CN104496468A - Method for realizing coercive field reduction and pressure resistance improvement of sodium bismuth titanate-based film - Google Patents
Method for realizing coercive field reduction and pressure resistance improvement of sodium bismuth titanate-based film Download PDFInfo
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Abstract
The invention belongs to the field of electronic functional materials, and concretely relates to a method for realizing coercive field reduction and pressure resistance improvement of a sodium bismuth titanate-based film. The general chemical formula of the film is Na0.5Bi0.5Ti1-xMnxO3-delta, wherein x is the mole content of manganese ions, x is greater than 0 and smaller than 0.05, and delta is the number of oxygen atoms which are lost to maintain the charge balance. An optimized chemical solution deposition preparation technology is adopted on the basis of the doping of the manganese ions to make the sodium bismuth titanate-based film with good ferroelectricity and dielectricity on an ITO/glass substrate. The sodium bismuth titanate-based film can be used to develop ferroelectric and dielectric functional materials and devices.
Description
Technical field
The invention belongs to electronic functional material and devices field, what be specifically related to is a kind of method reducing bismuth-sodium titanate base film coercive field and improve its resistance to pressure.
Background technology
Lead-free ferroelectric material bismuth-sodium titanate (Na
0.5bi
0.5tiO
3) due to it, there is higher Curie temperature (T
c=320 ° of C), (remnant polarization can reach P to stronger ferroelectricity
r=38 μ C/cm
2) and receive much concern.For thin-film state, high temperature crystallization (~ 700 ° of C) process inevitably also exists the volatilization of element, and the height caused thus electric leakage makes the residual polarization of film less than normal; And the factors such as the microtexture ununiformity caused in high temperature crystallization process can cause the increase of coercive field.Thus limit Na
0.5bi
0.5tiO
3the application of film in electronic component.In order to improve Na
0.5bi
0.5tiO
3the electrical properties of thin-film state, people have carried out a series of research, can be summarized as the following aspects: (i) improves the crystalline quality of film; As: the Na of (100) orientation
0.5bi
0.5tiO
3film under 330 kV/cm strength of electric field, residual polarization (P
r) be 12.6 μ C/cm
2, corresponding coercive field (E
c) be 92 kV/cm (reference: M. Bousquet, J.-R. Duclere, C. Champeaux, A. Boulle, P. Marchet, A. Catherinot, A. Wu, P.M. Vilarinho, S. D é putier, M. Guilloux-Viry, A. Crunteanu, B. Gautier, D. Albertini, and C. Bachelet, Macroscopic and nanoscale electrical properties of pulsed laser deposited (100) epitaxial lead-free Na
0.5bi
0.5tiO
3thin films,
j. Appl. Phys, 2010,
107, 034102.).(ii) heterogenous multilayer structure is built by introducing buffer layer; As: sandwich structure Pb (Zr
0.4ti
0.6) O
3/ (Na
0.5bi
0.5)
0.94ba
0.06tiO
3/ Pb (Zr
0.4ti
0.6) O
3film under 1000 kV/cm strength of electric field, residual polarization (P
r) be 17 μ C/cm
2, corresponding coercive field (E
c) be 56 kV/cm (reference: Y.P. Guo, M. Li, W. Zhao, D. Akai, K. Sawada, M. Ishida, M.Y. Gu, Ferroelectric and pyroelectric properties of (Na
0.5bi
0.5) TiO
3-BaTiO
3based trilayered thin films,
thin Solid Films, 2009,
517, 2974-2978.).(iii) by forming sosoloid with other ferroelectric material, especially there is the film of accurate homotype phase boundary; As: (Na
0.5bi
0.5)
0.94ba
0.06tiO
3film under 340 kV/cm strength of electric field, residual polarization (P
r) be 14.5 μ C/cm
2, corresponding coercive field (E
c) be 102 kV/cm (reference: D.Y. Wang, N.Y. Chan, S. Li, S.H. Choy, H.Y. Tian, H.L. W. Chan, Enhanced ferroelectric and piezoelectric properties in doped lead-free (Na
0.5bi
0.5)
0.94ba
0.06tiO
3thin films,
appl. Phys. Lett., 2010,
97, 212901.).(iv) ion doping; As: manganese ion doping Na prepared by pulsed laser deposition technique
0.5bi
0.5tiO
3film under 240 kV/cm strength of electric field, residual polarization (P
r) be 23 μ C/cm
2, corresponding coercive field (E
c) be 60 kV/cm (reference: M.M. Hejazi, E. Taghaddos, A. Safari, Reduced leakage current and enhanced ferroelectric properties in Mn-doped Na
0.5bi
0.5tiO
3-based thin films,
j. Mater. Sci., 2013,48,3511-3516.).Above example is relative to pure phase Na
0.5bi
0.5tiO
3film (under the peak voltage of 550 kV/cm, P
r=10 μ C/cm
2, corresponding E
c=130 kV/cm.Reference: Jinbao Xu, Yun Liu, Ray L. Withers, Frank Brink, Hui Yang, and Mark Wang, Ferroelectric and non-linear dielectric characteristics of Bi
0.5na
0.5tiO
3thin films deposited via a metallorganic decomposition process,
j. Appl. Phys, 2008,
104, 116101), the suppression of leakage current makes the residual polarization value of measurement all increase.And the ratio of coercive field in above-mentioned unleaded example and maximum field intensity is all greater than 0.2, relatively and lead-based ferroelectric thin film material, coercive field need further reduction.
As everyone knows, lead base ferroelectric material possesses the feature of high residual polarization and low coercive field simultaneously.Such as, 0.68Pb (Mg
1/3nb
2/3) O
3-0.32PbTiO
3film under 650 kV/cm, residual polarization (P
r) be 23 μ C/cm
2, corresponding coercive field (E
c) be about 40 kV/cm (reference: Y.Y. Zhao, X.L. Li, G.D. Hu, J.B. Xu, Low-temperature preparation of self-polarized Pb (Mg
1/3nb
2/3) O
3-PbTiO
3films on well crystallized LaNiO
3electrodes,
j. Alloy. Compd, 2013,
577, 606-609.).(001) 0.67Pb (Mg of orientation
1/3nb
2/3) O
3-0.33PbTiO
3monocrystal thin films under 600kV/cm, residual polarization (P
r) be about 19 μ C/cm
2, corresponding coercive field (E
c) less than 20 kV/cm (reference: S.H. Baek, J. Park, D.M. Kim, V.A. Aksyuk, R.R. Das, etc., Giant piezoelectricity on Si for hyperactive MEMs,
science, 2011,
334, 958-961.).The present invention had both reduced its coercive field by the improvement of preparation technology, turn improved the resistance to pressure of bismuth-sodium titanate base film, was expected to replace lead base ferroelectric material.
Summary of the invention
The object of the invention is to overcome Na
0.5bi
0.5tiO
3the problem that base film coercive field is large.More particularly disclose a kind of reduction Na
0.5bi
0.5tiO
3the coercive field of base film, turn improves the method for resistance to pressure simultaneously.The film prepared has the advantages that coercive field is little, resistance to pressure is strong, residual polarization is large.
Above-mentioned Na
0.5bi
0.5tiO
3the chemical general formula of base film is Na
0.5bi
0.5ti
1-xmn
xo
3-δ, wherein x is the doping of mn ion, and 0<x<0.05, δ are the numbers in order to maintain the Sauerstoffatom that charge balance loses.
Above-mentioned Na
0.5bi
0.5tiO
3the thickness of base film is about 300 ~ 500nm.
Above-mentioned Na
0.5bi
0.5tiO
3the preparation method of base film comprises following step:
(1) Na
0.5bi
0.5tiO
3the preparation of base film precursor solution:
1. choosing sodium-acetate, Bismuth trinitrate, manganese acetate and tetra-n-butyl titanate is raw material.According to Na
0.5bi
0.5ti
1-xmn
xo
3-δstoichiometric ratio, take raw material accurately.Separately take appropriate PEG 20000, for subsequent use;
2. measure appropriate methyl ethyl diketone in beaker, the tetra-n-butyl titanate then measuring equivalent dropwise adds in methyl ethyl diketone.Under room temperature, magnetic stirring apparatus stirs the chelating completing titanium for 4 ~ 8 hours, is defined as solution 1;
3. the sodium-acetate taken, Bismuth trinitrate and manganese acetate to be dissolved in appropriate ethylene glycol heated and stirred under 40 ~ 60 ° of C and, until dissolve completely, to be defined as solution 2;
4. the PEG 20000 taken to be dissolved in Glacial acetic acid heated and stirred under 50 ~ 70 ° of C and, until dissolve completely, to be defined as solution 3;
5., after all solution coolings, solution 2, solution 3 are successively joined in solution 1, and on magnetic stirring apparatus, stir 8-14 little of mixing;
(2) preparation of thin-film material: combine annealing process layer by layer with spin-coating method and prepare film:
1. utilize the method for spin coating to be coated in equably by precursor solution on ITO/glass substrate, then place it on electric heating panel and carry out pre-treatment, then be put in RTA stove and carry out anneal;
2. the film after anneal is repeated said process again, until the thickness of film reaches required thickness requirement.
In above-mentioned preparation process, the Volume fraction of tetra-n-butyl titanate and methyl ethyl diketone is 1:1, and the Volume fraction of ethylene glycol and Glacial acetic acid is 2:1.
In above-mentioned preparation process, time prepared by precursor solution, sodium-acetate and Bismuth trinitrate excessive 1 ~ 3mol% and 4 ~ 6mol% respectively.
In above-mentioned preparation process, the rotating speed of spin coating is 3000 ~ 7000r/min.The time of spin coating is 30s.
In above-mentioned preparation process, heat treatment process was: 250 ° of C pre-treatment 2 ~ 3 minutes, was incubated 120s at 300 ° of C, was then incubated 20s at 450 ° of C, was finally incubated 600s at 480 ~ 520 ° of C.
In above-mentioned preparation process, in annealing process, select different annealing atmospheres, be respectively oxygen and air.
The present invention has prepared the Na that coercive field is low, voltage endurance capability is strong first
0.5bi
0.5tiO
3base film.Prepared film has single perovskite structure.Na is improve by the improvement of preparation technology and the doping of ion
0.5bi
0.5tiO
3base film electric property.May be used for developing the functional materials and device with ferroelectric, dielectric characteristics.
Accompanying drawing explanation
Fig. 1 is the Na that embodiment 2 is prepared in air atmosphere
0.5bi
0.5ti
0.99mn
0.01o
3-δthe XRD figure spectrum of film.Wherein, X-coordinate is diffraction angle 2 θ, and ordinate zou is diffracted intensity.
Fig. 2 is the Na that embodiment 3 is prepared under oxygen atmosphere
0.5bi
0.5ti
0.99mn
0.01o
3-δthe scanning electron microscope (SEM) photograph of film.
Fig. 3 is the Na that embodiment 4 is prepared in air atmosphere
0.5bi
0.5ti
0.98mn
0.02o
3-δthe ferroelectric hysteresis loop figure of film.Wherein, X-coordinate is strength of electric field: kilovolt/centimetre, ordinate zou is polarizability: microcoulomb/square centimeter.
Fig. 4 is the Na that embodiment 4 is prepared in air atmosphere
0.5bi
0.5ti
0.98mn
0.02o
3-δthe capacitance-voltage relation figure of film.Wherein, X-coordinate is voltage: volt, and ordinate zou is electric capacity: pico farad.
Fig. 5 is the Na that embodiment 5 is prepared under oxygen atmosphere
0.5bi
0.5ti
0.98mn
0.02o
3-δthe ferroelectric hysteresis loop figure of film.Wherein, X-coordinate is strength of electric field: kilovolt/centimetre, ordinate zou is polarizability: microcoulomb/square centimeter.
Fig. 6 is the Na that embodiment 5 is prepared under oxygen atmosphere
0.5bi
0.5ti
0.98mn
0.02o
3-δthe capacitance-voltage relation figure of film.Wherein, X-coordinate is voltage: volt, and ordinate zou is electric capacity: pico farad.
Fig. 7 is the Na that embodiment 7 is prepared in air atmosphere
0.5bi
0.5ti
0.96mn
0.04o
3-δthe XRD figure spectrum of film.Wherein, X-coordinate is diffraction angle 2 θ, and ordinate zou is diffracted intensity.
Fig. 8 is the Na that embodiment 8 is prepared under oxygen atmosphere
0.5bi
0.5ti
0.96mn
0.04o
3-δthe scanning electron microscope (SEM) photograph of film.
Embodiment
Below in conjunction with specific embodiment, the present invention will be further elaborated, it should be noted that, following explanation is only to explain the present invention, does not limit its content.
embodiment 1
(1) according to Na
0.5bi
0.5ti
0.995mn
0.005o
3-δstoichiometric ratio, take the CH of 0.1673g exactly
3bi (the NO of COONa (excessive 1 %), 1.0191g
3)
35H
2the C of O (excessive 4 %), 0.0050g
4h
6mnO
44H
2the PEG 20000 of O and 0.25g, for subsequent use.Measure the methyl ethyl diketone of 1.38ml exactly in beaker, the tetra-n-butyl titanate then measuring 1.38ml dropwise adds in methyl ethyl diketone, magnetic stirring apparatus stirs the chelating completing titanium for 4 hours, is defined as solution 1.By load weighted CH
3cOONa, Bi (NO
3)
35H
2o, C
4h
6mnO
44H
2o to join in the beaker of the ethylene glycol filling 10ml heated and stirred under 40 ° of C, until all dissolve, is defined as solution 2.Load weighted PEG 20000 is joined in the beaker filling 5ml Glacial acetic acid, 50 ° of C heated and stirred until all dissolve, be defined as solution 3.After all solution coolings, solution 2 and 3 is slowly joined in solution 1 respectively.The solution mixed is positioned on magnetic stirring apparatus and stirs 8 hours.Obtaining concentration is the uniform and stable Na of 0.2mol/L
0.5bi
0.5ti
0.995mn
0.005o
3-δprecursor solution;
(2) adopt the method for spin-coating by Na with sol evenning machine
0.5bi
0.5ti
0.995mn
0.005o
3-δprecursor solution is deposited on ITO/glass substrate.The rotating speed of sol evenning machine is 7000r/min, and spin coating time is 30s.Then film is placed on pre-treatment on electric heating panel, pretreated temperature is 250 ° of C, and the pretreated time is about 2min.Finally film is placed in RTA stove and carries out anneal.The technological process of anneal is: be incubated 120s under 300 ° of C, is incubated 20s under 450 ° of C, is incubated 600s under 480 ° of C.Heat treated atmosphere is air atmosphere.Repeat above-mentioned technological process, until film thickness reaches about 300nm.
embodiment 2
(1) according to Na
0.5bi
0.5ti
0.99mn
0.01o
3-δstoichiometric ratio, take the CH of 0.3347g exactly
3bi (the NO of COONa (excessive 1 %), 2.0775g
3)
35H
2the C of O (excessive 6 %), 0.0198g
4h
6mnO
44H
2the PEG 20000 of O and 0.51g, for subsequent use.Measure the methyl ethyl diketone of 2.75ml exactly in beaker, the tetra-n-butyl titanate then measuring 2.75ml dropwise adds in methyl ethyl diketone, magnetic stirring apparatus stirs the chelating completing titanium for 6 hours, is defined as solution 1.By load weighted CH
3cOONa, Bi (NO
3)
35H
2o, C
4h
6mnO
44H
2o to join in the beaker of the ethylene glycol filling 10ml heated and stirred under 50 ° of C, until all dissolve, is defined as solution 2.Load weighted PEG 20000 is joined in the beaker filling 5ml Glacial acetic acid, 60 ° of C heated and stirred until all dissolve, be defined as solution 3.After all solution coolings, solution 2 and 3 is slowly joined in solution 1 respectively.The solution mixed is positioned on magnetic stirring apparatus and stirs 8 hours.Obtaining concentration is the uniform and stable Na of 0.4mol/L
0.5bi
0.5ti
0.99mn
0.01o
3-δprecursor solution;
(2) adopt the method for spin-coating by Na with sol evenning machine
0.5bi
0.5ti
0.99mn
0.01o
3-δprecursor solution is deposited on ITO/glass substrate.The rotating speed of sol evenning machine is 3000r/min, and spin coating time is 30s.Then film is placed on pre-treatment on electric heating panel, pretreated temperature is 250 ° of C, and the pretreated time is about 3min.Finally film is placed in RTA stove and carries out anneal.The technological process of anneal is: be incubated 120s under 300 ° of C, is incubated 20s under 450 ° of C, is incubated 600s under 520 ° of C.Heat treated atmosphere is air atmosphere.Repeat above-mentioned technological process, until film thickness reaches about 500nm.
As Fig. 1, through x-ray diffractometer (German Brooker, D8) to the Na under air atmosphere
0.5bi
0.5ti
0.99mn
0.01o
3-δfilm carries out structured testing, and prepared film is the single perovskite structure of polycrystalline.
embodiment 3
(1) according to Na
0.5bi
0.5ti
0.99mn
0.01o
3-δstoichiometric ratio, take the CH of 0.1690g exactly
3bi (the NO of COONa (excessive 2 %), 1.0290g
3)
35H
2the C of O (excessive 5 %), 0.0099g
4h
6mnO
44H
2the PEG 20000 of O and 0.25g, for subsequent use.Measure the methyl ethyl diketone of 1.38ml exactly in beaker, the tetra-n-butyl titanate then measuring 1.38ml dropwise adds in methyl ethyl diketone, magnetic stirring apparatus stirs the chelating completing titanium for 6 hours, is defined as solution 1.By load weighted CH
3cOONa, Bi (NO
3)
35H
2o, C
4h
6mnO
44H
2o to join in the beaker of the ethylene glycol filling 10ml heated and stirred under 60 ° of C, until all dissolve, is defined as solution 2.Load weighted PEG 20000 is joined in the beaker filling 5ml Glacial acetic acid, 70 ° of C heated and stirred until all dissolve, be defined as solution 3.After all solution coolings, solution 2 and 3 is slowly joined in solution 1 respectively.The solution mixed is positioned on magnetic stirring apparatus and stirs 10 hours.Obtaining concentration is the uniform and stable Na of 0.2mol/L
0.5bi
0.5ti
0.99mn
0.01o
3-δprecursor solution;
(2) adopt the method for spin-coating by Na with sol evenning machine
0.5bi
0.5ti
0.99mn
0.01o
3-δprecursor solution is deposited on ITO/glass substrate.The rotating speed of sol evenning machine is 6000r/min, and spin coating time is 30s.Then film is placed on pre-treatment on electric heating panel, pretreated temperature is 250 ° of C, and the pretreated time is about 2min.Finally film is placed in RTA stove and carries out anneal.The technological process of anneal is: be incubated 120s under 300 ° of C, is incubated 20s under 450 ° of C, is incubated 600s under 500 ° of C.Heat treated atmosphere is oxygen atmosphere.Repeat above-mentioned technological process, until film thickness reaches about 300nm.
Utilize scanning electronic microscope to the Na under oxygen atmosphere
0.5bi
0.5ti
0.99mn
0.01o
3-δsurface and the section of film characterize, as shown in Figure 2.The thickness of film is about 330nm, and film dense uniform, particle is little.
embodiment 4
(1) according to Na
0.5bi
0.5ti
0.98mn
0.02o
3-δstoichiometric ratio, take the CH of 0.2535g exactly
3bi (the NO of COONa (excessive 2 %), 1.5434g
3)
35H
2the C of O (excessive 5 %), 0.0297g
4h
6mnO
44H
2the PEG 20000 of O and 0.38g, for subsequent use.Measure the methyl ethyl diketone of 2.04ml exactly in beaker, the tetra-n-butyl titanate then measuring 2.04ml dropwise adds in methyl ethyl diketone, magnetic stirring apparatus stirs the chelating completing titanium for 6 hours, is defined as solution 1.By load weighted CH
3cOONa, Bi (NO
3)
35H
2o, C
4h
6mnO
44H
2o to join in the beaker of the ethylene glycol filling 10ml heated and stirred under 40 ° of C, until all dissolve, is defined as solution 2.Load weighted PEG 20000 is joined in the beaker filling 5ml Glacial acetic acid, 50 ° of C heated and stirred until all dissolve, be defined as solution 3.After all solution coolings, solution 2 and 3 is slowly joined in solution 1 respectively.The solution mixed is positioned on magnetic stirring apparatus and stirs 10 hours.Obtaining concentration is the uniform and stable Na of 0.3mol/L
0.5bi
0.5ti
0.98mn
0.02o
3-δprecursor solution;
(2) adopt the method for spin-coating by Na with sol evenning machine
0.5bi
0.5ti
0.98mn
0.02o
3-δprecursor solution is deposited on ITO/glass substrate.The rotating speed of sol evenning machine is 4000r/min, and spin coating time is 30s.Then film is placed on pre-treatment on electric heating panel, pretreated temperature is 250 ° of C, and the pretreated time is about 3min.Finally film is placed in RTA stove and carries out anneal.The technological process of anneal is: be incubated 120s under 300 ° of C, is incubated 20s under 450 ° of C, is incubated 600s under 500 ° of C.Heat treated atmosphere is air atmosphere.Repeat above-mentioned technological process, until film thickness reaches about 400nm.
Utilize ferroelectric test macro (Precision Pro. Radiant Technologies) to the Na prepared under air atmosphere
0.5bi
0.5ti
0.98mn
0.02o
3-δthe ferroelectric hysteresis loop of film characterizes, as shown in Figure 3.Under the voltage strength of about 2000kV/cm, residual polarization (P
r) be 20.5 μ C/cm
2, coercive field (E
c) be 178kV/cm.Fig. 4 is that under 100kHz, electric capacity is with biased change.Electric capacity is strong nonlinear relationship with institute's biasing, presents butterfly.
embodiment 5
(1) according to Na
0.5bi
0.5ti
0.98mn
0.02o
3-δstoichiometric ratio, take the CH of 0.2535g exactly
3bi (the NO of COONa (excessive 2 %), 1.5434g
3)
35H
2the C of O (excessive 5 %), 0.0297g
4h
6mnO
44H
2the PEG 20000 of O and 0.38g, for subsequent use.Measure the methyl ethyl diketone of 2.04ml exactly in beaker, the tetra-n-butyl titanate then measuring 2.04ml dropwise adds in methyl ethyl diketone, magnetic stirring apparatus stirs the chelating completing titanium for 6 hours, is defined as solution 1.By load weighted CH
3cOONa, Bi (NO
3)
35H
2o, C
4h
6mnO
44H
2o to join in the beaker of the ethylene glycol filling 10ml heated and stirred under 50 ° of C, until all dissolve, is defined as solution 2.Load weighted PEG 20000 is joined in the beaker filling 5ml Glacial acetic acid, 60 ° of C heated and stirred until all dissolve, be defined as solution 3.After all solution coolings, solution 2 and 3 is slowly joined in solution 1 respectively.The solution mixed is positioned on magnetic stirring apparatus and stirs 12 hours.Obtaining concentration is the uniform and stable Na of 0.3mol/L
0.5bi
0.5ti
0.98mn
0.02o
3-δprecursor solution;
(2) adopt the method for spin-coating by Na with sol evenning machine
0.5bi
0.5ti
0.98mn
0.02o
3-δprecursor solution is deposited on ITO/glass substrate.The rotating speed of sol evenning machine is 4000r/min, and spin coating time is 30s.Then film is placed on pre-treatment on electric heating panel, pretreated temperature is 250 ° of C, and the pretreated time is about 2min.Finally film is placed in RTA stove and carries out anneal.The technological process of anneal is: be incubated 120s under 300 ° of C, is incubated 20s under 450 ° of C, is incubated 600s under 500 ° of C.Heat treated atmosphere is oxygen atmosphere.Repeat above-mentioned technological process, until film thickness reaches about 400nm.
Utilize ferroelectric test macro (Precision Pro. Radiant Technologies) to the Na prepared under oxygen atmosphere
0.5bi
0.5ti
0.98mn
0.02o
3-δthe ferroelectric hysteresis loop of film characterizes, as shown in Figure 5.Under the voltage strength of about 2000kV/cm, residual polarization (P
r) be 23 μ C/cm
2, coercive field (E
c) be 217kV/cm.Fig. 6 is that under 100kHz, electric capacity is with biased change.Electric capacity is strong nonlinear relationship with institute's biasing, presents butterfly.
embodiment 6
(1) according to Na
0.5bi
0.5ti
0.97mn
0.03o
3-δstoichiometric ratio, take the CH of 0.3413g exactly
3bi (the NO of COONa (excessive 3 %), 2.0775g
3)
35H
2the C of O (excessive 6 %), 0.0594g
4h
6mnO
44H
2the PEG 20000 of O and 0.51g, for subsequent use.Measure the methyl ethyl diketone of 2.70ml exactly in beaker, the tetra-n-butyl titanate then measuring 2.70ml dropwise adds in methyl ethyl diketone, magnetic stirring apparatus stirs the chelating completing titanium for 8 hours, is defined as solution 1.By load weighted CH
3cOONa, Bi (NO
3)
35H
2o, C
4h
6mnO
44H
2o to join in the beaker of the ethylene glycol filling 10ml heated and stirred under 60 ° of C, until all dissolve, is defined as solution 2.Load weighted PEG 20000 is joined in the beaker filling 5ml Glacial acetic acid, 70 ° of C heated and stirred until all dissolve, be defined as solution 3.After all solution coolings, solution 2 and 3 is slowly joined in solution 1 respectively.The solution mixed is positioned on magnetic stirring apparatus and stirs 12 hours.Obtaining concentration is the uniform and stable Na of 0.4mol/L
0.5bi
0.5ti
0.97mn
0.03o
3-δprecursor solution;
(2) adopt the method for spin-coating by Na with sol evenning machine
0.5bi
0.5ti
0.97mn
0.03o
3-δprecursor solution is deposited on ITO/glass substrate.The rotating speed of sol evenning machine is 7000r/min, and spin coating time is 30s.Then film is placed on pre-treatment on electric heating panel, pretreated temperature is 250 ° of C, and the pretreated time is about 3min.Finally film is placed in RTA stove and carries out anneal.The technological process of anneal is: be incubated 120s under 300 ° of C, is incubated 20s under 450 ° of C, is incubated 600s under 520 ° of C.Heat treated atmosphere is oxygen atmosphere.Repeat above-mentioned technological process, until film thickness reaches about 350nm.
embodiment 7
(1) according to Na
0.5bi
0.5ti
0.96mn
0.04o
3-δstoichiometric ratio, take the CH of 0.2535g exactly
3bi (the NO of COONa (excessive 2 %), 1.5434g
3)
35H
2the C of O (excessive 5 %), 0.0594g
4h
6mnO
44H
2the PEG 20000 of O and 0.38g, for subsequent use.Measure the methyl ethyl diketone of 2.00ml exactly in beaker, the tetra-n-butyl titanate then measuring 2.00ml dropwise adds in methyl ethyl diketone, magnetic stirring apparatus stirs the chelating completing titanium for 6 hours, is defined as solution 1.By load weighted CH
3cOONa, Bi (NO
3)
35H
2o, C
4h
6mnO
44H
2o to join in the beaker of the ethylene glycol filling 10ml heated and stirred under 40 ° of C, until all dissolve, is defined as solution 2.Load weighted PEG 20000 is joined in the beaker filling 5ml Glacial acetic acid, 50 ° of C heated and stirred until all dissolve, be defined as solution 3.After all solution coolings, solution 2 and 3 is slowly joined in solution 1 respectively.The solution mixed is positioned on magnetic stirring apparatus and stirs 14 hours.Obtaining concentration is the uniform and stable Na of 0.3mol/L
0.5bi
0.5ti
0.96mn
0.04o
3-δprecursor solution;
(2) adopt the method for spin-coating by Na with sol evenning machine
0.5bi
0.5ti
0.96mn
0.04o
3-δprecursor solution is deposited on ITO/glass substrate.The rotating speed of sol evenning machine is 5000r/min, and spin coating time is 30s.Then film is placed on pre-treatment on electric heating panel, pretreated temperature is 250 ° of C, and the pretreated time is about 2min.Finally film is placed in RTA stove and carries out anneal.The technological process of anneal is: be incubated 120s under 300 ° of C, is incubated 20s under 450 ° of C, is incubated 600s under 500 ° of C.Heat treated atmosphere is air atmosphere.Repeat above-mentioned technological process, until film thickness reaches about 450nm.
As Fig. 7, through x-ray diffractometer (German Brooker, D8) to the Na under air atmosphere
0.5bi
0.5ti
0.96mn
0.04o
3-δfilm carries out structured testing, and prepared film is the single perovskite structure of polycrystalline.
embodiment 8
(1) according to Na
0.5bi
0.5ti
0.96mn
0.04o
3-δstoichiometric ratio, take 0.1706g exactly and starve CH
3bi (the NO of COONa (excessive 3 %), 1.0191g
3)
35H
2the C of O (excessive 4 %), 0.0396g
4h
6mnO
44H
2the PEG 20000 of O and 0.25g, for subsequent use.Measure the methyl ethyl diketone of 1.33ml exactly in beaker, the tetra-n-butyl titanate then measuring 1.33ml dropwise adds in methyl ethyl diketone, magnetic stirring apparatus stirs the chelating completing titanium for 6 hours, is defined as solution 1.By load weighted CH
3cOONa, Bi (NO
3)
35H
2o, C
4h
6mnO
44H
2o to join in the beaker of the ethylene glycol filling 10ml heated and stirred under 50 ° of C, until all dissolve, is defined as solution 2.Load weighted PEG 20000 is joined in the beaker filling 5ml Glacial acetic acid, 60 ° of C heated and stirred until all dissolve, be defined as solution 3.After all solution coolings, solution 2 and 3 is slowly joined in solution 1 respectively.The solution mixed is positioned on magnetic stirring apparatus and stirs 14 hours.Obtaining concentration is the uniform and stable Na of 0.2mol/L
0.5bi
0.5ti
0.96mn
0.04o
3-δprecursor solution;
(2) adopt the method for spin-coating by Na with sol evenning machine
0.5bi
0.5ti
0.96mn
0.04o
3-δprecursor solution is deposited on ITO/glass substrate.The rotating speed of sol evenning machine is 3000r/min, and spin coating time is 30s.Then film is placed on pre-treatment on electric heating panel, pretreated temperature is 250 ° of C, and the pretreated time is about 3min.Finally film is placed in RTA stove and carries out anneal.The technological process of anneal is: be incubated 120s under 300 ° of C, is incubated 20s under 450 ° of C, is incubated 600s under 480 ° of C.Heat treated atmosphere is oxygen atmosphere.Repeat above-mentioned technological process, until film thickness reaches about 350nm.
Utilize scanning electronic microscope to the Na under oxygen atmosphere
0.5bi
0.5ti
0.96mn
0.04o
3-δsurface and the section of film characterize, as shown in Figure 8.The thickness of film is about 370nm, and film dense uniform, particle is little.
Claims (8)
1. reduce bismuth-sodium titanate base film coercive field and improve the method for its resistance to pressure, adopt mn ion as dopant ion, preparation method is the chemical solution deposition optimized, and it is characterized in that: with chemical general formula Na
0.5bi
0.5ti
1-xmn
xo
3-δrepresent, wherein x is mole volume of mn ion, 0<x<0.05; δ is the number in order to maintain the Sauerstoffatom that charge balance loses.
2. a kind of method reducing bismuth-sodium titanate base film coercive field and improve its resistance to pressure as described in the appended claim 1, is characterized in that: the thickness of film is 300 ~ 500nm.
3. a kind of method reducing bismuth-sodium titanate base film coercive field and improve its resistance to pressure as described in the appended claim 1, is characterized in that: the preparation method of described bismuth-sodium titanate base film comprises following step:
(1) preparation of bismuth sodium titanate based thin film precursor solution
1. choosing sodium-acetate, Bismuth trinitrate, manganese acetate and tetra-n-butyl titanate is raw material, according to Na
0.5bi
0.5ti
1-xmn
xo
3-δstoichiometric ratio, take raw material accurately, separately take appropriate PEG 20000, for subsequent use;
2. measure appropriate methyl ethyl diketone in beaker, the tetra-n-butyl titanate then measuring equivalent dropwise adds in methyl ethyl diketone;
Under room temperature, magnetic stirring apparatus stirs the chelating completing titanium for 4 ~ 8 hours, is defined as solution 1;
3. the sodium-acetate taken, Bismuth trinitrate and manganese acetate to be dissolved in appropriate ethylene glycol heated and stirred under 40 ~ 60 ° of C and, until dissolve completely, to be defined as solution 2;
4. the PEG 20000 taken to be dissolved in Glacial acetic acid 50 ~ 70 ° of C heated and stirred until dissolve completely, to be defined as solution 3;
5., after all solution coolings, solution 2, solution 3 are successively joined in solution 1, and stirring 8 ~ 14 is little of mixing on magnetic stirring apparatus, the concentration of precursor solution controls at 0.2 ~ 0.4mol/L;
(2) preparation of thin-film material: combine annealing process layer by layer with spin-coating method and prepare film;
1. utilize the method for spin coating to be coated in equably by precursor solution on ITO/glass substrate, then place it on electric heating panel and carry out pre-treatment, then be put in RTA stove and carry out anneal;
2. the film after anneal is repeated said process again, until the thickness of film reaches 300 ~ 500nm thickness requirement.
4. a kind of method reducing bismuth-sodium titanate base film coercive field and improve its resistance to pressure as claimed in claim 3, it is characterized in that: the Volume fraction of tetra-n-butyl titanate and methyl ethyl diketone is 1:1, the Volume fraction of ethylene glycol and Glacial acetic acid is 2:1.
5. a kind of method reducing bismuth-sodium titanate base film coercive field and improve its resistance to pressure as claimed in claim 3, is characterized in that: sodium-acetate and Bismuth trinitrate excessive 1 ~ 3mol% and 4 ~ 6mol% respectively.
6. a kind of method reducing bismuth-sodium titanate base film coercive field and improve its resistance to pressure as claimed in claim 3, it is characterized in that: the rotating speed of spin coating is 3000 ~ 7000r/min, the time of spin coating is 30s.
7. a kind of method reducing bismuth-sodium titanate base film coercive field and improve its resistance to pressure as described in claim 3, it is characterized in that: 250 ° of C pre-treatment 2 ~ 3 minutes, be incubated 120s at 300 ° of C, be then incubated 20s at 450 ° of C, be finally incubated 600s at 480 ~ 520 ° of C.
8. a kind of method reducing bismuth-sodium titanate base film coercive field and improve its resistance to pressure as claimed in claim 3, is characterized in that: select different annealing atmospheres in annealing process, is respectively oxygen and air.
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