CN102001620A - Manufacturing method of carbon nano tube, manufacturing method of carbon nano tube membrane and manufacturing method of electronic equipment - Google Patents

Manufacturing method of carbon nano tube, manufacturing method of carbon nano tube membrane and manufacturing method of electronic equipment Download PDF

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Publication number
CN102001620A
CN102001620A CN2009101716198A CN200910171619A CN102001620A CN 102001620 A CN102001620 A CN 102001620A CN 2009101716198 A CN2009101716198 A CN 2009101716198A CN 200910171619 A CN200910171619 A CN 200910171619A CN 102001620 A CN102001620 A CN 102001620A
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cnt
solution
carbon nano
swcn
sample
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梶浦尚志
李勇明
王家平
孙静
高濂
王焱
张婧
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Sony Corp
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Sony Corp
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Priority to CN2009101716198A priority Critical patent/CN102001620A/en
Priority to JP2010181518A priority patent/JP2011051887A/en
Priority to US12/868,285 priority patent/US20110052479A1/en
Publication of CN102001620A publication Critical patent/CN102001620A/en
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures

Abstract

The invention provides a manufacturing method of a carbon nano tube, a manufacturing method of a carbon nano tube membrane and a manufacturing method of electronic equipment, which can repair the defects generated on the side wall of an acidulated carbon nano tube under a stable condition, and can manufacture the carbon nano tube with good characteristics. The manufacturing methods use uric acid solution or ammonia water to process the carbon nano tube after using refluxing in nitric acid to acidulate the carbon nano tube. The processing temperature is between 25 and 90 DEG C, and the processing time is over 2 days. Before the uric acid solution or the ammonia water is used for processing, thionyl chloride solution and the like are preferentially selected to process the carbon nano tube.

Description

Preparing method for carbon nano-tube, CNT film manufacturing method and electric equipment manufacturing method
Technical field
The present invention relates to preparation method for carbon nano-tube, CNT film manufacturing method and electric equipment manufacturing method, be applicable to the manufacturing of the various electronic equipments that for example use CNT or carbon nano-tube film.
Background technology
CNT particularly SWCN (SWNT) because at electricity, machinery, magnetic and configuration aspects characteristic good, so research and develop energetically.As the SWCN manufacture method, so far, using laser ablation method (non-patent literature 1), arc discharge method (non-patent literature 2), chemical vapor deposition (CVD) method several different methods such as (non-patent literatures 3).Inevitably: the carbon class or the metal impurities of the considerable amount of coexistence in the SWCN of making by these manufacture methods.
In the past, thus in order to remove the impurity acidifying from SWCN, use the chemical oxidation (non-patent literature 4) comprise liquid phase oxidation (acid treatment, backflow etc.) and electrochemical oxidation always.In this acidization, be accompanied by the generation of the defective of chemistry, always on the structure of SWCN, damage (non-patent literature 5).And, when SWCN is applied to the field of nanometer technology, disperses in order to make SWCN, or make the SWCN dissolving, usually carry out ultrasonic wave processing or fierce post processings such as chemical reaction ( non-patent literature 3,6,7).In the process of this post processing, SWCN is further destroyed.
Liu (non-patent literature 8), Wang (non-patent literature 9) etc. have reported and have passed through at ammonia (NH 3Thereby) in handle down the methods that SWCNs are repaired the structure of defective SWCN at 1000 ℃.Utilize after this method processing, by the intensity (I of the spectrometric D bands of a spectrum of Raman (Raman) (band) D) with the intensity (I of G bands of a spectrum G) ratio (I D/ I G) be reduced to below 0.01, the defective of the sidewall of this expression SWCN is repaired.
Technical literature formerly
Non-patent literature:
Non-patent literature 1:A.Thess, R.Lee, P.Nikolaev, H.J.Dai, P.Petit, J.Robert, C.H.Xu, Y.H.Lee, S.G.Kim, A.G.Rinzler, D.T.Colbert, G.E.Scuseria, D.Tomanek, J.E.Fischer and R.E.Smalley, Science, 1996,273,483-487
Non-patent literature 2:S.Iijima, Nature, 1991,354,56-58
Non-patent literature 3:J.L.Bahr, J.P.Yang, D.V.Kosykin, M.J.Bronikowski, R.E.Smalley and J.M.Tour, Journal of the American Chemical Society, 2001,123,6536-6542
Non-patent literature 4:P.X.Hou, C.Liu and H.M.Cheng, Carbon, 2008,46,2003-2025
Non-patent literature 5:J.Zhang, H.L.Zou, Q.Qing, Y.L.Yang, Q.W.Li, Z.F.Liu, X.Y.Guo anf Z.L.Du, Journal of Physical Chemistry B, 2003,107,3712-3718
Non-patent literature 6:D.Tasis, N.Tagmatarchis, A.Bianco and M.Prato, Chemical Reviews, 2006,106,1105-1136
Non-patent literature 7:D.Tasis, N.Tagmatarchis, V.Georgakilas and M.Prato, Chemistry, 2003,9,4000-4008
Non-patent literature 8:Y.Q.Liu, L.Gao, J.Sun, S.Zheng, L.Q.Jiang, Y.Wang, H.Kajiura, Y.M.Li and K.Noda, Carbon, 2007,45,1972-1978
Non-patent literature 9:Y.Wang, L.Gao, J.Sun, Y.Q.Liu, S.Zheng, H.Kajiura, Y.M.Li and K.Noda, Chemical Physics Letters, 2006,432,205-208
Non-patent literature 10:J.Chen, M.A.Hamon, H.Hu, Y. S.Chen, A.M.Rao, P.C.Eklund and R.C.Haddon, Science, 1998,282,95-98
Non-patent literature 11:C.Montalbetti and V.Falque, Tetrahedron, 2005,61,10827-10852
Non-patent literature 12:J.Jang, J.Bae and S.H.Yoon, Journal of Materials Chemistry, 2003,13,676-681
Non-patent literature 13:P.S.Wharlton and D.H.Bohlen, Journal of Organic Chemistry, 1961,26,3615-﹠amp;
Summary of the invention
Yet, thereby by in ammonia, under 1000 ℃, handling the above-mentioned existing methods of SWCN repair-deficiency, owing to the high-temperature process that needs 1000 ℃, so range of application is restricted.And, generate nitrogen and hydrogen because ammonia decomposes, so there is the danger of hydrogen explosion.
Therefore, the problem to be solved in the present invention provides a kind of preparation method for carbon nano-tube, and this method can be in the defective on the sidewall of easily repairing the CNT occur in acidifying under the stable condition, can make the good CNT of characteristic.
The other problems that the present invention will solve provides a kind of CNT film manufacturing method, and this method can use the defective and the good CNT of characteristic that produce on the sidewall of having repaired under the stable condition at the CNT of acidifying to make good carbon nano-tube film.
The other problems that the present invention further will solve provides a kind of electric equipment manufacturing method, and this method can be used the CNT that utilizes above-mentioned manufacture method manufacturing or use the carbon nano-tube film of this CNT manufacturing to make high performance electronic equipment.
In order to address the above problem, the invention provides a kind of preparation method for carbon nano-tube, wherein, comprise the step of using the CNT contain solution with amino compound or WITH AMMONIA TREATMENT acidifying.
And, the invention provides and a kind ofly make the CNT film manufacturing method of carbon nano-tube film with CNT, wherein, this CNT is to contain solution with amino compound or the CNT of WITH AMMONIA TREATMENT acidifying is made by use.
This CNT film manufacturing method comprises that typically the CNT that contains solution with amino compound or WITH AMMONIA TREATMENT acidifying by use makes the step of CNT.
And, the invention provides and a kind ofly use CNT or utilize the carbon nano-tube film of CNT manufacturing to make the electric equipment manufacturing method of electronic equipment, this CNT is to contain the solution with amino compound or the CNT that ammoniacal liquor is handled acidifying is made by use.
Thereby this electric equipment manufacturing method for example comprises the step of using the CNT that contains solution with amino compound or WITH AMMONIA TREATMENT acidifying to make CNT.Perhaps, this electric equipment manufacturing method comprises the step of using CNT to make carbon nano-tube film, and this CNT is to contain the solution with amino compound or the CNT that ammoniacal liquor is handled acidifying is made by use.Perhaps, this electric equipment manufacturing method comprises this two steps.
In the present invention, the CNT of acidifying is meant by refluxing in nitric acid for example and carries out acidated CNT, and the feature of this CNT is to be combined with carboxyl (COOH) on the sidewall of the CNT after the acidifying.CNT is gone up substantially and can be adopted any method synthetic, particularly, for example can adopt the whole bag of tricks such as laser ablation method, arc discharge method, chemical vapor deposition (CVD) method synthetic.Has amino (NH 2) compounds represented ground use such compound, promptly should amino and carboxyl (COOH) reaction replace this carboxyl then hydroxyl (OH).Therefore, the amino with amino compound need dissociate in containing the solution with amino compound easily.As mentioned above, be combined with on the sidewall of the CNT of acidifying-COOH.Therefore, if handle this CNT with containing the solution with amino compound, then the result is this amino and be combined in the carboxyl reaction on the CNT and replace hydroxyl in this carboxyl, makes it become CONH 2In this process, can repair the defective of the sidewall of CNT.Have amino compound and be preferably urea (NH 2CONH 2), but be not restricted to this.Ammoniacal liquor is the ammonia (NH that has dissolved gas 3) the aqueous solution, and contain solution identical effect arranged with amino compound.
Preferably, also further be included in to use and contain before the solution-treated CNT with amino compound, use and contain and the step of the solution-treated CNT of the compound of carboxyl reaction and generation-COCl.If be combined with the CNT of carboxyl with this solution-treated, the carboxyl that then is combined on this CNT becomes-COCl.If with the CNT of being combined with of containing that solution-treated with amino compound obtains like this-COCl, then be combined on this CNT-COCl becomes-CONH 2With the compound of carboxyl reaction generation-COCl be for example to be selected from by thionyl chloride (SOCl 2), oxalyl chloride (COCl) 2, phosphorus trichloride (PCl 3), phosphorous oxychloride (POCl 3) and phosphorus pentachloride (PCl 5) at least a compound in the group formed.
Usually, use that to contain temperature that solution with amino compound handles be more than 25 ℃ and be lower than the temperature of the boiling point of the solvent that contains solution with amino compound.It is more than 25 ℃, below 90 ℃ that use contains temperature that solution with amino compound handles representational, but is not restricted to this.Usually, use that to contain the temperature of handling with the solution of the compound of carboxyl reaction and generations-COCl be more than 25 ℃ and be lower than and contain and the carboxyl reaction temperature of the boiling point of the solvent of the solution of the compound of generation-COCl also.Usually, the temperature of using ammoniacal liquor to handle preferably is set to lower, to suppress the evaporation of ammonia.
CNT is SWCN typically, but also can be multilayer carbon nanotube.Carbon nano-tube film is single-wall carbon nanotube membrane typically, but also can be the multilayer carbon nanotube film.The diameter and the length that constitute the CNT of carbon nano-tube film have no particular limits.
This CNT or carbon nano-tube film can be used to various electronic equipments.As such electronic equipment, can be enumerated as: field emission element, field-effect transistor (FET) (comprising thin film transistor (TFT) (TFT)), single-electronic transistor, molecule sensor, solar cell, photo-electric conversion element, light-emitting component, memory etc.Carbon nano-tube film can be as for example membrane electrode or transparency electrode.
According to the present invention who constitutes as described above, contain solution or ammoniacal liquor by use and handle with amino compound, thereby can repair acidifying the time occur in defective on the sidewall of CNT.Usually, the temperature of this processing is low to moderate below 100 ℃ and carries out not using under the stable condition of strong acid, so, can prevent that CNT is cut off etc.And this processing can be carried out easy and efficiently.And, especially, by contain in use the solution with amino compound handle before, use contain with the sidewall that is combined in CNT on carboxyl reaction and the solution of the compound of generation-COCl handle, utilize reaction to take place easily thereby make, and can realize reducing the temperature of utilizing the processing that contains solution or shorten the time of handling with amino compound with amino compound.
According to the present invention, can be in the defective on the sidewall of easily repairing the CNT occur in acidifying under the stable condition, and can easily make and do not have CNT defective, that characteristic is good.And, use this CNT can easily make the good carbon nano-tube film of characteristic.Further, can use this CNT or carbon nano-tube film to make high performance electronic equipment.
Description of drawings
Fig. 1 is the photo that is used to replace picture, shows in the embodiment 1 corresponding with first embodiment of the present invention the transmission electron microscope image of the SWCN of acidifying by refluxing in nitric acid;
Fig. 2 is the photo that is used to replace picture, shows in the embodiment 1 corresponding with first embodiment of the present invention and uses NH 2CONH 2The transmission electron microscope image of the SWCN after solution is directly handled;
Fig. 3 is the photo that is used to replace picture, shows in the embodiment 2 corresponding with second embodiment of the present invention and uses SOCl 2Use NH after the solution-treated 2CONH 2The transmission electron microscope image of the SWCN after the solution-treated;
Fig. 4 shows and measure acidated SWCN in embodiment 1, the embodiment 2 corresponding with first embodiment of the present invention and second embodiment, uses NH 2CONH 2SWCN after solution is directly handled and use SOCl 2Use NH after the solution-treated 2CONH 2The result's of the Raman spectrum gained of the SWCN after the solution-treated schematic diagram (slightly Line figure);
Fig. 5 shows the schematic diagram of the TG-DTA curve of acidated SWCN in the embodiment 2 corresponding with second embodiment of the present invention;
Fig. 6 shows in the embodiment 2 corresponding with second embodiment of the present invention and uses SOCl 2Use NH after the solution-treated 2CONH 2The schematic diagram of the TG-DTA curve of the SWCN after the solution-treated;
Fig. 7 shows and measure acidated SWCN in embodiment 1, the embodiment 2 corresponding with first embodiment of the present invention and second embodiment, uses NH 2CONH 2SWCN after solution is directly handled and use SOCl 2Use NH after the solution-treated 2CONH 2The result's of the FT-IR collection of illustrative plates gained of the SWCN after the solution-treated schematic diagram;
Fig. 8 shows and measure acidated SWCN in embodiment 1, the embodiment 2 corresponding with first embodiment of the present invention and second embodiment, uses NH 2CONH 2SWCN after solution is directly handled and use SOCl 2Use NH after the solution-treated 2CONH 2The result's of the dispersion concentration gained of the SWCN after the solution-treated schematic diagram; And
Fig. 9 is used for illustrating that the embodiment 1 corresponding with first embodiment of the present invention uses NH 2CONH 2Thereby solution is handled the schematic diagram of the mechanism of the defective of repairing SWCN.
The specific embodiment
Below, describe at the mode that is used to carry out an invention (below be called " embodiment ").In addition, illustrate in the following order and carry out.
1, first embodiment (CNT and manufacture method thereof)
2, second embodiment (CNT and manufacture method thereof)
3, the 3rd embodiment (carbon nano-tube film and manufacture method thereof)
＜1, first embodiment 〉
[CNT and manufacture method thereof]
In the first embodiment, at first according to existing known method synthesizing carbon nanotubes.Particularly, it is synthetic that this CNT can pass through laser ablation method, arc discharge method, CVD method etc., but synthetic method is not restricted to this.
Then, utilize existing known method, the above-mentioned synthetic like that CNT of acidifying.Particularly, this acidifying is passed through for example at nitric acid (HNO 3) in the backflow CNT carry out.In this acidization, the oxidized generation carboxyl of the carbon of the annular arrangement of the sidewall of CNT (COOH), produces defective simultaneously.
Then, use to contain and have amino (NH 2) the solution of compound or the CNT of above-mentioned ground of WITH AMMONIA TREATMENT acidifying.Particularly, for example, this solution or ammoniacal liquor are mixed with CNT.By such processing, be combined in the amino of the compound that is contained in carboxyl on the sidewall of CNT and the solution or the ammonia react in the ammoniacal liquor, and the hydroxyl that is contained in the carboxyl (has been become-CONH by amino the replacement OH) 2And, should-CONH 2Finally from CNT, removed.By this a series of process, the defective of the sidewall of CNT is repaired.The solvent of this solution can be selected from existing known solvent as required.Particularly, for example using, water still is not restricted to this as this solvent.The temperature of this processing can be selected as required, but normally room temperature (for example 25 ℃) is above and be lower than the temperature of boiling point of the solvent of this solution, preferably than the temperature of low 10 ℃ of boiling point～more than 20 ℃.Particularly, the temperature of this processing for example is 25 ℃～90 ℃.This processing time is selected under the temperature conditions of considering processing as required, is generally 1 day～10 days.
Then, as described above, use is contained solution with amino compound or ammoniacal liquor carried out the CNT water handled etc. and clean, carry out centrifugation or isolated by filtration etc., afterwards, make its drying.
So just made CNT as target.
According to first embodiment, the defective that can on the sidewall of repairing easily and almost entirely under the stable condition at the CNT of acidifying, produce.In view of the above, can obtain not having the good CNT of characteristic of defective.This CNT can be used for for example various electronic equipments, can realize high performance electronic equipment in view of the above.
＜2, second embodiment 〉
[CNT and manufacture method thereof]
In second embodiment, at first, similarly carry out the synthetic and acidifying of CNT with first embodiment.
Then, use the as above acidated CNT of solution-treated contain with the compound of carboxyl reaction and generation-COCl.Particularly, for example this solution is mixed with CNT.Handle by this, be combined in carboxyl on the sidewall of CNT (COOH) with solution in the compound reaction that contained, the hydroxyl that is contained in the carboxyl (OH) is replaced generation-COCl by Cl.The solvent of this solution is selected among existing known all kinds of solvents as required.The temperature of this processing is selected as required, but normally room temperature (for example 25 ℃) is above and be lower than the temperature of boiling point of the solvent of this solution, preferably than the temperature of low 10 ℃ of boiling point～more than 20 ℃.Particularly, this treatment temperature for example is 25 ℃～90 ℃, but just enough under the common low temperature.This processing time is selected under the situation of considering treatment temperature as required, is generally 1 day～10 days.
Then, use like this after the solution-treated CNT contain with the compound of carboxyl reaction and generations-COCl, with first embodiment similarly, use solution or this CNT of WITH AMMONIA TREATMENT of containing compound with amino.Handle by this, compound that is combined on the sidewall of CNT-is contained in COCl and the solution or the ammonia react in the ammoniacal liquor, and-Cl that contained among the COCl is by amino replacement generation-CONH 2Like this, contain before the solution or WITH AMMONIA TREATMENT with amino compound in use, use and contain and the solution-treated CNT of the compound of carboxyl reaction and generations-COCl, utilize the reaction that contains solution with amino compound or the ammoniacal liquor generation (non-patent literature 10,11) easily that becomes thereby make.
Then, the same with first embodiment, use is contained solution with amino compound or the CNT water that WITH AMMONIA TREATMENT is crossed etc. clean, carry out centrifugation or isolated by filtration etc., afterwards, make its drying.
So just made CNT as target.
According to second embodiment, except with the same advantage of first embodiment, can also obtain following advantage.Promptly, by containing before the solution or WITH AMMONIA TREATMENT CNT with amino compound in use, use and contain and the solution of the compound of carboxyl reaction and generations-COCl is handled CNT, thereby can realize reducing the temperature of utilizing the processing that contains solution with amino compound or ammoniacal liquor or the time that shortens processing.
[embodiment 1]
Embodiment 1 is the embodiment corresponding with first embodiment.
As SWCN, used the SWCN that utilizes the chemical vapor deposition (CVD) method synthetic.This SWCN obtains from Chengdu organic chemistry research institute of Chinese research institute.This SWCN is with methane (CH 4) for raw material, be catalyst with CoMo, and under 1000 ℃, utilize the CVD method synthetic.
This SWCN is by the nitric acid (HNO at 2.6M 3Thereby) in reflux down at 140 ℃ and to remove impurity in 48 hours, carried out acidifying.
Then, the NH of dissolving 1g in the water of 2ml 2CONH 2, prepared NH 2CONH 2Solution.
Then, with the acidated as described above SWCN of 20mg and this NH 2CONH 2Solution mixes, and in water-bath to its ultrasonic processing 1 minute, afterwards, at this NH 2CONH 2Handle SWCN in the solution.25 ℃～90 ℃ of treatment temperatures, the processing time is more than 2 days.
Then, the mixture that obtains is filtered, the flushing back is dry.
So just made SWCN as target.
The yield of this SWCN is more than 95%.
[embodiment 2]
Embodiment 2 is embodiments corresponding with second embodiment.
As SWCN, used the SWCN that utilizes the CVD method synthetic.This SWCN obtains from Chengdu organic chemistry research institute of Chinese research institute.This SWCN is raw material with methane, is catalyst with CoMo, utilizes the CVD method synthetic under 1000 ℃.
This SWCN is by the nitric acid (HNO at 2.6M 3Thereby) in reflux down at 140 ℃ and to remove impurity in 48 hours, carried out acidifying.
Then, with the SOCl of 20ml 2Mix with the DMF (N, dinethylformamide) of 1ml, prepared SOCl 2Solution.
Then, with 100mg such as the acidated SWCN in above-mentioned ground and this SOCl 2After solution mixes, stirred 24 hours down, make SWCN and SOCl at 25 ℃ 2Solution reaction is (with reference to non-patent literature 10.)。
Then, use THF (oxolane) to clean the mixture of gained, and in a vacuum, make its drying under the room temperature.Like this, obtained on sidewall, being combined with-SWCN of COCl.
Then, the NH of dissolving 1g in the water of 2ml 2CONH 2, prepared NH 2CONH 2Solution.
What then, 20mg is obtained as described above is combined with on sidewall-SWCN and this NH of COCl 2CONH 2Solution mixes, and with its ultrasonic processing 1 minute in water-bath, afterwards, uses this NH 2CONH 2The solution-treated SWCN.25 ℃～90 ℃ of treatment temperatures, the processing time is more than 2 days.
Then, the mixture that obtains is washed, carry out making its drying after centrifugation or the isolated by filtration.
So just made SWCN as target.
The yield of this SWCN is more than 95%.
In order to estimate based on SOCl 2The effect of the pre-treatment of solution has compared and has used SOCl 2After the acidated SWCN of solution-treated, be immersed in 60 ℃ NH in the transparent vessel 2CONH 2In the solution and situation about handling and with 60 ℃ the NH of acidated SWCN direct impregnation in transparent vessel 2CONH 2In the solution and situation about handling.The result is, and utilizes SOCl 2The processing of solution and direct impregnation are at NH 2CONH 2Handle the volume of the SWCN of back acquisition in the solution and compare, utilize SOCl 2Be immersed in NH after the solution-treated again 2CONH 2The volume of handling the SWCN of back acquisition in the solution is 3 times approximately.This is because by utilizing SOCl 2Use NH after the solution-treated 2CONH 2Solution-treated is fully peeled off the tube bank (bandle) of SWCN, has reduced the diameter (non-patent literature 10) of tube bank then.Peeling off of the tube bank of SWCN is considered to make NH 2CONH 2The surface area of the SWCN integral body in the solution increases, consequently, and acidated SWCN and NH 2CONH 2The contact area of solution increases, and reaction speed is accelerated.Using SOCl 2Be impregnated into 90 ℃ NH in the transparent vessel after the acidated SWCN of solution-treated 2CONH 2Under the situation about handling in the solution, SWCN is present in NH 2CONH 2In the integral body of solution.Clearly, using SOCl 2That the acidated SWCN of solution-treated carries out afterwards, use NH 2CONH 2The temperature of the processing of solution is high more, acidated SWCN and NH 2CONH 2The contact area of solution increases, and then reaction speed becomes faster.And, with acidated SWCN direct impregnation at NH 2CONH 2Under the situation about handling in the solution, the color of the supernatant in the transparent vessel (supernatant) becomes buff, and is relative therewith, using SOCl 2After the solution-treated acidated SWCN is immersed in 60 ℃ NH 2CONH 2Under the situation about handling in the solution, the color of the supernatant in the transparent vessel does not change.Its reason is, by using SOCl 2The pre-treatment of solution makes SWCN and NH 2CONH 2Reaction speed between the solution is accelerated, and can prevent the generation of intermediate product.
Then, the result who estimates at the SWCN that embodiment 1,2 is made describes.
Below, the HNO that will pass through at 2.6M 3In refluxed 48 hours down and SWCN after the acidifying just is called " SWCN after the acidifying (SWNT) just " at 140 ℃.And, will carry out the SWCN of the processing of embodiment 1, promptly to HNO at 2.6M 3In carried out use NH at 140 ℃ of acidated SWCNs of mode that refluxed 48 hours down 2CONH 2The processing of solution is called the SWCN that obtains " sample 1 ".And, will carry out the SWCN of the processing of embodiment 2, promptly to HNO at 2.6M 3In at the SWCNs of 140 ℃ of mode acidifyings that refluxed 48 hours down, using SOCl 2Re-use NH after the solution-treated 2CONH 2Solution is handled, and the SWCN that obtains is called " sample 2 ".
The transmission electron microscope (TEM) that in Fig. 1～Fig. 3, shows SWCN, sample 1 and sample 2 after the acidifying just respectively as.According to Fig. 1～Fig. 3, observed impurity (agraphitic carbon, multilayer carbon nanotube, graphite nanoparticles, metal impurities etc.) in the SWCN after acidifying just, relative therewith, in sample 1 and sample 2, almost do not observe impurity.In view of the above, think that the impurity that contained in the SWCN after the acidifying just almost is removed by the processing of embodiment 1,2.And, can know that compare with the SWCN after the acidifying just, the length of the SWCN in sample 1 and the sample 2 does not all almost change.The NH with stable chemical property is used in the processing that this means embodiment 1,2 2CONH 2And carry out under low temperature, stable condition, SWCN is not cut off.
Table 1 shows by X ray energy dispersion spectrum (energy dispersive X-ray spectroscopy) and (EDS) SWCN after the acidifying just, sample 1 and sample 2 is carried out the result of elementary analysis gained.
Table 1
Figure B2009101716198D0000151
According to table 1, just the composition of composition of any one carbon (C) in the SWCN after the acidifying, sample 1 and the sample 2 (mole %) and oxygen (O) (mole %) and be 100 moles of % all, do not detect carbon and oxygen element in addition.This means, be used for the NH of the processing of embodiment 1,2 2CONH 2And SOCl 2All be both not carry out covalent bond also not carry out non-covalent the combination, be not adsorbed on the surface of SWCN with SWCN.These NH 2CONH 2And SOCl 2In the process of filtering, fully cleaned and removed.In SWCN after acidifying just, sample 1 and the sample 2, the composition of carbon is respectively 95.83 moles of %, 98.38 moles of %, 98.70 moles of %.And in the SWCN after acidifying just, sample 1 and the sample 2, the composition of oxygen is respectively 4.17 moles of %, 1.62 moles of %, 1.30 moles of %.At this, oxygen derives from the carboxyl on the sidewall that is combined in the SWCN after the acidifying.The composition that has carried out the oxygen of the sample 1 of processing of embodiment 1,2 and sample 2 is compared with the SWCN after the acidifying just significantly and is reduced, this just means that carboxyl reduces significantly in sample 1 and sample 2, so can know that defective reduces significantly in sample 1 and sample 2.Because the oxygen amount of sample 2 is less than the oxygen amount of sample 1, so expression SOCl 2Has more the effect that reduces the carboxyl on the sidewall that is combined in the SWCN after the acidifying.
Different between the SWCN of resolving SWCN and sample 1, sample 2 after the acidifying have just been carried out raman spectroscopy.Raman spectroscopy is an effective method for the defective that detects SWCN.Specifically, use the Raman spectrum of Reinshaw micro confocal raman spectroscopy meter (Renishaw Micro Raman spectrometer) the record wall carbon nano tube of excitation wavelength 633nm.
The Raman spectrum that obtains as shown in Figure 4.In Fig. 4, curve (a) is the Raman spectrum of the SWCN after the acidifying just, and curve (b) is the Raman spectrum of sample 1, and curve (c) is the Raman spectrum of sample 2.There are two main zones in the typical Raman spectrum of SWCN.They are respectively the corresponding 1330cm of degree with the destruction of turbostratic graphite and conjugated system -1Near D bands of a spectrum (band) and with the tangential corresponding 1590cm of (tangential) carbon-to-carbon (C-C) key stretching vibration -1Near G bands of a spectrum.The intensity I of D bands of a spectrum DIntensity I with the G bands of a spectrum GRatio (I D/ I G) be widely used as the yardstick (non-patent literature 8) of the importing of the skew of sidewall covalent bond or defective.The I of the SWCN after the acidifying just DExistence be owing to utilize as the oxidation of the nitric acid of strong acid and on the sidewall of SWCN, damage has taken place.The I of the SWCN after in addition, just synthetic D/ I GBe 0.03.
Table 2
Sample I D/I G
The SWNT after the acidifying just 0.2719
Sample 1 0.050
Sample 2 0.010
Table 2 shows the I of SWCN, sample 1 and sample 2 after the acidifying just D/ I GValue.
According to table 2, I D/ I GIn the SWCN after acidifying just be 0.2719, relative therewith, in sample 1 and sample 2, reduce significantly, be 0.050 in sample 1, be 0.010 in sample 2.Can think that in view of the above in the sample 1 of the processing of having carried out embodiment 1,2, sample 2, have defective on the SWCN hardly, the defective graphite-structure that exists is almost repaired fully on the SWCN after the acidifying just.And, compare the I of sample 2 with sample 1 D/ I GTo reduce amplitude big, this represents SOCl 2For the defective that helps reparation to have the SWCN of defective is effective.The result of this raman spectroscopy is consistent with the result of above-mentioned elementary analysis.
In embodiment 1, embodiment 2, investigated use NH 2CONH 2The temperature of the processing of the SWCN of solution is to the influence of the reparation of SWCN.For this reason, treatment temperature is changed to 25 ℃, 60 ℃ and 90 ℃, and handles.Processing time all is 8 days.Its result is presented in the table 3.Sample 1 (90 ℃), sample 1 (60 ℃) and sample 1 (25 ℃) are respectively the use NH that carries out under 90 ℃, 60 ℃ and 25 ℃ among the embodiment 1 2CONH 2The sample of the processing of the SWCN of solution.And sample 2 (90 ℃), sample 2 (60 ℃) and sample 2 (25 ℃) are respectively the use NH that carries out under 90 ℃, 60 ℃ and 25 ℃ among the embodiment 2 2CONH 2The sample of the processing of the SWCN of solution.
Table 3
Sample I D/I G
The SWNT after the acidifying just 0.2719
Sample 1 (90 ℃) 0.0567
Sample 1 (60 ℃) 0.1952
Sample 1 (25 ℃) 0.2312
Sample 2 (90 ℃) 0.0100
Sample 2 (60 ℃) 0.0205
Sample 2 (25 ℃) 0.1256
As shown in table 3, under the situation of sample 1, I D/ I GBe 0.2719 in the SWCN after acidifying just, relative therewith, in sample 1 (25 ℃), sample 1 (60 ℃) and sample 1 (90 ℃), reduce significantly, in sample 1 (25 ℃), be 0.2312, in sample 1 (60 ℃) is 0.1952, is 0.0567 in sample 1 (90 ℃).And, under the situation of sample 2, I D/ I GBe 0.2719 in the SWCN after acidifying just, relative therewith, in sample 2 (25 ℃), sample 2 (60 ℃) and sample 2 (90 ℃), reduce significantly, in sample 2 (25 ℃), be 0.1256, in sample 2 (60 ℃) is 0.0205, is 0.0100 in sample 2 (90 ℃).In view of the above as can be known, treatment temperature is high more, and the repairing effect of defective is good more.And,, then can know the I of sample 2 if under the same treatment temperature, compare D/ I GBe far smaller than the I of sample 1 D/ I GThis is because using NH 2CONH 2Use SOCl before the processing of solution 2The processing of solution, thereby the repairing effect of the defective of raising SWCN.Perhaps, using NH 2CONH 2Use SOCl before the processing of solution 2The processing of solution obtains identical I thereby can be implemented as D/ I GBe worth needed use NH 2CONH 2The temperature of the processing of solution reduces significantly.
In embodiment 2, investigated use NH 2CONH 2The time of the processing of the SWCN of solution is to the influence of the reparation of the defective of SWCN.For this reason, will be changed to 2 days the processing time, 4 days, 6 days and 8 days, and handle.Treatment temperature all is 90 ℃.It the results are shown in the table 4.Sample 2 (2 days), sample 2 (4 days), sample 2 (6 days) and sample 2 (8 days) are respectively to carry out using NH among the embodiment 2 in 2 days, 4 days, 6 days and 8 days 2CONH 2The sample of the processing of the SWCN of solution.
Table 4
Sample I D/I G
The SWNT after the acidifying just 0.2719
Sample 2 (2 days) 0.1387
Sample 2 (4 days) 0.0598
Sample 2 (6 days) 0.0194
Sample 2 (8 days) 0.0100
As shown in table 4, I D/ I GBe 0.2719 in the SWCN after acidifying just, relative therewith, in sample 2 (2 days), sample 2 (4 days) and sample 2 (6 days), reduce significantly, in sample 2 (2 days) is 0.1387, in sample 2 (4 days) is 0.0598, in sample 2 (6 days) is 0.0194, almost is reduced to 0 in sample 2 (8 days).In view of the above as can be known, the processing time is long more, and the repairing effect of defective is good more.
Measure the quality that (TG-DTA) estimated the SWCN of SWCN after the acidifying just and sample 2 simultaneously by differential heat-thermogravimetric.Fig. 5 shows the thermogravimetric mensuration (TG) of the SWCN after the acidifying just and the result of differential thermal analysis (DTA).And Fig. 6 shows the TG of sample 2 (90 ℃) and the result of DTA.This TG-DTA is determined under the following condition and carries out.With about 10mg of the sample of gained programming rate heating with 5 ℃/min.With air as environmental gas.Use empty platinum dish (platinum パ Application) in contrast.
According to Fig. 5 and Fig. 6, in the SWCN of acidifying just, ℃ beginning oxidation is relative therewith in temperature T=380, is using SOCl 2In the sample 2 after the solution-treated (90 ℃), T=485 ℃ of beginning oxidation.In view of the above as can be known, by using NH 2CONH 2Use SOCl before the solution-treated 2Solution is handled, and SWCN becomes and is difficult to oxidation.This means that the reparation of the defective of the sidewall of SWCN is more fully carried out in sample 2 (90 ℃).
SWCN, sample 1 and sample 2 after the acidifying have just been estimated by Fourier transform infrared beam split (FT-IR) method.FT-IR is to use FTIR spectrometer (FTIR, Bio-Rad FTS-185) to carry out.Fig. 7 shows the FTIR spectrum of gained.But the intensity of this FTIR spectrum is by standardization, so that can obtain identical I GTable 5 illustrates the vibration frequency (non-patent literature 5,12) at peak of FTIR spectrum of the SWCN of acidifying just.
Table 5
Figure B2009101716198D0000201
Combining the stretching vibration of C=O of hydrogen and the stretching vibration of C=O and derive from carbonyl (C=O) significantly, is owing to utilize the HNO that uses in the acidifying of SWCN 3Chemical oxidation caused.As shown in Figure 7, in sample 1 and sample 2, do not exist and the stretching vibration of C=O that combines hydrogen and the corresponding peak of stretching vibration of C=O, so think and do not have C=O.Like this, owing to do not have the C=O group after the processing of embodiment 1,2, this just means that C=O is by NH in sample 1 and sample 2 2CONH 2Reduction.This result is consistent with the result of EDS analysis and Raman analysis.And,, in sample 1 and sample 2, do not observe other peak according to Fig. 7.The carboxyl that this expression is combined on the SWCN after the acidifying is just removed from SWCN, and expression is not transformed into other organic group.
Use NH in order to estimate 2CONH 2The integrality of the sample 1 after the solution-treated and the SWCN of sample 2, SWCN after the acidifying just, sample 1 and sample 2 are dispersed in neopelex (SDBS) solution of 1 weight %, carrying out 1 hour horn shape (horn) ultrasonic wave handles, afterwards, carry out twice centrifugation (13000 change 30 minutes).By UV-Vis-NIR (ultraviolet-visible-near-infrared) absorbance that is determined at wavelength 550nm, the value of the SWCN after the acidifying just, sample 1 and sample 2 is respectively 0.31,0.12 and 0.10 as can be known.This result is illustrated in and uses NH 2CONH 2In the SWCN after the solution-treated, the concentration of SWCN reduces more than 3 times, in other words, uses NH 2CONH 2The dispersion of the sample 1 after the solution-treated and the SWCN of sample 2 is difficult.Obviously, this is because the minimizing of the defective of the SWCN of sample 1 and sample 2 causes.By in ammonia, handling SWCN down, when having repaired the structure of SWCN, also can confirm dispersed reduction (non-patent literature 8 and 9) with defective at 1000 ℃.The concentration of the SWCN of sample 2 is lower than the concentration of the SWCN of sample 1, in view of the above, can reaffirm and use SOCl 2The pre-treatment of solution helps the minimizing of the defective of SWCN.
As described above, in embodiment 1,2, be created in defective on the acidated SWCN by amino (NH 2) repair.Like this, do not explain as yet, can consider following mechanism though the processing by embodiment 1,2 reduces the mechanism of the defective of SWCN.
Fig. 9 shows using NH 2CONH 2Simple and the high response path of possibility of the reduction of the carboxyl of solution.As everyone knows, carboxylic acid the heating under with NH 2CONH 2Reaction generates acid amides.At acidated SWCN and NH 2CONH 2In the reaction of solution, at first generate SWNT-CONH as intermediate product 2The change color of aforesaid supernatant has been explained in the existence of this acid amides.That is because aromatic amine is painted.Utilize NH 2CONH 2The color of the acidated SWCNs that solution is handled under 90 ℃ is more than using NH 2CONH 2Solution is transparent at 60 ℃ of samples of handling down.Think that this may be because by further reaction, the use NH under higher temperature 2CONH 2SWNT-CONH has been quickened in the processing of solution 2Decomposition.Because this intermediate product does not detect the nitrogen element after flushing and drying, so think unsettled.
SWNT-CONH based on the amino of the SWCN that is used for the organic group desorb and is constructed fully 2Further reduction take place with the form of well-known fertile (Wharton) reaction (non-patent literature 13).That is to say that the ketone group of intermediate by-products is at first by at NH 2CONH 2The amino that generates in the water decomposition process that adds of solution reduces.New intermediate by-products is decomposed, and emits nitrogen (N 2), and generate final SWCN.In this case, SOCl 2Not only activated carboxyl and quicken acid and acid amides between reaction, and can fast reaction speed.
The＜3, the 3rd embodiment 〉
[carbon nano-tube film and manufacture method thereof]
In the 3rd embodiment, use and make carbon nano-tube film by the CNT of first embodiment or the second embodiment manufacturing.
That is to say, in the 3rd embodiment, at first, use CNT omitting the carbon nano-tube film that manufacturing is made of CNT on the illustrated substrate according to existing known method by first embodiment or the second embodiment manufacturing.Particularly, as the method that is used to make carbon nano-tube film, can use drop coating (Drop casting) method, method of spin coating, spray gun (air brushing) method, dip coated (dip casting) method, Langmuir film (Langmuir-Blodgett) method and the filtration method etc. of solvent.
When making carbon nano-tube film, use the CNT dispersion liquid typically, this CNT dispersion liquid uses surfactant so that CNT is separated from each other and fine dispersion in liquid.As surfactant, can use anion surfactant, cationic surfactant, amphoteric surfactant and non-ionic surface active agent etc., wherein, the preferred anionic surfactant.Anion surfactant for example is lauryl sodium sulfate (SDS), neopelex (SDBS), dodecyl sodium sulfate (SDSA) etc.
As the substrate that forms carbon nano-tube film can be various substrates, can select as required.Particularly, as substrate, for example can use glass substrate, quartz base plate, silicon substrate (particularly to form oxide-film (SiO on the surface 2Film) silicon substrate), can use various plastic bases as flexible base, board.For example can use the plastic base that constitutes by PETG, polyethylene, polypropylene, polystyrene, Merlon etc. as plastic base, but be not restricted to this.As transparent plastic substrate, can use the transparent plastic substrate that constitutes by PETG etc.
According to the 3rd embodiment, can use by the good CNT of characteristic of first embodiment or the second embodiment manufacturing and make the good carbon nano-tube film of characteristic.This carbon nano-tube film for example can be used as conducting film or nesa coating.Can make more than square resistance (sneet resistance) value of this conducting film or nesa coating compared with prior art reduces four one-tenth.Membrane electrode or transparency electrode that this conducting film or nesa coating for example can be applied to various electronic equipments can realize high performance electronic equipment in view of the above.
Though more than carried out specific description at embodiments of the present invention and embodiment, the present invention is not limited to above-mentioned embodiment and embodiment, according to technological thought of the present invention various distortion can be arranged.
For example, example just at the most such as cited numerical value, raw material, equipment, technology can use the numerical value different with these, raw material, equipment, technology etc. as required in above-mentioned embodiment and embodiment.

Claims (15)

1. a preparation method for carbon nano-tube is characterized in that, comprising:
Use contains the step of the CNT of solution with amino compound or WITH AMMONIA TREATMENT acidifying.
2. preparation method for carbon nano-tube according to claim 1 is characterized in that, further comprises:
Use described contain solution or the described CNT of WITH AMMONIA TREATMENT with amino compound before, use and contain and the step of the described CNT of solution-treated of the compound of carboxyl reaction and generation-COCl.
3. preparation method for carbon nano-tube according to claim 1 is characterized in that,
Described compound with amino is described amino and carboxyl reaction and the compound that replaces the hydroxyl that contains in the described carboxyl.
4. preparation method for carbon nano-tube according to claim 2 is characterized in that,
Described compound with carboxyl reaction and generation-COCl is to be selected from by SOCl 2, (COCl) 2, PCl 3, POCl 3And PCl 5At least a compound in the group that constitutes.
5. preparation method for carbon nano-tube according to claim 1 is characterized in that,
Use and describedly contain temperature that solution with amino compound handles, and be lower than the described boiling point that contains the solvent of solution with amino compound more than 25 ℃.
6. preparation method for carbon nano-tube according to claim 1 is characterized in that,
The temperature of using the described solution that contains the compound with amino to handle is more than 25 ℃, below 90 ℃.
7. preparation method for carbon nano-tube according to claim 1 is characterized in that,
Described CNT is a SWCN.
8. a CNT film manufacturing method is characterized in that, comprising:
Use CNT to make the step of carbon nano-tube film, described CNT is to contain the solution with amino compound or the CNT that ammoniacal liquor is handled acidifying is made by use.
9. CNT film manufacturing method according to claim 8 is characterized in that, comprising:
Thereby by using the described step that the solution with amino compound or the CNT that ammoniacal liquor is handled described acidifying are made described CNT that contains.
10. CNT film manufacturing method according to claim 9 is characterized in that, further comprises:
Use described contain solution with amino compound or ammoniacal liquor handle described CNT before, use and contain the step of handling described CNT with the solution of the compound of carboxyl reaction and generation-COCl.
11. an electric equipment manufacturing method is characterized in that,
Use CNT or utilize the carbon nano-tube film of described CNT manufacturing to make electronic equipment, described CNT is to contain the solution with amino compound or the CNT that ammoniacal liquor is handled acidifying is made by use.
12. electric equipment manufacturing method according to claim 11 is characterized in that, comprising:
Thereby by using the described step that the solution with amino compound or the CNT that ammoniacal liquor is handled described acidifying are made described CNT that contains.
13. electric equipment manufacturing method according to claim 11 is characterized in that, comprising:
Use CNT to make the step of described carbon nano-tube film, described CNT is describedly to contain the solution with amino compound or the CNT that ammoniacal liquor is handled described acidifying is made by using.
14. electric equipment manufacturing method according to claim 11 is characterized in that, comprising:
Thereby by using the described step that the solution with amino compound or the CNT that ammoniacal liquor is handled described acidifying are made described CNT that contains; And use described CNT to make the step of described carbon nano-tube film.
15. electric equipment manufacturing method according to claim 14 is characterized in that, further comprises:
Use described contain solution or the described CNT of WITH AMMONIA TREATMENT with amino compound before, use and contain and the step of the described CNT of solution-treated of the compound of carboxyl reaction and generation-COCl.
CN2009101716198A 2009-08-31 2009-08-31 Manufacturing method of carbon nano tube, manufacturing method of carbon nano tube membrane and manufacturing method of electronic equipment Pending CN102001620A (en)

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