CN102244192B - Composite solid solution film based on sodium bismuth titanate and bismuth ferric and preparation method thereof - Google Patents

Composite solid solution film based on sodium bismuth titanate and bismuth ferric and preparation method thereof Download PDF

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CN102244192B
CN102244192B CN 201110123826 CN201110123826A CN102244192B CN 102244192 B CN102244192 B CN 102244192B CN 201110123826 CN201110123826 CN 201110123826 CN 201110123826 A CN201110123826 A CN 201110123826A CN 102244192 B CN102244192 B CN 102244192B
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CN102244192A (en
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杨长红
芦泽宇
杨锋
胡广达
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University of Jinan
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Abstract

The invention discloses a composite solid solution film based on sodium bismuth titanate and bismuth ferric and a preparation method thereof. The film is represented by the general formula: (1-x)Na0.5(Bi0.95Ce0.05)0.5TiO(3-x)BiFe0.97Mn0.03O3, the sodium bismuth titanate is Na0.5(Bi0.95Ce0.05)0.5TiO3, and the bismuth ferric is BiFe0.97Mn0.03O3, wherein x is the molar content of BiFe0.97Mn0.03O3, which is greater than 0 and less than 1. According to the invention, the composite solid solution film is prepared by the spinning method-layer by layer annealing process, and does not have an impurity phase except that a pyrochlore impurity phase exists when x is less than or equal to 0.05; and moreover, the film has the advantages of low crystallizing temperature, low electric leakage, great residual polarization, stable dielectric property and the like, and can be well applied to novel high-density integrated piezoelectric ferroelectric devices in the future.

Description

A kind of compound solid solution body thin film based on bismuth sodium titanate based and ferrous acid bismuthino and preparation method thereof
Technical field
The present invention relates to a kind of binary ferroelectric thin film and preparation method thereof, be specifically related to the bismuth sodium titanate based of a kind of binary and ferrous acid bismuthino compound without thin film lead and preparation method thereof, belong to perovskite structure environmental harmony Ferroelectric thin film technique field.
Background technology
Along with the development of microelectric technique and the trend of Highgrade integration, need to develop the thin-film material that has with the comparable performance of block.The multifrequency natures such as ferroelectric thin film is ferroelectric owing to having, piezoelectric effect are widely used in the various fields such as memory, piezoelectric transducer and actuator.Now widely used performance comparative superiority mostly be plumbum-based material, such as Pb (Zr, Ti) O 3, Pb (Mg, Nb) O 3Deng, wherein the content of PbO is up to 60 ~ 70%.And lead is the non-biodegradable chemicals, and this will certainly cause serious harm to the mankind and biological environment in the processing procedure after producing, use and discarding.So, be necessary to explore high-quality leadless piezoelectric ferroelectric thin-flim materials.
Emerging bismuth-sodium titanate (Na 0.5Bi 0.5TiO 3) material is considered to get a good chance of replacing the environmental harmony shaped material of lead base piezoelectricity ferro material.Na 0.5Bi 0.5TiO 3Block have larger residual polarization (under the room temperature, pottery: P r=32 μ C/cm 2Crystal: P r=36 μ C/cm 2) and higher Curie temperature ( T C =320 ℃); But for Na 0.5Bi 0.5TiO 3Film, crystallization range is narrower; And up to about 700 ℃, the volatilization of bismuth and sodium element has caused departing from of stoichiometric proportion in the high-temperature annealing process.These give the Na of preparation pure phase 0.5Bi 0.5TiO 3Thin-film material has brought very large difficulty.Numerous result of the tests show Na 0.5Bi 0.5TiO 3Perovskite is easy to burnt green stone dephasign coexistence.In addition, the factors such as non-stoichiometric that the volatilization of element causes have caused the generation of film internal flaw, and the conduction electron that especially sinks into the oxygen room ionization generation of grain boundaries enters conduction band and increased Na 0.5Bi 0.5TiO 3The leakage property of film.Cause ferroelectric domain in polarization process, can't fully overturn, existing Na 0.5Bi 0.5TiO 3Ferroelectricity (the P of film rAt 10 μ C/cm 2About) well below Na 0.5Bi 0.5TiO 3The matrix body.
BiFeO 3To have simultaneously one of ferroelectricity and ferromagnetic material under the minority room temperature and since its have the ferroelectrie Curie temperature that is higher than room temperature ( T C =830 ℃) and antiferromagnetic Neel temperature ( T N =370 ℃) and enjoy researcher's concern.The beginning of this century, numerous researchers reported BiFeO 3Base film has very excellent ferroelectric, piezoelectricity and ferromagnetic property.Although utilize the BiFeO of chemical solution method preparation 3The film leakage current is higher, and coercive field is larger.But research is found: ion doping, comprise on the Bi position doping transition element on the doping lanthanide series and Fe position, and be in the news and can effectively improve BiFeO 3The electric leakage problem, and can reduce to a certain extent BiFeO 3The coercive field of film.And BiFeO 3The crystallization temperature of base film is lower, and annealing temperature is about 500 ℃.
Summary of the invention
The present invention is directed to existing bismuth-sodium titanate thin film crystallization and easily go out the deficiencies such as dephasign, leakage current are large, poor ferroelectric property in mutually, provide a kind of based on the bismuth sodium titanate based and compound solid solution body thin film ferrous acid bismuthino, this binary film has the advantages such as residual polarization is high, electric leakage is low, dielectricity is stable.
The present invention also provides the preparation method of this compound solid solution body thin film, and the method is simple to operate, and the gained film performance is good.
The present invention carries out combination with bismuth-sodium titanate base film and bismuth ferrite base film, has avoided Na 0.5Bi 0.5TiO 3Be easy to produce dephasign and the high difficult problem of annealing temperature in the film preparation process, and effectively reduce Na 0.5Bi 0.5TiO 3The film leakage current has strengthened its crushing resistance, has obtained having low electric leakage, high residual polarization, the stable ferroelectric sosoloid film of dielectricity, has a good application prospect in the novel high-density integrated piezoelectric ferro-electric device in future.Its concrete technical scheme is as follows:
A kind of based on the bismuth sodium titanate based and compound solid solution body thin film ferrous acid bismuthino, it is characterized in that: with general formula (1-x) Na 0.5(Bi 0.95Ce 0.05) 0.5TiO 3-xBiFe 0.97Mn 0.03O 3The expression, described bismuth sodium titanate based be Na 0.5(Bi 0.95Ce 0.05) 0.5TiO 3, described ferrous acid bismuthino is BiFe 0.97Mn 0.03O 3Wherein, x is BiFe 0.97Mn 0.03O 3Molar content, 0＜x＜1.
Further, in the described compound solid solution body thin film, x=0.1～0.9.
Further, in the described compound solid solution body thin film, x=0.3～0.7.
Further, described compound solid solution body thin film thickness is 0.2～1 μ m.
The present invention passes through respectively at Na 0.5Bi 0.5TiO 3And BiFeO 3Doped metal ion in the film, the performance that whole binary film is showed has had certain improvement.In addition, because BiFeO 3The ferroelectric properties of film is stronger, and therefore, along with the increase of its doping, bismuth sodium titanate based and performance bismuth ferrite based solid solution film also increases.General, under the electric field strength of 900kV/cm, residual polarization can reach 20～50 μ C/cm, and coercive field can reach 120～300kV/cm.
The preparation method of the compound solid solution body thin film based on bismuth sodium titanate based and ferrous acid bismuthino of the present invention is characterized in that may further comprise the steps:
(1), the preparation of precursor solution
1. take sodium acetate, five water bismuth nitrates, six water cerous nitrates, nine water ferric nitrates, two water manganese acetates and metatitanic acid four isopropyl esters as raw material, according to (1-x) Na 0.5(Bi 0.95Ce 0.05) 0.5TiO 3-xBiFe 0.97Mn 0.03O 3Stoichiometric proportion, accurately take by weighing each raw material, wherein five water bismuth nitrates are excessive a little, for subsequent use;
2. sodium acetate, five water bismuth nitrates, six water cerous nitrates are dissolved in the ethylene glycol solution, under 40～80 ℃ temperature, are stirred to fully dissolving;
3. in above-mentioned solution, add respectively nine water ferric nitrates and two water manganese acetates, at room temperature be stirred to fully dissolving after, add glacial acetic acid, continue to stir, be cooled to room temperature to solution;
4. after the solution cooling, to wherein adding acetylacetone,2,4-pentanedione and metatitanic acid four isopropyl esters, at room temperature stirred 8～12 hours respectively.
5. with above-mentioned steps solution filter 4., obtain the precursor solution that concentration is 0.05～0.5 mol/L;
(2), thin film technology: with spin-coating method-annealing process prepares film layer by layer
1. adopt spin-coating method with the precursor liquid deposition on backing material, then material is heat-treated, processing procedure is: first 250～300 ℃ of insulations 5～10 minutes, again 400～500 ℃ of insulations 3～10 minutes, then 600～650 ℃ of annealing is 3～10 minutes;
2. adopt above-mentioned identical method to continue precursor solution is spun on the backing material, until film thickness reaches 0.2～1 μ m, and get final product.
Among the above-mentioned preparation method, in order to remedy the volatilization of bismuth under the high temperature, five water bismuth nitrates need excessive 2mol%.
Among the above-mentioned preparation method, the volume ratio of ethylene glycol and glacial acetic acid is 2:1～10:1; The volume ratio of acetylacetone,2,4-pentanedione and metatitanic acid four isopropyl esters is 1:1.
Among the above-mentioned preparation method, described backing material is the LaNiO of (100)-orientation 3/ Si substrate.
Among the above-mentioned preparation method, in the described spin coating proceeding, rotating speed is 3000～7000 rev/mins, and the spin coating time is 20～40 seconds, and the precursor sample path length of each spin coating is generally between 20～50nm nanometer.
Among the above-mentioned preparation method, step 5. in, be that the injecting type filter of 0.2 μ m filters solution with the aperture, filter dust and contaminant particles.
The present invention combines sour bismuth sodium base film and bismuth ferrite base film first, forms the binary laminated film, and this film is solid solution, and each homogeneous chemical composition distributes in the film.In research process, the inventor once was combined together to form laminated film with bismuth-sodium titanate film and bismuth ferrite thin film, although form without dephasign, the film overall performance does not have too large improvement, and effect is bad.Therefore, in order to improve Na 0.5Bi 0.5TiO 3The Electrical performance is at Na 0.5Bi 0.5TiO 3In, 5% Bi 3+By Ce 3+Replace, the group of the lanthanides Ce elements has non-volatile, and its metallicity and stability all are better than bismuth, replace volatile bismuth by a certain amount of cerium, can strengthen structural stability, reduces the oxygen room.In order to suppress BiFeO 3The leakage property of film is at BiFeO 3In, 3% Fe 3+By Mn 3+Replace.Because BiFeO 3The depositing temperature of base film is very low, gets final product crystallization under the annealing temperature about 500 ℃.Na 0.5Bi 0.5TiO 3Base film solid solution BiFeO 3Behind the base, obviously reduced Na 0.5Bi 0.5TiO 3The crystallization temperature of base film, and avoided the generation of dephasign.
The present invention adopts layer by layer rta technique of chemical solution method combination, utilizes the heteroepitaxial growth technology, at the LaNiO of (100)-orientation 3On/Si the substrate, under 600～650 ℃ annealing temperature, obtained (100)-be orientated bismuth sodium titanate based and bismuth ferrite based solid solution film, film is except existing burnt green stone dephasign in x≤0.05, other situation all exists without dephasign, and this film has the advantages such as high residual polarization, low electric leakage, dielectricity be stable, has a good application prospect in the novel high-density integrated piezoelectric ferro-electric device in future.
Description of drawings
Fig. 1 is the 0.95Na of embodiment 1 preparation 0.5(Bi 0.95Ce 0.05) 0.5TiO 3-0.05BiFe 0.97Mn 0.03O 3The XRD collection of illustrative plates of film.Wherein, abscissa is the angle of diffraction 2 θ, and ordinate is diffracted intensity.
Fig. 2 is the 0.9Na of embodiment 2 preparations 0.5(Bi 0.95Ce 0.05) 0.5TiO 3-0.1BiFe 0.97Mn 0.03O 3The XRD collection of illustrative plates of film.Wherein, abscissa is the angle of diffraction 2 θ, and ordinate is diffracted intensity.
Fig. 3 is the 0.9Na of embodiment 2 preparations 0.5(Bi 0.95Ce 0.05) 0.5TiO 3-0.1BiFe 0.97Mn 0.03O 3The electric hysteresis loop collection of illustrative plates of film.Wherein, abscissa is electric field strength: kilovolt/square centimeter, ordinate are polarization intensity: microcoulomb/square centimeter.
Fig. 4 is the 0.7Na of embodiment 3 preparations 0.5(Bi 0.95Ce 0.05) 0.5TiO 3-0.3BiFe 0.97Mn 0.03O 3The XRD collection of illustrative plates of film.Wherein, abscissa is the angle of diffraction 2 θ, and ordinate is diffracted intensity.
Fig. 5 is the 0.7Na of embodiment 3 preparations 0.5(Bi 0.95Ce 0.05) 0.5TiO 3-0.3BiFe 0.97Mn 0.03O 3The electric hysteresis loop collection of illustrative plates of film.Wherein, abscissa is electric field strength: kilovolt/square centimeter, ordinate are polarization intensity: microcoulomb/square centimeter.
Fig. 6 is the 0.7Na of embodiment 3 preparations 0.5(Bi 0.95Ce 0.05) 0.5TiO 3-0.3BiFe 0.97Mn 0.03O 3The dielectric constant of film and dielectric loss are with the variation collection of illustrative plates of voltage.Wherein, abscissa is institute's making alive: volt, and left ordinate is relative dielectric constant, right ordinate is dielectric loss.
Fig. 7 is the 0.5Na of embodiment 4 preparations 0.5(Bi 0.95Ce 0.05) 0.5TiO 3-0.5BiFe 0.97Mn 0.03O 3The dielectric spectrogram of film.Wherein, abscissa is frequency: hertz, left ordinate is relative dielectric constant, right ordinate is dielectric loss.
Embodiment
The present invention will be further elaborated below in conjunction with the drawings and specific embodiments, should be understood that, following explanation only is in order to explain the present invention, its content not to be limited.
Embodiment 1
(1), according to 0.95Na 0.5(Bi 0.95Ce 0.05) 0.5TiO 3-0.05BiFe 0.97Mn 0.03O 3Stoichiometric proportion, accurately take by weighing the CH of 0.2951g 3COONa; 1.8788g Bi (NO 3) 35H 2O (excessive 2%); 0.0781g Ce (NO 3) 36H 2O is dissolved in the 41.55ml ethylene glycol solution, is stirred to fully dissolving at 40 ℃ temperature lower magnetic forces.Then Fe (the NO that adds respectively 0.1484g in the above-mentioned solution 3) 39H 2The C of O and 0.0031g 6H 9MnO 62H 2O, at room temperature magnetic agitation and adds the 4.15ml glacial acetic acid to complete dissolving, continue to stir and etc. solution be cooled to room temperature.At last, adding respectively volume ratio in the above-mentioned solution is 1:1 acetylacetone,2,4-pentanedione and metatitanic acid four isopropyl esters, namely adds first the 2.15ml acetylacetone,2,4-pentanedione, dropwise adds 2.15ml metatitanic acid four isopropyl esters again.And at room temperature continued magnetic agitation 8 hours.Be that the injecting type filter of 0.2 μ m filters dust and contaminant particles with the aperture at last, obtaining concentration is the 50ml precursor solution of the homogeneous transparent of 0.05mol/L.
(2), precursor solution is utilized spin-coating method at the LaNiO that is deposited on (100)-orientation 3On/Si the backing material, rotating speed is 3000 rev/mins during spin coating, and the spin coating time is 20 seconds.Then heat-treat technique.260 ℃ of insulations 5 minutes, again 400 ℃ of insulations 10 minutes, then annealed 3 minutes for 640 ℃ first.Repeat this layer by layer annealing process, until the thickness of film reaches 200 nm.
Such as Fig. 1, (German Brooker is D8) to 0.95Na through x-ray diffractometer 0.5(Bi 0.95Ce 0.05) 0.5TiO 3-0.05BiFe 0.97Mn 0.03O 3Film carries out structured testing, and prepared film presents along (100) direction preferential growth, but has burnt green stone dephasign near angle of diffraction is 30o.So, when x=0.05, i.e. BiFe0.97Mn 0.03O 3Molar content hour, recommendation not.
Embodiment 2
(1), according to 0.9Na 0.5(Bi 0.95Ce 0.05) 0.5TiO 3-0.1BiFe 0.97Mn 0.03O 3Stoichiometric proportion, accurately take by weighing the CH of 0.7456g 3COONa; 5.2728g Bi (NO 3) 35H 2O (excessive 2%); 0.1976g Ce (NO 3) 36H 2O is dissolved in the 31.30ml ethylene glycol solution, is stirred to fully dissolving at 80 ℃ temperature lower magnetic forces.Then Fe (the NO that adds respectively 0.8648g in the above-mentioned solution 3) 39H 2The C of O and 0.0152g 6H 9MnO 62H 2O, at room temperature magnetic agitation and adds the 7.82ml glacial acetic acid to complete dissolving, continue to stir and etc. solution be cooled to room temperature.Adding respectively volume ratio in the above-mentioned solution is 1:1 acetylacetone,2,4-pentanedione and metatitanic acid four isopropyl esters, namely adds first the 5.44ml acetylacetone,2,4-pentanedione, dropwise adds 5.44ml metatitanic acid four isopropyl esters again.And at room temperature continued magnetic agitation 12 hours.Be that the injecting type filter of 0.2 μ m filters dust and contaminant particles with the aperture at last, obtaining concentration is the 50ml precursor solution of the homogeneous transparent of 0.4 mol/L.
(2), precursor solution is utilized spin-coating method at the LaNiO that is deposited on (100)-orientation 3On/Si the backing material, rotating speed is 7000 rev/mins during spin coating, and the spin coating time is 30 seconds.Then heat-treat technique.300 ℃ of insulations 7 minutes, again 480 ℃ of insulations 8 minutes, then annealed 8 minutes for 620 ℃ first.Repeat this layer by layer annealing process, until the thickness of film reaches 300nm.
Fig. 2 is 0.9Na 0.5(Bi 0.95Ce 0.05) 0.5TiO 3-0.1BiFe 0.97Mn 0.03O 3The X-ray diffracting spectrum of film.As seen this crystalline property is good, presents along (100) direction preferential growth.Utilize ferroelectric test macro (Precision Pro. Radiant Technologies) to 0.9Na 0.5(Bi 0.95Ce 0.05) 0.5TiO 3-0.1BiFe 0.97Mn 0.03O 3The electric hysteresis loop of film characterizes, as shown in Figure 3.Under the electric field strength of 900kV/cm, residual polarization (P r) be 27 μ m/cm, coercive field (E c) be 140kV/cm.
Embodiment 3
(1), according to 0.7Na 0.5(Bi 0.95Ce 0.05) 0.5TiO 3-0.3BiFe 0.97Mn 0.03O 3Stoichiometric proportion, accurately take by weighing the CH of 0.4349g 3COONa; 4.7416g Bi (NO 3) 35H 2O (excessive 2%); 0.1151g Ce (NO 3) 36H 2O is dissolved in the 29ml ethylene glycol solution, is stirred to fully dissolving at 60 ℃ temperature lower magnetic forces.Then Fe (the NO that adds respectively 1.7903g in the above-mentioned solution 3) 39H 2The C of O and 0.0366g 6H 9MnO 62H 2O, at room temperature magnetic agitation and adds the 14.66ml glacial acetic acid to complete dissolving, continue to stir and etc. solution be cooled to room temperature.At last, adding respectively volume ratio in the above-mentioned solution is 1:1 acetylacetone,2,4-pentanedione and metatitanic acid four isopropyl esters, namely adds first the 3.17ml acetylacetone,2,4-pentanedione, dropwise adds 3.17ml metatitanic acid four isopropyl esters again.And at room temperature continued magnetic agitation 10 hours.Be that the injecting type filter of 0.2 μ m filters dust and contaminant particles with the aperture at last, obtaining concentration is the 50ml precursor solution of the homogeneous transparent of 0.3mol/L.
(2), precursor solution is utilized spin-coating method at the LaNiO that is deposited on (100)-orientation 3On/Si the backing material, rotating speed is 5000 rev/mins during spin coating, and the spin coating time is 40 seconds.Then heat-treat technique.280 ℃ of insulations 6 minutes, again 450 ℃ of insulations 5 minutes, then annealed 5 minutes for 650 ℃ first.Repeat this layer by layer annealing process, until the thickness of film reaches 500nm.
Such as Fig. 4, (German Brooker is D8) to 0.7Na through x-ray diffractometer 0.5(Bi 0.95Ce 0.05) 0.5TiO 3-0.3BiFe 0.97Mn 0.03O 3Film carries out structured testing, and prepared film presents along (100) direction preferential growth, is single perovskite structure.Utilize ferroelectric test macro (Precision Pro. Radiant Technologies) to 0.7Na 0.5(Bi 0.95Ce 0.05) 0.5TiO 3-0.3BiFe 0.97Mn 0.03O 3The electric hysteresis loop of film characterizes, as shown in Figure 5.Under the electric field strength of 900kV/cm, residual polarization (P r) be 36 μ m/cm, coercive field (E c) be 170kV/cm.Fig. 6 is that dielectric constant and dielectric loss are with biased variation under the small-signal (100kHz).Voltage is strong non-linear relation with electric capacity, presents butterfly; Curve is substantially equal about x=0 axle near symmetrical and positive negative direction electric capacity peak value.In addition, dielectric loss also is symmetry under generating positive and negative voltage.Test result shows 0.7Na 0.5(Bi 0.95Ce 0.05) 0.5TiO 3-0.3BiFe 0.97Mn 0.03O 3Film has by force (100) preferred orientation, i.e. good structural homogeneity; And has strong ferroelectric properties.
Embodiment 4
(1), according to 0.5Na 0.5(Bi 0.95Ce 0.05) 0.5TiO 3-0.5BiFe 0.97Mn 0.03O 3Stoichiometric proportion, accurately take by weighing the CH of 0.1035g 3COONa; 1.8429g Bi (NO 3) 35H 2O (excessive 2%); 0.0274g Ce (NO 3) 36H 2O is dissolved in the 37.72ml ethylene glycol solution, is stirred to fully dissolving at 50 ℃ temperature lower magnetic forces.Then Fe (the NO that adds respectively 0.9946g in the above-mentioned solution 3) 39H 2The C of O and 0.2031g 6H 9MnO 62H 2O, at room temperature magnetic agitation and adds the 4.72ml glacial acetic acid to complete dissolving, continue to stir and etc. solution be cooled to room temperature.Adding respectively volume ratio in the above-mentioned solution is 1:1 acetylacetone,2,4-pentanedione and metatitanic acid four isopropyl esters, namely adds first the 3.78ml acetylacetone,2,4-pentanedione, dropwise adds 3.78ml metatitanic acid four isopropyl esters again.And at room temperature continued magnetic agitation 9 hours.At last, be that the injecting type filter of 0.2 μ m filters dust and contaminant particles with the aperture, obtaining concentration is the 50ml precursor solution of the homogeneous transparent of 0.1mol/L.
(2), precursor solution is utilized spin-coating method at the LaNiO that is deposited on (100)-orientation 3On/Si the backing material, rotating speed is 4000 rev/mins during spin coating, and the spin coating time is 20 seconds.Then heat-treat technique.250 ℃ of insulations 10 minutes, again 500 ℃ of insulations 3 minutes, then annealed 10 minutes for 650 ℃ first.Repeat this layer by layer annealing process, until the thickness of film reaches 800nm.
As shown in Figure 7, use Agilent 4294A to 0.5Na 0.5(Bi 0.95Ce 0.05) 0.5TiO 3-0.5BiFe 0.97Mn 0.03O 3The dielectric property of film are tested, and dielectric constant is along with the overall trend of frequency change reduces gradually, and meanwhile the variation tendency integral body of fissipation factor is to reduce first rear increase.When frequency was 100kHz, dielectric constant and dielectric loss were respectively 220,0.04.
Embodiment 5
(1), according to 0.3Na 0.5(Bi 0.95Ce 0.05) 0.5TiO 3-0.7BiFe 0.97Mn 0.03O 3Stoichiometric proportion, accurately take by weighing the CH of 0.1243g 3COONa; 4.2106g Bi (NO 3) 35H 2O (excessive 2%); 0.0329g Ce (NO 3) 36H 2O is dissolved in the 40.15ml ethylene glycol solution, is stirred to fully dissolving at 50 ℃ temperature lower magnetic forces.Then Fe (the NO that adds respectively 2.7849g in the above-mentioned solution 3) 39H 2The C of O and 0.0569g 6H 9MnO 62H 2O, at room temperature magnetic agitation and adds the 8.03ml glacial acetic acid to complete dissolving, continue to stir and etc. solution be cooled to room temperature.Adding respectively volume ratio in the above-mentioned solution is 1:1 acetylacetone,2,4-pentanedione and metatitanic acid four isopropyl esters, namely adds first the 0.91ml acetylacetone,2,4-pentanedione, dropwise adds 0.91ml metatitanic acid four isopropyl esters again.And at room temperature continued magnetic agitation 11 hours.At last, be that the injecting type filter of 0.2 μ m filters dust and contaminant particles with the aperture, obtaining concentration is the 50ml precursor solution of the homogeneous transparent of 0.2mol/L.
(2), precursor solution is utilized spin-coating method at the LaNiO that is deposited on (100)-orientation 3On/Si the backing material, rotating speed is 3000 rev/mins during spin coating, and the spin coating time is 30 seconds.Then heat-treat technique.290 ℃ of insulations 8 minutes, again 420 ℃ of insulations 5 minutes, then annealed 5 minutes for 600 ℃ first.Repeat this layer by layer annealing process, until the thickness of film reaches 900nm.
The gained film has by force (100) preferred orientation, i.e. good structural homogeneity; And has strong ferroelectric properties.
Embodiment 6
(1), according to 0.1Na 0.5(Bi 0.95Ce 0.05) 0.5TiO 3-0.9BiFe 0.97Mn 0.03O 3Stoichiometric proportion, accurately take by weighing the CH of 0.1035g 3COONa; 11.8383g Bi (NO 3) 35H 2O (excessive 2%); 0.0329g Ce (NO 3) 36H 2O is dissolved in the 41.55ml ethylene glycol solution, is stirred to fully dissolving at 50 ℃ temperature lower magnetic forces.Then Fe (the NO that adds respectively 8.9064g in the above-mentioned solution 3) 39H 2The C of O and 0.1828g 6H 9MnO 62H 2O, at room temperature magnetic agitation and adds the 6.93ml glacial acetic acid to complete dissolving, continue to stir and etc. solution be cooled to room temperature.Adding respectively volume ratio in the above-mentioned solution is 1:1 acetylacetone,2,4-pentanedione and metatitanic acid four isopropyl esters, namely adds first 0.76 ml acetylacetone,2,4-pentanedione, dropwise adds 0.76 ml metatitanic acid, four isopropyl esters again.And at room temperature continued magnetic agitation 10 hours.At last, be that the injecting type filter of 0.2 μ m filters dust and contaminant particles with the aperture, obtaining concentration is the 50ml precursor solution of the homogeneous transparent of 0.5 mol/L.
(2), precursor solution is utilized spin-coating method at the LaNiO that is deposited on (100)-orientation 3On/Si the backing material, rotating speed is 6000 rev/mins during spin coating, and the spin coating time is 20 seconds.Then heat-treat technique.300 ℃ of insulations 6 minutes, again 460 ℃ of insulations 6 minutes, then annealed 6 minutes for 630 ℃ first.Repeat this layer by layer annealing process, until the thickness of film reaches 1 μ m.
The gained film has by force (100) preferred orientation, i.e. good structural homogeneity; And has strong ferroelectric properties.
Embodiment 7
(1), according to 0.05 Na 0.5(Bi 0.95Ce 0.05) 0.5TiO 3-0.95BiFe 0.97Mn 0.03O 3Stoichiometric proportion, accurately take by weighing the CH of 0.0259g 3COONa; 6.0831g Bi (NO 3) 35H 2O (excessive 2%); 0.0069g Ce (NO 3) 36H 2O is dissolved in the 42.53ml ethylene glycol solution, is stirred to fully dissolving at 50 ℃ temperature lower magnetic forces.Then Fe (the NO that adds respectively 4.7006g in the above-mentioned solution 3) 39H 2The C of O and 0.0964 g 6H 9MnO 62H 2O, at room temperature magnetic agitation and adds the 7.09ml glacial acetic acid to complete dissolving, continue to stir and etc. solution be cooled to room temperature.Adding respectively volume ratio in the above-mentioned solution is 1:1 acetylacetone,2,4-pentanedione and metatitanic acid four isopropyl esters, namely adds first 0.19 ml acetylacetone,2,4-pentanedione, dropwise adds 0.19ml metatitanic acid four isopropyl esters again.And at room temperature continued magnetic agitation 10 hours.At last, be that the injecting type filter of 0.2 μ m filters dust and contaminant particles with the aperture, obtaining concentration is the 50ml precursor solution of the homogeneous transparent of 0.25mol/L.
(2), precursor solution is utilized spin-coating method at the LaNiO that is deposited on (100)-orientation 3On/Si the backing material, rotating speed is 5000 rev/mins during spin coating, and the spin coating time is 30 seconds.Then heat-treat technique.270 ℃ of insulations 9 minutes, again 440 ℃ of insulations 7 minutes, then annealed 9 minutes for 610 ℃ first.Repeat this layer by layer annealing process, until the thickness of film reaches 400nm.
The gained film has by force (100) preferred orientation, i.e. good structural homogeneity; And has strong ferroelectric properties.

Claims (9)

1. one kind based on the bismuth sodium titanate based and compound solid solution body thin film ferrous acid bismuthino, it is characterized in that: with general formula (1-x) Na 0.5(Bi 0.95Ce 0.05) 0.5TiO 3-xBiFe 0.97Mn 0.03O 3The expression, described bismuth sodium titanate based be Na 0.5(Bi 0.95Ce 0.05) 0.5TiO 3, described ferrous acid bismuthino is BiFe 0.97Mn 0.03O 3Wherein, x is BiFe 0.97Mn 0.03O 3Molar content, 0＜x＜1.
2. compound solid solution body thin film according to claim 1 is characterized in that: x=0.1～0.9.
3. compound solid solution body thin film according to claim 2 is characterized in that: x=0.3～0.7.
4. compound solid solution body thin film according to claim 1, it is characterized in that: film thickness is 0.2～1 μ m.
5. the preparation method of the compound solid solution body thin film based on bismuth sodium titanate based and ferrous acid bismuthino claimed in claim 1 is characterized in that may further comprise the steps:
(1), the preparation of precursor solution
1. take sodium acetate, five water bismuth nitrates, six water cerous nitrates, nine water ferric nitrates, two water manganese acetates and metatitanic acid four isopropyl esters as raw material, according to (1-x) Na 0.5(Bi 0.95Ce 0.05) 0.5TiO 3-xBiFe 0.97Mn 0.03O 3Stoichiometric proportion, accurately take by weighing each raw material, wherein five water bismuth nitrates are excessive, for subsequent use;
2. sodium acetate, five water bismuth nitrates, six water cerous nitrates are dissolved in the ethylene glycol solution, under 40～80 ℃ temperature, are stirred to fully dissolving;
3. in above-mentioned solution, add respectively nine water ferric nitrates and two water manganese acetates, at room temperature be stirred to fully dissolving after, add glacial acetic acid, continue to stir, be cooled to room temperature to solution;
4. after the solution cooling, to wherein adding acetylacetone,2,4-pentanedione and metatitanic acid four isopropyl esters, at room temperature stirred 8～12 hours respectively;
5. with above-mentioned steps solution filter 4., obtain the precursor solution that concentration is 0.05～0.5 mol/L;
(2), thin film technology: with spin-coating method-annealing process prepares film layer by layer
1. adopt spin-coating method that precursor solution is deposited on the backing material, then material is heat-treated, processing procedure is: 250～300 ℃ are incubated 5～10 minutes first, again 400～500 ℃ of insulations 3～10 minutes, then anneal 3～10 minutes for 600～650 ℃;
2. adopt above-mentioned identical method to continue precursor solution is spun on the backing material, until film thickness reaches 0.2～1 μ m, and get final product.
6. preparation method according to claim 5 is characterized in that: when precursor solution prepares, and the excessive 2mol% of five water bismuth nitrates.
7. preparation method according to claim 5, it is characterized in that: the volume ratio of ethylene glycol and glacial acetic acid is 2:1～10:1; The volume ratio of acetylacetone,2,4-pentanedione and metatitanic acid four isopropyl esters is 1:1.
8. preparation method according to claim 5, it is characterized in that: in the described spin coating proceeding, rotating speed is 3000～7000 rev/mins, and the spin coating time is 20～40 seconds, the precursor solution thickness of each spin coating is 20～50nm.
9. preparation method according to claim 5 is characterized in that: described backing material is the LaNiO of (100)-orientation 3/ Si substrate.
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