CN104609856B - The highly preparation method of preferred orientation bismuth titanate sodium titanate-barium lead-free piezoelectric thin film - Google Patents
The highly preparation method of preferred orientation bismuth titanate sodium titanate-barium lead-free piezoelectric thin film Download PDFInfo
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Abstract
The present invention relates to the preparation method of height preferred orientation bismuth titanate sodium barium titanate lead-less piezoelectric membrane: (1) configures bismuth-sodium titanate Barium metatitanate. precursor solution；(2) at Pt/Ti/SiO2Nickel acid lanthanum is sputtered on/Si substrate, and 700 DEG C of heat treatments 30 minutes；(3) sputtering have the substrate of nickel acid lanthanum clean up post-drying；(4) on the substrate that step (3) obtains, use bismuth-sodium titanate Barium metatitanate. precursor solution successively to carry out rotary coating and obtain the thin film of desired thickness；(5) carry out making annealing treatment 120 minutes at 700 DEG C by the thin film that step (4) obtains, i.e. obtain the bismuth-sodium titanate barium titanate lead-less piezoelectric membrane of height preferred orientation.Under the bismuth-sodium titanate barium titanate lead-less high and low electric field of the piezoelectric membrane degree of orientation prepared by the present invention, there is higher electric field induced strain, higher dielectric constant and relatively low dielectric loss, have good practical prospect in fields such as high precision position shift controller and micro actuator.
Description
Technical field
The invention belongs to field of electronic materials, especially relate to a kind of height preferred orientation bismuth titanate sodium titanate-barium without
The preparation method of lead piezoelectric membrane.
Background technology
Piezoelectric membrane is i.e. to have piezoelectricity and gauge is the tens nanometer material to submicron.Same block materials
Comparing, piezoelectric membrane had both had a series of critical natures such as optical, electrical, hot, the sound similar to block materials, had again
Having volume little, running voltage is low, it is simple to development of small-scale device and the advantage such as mutually integrated with semiconductor technology, this makes
It has extensively in microelectronics, optoelectronics, integrated optics, micro mechanics and the contour technical field of microcomputer electricity
Application prospect.Along with the development of piezoelectric membrane technology of preparing, make the multiple of modern microelectronic technology and piezoelectric membrane
Function combines, and will develop numerous new function device, promotes the development of emerging technology.But, make in the past
With more piezoelectric lead titanates (PT), lead zirconate titanate (PZT) and the lead content of lead magnesio-niobate (PMN)
Account for about the 70% of raw material total amount.The piezoelectric too high in this kind of lead tolerance is being prepared and during use,
Bring infringement will to environment and the mankind.In order to protect the health of environment and the mankind, it is achieved the target of sustainable development,
The scientific worker of countries in the world is promptly studying few lead or unleaded piezoelectric.Wherein, bismuth-sodium titanate has
Good piezoelectricity and ferroelectricity, its Curie temperature higher (～320 DEG C).These features pair of bismuth-sodium titanate material
Preparing of piezoelectric membrane integrated device is highly beneficial.So, Bi0.5Na0.5TiO3(BNT) sill is inhaled in recent years
Draw the research interest of many researcheres.Pin-Yi Chen etc. introduces BT on the basis of BNT, and research is sent out
Existing BNT-BT has ferroelectricity and the piezoelectric property of excellence at its quasi-homotype phase boundary.(P.-Y.Chen,C.-S.Chen,
C.-S.Tu,T.-L.Chang,Large E-field induced strain and polar evolution in lead-free
Zr-doped 92.5% (Bi0.5Na0.5)TiO37.5%BaTiO3ceramics,Journal of the European
Ceramic Society.34(2014)4223-4233.)
Raising along with technology of thin film material preparation, research method and means of testing so that the property of piezoelectric film material
Can be greatly improved.But, the research process of piezoelectric film material yet suffers from some problems: as
(1) piezoelectric film material applied in electronic device at present is mainly based on lead base piezoelectric, but lead base
Piezoelectric in the preparation course of processing, cause the severe contamination of environment.(2) piezoelectric membrane prepared is generally of
Relatively low insulating properties and higher dielectric loss so that the service life of piezoelectric film material is greatly shortened.(3) pressure
The substrate that conductive film is generally selected in preparation process is Pt (111)/Ti/SiO2/ Si, causes in membrane-film preparation process,
Its texture degree is poor.Although some scholar utilizes pulsed laser deposition technique to prepare the piezoelectricity of height preferred orientation
Thin film, but required equipment cost is higher.(M.Bousquet,J.R.Duclère,C.Champeaux,A.
Boulle,P.Marchet,A.Catherinot,A.Wu,P.M.Vilarinho,S.Députier,M.Guilloux-Viry,
A.Crunteanu,B.Gautier,D.Albertini,C.Bachelet,Macroscopic and nanoscale
electrical properties of pulsed laser deposited(100)epitaxial lead-free Na0.5Bi0.5TiO3
Thin films, Journal of Applied Physics.107 (2010) 034102.) although also some scholar utilizes monocrystalline
SrTiO3、MgO、LaAlO3The thin film of substrate deposition has higher orientation, but due to the valency of single crystal substrates
Lattice are expensive, are unfavorable for application and the large-scale industrial production of large area Si integrated circuit.(R.Takayama,Y.
Tomita,Preparation of epitaxial Pb(ZrxTi1-x)O3thin films and their crystallographic,
pyroelectric,and ferroelectric properties,Journal of Applied Physics.65(1989)1666.)。
Chinese patent CN101805181A discloses the preparation method of a kind of sodium bismuth titanate-based ferroelectric film, belongs to
Electronic functional material and devices field, this is a kind of chemical preparation process, i.e. sol-gel process, and its substrate uses
Pt/Ti/SiO2/ Si, the concentration of precursor solution controls between 0.1M-0.3M, by add a kind of novel chelating agents-
Ammonia, obtains the bismuth sodium titanate-barium titanate colloidal sol of clear, and prepares ferroelectric thin film.Preparing that this patent uses is thin
The substrate of film is different with the application, the polycrystal film that the thin film of preparation is only randomly oriented.The most not with being,
The application does not use virose chelating agen ammonia, but the well-beaten method used obtains clarification uniformly
Colloid.Due to above-mentioned difference so that prepare the method that nickel acid lanthanum buffer layer thin film uses magnetron sputtering, as
The consistency of the inaccurate lanthanum nickelate thin film that may prepare of state modulator of fruit sputtering is relatively low, and degree of crystallinity is poor, from
And the poor-performing of the bismuth sodium titanate-barium titanate film prepared on nickel acid lanthanum.
Summary of the invention
The present invention is to solve the thin film alignment that existing piezoelectric film material majority lead tolerance is relatively big and prepares
Spend poor, cost is high, complex process and the problem that is unfavorable for large area Si Application of integrated circuit, it is provided that a kind of
The highly preparation method of the sodium bismuth titanate-barium titanate lead-free piezoelectric thin film of preferred orientation.
The purpose of the present invention can be achieved through the following technical solutions:
The highly preparation method of preferred orientation bismuth titanate sodium titanate-barium lead-free piezoelectric thin film, employing following steps:
(1) configuration bismuth sodium titanate-barium titanate precursor solution；
(2) at Pt/Ti/SiO2Nickel acid lanthanum is sputtered on/Si substrate, and 700 DEG C of heat treatments 30 minutes；
(3) sputtering have the substrate of nickel acid lanthanum clean up post-drying；
(4) on the substrate that step (3) obtains, bismuth sodium titanate-barium titanate precursor solution is used successively to carry out
Rotary coating obtains the thin film of desired thickness；
(5) carry out making annealing treatment 120 minutes at 700 DEG C by the thin film that step (4) obtains, the most highly selected
The sodium bismuth titanate-barium titanate lead-free piezoelectric thin film of excellent orientation.
Preferably, step (1) specifically uses following methods:
A, sodium acetate, bismuth nitrate are dissolved in acetic acid, utilize acetylacetone,2,4-pentanedione to be dissolved in by tetra-n-butyl titanate for chelating agent
Ethylene glycol monomethyl ether, more above-mentioned solution is mixed to get precursor solution A；
B, Barium acetate is dissolved in acetic acid, utilizes acetylacetone,2,4-pentanedione, for chelating agent, tetra-n-butyl titanate is dissolved in ethylene glycol first
Ether, more above-mentioned solution is mixed to get precursor solution B；
C, it is incorporated at 70 DEG C 5 hours prepared bismuth titanates of stirring by mixed for precursor solution A and precursor solution B
Sodium titanate-barium precursor solution, its concentration is adjusted to 0.1M.
Sodium acetate, bismuth nitrate, mol ratio 45-50:45-50:1-5 of Barium acetate.
Preferably, at Pt/Ti/SiO in step (2)2The nickel acid lanthanum of 150nm is sputtered on/Si substrate.
Preferably, step (3) is when cleaning substrate, and ultrasonic cleaning 30 minutes the most in acetone, then in steaming
Ultrasonic cleaning 30 minutes in distilled water, the most in ethanol ultrasonic cleaning 30 minutes.Dry up with high pure nitrogen after cleaning.
Preferably, step (4) specifically uses following methods: carry out on the substrate that step (3) obtains under room temperature
Rotary coating, rotary speed is 3000 revs/min, and spin coating time is 30 seconds；After having coated, at 150 DEG C
Heat treatment 5 minutes, 400 DEG C of heat treatments 5 minutes, 700 DEG C of heat treatments 10 minutes.Circulate after the same method
Operate 20 times.
The sodium bismuth titanate-barium titanate lead-free piezoelectric thin film prepared can be in microelectronics and microelectromechanical systems
Applying in field, its chemical composition is 0.94Na0.5Bi0.5TiO3-0.06BaTiO3。
Used in this application is at Pt/Ti/SiO2About 150nm nickel acid lanthanum (LaNiO is sputtered on/Si substrate3)
LNO/Pt/Ti/SiO2/ Si substrate, thus this patent has obtained what height (100) was orientated under the induction of nickel acid lanthanum
Piezoelectric membrane.Height-oriented thin film is compared with the thin film of random orientation can improve its piezoelectricity and Jie significantly
Electrical property.It addition, the introducing of nickel acid lanthanum cushion can also play the effect at the interface optimized between thin film and electrode,
Thus reduce the leakage current in thin film and dielectric loss.The collection being optimized for piezoelectric membrane and silicon technology of these performances
Become and application provides good condition.
Compared with prior art, the present invention overcomes lead-based piezoelectric thin film producing, using and in waste procedures to people
Class and the harm of ecological environment, it is provided that the sodium bismuth titanate-barium titanate lead-free piezoelectric thin film of a kind of height preferred orientation
Preparation method, the highly bismuth titanates of the sodium bismuth titanate-barium titanate lead-free piezoelectric thin film of preferred orientation and random orientation
Sodium titanate-barium lead-free piezoelectric thin film is compared has bigger electric field induced strain and higher dielectric constant, relatively low dielectric
Loss.
In method disclosed by the invention, its operating procedure can produce impact to the performance of the product of preparation.Such as make
The proportioning (0.94Bi of raw material0.5Na0.5TiO3-0.06BaTiO3) it is the quasi-homotype phase at bismuth sodium titanate-barium titanate
Near boundary (MPB), because material is generally of bigger piezoelectricity and ferroelectric properties near MPB composition.Spatter
Consistency and the crystalline quality of nickel acid lanthanum are had a great impact by the technological parameter penetrating nickel acid lanthanum.Successively carry out rotating being coated with
Quality and the performance of thin film are had a great impact by the technique and the relevant parameter that cover.The speed of such as rotary coating and time
Between directly affect the thickness of thin film.The temperature and time of every layer of heat treatment can affect degree of crystallinity and the rough surface of thin film
Degree.
From reaction mechanism analysis, the bismuth sodium titanate-barium titanate of height preferred orientation can be prepared by this method
The reason of lead-free piezoelectric thin film is as follows: first nickel acid lanthanum (LNO) can obtain height (100) at 700 DEG C of heat treatments
The counterfeit cubic perovskite structure of orientation, cell parameter and nickel acid lanthanum additionally, due to bismuth sodium titanate-barium titanate crystal are brilliant
The cell parameter of body closely, has the lattice of height, the most between the two hereafter in the mistake of heat treatment
In journey, bismuth sodium titanate-barium titanate film can be raw along the LNO thin film epitaxy of height (100) preferred orientation
Long, thus obtained the bismuth sodium titanate-barium titanate film of height (100) preferred orientation.
Accompanying drawing explanation
Fig. 1 is gained height preferred orientation and the bismuth-sodium titanate-metatitanic acid of random orientation in embodiment 1 and comparative example 1
The XRD figure spectrum of barium lead-free piezoelectric thin film.
Fig. 2 is gained height preferred orientation and the bismuth-sodium titanate-metatitanic acid of random orientation in embodiment 1 and comparative example 1
The strain of barium lead-free piezoelectric thin film is with the change curve of extra electric field.
Fig. 3 is gained height preferred orientation and the bismuth-sodium titanate-metatitanic acid of random orientation in embodiment 1 and comparative example 1
The dielectric constant of barium lead-free piezoelectric thin film and dielectric loss are with the change curve of extra electric field.
Detailed description of the invention
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1
The sodium bismuth titanate-barium titanate lead-free piezoelectric thin film of preparation height preferred orientation, its step is as follows:
(1) preparation of BNT-BT precursor solution:
A () is according to chemical general formula 0.94Bi0.5Na0.5TiO3-0.06BaTiO3Stoichiometric proportion weigh raw material, will
Sodium acetate, bismuth nitrate are dissolved in acetic acid, are stirred and heated to seethe with excitement 20～30 minutes obtained solutions 1.；Utilize levulinic
Ketone is that at 60 minutes obtained solutions of 50 DEG C of stirrings 2. tetra-n-butyl titanate is dissolved in ethylene glycol monomethyl ether by chelating agent；By molten
1. 2. liquid join solution, within 60 minutes, obtains precursor solution A 70 DEG C of stirrings.
B () is according to chemical general formula 0.94Bi0.5Na0.5TiO3-0.06BaTiO3Stoichiometric proportion weigh raw material, will
Barium acetate is dissolved in acetic acid, is stirred and heated to seethe with excitement 20～30 minutes obtained solutions 3.；Utilize acetylacetone,2,4-pentanedione for complexation
Tetra-n-butyl titanate is dissolved in ethylene glycol monomethyl ether by agent, at 60 minutes obtained solutions of 50 DEG C of stirrings 4.；4. solution is added
Enter to solution 3., within 60 minutes, obtain precursor solution B 70 DEG C of stirrings.
C precursor solution A and precursor solution B is mixed by (), the concentration using acetic acid to adjust solution is 0.1M,
And at 70 DEG C, stir the precursor solution of 300 minutes prepared BNT-BT.
(2)LNO/Pt/Ti/SiO2The preparation of/Si substrate:
First it is respectively washed Pt/Ti/SiO with acetone, distilled water and ethanol2/ Si substrate 30 minutes, treats that substrate is dried
Rear use magnetic control sputtering device is at Pt/Ti/SiO2The thick nickel acid lanthanum of about 150nm is sputtered on/Si substrate.Sputtering condition is:
Sputter temperature 550 DEG C, sputtering pressure 1Pa, sputtering power 40W, sputtering atmosphere Ar:O2=3:2, sputtering time
120 minutes.700 DEG C of heat treatments 30 minutes after having sputtered.
(3) preparation of thin film: the BNT-BT precursor solution prepared in step (1) is coated in spin-coating method
LNO/Pt/Ti/SiO2On/Si substrate:
A () is at LNO/Pt/Ti/SiO2One layer of BNT-BT precursor solution of rotary coating on/Si substrate, rotating speed is
3000 revolutions per seconds, the time is 30 seconds.
(b) by the thin film of step (a) gained afterwards successively in tube furnace 150 DEG C process 5 minutes, at 400 DEG C
Managing 5 minutes, 700 DEG C process 10 minutes.
C () repeats step (b) until obtaining the thin film of desired thickness, finally make annealing treatment 120 at 700 DEG C
Minute, prepare the sodium bismuth titanate-barium titanate lead-free piezoelectric thin film of height preferred orientation.
Comparative example 1
Preparing the sodium bismuth titanate-barium titanate lead-free piezoelectric thin film of random orientation, its step is as follows:
(1) preparation of BNT-BT precursor solution:
A () is according to chemical general formula 0.94Bi0.5Na0.5TiO3-0.06BaTiO3Stoichiometric proportion weigh raw material, will
Sodium acetate, bismuth nitrate are dissolved in acetic acid, are stirred and heated to seethe with excitement 20～30 minutes obtained solutions 1.；Utilize levulinic
Ketone is that at 60 minutes obtained solutions of 50 DEG C of stirrings 2. tetra-n-butyl titanate is dissolved in ethylene glycol monomethyl ether by chelating agent；By molten
1. 2. liquid join solution, within 60 minutes, obtains precursor solution A 70 DEG C of stirrings.
B () is according to chemical general formula 0.94Bi0.5Na0.5TiO3-0.06BaTiO3Stoichiometric proportion weigh raw material, will
Barium acetate is dissolved in acetic acid and is stirred and heated to seethe with excitement 20～30 minutes obtained solutions 3.；Utilize acetylacetone,2,4-pentanedione for chelating agent
Tetra-n-butyl titanate is dissolved in ethylene glycol monomethyl ether at 60 minutes obtained solutions of 50 DEG C of stirrings 4.；4. solution is joined
3. solution, obtain precursor solution B in 60 minutes 70 DEG C of stirrings.
C precursor solution A and precursor solution B is mixed by (), the concentration using acetic acid to adjust solution is 0.1M,
And at 70 DEG C, stir the precursor solution of 300 minutes prepared BNT-BT.
(2)Pt/Ti/SiO2The cleaning of/Si substrate:
By commercially available Pt/Ti/SiO2/ Si substrate cuts into the substrate of 1 × 1cm, divides with acetone, distilled water and ethanol
Other ultrasonic cleaning Pt/Ti/SiO2/ Si substrate 30 minutes, then dries up substrate with high pure nitrogen.By dry base
Sheet is 700 DEG C of heat treatments 30 minutes in tube furnace.
(3) preparation of thin film: the BNT-BT precursor solution prepared in step (1) is coated in spin-coating method
Pt/Ti/SiO2On/Si substrate:
A () is at Pt/Ti/SiO2One layer of BNT-BT precursor solution of rotary coating on/Si substrate, rotating speed is 3000
Revolutions per second, the time is 30 seconds.
(b) by the thin film of step (a) gained afterwards successively in tube furnace 150 DEG C process 5 minutes, at 400 DEG C
Managing 5 minutes, 700 DEG C process 10 minutes.
C () repeats step (b) until obtaining the thin film of desired thickness, finally make annealing treatment 120 at 700 DEG C
Minute, prepare the sodium bismuth titanate-barium titanate lead-free piezoelectric thin film of random orientation.
Fig. 1 gives sodium bismuth titanate-barium titanate lead-free piezoelectric thin film and the metatitanic acid of random orientation of height preferred orientation
The XRD figure spectrum of bismuth sodium titanate-barium lead-free piezoelectric thin film, contrast finds at LNO/Pt/Ti/SiO2Prepare on/Si substrate
Thin film there is (100) preferred orientation of height, and at Pt/Ti/SiO2On/Si substrate prepare thin film have with
Machine orientation texture.Fig. 2 gives the sodium bismuth titanate-barium titanate lead-free piezoelectric thin film of height preferred orientation and takes at random
To the strain of sodium bismuth titanate-barium titanate lead-free piezoelectric thin film with the change curve of applied voltage, can from figure
The bismuth sodium titanate-barium titanate film going out height preferred orientation has than the bismuth sodium titanate-barium titanate film of random orientation
Bigger dependent variable.Fig. 3 gives the sodium bismuth titanate-barium titanate lead-free piezoelectric thin film of height preferred orientation with random
Dielectric constant and the dielectric loss of the sodium bismuth titanate-barium titanate lead-free piezoelectric thin film of orientation close with the change of applied voltage
System, as can be seen from the figure under 100kHz, the dielectric constant of the thin film of height preferred orientation is 375, and dielectric is damaged
Consumption is 3%；The dielectric constant of the thin film of random orientation is 330, and dielectric loss is 8%.Can be obtained by Fig. 1-3
Go out conclusion: highly the sodium bismuth titanate-barium titanate lead-free piezoelectric thin film of preferred orientation is than the bismuth-sodium titanate-titanium of random orientation
Acid barium lead-free piezoelectric thin film has more excellent piezoelectric and dielectric properties.Prepared by the method provided in the present invention
The sodium bismuth titanate-barium titanate lead-free piezoelectric thin film of height preferred orientation at the microelectronics such as microdrive and microcapacitor
Device has good application prospect.
Embodiment 2
The highly preparation method of preferred orientation bismuth titanate sodium titanate-barium lead-free piezoelectric thin film, employing following steps:
(1) configuration bismuth sodium titanate-barium titanate precursor solution, specifically uses following methods:
A, sodium acetate, bismuth nitrate are dissolved in acetic acid, utilize acetylacetone,2,4-pentanedione to be dissolved in by tetra-n-butyl titanate for chelating agent
Ethylene glycol monomethyl ether, more above-mentioned solution is mixed to get precursor solution A；
B, Barium acetate is dissolved in acetic acid, utilizes acetylacetone,2,4-pentanedione, for chelating agent, tetra-n-butyl titanate is dissolved in ethylene glycol first
Ether, more above-mentioned solution is mixed to get precursor solution B；
C, it is incorporated at 70 DEG C stirring 5 hours by mixed for precursor solution A and precursor solution B, controls acetic acid
Sodium, bismuth nitrate, mol ratio 45:45:1 of Barium acetate, prepare bismuth sodium titanate-barium titanate precursor solution, and adjust
Concentration is to 0.1M；
(2) at Pt/Ti/SiO2150nm nickel acid lanthanum is sputtered on/Si substrate, and 700 DEG C of heat treatments 30 minutes；
(3) sputtering have the substrate of nickel acid lanthanum clean up post-drying, when cleaning substrate, the most in acetone
Ultrasonic cleaning 30 minutes, then ultrasonic cleaning 30 minutes, the most in ethanol ultrasonic cleaning 30 in distilled water
Minute.Dry up with high pure nitrogen after cleaning；
(4) on the substrate that step (3) obtains, bismuth sodium titanate-barium titanate precursor solution is used successively to carry out
Rotary coating obtains the thin film of desired thickness, specifically uses following methods: the base obtained in step (3) under room temperature
Carrying out a rotary coating on sheet, rotary speed is 3000 revs/min, and spin coating time is 30 seconds；After having coated,
150 DEG C of heat treatments 5 minutes, 400 DEG C of heat treatments 5 minutes, 700 DEG C of heat treatments 10 minutes.According to same
Method circulation operation 20 times；
(5) carry out making annealing treatment 120 minutes at 700 DEG C by the thin film that step (4) obtains, the most highly selected
The sodium bismuth titanate-barium titanate lead-free piezoelectric thin film of excellent orientation.The sodium bismuth titanate-barium titanate lead-free piezoelectric prepared is thin
Film can be applied in microelectronics and microelectromechanical systems field, and its chemical composition is
0.94Na0.5Bi0.5TiO3-0.06BaTiO3。
Embodiment 3
The highly preparation method of preferred orientation bismuth titanate sodium titanate-barium lead-free piezoelectric thin film, employing following steps:
(1) configuration bismuth sodium titanate-barium titanate precursor solution, specifically uses following methods:
A, sodium acetate, bismuth nitrate are dissolved in acetic acid, utilize acetylacetone,2,4-pentanedione to be dissolved in by tetra-n-butyl titanate for chelating agent
Ethylene glycol monomethyl ether, more above-mentioned solution is mixed to get precursor solution A；
B, Barium acetate is dissolved in acetic acid, utilizes acetylacetone,2,4-pentanedione, for chelating agent, tetra-n-butyl titanate is dissolved in ethylene glycol first
Ether, more above-mentioned solution is mixed to get precursor solution B；
C, it is incorporated at 70 DEG C stirring 5 hours by mixed for precursor solution A and precursor solution B, controls acetic acid
Sodium, bismuth nitrate, mol ratio 47:47:3 of Barium acetate, prepare bismuth sodium titanate-barium titanate precursor solution, and adjust
Concentration is to 0.1M；
(2) at Pt/Ti/SiO2150nm nickel acid lanthanum is sputtered on/Si substrate, and 700 DEG C of heat treatments 30 minutes；
(3) sputtering have the substrate of nickel acid lanthanum clean up post-drying, when cleaning substrate, the most in acetone
Ultrasonic cleaning 30 minutes, then ultrasonic cleaning 30 minutes, the most in ethanol ultrasonic cleaning 30 in distilled water
Minute.Dry up with high pure nitrogen after cleaning；
(4) on the substrate that step (3) obtains, bismuth sodium titanate-barium titanate precursor solution is used successively to carry out
Rotary coating obtains the thin film of desired thickness, specifically uses following methods: the base obtained in step (3) under room temperature
Carrying out a rotary coating on sheet, rotary speed is 3000 revs/min, and spin coating time is 30 seconds；After having coated,
150 DEG C of heat treatments 5 minutes, 400 DEG C of heat treatments 5 minutes, 700 DEG C of heat treatments 10 minutes.According to same
Method circulation operation 20 times；
(5) carry out making annealing treatment 120 minutes at 700 DEG C by the thin film that step (4) obtains, the most highly selected
The sodium bismuth titanate-barium titanate lead-free piezoelectric thin film of excellent orientation.The sodium bismuth titanate-barium titanate lead-free piezoelectric prepared is thin
Film can be applied in microelectronics and microelectromechanical systems field, and its chemical composition is
0.94Na0.5Bi0.5TiO3-0.06BaTiO3。
Embodiment 4
The highly preparation method of preferred orientation bismuth titanate sodium titanate-barium lead-free piezoelectric thin film, employing following steps:
(1) configuration bismuth sodium titanate-barium titanate precursor solution, specifically uses following methods:
A, sodium acetate, bismuth nitrate are dissolved in acetic acid, utilize acetylacetone,2,4-pentanedione to be dissolved in by tetra-n-butyl titanate for chelating agent
Ethylene glycol monomethyl ether, more above-mentioned solution is mixed to get precursor solution A；
B, Barium acetate is dissolved in acetic acid, utilizes acetylacetone,2,4-pentanedione, for chelating agent, tetra-n-butyl titanate is dissolved in ethylene glycol first
Ether, more above-mentioned solution is mixed to get precursor solution B；
C, it is incorporated at 70 DEG C stirring 5 hours by mixed for precursor solution A and precursor solution B, controls acetic acid
Sodium, bismuth nitrate, mol ratio 50:50:5 of Barium acetate, prepare bismuth sodium titanate-barium titanate precursor solution, and adjust
Concentration is to 0.1M；
(2) at Pt/Ti/SiO2150nm nickel acid lanthanum is sputtered on/Si substrate, and 700 DEG C of heat treatments 30 minutes；
(3) sputtering have the substrate of nickel acid lanthanum clean up post-drying, when cleaning substrate, the most in acetone
Ultrasonic cleaning 30 minutes, then ultrasonic cleaning 30 minutes, the most in ethanol ultrasonic cleaning 30 in distilled water
Minute.Dry up with high pure nitrogen after cleaning；
(4) on the substrate that step (3) obtains, bismuth sodium titanate-barium titanate precursor solution is used successively to carry out
Rotary coating obtains the thin film of desired thickness, specifically uses following methods: the base obtained in step (3) under room temperature
Carrying out a rotary coating on sheet, rotary speed is 3000 revs/min, and spin coating time is 30 seconds；After having coated,
150 DEG C of heat treatments 5 minutes, 400 DEG C of heat treatments 5 minutes, 700 DEG C of heat treatments 10 minutes.According to same
Method circulation operation 20 times；
(5) carry out making annealing treatment 120 minutes at 700 DEG C by the thin film that step (4) obtains, the most highly selected
The sodium bismuth titanate-barium titanate lead-free piezoelectric thin film of excellent orientation.The sodium bismuth titanate-barium titanate lead-free piezoelectric prepared is thin
Film can be applied in microelectronics and microelectromechanical systems field, and its chemical composition is
0.94Na0.5Bi0.5TiO3-0.06BaTiO3。
Claims (7)
1. the preparation method of height preferred orientation bismuth titanate sodium titanate-barium lead-free piezoelectric thin film, it is characterised in that the method employing following steps:
(1) configuration bismuth sodium titanate-barium titanate precursor solution, specifically uses following steps:
A, sodium acetate, bismuth nitrate are dissolved in acetic acid, utilize acetylacetone,2,4-pentanedione, for chelating agent, tetra-n-butyl titanate is dissolved in ethylene glycol monomethyl ether, more above-mentioned solution is mixed to get precursor solution A；
B, Barium acetate is dissolved in acetic acid, utilizes acetylacetone,2,4-pentanedione, for chelating agent, tetra-n-butyl titanate is dissolved in ethylene glycol monomethyl ether, more above-mentioned solution is mixed to get precursor solution B；
C, being incorporated at 70 DEG C 5 hours prepared bismuth sodium titanate-barium titanate precursor solutions of stirring by mixed for precursor solution A and precursor solution B, its concentration is adjusted to 0.1M；
(2) at Pt/Ti/SiO2Nickel acid lanthanum is sputtered on/Si substrate, and 700 DEG C of heat treatments 30 minutes；
(3) sputtering have the substrate of nickel acid lanthanum clean up post-drying；
(4) on the substrate that step (3) obtains, use bismuth sodium titanate-barium titanate precursor solution successively to carry out rotary coating and obtain the thin film of desired thickness；
(5) carry out making annealing treatment 120 minutes at 700 DEG C by the thin film that step (4) obtains, i.e. obtain the sodium bismuth titanate-barium titanate lead-free piezoelectric thin film of height preferred orientation.
The preparation method of height preferred orientation bismuth titanate sodium titanate-barium lead-free piezoelectric thin film the most according to claim 1, it is characterised in that the chemical composition of the sodium bismuth titanate-barium titanate lead-free piezoelectric thin film prepared is 0.94Na0.5Bi0.5TiO3-0.06BaTiO3。
The preparation method of height preferred orientation bismuth titanate sodium titanate-barium lead-free piezoelectric thin film the most according to claim 1, it is characterised in that sodium acetate, bismuth nitrate, the mol ratio of Barium acetate are 45-50:45-50:1-5.
The preparation method of height preferred orientation bismuth titanate sodium titanate-barium lead-free piezoelectric thin film the most according to claim 1, it is characterised in that at Pt/Ti/SiO in step (2)2The nickel acid lanthanum of 150nm is sputtered on/Si substrate.
The preparation method of height preferred orientation bismuth titanate sodium titanate-barium lead-free piezoelectric thin film the most according to claim 1, it is characterized in that, step (3) is when cleaning substrate, ultrasonic cleaning 30 minutes the most in acetone, then ultrasonic cleaning 30 minutes in distilled water, last ultrasonic cleaning 30 minutes in ethanol, dry up with high pure nitrogen after cleaning.
The preparation method of height preferred orientation bismuth titanate sodium titanate-barium lead-free piezoelectric thin film the most according to claim 1, it is characterized in that, step (4) specifically uses following methods: carry out a rotary coating under room temperature on the substrate that step (3) obtains, rotary speed is 3000 revs/min, and spin coating time is 30 seconds；After having coated, 150 DEG C of heat treatments 5 minutes, 400 DEG C of heat treatments 5 minutes, 700 DEG C of heat treatments 10 minutes, circulation operation 20 times after the same method.
The preparation method of height preferred orientation bismuth titanate sodium titanate-barium lead-free piezoelectric thin film the most according to claim 1, it is characterised in that the sodium bismuth titanate-barium titanate lead-free piezoelectric thin film prepared is applied in microelectronics and microelectromechanical systems field.
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