CN104478235A - A multiferroic Bi0.98-xSr0.02RExFe0.97Mn0.03O3-CuFe2O4 composite film and its preparation method - Google Patents
A multiferroic Bi0.98-xSr0.02RExFe0.97Mn0.03O3-CuFe2O4 composite film and its preparation method Download PDFInfo
- Publication number
- CN104478235A CN104478235A CN201410764963.9A CN201410764963A CN104478235A CN 104478235 A CN104478235 A CN 104478235A CN 201410764963 A CN201410764963 A CN 201410764963A CN 104478235 A CN104478235 A CN 104478235A
- Authority
- CN
- China
- Prior art keywords
- cufe
- film
- crystalline
- multiferroic
- precursor solution
- 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
- 239000002131 composite material Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229910016516 CuFe2O4 Inorganic materials 0.000 title 1
- 239000010408 film Substances 0.000 claims abstract description 189
- 239000000758 substrate Substances 0.000 claims abstract description 64
- 239000002243 precursor Substances 0.000 claims abstract description 55
- 239000010409 thin film Substances 0.000 claims abstract 7
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 71
- 239000011521 glass Substances 0.000 claims description 41
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 29
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 24
- 239000002904 solvent Substances 0.000 claims description 20
- 230000003749 cleanliness Effects 0.000 claims description 18
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 17
- 229910002651 NO3 Inorganic materials 0.000 claims description 10
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 10
- 239000013078 crystal Substances 0.000 claims description 10
- 150000002500 ions Chemical class 0.000 claims description 10
- 229910021645 metal ion Inorganic materials 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 6
- 229910052689 Holmium Inorganic materials 0.000 claims description 6
- 229910052765 Lutetium Inorganic materials 0.000 claims description 6
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 6
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 6
- 229910052684 Cerium Inorganic materials 0.000 claims description 5
- 229910052691 Erbium Inorganic materials 0.000 claims description 5
- 229910052693 Europium Inorganic materials 0.000 claims description 5
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 5
- 229910052779 Neodymium Inorganic materials 0.000 claims description 5
- 229910052772 Samarium Inorganic materials 0.000 claims description 5
- 229910052771 Terbium Inorganic materials 0.000 claims description 5
- 229910052775 Thulium Inorganic materials 0.000 claims description 5
- 238000000137 annealing Methods 0.000 claims description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims description 5
- 239000011572 manganese Substances 0.000 claims 23
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims 4
- 238000002156 mixing Methods 0.000 claims 2
- 238000004026 adhesive bonding Methods 0.000 claims 1
- 239000010949 copper Substances 0.000 claims 1
- 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 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims 1
- 238000004528 spin coating Methods 0.000 abstract description 42
- 230000005294 ferromagnetic effect Effects 0.000 abstract description 7
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- PPNKDDZCLDMRHS-UHFFFAOYSA-N dinitrooxybismuthanyl nitrate Chemical compound [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 description 30
- 239000012528 membrane Substances 0.000 description 29
- 239000007788 liquid Substances 0.000 description 26
- 239000003292 glue Substances 0.000 description 25
- 239000000243 solution Substances 0.000 description 19
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 16
- 230000005855 radiation Effects 0.000 description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- 238000004506 ultrasonic cleaning Methods 0.000 description 14
- 239000000463 material Substances 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- 238000004140 cleaning Methods 0.000 description 7
- 238000005520 cutting process Methods 0.000 description 7
- 239000012153 distilled water Substances 0.000 description 7
- 238000011010 flushing procedure Methods 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 230000005291 magnetic effect Effects 0.000 description 6
- 229910052761 rare earth metal Inorganic materials 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000005684 electric field Effects 0.000 description 4
- 238000003980 solgel method Methods 0.000 description 4
- 230000018199 S phase Effects 0.000 description 3
- 229910052797 bismuth Inorganic materials 0.000 description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000005307 ferromagnetism Effects 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- 229910000859 α-Fe Inorganic materials 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000005621 ferroelectricity Effects 0.000 description 2
- 230000005415 magnetization Effects 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 238000004549 pulsed laser deposition Methods 0.000 description 2
- 230000005536 Jahn Teller effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000002305 electric material Substances 0.000 description 1
- GAGGCOKRLXYWIV-UHFFFAOYSA-N europium(3+);trinitrate Chemical compound [Eu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GAGGCOKRLXYWIV-UHFFFAOYSA-N 0.000 description 1
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
- MWFSXYMZCVAQCC-UHFFFAOYSA-N gadolinium(iii) nitrate Chemical compound [Gd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O MWFSXYMZCVAQCC-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000005690 magnetoelectric effect Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000001451 molecular beam epitaxy Methods 0.000 description 1
- CFYGEIAZMVFFDE-UHFFFAOYSA-N neodymium(3+);trinitrate Chemical compound [Nd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CFYGEIAZMVFFDE-UHFFFAOYSA-N 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- YWECOPREQNXXBZ-UHFFFAOYSA-N praseodymium(3+);trinitrate Chemical compound [Pr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YWECOPREQNXXBZ-UHFFFAOYSA-N 0.000 description 1
- 230000005616 pyroelectricity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 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
- C03C17/3405—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 organic materials
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/70—Properties of coatings
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/11—Deposition methods from solutions or suspensions
- C03C2218/116—Deposition methods from solutions or suspensions by spin-coating, centrifugation
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Laminated Bodies (AREA)
Abstract
一种多铁性Bi0.98-xSr0.02RExFe0.97Mn0.03O3-CuFe2O4复合膜及其制备方法，该复合膜包括复合在一起的Bi0.98-xSr0.02RExFe0.97Mn0.03O3晶态膜和CuFe2O4晶态膜；制备时先分别配制Bi0.98-xSr0.02RExFe0.97Mn0.03O3前驱体溶液和CuFe2O4前驱液；然后在基片上旋涂制备多层CuFe2O4膜，再在CuFe2O4膜上旋涂制备多层Bi0.98-xSr0.02RExFe0.97Mn0.03O3膜，即得目标产物。本发明设备要求简单，制备的薄膜均匀性好，掺杂量易控，提高了薄膜的铁电和铁磁性能，有效降低了薄膜的漏电流密度。A multiferroic Bi 0.98-x Sr 0.02 RE x Fe 0.97 Mn 0.03 O 3 -CuFe 2 O 4 composite film and its preparation method, the composite film includes Bi 0.98-x Sr 0.02 RE x Fe 0.97 Mn composited together 0.03 O 3 crystalline film and CuFe 2 O 4 crystalline film; when preparing, firstly prepare Bi 0.98-x Sr 0.02 RE x Fe 0.97 Mn 0.03 O 3 precursor solution and CuFe 2 O 4 precursor solution respectively; then spin on the substrate Coating to prepare a multilayer CuFe 2 O 4 film, and then spin coating on the CuFe 2 O 4 film to prepare a multilayer Bi 0.98-x Sr 0.02 RE x Fe 0.97 Mn 0.03 O 3 film to obtain the target product. The invention has simple equipment requirements, good uniformity of the prepared thin film, easy control of doping amount, improved ferroelectric and ferromagnetic properties of the thin film, and effectively reduces the leakage current density of the thin film.
Description
Technical field
The invention belongs to field of functional materials, relate to multiferroic Bi
0.98-xsr
0.02rE
xfe
0.97mn
0.03o
3-CuFe
2o
4composite membrane and preparation method thereof.
Background technology
BiFeO
3be a kind of typical single-phase multiferroic perovskite material, at room temperature there is ferroelectricity (T simultaneously
c~ 1103k) and ferromegnetism (T
n~ 640k).Due to BiFeO
3material has magnetoelectric effect, has formed the research boom of a worldwide single-phase magnetic electric material in recent years.Along with the development of microelectronics, photoelectron and sensor technology, more and more higher to the requirement of material property, ferroelectric membranc, because of its good ferroelectric, the character such as piezoelectricity, dielectric, pyroelectricity, becomes the critical function material that can be widely used in the fields such as microtronics, photoelectronics, integrated optics and microelectromechanical systems.
But, pure phase BiFeO
3there is larger leakage current, the BiFeO that has its source in that leakage conductance exists
3middle existence is unstable, volatile Bi
3+ion, along with Bi
3+the volatilization of ion, sintering process can form Lacking oxygen in the material, and causes Fe
3+fluctuation (the Fe of ion combination valency
3+to Fe
2+ion is changed), produce certain conductance.Lacking oxygen in perovskite material also play the effect of space charge, and the increase of space charge concentration can cause farmland to produce pinning effect.And under the effect of electric field, the displacement of Lacking oxygen also forms leakage current, causes the decline of residual polarization.BiFeO
3leakage current large in material causes him cannot obtain saturated ferroelectric hysteresis loop and its weak ferromagnetism essence, thus limits the practical application of this material.
Summary of the invention
The object of the present invention is to provide a kind of multiferroic Bi
0.98-xsr
0.02rE
xfe
0.97mn
0.03o
3-CuFe
2o
4composite membrane and preparation method thereof, effectively can reduce BiFeO
3leakage current, improve its ferroelectric and ferromagnetic property simultaneously.
To achieve these goals, the present invention adopts following technical scheme:
A kind of multiferroic Bi
0.98-xsr
0.02rE
xfe
0.97mn
0.03o
3-CuFe
2o
4composite membrane, comprises the lower membrane and upper layer film that are combined with each other, and wherein lower membrane is CuFe
2o
4crystalline state film, upper layer film is Bi
0.98-xsr
0.02rE
xfe
0.97mn
0.03o
3crystalline state film, RE is La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu, x=0 ~ 0.15.
Described Bi
0.98-xsr
0.02rE
xfe
0.97mn
0.03o
3the crystal formation of crystalline state film is tripartite's phase, and space structure group is R3m:R, and unit cell parameters is a=b=c=3.9634, α=β=γ=89.72 °; CuFe
2o
4the crystal formation of crystalline state film is Emission in Cubic, and space structure group is Fd-3m (227).
Described x=0.03 ~ 0.15.
A kind of multiferroic Bi
0.98-xsr
0.02rE
xfe
0.97mn
0.03o
3-CuFe
2o
4the preparation method of composite membrane, comprises the following steps:
Step 1, by iron nitrate and cupric nitrate in molar ratio for 1:2 is dissolved in ethylene glycol monomethyl ether, adds diacetyl oxide again after stirring, obtains CuFe
2o
4precursor liquid, CuFe
2o
4in precursor liquid, the concentration of Cu ion is 0.15 ~ 0.25mol/L;
Step 2, is dissolved in solvent for 1.03-x:0.02:x:0.97:0.03 by Bismuth trinitrate, strontium nitrate, nitric acid RE, iron nitrate and manganous nitrate in molar ratio, obtains Bi
0.98-xsr
0.02rE
xfe
0.97mn
0.03o
3precursor solution, Bi
0.98-xsr
0.02rE
xfe
0.97mn
0.03o
3in precursor solution, the total concn of metal ion is 0.25 ~ 0.35mol/L, RE is La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu, x=0 ~ 0.15, and solvent is the mixed solution of ethylene glycol monomethyl ether and acetic anhydride;
Step 3, adopts spin-coating method spin coating CuFe on FTO/glass substrate
2o
4precursor liquid, obtains CuFe
2o
4film, CuFe
2o
4film toasts to obtain dry film after even glue at 180 ~ 210 DEG C, then anneals in atmosphere at 580 ~ 600 DEG C, obtains crystalline state CuFe
2o
4film;
Step 4, treats crystalline state CuFe
2o
4after film cooling, at crystalline state CuFe
2o
4repeating step 3 on film, until reach desired thickness, obtains CuFe
2o
4crystalline state film;
Step 5, at CuFe
2o
4spin coating Bi on crystalline state film
0.98-xsr
0.02rE
xfe
0.97mn
0.03o
3precursor solution, obtains Bi
0.98-xsr
0.02rE
xfe
0.97mn
0.03o
3film, Bi
0.98-xsr
0.02rE
xfe
0.97mn
0.03o
3film toasts to obtain dry film after even glue at 180 ~ 210 DEG C, then anneals in atmosphere at 540 ~ 550 DEG C, obtains crystalline state Bi
0.98-xsr
0.02rE
xfe
0.97mn
0.03o
3film;
Step 6, treats crystalline state Bi
0.98-xsr
0.02rE
xfe
0.97mn
0.03o
3after film cooling, at crystalline state Bi
0.98-xsr
0.02rE
xfe
0.97mn
0.03o
3repeating step 5 on film, until reach desired thickness, obtains multiferroic Bi
0.98-xsr
0.02rE
xfe
0.97mn
0.03o
3-CuFe
2o
4composite membrane.
Described CuFe
2o
4in precursor liquid, the volume ratio of ethylene glycol monomethyl ether and acetic anhydride is (2.5 ~ 3.5): 1;
In described solvent, the volume ratio of ethylene glycol monomethyl ether and acetic anhydride is (2.5 ~ 3.5): 1.
Described step 3 is first cleaned FTO/glass substrate before carrying out, then radiation treatment under ultraviolet light, makes FTO/glass substrate surface reach atomic cleanliness degree, then spin coating CuFe
2o
4precursor liquid;
Described step 5 before carrying out first to CuFe
2o
4crystalline state film carries out UV-irradiation process, makes CuFe
2o
4crystalline state film surface reaches atomic cleanliness degree, then spin coating Bi
0.98-xsr
0.02rE
xfe
0.97mn
0.03o
3precursor solution.
Even glue rotating speed in described step 3 and step 5 is 3800 ~ 4100r/min, and spin coating time is 12 ~ 15s.
Baking time in described step 3 and step 5 after even glue is 8 ~ 12min.
In described step 3, annealing time is 7 ~ 9min; In step 5, annealing time is 8 ~ 12min.
Crystalline state CuFe
2o
4the number of plies of film is 4 ~ 8 layers, crystalline state Bi
0.98-xsr
0.02rE
xfe
0.97mn
0.03o
3the number of plies of film is 8 ~ 12 layers.
Relative to prior art, beneficial effect of the present invention is:
1. multiferroic Bi provided by the invention
0.98-xsr
0.02rE
xfe
0.97mn
0.03o
3-CuFe
2o
4the preparation method of composite membrane, selects lanthanon rare earth elements RE and alkaline earth element Sr to carry out BiFeO
3a position doping, select transient metal Mn carry out BiFeO
3b position doping, because the ionic radius of rare earth elements RE is comparable to Bi
3+, the radius of Mn is less than Fe
3+, after doping, rare earth element and Mn can be melting into into lattice admittedly, and can make the approximate bismuth ferrite crystal lattices distortion in perovskite structure originally, structural aberration aggravates, simultaneously due to Sr
2+to Bi
3+further substitute, and Mn element appraising at the current rate in annealing process, the volatilization of the Bi that can effectively draw up, reduces Fe in film
2+with the content of Lacking oxygen, thus the polarizability of enhanced film under extra electric field, discharge its macroscopic magnetization simultaneously, improve ferroelectricity and the ferromegnetism of film.But due to BiFeO
3itself there is the essence of weak magnetic, so the present invention is in conjunction with CuFe
2o
4film meets with it.CuFe
2o
4have very strong magnetic, its magnetic coercive field is very little again simultaneously, is desirable matrix material.The present invention is by alkaline earth element Sr, rare earth elements RE and transition metal Mn element codoped BiFeO
3, and in conjunction with ferromagnetism CuFe
2o
4, formed and there is superior ferroelectric and ferromagnetic Bi simultaneously
0.98-xsr
0.02rE
xfe
0.97mn
0.03o
3-CuFe
2o
4laminated film.
2. at present for the preparation of BiFeO
3the method of film has a lot, as chemical Vapor deposition process (CVD), magnetron sputtering method (rf magnetron sputtering), deposition of metal organic method (MOD), metal-organic chemical vapor deposition equipment method (MOCVD), liquid phase deposition (LPD), molecular beam epitaxy (MBE), pulsed laser deposition (PLD), sol-gel method (Sol-Gel) etc.Compare additive method, Sol-Gel method due to equipment simple, reaction is easily carried out, temperature of reaction is lower, easy to operate, be suitable for preparing film on large surface and surface in irregular shape, easily realize the Uniform Doped on molecular level, and the advantage such as chemical composition controllable precise and be widely used for preparing ferroelectric material.Sol-gel method is adopted in the present invention, by rare earth elements RE, alkaline earth element Sr and transition metal Mn element codoped, simultaneously composite Cu Fe
2o
4film, Bi prepared by FTO substrate
0.98-xsr
0.02rE
xfe
0.97mn
0.03o
3-CuFe
2o
4composite membrane.Present device requires simple, and experiment condition easily reaches, and doping easily controls, by doping and CuFe
2o
4the compound of film can increase substantially the ferroelectric of film and ferromagnetic property, obtained Bi
0.98-xsr
0.02rE
xfe
0.97mn
0.03o
3-CuFe
2o
4composite membrane good uniformity, has lower leakage current density and higher anti-breakdown electric field, possesses comparatively excellent ferroelectric and ferromegnetism simultaneously.
3. multiferroic Bi provided by the invention
0.98-xsr
0.02rE
xfe
0.97mn
0.03o
3-CuFe
2o
4composite membrane, being originally similar to doped with rare-earth elements RE, alkaline earth element Sr and transition metal Mn in the bismuth ferrite crystal lattices in perovskite structure, make bismuth ferrite crystal lattices distortion, structural aberration aggravates, and reduces Fe in film simultaneously
2+with the content of Lacking oxygen, thus the polarizability of enhanced film under extra electric field, discharge its macroscopic magnetization simultaneously, improve ferroelectric properties and the ferromagnetic property of film, reduce the leakage current density of film, and in conjunction with the CuFe of ferromagnetism, low coercive field
2o
4film, makes multiferroic Bi of the present invention
0.98-xsr
0.02rE
xfe
0.97mn
0.03o
3-CuFe
2o
4composite membrane has excellent ferroelectric properties and ferromagnetic property simultaneously.
Accompanying drawing explanation
Fig. 1 is Bi prepared by the present invention
0.83sr
0.02pr
0.15fe
0.97mn
0.03o
3the XRD figure of crystalline state film;
Fig. 2 is Bi prepared by the present invention
0.83sr
0.02pr
0.15fe
0.97mn
0.03o
3the Raman spectrogram of crystalline state film;
Fig. 3 is Bi prepared by the present invention
0.83sr
0.02pr
0.15fe
0.97mn
0.03o
3the SEM figure of crystalline state film;
Fig. 4 is CuFe prepared by the present invention
2o
4the XRD figure of crystalline state film.
Embodiment
Below in conjunction with accompanying drawing and the preferred embodiment of the invention, the present invention is described in further detail.
Multiferroic Bi provided by the invention
0.98-xsr
0.02rE
xfe
0.97mn
0.03o
3-CuFe
2o
4composite membrane, comprises the lower membrane and upper layer film that are combined with each other, and wherein lower membrane is CuFe
2o
4crystalline state film, its crystal formation is Emission in Cubic, and space structure group is Fd-3m (227); Upper layer film is Bi
0.98-xsr
0.02rE
xfe
0.97mn
0.03o
3crystalline state film, its crystal formation is tripartite's phase, and space structure group is R3m:R, unit cell parameters is a=b=c=3.9634, α=β=γ=89.72 °, and RE is La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu, x=0 ~ 0.15, preferred x=0.03 ~ 0.15.
Embodiment 1
Step 1, by iron nitrate and cupric nitrate in molar ratio for 1:2 is dissolved in ethylene glycol monomethyl ether, after stirring 30min, then adds diacetyl oxide, obtains the stable CuFe that Cu ionic concn is 0.15mol/L
2o
4precursor liquid, CuFe
2o
4in precursor liquid, the volume ratio of ethylene glycol monomethyl ether and acetic anhydride is 3:1;
Step 2, is dissolved in (x=0, Bismuth trinitrate excessive 5%) in solvent for 1.03:0.02:0.97:0.03 in molar ratio by Bismuth trinitrate, strontium nitrate, iron nitrate and manganous nitrate, the total concn obtaining metal ion is the stable Bi of 0.25mol/L
0.98sr
0.02fe
0.97mn
0.03o
3precursor solution; Solvent is volume ratio is the ethylene glycol monomethyl ether of 3:1 and the mixed solution of acetic anhydride;
Step 3, selects FTO/glass substrate to be substrate, the FTO/glass substrate of well cutting is placed in washing composition, acetone, ethanol ultrasonic cleaning successively, with a large amount of distilled water flushing substrate after each ultrasonic cleaning 10min, finally dry up with nitrogen.Then FTO/glass substrate is put into 60 DEG C of baking oven baking 5min, take out and leave standstill to room temperature.Again the FTO/glass substrate of cleaning is placed in ultraviolet radiation instrument and irradiates 40min, substrate surface is reached " atomic cleanliness degree ".Adopt spin-coating method spin coating CuFe on FTO/glass substrate
2o
4precursor liquid, preparation CuFe
2o
4film, even glue rotating speed is 3800r/min, and spin coating time is 15s, after even cementing bundle, toasts 12min and obtain dry film at 180 DEG C of temperature, then the 9min that anneals layer by layer in air at 580 DEG C of temperature, obtains crystalline state CuFe
2o
4film;
Step 4, treats crystalline state CuFe
2o
4after film cooling, at crystalline state CuFe
2o
4repeating step 3 on film, repeats 3 times, obtains CuFe
2o
4crystalline state film;
Step 5, by CuFe
2o
4crystalline state film is placed in ultraviolet radiation instrument and irradiates 40min, makes its surface reach atomic cleanliness degree; Again at CuFe
2o
4spin coating Bi on crystalline state film
0.98sr
0.02fe
0.97mn
0.03o
3precursor solution, even glue rotating speed is 3800r/min, and spin coating time is 15s, after the even cementing bundle of even glue, toasts 12min and obtain dry film at 180 DEG C, then the 12min that anneals layer by layer in air at 540 DEG C, obtains crystalline state Bi
0.98sr
0.02fe
0.97mn
0.03o
3film;
Step 6, treats crystalline state Bi
0.98sr
0.02fe
0.97mn
0.03o
3after film cooling, at crystalline state Bi
0.98sr
0.02fe
0.97mn
0.03o
3repeating step 5 on film, repeats 7 times, obtains multiferroic Bi
0.98sr
0.02fe
0.97mn
0.03o
3-CuFe
2o
4composite membrane.
Embodiment 2
Step 1, by iron nitrate and cupric nitrate in molar ratio for 1:2 is dissolved in ethylene glycol monomethyl ether, after stirring 30min, then adds diacetyl oxide, obtains the stable CuFe that Cu ionic concn is 0.25mol/L
2o
4precursor liquid, CuFe
2o
4in precursor liquid, the volume ratio of ethylene glycol monomethyl ether and acetic anhydride is 2.5:1;
Step 2, Bismuth trinitrate, strontium nitrate, cerous nitrate, iron nitrate and manganous nitrate are dissolved in (RE=Ce in solvent for 1:0.02:0.03:0.97:0.03 in molar ratio, x=0.03, Bismuth trinitrate excessive 5%), the total concn obtaining metal ion is the stable Bi of 0.35mol/L
0.95sr
0.02ce
0.03fe
0.97mn
0.03o
3precursor solution; Solvent is volume ratio is the ethylene glycol monomethyl ether of 2.5:1 and the mixed solution of acetic anhydride;
Step 3, selects FTO/glass substrate to be substrate, the FTO/glass substrate of well cutting is placed in washing composition, acetone, ethanol ultrasonic cleaning successively, with a large amount of distilled water flushing substrate after each ultrasonic cleaning 10min, finally dry up with nitrogen.Then FTO/glass substrate is put into 60 DEG C of baking oven baking 5min, take out and leave standstill to room temperature.Again the FTO/glass substrate of cleaning is placed in ultraviolet radiation instrument and irradiates 40min, substrate surface is reached " atomic cleanliness degree ".Adopt spin-coating method spin coating CuFe on FTO/glass substrate
2o
4precursor liquid, preparation CuFe
2o
4film, even glue rotating speed is 3900r/min, and spin coating time is 14s, after even cementing bundle, toasts 11min and obtain dry film at 190 DEG C of temperature, then the 8min that anneals layer by layer in air at 590 DEG C of temperature, obtains crystalline state CuFe
2o
4film;
Step 4, treats crystalline state CuFe
2o
4after film cooling, at crystalline state CuFe
2o
4repeating step 3 on film, repeats 7 times, obtains CuFe
2o
4crystalline state film;
Step 5, by CuFe
2o
4crystalline state film is placed in ultraviolet radiation instrument and irradiates 40min, makes its surface reach atomic cleanliness degree; Again at CuFe
2o
4spin coating Bi on crystalline state film
0.95sr
0.02ce
0.03fe
0.97mn
0.03o
3precursor solution, even glue rotating speed is 3900r/min, and spin coating time is 14s, after the even cementing bundle of even glue, toasts 11min and obtain dry film at 190 DEG C, then the 10min that anneals layer by layer in air at 545 DEG C, obtains crystalline state Bi
0.95sr
0.02ce
0.03fe
0.97mn
0.03o
3film;
Step 6, treats crystalline state Bi
0.95sr
0.02ce
0.03fe
0.97mn
0.03o
3after film cooling, at crystalline state Bi
0.95sr
0.02ce
0.03fe
0.97mn
0.03o
3repeating step 5 on film, repeats 8 times, obtains multiferroic Bi
0.95sr
0.02ce
0.03fe
0.97mn
0.03o
3-CuFe
2o
4composite membrane.
Embodiment 3
Step 1, by iron nitrate and cupric nitrate in molar ratio for 1:2 is dissolved in ethylene glycol monomethyl ether, after stirring 30min, then adds diacetyl oxide, obtains the stable CuFe that Cu ionic concn is 0.22mol/L
2o
4precursor liquid, CuFe
2o
4in precursor liquid, the volume ratio of ethylene glycol monomethyl ether and acetic anhydride is 3.5:1;
Step 2, Bismuth trinitrate, strontium nitrate, neodymium nitrate, iron nitrate and manganous nitrate are dissolved in (RE=Nd in solvent for 0.98:0.02:0.05:0.97:0.03 in molar ratio, x=0.05, Bismuth trinitrate excessive 5%), the total concn obtaining metal ion is the stable Bi of 0.28mol/L
0.93sr
0.02nd
0.05fe
0.97mn
0.03o
3precursor solution; Solvent is volume ratio is the ethylene glycol monomethyl ether of 3.5:1 and the mixed solution of acetic anhydride;
Step 3, selects FTO/glass substrate to be substrate, the FTO/glass substrate of well cutting is placed in washing composition, acetone, ethanol ultrasonic cleaning successively, with a large amount of distilled water flushing substrate after each ultrasonic cleaning 10min, finally dry up with nitrogen.Then FTO/glass substrate is put into 60 DEG C of baking oven baking 5min, take out and leave standstill to room temperature.Again the FTO/glass substrate of cleaning is placed in ultraviolet radiation instrument and irradiates 40min, substrate surface is reached " atomic cleanliness degree ".Adopt spin-coating method spin coating CuFe on FTO/glass substrate
2o
4precursor liquid, preparation CuFe
2o
4film, even glue rotating speed is 4100r/min, and spin coating time is 12s, after even cementing bundle, toasts 8min and obtain dry film at 210 DEG C of temperature, then the 8.5min that anneals layer by layer in air at 585 DEG C of temperature, obtains crystalline state CuFe
2o
4film;
Step 4, treats crystalline state CuFe
2o
4after film cooling, at crystalline state CuFe
2o
4repeating step 3 on film, repeats 4 times, obtains CuFe
2o
4crystalline state film;
Step 5, by CuFe
2o
4crystalline state film is placed in ultraviolet radiation instrument and irradiates 40min, makes its surface reach atomic cleanliness degree; Again at CuFe
2o
4spin coating Bi on crystalline state film
0.93sr
0.02nd
0.05fe
0.97mn
0.03o
3precursor solution, even glue rotating speed is 4100r/min, and spin coating time is 12s, after the even cementing bundle of even glue, toasts 8min and obtain dry film at 210 DEG C, then the 11min that anneals layer by layer in air at 542 DEG C, obtains crystalline state Bi
0.93sr
0.02nd
0.05fe
0.97mn
0.03o
3film;
Step 6, treats crystalline state Bi
0.93sr
0.02nd
0.05fe
0.97mn
0.03o
3after film cooling, at crystalline state Bi
0.93sr
0.02nd
0.05fe
0.97mn
0.03o
3repeating step 5 on film, repeats 10 times, obtains multiferroic Bi
0.93sr
0.02nd
0.05fe
0.97mn
0.03o
3-CuFe
2o
4composite membrane.
Embodiment 4
Step 1, by iron nitrate and cupric nitrate in molar ratio for 1:2 is dissolved in ethylene glycol monomethyl ether, after stirring 30min, then adds diacetyl oxide, obtains the stable CuFe that Cu ionic concn is 0.2mol/L
2o
4precursor liquid, CuFe
2o
4in precursor liquid, the volume ratio of ethylene glycol monomethyl ether and acetic anhydride is 3:1;
Step 2, Bismuth trinitrate, strontium nitrate, praseodymium nitrate, iron nitrate and manganous nitrate are dissolved in (RE=Pr in solvent for 0.88:0.02:0.15:0.97:0.03 in molar ratio, x=0.15, Bismuth trinitrate excessive 5%), the total concn obtaining metal ion is the stable Bi of 0.3mol/L
0.83sr
0.02pr
0.15fe
0.97mn
0.03o
3precursor solution; Solvent is volume ratio is the ethylene glycol monomethyl ether of 3:1 and the mixed solution of acetic anhydride;
Step 3, selects FTO/glass substrate to be substrate, the FTO/glass substrate of well cutting is placed in washing composition, acetone, ethanol ultrasonic cleaning successively, with a large amount of distilled water flushing substrate after each ultrasonic cleaning 10min, finally dry up with nitrogen.Then FTO/glass substrate is put into 60 DEG C of baking oven baking 5min, take out and leave standstill to room temperature.Again the FTO/glass substrate of cleaning is placed in ultraviolet radiation instrument and irradiates 40min, substrate surface is reached " atomic cleanliness degree ".Adopt spin-coating method spin coating CuFe on FTO/glass substrate
2o
4precursor liquid, preparation CuFe
2o
4film, even glue rotating speed is 4000r/min, and spin coating time is 13s, after even cementing bundle, toasts 9min and obtain dry film at 200 DEG C of temperature, then the 7min that anneals layer by layer in air at 600 DEG C of temperature, obtains crystalline state CuFe
2o
4film;
Step 4, treats crystalline state CuFe
2o
4after film cooling, at crystalline state CuFe
2o
4repeating step 3 on film, repeats 5 times, obtains CuFe
2o
4crystalline state film;
Step 5, by CuFe
2o
4crystalline state film is placed in ultraviolet radiation instrument and irradiates 40min, makes its surface reach atomic cleanliness degree; Again at CuFe
2o
4spin coating Bi on crystalline state film
0.83sr
0.02pr
0.15fe
0.97mn
0.03o
3precursor solution, even glue rotating speed is 4000r/min, and spin coating time is 13s, after the even cementing bundle of even glue, toasts 9min and obtain dry film at 200 DEG C, then the 8min that anneals layer by layer in air at 550 DEG C, obtains crystalline state Bi
0.83sr
0.02pr
0.15fe
0.97mn
0.03o
3film;
Step 6, treats crystalline state Bi
0.83sr
0.02pr
0.15fe
0.97mn
0.03o
3after film cooling, at crystalline state Bi
0.83sr
0.02pr
0.15fe
0.97mn
0.03o
3repeating step 5 on film, repeats 9 times, obtains multiferroic Bi
0.83sr
0.02pr
0.15fe
0.97mn
0.03o
3-CuFe
2o
4composite membrane.
XRD is adopted to test multiferroic Bi
0.83sr
0.02pr
0.15fe
0.97mn
0.03o
3-CuFe
2o
4the thing phase composite structure of composite membrane, FE-SEM tests multiferroic Bi
0.83sr
0.02pr
0.15fe
0.97mn
0.03o
3-CuFe
2o
4the pattern of composite film surface.
Get multiferroic Bi prepared by the present invention
0.83sr
0.02pr
0.15fe
0.97mn
0.03o
3-CuFe
2o
4the upper strata Bi of composite membrane
0.83sr
0.02pr
0.15fe
0.97mn
0.03o
3crystalline state film carries out XRD test, and as shown in Figure 1, Fig. 1 and PDF72-2112 standard card coincide result, as can be seen from the figure, and Bi
0.83sr
0.02pr
0.15fe
0.97mn
0.03o
3crystalline state film is the perovskite structure of distortion, does not occur dephasign, and be the R3m:R space structure group of tripartite's phase, its unit cell parameters is a=b=c=3.9634, α=β=γ=89.72 °.
Fig. 2 is Bi
0.83sr
0.02pr
0.15fe
0.97mn
0.03o
3the Raman spectrogram of crystalline state film, with pure phase BiFeO
3film is compared and is had a very large change; Three strongest ones peak in pure phase film is occur A at low frequency
1vibrations mould, and at Bi
0.83sr
0.02pr
0.15fe
0.97mn
0.03o
3in crystalline state film, A
1the peak broadening of mould and intensity obviously reduce, and this is mainly because Pr and Sr substitutes a part of Bi
3+ion, has disperseed Bi-O key to cause; Be positioned at 625cm
-1place E-9 mould peak by force significantly strengthen and higher than A
1mould, this is attributable to Mn
2+ion substitution part Fe
3+ion, Bi
0.83sr
0.02pr
0.15fe
0.97mn
0.03o
3crystalline state film defines [(Fe, Mn) O by Jahn-Teller effect
6] octahedra.
Get multiferroic Bi prepared by the present invention
0.83sr
0.02pr
0.15fe
0.97mn
0.03o
3-CuFe
2o
4the upper strata Bi of composite membrane
0.83sr
0.02pr
0.15fe
0.97mn
0.03o
3crystalline state film carries out SEM test, observes its surface topography, and result as shown in Figure 3, shows the Bi that the present invention obtains
0.83sr
0.02pr
0.15fe
0.97mn
0.03o
3crystalline state film grain development is good, size uniform, surface compact, smooth.
Fig. 4 is the CuFe that the present invention obtains
2o
4the XRD figure of crystalline state film.The CuFe that can obtain pure phase is shown by Fig. 4
2o
4film, it is Fd-3m (227) the space structure group of Emission in Cubic.
Embodiment 5
Step 1, by iron nitrate and cupric nitrate in molar ratio for 1:2 is dissolved in ethylene glycol monomethyl ether, after stirring 30min, then adds diacetyl oxide, obtains the stable CuFe that Cu ionic concn is 0.18mol/L
2o
4precursor liquid, CuFe
2o
4in precursor liquid, the volume ratio of ethylene glycol monomethyl ether and acetic anhydride is 2.8:1;
Step 2, Bismuth trinitrate, strontium nitrate, samaric nitrate, iron nitrate and manganous nitrate are dissolved in (RE=Sm in solvent for 0.93:0.02:0.1:0.97:0.03 in molar ratio, x=0.1, Bismuth trinitrate excessive 5%), the total concn obtaining metal ion is the stable Bi of 0.32mol/L
0.88sr
0.02sm
0.1fe
0.97mn
0.03o
3precursor solution; Solvent is volume ratio is the ethylene glycol monomethyl ether of 2.8:1 and the mixed solution of acetic anhydride;
Step 3, selects FTO/glass substrate to be substrate, the FTO/glass substrate of well cutting is placed in washing composition, acetone, ethanol ultrasonic cleaning successively, with a large amount of distilled water flushing substrate after each ultrasonic cleaning 10min, finally dry up with nitrogen.Then FTO/glass substrate is put into 60 DEG C of baking oven baking 5min, take out and leave standstill to room temperature.Again the FTO/glass substrate of cleaning is placed in ultraviolet radiation instrument and irradiates 40min, substrate surface is reached " atomic cleanliness degree ".Adopt spin-coating method spin coating CuFe on FTO/glass substrate
2o
4precursor liquid, preparation CuFe
2o
4film, even glue rotating speed is 3850r/min, and spin coating time is 14.5s, after even cementing bundle, toasts 11.5min and obtain dry film at 185 DEG C of temperature, then the 7.5min that anneals layer by layer in air at 595 DEG C of temperature, obtains crystalline state CuFe
2o
4film;
Step 4, treats crystalline state CuFe
2o
4after film cooling, at crystalline state CuFe
2o
4repeating step 3 on film, repeats 6 times, obtains CuFe
2o
4crystalline state film;
Step 5, by CuFe
2o
4crystalline state film is placed in ultraviolet radiation instrument and irradiates 40min, makes its surface reach atomic cleanliness degree; Again at CuFe
2o
4spin coating Bi on crystalline state film
0.88sr
0.02sm
0.1fe
0.97mn
0.03o
3precursor solution, even glue rotating speed is 3850r/min, and spin coating time is 14.5s, after the even cementing bundle of even glue, toasts 11.5min and obtain dry film at 185 DEG C, then the 9min that anneals layer by layer in air at 548 DEG C, obtains crystalline state Bi
0.88sr
0.02sm
0.1fe
0.97mn
0.03o
3film;
Step 6, treats crystalline state Bi
0.88sr
0.02sm
0.1fe
0.97mn
0.03o
3after film cooling, at crystalline state Bi
0.88sr
0.02sm
0.1fe
0.97mn
0.03o
3repeating step 5 on film, repeats 12 times, obtains multiferroic Bi
0.88sr
0.02sm
0.1fe
0.97mn
0.03o
3-CuFe
2o
4composite membrane.
Embodiment 6
Step 1, by iron nitrate and cupric nitrate in molar ratio for 1:2 is dissolved in ethylene glycol monomethyl ether, after stirring 30min, then adds diacetyl oxide, obtains the stable CuFe that Cu ionic concn is 0.17mol/L
2o
4precursor liquid, CuFe
2o
4in precursor liquid, the volume ratio of ethylene glycol monomethyl ether and acetic anhydride is 3.2:1;
Step 2, Bismuth trinitrate, strontium nitrate, europium nitrate, iron nitrate and manganous nitrate are dissolved in (RE=Eu in solvent for 0.95:0.02:0.08:0.97:0.03 in molar ratio, x=0.08, Bismuth trinitrate excessive 5%), the total concn obtaining metal ion is the stable Bi of 0.27mol/L
0.9sr
0.02eu
0.08fe
0.97mn
0.03o
3precursor solution; Solvent is volume ratio is the ethylene glycol monomethyl ether of 3.2:1 and the mixed solution of acetic anhydride;
Step 3, selects FTO/glass substrate to be substrate, the FTO/glass substrate of well cutting is placed in washing composition, acetone, ethanol ultrasonic cleaning successively, with a large amount of distilled water flushing substrate after each ultrasonic cleaning 10min, finally dry up with nitrogen.Then FTO/glass substrate is put into 60 DEG C of baking oven baking 5min, take out and leave standstill to room temperature.Again the FTO/glass substrate of cleaning is placed in ultraviolet radiation instrument and irradiates 40min, substrate surface is reached " atomic cleanliness degree ".Adopt spin-coating method spin coating CuFe on FTO/glass substrate
2o
4precursor liquid, preparation CuFe
2o
4film, even glue rotating speed is 3950r/min, and spin coating time is 13.5s, after even cementing bundle, toasts 10min and obtain dry film at 195 DEG C of temperature, then the 8min that anneals layer by layer in air at 592 DEG C of temperature, obtains crystalline state CuFe
2o
4film;
Step 4, treats crystalline state CuFe
2o
4after film cooling, at crystalline state CuFe
2o
4repeating step 3 on film, repeats 5 times, obtains CuFe
2o
4crystalline state film;
Step 5, by CuFe
2o
4crystalline state film is placed in ultraviolet radiation instrument and irradiates 40min, makes its surface reach atomic cleanliness degree; Again at CuFe
2o
4spin coating Bi on crystalline state film
0.9sr
0.02eu
0.08fe
0.97mn
0.03o
3precursor solution, even glue rotating speed is 3950r/min, and spin coating time is 13.5s, after the even cementing bundle of even glue, toasts 10min and obtain dry film at 195 DEG C, then the 8min that anneals layer by layer in air at 550 DEG C, obtains crystalline state Bi
0.9sr
0.02eu
0.08fe
0.97mn
0.03o
3film;
Step 6, treats crystalline state Bi
0.9sr
0.02eu
0.08fe
0.97mn
0.03o
3after film cooling, at crystalline state Bi
0.9sr
0.02eu
0.08fe
0.97mn
0.03o
3repeating step 5 on film, repeats 9 times, obtains multiferroic Bi
0.9sr
0.02eu
0.08fe
0.97mn
0.03o
3-CuFe
2o
4composite membrane.
Embodiment 7
Step 1, by iron nitrate and cupric nitrate in molar ratio for 1:2 is dissolved in ethylene glycol monomethyl ether, after stirring 30min, then adds diacetyl oxide, obtains the stable CuFe that Cu ionic concn is 0.23mol/L
2o
4precursor liquid, CuFe
2o
4in precursor liquid, the volume ratio of ethylene glycol monomethyl ether and acetic anhydride is 3:1;
Step 2, Bismuth trinitrate, strontium nitrate, Gadolinium trinitrate, iron nitrate and manganous nitrate are dissolved in (RE=Gd in solvent for 0.91:0.02:0.12:0.97:0.03 in molar ratio, x=0.12, Bismuth trinitrate excessive 5%), the total concn obtaining metal ion is the stable Bi of 0.33mol/L
0.86sr
0.02gd
0.12fe
0.97mn
0.03o
3precursor solution; Solvent is volume ratio is the ethylene glycol monomethyl ether of 3:1 and the mixed solution of acetic anhydride;
Step 3, selects FTO/glass substrate to be substrate, the FTO/glass substrate of well cutting is placed in washing composition, acetone, ethanol ultrasonic cleaning successively, with a large amount of distilled water flushing substrate after each ultrasonic cleaning 10min, finally dry up with nitrogen.Then FTO/glass substrate is put into 60 DEG C of baking oven baking 5min, take out and leave standstill to room temperature.Again the FTO/glass substrate of cleaning is placed in ultraviolet radiation instrument and irradiates 40min, substrate surface is reached " atomic cleanliness degree ".Adopt spin-coating method spin coating CuFe on FTO/glass substrate
2o
4precursor liquid, preparation CuFe
2o
4film, even glue rotating speed is 4050r/min, and spin coating time is 12.5s, after even cementing bundle, toasts 8.5min and obtain dry film at 205 DEG C of temperature, then the 7min that anneals layer by layer in air at 598 DEG C of temperature, obtains crystalline state CuFe
2o
4film;
Step 4, treats crystalline state CuFe
2o
4after film cooling, at crystalline state CuFe
2o
4repeating step 3 on film, repeats 6 times, obtains CuFe
2o
4crystalline state film;
Step 5, by CuFe
2o
4crystalline state film is placed in ultraviolet radiation instrument and irradiates 40min, makes its surface reach atomic cleanliness degree; Again at CuFe
2o
4spin coating Bi on crystalline state film
0.86sr
0.02gd
0.12fe
0.97mn
0.03o
3precursor solution, even glue rotating speed is 4050r/min, and spin coating time is 12.5s, after the even cementing bundle of even glue, toasts 8.5min and obtain dry film at 205 DEG C, then the 10min that anneals layer by layer in air at 545 DEG C, obtains crystalline state Bi
0.86sr
0.02gd
0.12fe
0.97mn
0.03o
3film;
Step 6, treats crystalline state Bi
0.86sr
0.02gd
0.12fe
0.97mn
0.03o
3after film cooling, at crystalline state Bi
0.86sr
0.02gd
0.12fe
0.97mn
0.03o
3repeating step 5 on film, repeats 10 times, obtains multiferroic Bi
0.86sr
0.02gd
0.12fe
0.97mn
0.03o
3-CuFe
2o
4composite membrane.
RE in the nitric acid RE used in above-described embodiment also can be La, Tb, Dy, Ho, Er, Tm, Yb or Lu.
The multiferroic Bi that also can obtain in the present invention
0.98-xsr
0.02rE
xfe
0.97mn
0.03o
3-CuFe
2o
4au electrode prepared by composite film surface ion sputtering, then 295 DEG C are carried out electrode anneal process.Multiferroic Bi prepared by the present invention is tested again with Agilent2901A
0.98-xsr
0.02rE
xfe
0.97mn
0.03o
3-CuFe
2o
4the leakage current density of composite membrane, with the ferroelectric test system and test multiferroic Bi of TF2000
0.98-xsr
0.02rE
xfe
0.97mn
0.03o
3-CuFe
2o
4the ferroelectric properties of composite membrane, with the multiferroic Bi of superconductive quantum interference magnetic tester system testing invention preparation
0.98-xsr
0.02rE
xfe
0.97mn
0.03o
3-CuFe
2o
4the ferromagnetic property of composite membrane.
Present device requires simple, and experiment condition easily reaches, and the uniformity of film of preparation is better, and doping easily controls, by the suitable selection of doping, and CuFe
2o
4the interpolation of laminated magnetic film, can increase substantially the ferroelectric properties of film, reduces the leakage current density of film, improves the ferromegnetism of film simultaneously.
Above said content is in conjunction with concrete preferred implementation further description made for the present invention, it not whole or unique embodiment, the conversion of those of ordinary skill in the art by reading specification sheets of the present invention to any equivalence that technical solution of the present invention is taked, is claim of the present invention and contains.
Claims (10)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410764963.9A CN104478235B (en) | 2014-12-11 | 2014-12-11 | A multiferroic Bi0.98‑xSr0.02RExFe0.97Mn0.03O3‑CuFe2O4 composite film and its preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410764963.9A CN104478235B (en) | 2014-12-11 | 2014-12-11 | A multiferroic Bi0.98‑xSr0.02RExFe0.97Mn0.03O3‑CuFe2O4 composite film and its preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104478235A true CN104478235A (en) | 2015-04-01 |
| CN104478235B CN104478235B (en) | 2017-03-29 |
Family
ID=52752875
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410764963.9A Expired - Fee Related CN104478235B (en) | 2014-12-11 | 2014-12-11 | A multiferroic Bi0.98‑xSr0.02RExFe0.97Mn0.03O3‑CuFe2O4 composite film and its preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104478235B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105632756A (en) * | 2016-03-29 | 2016-06-01 | 陕西科技大学 | A kind of spinel type tetragonal phase CuFe2O4 ferromagnetic film and preparation method thereof |
| CN105837196A (en) * | 2016-03-29 | 2016-08-10 | 陕西科技大学 | A Bi0.92-xHo0.08AExFe0.97Mn0.03O3-Zn1-yNiyFe2O4 ferromagnetic composite thin film and its preparation method |
| CN105859273A (en) * | 2016-03-29 | 2016-08-17 | 陕西科技大学 | A kind of 2-2 type BiFeO3-CuFe2O4 composite film and its preparation method |
| CN105906221A (en) * | 2016-03-29 | 2016-08-31 | 陕西科技大学 | A multiferroic Bi0.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3-CuFe2O4 composite film and its preparation method |
| CN109336406A (en) * | 2018-09-18 | 2019-02-15 | 陕西科技大学 | A kind of BGSFMC/CFGO composite film with symmetrical rectangular hysteresis loop and preparation method |
| CN112206781A (en) * | 2020-10-22 | 2021-01-12 | 广州绿然环保新材料科技有限公司 | Catalyst for purifying waste gas and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06263486A (en) * | 1993-03-16 | 1994-09-20 | Central Glass Co Ltd | Heat ray shield glass |
| CN102482146A (en) * | 2009-06-24 | 2012-05-30 | 株式会社普利司通 | Heat ray-shielding glass and heat ray-shielding multilayer glass |
-
2014
- 2014-12-11 CN CN201410764963.9A patent/CN104478235B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06263486A (en) * | 1993-03-16 | 1994-09-20 | Central Glass Co Ltd | Heat ray shield glass |
| CN102482146A (en) * | 2009-06-24 | 2012-05-30 | 株式会社普利司通 | Heat ray-shielding glass and heat ray-shielding multilayer glass |
Non-Patent Citations (3)
| Title |
|---|
| GUOHUA DONG等: "Enhanced Ferroelectric and ferromagnetic performance of 2-2 type (Bi,Eu)(Fe,Mn)O3/CoFe2O4 bilayered thin film", 《JOURNAL OF ALLOYS AND COMPOUNDS》 * |
| GUOHUA DONG等: "Structural transformation and multiferroic properties of single-phase Bi0.89Tb0.11Fe1-xMnxO3 thin films", 《APPLIED SURFACE SCIENCE》 * |
| WENLONG LIU等: "Structure and multiferroic properties of Sr substituted Bi0.89-xSm0.11 SrxFe0.94(Mn0.04 Cr0.02)O3 thin films", 《CERMAICS INTERNATIONAL》 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105632756A (en) * | 2016-03-29 | 2016-06-01 | 陕西科技大学 | A kind of spinel type tetragonal phase CuFe2O4 ferromagnetic film and preparation method thereof |
| CN105837196A (en) * | 2016-03-29 | 2016-08-10 | 陕西科技大学 | A Bi0.92-xHo0.08AExFe0.97Mn0.03O3-Zn1-yNiyFe2O4 ferromagnetic composite thin film and its preparation method |
| CN105859273A (en) * | 2016-03-29 | 2016-08-17 | 陕西科技大学 | A kind of 2-2 type BiFeO3-CuFe2O4 composite film and its preparation method |
| CN105906221A (en) * | 2016-03-29 | 2016-08-31 | 陕西科技大学 | A multiferroic Bi0.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3-CuFe2O4 composite film and its preparation method |
| CN105632756B (en) * | 2016-03-29 | 2017-10-24 | 陕西科技大学 | A kind of spinel-type Tetragonal CuFe2O4 ferromagnetic thin films and preparation method thereof |
| CN105906221B (en) * | 2016-03-29 | 2019-02-19 | 陕西科技大学 | A kind of multiferroic Bi0.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3-CuFe2O4 composite film and preparation method thereof |
| CN105859273B (en) * | 2016-03-29 | 2019-07-30 | 陕西科技大学 | A kind of 2-2 type BiFeO3-CuFe2O4 laminated film and preparation method thereof |
| CN109336406A (en) * | 2018-09-18 | 2019-02-15 | 陕西科技大学 | A kind of BGSFMC/CFGO composite film with symmetrical rectangular hysteresis loop and preparation method |
| CN109336406B (en) * | 2018-09-18 | 2021-08-10 | 陕西科技大学 | BGSFMC/CFGO composite film with symmetrical rectangular hysteresis loop and preparation method thereof |
| CN112206781A (en) * | 2020-10-22 | 2021-01-12 | 广州绿然环保新材料科技有限公司 | Catalyst for purifying waste gas and preparation method thereof |
| CN112206781B (en) * | 2020-10-22 | 2021-05-28 | 广州尖峰生物制品有限公司 | Catalyst for purifying waste gas and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104478235B (en) | 2017-03-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104478235A (en) | A multiferroic Bi0.98-xSr0.02RExFe0.97Mn0.03O3-CuFe2O4 composite film and its preparation method | |
| CN104538140B (en) | Multiferroic Bi1-xRExFe0.97-yMn0.03TMyO3/CoFe2O4 composite film and preparation method thereof | |
| CN104478234B (en) | A kind of Bi0.90Er0.10Fe0.96Co0.02Mn0.02O3/Mn1-xCoxFe2O4 composite film and its preparation method | |
| CN105837196A (en) | A Bi0.92-xHo0.08AExFe0.97Mn0.03O3-Zn1-yNiyFe2O4 ferromagnetic composite thin film and its preparation method | |
| CN103058646B (en) | Method for preparing Tb and Cr co-doped BiFeO3 thin films with high remanent polarization by sol-gel method | |
| CN103708562B (en) | Bi0.90Ho0.10Fe1-XMnXO3 ferroelectric film with high remanent polarization and preparation method thereof | |
| CN103723770B (en) | A kind of high dielectric constant Bi0.92Ho0.08Fe1-XMnXO3 ferroelectric film and its preparation method | |
| CN104478236A (en) | A Bi0.92Ho0.08Fe0.97Mn0.03O3-Zn1-xNixFe2O4 multiferroic composite film and its preparation method | |
| CN103771527B (en) | A kind of Bi of low coercive field 0.92dy 0.08fe 1-xmn xo 3ferroelectric membranc and preparation method thereof | |
| CN104476832B (en) | A laminated BiFe0.97-xMn0.03TMxO3/CoFe2O4 multiferroic composite film and its preparation method | |
| CN105906221B (en) | A kind of multiferroic Bi0.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3-CuFe2O4 composite film and preparation method thereof | |
| CN104575907B (en) | Bi1-xRExFe1-yTMyO3/CoFe2O4 multiferroic composite film and preparation method thereof | |
| CN104478228B (en) | A kind of Bi0.85‑xPr0.15AExFe0.97Mn0.03O3Ferroelectric thin film and preparation method thereof | |
| CN109111127B (en) | A BLSFMC/CMFO film with resistive switching effect and its preparation method | |
| CN103601248A (en) | A kind of Tb, Mn and Ni ternary co-doped BiFeO3 film with low leakage current and preparation method thereof | |
| CN103601247B (en) | A high remnant polarization and low leakage current density Bi1-xSmxFe0.94Mn0.04Cr0.02O3 ferroelectric thin film and its preparation method | |
| CN103613144B (en) | A B-site Mn and Cu co-doped BiFeO3 thin film with high remnant polarization and its preparation method | |
| CN104538139B (en) | Bi1-xRExFeO3/CoFe2O4 multiferroic composite membrane and preparation method thereof | |
| CN104478229A (en) | A kind of Bi1-xRExFe0.96Co0.02Mn0.02O3 ferroelectric film and its preparation method | |
| CN107140848B (en) | A kind of GdSrMnCo co-doped bismuth ferrite superlattice film and preparation method thereof | |
| CN107140849B (en) | A kind of LaSrMnCo/GdSrMnCo co-doped bismuth ferrite superlattice film and preparation method thereof | |
| CN113248248A (en) | Solid solution multiferroic film, preparation method and electronic device applied to 5G storage technology | |
| CN104478230A (en) | A kind of multiferroic Bi0.92-xHo0.08AExFe0.97Mn0.03O3 film and its preparation method | |
| CN103723771B (en) | A kind of Bi of high-k 1-xdy xfeO 3film and preparation method thereof | |
| CN109205683B (en) | BLSFMC/CFLO composite film with symmetrical rectangular hysteresis loop and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170329 |