CN108727020B - Lead zirconate titanate film and preparation method thereof - Google Patents

Lead zirconate titanate film and preparation method thereof Download PDF

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CN108727020B
CN108727020B CN201710277126.7A CN201710277126A CN108727020B CN 108727020 B CN108727020 B CN 108727020B CN 201710277126 A CN201710277126 A CN 201710277126A CN 108727020 B CN108727020 B CN 108727020B
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zirconate titanate
lead zirconate
lead
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邹赫麟
李奇
王兴
韩梅
周毅
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Dalian University of Technology
Zhuhai Sailner 3D Technology Co Ltd
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Zhuhai Sailner 3D Technology Co Ltd
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Abstract

The invention provides a lead zirconate titanate film and a preparation method thereof. The method of the invention comprises the following steps: 1) dissolving tetrabutyl titanate in acetylacetone, adding zirconium nitrate, lead acetate, ethylene glycol monomethyl ether and formamide, and controlling the molar ratio of the lead acetate to the zirconium nitrate to be (1.1-1.3): y, preparation of Pb (Zr) of the formulayTi1‑y)O3The lead zirconate titanate buffer layer precursor solution; 2) depositing a lead zirconate titanate buffer layer precursor solution on a substrate, and carrying out heat treatment to obtain a lead zirconate titanate buffer layer; 3) dissolving tetrabutyl titanate in acetylacetone, adding zirconium nitrate, lead acetate, ethylene glycol monomethyl ether and formamide, and controlling the molar ratio of the lead acetate to the zirconium nitrate to be (1.15-1.25): y, preparation of Pb (Zr) of the formulayTi1‑y)O3Lead zirconate titanate precursor solution; 4) and depositing the lead zirconate titanate precursor solution on the lead zirconate titanate buffer layer, and performing heat treatment to obtain the lead zirconate titanate film. The method of the invention can prepare the lead zirconate titanate film with high dielectric constant and small dielectric loss.

Description

Lead zirconate titanate film and preparation method thereof
Technical Field
The invention relates to a piezoelectric film, in particular to a lead zirconate titanate film and a preparation method thereof.
Background
Lead zirconate titanate (abbreviation)PZT) of the formula Pb (Zr)yTi1-y)O3Is ABO3The perovskite phase compound has good dielectric, ferroelectric and piezoelectric properties when the chemical composition is near the morphotropic phase boundary, and is widely applied to random access memory devices and micro-electromechanical systems at present. The existing methods for preparing PZT piezoelectric films include laser pulse deposition, magnetron sputtering, metal organic chemical vapor deposition, chemical solution deposition, sol-gel method, etc.; among them, the sol-gel method is widely used due to the advantages of short preparation period, stable control of chemical components, compact structure of the prepared film, and the like.
In addition, in order to prepare a lead zirconate titanate thin film having more excellent dielectric properties, a method of doping modification or sputtering a seed layer or the like is generally used. The doping modification is to achieve the purpose of changing the performance of the PZT material by adding metal elements except Pb, Zr and Ti elements into the PZT material, and the doping modification modes comprise hard doping, equivalent doping, soft doping, composite doping and the like; the sputtered seed layer is usually formed by pre-sputtering a layer of a material that is lattice matched to the PZT thin film on the substrate as a seed layer, and the seed layer material may be, for example, SrRuO3、LaNiO3And the like. Although the method can improve the dielectric property of the lead zirconate titanate film to a certain extent, the method has the defects of high price, long preparation period and the like, and is not beneficial to the practical production and application of the lead zirconate titanate film.
In recent years, the improvement of dielectric and piezoelectric properties of lead zirconate titanate thin films by preparing buffer layers by a sol-gel method is one of the hot research focuses of lead zirconate titanate materials. For example, chinese patent publication No. CN 1513809 a discloses a method for preparing a high-performance lead zirconate titanate thin film, which comprises preparing a precursor solution by a sol-gel method, depositing the prepared precursor solution on a substrate with a PZT crystal seed layer by a sol-electro-spray method, and performing a heat treatment to form the lead zirconate titanate thin film. However, the zirconium source used in this method is zirconium propoxide, which is easily hydrolyzed in the atmospheric environment and thus has relatively high environmental requirements; in addition, the method for preparing the lead zirconate titanate film by using a sol-electric fog method has the defects of complex process operation, long preparation period, high manufacturing cost and the like; in addition, the relative dielectric constant of the lead zirconate titanate film prepared by the method is only 960, and the dielectric property of the film is poor.
Disclosure of Invention
The invention provides a lead zirconate titanate thin film and a preparation method thereof, and the method can prepare the lead zirconate titanate thin film with high dielectric constant and small dielectric loss.
The invention provides a preparation method of a lead zirconate titanate film, which comprises the following steps in sequence:
1) dissolving tetrabutyl titanate in acetylacetone, adding zirconium nitrate, lead acetate, ethylene glycol monomethyl ether and formamide, and controlling the molar ratio of the lead acetate to the zirconium nitrate to be (1.1-1.3): y, preparation of Pb (Zr) of the formulayTi1-y)O3The lead zirconate titanate buffer layer precursor solution of (1), wherein y is 0.52 to 0.53;
2) depositing the lead zirconate titanate buffer layer precursor solution on a substrate, and carrying out heat treatment to obtain a lead zirconate titanate buffer layer;
3) dissolving tetrabutyl titanate in acetylacetone, adding zirconium nitrate, lead acetate, ethylene glycol monomethyl ether and formamide, and controlling the molar ratio of the lead acetate to the zirconium nitrate to be (1.15-1.25): y, preparation of Pb (Zr) of the formulayTi1-y)O3Wherein y is 0.52 to 0.53;
4) and depositing the lead zirconate titanate precursor solution on the lead zirconate titanate buffer layer, and performing heat treatment to obtain the lead zirconate titanate film.
According to the method, lead acetate, zirconium nitrate and tetrabutyl titanate are used as raw materials, ethylene glycol monomethyl ether is used as a solvent, acetylacetone and formamide are used as stabilizers, a sol-gel method is used for preparing the lead zirconate titanate buffer layer, and the lead zirconate titanate film is prepared on the lead zirconate titanate buffer layer by using the sol-gel method. Wherein, acetylacetone and formamide are used as stabilizing agents, and other components are added after tetrabutyl titanate is dissolved in acetylacetone, which is beneficial to obtaining a stable precursor solution without precipitation; zirconium nitrate is used as a zirconium source, so that the operation process of the precursor solution can be simplified, and the manufacturing cost can be reduced; in particular, by dissolving tetrabutyl titanate in acetylacetone and controlling the molar ratio of lead acetate to zirconium nitrate within the above-specified range, a compact perovskite-structured lead zirconate titanate thin film can be advantageously obtained, and the lead zirconate titanate thin film has excellent dielectric properties.
Specifically, acetylacetone is mainly used for complexing with tetrabutyl titanate to form a titanium metal complex which is not easy to hydrolyze and condense, so that the solution is stable and no precipitation occurs; formamide is mainly used for keeping the solution stable and preventing the generation of precipitate. Therefore, acetylacetone and formamide are used as stabilizing agents, and other components are added after tetrabutyl titanate is dissolved in acetylacetone, which is beneficial to obtaining a stable precursor solution without precipitation.
Further, in the step 1), when preparing the lead zirconate titanate buffer layer precursor solution, the molar ratio of lead acetate, zirconium nitrate, tetrabutyl titanate, acetylacetone and formamide can be controlled to be (1.1-1.3): y: (1-y): (0.7-1.2): (1.8-2.4). Wherein (1.1-1.3) represents that lead is excessive by 10-30% when the lead zirconate titanate buffer layer precursor solution is prepared, and the excessive lead is used for compensating the volatilization of lead in the heat treatment process of preparing the lead zirconate titanate buffer layer; in particular, the lead excess can also compensate for the lead loss in the heat treatment for preparing the lead zirconate titanate film, thereby being beneficial to improving the dielectric properties of the lead zirconate titanate film.
Further, in the step 3), when preparing the lead zirconate titanate precursor solution, the molar ratio of lead acetate, zirconium nitrate, tetrabutyl titanate, acetylacetone and formamide can be controlled to be (1.15-1.25): y: (1-y): (0.7-1.2): (1.8-2.4). Wherein (1.15-1.25) represents a lead excess of 15-25% in the preparation of the lead zirconate titanate precursor solution, the lead excess being used to compensate for the volatilization of lead in the heat treatment for preparing the lead zirconate titanate film.
In particular, when the lead zirconate titanate buffer layer precursor solution and the lead zirconate titanate precursor solution are prepared, the molar ratio between acetylacetone and formamide is controlled to be (0.7-1.2): (1.8-2.4), which is beneficial to obtaining stable precursor solution, and the solution does not generate precipitate; through subsequent heat treatment, the film is easy to grow along the (100) crystal orientation, so that the lead zirconate titanate film with the (100) preferred orientation is obtained, the film has higher piezoelectric coefficient, and the application on a micro-electro-mechanical system is more advantageous.
Further, an acid-base regulator can be adopted to regulate the pH values of the lead zirconate titanate buffer layer precursor solution and the lead zirconate titanate precursor solution; the pH adjusting agent may be, for example, acetic acid. Particularly, the pH value of the lead zirconate titanate buffer layer precursor solution can be controlled to be 3.5-5.5, and the concentration is controlled to be 0.30-0.48 mol/L; moreover, the pH value of the lead zirconate titanate precursor solution can be controlled to be 3.5-5.5, and the concentration can be controlled to be 0.30-0.48 mol/L. The pH value range can avoid the crystallization of the precursor solution, so that the precursor solution with proper viscosity and good stability is easy to form, and the subsequent deposition and heat treatment are facilitated; in addition, the concentration refers to the total molar concentration of each component in the precursor solution, the concentration range can obtain a film with a single-layer thickness of 45-75 nanometers, the preparation process is good, the practical operation is convenient, and particularly, the film is easy to preferentially orient along (100), so that the (100) crystal orientation degree of the lead zirconate titanate film is improved.
The method for preparing the lead zirconate titanate buffer layer precursor solution and the lead zirconate titanate precursor solution is not strictly limited, and for example, the method may comprise the following steps in sequence:
a) dissolving tetrabutyl titanate in acetylacetone, heating to 40-65 ℃, and keeping the temperature for 50-85 min;
b) sequentially adding zirconium nitrate, lead acetate and ethylene glycol monomethyl ether into the mixed solution, stirring uniformly, heating to 85-120 ℃, and keeping the temperature for 50-85 min;
c) adding formamide into the mixed solution, stirring, cooling to 40-65 deg.C, and maintaining the temperature for 50-85 min;
d) adding acetic acid solution into the mixed solution, and keeping the temperature for 50-85 min.
Preferably, the lead zirconate titanate buffer layer precursor solution and the lead zirconate titanate precursor solution can be prepared under the same conditions, so that the lead zirconate titanate buffer layer and the lead zirconate titanate film have the same molecular structure and good lattice matching, and the dielectric property of the lead zirconate titanate film is favorably improved.
In the present invention, the deposition may be performed using a method conventional in the art, and the deposition method may include, for example: and (3) homogenizing the lead zirconate titanate buffer layer precursor solution or the lead zirconate titanate precursor solution for 10-15 seconds at 800-900 revolutions per minute, and then spinning the film for 20-30 seconds at 2600-3000 revolutions per minute. The above manner enables the lead zirconate titanate buffer layer precursor solution and the lead zirconate titanate precursor solution to uniformly cover the substrate.
The substrate of the invention may be a conventional substrate, such as Pt/Ti/SiO2a/Si substrate; SiO can be formed on a Si substrate by a conventional method such as thermal oxidation2Layer, then sputtering or other conventional methods on SiO2Forming a Ti layer and a Pt layer on the layer to obtain the Pt/Ti/SiO2a/Si substrate.
In a specific embodiment of the present invention, the heat treatment comprises: drying at 120-200 deg.c for 4-8 min; then thermally decomposing at the temperature of 300-450 ℃ for 4-8 minutes; then annealing at 600-650 ℃ for 10-15 minutes. The heat treatment under the above conditions can make the lead zirconate titanate film form a compact perovskite structure, which is beneficial to ensuring the dielectric property of the lead zirconate titanate film.
The target thicknesses of the lead zirconate titanate buffer layer and the lead zirconate titanate film are not strictly limited and can be reasonably selected according to actual needs, and the target thickness of the lead zirconate titanate buffer layer can be about 200 nanometers; the target thickness of the lead zirconate titanate thin film may be on the order of 1 micron. Specifically, before step 3), step 2) may be repeated until a lead zirconate titanate buffer layer having the above-mentioned target thickness is obtained; and, step 4) may be repeated until a lead zirconate titanate thin film having the above-mentioned target thickness is obtained.
The invention also provides a lead zirconate titanate film prepared by any one of the preparation methods.
Furthermore, the lead zirconate titanate film of the invention is of a perovskite structure; (100) the degree of orientation of the crystal orientation is > 82%, and further > 88%; the relative dielectric constant of the lead zirconate titanate film is more than 1438, more than 1548, and even more than 1571; dielectric loss < 0.064.
The implementation of the invention has at least the following advantages:
1. the preparation method of the invention does not need distillation, adopts zirconium nitrate to replace zirconium n-propoxide, and can simplify the operation process; in particular, a compact perovskite structure of the lead zirconate titanate film is ensured through a specific buffer layer process, and the dielectric property of the lead zirconate titanate film is improved.
2. The preparation method of the invention does not need sputtering or other coating equipment, and can shorten the preparation period and reduce the manufacturing cost by adopting a sol-gel method to prepare the lead zirconate titanate buffer layer and the lead zirconate titanate film; in particular, the dielectric property of the lead zirconate titanate film is improved by performing lead compensation during the preparation of the lead zirconate titanate buffer layer.
3. The crystal orientation degree of the lead zirconate titanate film (100) prepared by the invention is more than 80%, the relative dielectric constant can reach 1571, the dielectric loss is only 0.064, and the dielectric property of the film is excellent.
Drawings
FIG. 1 is a graph of the dielectric spectrum of a lead zirconate titanate thin film prepared in example 1;
FIG. 2 is a cross-sectional field emission scanning electron micrograph of the lead zirconate titanate thin film prepared in example 1;
FIG. 3 is an XRD plot of the lead zirconate titanate thin film prepared in example 1;
FIG. 4 is a graph of the dielectric spectrum of the lead zirconate titanate thin film prepared in example 2;
FIG. 5 is a cross-sectional field emission scanning electron micrograph of the lead zirconate titanate thin film prepared in example 2;
FIG. 6 is a graph of the dielectric spectrum of a lead zirconate titanate thin film prepared in example 3;
FIG. 7 is a cross-sectional field emission scanning electron micrograph of the lead zirconate titanate thin film prepared in example 3;
FIG. 8 is a graph showing the dielectric spectrum of a lead zirconate titanate thin film prepared in comparative example 1;
FIG. 9 is a cross-sectional field emission scanning electron micrograph of the lead zirconate titanate thin film prepared in comparative example 1.
FIG. 10 is a graph showing the dielectric spectrum of a lead zirconate titanate thin film prepared in comparative example 2;
FIG. 11 is a cross-sectional field emission scanning electron micrograph of a lead zirconate titanate thin film prepared in comparative example 2.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
This example provides a compound of the formula Pb (Zr)0.52Ti0.48)O3The preparation method of the lead zirconate titanate film comprises the following steps:
s101, preparing a lead zirconate titanate buffer layer precursor solution;
preparing materials according to the lead excess of 10%, firstly dissolving 2.9mL of tetrabutyl titanate in 1.7mL of acetylacetone, heating to 40 ℃, and preserving heat for 50 minutes; then, sequentially adding 4.02 g of zirconium nitrate, 7.54 g of lead acetate and 25mL of ethylene glycol monomethyl ether, stirring uniformly, heating to 85 ℃, and keeping the temperature for 50 minutes; then adding 1.8mL of formamide, stirring uniformly, then cooling to 40 ℃, and preserving heat for 50 minutes; finally, 12mL of 36 mass percent acetic acid solution is added, and the temperature is kept for 50 minutes to obtain Pb (Zr) with the chemical formula of about 3.0mol/L0.52Ti0.48)O3The lead zirconate titanate buffer layer precursor solution; wherein, the molar ratio of lead acetate, zirconium nitrate, tetrabutyl titanate, acetylacetone and formamide is 1.1: 0.52: 0.48: 0.7: 1.8.
s102, depositing and thermally treating a buffer layer;
the lead zirconate titanate buffer layer precursor solution is firstly subjected to glue homogenizing at 800 revolutions per minute for 10 seconds, and then is deposited on Pt/Ti/SiO through glue homogenizing and film throwing at 2600 revolutions per minute for 20 seconds2On a/Si substrate.
And (3) baking the wet film deposited on the substrate at 120 ℃ for 4 minutes, then thermally decomposing the wet film at 300 ℃ for 4 minutes, and finally annealing the wet film at 600 ℃ for 10 minutes to obtain the lead zirconate titanate single-layer buffer layer with the single-layer thickness of about 50 nanometers.
And repeating the step S102 for four times to prepare the lead zirconate titanate buffer layer with the thickness of about 200 nanometers.
S103, preparing a lead zirconate titanate precursor solution;
preparing materials according to the lead excess of 20%, firstly dissolving 2.9mL of tetrabutyl titanate in 1.7mL of acetylacetone, heating to 40 ℃, and preserving heat for 50 minutes; then, sequentially adding 4.02 g of zirconium nitrate, 10.51 g of lead acetate and 25mL of ethylene glycol monomethyl ether, stirring uniformly, heating to 85 ℃, and keeping the temperature for 50 minutes; then adding 1.8mL of formamide, stirring uniformly, then cooling to 40 ℃, and preserving heat for 50 minutes; finally, 12mL of 36 mass percent acetic acid solution is added, and the temperature is kept for 50 minutes to obtain lead zirconate titanate precursor solution with the concentration of about 0.30 mol/L; wherein, the molar ratio of lead acetate, zirconium nitrate, tetrabutyl titanate, acetylacetone and formamide is 1.2: 0.52: 0.48: 0.7: 1.8.
s104, depositing a lead zirconate titanate film and carrying out heat treatment.
And (3) uniformly coating the lead zirconate titanate precursor solution at 800 rpm for 10 seconds, and then uniformly coating and throwing the film at 2600 rpm for 20 seconds to deposit on the lead zirconate titanate buffer layer.
And (3) baking the wet film deposited on the lead zirconate titanate buffer layer at 120 ℃ for 4 minutes, then thermally decomposing the wet film at 300 ℃ for 4 minutes, and finally annealing the wet film at 600 ℃ for 10 minutes to obtain the lead zirconate titanate single-layer film with the single-layer thickness of about 50 nanometers.
Repeating the step S104 twenty times to prepare the lead zirconate titanate film with the thickness of about 1 micron.
The dielectric spectrum curve of the lead zirconate titanate film is shown in figure 1; wherein the dielectric constant of the lead zirconate titanate film is calculated according to the formula (1):
Figure BDA0001277647440000071
formula (A), (B) and1) middle, epsilonrIn terms of relative dielectric constant, C is the capacitance across the lead zirconate titanate film, d is the thickness of the lead zirconate titanate film, ε0A is the electrode area of the lead zirconate titanate film for the vacuum dielectric constant; the relative dielectric constant of the lead zirconate titanate thin film was 1548.50 and the dielectric loss was 0.065 at a frequency of 0.1 kHz.
The cross-sectional field emission scanning electron micrograph of the above lead zirconate titanate thin film is shown in FIG. 2; as is clear from fig. 2, the lead zirconate titanate thin film has a perovskite structure, and the perovskite structure is dense.
The XRD curve of the above lead zirconate titanate film is shown in figure 3; wherein the degree of orientation of the (100) crystal direction can be calculated according to the formula (2):
Figure BDA0001277647440000072
in the formula (2), α100Degree of orientation of (100) crystal orientation, I100、I110、I111The peak intensities of the respective crystal orientations (100), (110), and (111); the degree of orientation of the crystal orientation of the lead zirconate titanate thin film (100) was calculated to be 88.22%.
Example 2
This example provides a compound of the formula Pb (Zr)0.52Ti0.48)O3The preparation method of the lead zirconate titanate film comprises the following steps:
s201, preparing a lead zirconate titanate buffer layer precursor solution;
preparing materials according to the lead excess of 25%, firstly dissolving 6.3mL of tetrabutyl titanate in 3.9mL of acetylacetone, heating to 55 ℃, and preserving heat for 70 minutes; then, sequentially adding 8.69 g of zirconium nitrate, 18.25 g of lead acetate and 37mL of ethylene glycol monomethyl ether, uniformly stirring, heating to 105 ℃, and preserving heat for 70 minutes; then adding 3.4mL of formamide, stirring uniformly, cooling to 55 ℃, and preserving heat for 70 minutes; finally, adding 18mL of 36 mass percent acetic acid solution, and preserving the heat for 70 minutes to obtain lead zirconate titanate buffer layer precursor solution with the concentration of about 0.38 mol/L; wherein, the molar ratio of lead acetate, zirconium nitrate, tetrabutyl titanate, acetylacetone and formamide is 1.25: 0.52: 0.48: 0.99: 2.22.
s202, depositing and thermally treating a buffer layer;
the lead zirconate titanate buffer layer precursor solution is firstly subjected to uniform glue for 12 seconds at 850 revolutions per minute and then is deposited on Pt/Ti/SiO through uniform glue spinning for 25 seconds at 2800 revolutions per minute2On a/Si substrate.
And (3) baking the wet film deposited on the substrate at 160 ℃ for 6 minutes, then pyrolyzing the wet film at 400 ℃ for 6 minutes, and finally annealing the wet film at 620 ℃ for 12 minutes to obtain the lead zirconate titanate single-layer buffer layer with the single-layer thickness of about 60 nanometers.
And repeating the step S202 for four times to prepare the lead zirconate titanate buffer layer with the thickness of about 240 nanometers.
S203, preparing a lead zirconate titanate precursor solution;
proportioning materials according to the lead excess of 20%, firstly dissolving 6.3mL of tetrabutyl titanate in 3.9mL of acetylacetone, heating to 55 ℃, and preserving heat for 70 minutes; then, sequentially adding 8.69 g of zirconium nitrate, 14.61 g of lead acetate and 37mL of ethylene glycol monomethyl ether, uniformly stirring, heating to 105 ℃, and preserving heat for 70 minutes; then adding 3.4mL of formamide, stirring uniformly, cooling to 55 ℃, and preserving heat for 70 minutes; finally, 18mL of 36 mass percent acetic acid solution is added, and the temperature is kept for 70 minutes to obtain lead zirconate titanate precursor solution with the concentration of about 0.38 mol/L; wherein, the molar ratio of lead acetate, zirconium nitrate, tetrabutyl titanate, acetylacetone and formamide is 1.2: 0.52: 0.48: 0.99: 2.22.
and S204, depositing and thermally treating the lead zirconate titanate film.
And (3) uniformly coating the lead zirconate titanate precursor solution at 850 rpm for 12 seconds, and then uniformly coating and throwing the film at 2800 rpm for 25 seconds to deposit the lead zirconate titanate precursor solution on the lead zirconate titanate buffer layer.
And (3) baking the wet film deposited on the lead zirconate titanate buffer layer at 160 ℃ for 6 minutes, then thermally decomposing the wet film at 400 ℃ for 6 minutes, and finally annealing the wet film at 620 ℃ for 12 minutes to obtain the lead zirconate titanate single-layer film with the single-layer thickness of about 60 nanometers.
Repeating the step S204 seventeen times to prepare the lead zirconate titanate film with the thickness of about 1 micron.
The dielectric spectrum of the lead zirconate titanate thin film is shown in FIG. 4; the dielectric constant of the lead zirconate titanate thin film was calculated according to the above formula (1), and as a result, it was found that the relative dielectric constant of the lead zirconate titanate thin film was 1571.99 and the dielectric loss was 0.064 at a frequency of 0.1 kHz.
The cross-sectional field emission scanning electron micrograph of the above lead zirconate titanate thin film is shown in FIG. 5; as is clear from fig. 5, the lead zirconate titanate thin film has a perovskite structure, and the perovskite structure is dense.
Further, the degree of orientation of the (100) crystal direction of the lead zirconate titanate thin film is calculated in accordance with the above formula (2); the degree of orientation of the crystal orientation of the lead zirconate titanate thin film (100) was calculated to be 88.07%.
Example 3
This example provides a compound of the formula Pb (Zr)0.52Ti0.48)O3The preparation method of the lead zirconate titanate film comprises the following steps:
s301, preparing a lead zirconate titanate buffer layer precursor solution;
preparing materials according to the lead excess of 30%, firstly dissolving 3.2mL of tetrabutyl titanate in 1.8mL of acetylacetone, heating to 65 ℃, and preserving heat for 85 minutes; then, sequentially adding 4.37 g of zirconium nitrate, 9.76 g of lead acetate and 21mL of ethylene glycol monomethyl ether, uniformly stirring, heating to 120 ℃, and keeping the temperature for 85 minutes; then adding 1.9mL of formamide, stirring uniformly, cooling to 65 ℃, and keeping the temperature for 85 minutes; finally, 16mL of 36 mass percent acetic acid solution is added, and heat preservation is carried out for 85 minutes to obtain lead zirconate titanate buffer layer precursor solution with the concentration of about 0.48 mol/L; wherein, the molar ratio of lead acetate, zirconium nitrate, tetrabutyl titanate, acetylacetone and formamide is 1.3: 0.52: 0.48: 1.2: 2.4.
s302, depositing and thermally treating a buffer layer;
the precursor solution of the lead zirconate titanate buffer layer is firstly subjected to glue homogenizing at 900 revolutions per minute for 15 seconds and then is deposited on Pt/Ti/SiO through glue homogenizing and film throwing at 3000 revolutions per minute for 30 seconds2On a/Si substrate.
And (3) drying the wet film deposited on the substrate at 180 ℃ for 8 minutes, pyrolyzing the wet film at 450 ℃ for 8 minutes, and finally annealing the wet film at 650 ℃ for 15 minutes to obtain the lead zirconate titanate single-layer buffer layer with the single-layer thickness of about 75 nanometers.
Repeating the step S302 for three times to prepare the lead zirconate titanate buffer layer with the thickness of about 225 nanometers.
S303, preparing a lead zirconate titanate precursor solution;
preparing materials according to the lead excess of 20%, firstly dissolving 3.2mL of tetrabutyl titanate in 1.8mL of acetylacetone, heating to 65 ℃, and preserving heat for 85 minutes; then, sequentially adding 4.37 g of zirconium nitrate, 6.51 g of lead acetate and 21mL of ethylene glycol monomethyl ether, uniformly stirring, heating to 120 ℃, and keeping the temperature for 85 minutes; then adding 1.9mL of formamide, stirring uniformly, cooling to 65 ℃, and keeping the temperature for 85 minutes; finally, 16mL of 36 mass percent acetic acid solution is added, and the temperature is kept for 85 minutes to obtain lead zirconate titanate precursor solution with the concentration of about 0.48 mol/L; wherein, the molar ratio of lead acetate, zirconium nitrate, tetrabutyl titanate, acetylacetone and formamide is 1.2: 0.52: 0.48: 1.2: 2.4.
s304, depositing and heat treating the lead zirconate titanate film.
The lead zirconate titanate precursor solution is firstly subjected to glue homogenizing at 900 revolutions per minute for 15 seconds and then is deposited on a lead zirconate titanate buffer layer through glue homogenizing and film throwing at 3000 revolutions per minute for 30 seconds.
And (3) drying the wet film deposited on the lead zirconate titanate buffer layer at 180 ℃ for 8 minutes, then pyrolyzing the wet film at 450 ℃ for 8 minutes, and finally annealing the wet film at 650 ℃ for 15 minutes to obtain the lead zirconate titanate single-layer film with the single-layer thickness of about 75 nanometers.
Repeating the step S304 for thirteen times to prepare the lead zirconate titanate film with the thickness of about 1 micron.
The dielectric spectrum of the above lead zirconate titanate thin film is shown in FIG. 6; calculating the dielectric constant of the lead zirconate titanate film according to the formula (1); as a result, it was found that the above lead zirconate titanate thin film had a relative dielectric constant of 1438.30 and a dielectric loss of 0.065 at a frequency of 0.1 kHz.
The cross-sectional field emission scanning electron micrograph of the above lead zirconate titanate thin film is shown in FIG. 7; as is clear from fig. 7, the lead zirconate titanate thin film has a perovskite structure, and the perovskite structure is dense.
Further, the degree of orientation of the (100) crystal direction of the lead zirconate titanate thin film is calculated in accordance with the above formula (2); the degree of orientation of the crystal orientation of the lead zirconate titanate thin film (100) was calculated to be 82.23%.
Comparative example 1
This comparative example provides a chemical formula of Pb (Zr)0.52Ti0.48)O3The preparation method of the lead zirconate titanate film comprises the following steps:
1. preparing a lead zirconate titanate buffer layer precursor solution;
proportioning according to the excess lead, firstly dissolving 5.1mL of tetrabutyl titanate in 2.2mL of acetylacetone, heating to 55 ℃, and preserving heat for 65 minutes; then, sequentially adding 6.75 g of zirconium nitrate, 12.83 g of lead acetate and 33mL of ethylene glycol monomethyl ether, heating to 100 ℃, and preserving heat for 65 minutes; then adding 2.3mL of formamide, cooling to 55 ℃, and preserving heat for 65 minutes; finally, adding 14mL of 36 mass percent acetic acid solution, and preserving the heat for 65 minutes to obtain lead zirconate titanate buffer layer precursor solution with the concentration of about 0.45 mol/L; wherein, the molar ratio of lead acetate, zirconium nitrate, tetrabutyl titanate, acetylacetone and formamide is 1: 0.52: 0.48: 1.07: 2.21.
2. depositing and thermally treating a buffer layer;
the lead zirconate titanate buffer layer precursor solution is firstly subjected to uniform glue for 12 seconds at 850 revolutions per minute and then is deposited on Pt/Ti/SiO through uniform glue spinning for 25 seconds at 2800 revolutions per minute2On a/Si substrate.
And (3) drying the wet film deposited on the substrate at 120 ℃ for 5 minutes, pyrolyzing the wet film at 400 ℃ for 5 minutes, and finally annealing the wet film at 600 ℃ for 12 minutes to obtain the lead zirconate titanate single-layer buffer layer with the single-layer thickness of about 75 nanometers.
Repeating the step 2 for three times to prepare the lead zirconate titanate buffer layer with the thickness of about 225 nanometers.
3. Preparing a lead zirconate titanate precursor solution;
proportioning according to the lead excess of 10 percent, firstly dissolving 5.1mL of tetrabutyl titanate in 2.2mL of acetylacetone, heating to 55 ℃, and preserving heat for 65 minutes; then, sequentially adding 6.75 g of zirconium nitrate, 12.83 g of lead acetate and 33mL of ethylene glycol monomethyl ether, heating to 100 ℃, and preserving heat for 65 minutes; then adding 2.3mL of formamide, cooling to 55 ℃, and preserving heat for 65 minutes; finally, adding 14mL of 36 mass percent acetic acid solution, and preserving the heat for 65 minutes to obtain lead zirconate titanate precursor solution with the concentration of about 0.45 mol/L; wherein, the molar ratio of lead acetate, zirconium nitrate, tetrabutyl titanate, acetylacetone and formamide is 1.1: 0.52: 0.48: 1.07: 2.21.
4. depositing a lead zirconate titanate film and carrying out heat treatment.
And (3) uniformly coating the lead zirconate titanate precursor solution at 850 rpm for 12 seconds, and then uniformly coating and throwing the film at 2800 rpm for 25 seconds to deposit the lead zirconate titanate precursor solution on a lead zirconate titanate buffer layer.
And (3) drying the wet film deposited on the buffer layer at 120 ℃ for 5 minutes, then pyrolyzing the wet film at 400 ℃ for 5 minutes, and finally annealing the wet film at 600 ℃ for 12 minutes to obtain the lead zirconate titanate single-layer film with the single-layer thickness of about 75 nanometers.
Repeating the step 4 for thirteen times to prepare the lead zirconate titanate film with the thickness of about 1 micron.
The dielectric spectrum of the above lead zirconate titanate thin film is shown in FIG. 8. Calculating the dielectric constant of the lead zirconate titanate film according to the formula (1); as a result, it was found that the above lead zirconate titanate thin film had a relative dielectric constant of 976.30 and a dielectric loss of 0.094 at a frequency of 0.1 kHz.
The cross-sectional field emission scanning electron micrograph of the above lead zirconate titanate thin film is shown in FIG. 9. As can be seen from fig. 9, the lead zirconate titanate thin film has a loose pyrochlore structure.
Comparative example 2
This comparative example provides a chemical formula of Pb (Zr)0.52Ti0.48)O3The preparation method of the lead zirconate titanate film comprises the following steps:
1. preparing a lead zirconate titanate buffer layer precursor solution;
mixing materials according to lead excess of 15%, firstly dissolving 6.17 g of lead acetate, 5.1mL of tetrabutyl titanate and 3.32 g of zirconium nitrate in 16mL of ethylene glycol monomethyl ether, then heating to 70 ℃, and preserving heat for 80 minutes; then adding 1.7ml of acetylacetone and 1.4ml of formamide, subsequently heating to 90 ℃, and preserving the temperature for 80 minutes; finally, adding 13ml of 36 mass percent acetic acid solution, then cooling to 70 ℃, and preserving heat for 80 minutes to obtain lead zirconate titanate buffer layer precursor solution with the concentration of about 0.37 mol/L; wherein, the molar ratio of lead acetate, zirconium nitrate, tetrabutyl titanate, acetylacetone and formamide is 1.15: 0.52: 0.48: 0.81: 1.85.
2. depositing and thermally treating a buffer layer;
the precursor solution of the lead zirconate titanate buffer layer is firstly subjected to glue homogenizing at 880 rpm for 12 seconds, and then is deposited on Pt/Ti/SiO through glue homogenizing and film throwing at 3000 rpm for 25 seconds2On a/Si substrate.
And (3) drying the wet film deposited on the substrate at 120 ℃ for 6 minutes, then pyrolyzing the wet film at 400 ℃ for 6 minutes, and finally annealing the wet film at 600 ℃ for 15 minutes to obtain the lead zirconate titanate single-layer buffer layer with the single-layer thickness of about 60 nanometers.
Repeating the step 2 for four times to prepare the lead zirconate titanate buffer layer with the thickness of about 240 nanometers.
3. Preparing a lead zirconate titanate precursor solution;
preparing materials according to the lead excess of 20 percent, firstly dissolving 6.44 grams of lead acetate, 5.1mL of tetrabutyl titanate and 3.32 grams of zirconium nitrate in 16mL of ethylene glycol monomethyl ether, then heating to 70 ℃, and preserving heat for 80 minutes; then adding 1.7ml of acetylacetone and 1.4ml of formamide, subsequently heating to 90 ℃, and preserving the temperature for 80 minutes; finally, 13ml of 36 mass percent acetic acid solution is added, then the temperature is reduced to 70 ℃, and the temperature is kept for 80 minutes, so that lead zirconate titanate precursor solution with the concentration of about 0.37mol/L is obtained; wherein, the molar ratio of lead acetate, zirconium nitrate, tetrabutyl titanate, acetylacetone and formamide is 1.2: 0.52: 0.48: 0.81: 1.85.
4. depositing a lead zirconate titanate film and carrying out heat treatment.
And (3) uniformly coating the lead zirconate titanate precursor solution at 850 rpm for 12 seconds, and then uniformly coating and throwing the film at 2800 rpm for 25 seconds to deposit the lead zirconate titanate precursor solution on a lead zirconate titanate buffer layer.
And (3) drying the wet film deposited on the buffer layer at 120 ℃ for 6 minutes, then pyrolyzing the wet film at 400 ℃ for 6 minutes, and finally annealing the wet film at 600 ℃ for 15 minutes to obtain the lead zirconate titanate single-layer film with the single-layer thickness of about 60 nanometers.
Repeating the step 4 seventeen times to prepare the lead zirconate titanate film with the thickness of about 1 micron.
The dielectric spectrum of the above lead zirconate titanate thin film is shown in FIG. 10. Calculating the dielectric constant of the lead zirconate titanate film according to the formula (1); as a result, it was found that the above lead zirconate titanate thin film had a relative dielectric constant of 896.01 and a dielectric loss of 0.028 at a frequency of 0.1 kHz.
The cross-sectional field emission scanning electron micrograph of the above lead zirconate titanate thin film is shown in FIG. 11. As is clear from fig. 11, the lead zirconate titanate thin film had a partially pyrochlore structure because of its less dense crystals.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Claims (9)

1. A method for preparing a lead zirconate titanate film is characterized by comprising the following steps of:
1) dissolving tetrabutyl titanate in acetylacetone, heating to 40-65 ℃, and keeping the temperature for 50-85 min; sequentially adding zirconium nitrate, lead acetate and ethylene glycol monomethyl ether into the mixed solution, stirring uniformly, heating to 85-120 ℃, preserving heat for 50-85min, and controlling the molar ratio of the lead acetate to the zirconium nitrate to be (1.1-1.3): y; stirring, heating to 85-120 deg.C, and maintaining for 50-85 min; adding formamide into the mixed solution, stirring, cooling to 40-65 deg.C, and maintaining the temperature for 50-85 min; adding acetic acid solution into the mixed solution, and keeping the temperature for 50-85min to prepare Pb (Zr) with a chemical formulayTi1-y)O3The lead zirconate titanate buffer layer precursor solution of (1), wherein y is 0.52 to 0.53;
2) depositing the lead zirconate titanate buffer layer precursor solution on a substrate, and carrying out heat treatment to obtain a lead zirconate titanate buffer layer;
3) dissolving tetrabutyl titanate in acetylacetone, heating to 40-65 ℃, and keeping the temperature for 50-85 min; sequentially adding zirconium nitrate and acetic acidAdding lead and ethylene glycol monomethyl ether into the mixed solution, stirring uniformly, heating to 85-120 ℃, keeping the temperature for 50-85min, and controlling the molar ratio of lead acetate to zirconium nitrate to be (1.15-1.25): y; stirring, heating to 85-120 deg.C, and maintaining for 50-85 min; adding formamide into the mixed solution, stirring, cooling to 40-65 deg.C, and maintaining the temperature for 50-85 min; adding acetic acid solution into the mixed solution, and keeping the temperature for 50-85min to prepare Pb (Zr) with a chemical formulayTi1-y)O3Wherein y is 0.52 to 0.53;
4) and depositing the lead zirconate titanate precursor solution on the lead zirconate titanate buffer layer, and performing heat treatment to obtain the lead zirconate titanate film.
2. The method according to claim 1, wherein in step 1), the molar ratio of the lead acetate, the zirconium nitrate, the tetrabutyl titanate, the acetylacetone, and the formamide is controlled to (1.1-1.3): y: (1-y): (0.7-1.2): (1.8-2.4).
3. The method according to claim 1, wherein in the step 3), the molar ratio of the lead acetate, the zirconium nitrate, the tetrabutyl titanate, the acetylacetone, and the formamide is controlled to (1.15-1.25): y: (1-y): (0.7-1.2): (1.8-2.4).
4. The preparation method according to claim 1, wherein the pH value of the lead zirconate titanate buffer layer precursor solution is controlled to be 3.5-5.5, and the concentration is controlled to be 0.30-0.48 mol/L; controlling the pH value of the lead zirconate titanate precursor solution to be 3.5-5.5 and the concentration to be 0.30-0.48 mol/L.
5. The production method according to any one of claims 1 to 4, wherein the depositing includes:
and (3) homogenizing the lead zirconate titanate buffer layer precursor solution or the lead zirconate titanate precursor solution for 10-15 seconds at 800-900 revolutions per minute, and then spinning the film for 20-30 seconds at 2600-3000 revolutions per minute.
6. The method according to any one of claims 1 to 4, wherein the substrate is Pt/Ti/SiO2a/Si substrate.
7. The production method according to any one of claims 1 to 4, wherein the heat treatment comprises: drying at 120-200 deg.c for 4-8 min; then thermally decomposing at the temperature of 300-450 ℃ for 4-8 minutes; then annealing at 600-650 ℃ for 10-15 minutes.
8. The method of claim 7, wherein step 2) is repeated until a lead zirconate titanate buffer layer having a target thickness is obtained, prior to step 3); and repeating the step 4) until a lead zirconate titanate film with the target thickness is obtained.
9. A lead zirconate titanate thin film produced by the production method according to any one of claims 1 to 8.
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