CN103193482A - Lead zirconate titanate thick film and preparation method thereof - Google Patents
Lead zirconate titanate thick film and preparation method thereof Download PDFInfo
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- CN103193482A CN103193482A CN2013100753389A CN201310075338A CN103193482A CN 103193482 A CN103193482 A CN 103193482A CN 2013100753389 A CN2013100753389 A CN 2013100753389A CN 201310075338 A CN201310075338 A CN 201310075338A CN 103193482 A CN103193482 A CN 103193482A
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Abstract
The invention discloses a method for preparing a lead zirconate titanate thick film, which is used for generating the lead zirconate titanate thick film on titanium sheets. The method concretely includes: configuring a precursor solution in an autoclave; immersing the titanium sheets in the precursor solution vertically, placing the autoclave in a magnetic stirrer for magnetic stirring; and finally removing the titanium sheets, thus the formation of the lead zirconate titanate (PZT) thick film on the titanium sheets can be achieved. The present invention also discloses a lead zirconate titanate thick film prepared by the method. The preparation process of the present invention can be finished in the liquid phase once, does not need post heat treatment, and can prevent composition interdiffusion between a substrate and the thick film caused by excess temperature. The thickness of the film can be controlled by the number of times of recrystallization. The method is simple and feasible, the prepared film is not limited by the size and shape of the substrate, the PZT thick film can be prepared on surfaces of a three-dimensional structure, the PZT thick film is uniform in surface, and the components are in the vicinity of morphotropic phase boundary.
Description
Technical field
The invention belongs to the ceramic thick film preparation field, be specifically related to the preparation method of a kind of Pb-based lanthanumdoped zirconate titanates (PZT) thick film.
Background technology
Pb-based lanthanumdoped zirconate titanates (PZT) material shows good piezoelectricity, ferroelectric, dielectric properties at accurate homotype phase boundary place (Zr/Ti=52/48), not only operating voltage is low, frequency of utilization is high for the device made from PZT thick film (referring generally to thickness greater than the PZT film of 1 μ m), can with the semiconductor integrated circuit compatibility, and have an electric property close with piezoelectricity bulk device, therefore, the PZT thick film is used widely in fields such as the underwater sound, medical ultrasound diagnosis, MEMS in recent years.
The preparation method that Pb-based lanthanumdoped zirconate titanates (PZT) is commonly used generally has sol-gel method, silk screen print method, casting method, electrophoretic deposition and hydrothermal method several.What wherein sol-gel method used is more, but when being to use this method, because organism is more, easily produce pore, the probability of the PZT thick film cracking of preparation is bigger, and lower temperature is easy to generate burnt green stone dephasign, the thick film surface of preparation is more coarse, and density is good inadequately.The silk screen printing law technology is the most ripe, but slurry is difficult to mix, and the later stage calcining temperature is higher than 850 ℃, can cause the mutual diffusion of thick film and substrate and the volatilization of PbO, influences electrical property.Casting method and MEMS are incompatible, the thick film that makes need be adhered on the substrate, and technology more complicated, reliability are not high.The electrophoretic deposition shortcoming is strength of electric field thinner and higher coarse cracking of rete that easily causes of strength of electric field of the low prepared film of efficient when low, and other electrochemical reaction also easily takes place electrode.
At present, adopt hydrothermal method can overcome the defective that aforesaid method brings preferably.Generally, Hydrothermal Preparation PZT thick film adopts the mode of baking oven for heating usually, because the precursor aqueous solution of preparation PZT thick film is suspension liquid, when adopting baking oven for heating not introduce agitating function, layering can appear in the solution in the autoclave, cause the inhomogeneous and routine Zr/Ti=52/48 of departing from of zirconium titanium ratio of PZT thick film of preparation, thereby the composition of the PZT thick film of feasible preparation has departed from accurate homotype phase boundary, this has just influenced the electrical property of the PZT thick film of preparation greatly.
Summary of the invention
One of purpose of the present invention is to provide the preparation method of a kind of Pb-based lanthanumdoped zirconate titanates (PZT) thick film, and its technology is simple, and the PZT thick film surface of preparing is even, and its composition is at accurate homotype phase boundary place, and the electrical property tool improves a lot.
Method of the present invention is by utilizing the type of heating of heat collecting type thermostatically heating magnetic stirring apparatus, the Hydrothermal Preparation PZT high-temperature and high-pressure conditions of thick film not only can be provided, and utilize its magnetic agitation function that carries to guarantee the homogeneous of solution in the reaction process, greatly the solution of degree the problem that the PZT thick film surface is inhomogeneous, composition departs from accurate homotype phase boundary of baking oven for heating preparation.
Realize that the technical scheme that purpose of the present invention adopts is as follows:
A kind of preparation method of lead zirconate titanate thick film is used for generating lead zirconate titanate thick film at the titanium sheet, it is characterized in that this method specifically comprises:
In the autoclave inner bag, dispose precursor aqueous solution;
In the described precursor aqueous solution of the vertical immersion of described titanium sheet, and described autoclave is put into magnetic stirring apparatus carry out magnetic agitation;
At last, take out the titanium sheet, can be implemented in reaction generation Pb-based lanthanumdoped zirconate titanates (PZT) thick film on the titanium sheet.
As present invention further optimization, described precursor aqueous solution is formulated by lead nitrate, zirconium oxychloride, titanium tetrachloride and potassium hydroxide.
As present invention further optimization, described titanium tetrachloride is replaceable to be titanium dioxide or Butyl Phthalate.
As present invention further optimization, the molar ratio of Zr/Ti is preferably 52/48 in the described precursor aqueous solution.
As present invention further optimization, be filled with silicone oil in the described magnetic stirring apparatus, described autoclave submerges in the silicone oil by the magnetic force heated and stirred to react.
As present invention further optimization, described reacting by heating temperature is 110 ℃～130 ℃, and the reaction times can be 24 hours.
As present invention further optimization, described titanium sheet is by being arranged on vertical the immersion in the described precursor aqueous solution in the fixing back of shell fragment in the autoclave inner bag, and this shell fragment is fixed in above-mentioned inner bag by the bending at two ends.
As present invention further optimization, described shell fragment is made by the titanium sheet,
As present invention further optimization, described titanium sheet cleans pre-treatment earlier, to remove surface contaminant before immersing precursor aqueous solution.
Another object of the present invention is to provide a kind of prepared lead zirconate titanate thick film of above-mentioned preparation method that utilizes.
The PZT thick film surface homogeneous of method preparation of the present invention, composition have improved its electric property greatly at accurate homotype phase boundary place.Utilize the PZT thick film of this method preparation that following advantage is arranged:
1, preparation process is once finished in liquid phase, does not need later stage thermal treatment.
2, the temperature of usefulness lower (below 200 ℃) has avoided that temperature is too high to cause composition mutual diffusion between substrate and the thick film.
3, the thickness of film can be controlled simple possible by the number of times that repeats crystallisation process.
4, prepared film is not controlled by the size and dimension of substrate, and the PZT thick film can prepare the surface in three-dimensional structure.
5, prepared film need not polarization just piezoelectric property.
6, Zhi Bei PZT thick film surface is even, and composition is near accurate homotype phase boundary (Zr/Ti=52/48).7, equipment is simple, and cost is lower.
Description of drawings
Fig. 1 is the autoclave schematic internal view of the embodiment of the invention.
Fig. 2 is the oil bath Hydrothermal Preparation PZT thick film systems synoptic diagram of the embodiment of the invention.
Fig. 3 is the XRD phasor of the PZT thick film of the embodiment of the invention.
Fig. 4 is the SEM figure of the PZT thick film of the embodiment of the invention.
Among the figure, 1 is the autoclave stainless steel casing, and 2 is the Teflon inner bag, and 3 is the titanium sheet, and 4 is precursor aqueous solution, and 5 is magneton, and 6 is temperature sensor, and 7 is autoclave, and 8 is silicone oil, and 9 is heater strip.
Embodiment
In order to make purpose of the present invention, technical scheme and advantage clearer, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explaining the present invention, and be not used in restriction the present invention.
According to a preferred embodiment of the present invention, the preparation method of PZT thick film comprises following concrete steps:
1, the pre-treatment of Ti sheet
At first, the titanium sheet is cut into a certain size, and (area can be adjusted as required, preferred 2cm * 1cm in the present embodiment, also can adopt other dimensionss), then the Ti sheet is passed through mechanical grinding to remove the part of surface corrosion, and use deionized water rinsing, carry out alcohol ultrasonic (time is preferably 10min) then, again with carrying out acetone ultrasonic (time for example can be 10min) behind the deionized water rinsing, and then carry out alcohol ultrasonic (time is preferably 10min), clean up dry for standby at last again with deionized water.
2, the preparation of precursor aqueous solution
In the present embodiment, precursor aqueous solution is by being lead nitrate Pb (NO
3)
2, zirconium oxychloride ZrClO
2.8H
2O, titanium tetrachloride TiCl
4Configuration forms with potassium hydroxide KOH.In the polytetrafluoroethylliner liner of the preferred directly adding of above-mentioned raw materials autoclave, avoid secondary pollution.
At first, take by weighing the plumbous Pb (NO of lead nitrate according to mol ratio Zr/Ti=52/48
3)
2With zirconium oxychloride ZrClO
2.8H
2O mixes the back and adds deionized water and stirring certain hour (as 20min), adds TiCl then
4The aqueous solution stirs (time is preferably 10min), takes by weighing a certain amount of KOH and slowly adding again, at last mixing solutions is stirred certain hour (for example 40min) and forms precursor aqueous solution.In the present embodiment, the consumption of each composition can be according to the actual size adjustment of autoclave.In addition, present embodiment mesohigh still compactedness is preferably 80%, and zirconium and titanium ion mol ratio be Zr/Ti=52/48 preferably, also can adopt other ratios, and KOH concentration is preferably 4mol/l.
Comprehensive above-mentioned several conditions make the precursor aqueous solution for preparing the PZT thick film.
In the present embodiment, the concentration of KOH can be chosen as 2mol/l～6mol/l, but preferably adopt the PZT crystalline phase of prepared at concentrations of 4mol/l best, this is because low excessively concentration-response is slower, is unfavorable for the generation of reacting and too high concentration easily generates other impurity.
The molar ratio of Zr/Ti can generate PZT in 90/10～10/90 scope, but the ratio value of the Zr/Ti of precursor preferentially chooses 52/48 in the present embodiment, and the Zr/Ti in the PZT thick film sample of preparation is consistent with this ratio.
TiCl in the above-mentioned embodiment
4Can also be TiO
2And Butyl Phthalate, but use TiO
2Irregular with the surface topography of the PZT thick film of Butyl Phthalate preparation, and use TiCl
4The PZT thick film surface grain size homogeneous of preparation is tangible isometric particle, has the surface of good pattern, so the preferred TiCl of present embodiment
4Be the titanium source.
3, Ti sheet and magneton are put into autoclave
At first, with narrower Ti sheet (width can be adjusted as required, as 0.2-0.5 centimetre, in the present embodiment preferred 0.3 centimetre) make shell fragment, titanium sheet cleaned in the step 1 is fixed on the shell fragment.Then, the titanium sheet that will have a shell fragment is put into and is filled the autoclave inner bag of 2 precursor aqueous solutions that prepare set by step, utilizes the supporting role of shell fragment, keeps the Ti sheet solution that vertically submerges, and magneton is put into autoclave base, to react.As shown in Figure 1.
In the reaction process, the Ti sheet will vertically be put into, avoiding and autoclave inwall touching, cause in the precursor aqueous solution on the inhomogeneous Ti of the being deposited on sheet of reactant, and the Ti sheet precursor aqueous solution that will all submerge simultaneously, making has the PZT thick film to generate on the whole Ti sheet.
In the present embodiment, autoclave is put into heat collecting type thermostatically heating magnetic stirring apparatus, guarantee the autoclave silicone oil that submerges, as shown in Figure 2.It is 130 ℃ that reaction conditions can preferably set temperature of reaction, and the reaction times is 24h, adjusts rotating speed and reacts.
In the present embodiment, temperature of reaction is 110 ℃～130 ℃ all can prepare the PZT thick film, preferably adopts 130 ℃, and higher temperature can the accelerated reaction process
4, clean the PZT thick film
Reaction can generate the PZT thick film after finishing, and when treating that autoclave naturally cools to room temperature, drives still and takes out the PZT thick film, cleans up with deionized water, and uses oven for drying.
Those skilled in the art will readily understand; the above only is preferred embodiment of the present invention; not in order to limiting the present invention, all any modifications of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. the preparation method of a lead zirconate titanate thick film is used for generating lead zirconate titanate thick film at the titanium sheet, it is characterized in that this method specifically comprises:
In the autoclave inner bag, dispose precursor aqueous solution;
In the described precursor aqueous solution of the vertical immersion of described titanium sheet, and described autoclave is put into magnetic stirring apparatus carry out magnetic agitation;
At last, take out the titanium sheet, can be implemented in reaction generation Pb-based lanthanumdoped zirconate titanates (PZT) thick film on the titanium sheet.
2. the preparation method of a kind of lead zirconate titanate thick film according to claim 1, wherein, described precursor aqueous solution is formulated by lead nitrate, zirconium oxychloride, titanium tetrachloride and potassium hydroxide.
3. the preparation method of a kind of lead zirconate titanate thick film according to claim 2, wherein, described titanium tetrachloride is replaceable to be titanium dioxide or Butyl Phthalate.
4. according to the preparation method of each described a kind of lead zirconate titanate thick film among the claim 1-3, wherein, the mole value of Zr/Ti is 90/10～10/90 in the described precursor aqueous solution, is preferably 52/48.
5. according to the preparation method of each described a kind of lead zirconate titanate thick film among the claim 1-4, wherein, be filled with silicone oil in the described magnetic stirring apparatus, described autoclave submerges in the silicone oil and reacts by magnetic agitation under certain Heating temperature.
6. the preparation method of a kind of lead zirconate titanate thick film according to claim 5, wherein, described reacting by heating temperature is 110 ℃～130 ℃, the reaction times can be 24 hours.
7. according to the preparation method of each described a kind of lead zirconate titanate thick film among the claim 1-6, wherein, described titanium sheet is by being arranged on vertical the immersion in the described precursor aqueous solution in the fixing back of shell fragment in the autoclave inner bag, and this shell fragment is fixed in above-mentioned inner bag by the bending at two ends.
8. the preparation method of a kind of lead zirconate titanate thick film according to claim 7, wherein, described shell fragment is made by the titanium sheet,
9. according to the preparation method of each described a kind of lead zirconate titanate thick film among the claim 1-8, wherein, described titanium sheet cleans pre-treatment earlier, to remove surface contaminant before immersing precursor aqueous solution.
10. utilize the prepared lead zirconate titanate thick film of each described preparation method among the claim 1-9.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107267983A (en) * | 2017-06-26 | 2017-10-20 | 重庆正峰电子有限公司 | A kind of preparation method of PZT ceramic coatings |
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| JPH06314828A (en) * | 1993-04-28 | 1994-11-08 | Mitsubishi Kasei Corp | Manufacture of lamination type element |
| JPH09217178A (en) * | 1995-12-06 | 1997-08-19 | Tokai Rubber Ind Ltd | Production of thin film by hydrothermal synthesis method |
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| US20040118686A1 (en) * | 2002-10-02 | 2004-06-24 | Jan Ma | Piezoelectric tubes |
| CN1522985A (en) * | 2003-09-05 | 2004-08-25 | 中国科学院上海技术物理研究所 | Preparation method of lead zirconate titanate thick film material |
| JP2004284887A (en) * | 2003-03-24 | 2004-10-14 | Toin Gakuen | Method and apparatus for forming pzt crystal film by hydrothermal synthetic method |
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2013
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Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06314828A (en) * | 1993-04-28 | 1994-11-08 | Mitsubishi Kasei Corp | Manufacture of lamination type element |
| JPH09217178A (en) * | 1995-12-06 | 1997-08-19 | Tokai Rubber Ind Ltd | Production of thin film by hydrothermal synthesis method |
| CN1282715A (en) * | 2000-08-24 | 2001-02-07 | 中国科学院上海硅酸盐研究所 | One-step thermal filming process for preparing thick film of lead zirconotitanate |
| CN1288976A (en) * | 2000-09-19 | 2001-03-28 | 中国科学院上海硅酸盐研究所 | Preparationof plumbous zirconate titanate (PZT) |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107267983A (en) * | 2017-06-26 | 2017-10-20 | 重庆正峰电子有限公司 | A kind of preparation method of PZT ceramic coatings |
| CN107267983B (en) * | 2017-06-26 | 2018-12-25 | 重庆正峰电子有限公司 | A kind of preparation method of PZT ceramic coating |
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Inventor after: Zhu Benpeng Inventor after: Xu Jiong Inventor after: Guo Wanke Inventor after: Zhang Yue Inventor after: Chen Shi Inventor after: Yang Xiaofei Inventor before: Zhu Benpeng Inventor before: Guo Wanke Inventor before: Zhang Yue Inventor before: Chen Shi Inventor before: Yang Xiaofei |
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