CN105669248A - Vanadium dioxide thin film having regular truss network structure and preparation method thereof - Google Patents
Vanadium dioxide thin film having regular truss network structure and preparation method thereof Download PDFInfo
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Abstract
The invention provides a vanadium dioxide thin film having a regular truss network structure and a preparation method thereof. The vanadium oxide thin film is an M phase and has the regular truss network structure formed by uniformly connecting nanorods, wherein the nanorods are each of a monocrystal structure, the length of crystal grains is 200-500 nm and the width of the crystal grains is 30-60 nm. The method includes the steps: step (1), preparation of an initial product of the vanadium dioxide thin film; step (2), preparation of a semi-finished product of the vanadium dioxide thin film, and step (3), preparation of the vanadium oxide thin film. The vanadium dioxide thin film prepared by the method provided by the embodiment of the invention has excellent thermal induced phase transition performance and excellent heat induced resistance modulation capability, and also has relatively high visible light transmittance rate and relatively strong thermal radiation modulation performance. At the same time, the thin film morphology, size and density are effectively controlled through controlling reaction conditions, and the preparation method has the advantages of simple process, large-area production, easily obtained raw materials, low cost and the like and is suitable for use in industrialization.
Description
Technical field
The invention belongs to inorganic functional material field, be specifically related to a kind of vanadium dioxide film with regular truss network structure and the preparation method of a kind of vanadium dioxide film with regular truss network structure.
Background technology
Vanadium dioxide (VO2) it is typical electron strong correlation compound, Consideration of Metal--Insulator Transition (MIT) is there is at 68 DEG C, M phase (monoclinic phase) is occurred to be changed into the reversible transition of R phase (Tetragonal rutile structure), its phase transformation response speed is exceedingly fast, up to tens fs magnitudes, resistivity before and after phase transformation, light transmission rate and reflectance are undergone mutation. Change in resistance amplitude may be up to 4～5 orders of magnitude, and ultrared light transmission rate is also widely varied therewith. Low temperature semi conducting state VO2Infrared light is high transmission, low reflective condition by thin film; Higher than phase transition temperature, VO2Thin film is changed into metal phase, is low transmission, high reflective condition to the wavelength infrared light more than 1.3 μm, and extra electric field and stress field can realize MIT phase transformation regulation and control, and the performance of these excellences makes VO2It is with a wide range of applications in lasing safety, smart window, heat/photoswitch, many regulation and control fields such as electronic device, light storage device.
Along with the high speed development of integrated electronic and micro-electromechanical industry, device is integrated, trend toward miniaturization is notable all the more. Thin film and corresponding micro-nano structure lithographic technique have established the basis of modern electronic technology development. But based on the micro-nano device technology of preparing of lithographic technique, technical sophistication, cost are high. Currently, nano material and nanostructured control technique provide a kind of micro element from bottom to top and prepare thinking. One of nanostructured regulation and control study hotspot becoming current nanotechnology. Existing more report adopts either physically or chemically, 1-dimention nano unit (nano wire or rod) is assembled and forms two-dimensional nanostructure and device, but the usual crystalline orientation of one-dimensional material is random in the two-dimensional nanostructure constructed by this type of method, and lack coherent connection. Desirable two-dimensional nanostructure should be, one-dimensional material tends to consistent, coherence connects, cycle arrangement. So orderly nanostructured can give full play to the anisotropic properties of material, it is achieved long-range transports and cycle effect, is the practical effective way of nano material device. Currently, the preparation of this kind ordered nano-structure from bottom to top is still in the exploratory stage, and technological means concentrates on gaseous techniques. This type of gaseous techniques equipment is complicated, energy resource consumption is big, productivity is low, it is more difficult to realize practical production.
Preparation VO2Thin film generally adopts sol-gal process, Chinese patent, publication number: (CN104030357A);Magnetron sputtering method, Chinese patent, publication number: (CN104099563A); Electrodeposition process, Chinese patent, publication number: (CN102534731B, CN103556168A) and powder body-Organic substance composite mortar membrane formation process, Chinese patent, publication number: (CN102241482B). The shortcomings such as but these preparation methoies often exist complicated process of preparation, cost is high, large area film forming difficulty, unstable properties, can not really meet the demand of the marketization. Wherein hydro-thermal method prepares the thin film of powder body compound organic additive again formation is considered as that cost is minimum, also will be the easiest expanded a kind of successful method, but the arrangement of its powder body is disorderly and unsystematic, haphazard packing, it is impossible to realize nanostructured regulation and control. Visible light transmissivity is usually less than 60% by such thin film, it is impossible to meet daily demand. Additionally organic additive is easily oxidized and affect VO2Performance etc. these all limit VO2The marketization application.
Summary of the invention
The technical problem to be solved is to provide a kind of vanadium dioxide film with regular truss network structure overcoming the problems referred to above, and the preparation method of a kind of vanadium dioxide film with regular truss network structure, to realize optimizing thermal induced phase transition sudden change of resistivity performance and the infrared light modulating performance of vanadium dioxide film.
In order to solve the problems referred to above, the preparation method that the invention discloses a kind of vanadium dioxide film with regular truss network structure, said method comprising the steps of:
Step (1), vanadium dioxide film first product preparation;
The preparation of solution 1: heated and stirred to being completely dissolved, obtains solution 1 containing vanadium solid chemical compound, oxalic acid and distilled water mixture;
The preparation of solution 2: add distilled water in described solution 1, add in monohydric alcohol and two kinds of alcoholic solutions of dihydroxylic alcohols at least one, obtain solution 2, wherein, the volume ratio of the volume and described distilled water that add described alcoholic solution is 0:1～3:1, in described solution 2, vanadium ion concentration is 0.002mol/L～0.04mol/L, uses ammonia that the pH value of described solution 2 is adjusted to 1～7;
The preparation of thin film first product: signle crystal alumina substrate is soaked in described solution 2, and described solution 2 is placed in reactor and carries out hydro-thermal reaction together with described signle crystal alumina substrate, hydrothermal temperature is 190 DEG C～280 DEG C, the hydro-thermal reaction time is 30min～48h, generates described vanadium dioxide film first product on described signle crystal alumina substrate;
Step (2), the half-finished preparation of vanadium dioxide film;
After hydro-thermal reaction terminates, described signle crystal alumina substrate in described reactor is taken out, deionized water and dehydrated alcohol is used to rinse the surface deposits of described signle crystal alumina substrate respectively, re-use dry gas to dry up, described signle crystal alumina substrate obtains there are blue-black vanadium dioxide film semi-finished product;
Step (3), described vanadium dioxide film preparation;
When air pressure is 1kpa～50kpa, described vanadium dioxide film semi-finished product make annealing treatment 10s～1h through 300 DEG C～600 DEG C, it is thus achieved that described vanadium dioxide film.
Alternatively, in described step (1), the described solid chemical compound containing vanadium includes in vanadium oxysulfate, vanadic anhydride, vanadyl oxalate and ammonium metavanadate at least one.
Alternatively, in described step (1), described monohydric alcohol is at least one in methanol, ethanol and isopropanol, and described dihydroxylic alcohols is ethylene glycol.
Alternatively, in described step (1), containing vanadium solid chemical compound, described oxalic acid and described distilled water mixture to being completely dissolved described in use water-bath magnetic stirring apparatus heated and stirred, heating-up temperature is 50 DEG C～90 DEG C, and mixing time is 1h～48h.
Alternatively, described signle crystal alumina substrate has C axis oriented, M axle orientation or A axle orientation.
Alternatively, in described step (2), dry gas is 99.99% nitrogen.
Alternatively, in described step (3), using quartz intracavity quick anneal oven that described vanadium dioxide film semi-finished product are carried out handling return, annealing temperature is preferably 350 DEG C～450 DEG C, annealing time is preferably 10s～30min, and air pressure is preferably 1kpa～20kpa.
The invention also discloses a kind of vanadium dioxide film with regular truss network structure, described vanadium dioxide film is M phase, has the regular truss network structure connected to form by even rod, and described nanometer rods is mono-crystalline structures, the length of crystal grain is 200～500nm, and width is 30～60nm.
Compared with prior art, the present invention includes advantages below:
The preparation method that the invention provides a kind of vanadium dioxide film with regular truss network structure, with respect to the vanadium dioxide film that other existing preparation methoies prepare, the vanadium dioxide film prepared according to the preparation method of the present invention is M phase, thin film is more uniformly distributed, nanostructured is controlled, due to its regular nanostructured presented and single crystalline nature, make this vanadium dioxide film have excellent thermal induced phase transition performance and excellent thermic resistance modulation capability, and have higher visible light transmissivity and stronger heat radiation modulating performance concurrently.
Simultaneously, it is possible to realize the effective control to film morphology, size and density by controlling reaction condition, have technique simple, can large area produce, raw material be easy to get and with low cost, the cycle is short and low power consumption and other advantages, it is adaptable to industrialization uses.
It addition, it is substrate that preparation method provided by the invention chooses signle crystal alumina substrate, strict control reacts charging sequence, heating-up temperature, mixing time and annealing condition etc. Specifically, provide the preferred heating-up temperature 50 DEG C～90 DEG C of reaction mass, preferred mixing time 1h～48h, preferred annealing temperature 350 DEG C～450 DEG C, preferred annealing time 30s～30min and preferred air pressure 1kpa～20kpa etc., under above-mentioned optimum condition, the vanadium dioxide film of preparation has more excellent thermal induced phase transition performance and an excellent thermic resistance modulation capability, and higher visible light transmissivity and stronger heat radiation modulating performance.
Accompanying drawing explanation
Fig. 1 is the preparation method flow chart of the vanadium dioxide film with regular truss network structure of the embodiment of the present invention 1;
Fig. 2 is X-ray diffraction (XRD) figure of the vanadium dioxide film with regular truss network structure of the embodiment of the present invention 1 preparation;
Fig. 3 is transmission electron microscope (TEM) figure of the vanadium dioxide film with regular truss network structure of the embodiment of the present invention 1 preparation;
Fig. 4 is the thermal induced phase transition square resistance change test figure of the vanadium dioxide film with regular truss network structure of the embodiment of the present invention 1 preparation;
Fig. 5 is the scanning electron microscope diagram of the vanadium dioxide film with regular truss network structure of the embodiment of the present invention 1 preparation;
Fig. 6 is that the ultraviolet of the vanadium dioxide film with regular truss network structure of the embodiment of the present invention 2 preparation is to near-infrared transmission measurement figure;
Fig. 7 is the scanning electron microscope diagram of the vanadium dioxide film with regular truss network structure of the embodiment of the present invention 2 preparation;
Fig. 8 is the scanning electron microscope diagram of the vanadium dioxide film with regular truss network structure of the embodiment of the present invention 3 preparation;
Fig. 9 is X-ray diffraction (XRD) figure of the vanadium dioxide film with regular truss network structure of the embodiment of the present invention 5 preparation;
Figure 10 is the scanning electron microscope diagram of the vanadium dioxide film with regular truss network structure of the embodiment of the present invention 5 preparation;
Figure 11 is the scanning electron microscope diagram of the regular truss network structure vanadium dioxide film of the embodiment of the present invention 7 preparation.
Detailed description of the invention
Understandable for enabling the above-mentioned purpose of the present invention, feature and advantage to become apparent from, below in conjunction with the drawings and specific embodiments, the present invention is further detailed explanation.
By the examples below the flow process that realizes of material of the present invention and preparation method is described in detail.
The preparation method that the invention provides a kind of vanadium dioxide film with regular truss network structure. With reference to Fig. 1, it illustrates the preparation method flow chart of the vanadium dioxide film with regular truss network structure of the embodiment of the present invention 1, said method comprising the steps of:
Step 101, vanadium dioxide film first product preparation.
The preparation of solution 1: heated and stirred mixes to being completely dissolved containing vanadium solid chemical compound, oxalic acid and distilled water, obtains solution 1.
The preparation of solution 2: add distilled water in described solution 1, adds in monohydric alcohol and dihydroxylic alcohols at least one, obtains solution 2; Wherein, the volume ratio adding the described monohydric alcohol in described solution 1 and volume at least one in dihydroxylic alcohols and described distilled water is 0:1～3:1, so that the vanadium ion concentration in described solution 2 is 0.002mol/L～0.04mol/L, the pH value that ammonia regulates described solution 2 is used to regulate to 1～7.
The preparation of vanadium dioxide oxide first product: signle crystal alumina substrate is soaked in described solution 2, and described solution 2 is placed in reactor together with described signle crystal alumina substrate, carry out hydro-thermal reaction, reaction temperature is 190 DEG C～280 DEG C, the hydro-thermal reaction time is 30min～48h, generates vanadium dioxide oxide first product on described signle crystal alumina substrate.
The half-finished preparation of step 102, vanadium dioxide film.
After hydro-thermal reaction terminates, described signle crystal alumina substrate in described reactor is taken out, deionized water and dehydrated alcohol is used to rinse the surface deposits of described signle crystal alumina substrate respectively, re-use dry gas to dry up, described signle crystal alumina substrate obtains there are blue-black vanadium dioxide film semi-finished product.
Step 103, described vanadium dioxide film preparation.
When air pressure is 1kpa～50kpa, described vanadium dioxide film semi-finished product make annealing treatment 10s～1h through 300 DEG C～600 DEG C, it is thus achieved that described vanadium dioxide film.
The method of the embodiment of the present invention utilizes hydro-thermal reaction, adopt substrate inductive technology thinking, by controlling alcohol water ratio and vanadium ion concentration in raw material, and in conjunction with suitable Technology for Heating Processing, prepare the M phase hypovanadic oxide thin film with regular truss network structure, this vanadium dioxide film has excellent thermal induced phase transition performance and excellent thermic resistance modulation capability, and has higher visible light transmissivity and stronger heat radiation modulating performance concurrently.
In concrete preparation process, can pass through to change reaction condition and realize the effective control to film morphology, size and density, have technique simple, can large area produce, raw material be easy to get and with low cost, the cycle is short and low power consumption and other advantages, it is adaptable to industrialization uses.
Alternatively, in described step (1), the described solid chemical compound containing vanadium includes in vanadium oxysulfate, vanadic anhydride, vanadyl oxalate and ammonium metavanadate at least one.
Alternatively, in described step (1), described monohydric alcohol is at least one in methanol, ethanol and isopropanol, and described dihydroxylic alcohols is ethylene glycol.
Alternatively, in described step (1), using and mix to being completely dissolved containing vanadium solid chemical compound, described oxalic acid and described distilled water described in water-bath magnetic stirring apparatus heated and stirred, heating-up temperature is 50 DEG C～90 DEG C, and the heated and stirred time is 1h～48h.
Alternatively, described signle crystal alumina substrate has C axis oriented, M axle orientation and A axle orientation.
Alternatively, in described step (2), dry gas is 99.99% nitrogen.
Alternatively, in described step (3), using quartz intracavity quick anneal oven that described vanadium dioxide film semi-finished product are carried out handling return, annealing temperature is preferably 350 DEG C～450 DEG C, annealing time is preferably 10s～30min, and air pressure is preferably 1kpa～20kpa.
It is substrate that preparation method provided by the invention chooses signle crystal alumina substrate, and strict control reacts charging sequence, heating-up temperature, mixing time and annealing condition etc. Specifically, provide the preferred heating-up temperature 50 DEG C～90 DEG C of reaction mass, preferred mixing time 1h～48h, preferred annealing temperature 350 DEG C～450 DEG C, preferred annealing time 30s～30min and preferred air pressure 1kpa～20kpa etc., under above-mentioned optimum condition, the vanadium dioxide film of preparation has more excellent thermal induced phase transition performance and good visible light transmissivity.
For making those skilled in the art be more fully understood that the present invention, below by way of specific embodiment, the preparation method of the vanadium dioxide film with regular truss network structure of the present invention is described in detail.
The regular truss network structure vanadium dioxide film of preparation in following multiple embodiments is carried out one or more tests following:
(1) X-ray diffraction analysis:
The Rigaku-D/max-2550pc type X-ray diffractometer adopting HIT is tested, and uses Cu-k α as radiation source, and wavelength isAdopting Ni filter plate, pipe flow is 40mA, and pipe pressure is 40KV, and sweep limits is 10 °～90 °, and scanning speed is 8 °/min, and step-length is 0.02 °; Described rule truss network structure vanadium dioxide film is put in microscope slide middle, microscope slide is embedded instrument experiment groove center, tests; The qualification of thing phase and crystal structure information are by JADE5.0 software analysis.
(2) sem observation:
Adopt Hitachi S-4800 high-resolution Flied emission scanning electron microscope (SEM) that rule truss network structure vanadium dioxide film is carried out microstructure test.
(3) TEM transmission electron microscope analysis:
Adopt FEITecnaiG2F20S-TWIN type TEM to project Electronic Speculum to test; Utilize machinery to scrape described rule truss network structure vanadium dioxide film, make TEM and project sample, test when voltage is 150Kv.
(4) alternating temperature square resistance test:
Adopting the square resistance of Agilent U3606A ammeter test order truss network structure vanadium dioxide film, alternating temperature platform is self-control. Its test temperature is 30 DEG C～100 DEG C.
(5) alternating temperature ultraviolet is to near-infrared transmission measurement:
Adopting Japan's Shimadzu UV3600 spectrophotometer test, alternating temperature platform is made by oneself, the film substrate prepared is placed in buckle-type warm table, and allows testing light source pass through thin film center place. Transmitance wavelength measurement ranges for 300～3000nm, tests temperature respectively 30 DEG C (low temperature), 100 DEG C (high temperature).
Embodiment 1
The concrete grammar of the vanadium dioxide film that preparation has regular truss network structure may include that
(1) preparation of vanadium dioxide film first product.
By the V of 3.56g2O5Powder and 2 times of V2O5The oxalic acid of molal quantity mixes in 100ml distilled water, containing vanadium solid chemical compound, described oxalic acid and described distilled water mixture to being completely dissolved described in use water-bath magnetic stirring apparatus heated and stirred, it is placed in water-bath magnetic stirring apparatus heated and stirred and dissolves, heating-up temperature is 50 DEG C, stirring reaction 48h, obtain navy blue vanadyl oxalate solution, ie in solution 1.
Taking 1ml solution 1, add 99ml deionized water (volume ratio of alcohol to water is 0:1), be made into the solution 2 of 100ml, vanadium ion concentration is 0.004mol/L, and now the pH value of solution 2 is 1.
Take 40ml solution 2 to be placed in and carry out hydro-thermal reaction equipped with in 50ml polyparaphenylene reactor, C axis oriented alumina substrate is put in described reactor, by described reactor good seal and be put in drying oven, after being incubated 4h at 190 DEG C, supernatant liquid clarification in described reactor, hydro-thermal reaction completes.
(2) the half-finished preparation of vanadium dioxide film.
After hydro-thermal reaction completes, the supernatant in described reactor is gone, described signle crystal alumina substrate in described reactor is taken out, C axis oriented alumina substrate obtains uniform blue-black film, described thin film is rinsed with deionized water, dehydrated alcohol respectively and removes surface deposits, and to utilize purity be that film surface is dried up by 99.99% nitrogen.
(3) preparation of described vanadium dioxide film.
Thin film after drying up is placed in quartz cavate quick anneal oven and is annealed processing: remain air atmosphere, air pressure is 1kpa, annealing temperature is 450 DEG C, time is 6min, obtaining the vanadium dioxide film with rule nanometer truss network structure, described thin film is all covered in signle crystal alumina substrate surface.
The vanadium dioxide film that the present embodiment step (3) is prepared is tested, and test result is as follows:
(1) X-ray diffraction analysis:
With reference to Fig. 2, it is shown that X-ray diffraction (XRD) figure of the vanadium dioxide film with regular truss network structure of the embodiment of the present invention 1 preparation. As shown in Figure 2, the characteristic peak of the vanadium dioxide film of the embodiment of the present invention 1 preparation is consistent with the characteristic peak in JCPDS65-2358, this illustrates the vanadium dioxide material that vanadium dioxide film is M phase of embodiment 1 preparation, further illustrates the method according to embodiment 1 and can prepare the vanadium dioxide film of M phase. This thin film has (010) preferred orientation.
(2) TEM transmission electron microscope analysis:
With reference to Fig. 3, illustrating transmission electron microscope (TEM) figure of the vanadium dioxide film with regular truss network structure prepared by the embodiment of the present invention 1, wherein Fig. 3 includes transmission electron microscope (TEM) figure and diffraction pattern two parts of vanadium dioxide film. Schemed it can be seen that described thin film is regular network shape structure by the TEM of Fig. 3, and have space to exist. By the calculating of angle and length between the diffraction pattern of Fig. 3 and corresponding diffraction spot it can be seen that vanadium dioxide film prepared by the present embodiment is M phase.
(3) alternating temperature square resistance test:
With reference to Fig. 4, it is shown that the thermal induced phase transition square resistance change test figure of the vanadium dioxide film with regular truss network structure of the embodiment of the present invention 1 preparation. In Fig. 4, right side graph is the intensification phase transformation square resistance change test curve of the vanadium dioxide film of the present embodiment, and right side graph is the cooling phase transformation square resistance change test curve of the vanadium dioxide film of the present embodiment. From two resistance variations test curves, when square resistance is changed into high-temperature-phase (vanadium dioxide of Rutile Type) by low-temperature phase (vanadium dioxide of monoclinic phase), change in resistance reaches more than 4.9 orders of magnitude, illustrates that vanadium dioxide film prepared by the embodiment of the present invention 1 has good thermic resistance modulation capability.Meanwhile, in intensification phase transformation and cooling phase transition process, the gap of two resistance variations test curves is little, illustrates that M phase hypovanadic oxide thin film prepared by the embodiment of the present invention has good phase transformation recovery stability.
(4) sem observation:
With reference to Fig. 5, it is shown that the scanning electron microscope diagram of the vanadium dioxide film with regular truss network structure of the embodiment of the present invention 1 preparation. As shown in Figure 5, described thin film has rule nanometer truss network structure, and the nanometer rods of composition network configuration is mutually in 60 or 120 degree of growths, and the length of described nanometer rods is 350nm, and width is 50nm.
Embodiment 2
The concrete grammar of the vanadium dioxide film that preparation has regular truss network structure may include that
(1) taking the solution 1 of 1ml embodiment 1 preparation, add 199ml deionized water (volume ratio of alcohol to water is 0:1), be made into the solution 2 of 200ml, vanadium ion concentration is 0.002mol/L, with ammonia, the pH value of solution 2 is adjusted to 2.4.
Take the solution 2 after 40ml regulates pH to be placed in the reactor equipped with 50ml polyparaphenylene and carry out hydro-thermal reaction, C axis oriented alumina substrate is put in described reactor, and it is positioned in drying oven after described reactor good seal, it is incubated 4h at 230 DEG C, supernatant liquid clarification in described reactor, hydro-thermal reaction completes;
(2) after hydro-thermal reaction completes, the supernatant in described reactor is gone, C axis oriented alumina substrate obtains uniform blue-black film, described thin film is rinsed with deionized water, dehydrated alcohol respectively and removes surface deposits, and to utilize purity be that film surface is dried up by 99.99% nitrogen.
(3) thin film after drying up is placed in quartz cavate quick anneal oven it is annealed processing: remain air atmosphere, air pressure is 5kpa, annealing temperature is 600 DEG C, time is 10s, obtaining the vanadium dioxide film with rule nanometer truss network structure, described thin film is all covered in signle crystal alumina substrate surface.
The vanadium dioxide film that the present embodiment step (3) is prepared is tested, and test result is as follows:
(1) X-ray diffraction analysis:
The X-ray diffraction analysis result of described rule nanometer truss network structure vanadium dioxide film is as shown in Figure 1, the characteristic peak of described rule nanometer truss network structure vanadium dioxide film is consistent with the characteristic peak in JCPDS65-2358, therefore it is the vanadium dioxide nano material of M phase, it was shown that annealed process obtains the vanadium dioxide film of M phase. Thin film has (010) preferred orientation.
(2) ultraviolet is to near-infrared transmission measurement:
With reference to Fig. 6, it is shown that the ultraviolet of the vanadium dioxide film with regular truss network structure of the embodiment of the present invention 2 preparation is to near-infrared transmission measurement figure. As shown in Figure 6, the most high visible light transmissivity (780nm wavelength place) of the vanadium dioxide film of embodiment 2 preparation all can be maintained at more than 60% when undergoing phase transition front and back 30 DEG C (low-temperature phases) and 100 DEG C (high-temperature-phase) at vanadium dioxide film, and this structure is conducive to passing through of visible ray. 2500nm wavelength place before and after phase transformation, its near-infrared also can reach about 40% through rate variance. Result illustrates that this thin film has good modulation of infrared rays ability and also ensure that the transmitance of visible ray simultaneously, has significantly high actual application value.
(3) sem observation:
With reference to Fig. 7, it is shown that the scanning electron microscope diagram of the vanadium dioxide film with regular truss network structure of the embodiment of the present invention 2 preparation.As shown in Figure 7, described thin film has uniform rule nanometer truss network structure, and the nanometer rods of composition network configuration is mutually in 60 or 120 degree of growths. Meanwhile, vanadium dioxide film compared to embodiment 1 preparation, in the network structure of vanadium dioxide film prepared by the present embodiment, the edge of nanometer rods becomes relatively smooth, nanometer rods size shortens, this is owing to reaction solution concentration reduces, and causes that growing nano-rod desired ion amount reduces, reduces the size of nanometer rods, causing that Nanostructure Network space is increased, the change based on said structure makes the visible light transmissivity of vanadium dioxide film be improved. After shortening, the length of nanometer rods is 200nm, and width is 30nm.
Embodiment 3
The concrete grammar of the vanadium dioxide film that preparation has regular truss network structure may include that
(1) solution 1 of 1ml embodiment 1 preparation is taken, add the mixed solution of 99ml absolute methanol and deionized water, wherein absolute methanol is 1:1 with the volume ratio of deionized water, mix homogeneously is made into the solution 2 of 100ml, vanadium ion concentration is 0.004mol/L, with ammonia, the pH value of solution 2 is adjusted to 5.
Take 40ml to regulate the solution 2 after pH and be placed in 50ml polyparaphenylene reactor and carry out hydro-thermal reaction, C axis oriented alumina substrate is put in described reactor, and by described reactor good seal and be put in drying oven, after being incubated 24h at 250 DEG C, supernatant liquid clarification in described reactor, hydro-thermal reaction completes;
(2) after hydro-thermal reaction completes, the supernatant in described reactor is gone, C axis oriented alumina substrate obtains uniform blue-black film, described thin film is rinsed with deionized water, dehydrated alcohol respectively and removes surface deposits, and to utilize purity be that film surface is dried up by 99.99% nitrogen.
(3) thin film after drying up is placed in quartz cavate quick anneal oven it is annealed processing: remain air atmosphere, air pressure is 20kpa, annealing temperature is 500 DEG C, and the time is 3min, it is thus achieved that have the vanadium dioxide film of rule nanometer truss network structure.
The vanadium dioxide film that the present embodiment step (3) is prepared is tested, and test result is as follows:
(1) X-ray diffraction analysis:
The X-ray diffraction analysis result of described rule truss network structure vanadium dioxide film is as shown in Figure 1, the characteristic peak of described rule truss network structure vanadium dioxide film is consistent with the characteristic peak in JCPDS65-2358, therefore it is the vanadium dioxide nano material of M phase, it was shown that annealed process obtains the vanadium dioxide film of M phase. Thin film has (010) preferred orientation.
(2) sem observation:
With reference to Fig. 8, it is shown that the scanning electron microscope diagram of the vanadium dioxide film with regular truss network structure of the embodiment of the present invention 3 preparation. As shown in Figure 8, described thin film has uniform rule truss network structure, and the nanometer rods of composition network configuration is mutually in 60 or 120 degree of growths. Owing to the present embodiment introducing absolute methanol, the dielectric constant making reaction solution changes, inhibit the oriented growth of nanometer rods, decrease the draw ratio of nanometer rods, relative to embodiment 1 and embodiment 2, in the network structure of vanadium dioxide film prepared by the embodiment of the present invention, nanometer rods edge is more round and smooth, and length average out to about the 250nm of nanometer rods, width is 20～40nm. Controlling the draw ratio of nanometer rods in this way, it is possible to obtain different electrical property vanadium dioxide films, this is owing to draw ratio reduces the crystal boundary number that will increase thin film, considers carefully thus increasing thin film internal resistance with reducing electric transmission so that phase transition performance reduces.
Embodiment 4
(1) taking vanadyl oxalate 9.8g and be dissolved in deionized water, being configured to 100ml vanadium ion concentration is 0.04mol/L solution 1.Take the 1ml 49ml deionized water dilution in solution 1, add the mixed solution of absolute methanol that 50ml volume ratio is 1:1 and ethylene glycol, obtain solution 2, wherein absolute methanol is 1:1 with the volume ratio of ethylene glycol, the volume ratio of two kinds of alcohols materials and deionized water is 3:1, vanadium ion concentration is 0.004mol/L, with ammonia, the pH value of solution 2 is adjusted to 7; Take 40ml to regulate the solution 2 after pH and be placed in 50ml polyparaphenylene reactor and carry out hydro-thermal reaction, C axis oriented alumina substrate is put in described reactor, and by described reactor good seal and be put in drying oven, after being incubated 48h at 250 DEG C, supernatant liquid clarification in described reactor, hydro-thermal reaction completes;
(2) after hydro-thermal reaction completes, the supernatant in described reactor is gone, C axis oriented alumina substrate obtains uniform blue-black film, described thin film is rinsed with deionized water, dehydrated alcohol respectively and removes surface deposits, and to utilize purity be that film surface is dried up by 99.99% nitrogen;
(3) thin film after drying up is placed in quartz cavate quick anneal oven it is annealed processing: remain air atmosphere, air pressure is 20kpa, annealing temperature is 500 DEG C, and the time is 3min, it is thus achieved that a kind of rule truss network structure vanadium dioxide film of the present invention.
The vanadium dioxide film that the present embodiment step (3) is prepared is tested, and result is as follows:
(1) X-ray diffraction analysis:
The X-ray diffraction analysis result of described rule truss network structure vanadium dioxide film is as shown in Figure 1, the characteristic peak of described rule truss network structure vanadium dioxide film is consistent with the characteristic peak in JCPDS65-2358, therefore it is the vanadium dioxide nano material of M phase, it was shown that annealed process obtains the vanadium dioxide film of M phase. Thin film has (010) preferred orientation.
(2) sem observation:
The similar Fig. 8 of scanning electron microscope diagram of the vanadium dioxide film that the embodiment of the present invention obtains, described film morphology remains as uniform rule nanometer network shape structural membrane, and it is mutually 60 or 120 degree of growths by nanometer rods. Because ethylene glycol is similar for the growth effect of nanometer rods with absolute methanol, but ethylene glycol can increase solution viscosity, reduce ion transportation, it is more easy to suppression nanometer rods oriented growth, so to compare example 3 rounder and more smooth at the nanometer rods edge of the embodiment of the present invention, the length of described nanometer rods is 200nm, and width is 30nm.
Embodiment 5
(1) taking the solution 1 of 5ml embodiment 1 preparation, add 95ml deionized water (alcohol water specific volume=0:1), obtain solution 2, wherein vanadium ion concentration is 0.02mol/L, with ammonia, the pH value of solution 2 is adjusted to 2.4; Take 40ml to regulate the solution 2 after pH and be placed in 50ml polyparaphenylene reactor and carry out hydro-thermal reaction, M axle orientation alumina substrate is put in described reactor, and by described reactor good seal and be put in drying oven, after being incubated 48h at 250 DEG C, supernatant liquid clarification in described reactor, hydro-thermal reaction completes;
(2) after hydro-thermal reaction completes, the supernatant in described reactor is gone, M axle orientation alumina substrate obtains uniform blue-black film, described thin film is rinsed with deionized water, dehydrated alcohol respectively and removes surface deposits, and to utilize purity be that film surface is dried up by 99.99% nitrogen;
(3) thin film after drying up is placed in quartz cavate quick anneal oven it is annealed processing: remain air atmosphere, air pressure is 50kpa, annealing temperature is 300 DEG C, and the time is 1h, it is thus achieved that a kind of rule truss network structure vanadium dioxide film of the present invention.
The vanadium dioxide film that the present embodiment step (3) is prepared is tested, and result is as follows:
(1) X-ray diffraction analysis:
With reference to Fig. 9, it is shown that X-ray diffraction (XRD) figure of the vanadium dioxide film with regular truss network structure of the embodiment of the present invention 5 preparation. As shown in Figure 9, the characteristic peak of described rule truss network structure vanadium dioxide film is consistent with the characteristic peak in JCPDS65-2358, is therefore the vanadium dioxide nano material of M phase, it was shown that annealed process obtains the vanadium dioxide film of M phase. Thin film has (-201) preferred orientation.
(2) sem observation:
With reference to Figure 10, it is shown that the scanning electron microscope diagram of the vanadium dioxide film with regular truss network structure of the embodiment of the present invention 5 preparation. As shown in Figure 10, described film morphology is uniform rule truss network structural membrane, and it is grown along the same direction of growth by nanometer rods. This is owing to the orientation of growth of vanadium dioxide high-temperature metal phase is subject to the induction of M axle orientation alumina substrate, lattice constant match relation causes that nanometer rods presents single-orientated growth, its nanometer rods is that same direction cross-links mutually, forms uniformly rule truss network structure. Described nanometer rods is of a size of long 500nm, wide 50nm.
Embodiment 6
(1) by the ammonium metavanadate (NH of 4.68g4VO3) oxalic acid of powder and 5 times of V atomic molar numbers mixes in 100ml distilled water, being placed in water-bath magnetic stirring apparatus heated and stirred dissolves, and heating-up temperature is 75 DEG C, stirring reaction 24h, obtaining navy blue vanadyl oxalate solution, vanadium ion concentration is 0.4mol/L, ie in solution 1; Then 5ml solution 1 is taken, add 25ml deionized water, add the mixture (volume ratio of dehydrated alcohol and isopropanol is 2:1) of 20ml dehydrated alcohol and isopropanol, it is made into the solution 2 (alcohol water specific volume=2:3) of 50ml, vanadium ion concentration is 0.04mol/L, with ammonia, the pH value of solution 2 is adjusted to 3; Take 40ml to regulate the solution 2 after pH and be placed in 50ml polyparaphenylene reactor and carry out hydro-thermal reaction, A axle orientation alumina substrate is put in described reactor, and by described reactor good seal and be put in drying oven, after being incubated 30min at 280 DEG C, supernatant liquid clarification in described reactor, hydro-thermal reaction completes;
(2) after hydro-thermal reaction completes, the supernatant in described reactor is gone, A axle orientation alumina substrate obtains uniform blue-black film, described thin film is rinsed with deionized water, dehydrated alcohol respectively and removes surface deposits, and to utilize purity be that film surface is dried up by 99.99% nitrogen;
(3) thin film after drying up is placed in quartz cavate quick anneal oven it is annealed processing: remain air atmosphere, air pressure is 50kpa, annealing temperature is 350 DEG C, and the time is 30min, it is thus achieved that a kind of rule truss network structure vanadium dioxide film of the present invention.
The vanadium dioxide film that the present embodiment step (3) is prepared is tested, and result is as follows:
(1) X-ray diffraction analysis:
The X-ray diffraction analysis result of described rule truss network structure vanadium dioxide film is as shown in Figure 1, the characteristic peak of described rule truss network structure vanadium dioxide film is consistent with the characteristic peak in JCPDS65-2358, therefore it is the vanadium dioxide nano material of M phase, it was shown that annealed process obtains the vanadium dioxide film of M phase. Thin film has (010) preferred orientation.
(2) sem observation:
Similar Fig. 5 of scanning electron microscope diagram of described final vanadium dioxide film, described film morphology remains as uniform rule nanometer truss network shape structural membrane, it is by nanometer rods mutually in 60 or 120 degree of growths, and vanadium ion concentration higher in reaction solution decreases owing to the introducing of ethanol is to VO2Thin film crystallization grow up suppress impact, described nanometer rods is of a size of long 300nm, wide 60nm.
Embodiment 7
(1) by 4.68g ammonium metavanadate (NH4VO3), 3.26g vanadium oxysulfate (VOSO4) and the oxalic acid of 2 times of V atomic molar numbers mix in 100ml distilled water, be placed in water-bath magnetic stirring apparatus heated and stirred and dissolve, heating-up temperature is 90 DEG C, and stirring reaction 1h obtains navy blue vanadyl oxalate solution, and vanadium ion concentration is 0.4mol/L, ie in solution 1; Then taking 1ml solution 1, add 99ml deionized water (alcohol water specific volume=0:1), be made into the solution 2 of 100ml, vanadium ion concentration is 0.004mol/L, with ammonia, the pH value of solution 2 is adjusted to 2; Take 40ml to regulate the solution 2 after pH and be placed in 50ml polyparaphenylene reactor and carry out hydro-thermal reaction, C axis oriented alumina substrate is put in described reactor, and by described reactor good seal and be put in drying oven, after being incubated 10h at 210 DEG C, supernatant liquid clarification in described reactor, hydro-thermal reaction completes;
(2) after hydro-thermal reaction completes, the supernatant in described reactor is gone, C axis oriented alumina substrate obtains uniform blue-black film, described thin film is rinsed with deionized water, dehydrated alcohol respectively and removes surface deposits, and to utilize purity be that film surface is dried up by 99.99% nitrogen;
(3) thin film after drying up is placed in quartz cavate quick anneal oven it is annealed processing: remain air atmosphere, air pressure is 20kpa, annealing temperature is 450 DEG C, and the time is 6min, it is thus achieved that a kind of rule truss network structure vanadium dioxide film of the present invention.
The vanadium dioxide film that the present embodiment step (3) is prepared is tested, and result is as follows:
(1) X-ray diffraction analysis:
The X-ray diffraction analysis result of described rule truss network structure vanadium dioxide film is as shown in Figure 1, the characteristic peak of described rule truss network structure vanadium dioxide film is consistent with the characteristic peak in JCPDS65-2358, therefore it is the vanadium dioxide nano material of M phase, it was shown that annealed process obtains the vanadium dioxide film of M phase. Thin film has (010) preferred orientation.
(2) sem observation:
Figure 11 is the scanning electron microscope diagram of the regular truss network structure vanadium dioxide film of the embodiment of the present invention 7 preparation.
Scanning electron microscope diagram class such as Figure 10 of described final vanadium dioxide film, described film morphology remains as uniform rule truss network structural membrane, it is mutually 60 or 120 degree of growths by nanometer rods, introducing due to the ammonium metavanadate in raw material, neutralize part oxalic acid, have impact on the crystal growth of thin film so that the relatively example 2 of the space between nano net is bigger, the length of described nanometer rods is 200nm, and width is 30nm.
Present invention also offers a kind of vanadium dioxide film with regular truss network structure, described vanadium dioxide film is M phase, has the regular truss network structure connected to form by even rod, and described nanometer rods is mono-crystalline structures, the length of crystal grain is 200～500nm, and width is 30～60nm.
The vanadium dioxide film prepared according to the preparation method of the present invention is M phase, thin film is more uniformly distributed, nanostructured is controlled, due to its regular nanostructured presented and single crystalline nature, make this vanadium dioxide film have excellent thermal induced phase transition performance and excellent thermic resistance modulation capability, and have higher visible light transmissivity and stronger heat radiation modulating performance concurrently.
Above to a kind of vanadium dioxide film with regular truss network structure provided by the present invention, and the preparation method of a kind of vanadium dioxide film with regular truss network structure is described in detail, principles of the invention and embodiment are set forth by specific case used herein, and the explanation of above example is only intended to help to understand method and the core concept thereof of the present invention;Simultaneously for one of ordinary skill in the art, according to the thought of the present invention, all will change in specific embodiments and applications, in sum, this specification content should not be construed as limitation of the present invention.
Claims (8)
1. the preparation method of a vanadium dioxide film with regular truss network structure, it is characterised in that described method includes:
Step (1), vanadium dioxide film first product preparation;
The preparation of solution 1: heated and stirred to being completely dissolved, obtains solution 1 containing vanadium solid chemical compound, oxalic acid and distilled water mixture;
The preparation of solution 2: add distilled water in described solution 1, add in monohydric alcohol and two kinds of alcoholic solutions of dihydroxylic alcohols at least one, obtain solution 2, wherein, the volume ratio of the volume and described distilled water that add described alcoholic solution is 0:1～3:1, in described solution 2, vanadium ion concentration is 0.002mol/L～0.04mol/L, uses ammonia that the pH value of described solution 2 is adjusted to 1～7;
The preparation of thin film first product: signle crystal alumina substrate is soaked in described solution 2, and described solution 2 is placed in reactor and carries out hydro-thermal reaction together with described signle crystal alumina substrate, hydrothermal temperature is 190 DEG C～280 DEG C, the hydro-thermal reaction time is 30min～48h, generates described vanadium dioxide film first product on described signle crystal alumina substrate;
Step (2), the half-finished preparation of vanadium dioxide film;
After hydro-thermal reaction terminates, described signle crystal alumina substrate in described reactor is taken out, deionized water and dehydrated alcohol is used to rinse the surface deposits of described signle crystal alumina substrate respectively, re-use dry gas to dry up, described signle crystal alumina substrate obtains there are blue-black vanadium dioxide film semi-finished product;
Step (3), described vanadium dioxide film preparation;
When air pressure is 1kpa～50kpa, described vanadium dioxide film semi-finished product make annealing treatment 10s～1h through 300 DEG C～600 DEG C, it is thus achieved that described vanadium dioxide film.
2. preparation method according to claim 1, it is characterised in that in described step (1), the described solid chemical compound containing vanadium includes in vanadium oxysulfate, vanadic anhydride, vanadyl oxalate and ammonium metavanadate at least one.
3. preparation method according to claim 1, it is characterised in that in described step (1), described monohydric alcohol is at least one in methanol, ethanol and isopropanol, and described dihydroxylic alcohols is ethylene glycol.
4. preparation method according to claim 1, it is characterized in that, in described step (1), containing vanadium solid chemical compound, described oxalic acid and described distilled water mixture to being completely dissolved described in use water-bath magnetic stirring apparatus heated and stirred, heating-up temperature is 50 DEG C～90 DEG C, and mixing time is 1h～48h.
5. preparation method according to claim 1, it is characterised in that described signle crystal alumina substrate has C axis oriented, M axle orientation or A axle orientation.
6. preparation method according to claim 1, it is characterised in that in described step (2), dry gas is 99.99% nitrogen.
7. preparation method according to claim 1, it is characterized in that, in described step (3), use quartz intracavity quick anneal oven that described vanadium dioxide film semi-finished product are carried out handling return, annealing temperature is preferably 350 DEG C～450 DEG C, annealing time is preferably 10s～30min, and air pressure is preferably 1kpa～20kpa.
8. the vanadium dioxide film with regular truss network structure that prepared by the preparation method according to any one of claim 1～7, it is characterized in that, described vanadium dioxide film is M phase, there is the regular truss network structure connected to form by even rod, described nanometer rods is mono-crystalline structures, the length of crystal grain is 200～500nm, and width is 30～60nm.
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