CN101886261A - Vanadium oxide thin film for micro-metering bolometer and manufacturing method thereof - Google Patents
Vanadium oxide thin film for micro-metering bolometer and manufacturing method thereof Download PDFInfo
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Abstract
The invention discloses a vanadium oxide thin film for a micro-metering bolometer and a preparation method thereof. The preparation method comprises the following steps of: (1) cleaning a substrate, and then blow-drying the substrate for later use; (2) putting a prepared original or functionalized carbon nanotube into a beaker to mix with an organic solvent, performing ultrasonic dispersion, and then transferring dispersion liquid to the surface of the cleaned substrate to volatilize the solvent and form crisscross and interconnected carbon nanotube films; (3) putting the substrate diffused with the carbon nanotube films and obtained in the step (2) in to a vacuumized reactor, growing a layer of vanadium oxide film by using the reactor, and performing annealing to form a vanadium oxide-carbon nanotube composite film structure, wherein the grown vanadium oxide film is diffused on the surface of the carbon nano-tube and in gaps between tubes; (4) cooling the vanadium oxide-carbon nanotube composite film structure to the room temperature, and taking the vanadium oxide-carbon nanotube composite film structure out of the reactor; and (5) repeating the steps of carbon nanotube diffusion, vanadium oxide sedimentation and annealing in turn as required to form a vanadium oxide-carbon nanotube multi-layer composite film structure.
Description
Technical field
The present invention relates to that uncooled ir is surveyed, and non-refrigeration Terahertz Detection Techniques field, be specifically related to a kind of thermistor material of micro-metering bolometer and light absorbing material, with and preparation method thereof.
Background technology
Infrared eye is converted into detectable electrical signal to sightless infrared emanation, realizes the observation of affairs to external world.Infrared eye is divided into quantum detector and thermo detector two classes.Thermo detector claims the non-refrigeration type infrared eye again, can at room temperature work, and has advantages such as good stability, integrated level height and price are low, has wide practical use in field such as military, commercial and civilian.Non-refrigerated infrared detector mainly comprises three types of pyroelectricity, thermopair, thermistors etc., wherein, micro-metering bolometer focus planardetector based on thermistor, be that the very swift and violent a kind of non-refrigerated infrared detector of developed recently is (referring to LeonardP.Chen, " Advanced FPAs for Multiple Applications " Proc.SPIE, 4721,1-15 (2002) document).Terahertz detector is that the electromagenetic wave radiation of the longer terahertz wave band of wavelength is converted into detectable electrical signal, realizes the observation of affairs to external world.Terahertz also has the detector of multiple model, and wherein, non-refrigeration Terahertz micro-metering bolometer has and the similar structure of uncooled ir micro-metering bolometer, can obtain by the improvement to the latter.Infrared or the terahertz emission detection process of micro-metering bolometer is mainly finished by the micro-bridge structure that suspends, so the suspension microbridge is to influence the key factor that device is made success or failure and performance height.Micro-metering bolometer has special requirement to constructing the thermistor material of the thin-film material of its suspension microbridge, especially core, is embodied in: associated materials should have suitable electricity, optics, reach mechanical property etc.
There is multiple material can be used as the thermistor material of infrared eye or terahertz detector micro-metering bolometer.Wherein, vanadium oxide film has very good electricity and optical property, and the integrated level height of material preparation is the most frequently used high-performance non-refrigerated infrared detector or the thermistor material of non-refrigeration terahertz detector.The U.S. Pat P 5286976 that the people such as Barrett E.Cole of the Honeywll company that on February 15th, 1994 authorized declare, and document H.Jerominek, F.Picard, et al., " Micromachined, uncooled, VO
2-based, IR bolometer arrays ", Proc.SPIE, 2746,60-71 (1996) has described the infrared detector structure based on vanadium oxide thermistor film respectively.Yet, because the electronic structure of vanadium atom is 3d
34s
24s wherein and 3d track all can lose part or all of electronics, so, the preparation method of traditional vanadium oxide film, for example magnetron sputtering, electron beam evaporation, laser ablation deposition etc. contain the shortcoming that itself can't overcome: the valence state complexity of V element, film chemical stability of structure difference etc. in the promptly prepared vanadium oxide film.For example, when adopting magnetron sputtering to prepare vanadium oxide film, V element wherein generally comprises 0 ,+2 ,+3 ,+4 ,+multiple valence states such as 5 are (referring to Xiaomei Wang, Xiangdong Xu, et al., " Controlling the growth of VOx films for variousoptoelectronic applications ", Proceedings of the 2009 16th IEEE InternationalSymposium on the Physical and Failure Analysis of Integrated Circuits, IPFA, p572-576 (2009) document).Because the composition complexity of V element, preparation technology's subtle change all can produce bigger influence to the chemical constitution of vanadium oxide film, thereby make the performance generation considerable changes such as electricity, optics of film, and then have influence on the performance of device.So based on a main drawback of the micro-metering bolometer of vanadium oxide film be: preparation technology's difficulty of vanadium oxide film is big, the repeatability of product and poor stability.
The U.S. Pat P5288380 that the people such as David A.Jackson that authorized on February 22nd, 1994 declare, and the U.S. Pat P7250604 that on August 4th, 2005, the people such as Sung Mooon that authorize declared, a kind of method of cosputtering has been described, in order to improve the physicals of vanadium oxide film respectively.As sputtering target material, under certain condition, this mixture target of sputter makes it to form gaseous component, deposits film forming then this method the vanadium oxide material that is mixed with some metallic impurity (as Ni, Fe, Cr, Mn, W etc.) in advance; Perhaps, adopt two sputtering sources splash-proofing sputtering metal and two different target sources of vanadium oxide respectively, preparation contains the vanadium oxide (VM of certain metallic impurity
xO
y, M is metallic impurity) and film, with electric properties such as the resistance value of this controlled oxidation vanadium film, temperature coefficient of resistance, transformation temperatures, satisfy the needs of infrared eye.The shortcoming of cosputtering doping metals is: the sputter rate of metallic impurity and vanadium oxide is difficult to be consistent, so, vanadium oxide is often also inequality with target with the ratio of metallic impurity in the film of this method preparation, and, this ratio also may be along with the fluctuation of sputtering technology acute variation.So the method for cosputtering is difficult to obtain the VM with fixing metering ratio, stable performance
xO
yFilm.In addition, the required facility investment of cosputtering is big, Technology is complicated.
Collosol and gel (Sol-gel) method is another method for preparing vanadium oxide film, document V.N Ovsyuk, et al., " Uncooled microbolometer IR FPA based on sol-gel VO
x", Proc.SPIE, 5834,47-54 (2005) has just described the vanadium oxide thermosensitive film that utilizes Prepared by Sol Gel Method to be used for infrared eye.The advantage of sol-gel method is that equipment is simple, and, can obtain the vanadium oxide film that valence state relatively concentrates, the effective control that helps material property.But if there is not the adjusting of other impurity, so, the resistance value of the vanadium oxide film that conventional sol-gel method obtained is bigger, and, also have phase transition phenomena under the working temperature, be unfavorable for being applied in the middle of the infrared eye.The Chinese patent 200510020789.8 that the Huang dimension of authorizing on June 13rd, 2007 has just waited the people to declare, described a kind of method that adopts the inorganic sol gel to vanadium oxide carry out metal-doped, to improve the performance of relevant vanadium oxide film.This method is at first V
2O
5With MoO
3Mix mutually, be heated under the normal pressure about 900 ℃, form melts; Then, melts is poured in the water fast, added oxalic acid, NH
4F forms inorganic sol.At last, 350-500 ℃ of following anneal, the vanadium oxide material that obtains being mixed with Mo or W element and comprise the F element.The shortcoming of this inorganic sol gel method is: the temperature of (1) colloidal sol preparation is too high, and it is integrated to influence device; (2) comprise a large amount of nonmetal F impurity in the product, influence material property; (3) absorptivity of the vanadium oxide that is obtained is lower, is unfavorable for the absorbing detection of infrared light.These deficiencies make the inorganic sol gel method be difficult to directly be applied in the middle of the manufacturing of infrared eye or terahertz detector vanadium oxide thermosensitive film.
The U.S. Pat P6489613 that the people such as the Toru Mori of NEC Corporation that authorized on December 3rd, 2002 declare has then described another and has improved the sol-gel method of infrared acquisition with the vanadium oxide film performance.This invention utilizes the organosol gel technique, adopts vanadium alkoxide (VO (OR)
3) as reaction raw materials, under collosol state, in vanadium oxide, mix metallic impurity such as a certain amount of Cr, Al, Fe, Mn, Nb, Ta, Ti, through anneal, the metal-doped vanadium oxide film of formation, make the resistance value of vanadium oxide, the requirement that temperature coefficient of resistance electric properties such as (TCR) meets infrared eye by the control of doping metals amount.Adopt the organosol gel method, can obtain the vanadium oxide film that valence state is relatively concentrated, the parameters such as resistance value, transformation temperature, TCR that help film control effectively, and make it to satisfy the requirement of infrared eye.Importantly, the temperature of reaction of organosol gel method lower (＜200 ℃) helps reducing to the integrated negative impact of device.Regrettably, conventional organosol gel method contains some shortcomings identical with the inorganic sol gel method, comprise: (1) organic or inorganic sol gel method carries out when metal-doped, the poor stability of metallic impurity in vanadium oxide film, phenomenons such as diffusion of contaminants, segregation take place easily, the performance generation regression, the downgrade that cause vanadium oxide film are difficult to satisfy the long-time running needs of device; (2) organic or inorganic sol gel method carries out the absorbing properties that metal-doped method can't improve vanadium oxide film effectively.
On the other hand, carbon nanotube is a kind of very important monodimension nanometer material.From 1991, the Iijima of Japan has found since the carbon nanotube (referring to Sumio Iijima, " Helical microtubules of graphiticcarbon ", Nature, 354,56, (1991) document), studies show that more and more this special monodimension nanometer material has the physics and the chemical property of many uniquenesses, has broad application prospects in a lot of fields.At first, carbon nanotube has very excellent chemical stability, in vacuum condition, carbon nanotube is under 1200 ℃ high temperature, it is stable that its chemical structure can also keep, and in atmospheric environment, carbon nanotube also is being chemically stable below 650 ℃, obviously, the chemical stability of carbon nanotube is higher than vanadium oxide film far away.In addition, carbon nanotube also has good electricity, optics, and performance such as mechanics, and for example, the temperature coefficient of resistance of bibliographical information carbon nanotube (TCR) can reach 0.3～2.5%/K, and under the specified conditions, its photoabsorption coefficient can reach 10
4～5Cm
-1(referring to M.E.Itkis, F.Borondics, A.Yu.R.C.Haddon, " Bolometric InfraredPhotoresponse of Suspended Single-Walled Carbon Nanotube Films ", Science, 312,413-416 (2006) document).So carbon nanotube is a kind of thermistor material with potential using value, be expected to overcome some shortcomings of traditional vanadium oxide thermosensitive film.
Summary of the invention
Problem to be solved by this invention is: how a kind of vanadium oxide film that is used for micro-metering bolometers such as infrared eye or terahertz detector and preparation method thereof is provided; this film can improve working performance of devices; reduced the raw material manufacturing cost, suitable large-scale production.
Technical problem proposed by the invention is to solve like this: a kind of vanadium oxide film that is used for micro-metering bolometer is provided, it is characterized in that, this film is the vanadium oxide-carbon nano-tube compound film that is composited by one dimension carbon nanotube and bidimensional vanadium oxide film, and this vanadium oxide-carbon nano-tube compound film constitutes the thermistor material and the light absorbing material of micro-metering bolometer.
First kind of preparation method of above-mentioned vanadium oxide-carbon nano-tube compound film is characterized in that, may further comprise the steps:
1. clean substrate, it is standby to dry up the back;
2. the good original carbon nanotube without functionalization of prepared beforehand is placed in the middle of the beaker, mixes ultra-sonic dispersion with organic solvent, then, dispersion liquid is transferred to through the surface of the substrate of clean, made solvent evaporates, form staggered, interconnected carbon nano-tube film;
3. the substrate that is dispersed with carbon nano-tube film that 2. step is obtained is put into the reactor of vacuum pumping, utilize reactor growth one deck vanadium oxide membrane, the vanadium oxide membrane of being grown is dispersed in the middle of the gap of the surface of carbon nanotube and tube and tube, annealing forms vanadium oxide-carbon nano-tube compound film structure;
4. after being cooled to room temperature, from reactor, take out;
5. as required, repeat carbon nanotube dispersion, vanadium oxide deposition and annealing steps successively, form vanadium oxide-carbon nanotube multilayer structure of composite membrane.
Second kind of preparation method of above-mentioned vanadium oxide-carbon nano-tube compound film is characterized in that, may further comprise the steps:
1. clean substrate, it is standby to dry up the back;
2. the good carbon nanotube of prepared beforehand is placed in the beaker, adopt chemically treated mode earlier, introduce functional group on the surface of carbon nanotube, through filtration, washing and drying step, obtain functionalized carbon nanotube, then, this functionalized carbon nanotube is placed in the middle of the beaker, mixes with organic solvent, ultra-sonic dispersion, again dispersion liquid is transferred to through the surface of the substrate of clean, made solvent evaporates, form staggered, interconnected carbon nano-tube film;
3. being dispersed with of 2. obtaining of step put into the reactor of vacuum pumping through the substrate of the carbon nanotube of functionalization, utilize reactor growth one deck vanadium oxide membrane, the vanadium oxide membrane of being grown is dispersed in the middle of the gap of the surface of carbon nanotube and tube and tube, annealing forms vanadium oxide-carbon nano-tube compound film structure;
4. after being cooled to room temperature, from reactor, take out;
5. as required, repeat carbon nanotube dispersion, vanadium oxide deposition and annealing steps successively, form vanadium oxide-carbon nanotube multilayer structure of composite membrane.
According to the preparation method who is used for the vanadium oxide film of micro-metering bolometer provided by the present invention, it is characterized in that, step 2. in, the method that carbon nanotube is distributed to substrate surface is a kind of in the middle of spin coating or dip-coating method, spraying method, spread coating, electrodip process, electrophoresis, the printing transplanting etc., when adopting the method for spin coating, used dispersion liquid is a kind of in the middle of the organic solvents such as ethanol or Virahol, isopropylcarbinol, primary isoamyl alcohol, isohexyl alcohol.
According to the preparation method who is used for the vanadium oxide film of micro-metering bolometer provided by the present invention, it is characterized in that, the carbon nanotube accumbency that step is obtained in 2. on the surface of substrate, be staggered interconnect architecture, carbon nanotube is single wall or multi-walled carbon nano-tubes, the diameter of carbon nanotube is 1～50nm, and the length of carbon nanotube is 50～30000nm.
According to the second kind of preparation method who is used for the vanadium oxide film of micro-metering bolometer provided by the present invention, it is characterized in that, its step 2. in, the method for carbon nanotube being carried out functionalization is: adopt dense H
2SO
4With dense HNO
3A kind of in the middle of mixed solution, concentrated nitric acid, potassium permanganate, the processing of Fenton method etc., the surface of carbon nanotube introducing-COOH ,-COH or-CNH
2Functional group.
According to the preparation method who is used for the vanadium oxide film of micro-metering bolometer provided by the present invention, it is characterized in that, step 3. in, the preparation method of vanadium oxide membrane is a kind of in the middle of magnetron sputtering, electron beam evaporation, thermal evaporation, organometallics chemical vapour deposition, laser ablation deposition, the ald etc.; When adopting magnetically controlled sputter method, used target is the oxide compound VO of vanadium metal or vanadium
x, x satisfies 1.0≤x≤2.5, and used reactant gases is that the gas mixture and the per-cent of oxygen in gas mixture of argon gas and oxygen is 0.2～20%, and depositing temperature is 25～500 ℃.
A kind of vanadium oxide film that is used for micro-metering bolometer, it is characterized in that, this film is the vanadium oxide-carbon nano-tube compound film that is composited by one dimension carbon nanotube and bidimensional vanadium oxide film, as the thermistor material and the light absorbing material of infrared eye or terahertz detector micro-metering bolometer.Of particular note, the exist form of carbon nanotube in composite membrane is linear structure, is referred to as the one dimension carbon nanotube, and vanadium oxide film is a membrane structure, is referred to as the bidimensional vanadium oxide film.
According to the vanadium oxide film that is used for micro-metering bolometer provided by the present invention, it is characterized in that the vanadium oxide that vanadium oxide-carbon nano-tube compound film contains is non-crystalline state or crystalline structure, the molecular formula of vanadium oxide is expressed as VO
x, wherein, x satisfies 1.0≤x≤2.5, and the best is x=1.5,2.0,2.5.
According to the vanadium oxide film that is used for micro-metering bolometer provided by the present invention, it is characterized in that, described one dimension carbon nanotube is dispersed in the middle of the vanadium oxide, be staggered or reticulated structure, carbon nanotube is single wall or multi-walled carbon nano-tubes, the diameter of carbon nanotube is 1～50nm, and the best is 2nm, 5nm, 10nm, 15nm, 20nm, 25nm, 30nm etc.; The length of carbon nanotube is 50～30000nm, and the best is 500nm, 800nm, 1000nm, 1200nm, 1500nm, 2000nm etc.; The weight content of carbon nanotube in composite membrane is 0.1～98wt.%, and the best is 1wt.%, 1.5wt.%, 2wt.%, 2.5wt.%, 3wt.%, 3.5wt.%, 4wt.%, 4.5wt.%, 5wt.%, 5.5wt.%, 6wt.%, 8wt.%, 10wt.% etc.
According to the vanadium oxide film that is used for micro-metering bolometer provided by the present invention, it is characterized in that, the thickness of this composite membrane is 5～1500nm, and the best is 50nm, 100nm, 120nm, 150nm, 200nm, 250nm, 300nm, 350nm, 400nm, 450nm, 500nm etc.; Film side's resistance of composite membrane is 100 Ω/～5M Ω/, and the best is 10k Ω/, 20k Ω/, 50k Ω/, 70k Ω/, 90k Ω/, 100k Ω/, 120k Ω/, 150k Ω/, 170k Ω/, 200k Ω/, 300k Ω/, 400k Ω/, 500k Ω/ etc.; The temperature coefficient of resistance of composite membrane (TCR) is-0.5～-4.5%/K, the best is-1.0%/K ,-1.3%/K ,-1.5%/K ,-1.8%/K ,-1.9%/K ,-2.0%/K ,-2.1%/K ,-2.2%/K ,-2.5%/K etc.
Beneficial effect of the present invention: the present invention considers non-refrigerated infrared detector, and the particular requirement of non-refrigeration terahertz detector, simultaneously at the deficiency of the existing thermistor thin film of vanadium oxide in the device at aspects such as material property and preparation methods, propose a kind of employing one dimension carbon nanotube and bidimensional vanadium oxide mutually the compound material as infrared eye, or the method for the thermistor material of terahertz detector micro-metering bolometer and light absorbing material, utilize the carbon nanotube excellent chemical stability on the one hand, mechanical property and electroconductibility, improve shortcomings such as the low and poor chemical stability of the electroconductibility of conventional oxidation vanadium thermistor thin film, the negative impact of having avoided traditional doping process that vanadium oxide membrane is produced simultaneously, on the other hand, utilize the high resistance of vanadium oxide, with and absorptive character such as good temperature coefficient of resistance (TCR) and infrared light, remedy carbon nanotube deficiency in these areas, thereby improve the over-all properties of device.On this basis, by regulating the ratio between vanadium oxide and the carbon nanotube, can also be more prone to, trim film performance more exactly, satisfy the special requirement of infrared eye or terahertz detector.Utilize the infrared eye that this matrix material by special monodimension nanometer material and bidimensional film makes or the sensitive material of terahertz detector, improved working performance of devices, reduced the raw material manufacturing cost, suitable large-scale industrialized production.
Description of drawings
Fig. 1 is an orthographic plan of implementing the vanadium oxide-carbon nano-tube compound film structure of the present invention's proposition;
Fig. 2 is a sectional view of implementing the vanadium oxide-carbon nano-tube compound film structure of the individual layer that the present invention proposes;
Fig. 3 is a sectional view of implementing the multiwalled vanadium oxide-carbon nano-tube compound film structure of the present invention's proposition.
Wherein, 1, substrate, 2, vanadium oxide-carbon nano-tube compound film, 210, the carbon nanotube in the middle of vanadium oxide-carbon nano-tube compound film, 220, the vanadium oxide in the middle of vanadium oxide-carbon nano-tube compound film.
Embodiment
Below in conjunction with accompanying drawing the present invention is further described:
Guiding theory of the present invention is in vanadium oxide-carbon nano-tube compound film structure, utilize good separately electricity of carbon nanotube and vanadium oxide and optical property, prepare the better laminated film of over-all properties (as shown in Figure 1), as the thermistor material and the light absorbing material of uncooled microbolometer, improve the performance of infrared eye or terahertz detector.Preparation vanadium oxide of the present invention-carbon nano-tube compound film embodiment is as follows: 1. selects the substrate 1 of silicon wafer for use, with Piranha solution-treated and washed with de-ionized water, soaks with rare hydrofluoric acid solution then earlier as film growth, and after drying up with nitrogen, standby; 2. the carbon nanotube of getting ready in advance is placed in the beaker, adopts chemically treated method earlier, introduce some special functional groups on the surface of carbon nanotube, then, through filtration, washing, drying and other steps.Obtain functionalized carbon nanotube, standby; 3. through step 2. the carbon nanotube crossed of functionalization be placed in the middle of the beaker, mix ultra-sonic dispersion with organic solvent; Then, dispersion liquid is transferred to through the 1. surface of the substrate 1 crossed of clean of step, made solvent evaporates, form staggered, interconnected carbon nano-tube film 210; 4. the substrate 1 that the surface is dispersed with carbon nanotube 210 is put into the reactor of vacuum pumping, with vanadium metal as target, argon gas as sputter gas, oxygen as reactant gases, the method of employing direct current reaction magnetron sputtering, the layer thicknesses of growing under 200 ℃ are the vanadium oxide membrane 220 of 5～1500nm, vanadium oxide 220 covers in the middle of the gap of the surface of carbon nanotube 210 and tube and tube, annealing forms vanadium oxide-carbon nano-tube compound film 2; 5. after sample is cooled to room temperature, sample is taken out from magnetic control sputtering system; 6. as required, can repeat steps such as carbon nanotube 210 dispersions, vanadium oxide 220 depositions and annealing successively, form vanadium oxide-carbon nanotube multilayer structure of composite membrane 2.In the middle of vanadium oxide-carbon nano-tube compound film 2, the introducing of carbon nanotube 210, electric property, optical property and the steady chemical structure etc. of vanadium oxide 220 are effectively improved, met the requirement of non-refrigerated infrared detector or non-refrigeration terahertz detector micro-metering bolometer.
The concrete technology of above-mentioned preparation embodiment comprises: the preparation of (1) film growth substrate: select for use 4 inches Si (100) silicon chip as growth for Thin Film substrate 1, before the experiment, earlier with the Piranha solution (vitriol oil: hydrogen peroxide=7: 3 (volume ratio)) handled 10 minutes down in 80 ℃, rinse well with deionized water, be to soak 90 seconds under the room temperature in 1.5: 10 hydrofluoric acid (HF) solution in concentration then, dry up silicon chip with high pure nitrogen at last, standby; (2) functionalization of carbon nanotube: the mixed acid solution of the configuration 30ml vitriol oil, 10ml concentrated nitric acid, taking by weighing the 0.1000g multi-walled carbon nano-tubes puts in the middle of the mixed acid solution, mixing solutions was put into ultrasonic pond (50 ℃ of temperature, 80W) sonic oscillation 3 hours, with the membrane filtration of 0.4 μ m, and be 7 after reaction is finished with the deionized water wash filtering carbon nanotube, until the filtrate pH value.The carbon nanotube that filtration obtains is put into 60 ℃ of baking oven bakings 24 hours, standby; (3) dispersion of carbon nanotube 210: the carbon nanotube through functionalization is placed in the middle of the beaker, mixes ultra-sonic dispersion with alcohol solvent mutually; Then,, dispersion liquid is transferred to the surface of clean substrate, make the alcohol solvent volatilization, form staggered, interconnected carbon nano-tube film 210 by spin coating (Spin Coating) method; (4) deposition of vanadium oxide 220: the substrate 1 that the surface is dispersed with carbon nanotube 210 is put into the reactor of vacuum pumping, adopt superb vanadium (V) as target, superb argon gas (Ar) as sputter gas, superb oxygen (O
2) as reactant gases, utilizing the method for direct current reaction magnetron sputtering is the vanadium oxide membrane 220 of 5～1500nm at 200 ℃ of layer thicknesses of growing down.The representative condition of deposition vanadium oxide is: sputtering voltage is 350V; Power is 600W; The per-cent of oxygen in gas mixture is 2%; Underlayer temperature is 200 ℃; The about 10nm/min of sedimentation rate; Depositing time 10 minutes; The pressure of main vacuum chamber is 1.1Pa in the deposition; The thickness of vanadium oxide membrane is about 100nm; Anneal forms vanadium oxide-carbon nano-tube compound film 2; (5) sample cool to room temperature in main vacuum chamber then, takes out sample from vacuum chamber; (6) as required, can repeat steps such as carbon nanotube 210 dispersions, vanadium oxide 220 depositions and annealing successively, form vanadium oxide-carbon nanotube multilayer structure of composite membrane 2, satisfy the device needs.
Silicon chip of the present invention 1 cleans not to be only limited to and adopts Piranha and hydrofluoric acid solution, also comprises the cleaning that other solution known to the employing in the industry and method are carried out.The film growth substrate also is not particularly limited, and except Si (100) silicon chip, also comprises the monocrystalline silicon piece of other crystal orientation and size or non-crystalline silicon (a-Si) film, silicon nitride (SiN
x) film, silicon oxide (SiO
x) film, silicon oxynitride (SiN
xO
y) substrate (according to substrate kind difference, adopting suitable cleaning) of wherein a kind of such as film and their other materials such as composite membrane.Carbon nanotube 210 also is not particularly limited in the composite membrane, can be the single wall or the multi-walled carbon nano-tubes of different diameter, different lengths; And this carbon nanotube can be the carbon nanotube through functionalization, also can be the original carbon nanotube without functionalization; The method that among the present invention carbon nanotube is dispersed in substrate surface also is not particularly limited, except spin coating technique, also can be the method for other dispersing Nano carbon tubes known to dip-coating method, spraying method, spread coating, electrodip process, electrophoresis, the printing transplanting etc. in the industry.
The preparation method of vanadium oxide 220 films is not only limited to the direct current reaction magnetron sputtering technology among the present invention, also comprises the vanadium oxide film of other method preparation known to radio frequency reaction magnetron sputtering, electron beam evaporation (EBE), ald (ALD), laser ablation deposition (Laer ablation), the organometallics chemical vapour deposition (MOCVD) etc. in the industry.When adopting magnetron sputtering technique to prepare vanadium oxide 220 films, target is not only limited to vanadium metal, also comprises oxide compound, and the oxide compound of adulterated vanadium metal, adulterated vanadium etc. of vanadium.
Claims (10)
1. a preparation method who is used for the vanadium oxide film of micro-metering bolometer is characterized in that, may further comprise the steps:
1. clean substrate, it is standby to dry up the back;
2. the good original carbon nanotube without functionalization of prepared beforehand is placed in the middle of the beaker, mixes ultra-sonic dispersion with organic solvent, then, dispersion liquid is transferred to through the surface of the substrate of clean, made solvent evaporates, form staggered, interconnected carbon nano-tube film;
3. the substrate that is dispersed with carbon nanotube that 2. step is obtained is put into the reactor of vacuum pumping, utilize reactor growth one deck vanadium oxide membrane, the vanadium oxide membrane of being grown is dispersed in the middle of the gap of the surface of carbon nanotube and tube and tube, annealing forms vanadium oxide-carbon nano-tube compound film structure;
4. after being cooled to room temperature, from reactor, take out;
5. as required, repeat carbon nanotube dispersion, vanadium oxide deposition and annealing steps successively, form vanadium oxide-carbon nanotube multilayer structure of composite membrane.
2. a preparation method who is used for the vanadium oxide film of micro-metering bolometer is characterized in that, may further comprise the steps:
1. clean substrate, it is standby to dry up the back;
2. the good carbon nanotube of prepared beforehand is placed in the beaker, adopt chemically treated mode earlier, introduce functional group on the surface of carbon nanotube, through filtration, washing and drying step, obtain functionalized carbon nanotube, then, this functionalized carbon nanotube is placed in the middle of the beaker, mixes mutually with organic solvent, ultra-sonic dispersion, again dispersion liquid is transferred to through the surface of the substrate of clean, made solvent evaporates, form staggered, interconnected carbon nano-tube film;
3. being dispersed with of 2. obtaining of step put into the reactor of vacuum pumping through the substrate of the carbon nanotube of functionalization, utilize reactor growth one deck vanadium oxide membrane, the vanadium oxide membrane of being grown is dispersed in the middle of the gap of the surface of carbon nanotube and tube and tube, annealing forms vanadium oxide-carbon nano-tube compound film structure;
4. after being cooled to room temperature, from reactor, take out;
5. as required, repeat carbon nanotube dispersion, vanadium oxide deposition and annealing steps successively, form vanadium oxide-carbon nanotube multilayer structure of composite membrane.
3. the preparation method who is used for the vanadium oxide film of micro-metering bolometer according to claim 1 and 2, it is characterized in that, its step 2. in, the method that carbon nanotube is distributed to substrate surface is a kind of in the middle of spin coating or dip-coating method, spraying method, spread coating, electrodip process, electrophoresis, printing are transplanted, when adopting spin coating method, used dispersion liquid is a kind of in the middle of ethanol or Virahol, isopropylcarbinol, primary isoamyl alcohol, the isohexyl alcohol.
4. the preparation method who is used for the vanadium oxide film of micro-metering bolometer according to claim 1 and 2, it is characterized in that, 2. the carbon nanotube accumbency that is obtained in step on the surface of substrate, be staggered interconnect architecture, carbon nanotube is single wall or multi-walled carbon nano-tubes, the diameter of carbon nanotube is 1～50nm, and the length of carbon nanotube is 50～30000nm.
5. the preparation method who is used for the vanadium oxide film of micro-metering bolometer according to claim 2 is characterized in that, step 2. in, the method for carbon nanotube being carried out functionalization is: adopt dense H
2SO
4With dense HNO
3A kind of in the middle of mixed solution, concentrated nitric acid, potassium permanganate, Fenton method are handled, in carbon nanotube introducing-COOH ,-COH or-CNH
2Functional group.
6. the preparation method who is used for the vanadium oxide film of micro-metering bolometer according to claim 1 and 2, it is characterized in that, its step 3. in, the preparation method of vanadium oxide membrane is a kind of in the middle of the magnetron sputtering, electron beam evaporation, thermal evaporation, organometallics chemical vapour deposition, laser ablation deposition, ald; When adopting magnetically controlled sputter method, used target is the oxide compound VO of vanadium metal or vanadium
x, x satisfies 1.0≤x≤2.5, and used reactant gases is that the gas mixture and the per-cent of oxygen in gas mixture of argon gas and oxygen is 0.2～20%, and depositing temperature is 25～500 ℃.
7. vanadium oxide film that is used for micro-metering bolometer, it is characterized in that, this film is the vanadium oxide-carbon nano-tube compound film that is composited by one dimension carbon nanotube and bidimensional vanadium oxide film, as the thermistor material and the light absorbing material of micro-metering bolometer.
8. the vanadium oxide film that is used for micro-metering bolometer according to claim 7 is characterized in that, the vanadium oxide that vanadium oxide-carbon nano-tube compound film contains is non-crystalline state or crystalline structure, and the molecular formula of vanadium oxide is expressed as VO
x, wherein, x satisfies 1.0≤x≤2.5, and the best is x=1.5,2.0,2.5.
9. the vanadium oxide film that is used for micro-metering bolometer according to claim 7, it is characterized in that, described one dimension carbon nanotube is dispersed in the middle of the vanadium oxide, be staggered or reticulated structure, carbon nanotube is single wall or multi-walled carbon nano-tubes, the diameter of carbon nanotube is 1～50nm, and the length of carbon nanotube is 50～30000nm, and the weight content of carbon nanotube in composite membrane is 0.1～98wt.%.
10. the vanadium oxide film that is used for micro-metering bolometer according to claim 7, it is characterized in that, the thickness of this composite membrane is 5～1500nm, and the resistance of the film side of composite membrane is 100 Ω/～5M Ω/, the temperature coefficient of resistance of composite membrane is-0.5～-4.5%/K.
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| CN101915620A (en) * | 2010-08-20 | 2010-12-15 | 电子科技大学 | Vanadium oxide thin film for microbolometer and preparation method thereof |
| CN104947073A (en) * | 2014-03-26 | 2015-09-30 | 清华大学 | Preparation method of nanotube film |
| CN104611670B (en) * | 2015-01-21 | 2017-04-12 | 中国科学院半导体研究所 | Preparation method of vanadium oxide film with high resistance temperature coefficient |
| TWI630168B (en) * | 2016-10-12 | 2018-07-21 | 鴻海精密工業股份有限公司 | Actuator based on carbon nanotubes and actuating system using the same |
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| US10641252B2 (en) | 2016-10-12 | 2020-05-05 | Tsinghua University | Actuator based on carbon nanotubes and actuating system using the same |
| US10661448B2 (en) | 2016-10-12 | 2020-05-26 | Tsinghua University | Biomimetic limb and robot using the same |
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| CN109211459A (en) * | 2018-07-26 | 2019-01-15 | 西北工业大学 | A kind of flexible carbon nano tube thermosensitive film shear stress microsensor and its manufacturing method |
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| CN113764145A (en) * | 2020-06-05 | 2021-12-07 | 高尔科技股份有限公司 | Thermistor and microbolometer based on thermistor |
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