CN103708562A - Bi0.90Ho0.10Fe1-XMnXO3 ferroelectric film with high remanent polarization and preparation method thereof - Google Patents
Bi0.90Ho0.10Fe1-XMnXO3 ferroelectric film with high remanent polarization and preparation method thereof Download PDFInfo
- Publication number
- CN103708562A CN103708562A CN201310714707.4A CN201310714707A CN103708562A CN 103708562 A CN103708562 A CN 103708562A CN 201310714707 A CN201310714707 A CN 201310714707A CN 103708562 A CN103708562 A CN 103708562A
- Authority
- CN
- China
- Prior art keywords
- ferroelectric membranc
- film
- remnant polarization
- ferroelectric
- preparation
- 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
Images
Abstract
The invention relates to a Bi0.90Ho0.10Fe1-xMnXO3 ferroelectric film with high remanent polarization and a preparation method thereof, wherein x is equal to 0.01-0.05, and the film is of a distorted perovskite structure, has a diamond crystal system and has good uniformity, remanent polarization of 78-108 muC/cm<2>, and a dielectric constant of 196.2-271.8. The preparation method comprises the steps of dissolving bismuth nitrate, ferric nitrate, holmium nitrate and manganese acetate in a mixture prepared by mixing ethylene glycol monomethyl ether and acetic anhydride to obtain a precursor solution; spin-coating the precursor solution on a substrate, coating glue evenly, then baking to obtain a dry film, then annealing to obtain a Bi0.90Ho0.10Fe1-xMnXO3 film, and repeatedly spin-coating the precursor solution, baking and annealing to achieve the required film thickness to obtain the film. According to the Bi0.90Ho0.10Fe1-xMnXO3 ferroelectric film with high remanent polarization and the preparation method thereof, the requirements for equipment are simple, the doping amount is easy to control, and the ferroelectric properties of the BiFeO3 film can be greatly improved.
Description
Technical field
The invention belongs to field of functional materials, be specifically related to a kind of Bi of high remnant polarization
0.90ho
0.10fe
1-xmn
xo
3ferroelectric membranc and preparation method thereof.
Background technology
Due to BiFeO
3that present minority at room temperature shows ferroelectricity and ferromagnetic material (Tc=1103K, T simultaneously
n=640K).Therefore it has broad application prospects aspect magnetic storage, is expected to develop based on this type material simultaneously with ferroelectric material high reading speed and the high writing speed of ferromagnetic material.So there is in recent years a large amount of team to be engaged in BiFeO
3the research of material.
At present for the preparation of BiFeO
3the method of film has a lot, has 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.Yet, BiFeO
3the practical application of material has been subject to serious obstruction.Reason mainly contains: BiFeO
3there is higher leakage current; BiFeO
3nature has determined to be difficult to prepare pure phase; BiFeO
3film easily produces oxygen room, Fe in preparation process
3+the problems such as ion appraises at the current rate.So that it is difficult to obtain at normal temperatures saturated ferroelectric hysteresis loop.
Summary of the invention
The object of the present invention is to provide a kind of Bi of high remnant polarization
0.90ho
0.10fe
1-xmn
xo
3ferroelectric membranc and preparation method thereof, the method equipment requirements is simple, and experiment condition easily reaches, and the uniformity of film of preparation is better, and doping is easily controlled, and can increase substantially ferroelectric properties and the dielectric properties of film.
To achieve these goals, the present invention adopts following technical scheme:
A kind of Bi of high remnant polarization
0.90ho
0.10fe
1-xmn
xo
3ferroelectric membranc, its chemical formula is Bi
0.90ho
0.10fe
1-xmn
xo
3, x=0.01～0.05; Under 1kHz frequency, its remnant polarization is 78～108 μ C/cm
2, specific inductivity is 196.2～271.8.
It is the perovskite structure of distortion, rhombohedral system, and space group is R-3m (160), unit cell parameters
grain size is 50～60nm.
Comprise Bi
0.90ho
0.10fe
0.99mn
0.01o
3ferroelectric membranc, Bi
0.90ho
0.10fe
0.98mn
0.02o
3ferroelectric membranc, Bi
0.90ho
0.10fe
0.97mn
0.03o
3ferroelectric membranc and Bi
0.90ho
0.10fe
0.95mn
0.05o
3ferroelectric membranc;
And Bi
0.90ho
0.10fe
0.99mn
0.01o
3ferroelectric membranc is under the extra electric field of 917kV/cm, and remnant polarization is 108 μ C/cm
2, the specific inductivity under the frequency of 1kHz～1MHz is 218.1～271.8;
Bi
0.90ho
0.10fe
0.98mn
0.02o
3ferroelectric membranc is under the extra electric field of 1250kV/cm, and remnant polarization is 95 μ C/cm
2, the specific inductivity under the frequency of 1kHz～1MHz is 195.8～258.1;
Bi
0.90ho
0.10fe
0.97mn
0.03o
3ferroelectric membranc is under the extra electric field of 1250kV/cm, and remnant polarization is 88 μ C/cm
2, the specific inductivity under the frequency of 1kHz～1MHz is 166.9～231.9;
Bi
0.90ho
0.10fe
0.95mn
0.05o
3ferroelectric membranc is under the extra electric field of 1250kV/cm, and remnant polarization is 78 μ C/cm
2, the specific inductivity under the frequency of 1kHz～1MHz is 125.3～196.2.
The Bi of high remnant polarization
0.90ho
0.10fe
1-xmn
xo
3the preparation method of ferroelectric membranc, comprises the following steps:
Step 1: be 0.95:(1-x in molar ratio): 0.10:x is by Bi (NO
3)
35H
2o, Fe (NO
3)
39H
2o, Ho (NO
3)
36H
2o and C
4h
6mnO
44H
2o is dissolved in the mixed solution being mixed by ethylene glycol monomethyl ether and acetic anhydride, stirs, and obtains precursor liquid, and wherein in precursor liquid, total concentration of metal ions is 0.003～0.3mol/L, x=0.01～0.05;
Step 2: precursor liquid is spin-coated on FTO/glass substrate and prepares wet film, and wet film toasts to obtain dry film after even glue at 180～200 ℃, then 550～580 ℃ of annealing, obtains Bi
0.90ho
0.10fe
1-xmn
xo
3film;
Step 3: treat Bi
0.90ho
0.10fe
1-xmn
xo
3after film cooling, then at Bi
0.90ho
0.10fe
1-xmn
xo
3on film, repeating step 2, make Bi
0.90ho
0.10fe
1-xmn
xo
3film reaches desired thickness, obtains the Bi of high remnant polarization
0.90ho
0.10fe
1-xmn
xo
3ferroelectric membranc.
In described step 1, in mixed solution, the volume ratio of ethylene glycol monomethyl ether and acetic anhydride is (2.5～3.5): 1.
X=0.01,0.02,0.03 or 0.05 in described step 1.
In described step 2, first FTO/glass substrate cleaned, dry, then radiation treatment under UV-light, makes FTO/glass substrate surface reach atomic cleanliness degree, finally spin coating precursor liquid again.
Even glue speed in described step 2 during even glue is 3800～4100r/min, and the even glue time is 12～20s.
Baking time in described step 2 after even glue is 8～12min.
In described step 2, annealing time is 10～15min.
With respect to prior art, the present invention has following beneficial effect:
The invention provides a kind of Bi of high remnant polarization
0.90ho
0.10fe
1-xmn
xo
3the preparation method of ferroelectric membranc, adopts sol-gel method, by A position Ho and B position Mn codoped, prepares the Bi of high remnant polarization at FTO/glass substrate surface
0.90ho
0.10fe
1-xmn
xo
3ferroelectric membranc.The method selects lanthanon Ho to carry out the doping of A position, at BiFeO
3a position doping lanthanon can stablize the iron oxygen octahedra in perovskite structure, simultaneously because Ho has substituted part Bi, the volatile quantity of Bi in annealing process reduced, thereby reduced the generation in oxygen room, can make Bi
0.90ho
0.10fe
1-xmn
xo
3the insulativity of ferroelectric membranc effectively strengthens, and reduces leakage conductance, improves ferroelectricity.In addition, the present invention also selects Mn to carry out the doping of B position, and the doping of B position can improve BiFeO equally effectively
3the multi-ferrum property of film.Because the Mn selecting is+divalent, so at alternative Fe
3+time can because of charge compensation effect, reduce the generation in oxygen room, thereby can effectively reduce leakage current, the electrical property of raising film integral.Simultaneously to B position Fe
3+substituting of ion can affect the magnetic structure of its crystal grain inside consumingly, and then affects its magnetic and magnetoelectric effect.And Ho
3+radius is less than Bi
3+, Mn
2+radius is greater than Fe
3+, mixing altogether of these two kinds of ions can make the approximate bismuth ferrite crystal lattices distortion that is perovskite structure originally, structural aberration aggravation, thus greatly improved BiFeO
3the ferroelectric properties of film.So that the present invention adopts is the Bi that the ion co-doped method of A position rare earth ion and B position magnetic transition metal (i.e. so-called " compound substituting ") is prepared high remnant polarization
0.90ho
0.10fe
1-xmn
xo
3ferroelectric membranc.This method can be taken into account the advantage of two kinds of substitute element, and partly overcome single element of planting, replaces the shortcoming of bringing, and makes BiFeO
3ferroelectric properties be able to more significantly improve.And compare additive method, the sol-gel method equipment requirements that the present invention adopts is simple, do not need expensive vacuum apparatus, experiment condition easily reaches, reaction is easily carried out, preparation process is easy to control, temperature of reaction is lower, be conducive to solve the problem that Fe appraises at the current rate and Bi volatilizees in film preparation process, simultaneously suitablely on large surface and surface in irregular shape, prepare film, easy handling and doping vario-property, can effectively control component and the structure of film, film chemical composition is accurately controlled, doping is easily controlled, be particularly suitable for preparing multicomponent oxide film material, can accurately control the stoichiometric ratio of film, be easy to realize the Uniform Doped on molecular level.
The Bi of the high remnant polarization that the present invention makes
0.90ho
0.10fe
1-xmn
xo
3ferroelectric membranc (x=0.01～0.05) is the perovskite structure of distortion, rhombohedral system, and space group is R-3m (160), unit cell parameters
grain size is 50～60nm, good uniformity, and under 1kHz frequency, its remnant polarization is 78～108 μ C/cm
2, specific inductivity is 196.2～271.8, has increased substantially BiFeO
3the ferroelectric properties of film and dielectric properties.
Accompanying drawing explanation
Fig. 1 is the Bi of the high remnant polarization prepared of the present invention
0.90ho
0.10fe
1-xmn
xo
3the XRD spectra of ferroelectric membranc;
Fig. 2 is the Bi of the high remnant polarization prepared of the present invention
0.90ho
0.10fe
1-xmn
xo
3the SEM figure of ferroelectric membranc, the not doped with Mn that wherein (a) prepared for comparative example
2+bi
0.90ho
0.10feO
3the SEM collection of illustrative plates of film, (b)～(e) be respectively the Bi of embodiment 1～embodiment 4 preparation
0.90ho
0.10fe
1-xmn
xo
3the SEM figure of ferroelectric membranc; (f) be the Bi of embodiment 3 preparations
0.9ho
0.1fe
0.97mn
0.03o
3the section SEM figure of ferroelectric membranc;
Fig. 3 is the Bi of the high remnant polarization prepared of the present invention
0.90ho
0.10fe
1-xmn
xo
3the dielectric properties of ferroelectric membranc and the graph of a relation of frequency;
Fig. 4 is the Bi of the high remnant polarization prepared of the present invention
0.90ho
0.10fe
1-xmn
xo
3the ferroelectric hysteresis loop figure of ferroelectric membranc.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in further detail.
Comparative example
Step 1: selecting FTO/glass substrate is substrate, and the FTO/glass substrate of well cutting is placed in to washing composition, acetone, ethanol ultrasonic cleaning successively, with a large amount of distilled water flushing substrates, finally dries up with nitrogen after each ultrasonic cleaning 10min.Again FTO/glass substrate is put into 70 ℃ of baking oven baking 5min, taken out standing to room temperature.Finally clean FTO/glass substrate is placed in to ultraviolet radiation instrument and irradiates 40min, make substrate surface reach " atomic cleanliness degree ".
Step 2: in molar ratio for 0.95:1:0.10(is x=0) by Bi (NO
3)
35H
2o, Fe (NO
3)
39H
2o and Ho (NO
3)
36H
2o is dissolved in mixed solution, obtains even, stable precursor liquid after magnetic agitation 2.5h, and wherein mixed solution is by volume ratio, to be 3:1 ethylene glycol monomethyl ether and acetic anhydride mix, and in precursor liquid, total concentration of metal ions is 0.3mol/L.
Step 3: adopt spin-coating method spin coating precursor liquid on the FTO/glass substrate after step 1 is processed to prepare wet film, the even glue 20s of even glue speed with 4000r/min after even cementing bundle, toasts 10min and obtains dry film at 200 ℃, and then at 550 ℃ short annealing 10min, obtain Bi
0.90ho
0.10feO
3film.
Step 4: treat Bi
0.90ho
0.10feO
3after film cooling, then at Bi
0.90ho
0.10feO
3on film, repeating step 2, make Bi
0.90ho
0.10feO
3film reaches desired thickness, obtains Bi
0.90ho
0.10feO
3ferroelectric membranc.
At Bi
0.90ho
0.10feO
30.502mm is prepared in the sputter of ferroelectric membranc surface ion
2au electrode, then 280 ℃ insulation 25min carry out electrode anneal, electrode is contacted completely with substrate.Adopt XRD determining Bi
0.90ho
0.10feO
3the thing phase composite structure of ferroelectric membranc, as shown in Figure 1, Bi
0.90ho
0.10feO
3ferroelectric membranc belongs to the perovskite structure of distortion, rhombohedral system, and space group is R-3m (160), unit cell parameters
with FE-SEM, measure Bi
0.90ho
0.10feO
3the microscopic appearance of ferroelectric membranc, is about 80～100nm by known its grain-size of Fig. 2 (a), and film thickness is 590nm.With Agilent E4980A LCR test set test b i
0.90ho
0.10feO
3the dielectric properties of ferroelectric membranc, as seen from Figure 3, under the frequency of 1kHz～1MHz, Bi
0.90ho
0.10feO
3the specific inductivity of ferroelectric membranc is 200.7～287.5.With the ferroelectric test system and test Bi of TF2000
0.90ho
0.10feO
3the ferroelectric properties of ferroelectric membranc, can find out Bi by Fig. 4 (a)
0.90ho
0.10feO
3ferroelectric membranc does not obtain saturated ferroelectric hysteresis loop, and its remnant polarization is only 11.2 μ C/cm under the electric field of 250kV/cm
2.
Embodiment 1
Step 1: selecting FTO/glass substrate is substrate, and the FTO/glass substrate of well cutting is placed in to washing composition, acetone, ethanol ultrasonic cleaning successively, with a large amount of distilled water flushing substrates, finally dries up with nitrogen after each ultrasonic cleaning 10min.Again FTO/glass substrate is put into 70 ℃ of baking oven baking 5min, taken out standing to room temperature.Finally FTO/glass substrate is placed in to ultraviolet radiation instrument and irradiates 40min, make substrate surface reach " atomic cleanliness degree ".
Step 2: in molar ratio for 0.95:0.99:0.10:0.01(is x=0.01) by Bi (NO
3)
35H
2o, Fe (NO
3)
39H
2o, Ho (NO
3)
36H
2o and C
4h
6mnO
44H
2o is dissolved in mixed solution, obtains even, stable precursor liquid after magnetic agitation 2.5h, and wherein mixed solution is by volume ratio, to be 3:1 ethylene glycol monomethyl ether and acetic anhydride mix, and in precursor liquid, total concentration of metal ions is 0.3mol/L.
Step 3: adopt spin-coating method spin coating precursor liquid on the FTO/glass substrate after step 1 is processed to prepare wet film, the even glue 20s of even glue speed with 4000r/min after even cementing bundle, toasts 10min and obtains dry film at 200 ℃, and then at 550 ℃ short annealing 10min, obtain Bi
0.90ho
0.10fe
0.99mn
0.01o
3film.
Step 4: treat Bi
0.90ho
0.10fe
0.99mn
0.01o
3after film cooling, then at Bi
0.90ho
0.10fe
0.99mn
0.01o
3on film, repeating step 2, make Bi
0.90ho
0.10fe
0.99mn
0.01o
3film reaches desired thickness, obtains the Bi of high remnant polarization
0.90ho
0.10fe
0.99mn
0.01o
3ferroelectric membranc.
Bi in high remnant polarization
0.90ho
0.10fe
0.99mn
0.01o
30.502mm is prepared in the sputter of ferroelectric membranc surface ion
2au electrode, then 280 ℃ insulation 25min carry out electrode anneal, electrode is contacted completely with substrate.Adopt the Bi of the high remnant polarization of XRD determining
0.90ho
0.10fe
0.99mn
0.01o
3the thing phase composite structure of ferroelectric membranc, as shown in Figure 1, the Bi of high remnant polarization
0.90ho
0.10fe
0.99mn
0.01o
3ferroelectric membranc belongs to the perovskite structure of distortion, rhombohedral system, and space group is R-3m (160), unit cell parameters
with FE-SEM, measure the Bi of high remnant polarization
0.90ho
0.10fe
0.99mn
0.01o
3the microscopic appearance of ferroelectric membranc, is about 60nm left and right by known its grain-size of Fig. 2 (b), and film thickness is 560nm.With Agilent E4980A LCR test set, test the Bi of high remnant polarization
0.90ho
0.10fe
0.99mn
0.01o
3the dielectricity of ferroelectric membranc, as seen from Figure 3, the Bi of high remnant polarization under the frequency of 1kHz～1MHz
0.90ho
0.10fe
0.99mn
0.01o
3the specific inductivity of ferroelectric membranc is 218.1～271.8.Bi by the high remnant polarization of the ferroelectric test system and test of TF2000
0.90ho
0.10fe
0.99mn
0.01o
3the ferroelectric properties of ferroelectric membranc, can be found out by Fig. 4 (b), and under the extra electric field of 917kV/cm, its remnant polarization is 108 μ C/cm
2.
Embodiment 2
Step 1: selecting FTO/glass substrate is substrate, and the FTO/glass substrate of well cutting is placed in to washing composition, acetone, ethanol ultrasonic cleaning successively, with a large amount of distilled water flushing substrates, finally dries up with nitrogen after each ultrasonic cleaning 10min.Again FTO/glass substrate is put into 70 ℃ of baking oven baking 5min, taken out standing to room temperature.Finally FTO/glass substrate is placed in to ultraviolet radiation instrument and irradiates 40min, make substrate surface reach " atomic cleanliness degree ".
Step 2: in molar ratio for 0.95:0.98:0.10:0.02(is x=0.02) by Bi (NO
3)
35H
2o, Fe (NO
3)
39H
2o, Ho (NO
3)
36H
2o and C
4h
6mnO
44H
2o is dissolved in mixed solution, obtains even, stable precursor liquid after magnetic agitation 2.5h, and wherein mixed solution is by volume ratio, to be 3:1 ethylene glycol monomethyl ether and acetic anhydride mix, and in precursor liquid, total concentration of metal ions is 0.3mol/L.
Step 3: adopt spin-coating method spin coating precursor liquid on the FTO/glass substrate after step 1 is processed to prepare wet film, the even glue 20s of even glue speed with 4000r/min after even cementing bundle, toasts 10min and obtains dry film at 200 ℃, and then at 550 ℃ short annealing 10min, obtain Bi
0.90ho
0.10fe
0.98mn
0.02o
3film.
Step 4: treat Bi
0.90ho
0.10fe
0.98mn
0.02o
3after film cooling, then at Bi
0.90ho
0.10fe
0.98mn
0.02o
3on film, repeating step 2, make Bi
0.90ho
0.10fe
0.98mn
0.02o
3film reaches desired thickness, obtains the Bi of high remnant polarization
0.90ho
0.10fe
0.98mn
0.02o
3ferroelectric membranc.
Bi in high remnant polarization
0.90ho
0.10fe
0.98mn
0.02o
30.502mm is prepared in the sputter of ferroelectric membranc surface ion
2au electrode, then 280 ℃ insulation 25min carry out electrode anneal, electrode is contacted completely with substrate.Adopt the Bi of the high remnant polarization of XRD determining
0.90ho
0.10fe
0.98mn
0.02o
3the thing phase composite structure of ferroelectric membranc, as shown in Figure 1, the Bi of high remnant polarization
0.90ho
0.10fe
0.98mn
0.02o
3ferroelectric membranc belongs to the perovskite structure of distortion, rhombohedral system, and space group is R-3m (160), unit cell parameters
with FE-SEM, measure the Bi of high remnant polarization
0.90ho
0.10fe
0.98mn
0.02o
3the microscopic appearance of ferroelectric membranc, is about 60nm left and right by known its grain-size of Fig. 2 (c), and film thickness is 540nm.With Agilent E4980A LCR test set, test the Bi of high remnant polarization
0.90ho
0.10fe
0.98mn
0.02o
3the dielectric properties of ferroelectric membranc, as seen from Figure 3, under the frequency of 1kHz～1MHz, the Bi of high remnant polarization
0.90ho
0.10fe
0.98mn
0.02o
3the specific inductivity of ferroelectric membranc is 195.8～258.1.Bi by the high remnant polarization of the ferroelectric test system and test of TF2000
0.90ho
0.10fe
0.98mn
0.02o
3the ferroelectric properties of ferroelectric membranc, can be found out by Fig. 4 (c), and under the extra electric field of 1250kV/cm, its remnant polarization is 95 μ C/cm
2.
Embodiment 3
Step 1: selecting FTO/glass substrate is substrate, and the FTO/glass substrate of well cutting is placed in to washing composition, acetone, ethanol ultrasonic cleaning successively, with a large amount of distilled water flushing substrates, finally dries up with nitrogen after each ultrasonic cleaning 10min.Again FTO/glass substrate is put into 70 ℃ of baking oven baking 5min, taken out standing to room temperature.Finally FTO/glass substrate is placed in to ultraviolet radiation instrument and irradiates 40min, make substrate surface reach " atomic cleanliness degree ".
Step 2: in molar ratio for 0.95:0.97:0.10:0.03(is x=0.03) by Bi (NO
3)
35H
2o, Fe (NO
3)
39H
2o, Ho (NO
3)
36H
2o and C
4h
6mnO
44H
2o is dissolved in mixed solution, obtains even, stable precursor liquid after magnetic agitation 2.5h, and wherein mixed solution is by volume ratio, to be 3:1 ethylene glycol monomethyl ether and acetic anhydride mix, and in precursor liquid, total concentration of metal ions is 0.3mol/L.
Step 3: adopt spin-coating method spin coating precursor liquid on the FTO/glass substrate after step 1 is processed to prepare wet film, the even glue 20s of even glue speed with 4000r/min after even cementing bundle, toasts 10min and obtains dry film at 200 ℃, and then at 550 ℃ short annealing 10min, obtain Bi
0.90ho
0.10fe
0.97mn
0.03o
3film.
Step 4: treat Bi
0.90ho
0.10fe
0.97mn
0.03o
3after film cooling, then at Bi
0.90ho
0.10fe
0.97mn
0.03o
3on film, repeating step 2, make Bi
0.90ho
0.10fe
0.97mn
0.03o
3film reaches desired thickness, obtains the Bi of high remnant polarization
0.90ho
0.10fe
0.97mn
0.03o
3ferroelectric membranc.
Bi in high remnant polarization
0.90ho
0.10fe
0.97mn
0.03o
30.502mm is prepared in the sputter of ferroelectric membranc surface ion
2au electrode, then 285 ℃ insulation 25min carry out electrode anneal, electrode is contacted completely with substrate.Adopt the Bi of the high remnant polarization of XRD determining
0.90ho
0.10fe
0.97mn
0.03o
3the thing phase composite structure of ferroelectric membranc, as shown in Figure 1, the Bi of high remnant polarization
0.90ho
0.10fe
0.97mn
0.03o
3ferroelectric membranc belongs to the perovskite structure of distortion, rhombohedral system, and space group is R-3m (160), unit cell parameters
with FE-SEM, measure the Bi of high remnant polarization
0.90ho
0.10fe
0.97mn
0.03o
3the microscopic appearance of ferroelectric membranc, is about 50nm left and right by known its grain-size of Fig. 2 (d), and film thickness is 540nm.With Agilent E4980A LCR test set, test the Bi of high remnant polarization
0.90ho
0.10fe
0.97mn
0.03o
3the dielectric properties of ferroelectric membranc, as seen from Figure 3, under the frequency of 1kHz～1MHz, the Bi of high remnant polarization
0.90ho
0.10fe
0.97mn
0.03o
3the specific inductivity of ferroelectric membranc is 166.9～231.9.Bi by the high remnant polarization of the ferroelectric test system and test of TF2000
0.90ho
0.10fe
0.97mn
0.03o
3the ferroelectric properties of ferroelectric membranc, can be found out by Fig. 4 (d), and under the extra electric field of 1250kV/cm, its remnant polarization is 88 μ C/cm
2.
Embodiment 4
Step 1: selecting FTO/glass substrate is substrate, and the FTO/glass substrate of well cutting is placed in to washing composition, acetone, ethanol ultrasonic cleaning successively, with a large amount of distilled water flushing substrates, finally dries up with nitrogen after each ultrasonic cleaning 10min.Again FTO/glass substrate is put into 70 ℃ of baking oven baking 5min, taken out standing to room temperature.Finally FTO/glass substrate is placed in to ultraviolet radiation instrument and irradiates 40min, make substrate surface reach " atomic cleanliness degree ".
Step 2: in molar ratio for 0.95:0.95:0.10:0.05(is x=0.05) by Bi (NO
3)
35H
2o, Fe (NO
3)
39H
2o, Ho (NO
3)
36H
2o and C
4h
6mnO
44H
2o is dissolved in mixed solution, obtains even, stable precursor liquid after magnetic agitation 2.5h, and wherein mixed solution is by volume ratio, to be 3:1 ethylene glycol monomethyl ether and acetic anhydride mix, and in precursor liquid, total concentration of metal ions is 0.3mol/L.
Step 3: adopt spin-coating method spin coating precursor liquid on the FTO/glass substrate after step 1 is processed to prepare wet film, the even glue 20s of even glue speed with 4000r/min after even cementing bundle, toasts 10min and obtains dry film at 200 ℃, and then at 550 ℃ short annealing 10min, obtain Bi
0.90ho
0.10fe
0.95mn
0.05o
3film.
Step 4: treat Bi
0.90ho
0.10fe
0.95mn
0.05o
3after film cooling, then at Bi
0.90ho
0.10fe
0.95mn
0.05o
3on film, repeating step 2, make Bi
0.90ho
0.10fe
0.95mn
0.05o
3film reaches desired thickness, obtains the Bi of high remnant polarization
0.90ho
0.10fe
0.95mn
0.05o
3ferroelectric membranc.
Bi in high remnant polarization
0.90ho
0.10fe
0.95mn
0.05o
30.502mm is prepared in the sputter of ferroelectric membranc surface ion
2au electrode, then 280 ℃ insulation 25min carry out electrode anneal, electrode is contacted completely with substrate.Adopt the Bi of the high remnant polarization of XRD determining
0.90ho
0.10fe
0.95mn
0.05o
3the thing phase composite structure of ferroelectric membranc, as shown in Figure 1, the Bi of high remnant polarization
0.90ho
0.10fe
0.95mn
0.05o
3ferroelectric membranc belongs to the perovskite structure of distortion, rhombohedral system, and space group is R-3m (160), unit cell parameters
with FE-SEM, measure the Bi of high remnant polarization
0.90ho
0.10fe
0.95mn
0.05o
3the microscopic appearance of ferroelectric membranc, is about 50nm left and right by known its grain-size of Fig. 2 (e), and film thickness is 550nm.With Agilent E4980A LCR test set, test the Bi of high remnant polarization
0.90ho
0.10fe
0.95mn
0.05o
3the dielectric properties of ferroelectric membranc, as seen from Figure 3, under the frequency of 1kHz～1MHz, the Bi of high remnant polarization
0.90ho
0.10fe
0.95mn
0.05o
3the specific inductivity of ferroelectric membranc is 125.3～196.2.Bi by the high remnant polarization of the ferroelectric test system and test of TF2000
0.90ho
0.10fe
0.95mn
0.05o
3the ferroelectric properties of ferroelectric membranc, can be found out by Fig. 4 (e), and under the extra electric field of 1250kV/cm, its remnant polarization is 78 μ C/cm
2.。
Fig. 1 is different Mn
2+the Bi preparing under doping
0.90ho
0.10fe
1-xmn
xo
3the XRD figure spectrum of ferroelectric membranc, in Fig. 1, the a.u. of unit of ordinate zou represents that it is arbitrary unit, X-coordinate 2 θ are angle of diffraction.As can be seen from Figure 1 Bi
0.90ho
0.10fe
1-xmn
xo
3the diffraction peak of ferroelectric membranc (012) and (110) crystal face, along with the skew of turning left gradually that is increased in of doping, illustrates that variation has occurred film internal structure.
Embodiment 5
Step 1: selecting FTO/glass substrate is substrate, and the FTO/glass substrate of well cutting is placed in to washing composition, acetone, ethanol ultrasonic cleaning successively, with a large amount of distilled water flushing substrates, finally dries up with nitrogen after each ultrasonic cleaning 10min.Again FTO/glass substrate is put into 70 ℃ of baking oven baking 5min, taken out standing to room temperature.Finally FTO/glass substrate is placed in to ultraviolet radiation instrument and irradiates 40min, make substrate surface reach " atomic cleanliness degree ".
Step 2: in molar ratio for 0.95:0.96:0.10:0.04(is x=0.04) by Bi (NO
3)
35H
2o, Fe (NO
3)
39H
2o, Ho (NO
3)
36H
2o and C
4h
6mnO
44H
2o is dissolved in mixed solution, obtains even, stable precursor liquid after magnetic agitation 2.5h, and wherein mixed solution is by volume ratio, to be 3.5:1 ethylene glycol monomethyl ether and acetic anhydride mix, and in precursor liquid, total concentration of metal ions is 0.003mol/L.
Step 3: adopt spin-coating method spin coating precursor liquid on the FTO/glass substrate after step 1 is processed to prepare wet film, the even glue 15s of even glue speed with 3800r/min after even cementing bundle, toasts 8min and obtains dry film at 180 ℃, and then at 500 ℃ short annealing 15min, obtain Bi
0.90ho
0.10fe
0.96mn
0.04o
3film.
Step 4: treat Bi
0.90ho
0.10fe
0.96mn
0.04o
3after film cooling, then at Bi
0.90ho
0.10fe
0.96mn
0.04o
3on film, repeating step 2, make Bi
0.90ho
0.10fe
0.96mn
0.04o
3film reaches desired thickness, obtains the Bi of high remnant polarization
0.90ho
0.10fe
0.96mn
0.04o
3ferroelectric membranc.
Embodiment 6
Step 1: selecting FTO/glass substrate is substrate, and the FTO/glass substrate of well cutting is placed in to washing composition, acetone, ethanol ultrasonic cleaning successively, with a large amount of distilled water flushing substrates, finally dries up with nitrogen after each ultrasonic cleaning 10min.Again FTO/glass substrate is put into 70 ℃ of baking oven baking 5min, taken out standing to room temperature.Finally FTO/glass substrate is placed in to ultraviolet radiation instrument and irradiates 40min, make substrate surface reach " atomic cleanliness degree ".
Step 2: in molar ratio for 0.95:0.975:0.10:0.025(is x=0.025) by Bi (NO
3)
35H
2o, Fe (NO
3)
39H
2o, Ho (NO
3)
36H
2o and C
4h
6mnO
44H
2o is dissolved in mixed solution, obtains even, stable precursor liquid after magnetic agitation 2.5h, and wherein mixed solution is by volume ratio, to be 2.5:1 ethylene glycol monomethyl ether and acetic anhydride mix, and in precursor liquid, total concentration of metal ions is 0.1mol/L.
Step 3: adopt spin-coating method spin coating precursor liquid on the FTO/glass substrate after step 1 is processed to prepare wet film, the even glue 12s of even glue speed with 4100r/min after even cementing bundle, toasts 12min and obtains dry film at 190 ℃, and then at 580 ℃ short annealing 12min, obtain Bi
0.90ho
0.10fe
0.975mn
0.025o
3film.
Step 4:Bi
0.90ho
0.10fe
0.975mn
0.025o
3after film cooling, then at Bi
0.90ho
0.10fe
0.975mn
0.025o
3on film, repeating step 2, make Bi
0.90ho
0.10fe
0.975mn
0.025o
3film reaches desired thickness, obtains the Bi of high remnant polarization
0.90ho
0.10fe
0.975mn
0.025o
3ferroelectric membranc.
Above-described embodiment 1-6 prepares in the process of precursor liquid in step 1, Bismuth trinitrate (Bi (NO
3)
35H
2o), iron nitrate (Fe (NO
3)
39H
2o), holmium nitrate (Ho (NO
3)
36H
2o) and manganous acetate (C
4h
6mnO
44H
2o) theoretical molar is than being 0.90:(1-x): 0.10:x, x=0.01～0.05; But in the process of annealing in step 2, Bi
3+have the volatilization loss of part, therefore, the present invention is in the process of step 1 preparation precursor liquid, Bismuth trinitrate, iron nitrate, holmium nitrate and manganous acetate are according to 0.95:(1-x): the mol ratio of 0.10:x is carried out mixed preparing, adopts and adds the method for excessive bismuth ion to compensate Bi in annealing process
3+volatilization, and x=0.01～0.05.
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 any equivalence that those of ordinary skills take technical solution of the present invention by reading specification sheets of the present invention, is claim of the present invention and contains.
Claims (10)
1. the Bi of a high remnant polarization
0.90ho
0.10fe
1-xmn
xo
3ferroelectric membranc, is characterized in that: its chemical formula is Bi
0.90ho
0.10fe
1-xmn
xo
3, x=0.01～0.05; Under 1kHz frequency, its remnant polarization is 78～108 μ C/cm
2, specific inductivity is 196.2～271.8.
2. the Bi of high remnant polarization according to claim 1
0.90ho
0.10fe
1-xmn
xo
3ferroelectric membranc, is characterized in that: it is the perovskite structure of distortion, rhombohedral system, and space group is R-3m (160), unit cell parameters
grain size is 50～60nm.
3. the Bi of high remnant polarization according to claim 1 and 2
0.90ho
0.10fe
1-xmn
xo
3ferroelectric membranc, is characterized in that: comprise Bi
0.90ho
0.10fe
0.99mn
0.01o
3ferroelectric membranc, Bi
0.90ho
0.10fe
0.98mn
0.02o
3ferroelectric membranc, Bi
0.90ho
0.10fe
0.97mn
0.03o
3ferroelectric membranc and Bi
0.90ho
0.10fe
0.95mn
0.05o
3ferroelectric membranc;
And Bi
0.90ho
0.10fe
0.99mn
0.01o
3ferroelectric membranc is under the extra electric field of 917kV/cm, and remnant polarization is 108 μ C/cm
2, the specific inductivity under the frequency of 1kHz～1MHz is 218.1～271.8;
Bi
0.90ho
0.10fe
0.98mn
0.02o
3ferroelectric membranc is under the extra electric field of 1250kV/cm, and remnant polarization is 95 μ C/cm
2, the specific inductivity under the frequency of 1kHz～1MHz is 195.8～258.1;
Bi
0.90ho
0.10fe
0.97mn
0.03o
3ferroelectric membranc is under the extra electric field of 1250kV/cm, and remnant polarization is 88 μ C/cm
2, the specific inductivity under the frequency of 1kHz～1MHz is 166.9～231.9;
Bi
0.90ho
0.10fe
0.95mn
0.05o
3ferroelectric membranc is under the extra electric field of 1250kV/cm, and remnant polarization is 78 μ C/cm
2, the specific inductivity under the frequency of 1kHz～1MHz is 125.3～196.2.
4. the Bi of the high remnant polarization as described in any one in claim 1-3
0.90ho
0.10fe
1-xmn
xo
3the preparation method of ferroelectric membranc, is characterized in that, comprises the following steps:
Step 1: be 0.95:(1-x in molar ratio): 0.10:x is by Bi (NO
3)
35H
2o, Fe (NO
3)
39H
2o, Ho (NO
3)
36H
2o and C
4h
6mnO
44H
2o is dissolved in the mixed solution being mixed by ethylene glycol monomethyl ether and acetic anhydride, stirs, and obtains precursor liquid, and wherein in precursor liquid, total concentration of metal ions is 0.003～0.3mol/L, x=0.01～0.05;
Step 2: precursor liquid is spin-coated on FTO/glass substrate and prepares wet film, and wet film toasts to obtain dry film after even glue at 180～200 ℃, then 500～580 ℃ of annealing, obtains Bi
0.90ho
0.10fe
1-xmn
xo
3film;
Step 3: treat Bi
0.90ho
0.10fe
1-xmn
xo
3after film cooling, then at Bi
0.90ho
0.10fe
1-xmn
xo
3on film, repeating step 2, make Bi
0.90ho
0.10fe
1-xmn
xo
3film reaches desired thickness, obtains the Bi of high remnant polarization
0.90ho
0.10fe
1-xmn
xo
3ferroelectric membranc.
5. the Bi of high remnant polarization according to claim 4
0.90ho
0.10fe
1-xmn
xo
3the preparation method of ferroelectric membranc, is characterized in that: in described step 1, in mixed solution, the volume ratio of ethylene glycol monomethyl ether and acetic anhydride is (2.5～3.5): 1.
6. according to the Bi of the high remnant polarization described in claim 4 or 5
0.90ho
0.10fe
1-xmn
xo
3the preparation method of ferroelectric membranc, is characterized in that: x=0.01,0.02,0.03 or 0.05 in described step 1.
7. the Bi of high remnant polarization according to claim 4
0.90ho
0.10fe
1-xmn
xo
3the preparation method of ferroelectric membranc, is characterized in that: in described step 2, first FTO/glass substrate cleaned, dry, then radiation treatment under UV-light, makes FTO/glass substrate surface reach atomic cleanliness degree, finally spin coating precursor liquid again.
8. according to the Bi of the high remnant polarization described in claim 4 or 7
0.90ho
0.10fe
1-xmn
xo
3the preparation method of ferroelectric membranc, is characterized in that: the even glue speed in described step 2 during even glue is 3800～4100r/min, and the even glue time is 12～20s.
9. according to the Bi of the high remnant polarization described in claim 4 or 7
0.90ho
0.10fe
1-xmn
xo
3the preparation method of ferroelectric membranc, is characterized in that: the baking time in described step 2 after even glue is 8～12min.
10. according to the Bi of the high remnant polarization described in claim 4 or 7
0.90ho
0.10fe
1-xmn
xo
3the preparation method of ferroelectric membranc, is characterized in that: in described step 2, annealing time is 10～15min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310714707.4A CN103708562B (en) | 2013-12-20 | 2013-12-20 | Bi0.90Ho0.10Fe1-XMnXO3 ferroelectric film with high remanent polarization and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310714707.4A CN103708562B (en) | 2013-12-20 | 2013-12-20 | Bi0.90Ho0.10Fe1-XMnXO3 ferroelectric film with high remanent polarization and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103708562A true CN103708562A (en) | 2014-04-09 |
| CN103708562B CN103708562B (en) | 2015-06-24 |
Family
ID=50401965
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310714707.4A Active CN103708562B (en) | 2013-12-20 | 2013-12-20 | Bi0.90Ho0.10Fe1-XMnXO3 ferroelectric film with high remanent polarization and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103708562B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104478230A (en) * | 2014-12-11 | 2015-04-01 | 陕西科技大学 | Bi[0.92-x]Ho0.08AExFe0.97Mn0.03O3 multiferroic film and preparation method thereof |
| CN106379934A (en) * | 2016-11-23 | 2017-02-08 | 湖州师范学院 | Method for preparing Ho2TiO5 powder |
| CN107140971A (en) * | 2017-04-18 | 2017-09-08 | 陕西科技大学 | One kind has under high electric field to be stablized ferroelectric HoSrMnZn and is co-doped with bismuth ferrite ferroelectric thin film and preparation method thereof |
| CN113248248A (en) * | 2020-08-13 | 2021-08-13 | 深圳先进技术研究院 | Solid solution multiferroic film, preparation method and electronic device applied to 5G storage technology |
| CN113371760A (en) * | 2020-06-29 | 2021-09-10 | 贵州大学 | Perovskite-like structure bismuth ferrite material and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070138459A1 (en) * | 2005-10-13 | 2007-06-21 | Wong Stanislaus S | Ternary oxide nanostructures and methods of making same |
| CN102249659A (en) * | 2011-06-16 | 2011-11-23 | 桂林电子科技大学 | Bismuth ferrite-based leadless piezoelectric ceramic with high Curie temperature and preparation method thereof |
| CN102633443A (en) * | 2012-02-27 | 2012-08-15 | 陕西科技大学 | Method for preparing Tb-doped BiFeO3 ferroelectric film on surface of conductive glass substrate |
| CN102886934A (en) * | 2012-10-29 | 2013-01-23 | 哈尔滨工业大学 | Completely-crystallized multiferroic film without producing impure phase and preparation method thereof |
| CN102976764A (en) * | 2012-11-28 | 2013-03-20 | 陕西科技大学 | Preparation method of low-leakage current Bi0.92Tb0.08Fe(1-x)CrxO3 film |
| CN103121836A (en) * | 2012-11-28 | 2013-05-29 | 陕西科技大学 | Method for preparing BiFe1-xCrxO3 ferroelectric film by using sol-gel method |
-
2013
- 2013-12-20 CN CN201310714707.4A patent/CN103708562B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070138459A1 (en) * | 2005-10-13 | 2007-06-21 | Wong Stanislaus S | Ternary oxide nanostructures and methods of making same |
| CN102249659A (en) * | 2011-06-16 | 2011-11-23 | 桂林电子科技大学 | Bismuth ferrite-based leadless piezoelectric ceramic with high Curie temperature and preparation method thereof |
| CN102633443A (en) * | 2012-02-27 | 2012-08-15 | 陕西科技大学 | Method for preparing Tb-doped BiFeO3 ferroelectric film on surface of conductive glass substrate |
| CN102886934A (en) * | 2012-10-29 | 2013-01-23 | 哈尔滨工业大学 | Completely-crystallized multiferroic film without producing impure phase and preparation method thereof |
| CN102976764A (en) * | 2012-11-28 | 2013-03-20 | 陕西科技大学 | Preparation method of low-leakage current Bi0.92Tb0.08Fe(1-x)CrxO3 film |
| CN103121836A (en) * | 2012-11-28 | 2013-05-29 | 陕西科技大学 | Method for preparing BiFe1-xCrxO3 ferroelectric film by using sol-gel method |
Non-Patent Citations (7)
| Title |
|---|
| C.M.RAGHAVAN ET AL.: "Preparation and properties of rare earth (Eu, Tb, Ho)and transition metal (Co) co-doped BiFeO3 thin films", 《J SOL-GEL SCI TECHNOL》 * |
| C.M.RAGHAVAN ET AL.: "Structural and improved electrical properties of rare earth (Sm, Tb and Ho) doped BiFe0.975Mn0.025O3 thin films", 《J ELECTROCERAM》 * |
| CHENG CHUAN-PIN ET AL.: "Influence of pyrolysis temperature on ferroelectric properties of La and Mn co—doped BiFe03 thin films", 《TRANS．NONFERROUS MET．SOC．CHINA》 * |
| CHENG MENG ET AL.: "Preparation of Nd-dopedBiFeO3 films andtheirelectricalproperties", 《PHYSICA B》 * |
| WENLONG LIU ET AL.: "Structure transition and multiferroic properties of Mn-doped BiFeO3 thin films", 《J MATER SCI: MATER ELECTRON》 * |
| WENLONG LIU ET AL: "Lattice distortion and room-temperature ferroelectric properties of (Sm, Cr) co-doped BiFeO3 thin films", 《J MATER SCI: MATER ELECTRON》 * |
| 徐军等: "稀土元素钇和钬掺杂对铁酸铋磁性能的影响", 《武汉工程大学学报》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104478230A (en) * | 2014-12-11 | 2015-04-01 | 陕西科技大学 | Bi[0.92-x]Ho0.08AExFe0.97Mn0.03O3 multiferroic film and preparation method thereof |
| CN106379934A (en) * | 2016-11-23 | 2017-02-08 | 湖州师范学院 | Method for preparing Ho2TiO5 powder |
| CN107140971A (en) * | 2017-04-18 | 2017-09-08 | 陕西科技大学 | One kind has under high electric field to be stablized ferroelectric HoSrMnZn and is co-doped with bismuth ferrite ferroelectric thin film and preparation method thereof |
| CN107140971B (en) * | 2017-04-18 | 2020-06-30 | 陕西科技大学 | HoSrMnZn co-doped bismuth ferrite ferroelectric film with stable ferroelectricity under high electric field and preparation method thereof |
| CN113371760A (en) * | 2020-06-29 | 2021-09-10 | 贵州大学 | Perovskite-like structure bismuth ferrite material and preparation method and application thereof |
| CN113248248A (en) * | 2020-08-13 | 2021-08-13 | 深圳先进技术研究院 | Solid solution multiferroic film, preparation method and electronic device applied to 5G storage technology |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103708562B (en) | 2015-06-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103708562B (en) | Bi0.90Ho0.10Fe1-XMnXO3 ferroelectric film with high remanent polarization and preparation method thereof | |
| CN102534588B (en) | Method for preparing Nd/Co-codoped BiFeO3 film on FTO (fluorine-doped tin oxide)/glass substrate surface | |
| CN105271798B (en) | A kind of high-ferromagnetic can be with the Bi of ferroelectric properties0.9Er0.1Fe1‑xCoxO3Film and preparation method thereof | |
| CN104478234B (en) | A kind of Bi0.90er0.10fe0.96co0.02mn0.02o3/ Mn1-xcoxfe2o4composite membrane and preparation method thereof | |
| CN103723770B (en) | High-dielectric-constant Bi0.92Ho0.08Fe[1-x]MnxO3 ferroelectric film and preparation method thereof | |
| CN104445996A (en) | Multiferroic Bi0.96-xSr0.04RExFe0.94Mn0.04Cr0.02O3-NiFe2O4 composite film and preparation method thereof | |
| CN103044018A (en) | Method for preparing Bi0.85Sm0.15Fe1-xCrxO3 ferroelectric film via sol-gel process | |
| CN103121836B (en) | Method for preparing BiFe1-xCrxO3 ferroelectric film by using sol-gel method | |
| CN103771527B (en) | A kind of Bi of low coercive field 0.92dy 0.08fe 1-xmn xo 3ferroelectric membranc and preparation method thereof | |
| CN104478235A (en) | Multiferroic Bi(0.98-x)Sr0.02RExFe0.97Mn0.03O3-CuFe2O4 composite film and preparation method thereof | |
| CN102531405A (en) | Preparation method of Sm-doped BiFeO3 ferroelectric film on surface of fluorine-doped tin oxide (FTO)/glass substrate | |
| CN103771528B (en) | A kind of Bi of high-k 1-Xho xfeO 3ferroelectric membranc and preparation method thereof | |
| CN103601248B (en) | Tb, Mn and Ni ternary co-doped low leakage current BiFeO3 film and preparation method thereof | |
| CN104478236A (en) | Bi0.92Ho0.08Fe0.97Mn0.03O3-Zn1-xNixFe2O4 multiferroic composite film and preparation method thereof | |
| CN105906221B (en) | A kind of multiferroic Bi0.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3-CuFe2O4Composite membrane and preparation method thereof | |
| CN104478229B (en) | A kind of Bi1-xrExfe0.96co0.02mn0.02o3ferroelectric thin film and preparation method thereof | |
| CN103601247B (en) | Bi1-xSmxFe0.94Mn0.04Cr0.02O3 ferroelectric film with high remanent polarization and low leakage current density 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 | |
| CN103739019B (en) | A kind of BiFe of high remnant polarization 1-xmn xo 3ferroelectric membranc and preparation method thereof | |
| CN103663564B (en) | Bi0.90Dy0.10Fe1-XMnxO3 ferroelectric film with high dielectric constant, and preparation method for Bi0.90Dy0.10Fe1-XMnxO3 ferroelectric film with high dielectric constant | |
| CN104478228B (en) | A kind of Bi0.85‑xPr0.15AExFe0.97Mn0.03O3Ferroelectric thin film and preparation method thereof | |
| CN103626236B (en) | The BiFeO of a kind of B position Mn and Ni codoped high remnant polarization 3film and preparation method thereof | |
| CN104478230A (en) | Bi[0.92-x]Ho0.08AExFe0.97Mn0.03O3 multiferroic film and preparation method thereof | |
| CN103613144A (en) | B-site Mn and Cu codoped high remanent polarization BiFeO3 film and preparation method | |
| CN103693694B (en) | A kind of Bi 1-xdy xfeO 3low-leakage current film 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 | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |