CN101847459A - Composite carbon nanotube conductive thin film and preparation method and preparation device thereof - Google Patents
Composite carbon nanotube conductive thin film and preparation method and preparation device thereof Download PDFInfo
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Abstract
The invention provides a carbon nanotube conductive thin film, which comprises a carbon nanotube layer, and also comprises an adhesion enhancement layer which is used for enhancing the adhesion between the carbon nanotube and a glass substrate and is arranged between the carbon layer and the glass substrate. The invention also provides a preparation method of the carbon nanotube conductive thin film, which comprises the followings steps: preparing a carbon nanotube solution with good dispersion; preparing a solution for generating the adhesion enhancement layer; carrying out ultrasonic fogging for the solution, and spraying the generated fog to the surface of the glass substrate to form the adhesion enhancement layer by pyrolysis; and carrying out ultrasonic fogging for the carbon nanotube solution, and spraying the generated fog to the surface of the glass substrate with the adhesion enhancement layer to form the carbon nanotube layer by pyrolysis. The film preparation method can obtain the film with very good large-area uniformity and consistency, and the film thickness can be precisely controlled by adjusting the amount of fog and flow velocity.
Description
Technical field
The present invention relates to the carbon nanotube conductive thin film field, particularly a kind of composite carbon nanotube conductive thin film and preparation method thereof and preparation facilities.
Background technology
Since Iijima in 1991 found multi-walled carbon nano-tubes (MWCNT) and finds Single Walled Carbon Nanotube (SWCNT) after 2 years, the research of carbon nano-tube (CNT) had caused the great interest of people, contains especially so far.People constantly find the many very excellent characteristics of carbon nano-tube, and mechanical property is fabulous such as its very light in weight, and the tensile strength of Single Walled Carbon Nanotube and Young's modulus can reach 37GPa and 640Gpa respectively.It also has very good conductivity, thermal conductivity, gas permeability etc., and very stable, and the life-span is long.Therefore along with going deep into of studying, the above-mentioned series of advantages of carbon nano-tube allows increasing researcher see the huge applications prospect that it is potential.A series of excellent properties at carbon nano-tube, people have designed many application devices based on carbon nano-tube, such as carbon nano-tube driver, electric conductor, inductor, an emitting diode, catalytic templating, super capacitor, fuel cell, electromagnetic shield etc.Wherein having some devices to be based on carbon nano-tube microcosmic and one dimension uses, more device then is macroscopic view and large-area two dimensional application, particularly when laboratory technique was transferred to large-area suitability for industrialized production, it is particularly important that the coupling of technology seems.
One of focus of Recent study---carbon nano-tube paper (also being Bucky Paper) is exactly the typical case of carbon nano-tube macroscopic two dimensional application.The tensile strength that this carbon nano-tube paper is general can reach 10-80MPa, and Young's modulus can reach 10
2-10
3MPa, conductivity is generally 10
2-10
3S/cm.The most general technology of this carbon nano-tube paper of preparation is to adopt filtration method at present, but the carbon nano-tube paper that this method obtains depends on the size of filter membrane, therefore often has only cm
2Magnitude is difficult to the large-area carbon nano-tube paper of preparation.In addition, because when carbon nano-tube paper has only its THICKNESS CONTROL in the preparation in very little scope, just can obtain transparent conductive film, and therefore filtration method generally can't make transparent carbon nanotube conductive thin film owing to can't the thickness of prepared carbon nano-tube paper be controlled.
In the prior art, prepare transparent carbon nanotube conductive thin film and can adopt spin-coating method, dip-coating method (Chinese patent CN 101192492A, CN 101192493A), utilize the czochralski method (Chinese patent CN 100427388C) of LB film assembling, aerogel carbon nanotube sedimentation (Chinese patent CN 100386258C) etc.Spin-coating method wherein can under lab obtain the homogeneous film of small size, is not suitable for large-area production application, though it can obtain the film of different-thickness by changing spin coating rotating speed and solution concentration, but is difficult to accurately control thickness.
Dip-coating method is to form by glass elements being put into the carbon nano-tube slurry, formed one deck carbon nano-tube pulp layer by gravity and suction-operated at sample surfaces when lifting, need heating under inert gas shielding then.There is certain limitation in this method, must two blocks of immersion slurries of combining closely for plate glass, otherwise can all adsorb spreading mass in the both sides of flat glass film, if two blocks of glass have displacement, separation all can cause the local absorption in both sides slurry not exclusively equally greatly or slightly, operation easier is bigger.For the sample of surface imperfection shape, the pulp layer formed thickness on irregular different surfaces that relies on gravity and suction-operated to form in the process of lifting has very big difference, causes the final carbon nano-tube film that forms very inhomogeneous at different surfaces.And the czochralski method that utilizes gravity absorption need large volume slurry and can only vertical operation, seriously limited large tracts of land production.
Utilize the czochralski method of LB film assembling,, then also adopt dip-coating method that the monofilm on surface is collected earlier by diffuse to form the uniform single-layer carbon nano-tube film of thickness at liquid surface.This method has the common limitation of dip-coating method.
The aerogel carbon nanotube sedimentation needs earlier by external force the fragmentation of carbon nano pipe array sample, dispersing and settling in gas phase then.And its infall process needs vacuum to a certain degree or feed the air of certain flow rate in quartz ampoule so that CNT further expand after sedimentation again.The caliber of vacuum and quartz ampoule has all limited large-area sedimentation, and it is bad directly to be deposited in the adhesive force of the carbon nano-tube film of substrate of glass and substrate surface, is erased easily.
In view of prior art is preparing carbon nanotube conductive thin film, deficiency on the particularly large-area carbon nanotube conductive thin film, need a kind ofly can to prepare the large tracts of land carbon nanotube conductive thin film, and with low cost, technology is simple, condition is loose and the method that can be complementary with modern production technology.
Summary of the invention
An object of the present invention is to overcome the lower defective of adhesive force between existing carbon nanotube conductive thin film and substrate of glass, thereby a kind of composite carbon nanotube conductive thin film that has than high adhesion force is provided.
Another purpose of the present invention is to overcome the deficiency of prior art on preparation large tracts of land carbon nanotube conductive thin film, and a kind of with low cost, simple preparation method of technology is provided.
A further object of the present invention is to overcome existing carbon nanotube conductive thin film preparation facilities to be unfavorable for preparing the defective of large tracts of land carbon nanotube conductive thin film, thereby a kind of device that can prepare the large tracts of land carbon nanotube conductive thin film is provided.
To achieve these goals, the invention provides a kind of composite carbon nanotube conductive thin film, comprise carbon nanotube layer, also including the adhesion enhancement layer that is used to strengthen adhesive force between described carbon nanotube layer and described substrate of glass between described carbon nanotube layer and the substrate of glass.
In the technique scheme, also comprise the N type semiconductor nano particle in the carbon nano tube surface of described carbon nanotube layer.
In the technique scheme, described adhesion enhancement layer adopts the N type semiconductor material of good conductivity.
In the technique scheme, described N type semiconductor material comprises SnO
2, TiO
2, ZnO.
The present invention also provides a kind of composite carbon nanotube conductive thin film preparation method, comprising:
Step 1), preparation have the carbon nano-tube solution of good dispersion;
Step 2), preparation is used to generate the solution of adhesion enhancement layer;
Step 3), to step 2) solution that obtains does ultrasonic hazing, the fog that is generated sprays to glass basic surface and forms adhesion enhancement layer with pyrolysis;
Step 4), the resulting carbon nano-tube solution of step 1) is done ultrasonic hazing, the fog that is generated sprays to the resulting glass basic surface that has adhesion enhancement layer of step 3) and forms carbon nanotube layer with pyrolysis.
In the technique scheme, in described step 4), also comprise:
To resulting carbon nano-tube solution of step 1) and step 2) resulting solution does ultrasonic hazing respectively, and spray to the resulting glass basic surface that has adhesion enhancement layer of step 3) after resulting two kinds of fogs mix and form the carbon nanotube layer that the band connectivity strengthens nano particle with pyrolysis.
In the technique scheme, described step 1) comprises:
Step 1-1), pour carbon nano-tube into the phosphomolybdic acid aqueous solution, add thermal agitation 24-48 hour, then with the solution suction filtration that obtains 3 times;
Step 1-2), the moist carbon nano-tube on the filter paper behind the suction filtration is dissolved in the red fuming nitric acid (RFNA), stirring and refluxing 5-24 hour, the solution centrifugal after refluxing is gone the upper strata acid solution, suction filtration is washed to PH ≈ 7.0 then;
Step 1-3), the carbon nano-tube on the filter membrane that obtains is scraped ambient temperature overnight drying in vacuum drying chamber;
Step 1-4), the quality of the dried carbon nano-tube of weighing, the dried carbon nanotube after the weighing is dissolved in the deionized water, with ultrasonic in the cell pulverization machine after the refiner high-speed stirred, obtain dispersed well carbon nano-tube solution.
In the technique scheme, in described step 2) in, the described solution that is used to generate adhesion enhancement layer is SnCl
4Solution; Preparation SnCl
4Solution comprises:
LIQUID Sn Cl with 0.009mol-0.045mol
4Pour in the 300ml ethanol,, obtain the SnCl that concentration is 0.03M-0.15M at 70 ℃ of stirring and refluxing 5-10 hours
4Ethanolic solution.
In the technique scheme, in described step 2) in, the described solution that is used to generate adhesion enhancement layer is SnCl
4Solution; Preparation SnCl
4Solution comprises:
With the 0.009mol-0.045mol quality is m
1LIQUID Sn Cl
4Pour in the 300ml ethanol, 70 ℃ of stirring and refluxing 5 hours;
With the 0.015mol-0.075mol quality is m
2NH
4F pours the deionized water for stirring 5 hours of 3-5ml into, pours front SnCl then into
4Ethanolic solution stirring and refluxing 5-10 hour keeps mass ratio to be
Reduce to room temperature after the backflow, obtain mixing NH
4The SnCl of F
4Ethanolic solution.
In the technique scheme, described step 3) comprises:
Step 3-1), to step 2) solution that obtains does ultrasonic hazing, described ultrasonic haze haze speed between 2.5ml/min-4.0ml/min;
Step 3-2), resulting fog is being sprayed to temperature on 400 ℃-450 ℃ substrate of glass under the drive of dry air, described substrate of glass moves reciprocatingly under the drive of conveyer belt, thereby forms adhesion enhancement layer in described glass basic surface pyrolysis.
In the technique scheme, described step 4) comprises:
Step 4-1-1), the resulting carbon nano-tube solution of step 1) is done ultrasonic hazing, described ultrasonic haze haze speed between 2.5ml/min-4.0ml/min;
Step 4-1-2), resulting fog is being sprayed to temperature on 400 ℃-450 ℃ the substrate of glass that has adhesion enhancement layer under the drive of dry air, described substrate of glass moves reciprocatingly under the drive of conveyer belt, thereby forms carbon nanotube layer in described glass basic surface pyrolysis.
In the technique scheme, described step 4) also comprises:
Step 4-2-1), the resulting carbon nano-tube solution of step 1) is done ultrasonic hazing, described ultrasonic haze haze speed between 3.0ml/min-4.0ml/min;
Step 4-2-2), to step 2) solution that obtains does ultrasonic hazing, described ultrasonic haze haze speed between 1.0ml/min-2.0ml/min;
Step 4-2-3), with step 4-2-1) with step 4-2-2) resulting fog mixes mutually, mixed fog is spraying to temperature on 400 ℃-450 ℃ the substrate of glass that has adhesion enhancement layer under the drive of dry air, sprayed 80 seconds-400 seconds, in spraying process, described substrate of glass moves reciprocatingly under the drive of conveyer belt, thereby forms the carbon nanotube layer of band nano particle in described glass basic surface pyrolysis.
The present invention provides a kind of preparation facilities that is used to realize described composite carbon nanotube conductive thin film preparation method again, comprises liquid peristaltic pump tube, fog blender, gas flow rate control valve, fog conveyance conduit that is used for ultrasonic ultrasonic the day with fog that hazes, adjustable flow velocity and the spray chamber that comprises nozzle, air extractor; Wherein,
Described ultrasonic day with fog is connected to described fog blender by the liquid peristaltic pump tube of adjustable flow velocity, described fog blender is connected with the nozzle of described spray chamber by the fog conveyance conduit, is useful on the gas flow rate control valve that gas flow rate is controlled on described fog conveyance conduit.
In the technique scheme, described ultrasonic day with fog has two, and they are connected with described fog blender by the liquid peristaltic pump tube of described adjustable flow velocity respectively.
The invention has the advantages that:
1, adopt method for manufacturing thin film of the present invention can obtain large-area uniformity and the good rete of consistency, and thicknesses of layers can be accurately controlled by regulating fog amount and flow velocity.
2, carbon nanotube conductive thin film provided by the present invention has improved adhesive force with substrate by adhesion enhancement layer, and adhesion enhancement layer and connectivity strengthen nano particle and all obtain by same device spray pyrolysis, very convenient, improved the mechanics and the electric property of carbon nano-tube film greatly.
3, the ultrasonic spray pyrolysis that adopted during film in preparation of the present invention is a kind of technology that can directly combine with modern glass production Wiring technology.In the modern floatation glass production line, hot glass when the molten tin bath of floating area comes out about 600 ℃ through the cooling zone, finally reaches about 40 ℃.Therefore, the present invention can be applied in the initial end of cooling zone, promptly carries out plated film when glass when 600 ℃ are cooled to 450 ℃-400 ℃ interval.
4, ultrasonic spray pyrolysis of the present invention combines with modern industry production, has brought the significantly reduction of cost.
5, owing to adopt the ultrasonic mode that hazes, carbon nano-tube solution is in the ultrasound environments always when the preparation film in the present invention, and carbon nano-tube is dispersed to keep best, non-stop run for a long time, and to not influence of quality of forming film.
6, the present invention does not require airtight chamber and vacuum in the preparation thin-film process, does not need inert gas shielding, and production requirement is loose.
Description of drawings
The ultrasonic spray pyrolysis schematic representation of apparatus that Fig. 1 is among the present invention to be adopted.
Fig. 2 is the visible light transmissivity spectrum of carbon nano-tube film prepared among the embodiment 3.
Fig. 3 (a)-Fig. 3 (b) is the carbon nano-tube film electron scanning micrograph of embodiment 3 preparations.
Fig. 4 is the visible light transmissivity spectrum of the double-layer composite conductive film of embodiment 6 preparations.
Fig. 5 (a)-Fig. 5 (b) is the electron scanning micrograph of the double-layer composite conductive film of embodiment 6 preparations.
Fig. 6 is the visible light transmissivity spectrum of the mixed layer compound-type conducting film of embodiment 7 preparations.
Fig. 7 (a)-Fig. 7 (c) is the electron scanning micrograph of the mixed layer compound-type conducting film of embodiment 7 preparations.
Fig. 8 is the electron scanning micrograph of the double-layer composite conductive film of embodiment 8 preparations.
The drawing explanation
The liquid peristaltic pump tube 3 fog blenders of 1 ultrasonic day with fog 2 adjustable flow velocity
4 gas flow rate control valves, 5 fog conveyance conduits, 6 nozzles
7 air extractors, 8 spray chambers
Embodiment
The present invention will be described below in conjunction with the drawings and specific embodiments.
In the present invention, adopt ultrasonic spray pyrolysis to prepare large-area carbon nanotube conductive thin film.Adopt ultrasonic spray pyrolysis at first will carry out ultrasonic hazing, so-called ullrasonic spraying is meant the bottom that the ultrasonic transduction sheet is placed liquid, the ultrasonic wave that the ultrasonic transduction sheet is produced can cause near the liquid level disturbance of capillary wave and the air pocket formed cycle hydraulic pressure vibrations that interact to make liquid from surface isolation, thereby forms minimum drop.In general, ultrasonic hazing can obtain tens microns drops that distribute to sub-micron.Behind the ultrasonic fog that obtains forming that hazes, these fogs are sprayed onto the glass surface pyrolysis, thereby form needed film by minimum drop.
Provided the related device that is used for ultrasonic spray pyrolysis in Fig. 1, this device comprises liquid peristaltic pump tube 2, fog blender 3, gas flow rate control valve 4, the fog conveyance conduit 5 of ultrasonic day with fog 1, adjustable flow velocity and comprises the spray chamber 8 of nozzle 6, air extractor 7.In the embodiment shown in fig. 1, ultrasonic day with fog 1 has two, represent with first ultrasonic day with fog and second ultrasonic day with fog respectively, two ultrasonic days with fog are connected to the fog blender by the liquid peristaltic pump tube of adjustable flow velocity separately, gas in the fog blender arrives nozzle 6 via fog conveyance conduit 5 under the control of gas flow rate control valve 4, by the fog of nozzle 6 ejection in the glass surface pyrolysis, thereby generate needed film.In ultrasonic day with fog, include the ultrasonic transduction sheet that is used to generate minimum drop, the ultrasonic transduction sheet that described ultrasonic transduction sheet is 1.7MHz and 2.4MHz.In order to realize even film forming on full wafer glass width, device of the present invention adopts a plurality of nozzles, and arranges side by side between a plurality of nozzle, makes nozzle can cover the width of whole glass.In other embodiments, the number of ultrasonic day with fog 1 can be not limited to two, and the frequency of the ultrasonic transduction sheet in ultrasonic day with fog 1 also is not limited to 1.7MHz and 2.4MHz.
When adopting the large-area carbon nanotube conductive thin film of the preparation of device shown in Fig. 1, at first need the dispersed well carbon nano-tube solution of preparation, with carbon nano-tube solution by aforementioned means spray on glass after, can obtain composite carbon nanotube conductive thin film.
Among below the embodiment 1 and embodiment 2, the process of the carbon nano-tube solution that how to obtain having good dispersion is illustrated.
Embodiment 1
Take by weighing the 0.28g phosphomolybdic acid, pour the 100ml deionized water into, stirred 15 minutes, obtaining concentration is the phosphomolybdic acid aqueous solution of 0.00153M.Take by weighing commodity carbon nano-tube 0.5g, toward wherein pouring the phosphorus molybdenum acid solution for preparing gradually into, stirred 24 hours after being heated to 60 ℃, then with resulting solution suction filtration 3 times.Moist carbon nano-tube on the filter paper behind the suction filtration is dissolved in the red fuming nitric acid (RFNA) that 200ml concentration is 2.6M,, reduces to room temperature then 83 ℃ of stirring and refluxing 5 hours.Solution centrifugal after refluxing is gone the upper strata acid solution 3 times, be washed to PH ≈ 7.0 through 0.22 micron moisture film suction filtration then, the solution that leaches is near colourless.At last the carbon nano-tube on the filter membrane that obtains is scraped in the beaker gently ambient temperature overnight drying in vacuum drying chamber.The quality of the dried carbon nano-tube of weighing is 0.29g.Taking by weighing wherein, the dried carbon nano-tube of 0.1g is dissolved in the 200ml deionized water, pour the refiner high speed into after stirring a little and stir 2min, again CNT solution is poured in the beaker into the (sonicated 8 seconds of sonicated 5min in the cell pulverization machine from refiner, 2 seconds at interval, repeat 30 times).Obtain dispersed well CNT solution, in order to ullrasonic spraying.
Take by weighing the 0.55g phosphomolybdic acid, pour the 150ml deionized water into, stirred 20 minutes, obtaining concentration is the phosphomolybdic acid aqueous solution of 0.002M.Take by weighing commodity carbon nano-tube 0.5g, toward wherein pouring the phosphorus molybdenum acid solution for preparing into, be heated to 60 ℃ and stirred 48 hours, then with the solution suction filtration that obtains 3 times.Moist carbon nano-tube on the filter paper behind the suction filtration is dissolved in the red fuming nitric acid (RFNA) that 250ml concentration is 3.0M,, reduces to room temperature then 83 ℃ of stirring and refluxing 24 hours.Solution centrifugal after refluxing is gone the upper strata acid solution 2 times, be washed to PH ≈ 7.0 through 0.22 micron moisture film suction filtration then, the solution that leaches is near colourless.At last the carbon nano-tube on the filter membrane that obtains is scraped in the beaker gently ambient temperature overnight drying in vacuum drying chamber.The quality of the dried carbon nano-tube of weighing is 0.22g.Taking by weighing wherein, the dried carbon nano-tube of 0.1g is dissolved in the 200ml deionized water, pour the refiner high speed into after stirring a little and stir 3min, again CNT solution is poured in the beaker into the (sonicated 8 seconds of sonicated 10min in the cell pulverization machine from refiner, 2 seconds at interval, repeat 60 times).Obtain dispersed well CNT solution, in order to ullrasonic spraying.
After obtaining dispersed well carbon nano-tube solution, can prepare conductive film.Among the embodiment 3 below, the process that how to prepare conductive film is illustrated.
Embodiment 3
A, pour the CNT solution of the 0.1g/200ml that obtains among the embodiment 1 in the device shown in Figure 1 ultrasonic day with fog.Regulate the power of ultrasonic transduction sheet in ultrasonic the day with fog, the rate stabilization that hazes that makes each ultrasonic transduction sheet is at 2.5ml/min.The adjustments of gas flow velocity valve, the flow speed stability that makes dry air is at 20ml/s.Take the fog that produces to jet hole by the dry air that at the uniform velocity flows, jet hole is from the about 15mm of glass basic surface, 450 ℃ of substrate of glass temperature, drive the repeatedly reciprocating motion of substrate of glass by conveyer belt, the control spray time is 120 seconds, the about 50nm-70nm of CNT film thickness that obtains being attached to substrate of glass is (because often crooked the overlapping mutually of carbon nano-tube connects, the direction perk of small amount of carbon nanotubes meeting along vertical glass surface arranged, therefore be difficult to fixing accurate thickness of definition, here get that most CNT overlap mutually and the thickness approximation that obtains, definition herein Hereinafter the same) the CNT transparent conductive film.The face resistance that is recorded this film by RTS-9 four point probe instrument is 25k Ω/-28k Ω/, visible region (400nm-800nm) mean transmissivity is 78.17%, Fig. 2-A is the visible light transmissivity spectrum of this film, and Fig. 3 a is scanning electron microscopy (SEM) photo of this film.
B, the CNT solution of the 0.1g/200ml that obtains among the embodiment 2 is poured in ultrasonic the day with fog, regulated the power of ultrasonic transduction sheet, the rate stabilization that hazes that makes each transducing sheet is at 3.0ml/min.The adjustments of gas flow velocity valve, the flow speed stability that makes dry air is at 25ml/s.Take the fog that produces to jet hole by the dry air that at the uniform velocity flows, jet hole is from the about 15mm of glass basic surface, 400 ℃ of base reservoir temperatures, conveyer belt drives the substrate of glass reciprocating motion, the control spray time is 200 seconds, obtains being attached to the CNT transparent conductive film of the about 150nm of thickness of substrate of glass.The face resistance that is recorded this film by the four point probe instrument is 5.5k Ω/-6k Ω/, and the visible region mean transmissivity is 47.45%, and Fig. 2-B is the visible light transmissivity spectrum of this film, and Fig. 3 b is the SEM photo of this film.
Above-mentioned A experiment is tested the CNT transparent conductive film that all can obtain the large tracts of land uniformity with B.Yet these two experiments all are directly to do spray pyrolysis on substrate of glass, conductive film that obtains and substrate of glass adhesive force are bad, though along with the prolongation adhesive force of standing time can strengthen to some extent, but it is sticking once with the 3M adhesive tape with deionized water rinsing oven dry back, will find that film is gone a part by sticking, causes face resistance to rise 4 times and 11 times respectively.Therefore, can also plate one deck adhesion enhancement layer at glass basic surface in the present invention, on this adhesion enhancement layer, prepare carbon nanotube conductive thin film again.
The operation of plating adhesion enhancement layer also can be adopted the ullrasonic spraying method on substrate of glass.The material that is used to generate adhesion enhancement layer can be the better conductivity N type semiconductor, as SnO
2, TiO
2, ZnO etc., preferred SnO in the present invention
2Therefore, generate adhesion enhancement layer at first needs preparation to obtain SnO by ultrasonic spray pyrolysis
2Or mix the SnO of F
2Spray solution.In the present invention, this spray solution can be SnCl
4Ethanolic solution also can be to mix NH
4The SnCl of F
4Ethanolic solution.Among below the embodiment 4 and embodiment 5, just how to prepare SnCl respectively
4Ethanolic solution with mix NH
4The SnCl of F
4Ethanolic solution illustrates.
Embodiment 4
LIQUID Sn Cl with A mol
4Pour in the 300ml ethanol, 70 ℃ of stirring and refluxing 10 hours.Obtain the good SnCl of dissolubility
4Ethanolic solution is in order to ullrasonic spraying.Obtain the SnCl of variable concentrations
4Ethanolic solution is the table 1 of face as follows.
Table 1
With A mol quality is m
1LIQUID Sn Cl
4Pour in the 300ml ethanol, 70 ℃ of stirring and refluxing 5 hours; With B mol quality is m
2NH
4F pours the deionized water for stirring 5 hours of 3-5ml into, pours front SnCl then into
4Ethanolic solution stirring and refluxing 10 hours keeps mass ratio to be
Reduce to room temperature after the backflow, obtain dissolubility and well mix NH
4The SnCl of F
4Ethanolic solution is in order to ullrasonic spraying.Obtain the NH that mixes of variable concentrations
4The SnCl of F
4Ethanolic solution is the table 2 of face as follows.
Table 2
Embodiment 6
At the SnCl that obtains being used to generate adhesion enhancement layer
4Behind the solution, just can on substrate of glass, plate one deck adhesion enhancement layer earlier, deposit the CNT conductive film more thereon.In the present embodiment this process is illustrated.
SnCl to the variable concentrations that obtains among embodiment 4 and the embodiment 5
4Ethanolic solution a-j carries out ultrasonic spray pyrolysis respectively, the rate stabilization that hazes of regulating each ultrasonic transduction sheet is 2.5ml/min, air velocity 25ml/s, jet hole is from glass basic surface 20mm, 450 ℃ of base reservoir temperatures, conveyer belt drives substrate of glass and moves reciprocatingly, and control obtains the fabulous SnO of adhesive force on the substrate of glass
2Transparent conductive film.Obtain SnO
2The about 300-600nm of film thickness mixes the SnO of F
2The about 80-130nm of film thickness.Following table 3 be a-e and the pyrolysis of f-j solution spray are obtained the adhesion enhancement layer film resistivity relatively.
Table 3
Had after the adhesion enhancement layer, again ultrasonic spray pyrolysis last layer CNT conductive film thereon.The preparation of CNT conductive film can realize with diverse ways according to the difference of adhesion enhancement layer material, provide two kinds of implementation methods below.
I: the adhesion enhancement layer of utilizing the pyrolysis of c solution spray to obtain, this layer thickness is about 600nm.Utilize the step among the embodiment 2 to obtain CNT solution, be poured into ultrasonic day with fog, regulating the ultrasonic transduction sheet makes the rate stabilization that hazes at 2.5ml/min, the flow velocity of dry air is 30ml/s, jet hole is from the about 15mm of glass basic surface, 430 ℃ of substrate of glass temperature, conveyer belt drives the substrate of glass reciprocating motion, the control spray time is 120 seconds, obtain the CNT transparent conductive film of the about 100nm of thickness on the adhesion enhancement layer, form (adhesion enhancement layer/CNT thin layer) double-layer composite conductive film thus.Recording this THIN COMPOSITE face resistance with four point probe is 475 ± 5 Ω/, and the visible region mean transmissivity is 76.43%.Fig. 4-the 1st, the visible light transmissivity spectrum of this film, Fig. 5 a are the SEM photos of this film.
II: the adhesion enhancement layer of utilizing the pyrolysis of h solution spray to obtain, this layer thickness is about 90nm.Utilize the step among the embodiment 1 to obtain CNT solution then, be poured into ultrasonic day with fog, adjusting ultrasonic transduction sheet makes and hazes rate stabilization at 3.0ml/min, the flow velocity of dry air is at 30ml/s, jet hole is from the about 15mm of glass basic surface, 400 ℃ of substrate of glass temperature, conveyer belt drives the substrate of glass reciprocating motion, the control spray time is 180 seconds, obtain the CNT transparent conductive film of the about 150nm of thickness on the adhesion enhancement layer, form (adhesion enhancement layer/CNT thin layer) double-layer composite conductive film thus.Recording this THIN COMPOSITE face resistance with four point probe is 315 ± 5 Ω/, and the visible region mean transmissivity is 64.20%.Fig. 4-II is the visible light transmissivity spectrum of this film, and Fig. 5 b is this film SEM photo.
I method and II method have obtained the double-layer composite conductive film respectively, the individual layer conductive film that obtains among the adhesive force of this kind composite membrane and substrate and the embodiment 3 has been compared greatly and has been improved, this film is difficult to be erased, sticking once with deionized water rinsing oven dry back with the 3M adhesive tape, measurement face resistance only improves about 5%-10%, and SnO is described
2Adhesion enhancement layer has increased the adhesive force between CNT and the substrate widely.
Common practise by this area can know that single carbon nano-tube has fabulous conductivity, and is connected to each other the main Van der Waals force that leans between the carbon nano-tube, causes the conductibility of electronics between carbon nano-tube not as carbon nano-tube inside.This has just influenced the raising of the conductivity of carbon nanotube conductive thin film.The connectivity of carbon nano-tube between mutually can be sneaked into a spot of SnCl in the fog of the CNT aqueous solution when strengthening film forming
4Ethanol fog, thus when forming the CNT film, in carbon nano tube surface, particularly the junction between the carbon nano-tube deposits simultaneously to coat and goes up SnO
2Nano particle.Because SnO
2Be N type semiconductor, and between itself and the carbon nano-tube by C-O key strong bonded, therefore can improve the electrical conductivity character between the carbon nano-tube greatly.Though be SnO at the nano particle that carbon nano tube surface deposited in the present embodiment,
2Nano particle, but by other N type semiconductor material (as TiO
2, ZnO) formed nano particle is suitable equally.
Provided in the present embodiment to be used for generating and contained SnO
2A plurality of examples of the conductive membrane layer of nano particle are described below respectively.
1, elder generation's spray pyrolysis one deck adhesion enhancement layer in substrate: with the 19.15% mass ratio NH that mixes of 0.075M
4The SnCl of F
4Ethanolic solution is poured ultrasonic day with fog in the device shown in Figure 1 into, controlling the feasible speed that hazes of each transducing sheet is 3.0ml/min, air velocity is 30ml/s, jet hole is from the about 20mm of glass basic surface, 450 ℃ of substrate of glass temperature, conveyer belt drives the substrate of glass reciprocating motion, control spray time 5min.The speed that hazes with the transducing sheet of this ultrasonic day with fog after spraying finishes is adjusted to 1.0ml/min.To utilize the CNT solution of the 0.1g/200ml that embodiment 1 method obtains to pour in another ultrasonic day with fog then, the transducing sheet of regulating it makes and hazes rate stabilization at 3.0ml/min.After fog in two ultrasonic days with fog mixes in the fog blender, take jet hole by flow velocity to for the 25ml/s dry air, jet hole is from the about 20mm of glass basic surface, the substrate of glass temperature is at 450 ℃, conveyer belt drives the substrate of glass reciprocating motion, controlling common spray time is 80 seconds, obtain the CNT transparent conductive film of the about 50nm of thickness on the adhesion enhancement layer, and carbon nano tube surface is coated with a spot of SnO
2Nano particle, grain diameter 2-5nm.The four point probe view records this compound-type conducting pellicular front resistance 580 ± 5 Ω/.The visible light mean transmissivity is 90.66%.Fig. 6-A is the visible light transmissivity spectrum of this compound-type conducting film, and Fig. 7 a is the SEM photo of this film.
2, elder generation's spray pyrolysis one deck adhesion enhancement layer in substrate: with the 19.15% mass ratio NH that mixes of 0.1M
4The SnCl of F
4Ethanolic solution is poured a ultrasonic day with fog into, and controlling the feasible speed that hazes of each transducing sheet is 3.5ml/min, and air velocity is 30ml/s, jet hole is from the about 15mm of glass basic surface, 450 ℃ of base reservoir temperatures, conveyer belt drives the substrate of glass reciprocating motion, control spray time 5min.The feasible speed that hazes of transducing sheet that the adhesion enhancement layer spraying finishes to regulate this ultrasonic day with fog in the back is adjusted to 1.5ml/min.To utilize the CNT solution of the 0.1g/200ml that the method among the embodiment 2 obtains to pour in another ultrasonic day with fog then, the rate stabilization that hazes of transducing sheet of regulating it is at 3.0ml/min.After fog in two ultrasonic days with fog mixes in the fog blender, take jet hole by flow velocity to for the 30ml/s dry air, jet hole is from the about 20mm of glass basic surface, the substrate of glass temperature is 450 ℃, conveyer belt drives the substrate of glass reciprocating motion, controlling common spray time is 100 seconds, obtain the CNT transparent conductive film of the about 80nm of thickness on the adhesion enhancement layer, and carbon nano tube surface is coated with more SnO
2Nano particle, grain diameter 10-20nm.The four point probe view records this compound-type conducting pellicular front resistance 455 ± 5 Ω/.The visible light mean transmissivity is 89.57%.Fig. 6-B is the visible light transmissivity spectrum of this compound-type conducting film, and Fig. 7 b is the SEM photo of this film.
3, elder generation's spray pyrolysis one deck adhesion enhancement layer in substrate: with the 19.15% mass ratio NH that mixes of 0.05M
4The SnCl of F
4Ethanolic solution is poured a ultrasonic day with fog into, and controlling the feasible speed that hazes of each transducing sheet is 4.0ml/min, and air velocity is 30ml/s, jet hole is from the about 10mm of glass basic surface, 430 ℃ of base reservoir temperatures, conveyer belt drives the substrate of glass reciprocating motion, and the control spray time is 5min.The feasible speed that hazes of transducing sheet that spraying finishes to regulate this ultrasonic day with fog in the back is 2.0ml/min.To utilize the CNT solution of the 0.1g/200ml that the method among the embodiment 1 obtains to pour in another ultrasonic day with fog then, each transducing sheet of regulating it makes and hazes rate stabilization at 4.0ml/min.After fog in two ultrasonic days with fog mixes in the fog blender, take jet hole by flow velocity to for the 30ml/s dry air, jet hole is from the about 20mm of glass basic surface, the substrate of glass temperature is 430 ℃, conveyer belt drives the substrate of glass reciprocating motion, controlling common spray time is 150 seconds, obtain the CNT transparent conductive film of the about 200nm of thickness on the adhesion enhancement layer, and carbon nano tube surface has covered SnO
2Nano particle, the particularly junction between the carbon nano-tube cover has expired this nano particle, grain diameter 20-50nm.The four point probe view records this compound-type conducting pellicular front resistance 230 ± 3 Ω/.(can know that from the explanation of front the effect that increases nano particle is the conductivity that strengthens conducting film, reduces resistance.The face resistance of the conductive film that is generated among the II with the conductive film face resistance mentioned here and front embodiment 6 compares).The visible light mean transmissivity is 86.43%.Fig. 6-C is the visible light transmissivity spectrum of this compound-type conducting film, and Fig. 7 c is the SEM photo of this film.
Above-mentioned 3 kinds of methods have all obtained the compound-type conducting film of the CNT laminate structure of adhesion enhancement layer/band connectivity enhancing nano particle, this kind adhesive force is extremely strong, sticking once with the 3M adhesive tape with deionized water rinsing oven dry back, face resistance does not almost change (＜1%).Its spectral transmittance is also stronger than the film that does not add the connectivity nano particle with the combination property of conductivity.
Embodiment 8
In aforesaid explanation, the multiple implementation that how to prepare carbon nanotube conductive thin film is illustrated, in the present embodiment,, the preparation of carbon nanotube conductive thin film is described in conjunction with a concrete example.
In DSSC (DSC), can do electrode with platinum or carbon.Because material with carbon element particularly carbon nano-tube has good catalytic activity, and low price, be considered to substitute the optimal material of noble metal platinum.Need to prepare the carbon nanotube conductive thin film to electrode in the present embodiment as DSC.
Since as the DSC battery to electrode, so carbon nanotube conductive thin film is not required transmitance.Elder generation's spray pyrolysis one deck adhesion enhancement layer in substrate: with the 19.15% mass ratio NH that mixes of 0.075M
4The SnCl of F
4Ethanolic solution is poured a ultrasonic day with fog into, and controlling each transducing sheet, to make the speed that hazes be 4.0ml/min, air velocity 40ml/s, jet hole is from the about 10mm of glass basic surface, 430 ℃ of base reservoir temperatures, conveyer belt drives the substrate of glass reciprocating motion, and the control spray time is 20min.Utilize similar approach among the embodiment 2 to obtain the CNT solution of 0.2g/200ml, be poured into another ultrasonic day with fog, regulating the ultrasonic transduction sheet makes the rate stabilization that hazes at 3.0ml/min, the flow velocity of dry air is 25ml/s, jet hole is from the about 15mm of glass basic surface, 430 ℃ of base reservoir temperatures, conveyer belt drives the substrate of glass reciprocating motion, the control spray time is 5min, obtain the CNT transparent conductive film of the about 400nm of thickness on the adhesion enhancement layer, form (adhesion enhancement layer/CNT thin layer) double-layer composite conductive film thus.Record this compound-type conducting pellicular front resistance 6 ± 0.1 Ω/ with the four point probe view.Fig. 8 is the SEM photo of this film.One fritter of taking this composite carbon nanotube conductive thin film with the deionized water rinsing oven dry after, sticking once with the 3M adhesive tape, it is about 2.5% that face resistance improves, and SnO is described
2Layer can improve the adhesive force of CNT film and substrate greatly, and SnO
2Layer increases surface roughness with thickness and increases, thereby adhesive force also further increases.Get another fritter as the DSC battery to electrode, DSC cell area 0.15cm
2, under AM1.5 standard sunlight, obtain battery efficiency 5.3%.
It should be noted last that above embodiment is only unrestricted in order to technical scheme of the present invention to be described.Although the present invention is had been described in detail with reference to embodiment, those of ordinary skill in the art is to be understood that, technical scheme of the present invention is made amendment or is equal to replacement, do not break away from the spirit and scope of technical solution of the present invention, it all should be encompassed in the middle of the claim scope of the present invention.
Claims (14)
1. a composite carbon nanotube conductive thin film comprises carbon nanotube layer, it is characterized in that, is also including the adhesion enhancement layer that is used to strengthen adhesive force between described carbon nanotube layer and described substrate of glass between described carbon nanotube layer and the substrate of glass.
2. composite carbon nanotube conductive thin film according to claim 1 is characterized in that, also comprises the N type semiconductor nano particle in the carbon nano tube surface of described carbon nanotube layer.
3. composite carbon nanotube conductive thin film according to claim 1 and 2 is characterized in that, described adhesion enhancement layer adopts the N type semiconductor material of good conductivity.
4. composite carbon nanotube conductive thin film according to claim 3 is characterized in that, described N type semiconductor material comprises SnO
2, TiO
2, ZnO.
5. composite carbon nanotube conductive thin film preparation method comprises:
Step 1), preparation have the carbon nano-tube solution of good dispersion;
Step 2), preparation is used to generate the solution of adhesion enhancement layer;
Step 3), to step 2) solution that obtains does ultrasonic hazing, the fog that is generated sprays to glass basic surface and forms adhesion enhancement layer with pyrolysis;
Step 4), the resulting carbon nano-tube solution of step 1) is done ultrasonic hazing, the fog that is generated sprays to the resulting glass basic surface that has adhesion enhancement layer of step 3) and forms carbon nanotube layer with pyrolysis.
6. composite carbon nanotube conductive thin film preparation method according to claim 5 is characterized in that, in described step 4), also comprises:
To resulting carbon nano-tube solution of step 1) and step 2) resulting solution does ultrasonic hazing respectively, and spray to the resulting glass basic surface that has adhesion enhancement layer of step 3) after resulting two kinds of fogs mix and form the carbon nanotube layer that the band connectivity strengthens nano particle with pyrolysis.
7. according to claim 5 or 6 described composite carbon nanotube conductive thin film preparation methods, it is characterized in that described step 1) comprises:
Step 1-1), pour carbon nano-tube into the phosphomolybdic acid aqueous solution, add thermal agitation 24-48 hour, then with the solution suction filtration that obtains 3 times;
Step 1-2), the moist carbon nano-tube on the filter paper behind the suction filtration is dissolved in the red fuming nitric acid (RFNA), stirring and refluxing 5-24 hour, the solution centrifugal after refluxing is gone the upper strata acid solution, suction filtration is washed to PH ≈ 7.0 then;
Step 1-3), the carbon nano-tube on the filter membrane that obtains is scraped ambient temperature overnight drying in vacuum drying chamber;
Step 1-4), the quality of the dried carbon nano-tube of weighing, the dried carbon nanotube after the weighing is dissolved in the deionized water, with ultrasonic in the cell pulverization machine after the refiner high-speed stirred, obtain dispersed well carbon nano-tube solution.
8. according to claim 5 or 6 described composite carbon nanotube conductive thin film preparation methods, it is characterized in that, in described step 2) in, the described solution that is used to generate adhesion enhancement layer is SnCl
4Solution; Preparation SnCl
4Solution comprises:
LIQUID Sn Cl with 0.009mol-0.045mol
4Pour in the 300ml ethanol,, obtain the SnCl that concentration is 0.03M-0.15M at 70 ℃ of stirring and refluxing 5-10 hours
4Ethanolic solution.
9. according to claim 5 or 6 described composite carbon nanotube conductive thin film preparation methods, it is characterized in that, in described step 2) in, the described solution that is used to generate adhesion enhancement layer is SnCl
4Solution; Preparation SnCl
4Solution comprises:
With the 0.009mol-0.045mol quality is m
1LIQUID Sn Cl
4Pour in the 300ml ethanol, 70 ℃ of stirring and refluxing 5 hours;
With the 0.015mol-0.075mol quality is m
2NH
4F pours the deionized water for stirring 5 hours of 3-5ml into, pours front SnCl then into
4Ethanolic solution stirring and refluxing 5-10 hour keeps mass ratio to be
Reduce to room temperature after the backflow, obtain mixing NH
4The SnCl of F
4Ethanolic solution.
10. according to claim 5 or 6 described composite carbon nanotube conductive thin film preparation methods, it is characterized in that described step 3) comprises:
Step 3-1), to step 2) solution that obtains does ultrasonic hazing, described ultrasonic haze haze speed between 2.5ml/min-4.0ml/min;
Step 3-2), resulting fog is being sprayed to temperature on 400 ℃-450 ℃ substrate of glass under the drive of dry air, described substrate of glass moves reciprocatingly under the drive of conveyer belt, thereby forms adhesion enhancement layer in described glass basic surface pyrolysis.
11. composite carbon nanotube conductive thin film preparation method according to claim 5 is characterized in that, described step 4) comprises:
Step 4-1-1), the resulting carbon nano-tube solution of step 1) is done ultrasonic hazing, described ultrasonic haze haze speed between 2.5ml/min-4.0ml/min;
Step 4-1-2), resulting fog is being sprayed to temperature on 400 ℃-450 ℃ the substrate of glass that has adhesion enhancement layer under the drive of dry air, described substrate of glass moves reciprocatingly under the drive of conveyer belt, thereby forms carbon nanotube layer in described glass basic surface pyrolysis.
12. composite carbon nanotube conductive thin film preparation method according to claim 6 is characterized in that, described step 4) also comprises:
Step 4-2-1), the resulting carbon nano-tube solution of step 1) is done ultrasonic hazing, described ultrasonic haze haze speed between 3.0ml/min-4.0ml/min;
Step 4-2-2), to step 2) solution that obtains does ultrasonic hazing, described ultrasonic haze haze speed between 1.0ml/min-2.0ml/min;
Step 4-2-3), with step 4-2-1) with step 4-2-2) resulting fog mixes mutually, mixed fog is spraying to temperature on 400 ℃-450 ℃ the substrate of glass that has adhesion enhancement layer under the drive of dry air, sprayed 80 seconds-400 seconds, in spraying process, described substrate of glass moves reciprocatingly under the drive of conveyer belt, thereby forms the carbon nanotube layer of band nano particle in described glass basic surface pyrolysis.
13. preparation facilities that is used to realize the composite carbon nanotube conductive thin film preparation method of one of claim 5-12, it is characterized in that, comprise liquid peristaltic pump tube (2), fog blender (3), gas flow rate control valve (4), fog conveyance conduit (5) that is used for ultrasonic ultrasonic the day with fog (1) that hazes, adjustable flow velocity and the spray chamber (8) that comprises nozzle (6), air extractor (7); Wherein,
Described ultrasonic day with fog (1) is connected to described fog blender (3) by the liquid peristaltic pump tube (2) of adjustable flow velocity, described fog blender (3) is connected with the nozzle (6) of described spray chamber (8) by fog conveyance conduit (5), is useful on the gas flow rate control valve (4) that gas flow rate is controlled on described fog conveyance conduit (5).
14. preparation facilities according to claim 13 is characterized in that, described ultrasonic day with fog (1) has two, and they are connected with described fog blender (3) by the liquid peristaltic pump tube (2) of described adjustable flow velocity respectively.
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