CN101654779A - Preparation method of Bi3.2Nd0.8Ti3O12 ferroelectric film - Google Patents

Preparation method of Bi3.2Nd0.8Ti3O12 ferroelectric film Download PDF

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Publication number
CN101654779A
CN101654779A CN200910023721A CN200910023721A CN101654779A CN 101654779 A CN101654779 A CN 101654779A CN 200910023721 A CN200910023721 A CN 200910023721A CN 200910023721 A CN200910023721 A CN 200910023721A CN 101654779 A CN101654779 A CN 101654779A
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solution
substrate
bismuth
film
precursor solution
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贺海燕
曹丽云
黄剑锋
吴建鹏
于慧阳
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Shaanxi University of Science and Technology
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Shaanxi University of Science and Technology
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Abstract

A preparation method of a Bi3.2Nd0.8Ti3O12 ferroelectric film comprises the following steps: respectively dissolving bismuth nitrate or bismuth acetate and lanthanum nitrate or lanthanum acetate intoglacial acetic acid according to the Bi3.2Nd0.8Ti3O12 chemical formula to obtain solution A and then regulating the solution A until the pH value is less than 3 to obtain solution B; dissolving butyltitanate or tetrabutyl titanate into the glacial acetic acid to obtain solution C and then adding acetylacetone into the solution C to obtain solution D; mixing the solution B and the solution D to obtain precursor solution, coating the precursor solution on a substrate by the technology of dip coating or spin coating and cooling the coated substrate at different annealing temperatures to obtain ac-oriented film or an a-oriented film. In the method, the Bi3.2Nd0.8Ti3O12 film is deposited on the single crystal silicon substrate by a chemical solution deposition method and a metal organic solution method. The singly c-oriented Bi3.2Nd0.8Ti3O12 ferroelectric film is obtained by quick temperature rise between 650 DEG C and 1000 DEG C, and the a-oriented Bi3.2Nd0.8Ti3O12 ferroelectric film isobtained by preheating treatment at 350-400 DEG C and further annealing at 650-750 DEG C.

Description

A kind of Bi 3.2La 0.8Ti 3O 12The preparation method of ferroelectric membranc
Technical field
The present invention relates to a kind of preparation method of ferroelectric membranc, be specifically related to a kind of Bi 3.2La 0.8Ti 3O 12The preparation method of ferroelectric membranc.
Background technology
Bi 3.2La 0.8Ti 3O 12Ferroelectric membranc has the characteristics of the big and antifatigue of polarization.It is very important electron material of the class with potential using value of permanent random access memory (NVRAM) and dynamic randon access memory in (DRAM).In these are used, require film that low coercive field, high residual polarization, low leakage current and low polarization fatigue are arranged.Big residual polarization is arranged Pb-based lanthanumdoped zirconate titanates (PZT) film but anti-fatigue performance is poor.Barium titanate, barium strontium titanate ferroelectric film have preferably anti-fatigue performance but poor-performings such as residual polarization.(Wang H., Ren M.F., Effects of Orientated Growth on Propertiesof Ag/Bi such as Smolenskii 4Ti 3O 12/ p-Si Heterostructure Prepared by Sol-gel Method with RapidThermal Annealing Techniques, J.Mat.Sci.:Mat.In Eletronics, 2005,16,209-213) find bismuth layer perovskite structure pottery (SrB i 2Ta 2O 9, SrB i 2NbTaO 9, SrB i 4Ta 4O 15And Bi 4Ti 3O 12Deng) have ferroelectricity and high Curie temperature and big anti-fatigue performance are arranged.But the remnant polarization of their thin-film material is then relatively low.In order to utilize Bi 4Ti 3O 12The advantage of the high-curie temperature of ferroelectric material and big residual polarization overcomes the fatiguability characteristics, discovers that lanthanum, neodymium, samarium and ruthenium ion partly replace bismuth ion and enter the electropolarization performance that the bismuth layer can improve film, significantly improves anti-fatigue performance.Just ion Bi is thought in some researchs 4Ti 3O 12The electropolarization direction of film is the a-axle, then thinks ion doping Bi in other researchs 4Ti 3O 12The electropolarization direction of film is at the c-axle.But a large amount of data in literature shows that so-called orientation is actually indirect or several orientations and exists the orientation degree on certain orientation just bigger simultaneously.On the electropolarization direction, increase orientation degree and mean the increase polarization.Therefore, for the electropolarization discovery of studying such film and the film that obtains large electrode intensity, be necessary to prepare the high-orientation film of two kinds of orientations, research obtains the processing condition of various oriented films.Still also there is dispute in the electropolarization direction of such film at the c-axle at the a-axle at present, and lacks the technology of preparing of single oriented film, though can prepare the bigger film of orientation degree on a certain direction, it then is difficult preparing single oriented film.Orientation degree and single orientation big on the electropolarization direction mean big polarization.Therefore, be necessary to obtain the film preparing technology of single orientation of two kinds of orientations of high-orientation.
Summary of the invention
The object of the present invention is to provide the simple Bi of a kind of preparation technology 3.2La 0.8Ti 3O 12The preparation method of ferroelectric membranc can prepare single oriented film that high a-is orientated and high c-is orientated by preparation method of the present invention.
For achieving the above object, the technical solution used in the present invention is:
1) preparation precursor solution:
At first, press Bi 3.2La 0.8Ti 3O 12Chemical formula is got Bismuth trinitrate or bismuth acetate respectively, lanthanum nitrate or lanthanum acetate and butyl (tetra) titanate or tetrabutyl titanate, then Bismuth trinitrate or bismuth acetate and lanthanum nitrate or lanthanum acetate are dissolved in and obtain solution A in the glacial acetic acid, in solution A, add again after the Bismuth trinitrate of Bismuth trinitrate in the solution A or bismuth acetate quality 5～10% or the bismuth acetate with hydrochloric acid regulate pH＜3 solution B;
Secondly, butyl (tetra) titanate or tetrabutyl titanate be dissolved in obtain solution C in the glacial acetic acid, in solution C, add methyl ethyl diketone again and obtain solution D;
At last, solution B and solution D are mixed, in mixing solutions, regulate the concentration of mixing solutions to metal ion Ti with glacial acetic acid behind adding ethylene glycol and the citric acid again 4+Volumetric molar concentration be that 0.01mol/l obtains precursor solution, metal ion in the precursor solution: ethylene glycol: citric acid: methyl ethyl diketone=1: (1～4): (1～2): 0.1;
2) film: adopt dip-coating or spin coating proceeding that precursor solution is coated on the substrate, after each coating with it 120-150 ℃ of drying, above-mentioned repeatedly coating and drying process are until the film that obtains required thickness;
3) annealing:
The substrate of substrate after filming from room temperature is warming up to 650～1000 ℃ of annealing 3min or directly will films with the temperature rise rate of 200～300 ℃/min after put into take out cooling from stove immediately behind 650-1000 ℃ the High Temperature Furnaces Heating Apparatus annealing 3min and obtain c-orientation Bi 3.2La 0.8Ti 3O 12Ferroelectric membranc;
Substrate after maybe will filming is warming up to 650-750 ℃ of annealing 3-60min with the temperature rise rate greater than 200～300 ℃/min and obtains a-orientation Bi behind 350-400 ℃ of thermal pretreatment 10min 3.2La 0.8Ti 3O 12Ferroelectric membranc.
The present invention is in order to reduce the viscosity of precursor solution, with precursor solution at 60-80 ℃ of gelation 30-60min; Said substrate adopts monocrystalline silicon substrate, uses dehydrated alcohol and acetone respectively to the monocrystalline silicon substrate drying in air after ultrasonic cleaning before filming.
Applied chemistry solution-deposition method of the present invention and organic metal solution method deposit Bi on monocrystalline silicon substrate 3.2La 0.8Ti 3O 12Film.At 650-1000 ℃ of list orientation Bi that is rapidly heated and obtains the c-orientation 3.2La 0.8Ti 3O 12Ferroelectric membranc.Obtain a-orientation Bi in 350-400 ℃ of thermal pretreatment and 650-750 ℃ of further annealing 3.2La 0.8Ti 3O 12Ferroelectric membranc.
Description of drawings
Fig. 1 (a) is the Bi with c-orientation that 700 ℃ of short annealing 3min of the present invention obtain 3.2La 0.8Ti 3O 12The XRD figure of film, Fig. 1 (b) is the Bi with a-orientation that obtains behind 700 ℃ of annealing 3min behind 400 ℃ of annealing of the present invention 10min 3.2La 0.8Ti 3O 12The XRD figure of film;
Embodiment
Below in conjunction with drawings and Examples the present invention is described in further detail.
Embodiment 1:
1) preparation precursor solution:
At first, press Bi 3.2La 0.8Ti 3O 12Chemical formula is got Bismuth trinitrate respectively, lanthanum nitrate and butyl (tetra) titanate, then Bismuth trinitrate and lanthanum nitrate are dissolved in and obtain solution A in the glacial acetic acid, in order to remedy the Bi ion pyritous volatilization loss adds the Bismuth trinitrate of Bismuth trinitrate quality 8% in the solution A again in solution A after, with the formation of the oxysalt that prevents insoluble bismuth with hydrochloric acid regulate pH＜3 solution B;
Secondly, butyl (tetra) titanate is dissolved in obtains solution C in the glacial acetic acid, in solution C, add methyl ethyl diketone again and obtain solution D;
At last, solution B and solution D are mixed, in mixing solutions, regulate the concentration of mixing solutions to metal ion Ti with glacial acetic acid behind adding ethylene glycol and the citric acid again 4+Volumetric molar concentration be that 0.01mol/l obtains precursor solution, metal ion in the precursor solution: ethylene glycol: citric acid: methyl ethyl diketone=1: 1: 2: 0.1, in order to reduce the viscosity of precursor solution, with precursor solution at 70 ℃ of gelation 45min,
2) film: use dehydrated alcohol and acetone respectively to the monocrystalline silicon substrate drying in air after ultrasonic cleaning monocrystalline silicon substrate, adopt dip-coating or spin coating proceeding that precursor solution is coated on the substrate, after each coating with it 130 ℃ of dryings, above-mentioned repeatedly coating and drying process are until the film that obtains required thickness;
3) annealing:
The substrate of substrate after filming from room temperature is warming up to 650 ℃ of annealing 3min or directly will films with the temperature rise rate of 260 ℃/min after put into take out cooling from stove immediately behind 650 ℃ the High Temperature Furnaces Heating Apparatus annealing 3min and obtain c-orientation Bi 3.2La 0.8Ti 3O 12(Fig. 1 a) for ferroelectric membranc;
Substrate after maybe will filming is warming up to the temperature rise rate of 260 ℃/min behind 400 ℃ of thermal pretreatment 10min and takes out cooling immediately behind 700 ℃ of annealing 30min from stove and obtain a-orientation Bi 3.2La 0.8Ti 3O 12Ferroelectric membranc (Fig. 1 b).
Embodiment 2:
1) preparation precursor solution:
At first, press Bi 3.2La 0.8Ti 3O 12Chemical formula is got bismuth acetate respectively, lanthanum acetate and tetrabutyl titanate, then bismuth acetate and lanthanum acetate are dissolved in and obtain solution A in the glacial acetic acid, in order to remedy the Bi ion pyritous volatilization loss adds the bismuth acetate of bismuth acetate quality 5% in the solution A again in solution A after, with the formation of the oxysalt that prevents insoluble bismuth with hydrochloric acid regulate pH＜3 solution B;
Secondly, tetrabutyl titanate is dissolved in obtains solution C in the glacial acetic acid, in solution C, add methyl ethyl diketone again and obtain solution D;
At last, solution B and solution D are mixed, in mixing solutions, regulate the concentration of mixing solutions to metal ion Ti with glacial acetic acid behind adding ethylene glycol and the citric acid again 4+Volumetric molar concentration be that 0.01mol/l obtains precursor solution, metal ion in the precursor solution: ethylene glycol: citric acid: methyl ethyl diketone=1: 3: 1: 0.1, in order to reduce the viscosity of precursor solution, with precursor solution at 80 ℃ of gelation 30min,
2) film: use dehydrated alcohol and acetone respectively to the monocrystalline silicon substrate drying in air after ultrasonic cleaning monocrystalline silicon substrate, adopt dip-coating or spin coating proceeding that precursor solution is coated on the substrate, after each coating with it 120 ℃ of dryings, above-mentioned repeatedly coating and drying process are until the film that obtains required thickness;
3) annealing:
The substrate of substrate after filming from room temperature is warming up to 850 ℃ of annealing 3min or directly will films with the temperature rise rate of 300 ℃/min after put into take out cooling from stove immediately behind 850 ℃ the High Temperature Furnaces Heating Apparatus annealing 3min and obtain c-orientation Bi 3.2La 0.8Ti 3O 12Ferroelectric membranc;
Substrate after maybe will filming is warming up to the temperature rise rate of 300 ℃/min behind 350 ℃ of thermal pretreatment 10min and takes out cooling immediately behind 650 ℃ of annealing 60min from stove and obtain a-orientation Bi 3.2La 0.8Ti 3O 12Ferroelectric membranc.
Embodiment 3:
1) preparation precursor solution:
At first, press Bi 3.2La 0.8Ti 3O 12Chemical formula is got Bismuth trinitrate respectively, lanthanum acetate and butyl (tetra) titanate, then Bismuth trinitrate and lanthanum acetate are dissolved in and obtain solution A in the glacial acetic acid, in order to remedy the Bi ion pyritous volatilization loss adds the Bismuth trinitrate of Bismuth trinitrate quality 10% in the solution A again in solution A after, with the formation of the oxysalt that prevents insoluble bismuth with hydrochloric acid regulate pH＜3 solution B;
Secondly, butyl (tetra) titanate is dissolved in obtains solution C in the glacial acetic acid, in solution C, add methyl ethyl diketone again and obtain solution D;
At last, solution B and solution D are mixed, in mixing solutions, regulate the concentration of mixing solutions to metal ion Ti with glacial acetic acid behind adding ethylene glycol and the citric acid again 4+Volumetric molar concentration be that 0.01mol/l obtains precursor solution, metal ion in the precursor solution: ethylene glycol: citric acid: methyl ethyl diketone=1: 4: 1.5: 0.1, in order to reduce the viscosity of precursor solution, with precursor solution at 60 ℃ of gelation 60min,
2) film: use dehydrated alcohol and acetone respectively to the monocrystalline silicon substrate drying in air after ultrasonic cleaning monocrystalline silicon substrate, adopt dip-coating or spin coating proceeding that precursor solution is coated on the substrate, after each coating with it 150 ℃ of dryings, above-mentioned repeatedly coating and drying process are until the film that obtains required thickness;
3) annealing:
The substrate of substrate after filming from room temperature is warming up to 1000 ℃ of annealing 3min or directly will films with the temperature rise rate of 200 ℃/min after put into take out cooling from stove immediately behind 1000 ℃ the High Temperature Furnaces Heating Apparatus annealing 3min and obtain c-orientation Bi 3.2La 0.8Ti 3O 12Ferroelectric membranc;
Substrate after maybe will filming is warming up to the temperature rise rate of 200 ℃/min behind 380 ℃ of thermal pretreatment 10min and takes out cooling immediately behind 750 ℃ of annealing 3min from stove and obtain a-orientation Bi 3.2La 0.8Ti 3O 12Ferroelectric membranc.

Claims (3)

1, a kind of Bi 3.2La 0.8Ti 3O 12The preparation method of ferroelectric membranc is characterized in that, may further comprise the steps:
1) preparation precursor solution:
At first, press Bi 3.2La 0.8Ti 3O 12Chemical formula is got Bismuth trinitrate or bismuth acetate respectively, lanthanum nitrate or lanthanum acetate and butyl (tetra) titanate or tetrabutyl titanate, then Bismuth trinitrate or bismuth acetate and lanthanum nitrate or lanthanum acetate are dissolved in and obtain solution A in the glacial acetic acid, in solution A, add again after the Bismuth trinitrate of Bismuth trinitrate in the solution A or bismuth acetate quality 5～10% or the bismuth acetate with hydrochloric acid regulate pH＜3 solution B;
Secondly, butyl (tetra) titanate or tetrabutyl titanate be dissolved in obtain solution C in the glacial acetic acid, in solution C, add methyl ethyl diketone again and obtain solution D;
At last, solution B and solution D are mixed, in mixing solutions, regulate the concentration of mixing solutions to metal ion Ti with glacial acetic acid behind adding ethylene glycol and the citric acid again 4+Volumetric molar concentration be that 0.01mol/l obtains precursor solution, metal ion in the precursor solution: ethylene glycol: citric acid: methyl ethyl diketone=1: (1～4): (1～2): 0.1;
2) film: adopt dip-coating or spin coating proceeding that precursor solution is coated on the substrate, after each coating with it 120-150 ℃ of drying, above-mentioned repeatedly coating and drying process are until the film that obtains required thickness;
3) annealing:
The substrate of substrate after filming from room temperature is warming up to 650～1000 ℃ of annealing 3min or directly will films with the temperature rise rate of 200～300 ℃/min after put into take out cooling from stove immediately behind 650-1000 ℃ the High Temperature Furnaces Heating Apparatus annealing 3min and obtain c-orientation Bi 3.2La 0.8Ti 3O 12Ferroelectric membranc;
Substrate after maybe will filming is warming up to 650-750 ℃ of annealing 3-60min with the temperature rise rate greater than 200～300 ℃/min and obtains a-orientation Bi behind 350-400 ℃ of thermal pretreatment 10min 3.2La 0.8Ti 3O 12Ferroelectric membranc.
2, Bi according to claim 1 3.2La 0.8Ti 3O 12The preparation method of ferroelectric membranc is characterized in that: in order to reduce the viscosity of precursor solution, with precursor solution at 60-80 ℃ of gelation 30-60min.
3, Bi according to claim 1 3.2La 0.8Ti 3O 12The preparation method of ferroelectric membranc is characterized in that: said substrate adopts monocrystalline silicon substrate, uses dehydrated alcohol and acetone respectively to the monocrystalline silicon substrate drying in air after ultrasonic cleaning before filming.
CN200910023721A 2009-08-28 2009-08-28 Preparation method of Bi3.2Nd0.8Ti3O12 ferroelectric film Pending CN101654779A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102534610A (en) * 2012-02-24 2012-07-04 陕西科技大学 Method for depositing compact barium strontium titanate film on glass substrate
CN102888599A (en) * 2012-11-01 2013-01-23 哈尔滨工业大学 Method for preparing high-density metal oxide membrane on porous base material
CN108883035A (en) * 2016-04-06 2018-11-23 兰达拉伯斯（2012）有限公司 UV protection component and application thereof
CN115895656A (en) * 2021-08-24 2023-04-04 浙江理工大学 Photoluminescent terbium-doped tin oxide film and preparation method thereof
CN115895656B (en) * 2021-08-24 2024-05-03 浙江理工大学 Photoluminescent terbium-doped tin oxide film and preparation method thereof

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102534610A (en) * 2012-02-24 2012-07-04 陕西科技大学 Method for depositing compact barium strontium titanate film on glass substrate
CN102888599A (en) * 2012-11-01 2013-01-23 哈尔滨工业大学 Method for preparing high-density metal oxide membrane on porous base material
CN102888599B (en) * 2012-11-01 2014-06-11 哈尔滨工业大学 Method for preparing high-density metal oxide membrane on porous base material
CN108883035A (en) * 2016-04-06 2018-11-23 兰达拉伯斯（2012）有限公司 UV protection component and application thereof
CN108883035B (en) * 2016-04-06 2021-09-28 兰达拉伯斯（2012）有限公司 UV-protective composition and use thereof
CN115895656A (en) * 2021-08-24 2023-04-04 浙江理工大学 Photoluminescent terbium-doped tin oxide film and preparation method thereof
CN115895656B (en) * 2021-08-24 2024-05-03 浙江理工大学 Photoluminescent terbium-doped tin oxide film and preparation method thereof

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