CN112397643B - Thin film material with high electrocaloric effect near room temperature and preparation method thereof - Google Patents
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Abstract
The invention relates to a thin film material with high electrocaloric effect near room temperature and a preparation method thereof, wherein the chemical general formula of the thin film material is (1-x) Ba (Ti) 0.8 Zr 0.2 )O 3 ‑x(Ba 0.7 Ca 0.3 )TiO 3 ySn, x ranges from 0.1 to 0.7, and y ranges from 0 to 0.06. The invention provides (1-x) Ba (Ti) 0.8 Zr 0.2 )O 3 ‑x(Ba 0.7 Ca 0.3 )TiO 3 the-ySn film material coexists in multiple phases near room temperature, and the Curie temperature is reduced along with the introduction of Sn, so that (1-x) Ba (Ti) 0.8 Zr 0.2 )O 3 ‑x(Ba 0.7 Ca 0.3 )TiO 3 the-ySn film material can obtain large temperature change of the electric card near room temperature, is beneficial to widening a working temperature zone, and has wide application prospect in the field of electric card refrigeration devices.
Description
Technical Field
The invention belongs to the technical field of ceramic compositions taking barium titanate as a base material, and particularly relates to a thin film material with high electrocaloric effect near room temperature and a preparation method thereof.
Background
With the rapid development of the microelectronic industry, in order to overcome the safety problems and limitations caused by thermal failure, the design and development of high-efficiency micro-refrigeration devices are concerned. The electrocaloric effect refers to that under the adiabatic condition, when an electric field is applied or removed to a ferroelectric material, dipoles inside the material change between a disordered state and an ordered state, so that the temperature or entropy of the material changes. The novel refrigerating device is designed based on the electrocaloric effect, has high energy efficiency, low cost, easy miniaturization, simple equipment structure and environmental friendliness, and is an ideal novel refrigerating mode.
In order to make the electric card refrigeration device meet the requirements in practical application, the electric card material is required to be capable of achieving large electric card temperature change near room temperature and simultaneously have a wider working temperature zone. At present, lead-based materials such as PZT (lead zirconate titanate piezoelectric ceramic) and the like, such as PZT ferroelectric thin film materials, which can obtain large electrical card temperature change, have been proved to be capable of obtaining a large electrical card effect of 12K around the curie temperature. However, the lead-based material cannot meet the practical application of the electrocaloric effect due to the fact that the curie temperature is far higher than the room temperature and the harm of Pb to the environment.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a ferroelectric film with an electric card temperature higher than 12K near room temperature and a preparation method thereof, so that the ferroelectric film can better meet the requirements of refrigeration devices in practical application.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
providing a thin film material with high electrocaloric effect at the room temperature, wherein the chemical formula of the thin film material is (1-x) Ba (Ti) 0.8 Zr 0.2 )O 3 -x(Ba 0.7 Ca 0.3 )TiO 3 ySn, x ranges from 0.1 to 0.7, and y ranges from 0 to 0.06.
Preferably, the chemical formula of the thin film material is (1-x) Ba (Ti) 0.8 Zr 0.2 )O 3 -x(Ba 0.7 Ca 0.3 )TiO 3 ySn, x is 0.32 and y is 0.02.
The invention also comprises a preparation method of the film material with high electrocaloric effect near room temperature, which comprises the following steps:
1) Weighing the raw materials according to a stoichiometric ratio for later use;
2) Adding barium acetate and calcium acetate into acetic acid, adding tin acetate according to needs, stirring at 40-80 ℃ until the tin acetate is completely dissolved to obtain a solution A, dissolving zirconium n-propoxide in ethylene glycol monomethyl ether, stirring at room temperature until the zirconium n-propoxide is completely dissolved, then mixing the obtained zirconium n-propoxide solution with the solution A, stirring at 40-50 ℃ for 0.5-1 hour, cooling to room temperature to obtain a solution B, adding tetrabutyl titanate into the solution B, uniformly mixing, adjusting the concentration of the solution by using ethylene glycol monomethyl ether, stirring at room temperature for 12-24 hours, filtering the solution, and standing for 24 hours to obtain sol;
3) Coating the sol obtained in the step 2) on a clean substrate by using a spin coater, drying and pre-burning the sol to obtain a dried and shaped film material on the surface of the substrate, repeatedly coating the sol on the surface of the film material according to needs and carrying out preheating treatment, then placing the substrate with the film coated on the surface in a tube furnace for annealing treatment, cooling the substrate to room temperature, taking the substrate out, and obtaining the film material with high electrocaloric effect near the room temperature on the surface of the substrate.
According to the scheme, the volume ratio of the acetic acid to the sol in the step 2) is 1:3.5-4.5.
According to the scheme, (1-x) Ba (Ti) in the sol obtained in the step 2) 0.8 Zr 0.2 )O 3 -x(Ba 0.7 Ca 0.3 )TiO 3 The concentration of-ySn is 0.2-0.3 mol/L (theoretical calculation value), and the pH value of the sol is 3-4.
According to the scheme, the substrate in the step 3) is selected from Pt/Ti/SiO 2 One of a/Si substrate, a Pt/Si substrate, and a (100) oriented single crystal silicon wafer was washed with acetone, alcohol, and deionized water in this order before use.
According to the scheme, the rotating speed of the spin coater in the step 3) for coating the sol is 4300 to 5200r/min.
According to the scheme, the drying process conditions in the step 3) are as follows: heating at 110-120 deg.C for 10min; the pre-sintering treatment process conditions are as follows: heating at 400-450 deg.c for 10-30 min.
According to the scheme, the annealing treatment process conditions in the step 3) are as follows: heating at 700-850 deg.c for 10-15 min in oxygen atmosphere.
Preferably, the thickness of the thin film material with high electrocaloric effect in the step 3) is 200-400 nm.
The invention also comprises the application of the thin film material with high electric card effect near room temperature in the field of electric card refrigeration devices.
The applicant found that (1-x) Ba (Ti) at x =0.32 0.8 Zr 0.2 )O 3 -x(Ba 0.7 Ca 0.3 )TiO 3 The material has three-phase transformation points, at the moment, a trigonal (R) phase, a tetragonal (T) phase and a paraelectric (C) phase coexist, the energy barrier of the system is reduced, and under the condition, more excellent electrical properties can be obtained, and the introduction of the Sn element can increase the relaxivity of the material, reduce the Curie temperature of the material, and enable the orthogonal O phase existing below room temperature to move to a normal temperature region, thereby being beneficial to the realization of multiphase coexistence. When the material is in a multi-phase coexistence state, the energy barriers among multiple polarization phases are greatly reduced, polarization steering is facilitated, and the material has larger entropy change under a changing electric field, so that (1-x) Ba (Ti) is enabled by adjusting x =0.32 and Sn doping 0.8 Zr 0.2 )O 3 -x(Ba 0.7 Ca 0.3 )TiO 3 The material realizes the coexistence of three ferroelectric phases of a three-party (R) phase, a four-party (T) phase and an orthogonal (O) phase, thereby obtaining larger temperature change of the electric card, reducing the Curie temperature to be close to the room temperature, and being beneficial to the application of the material on the electric card to meet the requirement of practical application.
The invention has the beneficial effects that: 1. the invention provides (1-x) Ba (Ti) 0.8 Zr 0.2 )O 3 -x(Ba 0.7 Ca 0.3 )TiO 3 the-ySn film material coexists in multiple phases near room temperature, and the Curie temperature is reduced along with the introduction of Sn, so that (1-x) Ba (Ti) 0.8 Zr 0.2 )O 3 -x(Ba 0.7 Ca 0.3 )TiO 3 the-ySn film material can obtain large temperature change of the electric card near room temperature, is beneficial to widening a working temperature zone, and has wide application prospect in the field of electric card refrigeration devices. 2. The invention adopts sol-gel method to prepare film material and processThe method is simple and low in cost, can accurately control the composition proportion of the material, and prepares a uniform and compact (1-x) Ba (Ti0.8Zr0.2) O3-x (Ba0.7Ca0.3) TiO3-ySn thin film by using proper process conditions, so that the thin film can bear a higher external electric field, and higher electrocaloric temperature change delta T is obtained.
Drawings
FIG. 1 shows that x =0.32, y =0, 0.01, 0.02, 0.04, 0.06, (1-x) Ba (Ti) prepared in example 1 and examples 3-6 of the present invention 0.8 Zr 0.2 )O 3 -x(Ba 0.7 Ca 0.3 )TiO 3 -XRD pattern of ySn film;
FIG. 2 shows (1-x) Ba (Ti) when x =0.32, y =0, prepared in example 1 0.8 Zr 0.2 )O 3 -x(Ba 0.7 Ca 0.3 )TiO 3 -electrical caliper versus temperature plot for ySn films at different electric field strengths;
FIG. 3 shows (1-x) Ba (Ti) when x =0.32, y =0.02 obtained in example 4 0.8 Zr 0.2 )O 3 -x(Ba 0.7 Ca 0.3 )TiO 3 Graph of electrical caliper change versus temperature for the-ySn film at different electric field strengths.
Detailed Description
In order to make the technical solutions of the present invention better understood, the present invention is further described in detail below with reference to the accompanying drawings.
Tetrabutyl titanate used in the embodiment of the invention is chemically pure, and barium acetate, calcium acetate, zirconium n-propoxide, tin acetate, acetic acid and ethylene glycol monomethyl ether are analytically pure.
Examples 1 to 2
(1-x) Ba (Ti) 0.8 Zr 0.2 )O 3 -x(Ba 0.7 Ca 0.3 )TiO 3 The film, x takes the value of 0.32, 0.5 separately, its preparation method includes the following steps:
1) Barium acetate, calcium acetate, zirconium n-propoxide and tetrabutyl titanate are used as raw materials, and the Ba (Ti) is 1-x when the x value is 0.32 and 0.5 0.8 Zr 0.2 )O 3 -x(Ba 0.7 Ca 0.3 )TiO 3 Calculating and weighing corresponding raw materials according to the stoichiometric ratio;
2) Dissolving weighed barium acetate and calcium acetate in acetic acid, stirring at 50-60 ℃ until the barium acetate and the calcium acetate are completely dissolved to obtain a solution A, dissolving zirconium n-propoxide in ethylene glycol monomethyl ether, stirring at room temperature until the zirconium n-propoxide is completely dissolved, then mixing the obtained zirconium n-propoxide solution with the solution A, stirring at 50 ℃ for 1 hour, cooling to room temperature to obtain a solution B, adding tetrabutyl titanate into the solution B, uniformly mixing, and diluting with ethylene glycol monomethyl ether to obtain (1-x) Ba (Ti) 0.8 Zr 0.2 )O 3 -x(Ba 0.7 Ca 0.3 )TiO 3 The theoretical calculation concentration is 0.2mol/L, stirring is carried out for 12h at room temperature, the solution is filtered and kept stand for 24h to obtain sol, the pH value of the sol is 3-4, and the volume ratio of the acetic acid to the sol is 1:4;
3) Using a spin coater to wash the sol obtained in the step 1) in Pt/Ti/SiO cleaned by acetone, alcohol and deionized water in advance 2 Spreading a silicon (Si) substrate, setting the rotating speed of a spin coater to 4800r/min, and carrying out spin coating for 30s;
4) Preserving the heat of the wet film obtained in the step 3) at 120 ℃ for 10min, taking out, preserving the heat of the dried film at 400 ℃ for 30min, cooling to room temperature, and taking out;
5) Repeating the step 3) and the step 4) for 6 times, annealing the obtained substrate coated with the film in a tubular furnace at 800 ℃ for 15min, cooling to room temperature, and taking out to obtain the (1-x) Ba (Ti) 0.8 Zr 0.2 )O 3 -x(Ba 0.7 Ca 0.3 )TiO 3 Thin film (film thickness 300 nm).
(1-x) Ba (Ti) prepared in example 1-2 0.8 Zr 0.2 )O 3 -x(Ba 0.7 Ca 0.3 )TiO 3 And (3) testing a variable-temperature hysteresis loop of the film, and calculating by a Maxwell equation derivative to obtain the electrocaloric temperature change of the film, wherein the temperature range is 25-100 ℃.
In fig. 1, y =0 is 0.68Ba (Ti) prepared in this example 0.8 Zr 0.2 )O 3 -0.32(Ba 0.7 Ca 0.3 )TiO 3 The XRD pattern of the film can be known, and the film material has a perovskite structure and no second phase at the ratio.The diffraction peak was broadened and cleaved at 2 θ =45 °, indicating that the three-dimensional R phase and the four-dimensional T phase coexisted at room temperature.
FIG. 2 shows 0.68Ba (Ti) 0.8 Zr 0.2 )O 3 -0.32(Ba 0.7 Ca 0.3 )TiO 3 The graph shows that the magnitude of the external electric field influences the electric clamping temperature change value of the film material, the electric clamping temperature change of the material is increased along with the increase of the external electric field, the electric clamping temperature change delta T of the film material is also changed along with the temperature of the material, and the maximum electric clamping temperature change of 5.4K is obtained near 348K under the condition that the strength of the external electric field is 400 kV/cm.
(1-x) Ba (Ti) prepared under the condition that x is respectively 0.32 and 0.5 0.8 Zr 0.2 )O 3 -x(Ba 0.7 Ca 0.3 )TiO 3 The temperature T at which the film achieved the maximum temperature change and the maximum electrical calorie temperature change Δ T results are shown in Table 1.
TABLE 1
| x | T(K) | ΔT(K) |
| 0.32 | 348 | 5.4 |
| 0.5 | 338 | 4.6 |
Table 1 shows (1-x) Ba (T) prepared according to the preparation method provided by the inventioni 0.8 Zr 0.2 )O 3 -x(Ba 0.7 Ca 0.3 )TiO 3 The film obtained maximum electrocaloric temperature change temperature and maximum electrocaloric temperature change at x =0.32 and 0.5, where x =0.32 obtained maximum electrocaloric temperature change of 5.4K at 348K (applied electric field E =400 kV/cm); at x =0.5, a maximum electrical caloric change of 4.6K was obtained at 338K (applied electric field E =400 kV/cm). The temperatures at which the maximum electrical calorie temperature change is obtained at this ratio are all higher than room temperature, and the electrical calorie temperature obtained at x =0.32 is higher than x =0.5.
Examples 3 to 6
0.68Ba (Ti) 0.8 Zr 0.2 )O 3 -0.32(Ba 0.7 Ca 0.3 )TiO 3 ySn film, y is 0.01, 0.02, 0.04, 0.06, the preparation method comprises the following steps:
1) Barium acetate, calcium acetate, zirconium n-propoxide, tin acetate, and tetrabutyl titanate as raw materials, and according to the y value of 0.01, 0.02, 0.04, and 0.06, 0.68Ba (Ti) 0.8 Zr 0.2 )O 3 -0.32(Ba 0.7 Ca 0.3 )TiO 3 -ySn, calculating and weighing the corresponding raw materials;
2) Dissolving weighed tin acetate in acetic acid, stirring for 30-60min at 70-80 ℃, then adding barium acetate and calcium acetate, stirring to be clear at 40-50 ℃ to obtain a solution A, dissolving zirconium n-propoxide in ethylene glycol monomethyl ether, stirring at room temperature to be completely dissolved, then mixing the obtained zirconium n-propoxide solution with the solution A, stirring at 50 ℃ for 1 hour, cooling to room temperature to obtain a solution B, adding tetrabutyl titanate into the solution B, uniformly mixing, and diluting with ethylene glycol monomethyl ether to 0.68Ba (Ti) and 0.8 Zr 0.2 )O 3 -0.32(Ba 0.7 Ca 0.3 )TiO 3 ySn with a theoretical calculated concentration of 0.2mol/L, stirring at room temperature for 12h, filtering the solution and standing for 24h to obtain the desired sol, the sol having a pH of 3 to 4, the volume ratio of acetic acid to sol being 1:4;
3) Using a spin coater to wash the sol obtained in the step 1) in Pt/Ti/SiO cleaned by acetone, alcohol and deionized water in advance 2 Spreading a silicon (Si) substrate, setting the rotating speed of a spin coater to 4800r/min, and carrying out spin coating for 30s;
4) Directly taking out the wet film obtained in the step 3) after heat preservation at 120 ℃ for 10min, then preserving the heat of the dried film at 400 ℃ for 30min, cooling to room temperature and taking out;
5) Repeating the step 3) and the step 4) for 6 times, annealing the obtained substrate coated with the film in a tubular furnace, filling oxygen in the tubular furnace, keeping the annealing temperature at 800 ℃, keeping the temperature for 15min, cooling to room temperature, and taking out to obtain the 0.68Ba (Ti) 0.8 Zr 0.2 )O 3 -0.32(Ba 0.7 Ca 0.3 )TiO 3 ySn film (film thickness about 300 nm).
0.68Ba (Ti) prepared for examples 3-6 0.8 Zr 0.2 )O 3 -0.32(Ba 0.7 Ca 0.3 )TiO 3 And testing the ySn film by a variable-temperature hysteresis loop, and calculating by a Maxwell equation derivative to obtain the electrical clamping temperature change of the film.
In fig. 1, when y =0, 0.01, 0.02, 0.04, 0.06, 0.68Ba (Ti) 0.8 Zr 0.2 )O 3 -0.32(Ba 0.7 Ca 0.3 )TiO 3 XRD pattern of ySn film (labeled 0,1%,2%,4%,6%, respectively in the figure). As is clear from fig. 1, when y =0.01, 0.02, 0.04, 0.06, the diffraction peaks at 2 θ =45 ° were broadened and cleaved, indicating that the three-dimensional R phase and the four-dimensional T phase coexisted at room temperature. And y =0.02, the diffraction peak appeared sub-peaked around 2 θ =66.5 °, demonstrating the presence of the orthogonal O phase, i.e., 0.68Ba (Ti) prepared at room temperature 0.8 Zr 0.2 )O 3 -0.32(Ba 0.7 Ca 0.3 )TiO 3 The-0.02 Sn thin film has three ferroelectric phases of a trigonal phase, a tetragonal phase and an orthorhombic phase, so that the electric calorie variation is increased. Meanwhile, the temperature of the obtained maximum electric card temperature change is close to the room temperature, and the standard of practical application is better met.
FIG. 3 shows 0.68Ba (Ti) 0.8 Zr 0.2 )O 3 -0.32(Ba 0.7 Ca 0.3 )TiO 3 -0.02Sn film electrical card temperature variation as a function of temperature at different electric field strengths. As can be seen from FIG. 3, the electrical calorie variation Δ T of the thin film material varies with the temperature of the material when electricity is appliedAt a field E =400kV/cm, a maximum electrical caloric change of 23.4K is obtained around 328K. As compared with fig. 2, it can be found that the electric calorie temperature change peak increases and moves toward a low temperature region, closer to room temperature.
Examples 3-6 prepared 0.68Ba (Ti) with y values of 0.01, 0.02, 0.04, 0.06, respectively 0.8 Zr 0.2 )O 3 -0.32(Ba 0.7 Ca 0.3 )TiO 3 The results of temperature T and maximum electrical calorie temperature change Δ T for the-ySn film obtained are shown in Table 2.
TABLE 2
| y | T(K) | ΔT(K) |
| 0.01 | 338 | 14.2 |
| 0.02 | 328 | 23.4 |
| 0.04 | 313 | 9.7 |
| 0.06 | 308 | 7.5 |
Table 2 shows 0.68Ba (Ti) prepared in examples 3-6 0.8 Zr 0.2 )O 3 -0.32(Ba 0.7 Ca 0.3 )TiO 3 The temperature and the maximum electrical calorie variation of the-ySn film at y =0.01, 0.02, 0.04, 0.06, both below 338K. When the doping content of Sn is 2%, the maximum electrical card temperature change of 23.4K (external electric field E =400 kV/cm) is obtained at 328K, and the maximum electrical card temperature change value is obviously improved compared with that obtained in example 1.
Claims (9)
1. The thin film material with high electrocaloric effect at the room temperature is characterized in that the chemical general formula of the thin film material is (1-x) Ba (Ti) 0.8 Zr 0.2 )O 3 -x(Ba 0.7 Ca 0.3 )TiO 3 ySn, x is 0.32 and y is 0.02.
2. The preparation method of the thin film material with high electrocaloric effect at the temperature around room temperature, which is characterized by comprising the following steps:
1) Weighing the raw materials according to a stoichiometric ratio for later use;
2) Adding barium acetate and calcium acetate into acetic acid, adding tin acetate according to needs, stirring at 40-80 ℃ until the tin acetate is completely dissolved to obtain a solution A, dissolving zirconium n-propoxide in ethylene glycol monomethyl ether, stirring at room temperature until the zirconium n-propoxide is completely dissolved, then mixing the obtained zirconium n-propoxide solution with the solution A, stirring at 40-50 ℃ for 0.5-1 hour, cooling to room temperature to obtain a solution B, adding tetrabutyl titanate into the solution B, uniformly mixing, adjusting the concentration of the solution by using ethylene glycol monomethyl ether, stirring at room temperature for 12-24 hours, filtering the solution, and standing for 24 hours to obtain sol;
3) Coating the sol obtained in the step 2) on a clean substrate by using a spin coater, drying and pre-sintering to obtain a dried and shaped film material on the surface of the substrate, repeatedly coating the sol on the surface of the film material according to needs and carrying out pre-heating treatment, then placing the substrate with the film coated on the surface in a tube furnace for annealing treatment, cooling to room temperature, taking out, and obtaining the film material with high electric card effect near the room temperature on the surface of the substrate.
3. The method for preparing a thin film material with high electrocaloric effect at the temperature around room temperature as claimed in claim 2, wherein the volume ratio of the acetic acid to the sol in the step 2) is 1:3.5-4.5.
4. The method for preparing a thin film material with high electrocaloric effect at around room temperature as claimed in claim 2, wherein (1-x) Ba (Ti) is added in the sol of step 2) 0.8 Zr 0.2 )O 3 -x(Ba 0.7 Ca 0.3 )TiO 3 The concentration of-ySn is 0.2-0.3 mol/L, and the pH value of the sol is 3-4.
5. The method for preparing a thin film material with high electrocaloric effect at around room temperature as claimed in claim 2, wherein the substrate in step 3) is selected from Pt/Ti/SiO 2 One of a/Si substrate, a Pt/Si substrate, and a (100) oriented single crystal silicon wafer was washed with acetone, alcohol, and deionized water in this order before use.
6. The method for preparing a thin film material with a high electrocaloric effect at about room temperature according to claim 2, wherein the sol is coated by the spin coater in the step 3) at a rotation speed of 4300 to 5200r/min.
7. The method for preparing a thin film material with high electrocaloric effect at about room temperature as claimed in claim 2, wherein the drying process conditions in step 3) are as follows: heating at 110-120 deg.C for 10min; the pre-sintering treatment process conditions are as follows: heating at 400-450 deg.c for 10-30 min; the annealing treatment process conditions are as follows: heating at 700-850 deg.c for 10-15 min in oxygen atmosphere.
8. The method for preparing a thin film material with high electrocaloric effect at around room temperature as claimed in claim 2, wherein the thickness of the thin film material with high electrocaloric effect at around room temperature in the step 3) is 200-400 nm.
9. Use of the thin film material with high electrocaloric effect at around room temperature according to claim 1 in electrocaloric refrigeration devices.
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