CN102731107A - Method for preparing Mn-doped bismuth sodium titanate-barium titanate film - Google Patents
Method for preparing Mn-doped bismuth sodium titanate-barium titanate film Download PDFInfo
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- CN102731107A CN102731107A CN2012102403277A CN201210240327A CN102731107A CN 102731107 A CN102731107 A CN 102731107A CN 2012102403277 A CN2012102403277 A CN 2012102403277A CN 201210240327 A CN201210240327 A CN 201210240327A CN 102731107 A CN102731107 A CN 102731107A
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- barium titanate
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Abstract
The invention discloses a method for preparing a Mn-doped bismuth sodium titanate-barium titanate film, comprising the following steps that: high-purity Bi2O3, Na2CO3, BaCO3 and TiO2 are taken as the raw materials and subjected to wet milling by a zirconium ball in absolute ethyl alcohol, drying, tabletting and calcination at a certain air pressure to obtain perovskite structure powder; the obtained perovskite structure powder is subjected to secondary ball milling, drying, tabletting and heat preservation for 1-4 hours at the temperature of 1200 DEG C to obtain a target material by sintering; the target material and the substrate are installed and the target-substrate distance, the sputtering temperature, the power and the frequency are adjusted; after the sputtering, in-situ annealing is performed, the oxygen pressure is maintained and the temperature is lowered to room temperature by naturally cooling to prepare the Mn-doped bismuth sodium titanate-barium titanate film. The orientation and the thickness of the film can be adjusted by technological parameters and the prepared lead-free piezoelectric film shows better ferroelectric and dielectric properties. The method has the advantages of convenience in operation and good repeatability.
Description
Technical field
The present invention relates to a kind of preparation method controlled, environmental friendliness leadless piezoelectric film that is orientated, be specially the preparation method of the bismuth sodium titanate-barium titanate film of a kind of Mn of mixing, belong to the ferroelectric thin-flim materials field.
Background technology
From the eighties in 20th century so far; Developing rapidly of semiconductor device technology and film preparing technology; Cause the great interest that people use in fields such as memory, microelectromechanical systems, high frequency microelectronics for ferroelectric piezoelectric membrane; The preparation research of ferroelectric piezoelectric membrane is fallen over each other to carry out in countries in the world, and Application Areas spreads all over various fields such as communication, sensing, medical treatment, space flight, machinery, biology.In ferroelectric memory, microsensor, driving mechanism etc. were used, at present common mainly is with Pb-based lanthanumdoped zirconate titanates (PZT) was the piezoelectric film material of representative.This type film is because of having big remnant polarization, high piezo-electric modulus, electromechanical coupling factor, and have that power consumption is little, moment is big; Outstanding advantages such as the time of response is fast; Receive the western developed country positive regard, carried out a large amount of development works, and obtained significant progress about piezoelectric membrane; At present, piezo-electric modulus is near pure PZT stupalith.But it should be noted that and contain a large amount of lead element (mass percent reaches more than 60%) in these piezoelectricity systems, in the preparation process, very easily cause harm environment.Therefore; With the U.S., Japan, the European Economic Community and China is all to have made laws strict restriction has been carried out in the use of lead-containing materials in the countries in the world of representative; Project verification simultaneously drops into the research and development that huge fund has been carried out leadless piezoelectric material material; Said as famous scholar Cross, " lead free at last ", development novel high-performance eco-friendly ferroelectric piezoelectric have become one of focus material of countries in the world in recent years endeavouring to research and develop.
Through aiming at discovering of homotype phase boundary leadless piezoelectric body material early stage; Mix bismuth sodium titanate-barium titanate monocrystalline piezoelectric coefficient behind the Mn near 500pC/N; Suitable with conventional P ZT piezoelectric ceramics coefficient, carry out corresponding thin film system preparation research for promoting that its application in MEMS has important value.
Based on this, the invention provides the preparation method that a kind of preparation has the controlled bismuth-sodium titanate-barium titanate film of mixing Mn of orientation, demonstrate ferroelectric properties preferably.
Summary of the invention
The object of the invention is to provide the preparation method of the bismuth sodium titanate-barium titanate film of a kind of Mn of mixing, to solve the problems referred to above of prior art.
The object of the invention can be realized through following technical scheme:
A kind of preparation method who mixes the bismuth sodium titanate-barium titanate film of Mn, its preparation technology's flow process is following:
(1) preparation of target: with high-purity Bi
2O
3, Na
2CO
3, BaCO
3, TiO
2Be raw material, according to chemical formula (1-x) Bi
0.5Na
0.5TiO
3: xBaTiO
3: the stoichiometric ratio weighing of 0.005Mn, wherein 0.03≤x≤0.09; With raw material in absolute ethyl alcohol with the wet-milling of zirconium ball, oven dry, compressing tablet under 800-900 ℃ of normal atmosphere calcination 1-4 hour, make the calcium titanium ore structure powder then; With gained calcium titanium ore structure powder secondary ball milling oven dry back compressing tablet, and 1-4 hour sintering of insulation obtains target under 1200 ℃;
(2) preparation of film:
(a) install target and substrate, regulate target-substrate distance 5.5cm;
(b) sputter temperature 650-700 ℃, power 300mJ, frequency 8Hz feeds a certain amount of oxygen, deposition pressure 30-50Pa;
(c) the sputter 30min that anneals in position that finishes keeps oxygen to press also and naturally cools to room temperature, makes the bismuth sodium titanate-barium titanate film of mixing Mn.
Described film is to prepare through the excimer pulsed laser sedimentation.
The substrate that adopts in the described film preparation is Pt (111)/Ti/SiO
2/ Si.
The prepared bismuth sodium titanate-barium titanate film of mixing Mn is the leadless piezoelectric film, is applicable to the MEMS field.
The present invention is on the bismuth sodium titanate-barium titanate basis of mixing Mn with good electromechanical coupling response; At first utilize solid reaction process to prepare target; Utilize impulse laser deposition system on the platinum substrate, to prepare corresponding film then; Regulation and control through processing parameters such as temperature, oxygen pressure, sputtering power, frequencies can realize the regulation and control to thin film alignment, and preparation has the environmental friendliness thin-film material of good ferroelectric properties.This method prepares simple, good reproducibility, is suitable as the driving and the sensing member in MEMS field.Through the orientation and the thickness of processing parameter regulation and control film, the leadless piezoelectric film of preparation demonstrates ferroelectric preferably and dielectric properties, have easy to operate, the advantage of good reproducibility.
Description of drawings
Fig. 1 is the XRD of BNBT-Mn film under the different deposition temperatures of embodiment 1 preparation;
Fig. 2 is the BNBT-Mn film surface SEM of 680 ℃ of preparations among the embodiment 1;
Fig. 3 is the BNBT-Mn thin-membrane section SEM of 680 ℃ of preparations among the embodiment 1;
Fig. 4 is the BNBT-Mn film surface SEM of 700 ℃ of preparations among the embodiment 1;
Fig. 5 is the BNBT-Mn thin-membrane section SEM of 700 ℃ of preparations among the embodiment 1;
Fig. 6 is the ferroelectric hysteresis loop of the BNBT-Mn film of 680 ℃ of preparations among the embodiment 1;
Fig. 7 is the ferroelectric hysteresis loop of the BNBT-Mn film of 700 ℃ of preparations among the embodiment 1;
Fig. 8 is that relative permittivity and the loss of 680 ℃ of preparation BNBT-Mn films among the embodiment 1 is with frequency variation curve;
Fig. 9 is that relative permittivity and the loss of 700 ℃ of preparation BNBT-Mn films among the embodiment 1 is with frequency variation curve.
Embodiment
Further set forth technical characterstic of the present invention below in conjunction with accompanying drawing and specific embodiment.
(1) preparation of target: with high-purity Bi
2O
3, Na
2CO
3, BaCO
3, TiO
2Be raw material, according to chemical formula 0.935Bi
0.5Na
0.5TiO
3-0.065BaTiO
3The stoichiometric ratio weighing of-0.005Mn, with raw material in absolute ethyl alcohol with zirconium ball wet-milling 6 hours, then the oven dry, compressing tablet, calcination is 2 hours under 850 ℃ of normal atmosphere, makes the calcium titanium ore structure powder; With gained calcium titanium ore structure powder secondary ball milling oven dry back compressing tablet, and 2 hours sintering of insulation obtain target under 1200 ℃.
(2) utilize impulse laser deposition system to prepare film, regulate target-substrate distance 5.5cm, 650 ℃ of sputter temperature; 680 ℃ and 700 ℃, power 300mJ, frequency 8Hz; Aerating oxygen, air pressure adjustment are 30Pa, sputter 40min; At depositing temperature annealing 30min, keep oxygen to press and naturally cool to room temperature and make the bismuth sodium titanate-barium titanate film of mixing Mn subsequently.
(3) test XRD plates the Au electrode, and diameter 0.2mm tests ferroelectric hysteresis loop and dielectric spectra under its 1kHz.
Embodiment 2
Present embodiment and embodiment 1 each step are basic identical, and difference is being pressed chemical formula 0.97Bi
0.5Na
0.5TiO
3-0.03BaTiO
3-0.005Mn prepares burden.
Embodiment 3
Present embodiment and embodiment 1 each step are basic identical, and difference is being pressed chemical formula 0.96Bi
0.5Na
0.5TiO
3-0.04BaTiO
3-0.005Mn prepares burden.
Embodiment 4
Present embodiment and embodiment 1 each step are basic identical, and difference is being pressed chemical formula 0.95Bi
0.5Na
0.5TiO
3-0.05BaTiO
3-0.005Mn prepares burden.
Embodiment 5
Present embodiment and embodiment 1 each step are basic identical, and difference is being pressed chemical formula 0.91Bi
0.5Na
0.5TiO
3-0.09BaTiO
3-0.005Mn prepares burden.
By finding out among Fig. 1 that film has pure calcium titanium ore structure among the embodiment 1, the film of 680 ℃ of preparations mainly is < 100>orientation, and the film of 700 ℃ of preparations is the polycrystalline orientation.Can find out that by Fig. 2 film presents compactness preferably.Can find out the about 260nm of the thickness of prepared film by Fig. 3.
Can find out that by Fig. 4 film has compactness preferably.Can find out the about 400nm of thickness of prepared film by Fig. 5.
By shown in Figure 6, the ferroelectric hysteresis loop of the BNBT-Mn film of 680 ℃ of preparations among the embodiment, test frequency 1kHz, the about 12 μ C/cm of remnant polarization
2, the about 12kV/mm of coercive field.Can find out the hysteresis frequency 1kHz of the BNBT-Mn film of 700 ℃ of preparations among the embodiment, the about 12 μ C/cm of remnant polarization by Fig. 7
2, the about 10kV/mm of coercive field.
Visible by Fig. 8, the relative permittivity of 680 ℃ of preparation BNBT-Mn films and loss are with frequency variation curve among the embodiment, and along with frequency increases, specific inductivity decreases.By shown in Figure 9, the relative permittivity of 700 ℃ of preparation BNBT-Mn films and loss are with frequency variation curve among the embodiment, and along with frequency increases, specific inductivity decreases.
The test result of embodiment 2-5 is similar with embodiment 1.Among the present invention, utilize temperature can realize regulation and control to the film growth direction.680 ℃ of films that prepare down have single<100>Orientation, thickness 260nm, specific inductivity and loss are about 850 and 0.12 under the 1kHz, the about 12 μ C/cm of remnant polarization and coercive field
2With about 12kV/mm; 700 ℃ of films that prepare down present the polycrystalline orientation, about 400nm, and specific inductivity and loss are about 1400 and 0.2 under the 1kHz, the about respectively 12 μ C/cm of remnant polarization and coercive field
2And 10kV/mm.
Claims (3)
1. preparation method who mixes the bismuth sodium titanate-barium titanate film of Mn, it is characterized in that: its preparation technology's flow process is following:
(1) preparation of target: with high-purity Bi
2O
3, Na
2CO
3, BaCO
3, TiO
2Be raw material, according to chemical formula (1-x) Bi
0.5Na
0.5TiO
3-xBaTiO
3The stoichiometric ratio weighing of-0.005Mn, wherein 0.03≤x≤0.09; With raw material in absolute ethyl alcohol with the wet-milling of zirconium ball, oven dry, compressing tablet under 800-900 ℃ of normal atmosphere calcination 1-4 hour, make the calcium titanium ore structure powder then; With gained calcium titanium ore structure powder secondary ball milling oven dry back compressing tablet, and 1-4 hour sintering of insulation obtains target under 1200 ℃;
(2) preparation of film:
(a) install target and substrate, regulate target-substrate distance 5.5cm;
(b) sputter temperature 650-700 ℃, power 300mJ, frequency 8Hz feeds a certain amount of oxygen, deposition pressure 30-50Pa;
(c) the sputter 30min that anneals in position that finishes keeps oxygen to press also and naturally cools to room temperature, makes the bismuth sodium titanate-barium titanate film of mixing Mn.
2. a kind of preparation method who mixes the bismuth sodium titanate-barium titanate film of Mn according to claim 1 is characterized in that: the substrate that adopts in the described film preparation is Pt (111)/Ti/SiO
2/ Si.
3. a kind of preparation method who mixes the bismuth sodium titanate-barium titanate film of Mn according to claim 1 is characterized in that: the prepared bismuth sodium titanate-barium titanate film of mixing Mn is the leadless piezoelectric film, is applicable to the MEMS field.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103708828A (en) * | 2013-12-06 | 2014-04-09 | 西安交通大学 | Preparation method of bismuth sodium titanate-barium titanate lead-free composite piezoelectric thick film |
| CN104868047A (en) * | 2014-02-26 | 2015-08-26 | 松下知识产权经营株式会社 | Piezoelectric film and usage thereof |
| CN105060883A (en) * | 2015-07-30 | 2015-11-18 | 天津大学 | Preparation method of high density BNT target for magnetron sputtering |
| CN106119777A (en) * | 2016-07-23 | 2016-11-16 | 安阳华森纸业有限责任公司 | Lead-free piezoelectric film material and preparation method thereof |
| CN110372371A (en) * | 2019-06-27 | 2019-10-25 | 宁波大学 | Ferroelectric material and preparation method thereof based on metal cation doping |
| AT17569U1 (en) * | 2019-09-30 | 2022-07-15 | Tdk Electronics Ag | Polycrystalline ceramic solid, dielectric electrode with the solid, device with the electrode and method of manufacture |
Citations (1)
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| CN1699277A (en) * | 2005-05-24 | 2005-11-23 | 南京大学 | High-performance (1-x) BaTi3-xNaNbO3 microwave dielectric film and preparation thereof |
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2012
- 2012-07-12 CN CN2012102403277A patent/CN102731107A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1699277A (en) * | 2005-05-24 | 2005-11-23 | 南京大学 | High-performance (1-x) BaTi3-xNaNbO3 microwave dielectric film and preparation thereof |
Non-Patent Citations (2)
| Title |
|---|
| MIN XU ET AL.: "Phase diagram and electric properties of the (Mn,K)-modified Bi0.5Na0.5TiO3-BaTiO3 lead-free ceramics", 《J MATER SCI》, no. 46, 18 February 2011 (2011-02-18), pages 4676 * |
| X.H.ZHU ET AL.: "Effects of growth temperature and film thickness on the electrical properties of Ba0.7Sr0.3TiO3 thin films grown on platinized silicon substrates by pulsed laser deposition", 《THIN SOLID FILMS》, vol. 496, 20 October 2005 (2005-10-20), pages 377 - 2 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103708828A (en) * | 2013-12-06 | 2014-04-09 | 西安交通大学 | Preparation method of bismuth sodium titanate-barium titanate lead-free composite piezoelectric thick film |
| CN104868047A (en) * | 2014-02-26 | 2015-08-26 | 松下知识产权经营株式会社 | Piezoelectric film and usage thereof |
| CN104868047B (en) * | 2014-02-26 | 2017-06-23 | 松下知识产权经营株式会社 | Piezoelectric body film and application thereof |
| CN105060883A (en) * | 2015-07-30 | 2015-11-18 | 天津大学 | Preparation method of high density BNT target for magnetron sputtering |
| CN106119777A (en) * | 2016-07-23 | 2016-11-16 | 安阳华森纸业有限责任公司 | Lead-free piezoelectric film material and preparation method thereof |
| CN110372371A (en) * | 2019-06-27 | 2019-10-25 | 宁波大学 | Ferroelectric material and preparation method thereof based on metal cation doping |
| AT17569U1 (en) * | 2019-09-30 | 2022-07-15 | Tdk Electronics Ag | Polycrystalline ceramic solid, dielectric electrode with the solid, device with the electrode and method of manufacture |
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Application publication date: 20121017 |