CN104609856A - Preparation method of highly preferred oriented sodium bismuth titanate-barium titanate lead-free piezoelectric thin film - Google Patents
Preparation method of highly preferred oriented sodium bismuth titanate-barium titanate lead-free piezoelectric thin film Download PDFInfo
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Abstract
The invention relates to a preparation method of a highly preferred oriented sodium bismuth titanate-barium titanate lead-free piezoelectric thin film. The preparation method comprises the following steps: (1) preparing a sodium bismuth titanate-barium titanate precursor solution; (2) sputtering lanthanum nickelate on a Pt/Ti/SiO2/Si substrate and performing heat treatment at 700 DEG C for 30 minutes; (3) cleaning and drying the substrate with the lanthanum nickelate; (4) performing spin-coating on the substrate obtained in the step (3) by use of the sodium bismuth titanate-barium titanate precursor solution layer by layer until the thin film of the desired thickness is obtained; (5) performing annealing treatment on the thin film obtained in the step (4) at 700 DEG C for 120 minutes, thereby obtaining the highly preferred oriented sodium bismuth titanate-barium titanate lead-free piezoelectric thin film. The highly preferred oriented sodium bismuth titanate-barium titanate lead-free piezoelectric thin film prepared by use of the method is high in degree of orientation, has relatively high electrostrictive strain, a relatively high dielectric constant and relatively low dielectric loss under a low electric field, and has favorable application prospect in the fields of high-precision displacement controllers, micro-actuators and the like.
Description
Technical field
The invention belongs to field of electronic materials, especially relate to a kind of preparation method of height preferred orientation bismuth titanate sodium titanate-barium lead-free piezoelectric thin film.
Background technology
Namely piezoelectric membrane is have piezoelectricity and gauge is the material that tens nanometer arrives submicron.Compare with block materials, piezoelectric membrane had both had a series of critical natures such as similar to block materials optical, electrical, hot, sound, there is again volume little, operating voltage is low, be convenient to development of small-scale device and with the advantage such as semiconductor technology is mutually integrated, this makes it be with a wide range of applications in microtronics, photoelectronics, integrated optics, micro mechanics and the contour technical field of microcomputer electricity.Along with the development of piezoelectric membrane technology of preparing, modern microelectronic technology is combined with the several functions of piezoelectric membrane, numerous new function device will be developed, promote the development of emerging technology.But, use the lead content of more piezoelectric lead titanate (PT), Pb-based lanthanumdoped zirconate titanates (PZT) and lead magnoniobate (PMN) to account for about 70% of raw material total amount in the past.The piezoelectric too high in this kind of lead tolerance is being prepared and in use procedure, brought infringement all can to environment and the mankind.In order to the health of protection of the environment and the mankind, realize the target of Sustainable development, the scientific worker of the countries in the world promptly few plumbous or unleaded piezoelectric of research.Wherein, bismuth-sodium titanate has good piezoelectricity and ferroelectricity, its Curie temperature higher (~ 320 DEG C).The preparation of these features to piezoelectric membrane integrated device of bismuth-sodium titanate material is highly beneficial.So, Bi
0.5na
0.5tiO
3(BNT) sill has attracted the research interest of many investigators in recent years.Pin-Yi Chen etc. introduces BT on the basis of BNT, and research finds that BNT-BT has excellent ferroelectric and piezoelectric property at its accurate homotype phase boundary place.(P.-Y.Chen,C.-S.Chen,C.-S.Tu,T.-L.Chang,Large E-field induced strain and polar evolution in lead-freeZr-doped 92.5％(Bi
0.5Na
0.5)TiO
3–7.5％BaTiO
3ceramics,Journal of the EuropeanCeramic Society.34(2014)4223-4233.)
Along with the raising of technology of thin film material preparation, research method and means of testing, the performance of piezoelectric film material is greatly improved.But, still there are some problems: the piezoelectric film material applied in electron device as (1) is current is mainly based on lead base piezoelectric, but the piezoelectric of lead base causes the severe contamination of environment in the preparation course of processing in the research process of piezoelectric film material.(2) piezoelectric membrane prepared has lower insulativity and higher dielectric loss usually, and the work-ing life of piezoelectric film material is shortened greatly.(3) substrate that piezoelectric membrane is usually selected in preparation process is Pt (111)/Ti/SiO
2/ Si, causes in membrane-film preparation process, and its texture degree is poor.Although the piezoelectric membrane of height preferred orientation that some scholar has utilized pulsed laser deposition technique to prepare, required equipment cost is higher.(M.Bousquet, J.R.Duclere, C.Champeaux, A.Boulle, P.Marchet, A.Catherinot, A.Wu, P.M.Vilarinho, S.D é putier, M.Guilloux-Viry, A.Crunteanu, B.Gautier, D.Albertini, C.Bachelet, Macroscopic and nanoscaleelectrical properties of pulsed laser deposited (100) epitaxial lead-free Na
0.5bi
0.5tiO
3thin films, Journal of Applied Physics.107 (2010) 034102.) although also some scholar utilizes monocrystalline SrTiO
3, MgO, LaAlO
3the film of substrate deposition has higher orientation, but expensive due to single crystal substrates, be unfavorable for application and the large-scale industrial production of big area Si unicircuit.(R.Takayama,Y.Tomita,Preparation of epitaxial Pb(Zr
xTi
1-x)O
3thin films and their crystallographic,pyroelectric,and ferroelectric properties,Journal of Applied Physics.65(1989)1666.)。
Chinese patent CN101805181A discloses a kind of preparation method of sodium bismuth titanate-based ferroelectric film, belongs to electronic functional material and devices field, and this is a kind of chemical preparation process, i.e. sol-gel method, and its substrate adopts Pt/Ti/SiO
2/ Si, the concentration of precursor solution controls between 0.1M-0.3M, by adding a kind of novel chelating agents-ammoniacal liquor, obtaining the bismuth sodium titanate-barium titanate colloidal sol of clear, and preparing ferroelectric membranc.The substrate preparing film that this patent uses is different with the application, and the film of preparation is the polycrystal film of random orientation.In addition not with being, in the application, do not use virose sequestrant ammoniacal liquor, but the well-beaten method adopted obtains clarifying uniform colloid.Due to above-mentioned difference, make to prepare the method that nickel acid lanthanum buffer layer thin film uses magnetron sputtering, if the density of the inaccurate lanthanum nickelate thin film that may prepare of state modulator of sputtering is lower, degree of crystallinity is poor, thus the poor-performing of the bismuth sodium titanate-barium titanate film prepared on nickel acid lanthanum.
Summary of the invention
The present invention be to solve that the most lead tolerance of existing piezoelectric film material thin film alignment degree that is comparatively large and that prepare is poor, cost is high, complex process and be unfavorable for the problem of big area Si Application of integrated circuit, provide a kind of preparation method of sodium bismuth titanate-barium titanate lead-free piezoelectric film of height preferred orientation.
Object of the present invention can be achieved through the following technical solutions:
The preparation method of height preferred orientation bismuth titanate sodium titanate-barium lead-free piezoelectric thin film, adopts following steps:
(1) bismuth sodium titanate-barium titanate precursor solution is configured;
(2) at Pt/Ti/SiO
2/ Si substrate sputters nickel acid lanthanum, and 700 DEG C of thermal treatments 30 minutes;
(3) substrate of nickel acid lanthanum sputtering is had to clean up post-drying;
(4), on the substrate obtained in step (3), bismuth sodium titanate-barium titanate precursor solution is used successively to carry out the film that rotary coating obtains desired thickness;
(5) film that step (4) obtains is carried out anneal 120 minutes at 700 DEG C, namely obtain the sodium bismuth titanate-barium titanate lead-free piezoelectric film of height preferred orientation.
Preferably, step (1) specifically adopts following methods:
A, sodium acetate, Bismuth trinitrate are dissolved in acetic acid, utilize methyl ethyl diketone tetra-n-butyl titanate to be dissolved in ethylene glycol monomethyl ether for complexing agent, more above-mentioned solution is mixed to get precursor solution A;
B, barium acetate is dissolved in acetic acid, utilizes methyl ethyl diketone tetra-n-butyl titanate to be dissolved in ethylene glycol monomethyl ether for complexing agent, more above-mentioned solution is mixed to get precursor solution B;
C, by mixed for precursor solution A and precursor solution B be incorporated in 70 DEG C at stir 5 hours obtained bismuth sodium titanate-barium titanate precursor solutions, its concentration is adjusted to 0.1M.
The mol ratio 45-50:45-50:1-5 of sodium acetate, Bismuth trinitrate, barium acetate.
Preferably, in step (2) at Pt/Ti/SiO
2/ Si substrate sputters the nickel acid lanthanum of 150nm.
Preferably, step (3) when cleaning substrate, ultrasonic cleaning 30 minutes first in acetone, then ultrasonic cleaning 30 minutes in distilled water, finally ultrasonic cleaning 30 minutes in ethanol.Dry up with high pure nitrogen after cleaning.
Preferably, step (4) specifically adopts following methods: the substrate obtained in step (3) under room temperature carries out a rotary coating, and speed of rotation is 3000 revs/min, and spin coating time is 30 seconds; After having applied, 150 DEG C of thermal treatments 5 minutes, 400 DEG C of thermal treatment 5 minutes, 700 DEG C of thermal treatment 10 minutes.Cyclical operation 20 times after the same method.
The sodium bismuth titanate-barium titanate lead-free piezoelectric film prepared can be applied in microtronics and microelectromechanical systems field, and its chemical composition is 0.94Na
0.5bi
0.5tiO
3-0.06BaTiO
3.
Used in this application is at Pt/Ti/SiO
2/ Si substrate sputters about 150nm nickel acid lanthanum (LaNiO
3) LNO/Pt/Ti/SiO
2/ Si substrate, thus this patent obtains the piezoelectric membrane of height (100) orientation under the induction of nickel acid lanthanum.Height-oriented film is compared with the film of random orientation can improve its piezoelectric and dielectric properties significantly.In addition, the introducing of nickel acid lanthanum buffer layer also can play the effect at the interface optimized between film and electrode, thus the leakage current reduced in film and dielectric loss.Integrated and the application being optimized for piezoelectric membrane and silicon technology of these performances provides good condition.
Compared with prior art, the present invention overcome lead-based piezoelectric thin film producing, use and in waste procedures to the harm of the mankind and ecotope, provide a kind of preparation method of sodium bismuth titanate-barium titanate lead-free piezoelectric film of height preferred orientation, the sodium bismuth titanate-barium titanate lead-free piezoelectric film of height preferred orientation has larger electric field induced strain and higher specific inductivity, lower dielectric loss compared with the sodium bismuth titanate-barium titanate lead-free piezoelectric film of random orientation.
In method disclosed by the invention, its operation steps can have an impact to the performance of the product of preparation.Proportioning (the 0.94Bi of the raw material such as used
0.5na
0.5tiO
3-0.06BaTiO
3) be near the accurate homotype phase boundary (MPB) of bismuth sodium titanate-barium titanate, because material has larger piezoelectricity and ferroelectric properties usually near MPB composition.The processing parameter of sputtering nickel acid lanthanum has a great impact the density of nickel acid lanthanum and crystalline quality.The technique and the quality and performance of correlation parameter to film that successively carry out rotary coating have a great impact.The speed of such as rotary coating and time directly affect the thickness of film.Every layer of heat treated temperature and time can affect degree of crystallinity and the surfaceness of film.
From reaction mechanism analysis, the reason that can be prepared the sodium bismuth titanate-barium titanate lead-free piezoelectric film of height preferred orientation by present method is as follows: first nickel acid lanthanum (LNO) can obtain the counterfeit cubic perovskite structure of height (100) orientation 700 DEG C of thermal treatments, in addition due to the unit cell parameters of bismuth sodium titanate-barium titanate crystal and nickel acid lanthanum crystal unit cell parameters closely, there is the lattice of height so between the two, after this in heat treated process bismuth sodium titanate-barium titanate film can along height (100) preferred orientation LNO thin film epitaxial growth, thus obtain the bismuth sodium titanate-barium titanate film of height (100) preferred orientation.
Accompanying drawing explanation
Fig. 1 is the XRD figure spectrum of the sodium bismuth titanate-barium titanate lead-free piezoelectric film of gained height preferred orientation and random orientation in embodiment 1 and comparative example 1.
Fig. 2 is the change curve of strain with extra electric field of the sodium bismuth titanate-barium titanate lead-free piezoelectric film of gained height preferred orientation and random orientation in embodiment 1 and comparative example 1.
Fig. 3 is the specific inductivity of the sodium bismuth titanate-barium titanate lead-free piezoelectric film of gained height preferred orientation and random orientation in embodiment 1 and comparative example 1 and the dielectric loss change curve with extra electric field.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
Embodiment 1
The sodium bismuth titanate-barium titanate lead-free piezoelectric 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 0.94Bi
0.5na
0.5tiO
3-0.06BaTiO
3stoichiometric ratio take raw material, sodium acetate, Bismuth trinitrate are dissolved in acetic acid, stir and be heated to boiling 20 ~ 30 minutes obtained solutions 1.; Methyl ethyl diketone is utilized to stir 60 minutes obtained solutions 2. for tetra-n-butyl titanate is dissolved in ethylene glycol monomethyl ether by complexing agent at 50 DEG C; 1. 2. solution is joined solution, within 60 minutes, obtains precursor solution A 70 DEG C of stirrings.
B () is according to chemical general formula 0.94Bi
0.5na
0.5tiO
3-0.06BaTiO
3stoichiometric ratio take raw material, barium acetate is dissolved in acetic acid, stirs and be heated to boiling 20 ~ 30 minutes obtained solutions 3.; Utilize methyl ethyl diketone, for complexing agent, tetra-n-butyl titanate is dissolved in ethylene glycol monomethyl ether, stir 60 minutes obtained solutions 4. at 50 DEG C; 3. 4. solution is joined solution, within 60 minutes, obtains precursor solution B 70 DEG C of stirrings.
C precursor solution A and precursor solution B mixes by (), the concentration using acetic acid adjustment solution is 0.1M, and stirs the precursor solution of 300 minutes obtained BNT-BT at 70 DEG C.
(2) LNO/Pt/Ti/SiO
2the preparation of/Si substrate:
First Pt/Ti/SiO is cleaned respectively with acetone, distilled water and ethanol
2/ Si substrate 30 minutes, uses magnetic control sputtering device at Pt/Ti/SiO after substrate drying
2/ Si substrate sputters the nickel acid lanthanum that about 150nm is thick.Sputtering condition is: sputter temperature 550 DEG C, sputtering pressure 1Pa, sputtering power 40W, sputtering atmosphere Ar:O
2=3:2, sputtering time 120 minutes.700 DEG C of thermal treatments 30 minutes after having sputtered.
(3) preparation of film: BNT-BT precursor solution obtained in step (1) is coated in LNO/Pt/Ti/SiO with spin-coating method
2on/Si substrate:
A () is at LNO/Pt/Ti/SiO
2rotary coating one deck BNT-BT precursor solution on/Si substrate, rotating speed is 3000 revolutions per seconds, and the time is 30 seconds.
(b) by step (a) afterwards gained film successively in tube furnace 150 DEG C process 5 minutes, 400 DEG C process 5 minutes, 700 DEG C process 10 minutes.
(c) repeating step (b) until obtain the film of desired thickness, finally 700 DEG C of anneal 120 minutes, the sodium bismuth titanate-barium titanate lead-free piezoelectric film of obtained height preferred orientation.
Comparative example 1
Prepare the sodium bismuth titanate-barium titanate lead-free piezoelectric film of random orientation, its step is as follows:
(1) preparation of BNT-BT precursor solution:
A () is according to chemical general formula 0.94Bi
0.5na
0.5tiO
3-0.06BaTiO
3stoichiometric ratio take raw material, sodium acetate, Bismuth trinitrate are dissolved in acetic acid, stir and be heated to boiling 20 ~ 30 minutes obtained solutions 1.; Methyl ethyl diketone is utilized to stir 60 minutes obtained solutions 2. for tetra-n-butyl titanate is dissolved in ethylene glycol monomethyl ether by complexing agent at 50 DEG C; 1. 2. solution is joined solution, within 60 minutes, obtains precursor solution A 70 DEG C of stirrings.
B () is according to chemical general formula 0.94Bi
0.5na
0.5tiO
3-0.06BaTiO
3stoichiometric ratio take raw material, barium acetate is dissolved in acetic acid and stirs and be heated to boiling 20 ~ 30 minutes obtained solutions 3.; Methyl ethyl diketone is utilized to stir 60 minutes obtained solutions 4. for tetra-n-butyl titanate is dissolved in ethylene glycol monomethyl ether by complexing agent at 50 DEG C; 3. 4. solution is joined solution, within 60 minutes, obtains precursor solution B 70 DEG C of stirrings.
C precursor solution A and precursor solution B mixes by (), the concentration using acetic acid adjustment solution is 0.1M, and stirs the precursor solution of 300 minutes obtained BNT-BT at 70 DEG C.
(2) Pt/Ti/SiO
2the cleaning of/Si substrate:
By commercially available Pt/Ti/SiO
2/ Si substrate cuts into the substrate of 1 × 1cm, with acetone, distilled water and ethanol ultrasonic cleaning Pt/Ti/SiO respectively
2/ Si substrate 30 minutes, then dries up substrate with high pure nitrogen.By the 700 DEG C of thermal treatment 30 minutes in tube furnace of the substrate of drying.
(3) preparation of film: BNT-BT precursor solution obtained in step (1) is coated in Pt/Ti/SiO with spin-coating method
2on/Si substrate:
A () is at Pt/Ti/SiO
2rotary coating one deck BNT-BT precursor solution on/Si substrate, rotating speed is 3000 revolutions per seconds, and the time is 30 seconds.
(b) by step (a) afterwards gained film successively in tube furnace 150 DEG C process 5 minutes, 400 DEG C process 5 minutes, 700 DEG C process 10 minutes.
(c) repeating step (b) until obtain the film of desired thickness, finally 700 DEG C of anneal 120 minutes, the sodium bismuth titanate-barium titanate lead-free piezoelectric film of obtained random orientation.
Fig. 1 gives the XRD figure spectrum of the height sodium bismuth titanate-barium titanate lead-free piezoelectric film of preferred orientation and the sodium bismuth titanate-barium titanate lead-free piezoelectric film of random orientation, and contrast finds at LNO/Pt/Ti/SiO
2film obtained on/Si substrate has (100) preferred orientation of height, and at Pt/Ti/SiO
2film obtained on/Si substrate has random orientation structure.Fig. 2 gives the change curve of strain with impressed voltage of the height sodium bismuth titanate-barium titanate lead-free piezoelectric film of preferred orientation and the sodium bismuth titanate-barium titanate lead-free piezoelectric film of random orientation, and as can be seen from the figure the bismuth sodium titanate-barium titanate film of height preferred orientation has larger dependent variable than the bismuth sodium titanate-barium titanate film of random orientation.Fig. 3 gives the height sodium bismuth titanate-barium titanate lead-free piezoelectric film of preferred orientation and the specific inductivity of the sodium bismuth titanate-barium titanate lead-free piezoelectric film of random orientation and the dielectric loss variation relation with impressed voltage, as can be seen from the figure under 100kHz, the specific inductivity of the film of height preferred orientation is 375, and dielectric loss is 3%; The specific inductivity of the film of random orientation is 330, and dielectric loss is 8%.Can be reached a conclusion by Fig. 1-3: the sodium bismuth titanate-barium titanate lead-free piezoelectric film of height preferred orientation has more excellent piezoelectric and dielectric properties than the sodium bismuth titanate-barium titanate lead-free piezoelectric film of random orientation.The sodium bismuth titanate-barium titanate lead-free piezoelectric film of the height preferred orientation prepared by the method provided in the present invention has good application prospect in the microelectronic device such as microdrive and trimmer capacitor.
Embodiment 2
The preparation method of height preferred orientation bismuth titanate sodium titanate-barium lead-free piezoelectric thin film, adopts following steps:
(1) configure bismuth sodium titanate-barium titanate precursor solution, specifically adopt following methods:
A, sodium acetate, Bismuth trinitrate are dissolved in acetic acid, utilize methyl ethyl diketone tetra-n-butyl titanate to be dissolved in ethylene glycol monomethyl ether for complexing agent, more above-mentioned solution is mixed to get precursor solution A;
B, barium acetate is dissolved in acetic acid, utilizes methyl ethyl diketone tetra-n-butyl titanate to be dissolved in ethylene glycol monomethyl ether for complexing agent, more above-mentioned solution is mixed to get precursor solution B;
C, by mixed for precursor solution A and precursor solution B be incorporated in 70 DEG C at stir 5 hours, control the mol ratio 45:45:1 of sodium acetate, Bismuth trinitrate, barium acetate, obtained bismuth sodium titanate-barium titanate precursor solution, and adjust concentration to 0.1M;
(2) at Pt/Ti/SiO
2/ Si substrate sputters 150nm nickel acid lanthanum, and 700 DEG C of thermal treatments 30 minutes;
(3) substrate of nickel acid lanthanum sputtering is had to clean up post-drying, when cleaning substrate, ultrasonic cleaning 30 minutes first in acetone, then ultrasonic cleaning 30 minutes in distilled water, finally ultrasonic cleaning 30 minutes in ethanol.Dry up with high pure nitrogen after cleaning;
(4) on the substrate obtained in step (3), bismuth sodium titanate-barium titanate precursor solution is used successively to carry out the film that rotary coating obtains desired thickness, concrete employing following methods: the substrate obtained in step (3) under room temperature carries out a rotary coating, speed of rotation is 3000 revs/min, and spin coating time is 30 seconds; After having applied, 150 DEG C of thermal treatments 5 minutes, 400 DEG C of thermal treatment 5 minutes, 700 DEG C of thermal treatment 10 minutes.Cyclical operation 20 times after the same method;
(5) film that step (4) obtains is carried out anneal 120 minutes at 700 DEG C, namely obtain the sodium bismuth titanate-barium titanate lead-free piezoelectric film of height preferred orientation.The sodium bismuth titanate-barium titanate lead-free piezoelectric film prepared can be applied in microtronics and microelectromechanical systems field, and its chemical composition is 0.94Na
0.5bi
0.5tiO
3-0.06BaTiO
3.
Embodiment 3
The preparation method of height preferred orientation bismuth titanate sodium titanate-barium lead-free piezoelectric thin film, adopts following steps:
(1) configure bismuth sodium titanate-barium titanate precursor solution, specifically adopt following methods:
A, sodium acetate, Bismuth trinitrate are dissolved in acetic acid, utilize methyl ethyl diketone tetra-n-butyl titanate to be dissolved in ethylene glycol monomethyl ether for complexing agent, more above-mentioned solution is mixed to get precursor solution A;
B, barium acetate is dissolved in acetic acid, utilizes methyl ethyl diketone tetra-n-butyl titanate to be dissolved in ethylene glycol monomethyl ether for complexing agent, more above-mentioned solution is mixed to get precursor solution B;
C, by mixed for precursor solution A and precursor solution B be incorporated in 70 DEG C at stir 5 hours, control the mol ratio 47:47:3 of sodium acetate, Bismuth trinitrate, barium acetate, obtained bismuth sodium titanate-barium titanate precursor solution, and adjust concentration to 0.1M;
(2) at Pt/Ti/SiO
2/ Si substrate sputters 150nm nickel acid lanthanum, and 700 DEG C of thermal treatments 30 minutes;
(3) substrate of nickel acid lanthanum sputtering is had to clean up post-drying, when cleaning substrate, ultrasonic cleaning 30 minutes first in acetone, then ultrasonic cleaning 30 minutes in distilled water, finally ultrasonic cleaning 30 minutes in ethanol.Dry up with high pure nitrogen after cleaning;
(4) on the substrate obtained in step (3), bismuth sodium titanate-barium titanate precursor solution is used successively to carry out the film that rotary coating obtains desired thickness, concrete employing following methods: the substrate obtained in step (3) under room temperature carries out a rotary coating, speed of rotation is 3000 revs/min, and spin coating time is 30 seconds; After having applied, 150 DEG C of thermal treatments 5 minutes, 400 DEG C of thermal treatment 5 minutes, 700 DEG C of thermal treatment 10 minutes.Cyclical operation 20 times after the same method;
(5) film that step (4) obtains is carried out anneal 120 minutes at 700 DEG C, namely obtain the sodium bismuth titanate-barium titanate lead-free piezoelectric film of height preferred orientation.The sodium bismuth titanate-barium titanate lead-free piezoelectric film prepared can be applied in microtronics and microelectromechanical systems field, and its chemical composition is 0.94Na
0.5bi
0.5tiO
3-0.06BaTiO
3.
Embodiment 4
The preparation method of height preferred orientation bismuth titanate sodium titanate-barium lead-free piezoelectric thin film, adopts following steps:
(1) configure bismuth sodium titanate-barium titanate precursor solution, specifically adopt following methods:
A, sodium acetate, Bismuth trinitrate are dissolved in acetic acid, utilize methyl ethyl diketone tetra-n-butyl titanate to be dissolved in ethylene glycol monomethyl ether for complexing agent, more above-mentioned solution is mixed to get precursor solution A;
B, barium acetate is dissolved in acetic acid, utilizes methyl ethyl diketone tetra-n-butyl titanate to be dissolved in ethylene glycol monomethyl ether for complexing agent, more above-mentioned solution is mixed to get precursor solution B;
C, by mixed for precursor solution A and precursor solution B be incorporated in 70 DEG C at stir 5 hours, control the mol ratio 50:50:5 of sodium acetate, Bismuth trinitrate, barium acetate, obtained bismuth sodium titanate-barium titanate precursor solution, and adjust concentration to 0.1M;
(2) at Pt/Ti/SiO
2/ Si substrate sputters 150nm nickel acid lanthanum, and 700 DEG C of thermal treatments 30 minutes;
(3) substrate of nickel acid lanthanum sputtering is had to clean up post-drying, when cleaning substrate, ultrasonic cleaning 30 minutes first in acetone, then ultrasonic cleaning 30 minutes in distilled water, finally ultrasonic cleaning 30 minutes in ethanol.Dry up with high pure nitrogen after cleaning;
(4) on the substrate obtained in step (3), bismuth sodium titanate-barium titanate precursor solution is used successively to carry out the film that rotary coating obtains desired thickness, concrete employing following methods: the substrate obtained in step (3) under room temperature carries out a rotary coating, speed of rotation is 3000 revs/min, and spin coating time is 30 seconds; After having applied, 150 DEG C of thermal treatments 5 minutes, 400 DEG C of thermal treatment 5 minutes, 700 DEG C of thermal treatment 10 minutes.Cyclical operation 20 times after the same method;
(5) film that step (4) obtains is carried out anneal 120 minutes at 700 DEG C, namely obtain the sodium bismuth titanate-barium titanate lead-free piezoelectric film of height preferred orientation.The sodium bismuth titanate-barium titanate lead-free piezoelectric film prepared can be applied in microtronics and microelectromechanical systems field, and its chemical composition is 0.94Na
0.5bi
0.5tiO
3-0.06BaTiO
3.
Claims (8)
1. the preparation method of height preferred orientation bismuth titanate sodium titanate-barium lead-free piezoelectric thin film, it is characterized in that, the method adopts following steps:
(1) bismuth sodium titanate-barium titanate precursor solution is configured;
(2) at Pt/Ti/SiO
2/ Si substrate sputters nickel acid lanthanum, and 700 DEG C of thermal treatments 30 minutes;
(3) substrate of nickel acid lanthanum sputtering is had to clean up post-drying;
(4), on the substrate obtained in step (3), bismuth sodium titanate-barium titanate precursor solution is used successively to carry out the film that rotary coating obtains desired thickness;
(5) film that step (4) obtains is carried out anneal 120 minutes at 700 DEG C, namely obtain the sodium bismuth titanate-barium titanate lead-free piezoelectric film of height preferred orientation.
2. the preparation method of height preferred orientation bismuth titanate sodium titanate-barium lead-free piezoelectric thin film according to claim 1, is characterized in that, the chemical composition of the sodium bismuth titanate-barium titanate lead-free piezoelectric film prepared is 0.94Na
0.5bi
0.5tiO
3-0.06BaTiO
3.
3. the preparation method of height preferred orientation bismuth titanate sodium titanate-barium lead-free piezoelectric thin film according to claim 1, it is characterized in that, step (1) specifically adopts following methods:
A, sodium acetate, Bismuth trinitrate are dissolved in acetic acid, utilize methyl ethyl diketone tetra-n-butyl titanate to be dissolved in ethylene glycol monomethyl ether for complexing agent, more above-mentioned solution is mixed to get precursor solution A;
B, barium acetate is dissolved in acetic acid, utilizes methyl ethyl diketone tetra-n-butyl titanate to be dissolved in ethylene glycol monomethyl ether for complexing agent, more above-mentioned solution is mixed to get precursor solution B;
C, by mixed for precursor solution A and precursor solution B be incorporated in 70 DEG C at stir 5 hours obtained bismuth sodium titanate-barium titanate precursor solutions, its concentration is adjusted to 0.1M.
4. the preparation method of height preferred orientation bismuth titanate sodium titanate-barium lead-free piezoelectric thin film according to claim 3, is characterized in that, the mol ratio of sodium acetate, Bismuth trinitrate, barium acetate is 45-50:45-50:1-5.
5. the preparation method of height preferred orientation bismuth titanate sodium titanate-barium lead-free piezoelectric thin film according to claim 1, is characterized in that, at Pt/Ti/SiO in step (2)
2/ Si substrate sputters the nickel acid lanthanum of 150nm.
6. the preparation method of height preferred orientation bismuth titanate sodium titanate-barium lead-free piezoelectric thin film according to claim 1, it is characterized in that, step (3) is when cleaning substrate, first ultrasonic cleaning 30 minutes in acetone, then ultrasonic cleaning 30 minutes in distilled water, finally ultrasonic cleaning 30 minutes in ethanol.Dry up with high pure nitrogen after cleaning.
7. the preparation method of height preferred orientation bismuth titanate sodium titanate-barium lead-free piezoelectric thin film according to claim 1, it is characterized in that, step (4) specifically adopts following methods: the substrate obtained in step (3) under room temperature carries out a rotary coating, speed of rotation is 3000 revs/min, and spin coating time is 30 seconds; After having applied, 150 DEG C of thermal treatments 5 minutes, 400 DEG C of thermal treatment 5 minutes, 700 DEG C of thermal treatment 10 minutes.Cyclical operation 20 times after the same method.
8. the preparation method of height preferred orientation bismuth titanate sodium titanate-barium lead-free piezoelectric thin film according to claim 1, it is characterized in that, the sodium bismuth titanate-barium titanate lead-free piezoelectric film prepared is applied in microtronics and microelectromechanical systems field.
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