CN108069715B - Gadolinium-doped lead zirconate titanate film with (100) orientation and preparation method thereof - Google Patents

Gadolinium-doped lead zirconate titanate film with (100) orientation and preparation method thereof Download PDF

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CN108069715B
CN108069715B CN201611000288.8A CN201611000288A CN108069715B CN 108069715 B CN108069715 B CN 108069715B CN 201611000288 A CN201611000288 A CN 201611000288A CN 108069715 B CN108069715 B CN 108069715B
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gadolinium
zirconate titanate
lead zirconate
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邹赫麟
许文才
李奇
周毅
王文强
韩梅
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Dalian University of Technology
Zhuhai Sailner 3D Technology Co Ltd
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Abstract

The invention provides a gadolinium-doped lead zirconate titanate thin film with (100) orientation and a preparation method thereof. The preparation method of the gadolinium-doped lead zirconate titanate film with (100) orientation comprises the following steps of: 1) lead acetate, gadolinium nitrate, 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, and the chemical formula of the preparation method is Pb1‑xGdx(ZryTi1‑y)O3The gadolinium-doped lead zirconate titanate precursor solution of (1), wherein x is 0.01 to 0.05, y is 0.52 to 0.53, and the molar ratio of acetylacetone to formamide is (0.80 to 1.50): (2.00-2.55); 2) depositing the gadolinium-doped lead zirconate titanate precursor solution on a substrate, and carrying out heat treatment to obtain a gadolinium-doped lead zirconate titanate film with (100) orientation, wherein the heat treatment comprises the following steps: firstly, rapidly drying at 150-180 ℃, then thermally decomposing at 350-450 ℃, and then annealing at 600-700 ℃. The preparation method can prepare the gadolinium-doped lead zirconate titanate film (100) with high crystal orientation degree and excellent dielectric property.

Description

Gadolinium-doped lead zirconate titanate film with (100) orientation and preparation method thereof
Technical Field
The invention relates to a lead zirconate titanate film, in particular to a gadolinium-doped lead zirconate titanate film with (100) orientation and a preparation method thereof.
Background
Lead zirconate titanate (PZT) has the chemical formula of PbZryTi1-yO3Is ABO3The perovskite-type compound has particularly outstanding dielectric, ferroelectric and piezoelectric properties at a curie temperature or lower when the atomic ratio Zr/Ti is 0.52:0.48 or 0.53:0.47 (i.e., y is 0.52 or 0.53).
At present, lead zirconate titanate materials have been widely used in ultrasonic transducers. In addition, with the development of micro-mechanical electronic systems (MEMS), the material is also widely used in micro-electromechanical systems, such as micro-actuators, micro-sensors, etc., and the execution units thereof mostly utilize the material as a driving part. Since the micro-electro-mechanical system has a feature of a micro size, etc., the thickness of the PZT material is required to be in a micro-scale range.
The existing method for preparing the PZT piezoelectric thin film comprises the following steps: laser pulse deposition (PLD), radio frequency sputtering, vapor deposition (CVD), Chemical Solution Deposition (CSD), Sol-gel (Sol-gel), and the like. 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.
Furthermore, studies have shown that: (100) the PZT piezoelectric film with preferred orientation has higher piezoelectric coefficient and has more advantages in application to micro-electro-mechanical systems. In order to prepare a PZT piezoelectric film with a higher (100) orientation degree, a layer of PZT film with a preferred (100) orientation is sputtered on a substrate in advance to have a lattice comparison with that of the PZT filmFor the purpose of matching the material as a seed layer, the seed layer material can be, for example, SrRuO3、LaNiO3And the like. The method for sputtering the seed crystal layer has long manufacturing period and high price.
In recent years, doping modification of PZT materials is one of the hot research focuses of the materials. Doping modification of PZT materials generally refers to a method of adding metal elements other than Pb, Zr, and Ti elements to achieve a change in the properties of PZT materials. The doping modification mode can be divided into hard doping, equivalent doping, soft doping, composite doping and the like; wherein, the hard doping is low-valence doping, and the low-valence ions are introduced to replace high-valence ions to form an acceptor doping effect; equivalent doping is ions with the similar properties of the radius, chemical valence and the like of the doped ions; soft doping, namely high-valence doping, wherein original ions are replaced by introducing high-valence ions to form donor doping effect; the ions doped by the composite doping can replace the ions at the A site and the B site, and a plurality of ions can be adopted for doping.
Gadolinium-doped lead zirconate titanate (PGZT) is prepared by introducing Gd into a PZT material3+Ions, which can provide some improvement in dielectric, ferroelectric, piezoelectric and fatigue resistance of the thin film. The Gd-doped PZT ferroelectric thin film was prepared and the microstructure and ferroelectricity thereof were studied (see Sun autumn et al, microstructure and ferroelectricity research of Gd-doped PZT ferroelectric thin film [ J)]Rare metal materials and engineering, vol.34, journal of 2005, page 841-844). However, the zirconium source used in the method is zirconium alkoxide, and since the alkoxide is easily hydrolyzed, the precursor is required to be operated in a dry and closed environment when being prepared, the process is relatively complex, and the manufacturing cost is increased; in particular, the orientation of the crystal orientation of the thin film prepared by the method is disordered, and the orientation degree alpha of the (100) crystal orientation100It is only 59% and the dielectric properties are not good. Therefore, a method for preparing a gadolinium-doped lead zirconate titanate thin film having a high orientation of (100) is particularly desired.
Disclosure of Invention
The invention provides a gadolinium-doped lead zirconate titanate thin film with (100) orientation and a preparation method thereof, wherein the preparation method can prepare the gadolinium-doped lead zirconate titanate thin film with high (100) crystal orientation degree and excellent dielectric property.
The invention provides a preparation method of a gadolinium-doped lead zirconate titanate film with (100) orientation, which comprises the following steps in sequence:
1) lead acetate, gadolinium nitrate, 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, and the chemical formula of the preparation method is Pb1-xGdx(ZryTi1-y)O3The gadolinium-doped lead zirconate titanate precursor solution of (1), wherein x is 0.01 to 0.05, y is 0.52 to 0.53, and the molar ratio of acetylacetone to formamide is (0.80 to 1.50): (2.00-2.55);
2) depositing the gadolinium-doped lead zirconate titanate precursor solution on a substrate, and carrying out heat treatment to obtain a gadolinium-doped lead zirconate titanate film with (100) orientation, wherein the heat treatment comprises the following steps: firstly, rapidly drying at 150-180 ℃, then thermally decomposing at 350-450 ℃, and then annealing at 600-700 ℃.
The method adopts the specific raw materials, solvent and stabilizer, utilizes a sol-gel method to prepare the gadolinium-doped lead zirconate titanate film, and dopes gadolinium into precursor solution to ensure that Gd is doped3+Ion-substituted part of Pb2+Lead vacancy appears in the crystal to promote electric domain motion, gadolinium replaces partial lead position, the gadolinium is effectively dissolved in the unit cell of lead zirconate titanate, and the film presents (100) preferred orientation; the method can lead the film to present preferred orientation of (100) without arranging a seed crystal layer on the substrate, and greatly improve the dielectric, piezoelectric and fatigue resistance of the film.
In the invention, the 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. Controlling the molar ratio of acetylacetone to formamide to be (0.80-1.50): (2.00-2.55) is favorable for obtaining the gadolinium-doped lead zirconate titanate precursor solution which is stable and has no precipitate.
Further, x is 0.01 to 0.03; y is 0.52 or 0.53; this degree of doping favors the (100) preferred orientation of the film.
In particular, when preparing the gadolinium-doped lead zirconate titanate precursor solution, the molar ratio (1.1-1.3) (1-x) between lead acetate, gadolinium nitrate, zirconium nitrate, tetrabutyl titanate, acetylacetone and formamide can be controlled: x: y: (1-y): (0.80-1.50): (2.00-2.55); wherein: (1.1-1.3) is the supplement amount of lead, namely the lead is excessive by 10-30 percent so as to compensate the volatilization of the lead in the subsequent heat treatment process. The proportion is favorable for obtaining stable gadolinium-doped lead zirconate titanate precursor solution, and the solution does not generate precipitate; through heat treatment, the film can grow along the (100) crystal orientation by self without the induction growth of the seed crystal layer, and the gadolinium-doped lead zirconate titanate film with the (100) preferred orientation is easily obtained.
Further, an acid-base regulator can be adopted to regulate the pH value of the gadolinium-doped lead zirconate titanate precursor solution; the pH adjusting agent may be, for example, acetic acid. Particularly, the pH value of the gadolinium-doped lead zirconate titanate precursor solution can be controlled to be 4.3-5.5, and the total concentration can be controlled to be 0.20-0.50 mol/L; the above conditions are easy to form a precursor solution with appropriate and stable viscosity, a continuous and uniform wet film is prepared by spin coating, and then the film is easy to be preferentially oriented along (100) by heat treatment, and the (100) crystal orientation degree of the gadolinium-doped lead zirconate titanate film can be improved.
In a specific embodiment of the present invention, the preparation method of the gadolinium-doped lead zirconate titanate precursor solution includes the following steps performed in sequence:
a) dissolving tetrabutyl titanate in acetylacetone, heating to 40-60 ℃, and keeping the temperature for 45-80 min;
b) sequentially adding zirconium nitrate, lead acetate and gadolinium nitrate into the mixed solution, then adding ethylene glycol monomethyl ether, stirring, heating to 90-120 ℃, and keeping the temperature for 45-80 min;
c) adding formamide into the mixed solution, stirring, cooling to 40-60 deg.C, and maintaining the temperature for 45-80 min.
Further, after step c), the method further comprises the following steps:
d) adding acetic acid solution into the above mixed solution, and keeping the temperature for 45-80 min.
The gadolinium-doped lead zirconate titanate precursor solution prepared by the preparation method has good stability, is beneficial to the improvement of the (100) preferred orientation and the (100) crystal orientation degree of the film, and has excellent dielectric, piezoelectric and fatigue resistance performances.
In the present invention, the gadolinium-doped lead zirconate titanate precursor solution may be deposited on a substrate using methods conventional in the art, and the deposition method may include, for example: the gadolinium-doped lead zirconate titanate precursor solution is homogenized for 9-15 seconds at the speed of 550-600 revolutions per minute, and then the film is spun on the substrate for 25-40 seconds at the speed of 2500-3200 revolutions per minute. The method can lead the gadolinium-doped lead zirconate titanate precursor solution to be uniformly covered on the substrate.
The substrate of the present invention may be a conventional substrate, such as a Pt-plated single crystal silicon substrate; in particular, the substrate is a Pt-plated monocrystalline silicon substrate which is dried for 8-20 minutes at the temperature of 150-200 ℃. Before deposition, the Pt-plated monocrystalline silicon substrate is dried to remove the moisture of the substrate, so that the bonding strength between the substrate and the film is improved, and the quality, the dielectric property and other properties of the gadolinium-doped lead zirconate titanate film formed on the substrate are ensured.
In a specific embodiment of the present invention, the heat treatment comprises: firstly, rapidly drying the mixture for 5 to 10 minutes at the temperature of 150 ℃ and 180 ℃; then thermally decomposing for 5-10 minutes at the temperature of 350-450 ℃; then annealing at 600-700 ℃ for 8-20 minutes. The heat treatment is carried out under the condition, the conversion from the pyrochlore phase to the perovskite phase in the PZT film is facilitated, the gadolinium-doped lead zirconate titanate film with the perovskite structure is obtained, the (100) crystal orientation degree of the film is high, and the piezoelectric property of the film is further facilitated to be improved.
The preparation method can obtain the gadolinium-doped lead zirconate titanate film with a single-layer thickness of 45-80nm and (100) orientation; further, the above step 2) may be repeated until a gadolinium doped lead zirconate titanate thin film having a (100) orientation with a target thickness is obtained; the target thickness may be, for example, 1 μm. Further, the deposition in the step 2) and the drying and thermal decomposition in the thermal treatment may be repeated, and the annealing treatment may be performed once again after the target thickness is reached, thereby obtaining the gadolinium-doped lead zirconate titanate thin film having the target thickness and the (100) orientation.
The invention also provides a gadolinium-doped lead zirconate titanate thin film with (100) orientation, which is prepared by the preparation method.
Further, the gadolinium-doped lead zirconate titanate thin film with (100) orientation of the invention has a perovskite structure; (100) the degree of orientation of the crystal orientation is more than 66 percent, further more than or equal to 85 percent, and further more than or equal to 90 percent; the relative dielectric constant is more than 1000, further more than 1200, still further more than 1310; the dielectric loss is less than 0.12, and further less than or equal to 0.060.
The implementation of the invention has at least the following advantages:
1. the method of the invention does not need distillation, adopts zirconium nitrate to replace alkoxide of zirconium, can simplify the operation process of precursor solution and reduce the manufacturing cost, dopes gadolinium in the precursor solution through a specific process and optimizes the heat treatment process, so that the film presents (100) preferred orientation, and the gadolinium-doped lead zirconate titanate film with (100) orientation can be obtained without arranging a seed crystal layer on a substrate.
2. The gadolinium-doped lead zirconate titanate thin film (100) prepared by the invention has the advantages that the crystal orientation degree can reach 90%, the relative dielectric constant can reach 1310, the dielectric loss is only 0.062, and the dielectric property of the thin film is excellent.
Drawings
FIG. 1 is an XRD plot of the gadolinium doped lead zirconate titanate thin film prepared in example 1;
FIG. 2 is a plot of the room temperature dielectric spectrum of the gadolinium doped lead zirconate titanate film prepared in example 1;
FIG. 3 is an XRD plot of the gadolinium doped lead zirconate titanate thin film prepared in example 2;
FIG. 4 is a plot of the room temperature dielectric spectrum of the gadolinium doped lead zirconate titanate film prepared in example 2;
FIG. 5 is an XRD plot of the gadolinium doped lead zirconate titanate thin film prepared in example 3;
FIG. 6 is a plot of the room temperature dielectric spectrum of the gadolinium doped lead zirconate titanate film prepared in example 3;
FIG. 7 is an XRD plot of the gadolinium doped lead zirconate titanate thin film prepared in comparative example 1;
FIG. 8 is a graph showing the room temperature dielectric spectrum of the gadolinium-doped lead zirconate titanate thin film prepared in comparative example 1;
FIG. 9 is an XRD plot of a gadolinium doped lead zirconate titanate thin film prepared in comparative example 2;
FIG. 10 is a graph of the room temperature dielectric spectrum of a gadolinium-doped lead zirconate titanate film prepared in comparative example 2;
FIG. 11 is an XRD plot of a gadolinium doped lead zirconate titanate thin film prepared in comparative example 3;
FIG. 12 is a graph of the room temperature dielectric spectrum of a gadolinium-doped lead zirconate titanate film prepared in comparative example 3;
wherein: py represents the pyrochlore phase.
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 drawings and 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 preparation of Pb0.99Gd0.01(Zr0.52Ti0.48)O3Film(s)
This example provides a compound of formula Pb having an (100) orientation0.99Gd0.01(Zr0.52Ti0.48)O3The gadolinium-doped lead zirconate titanate thin film is prepared.
1. Preparation of gadolinium-doped lead zirconate titanate precursor solution
Preparing materials according to the lead excess of 20%, firstly dissolving 2.87 g of tetrabutyl titanate in 1.58 g of acetylacetone, then heating to 50 ℃, and preserving heat for 1 hour to obtain a first mixed solution;
then, 3.85 g of zirconium nitrate, 7.75 g of lead acetate and 0.08 g of gadolinium nitrate are sequentially added into the first mixed solution; then, adding 30mL of ethylene glycol monomethyl ether into the first mixed solution, fully stirring until the ethylene glycol methyl ether is dissolved, heating to 100 ℃, and preserving the temperature for 1 hour to obtain a second mixed solution;
adding 1.72 g of formamide into the second mixed solution, cooling to 50 ℃, and preserving heat for 1 hour to obtain a third mixed solution;
and finally, adding an acetic acid solution with the mass content of 36% into the third mixed solution, and preserving the heat for 1 hour to obtain a gadolinium-doped lead zirconate titanate precursor solution which has the pH value of about 4.9 and the concentration of about 0.33mol/L and meets the chemical formula.
2. Deposition and thermal treatment
And (3) homogenizing the gadolinium-doped lead zirconate titanate precursor solution at 550 rpm for 10 seconds, homogenizing and spinning the film at 2900 rpm for 30 seconds, and depositing the stable gadolinium-doped lead zirconate titanate precursor solution on a Pt-plated single crystal silicon substrate which is dried at 180 ℃ for 15 minutes in advance.
And drying the Pt-plated monocrystalline silicon substrate subjected to the deposition treatment in a drying oven at 160 ℃ for 8 minutes, then pyrolyzing the Pt-plated monocrystalline silicon substrate at 450 ℃ for 8 minutes, and annealing the Pt-plated monocrystalline silicon substrate at 650 ℃ for 12 minutes to obtain the gadolinium-doped lead zirconate titanate monolayer film with the monolayer thickness of about 50 nm.
Repeating the step 2 twenty times to prepare the gadolinium-doped lead zirconate titanate film with the thickness of 1 mu m.
The XRD curve and the room temperature dielectric spectrum curve of the gadolinium-doped lead zirconate titanate thin film are respectively shown in figure 1 and figure 2. As can be seen from fig. 1: the gadolinium-doped lead zirconate titanate thin film is of a perovskite structure, and can grow along the (100) crystal orientation by self without any crystal layer induced growth, and the orientation degree of the (100) crystal orientation can be calculated according to the formula (1):
Figure BDA0001152335650000061
in the formula (1), 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 gadolinium-doped lead zirconate titanate thin film (100) was calculated to be 90.0%.
In addition, the dielectric constant of the gadolinium-doped lead zirconate titanate thin film can be calculated according to the formula (2):
Figure BDA0001152335650000062
in the formula (2), epsilonrIs the relative dielectric constant, C is the capacitance across the film, d is the thickness of the film, ε0Is vacuumDielectric constant, a is the electrode area of the membrane; the gadolinium-doped lead zirconate titanate thin film has the relative dielectric constant of 1310.35 and the dielectric loss of 0.060 of a 1-micron gadolinium-doped lead zirconate titanate thin film when the frequency is 0.1 kHz; at a frequency of 100kHz, the relative dielectric constant of a 1 micron gadolinium doped lead zirconate titanate film is 1086.80.
Example 2 preparation of Pb0.98Gd0.02(Zr0.53Ti0.47)O3Film(s)
This example provides a compound of formula Pb having an (100) orientation0.98Gd0.02(Zr0.53Ti0.47)O3The gadolinium-doped lead zirconate titanate thin film is prepared.
1. Preparation of gadolinium-doped lead zirconate titanate precursor solution
Preparing materials according to the lead excess of 10%, firstly dissolving 1.28 g of tetrabutyl titanate in 0.65 g of acetylacetone, then heating to 40 ℃, and preserving heat for 45 minutes to obtain a first mixed solution;
then, 1.82 g of zirconium nitrate, 3.27 g of lead acetate and 0.07 g of gadolinium nitrate are added to the first mixed solution in sequence; then, adding 25mL of ethylene glycol monomethyl ether into the first mixed solution, fully stirring until the ethylene glycol methyl ether is dissolved, heating to 90 ℃, and preserving the temperature for 45 minutes to obtain a second mixed solution;
adding 0.72 g of formamide into the second mixed solution, cooling to 40 ℃, and preserving heat for 45 minutes to obtain a third mixed solution;
and finally, adding an acetic acid solution with the mass content of 36% into the third mixed solution, and preserving the heat for 45 minutes to obtain a gadolinium-doped lead zirconate titanate precursor solution which has the pH value of about 4.3 and the concentration of about 0.20mol/L and meets the chemical formula.
2. Deposition and thermal treatment
And (3) homogenizing the gadolinium-doped lead zirconate titanate precursor solution at 550 rpm for 9 seconds, homogenizing and spinning the film at 2500 rpm for 25 seconds, and depositing the obtained stable gadolinium-doped lead zirconate titanate precursor solution on a Pt-plated monocrystalline silicon substrate which is dried at 150 ℃ for 20 minutes in advance.
And drying the Pt-plated monocrystalline silicon substrate subjected to the deposition treatment in a drying oven at 150 ℃ for 5 minutes, then pyrolyzing the Pt-plated monocrystalline silicon substrate at 350 ℃ for 5 minutes, and annealing the Pt-plated monocrystalline silicon substrate at 600 ℃ for 8 minutes to obtain the gadolinium-doped lead zirconate titanate single-layer film with the single-layer thickness of about 35 nm.
Repeating the step 2 twenty-eight times to prepare the gadolinium-doped lead zirconate titanate film with the thickness of 1 mu m.
The XRD curve and the room temperature dielectric spectrum curve of the gadolinium-doped lead zirconate titanate thin film are respectively shown in FIG. 3 and FIG. 4. As can be seen from fig. 3: the gadolinium-doped lead zirconate titanate thin film is of a perovskite structure, and can grow along the (100) crystal orientation by itself without any seed crystal layer induced growth.
Further, the orientation degree and the dielectric constant of the crystal orientation of the thin film (100) are calculated according to the above formula (1) and formula (2), respectively; the results show that: the orientation degree of the crystal orientation of the gadolinium-doped lead zirconate titanate thin film (100) is 69.2%; when the frequency of the film is 0.1kHz, the relative dielectric constant of the 1 micron gadolinium-doped lead zirconate titanate film is 1234.98, and the dielectric loss is 0.062; at a frequency of 100kHz, the relative dielectric constant of a 1 micron gadolinium doped lead zirconate titanate film is 1036.54.
Example 3 preparation of Pb0.97Gd0.03(Zr0.53Ti0.47)O3Film(s)
This example provides a compound of formula Pb having an (100) orientation0.97Gd0.03(Zr0.53Ti0.47)O3The gadolinium-doped lead zirconate titanate thin film is prepared.
1. Preparation of gadolinium-doped lead zirconate titanate precursor solution
Preparing materials according to the lead excess of 30%, firstly dissolving 3.20 g of tetrabutyl titanate in 3.00 g of acetylacetone, then heating to 60 ℃, and preserving heat for 80 minutes to obtain a first mixed solution;
then, 4.55 g of zirconium nitrate, 9.85 g of lead acetate and 0.28 g of gadolinium nitrate are sequentially added into the first mixed solution; then, adding 20mL of ethylene glycol monomethyl ether into the first mixed solution, fully stirring until the ethylene glycol methyl ether is dissolved, heating to 120 ℃, and preserving the temperature for 80 minutes to obtain a second mixed solution;
adding 2.30 g of formamide into the second mixed solution, cooling to 60 ℃, and preserving heat for 80 minutes to obtain a third mixed solution;
and finally, adding an acetic acid solution with the mass content of 36% into the third mixed solution, and preserving the heat for 80 minutes to obtain a gadolinium-doped lead zirconate titanate precursor solution which has the pH value of about 5.5 and the concentration of about 0.50mol/L and meets the chemical formula.
2. Deposition and thermal treatment
And (3) homogenizing the gadolinium-doped lead zirconate titanate precursor solution at 600 revolutions per minute for 15 seconds, homogenizing and spinning the film for 40 seconds at 3200 revolutions per minute, and depositing the stable gadolinium-doped lead zirconate titanate precursor solution on a Pt-plated single crystal silicon substrate which is dried at 200 ℃ for 8 minutes in advance.
And drying the Pt-plated monocrystalline silicon substrate subjected to the deposition treatment in a drying oven at 180 ℃ for 10 minutes, then pyrolyzing the Pt-plated monocrystalline silicon substrate at 450 ℃ for 10 minutes, and annealing the Pt-plated monocrystalline silicon substrate at 670 ℃ for 12 minutes to obtain the gadolinium-doped lead zirconate titanate monolayer film with the monolayer thickness of about 60 nm.
Repeating the step 2 seventeen times to prepare the gadolinium-doped lead zirconate titanate film with the thickness of 1 mu m.
The XRD curve and the room temperature dielectric spectrum curve of the gadolinium-doped lead zirconate titanate thin film are respectively shown in FIG. 5 and FIG. 6. As can be seen from fig. 5: the gadolinium-doped lead zirconate titanate thin film is of a perovskite structure, and can grow along the (100) crystal orientation by itself without any seed crystal layer induced growth.
Further, the orientation degree and the dielectric constant of the crystal orientation of the thin film (100) are calculated according to the above formula (1) and formula (2), respectively; the results show that: the orientation degree of the crystal orientation of the gadolinium-doped lead zirconate titanate thin film (100) is 66.8%; when the frequency of the film is 0.1kHz, the relative dielectric constant of the 1-micron gadolinium-doped lead zirconate titanate film is 1195.16, and the dielectric loss is 0.057; at a frequency of 100kHz, the relative dielectric constant of a 1 micron gadolinium doped lead zirconate titanate film is 1002.01.
Example 4 preparation of Pb0.99Gd0.01(Zr0.52Ti0.48)O3Film(s)
This example provides a compound of formula Pb having an (100) orientation0.99Gd0.01(Zr0.52Ti0.48)O3The gadolinium-doped lead zirconate titanate thin film is prepared.
1. Preparation of gadolinium-doped lead zirconate titanate precursor solution
Preparing materials according to the lead excess of 20%, firstly dissolving 2.87 g of tetrabutyl titanate in 1.58 g of acetylacetone, then heating to 50 ℃, and preserving heat for 1 hour to obtain a first mixed solution;
then, 3.85 g of zirconium nitrate, 7.75 g of lead acetate and 0.08 g of gadolinium nitrate are sequentially added into the first mixed solution; then, adding 30mL of ethylene glycol monomethyl ether into the first mixed solution, fully stirring until the ethylene glycol methyl ether is dissolved, heating to 100 ℃, and preserving the temperature for 1 hour to obtain a second mixed solution;
adding 1.72 g of formamide into the second mixed solution, cooling to 50 ℃, and preserving heat for 1 hour to obtain a third mixed solution;
and finally, adding an acetic acid solution with the mass content of 36% into the third mixed solution, and preserving the heat for 1 hour to obtain a gadolinium-doped lead zirconate titanate precursor solution which has the pH value of about 4.5 and the concentration of about 0.33mol/L and meets the chemical formula.
2. Deposition and thermal treatment
1) And (3) homogenizing the gadolinium-doped lead zirconate titanate precursor solution at 550 rpm for 10 seconds, homogenizing and spinning the film at 2900 rpm for 30 seconds, and depositing the stable gadolinium-doped lead zirconate titanate precursor solution on a Pt-plated single crystal silicon substrate which is dried at 180 ℃ for 15 minutes in advance.
2) Drying the Pt-plated monocrystalline silicon substrate subjected to the deposition treatment in a drying oven at 160 ℃ for 8 minutes, and then pyrolyzing the Pt-plated monocrystalline silicon substrate at 450 ℃ for 8 minutes;
3) repeating the steps 1) and 2) for 1 time;
4) annealing at 700 ℃ for 20 minutes to prepare the gadolinium-doped lead zirconate titanate film with the thickness of 0.1 mu m.
5) Repeating the steps 1) to 4) for 10 times to prepare the gadolinium-doped lead zirconate titanate film with the thickness of 1 mu m.
Calculating the orientation degree and the dielectric constant of the crystal orientation of the gadolinium-doped lead zirconate titanate film (100) according to the formula (1) and the formula (2); the results show that: the orientation degree of the crystal orientation of the gadolinium-doped lead zirconate titanate thin film (100) is 85%; at a frequency of 0.1kHz, the relative dielectric constant of a 1 micron gadolinium-doped lead zirconate titanate film is 1251.25, and the dielectric loss is 0.060.
Comparative example 1 preparation of PbZr0.52Ti0.48O3Film(s)
1. Preparation of lead zirconate titanate precursor solution
Preparing materials according to the lead excess of 20%, firstly dissolving 2.87 g of tetrabutyl titanate in 1.58 g of acetylacetone, then heating to 50 ℃, and preserving heat for 1 hour to obtain a first mixed solution;
then, 3.85 g of zirconium nitrate and 7.83 g of lead acetate were sequentially added to the first mixed solution; then, adding 30mL of ethylene glycol monomethyl ether into the first mixed solution, fully stirring until the ethylene glycol methyl ether is dissolved, heating to 100 ℃, and preserving the temperature for 1 hour to obtain a second mixed solution;
adding 1.72 g of formamide into the second mixed solution, cooling to 50 ℃, and preserving heat for 1 hour to obtain a third mixed solution;
and finally, adding an acetic acid solution with the mass content of 36% into the third mixed solution, and preserving the heat for 1 hour to obtain the lead zirconate titanate precursor solution which has the pH value of about 4.5 and the concentration of about 0.33mol/L and meets the chemical formula.
2. Deposition and thermal treatment
And (3) homogenizing the lead zirconate titanate precursor solution at 550 revolutions per minute for 10 seconds, homogenizing and spinning the film at 2900 revolutions per minute for 30 seconds, and depositing the obtained lead zirconate titanate precursor solution on a Pt-plated monocrystalline silicon substrate which is dried at 180 ℃ for 15 minutes in advance.
And drying the Pt-plated monocrystalline silicon substrate subjected to the deposition treatment in a drying oven at 160 ℃ for 8 minutes, then pyrolyzing the Pt-plated monocrystalline silicon substrate at 450 ℃ for 8 minutes, and annealing the Pt-plated monocrystalline silicon substrate at 650 ℃ for 12 minutes to obtain the lead zirconate titanate single-layer film with the single-layer thickness of about 50 nm.
Repeating the step 2 twenty times to prepare the lead zirconate titanate film with the thickness of 1 mu m.
The XRD profile and room temperature dielectric spectrum profile of the above lead zirconate titanate thin film are shown in FIG. 7 and FIG. 8, respectively. As can be seen from fig. 7: the crystal orientation of the lead zirconate titanate thin film tends to be disordered, and the orientation degree of the crystal orientation of the thin film (100) is calculated according to the formula (1); the results show that: the degree of orientation of the crystal orientation of the gadolinium-free lead zirconate titanate thin film (100) was 59.3%.
Further, the dielectric constant of the lead zirconate titanate thin film was calculated in accordance with the above formula (2); the results show that: at a frequency of 0.1kHz, the relative dielectric constant of the lead zirconate titanate thin film of 1 micron is 976.30, and the dielectric loss is 0.094; at a frequency of 100kHz, the gadolinium-doped lead zirconate titanate thin film of 1 micron had a relative dielectric constant of 754.94 and a dielectric loss of 0.113.
Comparative example 2 preparation of Pb0.99Gd0.01(Zr0.52Ti0.48)O3Film(s)
1. Preparation of lead zirconate titanate precursor solution
Firstly, controlling the molar ratio of lead acetate, gadolinium nitrate, zirconium nitrate, tetrabutyl titanate, acetylacetone and formamide to be 1.05 (1-x): x: y: (1-y): 3.0: 1.0, wherein x is 0.01 and y is 0.52.
Dissolving 3.59 g of tetrabutyl titanate in 6.60 g of acetylacetone, heating to 40 ℃, and preserving heat for 30min to obtain a first mixed solution;
then, 4.90 g of zirconium nitrate and 8.76 g of lead acetate are sequentially added into the first mixed solution; then, adding 20mL of ethylene glycol monomethyl ether into the first mixed solution, fully stirring until the ethylene glycol methyl ether is dissolved, heating to 80 ℃, and preserving the temperature for 1 hour to obtain a second mixed solution;
adding 0.80 g of formamide into the second mixed solution, cooling to 50 ℃, and preserving heat for 1 hour to obtain a third mixed solution;
and finally, adding an acetic acid solution with the mass content of 36% into the third mixed solution, and preserving the heat for 1 hour to obtain the lead zirconate titanate precursor solution which has the pH value of about 6.0 and the concentration of about 0.55mol/L and meets the chemical formula.
2. Deposition and thermal treatment
And (3) homogenizing the lead zirconate titanate precursor solution at 550 rpm for 10 seconds, homogenizing and spinning the film at 2900 rpm for 30 seconds, and depositing the obtained lead zirconate titanate precursor solution on the Pt-plated single crystal silicon substrate.
And drying the Pt-plated monocrystalline silicon substrate subjected to the deposition treatment in a drying oven at 160 ℃ for 8 minutes, then pyrolyzing the Pt-plated monocrystalline silicon substrate at 450 ℃ for 8 minutes, and annealing the Pt-plated monocrystalline silicon substrate at 650 ℃ for 12 minutes to obtain the lead zirconate titanate single-layer film with the single-layer thickness of about 85 nm.
Repeating the step 2 for twelve times to prepare the lead zirconate titanate film with the thickness of 1 mu m.
The XRD curve and the room temperature dielectric spectrum curve of the lead zirconate titanate thin film are respectively shown in FIG. 9 and FIG. 10. As can be seen from fig. 9: the lead zirconate titanate thin film has a disordered crystal orientation and a pyrochlore phase of lead zirconate titanate PGZT (Py).
Further, the dielectric constant of the lead zirconate titanate thin film was calculated in accordance with the above formula (2); the results show that: at a frequency of 0.1kHz, the relative dielectric constant of the lead zirconate titanate thin film of 1 micron is 743.30, and the dielectric loss is 0.043; at a frequency of 100kHz, the relative dielectric constant of a 1 micron gadolinium-doped lead zirconate titanate film was 650.16, and the dielectric loss was 0.077.
Comparative example 3 preparation of Pb0.98Gd0.02(Zr0.52Ti0.48)O3Film(s)
1. Preparation of gadolinium-doped lead zirconate titanate precursor solution
Preparing materials according to the lead excess of 20%, firstly dissolving 2.87 g of tetrabutyl titanate in 1.58 g of acetylacetone, then heating to 50 ℃, and preserving heat for 1 hour to obtain a first mixed solution;
then, 3.85 g of zirconium nitrate, 7.67 g of lead acetate and 0.16 g of gadolinium nitrate are sequentially added to the first mixed solution; then, adding 30mL of ethylene glycol monomethyl ether into the first mixed solution, fully stirring until the ethylene glycol methyl ether is dissolved, heating to 100 ℃, and preserving the temperature for 1 hour to obtain a second mixed solution;
adding 1.72 g of formamide into the second mixed solution, cooling to 50 ℃, and preserving heat for 1 hour to obtain a third mixed solution;
and finally, adding an acetic acid solution with the mass content of 36% into the third mixed solution, and preserving the heat for 1 hour to obtain a gadolinium-doped lead zirconate titanate precursor solution which has the pH value of about 4.5 and the concentration of about 0.33mol/L and meets the chemical formula.
2. Deposition and thermal treatment
And (3) homogenizing the gadolinium-doped lead zirconate titanate precursor solution at 550 rpm for 10 seconds, homogenizing and spinning the film at 2900 rpm for 30 seconds, and depositing the stable gadolinium-doped lead zirconate titanate precursor solution on a Pt-plated single crystal silicon substrate which is dried at 180 ℃ for 15 minutes in advance.
And drying the Pt-plated monocrystalline silicon substrate subjected to the deposition treatment in a drying oven at 120 ℃ for 8 minutes, then pyrolyzing the Pt-plated monocrystalline silicon substrate at 250 ℃ for 8 minutes, and annealing the Pt-plated monocrystalline silicon substrate at 550 ℃ for 12 minutes to obtain the gadolinium-doped lead zirconate titanate monolayer film with the monolayer thickness of about 50 nm.
Repeating the step 2 twenty times to prepare the gadolinium-doped lead zirconate titanate film with the thickness of 1 mu m.
The XRD curve and the room temperature dielectric spectrum curve of the gadolinium-doped lead zirconate titanate thin film are respectively shown in FIG. 11 and FIG. 12. As can be seen from fig. 11: the gadolinium-doped lead zirconate titanate thin film has disordered crystal orientation and mainly takes pyrochlore phase, namely PGZT (Py).
In addition, the dielectric constants of the films are calculated according to the above formula (2), respectively; the results show that: when the frequency of the film is 0.1kHz, the relative dielectric constant of the 1-micron gadolinium-doped lead zirconate titanate film is 81.66, and the dielectric loss is 0.017; at a frequency of 100kHz, the gadolinium-doped lead zirconate titanate thin film of 1 micron had a relative dielectric constant of 76.95 and a dielectric loss of 0.020.
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 (8)

1. A method for preparing a gadolinium-doped lead zirconate titanate thin film having a (100) orientation, wherein the gadolinium-doped lead zirconate titanate thin film has a degree of (100) crystal orientation greater than 66%, the method comprising the sequential steps of:
1) lead acetate, gadolinium nitrate, 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, and a chemical formula is preparedIs Pb1-xGdx(ZryTi1-y)O3The gadolinium-doped lead zirconate titanate precursor solution of (1), wherein x is 0.01 to 0.05, y is 0.52 to 0.53, and the molar ratio of acetylacetone to formamide is (0.80 to 1.50): (2.00-2.55);
the preparation method of the gadolinium-doped lead zirconate titanate precursor solution comprises the following steps of:
a) dissolving tetrabutyl titanate in acetylacetone, heating to 40-60 ℃, and keeping the temperature for 45-80 min;
b) sequentially adding zirconium nitrate, lead acetate and gadolinium nitrate into the mixed solution, then adding ethylene glycol monomethyl ether, stirring, heating to 90-120 ℃, and keeping the temperature for 45-80 min;
c) adding formamide into the mixed solution, stirring, cooling to 40-60 deg.C, and maintaining for 45-80 min;
d) adding acetic acid solution into the mixed solution, and keeping the temperature for 45-80 min;
2) depositing the gadolinium-doped lead zirconate titanate precursor solution on a substrate, and carrying out heat treatment to obtain a gadolinium-doped lead zirconate titanate film with (100) orientation, wherein the heat treatment comprises the following steps: firstly, rapidly drying at 150-180 ℃, then thermally decomposing at 350-450 ℃, and then annealing at 600-700 ℃.
2. The method according to claim 1, wherein the molar ratio (1.1-1.3) (1-x) between lead acetate, gadolinium nitrate, zirconium nitrate, tetrabutyl titanate, acetylacetone, and formamide is controlled in preparing the gadolinium-doped lead zirconate titanate precursor solution: x: y: (1-y): (0.80-1.50): (2.00-2.55).
3. The preparation method according to claim 1, wherein the gadolinium-doped lead zirconate titanate precursor solution has a pH value of 4.3-5.5 and a concentration of 0.20-0.50 mol/L.
4. The production method according to any one of claims 1 to 3, wherein the depositing includes:
the gadolinium-doped lead zirconate titanate precursor solution is homogenized for 9-15 seconds at the speed of 550-600 revolutions per minute, and then the film is spun on the substrate for 25-40 seconds at the speed of 2500-3200 revolutions per minute.
5. The method as claimed in claim 4, wherein the substrate is a Pt-plated single crystal silicon substrate which is dried at 200 ℃ for 8-20 minutes.
6. The production method according to any one of claims 1 to 3 and 5, wherein the heat treatment comprises: firstly, rapidly drying the mixture for 5 to 10 minutes at the temperature of 150 ℃ and 180 ℃; then thermally decomposing for 5-10 minutes at the temperature of 350-450 ℃; then annealing at 600-700 ℃ for 8-20 minutes.
7. The method of claim 6, wherein step 2) is repeated until a gadolinium doped lead zirconate titanate film having a target thickness and a (100) orientation is obtained.
8. A gadolinium-doped lead zirconate titanate thin film having a (100) orientation, characterized in that it is produced by the process according to any one of claims 1 to 7.
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