CN106409428B - Can self-supporting ultrathin transparent conductive carbon nanotube film and preparation method and application - Google Patents
Can self-supporting ultrathin transparent conductive carbon nanotube film and preparation method and application Download PDFInfo
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Abstract
Can self-supporting ultrathin transparent conductive carbon nanotube film and preparation method and application the invention discloses one kind.The present invention by carbon nano tube dispersion liquid by being transferred to selected solution surface, then removes the selected solution, obtains carbon nano-tube film；And, the carbon nano-tube film is transferred in ink interface and carries out self assembly and forms carbon nano-tube hybridization film.The present invention can self-supporting ultrathin transparent conductive carbon nanotube film combination property it is good, such as its thickness about 20nm~100nm, surface roughness is less than 1.5nm, and light transmittance is more than 86%, and sheet resistance is less than 1500 Ω/m2, while its preparation technology flow is simple and convenient to operate, requires low to environmental factor, and surrounding environment will not be adversely affected, the demand for disclosure satisfy that industrialization large area, producing in enormous quantities.
Description
Technical field
The present invention relates to a kind of carbon nano-tube film material and its preparation technology, more particularly to one kind can self-supporting it is ultra-thin
Bright conductive carbon nanotube film and its environment-friendly preparation method thereof and application, belong to materials science field.
Background technology
Transparent conductive film is as electrode in electronics such as photovoltaic, light emitting diode, flat-panel screens and touch-screens
Had a wide range of applications in field.Conventional transparent conductive film is mainly tin indium oxide (ITO) film at present.But, ITO is thin
Film exist resource shortage, it is expensive, flexible it is poor, bend the outstanding problem such as brittle, its development is restricted, therefore development is newly
Material come replace ITO turn into inexorable trend.Present most promising ITO alternatives include conducting polymer, metal nanometer line and
CNT.Compared with conducting polymer and metal nanometer line, CNT (CNTs) have much higher mechanical strength and
Chemical stability, can produce more stable and robust transparent conductive coating.
Meanwhile, CNTs has excellent and unique optics, electricity and mechanical characteristic.CNTs is axially being passed with high electronics
Ability is led, is then suppressed in radial direction, and does not have obvious characteristic absorption to visible ray and near infrared light, these features make CNTs
Film can have transparent and conductive ability concurrently.In addition, CNTs films are also equipped with good pliability, a certain degree of bending and
Fold influences smaller to its conductive capability, is most to be hopeful to substitute ITO as the ideal material of flexible transparent conductive film.So far
The present, CNTs electrically conducting transparent flexible electrodes have been widely used for light emitting diode (OLED), solar cell, Flied emission and liquid crystal
The fields such as display.
In recent years, the method that people have worked out a variety of continuous CNTs films of synthesis.Wherein, rear sedimentation is domestic and international report
The main method for preparing flexible and transparent conductive CNTs films, but rear deposition process is complicated, obtained CNTs film needs
It is attached on substrate, and is related to chemical modification process, on the immeasurable influence of the presence of the electrical properties of CNTs films.Especially
It is to be difficult to obtain the pure CNTs films of self-supporting, continuous flexible and transparent conductive by rear sedimentation.Therefore, how directly to prepare
Go out the electrically conducting transparent CNTs films of continuous ultra-thin self-supporting, promote its large-scale production and in flexible and transparent electronic device
Extensive use, have become one of significant challenge that this area scientific worker faces.
The content of the invention
In view of the deficiencies in the prior art, it is a primary object of the present invention to provide it is a kind of can self-supporting ultrathin transparent it is conductive
CNTs films and its environment-friendly preparation method thereof and application.
To realize that the one kind provided among aforementioned invention purpose, some embodiments of the invention can self-supporting ultrathin transparent
The preparation method of conductive carbon nanotube film includes：
Carbon nano tube dispersion liquid is transferred to selected solution surface, then removes the selected solution, carbon nano-tube film is obtained；
And, carbon nano-tube film is transferred in ink interface and carries out self assembly and forms carbon nano-tube hybridization film.
And among one more specific embodiment, described preparation method may include steps of：
(1) carbon nano tube dispersion liquid is transferred to selected solution surface, then removes the selected solution, obtain CNT thin
Film；
(2) carbon nano-tube film is transferred in the first ink interface and carries out self assembly and to form carbon nano-tube hybridization thin
Film；
(3) carbon nano-tube hybridization film is transferred in the second ink interface and carries out self assembly and form carbon nano tube hybrid
Film.
More preferred, the preparation method can include：Circulating repetition carry out step (2) and/or step (3) twice with
On, until the ultrathin transparent conductive carbon nanotube film needed for obtaining.
The present invention some embodiments among additionally provide one kind can self-supporting ultrathin transparent conductive carbon nanotube film,
Prepared by particularly a kind of use preceding method can self-supporting ultrathin transparent conductive carbon nanotube film.
It is more typical, it is described can self-supporting ultrathin transparent conductive carbon nanotube film include carbon nano tube network and knot
Together in the electrically conducting transparent macromolecule of carbon nano tube network bottom.
Further, the thickness of the film is 20nm~100nm.
Further, the surface roughness of the film is less than 1.5nm.
Further, the light transmittance of the film is more than 86%.
Further, the sheet resistance of the film is less than 1500 Ω/m2。
Can self-supporting ultrathin transparent conductive carbon nanotube film described in being additionally provided among some embodiments of the present invention
Purposes, for example preparing Optical devices, electronic installation or photoelectron device, particularly preparing the use in flexible optoelectronic sub-device
On the way.
Compared with prior art, advantages of the present invention includes：
(1) this can self-supporting ultrathin transparent conductive carbon nanotube film preparation technology it is simple, without expensive preparing instrument
Device, high temperature action and catalyst, take less, CNTs films can be continuously collected on a large scale；
(2) this can self-supporting ultrathin transparent conductive carbon nanotube film preparation technology controllability it is high, for example, passing through control
The concentration of CNTs dispersion liquids can effectively control the thickness of CNTs films, and by controlling time of repose and oil of the CNTs in ink
The temperature of ink can effectively control the thickness of conducting polymer；
(3) this matting can need to only use second among preparation technology of self-supporting ultrathin transparent conductive carbon nanotube film
Alcohol and water etc., it is possible to decrease the surface contamination of CNTs films, while environment-friendly；
(4) this can self-supporting ultrathin transparent conductive carbon nanotube film there is good intensity, can be formed it is stable from
Supporting construction, while electric conductivity is good, transparency is higher, can be widely used in light, on electrical part, for example, can be used as electrode
Using on touch panel.
In a word, the present invention prepare can self-supporting ultrathin transparent conductive carbon nanotube film combination property it is good, while this
The preparation technology flow of invention is simple and convenient to operate, requires low to environmental factor, and does not have any impact, and disclosure satisfy that work
Industry large area, the demand produced in enormous quantities.
More detailed explanation will hereafter be made to technical scheme.It is understood, however, that in model of the present invention
, can between above-mentioned each technical characteristic of the invention and each technical characteristic specifically described in below (eg embodiment) in enclosing
It is combined with each other, so as to constitute new or preferred technical scheme.As space is limited, no longer tire out one by one herein and state.
Brief description of the drawings
Fig. 1 is a kind of preparation technology flow chart of CNTs films among a typical embodiments of the invention；
Fig. 2 be among a typical embodiments of the invention it is a kind of can self-supporting ultrathin transparent conduction CNTs hybrid films system
6 be the first solution in standby process chart, figure, and 9 be the first ink, and 16 be the second ink；
Fig. 3 is the photo that electrically conducting transparent CNTs films are obtained in the embodiment of the present invention 1；
Fig. 4 is the schematic diagram that obtained CNTs films are transferred to in the embodiment of the present invention 1 interface of ink 1；
Fig. 5 be the embodiment of the present invention 1 obtain can self-supporting ultrathin transparent conduction CNTs hybrid films cross section SEM figure；
Fig. 6 be the embodiment of the present invention 1 obtain can self-supporting ultrathin transparent conduction CNTs hybrid films SEM figure.
Embodiment
As it was previously stated, in view of many deficiencies of prior art, inventor's in-depth study and a large amount of by long-term
Practice, is able to propose technical scheme, as detailed below.
One aspect of the present invention provide one kind can self-supporting ultrathin transparent conductive carbon nanotube film (also referred to as surpass
Thin CNTs hybrid films or ultra-thin CNTs hybrid films etc.), its be it is a kind of can self-supporting nanoscale hybrid film (as follows also referred to as
For hybrid film), comprising：
CNT (CNTs) network,
And, it is distributed in the electrically conducting transparent organic material of CNTs networks bottom, particularly electrically conducting transparent macromolecule.
Further, the thickness of the hybrid film about 20nm~100nm, surface roughness is less than 1.5nm.
Further, the optical transmittance of the hybrid film is more than 86%, and sheet resistance is less than about 1500 Ω/m2。
Further, the hybrid film is 1 comprising mass ratio:10~1:50 CNT and electrically conducting transparent macromolecule.
Another aspect of the present invention provides a kind of method for preparing the hybrid film, and it may include：
Carbon nano tube dispersion liquid is transferred to selected solution surface, then removes the selected solution, carbon nano-tube film is obtained；
And, carbon nano-tube film is transferred in ink interface and carries out self assembly and forms carbon nano-tube hybridization film.
Further, the preparation method can include：
One or more CNTs is provided；
Described one or more CNTs are uniformly dispersed in certain solvent, so as to form carbon nano tube dispersion liquid
(CNTs dispersion liquids).
Wherein it is possible to the CNTs dispersion liquids are formed using any one suitable method known in the art, such as ultrasound,
High-speed stirred etc..
Among some embodiments, it can make CNTs is scattered to form the CNTs dispersion liquids using ultrasonic power, use
The ultrasonic disperse time can be 5h~20h, but not limited to this.
Among some preferred embodiments, the concentration of the CNTs dispersion liquids is 0.005mg/mL~0.2mg/mL.
Wherein, described one or more CNTs can be single wall CNTs, many wall CNTs etc..
More preferred, described one or more CNTs can be treated by chemical functionalization.And it is corresponding
Chemical functionalization method may each be known to industry, for example may be referred to " functionalized carbon nano-tube and its composite
Prepare and studied with catalytic performance " (Harbin Institute of Technology's Doctor of engineering academic dissertation, in June, 2014), " function of CNT
Change research " (natural science is in progress, 2009,19 (2):The document such as 148-156).
More preferred, the group on the CNTs of functionalized processing includes-NH2,-COOH, one kind among-OH etc. or
It is a variety of.
By carrying out foregoing functionalization to CNT, the dissolubility of CNT in a solvent can be effectively lifted
And dispersiveness, beneficial to subsequent machining operations, in addition, the mutual group of function by modification on the carbon nanotubes, can also pass through chemistry
Or the method for physics can also prepare the surface of other functional groups or Material cladding to CNT multi-functional material.
Among some more preferred embodiment, the preparation method can include：
(1) carbon nano tube dispersion liquid is transferred to selected solution surface, then removes the selected solution, obtain CNT thin
Film；
(2) carbon nano-tube film is transferred in the first ink interface and carries out self assembly and to form carbon nano-tube hybridization thin
Film；
(3) carbon nano-tube hybridization film is transferred in the second ink interface and carries out self assembly and form carbon nano tube hybrid
Film.
And among one more specifically embodiment, refering to Fig. 1-Fig. 2, the preparation method can further include：
(1) surface that the CNTs dispersion liquids are transferred to the first solution is injected by peristaltic pump, then passes through wriggling pumping
Go out the first solution to obtain CNTs films；
(2) the CNTs films are carried out in the first ink interface being self-assembly of stable CNTs hybrid films；
(3) CNTs hybrid films are transferred to the progress interface self assembly of the second ink pellet surface and further form CNTs and mix
Film.
Further, described certain solvent can it is any in ethanol, glycerine, ethylene glycol, water or they
Mixture according to different volumes than formation, and not limited to this.
More specifically, abovementioned steps (1) include：First by a certain amount of functionalized carbon nano-tube under certain speed
The surface of certain solvent is expelled to by the method for injection of wriggling, CNT will form one layer of fine and close film；Then, lead to
Peristaltic pump is crossed to extract solvent with certain speed out；Finally, it is (such as common with rigid basement (such as silicon chip) or flexible substrates
Organic group bottom) carbon nano-tube film is taken out.
More preferred, among step (1), the speed of the peristaltic pump injection can be 5mL/min~20mL/min.
More preferred, among step (1), the speed that the peristaltic pump extracts liquid out can be 5mL/min~20mL/
min。
If foregoing peristaltic pump injection or extraction speed are too small, take excessively, if speed is excessive, be easily caused liquid level
Disturbance is excessive and produces the film rupture at film initial stage, or even can not film forming.
Further, first solution can it is any in ethanol, glycerine, ethylene glycol, water or they press
Mixture according to different volumes than formation, and not limited to this.
It is more preferred, first ink include cationic electroconductive polyelectrolyte, for example preferably from quaternary ammonium type sun from
Sub- surfactant and heterocyclic cationic surfactant.
Further, the formula of the quaternary ammonium cation surfactant is [N (R1R2R3)]+X-, R is C in formula10~
C18Chain alkyl, R1、R2、R3Can be first, ethyl, it is possibility to have one is benzyl or chain alkyl, X be chlorine, bromine, iodine or its
His anionic group, such as C12~16Alkyl [(dichlorophenyl) methyl] dimethyl quaternary ammonium hydrochloride, C12-14- alkyl trimethyl quaternary ammonium
Hydrochloride, polyquaternium -2, polyquaternium -6, polyquaternium -7, Polyquaternium-10, polyquaternium -11, Merquat 280,
Polyquaternium -28, polyquaternium -32, polyquaternium -33, polyquaternium -37, polyquaternium -39, polyquaternium -44, poly- season
Ammonium salt -47, but not limited to this.
Further, the heterocyclic cationic surfactant includes containing morpholine ring, pyridine ring, imidazole ring, piperazine
One or more of conducting polymers in ring, quinoline ring, for example：Poly- 2- bases imidazoline, poly- 2- alkylaminoethyls imidazoline
Deng, but not limited to this.
More preferred, the molecular weight of solute is 1000g/mol~50000g/mol in first ink.
Further, the solvent of first ink can appoint in ethanol, glycerine, ethylene glycol, ethyl acetate, water
What a kind of or their different proportions mixture, but not limited to this.
More preferred, the concentration of first ink is 0.5mg/mL~5mg/mL.
More preferred, the CNTs films are 0.5h~2h in the time of the first ink interface self assembly, self assembly
Temperature is 20~60 DEG C.
More preferred, second ink includes anionic electroconductive polyelectrolyte, the poly- electrolysis of such as alkyl carboxylic acid salt form
Matter, alkylbenzenesulfonate polyelectrolyte, alkyl sulfate salt form polyelectrolyte, alkyl phosphate salt form polyelectrolyte, alpha-olefin
Sulfonate polyelectrolyte, alkyl sulfonic acid salt form polyelectrolyte, sulphosuccinates type polyelectrolyte, high fatty acid amide sulfonic acid
Salt form polyelectrolyte and other anionic surfactant types, but not limited to this.
More preferred, the molecular weight of solute is 2000g/mol~50000g/mol in second ink.
Further, the solvent of first ink can appoint in ethanol, glycerine, ethylene glycol, ethyl acetate, water
A kind of what or their mixture, but not limited to this.
More preferred, the concentration of second ink is 1.0mg/mL-8mg/mL.
More preferred, the CNTs hybrid films are 0.5h~4h in the time of the second ink interface self assembly, from group
It is 20~50 DEG C to fill temperature.
Further, circulation step (2) and/or step (3) are also repeated, thus formed can self-supporting, with optics
The CNTs mixed films of transparent and electrical conductivity.More preferred, cycle-index is 5~10 times.
It is more preferred, obtained among the present embodiment can self-supporting ultrathin transparent conductive carbon nanotube film include quality
Than for 1:5:5~1:25:25 CNT, the electrically conducting transparent macromolecule from the first ink and from the second ink
Electrically conducting transparent macromolecule.
Among some more specifically case study on implementation, the preparation method of the hybrid film can include：
(1) a certain amount of CNTs is taken, a certain amount of oxidant is added, 40~60 DEG C of water-bath 4h~7h are centrifuged, dried, obtain
Obtain the CNTs of functionalization；
(2) CNTs of functionalization is subjected to ultrasonic disperse with certain solvent, it is 0.05mg/mL~2mg/mL's to obtain concentration
CNTs dispersion liquids；
(3) speed that step (2) is obtained into CNTs dispersion liquids by peristaltic pump to set slowly is expelled to certain solution
Interface, then solution is extracted out with certain speed by peristaltic pump again, so that it is thin to form uniform, the transparent CNTs of thickness
Film；
(4) it is the first of 1.0mg/mL-8mg/mL to obtain uniform, transparent CNTs films to be transferred to concentration by step (3)
Self assembly in ink interface, stands 10min~2h, the temperature of self-assembly system is 20~60 DEG C；
(5) step (4) is obtained into CNTs hybrid films and is further transferred to the second oil that concentration is 1.0mg/mL-8mg/mL
Self assembly on the interface of ink, stands 10min~2h, the temperature of self-assembly system is 20~50 DEG C；
(6) step (5) is obtained into CNTs hybrid films to stand, dries, repeat step (4) and/or step (5), from
And obtain it is a kind of can self-supporting ultrathin transparent conduction CNTs films.
Among abovementioned steps (5), oxidant can be selected from nitric acid, potassium permanganate, potassium bichromate etc., and not limited to this.
Among abovementioned steps (5), step (4) can be obtained into CNTs hybrid films with certain solvent (for example first
Water, ethanol or its mixture etc.) cleaning, self assembly on the interface of the second ink is transferred to afterwards.
Thickness about 20nm~100nm of the CNTs hybrid films of the present invention, surface roughness is less than 1.5nm, it is seen that light printing opacity
Degree is more than 86%, and sheet resistance is less than 1500 Ω/m2, its combination property is good, meets the requirement of touch-screen, is expected to substitute ITO
Film is used in the research of flexible and transparent electronics and element manufacturing.
Below in conjunction with some embodiments and accompanying drawing the technical solution of the present invention is further explained explanation.
Embodiment 1
1st, 0.2g carboxylated CNTs (is referred into " the p- carbon fiber epoxy resin composite material of functionalized multi-wall carbonnanotubes
The influence of energy ", fiberglass/composite, 2010,1,136-45. " CNT carboxylated and its Electrochemical Properties ",
2013,41 (7):149-157) it is dissolved in (v in 50mL ethanol/water mixed solvents：V=2：1), ultrasonic disperse 10h so that CNTs is equal
It is even to be dispersed in alcohol solvent, form CNTs dispersion liquids；
2nd, 2g DTABs are taken to be dissolved in 300mL ethylene glycol, ultrasonic disperse 2h forms dodecyl three
Methyl bromide ammonium salt solution；
3rd, 4g SSSs are taken to be dissolved in 300mL ethanol, ultrasonic disperse 2h forms styrene sulfonic acid sodium solution；
4th, by 10mL ethanol add surface plate in, then by the CNTs dispersion liquids of 2mL carboxylated by peristaltic pump with 6mL/
Min speed is expelled on ethanol interface, forms the CNTs films of stable transparent；
5th, styrene sulfonic acid sodium solution is heated to 30 DEG C, and step (4) is obtained into CNTs film titanium dioxides silicon chip turn
On the interface for moving to styrene sulfonic acid sodium solution, 30min is stood, CNTs hybrid films are formed；
6th, step (5) is obtained into CNTs hybrid films with pure water and cleans secondary；
7th, DTAB solution is heated to 40 DEG C, and it is thin through step (6) to obtain CNTs hydridization again
Film is transferred on the interface of DTAB with titanium dioxide silicon chip, stands 0.5h；
8th, step (7) is obtained into CNTs hybrid films with ethanol and cleans secondary；
9th, according to the operation of step (5)-step (8), circulate 5 times；
10th, step (9) is obtained into CNTs mixed film silicon chip extractings, is cleaned twice, dried with ethanol and pure water respectively；
11st, the carbon nano tube hybrid film of the drying obtained to step (10) carries out pattern, optical property and conductive capability
Sign, it is as a result as follows：The thickness of the carbon nano tube hybrid film is about 100nm, and conducting polymer is well-proportioned is distributed in
CNTs surface, it is seen that light light transmittance is about 87%, sheet resistance is about 450 Ω/sq.
Embodiment 2
1st, the amidized CNTs of 0.2g (with reference to CN1927706A, CN101177260A etc.) are dissolved in into 40mL ethanol/waters to mix
(v in bonding solvent：V=1：1), ultrasonic disperse 8h so that CNTs is dispersed in alcohol solvent, forms CNTs dispersion liquids；
2nd, 3g polyquaterniums -6 are taken to be dissolved in 300mL ethylene glycol, ultrasonic disperse 2h forms the solution of polyquaternium -6；
3rd, 4g SSSs are taken to be dissolved in 200mL ethanol, ultrasonic disperse 2h forms cetyl phenyl-hydrogen-sulfate sodium molten
Liquid；
4th, by 15mL ethanol add surface plate in, then by the CNTs dispersion liquids of 2mL carboxylated by peristaltic pump with 8mL/
Min speed is expelled on ethanol interface, forms the CNTs films of stable transparent；
5th, the solution of polyquaternium -6 is carried out being heated to 40 DEG C, and the CNTs films are transferred to titanium dioxide silicon chip poly-
On the interface of the solution of quaternary ammonium salt -6,1h is stood, CNTs hybrid films are formed；
6th, the CNTs hybrid films for being obtained step (5) are cleaned 3 times with pure water；
7th, styrene sulfonic acid sodium solution is heated to 50 DEG C, and again turned the CNTs hybrid films with titanium dioxide silicon chip
On the interface for moving to cetyl phenyl-hydrogen-sulfate sodium solution, 1h is stood；
8th, step (7) is obtained into CNTs hybrid films with ethanol and cleans secondary；
9th, according to the operation of step (5)-step (8), circulate 6 times；
10th, step (9) is obtained into CNTs mixed film silicon chip extractings, cleaned 3 times with ethanol and pure water respectively, dried；
11st, the carbon nano tube hybrid film of step (10) resulting dried is subjected to pattern, optical property and conductive capability
Characterize, it is as a result as follows：The thickness of the carbon nano tube hybrid film about 90nm, it is seen that light light transmittance about 89%, sheet resistance about 100
Ω/sq, its result is satisfied with the requirement of touch-screen, is expected to substitute ito thin film for the research of flexible and transparent electronics and device system
In work.
In addition, inventor also utilizes the alternate embodiment such as listed other raw materials and other process conditions above
Various raw materials and corresponding process conditions in 1-2 have carried out corresponding experiment, and obtaining can self-supporting ultrathin transparent conductive carbon nanotube
Pattern, the performance of film etc. are also ideal, substantially similar to embodiment 1-2 products.
It should be noted last that, the above embodiments are merely illustrative of the technical solutions of the present invention and it is unrestricted.Although ginseng
The present invention is described in detail according to embodiment, it will be understood by those within the art that, to the technical side of the present invention
Case is modified or equivalent substitution, and without departure from the spirit and scope of technical solution of the present invention, it all should cover in the present invention
Right among.
Claims (22)
1. it is a kind of can self-supporting ultrathin transparent conductive carbon nanotube film preparation method, it is characterised in that including：
Carbon nano tube dispersion liquid is transferred to selected solution surface, then removes the selected solution, carbon nano-tube film is obtained；
And, carbon nano-tube film is transferred in ink interface and carries out self assembly and forms carbon nano-tube hybridization film；
Wherein, the ink includes cationic electroconductive polyelectrolyte and/or anionic electroconductive polyelectrolyte；The cationic electroconductive
Polyelectrolyte includes quaternary ammonium cation surfactant and/or heterocyclic cationic surfactant, quaternary ammonium type sun from
The formula of sub- surfactant is [N (R1R2R3)]+X-, R is at least selected from C10~C18Chain alkyl, R1、R2、R3At least it is selected from first
Base, ethyl, benzyl or chain alkyl, X include chlorine, bromine, iodine or anion organic group；
Self assembly temperature of the carbon nano-tube film in ink interface is 20~60 DEG C, and the time is 0.5h~4h.
2. preparation method according to claim 1, it is characterised in that comprise the following steps：
(1) carbon nano tube dispersion liquid is transferred to selected solution surface, then removes the selected solution, obtain carbon nano-tube film；
(2) carbon nano-tube film is transferred in the first ink interface and carries out self assembly and form carbon nano-tube hybridization film；
(3) carbon nano-tube hybridization film is transferred in the second ink interface and carries out self assembly and to form carbon nano tube hybrid thin
Film.
3. preparation method according to claim 2, it is characterised in that including：Circulating repetition carries out step (2) and/or step
(3) more than twice, the ultrathin transparent conductive carbon nanotube film needed for obtaining.
4. preparation method according to claim 3, it is characterised in that：Cycle-index is 5~10 times.
5. preparation method according to claim 1 or 2, it is characterised in that including：
The carbon nano tube dispersion liquid is transferred to by selected solution surface using peristaltic pump injection system, and/or, using peristaltic pump
Extraction mode removes the selected solution surface.
6. preparation method according to claim 5, it is characterised in that including：The CNT point is injected using peristaltic pump
The speed of dispersion liquid is 5mL/min~20mL/min, and/or, use and the speed of solution is selected described in peristaltic pump pumps for 5mL/min
~20mL/min.
7. preparation method according to claim 1 or 2, it is characterised in that：
The carbon nano tube dispersion liquid includes solvent and the CNT being dispersed in the solvent；
The CNT includes single-walled carbon nanotube and/or multi-walled carbon nanotube；
And/or, the solvent includes any one or two or more mixtures in ethanol, glycerine, ethylene glycol, water.
8. preparation method according to claim 7, it is characterised in that：The CNT is selected from the carbon nanometer of functionalization
Pipe, functional group therein includes-NH2,-COOH, in-OH any one or it is two or more.
9. preparation method according to claim 7, it is characterised in that：The concentration of the carbon nano tube dispersion liquid is
0.005mg/mL~0.2mg/mL.
10. preparation method according to claim 1 or 2, it is characterised in that：The selected solution include ethanol, glycerine,
Any one in ethylene glycol, water or two or more mixtures.
11. preparation method according to claim 1 or 2, it is characterised in that：The heterocyclic cationic surfactant bag
Include containing any one in morpholine ring, pyridine ring, imidazole ring, piperazine ring, quinoline ring or two or more combinations；
And/or, the anionic electroconductive polyelectrolyte includes the poly- electrolysis of alkyl carboxylic acid salt form polyelectrolyte, alkylbenzenesulfonate
Matter, alkyl sulfate salt form polyelectrolyte, alkyl phosphate salt form polyelectrolyte, alpha-alkene sulfonate polyelectrolyte, alkyl sulphur
It is any in hydrochlorate type polyelectrolyte, sulphosuccinates type polyelectrolyte, high fatty acid amide sulfonate type polyelectrolyte
One or more kinds of combinations.
12. preparation method according to claim 1 or 2, it is characterised in that：The molecular weight 1000g/ of solute in the ink
Mo1~50000g/mol；
And/or, the concentration of the ink is 0.5mg/mL~8mg/mL；
And/or, the solvent of the ink includes any one in ethanol, glycerine, ethylene glycol, ethyl acetate, water or two kinds
Combination above.
13. preparation method according to claim 2, it is characterised in that：The molecular weight of solute is in first ink
1000g/mo1~50000g/mol；
And/or, the molecular weight of solute is 2000g/mo1~50000g/mol in second ink.
14. preparation method according to claim 13, it is characterised in that：The concentration of first ink be 0.5mg/mL~
5mg/mL。
15. preparation method according to claim 13, it is characterised in that：The carbon nano-tube film is in the first ink interface
On self assembly temperature be 20~60 DEG C, the time be 0.5h~2h.
16. preparation method according to claim 13, it is characterised in that：The concentration of second ink is 1.0mg/mL-
8mg/mL。
17. preparation method according to claim 13, it is characterised in that：The carbon nano-tube film is in the second ink interface
On self assembly temperature be 20~50 DEG C, the time be 0.5h~4h.
18. preparation method according to claim 13, it is characterised in that：It is described can self-supporting ultrathin transparent conductive carbon nanotube
Pipe film is 1 comprising mass ratio:5:5~1:25:25 CNT, the electrically conducting transparent macromolecule from the first ink and come
Come from the electrically conducting transparent macromolecule of the second ink.
19. as any one of claim 1-18 method prepare can self-supporting ultrathin transparent conductive carbon nanotube film,
It is characterized in that including carbon nano tube network and being incorporated into the electrically conducting transparent macromolecule of carbon nano tube network bottom.
20. according to claim 19 can self-supporting ultrathin transparent conductive carbon nanotube film, it is characterised in that：
The film is 1 comprising mass ratio:10~1:50 CNT and electrically conducting transparent macromolecule；
And/or, the thickness of the film is 20nm~100nm, and surface roughness is less than 1.5nm, it is seen that light light transmittance is more than
86%, sheet resistance is less than 1500 Ω/m2。
21. a kind of device, it is characterised in that comprising described in claim 19 or 20 can self-supporting ultrathin transparent conductive carbon nanotube
Pipe film, described device includes Optical devices, electronic installation or photoelectron device.
22. device according to claim 21, it is characterised in that：Described device includes flexible optoelectronic sub-device.
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