.03Fe0.94Mn0.04Co0.02O3Film cooling is to room temperature, and repeat step 2 is until reaching
Required thickness, that is, obtain LaSrMnCo and be co-doped with many iron thin films of bismuth ferrite.
5. LaSrMnCo according to claim 4 is co-doped with the preparation method of many iron thin films of bismuth ferrite, it is characterised in that described
The total concentration of metal ion is 0.2~0.4mol/L in precursor liquid in step 1.
6. LaSrMnCo according to claim 4 is co-doped with the preparation method of many iron thin films of bismuth ferrite, it is characterised in that described
Ethylene glycol monomethyl ether and the volume ratio of acetic anhydride are (2.5~3.5) in precursor liquid:1.
7. LaSrMnCo according to claim 4 is co-doped with the preparation method of many iron thin films of bismuth ferrite, it is characterised in that described
Step 2 first cleans up FTO/glass substrates before carrying out, and then irradiates under ultraviolet light, reaches FTO/glass substrate surfaces
To atomic cleanliness degree.
8. LaSrMnCo according to claim 4 is co-doped with the preparation method of many iron thin films of bismuth ferrite, it is characterised in that described
Spin coating rotating speed in step 2 during spin coating is 3600~4200r/min, and spin coating time is 12~18s.
9. LaSrMnCo according to claim 4 is co-doped with the preparation method of many iron thin films of bismuth ferrite, it is characterised in that described
Baking time in step 2 after spin coating is 6~8min.
10. LaSrMnCo according to claim 4 is co-doped with the preparation method of many iron thin films of bismuth ferrite, it is characterised in that institute
It is 20~25min to state the annealing time in step 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710254704.5A CN107117830B (en) | 2017-04-18 | 2017-04-18 | LaSrMnCo co-doped bismuth ferrite multiferroic film and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710254704.5A CN107117830B (en) | 2017-04-18 | 2017-04-18 | LaSrMnCo co-doped bismuth ferrite multiferroic film and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107117830A true CN107117830A (en) | 2017-09-01 |
| CN107117830B CN107117830B (en) | 2019-12-13 |
Family
ID=59725945
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710254704.5A Active CN107117830B (en) | 2017-04-18 | 2017-04-18 | LaSrMnCo co-doped bismuth ferrite multiferroic film and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107117830B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109111126A (en) * | 2018-09-18 | 2019-01-01 | 陕西科技大学 | A kind of laminated film and preparation method thereof of Mn doping regulation resistance switch effect |
| CN109111127A (en) * | 2018-09-18 | 2019-01-01 | 陕西科技大学 | A kind of BLSFMC/CMFO film and preparation method thereof with resistance switch effect |
| 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 |
| CN111074244A (en) * | 2018-10-19 | 2020-04-28 | 营口理工学院 | Nickel-cerium co-doped bismuth ferrite film material and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104445996A (en) * | 2014-12-11 | 2015-03-25 | 陕西科技大学 | Multiferroic Bi0.96-xSr0.04RExFe0.94Mn0.04Cr0.02O3-NiFe2O4 composite film and preparation method thereof |
| CN105906221A (en) * | 2016-03-29 | 2016-08-31 | 陕西科技大学 | Multiferroic Bi0.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3-CuFe2O4 composite film and preparation method thereof |
-
2017
- 2017-04-18 CN CN201710254704.5A patent/CN107117830B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104445996A (en) * | 2014-12-11 | 2015-03-25 | 陕西科技大学 | Multiferroic Bi0.96-xSr0.04RExFe0.94Mn0.04Cr0.02O3-NiFe2O4 composite film and preparation method thereof |
| CN105906221A (en) * | 2016-03-29 | 2016-08-31 | 陕西科技大学 | Multiferroic Bi0.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3-CuFe2O4 composite film and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| GUOQIANG TAN: "Structural and multiferroic properties of Bi0.922xHo0.08SrxFe0.97Mn0.03O3 thin films", 《JOURNAL OF MATERIAL SCIENCE》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109111126A (en) * | 2018-09-18 | 2019-01-01 | 陕西科技大学 | A kind of laminated film and preparation method thereof of Mn doping regulation resistance switch effect |
| CN109111127A (en) * | 2018-09-18 | 2019-01-01 | 陕西科技大学 | A kind of BLSFMC/CMFO film and preparation method thereof with resistance switch effect |
| CN109111127B (en) * | 2018-09-18 | 2021-06-29 | 陕西科技大学 | BLSFMC/CMFO film with resistance switching effect and preparation method thereof |
| CN109111126B (en) * | 2018-09-18 | 2021-10-29 | 陕西科技大学 | Mn-doped composite film for regulating resistance switching effect and preparation method thereof |
| CN111074244A (en) * | 2018-10-19 | 2020-04-28 | 营口理工学院 | Nickel-cerium co-doped bismuth ferrite film material and preparation method 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107117830B (en) | 2019-12-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107117830A (en) | A kind of LaSrMnCo is co-doped with many iron thin films of bismuth ferrite and preparation method thereof | |
| CN107032631B (en) | A kind of GdSrMnCo is co-doped with more iron thin films of bismuth ferrite and preparation method thereof | |
| CN105837196A (en) | Bi0.92-xHo0.08AExFe0.97Mn0.03O3-Zn1-yNiyFe2O4 ferromagnetic composite film and preparation method thereof | |
| CN105271798B (en) | A kind of high-ferromagnetic can be with the Bi of ferroelectric properties0.9Er0.1Fe1‑xCoxO3Film and preparation method thereof | |
| CN103723770B (en) | High-dielectric-constant Bi0.92Ho0.08Fe[1-x]MnxO3 ferroelectric film and preparation method thereof | |
| CN107082576A (en) | A kind of HoSrMnNi is co-doped with many iron thin films of bismuth ferrite and preparation method thereof | |
| CN105906221B (en) | A kind of multiferroic Bi0.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3-CuFe2O4Composite membrane and preparation method thereof | |
| CN104478228B (en) | A kind of Bi0.85‑xPr0.15AExFe0.97Mn0.03O3Ferroelectric thin film and preparation method thereof | |
| CN104478229B (en) | A kind of Bi1-xrExfe0.96co0.02mn0.02o3ferroelectric thin film and preparation method thereof | |
| CN103771528B (en) | A kind of Bi of high-k 1-Xho xfeO 3ferroelectric membranc and preparation method thereof | |
| CN105859152B (en) | A kind of high magnetism Bi0.96Sr0.04FeO3Base/CoFe2O4Laminated film and preparation method thereof | |
| CN103601249B (en) | A kind of high remnant polarization and high-k BiFe 0.96-ymn 0.04cr yo 3ferroelectric membranc and preparation method thereof | |
| CN105845436A (en) | SrFeO2.5 magnetic thin film and preparation method therefor | |
| CN103739019B (en) | A kind of BiFe of high remnant polarization 1-xmn xo 3ferroelectric membranc and preparation method thereof | |
| CN107082579A (en) | A kind of HoSrMnZn is co-doped with many iron thin films of bismuth ferrite and preparation method thereof | |
| CN104478230A (en) | Bi[0.92-x]Ho0.08AExFe0.97Mn0.03O3 multiferroic film and preparation method thereof | |
| CN105837199B (en) | A kind of Bi0.96Sr0.04Fe0.98-xMnxCo0.02O3More iron thin films and preparation method thereof | |
| CN109336406B (en) | BGSFMC/CFGO composite film with symmetrical rectangular hysteresis loop and preparation method thereof | |
| CN109205683B (en) | BLSFMC/CFLO composite film with symmetrical rectangular hysteresis loop and preparation method thereof | |
| CN106517814A (en) | (012) crystal face preferred orientation Bi1-xYbxFe0.98Mn0.02O3 ferroelectric film and preparing method thereof | |
| CN107021649B (en) | A kind of LaSrMnCo is co-doped with bismuth ferrite superlattice film and preparation method thereof | |
| CN109467318B (en) | BGSFMC/CNFO multiferroic composite film and preparation method thereof | |
| CN105859273B (en) | A kind of 2-2 type BiFeO3-CuFe2O4 laminated film and preparation method thereof | |
| CN109111126B (en) | Mn-doped composite film for regulating resistance switching effect and preparation method thereof | |
| CN107082577B (en) | A kind of HoSrMnZn is co-doped with bismuth ferrite/Mn and mixes zinc ferrite laminated film and preparation method thereof |
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 | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20240802 Address after: 810, 8th Floor, Building 10, Courtyard 1, Tianxing Street, Fangshan District, Beijing, 102400 Patentee after: Beijing Zhichanhui Technology Co.,Ltd. Country or region after: China Address before: No. 1, Weiyang District university garden, Xi'an, Shaanxi Province, Shaanxi Patentee before: SHAANXI University OF SCIENCE & TECHNOLOGY Country or region before: China |
|
| TR01 | Transfer of patent right |