CN102419212A - Vanadium oxide composite film and preparation method thereof - Google Patents
Vanadium oxide composite film and preparation method thereof Download PDFInfo
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- CN102419212A CN102419212A CN2011102367064A CN201110236706A CN102419212A CN 102419212 A CN102419212 A CN 102419212A CN 2011102367064 A CN2011102367064 A CN 2011102367064A CN 201110236706 A CN201110236706 A CN 201110236706A CN 102419212 A CN102419212 A CN 102419212A
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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 laminated film that is used for non-refrigeration terahertz detector or non-refrigerated infrared detector and preparation method thereof.
Background technology
Terahertz is meant that wavelength coverage is the electromagnetic wave of 30 ~ 3000um, has peculiar properties such as transient state property, broadband property, low energy property and coherence.Terahertz is with a wide range of applications in fields such as astronomy, medical science, national defence and safety checks.Wherein, the non-refrigeration of Terahertz (room temperature) survey be the importance used of Terahertz (referring to Linda Marchese, 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 accomplish through the micro-metering bolometer that suspends, so the micro-metering bolometer microbridge of suspension is to influence 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 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 non-refrigeration detector thermistor material of high-performance.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 the vanadium oxide thermistor thin film respectively.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, for example magnetron sputtering, electron beam evaporation, pulsed laser deposition etc. contain the shortcoming that itself can't overcome: the valence state of V element complicacy, 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 (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 take place, and then has influence on the performance of device.So based on a major defect of the detector of vanadium oxide film be: preparation technology's difficulty of vanadium oxide film is big, the repeatability of product and poor stability.
Sol-gal process is other a kind of 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-gal process 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 composition, so, the resistance value of the conventional vanadium oxide film that sol-gal process obtained is bigger, 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.This method is at first V
2O
5With MoO
3Mix mutually, be heated to 900 under the normal pressure
oAbout C, form fused mass; Pour fused mass fast in the water then, add oxalic acid, NH
4F forms inorganic sol.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 non-metallic impurities F in the product, influence material property; The absorptivity of the vanadium oxide that (3) is obtained is lower, is unfavorable for absorbing detection.These deficiencies make the inorganic sol gel method be difficult to directly be applied in the manufacturing of vanadium oxide thermo-sensitive material.
The U.S. Pat P 6489613 that the people such as the Toru Mori of NEC Corporation that authorized on Dec 3rd, 2002 declare has then described other a kind of sol-gel method that improves 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 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 through 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 help film control effectively, and make it to satisfy the requirement of detector.The more important thing is, the temperature of reaction of organosol gel method lower (<200
oC), help reducing to the integrated negative effect of device.Regrettably; Traditional organosol gel method contains some shortcomings identical with the inorganic sol gel method; Comprise: (1) is on the amorphous substrate; The vanadium oxide film of the attitude of polycrystalline often that the organic or inorganic sol-gal process obtains, this polycrystal film are 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 phenomenons such as diffusion of contaminants, segregation also take place in this film easily; Cause performance generation regression, the quality of vanadium oxide film to descend, be difficult to satisfy the needs of long term device operation; (3) the metal-doped absorbing properties that can't improve vanadium oxide film effectively that carries out of organic or inorganic sol-gal process.
On the other hand, the stretching vibration of the various V-O chemical bonds (like 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 CNT is a kind of important nano material, has good electricity and optical property; For this reason; On Dec 1st, 2010, disclosed Chinese invention patent CA 101900607 A that wait the people to declare eastwards perhaps described a kind of vanadium oxide-carbon nano-tube coextruded film and preparation method thereof.This invention utilizes bidimensional vanadium oxide and good separately electricity and the optical property of one dimension CNT, 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 CNT in the composite membrane is horizontal, interconnected reticulate texture.There is a shortcoming in this one dimension CNT of laterally arranging: promptly the one dimension CNT has anisotropy to the response of light.That is to say that the absorptivity of CNT changes with the variation of CNT and seized incident light angle, have only when CNT axle and Terahertz or infrared incident light direction parallel, 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 big difficulty to device manufacturing, input etc.That is to say that for Terahertz room temperature detector or infrared room temperature detector, there is deficiency in two yuan of composite membranes of vanadium oxide-CNT technically as thermistor thin film.
Fullerene (Fullerene) is meant 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 are formed are nonpolar, contain big 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 influence of photoelectric response of one dimension CNT.So, adopt zero dimension fullerene and vanadium oxide-fullerene laminated film that obtain mutually compound to have than excellent comprehensive performances more such as simple vanadium oxide film, vanadium oxide-carbon nano-tube coextruded film with the bidimensional vanadium oxide.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.Likewise, if be applied to this vanadium oxide-fullerene composite membrane 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 CNT.
So, as the thermistor material of terahertz detector or infrared eye, simple vanadium oxide, CNT, 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 laminated film and preparation method thereof is provided, and this film has combination properties such as better electricity, optics.This vanadium oxide laminated 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 working performance of devices, 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 laminated film is provided; It is characterized in that this laminated film is by bidimensional vanadium oxide and zero dimension fullerene and three kinds of vanadium oxide-fullerene-carbon nanometer pipe ternary laminated films that become phase-splitting to be composited of one dimension CNT.
According to vanadium oxide laminated film provided by the present invention, it is characterized in that the vanadium oxide that contains in the vanadium oxide laminated 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 does
x=1.5,2,2.5.
According to vanadium oxide laminated film provided by the present invention, it is characterized in that the fullerene that contains in the vanadium oxide 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 functionalization fullerene C of ,-functional groups such as COOH
60, or functionalization fullerene C
70
According to vanadium oxide laminated film provided by the present invention; It is characterized in that; The CNT that contains in the vanadium oxide laminated film is original or the single wall or the multi-walled carbon nano-tubes of functionalization; The diameter of CNT 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 CNT 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 laminated 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 CNT is a fullerene
:CNT=1:1000 ~ 1000:1, the best is a fullerene
:CNT=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 CNT 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 laminated film provided by the present invention; It is characterized in that; The thickness of this vanadium oxide 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 side resistance of laminated film for ~ 500 Ω/50M Ω/, the best be Ω/, Ω/, Ω/, Ω/, Ω/, Ω/, Ω/, Ω/, Ω/, Ω/, Ω/, 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 laminated film is characterized in that, may further comprise the steps:
1. clean substrate, it is subsequent use to dry up the back;
2. according to specific part by weight, be ready to the potpourri of zero dimension fullerene and one dimension CNT in advance, subsequent use;
3. the preparation of vanadium oxide colloidal sol: the vanadium oxide powder is mixed with organic solvent mutually, and reacting by heating then through centrifuging, is removed insolubles, extracts supernatant and leaves standstill, and carries out centrifuging again, so repeatedly, and until removing insolubles fully.Obtain not have the vanadium oxide organosol of deposition, subsequent use;
4. the reaction of vanadium oxide and fullerene and CNT: the fullerene of 2. preparing step and the potpourri of CNT mix with the vanadium oxide colloidal sol that 3. step prepares mutually; Ultrasonic dispersion fullerene and CNT form the new colloidal sol that vanadium oxide and fullerene and CNT mix mutually;
5. the preparation of laminated film: the substrate surface that is spin-coated on step vanadium oxide that 4. prepares and the new colloidal sol that fullerene and CNT mix mutually 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 CNT, 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 laminated 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; It is characterized in that; Step 2. in; The CNT that adopts is original or the single wall or the multi-walled carbon nano-tubes of functionalization, and the diameter of CNT 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 CNT 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, step 2. in, the weight ratio of fullerene and two kinds of compositions of CNT is a fullerene in the potpourri
:CNT=1:1000 ~ 1000:1, the best is a fullerene
:CNT=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 laminated 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 laminated film provided by the present invention; It is characterized in that; Step 3. in, the solvent of the preparation vanadium oxide colloidal sol of employing is the mixed solution of organic solvent A and two kinds of reagent of organic solvent B, wherein; Organic solvent A is a 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 laminated 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 a 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 an isobutyl alcohol.
Preparation method according to vanadium oxide laminated film provided by the present invention; It is characterized in that; Step 4. in, the fullerene that is added and CNT are a kind of in the middle of the fullerene that do not mix mutually with any solvent and CNT solid mixture or fullerene that mixes mutually with organic solvent in advance and the carbon nano tube suspension.
Preparation method according to vanadium oxide laminated 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 superior to 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 to vanadium oxide thermistor thin film in the existing device in the deficiency of aspects such as material property and preparation method; Propose a kind of three kinds of zero dimension fullerene and one dimension CNT and bidimensional vanadium oxides that adopt and become the method for the compound and trielement composite material that forms of phase-splitting as the thermistor material and the light absorbing material of terahertz detector or infrared eye; Utilize the special cage structure of zero dimension fullerene and one dimension CNT excellent chemical stability and electric property on the one hand; Improve that conventional oxidation vanadium thermistor thin film electric conductivity is low, poor chemical stability and to shortcomings such as the Terahertz absorptivity are low, the negative effect of having avoided traditional doping process that vanadium oxide film is produced simultaneously; On the other hand, utilize vanadium oxide high resistance, film forming continuity, with and good temperature-coefficient of electrical resistance, remedy fullerene and CNT deficiency in these areas, thereby improve the combination property of device.On this basis, through regulating the ratio between vanadium oxide and fullerene and three kinds of compositions of CNT, can also be more prone to, trim film performance more exactly, satisfy the special requirement of terahertz detector or infrared eye.Utilize the terahertz detector thermo-sensitive material of this trielement composite material preparation that constitutes by special zero dimension and monodimension nanometer material and bidimensional film, improved working performance of devices, reduced the starting material manufacturing cost, suitable large-scale industrialized production.
Description of drawings
Fig. 1 is the planimetric map of the vanadium oxide-fullerene-carbon nanometer pipe ternary complex thin film structure of embodiment of the present invention proposition;
Fig. 2 is the sectional view of the vanadium oxide-fullerene-carbon nanometer pipe ternary complex thin film structure of the individual layer that proposes of embodiment of the present invention;
Fig. 3 is the sectional view of the vanadium oxide-fullerene-carbon nanometer pipe ternary complex thin film structure of the multilayer that proposes of embodiment of the present invention;
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 CNT 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
Below in conjunction with accompanying drawing and embodiment the present invention is further described:
Thought of the present invention is in vanadium oxide-fullerene-carbon nanometer pipe ternary complex thin film structure; Utilize zero dimension fullerene, one dimension CNT and good separately electricity and the optical property of three kinds of compositions of bidimensional vanadium oxide; Prepare the better ternary laminated film of combination property; As the 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 following 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, dry up subsequent use then with nitrogen; 2. according to certain ratio, be ready to the zero dimension fullerene of functionalization and the potpourri of the one dimension CNT of functionalization in advance, subsequent use; 3. get a certain amount of vanadium pentoxide powder and mix reacting by heating mutually with phenmethylol and isobutyl alcohol organic solvent.Through centrifuging, remove insolubles then.The supernatant that extracts is placed, carried out the centrifuging second time again, so repeatedly,, obtain not have the vanadium oxide organosol of deposition until removing insolubles fully; 4. pass through a certain amount of fullerene of 2. preparing through step and carbon nanotube mixture vanadium oxide colloidal sol that 3. step prepare and mix mutually and carry out sonicated with a certain amount of, until fullerene and CNT evenly dispersion in vanadium oxide; 5. be spin-coated on the vanadium oxide of 4. preparation and the new colloidal sol that fullerene and CNT mix mutually 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 CNT 220 form vanadium oxide-fullerene-carbon nanometer pipe ternary multi-layer compound film structure 2 successively; 7. after sample is cooled to room temperature, from annealing furnace, take out sample.In vanadium oxide-fullerene-carbon nanometer pipe ternary laminated film 2; The introducing of functionalization fullerene 210 and functionalized carbon nano-tube 220; Electric property, optical property and the steady chemical structure property etc. of vanadium oxide 230 are effectively improved, met the requirement of terahertz detector or infrared eye.
The concrete technology of above-mentioned preparation embodiment comprises: the preparation of (1) film growth substrate: the 650nm SiN that selects 2cm * 2cm for use
x / Si (100) silicon chip; Growth substrates 1 as vanadium oxide-fullerene-carbon nanometer pipe ternary laminated film; Before the experiment, clean the impurity such as greasy dirt of substrate surface earlier with washing agent, use deionized water rinsing; Use acetone, absolute ethyl alcohol and deionized water ultrasonic cleaning 20 minutes then respectively, dry up silicon chip with high pure nitrogen then; (2) preparation of fullerene and carbon nanotube mixture: take by weighing 28.8mg and contain-the basic functionalization fullerene C of OH
60, and 28.8mg contain-functionalized carbon nano-tube of OH base, mix ultrasonic 60 minutes (50 ℃, 70W), form the isobutyl alcohol suspending liquid of fullerene and CNT mutually 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; Stirring and refluxing was taken out reactant liquor after 4 hours in 110 ℃ of silicone oil then;, above-mentioned clear liquid is left standstill back secondary centrifuging under identical condition further remove small amount of impurities with centrifugal 20 minutes of 2500 rev/mins rotating speed and take out supernatant with hydro-extractor, obtain not have the vanadium oxide organosol that precipitates; (4) reaction of vanadium oxide and fullerene and CNT: mutually mix sonicated 30 minute (50 ℃, 70W) to the fullerene through step (2) prepared with 10ml through the vanadium oxide colloidal sol that step (3) prepares with the isobutyl alcohol suspending liquid of CNT; (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 CNT; Adopt the secondary spin coating method of spin coating technique to carry out gluing; Technology 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, and spin coating is 4 times altogether, after each spin coating, film are put into air dry oven 180 ℃ of maintenances 20 minutes down; Carry out spin coating next time after cooling, to prevent the formation piebald that dissolves each other between layer and the layer.Then the sample of preparation is put into muffle furnace and annealed 1 hour down, form vanadium oxide-fullerene-carbon nanometer pipe ternary laminated film 2 at 400 ℃; (6) as required, the steps such as hybrid reaction, colloidal sol spin coating and annealing of repeated oxidation vanadium 230 and fullerene 210, CNT 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, from muffle furnace, takes out sample then, is vanadium oxide-fullerene-carbon nanometer pipe ternary laminated film 2 materials that the present invention proposes.
The growth substrates 1 of vanadium oxide-fullerene-carbon nanometer pipe ternary laminated film 2 does not receive special restriction, except 650nm SiN
x / Si (100) also comprises 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 constitutes of wherein a kind of such as film and their other materials such as composite membrane.Fullerene 210 does not receive special restriction yet 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.CNT 220 does not receive special restriction yet in the composite membrane, can be SWCN original or functionalization or multi-walled carbon nano-tubes.Vanadium oxide 230 does not receive special restriction yet 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 method for preparing vanadium oxide film; Be by zero dimension fullerene and one dimension CNT and three kinds of vanadium oxide-fullerene-carbon nanometer pipe ternary laminated films that become phase-splitting to be composited of bidimensional vanadium oxide, as the 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 does
x=1.5,2,2.5; Zero dimension fullerene and one dimension CNT are dispersed in the 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 functionalization fullerene C of ,-functional groups such as COOH
60, or functionalization fullerene C
70The CNT that contains in the composite membrane is original or the single wall or the multi-walled carbon nano-tubes of functionalization; The diameter of CNT 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 CNT 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 CNT 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 CNT is a fullerene
:CNT=1:1000 ~ 1000:1, the best is a fullerene
:CNT=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 side resistance of laminated film for ~ 500 Ω/50M Ω/, the best be Ω/, Ω/, Ω/, Ω/, Ω/, Ω/, Ω/, Ω/, Ω/, Ω/, Ω/, 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 functionalized carbon nanotube 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 film more continuous, smooth, tight simultaneously; 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 CNT, simple vanadium oxide material deficiency, improve the combination property of device in electricity and optical property.
Summary is got up; The present invention is through adding zero dimension fullerene and one dimension CNT 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-fullerene-carbon nanometer pipe ternary the laminated film of the present invention has following advantage: (1) utilizes the vanadium oxide of zero dimension fullerene, one dimension CNT and bidimensional good separately electricity, optical property; 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 through zero dimension fullerene, one dimension CNT, bidimensional vanadium oxide three content ratio; Can be more prone to, the film performance of trim more exactly, 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 electricity and optical property are obviously strengthened; Avoid the negative effect of traditional doping process to the vanadium oxide chemical constitution simultaneously, 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 cost and complex equipment, has reduced manufacturing cost.So; Vanadium oxide-fullerene-carbon nanometer pipe ternary the laminated film that obtains the present invention 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-carbon nanometer pipe ternary laminated film that the present invention proposes 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 (12)
1. a vanadium oxide laminated film is characterized in that, this laminated film is by bidimensional vanadium oxide and zero dimension fullerene and three kinds of vanadium oxide-fullerene-carbon nanometer pipe ternary laminated films that become phase-splitting to be composited of one dimension CNT.
2. vanadium oxide laminated film according to claim 1 is characterized in that, the vanadium oxide that contains in the vanadium oxide laminated 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.
3. vanadium oxide laminated film according to claim 1 is characterized in that, the fullerene that contains in the vanadium oxide laminated film 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.
4. vanadium oxide laminated film according to claim 1; It is characterized in that; The CNT that contains in the vanadium oxide laminated film is original or the single wall or the multi-walled carbon nano-tubes of functionalization, and the diameter of CNT is 1 ~ 50 nm, and the length of CNT is 10 ~ 30000 nm.
5. vanadium oxide laminated film according to claim 1 is characterized in that, in the laminated film, the weight ratio of fullerene and two kinds of compositions of CNT is a fullerene
:CNT=1:1000 ~ 1000:1, fullerene and the weight content of CNT general assembly (TW) in laminated film are 0.1 ~ 97wt.%.
6. vanadium oxide laminated film according to claim 1 is characterized in that, the thickness of this vanadium oxide laminated film is 5 ~ 2000nm, the side resistance of laminated film for ~ 50M Ω/500 Ω/, the temperature-coefficient of electrical resistance of laminated film is-0.5 ~-6.5%/K.
7. the preparation method of a vanadium oxide laminated film is characterized in that, may further comprise the steps:
1. clean substrate, it is subsequent use to dry up the back;
2. according to specific part by weight, be ready to the potpourri of zero dimension fullerene and one dimension CNT in advance, subsequent use;
3. the preparation of vanadium oxide colloidal sol: the vanadium oxide powder is mixed with organic solvent mutually, and reacting by heating is then through centrifuging; Remove insolubles, extract supernatant and leave standstill, carry out centrifuging again; So repeatedly; Until removing insolubles fully, obtain not have the vanadium oxide organosol of deposition, subsequent use;
4. the reaction of vanadium oxide and fullerene and CNT: the fullerene of 2. preparing step and the potpourri of CNT mix with the vanadium oxide colloidal sol that 3. step prepares mutually; Ultrasonic dispersion fullerene and CNT form the new colloidal sol that vanadium oxide and fullerene and CNT mix mutually;
5. the preparation of laminated film: the substrate surface that is spin-coated on step vanadium oxide that 4. prepares and the new colloidal sol that fullerene and CNT mix mutually 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 CNT, colloidal sol spin coating and annealing steps form vanadium oxide-fullerene-carbon nanometer pipe ternary multi-layer compound film structure successively.
8. the preparation method of vanadium oxide laminated film according to claim 7 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 CNT that adopts is for being original or the single wall or the multi-walled carbon nano-tubes of functionalization, and the diameter of CNT is 1 ~ 50 nm, and the length of CNT is 10 ~ 30000 nm.
9. the preparation method of vanadium oxide film according to claim 7 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 a phenmethylol, and organic solvent B is central a kind of of isopropyl alcohol, isobutyl alcohol, isoamylol, isohexyl alcohol.
10. the preparation method of vanadium oxide laminated film according to claim 9 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.
11. the preparation method of vanadium oxide laminated film according to claim 7; It is characterized in that; Step 4. in, the fullerene that is added and CNT are a kind of in the middle of the fullerene that do not mix mutually with any solvent and CNT solid mixture or fullerene that mixes mutually with organic solvent in advance and the carbon nano tube suspension.
12. the preparation method of vanadium oxide laminated film according to claim 7; 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 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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| US10340459B2 (en) | 2016-03-22 | 2019-07-02 | International Business Machines Corporation | Terahertz detection and spectroscopy with films of homogeneous carbon nanotubes |
| CN113281298A (en) * | 2021-05-19 | 2021-08-20 | 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 |
| JP2022094276A (en) * | 2020-12-14 | 2022-06-24 | ツィンファ ユニバーシティ | Light absorber and method for producing the same |
| JP2022094277A (en) * | 2020-12-14 | 2022-06-24 | ツィンファ ユニバーシティ | Light absorber prefabricated liquid and method for producing the same |
| JP2022094275A (en) * | 2020-12-14 | 2022-06-24 | ツィンファ ユニバーシティ | Infrared detector and infrared imager |
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| JP2022094276A (en) * | 2020-12-14 | 2022-06-24 | ツィンファ ユニバーシティ | Light absorber and method for producing the same |
| JP2022094277A (en) * | 2020-12-14 | 2022-06-24 | ツィンファ ユニバーシティ | Light absorber prefabricated liquid and method for producing the same |
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| CN113281298A (en) * | 2021-05-19 | 2021-08-20 | 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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