CN101805182A - Zirconium-rich lead zirconate-titanate ferroelectric (high-temperature) -ferroelectric (low temperture) phase change film material and preparation method thereof - Google Patents
Zirconium-rich lead zirconate-titanate ferroelectric (high-temperature) -ferroelectric (low temperture) phase change film material and preparation method thereof Download PDFInfo
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- CN101805182A CN101805182A CN201010107909A CN201010107909A CN101805182A CN 101805182 A CN101805182 A CN 101805182A CN 201010107909 A CN201010107909 A CN 201010107909A CN 201010107909 A CN201010107909 A CN 201010107909A CN 101805182 A CN101805182 A CN 101805182A
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Abstract
The invention relates to a zirconium-rich lead zirconate-titanate ferroelectric (high-temperature) -ferroelectric (low temperture) phase change film material which is sensitive to temperature and has the chemical composition of Pb (Zr1-XTiX)O3, wherein X equals to 0.03-0.099, and thickness is 600-1000 nm. The preparation method is as follows: lead salt, zircon salt and titanium salt are dissolved in glycol or ethylene glycol methyl ether, the ratio of Pb:Zr:Ti is 1: (1-X):X, and lead zirconate-titanate presoma sol of which the Pb+2 density is 0.5-0.6 mol/L is formed; the film is formed by coating, is pretreated for 3-12 minutes at the temperature of 330-360 DEG C and is performed with annealing treatment at the temperature of 630-670 DEG C; within the temperature range of 80-110 DEG C, the film is polarized for 5-10 minutes at the electric-field intensity of 2000-5000 V/mm. The material has small possibility of fragmentation, can carry out ferroelectric (high-temperature) -ferroelectric (low temperature) phase change at the temperature of about 26-48 DEG C, has small volume and small heat capacity and is favourable for further improving energy conversion efficiency.
Description
Technical field
The present invention relates to the ferroelectric phase transition material, especially a kind of lead zirconate-titanate ferroelectric of thermally sensitive rich zirconium (high temperature)-ferroelectric (low temperature) phase change film material.
Background technology
The novel pattern that novel energy material and multi-form energy coupling material utilize for new energy development, clean energy and the development of sensing technology are all very important, ferroelectric material has a good application prospect aspect thermoelectric, and utilizing ferroelectric material to carry out energy transformation has three kinds of main patterns: 1, ferroelectric-para-electric phase transformation; 2, ferroelectric-antiferroelectric phase transformation; 3, ferroelectric (high temperature)-ferroelectric (low temperature) phase transformation.Preceding two kinds of transducing patterns need repeat the working medium that polarizes, and a kind of transducing form in back is reversible because of its phase transition process, thus can repeat polarization, easy to use.
Have ferroelectric (high temperature)-ferroelectric membranc of ferroelectric (low temperature) phase-change characteristic compares with material in the past, have the superiority that volume is little, thermal absorptivity is high, compressive strength is high, make the efficient of thermoelectric and output power of unit volume to be significantly improved.
Summary of the invention
The present invention aims to provide lead zirconate-titanate ferroelectric (high temperature)-ferroelectric (low temperature) phase change film material of a kind of rich zirconium, can be by thermoinducible generation ferroelectric (high temperature)-ferroelectric (low temperature) phase transformation, and phase transition process is reversible, carry out the application of thermoelectric, improve the conversion efficiency and the output power density of thermoelectric system.
The present invention also provides the preparation method of above-mentioned thin-film material.
Technical scheme is, a kind of lead zirconate-titanate ferroelectric of rich zirconium (high temperature)-ferroelectric (low temperature) phase change film material, and the thickness of film is 600～1000nm, its chemical constitution is: Pb (Zr
1-XTi
X) O
3, X=0.03～0.099.
The substrate of the lead zirconate-titanate ferroelectric of this rich zirconium (high temperature)-ferroelectric (low temperature) phase change film material is a silicon chip, and bottom electrode is Pt.
The preparation method of the lead zirconate-titanate ferroelectric of above-mentioned rich zirconium (high temperature)-ferroelectric (low temperature) phase change film material is for comprising the steps:
1) lead salt, zirconates and titanium salt are dissolved in ethylene glycol or the ethylene glycol monomethyl ether, make the Pb-based lanthanumdoped zirconate titanates precursor sol with sol method; Wherein the mol ratio of lead element, zr element and titanium elements is 1: (1-X): X, X=0.03～0.099; The volumetric molar concentration of lead element is 0.5～0.6mol/L, is preferably 0.55～0.58mol/L; Described lead salt is selected from plumbic acetate or lead chloride, and zirconates is selected from zirconium-n-butylate or zirconium-n-propylate, and titanium salt is selected from titanium ethanolate or titanium isopropylate;
2) step 1) gained Pb-based lanthanumdoped zirconate titanates precursor sol is coated on the substrate that has bottom electrode, forms film; 330～360 ℃ of following pre-treatment 3～12 minutes, again through 630～670 ℃ of anneal 3～10 minutes; Used substrate is preferably silicon substrate, and used bottom electrode is preferably Pt;
3) in 80～110 ℃ temperature range, with the strength of electric field of 2000～5000V/mm to step 2) resulting film polarized 5～10 minutes, obtain spontaneous polarization along the direction of polarization orientation, can be by lead zirconate-titanate ferroelectric (high temperature)-ferroelectric (low temperature) phase change film material of thermoinducible rich zirconium; During polarization preferably to steam Pt as top electrode.
Because the range of temperature broad of thermal source in some cases, in order to enlarge the use range of material, improve thermoelectric efficient, need preparation that the material of ferroelectric (high temperature)-ferroelectric (low temperature) phase transformation can take place in wide warm area, this can realize by multi-layer coated formation gradient material.Can also be prepared by the following method lead zirconate-titanate ferroelectric (high temperature)-ferroelectric (low temperature) phase change film material of this rich zirconium:
1) plumbic acetate, zirconium-n-butylate and titanium ethanolate are dissolved in the ethylene glycol, make the Pb-based lanthanumdoped zirconate titanates precursor sol; Wherein the mol ratio of lead element, zr element and titanium elements is 1: (1-X): X, X=0.03～0.099; The volumetric molar concentration of lead element is 0.5～0.6mol/L, is preferably 0.55～0.58mol/L;
2) the different Pb-based lanthanumdoped zirconate titanates precursor sol of step 1) gained zr element molar content, the Pb-based lanthanumdoped zirconate titanates presomas that the zr element molar content is different are from the low levels to the high-content, perhaps from the high-content to the low levels, separate application is having on the substrate of bottom electrode successively, form film, the timed interval of each coating is 5min～20min; At 330～360 ℃ of following pre-treatment 3-12 minutes, again through 630～670 ℃ of anneal 3～10 minutes; Used substrate is preferably silicon substrate, and used bottom electrode is preferably Pt;
3) in 80～110 ℃ temperature range, with the polarization of the strength of electric field of 2000～5000V/mm to step 2) resulting film polarizes, obtain spontaneous polarization along the direction of polarization orientation, can be by lead zirconate-titanate ferroelectric (high temperature)-ferroelectric (low temperature) phase change film material of thermoinducible rich zirconium; During polarization preferably to steam Pt as top electrode.
Pb (the Zr that makes with sol-gel method that proposes according to above technical scheme
1-XTi
X) O
3Ferroelectric (high temperature)-ferroelectric (low temperature) phase transformation takes place in ferroelectric membranc near 26-48 ℃, the transformation temperature width is about 3 ℃, and in phase transition process, the spontaneous polarization variation reaches as high as 0.88 μ C/cm
2, and this phase transformation is reversible with temperature, need not repeat polarization in the working process, thereby can be applied to thermoelectric easily.Simultaneously, because this thin-film material volume change in phase transition process is little, and stress obtains discharging easily, so sample is not easily broken; In addition, the volume of film sample is little, thermal capacitance is little, also helps further improving conversion efficiency.
Embodiment
The making of the film of embodiment 1 big transducing
With plumbic acetate, zirconium-n-butylate and titanium ethanolate mixed dissolution in solvent ethylene glycol, Pb
2+, Zr
2+And Ti
2+Mol ratio be 100: 97: 3, make Pb with sol method
2+Concentration is the precursor sol of 0.55mol/L.
It is on the silicon chip substrate of bottom electrode that above-mentioned precursor sol is coated on Pt, forms gelatinous membrane.At 330～350 ℃ of following pre-treatment 10min, under 650～670 ℃ of temperature, make anneal 10min again, make Pb (Zr
0.97Ti
0.03) O
3Ferroelectric membranc.
To steam Pt as top electrode, in 80～90 ℃ temperature range, strength of electric field polarization 5min with 4000～5000V/mm, obtaining spontaneous polarization is orientated along direction of polarization, can be by the ferroelectric membranc of thermoinducible reversible ferroelectric (high temperature)-ferroelectric (low temperature) phase transformation, thickness is 600～1000nm, and the spontaneous polarization variation can reach 0.88 μ C/cm in the phase transition process
2
Resulting film has ferroelectric (high temperature)-ferroelectric (low temperature) phase-change characteristic, utilizes the iron electric polarization tester to measure the electric hysteresis line of wandering under differing temps, records its transformation temperature at 26 ℃.
Near the making of transducing film embodiment 2 human body temperature.
Technological process is similar with embodiment 1, mainly is that chemical constitution is adjusted.Chemical constitution is chosen as: Pb (Zr
0.93Ti
0.07) O
3
With plumbic acetate, zirconium-n-butylate and titanium isopropylate mixed dissolution in the solvent ethylene glycol methyl ether, Pb
2+, Zr
2+And Ti
2+Mol ratio be 100: 93: 7, make Pb with sol method
2+Concentration is the precursor sol of 0.58mol/L.
It is on the silicon chip substrate of bottom electrode that above-mentioned precursor sol is coated on Pt, forms film.At 350～360 ℃ of following pre-treatment 5min, under 630～650 ℃ of temperature, make anneal 5min again, make Pb (Zr
0.93Ti
0.07) O
3Ferroelectric membranc.
To steam Pt as top electrode, in 100～110 ℃ temperature range, strength of electric field polarization 10min with 3500～4000V/mm, obtaining spontaneous polarization is orientated along direction of polarization, can be by the ferroelectric membranc of thermoinducible reversible ferroelectric (high temperature)-ferroelectric (low temperature) phase transformation, thickness is 600～1000nm.
Resulting film has ferroelectric (high temperature)-ferroelectric (low temperature) phase-change characteristic, utilizes the iron electric polarization tester to measure the electric hysteresis line of wandering under differing temps, records its transformation temperature near 37 ℃.The spontaneous polarization variation can reach 0.75 μ C/cm in the phase transition process
2, can utilize the body temperature of human body to carry out the thermoelectric energy conversion.
The making of the film that embodiment 3 comparatively high tempss use down.
Utilization at thermals source such as trade effluent that has certain residual temperature and sanitary wastewaters, regulate ferroelectric (high temperature)-ferroelectric (low temperature) transformation temperature is necessary, can improve transformation temperature is located near the use temperature, the quantity of electric charge that ferroelectric membranc is exported in temperature changing process increases greatly, and this can realize by the chemical constitution that changes material.
With lead chloride, zirconium-n-propylate and titanium ethanolate mixed dissolution in solvent ethylene glycol, Pb
2+, Zr
2+And Ti
2+Mol ratio be 100: 90.5: 9.5, make Pb with sol method
2+Concentration is the precursor sol of 0.55mol/L.
It is on the silicon chip substrate of bottom electrode that above-mentioned precursor sol is coated on Pt, forms film.At 340～360 ℃ of following pre-treatment 10min, anneal 3min under 640～660 ℃ of temperature makes Pb (Zr again
0.905Ti
0.095) O
3Ferroelectric membranc.
Be upper current conducting cap to steam Pt again, in 90～100 ℃ temperature range, the strength of electric field polarization 10min with 2500-3000V/mm obtains spontaneous polarization and is orientated along direction of polarization, can be by the ferroelectric membranc of thermoinducible reversible ferroelectric (high temperature)-ferroelectric (low temperature) phase transformation, thickness is 600～1000nm.
Resulting thin film phase change temperature is at 45 ℃, and the spontaneous polarization variation can reach 0.58 μ C/cm in the phase transition process
2, be suitable under higher temperature, using.
The making of the film that embodiment 4 wide warm areas use.
Because the range of temperature broad of thermal source in some cases, in order to enlarge the use range of material, improve thermoelectric efficient, need preparation that the material of ferroelectric (high temperature)-ferroelectric (low temperature) phase transformation can take place in wide warm area, this can realize by multi-layer coated formation gradient material.The colloidal sol that at first prepares different components, chemical constitution is: Pb (Zr
1-XTi
X) O
3, wherein X is respectively 0.04,0.06,0.08, and the prepared process of colloidal sol is dissolved in plumbic acetate, zirconium-n-butylate and titanium ethanolate in the ethylene glycol Pb with embodiment 1
2+, Zr
2+And Ti
2+By corresponding mixed, make Pb respectively
2+Concentration is 0.55mol/L, but three kinds of different precursor sols of component.
At first on the silicon chip substrate that with Pt is bottom electrode, be coated with Pb (Zr
0.96TiO
0.04) O
3Colloidal sol is coated with Pb (Zr again after 10 minutes
0.94TiO
0.06) O
3Colloidal sol; After 10 minutes, coating Pb (Zr
0.92TiO
0.08) O
3Colloidal sol.Different components must be coated with successively, and has certain time interval when the coating different components, mixes mutually to avoid different components.
At 330～350 ℃ of following pre-treatment 5min, under 650～670 ℃ of temperature, make anneal 5min again, utilize thermodiffusion to form the material of forming distribution gradient.
Be upper current conducting cap to steam Pt again, in 80～110 ℃ temperature range, the strength of electric field polarization with 2000～4000V/mm obtains spontaneous polarization and is orientated along direction of polarization, can be by the ferroelectric membranc of thermoinducible reversible ferroelectric (high temperature)-ferroelectric (low temperature) phase transformation, thickness is 600～1000nm.In 30～40 ℃ temperature range, ferroelectric (high temperature)-ferroelectric (low temperature) phase transformation all can take place in this film, thereby makes this material have more extensive applicability.
Claims (7)
1. the lead zirconate-titanate ferroelectric of a rich zirconium (high temperature)-ferroelectric (low temperature) phase change film material is characterized in that chemical constitution is: Pb (Zr
1-XTi
X) O
3, X=0.03～0.099, thickness is 600～1000nm.
2. the lead zirconate-titanate ferroelectric of the described rich zirconium of claim 1 (high temperature)-ferroelectric (low temperature) phase change film material is characterized in that its substrate is a silicon chip, and bottom electrode is Pt.
3. the preparation method of the lead zirconate-titanate ferroelectric (high temperature) of claim 1 or 2 described rich zirconiums-ferroelectric (low temperature) phase change film material is characterized in that, comprises the steps:
1) lead salt, zirconates and titanium salt are dissolved in ethylene glycol or the ethylene glycol monomethyl ether, make the Pb-based lanthanumdoped zirconate titanates precursor sol; Wherein the mol ratio of lead element, zr element and titanium elements is 1: (1-X): X, X=0.03～0.099; The volumetric molar concentration of lead element is 0.5～0.6mol/L;
Described lead salt is selected from plumbic acetate or lead chloride, and zirconates is selected from zirconium-n-butylate or zirconium-n-propylate, and titanium salt is selected from titanium ethanolate or titanium isopropylate;
2) step 1) gained Pb-based lanthanumdoped zirconate titanates precursor sol is coated on on the substrate that has bottom electrode, forms film; At 330～360 ℃ of following pre-treatment 3～12min, again through 630～670 ℃ of anneal 3～10min;
3) in 80～110 ℃ temperature range, with the polarization of the strength of electric field of 2000～5000V/mm to step 2) the resulting film 5～10min that polarizes.
4. the preparation method of the lead zirconate-titanate ferroelectric of the described rich zirconium of claim 3 (high temperature)-ferroelectric (low temperature) phase change film material is characterized in that, comprises the steps:
1) lead salt, zirconates and titanium salt are dissolved in ethylene glycol or the ethylene glycol monomethyl ether, make the Pb-based lanthanumdoped zirconate titanates precursor sol; Wherein the mol ratio of lead element, zr element and titanium elements is 1: (1-X): X, X=0.03～0.099; The volumetric molar concentration of lead element is 0.5～0.6mol/L;
Described lead salt is selected from plumbic acetate or lead chloride, and zirconates is selected from zirconium-n-butylate or zirconium-n-propylate, and titanium salt is selected from titanium ethanolate or titanium isopropylate;
2) Pb-based lanthanumdoped zirconate titanates precursor sol that step 1) gained zr element molar content is different according to from the zr element low levels to high-content, perhaps from the zr element high-content to low levels, separate application is having on the substrate of bottom electrode successively, form film, the timed interval of each coating is 5min～20min; 330～360 ℃ of following pre-treatment 3～12 minutes, again through 630～670 ℃ of anneal 3～10min;
3) in 80～110 ℃ temperature range, with the strength of electric field of 2000～5000V/mm to step 2) resulting film polarized 5～10 minutes.
5. the preparation method of the lead zirconate-titanate ferroelectric (high temperature) of claim 3 or 4 described rich zirconiums-ferroelectric (low temperature) phase change film material is characterized in that the volumetric molar concentration of lead element is 0.55～0.58mol/L in the precursor sol of Pb-based lanthanumdoped zirconate titanates described in the step 1).
6. the preparation method of the lead zirconate-titanate ferroelectric (high temperature) of claim 3 or 4 described rich zirconiums-ferroelectric (low temperature) phase change film material is characterized in that step 2) described in substrate be silicon substrate, bottom electrode is Pt.
7. the preparation method of the lead zirconate-titanate ferroelectric (high temperature) of claim 3 or 4 described rich zirconiums-ferroelectric (low temperature) phase change film material is characterized in that, Pt is very steamed in used powering on when polarizing in the step 3).
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| CN103693959A (en) * | 2013-12-10 | 2014-04-02 | 清华大学 | A (Pb, bi) (Ni, zr, ti) O3solid solution ferroelectric film with both high piezoelectric constant and high energy storage density and its preparation method |
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| CN110359058A (en) * | 2019-07-22 | 2019-10-22 | 肇庆市华师大光电产业研究院 | A kind of preparation method of the bloodstone nanometer stick array light anode of lead zirconate titanate modification |
| CN111740005A (en) * | 2020-06-17 | 2020-10-02 | 中国科学院上海微***与信息技术研究所 | High-temperature polarization method for piezoelectric film |
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| CN103693959A (en) * | 2013-12-10 | 2014-04-02 | 清华大学 | A (Pb, bi) (Ni, zr, ti) O3solid solution ferroelectric film with both high piezoelectric constant and high energy storage density and its preparation method |
| CN107326443A (en) * | 2017-06-05 | 2017-11-07 | 西安交通大学 | A kind of method of nonlinear optical material relaxor ferroelectric monocrystal poling |
| CN107326443B (en) * | 2017-06-05 | 2019-10-11 | 西安交通大学 | A kind of method of nonlinear optical material relaxor ferroelectric monocrystal poling |
| CN109036878A (en) * | 2018-06-06 | 2018-12-18 | 华南师范大学 | A kind of ferroelectric thin-flim materials device and preparation method thereof |
| CN109036878B (en) * | 2018-06-06 | 2020-04-07 | 华南师范大学 | Ferroelectric film material device and preparation method thereof |
| CN110359058A (en) * | 2019-07-22 | 2019-10-22 | 肇庆市华师大光电产业研究院 | A kind of preparation method of the bloodstone nanometer stick array light anode of lead zirconate titanate modification |
| CN110359058B (en) * | 2019-07-22 | 2021-08-03 | 肇庆市华师大光电产业研究院 | Preparation method of lead zirconate titanate modified hematite nanorod array photoanode |
| CN111740005A (en) * | 2020-06-17 | 2020-10-02 | 中国科学院上海微***与信息技术研究所 | High-temperature polarization method for piezoelectric film |
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Application publication date: 20100818 |