Pb based on powder-assisted sol-gel (1-x) Ln x (Zr 0.52 Ti 0.48 O3-based piezoelectric thick film materials and their preparation methods

Abstract

The application discloses a Pb (1‑x) Ln x (Zr 0.52 Ti 0.48 )O3-based piezoelectric thick film material and a preparation method thereof. The implementation scheme is as follows: lead oxide, zirconium dioxide, titanium dioxide and oxide of a lanthanide element are fired to form pre-fired powder; lead acetate trihydrate, tetrabutyl titanate, oxide of the lanthanide element and zirconium n-propyl alcohol or zirconium isopropyl alcohol are mixed into a precursor solution by a sol-gel method; the powder and the gel are mixed to form slurry, the slurry is spin-coated on a substrate, and after drying and pyrolysis treatment, annealing is performed in an air atmosphere or an ACB atmosphere compensation, so as to obtain Pb (1‑x) Ln x (Zr 0.52 Ti 0.48 )O3 piezoelectric thick film with a thickness greater than 10 microns. The application has the advantages of high crystallinity, good compactness, high breakdown field strength, high electrical comprehensive performance, simple process and good repeatability, and can be used in micro-electro-mechanical system (MEMS), micro-actuator, sensor and ultrasonic transducer.

Description

Technical Field

[0001] This invention belongs to the field of chemical materials technology, and specifically relates to a Pb based on powder-assisted sol-gel. (1-x) Ln x (Zr 0.52 Ti 0.48 O3-based piezoelectric thick film materials and their preparation methods can be used in microelectromechanical systems (MEMS), microactuators, sensors, and ultrasonic transducers. Background Technology

[0002] Lead zirconate titanate (PZT) piezoelectric ceramics are widely used in microelectromechanical systems (MEMS), microactuators, sensors, ultrasonic transducers, and ferroelectric memories due to their excellent dielectric, piezoelectric, and ferroelectric properties. To further enhance the overall performance of this material, rare earth elements such as La, Nd, and Sm are typically introduced into the PZT matrix for modification. The general chemical formula is Pb. (1-x) Ln x (Zr 0.52 Ti 0.48 O3 piezoelectric ceramic materials, due to their composition being located near the quasi-isomorphic phase boundary MPB, and through the donor doping effect of rare earth elements, can significantly improve the dielectric constant, piezoelectric constant, and electromechanical coupling coefficient of the material, while also improving the fatigue resistance of the material, are currently a research hotspot for high-performance piezoelectric applications.

[0003] With the trend towards device miniaturization and integration, traditional bulk piezoelectric ceramics are increasingly unable to meet the demands of MEMS devices due to limitations in processing size and poor compatibility with semiconductor processes. On the other hand, piezoelectric films prepared by conventional magnetron sputtering or sol-gel methods are typically less than 2 μm thick. While they offer good process compatibility, their small size limits the driving force and displacement they can generate, making them unsuitable for applications requiring large driving displacement and output force, such as microfluidic pumps and ultrasonic motors. To achieve the greater driving energy and mechanical output required by these high-performance micro-devices, the effective working volume of the piezoelectric material must be significantly increased. Therefore, preparing high-quality piezoelectric thick films with a thickness greater than 10 μm has become a key technological bridge connecting thin films and bulk materials. Currently, methods for preparing piezoelectric thick films mainly include screen printing, casting, and sol-gel methods. While screen printing and casting methods can easily produce relatively thick films of 10-100 μm, the resulting films typically exhibit poor density, high porosity, and require high sintering temperatures. This can easily lead to lead volatilization and diffusion reactions in the substrate, severely impacting the film's electrical properties. The traditional sol-gel method, with its advantages of precise stoichiometry, good component uniformity, and low synthesis temperature, is the preferred method for preparing high-quality ferroelectric thin films. However, applying the sol-gel method to prepare films thicker than 10 μm presents significant technical challenges. The single-layer film thickness is only around 100 nm, the process cycle is long, and the efficiency is extremely low. Furthermore, the drying and crystallization of the sol involves significant organic decomposition and solvent evaporation, resulting in substantial volume shrinkage. As the film thickness increases, enormous internal stresses are generated within the film and between the film and the substrate, easily leading to cracking, peeling, or warping during sintering, severely compromising the film's integrity and electrical properties.

[0004] Patent document CN101215172A discloses "a method for preparing sodium bismuth titanate-based lead-free piezoelectric thick films." This method involves screen printing ceramic slurry to form a thick film preform, and then using vertical centrifugal force to drive a composite sol to fill the pores of the thick film to improve density. While this method can produce high-density, lead-free piezoelectric thick films with excellent electrical properties, its extremely complex process involves multiple independent and time-consuming steps, including solid-phase synthesis of ceramic powder, preparation of organic slurry, screen printing, multiple pre-firing, preparation of composite sol, repeated centrifugal permeation and filling of the sol, annealing and crystallization, and final high-temperature sintering. These steps need to be repeated 4-10 times, resulting in a long overall process cycle, numerous control points, and low production efficiency, which is not conducive to achieving stable, high-consistency, and large-scale production.

[0005] Patent document CN102826846A discloses a "method for preparing a high-performance lead nickel niobate-lead zirconate titanate piezoelectric thick film on an alumina substrate." This method involves adding ZnO and La2O3 to PNN-PZT powder, along with glass frit and an organic carrier to form a slurry. This slurry is then multi-layered and printed onto a substrate using screen printing. Finally, the film is prepared through delamination and low-temperature co-sintering. While this method lowers the sintering temperature to 750℃ and achieves certain piezoelectric properties through specific element doping, it still relies on traditional screen printing technology. This requires the preparation of complex organic carriers and the addition of glass frit. Furthermore, this printing method typically results in poor film density, high internal porosity, and a tendency for microcracks, severely limiting further improvements in the material's breakdown field strength and crystallinity. In addition, the multi-layer printing, repeated drying, and complex co-sintering processes remain cumbersome, making it difficult to meet the demand for simple, rapid, and highly repeatable preparation of high-quality piezoelectric thick films.

[0006] In summary, existing piezoelectric thick film fabrication methods struggle to simultaneously achieve a combination of properties, including simple and efficient processing, high film density, and strong breakdown field resistance, when fabricating films thicker than 10 μm. Therefore, it is necessary to develop a simple process that can effectively fabricate dense, crack-free Pb films with a thickness greater than 10 μm. (1-x) Ln x (Zr 0.52 Ti 0.48 The method of developing O3-based piezoelectric thick films is a technical problem that urgently needs to be solved in this field. Summary of the Invention

[0007] The purpose of this invention is to address the shortcomings of the prior art described above. It proposes a Pb-based sol-gel method. (1-x) Ln x (Zr 0.52 Ti 0.48 O3-based piezoelectric thick film materials and their preparation methods are proposed to avoid microcracks that easily occur in the film during the preparation of piezoelectric thick films, reduce lead volatilization, simplify the preparation process, and improve the crystallization quality and piezoelectric properties of thick films.

[0008] To achieve the above objectives, the technical solution of the present invention includes:

[0009] 1. A Pb based on powder-assisted sol-gel (1-x) Ln x (Zr 0.52 Ti 0.48 O3-based piezoelectric thick film material, comprising a substrate and a piezoelectric film, characterized in that:

[0010] The thickness of the piezoelectric film is >10μm;

[0011] The piezoelectric film is composed of Pb(1-x) Ln x (Zr 0.52 Ti 0.48 O3, where Ln is a composite of one or more elements from La, Sm, Y, Ce, and x is the doping amount.

[0012] Preferably, the doping amount x is between 0.001 and 0.05.

[0013] Preferably, the substrate includes ITO conductive glass and a silicon-based substrate.

[0014] 2. A Pb based on powder-assisted sol-gel (1-x) Ln x (Zr 0.52 Ti 0.48 A method for preparing O3-based piezoelectric thick film materials, characterized by comprising:

[0015] (1) Anhydrous ethanol was added to weighed raw materials of lead oxide (PbO), zirconium dioxide (ZrO2), titanium dioxide (TiO2), and lanthanide oxide (Ln2O3) and the mixture was ball-milled, dried, sieved, and then calcined in air to obtain Pb. (1-x) Ln x (Zr 0.52 Ti 0.48 O3 pre-calcined powder was then subjected to a second ball milling under the same conditions, followed by drying and sieving to obtain Pb. (1-x) Ln x (Zr 0.52 Ti 0.48 O3 powder, where x = 0.001 to 0.05, and Ln is a composite of one or more elements such as La, Sm, Y, and Ce;

[0016] (2) Dissolve the weighed lead acetate trihydrate Pb(CH3COO)2·3H2O in glacial acetic acid CH3COOH to obtain a Pb solution, and dissolve tetrabutyl titanate C 16 H 36 O4Ti, lanthanide oxides Ln2O3, and zirconium n-propoxide C 12 H 28 Dissolving O4Zr or zirconium isopropoxide (C3H8OZr) in glacial acetic acid (CH3COOH) or anhydrous ethanol yields a metal-organic precursor solution. The two solutions are then mixed, stirred, and allowed to stand to obtain transparent Pb. (1-x) Ln x (Zr 0.52 Ti 0.48 O3 precursor solution.

[0017] (3) Pb (1-x) Ln x (Zr0.52 Ti 0.48 O3 pre-calcined powder with Pb of the same composition (1-x) Ln x (Zr 0.52 Ti 0.48 A composite slurry was prepared by mixing, dispersing and ball milling in O3 sol, and then spin-coating it onto a substrate to obtain a wet film.

[0018] (4) The sample obtained in step (3) is dried, pyrolyzed and annealed in sequence to obtain a monolayer of Pb. (1-x) Ln x (Zr 0.52 Ti 0.48 )O3 thick film;

[0019] (5) Repeat steps (3) and (4) to prepare multilayer Pb. (1-x) Ln x (Zr 0.52 Ti 0.48 O3 thick film, to complete Pb (1-x) Ln x (Zr 0.52 Ti 0.48 Preparation of O3-based piezoelectric thick film materials.

[0020] Preferably, the stirring in step (2) is carried out at a temperature of 50-100℃, with a standing aging time of 12-48h and a concentration of 0.2-0.4mol / L.

[0021] Preferably, in step (3) Pb (1-x) Ln x (Zr 0.52 Ti 0.48 O3 pre-calcined powder with Pb of the same composition (1-x) Ln x (Zr 0.52 Ti 0.48 The pre-calcined powder was mixed, dispersed, and ball-milled in O3 sol, with the mass ratio of the pre-calcined powder to the volume of the sol being: 5-60 mL of Pb per 10-60 g of pre-calcined powder. (1-x) Ln x (Zr 0.52 Ti 0.48 O3 sol was mixed and then ball-milled at 200-1000 rpm / min for 2-24 h to obtain a uniform and stable slurry.

[0022] Compared with the prior art, the present invention has the following advantages:

[0023] Firstly, this invention combines the component precision of the sol-gel method with the high solids content advantage introduced by powder. It employs a powder-assisted sol-gel method, dispersing pre-calcined powders of the same composition within a precursor sol to form a composite slurry. This allows for the achievement of greater thicknesses, significantly reducing the number of spin-coating and heat treatment cycles required to prepare films thicker than 10 micrometers, resulting in high process efficiency and a short cycle time. Simultaneously, the use of this powder effectively alleviates volume shrinkage stress during drying and pyrolysis, fundamentally preventing cracking and peeling of the thick film during sintering, thus obtaining a highly dense, defect-free film structure.

[0024] Secondly, due to the simplified slurry preparation process and shortened thick-film heat treatment time, this invention significantly reduces lead volatilization at high temperatures, which helps maintain the stoichiometry of the material, thus enabling the production of perovskite phases with high crystallinity and pure phase structure. The prepared Pb (1-x) Ln x (Zr 0.52 Ti 0.48 O3-based piezoelectric thick films possess high crystallinity, high density, high breakdown field strength, and excellent comprehensive piezoelectric properties. Attached Figure Description

[0025] Figure 1 This invention relates to Pb based on powder-assisted sol-gel. (1-x) Ln x (Zr 0.52 Ti 0.48 Schematic diagram of O3-based piezoelectric thick film material structure;

[0026] Figure 2 This invention prepares Pb based on powder-assisted sol-gel. (1-x) Ln x (Zr 0.52 Ti 0.48 Flowchart of the realization of O3-based piezoelectric thick film materials;

[0027] Figure 3 Pb of the present invention (1-x) Ln x (Zr 0.52 Ti 0.48 X-ray diffraction pattern of O3 thick film;

[0028] Figure 4 Pb of the present invention (1-x) Ln x (Zr 0.52 Ti 0.48 Cross-sectional scanning electron microscope images of O3 thick films;

[0029] Figure 5 Pb of the present invention (1-x) Ln x (Zr 0.52 Ti0.48 A graph showing the effective piezoelectric constant of O3 thick film as a function of corona polarization voltage. Detailed Implementation

[0030] The embodiments of the present invention will be further described in detail below with reference to the accompanying drawings. However, the implementation of the present invention is not limited to the scope shown in the embodiments. These embodiments are only used to illustrate the present invention and are not intended to limit the scope of the present invention. Furthermore, after reading the contents of this invention, those skilled in the art can make various modifications to the present invention, and these equivalent changes also fall within the scope defined by the appended claims.

[0031] Reference Figure 1 This invention is based on powder-assisted sol-gel Pb (1-x) Ln x (Zr 0.52 Ti 0.48 O3-based piezoelectric thick film materials, including a substrate and a piezoelectric film, wherein,

[0032] The substrate is made of ITO conductive glass or silicon-based substrate.

[0033] The piezoelectric film, located on the substrate, has a thickness >10 μm and is composed of Pb. (1-x) Ln x (Zr 0.52 Ti 0.48 O3, where Ln is a composite of one or more elements from La, Sm, Y, Ce; x is the doping amount, which ranges from 0.001 to 0.05.

[0034] Reference Figure 2 This invention provides a method for preparing Pb (1-x) Ln x (Zr 0.52 Ti 0.48 Three embodiments of O3-based piezoelectric thick film materials.

[0035] Example 1: The substrate was prepared as a silicon-based substrate, where Ln was selected as La, x = 0.001, and Pb... 0.999 La 0.001 (Zr 0.52 Ti 0.48 The O3 powder was prepared with a 1% excess of PbO and annealed in an ACB atmosphere, resulting in two layers of PbO. 0.999 La 0.001 (Zr 0.52 Ti 0.48 O3 piezoelectric thick film.

[0036] Step 1: Preparation of Pb 0.999 La 0.001 (Zr 0.52 Ti0.48 )O3 powder.

[0037] Lead oxide (PbO), zirconium dioxide (ZrO2), titanium dioxide (TiO2), and lanthanum trioxide (La2O3) powders were weighed according to a molar ratio of 0.999:0.001:0.52:0.48, with lead oxide (PbO) powder in excess by 1%. The weighed powders were placed in a ball mill jar, and an appropriate amount of anhydrous ethanol was added. The mixture was ball-milled at 200 rpm for 4 hours. The thoroughly mixed slurry was then dried, sieved, and placed in an alumina crucible, where it was calcined at 750°C in air for 3 hours.

[0038] The calcined powder was subjected to a second ball milling under the same conditions described above, followed by drying and sieving to prepare Pb. 0.999 La 0.001 (Zr 0.52 Ti 0.48 O3 pre-calcined powder.

[0039] Step 2, Preparation of Pb 0.999 La 0.001 (Zr 0.52 Ti 0.48 O3 sol.

[0040] Lead acetate trihydrate (Pb(CH3COO)2·3H2O) and zirconium n-propoxide (C) were weighed according to a molar ratio of 0.999:0.001:0.52:0.48. 12 H 28 O4Zr, Tetrabutyl titanate C 16 H 36 O4Ti and lanthanum trioxide (La2O3);

[0041] Lead acetate trihydrate (Pb(CH3COO)2·3H2O) was first dissolved in glacial acetic acid (CH3COOH) to obtain a Pb solution; zirconium propoxide (C) was then added. 12 H 28 O4Zr, Tetrabutyl titanate C 16 H 36 O4Ti and lanthanum trioxide La2O3 were dissolved in glacial acetic acid CH3COOH to obtain a mixed organometallic precursor solution;

[0042] The two solutions were then mixed at 50°C and left to stand for 12 hours to obtain a transparent Pb solution with a concentration of 0.2 mol / L. 0.999 La 0.001 (Zr 0.52 Ti 0.48 O3 precursor solution.

[0043] Step 3, Preparation of Pb 0.999 La 0.001 (Zr0.52 Ti 0.48 O3 slurry.

[0044] Take 10g of the pre-calcined powder from step 1 and 5ml of the sol from step 2 and place them in a ball mill jar. Set the ball mill speed to 200rpm / min and ball mill them for 2 hours to obtain uniform and stable Pb. 0.999 La 0.001 (Zr 0.52 Ti 0.48 O3 slurry.

[0045] Step 4, Preparation of Pb 0.999 La 0.001 (Zr 0.52 Ti 0.48 )O3 thick film.

[0046] 4.1) The Pb obtained in step 3 0.999 La 0.009 (Zr 0.52 Ti 0.48 O3 slurry was spin-coated on a silicon substrate at a speed of 1000 rpm / min for 30 seconds to obtain a wet film;

[0047] 4.2) The wet film obtained in step 4.1) is dried at 200℃ for 1 min, pyrolyzed at 300℃ for 2 min, and then annealed at 500℃ for 5 min in an ACB atmosphere in a tube furnace to obtain Pb. 0.995 La 0.005 (Zr 0.52 Ti 0.48 O3 thick film sample;

[0048] 4.3) Repeat steps 4.1) and 4.2) twice to obtain two layers of Pb with a total thickness of 20 μm. 0.995 La 0.005 (Zr 0.52 Ti 0.48 )O3 thick film.

[0049] Example 2: The substrate was prepared as an ITO glass substrate, where Ln was selected as Sm, x=0.01, and Pb... 0.99 Sm 0.01 (Zr 0.52 Ti 0.48 The O3 powder was prepared with a 10% excess of PbO and annealed in air to form a three-layer PbO layer. 0.99 Sm 0.01 (Zr 0.52 Ti 0.48 O3 piezoelectric thick film.

[0050] Step 1, Preparation of Pb 0.99 La0.01 (Zr 0.52 Ti 0.48 )O3 powder.

[0051] First, lead oxide (PbO), zirconium dioxide (ZrO2), titanium dioxide (TiO2), and samarium trioxide (Sm2O3) raw material powders were weighed out according to a molar ratio of 0.99:0.01:0.52:0.48, with lead oxide (PbO) powder in excess by 10%. The weighed raw material powders were then placed in a ball mill jar, and an appropriate amount of anhydrous ethanol was added. The mixture was ball-milled at 600 rpm for 7 hours. After thorough mixing, the slurry was dried, sieved, and then placed in an alumina crucible for calcination in air at 800°C for 3 hours. The calcined powder was then ball-milled again under the same conditions, followed by drying and sieving to prepare PbO. 0.99 Sm 0.01 (Zr 0.52 Ti 0.48 O3 pre-calcined powder.

[0052] Step 2, Preparation of Pb 0.99 La 0.01 (Zr 0.52 Ti 0.48 O3 sol.

[0053] Lead acetate trihydrate (Pb(CH3COO)2·3H2O) and zirconium n-propoxide (C) were weighed according to a molar ratio of 0.99:0.01:0.52:0.48. 12 H 28 O4Zr, Tetrabutyl titanate C 16 H 36 O4Ti and lanthanum trioxide La2O3 were used to first dissolve lead acetate trihydrate Pb(CH3COO)2·3H2O in glacial acetic acid CH3COOH to obtain a Pb solution; simultaneously, zirconium propoxide C4Ti was added. 12 H 28 O4Zr, Tetrabutyl titanate C 16 H 36 O4Ti and lanthanum trioxide (La2O3) were dissolved in glacial acetic acid (CH3COOH) to obtain a mixed organometallic precursor solution; the two solutions were then mixed again at 80°C and left to stand for 30 h to obtain a transparent Pb solution with a concentration of 0.3 mol / L. 0.99 La 0.01 (Zr 0.52 Ti 0.48 O3 precursor solution.

[0054] Step 3, Preparation of Pb 0.99 La 0.01 (Zr 0.52 Ti 0.48 O3 slurry.

[0055] Take 35g of the powder from step one and 35ml of the sol from step two, place them in a ball mill jar, and ball mill at 700rpm / min for 13h to obtain uniform and stable Pb. 0.99 La 0.01 (Zr 0.52 Ti 0.48 O3 slurry.

[0056] Step 4, Preparation of Pb 0.99 La 0.01 (Zr 0.52 Ti 0.48 )O3 thick film.

[0057] First, take the Pb obtained in step three. 0.99 La 0.01 (Zr 0.52 Ti 0.48 O3 slurry was spin-coated onto an ITO glass substrate at 3000 rpm for 35 s using a spin coater to obtain a wet film. This wet film was then sequentially dried at 300°C for 5 min, pyrolyzed at 500°C for 6 min, and annealed at 700°C for 30 min in an air atmosphere in a tube furnace to obtain a Pb layer. 0.99 La 0.01 (Zr 0.52 Ti 0.48 O3 thick film sample;

[0058] Repeat the above process three times to obtain three layers of Pb. 0.995 La 0.005 (Zr 0.52 Ti 0.48 The O3 thick film has a total thickness of 30 μm.

[0059] Example 3: The substrate was prepared as a silicon-based substrate, where Ln was selected as Y, x = 0.05, and Pb... 0.95 Y 0.05 (Zr 0.52 Ti 0.48 The O3 powder was prepared with a 20% excess of PbO and annealed in an ACB atmosphere, resulting in a four-layer PbO powder. 0.95 Y 0.05 (Zr 0.52 Ti 0.48 O3 piezoelectric thick film.

[0060] Step A, Preparation of Pb 0.95 La 0.05 (Zr 0.52 Ti 0.48 )O3 powder.

[0061] A1) Weigh out lead oxide (PbO), zirconium dioxide (ZrO2), titanium dioxide (TiO2), and yttrium oxide (Y2O3) raw material powders according to a molar ratio of 0.95:0.05:0.52:0.48, with lead oxide (PbO) powder in excess by 20%.

[0062] A2) Place the weighed raw material powder into a ball mill jar, add an appropriate amount of anhydrous ethanol, and ball mill it in a ball mill at a speed of 1000 rpm / min for 12 hours before taking it out.

[0063] A3) The ball-milled powder was dried, sieved, and then placed in an alumina crucible and calcined in air at 950°C for 6 hours;

[0064] A3) The calcined powder was ball-milled a second time under the same conditions as described above, and then dried and sieved in sequence to prepare Pb. 0.95 Y 0.05 (Zr 0.52 Ti 0.48 O3 pre-calcined powder.

[0065] Step B, Preparation of Pb 0.95 La 0.05 (Zr 0.52 Ti 0.48 O3 sol.

[0066] B1) Weigh out lead acetate trihydrate Pb(CH3COO)2·3H2O and zirconium n-propoxide C according to a molar ratio of 0.95:0.05:0.52:0.48. 12 H 28 O4Zr, Tetrabutyl titanate C 16 H 36 O4Ti and yttrium trioxide Y2O3 were used to first dissolve lead acetate trihydrate Pb(CH3COO )2·3H2O in glacial acetic acid CH3COOH to obtain a Pb solution;

[0067] B2) Zirconium n-propoxide C 12 H 28 O4Zr, Tetrabutyl titanate C 16 H 36 O4Ti and yttrium trioxide (Y2O3) were dissolved in glacial acetic acid (CH3COOH) to obtain a mixed organometallic precursor solution.

[0068] B3) The two mixtures were mixed again at 100°C and left to stand for 48 hours to obtain a transparent Pb solution with a concentration of 0.4 mol / L. 0.95 Y 0.05 (Zr 0.52 Ti 0.48 O3 precursor solution.

[0069] Step C, Preparation of Pb 0.95 La 0.05 (Zr 0.52 Ti 0.48 O3 slurry.

[0070] Take 60g of the powder from step A and 60ml of the sol from step B into a ball mill jar, set the ball mill speed to 1000rpm / min, and ball mill them for 24h to obtain uniform and stable Pb. 0.95 Y 0.05 (Zr 0.52 Ti 0.48 O3 slurry.

[0071] Step D, Preparation of Pb 0.95 La 0.05 (Zr 0.52 Ti 0.48 )O3 thick film.

[0072] D1) The Pb obtained in step C 0.95 Y 0.05 (Zr 0.52 Ti 0.48 O3 slurry was spin-coated onto a silicon substrate for 40 seconds using a spin coater at a speed of 6000 rpm / min to obtain a wet film.

[0073] D2) The wet film obtained in step D1) is dried and pyrolyzed at 400℃ and 600℃ for 10 min each, and then annealed at 700℃ for 60 min in a tube furnace under an ACB atmosphere to obtain Pb. 0.95 Y 0.05 (Zr 0.52 Ti 0.48 O3 thick film sample;

[0074] D3) Repeat steps D1) and D2) a total of 4 times to obtain 4 layers of Pb. 0.95 Y 0.05 (Zr 0.52 Ti 0.48 The O3 thick film has a total thickness of 40 μm.

[0075] The effectiveness of this invention can be further illustrated by test results:

[0076] Test 1: An X-ray diffraction test was performed on Embodiment 1 of the present invention at a test angle of [value missing]. The results are as follows: Figure 3 As shown, from Figure 3 As can be seen, the thick film sample exhibits a pure perovskite phase without any other impurities.

[0077] Test 2: A cross-sectional scanning electron microscope test was performed on Embodiment 1 of the present invention, and the results are as follows. Figure 4 As shown, from Figure 4 It can be seen that the thickness of the two-layer thick film prepared by the present invention is 20 μm, and the cross-section is dense with no cracks.

[0078] Test 3: The effective piezoelectric constant of Embodiment 1 of the present invention was tested as a function of corona polarization voltage. The results are as follows: Figure 5 As shown, from Figure 5 As can be seen from the figure, the effective piezoelectric constant of the thick film prepared by the present invention increases with the increase of polarization voltage. When the corona polarization voltage increases to 9kV, the polarization reaches saturation, and the effective piezoelectric constant can reach 293pC / N at 12kV.

[0079] The above test results show that the thick film obtained by the present invention has a pure perovskite phase, a dense structure, no second phase is generated, and it also has excellent piezoelectric properties.

[0080] The above description is only a few specific embodiments of the present invention and does not constitute any limitation on the present invention. Obviously, those skilled in the art, after understanding the content and principle of the present invention, may make various modifications and changes in form and details without departing from the principle and structure of the present invention. For example, in addition to selecting La, Sm and Y in the above examples, Ce can also be selected.

[0081] However, these modifications and alterations based on the ideas of this invention are still within the scope of protection of the claims of this invention.

Claims

1. A Pb based on powder-assisted sol-gel (1-x) Ln x (Zr 0.52 Ti 0.48 O3-based piezoelectric thick film material, comprising a substrate and a piezoelectric film, characterized in that: The thickness of the piezoelectric film is >10μm; The piezoelectric film is composed of Pb (1-x) Ln x (Zr 0.52 Ti 0.48 O3, where Ln is a composite of one or more elements from La, Sm, Y, Ce, and x is the doping amount.

2. The material according to claim 1, characterized in that, The doping amount x is between 0.001 and 0.

05.

3. The material according to claim 1, characterized in that, The substrate includes ITO conductive glass and a silicon-based substrate.

4. A Pb based on powder-assisted sol-gel (1-x) Ln x (Zr 0.52 Ti 0.48 The method for preparing O3-based piezoelectric thick film materials is characterized by, include: (1) Anhydrous ethanol was added to weighed raw materials of lead oxide (PbO), zirconium dioxide (ZrO2), titanium dioxide (TiO2), and lanthanide oxide (Ln2O3) and the mixture was ball-milled, dried, sieved, and then calcined in air to obtain Pb. (1-x) Ln x (Zr 0.52 Ti 0.48 O3 pre-calcined powder was then subjected to a second ball milling under the same conditions, followed by drying and sieving to obtain Pb. (1-x) Ln x (Zr 0.52 Ti 0.48 O3 powder, where x = 0.001 to 0.05, and Ln is a composite of one or more elements such as La, Sm, Y, and Ce; (2) Dissolve the weighed lead acetate trihydrate Pb(CH3COO)2·3H2O in glacial acetic acid CH3COOH to obtain a Pb solution, and dissolve tetrabutyl titanate C 16 H 36 O4Ti, lanthanide oxides Ln2O3, and zirconium n-propoxide C 12 H 28 Dissolving O4Zr or zirconium isopropoxide (C3H8OZr) in glacial acetic acid (CH3COOH) or anhydrous ethanol yields a metal-organic precursor solution. The two solutions are then mixed, stirred, and allowed to stand to obtain transparent Pb. (1-x) Ln x (Zr 0.52 Ti 0.48 O3 precursor solution; (3) Pb (1-x) Ln x (Zr 0.52 Ti 0.48 O3 pre-calcined powder with Pb of the same composition (1-x) Ln x (Zr 0.52 Ti 0.48 A composite slurry was prepared by mixing, dispersing and ball milling in O3 sol, and then spin-coating it onto a substrate to obtain a wet film. (4) The sample obtained in step (3) is dried, pyrolyzed and annealed in sequence to obtain a monolayer of Pb. (1-x) Ln x (Zr 0.52 Ti 0.48 )O3 thick film; (5) Repeat steps (3) and (4) to prepare multilayer Pb. (1-x) Ln x (Zr 0.52 Ti 0.48 O3 thick film, to complete Pb (1-x) Ln x (Zr 0.52 Ti 0.48 Preparation of O3-based piezoelectric thick film materials.

5. The method according to claim 4, characterized in that, The ball milling mixing in step (1) is carried out by a ball mill with a rotation speed of 200-1000 rpm / min for 2-12 hours; the calcination is carried out at a temperature of 750-950℃ for 1-6 hours; the Pb (1-x) Ln x (Zr 0.52 Ti 0.48 The lead oxide (PbO) powder in the O3 powder is in excess at 1-20%.

6. The method according to claim 4, characterized in that, The stirring in step (2) is carried out at a temperature of 50-100℃, with a standing aging time of 12-48h and a concentration of 0.2-0.4mol / L.

7. The method according to claim 4, characterized in that, In step (3), Pb (1-x) Ln x (Zr 0.52 Ti 0.48 O3 pre-calcined powder with Pb of the same composition (1-x) Ln x (Zr 0.52 Ti 0.48 The pre-calcined powder was mixed, dispersed, and ball-milled in O3 sol, with the mass ratio of the pre-calcined powder to the volume of the sol being: 5-60 mL of Pb per 10-60 g of pre-calcined powder. (1-x) Ln x (Zr 0.52 Ti 0.48 O3 sol was mixed and then ball-milled at 200-1000 rpm / min for 2-24 h to obtain a uniform and stable slurry.

8. The method according to claim 4, characterized in that, The substrate mentioned in step (3) is ITO conductive glass and silicon-based substrate; the ball milling medium is made of zirconium oxide.

9. The method according to claim 4, characterized in that, The spin coating speed in step (3) is 1000-6000 rpm / min, and the spin coating time is 30-40 s.

10. The method according to claim 4, characterized in that, In step (4): The drying temperature is 200-400℃, and the drying time is 1-10 min; The pyrolysis temperature is 300-600℃, and the pyrolysis time is 2-10 min; The annealing temperature is 500-800℃, the annealing time is 5-60min, and the annealing environment is an air atmosphere or an atmosphere containing ACB.

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