CN103723770B - High-dielectric-constant Bi0.92Ho0.08Fe[1-x]MnxO3 ferroelectric film and preparation method thereof - Google Patents
High-dielectric-constant Bi0.92Ho0.08Fe[1-x]MnxO3 ferroelectric film and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a high-dielectric-constant Bi0.92Ho0.08Fe[1-x]MnxO3 ferroelectric film (x=0.01-0.05) and a preparation method thereof. The film is in a distorted perovskite structure belonging to a rhombohedral system, and has favorable uniformity; and the remanent polarization is 88-116 mu C/cm<2>, and the dielectric constant is 223.1-327.3. The preparation method comprises the following steps: dissolving bismuth nitrate, iron nitrate, holmium nitrate and manganese acetate in an ethylene glycol monomethyl ether-acetic anhydride mixed solution to obtain a precursor solution; evenly spin-coating the precursor solution on a substrate, baking to obtain a dry film, and annealing to obtain a Bi0.92Ho0.08Fe[1-x]MnxO3 film; and spin-coating the precursor solution again, baking and annealing to the required film thickness, thereby obtaining the film. The method has the advantages of simple facility request and controllable doping amount, and can greatly enhance the dielectric properties of the BiFeO3 film.
Description
Technical field
The invention belongs to field of functional materials, be specifically related to a kind of Bi of high-k
0.92ho
0.08fe
1-xmn
xo
3ferroelectric membranc and preparation method thereof.
Background technology
As the typical single-phase multiferroic perovskite material of one, BiFeO
3that minority at room temperature has one of ferroelectricity and ferromagnetic material (T simultaneously
c=1103K, T
n=640K).BiFeO
3under room temperature, there is magneto-electric coupled character, in message memory, spin electric device and pyroelectric effect etc., have potential application prospect, so make BiFeO
3become the focus studied in recent years.
But, pure phase BiFeO
3material has 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+price reduction is Fe
2+, 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.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.Due to the restriction of preparation technology and apparatus for preparation, and BiFeO
3the temperature range existed is very narrow, so can produce dephasign unavoidably when preparing sample, thus causes BiFeO
3material has that larger leakage current, resistivity are lower, specific inductivity is less, and withstand voltage is low, is difficult to obtain saturated magnetic hysteresis loop and large residual polarization, thus seriously hinders this application of material in fields such as magnetic storages.
Summary of the invention
The object of the present invention is to provide a kind of Bi of high-k
0.92ho
0.08fe
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 easily controls, and can increase substantially the dielectric properties of film.
To achieve these goals, the present invention adopts following technical scheme:
A kind of Bi of high-k
0.92ho
0.08fe
1-xmn
xo
3ferroelectric membranc, its chemical formula is Bi
0.92ho
0.08fe
1-xmn
xo
3, x=0.01 ~ 0.05; Under 1kHz frequency, its remnant polarization is 88 ~ 116 μ C/cm
2, specific inductivity is 223.1 ~ 327.3.
Its perovskite structure being distortion, rhombohedral system, space group is R-3m (160), unit cell parameters
grain size is 50 ~ 60nm.
Comprise Bi
0.92ho
0.08fe
0.99mn
0.01o
3ferroelectric membranc, Bi
0.92ho
0.08fe
0.98mn
0.02o
3ferroelectric membranc, Bi
0.92ho
0.08fe
0.97mn
0.03o
3ferroelectric membranc and Bi
0.92ho
0.08fe
0.95mn
0.05o
3ferroelectric membranc;
And Bi
0.92ho
0.08fe
0.99mn
0.01o
3ferroelectric membranc is under the extra electric field of 917kV/cm, and remnant polarization is 100 μ C/cm
2, the specific inductivity under the frequency of 1kHz ~ 1MHz is 188.1 ~ 237.1;
Bi
0.92ho
0.08fe
0.98mn
0.02o
3ferroelectric membranc is under the extra electric field of 1000kV/cm, and remnant polarization is 88 μ C/cm
2, the specific inductivity under the frequency of 1kHz ~ 1MHz is 168.8 ~ 223.1;
Bi
0.92ho
0.08fe
0.97mn
0.03o
3ferroelectric membranc is under the extra electric field of 1083kV/cm, and remnant polarization is 116 μ C/cm
2, the specific inductivity under the frequency of 1kHz ~ 1MHz is 235.2 ~ 305.2;
Bi
0.92ho
0.08fe
0.95mn
0.05o
3ferroelectric membranc is under the extra electric field of 917kV/cm, and remnant polarization is 92 μ C/cm
2, the specific inductivity under the frequency of 1kHz ~ 1MHz is 227.6 ~ 327.3.
The Bi of high-k
0.92ho
0.08fe
1-xmn
xo
3the preparation method of ferroelectric membranc, comprises the following steps:
Step 1: be 0.97:(1-x in molar ratio): 0.08: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 mixed by ethylene glycol monomethyl ether and acetic anhydride, stirs, and obtains precursor liquid, and wherein total in precursor liquid concentration of metal ions is 0.003 ~ 0.3mol/L, x=0.01 ~ 0.05;
Step 2: be spin-coated on by precursor liquid on FTO/glass substrate and prepare wet film, wet film toasts to obtain dry film after even glue at 180 ~ 200 DEG C, then 500 ~ 580 DEG C of annealing, obtain Bi
0.92ho
0.08fe
1-xmn
xo
3film;
Step 3: treat Bi
0.92ho
0.08fe
1-xmn
xo
3after film cooling, then at Bi
0.92ho
0.08fe
1-xmn
xo
3on film, repeating step 2, makes Bi
0.92ho
0.08fe
1-xmn
xo
3film reaches desired thickness, namely obtains the Bi of high-k
0.92ho
0.08fe
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.
First cleaned by FTO/glass substrate in described step 2, dry, then radiation treatment under ultraviolet 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 spin coating 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.
Relative to prior art, the present invention has following beneficial effect:
The invention provides a kind of Bi of high-k
0.92ho
0.08fe
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-k at FTO/glass substrate surface
0.92ho
0.08fe
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 iron oxygen octahedra in perovskite structure, simultaneously because Ho instead of part Bi, the volatile quantity of Bi in annealing process is reduced, thus decreases the generation of Lacking oxygen, can Bi be made
0.92ho
0.08fe
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 selected is+divalent, so at alternative Fe
3+time to reduce the generation of Lacking oxygen because of charge compensation effect, thus effectively can reduce leakage current, the electrical property of raising film integral.Simultaneously to B position Fe
3+the alternative magnetic structure that can affect its intra-die consumingly of ion, and then affect 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 in perovskite structure originally, and structural aberration aggravates, thus drastically increases 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 is alternative ") prepares high-k
0.92ho
0.08fe
1-xmn
xo
3ferroelectric membranc.This method can take into account the advantage of two kinds of substitute element, and partly overcomes single element and replace the shortcoming brought, 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 the problem that the Fe solved in membrane-film preparation process appraises at the current rate and Bi volatilizees, be suitable for preparing film on large surface and surface in irregular shape simultaneously, easy handling and doping vario-property, effectively can control component and the structure of film, film chemical composition controllable precise, doping easily controls, be particularly suitable for preparation multicomponent oxide film material, accurately can control the stoichiometric ratio of film, be easy to the Uniform Doped realized on molecular level.
The Bi of the high-k that the present invention obtains
0.92ho
0.08fe
1-xmn
xo
3the perovskite structure that ferroelectric membranc (x=0.01 ~ 0.05) is distortion, rhombohedral system, space group is R-3m (160), unit cell parameters
grain size is 50 ~ 60nm, good uniformity, and under 1kHz frequency, its remnant polarization is 88 ~ 116 μ C/cm
2, specific inductivity is 223.1 ~ 327.3, has increased substantially BiFeO
3the ferroelectric properties of film and dielectric properties.
Accompanying drawing explanation
Fig. 1 is the Bi of high-k prepared by the present invention
0.92ho
0.08fe
1-xmn
xo
3the XRD spectra of ferroelectric membranc;
Fig. 2 is the Bi of high-k prepared by the present invention
0.92ho
0.08fe
1-xmn
xo
3the SEM figure of ferroelectric membranc, wherein (a) non-doped with Mn of preparing for comparative example
2+bi
0.92ho
0.08feO
3the SEM collection of illustrative plates of film, (b) ~ (e) is respectively Bi prepared by embodiment 1 ~ embodiment 4
0.92ho
0.08fe
1-xmn
xo
3the SEM collection of illustrative plates of ferroelectric membranc, the Bi that (f) is prepared for embodiment 2
0.92ho
0.08fe
0.98mn
0.02o
3the section SEM of ferroelectric membranc schemes;
Fig. 3 is the Bi of high-k prepared by the present invention
0.92ho
0.08fe
1-xmn
xo
3the ferroelectric hysteresis loop figure of ferroelectric membranc;
Fig. 4 is the Bi of high-k prepared by the present invention
0.92ho
0.08fe
1-xmn
xo
3the dielectric properties of ferroelectric membranc and frequency relation figure.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in further detail.
Comparative example
Step 1: select 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.Again FTO/glass substrate is put into 70 DEG C of baking oven baking 5min, take out and leave standstill to room temperature.Finally FTO/glass substrate is placed in ultraviolet radiation instrument and irradiates 40min, substrate surface is reached " atomic cleanliness degree ".
Step 2: be 0.97:1:0.08(and x=0 in molar ratio) 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 that the ethylene glycol monomethyl ether of 3:1 and acetic anhydride mix by volume ratio, and concentration of metal ions total in precursor liquid is 0.3mol/L.
Step 3: adopt spin coating precursor liquid on the FTO/glass substrate of spin-coating method after processing through step 1 to prepare wet film, with the even glue 20s of even glue speed of 4000r/min, after even cementing bundle, at 200 DEG C, toast 10min obtain dry film, and then at 550 DEG C short annealing 10min, obtain Bi
0.92ho
0.08feO
3film.
Step 4: treat Bi
0.92ho
0.08feO
3after film cooling, then at Bi
0.92ho
0.08feO
3on film, repeating step 2, makes Bi
0.92ho
0.08feO
3film reaches desired thickness, namely obtains Bi
0.92ho
0.08feO
3ferroelectric membranc.
At Bi
0.92ho
0.08feO
3ferroelectric membranc surface ion Slag coating 0.502mm
2au electrode, then 280 DEG C insulation 25min carry out electrode anneal process, electrode is contacted completely with substrate.Adopt XRD determining Bi
0.92ho
0.08feO
3the thing phase composite structure of ferroelectric membranc, as shown in Figure 1, Bi
0.92ho
0.08feO
3ferroelectric membranc belongs to the perovskite structure of distortion, rhombohedral system, and space group is R-3m (160), unit cell parameters
bi is measured with FE-SEM
0.92ho
0.08feO
3the microscopic appearance of film, be about 100 ~ 120nm by Fig. 2 (a) its grain-size known, film thickness is 580nm.With the ferroelectric test system and test Bi of TF2000
0.92ho
0.08feO
3the ferroelectric properties of ferroelectric membranc, can find out Bi by Fig. 3 (a)
0.92ho
0.08feO
3film there is no saturated ferroelectric hysteresis loop, and under the electric field of 333kV/cm, remains polarization value only have 47 μ C/cm
2.With Agilent E4980A LCR test set test b i
0.92ho
0.08feO
3the dielectric properties of ferroelectric membranc, as seen from Figure 4, under the frequency of 1kHz ~ 1MHz, Bi
0.92ho
0.08feO
3the specific inductivity of ferroelectric membranc is 212.7 ~ 257.1.
Embodiment 1
Step 1: select 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.Again FTO/glass substrate is put into 70 DEG C of baking oven baking 5min, take out and leave standstill to room temperature.Finally FTO/glass substrate is placed in ultraviolet radiation instrument and irradiates 40min, substrate surface is reached " atomic cleanliness degree ".
Step 2: be 0.97:0.99:0.08:0.01(and x=0.01 in molar ratio) 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 that the ethylene glycol monomethyl ether of 3:1 and acetic anhydride mix by volume ratio, and concentration of metal ions total in precursor liquid is 0.3mol/L.
Step 3: adopt spin coating precursor liquid on the FTO/glass substrate of spin-coating method after processing through step 1 to prepare wet film, with the even glue 20s of even glue speed of 4000r/min, after even cementing bundle, at 200 DEG C, toast 10min obtain dry film, and then at 550 DEG C short annealing 10min, obtain Bi
0.92ho
0.08fe
0.99mn
0.01o
3film.
Step 4: treat Bi
0.92ho
0.08fe
0.99mn
0.01o
3after film cooling, then at Bi
0.92ho
0.08fe
0.99mn
0.01o
3on film, repeating step 2, makes Bi
0.92ho
0.08fe
0.99mn
0.01o
3film reaches desired thickness, namely obtains the Bi of high-k
0.92ho
0.08fe
0.99mn
0.01o
3ferroelectric membranc.
At the Bi of high-k
0.92ho
0.08fe
0.99mn
0.01o
3ferroelectric membranc surface ion Slag coating 0.502mm
2au electrode, then 280 DEG C insulation 25min carry out electrode anneal process, electrode is contacted completely with substrate.Adopt the Bi of XRD determining high-k
0.92ho
0.08fe
0.99mn
0.01o
3the thing phase composite structure of ferroelectric membranc, as shown in Figure 1, the Bi of high-k
0.92ho
0.08fe
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
bi is measured with FE-SEM
0.92ho
0.08fe
0.99mn
0.01o
3the microscopic appearance of ferroelectric membranc, be about 60nm by Fig. 2 (b) its grain-size known, film thickness is 530nm.With the Bi of the ferroelectric test system and test high-k of TF2000
0.92ho
0.08fe
0.99mn
0.01o
3the ferroelectric properties of ferroelectric membranc, as can be seen from Fig. 3 (b), under the extra electric field of 917kV/cm, its remnant polarization is 100 μ C/cm
2.With the Bi of Agilent E4980A LCR test set test high-k
0.92ho
0.08fe
0.99mn
0.01o
3the dielectric properties of ferroelectric membranc, as seen from Figure 4, under the frequency of 1kHz ~ 1MHz, its specific inductivity is 188.1 ~ 237.1.
Embodiment 2
Step 1: select 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.Again FTO/glass substrate is put into 70 DEG C of baking oven baking 5min, take out and leave standstill to room temperature.Finally FTO/glass substrate is placed in ultraviolet radiation instrument and irradiates 40min, substrate surface is reached " atomic cleanliness degree ".
Step 2: be 0.97:0.98:0.08:0.02(and x=0.02 in molar ratio) 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 that the ethylene glycol monomethyl ether of 3:1 and acetic anhydride mix by volume ratio, and concentration of metal ions total in precursor liquid is 0.3mol/L.
Step 3: adopt spin coating precursor liquid on the FTO/glass substrate of spin-coating method after processing through step 1 to prepare wet film, with the even glue 20s of even glue speed of 4000r/min, after even cementing bundle, at 200 DEG C, toast 10min obtain dry film, and then at 550 DEG C short annealing 10min, obtain Bi
0.92ho
0.08fe
0.98mn
0.02o
3film.
Step 4: treat Bi
0.92ho
0.08fe
0.98mn
0.02o
3after film cooling, then at Bi
0.92ho
0.08fe
0.98mn
0.02o
3on film, repeating step 2, makes Bi
0.92ho
0.08fe
0.98mn
0.02o
3film reaches desired thickness, namely obtains the Bi of high-k
0.92ho
0.08fe
0.98mn
0.02o
3ferroelectric membranc.
At the Bi of high-k
0.92ho
0.08fe
0.98mn
0.02o
3ferroelectric membranc surface ion Slag coating 0.502mm
2au electrode, then 280 DEG C insulation 25min carry out electrode anneal process, electrode is contacted completely with substrate.Adopt the Bi of XRD determining high-k
0.92ho
0.08fe
0.98mn
0.02o
3the thing phase composite structure of ferroelectric membranc, as shown in Figure 1, the Bi of high-k
0.92ho
0.08fe
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
the Bi of high-k is measured with FE-SEM
0.92ho
0.08fe
0.98mn
0.02o
3the microscopic appearance of ferroelectric membranc, be about 50nm by Fig. 2 (c) its grain-size known, film thickness is 500nm.With the Bi of the ferroelectric test system and test high-k of TF2000
0.92ho
0.08fe
0.98mn
0.02o
3the ferroelectric properties of ferroelectric membranc, as can be seen from Fig. 3 (c), under the extra electric field of 1000kV/cm, its remnant polarization is 88 μ C/cm
2.With the Bi of Agilent E4980A LCR test set test high-k
0.92ho
0.08fe
0.98mn
0.02o
3the dielectric properties of ferroelectric membranc, as seen from Figure 4, under the frequency of 1kHz ~ 1MHz, its specific inductivity is 168.8 ~ 223.1.
Embodiment 3
Step 1: select 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.Again FTO/glass substrate is put into 70 DEG C of baking oven baking 5min, take out and leave standstill to room temperature.Finally FTO/glass substrate is placed in ultraviolet radiation instrument and irradiates 40min, substrate surface is reached " atomic cleanliness degree ".
Step 2: be 0.97:0.97:0.08:0.03(and x=0.03 in molar ratio) 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 that the ethylene glycol monomethyl ether of 3:1 and acetic anhydride mix by volume ratio, and concentration of metal ions total in precursor liquid is 0.3mol/L.
Step 3: adopt spin coating precursor liquid on the FTO/glass substrate of spin-coating method after processing through step 1 to prepare wet film, with the even glue 20s of even glue speed of 4000r/min, after even cementing bundle, at 200 DEG C, toast 10min obtain dry film, and then at 550 DEG C short annealing 10min, obtain Bi
0.92ho
0.08fe
0.97mn
0.03o
3film.
Step 4: treat Bi
0.92ho
0.08fe
0.97mn
0.03o
3after film cooling, then at Bi
0.92ho
0.08fe
0.97mn
0.03o
3on film, repeating step 2, makes Bi
0.92ho
0.08fe
0.97mn
0.03o
3film reaches desired thickness, namely obtains the Bi of high-k
0.92ho
0.08fe
0.97mn
0.03o
3ferroelectric membranc.
At the Bi of high-k
0.92ho
0.08fe
0.97mn
0.03o
3ferroelectric membranc surface ion Slag coating 0.502mm
2au electrode, then 280 DEG C insulation 25min carry out electrode anneal process, electrode is contacted completely with substrate.Adopt the Bi of XRD determining high-k
0.92ho
0.08fe
0.97mn
0.03o
3the thing phase composite structure of ferroelectric membranc, as shown in Figure 1, the Bi of high-k
0.92ho
0.08fe
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
the Bi of high-k is measured with FE-SEM
0.92ho
0.08fe
0.97mn
0.03o
3the microscopic appearance of ferroelectric membranc, be about 60nm by Fig. 2 (d) its grain-size known, film thickness is 510nm.With the Bi of the ferroelectric test system and test high-k of TF2000
0.92ho
0.08fe
0.97mn
0.03o
3the ferroelectric properties of ferroelectric membranc, under the extra electric field of 1083kV/cm, its remnant polarization is 116 μ C/cm
2.With the Bi of Agilent E4980A LCR test set test high-k
0.92ho
0.08fe
0.97mn
0.03o
3the dielectric properties of ferroelectric membranc, as seen from Figure 4, under the frequency of 1kHz ~ 1MHz, its specific inductivity is 235.2 ~ 305.2.
Embodiment 4
Step 1: select 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.Again FTO/glass substrate is put into 70 DEG C of baking oven baking 5min, take out and leave standstill to room temperature.Finally FTO/glass substrate is placed in ultraviolet radiation instrument and irradiates 40min, substrate surface is reached " atomic cleanliness degree ".
Step 2: be 0.97:0.95:0.08:0.05(and x=0.05 in molar ratio) 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 that the ethylene glycol monomethyl ether of 3:1 and acetic anhydride mix by volume ratio, and concentration of metal ions total in precursor liquid is 0.3mol/L.
Step 3: adopt spin coating precursor liquid on the FTO/glass substrate of spin-coating method after processing through step 1 to prepare wet film, with the even glue 20s of even glue speed of 4000r/min, after even cementing bundle, at 200 DEG C, toast 10min obtain dry film, and then at 550 DEG C short annealing 10min, obtain Bi
0.92ho
0.08fe
0.95mn
0.05o
3film.
Step 4: treat Bi
0.92ho
0.08fe
0.95mn
0.05o
3after film cooling, then at Bi
0.92ho
0.08fe
0.95mn
0.05o
3on film, repeating step 2, makes Bi
0.92ho
0.08fe
0.95mn
0.05o
3film reaches desired thickness, namely obtains the Bi of high-k
0.92ho
0.08fe
0.95mn
0.05o
3ferroelectric membranc.
At the Bi of high-k
0.92ho
0.08fe
0.95mn
0.05o
3ferroelectric membranc surface ion Slag coating 0.502mm
2au electrode, then 280 DEG C insulation 25min carry out electrode anneal process, electrode is contacted completely with substrate.Adopt the Bi of XRD determining high-k
0.92ho
0.08fe
0.95mn
0.05o
3the thing phase composite structure of ferroelectric membranc, as shown in Figure 1, the Bi of high-k
0.92ho
0.08fe
0.95mn
0.05o
3ferroelectric membranc belongs to the perovskite structure of distortion, rhombohedral system, and space group is R3m (160), unit cell parameters
the Bi of high-k is measured with FE-SEM
0.92ho
0.08fe
0.95mn
0.05o
3the microscopic appearance of ferroelectric membranc, be about 50nm by Fig. 2 (e) its grain-size known, film thickness is 500nm.With the Bi of the ferroelectric test system and test high-k of TF2000
0.92ho
0.08fe
0.95mn
0.05o
3the ferroelectric properties of ferroelectric membranc, as can be seen from Fig. 3 (e), under the extra electric field of 917kV/cm, its remnant polarization is 92 μ C/cm
2.With the Bi of Agilent E4980A LCR test set test high-k
0.92ho
0.08fe
0.95mn
0.05o
3the dielectric properties of ferroelectric membranc, as seen from Figure 4, under the frequency of 1kHz ~ 1MHz, its specific inductivity is 227.6 ~ 327.3.
Fig. 1 is different Mn
2+the Bi prepared under doping
0.92ho
0.08fe
1-xmn
xo
3the XRD figure spectrum of ferroelectric membranc, in Fig. 1, the unit a.u. of ordinate zou represents that it is arbitrary unit, and X-coordinate 2 θ is angle of diffraction.As can be seen from Figure 1 Bi
0.92ho
0.08fe
1-xmn
xo
3the diffraction peak of ferroelectric membranc (012) and (110) crystal face is increased in along with doping skew of turning left gradually, illustrates that film internal structure there occurs change.
Embodiment 5
Step 1: select 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.Again FTO/glass substrate is put into 70 DEG C of baking oven baking 5min, take out and leave standstill to room temperature.Finally FTO/glass substrate is placed in ultraviolet radiation instrument and irradiates 40min, substrate surface is reached " atomic cleanliness degree ".
Step 2: be 0.97:0.96:0.08:0.04(and x=0.04 in molar ratio) 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 that the ethylene glycol monomethyl ether of 3.5:1 and acetic anhydride mix by volume ratio, and concentration of metal ions total in precursor liquid is 0.003mol/L.
Step 3: adopt spin coating precursor liquid on the FTO/glass substrate of spin-coating method after processing through step 1 to prepare wet film, with the even glue 15s of even glue speed of 3800r/min, after even cementing bundle, at 180 DEG C, toast 8min obtain dry film, and then at 500 DEG C short annealing 15min, obtain Bi
0.92ho
0.08fe
0.96mn
0.04o
3film.
Step 4: treat Bi
0.92ho
0.08fe
0.96mn
0.04o
3after film cooling, then at Bi
0.92ho
0.08fe
0.96mn
0.04o
3on film, repeating step 2, makes Bi
0.92ho
0.08fe
0.96mn
0.04o
3film reaches desired thickness, namely obtains the Bi of high-k
0.92ho
0.08fe
0.96mn
0.04o
3ferroelectric membranc.
Embodiment 6
Step 1: select 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.Again FTO/glass substrate is put into 70 DEG C of baking oven baking 5min, take out and leave standstill to room temperature.Finally FTO/glass substrate is placed in ultraviolet radiation instrument and irradiates 40min, substrate surface is reached " atomic cleanliness degree ".
Step 2: be 0.97:0.975:0.08:0.025(and x=0.025 in molar ratio) 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 that the ethylene glycol monomethyl ether of 2.5:1 and acetic anhydride mix by volume ratio, and concentration of metal ions total in precursor liquid is 0.1mol/L.
Step 3: adopt spin coating precursor liquid on the FTO/glass substrate of spin-coating method after processing through step 1 to prepare wet film, with the even glue 12s of even glue speed of 4100r/min, after even cementing bundle, at 190 DEG C, toast 12min obtain dry film, and then at 580 DEG C short annealing 12min, obtain Bi
0.92ho
0.08fe
0.975mn
0.025o
3film.
Step 4:Bi
0.92ho
0.08fe
0.975mn
0.025o
3after film cooling, then at Bi
0.92ho
0.08fe
0.975mn
0.025o
3on film, repeating step 2, makes Bi
0.92ho
0.08fe
0.975mn
0.025o
3film reaches desired thickness, namely obtains the Bi of high-k
0.92ho
0.08fe
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
2and manganous acetate (C O)
4h
6mnO
44H
2o) theoretical molar is than being 0.92:(1-x): 0.08:x, x=0.01 ~ 0.05; But due in the process of carrying out annealing in step 2, Bi
3+have the volatilization loss of part, therefore, the present invention prepares in the process of precursor liquid in step 1, Bismuth trinitrate, iron nitrate, holmium nitrate and manganous acetate are according to 0.97:(1-x): the mol ratio of 0.08:x carries out mixed preparing, namely adopts the method adding 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 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 (7)
1. the Bi of a high-k
0.92ho
0.08fe
1-xmn
xo
3the preparation method of ferroelectric membranc, is characterized in that, comprises the following steps:
Step 1: be 0.97:(1-x in molar ratio): 0.08: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 mixed by ethylene glycol monomethyl ether and acetic anhydride, stirs, and obtains precursor liquid, and wherein total in precursor liquid concentration of metal ions is 0.003 ~ 0.3mol/L, x=0.01 ~ 0.05;
Step 2: be spin-coated on by precursor liquid on FTO/glass substrate and prepare wet film, wet film toasts 8 ~ 12min and obtains dry film after even glue at 180 ~ 200 DEG C, then at 500 ~ 580 DEG C of annealing 10 ~ 15min, obtains Bi
0.92ho
0.08fe
1-xmn
xo
3film;
Step 3: treat Bi
0.92ho
0.08fe
1-xmn
xo
3after film cooling, then at Bi
0.92ho
0.08fe
1-xmn
xo
3on film, repeating step 2, makes Bi
0.92ho
0.08fe
1-xmn
xo
3film reaches desired thickness, namely obtains the Bi of high-k
0.92ho
0.08fe
1-xmn
xo
3ferroelectric membranc.
2. the Bi of high-k according to claim 1
0.92ho
0.08fe
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.
3. the Bi of high-k according to claim 1 and 2
0.92ho
0.08fe
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.
4. the Bi of high-k according to claim 1
0.92ho
0.08fe
1-xmn
xo
3the preparation method of ferroelectric membranc, is characterized in that: first cleaned by FTO/glass substrate in described step 2, dry, then radiation treatment under ultraviolet light, makes FTO/glass substrate surface reach atomic cleanliness degree, then spin coating precursor liquid.
5. the Bi of the high-k according to claim 1 or 4
0.92ho
0.08fe
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 spin coating time is 12 ~ 20s.
6. the Bi of a high-k
0.92ho
0.08fe
1-xmn
xo
3ferroelectric membranc, is characterized in that: its chemical formula is Bi
0.92ho
0.08fe
1-xmn
xo
3, 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; Under 1kHz frequency, its remnant polarization is 88 ~ 116 μ C/cm
2, specific inductivity is 223.1 ~ 327.3.
7. the Bi of high-k according to claim 6
0.92ho
0.08fe
1-xmn
xo
3ferroelectric membranc, is characterized in that: comprise Bi
0.92ho
0.08fe
0.99mn
0.01o
3ferroelectric membranc, Bi
0.92ho
0.08fe
0.98mn
0.02o
3ferroelectric membranc, Bi
0.92ho
0.08fe
0.97mn
0.03o
3ferroelectric membranc and Bi
0.92ho
0.08fe
0.95mn
0.05o
3ferroelectric membranc;
And Bi
0.92ho
0.08fe
0.99mn
0.01o
3ferroelectric membranc is under the extra electric field of 917kV/cm, and remnant polarization is 100 μ C/cm
2, the specific inductivity under the frequency of 1kHz ~ 1MHz is 188.1 ~ 237.1;
Bi
0.92ho
0.08fe
0.98mn
0.02o
3ferroelectric membranc is under the extra electric field of 1000kV/cm, and remnant polarization is 88 μ C/cm
2, the specific inductivity under the frequency of 1kHz ~ 1MHz is 168.8 ~ 223.1;
Bi
0.92ho
0.08fe
0.97mn
0.03o
3ferroelectric membranc is under the extra electric field of 1083kV/cm, and remnant polarization is 116 μ C/cm
2, the specific inductivity under the frequency of 1kHz ~ 1MHz is 235.2 ~ 305.2;
Bi
0.92ho
0.08fe
0.95mn
0.05o
3ferroelectric membranc is under the extra electric field of 917kV/cm, and remnant polarization is 92 μ C/cm
2, the specific inductivity under the frequency of 1kHz ~ 1MHz is 227.6 ~ 327.3.
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| 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 |
| CN107032631B (en) * | 2017-04-18 | 2019-10-29 | 陕西科技大学 | A kind of GdSrMnCo is co-doped with more iron thin films of bismuth ferrite and preparation method thereof |
| CN107098395B (en) * | 2017-04-18 | 2018-11-09 | 陕西科技大学 | A kind of HoSrMnZn is co-doped with tripartite's bismuth ferrite superlattice film and preparation method thereof |
| CN110137346B (en) * | 2019-06-18 | 2023-04-18 | 西安工业大学 | Manganese-doped holmium ferrite HoMn x Fe 1-x O 3 Preparation method of magnetoelectric material |
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| CN102557473A (en) * | 2011-12-19 | 2012-07-11 | 陕西科技大学 | Method for preparing porous bismuth ferrate thin film by CSD (Chemical Solution Deposition) method |
| CN103058646A (en) * | 2012-11-07 | 2013-04-24 | 陕西科技大学 | Method for preparing Tb/Cr-codoped high-remanent-polarization BiFeO3 film by sol-gel process |
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