CN107068853B - DAST single crystal piezoelectric material and preparation method thereof - Google Patents
DAST single crystal piezoelectric material and preparation method thereof Download PDFInfo
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/80—Constructional details
- H10N30/85—Piezoelectric or electrostrictive active materials
- H10N30/857—Macromolecular compositions
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/01—Manufacture or treatment
- H10N30/09—Forming piezoelectric or electrostrictive materials
- H10N30/098—Forming organic materials
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- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
- Pyridine Compounds (AREA)
Abstract
The invention relates to a DAST single crystal piezoelectric material and a preparation method thereof; the invention discloses application of DAST single crystal as a piezoelectric material; the invention also discloses DAST organic single crystal piezoelectric material which comprises DAST single crystal, electrodes plated on two parallel surfaces of the DAST single crystal and leads led out by the electrodes; the preparation method of the DAST single-crystal piezoelectric material comprises the steps of preparing solution, placing an inclined plate, roughly cooling, finely cooling, cleaning, manufacturing electrodes, leads and the like. The DAST single-crystal piezoelectric material overcomes the defects of the existing piezoelectric material, has obvious piezoelectric effect, is flexible, does not contain lead, does not contain fluorine, is nontoxic, has simple manufacturing method, does not need harsh conditions such as high temperature, high pressure and the like, and has low manufacturing cost.
Description
Technical Field
The invention belongs to the field of piezoelectric materials, and particularly relates to a DAST single-crystal piezoelectric material and a preparation method thereof.
Background
The piezoelectric effect is that a dielectric body deforms under the action of mechanical force, so that the centers of positive and negative charges in the dielectric body relatively displace to generate polarization, and binding charges with opposite signs are accumulated on the surface of a crystal electrode. This phenomenon of conversion from mechanical energy to electrical energy is referred to as the positive piezoelectric effect. On the contrary, the phenomenon of converting electrical energy into mechanical energy is called inverse piezoelectric effect. If a centrosymmetric dielectric is subjected to pressure, the interior of the dielectric deforms uniformly. In this case, the external force cannot break the arrangement of the positive and negative charge centers symmetrically, that is, the external force cannot cause the positive and negative charge centers of the centrosymmetric dielectric to be asymmetrically displaced relative to each other, and thus the dielectric cannot be polarized. Therefore, a dielectric body having central symmetry does not produce a piezoelectric effect. As such, materials capable of producing a piezoelectric effect are generally non-centrosymmetric materials. Conventional piezoelectric materials are: ceramics, quartz crystals, lithium gallate, lithium germanate, titanium germanate, lithium niobate, lithium tantalate, PVDF, and the like. The piezoelectric material can be applied to the fields of transducers, filters, piezoelectric sensors, oscillators, high-voltage generators and the like.
The traditional inorganic piezoelectric materials (such as ZnO, lead zirconate titanate (PZT), ceramic materials and the like) have excellent piezoelectric performance and mature preparation process, and are widely applied to devices such as sensors, drivers and the like. However, the preparation process of the inorganic piezoelectric material is complicated, and harsh conditions such as high temperature and high pressure are required. In contrast, the preparation conditions of the organic piezoelectric material are relatively mild. Among them, polyvinylidene fluoride (PVDF) is an organic piezoelectric material that is widely used. The material changes the structural symmetry of polyethylene through strong polar F atoms, so that the polyethylene has piezoelectric characteristics, and has the advantages of light weight, good mechanical properties and the like. Unfortunately, PVDF has a weak piezoelectric response, low piezoelectric output, and is susceptible to a variety of external factors.
Disclosure of Invention
The invention aims to: the DAST single-crystal piezoelectric material has the advantages of obvious piezoelectric effect, flexibility, no lead, no fluorine, no toxicity, simple manufacturing method, no need of harsh conditions such as high temperature, high pressure and the like, and low manufacturing cost.
In order to achieve the purpose, the invention adopts the technical scheme that:
the DAST is a chemical full name of 4- (4-dimethylamino styryl) methylpyridine p-toluenesulfonate, is called DAST for short, and is an organic nonlinear material. The invention discovers that the DAST single crystal has a piezoelectric effect, and the DAST single crystal can generate voltage by applying pressure on the a axis, the b axis and the c axis of the DAST single crystal or any direction formed by slicing the single crystal, and convert mechanical energy into electric energy. Conversely, electrical energy can also be converted into mechanical energy by a DAST single crystal. Therefore, the DAST single crystal can be applied as a piezoelectric material.
A DAST single crystal piezoelectric material comprises a DAST single crystal, electrodes plated on two parallel surfaces of the DAST single crystal and leads led out from the electrodes; the two parallel surfaces of the DAST single crystal are two parallel surfaces which are perpendicular to one direction of a, b and c axes of the DAST single crystal or two parallel surfaces which are formed by slicing the DAST single crystal.
The electrode is an electrode consisting of one or more of aluminum, gold, titanium nitride, titanium silicide, titanium tungsten alloy, tungsten silicide, tungsten nitride, nickel silicide, nickel nitride, tantalum nitride, iron, platinum, copper, silver, chromium and nickel-chromium alloy, and the thickness of the electrode is 5-4000 nm.
The preparation method of the DAST single-crystal piezoelectric material comprises the following steps:
(1) preparing a solution: preparing 0.5-5 wt% DAST methanol solution, and placing in a sealed environment;
(2) placing an inclined plate: placing a polytetrafluoroethylene inclined plate in the DAST methanol solution in the step (1) at an inclined angle of 2-85 degrees, sealing, and placing in a temperature control box;
(3) and (3) roughly cooling: controlling the temperature of the temperature control box in the step (2) at 40-60 ℃ and keeping for 1-3 days; then, reducing the temperature of the temperature control box to 30-45 ℃ at a cooling rate of 0.1-5 ℃/h, and collecting formed crystal nuclei on a polytetrafluoroethylene inclined plate;
(4) fine cooling: continuously and slowly reducing the temperature of the temperature control box to room temperature at the cooling speed of 0.01-5 ℃/day, stabilizing the temperature for 5-100 days, and slowly growing the crystal nucleus into DAST single crystal;
(5) cleaning: cleaning and drying the DAST single crystal obtained in the step (4);
(6) manufacturing an electrode: plating a layer of electrode on two parallel surfaces of the DAST single crystal cleaned in the step (5) respectively; the two parallel surfaces of the DAST single crystal are two parallel surfaces which are vertical to one direction of a, b and c axes of the DAST single crystal or two parallel surfaces which are formed by slicing the DAST single crystal;
(7) leading wires: and leading out wires on the surfaces of the electrodes by using conductive gel respectively to obtain the DAST single-crystal piezoelectric material.
In the preferable scheme of the invention, in the step (2), a plurality of parallel grooves are processed on the surface of the polytetrafluoroethylene sloping plate, the depth of the grooves is 0.5-30mm, and the width of the grooves is 0.5-30 mm.
As a preferred embodiment of the present invention, in the step (5), a specific method for cleaning and drying the DAST single crystal is:
a) preparing a mixed solution of ethyl acetate and isopropanol in a volume ratio of 1:10-10:1, then putting the DAST single crystal into the mixed solution, and ultrasonically cleaning for 1-60 seconds to clean powder particle impurities on the surface of the DAST single crystal;
b) preparing a mixed solution of absolute ethyl alcohol and tetrahydrofuran in a volume ratio of 1:10-10:1, putting the DAST single crystal cleaned in the step a) into the mixed solution, and ultrasonically cleaning for 1-60 seconds to clean the discolored surface of the DAST crystal due to water absorption;
c) putting the DAST crystal cleaned in the step b) into a methanol solvent, ultrasonically cleaning for 1-60 seconds, and cleaning a cleaning agent stained on the surface of the DAST crystal to obtain a clean crystal surface;
d) vacuum drying cleaned DAST crystal at 20-70 deg.C for 5-120 min.
In a preferred embodiment of the present invention, in the step (6), the method for plating the electrodes on the two parallel surfaces of the DAST single crystal is electron beam evaporation, vacuum thermal evaporation, atomic layer deposition, chemical vapor deposition, or magnetron sputtering.
The invention has the beneficial effects that:
(1) the DAST single crystal can be used as a piezoelectric material.
DAST single crystals are capable of converting mechanical energy into electrical energy: applying pressure to the a, b and c axes of DAST single crystal or any direction formed by slicing the single crystal can generate voltage and convert mechanical energy into electric energy; under the same external force, the a, b, c axes of the DAST single crystal or other directions formed by slicing the single crystal will generate different degrees of open-circuit voltage and short-circuit current, thereby generating different detection signals; as the applied pressure increases, both the voltage and current generated increase; conversely, if the applied external force is reduced, the generated voltage and current will also be reduced.
Conversely, a DAST single crystal is also capable of converting electrical energy into mechanical energy: when a voltage is applied, the mechanical deformation or stress generated in the a, b, c axes of the DAST single crystal or in any direction in which the single crystal is sliced increases as the applied voltage increases; conversely, if the applied voltage is reduced, the resulting mechanical deformation or stress will also be reduced.
(2) The DAST single crystal piezoelectric material has the advantages of simple manufacturing method, no need of harsh conditions such as high temperature, high pressure and the like, and low manufacturing cost.
(3) The DAST single-crystal piezoelectric material disclosed by the invention has the characteristics of flexibility, no lead, no fluorine, no toxicity and the like, and can be applied to the fields of transducers, energy storages, oscillators, sensors and the like, and also can be applied to the fields of biomedical instruments, wearable equipment and the like.
Drawings
FIG. 1 shows the arrangement of DAST molecules in a single crystal;
fig. 2 is a schematic structural diagram of a DAST single crystal piezoelectric material, in which 1 is a DAST single crystal, 2 is upper and lower electrodes plated on two parallel surfaces of the DAST single crystal, and 3 is a lead of the electrode;
FIG. 3 shows an electrical signal generated by DAST single crystal piezoelectric material under the action of ultrasonic waves;
FIG. 4 is a schematic view of a piezoelectric performance testing apparatus for DAST single-crystal piezoelectric material;
fig. 5 is a graph of a periodic measured voltage and a current generated when an external force acts in the c-axis direction of the DAST single crystal piezoelectric material, where fig. 5 (a) is the generated periodic measured voltage and fig. 5 (b) is the generated periodic measured current;
fig. 6 shows different levels of measured voltage and current generated by c-axis direction of DAST single crystal piezoelectric material under different levels of pressure, where fig. 6 (a) generates different levels of measured voltage and fig. 6 (b) generates different levels of measured current.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, preferred embodiments of the present invention will be described in detail below with reference to the accompanying drawings.
Fig. 1 is a schematic diagram of arrangement of DAST molecules in a crystal, and it can be seen that the DAST molecules are highly asymmetric. The DAST single crystal has a piezoelectric effect, and generates different detection electric signals by generating different degrees of open-circuit voltage and short-circuit current in the a, b, and c axes of the DAST single crystal or in other directions obtained by slicing the single crystal under the same external force. Figure 1 also shows that there are two large pi bonds on the cationic chromophore, the charge is transferred via the conjugate bridge and to a large extent, and that there is a 20 ° shift between the a-axis of the DAST crystal and the charge transfer axis of the chromophore. If pressure is applied to the DAST single crystal along the a or b axis of the DAST single crystal, especially along the direction of the DAST chromophore, the positive and negative charge centers of the DAST single crystal are more easily displaced relative to each other, and the charges are more easily transferred, so that opposite-sign charges are formed on the upper and lower surfaces, respectively, and therefore, a stronger piezoelectric effect is detected.
Fig. 2 is a schematic structural diagram of a DAST single crystal piezoelectric material, in which 1 is a DAST single crystal, 2 is upper and lower electrodes plated on two parallel surfaces of the DAST single crystal, and 3 is a lead of the electrode. The two parallel surfaces of the DAST single crystal are two parallel surfaces which are perpendicular to one direction of a, b and c axes of the DAST single crystal or two parallel surfaces which are formed by slicing the DAST single crystal.
The preparation method of the DAST single-crystal piezoelectric material comprises the following steps:
(1) preparing a solution: adding 3g of DAST powder into 70ml of methanol solution at room temperature, carrying out ultrasonic treatment for 1 hour, carrying out magnetic stirring for 1 hour to fully dissolve the DAST powder, and filling the prepared DAST solution into a brown flask;
(2) placing an inclined plate: putting a polytetrafluoroethylene inclined plate with a groove on the surface into a brown flask filled with DAST solution, enabling the polytetrafluoroethylene inclined plate to form an included angle of 30 degrees with the bottom of the flask, and sealing;
(3) and (3) roughly cooling: putting the sealed brown flask obtained in the step (2) into a temperature control box, and controlling the temperature to be 45-55 ℃ for two days; then, the temperature is reduced to 40 ℃ at the cooling speed of 1 ℃/hour;
(4) fine cooling: after the temperature is reduced to 40 ℃, slowly reducing the temperature to room temperature at the cooling speed of 1 ℃/day, stabilizing the temperature for 40 days, and growing DAST single crystals;
(5) cleaning and drying the surface of the DAST single crystal grown in the step (4), wherein the process flow is as follows: firstly, putting the DAST crystal into a mixed solution of ethyl acetate and isopropanol, and ultrasonically cleaning for 10 seconds; then, the DAST crystal is put into the mixed solution of absolute ethyl alcohol and tetrahydrofuran again, and ultrasonic cleaning is carried out for 10 seconds; then, the DAST crystal is placed in a methanol solvent, and ultrasonic cleaning is carried out for 5 seconds; finally, drying the cleaned DAST crystal at 50 ℃ for 20 minutes in vacuum;
(6) respectively depositing a layer of continuous Al metal film with the thickness of 200nm on two parallel surfaces of the DAST single crystal cleaned in the step (5) by adopting a magnetron sputtering technology;
(7) and (4) respectively leading out metal wires on the surfaces of the two continuous Al metal films prepared in the step (6) by adopting conductive gel, thus obtaining the DAST single-crystal piezoelectric material.
The following analysis proves that the DAST single-crystal piezoelectric material can generate open-circuit voltage and short-circuit current under the action of ultrasonic vibration or periodic pressure, converts mechanical energy into electric energy, and can be applied to the fields of transducers, sensors, oscillators, biological instruments, wearable equipment and the like.
As shown in fig. 3, the DAST single-crystal piezoelectric material displays a voltage signal corresponding to an ultrasonic waveform on an oscilloscope under the vibration of the ultrasonic wave. This indicates that under the action of the ultrasonic wave, the centers of positive and negative charges of the DAST single crystal are asymmetrically displaced relative to each other, so that opposite-sign charges appear on the two end surfaces of the DAST single crystal, and thus, mechanical energy is converted into electric energy.
The DAST single crystal piezoelectric material can detect periodic open circuit voltage and short circuit current under the pressure of the apparatus of fig. 4. The pressure providing device is mainly a linear motor and a plate, wherein a push rod in the linear motor device moves forwards to touch the crystal, so that periodic pressure is generated, and the plate is used for fixing the DAST single crystal piezoelectric material.
As shown in FIG. 5 (a) and FIG. 5 (b), the voltage and current generated by the DAST single-crystal piezoelectric material under the device of FIG. 4 show that the open-circuit voltage generated at a distance of 80-130mm is 0.8V and the short-circuit current is 45 nA. Wherein the linear motor is set to an acceleration of 1m/s2The maximum speed is 1m/s, the starting position of the push rod is 90mm, and the ending position of the push rod is 130 mm. The voltage generated by the traditional PVDF film in a steel bar deformation experiment is only dozens to hundreds of mV, and about 1V voltage can be generated under the direct action of external force. In contrast, the present invention provides that the c-axis direction pressure applied at the weakest piezoelectric performance of the DAST single crystal detects a voltage of the same magnitude as PVDF. Wherein the c-axis of the DAST single crystal is perpendicular to the a-and b-axes of the DAST single crystal shown in FIG. 1. Obviously, if pressure is applied to the DAST single crystal along the a or b axis of the DAST single crystal, especially along the direction of the DAST chromophore (fig. 1), the positive and negative charge centers of the DAST single crystal will be more easily displaced relative to each other, and a more pronounced piezoelectric effect will be generated.
In the case that the acceleration and the maximum speed are kept unchanged, if only the movement distance of the push rod is changed, the force applied is changed. In this case, the larger the location of termination, the greater the force will be applied to the DAST single crystal. As shown in fig. 6 (a) and 6 (b), the voltage and current values measured at different distances by the DAST single crystal piezoelectric material show that as the end point distance value increases, the applied force increases, and the voltage and current values generated by the DAST single crystal through the piezoelectric effect also increase.
The test results of fig. 5 (a) and 5 (b) and fig. 6 (a) and 6 (b) demonstrate that the DAST single crystal has piezoelectric properties that can meet the requirements for the production of sensors, oscillators, biological instruments, and wearable devices. FIGS. 5 (a) and 5 (b) and FIGS. 6 (a) and 6 (b) are views in which the electrodes are plated on the plane of the a-and b-axes where DAST single crystal is most likely to be plated, that is, a force is applied in the c-axis direction. According to the crystal structure of DAST (fig. 1), if an external force is applied to the a-axis or b-axis of the DAST single crystal or at an angle of 20 ° to the a-axis, better piezoelectric performance is obtained, and larger detection voltage and current are generated. Compared with the existing piezoelectric material, the DAST single-crystal piezoelectric material has the advantages of flexibility, no lead, no fluorine, no harm to human bodies and the like, can be prepared under the conditions of normal temperature and normal pressure, has simple process, can be produced in a large scale, and can overcome the defects of the existing piezoelectric material.
Finally, it is noted that the above-mentioned embodiments illustrate rather than limit the invention, and that, while the invention has been described with reference to preferred embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (6)
1. A device based on DAST single crystal piezoelectric material, characterized by: the device comprises a DAST (4- (4-dimethylamino styryl) picoline p-toluenesulfonate) single crystal, electrodes plated on two parallel surfaces of the DAST single crystal and leads led out by the electrodes; the two parallel surfaces of the DAST single crystal are two parallel surfaces which are perpendicular to one direction of a, b and c axes of the DAST single crystal, and an external force is applied to the a or b axis of the DAST single crystal or the direction which has an included angle of 20 degrees with the a axis, so that better piezoelectric performance is obtained, and larger detection voltage and current are generated.
2. The DAST single-crystal piezoelectric material-based device of claim 1, wherein: the electrode is an electrode consisting of one or more of aluminum, gold, titanium nitride, titanium silicide, titanium tungsten alloy, tungsten silicide, tungsten nitride, nickel silicide, nickel nitride, tantalum nitride, iron, platinum, copper, silver and chromium, and the thickness of the electrode is 5-4000 nm.
3. The method for producing a device based on a DAST single-crystal piezoelectric material according to claim 1 or 2, characterized in that: the method comprises the following steps:
(1) preparing a solution: preparing 0.5-5 wt% DAST methanol solution, and placing in a sealed environment;
(2) placing an inclined plate: placing a polytetrafluoroethylene inclined plate in the DAST methanol solution in the step (1) at an inclined angle of 2-85 degrees, sealing, and placing in a temperature control box;
(3) and (3) roughly cooling: controlling the temperature of the temperature control box in the step (2) at 40-60 ℃ and keeping for 1-3 days; then, reducing the temperature of the temperature control box to 30-45 ℃ at a cooling rate of 0.1-5 ℃/h, and collecting formed crystal nuclei on a polytetrafluoroethylene inclined plate;
(4) fine cooling: continuously and slowly reducing the temperature of the temperature control box to room temperature at the cooling speed of 0.01-5 ℃/day, stabilizing the temperature for 5-100 days, and slowly growing the crystal nucleus into DAST single crystal;
(5) cleaning: cleaning and drying the DAST single crystal obtained in the step (4);
(6) manufacturing an electrode: plating a layer of electrode on two parallel surfaces of the DAST single crystal cleaned in the step (5) respectively;
(7) leading wires: and leading out wires on the surfaces of the electrodes by using conductive gel respectively to obtain the device based on the DAST single-crystal piezoelectric material.
4. The method for manufacturing a device based on DAST single-crystal piezoelectric material according to claim 3, characterized in that: in the step (2), a plurality of parallel grooves are processed on the surface of the polytetrafluoroethylene sloping plate, the depth of each groove is 0.5-30mm, and the width of each groove is 0.5-30 mm.
5. The method for manufacturing a device based on DAST single-crystal piezoelectric material according to claim 3, characterized in that: in the step (5), the specific method for cleaning and drying the DAST single crystal is as follows:
a) preparing a mixed solution of ethyl acetate and isopropanol in a volume ratio of 1:10-10:1, putting the DAST single crystal into the mixed solution, and ultrasonically cleaning for 1-60 seconds to clean powder particle impurities on the surface of the DAST single crystal;
b) preparing a mixed solution of absolute ethyl alcohol and tetrahydrofuran in a volume ratio of 1:10-10:1, putting the DAST single crystal cleaned in the step a) into the mixed solution, and ultrasonically cleaning for 1-60 seconds to clean the discolored surface of the DAST single crystal due to water absorption;
c) putting the DAST single crystal cleaned in the step b) into a methanol solvent, ultrasonically cleaning for 1-60 seconds, and cleaning a cleaning agent stained on the surface of the DAST single crystal to obtain a clean single crystal surface;
d) vacuum drying the cleaned DAST single crystal at 20-70 deg.C for 5-120 min.
6. The method for manufacturing a device based on DAST single-crystal piezoelectric material according to claim 3, characterized in that: in the step (6), the method for plating the electrodes on the two parallel surfaces of the DAST single crystal is electron beam evaporation, vacuum thermal evaporation, atomic layer deposition, chemical vapor deposition or magnetron sputtering.
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| US20050201684A1 (en) * | 2004-03-10 | 2005-09-15 | Yakymyshyn Christopher P. | Conductive electrode structure for an electro-optic material |
| CN103305919A (en) * | 2013-07-11 | 2013-09-18 | 青岛大学 | Growth method of organic nonlinear optical crystal |
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| US20050201684A1 (en) * | 2004-03-10 | 2005-09-15 | Yakymyshyn Christopher P. | Conductive electrode structure for an electro-optic material |
| CN103305919A (en) * | 2013-07-11 | 2013-09-18 | 青岛大学 | Growth method of organic nonlinear optical crystal |
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