CN112938893A - Vanadium dioxide single crystal driver and preparation method and application thereof - Google Patents
Vanadium dioxide single crystal driver and preparation method and application thereof Download PDFInfo
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- 239000013078 crystal Substances 0.000 title claims abstract description 80
- 229910021542 Vanadium(IV) oxide Inorganic materials 0.000 title claims abstract description 68
- GRUMUEUJTSXQOI-UHFFFAOYSA-N vanadium dioxide Chemical compound O=[V]=O GRUMUEUJTSXQOI-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000000843 powder Substances 0.000 claims abstract description 70
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 43
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 43
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 42
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000010438 heat treatment Methods 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 239000000758 substrate Substances 0.000 claims abstract description 15
- 230000001681 protective effect Effects 0.000 claims abstract description 9
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 8
- DZKDPOPGYFUOGI-UHFFFAOYSA-N tungsten(iv) oxide Chemical compound O=[W]=O DZKDPOPGYFUOGI-UHFFFAOYSA-N 0.000 claims description 34
- 235000012239 silicon dioxide Nutrition 0.000 claims description 25
- 239000010453 quartz Substances 0.000 claims description 22
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 239000001307 helium Substances 0.000 claims description 5
- 229910052734 helium Inorganic materials 0.000 claims description 5
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 3
- 230000002829 reductive effect Effects 0.000 abstract description 10
- 230000008859 change Effects 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 8
- 238000005260 corrosion Methods 0.000 abstract description 5
- 230000007797 corrosion Effects 0.000 abstract description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 23
- 239000001301 oxygen Substances 0.000 description 23
- 229910052760 oxygen Inorganic materials 0.000 description 23
- 239000002070 nanowire Substances 0.000 description 20
- 238000005452 bending Methods 0.000 description 8
- 230000002457 bidirectional effect Effects 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 4
- 230000002441 reversible effect Effects 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000002019 doping agent Substances 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000012466 permeate Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 239000006004 Quartz sand Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000012938 design process Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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Abstract
The invention provides a vanadium dioxide single crystal driver and a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) mixing vanadium pentoxide powder and silicon dioxide powder according to the mass ratio of (1-2) to 1 to obtain vanadium source powder; (2) placing the growth substrate right above the vanadium source powder obtained in the step (1) and putting the growth substrate into a heating system; (3) and (3) vacuumizing the heating system in the step (2), introducing protective gas, starting a temperature-raising program to perform chemical vapor deposition reaction, and obtaining the vanadium dioxide single crystal driver. According to the invention, the M2 phase and the T phase are controllably applied to the vanadium dioxide single crystal driver, the M2-R phase change and the T-M2 phase change are fully utilized to realize the theoretical optimal driving performance, the energy loss in the driving process is reduced, and the stability and the corrosion resistance of the driver are improved.
Description
Technical Field
The invention belongs to the technical field of advanced micro-nano drivers, relates to a single crystal driver, and particularly relates to a vanadium dioxide single crystal driver and a preparation method and application thereof.
Background
Researchers have found that M1 phase vanadium dioxide can be converted to R phase vanadium dioxide when heated to 68 ℃ and produce a compressive strain of about 1% in the [001] direction of the R phase, a characteristic that allows vanadium dioxide to be used to make thermally driven devices. In recent years, scholars at home and abroad find that the vanadium dioxide thermal excitation micro-driver can simultaneously meet the application requirements of high frequency, high amplitude and high output power. Among them, the driver based on the vanadium dioxide single crystal micro nanowire (grown in the [001] direction of the R phase) exhibited the most excellent driving ability.
In 2010, Wu military bridge professor of Larrenburli national laboratory in USA combines vanadium dioxide single crystal nanowire and chromium metal into a double crystal driver, which can produce the output of 2.5 × 104m-1Curvature change of (2) and 7J/cm3Theoretical work density (Journal of Applied Physics 108,083538 (2010)). In 2013, the problem group explores the performance limit of a double-crystal micro-driver of vanadium dioxide nanowires and chromium, and finds that the device can also achieve the working rate of kilohertz level, and the efficiency of converting thermal energy into mechanical energy can reach 0.85%. Meanwhile, the work also finds that the bimorph interface stress when the driver bends can introduce the generation of metastable M2 phase vanadium dioxide, and the strain can be up to 2 percent due to the transformation of M2 phase to R phase. Thus, the double layer deviceThe element can produce larger amplitude and higher energy conversion efficiency (3.4%) (Wang K, Cheng C, Cardona E, et al. Performance limits of micro-actuation with a vanadium dioxide as a solid engine [ J ]]ACS nano,2013,7(3): 2266-. In 2019, the group of inventors developed a method for preparing a single-crystal Vanadium Dioxide nanowire driver, by doping tungsten and spatially asymmetric distribution of reaction conditions, a lateral oxygen concentration gradient and a lateral asymmetric phase change are formed in the prepared single-crystal nanowire to realize a bidirectional self-bending behavior of a single Vanadium Dioxide nanowire, the driving performance of the single-crystal Vanadium Dioxide nanowire driver is equivalent to that of a twin-crystal Vanadium Dioxide nanowire driver, and the single-crystal Vanadium Dioxide nanowire driver exhibits superior cycle stability (Shi R, Cai X, Wang W, et al].Advanced Functional Materials,2019,29(20):1900527)。
However, the driving capability of the nanowire/metal bimorph driver is directly affected by the thickness ratio of the double layers and the interface contact condition, so that there are objective problems such as poor stability and poor corrosion resistance caused by coating peeling. While the single crystal drivers developed heretofore overcome the problems in the twin crystal drivers, they have not been able to utilize the M2-R phase change to achieve the theoretically optimal driving performance. The generation of the M2 phase in the twin crystal system cannot be reasonably controlled and utilized, so that how to controllably apply the M2 phase to the vanadium dioxide single crystal driver is still a key problem. In addition, a transition phase T phase exists between the M1 phase and the M2 phase, researchers find that linear strain of up to 0.7% can be generated by the transformation from the T phase to the M2 phase, and the energy required by the transformation is far lower than that required by the transformation from the M1 phase or the M2 phase to the R phase, so whether the T phase can be introduced into a driver to reduce the energy loss in the driving process becomes an important consideration in the design and manufacturing process of the driving device.
Therefore, how to provide a vanadium dioxide single crystal driver and a preparation method and application thereof can be seen, the M2 phase and the T phase are controllably applied to the vanadium dioxide single crystal driver, the M2-R phase transition and the T-M2 phase transition are fully utilized to realize the theoretical optimal driving performance, the energy loss in the driving process is reduced, the stability and the corrosion resistance of the driver are improved, and the problem which needs to be solved urgently by technical personnel in the field at present is solved.
Disclosure of Invention
The invention aims to provide a vanadium dioxide single crystal driver and a preparation method and application thereof, wherein the preparation method controllably applies M2 phase and T phase to the vanadium dioxide single crystal driver, fully utilizes M2-R phase change and T-M2 phase change to realize the theoretical optimal driving performance, reduces the energy loss in the driving process and improves the stability and corrosion resistance of the driver.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for manufacturing a vanadium dioxide single crystal driver, the method comprising the steps of:
(1) mixing vanadium pentoxide powder and silicon dioxide powder according to the mass ratio of (1-2) to 1 to obtain vanadium source powder;
(2) placing the growth substrate right above the vanadium source powder obtained in the step (1) and putting the growth substrate into a heating system;
(3) and (3) vacuumizing the heating system in the step (2), introducing protective gas, starting a temperature-raising program to perform chemical vapor deposition reaction, and obtaining the vanadium dioxide single crystal driver.
In the present invention, the step (1) of mixing the vanadium pentoxide powder and the silicon dioxide powder in a mass ratio of (1-2):1, for example, 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1 or 2:1, but is not limited to the enumerated values, and other unrecited values within the numerical range are also applicable.
The method of mixing silicon dioxide into vanadium pentoxide effectively adjusts the oxygen partial pressure of the reaction system, so that excessive oxygen permeates into the synthesized vanadium dioxide micro-nano wire, and the metastable M2 phase and T phase can stably exist at room temperature. Meanwhile, the formation of the lateral oxygen concentration gradient of the vanadium dioxide micro-nanowire is realized through a liquid layer auxiliary growth mode of the vanadium pentoxide reduction reaction at low temperature and low pressure, and the T-M2 type single crystal driver with good driving capability is prepared. The energy required for the phase conversion of the T phase to the M2 phase is only 20% of that of the M1 phase to the R phase, and the driving amplitude can reach 70% of that of an M1-R type driver, so that the high-efficiency single crystal driver with low energy consumption can be used.
Preferably, tungsten dioxide powder is also mixed in the vanadium source powder in the step (1).
Preferably, the tungsten dioxide powder is 20-40% of the total mass of the vanadium source powder, for example 20%, 22%, 24%, 26%, 28%, 30%, 32%, 34%, 36%, 38% or 40%, but not limited to the recited values, and other values not recited within the range of values are also applicable.
In the invention, the total mass of the vanadium source powder is the total mass of the vanadium source powder mixed with the tungsten dioxide powder, namely the mass sum of the vanadium pentoxide powder, the silicon dioxide powder and the tungsten dioxide powder.
According to the invention, the oxygen content in a vanadium dioxide system can be selectively reduced by adding the reductive tungsten dioxide dopant, so that the oxygen concentration gradient is increased, the coexistence of M2 phase and R phase is realized, the maximum bending driving behavior is realized, and the prepared M2-R type single crystal driver reaches the performance limit of the vanadium dioxide driver in all aspects.
In the invention, the tungsten dioxide powder accounts for less than 50% of the total mass of the vanadium source powder, otherwise, the lateral oxygen concentration gradient is too high, so that the corrosion of the vanadium dioxide nanowire is serious, and the driving behavior can not be realized.
In the invention, the mixing in the step (1) is carried out in a quartz boat.
Preferably, the growth substrate of step (2) comprises a quartz plate.
Preferably, the surface average particle size of the quartz piece is 300-340 meshes, such as 300 meshes, 305 meshes, 310 meshes, 315 meshes, 320 meshes, 325 meshes, 330 meshes, 335 meshes or 340 meshes, but not limited to the listed values, and other values not listed in the range of the values are also applicable.
In the invention, the surface average particle size is specifically expressed as the average mesh number of quartz sand on the surface of the quartz plate.
Preferably, the distance between the growth substrate and the vanadium source powder in step (2) is 0.1-1cm, and may be, for example, 0.1cm, 0.2cm, 0.3cm, 0.4cm, 0.5cm, 0.6cm, 0.7cm, 0.8cm, 0.9cm or 1cm, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
In the invention, the heating system in the step (2) is a tube furnace.
Preferably, the degree of vacuum in step (3) is less than or equal to 10Pa, such as 1Pa, 2Pa, 3Pa, 4Pa, 5Pa, 6Pa, 7Pa, 8Pa, 9Pa or 10Pa, but not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the protective gas in step (3) includes any one of nitrogen, argon or helium.
Preferably, the flow rate of the protective gas in step (3) is 7-20sccm, such as 7sccm, 8sccm, 10sccm, 12sccm, 14sccm, 16sccm, 18sccm or 20sccm, but not limited to the recited values, and other values in the range are also applicable.
Preferably, the pressure of the heating system after the introduction of the protective gas in step (3) is 2to 4Torr, and may be, for example, 2Torr, 2.2Torr, 2.4Torr, 2.6Torr, 2.8Torr, 3Torr, 3.2Torr, 3.4Torr, 3.6Torr, 3.8Torr or 4Torr, but not limited to the enumerated values, and other unrecited values in this range of values are also applicable.
Preferably, the temperature raising procedure in step (3) is specifically: and raising the temperature to a first temperature in a first time period, then raising the temperature to a second temperature at a first temperature raising rate, keeping the temperature for a second time period, and finally lowering the temperature.
Preferably, the first period of time is 25-35min, and may be, for example, 25min, 26min, 27min, 28min, 29min, 30min, 31min, 32min, 33min, 34min or 35min, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the first temperature is 500-.
Preferably, the first temperature increase rate is 8-12 ℃/min, and may be, for example, 8 ℃/min, 8.5 ℃/min, 9 ℃/min, 9.5 ℃/min, 10 ℃/min, 10.5 ℃/min, 11 ℃/min, 11.5 ℃/min, or 12 ℃/min, but is not limited to the recited values, and other values not recited within the range of values are also applicable.
Preferably, the second temperature is 800-.
Preferably, the second period of time is 1-10min, and may be, for example, 1min, 2min, 3min, 4min, 5min, 6min, 7min, 8min, 9min or 10min, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
As a preferred technical solution of the first aspect of the present invention, the preparation method comprises the steps of:
(1) mixing vanadium pentoxide powder and silicon dioxide powder according to the mass ratio of (1-2) to 1 to obtain vanadium source powder; and mixing tungsten dioxide powder accounting for 20-40% of the total weight of the vanadium source powder;
(2) placing a quartz plate with the surface average granularity of 300-340 meshes as a growth substrate at a position of 0.1-1cm above the vanadium source powder obtained in the step (1) and placing the quartz plate and the vanadium source powder into a heating system;
(3) vacuumizing the heating system in the step (2) until the absolute vacuum degree is less than or equal to 10Pa, introducing nitrogen, argon or helium with the flow of 7-20sccm until the air pressure of the heating system is 2-4Torr, and starting a temperature-raising program to perform chemical vapor deposition reaction to prepare a vanadium dioxide single crystal driver; the temperature rise program specifically comprises the following steps: heating to 500-.
In a second aspect, the invention provides a vanadium dioxide single crystal driver prepared by the preparation method of the first aspect.
The types of the vanadium dioxide single crystal driver obtained by the invention comprise an M2-R type single crystal driver, a T-M2 type single crystal driver and an M1-R type single crystal driver, and the length range of the single crystal driver is 10 mu M-1mm, and the width range of the single crystal driver is 200nm-30 mu M.
In a third aspect, the invention provides an application of the vanadium dioxide single crystal driver in the second aspect in micro-nano driving.
Compared with the prior art, the invention has the following beneficial effects:
(1) the method of mixing silicon dioxide into vanadium pentoxide effectively adjusts the oxygen partial pressure of the reaction system, so that excessive oxygen permeates into the synthesized vanadium dioxide micro-nano wire, and the metastable M2 phase and T phase can stably exist at room temperature;
(2) according to the invention, the formation of the lateral oxygen concentration gradient of the vanadium dioxide micro-nanowire is realized through the liquid layer assisted growth mode of the vanadium pentoxide reduction reaction at low temperature and low pressure, and the T-M2 type single crystal driver with good driving capability is prepared; the energy required by the phase conversion from the T phase to the M2 phase is only 20% of that of the phase conversion from the M1 phase to the R phase, and the driving amplitude can reach 70% of that of an M1-R type single crystal driver, so that the high-efficiency single crystal driver with low energy consumption can be used;
(3) according to the invention, the oxygen content in a vanadium dioxide system can be selectively reduced by adding the reductive tungsten dioxide dopant, so that the oxygen concentration gradient is increased, the coexistence of M2 phase and R phase is realized, the maximum bending driving behavior is realized, and the prepared M2-R type single crystal driver reaches the performance limit of the vanadium dioxide driver in all aspects.
Drawings
FIG. 1 is an optical picture and Raman spectrum of an asymmetric domain pattern of a vanadium dioxide single crystal driver provided in example 1;
FIG. 2 is an optical picture of the temperature-varying driving behavior of the vanadium dioxide single crystal driver provided in example 1;
FIG. 3 is an optical picture and Raman spectrum of the asymmetric domain pattern of the vanadium dioxide single crystal driver provided in example 2;
FIG. 4 is an optical picture of the temperature-varying driving behavior of the vanadium dioxide single crystal driver provided in example 2;
FIG. 5 is an optical picture of vanadium dioxide nanowires etched by excess tungsten provided in example 5;
fig. 6 is a schematic diagram of the working principle of two novel single crystal drivers obtained in embodiment 1 and embodiment 2.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a vanadium dioxide single crystal driver and a preparation method thereof, wherein the preparation method comprises the following steps:
(1) mixing 3mg of vanadium pentoxide powder and 2mg of silicon dioxide powder in a quartz boat according to the mass ratio of 1.5:1 to obtain vanadium source powder; and tungsten dioxide powder accounting for 30 percent of the total weight of the vanadium source powder is mixed into the vanadium source powder;
(2) taking a quartz plate with the surface average granularity of 320 meshes as a growth substrate, placing the quartz plate at a position of 0.5cm above the vanadium source powder obtained in the step (1), and putting the quartz plate and the vanadium source powder into a tubular furnace;
(3) vacuumizing the tube furnace in the step (2) to an absolute vacuum degree of 5Pa, introducing argon with the flow of 15sccm to the pressure of the tube furnace of 3Torr, and starting a temperature-raising program to perform chemical vapor deposition reaction to prepare a vanadium dioxide single crystal driver; the temperature rise program specifically comprises the following steps: heating to 550 deg.C within 30min, heating to 850 deg.C at 10 deg.C/min, maintaining for 5min, and cooling.
The vanadium dioxide single crystal driver obtained in the embodiment is an M2-R type single crystal driver, a part of samples show a large lateral oxygen concentration gradient, an asymmetric domain pattern of a side M2 phase and a side R phase is shown in figure 1 when the temperature is increased, the single crystal driver generates a very large bidirectional bending behavior when the temperature is changed due to the strain of 1.7% generated when the M2 phase is converted to the R phase, and the process is reversible when the temperature is reduced.
Example 2
The embodiment provides a vanadium dioxide single crystal driver and a preparation method thereof, wherein the preparation method comprises the following steps:
(1) mixing 3mg of vanadium pentoxide powder and 2mg of silicon dioxide powder in a quartz boat according to the mass ratio of 1.5:1 to obtain vanadium source powder;
(2) placing a quartz plate with the surface average granularity of 300 meshes as a growth substrate at a position 1cm above the vanadium source powder obtained in the step (1) and putting the quartz plate and the vanadium source powder into a tube furnace;
(3) vacuumizing the tube furnace in the step (2) to an absolute vacuum degree of 1Pa, introducing nitrogen with the flow of 7sccm to the pressure of the tube furnace of 2Torr, and starting a temperature-raising program to perform chemical vapor deposition reaction to prepare a vanadium dioxide single crystal driver; the temperature rise program specifically comprises the following steps: heating to 500 deg.C within 25min, heating to 800 deg.C at 8 deg.C/min, maintaining for 10min, and cooling.
The vanadium dioxide single crystal driver obtained in the embodiment is a T-M2 type single crystal driver, a part of samples show smaller lateral oxygen concentration gradient, and an asymmetric domain pattern of a side M2 phase and a side T phase is shown in a temperature rise (see figure 3), because the T phase is converted to the M2 phase, a strain of 0.7% is generated, the single crystal driver can generate bidirectional bending behavior in the temperature change (see figure 4), and the process is reversible in the temperature reduction.
Example 3
The embodiment provides a vanadium dioxide single crystal driver and a preparation method thereof, wherein the preparation method comprises the following steps:
(1) mixing 4mg of vanadium pentoxide powder and 2mg of silicon dioxide powder in a quartz boat according to the mass ratio of 2:1 to obtain vanadium source powder; and tungsten dioxide powder accounting for 20 percent of the total weight of the vanadium source powder is mixed into the vanadium source powder;
(2) placing a quartz plate with the surface average granularity of 340 meshes as a growth substrate at a position of 0.1cm right above the vanadium source powder obtained in the step (1) and putting the quartz plate and the vanadium source powder into a tubular furnace;
(3) vacuumizing the tube furnace in the step (2) to an absolute vacuum degree of 10Pa, introducing helium with the flow of 20sccm into the tube furnace until the air pressure of the tube furnace is 4Torr, and starting a temperature-raising program to perform a chemical vapor deposition reaction to obtain a vanadium dioxide single crystal driver; the temperature rise program specifically comprises the following steps: heating to 600 deg.C within 35min, heating to 900 deg.C at a rate of 12 deg.C/min, maintaining for 1min, and cooling.
The vanadium dioxide single crystal driver obtained in the embodiment is an M1-R type single crystal driver, a part of samples show smaller lateral oxygen concentration gradient, an asymmetric domain pattern of one side M1 phase and one side R phase is shown when the temperature is increased, and the single crystal driver generates bidirectional bending behavior when the temperature is changed and the process is reversible when the temperature is reduced because strain of 1% is generated when the M1 phase is converted to the R phase.
Example 4
The embodiment provides a vanadium dioxide single crystal driver and a preparation method thereof, wherein the preparation method is implemented by changing the step (1) into: mixing 2.5mg of vanadium pentoxide powder and 2.5mg of silicon dioxide powder in a quartz boat according to the mass ratio of 1:1 to obtain vanadium source powder; and tungsten dioxide powder accounting for 30 percent of the total weight of the vanadium source powder is mixed into the vanadium source powder; the rest of the conditions are the same as those in example 1, and thus are not described herein.
The vanadium dioxide single crystal driver obtained in the embodiment is an M2-R type single crystal driver, a part of samples show a large lateral oxygen concentration gradient, an asymmetric domain pattern of a side M2 phase and a side R phase is shown when the temperature is increased, the single crystal driver generates a large bidirectional bending behavior when the temperature is changed due to the fact that strain of 1.7% is generated when the M2 phase is converted to the R phase, and the process is reversible when the temperature is reduced.
Example 5
The embodiment provides a vanadium dioxide single crystal driver and a preparation method thereof, wherein the preparation method is implemented by changing the step (1) into: mixing 3mg of vanadium pentoxide powder and 2mg of silicon dioxide powder in a quartz boat according to the mass ratio of 1.5:1 to obtain vanadium source powder; and tungsten dioxide powder accounting for 50 percent of the total weight of the vanadium source powder is mixed into the vanadium source powder; the rest of the conditions are the same as those in example 1, and thus are not described herein.
The vanadium dioxide nanowires obtained in the embodiment are severely corroded, and cannot realize driving behavior (see fig. 5).
Comparative example 1
The preparation method is the same as that of embodiment 1 except that the vanadium source powder in the step (1) is changed into 5mg of vanadium pentoxide powder, and no silicon dioxide powder and tungsten dioxide powder are added, so that the details are not repeated herein.
The vanadium dioxide nanowires obtained by the comparative example are all M1 phase crystals, and do not have stable M2 phase and T phase, so that the driving behavior can not be realized.
It can be seen that the working principle of the two new single crystal drivers obtained in example 1 and example 2 is as follows (see fig. 6):
(1) for M2-R type single crystal drive: the side with less oxygen content is changed into the R phase first during the temperature rise, and the other side is changed into the M2 phase at the moment, and the M2 phase is longer than the R phase in the axial direction, so that the driver bends to the side occupied by the R phase;
(2) for T-M2 type single crystal drive: at the time of temperature rise, the side with the smaller oxygen content first changes to the M2 phase, and at this time, the other side becomes the T phase, and since the M2 phase is axially longer than the T phase, the actuator bends to the side occupied by the T phase.
In conclusion, the method of mixing silicon dioxide into vanadium pentoxide effectively adjusts the oxygen partial pressure of the reaction system, so that excessive oxygen permeates into the synthesized vanadium dioxide micro-nano wire, and the metastable M2 phase and T phase can stably exist at room temperature; in addition, the formation of the lateral oxygen concentration gradient of the vanadium dioxide micro-nanowire is realized through a liquid layer auxiliary growth mode of the vanadium pentoxide reduction reaction at low temperature and low pressure, and a T-M2 type single crystal driver with good driving capability is prepared; the energy required for the phase conversion of the T phase to the M2 phase is only 20% of that of the M1 phase to the R phase, and the driving amplitude can reach 70% of that of an M1-R type single crystal driver, so that the high-efficiency single crystal driver with low energy consumption can be used. The invention can selectively reduce the oxygen content in the vanadium dioxide system by adding the reductive tungsten dioxide dopant, further increase the oxygen concentration gradient, realize the coexistence of M2 phase and R phase, so as to realize the maximum bending driving behavior, and the prepared M2-R type single crystal driver reaches the performance limit of the vanadium dioxide driver in all aspects.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. A preparation method of a vanadium dioxide single crystal driver is characterized by comprising the following steps:
(1) mixing vanadium pentoxide powder and silicon dioxide powder according to the mass ratio of (1-2) to 1 to obtain vanadium source powder;
(2) placing the growth substrate right above the vanadium source powder obtained in the step (1) and putting the growth substrate into a heating system;
(3) and (3) vacuumizing the heating system in the step (2), introducing protective gas, starting a temperature-raising program to perform chemical vapor deposition reaction, and obtaining the vanadium dioxide single crystal driver.
2. The method according to claim 1, wherein tungsten dioxide powder is further mixed in the vanadium source powder in the step (1);
preferably, the tungsten dioxide powder accounts for 20-40% of the total mass of the vanadium source powder.
3. The production method according to claim 1 or 2, wherein the growth substrate of step (2) comprises a quartz plate;
preferably, the surface average particle size of the quartz piece is 300-340 meshes.
4. The production method according to any one of claims 1 to 3, wherein the distance between the growth substrate of step (2) and the vanadium source powder is 0.1 to 1 cm.
5. The method according to any one of claims 1 to 4, wherein the degree of vacuum in step (3) is 10Pa or less;
preferably, the protective gas in step (3) comprises any one of nitrogen, argon or helium;
preferably, the flow rate of the protective gas in the step (3) is 7-20 sccm;
preferably, the pressure of the protective gas introduced into the post-heating system in the step (3) is 2to 4 Torr.
6. The production method according to any one of claims 1 to 5, wherein the temperature raising procedure in step (3) is specifically: and raising the temperature to a first temperature in a first time period, then raising the temperature to a second temperature at a first temperature raising rate, keeping the temperature for a second time period, and finally lowering the temperature.
7. The method of claim 6, wherein the first period of time is 25-35 min;
preferably, the first temperature is 500-;
preferably, the first heating rate is 8-12 ℃/min;
preferably, the second temperature is 800-;
preferably, the second period of time is 1-10 min.
8. The method of any one of claims 1 to 7, comprising the steps of:
(1) mixing vanadium pentoxide powder and silicon dioxide powder according to the mass ratio of (1-2) to 1 to obtain vanadium source powder; and mixing tungsten dioxide powder accounting for 20-40% of the total weight of the vanadium source powder;
(2) placing a quartz plate with the surface average granularity of 300-340 meshes as a growth substrate at a position of 0.1-1cm above the vanadium source powder obtained in the step (1) and placing the quartz plate and the vanadium source powder into a heating system;
(3) vacuumizing the heating system in the step (2) until the absolute vacuum degree is less than or equal to 10Pa, introducing nitrogen, argon or helium with the flow of 7-20sccm until the air pressure of the heating system is 2-4Torr, and starting a temperature-raising program to perform chemical vapor deposition reaction to prepare a vanadium dioxide single crystal driver; the temperature rise program specifically comprises the following steps: heating to 500-.
9. A vanadium dioxide single crystal actuator produced by the production method according to any one of claims 1 to 8.
10. Application of the vanadium dioxide single crystal driver of claim 9 in micro-nano driving.
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| CN106187318A (en) * | 2016-07-15 | 2016-12-07 | 天津大学 | A kind of preparation method of the ceramic base Vanadium dioxide nanometer rod structure of freedom and on-plane surface growth |
| CN106637404A (en) * | 2016-12-06 | 2017-05-10 | 东华理工大学 | Method for growing large-area mono-crystal vanadium dioxide thin film by utilizing tubular furnace |
| CN110699670A (en) * | 2019-11-13 | 2020-01-17 | 西安近代化学研究所 | Preparation method of vanadium dioxide film |
| CN111850684A (en) * | 2019-04-30 | 2020-10-30 | 中国科学技术大学 | Preparation method of vanadium dioxide-based single crystal and vanadium dioxide-based single crystal |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106187318A (en) * | 2016-07-15 | 2016-12-07 | 天津大学 | A kind of preparation method of the ceramic base Vanadium dioxide nanometer rod structure of freedom and on-plane surface growth |
| CN106637404A (en) * | 2016-12-06 | 2017-05-10 | 东华理工大学 | Method for growing large-area mono-crystal vanadium dioxide thin film by utilizing tubular furnace |
| CN111850684A (en) * | 2019-04-30 | 2020-10-30 | 中国科学技术大学 | Preparation method of vanadium dioxide-based single crystal and vanadium dioxide-based single crystal |
| CN110699670A (en) * | 2019-11-13 | 2020-01-17 | 西安近代化学研究所 | Preparation method of vanadium dioxide film |
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