CN103922735B - Preparation method of low-temperature crystalized BZT-BCT piezoelectric film - Google Patents
Preparation method of low-temperature crystalized BZT-BCT piezoelectric film Download PDFInfo
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Abstract
The invention provides a preparation method of a low-temperature crystalized BZT-BCT piezoelectric film and relates to a preparation method preparation method of a Ba-family piezoelectric film. The preparation method is used for solving the technical problem that the crystallization temperature of an existing Ba-family piezoelectric film material is overhigh, which is not beneficial to energy conservation and large-area use for Si integration. The preparation method comprises the following steps: preparing a solution F and a sol E; preparing a sol D; preparing a lead titanate lanthanum calcium sol; preparing a BZT-BCT sol; preparing a seed layer film on a substrate, performing spin coating of the BZT-BCT sol on the seed layer film, performing thermal decomposition and crystallization treatment, thereby obtaining the low-temperature crystalized BZT-BCT piezoelectric film. After being subjected to crystallization treatment at a temperature of 700 DEG C, the BZT-BC piezoelectric film generates a perovskite structure and has favorable piezoelectric property; by virtue of intruding the PLCT seed layer, after low-temperature crystallization at a temperature of 500 DEG C, the BZT-BCT piezoelectric film also generates a perovskite structure and has the same favorable piezoelectric property. The preparation method belongs to the preparation field of piezoelectric films.
Description
Technical field
The present invention relates to the preparation method of a kind of Ba system piezoelectric membrane.
Background technology
Barium titanate-based lead-free piezoelectric ceramics is one of focus of Recent study.Nearest research finds 0.5BZT-0.5BCT (0.5 (Ba
0.7ca
0.3tiO
3)-0.5 [Ba (Zr
0.2ti
0.8) O
3]) high piezoelectric characteristic of piezoelectric ceramics can compare favourably with present most widely used lead base piezoelectric ceramics.Due to the environmental pollution that lead volatility brings, cause the application of lead base piezoelectric ceramics to receive larger restriction, thus BZT-BCT is the ideal material replacing lead base piezoelectricity system.Along with the rapid expansion of MEMS and integrated circuit fields, piezoelectric membrane and Si circuit integrated be that it applies necessary ways.But for Ba system piezoelectric membrane, this system crystallization often needs higher temperature (more than 700 DEG C), but the ultimate temperature that Si circuit is general born is 500 DEG C, this just requires under lower Tc (500 DEG C and following), to realize the preparation of better piezoelectric property BZT-BCT film.
Summary of the invention
The object of the invention is to solve existing Ba system piezoelectric film material crystallization temperature too high, being unfavorable for energy-conservation and integrated with big area Si use; The application problem of numerous reality such as complicated process of preparation, and the method for Ba system film piezo-electric performance is improved under a kind of low crystallization temperature provided.
The preparation method of low temperature crystallized BZT-BCT piezoelectric membrane carries out according to following steps:
One, in acetic acid, lanthanum acetate and calcium acetate is added, at temperature is 70 DEG C, after stirring 30min with the speed of 300r/min, obtain solution F, ethylene glycol monomethyl ether is added, at temperature is 80 DEG C, after stirring 30min with the speed of 300r/min in solution F, filter, be cooled to room temperature, obtain solution G, then add tetrabutyl titanate in solution G, after stirring 30min with the speed of 300r/min, obtain colloidal sol E; Wherein, lanthanum acetate in colloidal sol E and the mass volume ratio of tetrabutyl titanate are (0.50 ~ 0.55) g:1ml, the mass volume ratio of calcium acetate and tetrabutyl titanate is (0.25 ~ 0.30) g:1ml, the volume ratio (7.79 ~ 10.25) of acetic acid and tetrabutyl titanate: 1, the volume ratio (2.87 ~ 5.33) of ethylene glycol monomethyl ether and tetrabutyl titanate: 1;
Two, in ethylene glycol monomethyl ether, add plumbic acetate, at temperature is 70 DEG C, stirs 20min with the speed of 300r/min, be cooled to room temperature, then add tetrabutyl titanate, stir 30min with the speed of 300r/min, obtain colloidal sol D; Wherein, in colloidal sol D, the mass volume ratio of plumbic acetate and tetrabutyl titanate is (1.15 ~ 1.26) g:1ml, and the volume ratio of ethylene glycol monomethyl ether and tetrabutyl titanate is (2.70 ~ 4.50): 1;
Three, after being mixed by colloidal sol D and colloidal sol E, obtain mixed sols, then adding ethylene glycol monomethyl ether adjustment mixed sols concentration is 0.05mol/L ~ 0.2mol/L, then after stirring 30min with the speed of 300r/min, obtains load lanthanium titanate calcium sol;
Four, barium acetate and calcium acetate are dissolved in Glacial acetic acid, then under the condition of 70 DEG C, 30min is stirred with the speed of 300r/min, cool to room temperature, obtain clarifying uniform solution A, the mass volume ratio of barium acetate and Glacial acetic acid is (0.381 ~ 0.386) g:1mL, the mass volume ratio of calcium acetate and Glacial acetic acid is (0.039 ~ 0.045) g:1ml, add ethylene glycol monomethyl ether, methyl ethyl diketone, tetrabutyl titanate and zirconium iso-propoxide, under the condition of room temperature, control speed is that 300r/min stirs 30min, obtain the sol B of evenly clarification, the volume ratio (0.331 ~ 0.335) of methyl ethyl diketone and ethylene glycol monomethyl ether: 1, the volume ratio (0.273 ~ 0.276) of tetrabutyl titanate and ethylene glycol monomethyl ether: 1, the volume ratio (0.036 ~ 0.038) of zirconium iso-propoxide and ethylene glycol monomethyl ether: 1, by solution A and B colloidal sol Homogeneous phase mixing, adding ethylene glycol monomethyl ether to concentration is again 0.3mol/L ~ 0.4mol/L, again at ambient temperature, control speed is that 300r/min stirs 30min, then ageing 24h ~ 28h, obtain zirconium barium titanate calcium sol,
Five, at (111) Pt/Ti/SiO
2first rotary coating load lanthanium titanate calcium sol in/Si substrate, obtain 1 ~ 4 layer of load lanthanium titanate calcium film, the rotating speed applying every layer of load lanthanium titanate calcium film is 5000rpm ~ 5500rpm, time is 15s ~ 20s, then being placed on temperature is carry out thermolysis at 425 DEG C ~ 475 DEG C, obtain Seed Layer film, then rotary coating barium titanate calcium colloidal sol on Seed Layer film, obtain 3 ~ 5 layers of barium calcium zirconate titanate film, thermolysis is carried out under being placed in 425 DEG C ~ 475 DEG C conditions again, the annealing furnace being finally placed in 475 DEG C ~ 550 DEG C carries out Crystallizing treatment, obtain low temperature crystallized BZT-BCT piezoelectric membrane, the time applied needed for every layer of barium calcium zirconate titanate film is 15s ~ 20s, and the rotating speed of coating is 5000rpm ~ 5500rpm.
The invention has the beneficial effects as follows:
One, in most cases, the Annealing Crystallization temperatures as high about 700 DEG C of this thin film system.One of projecting point of the present invention successfully prepares low temperature crystallized BZT-BCT piezoelectric membrane, and piezoelectric property is large.The basis that its piezoelectric property provides theory and practice improved to low-temperature growth BZT-BCT piezoelectric film material.
Two, BZT-BC piezoelectric membrane of the present invention generates perovskite structure under 700 DEG C of Crystallizing treatment, shows comparatively good piezoelectric performance.By the introducing of PLCT Seed Layer, the BZT-BCT piezoelectric membrane under 500 DEG C low temperature crystallized also creates perovskite structure, shows same excellent piezoelectric property.
In the piezoelectric membrane of three, 500 DEG C ~ 700 DEG C of crystallization, the low temperature crystallized application also helping big area Si unicircuit of 500 DEG C.
Four, present invention process is simple and clear, equipment is simple, and raw materials is that market is sold, cheap, cost is lower, is easy to device integrated, is suitable for suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is the XRD thing scanning phase graphic representation of film prepared by experiment one, and in figure, ■ represents the diffraction peak of BZT-0.5BCT, ● represent the diffraction peak of burnt green stone, represents Pt
xthe diffraction peak of Ti.
Fig. 2 is the D-V displacement-voltage control sigmoid curve figure of film prepared by experiment one;
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: the preparation method of BZT-BCT piezoelectric membrane low temperature crystallized in present embodiment carries out according to following steps:
One, in acetic acid, lanthanum acetate and calcium acetate is added, at temperature is 70 DEG C, after stirring 30min with the speed of 300r/min, obtain solution F, ethylene glycol monomethyl ether is added, at temperature is 80 DEG C, after stirring 30min with the speed of 300r/min in solution F, filter, be cooled to room temperature, obtain solution G, then add tetrabutyl titanate in solution G, after stirring 30min with the speed of 300r/min, obtain colloidal sol E; Wherein, lanthanum acetate in colloidal sol E and the mass volume ratio of tetrabutyl titanate are (0.50 ~ 0.55) g:1ml, the mass volume ratio of calcium acetate and tetrabutyl titanate is (0.25 ~ 0.30) g:1ml, the volume ratio (7.79 ~ 10.25) of acetic acid and tetrabutyl titanate: 1, the volume ratio (2.87 ~ 5.33) of ethylene glycol monomethyl ether and tetrabutyl titanate: 1;
Two, in ethylene glycol monomethyl ether, add plumbic acetate, at temperature is 70 DEG C, stirs 20min with the speed of 300r/min, be cooled to room temperature, then add tetrabutyl titanate, stir 30min with the speed of 300r/min, obtain colloidal sol D; Wherein, in colloidal sol D, the mass volume ratio of plumbic acetate and tetrabutyl titanate is (1.15 ~ 1.26) g:1ml, and the volume ratio of ethylene glycol monomethyl ether and tetrabutyl titanate is (2.70 ~ 4.50): 1;
Three, after being mixed by colloidal sol D and colloidal sol E, obtain mixed sols, then adding ethylene glycol monomethyl ether adjustment mixed sols concentration is 0.05mol/L ~ 0.2mol/L, then after stirring 30min with the speed of 300r/min, obtains load lanthanium titanate calcium sol;
Four, barium acetate and calcium acetate are dissolved in Glacial acetic acid, then under the condition of 70 DEG C, 30min is stirred with the speed of 300r/min, cool to room temperature, obtain clarifying uniform solution A, the mass volume ratio of barium acetate and Glacial acetic acid is (0.381 ~ 0.386) g:1mL, the mass volume ratio of calcium acetate and Glacial acetic acid is (0.039 ~ 0.045) g:1ml, add ethylene glycol monomethyl ether, methyl ethyl diketone, tetrabutyl titanate and zirconium iso-propoxide, under the condition of room temperature, control speed is that 300r/min stirs 30min, obtain the sol B of evenly clarification, the volume ratio (0.331 ~ 0.335) of methyl ethyl diketone and ethylene glycol monomethyl ether: 1, the volume ratio (0.273 ~ 0.276) of tetrabutyl titanate and ethylene glycol monomethyl ether: 1, the volume ratio (0.036 ~ 0.038) of zirconium iso-propoxide and ethylene glycol monomethyl ether: 1, by solution A and B colloidal sol Homogeneous phase mixing, adding ethylene glycol monomethyl ether to concentration is again 0.3mol/L ~ 0.4mol/L, again at ambient temperature, control speed is that 300r/min stirs 30min, then ageing 24h ~ 28h, obtain zirconium barium titanate calcium sol,
Five, at (111) Pt/Ti/SiO
2first rotary coating load lanthanium titanate calcium sol in/Si substrate, obtain 1 ~ 4 layer of load lanthanium titanate calcium film, the rotating speed applying every layer of load lanthanium titanate calcium film is 5000rpm ~ 5500rpm, time is 15s ~ 20s, then being placed on temperature is carry out thermolysis at 425 DEG C ~ 475 DEG C, obtain Seed Layer film, then rotary coating barium titanate calcium colloidal sol on Seed Layer film, obtain 3 ~ 5 layers of barium calcium zirconate titanate film, thermolysis is carried out under being placed in 425 DEG C ~ 475 DEG C conditions again, the annealing furnace being finally placed in 475 DEG C ~ 550 DEG C carries out Crystallizing treatment, obtain low temperature crystallized BZT-BCT piezoelectric membrane, the time applied needed for every layer of barium calcium zirconate titanate film is 15s ~ 20s, and the rotating speed of coating is 5000rpm ~ 5500rpm.
Embodiment two: present embodiment and embodiment one are 0.52g:1ml unlike the mass volume ratio of the lanthanum acetate in colloidal sol E in step one and tetrabutyl titanate; The mass volume ratio of calcium acetate and tetrabutyl titanate is 0.27g:1ml, and the volume ratio of acetic acid and tetrabutyl titanate is 9.02:1, and the volume ratio of ethylene glycol monomethyl ether and tetrabutyl titanate is 4.10:1.Other is identical with embodiment one.
Embodiment three: one of present embodiment and embodiment one or two are 1.21g:1ml unlike the mass volume ratio of the plumbic acetate in the colloidal sol D in step 2 and tetrabutyl titanate, the volume ratio of ethylene glycol monomethyl ether and tetrabutyl titanate is 3.60:1.Other is identical with one of embodiment one or two.
Embodiment four: one of present embodiment and embodiment one to three are 0.05mol/L unlike spent glycol methyl ether adjustment mixed sols concentration in step 3.Other is identical with one of embodiment one to three.
Embodiment five: one of present embodiment and embodiment one to four are 0.383g:1mL unlike the mass volume ratio of barium acetate in step 4 and Glacial acetic acid, the mass volume ratio of calcium acetate and Glacial acetic acid is 0.042g:1ml.Other is identical with one of embodiment one to four.
Embodiment six: one of present embodiment and embodiment one to five are unlike the volume ratio 0.333:1 of methyl ethyl diketone in step 4 and ethylene glycol monomethyl ether, the volume ratio 0.275:1 of tetrabutyl titanate and ethylene glycol monomethyl ether, the volume ratio 0.037:1 of zirconium iso-propoxide and ethylene glycol monomethyl ether.Other is identical with one of embodiment one to five.
Embodiment seven: one of present embodiment and embodiment one to six are 0.35mol/L unlike adding ethylene glycol monomethyl ether to concentration in step 4, ageing 24h.Other is identical with one of embodiment one to six.
Embodiment eight: one of present embodiment and embodiment one to seven, unlike first applying 4 layers of load lanthanium titanate calcium film in step 5, then apply 4 layers of barium calcium zirconate titanate film.Wherein the time of the every thin film of spin coating is 18s; The speed of rotation applying every thin film is 5200rpm.Other is identical with one of embodiment one to seven.
Embodiment nine: one of present embodiment and embodiment one to eight are 450 DEG C unlike pyrolysis temperature in step 5.Other is identical with one of embodiment one to eight.
Embodiment ten: one of present embodiment and embodiment one to nine carry out Crystallizing treatment unlike being 500 DEG C in temperature in step 5 in conventional anneal stove.Other is identical with one of embodiment one to nine.
Adopt following experimental verification effect of the present invention:
Low temperature crystallized BZT-BCT piezoelectric membrane
Experiment: this experiment is divided into experimental group and control group.Experimental group is with PLCT Seed Layer BZT-BCT piezoelectric membrane, and control group is the BZT-BCT piezoelectric membrane without PLCT Seed Layer.
The low temperature crystallized BZT-BCT piezoelectric membrane of experimental group, specifically completes according to the following steps:
One, in acetic acid, lanthanum acetate and calcium acetate is added, at temperature is 70 DEG C, after stirring 30min with the speed of 300r/min, obtain solution F, ethylene glycol monomethyl ether is added, at temperature is 80 DEG C, after stirring 30min with the speed of 300r/min in solution F, filter, be cooled to room temperature, obtain solution G, then add tetrabutyl titanate in solution G, after stirring 30min with the speed of 300r/min, obtain colloidal sol E; Wherein, lanthanum acetate in colloidal sol E and the mass volume ratio of tetrabutyl titanate are 0.52g:1ml, the mass volume ratio of calcium acetate and tetrabutyl titanate is the volume ratio 4.10:1 of the volume ratio 9.02:1 of 0.27g:1ml, acetic acid and tetrabutyl titanate, ethylene glycol monomethyl ether and tetrabutyl titanate;
Two, in ethylene glycol monomethyl ether, add plumbic acetate, at temperature is 70 DEG C, stirs 20min with the speed of 300r/min, be cooled to room temperature, then add tetrabutyl titanate, stir 30min with the speed of 300r/min, obtain colloidal sol D; Wherein, in colloidal sol D, the mass volume ratio of plumbic acetate and tetrabutyl titanate is 1.21g:1ml, and the volume ratio of ethylene glycol monomethyl ether and tetrabutyl titanate is 3.60:1;
Three, after being mixed by colloidal sol D and colloidal sol E, obtain mixed sols, then adding ethylene glycol monomethyl ether adjustment mixed sols concentration is 0.05mol/L, then after stirring 30min with the speed of 300r/min, obtains load lanthanium titanate calcium sol;
Four, weigh barium acetate and be with calcium acetate to be dissolved in Glacial acetic acid, then under the condition of 70 DEG C, control speed is 300r/min
Stir 30min, cool to room temperature, obtains clarifying uniform solution A, and the mass volume ratio of barium acetate and Glacial acetic acid is 0.383g:1mL, and the mass volume ratio of calcium acetate and ethylene glycol monomethyl ether is 0.042g:1ml.Measure ethylene glycol monomethyl ether, methyl ethyl diketone, tetrabutyl titanate and zirconium iso-propoxide, under the condition of room temperature, control speed is that 300r/min stirs 30min, obtains the sol B of evenly clarification.The volume ratio 0.333:1 of methyl ethyl diketone and ethylene glycol monomethyl ether, the volume ratio 0.275:1 of tetrabutyl titanate and ethylene glycol monomethyl ether, the volume ratio 0.037:1 of zirconium iso-propoxide and ethylene glycol monomethyl ether.The B colloidal sol Homogeneous phase mixing of solution A and step is obtained zirconium barium titanate calcium sol, then measures ethylene glycol monomethyl ether, the concentration of adjustment mixed sols is 0.35mol/L, again at ambient temperature, control speed is that 300r/min stirs 30min, then ageing 24h, obtains zirconium barium titanate calcium sol.
Five, first at (111) Pt/Ti/SiO
2first rotary coating 4 layers of load lanthanium titanate calcium film in/Si substrate, rotating speed is 5200rpm, time is 18s, then being placed on temperature is carry out thermolysis at 450 DEG C, obtain Seed Layer film, then rotary coating 4 layers of barium calcium zirconate titanate film on Seed Layer film, then carry out thermolysis under being placed in 450 conditions, the conventional anneal stove being finally placed in 500 DEG C carries out Crystallizing treatment, namely obtains with PLCT Seed Layer BZT-BCT piezoelectric membrane; The required time applying every layer of barium calcium zirconate titanate film is 18s, and the rotating speed of coating is 5200rpm.
The preparation method of control group BZT-BCT piezoelectric membrane is:
One, weighing barium acetate and calcium acetate are dissolved in Glacial acetic acid, and then under the condition of 70 DEG C, control speed is 300r/min
Stir 30min, cool to room temperature, obtains clarifying uniform solution A, and the mass volume ratio of barium acetate and Glacial acetic acid is 0.383g:1mL, and the mass volume ratio of calcium acetate and ethylene glycol monomethyl ether is 0.042g:1ml.
Two, measure ethylene glycol monomethyl ether, methyl ethyl diketone, tetrabutyl titanate and zirconium iso-propoxide, under the condition of room temperature, control speed is that 300r/min stirs 30min, obtains the sol B of evenly clarification.The volume ratio 0.333:1 of methyl ethyl diketone and ethylene glycol monomethyl ether, the volume ratio 0.275:1 of tetrabutyl titanate and ethylene glycol monomethyl ether, the volume of zirconium iso-propoxide and the volume ratio 0.037:1 of ethylene glycol monomethyl ether.The B colloidal sol Homogeneous phase mixing of solution A and step is obtained zirconium barium titanate calcium sol, then measures ethylene glycol monomethyl ether, the concentration of adjustment mixed sols is 0.35mol/L, again at ambient temperature, control speed is that 300r/min stirs 30min, then ageing 24h, obtains zirconium barium titanate calcium sol.
Three, directly at (111) Pt/Ti/SiO
2/ Si substrate applies barium calcium zirconate titanate, and rotating speed is 5200rpm, and the time is 18s,, apply 4 layers of barium calcium zirconate titanate film, every layer all will be placed in temperature is carry out thermolysis at 450 DEG C, finally be put in the conventional anneal stove of 500 DEG C and 700 DEG C and carry out Crystallizing treatment, obtain BZT-BCT piezoelectric membrane.
The acetic acid of this experiment and (111) Pt/Ti/SiO
2/ Si substrate is commercially available prod, and the mass percentage of acetic acid is for being not less than 99.5%.
The BZT-BCT piezoelectric membrane processed under different annealing temperatures, carry out XRD thing scanning phase, result as shown in Figure 1, a and c is that 4 layers of BZT-BCT (its thickness the is 300nm) piezoelectric membrane of control group carries out anneal respectively 500 DEG C and 700 DEG C, b is 4 layers of PLCT (its thickness 18nm) Seed Layer and 4 layers of BZT-BCT piezoelectric membrane of experimental group, in the anneal that 500 DEG C are carried out.As can be seen from Figure 1 through the pure BZT-BCT piezoelectric membranes of 500 DEG C of annealing thing mutually in have dephasign and the Pt of pyrochlore structure
xti, and the diffraction peak not occurring uhligite, illustrate pure BZT-BCT piezoelectric membrane, under 500 DEG C of annealing, and can not crystallization; When annealing temperature reaches 700 DEG C, pure BZT-BCT piezoelectric membrane presents homogeneous perovskite structure, has more weak (110) diffraction peak, without preferred orientation.And b curve negotiating introduces 4 layers of PLCT Seed Layer, through the inducing action of Seed Layer, piezoelectric membrane shows preferred orientation, under the low temperature of 500 DEG C, crystallization becomes obvious perovskite structure, and presenting height (100) preferred orientation, this illustrates that PLCT Seed Layer serves the effect of regulation and control film texture.
Can be obtained by a, c and the b in comparison diagram 1: the BZT-BCT piezoelectric membrane without Seed Layer prepared by this experiment contrast group is amorphous after 500 DEG C of anneal, there is burnt green stone dephasign and Pt
xti, therefore it does not have piezoelectric property, does not obtain piezo-electric modulus; Although and through the BZT-BCT film complete crystallization of 700 DEG C of anneal, without preferred orientation, do not show the diffraction peak of (100) orientation.And through the induced orientation of PLCT Seed Layer, the BZT-BCT piezoelectric membranes of 500 DEG C of annealing show height (100) preferred orientation, piezoelectric membrane crystallization is abundant.
Carry out piezoelectric property test to sample, its result is as Fig. 2.Butterfly curve d is the pure BZT-BCT piezoelectric membrane of 700 DEG C of annealing, and butterfly curve e is the band PLCT Seed Layer BZT-BCT piezoelectric membrane through 500 DEG C of annealing.Can find out in d figure, although maximal dilation amount reaches 0.4nm when voltage reaches 9v, whole figure is not full symmetric, and always along with vibrations by a small margin, piezoelectric property performance is also unstable; And in e figure, after the low-temperature annealing process of 500 DEG C, when voltage reaches 9v, maximal dilation amount also reaches 0.4nm, and butterfly curve symmetric degree is very good, and graphic representation is also comparatively level and smooth, therefore piezoelectric property performance is stable.Contrast butterfly curve d and e can draw, through the BZT-BCT of Seed Layer induction, excellent piezoelectric property can be shown at low temperature (500 DEG C), show the piezoelectric property suitable with the BZT-BCT piezoelectric membrane of annealing through high temperature (700 DEG C).
From Fig. 1 and Fig. 2, regulated and controled by the texture of PLCT Seed Layer, not only reduce the crystallization temperature of BZT-BCT piezoelectric membrane, and because the induction of seed, there is preferred orientation in film, show height (100) preferred orientation, the BZT-BCT piezoelectric membrane having PLCT Seed Layer of low temperature (500 DEG C) crystallization, its piezoelectric property and high temperature (700 DEG C) crystallization BZT-BCT piezoelectric membrane suitable.Therefore under providing a kind of low crystallization temperature, improve the method for Ba system film piezo-electric performance.
First the present invention chooses the BZT-BCT system of piezoelectric property excellence.Based on the theory of the accurate homotype phase boundary of tricritical point, by the regulation and control of Seed Layer, successfully prepare the piezoelectric membrane of low temperature (500 DEG C) crystallization, under the external electric field of 9V, the displacement of BZT-BCT reaches 0.4nm, piezoelectric constant reaches 44.4pm/v, and bismuth sodium potassium titanate (NKBT) film of height (100) orientation of low temperature (450 DEG C) crystallization prepared before this, its piezoelectric constant is 34pm/v.Therefore the piezoelectric property of low temperature crystallized BZT-BCT film is better than NKBT film.Piezoelectric property significantly improves.
Claims (9)
1. the preparation method of low temperature crystallized BZT-BCT piezoelectric membrane, is characterized in that the preparation method of low temperature crystallized BZT-BCT piezoelectric membrane carries out according to following steps:
One, in acetic acid, lanthanum acetate and calcium acetate is added, at temperature is 70 DEG C, after stirring 30min with the speed of 300r/min, obtain solution F, ethylene glycol monomethyl ether is added, at temperature is 80 DEG C, after stirring 30min with the speed of 300r/min in solution F, filter, be cooled to room temperature, obtain solution G, then add tetrabutyl titanate in solution G, after stirring 30min with the speed of 300r/min, obtain colloidal sol E; Wherein, lanthanum acetate in colloidal sol E and the mass volume ratio of tetrabutyl titanate are (0.50 ~ 0.55) g:1ml, the mass volume ratio of calcium acetate and tetrabutyl titanate is (0.25 ~ 0.30) g:1ml, the volume ratio (7.79 ~ 10.25) of acetic acid and tetrabutyl titanate: 1, the volume ratio (2.87 ~ 5.33) of ethylene glycol monomethyl ether and tetrabutyl titanate: 1;
Two, in ethylene glycol monomethyl ether, add plumbic acetate, at temperature is 70 DEG C, stirs 20min with the speed of 300r/min, be cooled to room temperature, then add tetrabutyl titanate, stir 30min with the speed of 300r/min, obtain colloidal sol D; Wherein, in colloidal sol D, the mass volume ratio of plumbic acetate and tetrabutyl titanate is (1.15 ~ 1.26) g:1ml, and the volume ratio of ethylene glycol monomethyl ether and tetrabutyl titanate is (2.70 ~ 4.50): 1;
Three, after being mixed by colloidal sol D and colloidal sol E, obtain mixed sols, then adding ethylene glycol monomethyl ether adjustment mixed sols concentration is 0.05mol/L ~ 0.2mol/L, then after stirring 30min with the speed of 300r/min, obtains load lanthanium titanate calcium sol;
Four, barium acetate and calcium acetate are dissolved in Glacial acetic acid, then under the condition of 70 DEG C, 30min is stirred with the speed of 300r/min, cool to room temperature, obtain clarifying uniform solution A, the mass volume ratio of barium acetate and Glacial acetic acid is (0.381 ~ 0.386) g:1mL, the mass volume ratio of calcium acetate and Glacial acetic acid is (0.039 ~ 0.045) g:1ml, add ethylene glycol monomethyl ether, methyl ethyl diketone, tetrabutyl titanate and zirconium iso-propoxide, under the condition of room temperature, control speed is that 300r/min stirs 30min, obtain the sol B of evenly clarification, the volume ratio (0.331 ~ 0.335) of methyl ethyl diketone and ethylene glycol monomethyl ether: 1, the volume ratio (0.273 ~ 0.276) of tetrabutyl titanate and ethylene glycol monomethyl ether: 1, the volume ratio (0.036 ~ 0.038) of zirconium iso-propoxide and ethylene glycol monomethyl ether: 1, by solution A and B colloidal sol Homogeneous phase mixing, adding ethylene glycol monomethyl ether to concentration is again 0.3mol/L ~ 0.4mol/L, again at ambient temperature, control speed is that 300r/min stirs 30min, then ageing 24h ~ 28h, obtain zirconium barium titanate calcium sol,
Five, at (111) Pt/Ti/SiO
2first rotary coating load lanthanium titanate calcium sol in/Si substrate, obtain 1 ~ 4 layer of load lanthanium titanate calcium film, the rotating speed applying every layer of load lanthanium titanate calcium film is 5000rpm ~ 5500rpm, time is 15s ~ 20s, then being placed on temperature is carry out thermolysis at 425 DEG C ~ 475 DEG C, obtain Seed Layer film, then rotary coating barium titanate calcium colloidal sol on Seed Layer film, obtain 3 ~ 5 layers of barium calcium zirconate titanate film, thermolysis is carried out under being placed in 425 DEG C ~ 475 DEG C conditions again, the annealing furnace being finally placed in 475 DEG C ~ 550 DEG C carries out Crystallizing treatment, obtain low temperature crystallized BZT-BCT piezoelectric membrane, the time applied needed for every layer of barium calcium zirconate titanate film is 15s ~ 20s, and the rotating speed of coating is 5000rpm ~ 5500rpm.
2. the preparation method of BZT-BCT piezoelectric membrane low temperature crystallized according to claim 1, is characterized in that the mass volume ratio of lanthanum acetate in step one in colloidal sol E and tetrabutyl titanate is 0.52g:1ml; The mass volume ratio of calcium acetate and tetrabutyl titanate is 0.27g:1ml, and the volume ratio of acetic acid and tetrabutyl titanate is 9.02:1, and the volume ratio of ethylene glycol monomethyl ether and tetrabutyl titanate is 4.10:1.
3. the preparation method of BZT-BCT piezoelectric membrane low temperature crystallized according to claim 1, the mass volume ratio that it is characterized in that plumbic acetate in the colloidal sol D in step 2 and tetrabutyl titanate is 1.21g:1ml, and the volume ratio of ethylene glycol monomethyl ether and tetrabutyl titanate is 3.60:1.
4. the preparation method of BZT-BCT piezoelectric membrane low temperature crystallized according to claim 1, is characterized in that in step 3, spent glycol methyl ether adjustment mixed sols concentration is 0.05mol/L.
5. the preparation method of BZT-BCT piezoelectric membrane low temperature crystallized according to claim 1, is characterized in that the mass volume ratio of barium acetate and Glacial acetic acid in step 4 is 0.383g:1mL, and the mass volume ratio of calcium acetate and Glacial acetic acid is 0.042g:1ml.
6. the preparation method of BZT-BCT piezoelectric membrane low temperature crystallized according to claim 1, it is characterized in that the volume ratio 0.333:1 of methyl ethyl diketone and ethylene glycol monomethyl ether in step 4, the volume ratio 0.275:1 of tetrabutyl titanate and ethylene glycol monomethyl ether, the volume ratio 0.037:1 of zirconium iso-propoxide and ethylene glycol monomethyl ether.
7. the preparation method of BZT-BCT piezoelectric membrane low temperature crystallized according to claim 1, is characterized in that adding ethylene glycol monomethyl ether to concentration in step 4 is 0.35mol/L, ageing 24h.
8. the preparation method of BZT-BCT piezoelectric membrane low temperature crystallized according to claim 1, is characterized in that first applying 4 layers of load lanthanium titanate calcium film in step 5, and then apply 4 layers of barium calcium zirconate titanate film, wherein the time of the every thin film of spin coating is 18s; The speed of rotation applying every thin film is 5200rpm.
9. the preparation method of BZT-BCT piezoelectric membrane low temperature crystallized according to claim 1, is characterized in that be 500 DEG C in temperature in step 5 carries out Crystallizing treatment in conventional anneal stove.
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| CN103073303A (en) * | 2012-12-26 | 2013-05-01 | 哈尔滨理工大学 | Method for preparing highly oriented (100) lead-free piezoelectric thin film |
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