CN102419212B - Vanadium oxide composite film and preparation method thereof - Google Patents
Vanadium oxide composite film and preparation method thereof Download PDFInfo
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- CN102419212B CN102419212B CN 201110236706 CN201110236706A CN102419212B CN 102419212 B CN102419212 B CN 102419212B CN 201110236706 CN201110236706 CN 201110236706 CN 201110236706 A CN201110236706 A CN 201110236706A CN 102419212 B CN102419212 B CN 102419212B
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Abstract
The invention discloses a vanadium oxide composite film and a preparation method thereof. The vanadium oxide composite film is characterized by being a vanadium oxide-fullerene-CNT (carbon nano tube) ternary composite film which is compounded from three components, namely two-dimensional vanadium oxide, zero-dimensional fullerene and one-dimensional CNTs. Compared with a single vanadium oxide film or binary composite films comprising vanadium oxide-CNT, vanadium oxide-fullerene and the like, the vanadium oxide-fullerene-CNT ternary composite film can integrate the advantages of the three components and has more excellent performance such as electrical performance, optical performance and the like; and through regulating the proportions of the three components (vanadium oxide, fullerene and the CNTs), the performance of the composite film can be controlled more flexibly and more accurately. By utilizing the vanadium oxide-fullerene-CNT ternary composite film as a thermistor material and a light absorbing material of a terahertz detector or an infrared detector, the comprehensive device performance can be improved.
Description
Technical field
The present invention relates to technical field of photoelectric detection, be specifically related to a kind of vanadium oxide composite film for non-refrigeration terahertz detector or non-refrigerated infrared detector and preparation method thereof.
Background technology
Terahertz refers to that wavelength coverage is the electromagnetic wave of 30 ~ 3000um, has the peculiar properties such as transient state, broadband property, low energy and coherence.Terahertz is with a wide range of applications in fields such as astronomy, medical science, national defence and safety checks.Wherein, it is that the importance used of Terahertz is (referring to Linda Marchese that the non-refrigeration of Terahertz (room temperature) is surveyed, Martin Bolduc, Bruno Tremblay, Michel Doucet, Hassane Oulachgar, Lo c Le Noc, Fraser Williamson, Christine Alain, Hubert Jerominek, Alain Bergeron, " A microbolometer-based THz imager ", Proc. SPIE, 7671,76710Z-8 (2010) document).The room temperature detection process of Terahertz mainly is to finish by the micro-metering bolometer that suspends, so the micro-metering bolometer microbridge of suspension is to affect the key factor that detector is made success or failure and performance height.Micro-metering bolometer is to constructing the membraneous material of its suspension microbridge, and especially the thermistor material of device core has special requirement, is embodied in: associated materials should have the performances such as suitable electricity, optics.
There is multiple material can be used as the thermo-sensitive material of micro-metering bolometer.Wherein, vanadium oxide film has very good electric property and optical property, and the integrated level of material is high, is the most frequently used high-performance uncooled detector thermistor material.The US Patent No. 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 respectively the infrared detector structure based on the vanadium oxide thermistor thin film.Yet, because the electronic structure of vanadium atom is 3d
34s
24s wherein and 3d track all can lose some or all of electronics, so, the preparation method of traditional vanadium oxide film, such as magnetron sputtering, electron beam evaporation, pulsed laser deposition etc. contained the shortcoming that itself can't overcome: i.e. the poor stability of complicated, the film chemical structure of the valence state of V element etc. in the prepared vanadium oxide film.For example, when adopting magnetron sputtering to prepare vanadium oxide film, V element wherein generally comprises 0 ,+2 ,+3 ,+4 ,+the multiple valence states such as 5 (referring to Xiaomei Wang, Xiangdong Xu, et al., " Controlling the growth of VO
x Films for various optoelectronic applications "; Proceeding of the 2009 16thIEEE International Symposium on the Physical and Failure Analysis of Integrated Circuits; IPFA, p 572-576(2009) document).Because the composition of V element is complicated, preparation technology's subtle change all can produce considerable influence to the chemical composition of vanadium oxide film, thereby makes electricity, optics and the mechanical property etc. of film that significant change occur, and then has influence on performance of devices.So based on a major defect of the detector of vanadium oxide film be: preparation technology's difficulty of vanadium oxide film is large, the repeatability of product and poor stability.
Sol-gal process 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), just described and utilized sol-gal process for the preparation of the vanadium oxide thermosensitive film of infrared eye.The advantage of sol-gal process is that equipment is simple, and can obtain the vanadium oxide film that valence state relatively concentrates, the effective control that is conducive to material property.But if there is not the adjusting of other composition, so, the resistance value of the vanadium oxide film that conventional sol-gal process obtains is larger, and also has phase transition phenomena under the working temperature, is unfavorable for being applied in the middle of the detector.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 employing inorganic sol-gel method vanadium oxide is carried out metal-doped, to improve the performance of relevant vanadium oxide film.The method is at first V
2O
5With MoO
3Mix mutually, be heated to 900 under the normal pressure
oAbout C, form fused mass; Then fused mass is poured into water fast, adds oxalic acid, NH
4F forms inorganic sol.The shortcoming of this inorganic sol-gel method is: the excess Temperature of (1) colloidal sol preparation, and it is integrated to affect device; (2) comprise a large amount of non-metallic impurities F in the product, affect material property; The absorptivity of the vanadium oxide that (3) obtains is lower, is unfavorable for absorbing detection.These deficiencies make inorganic sol-gel method be difficult to directly be applied in the manufacturing of vanadium oxide thermo-sensitive material.
The US Patent No. P 6489613 that the people such as the Toru Mori of NEC Corporation that authorized on Dec 3rd, 2002 declare has then described another and has improved the sol-gel method of vanadium oxide film.This invention utilizes the organosol gel technique, adopts vanadium alkoxide (VO (OR)
3) as reaction raw materials, under collosol state, in vanadium oxide, mix the metallic impurity such as a certain amount of Cr, Al, Fe, Mn, Nb, Ta, Ti, annealed processing forms metal-doped vanadium oxide film, makes the requirement of the electric property coincidence detector such as resistance value, temperature-coefficient of electrical resistance of vanadium oxide by the control of doping metals amount.Adopt the organosol gel method, can obtain the vanadium oxide film that valence state is relatively concentrated, resistance value, phase transition temperature and the temperature-coefficient of electrical resistance etc. that are conducive to film control effectively, and make it to satisfy the requirement of detector.The more important thing is that the temperature of reaction of organosol gel method is lower by (＜200
oC), be conducive to reduce to the integrated negative effect of device.Regrettably, traditional organosol gel method contains some shortcomings identical with inorganic sol-gel method, comprise: (1) is on the amorphous substrate, the vanadium oxide film of the often polycrystalline attitude that the organic or inorganic sol-gal process obtains, this polycrystal film is serious to the diffuse reflectance of incident light, noise is high, so be unfavorable for being applied directly in the detector; (2) metallic impurity are that physical mixes in the prepared vanadium oxide film of organic or inorganic sol-gal process, it is the effect that does not have chemical bond between itself and the vanadium oxide, so the phenomenons such as Impurity Diffusion, segregation also occur in this film easily, the performance generation regression, the Quality Down that cause vanadium oxide film are difficult to satisfy the needs that long term device is moved; (3) the metal-doped absorbing properties that can't effectively improve vanadium oxide film that carries out of organic or inorganic sol-gal process.
On the other hand, the stretching vibration of the various V-O chemical bonds (such as V=O, O-V-O etc.) of vanadium oxide and the absorption peak of flexural vibrations all are in mid infrared region (about 10 μ m), and at Terahertz scope (30 ~ 3000 μ m), a little less than it absorbs.So simple vanadium oxide film is difficult to satisfy the optics requirement of the terahertz detector that sensitivity has relatively high expectations.Consider that carbon nano-tube is a kind of important nano material, has good electrical and optical properties, for this reason, on Dec 1st, 2010, disclosed Chinese invention patent CA 101900607 A that perhaps wait the people to declare eastwards described a kind of vanadium oxide-carbon nano-tube coextruded film and preparation method thereof.This invention utilizes separately good electrical and optical properties of bidimensional vanadium oxide and one dimension carbon nano-tube, obtains the better vanadium oxide-carbon nano-tube coextruded film of combination property, is used in the middle of the non-refrigerated infrared detector.Wherein, the carbon nano-tube in the composite membrane is horizontal, interconnected reticulate texture.There is a shortcoming in this one dimension carbon nano-tube of laterally arranging: namely the one dimension carbon nano-tube has anisotropy to the response of light.That is to say that the absorptivity of carbon nano-tube changes with the variation of carbon nano-tube and tested incident light angle, only have when the carbon nano-tube axle parallels with Terahertz or infrared incident light direction, could obtain maximum absorptivity.The anisotropy of this photoresponse will make the different angles of same object measure and produce the detection signal that the order of magnitude changes, and bring larger difficulty to device manufacturing, input etc.That is to say that for Terahertz room temperature detector or infrared room temperature detector, two yuan of composite membranes of vanadium oxide-carbon nano-tube are as thermistor thin film Shortcomings technically.
Fullerene (Fullerene) refers to the cage shape molecule C of full carbon hollow
n, wherein, n satisfies n 〉=20.Wherein, fullerene C
6032 body ball-type molecules by 60 carbon atoms form are nonpolar, contain large p key, have sealing, stable " cage shape " nanometer cavity configuration (referring to H.W. Kroto, J.R. Health, R.E. Smalley, et al, " C
60: Buckminsterfullerence ", Nature, 318,162 (1985) documents).Because fullerene C
60Be zero-dimension structural, the response to light on all directions is all identical, thereby can avoid the anisotropic impact of photoelectric response of one dimension carbon nano-tube.So, adopt the zero dimension fullerene mutually compound with the bidimensional vanadium oxide and the vanadium oxide that obtains-fullerene laminated film has the combination property better than simple vanadium oxide film, vanadium oxide-carbon nano-tube coextruded film etc.If further to fullerene C
60Carry out targetedly surface chemical modification and make it mutually compound with vanadium oxide better, be expected to obtain the more excellent laminated film of performance, overcome the shortcoming of current material, break through the technical bottleneck of terahertz detector thermistor material preparation.Similarly, if this vanadium oxide-fullerene composite membrane is applied in the infrared eye, also can improve the combination property of device.But the electric conductivity of zero dimension fullerene and chemical stability are not as the one dimension carbon nano-tube.
So, as the thermistor material of terahertz detector or infrared eye, simple vanadium oxide, carbon nano-tube, the fullerene-based material part that all comes with some shortcomings.
Summary of the invention
Problem to be solved by this invention is: how a kind of vanadium oxide composite film and preparation method thereof is provided, and this film has the combination properties such as better electricity, optics.This vanadium oxide composite film is applied in the middle of non-refrigeration terahertz detector or the non-refrigerated infrared detector as thermistor material and light absorbing material, can improve the serviceability of device, reduces the raw material manufacturing cost, suitable large-scale production.
Technical matters proposed by the invention is to solve like this: a kind of vanadium oxide composite film is provided, it is characterized in that this laminated film is to become vanadium oxide-fullerene that phase-splitting is composited-carbon nanometer pipe ternary laminated film by three kinds of bidimensional vanadium oxide and zero dimension fullerene and one dimension carbon nano-tube.
According to vanadium oxide composite film provided by the present invention, it is characterized in that the vanadium oxide that contains in the vanadium oxide composite film is amorphous state or crystallite attitude, crystalline state nanometer, the molecular formula of vanadium oxide is expressed as VO
x , wherein,
x Satisfy 1≤
x≤ 2.5, the best is
x=1.5,2,2.5.
According to vanadium oxide composite film provided by the present invention, it is characterized in that the fullerene that contains in the vanadium oxide composite film is original fullerene C
60, or fullerene C
70, other satisfies the full carbon hollow cage shape fullerene molecule C of n 〉=20
n, fullerene derivate, fullerene, one or several in the middle of the fullerene derivate of functionalization of functionalization, best for contain-OH or-NH
2The Functional Fullerene C of the ,-functional groups such as COOH
60, or Functional Fullerene C
70
According to vanadium oxide composite film provided by the present invention, it is characterized in that, the carbon nano-tube that contains in the vanadium oxide composite film is original or single wall or the multi-walled carbon nano-tubes of functionalization, the diameter of carbon nano-tube is 1 ~ 50 nm, and the best is 2 nm, 5 nm, 10 nm, 15 nm, 20 nm, 25 nm, 30 nm, 40 nm, 50 nm etc.; The length of carbon nano-tube is 10 ~ 30000 nm, and the best is 50 nm, 100 nm, 200 nm, 500 nm, 800 nm, 1000 nm, 1200 nm, 1500 nm, 2000 nm etc.
According to vanadium oxide composite film provided by the present invention, it is characterized in that in the laminated film, the weight ratio of fullerene and two kinds of compositions of carbon nano-tube is fullerene
:Carbon nano-tube=1:1000 ~ 1000:1, the best is fullerene
:Carbon nano-tube=1
:10,1
:8,1
:5,1
:4,1
:3,1
:2,1
:1,2
:1,3
:1,4
:1,5
:1,8
:1,10
:1 etc.; Fullerene and the weight content of carbon nano-tube general assembly (TW) in laminated film are 0.1 ~ 97wt.%, and the best is 1 wt.%, 2 wt.%, 2.5 wt.%, 3 wt.%, 3.5 wt.%, 4 wt.%, 5 wt.%, 6 wt.%, 7 wt.%, 8 wt.%, 9 wt.%, 10 wt.%, 15 wt.%, 20 wt.%, 25 wt.%, 30 wt.% etc.
According to vanadium oxide composite film provided by the present invention, it is characterized in that, the thickness of this vanadium oxide composite film is 5 ~ 2000nm, and the best is 50nm, 80 nm, 100 nm, 120 nm, 150 nm, 200 nm, 250 nm, 300 nm, 350 nm, 400 nm, 450 nm, 500 nm etc.; The sheet resistance of laminated film be ~ 500 Ω/50M Ω/, the best be 10 K Ω/, 20 K Ω/, 50 K Ω/, 70 K Ω/, 90 K Ω/, 120 K Ω/, 150 K Ω/, 170 K Ω/, 200 K Ω/, 300 K Ω/, 400 K Ω/, 500 K Ω/etc.; The temperature-coefficient of electrical resistance of laminated film is-0.5 ~-6.5%/K, the best is-1.5%/K ,-1.8%/K ,-1.9%/K ,-2.0%/K ,-2.1%/K ,-2.2%/K ,-2.5%/K ,-3.0%/K ,-3.5%/K ,-4.0%/K etc.
The preparation method of above-mentioned vanadium oxide composite film is characterized in that, may further comprise the steps:
1. clean substrate, dry up rear for subsequent use;
2. according to specific part by weight, be ready in advance the potpourri of zero dimension fullerene and one dimension carbon nano-tube, for subsequent use;
3. the preparation of vanadium oxide colloidal sol: the vanadium oxide powder is mixed mutually with organic solvent, add thermal response, then by centrifuging, remove insolubles, extract supernatant and leave standstill, carry out again centrifuging, so repeatedly, until remove insolubles fully.Obtain not have the vanadium oxide organosol of precipitation, for subsequent use;
4. the reaction of vanadium oxide and fullerene and carbon nano-tube: the fullerene that 2. step is prepared and the potpourri of carbon nano-tube mix mutually with the vanadium oxide colloidal sol that 3. step prepares, ultrasonic dispersion fullerene and carbon nano-tube form the new colloidal sol that vanadium oxide and fullerene and carbon nano-tube are mixed mutually;
5. the preparation of laminated film: the substrate surface that the step vanadium oxide that 4. prepares and the new colloidal sol that fullerene and carbon nano-tube are mixed mutually is spin-coated on cleaning, annealed processing, evaporate organic solvent, form vanadium oxide-fullerene-carbon nanometer pipe ternary laminated film;
6. after being cooled to room temperature, from reactor, take out;
7. as required, the hybrid reaction of repeated oxidation vanadium and fullerene and carbon nano-tube, colloidal sol spin coating and annealing steps form vanadium oxide-fullerene-carbon nanometer pipe ternary multi-layer compound film structure successively.
Preparation method according to vanadium oxide composite film provided by the present invention is characterized in that, step 2. in, the fullerene of employing is original fullerene C
60, or fullerene C
70, other satisfies the full carbon hollow cage shape fullerene molecule C of n 〉=20
n, fullerene derivate, fullerene, one or several in the middle of the fullerene derivate of functionalization of functionalization.
Preparation method according to vanadium oxide film provided by the present invention is characterized in that, in step
In, the carbon nano-tube of employing is original or single wall or the multi-walled carbon nano-tubes of functionalization, and the diameter of carbon nano-tube is 1 ~ 50 nm, and the best is 2 nm, 5 nm, 10 nm, 15 nm, 20 nm, 25 nm, 30 nm, 40 nm, 50 nm etc.; The length of carbon nano-tube is 10 ~ 30000 nm, and the best is 50 nm, 100 nm, 200 nm, 500 nm, 800 nm, 1000 nm, 1200 nm, 1500 nm, 2000 nm etc.
Preparation method according to vanadium oxide film provided by the present invention is characterized in that, in step
In, the weight ratio of fullerene and two kinds of compositions of carbon nano-tube is fullerene in the potpourri
:Carbon nano-tube=1:1000 ~ 1000:1, the best is fullerene
:Carbon nano-tube=1
:10,1
:8,1
:5,1
:4,1
:3,1
:2,1
:1,2
:1,3
:1,4
:1,5
:1,8
:1,10
:1 etc.
Preparation method according to vanadium oxide composite film provided by the present invention is characterized in that, step 3. in, the molecular formula of the vanadium oxide of employing is expressed as VO
x , wherein,
x Satisfy 1≤
x≤ 2.5.
Preparation method according to vanadium oxide composite film provided by the present invention, it is characterized in that, step 3. in, the solvent of the preparation vanadium oxide colloidal sol that adopts is the mixed solution of organic solvent A and two kinds of reagent of organic solvent B, wherein, organic solvent A is phenmethylol, and organic solvent B is a kind of in the middle of the isopropyl alcohol, isobutyl alcohol, isoamylol, isohexyl alcohol.
Preparation method according to vanadium oxide composite film provided by the present invention is characterized in that, step 3. in, the vanadium oxide that preparation vanadium oxide colloidal sol adopts and the mol ratio of organic solvent A and three kinds of reagent of organic solvent B are vanadium oxide
:Organic solvent A
:Organic volume B=1
:4
:4 ~ 1
:4
:100, wherein, organic solvent A is phenmethylol, and organic volume B is a kind of in the middle of the isopropyl alcohol, isobutyl alcohol, isoamylol, isohexyl alcohol, and the best is isobutyl alcohol.
Preparation method according to vanadium oxide composite film provided by the present invention, it is characterized in that, step 4. in, the fullerene that adds and carbon nano-tube are a kind of in the middle of the fullerene that do not mix with any solvent phase and carbon nano-tube solid mixture or the fullerene that mixes mutually with organic solvent in advance and the carbon nano tube suspension.
Preparation method according to vanadium oxide composite film provided by the present invention, it is characterized in that, step 5. with step 7. in, the annealing temperature of described vanadium oxide-fullerene-carbon nanotube sol is 100 ~ 700 ℃, and the best is 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃; Annealing atmosphere is that air, vacuum, Ar add a kind of, best for to be better than 10 in vacuum tightness in the middle of three kinds of atmosphere of reducibility gas
-6Carry out vacuum annealing under the condition of Torr; Annealing time is 0.5 ~ 24 hour, and the best is 1 hour, 2 hours, 3 hours, 4 hours, 5 hours.
The present invention considers the specific (special) requirements of terahertz detector and infrared eye, simultaneously for vanadium oxide thermistor thin film in the existing device in the deficiency of the aspects such as material property and preparation method, proposing a kind of three kinds of zero dimension fullerene and one dimension carbon nano-tube and bidimensional vanadium oxides that adopt becomes the compound and trielement composite material that forms of phase-splitting as the method for thermistor material and the light absorbing material of terahertz detector or infrared eye, utilize on the one hand the special cage structure of zero dimension fullerene, and good chemical stability and the electric property of one dimension carbon nano-tube, it is low to improve conventional oxidation vanadium thermistor thin film electric conductivity, poor chemical stability and to shortcomings such as the Terahertz absorptivity are low, the negative effect of having avoided simultaneously traditional doping process that vanadium oxide film is produced; On the other hand, utilize vanadium oxide high resistance, film forming continuity, with and good temperature-coefficient of electrical resistance, remedy fullerene and carbon nano-tube deficiency in these areas, thereby improve the combination property of device.On this basis, by regulating the ratio between vanadium oxide and fullerene and three kinds of compositions of carbon nano-tube, can also be more prone to, regulate more exactly the device film performance, satisfy the special requirement of terahertz detector or infrared eye.Utilize the terahertz detector thermo-sensitive material of this trielement composite material preparation that is consisted of by special zero dimension and monodimension nanometer material and bidimensional film, improved the serviceability of device, reduced the starting material manufacturing cost, suitable large-scale industrialized production.
Description of drawings
Fig. 1 is the planimetric map of implementing vanadium oxide-fullerene that the present invention proposes-carbon nanometer pipe ternary complex thin film structure;
Fig. 2 is the sectional view of vanadium oxide-fullerene of implementing the individual layer that the present invention proposes-carbon nanometer pipe ternary complex thin film structure;
Fig. 3 is the sectional view of vanadium oxide-fullerene of implementing the multilayer that the present invention proposes-carbon nanometer pipe ternary complex thin film structure;
Wherein, 1, substrate, 2, vanadium oxide-fullerene-carbon nanometer pipe ternary laminated film, 210, the fullerene in the middle of vanadium oxide-fullerene-carbon nanometer pipe ternary laminated film, 220, the carbon nano-tube in the middle of vanadium oxide-fullerene-carbon nanometer pipe ternary laminated film, 230, the vanadium oxide in the middle of vanadium oxide-fullerene-carbon nanometer pipe ternary laminated film.
Embodiment
The invention will be further described below in conjunction with accompanying drawing and embodiment:
Thought of the present invention is in vanadium oxide-fullerene-carbon nanometer pipe ternary complex thin film structure, utilize separately good electricity and optical property of zero dimension fullerene, one dimension carbon nano-tube and three kinds of compositions of bidimensional vanadium oxide, prepare the good tri compound film of comprehensive comparison, as thermistor material and the light absorbing material of terahertz detector or infrared eye micro-metering bolometer, improve the combination property of terahertz detector or infrared eye.Embodiment is as follows for preparation vanadium oxide-fullerene of the present invention-carbon nanometer pipe ternary laminated film: 1. clean the substrate 1 that is used for film growth, then dry up for subsequent use with nitrogen; 2. according to certain ratio, be ready in advance the zero dimension fullerene of functionalization and the potpourri of the one dimension carbon nano-tube of functionalization, for subsequent use; 3. get a certain amount of vanadium pentoxide powder and mix mutually with phenmethylol and isobutyl alcohol organic solvent, add thermal response.Then by centrifuging, remove insolubles.The supernatant that extracts is placed, carried out again the centrifuging second time, so repeatedly, until remove insolubles fully, obtain not have the vanadium oxide organosol of precipitation; 4. a certain amount of fullerene of 2. preparing through step and carbon nanotube mixture are passed through vanadium oxide colloidal sol that 3. step prepare and mixed mutually and carry out ultrasonic processing with a certain amount of, until fullerene and carbon nano-tube Uniform Dispersion in vanadium oxide; 5. the vanadium oxide of 4. preparation and the new colloidal sol that fullerene and carbon nano-tube are mixed mutually are spin-coated on substrate 1 surface of cleaning.Then, annealed processing evaporates organic solvent, forms vanadium oxide-fullerene-carbon nanometer pipe ternary laminated film 2; 6. as required, the steps such as hybrid reaction, colloidal sol spin coating and annealing of repeated oxidation vanadium 230 and fullerene 210 and carbon nano-tube 220 form vanadium oxide-fullerene-carbon nanometer pipe ternary multi-layer compound film structure 2 successively; 7. after sample is cooled to room temperature, sample is taken out from annealing furnace.In vanadium oxide-fullerene-carbon nanometer pipe ternary laminated film 2, the introducing of Functional Fullerene 210 and functionalized carbon nano-tube 220, electric property, optical property and the steady chemical structure etc. of vanadium oxide 230 are effectively improved, met the requirement of terahertz detector or infrared eye.
The concrete technology of above-mentioned Preparation Example comprises: the preparation of (1) film growth substrate: the 650nm SiN that selects 2cm * 2cm
x / Si (100) silicon chip, growth substrates 1 as vanadium oxide-fullerene-carbon nanometer pipe ternary laminated film, before the experiment, clean first the impurity such as greasy dirt of substrate surface with washing agent, use deionized water rinsing, then use respectively acetone, absolute ethyl alcohol and deionized water ultrasonic cleaning 20 minutes, then dry up silicon chip with high pure nitrogen; (2) preparation of fullerene and carbon nanotube mixture: take by weighing 28.8mg to contain-the Functional Fullerene C of OH base
60, and 28.8mg contain-functionalized carbon nano-tube of OH base, mix mutually ultrasonic 60 minutes (50 ℃, 70W), form the isobutyl alcohol suspending liquid of fullerene and carbon nano-tube with the 5ml isobutyl alcohol; (3) preparation of vanadium oxide colloidal sol: take by weighing 2.1884g V
2O
5Mix mutually with 5ml phenmethylol and 35ml isobutyl alcohol, this potpourri is put into beaker, then stirring and refluxing was taken out reactant liquor after 4 hours in 110 ℃ of silicone oil, with hydro-extractor with centrifugal 20 minutes of 2500 rev/mins rotating speed and take out supernatant, after above-mentioned clear liquid left standstill under identical condition secondary centrifuging further remove a small amount of impurity, obtain not have the vanadium oxide organosol that precipitates; (4) reaction of vanadium oxide and fullerene and carbon nano-tube: the fullerene of preparing through step (2) is mutually mixed ultrasonic processing 30 minute (50 ℃, 70W) with 10ml through the vanadium oxide colloidal sol that step (3) prepares with the isobutyl alcohol suspending liquid of carbon nano-tube; (5) preparation of vanadium oxide-fullerene-carbon nanometer pipe ternary laminated film: the vanadium oxide of the step of learning from else's experience (4) preparation and the mixed sols of fullerene and carbon nano-tube, adopt the secondary rotary coating method of spin coating technique to carry out gluing, technique comprises that the one-level spin coating adopts 1000 rev/mins of 5 seconds of spin coating, 2500 rev/mins of 40 seconds of spin coating are adopted in the secondary spin coating, spin coating is 4 times altogether, after each spin coating, film is put into air dry oven 180 ℃ of lower maintenances 20 minutes, carry out after cooling next time spin coating, to prevent the formation piebald that dissolves each other between layers.Then the sample of preparation is put into muffle furnace 400 ℃ of lower annealing 1 hour, formed vanadium oxide-fullerene-carbon nanometer pipe ternary laminated film 2; (6) as required, the steps such as hybrid reaction, colloidal sol spin coating and annealing of repeated oxidation vanadium 230 and fullerene 210, carbon nano-tube 220 form vanadium oxide-fullerene-carbon nanometer pipe ternary multi-layer compound film structure 2 successively; (7) sampling: after step (6), sample is cool to room temperature in muffle furnace, then sample is taken out from muffle furnace, is vanadium oxide-fullerene that the present invention proposes-carbon nanometer pipe ternary laminated film 2 materials.
The growth substrates 1 of vanadium oxide-fullerene-carbon nanometer pipe ternary laminated film 2 is not particularly limited, except 650nm SiN
x / Si(100), also comprise the monocrystalline silicon piece of other crystal orientation and size or the silicon nitride (SiN of polymer film, glass, pottery, metal, amorphous silicon (a-Si) film, other thickness and component
x ) film, monox (SiO
x ) film, silicon oxynitride (SiN
x O
y ) substrate (different according to the substrate kind, as to adopt suitable cleaning) that consists of of wherein a kind of such as film and their other materials such as composite membrane.Fullerene 210 also is not particularly limited in the composite membrane, can be fullerene C original or functionalization
60, or fullerene C
70, other satisfies the full carbon hollow cage shape fullerene molecule C of n 〉=20
n, in the middle of the fullerene derivate one or several.Carbon nano-tube 220 also is not particularly limited in the composite membrane, can be Single Walled Carbon Nanotube original or functionalization or multi-walled carbon nano-tubes.Vanadium oxide 230 also is not particularly limited in the composite membrane, can be V
2O
5, or VO
2, V
2O
3, other single valence or mixed valence vanadium oxide VO
x Central is a kind of.
Adopt the said method preparation vanadium oxide film, to become vanadium oxide-fullerene that phase-splitting is composited-carbon nanometer pipe ternary laminated film by three kinds of zero dimension fullerene and one dimension carbon nano-tube and bidimensional vanadium oxides, as thermistor material and the light absorbing material of terahertz detector or infrared eye.The vanadium oxide that vanadium oxide-fullerene-the carbon nanometer pipe ternary laminated film contains is amorphous state or crystallite attitude, crystalline state nanometer, and the molecular formula of vanadium oxide is expressed as VO
x , wherein,
xSatisfy 1≤
x≤ 2.5, the best is
x=1.5,2,2.5; Zero dimension fullerene and one dimension carbon nanotube dispersed are in vanadium oxide, and wherein, the fullerene that contains in the laminated film is original fullerene C
60, or fullerene C
70, other satisfies the full carbon hollow cage shape fullerene molecule C of n 〉=20
n, fullerene derivate, fullerene, one or several in the middle of the fullerene derivate of functionalization of functionalization, best for contain-OH or-NH
2The Functional Fullerene C of the ,-functional groups such as COOH
60, or Functional Fullerene C
70The carbon nano-tube that contains in the composite membrane is original or single wall or the multi-walled carbon nano-tubes of functionalization, the diameter of carbon nano-tube is 1 ~ 50 nm, and the best is 2 nm, 5 nm, 10 nm, 15 nm, 20 nm, 25 nm, 30 nm, 40 nm, 50 nm etc.; The length of carbon nano-tube is 10 ~ 30000 nm, and the best is 50 nm, 100 nm, 200 nm, 500 nm, 800 nm, 1000 nm, 1200 nm, 1500 nm, 2000 nm etc.; Fullerene and the weight content of carbon nano-tube general assembly (TW) in laminated film are 0.1 ~ 97wt.%, and the best is 1 wt.%, 2 wt.%, 2.5 wt.%, 3 wt.%, 3.5 wt.%, 4 wt.%, 5 wt.%, 6 wt.%, 7 wt.%, 8 wt.%, 9 wt.%, 10 wt.%, 15 wt.%, 20 wt.%, 25 wt.%, 30 wt.% etc.; In the composite membrane, the weight ratio of fullerene and two kinds of compositions of carbon nano-tube is fullerene
:Carbon nano-tube=1:1000 ~ 1000:1, the best is fullerene
:Carbon nano-tube=1
:10,1
:8,1
:5,1
:4,1
:3,1
:2,1
:1,2
:1,3
:1,4
:1,5
:1,8
:1,10
:1 etc.; The thickness of laminated film is 5 ~ 2000nm, and the best is 50nm, 80 nm, 100 nm, 120 nm, 150 nm, 200 nm, 250 nm, 300 nm, 350 nm, 400 nm, 450 nm, 500 nm etc.; The sheet resistance of laminated film be ~ 500 Ω/50M Ω/, the best be 10 K Ω/, 20 K Ω/, 50 K Ω/, 70 K Ω/, 90 K Ω/, 120 K Ω/, 150 K Ω/, 170 K Ω/, 200 K Ω/, 300 K Ω/, 400 K Ω/, 500 K Ω/etc.; The temperature-coefficient of electrical resistance of laminated film is-0.5 ~-6.5%/K, the best is-1.5%/K ,-1.8%/K ,-1.9%/K ,-2.0%/K ,-2.1%/K ,-2.2%/K ,-2.5%/K ,-3.0%/K ,-3.5%/K ,-4.0%/K etc.Mode with chemical bond between the fullerene of functionalization and the carbon nano-tube of functionalization and the vanadium oxide combines, and forms uniform nano compound film.This complex method, making originally is that the higher vanadium oxide of crystallization degree becomes amorphous state or crystallite attitude, crystalline state nanometer, makes simultaneously film more continuous, smooth, tight; The more important thing is, make film resistance obviously reduce, and the absorbing properties of film obviously strengthens.Adopt this vanadium oxide-fullerene-carbon nanometer pipe ternary laminated film to be used for the making of terahertz detector or infrared eye, overcome the negative effect that existing manufacturing technology causes the sensitive thin film chemical constitution, can also overcome simultaneously simple fullerene or simple carbon nano-tube, simple vanadium oxide material in the deficiency of electricity and optical property, improve the combination property of device.
Sum up, the present invention is by adding zero dimension fullerene and one dimension carbon nano-tube composition compound substance in the bidimensional vanadium oxide film, electric property, optical property and the chemical stability etc. of vanadium oxide film are effectively improved, met the needs of terahertz detector or infrared eye.Prepared vanadium oxide-the fullerene of the present invention-carbon nanometer pipe ternary laminated film has the following advantages: the vanadium oxide that (1) utilizes zero dimension fullerene, one dimension carbon nano-tube and bidimensional is good electricity, optical property separately, obtain the more excellent vanadium oxide-fullerene of combination property-carbon nanometer pipe ternary laminated film, satisfy the specific (special) requirements of terahertz detector or infrared eye; (2) the quantitative adjusting by zero dimension fullerene, one dimension carbon nano-tube, bidimensional vanadium oxide three content ratio, can be more prone to, regulate more exactly the film performance of device, satisfy the special requirement of terahertz detector or infrared eye micro-metering bolometer; (3) vanadium oxide-fullerene-carbon nanometer pipe ternary complex thin film structure can also be under the prerequisite that keeps the vanadium oxide premium properties, its electrical and optical properties is obviously strengthened, avoid simultaneously traditional doping process to the negative effect of vanadium oxide chemical constitution, this is the advantage that simple vanadium oxide film can't possess; (4) adopt organosol gel method of the present invention to prepare the method for vanadium oxide-fullerene-carbon nanometer pipe ternary laminated film, low for equipment requirements, film-forming process is simple, need not the equipment of complex and expensive, has reduced manufacturing cost.So, vanadium oxide-fullerene that the present invention is obtained-carbon nanometer pipe ternary laminated film is used for the making of terahertz detector or infrared eye, can overcome existing defective in the prior art, reduce technology difficulty, improve device performance, suitable large-scale industrialized production.
In addition, vanadium oxide-fullerene that the present invention proposes-carbon nanometer pipe ternary laminated film is not only limited to and is applied in terahertz detector or infrared eye, and this laminated film can also be used for other purposes.
Claims (9)
1. vanadium oxide composite film, be used for non-refrigeration terahertz detector or non-refrigerated infrared detector, it is characterized in that, this vanadium oxide composite film is to become vanadium oxide-fullerene that phase-splitting is composited-carbon nanometer pipe ternary laminated film by three kinds of bidimensional vanadium oxide and zero dimension fullerene and one dimension carbon nano-tube, the vanadium oxide that wherein contains in the vanadium oxide composite film is amorphous state or crystallite attitude, crystalline state nanometer, and the molecular formula of vanadium oxide is expressed as VO
x , wherein,
xSatisfy 1≤
x≤ 2.5; The fullerene that contains is the original full carbon hollow cage shape fullerene molecule C that satisfies n 〉=20
n, fullerene derivate, fullerene, one or several in the middle of the fullerene derivate of functionalization of functionalization; The carbon nano-tube that contains is original or single wall or the multi-walled carbon nano-tubes of functionalization, and the diameter of carbon nano-tube is 1 ~ 50 nm, and the length of carbon nano-tube is 10 ~ 30000 nm.
2. vanadium oxide composite film according to claim 1 is characterized in that, in this laminated film, the weight ratio of fullerene and two kinds of compositions of carbon nano-tube is fullerene
:Carbon nano-tube=1:1000 ~ 1000:1, fullerene and the weight content of carbon nano-tube general assembly (TW) in laminated film are 0.1 ~ 97wt.%.
3. vanadium oxide composite film according to claim 1 is characterized in that, the thickness of this vanadium oxide composite film is 5 ~ 2000nm, the temperature-coefficient of electrical resistance of laminated film is-0.5 ~-6.5%/K.
4. the preparation method of a vanadium oxide composite film as claimed in claim 1 is characterized in that, may further comprise the steps:
1. clean substrate, dry up rear for subsequent use;
2. according to specific part by weight, be ready in advance the potpourri of zero dimension fullerene and one dimension carbon nano-tube, for subsequent use;
3. the preparation of vanadium oxide colloidal sol: the vanadium oxide powder is mixed mutually with organic solvent, add thermal response, then by centrifuging, remove insolubles, extract supernatant and leave standstill, carry out again centrifuging, so repeatedly, until remove insolubles fully, obtain not have the vanadium oxide organosol of precipitation, for subsequent use;
4. the reaction of vanadium oxide and fullerene and carbon nano-tube: the fullerene that 2. step is prepared and the potpourri of carbon nano-tube mix mutually with the vanadium oxide colloidal sol that 3. step prepares, ultrasonic dispersion fullerene and carbon nano-tube form the new colloidal sol that vanadium oxide and fullerene and carbon nano-tube are mixed mutually;
5. the preparation of laminated film: the substrate surface that the step vanadium oxide that 4. prepares and the new colloidal sol that fullerene and carbon nano-tube are mixed mutually is spin-coated on cleaning, annealed processing, evaporate organic solvent, form vanadium oxide-fullerene-carbon nanometer pipe ternary laminated film;
6. after being cooled to room temperature, from reactor, take out;
7. as required, the hybrid reaction of repeated oxidation vanadium and fullerene and carbon nano-tube, colloidal sol spin coating and annealing steps form vanadium oxide-fullerene-carbon nanometer pipe ternary multi-layer compound film structure successively.
5. the preparation method of vanadium oxide composite film according to claim 4 is characterized in that, step 2. in, the fullerene of employing is the original full carbon hollow cage shape fullerene molecule C that satisfies n 〉=20
n, fullerene derivate, fullerene, one or several in the middle of the fullerene derivate of functionalization of functionalization; The carbon nano-tube that adopts is original or single wall or the multi-walled carbon nano-tubes of functionalization, and the diameter of carbon nano-tube is 1 ~ 50 nm, and the length of carbon nano-tube is 10 ~ 30000 nm.
6. the preparation method of vanadium oxide film according to claim 4 is characterized in that, step 3. in, the molecular formula of the vanadium oxide of employing is expressed as VO
x , wherein,
xSatisfy 1≤
x≤ 2.5; The organic solvent of the preparation vanadium oxide colloidal sol that adopts is the mixed solution of organic solvent A and two kinds of reagent of organic solvent B, and wherein, organic solvent A is phenmethylol, and organic solvent B is central a kind of of isopropyl alcohol, isobutyl alcohol, isoamylol, isohexyl alcohol.
7. the preparation method of vanadium oxide composite film according to claim 6 is characterized in that, step 3. in, the vanadium oxide that preparation vanadium oxide colloidal sol adopts and the mol ratio of organic solvent A and three kinds of reagent of organic solvent B are vanadium oxide
:Organic solvent A
:Organic solvent B=1
:4
:4 ~ 1
:4
:100.
8. the preparation method of vanadium oxide composite film according to claim 4, it is characterized in that, step 4. in, the fullerene that adds and carbon nano-tube are a kind of in the middle of the fullerene that do not mix with any solvent phase and carbon nano-tube solid mixture or the fullerene that mixes mutually with organic solvent in advance and the carbon nano tube suspension.
9. the preparation method of vanadium oxide composite film according to claim 4, it is characterized in that, step 5. with step 7. in, the annealing temperature of described vanadium oxide-fullerene-carbon nanotube sol is 100 ~ 700 ℃, annealing atmosphere is that air, vacuum, Ar add a kind of in the middle of three kinds of atmosphere of reducibility gas, and annealing time is 0.5 ~ 24 hour.
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| CN113281298B (en) * | 2021-05-19 | 2022-07-12 | 中国电子科技集团公司第四十一研究所 | Terahertz material micro-nano defect detection device and method based on multi-frequency point information fusion |
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