CN116178886A - Method for depositing semiconductor carbon nano tube film by utilizing light-driven polymer and semiconductor carbon nano tube film - Google Patents
Method for depositing semiconductor carbon nano tube film by utilizing light-driven polymer and semiconductor carbon nano tube film Download PDFInfo
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
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- C08J2361/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
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Abstract
The invention provides a method for depositing a semiconductor carbon nano tube film by utilizing a light-driven polymer, which is characterized in that the semiconductor carbon nano tube is wrapped by the polymer with an azobenzene structure, the semiconductor carbon nano tube is stably and uniformly dispersed under the action of the polymer, and then the deposition of the semiconductor carbon nano tube on a substrate is accelerated under the irradiation of a specific wavelength light source, so that the compact and uniform semiconductor carbon nano tube film is obtained. The method has the advantages of easy operation, loose experimental limiting conditions and high repeatability, greatly improves the density, efficiency and uniformity of carbon nano tube network deposition, and provides guidance for research of other materials and methods.
Description
Technical Field
The invention relates to the technical field of carbon materials, in particular to a method for depositing a semiconductor carbon nano tube network film by utilizing a light-driven polymer and the semiconductor carbon nano tube film.
Background
Among the many new semiconductor materials recommended by the emerging materials working group, carbon nanotubes have received attention and extensive research because of their natural one-dimensional structure and because of their excellent thermal, electrical, magnetic and mechanical properties, being ideal nanoelectronic and optoelectronic materials. According to research, the comprehensive energy efficiency of the carbon nanotube is improved by 5-10 times compared with that of a traditional transistor, the requirement of continuing the moore's law is fully met, and the carbon nanotube is one of the research directions of important substitute materials in the current later moore age.
Through research in more than twenty years, great progress has been made in field effect transistor devices based on carbon nanotube materials. However, if it is desired to further advance the development of carbon-based electronics, such as for use in various applications in life, it is required to be able to form stable and large-scale preparations, particularly carbon nanotube preparations in which a high semiconductor purity of a whole wafer level is to be achieved.
In various carbon nanotube preparation, the preparation of the carbon nanotube network film by using the carbon nanotube solution is the most mature means in the whole carbon nanotube industrial manufacture at the present stage, and the prepared carbon nanotube network film has two requirements: the high density is that 50-60 carbon nanotubes can be obtained at each micrometer scale, so that the high density can provide excellent performance for other devices on the high density; secondly, the uniformity is high, namely the density is required to be almost similar to that of different areas of the film and the areas are randomly oriented, if the densities of the different areas are different more or the carbon nanotubes of the different areas are oriented differently, the performance difference of devices prepared on the different areas is too large, so that the preparation system is unstable and cannot be promoted to industrialization.
At present, the existing carbon nano tube network film deposition technology mainly comprises two methods, namely a direct deposition method, namely, a substrate is directly placed into a carbon nano tube solution for deposition, the carbon nano tube network film prepared by the method is uniformly distributed on the substrate but has lower density, and the method needs to consume a large amount of time, and generally needs to be different from 24 to 48 hours in experiments; the second pulling method is to vertically insert the substrate into the carbon nano tube solution and pull the liquid level at a constant speed, and deposit the carbon nano tube network film on the substrate by utilizing the volatility of the carbon nano tube solution, although the method is faster than the previous direct deposition method, the carbon nano tube network film deposited by the method is not uniformly distributed and is not completely randomly oriented when being deposited on the substrate due to the volatilization of the solution, the action of capillary flow and the action of quadrupoles.
Therefore, there is a need to develop a preparation method capable of obtaining a carbon nanotube film with high density and high uniformity.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for depositing a semiconductor carbon nano tube film by utilizing a light-driven polymer, wherein the semiconductor carbon nano tube is wrapped by the polymer with an azobenzene structure, and the deposition of the semiconductor carbon nano tube on a substrate is accelerated under the irradiation of a light source with a specific wavelength, so that the semiconductor carbon nano tube film with high density and high uniformity is obtained.
A first aspect of the present invention relates to a method for depositing a semiconducting carbon nanotube film using a light driven polymer, comprising the steps of:
placing the polymer and the semiconductor carbon nano tube in a first organic solvent for mixing, so that the polymer is wound on the semiconductor carbon nano tube, and the semiconductor carbon nano tube is uniformly dispersed in the first organic solvent to obtain a first mixed solution; wherein the polymer is a polymer containing an azobenzene structure;
filtering the first mixed solution to obtain a precipitate, and completely dispersing the precipitate in a second organic solvent to obtain a second mixed solution;
uniformly distributing the second mixed solution on the substrate, irradiating by adopting a light source, and inducing the polymer to be adsorbed on the surface of the substrate by illumination so as to deposit the semiconductor carbon nano tube on the substrate and achieve the required density;
and cleaning the substrate deposited with the second mixed solution to obtain the substrate with the semiconductor carbon nano tube film.
As an alternative embodiment, the polymer containing the azobenzene structure is polyfluorene-azo, and the molecular structural formula is shown as formula I;
as an alternative embodiment, the polyfluorene-azo preparation is as follows:
and placing the monomer 9, 9-didodecyl-9H-fluorene-2, 7-dicarboxaldehyde and 4,4' -azo diphenylamine in a third organic solvent to obtain a third mixed solution, adding a dehydrating agent and a catalyst into the third mixed solution, condensing and refluxing, and obtaining the polymer polyfluorene-azo after the reaction is finished.
As an alternative embodiment, the molar ratio of 9, 9-didodecyl-9H-fluorene-2, 7-dicarboxaldehyde to 4,4' -azobis-aniline is 1:1, and the condensing reflux time is 24-48H.
As an alternative embodiment, the dehydrating agent is anhydrous sodium sulfate, the catalyst is p-toluenesulfonic acid, and the third organic solvent is at least one of toluene or chloroform.
As an alternative embodiment, the light source is selected depending on the absorption peak position of the polymer, and the light source with a wavelength close to the absorption peak position of the polymer is selected.
As an alternative embodiment, the distance between the light source and the substrate is 5-10 cm, and the irradiation time is 0.5-1 h.
As an alternative embodiment, the first mixed solution and the second mixed solution are prepared as follows:
placing a polymer and a semiconductor carbon nano tube in a first organic solvent, and performing ultrasonic treatment by using a cell pulverizer to obtain a first mixed solution after ultrasonic treatment; filtering the free polymer in vacuum, and completely dispersing the sediment after the filtering in a second organic solvent by adopting water bath ultrasonic to obtain a second mixed solution.
As an alternative embodiment, the mass ratio of the polymer to the semiconducting carbon nanotubes placed in the first organic solvent is (1:1) - (4:1), and the concentration of the polymer in the first mixed solution is 1-2 mg/mL;
in the second mixed solution, the concentration ratio of the polymer to the semiconductor carbon nano tube is (1:1) - (10:1);
the first organic solvent and the second organic solvent are the same and are at least one of toluene, THF or chloroform.
As an alternative embodiment, the second mixed solution is uniformly distributed on the substrate by dropping the second mixed solution onto the surface of the substrate and covering the entire substrate with a transparent cover sheet; wherein the volume of the second mixed solution dropwise added on the surface of the substrate is more than or equal to 200 mu L/cm 2 。
As an alternative embodiment, the substrate is Si, siO 2 Glass or other flexible substrate.
The second aspect of the invention relates to a semiconductor carbon nanotube film prepared by the method.
According to the technical scheme provided by the invention, the method for depositing the semiconductor carbon nano tube film by utilizing the optical driving polymer is characterized in that the semiconductor carbon nano tube is wrapped by the special polymer, the semiconductor carbon nano tube is stably and uniformly dispersed by the action of the polymer, and then the polymer is induced to be rapidly adsorbed on the surface of the substrate by illumination under the irradiation of the light source with the corresponding wavelength, so that the semiconductor carbon nano tube is uniformly and densely deposited on the surface of the substrate, and the semiconductor carbon nano tube film with high density and high uniformity is obtained, and has the advantages of short preparation time, high efficiency and industrial application prospect.
The method has the advantages of easy operation, loose experimental limiting conditions and high repeatability, greatly improves the deposition density, efficiency and uniformity of the semiconductor carbon nano tube film, and provides guidance for the research of other materials and methods.
Drawings
FIG. 1 is a flow chart of a method of depositing a semiconducting carbon nanotube film using a light driven polymer according to the present invention.
FIG. 2 is a schematic illustration of the deposition of a semiconducting carbon nanotube film using a light driven polymer in a method of the present invention.
FIG. 3 is a schematic illustration of a method for depositing a semiconducting carbon nanotube film using a light-driven polymer according to the present invention.
FIG. 4 is a graph of UV-Vis absorption spectra of 20ug/mL of polymer (PF-N-AB) in toluene.
FIG. 5 is a graph showing UV-Vis absorption spectra of each standard solution of the polymer in example 1 of the present invention.
FIG. 6 is an SEM image of a thin film obtained in example 1 of the present invention.
FIG. 7 is an SEM image (part a) of the film obtained in example 2 of the present invention, and an SEM image (part b) of the film obtained in comparative example 3.
FIG. 8 is an SEM image of a thin film obtained in example 3 of the present invention.
FIG. 9 is an SEM image of a thin film obtained in example 4 of the present invention.
FIG. 10 is an SEM image of a thin film obtained in comparative example 1 of the present invention.
FIG. 11 is an SEM image of a thin film obtained in comparative example 2 of the present invention.
FIG. 12 is a graph showing the relationship between the density of semiconductor carbon nano-meter and the resistance value in the thin films obtained in examples 4 to 10 according to example 1 of the present invention.
Detailed Description
For a better understanding of the technical content of the present invention, specific examples are set forth below, along with the accompanying drawings.
Aspects of the invention are described in this disclosure with reference to the drawings, in which are shown a number of illustrative embodiments. The embodiments of the present disclosure are not necessarily intended to include all aspects of the invention. It should be appreciated that the various concepts and embodiments described above, as well as those described in more detail below, may be implemented in any of a wide variety of ways.
In the semiconductor carbon nano film, the density of the semiconductor carbon nano tube refers to the number of the carbon nano tube on each micrometer scale. The higher the density, the more channels are connected between the source and drain of the device, the better the device performance, and the density of 50-60 carbon nanotubes is generally preferred, because the contact between the carbon nanotubes affects the transmission during conduction, and the excessive contact can cause excessive conduction loss and lower performance.
The high uniformity of the semiconductor carbon nanotubes means that the density is required to be almost similar to that of different areas of the film and the carbon nanotubes are randomly oriented, and if the densities of the different areas are different more or the carbon nanotubes of the different areas are oriented differently, the performance of devices prepared on the different areas is excessively different, so that the preparation system is unstable.
Therefore, in order to obtain the semiconductor carbon nanotube film with high density and high uniformity, the invention provides a method for growing the semiconductor carbon nanotube film structure, which utilizes light to drive polymer to deposit the semiconductor carbon nanotube film, wraps the semiconductor carbon nanotube with polymer with azobenzene structure, ensures that the semiconductor carbon nanotube is stably and uniformly dispersed under the action of the polymer, and then accelerates the deposition of the semiconductor carbon nanotube on a substrate under the irradiation of a light source with specific wavelength to obtain the compact and uniform semiconductor carbon nanotube film.
The semiconductor carbon nano tube network provided by the invention can form a denser network film in an illumination area, enriches the thought of device design based on the semiconductor carbon nano tube film, and provides more choices for device design based on the semiconductor carbon nano tube film.
Referring to fig. 1 and 2, in one embodiment of the present invention, a method for depositing a semiconducting carbon nanotube film using a light-driven polymer is provided, comprising the steps of:
placing the polymer and the semiconductor carbon nano tube in a first organic solvent for mixing, so that the polymer is wound on the semiconductor carbon nano tube, and the semiconductor carbon nano tube is uniformly dispersed in the first organic solvent to obtain a first mixed solution; wherein the polymer is a polymer containing an azobenzene structure;
filtering the first mixed solution to obtain a precipitate, and completely dispersing the precipitate in a second organic solvent to obtain a second mixed solution;
uniformly distributing the second mixed solution on the substrate, irradiating by adopting a light source, and inducing the polymer to be adsorbed on the surface of the substrate by illumination so as to deposit the semiconductor carbon nano tube on the substrate and achieve the required density;
and cleaning the substrate deposited with the second mixed solution to obtain the substrate with the semiconductor carbon nano tube film.
As an alternative embodiment, the polymer containing the azobenzene structure is polyfluorene-azo, and the molecular structural formula is shown as formula I;
as an alternative embodiment, the polyfluorene-azo preparation is as follows:
and placing the monomer 9, 9-didodecyl-9H-fluorene-2, 7-dicarboxaldehyde and 4,4' -azo diphenylamine in a third organic solvent to obtain a third mixed solution, adding a dehydrating agent and a catalyst into the third mixed solution, condensing and refluxing, and obtaining the polymer polyfluorene-azo after the reaction is finished.
As an alternative embodiment, the molar ratio of 9, 9-didodecyl-9H-fluorene-2, 7-dicarboxaldehyde to 4,4' -azobis-aniline is 1:1, and the condensing reflux time is 24-48H.
As an alternative embodiment, the mass of the catalyst is 1% of the total mass of the two monomers; the mass of the dehydrating agent is larger than that of the water-producing substance in the reaction, and in the smaller reaction, generally 10g or less of the dehydrating agent can be satisfied.
The amount of the third organic solvent is at least 10 times the volume of the total mass of the reactants, more than 500g of reaction, and generally at least 5 times the volume of the total mass of the reactants. The third organic solvent may be subjected to a re-evaporation treatment to reduce the moisture in the system.
As an alternative embodiment, the dehydrating agent is anhydrous sodium sulfate, the catalyst is p-toluenesulfonic acid, and the third organic solvent is at least one of toluene or chloroform.
As an alternative embodiment, the light source is selected depending on the absorption peak position of the polymer, and the light source with a wavelength close to the absorption peak position of the polymer is selected.
In an exemplary embodiment, an ultraviolet-visible photometer is used to measure the absorption spectrum of the polymer, obtain the wavelength of the characteristic peak, and select a light source having the characteristic peak wavelength or the surrounding wavelength as the deposition irradiation light source according to the actual situation.
As an alternative embodiment, the distance between the light source and the substrate is 5-10 cm, and the irradiation time is 0.5-1 h.
As an alternative embodiment, the first mixed solution and the second mixed solution are prepared as follows:
placing a polymer and a semiconductor carbon nano tube in a first organic solvent, and performing ultrasonic treatment by using a cell pulverizer to obtain a first mixed solution after ultrasonic treatment; filtering the free polymer in vacuum, and completely dispersing the sediment after the filtering in a second organic solvent by adopting water bath ultrasonic to obtain a second mixed solution.
As an alternative embodiment, the mass ratio of the polymer to the semiconducting carbon nanotubes placed in the first organic solvent is (1:1) - (4:1), and the concentration of the polymer in the first mixed solution is 1-2 mg/mL;
in the second mixed solution, the concentration ratio of the polymer to the semiconductor carbon nano tube is (1:1) - (10:1);
the first organic solvent and the second organic solvent are the same and are at least one of toluene, THF or chloroform.
It should be understood that in the process of preparing the first mixed solution, the mass ratio of the polymer to the semiconductor carbon nanotube is controlled according to the molecular weight of the prepared polymer, the molecular weight of the polymer is large, the addition amount of the polymer is reduced, whereas the molecular weight of the polymer is small, and the addition amount of the polymer is increased.
In one exemplary embodiment, the configuration of the second mixed solution may be performed as follows:
equation (1) is obtained according to a standard curve of absorbance versus concentration of characteristic peaks of carbon nanotubes fitted in literature High-yield and low-cost separation of High-purity semiconducting single-walled carbon nanotubes with closed-loop recycling of raw materials and solvents: y=32.23x (y is the absorbance of the characteristic peak; x is the concentration, mg/mL), measuring the ultraviolet absorption spectrum of the first mixed solution to obtain the absorbance of the characteristic peak of the semiconductor carbon nanotube, and obtaining the concentration C1 of the semiconductor carbon nanotube in the first mixed solution according to equation (1).
The approximate mass M1 of the semiconductor carbon nanotubes in the precipitate is obtained according to C1, and a second mixed solution is prepared according to the expected concentration of the semiconductor carbon nanotubes in the second mixed solution. For example, if the concentration of the semiconducting carbon nanotubes in the second mixed solution is desired to be 30ug/mL, then the volume of the second organic solvent = M1/30.
In another exemplary embodiment, the concentration values of the semiconducting carbon nanotubes and the polymer in the second mixed solution are determined by:
and (3) measuring the ultraviolet absorption spectrum of the second mixed solution to obtain the absorbance of the characteristic peak of the semiconductor carbon nano tube, and obtaining the accurate concentration C2 of the semiconductor carbon nano tube in the second mixed solution again according to the equation (1).
Weighing the synthesized polymer, and preparing a standard solution with a series of concentrations by taking a second organic solvent as a solvent, wherein the concentration of the polymer can be preferably: 3ug/mL,5ug/mL,8ug/mL,10ug/mL,12ug/mL,15ug/mL,18ug/mL,20ug/mL.
Measuring the ultraviolet absorption spectrum of each standard solution to obtain the absorbance of the characteristic peak of the polymer, obtaining an equation (2) by fitting a standard curve of the absorbance and the concentration of the characteristic peak of the polymer, measuring the ultraviolet absorption spectrum of the second mixed solution to obtain the absorbance of the characteristic peak of the polymer, and obtaining the accurate concentration C3 of the polymer in the second mixed solution according to the equation (2).
The density and uniformity of the film can be better regulated and controlled by determining the concentration of the semiconductor carbon nano tube and the polymer in the second mixed solution.
As an alternative embodiment, the mixed solution is uniformly distributed on the substrate by dropping the second mixed solution onto the surface of the substrate and covering the entire substrate with a transparent cover sheet; wherein the volume of the second mixed solution dropwise added on the surface of the substrate is more than or equal to 200 mu L/cm 2 。
The transparent cover plate is a cover plate with good light transmittance, and is made of materials with good light transmittance such as glass, quartz and the like, and the cover plate is adopted to cover the whole substrate, so that the dripped second mixed solution is uniformly distributed on the surface of the substrate.
As an alternative implementation mode, the solution is always kept on the substrate during the deposition process, and the second mixed solution on the substrate is ensured not to dry, so that the deposition density of the carbon nano tubes is ensured to be equal everywhere on the substrate.
As an alternative implementation mode, after the deposition is finished, an organic solvent which has a certain solubility to the polymer but has a non-highest solubility is generally selected, so that not only is the unstable carbon nano tube deposited by cleaning ensured, but also the adsorbed carbon nano tube is prevented from falling off, and the carbon nano tube is more uniform. For example, the substrate may be washed by a light shaking wash using a first organic solvent used in preparing the first mixed solution.
As an alternative embodiment, the substrate is Si, siO 2 Glass or other flexible substrate, such as, for example, a parylene film (parylene C), a polyimide film (PI), a polyethylene terephthalate film (PET), and the like.
The time required for preparation can be greatly reduced by controlling the light intensity, the solution and the concentration of the carbon nanotubes in the solution, and the semiconductor carbon nanotube film with various densities can be prepared by controlling the light intensity, the solution and the concentration of the carbon nanotubes in the solution, so that the preparation can be adjusted according to actual conditions by a person skilled in the art.
Referring to fig. 3, in an exemplary embodiment, a method for depositing a semiconducting carbon nanotube film using an optically driven polymer is provided, comprising the following steps:
(1) Preparation of polyfluorene-azo (PF-N-AB)
The two monomers 9, 9-didodecyl-9H-fluorene-2, 7-dicarboxaldehyde and 4,4' -azo diphenylamine are added into 25-30 mL of toluene according to the ratio of 1:1, a proper amount of dehydrating agents such as anhydrous sodium sulfate and the like and catalysts such as p-toluenesulfonic acid and the like are added, and condensation reflux reaction is carried out for 24-48 hours in a nitrogen atmosphere, so that the polymer PF-N-AB is obtained.
(2) Preparation of the first Mixed solution
Putting the prepared PF-N-AB and the semiconductor carbon nano tube powder into toluene according to the mass ratio of (1:1) - (4:1), putting an ultrasonic probe of a cell grinder into the middle position of the solution to start ultrasonic treatment, obtaining a first mixed solution after ultrasonic treatment is finished, filtering the first mixed solution by using a vacuum filter device, filtering out most of polymers free in the solution by using a vacuum filter device, dispersing the sediment after the suction filtration again by using toluene, obtaining a second mixed solution, measuring the absorbance of the second mixed solution, and obtaining the concentration of the semiconductor carbon nano tube in the second mixed solution according to a standard curve in the prior art.
(3) Light deposition
Two side supports 2 are placed in the container 1 at a distance and height as required, the distance between the supports being dependent on the size of the substrate, the height difference between the supports and the substrate typically being around 0.5mm to provide sufficient space for the solution to fill.
The substrate 3 is placed between the supports, and after a sufficient amount of the second mixed solution is added dropwise to the substrate, a cover slip 4 is placed over the supports to cover the entire substrate and allow the solution to be uniformly distributed over the substrate.
The absorption spectrum of 20ug/mL polymer PF-N-AB was measured by an ultraviolet-visible photometer, and the characteristic peak wavelength was about 400nm, as shown in FIG. 4, and blue light of 455nm was selected as a light-induced light source according to practical conditions.
It should be understood that when measuring the ultraviolet absorption spectrum, the polymer PF-N-AB is dissolved in a soluble solvent to prepare a solution, the concentration is not limited to 20ug/mL, and the prepared concentration only needs to adjust the peak height between 0.8 and 1.2.
And (3) placing the light source at the height of 5-10 cm above the substrate, starting the light source, performing a photoinduction process until the carbon nano tube film with the required density is deposited on the substrate, taking out the substrate, and cleaning the surface of the substrate by toluene, wherein the process ensures that the solution on the substrate is not dried.
In another embodiment of the present invention, a semiconducting carbon nanotube film prepared by the foregoing method is provided, the resulting semiconducting carbon nanotube film having high density and high uniformity, providing superior performance to other devices thereon.
It should be understood that the measurement of all the characteristic peaks described above, the concentration of the measurement solution should be selected and controlled according to the accuracy of the instrument used, and that multiple measurements, as well as dilution measurements, may be performed as necessary to ensure the accuracy of the test.
For better understanding, the present invention will be further described with reference to specific examples, but the preparation method is not limited thereto, and the present invention is not limited thereto.
Example 1
Synthesis
The monomers 9, 9-didodecyl-9H-fluorene-2, 7-dicarboxaldehyde and 4,4 '-azobis-aniline were added in a ratio of 1mmol to 1mmol (1 mmol of 4,4' -azobis-aniline: 212.25mg, and 1mmol of 9, 9-didodecyl-9H-fluorene-2, 7-dicarboxaldehyde: 558.88 mg) to a three-neck flask in which 28mL of a redistilled toluene solution had been placed, 8 molecular sieves and 1g of anhydrous sodium sulfate were added to the solution, 10mg of p-toluene sulfonic acid was further added, nitrogen (N2) was blown in on the left side for 30min, the both ends were sealed after air was extruded out, a condenser tube was placed on the middle bottle, and the solution was heated to 90℃and kept at a temperature for condensation reflux for 24H. The toluene solution was then added dropwise to the methanol solution to obtain the desired PF-N-AB polymer.
[ solution preparation ]
The semiconductor carbon nano tube powder and the synthesized PF-N-AB are mixed according to the following ratio of 20mg:40mg of the mixture was put into 40mL of toluene solution, and the mixture was sonicated with a cell pulverizer at 900 W.times.30% for 30min to obtain a mixed solution A.
And measuring the ultraviolet absorption spectrum of the mixed solution A to obtain the absorbance of the characteristic peak of the semiconductor carbon nano tube as 0.5791, and obtaining the concentration of the semiconductor carbon nano tube in the mixed solution A as 18ug/mL according to the equation (1), wherein the concentration of the semiconductor carbon nano tube in the mixed solution A is 720ug.
If the concentration of the semiconductor carbon nanotubes in the mixed solution B is desired to be 30ug/mL, 24mL of toluene is required for the mixed solution B.
And (3) selecting filter paper with the specification of 0.22um, carrying out vacuum suction filtration on the mixed solution A, removing most of polymers which are dissociated in the mixed solution A, carrying out ultrasonic treatment on the carbon nano tube and the polymers on the filter paper by using a power water bath with the power of 100W, and dissolving the fixed matters which are subjected to ultrasonic treatment in 24mL of toluene to obtain a mixed solution B.
And (3) carrying out UV-Vis measurement on the mixed solution B to obtain the absorbance of the semiconductor carbon nano tube of 0.98, and obtaining the concentration of the carbon nano tube in the mixed solution B of 30.4ug/mL according to the equation (1).
The polymer concentrations were 3ug/mL,5ug/mL,8ug/mL,10ug/mL,12ug/mL,15ug/mL,18ug/mL,20ug/mL of toluene solution as standard solution, and the ultraviolet absorption spectrum of the standard solution was measured, and the results were as shown in FIG. 5, and fitted with a curve to obtain equation (2): y=a+bx, where a= 0.29597 ± 0.06663; b= 0.06364 ± 0.00525; y is the absorbance of the characteristic peak of the polymer; x is concentration, ug/mL.
The ultraviolet absorption spectrum of the mixed solution B was measured, and the solution was diluted 1/10 to a clean toluene solution to measure a characteristic peak value of 0.632, and according to equation (2) (when the absorbance value was between 0.8 and 1.2, a=0.29597, b= 0.06364; if the absorbance was less than 0.8, a= 0.29597 and 0.06663, b=0.0606060664+0.00525; if the absorbance was greater than 1.2, a=0.29597+0.06663, b= 0.06364 and 0.00525), the exact concentration of the measured solution was 5.85ug/mL, the concentration of the polymer in the mixed solution B was about 60ug/mL.
Namely, the mixed solution B is toluene solution of 30ug/mL of carbon nano tube and 60ug/mL of polymer.
[ light deposition ]
SiO with the thickness of 100nm at the size of 1cm x 1cm 2 The glass sheet with the size of 1.7cm x 2cm is covered on the sheet, 200uL of mixed solution B is added into the solution from the side surface, and the solution gradually diffuses to SiO from the side surface 2 On a chip, on SiO 2 And a solution interlayer is formed between the glass sheets.
Blue light with the wavelength of 455nm is turned on to be positioned right above the glass sheet and the distance is 8cm, the power is 80W 15%, and the substrate deposited with the carbon nano tube network film is put into clean toluene solution to be washed by shaking after 1h of illumination.
Example 2
Synthesis
The monomer 9, 9-didodecyl-9H-fluorene-2, 7-dicarboxaldehyde and the monomer 4 '-azobis-aniline were added in a ratio of 1mmol to 1mmol (1 mmol of 4,4' -azobis-aniline is 212.25mg, 1mmol of 9, 9-didodecyl-9H-fluorene-2, 7-dicarboxaldehyde is 558.88 mg) to a three-necked flask in which 28mL of a redistilled toluene solution had been placed, 8 molecular sieves and 1g of anhydrous sodium sulfate were added to the solution, 10mg of p-toluene sulfonic acid was further added, nitrogen (N2) was blown for 30min on the left side, the air was extruded from the right side, the both end necks were sealed, a condenser tube was placed on the middle neck, and the solution was heated to 90℃and kept at a temperature for reflux for 24 hours. The toluene solution was then added dropwise to the methanol solution to obtain the desired PF-N-AB polymer.
[ solution preparation ]
The semiconductor carbon nano tube powder and the synthesized PF-N-AB are mixed according to 20mg:40mg of the mixture was put into 40mL of toluene solution, and the mixture was sonicated with a cell pulverizer at 900 W.times.30% for 30min to obtain a mixed solution A.
The semiconductor carbon nanotubes in the mixed solution A were calculated to be 720ug by the method in example 1.
If the concentration of the semiconductor carbon nanotubes in the mixed solution B is desired to be 5ug/mL, 144mL of toluene is required for the mixed solution B.
And (3) selecting filter paper with the specification of 0.22um, carrying out vacuum suction filtration on the mixed solution A, removing most of polymers which are dissociated in the mixed solution A, carrying out ultrasonic treatment on the carbon nano tube and the polymers on the filter paper by using a power water bath with the power of 100W, and dissolving the fixed solution obtained by ultrasonic treatment in 144mL of toluene to obtain a mixed solution B.
The concentration of carbon nanotubes in the resulting mixed solution B was about 5ug/mL and the concentration of polymer was about 10ug/mL by the method of example 1.
Namely, the mixed solution B is toluene solution of 5ug/mL of carbon nanotube and 10ug/mL of polymer.
[ light deposition ]
SiO with the thickness of 100nm at the size of 1cm x 1cm 2 The glass sheet with the size of 1.7cm x 2cm is covered on the sheet, 200uL of mixed solution B is added into the solution from the side surface, and the solution gradually diffuses to SiO from the side surface 2 On a chip, on SiO 2 And a solution interlayer is formed between the glass sheets. And (3) opening the purchased 455nm blue light to enable the blue light to be positioned right above the glass sheet and have a distance of 8cm and a power of 80W and 15%, and putting the substrate on which the carbon nano tube network film is deposited into a clean toluene solution for shaking and cleaning after illumination for 30min.
Example 3
And (3) synthesis: PF-N-AB polymer was obtained by the synthesis method in example 1.
Preparing a solution: the solution preparation method in example 1 was used to obtain a mixed solution B.
And (3) light deposition: the photodecomposition method in example 1 was employed except that the substrate was changed to Si sheet.
Example 4
And (3) synthesis: PF-N-AB polymer was obtained by the synthesis method in example 1.
Preparing a solution: the solution preparation method in example 1 was used to obtain a mixed solution B.
And (3) light deposition: the photodecomposition method in example 1 was used except that the substrate was changed to a p-xylene film sheet.
Example 5
And (3) synthesis: PF-N-AB polymer was obtained by the synthesis method in example 1.
Preparing a solution: the solution preparation method in example 1 was used to obtain a mixed solution B.
And (3) light deposition: the light deposition method in example 1 was used except that the light time was changed to 15min.
Example 6
And (3) synthesis: PF-N-AB polymer was obtained by the synthesis method in example 1.
Preparing a solution: the solution preparation method in example 1 was used to obtain a mixed solution B.
And (3) light deposition: the light deposition method in example 1 was used except that the light time was changed to 30min.
Example 7
And (3) synthesis: PF-N-AB polymer was obtained by the synthesis method in example 1.
Preparing a solution: the solution preparation method in example 1 was used to obtain a mixed solution B.
And (3) light deposition: the light deposition method in example 1 was used except that the light time was changed to 45min.
Example 8
And (3) synthesis: PF-N-AB polymer was obtained by the synthesis method in example 1.
Preparing a solution: the solution preparation method in example 1 was used to obtain a mixed solution B.
And (3) light deposition: the light deposition method in example 1 was used except that the light time was changed to 75min.
Example 9
And (3) synthesis: PF-N-AB polymer was obtained by the synthesis method in example 1.
Preparing a solution: the solution preparation method in example 1 was used to obtain a mixed solution B.
And (3) light deposition: the light deposition method in example 1 was used except that the light time was changed to 90min.
Example 10
And (3) synthesis: PF-N-AB polymer was obtained by the synthesis method in example 1.
Preparing a solution: the solution preparation method in example 1 was used to obtain a mixed solution B.
And (3) light deposition: the light deposition method in example 1 was used except that the light time was changed to 105min.
Example 11
And (3) synthesis: PF-N-AB polymer was obtained by the synthesis method in example 1.
Preparing a solution: the solution preparation method in example 1 was used to obtain a mixed solution B.
And (3) light deposition: the light deposition method in example 1 was used except that the light time was changed to 120min.
Comparative example 1
[ direct deposition method ]
And (3) synthesis: PF-N-AB polymer was obtained by the synthesis method in example 1.
Preparing a solution: the solution preparation method in example 1 was used to obtain a mixed solution B.
Solution direct deposition: siO with the thickness of 100nm at the size of 1cm x 1cm 2 Put into 1.5mL of the mixed solution B, put for 24 hours, taken out, put into clean toluene solution and shake-clean.
Comparative example 2
[ Czochralski method ]
And (3) synthesis: PF-N-AB polymer was obtained by the synthesis method in example 1.
Preparing a solution: the solution preparation method in example 1 was used to obtain a mixed solution B.
Solution direct deposition: siO with the thickness of 100nm at the size of 2cm x 1cm 2 A vertical placement in 4mL of mixed solution B was clamped using a pulling machine and then pulling was started at a speed of 3um/s until the liquid surface was completely pulled out, and then placed in a clean toluene solution for shaking and washing.
Comparative example 3
[ deposition without illumination ]
And (3) synthesis: PF-N-AB polymer was obtained by the synthesis method in example 2.
Preparing a solution: the solution preparation method in example 2 was used to obtain a mixed solution B.
Solution deposition: siO with the thickness of 100nm at the size of 1cm x 1cm 2 The glass sheet with the size of 1.7cm x 2cm is covered on the sheet, 200uL of mixed solution B is added into the solution from the side surface, and the solution gradually diffuses to SiO from the side surface 2 On a chip, on SiO 2 And a solution interlayer is formed between the glass sheets. And (3) placing the substrate deposited with the carbon nano tube network film into a clean toluene solution for shaking and cleaning after depositing for 30min under the condition of no illumination.
SEM test
SEM tests were performed on the samples of examples 1 to 4 and comparative examples 1 to 3, and the results are shown in fig. 6 to 11.
As can be seen from fig. 6, fig. 7, section a, fig. 8 and fig. 9, the films obtained in examples 1-3 have a large-scale uniformity of 100um in five regions near the middle and periphery of the film, and have no large defects, and the densities of the carbon nanotubes in the 500nm scale are substantially the same, so that the uniformity of the obtained semiconductor carbon nanotube film is very good.
Meanwhile, the thin film of the embodiment 1 has 50 semiconductor carbon nanotubes per micron, and the high density requirement of 50-60 semiconductor carbon nanotubes per micron can be met.
As can be seen from fig. 10, 11 and 7, the semiconductor carbon nanotube film of comparative example 1 obtained by the direct deposition method has a low density; the semiconductor carbon nano tube film obtained by the pulling method in the comparative example 2 has very high density, but the carbon nano tube orientation is different among different areas, and the uniformity is poor; the semiconductor carbon nanotube film obtained by the non-illumination deposition in comparative example 3 has poor density and uniformity.
Therefore, the invention can prove that the semiconductor carbon nano tube film with high density and high uniformity is successfully prepared.
Film Performance test
The resistance of the film at a distance of 1cm was measured using a multimeter, and seven sites were randomly measured.
The thin film carbon nanotubes obtained in examples 1 and 5 to 11 were measured for their resistance values and density, respectively, and the results are shown in the following table
As can be seen from the above table, the films obtained in examples 1, examples 5-11, and the seven measured data for each sample differ less, further illustrate that the films prepared by the method of the present invention have better uniformity, and the average resistance is smaller, and the smaller the resistance, the better the performance, and the excellent the performance of the films obtained by the method of the present invention.
Based on the measured resistance value, a comparison of resistance and density was made, and the result is shown in fig. 12.
As can be seen from the figure, the higher the density, the smaller the resistance value, indicating that the better the conductivity of the film, the more excellent the high-density film performance can be demonstrated from the side.
While the invention has been described with reference to preferred embodiments, it is not intended to be limiting. Those skilled in the art will appreciate that various modifications and adaptations can be made without departing from the spirit and scope of the present invention. Accordingly, the scope of the invention is defined by the appended claims.
Claims (12)
1. A method for depositing a semiconducting carbon nanotube film using a light driven polymer, comprising the steps of:
placing the polymer and the semiconductor carbon nano tube in a first organic solvent for mixing, so that the polymer is wound on the semiconductor carbon nano tube, and the semiconductor carbon nano tube is uniformly dispersed in the first organic solvent to obtain a first mixed solution; wherein the polymer is a polymer containing an azobenzene structure;
filtering the first mixed solution to obtain a precipitate, and completely dispersing the precipitate in a second organic solvent to obtain a second mixed solution;
uniformly distributing the second mixed solution on the substrate, irradiating by adopting a light source, and inducing the polymer to be adsorbed on the surface of the substrate by illumination so as to deposit the semiconductor carbon nano tube on the substrate and achieve the required density;
and cleaning the substrate deposited with the second mixed solution to obtain the substrate with the semiconductor carbon nano tube film.
2. The method for depositing a semiconducting carbon nanotube film using an optically driven polymer according to claim 1, wherein the polymer having an azobenzene structure is polyfluorene-azo, and the molecular structural formula is shown in formula i;
3. the method for depositing a semiconducting carbon nanotube film using an optically driven polymer according to claim 2, wherein the polyfluorene-azo is prepared by the following process:
and placing the monomer 9, 9-didodecyl-9H-fluorene-2, 7-dicarboxaldehyde and 4,4' -azo diphenylamine in a third organic solvent to obtain a third mixed solution, adding a dehydrating agent and a catalyst into the third mixed solution, condensing and refluxing, and obtaining the polymer polyfluorene-azo after the reaction is finished.
4. The method for depositing a semiconducting carbon nanotube film using an optically driven polymer according to claim 3, wherein the molar ratio of 9, 9-didodecyl-9H-fluorene-2, 7-dicarboxaldehyde to 4,4' -azobis-aniline is 1:1, and the time of condensation reflux is 24-48 hours.
5. The method for depositing a semiconducting carbon nanotube film using an optically driven polymer of claim 3 wherein the dehydrating agent is anhydrous sodium sulfate, the catalyst is p-toluene sulfonic acid, and the third organic solvent is at least one of toluene or chloroform.
6. The method of claim 1, wherein the selecting the light source is dependent on the absorption peak of the polymer, and the light source having a wavelength near the absorption peak of the polymer is selected.
7. The method for depositing a semiconducting carbon nanotube film using a light-driven polymer according to claim 1, wherein the light source is spaced from the substrate by a distance of 5-10 cm and the irradiation time is 0.5-1 h.
8. The method for depositing a semiconducting carbon nanotube film using an optically driven polymer according to claim 1, wherein the first and second mixed solutions are prepared by:
placing a polymer and a semiconductor carbon nano tube in a first organic solvent, and performing ultrasonic treatment by using a cell pulverizer to obtain a first mixed solution after ultrasonic treatment; filtering the free polymer in vacuum, and completely dispersing the sediment after the filtering in a second organic solvent by adopting water bath ultrasonic to obtain a second mixed solution.
9. The method for depositing a semiconducting carbon nanotube film using an optically driven polymer according to claim 8, wherein the mass ratio of the polymer to the semiconducting carbon nanotube in the first organic solvent is (1:1) - (4:1) and the concentration of the polymer in the first mixed solution is 1-2 mg/mL;
in the second mixed solution, the concentration ratio of the polymer to the semiconductor carbon nano tube is (1:1) - (10:1);
the first organic solvent and the second organic solvent are the same and are at least one of toluene, THF or chloroform.
10. The method for depositing a semiconducting carbon nanotube film using an optically driven polymer according to claim 1, wherein the second mixed solution is uniformly distributed on the substrate by dropping the second mixed solution onto the surface of the substrate and covering the entire substrate with a transparent cover sheet; wherein the volume of the second mixed solution dropwise added on the surface of the substrate is more than or equal to 200 mu L/cm 2 。
11. The method of depositing semiconducting carbon nanotube film with light driven polymer according to any of claims 1-10 wherein the substrate is Si, siO2, glass or other flexible substrate.
12. A semiconducting carbon nanotube film prepared by the method of any of claims 1-11.
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