CN115094509A - Lead zirconate titanate single crystal and preparation method and application thereof - Google Patents
Lead zirconate titanate single crystal and preparation method and application thereof Download PDFInfo
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- 239000013078 crystal Substances 0.000 title claims abstract description 124
- 229910052451 lead zirconate titanate Inorganic materials 0.000 title claims abstract description 115
- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 60
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000001816 cooling Methods 0.000 claims abstract description 32
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 30
- 239000000155 melt Substances 0.000 claims abstract description 22
- 238000002844 melting Methods 0.000 claims abstract description 19
- 230000008018 melting Effects 0.000 claims abstract description 19
- 239000006184 cosolvent Substances 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- 238000007789 sealing Methods 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000010936 titanium Substances 0.000 claims abstract description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 229910001928 zirconium oxide Inorganic materials 0.000 claims abstract description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 8
- 238000005245 sintering Methods 0.000 claims abstract description 8
- 238000002791 soaking Methods 0.000 claims abstract description 8
- 238000005498 polishing Methods 0.000 claims abstract description 6
- 238000000227 grinding Methods 0.000 claims abstract description 5
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 5
- 238000004140 cleaning Methods 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 229910000464 lead oxide Inorganic materials 0.000 claims abstract 5
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 claims abstract 5
- 239000011698 potassium fluoride Substances 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 8
- 238000011049 filling Methods 0.000 claims description 6
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 5
- 229910052810 boron oxide Inorganic materials 0.000 claims description 3
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 3
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 claims description 3
- 235000003270 potassium fluoride Nutrition 0.000 claims 2
- 239000000919 ceramic Substances 0.000 abstract description 13
- 238000011161 development Methods 0.000 abstract description 3
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 23
- 230000009467 reduction Effects 0.000 description 8
- 229910010413 TiO 2 Inorganic materials 0.000 description 7
- 238000003384 imaging method Methods 0.000 description 7
- 238000001069 Raman spectroscopy Methods 0.000 description 6
- 230000006911 nucleation Effects 0.000 description 6
- 238000010899 nucleation Methods 0.000 description 6
- 230000002269 spontaneous effect Effects 0.000 description 6
- 238000010583 slow cooling Methods 0.000 description 5
- 238000003746 solid phase reaction Methods 0.000 description 5
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- 238000001453 impedance spectrum Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 238000001237 Raman spectrum Methods 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
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- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- GEIAQOFPUVMAGM-UHFFFAOYSA-N Oxozirconium Chemical compound [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
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- 210000004204 blood vessel Anatomy 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
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- 238000013461 design Methods 0.000 description 1
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- 230000005684 electric field Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002608 intravascular ultrasound Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 230000035772 mutation Effects 0.000 description 1
- 238000009659 non-destructive testing Methods 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B9/00—Single-crystal growth from melt solutions using molten solvents
- C30B9/04—Single-crystal growth from melt solutions using molten solvents by cooling of the solution
- C30B9/08—Single-crystal growth from melt solutions using molten solvents by cooling of the solution using other solvents
- C30B9/12—Salt solvents, e.g. flux growth
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B06—GENERATING OR TRANSMITTING MECHANICAL VIBRATIONS IN GENERAL
- B06B—METHODS OR APPARATUS FOR GENERATING OR TRANSMITTING MECHANICAL VIBRATIONS OF INFRASONIC, SONIC, OR ULTRASONIC FREQUENCY, e.g. FOR PERFORMING MECHANICAL WORK IN GENERAL
- B06B1/00—Methods or apparatus for generating mechanical vibrations of infrasonic, sonic, or ultrasonic frequency
- B06B1/02—Methods or apparatus for generating mechanical vibrations of infrasonic, sonic, or ultrasonic frequency making use of electrical energy
- B06B1/06—Methods or apparatus for generating mechanical vibrations of infrasonic, sonic, or ultrasonic frequency making use of electrical energy operating with piezoelectric effect or with electrostriction
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/16—Oxides
- C30B29/22—Complex oxides
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- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The invention provides a lead zirconate titanate single crystal and a preparation method and application thereof, wherein the preparation method comprises the following steps: the raw materials of lead oxide, zirconium oxide and titanium dioxide are mixed according to Pb (Zr) 1‑x Ti x )O 3 Proportioning according to the stoichiometric ratio, placing x being 0.45-0.48 in a platinum crucible, mixing with a cosolvent, and sealing; placing the platinum crucible in an alumina crucible, sintering the sealed alumina crucible at a high temperature, melting a melt, growing, and cooling after the growth is finished; taking down lead zirconate titanate crystal grains by adopting a heating and soaking mode of dilute nitric acid, and grinding, polishing and cleaning; compared with the traditional lead zirconate titanate ceramic, the lead zirconate titanate single crystal has higher piezoelectric performance, and compared with PMN-xPT single crystal, the lead zirconate titanate single crystal has higher temperature stability and consistency, thereby improving the piezoelectric performance of the material, and further improving the piezoelectric performance of the materialThe transducer is fundamentally improved, and therefore, the method has great significance for the development of commercial high-frequency ultrasonic transducers.
Description
Technical Field
The invention belongs to the technical field of crystal growth, and particularly relates to a lead zirconate titanate single crystal, a preparation method and application thereof, which are specially used for preparing a miniature high-frequency ultrasonic transducer.
Background
Compared with millimeter-level resolution of the traditional medical ultrasonic imaging technology, the spatial resolution of high-frequency medical ultrasonic imaging can reach dozens of micrometers, so that ultrasonic imaging and nondestructive diagnosis of fine structures of human tissues such as eyes, skin and vessel walls can be realized. The performance of the high-frequency ultrasonic transducer, which is used as a core component of a high-frequency ultrasonic imaging system, determines the imaging quality, and the piezoelectric material with high piezoelectricity, high stability and low cost is the key for commercially preparing the high-frequency ultrasonic transducer.
Lead zirconate titanate (PZT) ceramics are the most widely used piezoelectric materials at present, and have excellent comprehensive performances such as piezoelectricity, temperature stability and the like. Currently, commercial high frequency ultrasonic transducers still use PZT ceramics. The ferroelectric single crystal generally has a higher piezoelectric performance 4-5 times higher than that of ceramics of the same composition, for example, a large-sized PMN-xPT single crystal which has been successfully grown and has a piezoelectric coefficient d 33 The temperature stability and consistency of the ceramic reaches 2000pC/N, but in practical application, the ceramic is lower than PZT ceramic. Although the piezoelectric coefficient of PZT ceramic is only one third of that of PMN-xPT single crystal (d) 33 660 pC/N), but if PZT is prepared into single crystal, the piezoelectric coefficient of the PZT reaches the PMN-xPT single crystal level, and the PZT has higher temperature stability and consistency, and is beneficial to preparing a new generation of high-performance high-frequency ultrasonic probe. However, PZT itself is difficult to crystallize, centimeter-sized and large-sized PZT single crystals are difficult to obtain, and the size of the high-quality PZT single crystals which can be prepared is 1-2 mm.
The center frequency of a high-frequency medical ultrasonic transducer represented by intravascular ultrasound (IVUS) reaches 40MHz or more, and the thickness of a piezoelectric material is required to be less than 50 μm. At the same time, its transverse dimension is less than 0.5 mm. Therefore, the advantages of the conventional large-sized PMN-xPT single crystal in the high-frequency ultrasonic transducer application are not significant. The PZT single crystal can realize 1-2mm of single high-quality crystal grains, is just suitable for the size of a high-frequency ultrasonic transducer, and has high performance and high temperature stability. Therefore, the development of a PZT single crystal preparation method for preparing high-quality PZT single crystals at low cost is of great significance for the development of commercial high-performance high-frequency ultrasonic transducers.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a PZT single crystal and a preparation method and application thereof.
In order to achieve the purpose, the solution of the invention is as follows:
in a first aspect, the present invention provides a method for preparing a PZT single crystal, comprising the steps of:
(1) lead oxide (PbO) and zirconium oxide (ZrO) as raw materials 2 ) And titanium dioxide (TiO) 2 ) According to Pb (Zr) 1-x Ti x )O 3 Proportioning according to a stoichiometric ratio, wherein x is 0.45-0.48, then putting the mixture into a platinum crucible, mixing the mixture with a cosolvent, and sealing;
(2) after sealing, placing the platinum crucible in an alumina crucible, and filling a gap between the alumina crucible and the platinum crucible with alumina powder;
(3) sintering the sealed alumina crucible at high temperature until the melt is melted;
(4) melting the melt, growing, and cooling after the growth is finished;
(5) and after cooling, taking down the lead zirconate titanate crystal grains by adopting a heating and soaking mode of dilute nitric acid, and grinding, polishing and cleaning to obtain the PZT single crystal.
Preferably, in step (1), PbO, ZrO 2 And TiO 2 The purities of the compounds are all more than 99.8 percent.
Preferably, in the step (1), the cosolvent is PbO, potassium fluoride (KF) and lead chloride (PbCl) 2 ) And boron oxide (B) 2 O 3 ) A mixture of (a).
Preferably, in the step (1), Pb (Zr) 1-x Ti x )O 3 And co-solvent of PbO, KF and PbCl 2 And B 2 O 3 Is (10 +/-2): (4 ± 1): (2 ± 0.5): (4 ± 1): (3 ± 0.5), wherein x is 0.45-0.48.
Preferably, in the step (3), the temperature for melting the melt is 1050-.
Preferably, in the step (4), the temperature of the growth is 1150-.
Preferably, in the step (4), the temperature reduction rate after the growth is finished is 15-50 ℃/h.
In a second aspect, the present invention provides a PZT single crystal obtained by the above-described production method.
In a third aspect, the invention provides an application of the PZT single crystal, and the application of the PZT single crystal in the preparation of a miniature high-frequency ultrasonic transducer.
Due to the adoption of the scheme, the invention has the beneficial effects that:
compared with the traditional PZT ceramic, the obtained PZT single crystal has higher piezoelectric performance, and compared with the PMN-xPT single crystal, the PZT single crystal has higher temperature stability and consistency, so that the piezoelectric performance of the material is improved, and the transducer is fundamentally improved.
Drawings
FIG. 1 is a drawing showing a PZT single crystal grown in example 1 of the present invention.
FIG. 2 is an X-ray polycrystalline diffraction pattern of a PZT crystal in example 1 of the present invention.
FIG. 3 is an X-ray single crystal diffraction pattern of a PZT crystal grown in example 2 of the present invention.
Fig. 4 is a raman spectrum corresponding to two ferroelectric domains in the PZT crystal in example 2 of the present invention.
FIG. 5 is a graph showing the change of the electrical resistance property of a PZT crystal with frequency (impedance spectrum) and the change of the impedance spectrum with temperature in example 3 of the present invention.
FIG. 6 is a structural view of a miniature high frequency ultrasonic transducer of a PZT crystal design grown in embodiment 4 of the present invention.
FIG. 7 is a graph showing the echo signal and bandwidth of a miniature high-frequency ultrasonic transducer made of a PZT crystal grown in example 4 of the present invention.
Reference numerals: 1-PZT single chip, 2-inner matching layer, 3-outer matching layer, 4-back lining, 5-lead, 6-stainless steel needle tube and 7-intravascular ultrasonic transducer.
Detailed Description
The invention provides a PZT single crystal and a preparation method and application thereof.
The preparation method of the PZT single crystal of the present invention comprises the steps of:
(1) and raw material pretreatment: raw materials of PbO and ZrO 2 And TiO 2 2 According to Pb (Zr) 1-x Ti x )O 3 Proportioning according to a stoichiometric ratio, wherein x is 0.45-0.48, and synthesizing PZT powder; then placing the mixture into a platinum crucible to be mixed with a cosolvent to carry out solid-phase reaction, and sealing;
(2) after the platinum crucible is tightly sealed, the platinum crucible is placed in an alumina crucible, and a gap between the alumina crucible and the platinum crucible is filled with alumina powder to prevent the platinum crucible from collapsing and leaking;
(3) heating and melting: placing the sealed alumina crucible into a high-temperature furnace for high-temperature sintering, and heating at high temperature until the melt is completely melted;
(4) growing and cooling: growing after the melt is melted, growing PZT grains in a spontaneous nucleation mode, cooling after the growth is finished, and separating out the PZT grains in the spontaneous nucleation mode;
(5) taking out crystals: and after cooling, separating the platinum crucible from the alumina crucible, taking down the PZT crystal grains by adopting a mode of heating and soaking by using dilute nitric acid, carrying out grinding and polishing operations on the single crystal grains by using a polishing machine, and then cleaning the surface of the single crystal by using ultrasonic waves to obtain the PZT single crystal.
In the step (1), both the raw material and the cosolvent contain PbO, wherein PbO in the raw material is used for preparing PZT to meet the stoichiometric ratio in the chemical formula of PZT, and PbO in the cosolvent is added subsequently to promote dissolution of the raw material and reduce the melting point.
In step (1), PbO, ZrO 2 And TiO 2 The purities of the compounds are all more than 99.8 percent.
In the step (1), the cosolvent is PbO, KF or PbCl 2 And B 2 O 3 And Pb (Zr) 1-x Ti x )O 3 And cosolvent PbO, KF and PbCl 2 And B 2 O 3 Is (10 +/-2): (4 ± 1): (2 ± 0.5): (4 ± 1): (3 ± 0.5), wherein x is 0.45-0.48.
In step (3), the temperature for melting the melt can be 1050-; the time can be 6-9h, preferably 9h (both higher melting temperature and longer melting time are chosen to allow more complete dissolution of the PZT feedstock in the co-solvent for subsequent growth to obtain a high quality single crystal).
In the step (4), a cosolvent slow cooling method is adopted for growth, and the temperature is reduced to be below the melting point (1080 ℃) of the melt during growth, namely the temperature reduction temperature for growth is 1150-1050 ℃; the temperature reduction in the growth stage is to slowly precipitate crystals, so the temperature reduction rate is slow and needs to be controlled accurately, and the temperature reduction rate of the growth can be 5-7 ℃/h, and is preferably 7 ℃/h. The cooling rate during crystal growth directly influences the rate of growing the crystal, thereby controlling the growth quality of the crystal, and the slower the cooling rate is, the better the quality of the grown crystal is.
In the step (4), the cooling-down stage after the growth is finished is to rapidly cool down to room temperature and take out the crystal, so that the cooling-down rate can be increased to save time, and therefore, the cooling-down rate can be 15-50 ℃/h, and is preferably 40 ℃/h. The main purpose of cooling is to cool the temperature in the furnace to room temperature so as to take out the crystal. The cooling rate can be increased at this time to save time. Meanwhile, the temperature reduction rate is selected in consideration of the tolerance capacity of the furnace to rapid temperature reduction, so that the growth furnace is prevented from being damaged.
The PZT single crystal of the present invention is obtained by the above-mentioned preparation method in a bulk shape having a size of 2mm × 2mm × 1 mm. Electromechanical coupling coefficient k of PZT single crystal t 64 to 67% of a dielectric constant ε r 4000-4200, the dielectric loss tan delta is 0.5-0.6%, and the piezoelectric constant d 33 Is 1200-1500 pC/N.
Piezoelectric constant d of PMN-xPT single crystal which is practically commercially available 33 1300-2000pC/N, the piezoelectric constant d of the PZT single crystal of the present invention 33 Is 1200-1500pC/N, which are at the same level and belong to high-performance piezoelectric materials. In addition, the piezoelectric constant d of PZT ceramics which are widely used at present 33 660pC/N, the piezoelectricity of the PZT single crystal prepared by the invention is far better than that of the commercial PZT ceramic, so the PZT single crystal has stronger piezoelectric response.
The PZT single crystal of the present invention is applied to the preparation of a miniature high-frequency ultrasonic transducer, and the size of a PZT wafer required for manufacturing a piezoelectric vibration element of the miniature high-frequency ultrasonic transducer is 0.5mm multiplied by 50 mu m.
And plating gold electrodes on the upper surface and the lower surface of the cleaned and dried wafer by magnetron sputtering according to the frequency requirement of the transducer. And then the PZT crystal grains are polarized by adding direct current voltage to ensure that the PZT crystal grains have piezoelectric performance, and then the PZT crystal grains are placed on an impedance analyzer to measure an impedance spectrum of the PZT crystal grains.
In conclusion, the invention can obtain the PZT single crystal with complete structure and high quality and performance, and the size of the PZT single crystal is more than 1mm, so the PZT single crystal can be used for preparing the miniature high-frequency ultrasonic transducer in the fields of medical ultrasonic imaging, nondestructive testing and the like.
The invention is further illustrated by the following specific examples and the accompanying drawings. The following modes are only for illustrating the present invention and do not limit the present invention.
Example 1:
the method for preparing a PZT single crystal of this example (i.e., using the slow cooling method) includes the steps of:
(1) the purity of PbO and ZrO is more than 99.8 percent 2 And TiO 2 2 According to Pb (Zr) 0.55 Ti 0.45 )O 3 Proportioning according to a chemical formula, and then placing the mixture in a platinum crucible to neutralize PbO, KF and PbCl 2 And B 2 O 3 As a cosolvent, PZT: PbO: KF: PbCl 2 :B 2 O 3 The molar ratio of the raw materials is 10:4:2:4:3, solid-phase reaction is carried out, and sealing is carried out;
(2) after sealing tightly, placing the platinum crucible in an alumina crucible, and filling the gap between the alumina crucible and the platinum crucible with alumina powder;
(3) and placing the sealed alumina crucible into a high-temperature furnace for high-temperature sintering, and heating at a high temperature until the melt is completely melted, wherein the melting temperature is 1150 ℃ and the melting time is 9 hours.
(4) After the melt is melted, the melt grows, the temperature is slowly reduced from 1150 ℃ to 1050 ℃, crystals can be separated out, and the cooling rate during the growth is 7 ℃/h; cooling after the growth is finished, quickly cooling from 1050 ℃ to 25 ℃ at the cooling rate of 40 ℃/h, and separating out PZT grains in a spontaneous nucleation mode;
(5) and after cooling, separating the platinum crucible from the alumina crucible, and taking down PZT grains with the grain size of 2.0mm by adopting a heating and soaking mode of dilute nitric acid, as shown in figure 1. Then, 5g of PZT grains were pulverized with an agate mortar, sieved, compacted, and subjected to powder XRD test, the results are shown in FIG. 2. From XRD spectrum, the grown PZT monocrystal has pure perovskite crystal structure, good crystallinity, complete crystal, no defect and no impurity phase.
Example 2:
the method for preparing a PZT single crystal of this example (i.e., using the slow cooling method) includes the steps of:
(1) the purity of PbO and ZrO is more than 99.8 percent 2 And TiO 2 According to Pb (Zr) 0.54 Ti 0.46 )O 3 Proportioning according to a chemical formula, and then placing the mixture in a platinum crucible to neutralize PbO, KF and PbCl 2 And B 2 O 3 As a cosolvent, PZT: PbO: KF: PbCl 2 :B 2 O 3 The molar ratio of the raw materials is 10:4:2:4:3, solid-phase reaction is carried out, and sealing is carried out;
(2) after sealing tightly, placing the platinum crucible in an alumina crucible, and filling the gap between the alumina crucible and the platinum crucible with alumina powder;
(3) placing the sealed alumina crucible into a high-temperature furnace for high-temperature sintering, and heating at a high temperature until the melt is completely melted, wherein the melting temperature is 1150 ℃ and the melting time is 9 hours;
(4) the melt is melted and then grows, the temperature is slowly reduced from 1150 ℃ to 1050 ℃ to precipitate crystals, and the temperature reduction rate during growth is 6 ℃/h; cooling after the growth is finished, quickly cooling from 1050 ℃ to 25 ℃ at the cooling rate of 40 ℃/h, and separating out PZT grains in a spontaneous nucleation mode;
(5) and after cooling, separating the platinum crucible from the alumina crucible, and taking down the PZT crystal grains by adopting a heating and soaking mode of dilute nitric acid. Judging the crystal face orientation according to the cleavage plane of the crystal grain, adhering the crystal grain on a glass substrate, carrying out X-ray single crystal orientation, and grinding and polishing the surface. The polished wafer is subjected to X-ray single crystal diffraction, as shown in FIG. 3, the single crystal diffraction peak of the crystal face of the PZT crystal (200) is a single crystal diffraction peak with good peak shape and narrow peak width, which indicates that the grown PZT single crystal is perfect in crystallinity and is a complete single crystal. In addition, raman spectroscopy of the ferroelectric domain was performed on the PZT single crystal (200) crystal plane using raman spectroscopy, as shown in fig. 4, all raman-activated vibration modes corresponded to the standard PZT raman scattering peak, and the raman scattering peak (ferroelectric domain 2) of the PZT single crystal was sharper than the conventional PZT ceramic (ferroelectric domain 1), indicating that the PZT single crystal grown in this example has a domain structure of ferroelectric, and the symmetry of the micro lattice corresponded exactly to the PZT quasi-morphotropic phase boundary component, which was closer to ideal in the symmetry of the micro lattice, and the crystal quality was high.
Example 3:
the method for preparing a PZT single crystal of this example (i.e., using the slow cooling method) includes the steps of:
(1) the purity of PbO and ZrO is more than 99.8 percent 2 And TiO 2 According to Pb (Zr) 0.53 Ti 0.47 )O 3 Proportioning according to a chemical formula, and then placing the mixture in a platinum crucible to neutralize PbO, KF and PbCl 2 And B 2 O 3 As a cosolvent, PZT, PbO, KF, PbCl 2 :B 2 O 3 The molar ratio of (1) is 12:5:2.5:5:3.5, solid phase reaction is carried out, and sealing is carried out;
(2) after sealing tightly, placing the platinum crucible in an alumina crucible, and filling the gap between the alumina crucible and the platinum crucible with alumina powder;
(3) placing the sealed alumina crucible into a high-temperature furnace for high-temperature sintering, and heating at a high temperature until the melt is completely melted, wherein the melting temperature is 1150 ℃ and the melting time is 9 hours;
(4) after the melt is melted, the melt grows, the temperature is slowly reduced from 1150 ℃ to 1050 ℃, crystals can be separated out, and the cooling rate during the growth is 7 ℃/h; cooling after the growth is finished, quickly cooling from 1050 ℃ to 25 ℃ at the cooling rate of 40 ℃/h, and separating out PZT grains in a spontaneous nucleation mode;
(5) and after cooling, separating the platinum crucible from the alumina crucible, and taking down PZT crystal grains with the size of 2.0mm by adopting a mode of heating and soaking by dilute nitric acid. And judging the orientation of a crystal face according to the cleavage plane of the crystal grain, adhering the crystal to a glass substrate, thinning and scribing to obtain a complete wafer which has no macroscopic defect and has the size of 1 mm. Plating gold electrodes on the upper and lower surfaces of the wafer by ion sputtering, and polarizing in silicone oil for 30min with a polarizing electric field of 1000V/mm. Then, the ferroelectric property, the piezoelectric property, the dielectric property and the impedance spectrum were tested, as shown in fig. 5. The main performance is that the electromechanical coupling coefficient k t About 65% and a dielectric constant ε r About 4000, dielectric loss tan delta of about 0.5%, and piezoelectric constant d 33 About 1200 pC/N. Therefore, the PZT crystal grown by the method of the embodiment has stronger piezoelectric response. Firstly, compared with the traditional PZT ceramic, the PZT single crystal prepared by the invention has strong scattering peak intensity and narrow peak width in Raman spectrum, and reflects that the crystal lattice vibration mode is very pure. Secondly, the number of the measured Raman activation scattering peaks is completely consistent with the theoretical calculation, and no redundant scattering peaks exist, which indicates that the vibration mode is relatively pure and the microstructure is very complete. Piezoelectric constant d of PZT crystal during temperature rise 33 Can maintain a stable value at 150 ℃, the piezoelectric performance is relatively stable, and the piezoelectric constant d of the PMN-xPT monocrystal 33 The piezoelectric ceramic material has mutation at 80 ℃, and has stable piezoelectric performance below 80 ℃; the piezoelectric properties of PZT single crystals in different batches do not change greatly, while the PMN-xPT single crystals are influenced by the internal domain structure, and the piezoelectric properties of samples in different batches fluctuate greatly, such as the piezoelectric constant d of 100 PZT single crystals 33 Variance of less than 5 and piezoelectric constant d of PMN-xPT wafer 33 The variance of (a) is less than 100, so that the PZT single crystal of this example has better temperature stability and consistency than the PMN-xPT single crystal.
Example 4:
the method for preparing a PZT single crystal of this example (i.e., using the slow cooling method) includes the steps of:
(1) the purity of PbO and ZrO is more than 99.8 percent 2 And TiO 2 According to Pb (Zr) 0.52 Ti 0.48 )O 3 Proportioning according to a chemical formula, and then placing the mixture in a platinum crucible to neutralize PbO, KF and PbCl 2 And B 2 O 3 As a cosolvent, PZT: PbO: KF: PbCl 2 :B 2 O 3 In a molar ratio of 12:5:2.5:5:3.5, carrying out solid phase reaction, and sealing;
(2) after sealing tightly, placing the platinum crucible in an alumina crucible, and filling the gap between the alumina crucible and the platinum crucible with alumina powder;
(3) placing the sealed alumina crucible into a high-temperature furnace for high-temperature sintering, and heating at a high temperature until the melt is completely melted, wherein the melting temperature is 1150 ℃ and the melting time is 9 hours;
(4) after the melt is melted, the melt grows, the temperature is slowly reduced from 1150 ℃ to 1050 ℃, crystals can be separated out, and the cooling rate during the growth is 7 ℃/h; cooling after the growth is finished, quickly cooling from 1050 ℃ to 25 ℃ at the cooling rate of 30 ℃/h, and separating out PZT grains in a spontaneous nucleation mode;
(5) and after cooling, separating the platinum crucible from the alumina crucible, and taking down the PZT crystal grains by adopting a heating and soaking mode of dilute nitric acid. And a high-frequency intravascular ultrasonic transducer 7 made of PZT single crystals is used for ultrasonic imaging of a blood vessel wall, namely, the PZT single crystal sheet 1, the inner matching layer 2 and the outer matching layer 3 are sequentially arranged on the surface of the backing 4 from bottom to top and are connected by a lead 5 and are arranged in a stainless steel needle tube 6 (as shown in figure 6). First, PZT single crystal is thinned to 50 μm and cut into piezoelectric array elements of 0.5mm × 0.5mm size, plated with gold electrodes on the upper and lower surfaces, and polarized at 150V for 20 min. The transducer structure is then designed according to KLM theory, as shown in FIG. 6, and the acoustic impedance of the inner layer is determined to be Z 1 10MRayl, outer acoustic impedance Z 2 The backing acoustic impedance was 6.2MRayl, 3.4 MRayl. Further, a pulse echo method is adopted to carry out performance test on the transducer. The sound transmission medium is water, the reflector is a steel plate with a smooth surface, and the distance between the probe and the steel plate is 5.0 mm. The performance test result of the PZT single crystal transducer is shown in FIG. 7, the center frequency is 30MHz, the sensitivity is 32dB, the bandwidth reaches 81.5 percent, and the longitudinal resolution of the transducerUp to 50 μm. The result shows that the PZT single crystal prepared by the method of the embodiment can obtain a high-performance high-frequency ultrasonic transducer, and the method of the embodiment can directly obtain a small-size piezoelectric vibrator required by high-frequency ultrasound, thereby reducing the cost and being suitable for practical industrial preparation and application.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. It will be apparent to those skilled in the art that various modifications to these embodiments can be readily made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments. Those skilled in the art should appreciate that many modifications and variations are possible in light of the above teaching without departing from the scope of the invention.
Claims (9)
1. A preparation method of lead zirconate titanate single crystal is characterized by comprising the following steps: the method comprises the following steps:
(1) the raw materials of lead oxide, zirconium oxide and titanium dioxide are mixed according to Pb (Zr) 1-x Ti x )O 3 Mixing materials, wherein x is 0.45-0.48, and then placing the materials in a platinum crucible to be mixed with a cosolvent;
(2) after sealing, placing the platinum crucible in an alumina crucible, and filling a gap between the alumina crucible and the platinum crucible with alumina powder;
(3) sintering the sealed alumina crucible at high temperature until the melt is melted;
(4) melting the melt, growing, and cooling after the growth is finished;
(5) and after cooling, taking down the lead zirconate titanate crystal grains by adopting a heating and soaking mode of dilute nitric acid, and grinding, polishing and cleaning to obtain the lead zirconate titanate single crystal.
2. The method for producing a lead zirconate titanate single crystal according to claim 1, wherein: in the step (1), the purities of the lead oxide, the zirconium oxide and the titanium dioxide are all more than 99.8%.
3. The method for producing a lead zirconate titanate single crystal according to claim 1, wherein: in the step (1), the cosolvent is a mixture of lead oxide, potassium fluoride, lead chloride and boron oxide.
4. The method for producing a lead zirconate titanate single crystal according to any one of claims 1 to 3, wherein: in the step (1), the Pb (Zr) 1-x Ti x )O 3 And the molar ratio of lead oxide, potassium fluoride, lead chloride and boron oxide in the cosolvent is (10 +/-2): (4 ± 1): (2 ± 0.5): (4 ± 1): (3 ± 0.5), wherein x is 0.45-0.48.
5. The method for producing a lead zirconate titanate single crystal according to claim 1, wherein: in the step (3), the melting temperature of the melt is 1050-1150 ℃, and the time is 6-9 h.
6. The method for producing a lead zirconate titanate single crystal according to claim 1, wherein: in the step (4), the temperature of the growth is 1150-.
7. The method for producing a lead zirconate titanate single crystal according to claim 1, wherein: in the step (4), the cooling rate is 15-50 ℃/h after the growth is finished.
8. A lead zirconate titanate single crystal, characterized by: which is obtained by the production method according to any one of claims 1 to 7.
9. Use of the lead zirconate titanate single crystal according to claim 8 in the production of miniature high-frequency ultrasonic transducers.
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| CN103774228A (en) * | 2014-02-26 | 2014-05-07 | 西安工业大学 | Lead scandium niobate-lead magnesium diniobate-lead titanate ferroelectric monocrystal and preparation method thereof |
| US20150233015A1 (en) * | 2012-11-30 | 2015-08-20 | Quest Integrated, Inc. | Method of growth of lead zirconate titanate single crystals |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20150233015A1 (en) * | 2012-11-30 | 2015-08-20 | Quest Integrated, Inc. | Method of growth of lead zirconate titanate single crystals |
| CN103774228A (en) * | 2014-02-26 | 2014-05-07 | 西安工业大学 | Lead scandium niobate-lead magnesium diniobate-lead titanate ferroelectric monocrystal and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| J. A. PÉREZ 等: "Growth of Lead Zirconate Titanate Single Crystals by the High Temperature Solution Method", MATERIALS SCIENCE FORUM, vol. 514, pages 184 - 187 * |
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