CN109065463B - Rectification method - Google Patents
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- CN109065463B CN109065463B CN201810916518.8A CN201810916518A CN109065463B CN 109065463 B CN109065463 B CN 109065463B CN 201810916518 A CN201810916518 A CN 201810916518A CN 109065463 B CN109065463 B CN 109065463B
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Abstract
The invention discloses a rectification method, which comprises the following steps: providing a material having a stable internal strain gradient; and applying an external voltage to two ends of the material with the stable internal strain gradient, wherein the material with the stable internal strain gradient keeps unidirectional conductivity under the external voltage. If a strain gradient exists in the material, which can produce dielectric polarization due to the flexoelectric effect, the internal strain gradient can be equivalent to an internal electric field: "flexural electric field". The "flexoelectric field" generated due to the flexoelectric effect can affect the conductive behavior of the material, thereby producing a similar rectifying effect as a conventional rectifying device. The material with stable internal strain gradient can be selected from any material meeting the requirement, and the method for realizing rectification by virtue of the flexoelectric effect provides a selection with high practical value for the current electronic industry.
Description
Technical Field
The invention relates to the technical field of rectifying devices, in particular to a rectifying method.
Background
The rectifying behavior of the semiconductor diode refers to the unidirectional conduction behavior under the applied voltage, and the possibility of effectively performing circuit control is provided. Accordingly, a device having such behavior may be referred to as a rectifying device. Common rectifying devices are based on semiconductor materials such as crystalline silicon, which achieve a rectifying behavior through a barrier layer formed by a mechanism such as forming a PN junction, a schottky barrier, etc. at a semiconductor interface. The existence of the interface barrier layer makes the carrier migration along a certain direction under the external electric field easier, and the migration along the opposite direction becomes difficult, namely, the rectification behavior is presented.
However, the current rectifying method generally uses a semiconductor diode, which has a high manufacturing cost and a complicated process.
In summary, how to effectively reduce the cost of the rectification method or simplify the process is a problem to be solved by those skilled in the art.
Disclosure of Invention
In view of the above, the present invention provides a rectifying method, which can effectively reduce the cost of the rectifying method and simplify the process.
In order to achieve the purpose, the invention provides the following technical scheme:
a method of rectifying, comprising:
providing a material having a stable internal strain gradient;
and applying an external voltage to two ends of the material with the stable internal strain gradient, wherein the material with the stable internal strain gradient keeps unidirectional conductivity under the external voltage.
Preferably, in the rectifying method, the material having a stable internal strain gradient is formed by asymmetrically chemically reducing both ends of the oxide dielectric material.
Preferably, in the rectification method, asymmetric chemical reduction is performed on both ends of the oxide dielectric material, specifically:
A) disposing a reducing agent at a first end of the oxide dielectric material;
B) heating the oxide dielectric material at a first set temperature for a first set time to chemically react a first end of the oxide dielectric material with the reducing agent.
Preferably, in the above rectification method, between the step a) and the step B), further comprising:
A1) an alumina plate is disposed at a second end of the oxide dielectric material.
Preferably, in the rectification method, the reducing agent is graphite block, hydrogen gas or carbon monoxide.
Preferably, in the above rectifying method, the oxide dielectric material is a ferroelectric ceramic material.
Preferably, in the rectification method, the ferroelectric ceramic material is a sodium bismuth titanate-based ferroelectric ceramic material.
Preferably, in the rectification method, the preparation method of the sodium bismuth titanate-based ferroelectric ceramic material comprises:
a) bi to be set in proportion2O3、Na2CO3、BaCO3And TiO2Mixing, adding alcohol into the mixture, and then ball-milling for a second set time;
b) drying the powder obtained by ball milling in the step a), and then keeping the temperature at a second set temperature for a third set time to form powder;
c) adding alcohol into the formed powder, ball-milling for a fourth set time, and drying;
d) adding a binder, pressing into a blank, standing the blank at a high temperature to remove the binder, and then keeping the blank at a third set temperature for a fifth set time to sinter.
Preferably, in the above rectifying method, the material having a stable internal strain gradient has an asymmetric composition gradient between both ends.
The rectification method provided by the invention comprises the following steps:
s1) providing a material with a stable internal strain gradient;
any material with a stable internal strain gradient can be selected, and the material with the stable internal strain gradient has a first end and a second end, and a macroscopic potential difference caused by a flexoelectric effect is presented between the first end and the second end of the material with the stable internal strain gradient.
S2) applying an external voltage across the material having the stable internal strain gradient, the material having the stable internal strain gradient maintaining unidirectional electrical conduction under the external voltage.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a flow chart of a rectifying action provided by an embodiment of the present invention;
FIG. 2 is a schematic view of a placement configuration of an oxide dielectric material being asymmetrically reduced according to an embodiment of the present invention;
FIG. 3a is 0.92Na after asymmetric reduction provided by embodiments of the present invention0.5Bi0.5TiO3-0.08BaTiO3Open circuit voltage U tested in (NBT8) ceramic waferopenA curve that varies with temperature;
FIG. 3b shows asymmetrically reduced 0.92Na0.5Bi0.5TiO3-0.08BaTiO3(NBT8) ceramic wafer testedCurrent density-voltage curve of (a);
FIG. 4 shows asymmetrically reduced 0.92Na0.5Bi0.5TiO3-0.08BaTiO3(NBT8) ceramic wafer, current density-voltage curves tested at different temperatures.
In fig. 2:
1-alumina plate, 2-oxide dielectric material and 3-graphite block.
Detailed Description
The invention aims to provide a rectification method which can effectively reduce the cost of the rectification method.
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The inventors have found that the flexoelectric effect describes the coupling effect between electrical polarization and strain gradient, or between stress and electric field gradient, in a dielectric material. Due to the unique electromechanical coupling characteristics, the material can be controlled indirectly in electrical behavior through mechanical means. If there is a strain gradient in the material, dielectric polarization due to flexoelectric effect can be generated, and the strain gradient can be equivalent to an internal electric field: "flexural electric field". The flexoelectric field generated by the flexoelectric effect can influence the conductive behavior of the material, and the method for realizing rectification by the flexoelectric effect can provide a choice with practical value for the current electronic industry.
Based on this, referring to fig. 1, the rectification method provided by the embodiment of the present invention includes the steps of:
s1) providing a material with a stable internal strain gradient;
any material with a stable internal strain gradient can be selected, and the material with the stable internal strain gradient has a first end and a second end, and a macroscopic potential difference caused by a flexoelectric effect is presented between the first end and the second end of the material with the stable internal strain gradient.
S2) applying an external voltage across the material having the stable internal strain gradient, the material having the stable internal strain gradient maintaining unidirectional electrical conduction under the external voltage.
The material with the stable internal strain gradient can be selected from any material meeting the requirements, and the cost is lower than the manufacturing cost of a semiconductor diode, so that the cost of the whole rectifying method is reduced.
Preferably, the material having a stable internal strain gradient is formed by asymmetrically chemically reducing both ends of the oxide dielectric material 2. That is, the asymmetric chemical reduction means that the degree of reduction of the first end of the oxide dielectric material 2 is different from the degree of reduction of the second end, and the first end and the second end of the oxide dielectric material 2 are asymmetrically reduced. Wherein the oxide dielectric material 2 belongs to both dielectric and oxide. Of course, the material having a stable internal strain gradient may be other materials, and is not limited herein.
In this embodiment, by performing asymmetric chemical reduction across the oxide dielectric material 2, a compositional gradient is created within the oxide dielectric material 2, causing it to exhibit a macroscopic potential difference due to the flexoelectric effect. When an external voltage is applied across the asymmetrically reduced oxide dielectric material 2, the macroscopic internal potential in the oxide dielectric material 2 can enhance or attenuate the influence of the applied electric field, thereby changing its apparent conductivity to cause it to exhibit rectifying behavior. Since the flexoelectric effect exists in all dielectric materials regardless of the crystal structure of the material, the asymmetrically reduced oxide material can exhibit rectifying behavior even under high temperature conditions.
Further, the two ends of the oxide dielectric material 2 are asymmetrically chemically reduced, specifically:
A) disposing a reducing agent at a first end of the oxide dielectric material 2;
i.e., the oxide dielectric material 2 has a first end and a second end, the first end of the oxide dielectric material 2 may be directly contacted with the reducing agent, or the reducing agent may be located on the lower side of the oxide dielectric material 2, and the first end of the oxide dielectric material 2 may be directly placed on the reducing agent having a flat surface.
B) The oxide dielectric material 2 is heated at a first set temperature for a first set time to chemically react a first end of the oxide dielectric material 2 with the reducing agent.
The oxide dielectric material 2 and the reducing agent are heated together at a first set temperature for a first set time. The first end of the oxide dielectric material 2 and the reducing agent are subjected to a reduction reaction at a high temperature, and the two ends of the oxide dielectric material 2 are subjected to asymmetric reduction.
Further, between step A) and step B), the method also comprises the following steps: A1) an alumina plate 1 is provided at a second end of the oxide dielectric material 2. The second end of the oxide dielectric material 2 does not chemically react with the alumina plate 1, when the oxide dielectric material 2 is heated at a first set temperature for a first set time, the oxide dielectric material 2 protects the second end of the oxide dielectric material 2 from being reduced by the graphite block 3, and simultaneously the alumina plate 1 presses on the oxide dielectric material 2 so that the first end of the oxide dielectric material 2 is always in contact with the graphite block 3.
In the step B), the first set temperature is 750-. The oxide dielectric material 2 is placed at the temperature of 750-850 ℃ for reaction for 1.5-2.5h, and can also be reacted for 2 h.
Specifically, the reducing agent may be graphite block 3, carbon monoxide, hydrogen, or the like, and is not limited thereto.
Specifically, the asymmetric chemical reduction is performed on both ends of the oxide dielectric material 2, and a composition gradient in the thickness direction (the direction from the first end to the second end) is formed in the oxide dielectric material 2. Electrodes are prepared on both end faces when cooled to room temperature, which exhibit a rectifying behavior when voltages in different directions are applied thereto. In the range lower than the first set temperature, a macroscopic strain gradient due to uneven shrinkage exists in the material. Due to the universality of the flexoelectric effect, the interior of the asymmetrically reduced oxide dielectric material 2 will exhibit an internal potential due to the flexoelectric effect. When voltages in different directions are applied to the asymmetrically reduced oxide dielectric material 2, the internal potential can enhance or weaken the influence of the applied electric field, so that different conductive currents are generated in the material corresponding to the applied voltages in different directions, and the material shows a rectifying behavior.
Since the asymmetric reduction process causes a more stable change within the oxide dielectric material 2, the structure exhibits a stable rectifying behavior over a larger temperature range. Except that the potential difference and the electrical conductivity in the oxide dielectric material 2 vary with the temperature of the environment, and accordingly, the rectification ratio (the current ratio under forward/reverse bias having the same absolute value) exhibited at different temperatures varies.
In one embodiment, the oxide dielectric material 2 is a ferroelectric ceramic material. Further, the oxide dielectric material 2 may be a sodium bismuth titanate-based ferroelectric ceramic having a chemical composition of general formula (1-x) Na0.5Bi0.5TiO3-xBaTiO3(0<x<0.7, abbreviated NBT100 x). Of course, the oxide dielectric material 2 may also be BaTiO3Ferroelectric material based on SrTiO3Ferroelectric material based on LiNbO3The ferroelectric material is not limited herein.
In another embodiment, step B) is followed by: C) cooling the oxide dielectric material 2 reacted with the reducing agent in the step B) to room temperature in air, and arranging gold electrodes at the first end and the second end of the oxide dielectric material 2. Specifically, gold electrodes may be provided at the first and second ends of the oxide dielectric material 2 by means of ion sputtering.
The oxide dielectric material 2 is cylindrical in its entirety and the thickness of the cylindrical oxide dielectric material 2 is 0.4-0.6mm, preferably 0.5 mm. The thickness of the cylindrical oxide dielectric material 2 is defined as the distance extending along the axis thereof.
When preparing the asymmetrically reduced oxide dielectric material 2, the first end of the oxide dielectric material 2 is placed on the flat graphite block 3, and the second end of the oxide dielectric material 2 is covered with an alumina plate 1 (aluminum sesquioxide plate) to ensure that the oxide dielectric material 2 is tightly attached to the graphite block 3. Then the oxide dielectric material 2, the graphite block 3 and the alumina plate 1 are placed in a resistance furnace together and placed for 2 hours at the temperature of 750-850 ℃ to realize the high-temperature chemical reduction reaction of the first end of the oxide dielectric material 2. The oxide dielectric material 2 after the high-temperature reduction is taken out of the resistance furnace, cooled to room temperature in the air, and then gold electrodes are plated on both ends of the sample by using an ion sputtering method.
In a high-temperature environment, both ends of the oxide dielectric material 2 are asymmetrically reduced, and electrodes are prepared at both ends of the oxide dielectric material 2 when cooled to room temperature. The oxide dielectric material 2 can form asymmetric component gradient after asymmetric chemical reduction under high temperature condition, and the conductivity is greatly improved. Since the oxide dielectric material 2 is normally at a lower temperature than that during reduction, there is a macroscopic strain gradient in the material due to uneven shrinkage.
In another embodiment, the method for manufacturing the sodium bismuth titanate-based ferroelectric ceramic material comprises the following steps:
a) bi to be set in proportion2O3、Na2CO3、BaCO3And TiO2Mixing, adding alcohol into the mixture, and then ball-milling for a second set time;
i.e. Bi in the stoichiometrically to be set2O3、Na2CO3、BaCO3And TiO2Mixing, adding alcohol into the mixture, and performing ball milling, wherein the second set time can be 12 hours or 11-13 hours, which is not limited herein.
b) Drying the powder obtained by ball milling in the step a), and then keeping the temperature at a second set temperature for a third set time to form powder;
drying the powder obtained after ball milling in the step a) to remove alcohol, and then keeping the temperature at a second set temperature for a third set time to form powder. The second set temperature is 850 ℃, and the third set time is 2-4 h.
c) Adding alcohol into the formed powder, ball-milling for a fourth set time, and drying;
the fourth setting time is 12h, and the drying aims at removing alcohol and volatilizing the alcohol.
d) Adding a binder, pressing into a blank, standing the blank at a high temperature to remove the binder, and then keeping the blank at a third set temperature for a fifth set time to sinter. The third setting temperature is 1140-1180 ℃, and the fifth setting time is 2-4 h.
In another specific embodiment, a material with a stable internal strain gradient has an asymmetric composition gradient between its two ends, causing it to exhibit a macroscopic potential difference due to the flexoelectric effect. When an external voltage is applied across the asymmetrically reduced oxide dielectric material 2, the macroscopic internal potential in the oxide dielectric material 2 can enhance or attenuate the influence of the applied electric field, thereby changing its apparent conductivity to cause it to exhibit rectifying behavior.
In addition, the inventors also tested materials with stable internal strain gradients under multiple temperature conditions. The asymmetrically reduced oxide dielectric material exhibits stable rectifying behavior over a wide temperature range. Except that the potential difference and the conductivity in the asymmetrically reduced oxide dielectric material vary with the temperature of the environment, and accordingly, the rectification ratio (the current ratio under forward/reverse bias with the same absolute value) exhibited at different temperatures varies, as shown in fig. 3 a-4.
Wherein FIG. 3a shows 0.92Na after asymmetric reduction0.5Bi0.5TiO3-0.08BaTiO3Open circuit voltage U tested in (NBT8) ceramic waferopenThe graph of the change along with the temperature is a schematic diagram of the test circuit; FIG. 3b is 0.92Na after asymmetric reduction0.5Bi0.5TiO3-0.08BaTiO3(NBT8) the current density-voltage curve (applied voltage sequence: from-2V to +2V) tested in the ceramic wafer, the lower right insert is the test circuit schematic. The dashed lines in both figures represent the results of the test after inverting the sample.
FIG. 4 shows 0.92Na after asymmetric reduction0.5Bi0.5TiO3-0.08BaTiO3(NBT8) ceramic wafer, differentA current density-voltage curve measured at temperature, wherein the sequence of applied voltages is: from-2V to + 2V).
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (9)
1. A method of rectifying, comprising:
providing a material having a stable internal strain gradient;
and applying external voltages in different directions to two ends of the material with the stable internal strain gradient, wherein the material with the stable internal strain gradient keeps unidirectional conductivity under the external voltage when the direction of the applied voltage is changed.
2. Method for rectifying according to claim 1, characterized in that said material with a stable internal strain gradient is formed by asymmetric chemical reduction of the oxide dielectric material (2) at both ends.
3. The method for rectifying according to claim 2, wherein the asymmetric chemical reduction is performed on both ends of the oxide dielectric material (2), specifically:
A) disposing a reducing agent at a first end of the oxide dielectric material (2);
B) heating the oxide dielectric material (2) at a first set temperature for a first set time to chemically react a first end of the oxide dielectric material (2) with the reducing agent.
4. The method for rectifying current of claim 3, further comprising, between step A) and step B):
A1) an alumina plate (1) is arranged at the second end of the oxide dielectric material (2).
5. The method for rectifying current according to claim 3, wherein the reducing agent is graphite block (3), hydrogen gas, or carbon monoxide.
6. Method for rectifying according to claim 2, characterized in that said oxide dielectric material (2) is a ferroelectric ceramic material.
7. The method for rectifying current of claim 6, wherein the ferroelectric ceramic material is a sodium bismuth titanate-based ferroelectric ceramic material.
8. The rectification method of claim 7, wherein the preparation method of the sodium bismuth titanate-based ferroelectric ceramic material is as follows:
a) bi to be set in proportion2O3、Na2CO3、BaCO3And TiO2Mixing, adding alcohol into the mixture, and then ball-milling for a second set time;
b) drying the powder obtained by ball milling in the step a), and then keeping the temperature at a second set temperature for a third set time to form powder;
c) adding alcohol into the formed powder, ball-milling for a fourth set time, and drying;
d) adding a binder, pressing into a blank, standing the blank at a high temperature to remove the binder, and then keeping the blank at a third set temperature for a fifth set time to sinter.
9. The method for rectifying current of claim 2, wherein the material having the stable internal strain gradient has an asymmetric composition gradient between its two ends.
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| CN110379860B (en) * | 2019-07-12 | 2023-04-25 | 中国科学院合肥物质科学研究院 | Method for realizing electric polarization rectification effect |
| CN116573932A (en) * | 2023-06-01 | 2023-08-11 | 中国科学技术大学 | Can improve MTiO 3 Sintering preparation method of ceramic flex electric response |
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