CN114108069A - Preparation method and application of organic-inorganic hybrid lead-free piezoelectric crystal - Google Patents

Preparation method and application of organic-inorganic hybrid lead-free piezoelectric crystal Download PDF

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CN114108069A
CN114108069A CN202111400679.XA CN202111400679A CN114108069A CN 114108069 A CN114108069 A CN 114108069A CN 202111400679 A CN202111400679 A CN 202111400679A CN 114108069 A CN114108069 A CN 114108069A
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inorganic hybrid
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piezoelectric crystal
free piezoelectric
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CN114108069B (en
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孙绚
张宗一
张一凡
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Shandong University
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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
    • C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
    • C30B7/14—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions the crystallising materials being formed by chemical reactions in the solution
    • 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
    • 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
    • C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
    • C30B7/08—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by cooling of the solution

Abstract

The invention relates to a preparation method of an organic-inorganic hybrid lead-free piezoelectric crystal, which comprises the following steps: uniformly mixing bismuth oxide, hydrobromic acid and R (+) -alpha-methylbenzylamine, heating in an oven, and then carrying out two cooling processes to obtain the organic-inorganic hybrid lead-free piezoelectric crystal. Compared with a pure organic piezoelectric material, the piezoelectric performance is improved. The bismuth atom is adopted to replace the lead atom as the central atom, so that the preparation of the lead-free material is realized, and the lead-free material is more environment-friendly.

Description

Preparation method and application of organic-inorganic hybrid lead-free piezoelectric crystal
Technical Field
The invention relates to the technical field of piezoelectric materials, in particular to a preparation method and application of an organic-inorganic hybrid lead-free piezoelectric crystal.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
The piezoelectric material is an important material for manufacturing a piezoelectric device, PZT and BTO piezoelectric materials with excellent performance are widely concerned by a plurality of researchers, but due to the influence of the inherent properties of the materials, the ferroelectric ceramic material needs higher preparation temperature, is fragile and almost free of mechanical flexibility, and contains heavy metal elements such as lead, and the like, so that the piezoelectric material has great influence on organisms and the environment.
For lead-free piezoelectric materials, Lanthanum Gallium Silicate (LGS) crystals have excellent piezoelectric performance, the piezoelectric coefficient and the electromechanical coupling coefficient of the crystals are 3 times of those of quartz crystals, but the application of the crystals is limited by the high cost of raw materials; the rare earth borate crystal also faces a problem of higher production cost. In addition, although lead-free organic piezoelectric materials have good flexibility, piezoelectric properties are generally low, and thus lead-free organic piezoelectric materials cannot replace PZT piezoelectric materials.
Chinese patent "piezoelectric crystal with four lattice site structure" (CN101275279) discloses Ca3TaAl3Si2O14(CTAS) and Sr3TaAl3Si2O14(STAS) crystals using Al in the C site3+Substitute Ga3+Due to Al2O3The price of is far lower than that of Ga2O3The present inventors have found that the above-mentioned Al is present in crystal growth while the crystal cost is greatly reduced and the excellent piezoelectric properties are also exhibited3+Substitute Ga3+The crystallinity of the new crystal is poor, and a large-size single crystal without macroscopic defects is difficult to obtain. Meanwhile, the conventional preparation method cannot ensure that the normal growth and good morphology of the crystal are ensured while the preparation efficiency is improved.
Therefore, the preparation of the lead-free piezoelectric material which has low raw material cost, no macroscopic defects, large size, higher piezoelectric performance and improved preparation efficiency is of great significance.
Disclosure of Invention
In order to overcome the problems, the invention designs a preparation method of an organic-inorganic hybrid lead-free piezoelectric crystal, and the obtained product has higher piezoelectric property, and the preparation method is simple and easy to operate.
Based on the research results, the invention provides the following technical scheme:
in a first aspect of the invention, a method for preparing an organic-inorganic hybrid lead-free piezoelectric crystal is provided, which comprises the following steps: uniformly mixing bismuth oxide, hydrobromic acid and R (+) -alpha-methylbenzylamine, then heating, and then carrying out two cooling processes to obtain the organic-inorganic hybrid lead-free piezoelectric crystal.
In a second aspect of the invention, the organic-inorganic hybrid lead-free piezoelectric crystal obtained by the preparation method is provided.
In a third aspect of the invention, the organic-inorganic hybrid lead-free piezoelectric crystal is applied to the fields of piezoelectric transducers, drivers, filters and sensors.
One or more embodiments of the invention achieve at least the following technical effects:
(1) the raw materials used in the preparation method are low in cost and easy to obtain, and the large-size crystal (the length of the crystal is 7-8mm, and the width of the crystal is 5-6mm) which is excellent in crystallization performance and free of macroscopic defects can be prepared, so that the macroscopic piezoelectric performance can be conveniently tested; the crystal structure has chiral characteristics and belongs to the space group P21Chiral space group without symmetric center, excellent piezoelectric performance, and calculated shear piezoelectric coefficient d36＝32.5pC/N。
(2) Compared with a pure organic piezoelectric material, the piezoelectric performance is improved. The bismuth atom is adopted to replace the lead atom as the central atom, so that the preparation of the lead-free material is realized, and the lead-free material is more environment-friendly.
(3) The organic-inorganic hybrid lead-free piezoelectric crystal is prepared by adopting two cooling processes, so that the preparation efficiency of the crystal is improved, and the normal growth of the crystal can be ensured.
Drawings
FIG. 1 is a graph comparing the analytic diffraction and powder X-ray diffraction of single crystals of organic-inorganic hybrid lead-free piezoelectric crystals prepared in example 1 of the present invention.
FIG. 2 is a macro-topography of the organic-inorganic hybrid lead-free piezoelectric crystal prepared in example 1 of the present invention.
FIG. 3 is a schematic diagram showing the molecular arrangement of the organic-inorganic hybrid lead-free piezoelectric crystal prepared in example 1 of the present invention (hydrogen ions are hidden in the figure for clarity).
FIG. 4 is an orientation diagram of an organic-inorganic hybrid lead-free piezoelectric crystal prepared in example 1 of the present invention, a) is a diagram showing diffraction peaks corresponding to (1,1,0) crystal planes of the crystal, and b) is a diagram showing diffraction peaks corresponding to (0,0,1) crystal planes of the crystal.
FIG. 5 is a thermogram of an organic-inorganic hybrid lead-free piezoelectric crystal prepared in example 1 of the present invention.
FIG. 6 is a schematic diagram of the test after the organic-inorganic hybrid lead-free piezoelectric crystal prepared in example 1 of the present invention is fabricated into an electrode.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
As described in the background art, the existing piezoelectric materials contain toxic substances of lead heavy metals, and have low piezoelectric constants, which are not beneficial to relevant applications. Therefore, the invention provides a preparation method of the organic-inorganic hybrid lead-free piezoelectric crystal, which improves the piezoelectric performance and realizes the preparation of the lead-free material.
In a first aspect of the invention, a method for preparing an organic-inorganic hybrid lead-free piezoelectric crystal is provided, which comprises the following steps: uniformly mixing bismuth oxide, hydrobromic acid and R (+) -alpha-methylbenzylamine, heating in an oven, and then carrying out two cooling processes to obtain the organic-inorganic hybrid lead-free piezoelectric crystal.
In a typical embodiment, the temperature is increased to 90-120 ℃, and then the temperature is reduced to 35-50 ℃ to prepare the organic-inorganic hybrid lead-free piezoelectric crystal.
In a typical embodiment, the molar ratio of bismuth oxide powder to R (+) -alpha-methylbenzylamine is (0.3-0.6): (0.7-1.2), preferably 0.5: 1.
In a typical embodiment, the ratio of the volume of the hydrobromic acid solution to the mass of the bismuth oxide powder is (10.56-14.32) ml: (0.5-1.3) g, preferably 11.45 ml: 1g, all are common commercial products.
In a typical embodiment, the holding time after the temperature rise to 90-120 ℃ is 1.5-3h, preferably 2 h.
In a typical embodiment, the oven is a program temperature control oven, the temperature control precision is 0.1 ℃, the time required for heating to 90-120 ℃ is 3-5h, preferably the time required for heating to 100 ℃ is 4 h; further, the state of the solution at 100 ℃ was a yellow clear solution.
In a typical embodiment, the two cooling processes are specifically: cooling from 90-120 deg.C to 40-65 deg.C for 20-27h, preferably from 100 deg.C to 50 deg.C for 24 h; then cooling from 40-65 ℃ to 30-50 ℃ for 45-52 h, preferably from 50 ℃ to 35 ℃ for 48 h.
In a typical embodiment, the method further involves a subsequent processing process, specifically: taking out the organic-inorganic hybrid lead-free piezoelectric crystal, washing and drying to obtain a pure organic-inorganic hybrid lead-free piezoelectric crystal; further, washing with n-hexane for 3-4 times, and naturally volatilizing in the environment for 1-2 h.
The invention adopts two cooling processes based on the following considerations: the raw materials are put into a reaction vessel and can not be completely dissolved, and the temperature is firstly raised to 90-120 ℃ so as to ensure that the solution reaches a supersaturated state and be beneficial to the precipitation of crystals in the later period. When the temperature is reduced to 40-50 ℃ in the first cooling process, crystals begin to be separated out, and the second cooling process adopts a slow cooling process to ensure the normal growth of the crystals. The inventor finds that if the rapid cooling process is adopted in the second cooling process, the crystal growth is not facilitated, the crystal size is reduced, large-size blocky crystals with good appearance are difficult to grow, the slow cooling process is favorable for generating crystals with large size and good appearance, the crystal preparation efficiency can be improved through the two cooling processes, and meanwhile, the normal growth of the crystals can be ensured.
In a second aspect of the invention, the organic-inorganic hybrid lead-free piezoelectric crystal obtained by the preparation method is provided.
In a typical embodiment, the organic-inorganic hybrid lead-free piezoelectric crystal is a yellow transparent parallelogram block crystal, and further, the crystal has a length of 7-8mm and a width of 5-6 mm.
In a third aspect of the invention, the organic-inorganic hybrid lead-free piezoelectric crystal is applied to the fields of piezoelectric transducers, drivers, filters and sensors.
In order to make the technical solution of the present invention more clearly understood by those skilled in the art, the technical solution of the present invention will be described in detail below with reference to specific examples and comparative examples.
Example 1
3.4947g of bismuth oxide powder is weighed and poured into a 100ml wide-mouth glass bottle, 40ml of hydrobromic acid solution is weighed and poured into the wide-mouth bottle and the cover is covered, 1.92ml of R (+) -alpha-methylbenzylamine is absorbed by a liquid transfer gun and added into the wide-mouth bottle and the cover is covered in time. Putting the wide-mouth bottle into a program temperature control oven, and setting a temperature rise and drop program: the temperature is raised from the ambient temperature to 100 ℃ for 4h, the temperature is kept at 100 ℃ for 2h, the temperature is reduced from 100 ℃ to 50 ℃ for 24h, the temperature is reduced from 50 ℃ to 40 ℃ for 48h, and then the temperature is maintained at 40 ℃. And after the temperature of the oven is stabilized at 40 ℃, taking out the wide-mouth bottle, and separating out yellow transparent block-shaped objects at the bottom of the bottle to obtain the organic-inorganic hybrid lead-free piezoelectric crystal. Taking out the crystal, and washing with n-hexane for 4 times.
The following table 1 shows the unit cell parameters of the crystal prepared in example 1, and these performance parameters show that the organic-inorganic hybrid lead-free piezoelectric crystal of the present invention has good crystallization performance and certain potential in preparing piezoelectric materials.
TABLE 1 crystallographic data Table
Figure BDA0003364661150000041
Figure BDA0003364661150000051
Example 2
2.5732g of bismuth oxide powder is weighed and poured into a 100ml wide-mouth glass bottle, 54ml of hydrobromic acid solution is weighed and poured into the wide-mouth bottle and the cover is covered, 2.32ml of R (+) -alpha-methylbenzylamine is absorbed by a liquid transfer gun and added into the wide-mouth bottle and the cover is covered in time. Putting the wide-mouth bottle into a program temperature control oven, and setting a temperature rise and drop program: increasing the temperature from the ambient temperature to 95 ℃ for 3.5h, keeping the temperature at 95 ℃ for 2.5h, reducing the temperature from 95 ℃ to 55 ℃ for 22h, reducing the temperature from 55 ℃ to 35 ℃ for 48h, and then maintaining the temperature at 35 ℃. And after the temperature of the oven is stabilized at 35 ℃, taking out the wide-mouth bottle, and separating out yellow transparent block-shaped objects at the bottom of the bottle to obtain the organic-inorganic hybrid lead-free piezoelectric crystal. Taking out the crystal, and washing with n-hexane for 4 times.
Example 3
3.7984g of bismuth oxide powder is weighed and poured into a 100ml wide-mouth glass bottle, 42ml of hydrobromic acid solution is weighed and poured into the wide-mouth bottle and the cover is covered, 1.77ml of R (+) -alpha-methylbenzylamine is absorbed by a liquid transfer gun and added into the wide-mouth bottle and the cover is covered in time. Putting the wide-mouth bottle into a program temperature control oven, and setting a temperature rise and drop program: the temperature is raised from the ambient temperature to 110 ℃ for 4.5h, kept at 110 ℃ for 2h, cooled from 110 ℃ to 60 ℃ for 24h, cooled from 60 ℃ to 35 ℃ for 48h, and then kept at 35 ℃. And after the temperature of the oven is stabilized at 35 ℃, taking out the wide-mouth bottle, and separating out yellow transparent block-shaped objects at the bottom of the bottle to obtain the organic-inorganic hybrid lead-free piezoelectric crystal. Taking out the crystal, and washing with n-hexane for 4 times.
Fig. 1 is an X-ray diffraction spectrum of the organic-inorganic lead-free piezoelectric crystal material prepared in example 1, and it can be seen that it is well matched with the simulation results, no impurity phase exists, and the crystallization condition is good.
FIG. 2 is a macro-morphology diagram of the crystal, from which it can be seen that it has no macro-defects, regular crystal morphology, length of 7mm and width of 5 mm.
FIG. 3 shows the molecular stacking pattern of the crystal obtained in the example obtained by single crystal XRD analysis simulation, XRD diffraction is performed on the sample, and the crystal orientation is determined by comparing the peak position with the peak position analyzed by the single crystal structure, so as to achieve the purpose of judging the crystal orientation.
Fig. 4 shows the crystal orientation of each plane of the crystal determined by X-ray diffraction, specifically, the (0,0,1) crystal plane and the (1,1,0) crystal plane of the crystal are determined, and thus the three-dimensional direction of the crystal is determined.
Fig. 5 is a Thermogravimetric (TG) graph of the organic-inorganic lead-free piezoelectric crystal prepared in example, and it is known that it has excellent thermal stability at 200 ℃.
Example 4
The specific process for testing the piezoelectric performance by using the organic-inorganic lead-free piezoelectric crystal prepared in example 1 is as follows: the crystal is prepared into an electrode to facilitate the subsequent dynamic method to measure the piezoelectric constant of the crystal. The crystal is selected to ensure the length > thickness and the width > thickness, the copper adhesive tape is cut according to the shape of the crystal by adopting a copper adhesive tape pasting mode, the (0,0,1) crystal face and the (0,0, -1) crystal face are completely covered by the copper adhesive tape and are not conducted as far as possible, and the prepared electrode is ensured to be in a non-point contact state in the testing process, namely, the good contact state is ensured. A test schematic of the thickness shear vibration mode is shown in fig. 6.
Then, the piezoelectric constant of the crystal was calculated by resonance test. 36 the calculation method of the relevant parameters of the vibration mode is as follows:
Figure BDA0003364661150000071
wherein the content of the first and second substances,
Figure BDA0003364661150000072
66 component of the elastic stiffness constant at constant electrical displacement, l (m) is the electrode length, ρ (kg/m)3) Is the crystal density, fa(MHz) is the antiresonance frequency.
Figure BDA0003364661150000073
k36Electromechanical coupling coefficient, f, for 36 vibration modesr(MHz) is the resonant frequency, and Δ f (mHz) is the difference between the anti-resonant frequency and the resonant frequency.
Figure BDA0003364661150000074
Figure BDA0003364661150000075
Is the 66 component of the elastic stiffness constant at constant electric field.
Figure BDA0003364661150000076
Figure BDA0003364661150000077
Figure BDA0003364661150000078
d36Is a 36-component of the piezoelectric strain constant,
Figure BDA0003364661150000079
33 component of free dielectric constant, CTIs a 36-vibrator capacitance in the x direction at low frequency (1kHz),
Figure BDA00033646611500000710
to clamp the dielectric constant. w (m) is the electrode width, and t (m) is the electrode thickness.
Testing the prepared electrodes by an Agilent 4294a precision impedance analyzer to respectively obtain fr＝0.406(MHz)，fa0.386(MHz), capacitance CpThe crystal size was measured with a vernier caliper to give a crystal length of 2.48mm and a width of 2.36mm ═ 0.388pCThe thickness of the electrode was 1.30mm, and the density ρ of the crystal was 2296 (kg/m) from the single crystal analysis data3). Finally calculating to obtain the shearing piezoelectric coefficient d36It is well demonstrated that the present invention produces materials with excellent piezoelectric properties, 32.5 pC/N.
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A preparation method of an organic-inorganic hybrid lead-free piezoelectric crystal is characterized by comprising the following steps: the method comprises the following steps: uniformly mixing bismuth oxide, hydrobromic acid and R (+) -alpha-methylbenzylamine, heating in an oven, and then carrying out two cooling processes to obtain the organic-inorganic hybrid lead-free piezoelectric crystal.
2. The method of claim 1, wherein: the molar ratio of bismuth oxide to R (+) -alpha-methylbenzylamine is (0.3-0.6): (0.7-1.2), preferably 0.5: 1.
3. The method of claim 1, wherein: the volume ratio of the hydrobromic acid solution to the mass of the bismuth oxide is (10.56-14.32) ml: (0.5-1.3) g, preferably 11.45 ml: 1g of the total weight of the composition.
4. The method of claim 1, wherein: the temperature is raised to 90-120 ℃ and then the heat preservation time is 1.5-3h, preferably 2 h.
5. The method of claim 1, wherein: the oven is a program temperature control oven, and the temperature control precision is 0.1 ℃; further, after the temperature is increased to 90-120 ℃, the temperature is reduced to 35-50 ℃ to prepare the organic-inorganic hybrid lead-free piezoelectric crystal; the time for heating to 90-120 ℃ is 3-5h, preferably the time for heating to 100 ℃ is 4 h; further, the state of the solution at 100 ℃ was a yellow clear solution.
6. The method of claim 1, wherein: the two cooling processes are specifically as follows: cooling from 90-120 deg.C to 40-65 deg.C for 20-27h, preferably from 100 deg.C to 50 deg.C for 24 h; then cooling from 40-65 ℃ to 30-50 ℃ for 45-52 h, preferably from 50 ℃ to 40 ℃ for 48 h.
7. The method of claim 1, wherein: still relate to the follow-up processing process, specifically do: taking out the organic-inorganic hybrid lead-free piezoelectric crystal, washing and drying to obtain a pure organic-inorganic hybrid lead-free piezoelectric crystal; further, washing with n-hexane for 3-4 times, and naturally volatilizing in the environment for 1-2 h.
8. An organic-inorganic hybrid lead-free piezoelectric crystal obtained by the production method according to any one of claims 1 to 7.
9. The organic-inorganic hybrid lead-free piezoelectric crystal according to claim 8, characterized in that: the organic-inorganic hybrid lead-free piezoelectric crystal is a yellow transparent parallelogram block crystal, and further has a length of 7-8mm and a width of 5-6 mm.
10. The use of the organic-inorganic hybrid lead-free piezoelectric crystal according to claim 8 in the fields of piezoelectric transducers, drivers, filters and sensors.
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