CN107298436B - Method for obtaining high-purity semiconductor single-walled carbon nanotubes - Google Patents
Method for obtaining high-purity semiconductor single-walled carbon nanotubes Download PDFInfo
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Abstract
The invention discloses a method for obtaining a high-purity semiconductor single-walled carbon nanotube, which comprises the following steps: uniformly mixing the single-walled carbon nanotube and the compound acene micromolecule dispersing agent in a dispersing medium to form a dispersing solution; separating the dispersion solution to form a solid phase portion and a liquid phase portion, and collecting the semiconducting single-walled carbon nanotubes from the liquid phase portion. The invention utilizes the characteristic that the conjugated benzene micromolecule dispersant has excellent selectivity on the semiconductor single-walled carbon nano-tubes (s-SWCNTs), can prepare the high-purity semiconductor single-walled carbon nano-tubes in a large scale through simple operation, and the obtained high-purity semiconductor single-walled carbon nano-tubes can be directly used for preparing high-performance thin film transistors and can also be used as a hole transmission layer in solar cells.
Description
Technical Field
The invention belongs to the technical field of carbon nanotubes, and particularly relates to a method for obtaining a high-purity semiconductor single-walled carbon nanotube by selectively separating a metallic single-walled carbon nanotube from a semiconductor single-walled carbon nanotube.
Background
Semiconducting single-walled carbon nanotubes have gained great attention in the electronics field as one of the most promising one-dimensional semiconducting materials. However, single-walled carbon nanotubes (SWNTs) are inevitably mixed with metallic single-walled carbon nanotubes (m-SWCNTs) and semiconducting single-walled carbon nanotubes (s-SWCNTs) during their synthesis. The mixing of metallic single-walled carbon nanotubes (m-SWCNTs) greatly limits the further research and application of semiconducting single-walled carbon nanotubes (s-SWCNTs) in the fields of molecular electronics and optoelectronics.
Currently, methods for obtaining semiconducting single-walled carbon nanotubes (s-SWCNTs) are mainly divided into two categories, namely: direct growth method and post-treatment separation method. The post-treatment separation method has the advantages of easiness in realization of large-scale preparation, high purity of the semiconductor single-walled carbon nanotubes (s-SWCNTs), strong repeatability and the like.
The method for obtaining semiconducting single-walled carbon nanotubes (s-SWCNTs) by post-treatment separation mainly comprises the following steps: density gradient centrifugation, column chromatography, aqueous two-phase separation, and conjugate molecule separation. The conjugated molecule separation method has the characteristics of simple process, high purity of the semiconductor single-walled carbon nanotubes (s-SWCNTs), large-scale preparation and the like. However, most of the selected conjugated molecules in the prior art are conjugated polymers, and no reports are found in the current scheme for separating high-purity semiconducting single-walled carbon nanotubes by using small molecules.
disclosure of Invention
the invention mainly aims to provide a method for obtaining high-purity semiconductor single-walled carbon nanotubes, so as to overcome the defects in the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the method for obtaining the high-purity semiconductor single-walled carbon nanotube provided by the embodiment of the invention comprises the following steps:
Uniformly mixing the single-walled carbon nanotube and the compound acene micromolecule dispersing agent in a dispersing medium to form a dispersing solution;
Separating the dispersion solution to form a solid phase portion and a liquid phase portion, and collecting the semiconducting single-walled carbon nanotubes from the liquid phase portion.
wherein the single-walled carbon nanotubes comprise mixed metallic single-walled carbon nanotubes and semiconducting single-walled carbon nanotubes.
The embodiment of the invention also provides application of the conjugated benzene micromolecule dispersing agent as a selective separating agent of the metallic single-walled carbon nanotube and the semiconductor single-walled carbon nanotube.
Compared with the prior art, the invention has the advantages that: the method has the advantages that the conjugated benzene micromolecule dispersing agent has excellent selectivity on the semiconductor single-walled carbon nanotubes (s-SWCNTs), and the high-purity semiconductor single-walled carbon nanotubes can be prepared in a large scale through simple operation, can be directly used for preparing high-performance thin film transistors, and can also be used as a hole transport layer in a solar cell.
Drawings
Fig. 1 is a flow chart of a process for separating high purity semiconducting single-walled carbon nanotubes according to one embodiment of the present invention.
FIG. 2a is a diagram of the UV-VIS absorption spectrum of the polyacene small-molecule dispersant in one embodiment of the present invention.
Fig. 2b is an ultraviolet-visible light absorption spectrum of the single-walled carbon nanotube after the selective dispersion of the small rylene molecules in accordance with one embodiment of the present invention.
FIG. 2c shows Raman spectra (RBM peak) at 633nm excitation wavelength of the original single-walled carbon nanotube and the single-walled carbon nanotube after selective dispersion of different small molecules of the conjugated benzenes in one embodiment of the present invention.
FIG. 2d shows Raman spectra (G peak) at 633nm excitation wavelength of the original single-walled carbon nanotube and the single-walled carbon nanotube after different selectively dispersed complex acene small molecules according to one embodiment of the present invention.
FIG. 3a is an AFM image of single-walled carbon nanotubes after selective dispersion of small rylene molecules in accordance with one embodiment of the present invention.
FIG. 3b is a graph showing the height phase of carbon nanotubes on an AFM after selective dispersion of small molecules of polyacenes in accordance with one embodiment of the present invention.
FIG. 4a is an AFM image of single-walled carbon nanotubes after selective dispersion of small polybenzene molecules in accordance with an embodiment of the present invention before illumination.
FIG. 4b is an AFM image of single-walled carbon nanotubes after selective dispersion of small rylene molecules in accordance with one embodiment of the present invention.
FIG. 4c is a diagram showing the height phase of single-walled carbon nanotubes after selective dispersion of small rylene molecules before and after illumination.
FIG. 5a is an AFM image of acid-washed single-walled carbon nanotubes after selective dispersion of small polyacene molecules in accordance with one embodiment of the present invention.
FIG. 5b is a diagram showing the height phase of single-walled carbon nanotubes on AFM after acid washing after selective dispersion of small polybenzene molecules in accordance with one embodiment of the present invention.
FIG. 6a is an AFM image of single-walled carbon nanotubes after gas etching after selective dispersion of small molecules of polyacenes in accordance with one embodiment of the present invention.
FIG. 6b is a diagram showing the height phase of the carbon nanotubes on the AFM after gas etching after the selective dispersion of the small polyacene molecules in the embodiment of the present invention.
Detailed Description
The present invention will be described in detail below with reference to specific embodiments shown in the drawings. These embodiments are not intended to limit the present invention, and structural, methodological, or functional changes made by those skilled in the art according to these embodiments are included in the scope of the present invention.
One aspect of an embodiment of the present invention provides a method for obtaining high purity semiconducting single-walled carbon nanotubes, comprising:
Uniformly mixing the single-walled carbon nanotube and the compound acene micromolecule dispersing agent in a dispersing medium to form a dispersing solution;
Separating the dispersion solution to form a solid phase portion and a liquid phase portion, and collecting the semiconducting single-walled carbon nanotubes from the liquid phase portion. The semiconducting single-walled carbon nanotubes are characterized by absorption spectrum and Raman spectrum, and the semiconducting purity is confirmed to be more than 99.9%.
Wherein the single-walled carbon nanotubes comprise mixed metallic single-walled carbon nanotubes and semiconducting single-walled carbon nanotubes.
More preferably, the polyacene small molecule dispersant may have at least a structure represented by any one of the following formulas A, B, C, D:
Wherein R is at least selected from any one of hydrogen atoms or straight chain, branched chain or cyclic alkyl chains with 1-20 carbon atoms, and the substitution position of R on the benzene ring in the formula B comprises para position, meta position or ortho position.
Further, the dispersion medium may preferably be an organic solvent, and for example, any one or a combination of two or more of toluene, xylene, chloroform, methylene chloride, cyclohexane, Nitrogen Methyl Pyrrolidone (NMP), and tetrahydrofuran may be used without being limited thereto.
Further, in the method for obtaining the high-purity semiconducting single-walled carbon nanotube, at least one of the modes of ultrasound, oscillation, stirring, ball milling and the like can be selected to uniformly mix the single-walled carbon nanotube and the polyacene small-molecule dispersant in the dispersion medium to form the dispersion solution.
For example, in some embodiments of the present invention, the dispersing solution may be formed by uniformly mixing the single-walled carbon nanotubes and the polyacene small-molecule dispersant in a dispersing medium through ultrasonic treatment, wherein the ultrasonic power is preferably 5W to 100W, and the ultrasonic time is preferably 2h to 10 h.
Further, the mass ratio of the complex rylene micromolecule dispersant to the single-walled carbon nanotube can be preferably 1: 0.5 to 2.
furthermore, the concentration of the compound rylene small molecular dispersing agent in the dispersing medium can be preferably 0.5-2 mg/ml.
in some embodiments of the present invention, the dispersion solution may be separated into a solid phase portion (or "precipitate") and a liquid phase portion (or "supernatant") by subjecting the dispersion solution to centrifugation at a rotation speed of preferably 10000g to 200000g for a time of preferably 10 minutes to 10 hours. Wherein the metallic single-walled carbon nanotubes are enriched in the solid phase portion.
Further, the liquid phase fraction comprises enriched semiconducting single-walled carbon nanotubes incorporating the polyacene small molecule dispersants.
Furthermore, the conjugated benzene micromolecule dispersing agent is coated on the surface of the semiconductor single-walled carbon nanotube.
In some embodiments of the present invention, the semiconducting single-walled carbon nanotubes with the surface bound with the conjugated small-molecule benzene dispersant can be obtained by subjecting the liquid phase part to microfiltration (with a pore size of about 0.1 μm) or centrifugation at 20000g for 0.5 h. Specifically, in these embodiments, semiconducting single-walled carbon nanotubes (s-SWCNTs) coated with a small molecular dispersant of a conjugated benzene series can be deposited to facilitate collection by subjecting the aforementioned liquid phase fraction (supernatant) to filtration or re-centrifugation.
Furthermore, the pore size of the filter membrane used for filtering the liquid phase part can be 0.1-0.3 μm, preferably about 0.2 μm.
In some preferred embodiments of the present invention, high purity semiconducting single-walled carbon nanotubes can also be obtained by removing the polyacene small molecule dispersant associated with the semiconducting single-walled carbon nanotubes.
for example, in some embodiments of the present invention, the polyacene small molecule dispersant bound to the semiconductor single-walled carbon nanotube can be removed by cracking the polyacene small molecule dispersant by at least one of acid washing (for example, soaking in 5% to 20% trifluoroacetic acid or hydrochloric acid for about 10 minutes), gas etching (treatment under argon protection at 50 to 700 ℃ for 20 to 120 minutes), or light irradiation (irradiation under light source 20W at 350nm to 450nm for 10 to 30 minutes).
Further, the acid used in the acid washing may be selected from protonic acids such as trifluoroacetic acid, hydrochloric acid, sulfuric acid, and nitric acid, but is not limited thereto.
Furthermore, the gas etching mode can adopt a hydrogen plasma etching mode and the like, the etching power is preferably 100-500W, the gas flow is preferably 100-500 sccm, and the etching time is preferably 3-5 min.
Further, the light irradiation mode can be realized by irradiating the semiconducting single-walled carbon nanotube bonded with the double-acene small-molecule dispersant with a light source having a wavelength of 450nm or less, preferably 350 to 400 nm.
Wherein, if acid washing or lighting is adopted, the acid substance can be directly added into the liquid phase part or the light source with the wavelength directly irradiates the liquid phase part, so that the cracking of the conjugated benzene micromolecule dispersant can be realized, the semiconductor single-walled carbon nano-tube with clean surface is obtained, and then the liquid phase part is processed by the filtering or re-centrifuging way, so that the semiconductor single-walled carbon nano-tube with high purity can be obtained.
Of course, the semiconductive single-walled carbon nanotubes to which the polyacene small-molecule dispersants have been bound may be separated from the liquid phase by filtration, centrifugation, or the like, and then subjected to the acid washing, gas etching, or light irradiation treatment.
By the method, a large amount of high-purity semiconductor single-walled carbon nanotubes (s-SWCNTs) with uniform diameter distribution can be obtained.
another aspect of embodiments of the invention provides the use of a polyacene small molecule dispersant as a selective separating agent for metallic single-walled carbon nanotubes and semiconducting single-walled carbon nanotubes.
Further, the polyacene small molecule dispersant may have at least a structure represented by any one of the following formulas A, B, C, D:
Wherein R is at least selected from any one of hydrogen atoms or straight chain, branched chain or cyclic alkyl chains with 1-20 carbon atoms, and the substitution position of R on the benzene ring in the formula B comprises para position, meta position or ortho position.
referring to fig. 1, a method for obtaining high purity semiconducting single-walled carbon nanotubes according to an exemplary embodiment of the present invention may include the steps of:
S1, dispersing the single-walled carbon nanotubes mixed with metallic single-walled carbon nanotubes (m-SWCNTs) and semiconductor single-walled carbon nanotubes (S-SWCNTs) and the small-molecule double-acene dispersing agent in an organic solvent to prepare a dispersion solution.
The molecular structure and the like of the polyacene small-molecule dispersant can be as described above, and the description thereof is not repeated here.
Wherein the raw material of the single-walled carbon nanotube can be prepared or purchased by a method known in the industry. For example, the single-walled carbon nanotubes may be synthesized by the HiPCO method, the CoMocat method, the ACCVD method, the arc discharge method, the laser ablation method, or the like.
in the step S1, the single-walled carbon nanotubes and the double acene small molecule dispersants, which are mixed with the metallic single-walled carbon nanotubes (m-SWCNTs) and the semiconducting single-walled carbon nanotubes (S-SWCNTs), may be added to an organic solvent, and subjected to ultrasonic treatment, so that the carbon nanotubes and the double acene small molecule dispersants, which are mixed with the metallic single-walled carbon nanotubes (m-SWCNTs) and the semiconducting single-walled carbon nanotubes (S-SWCNTs), are uniformly dispersed in the organic solvent, the ultrasonic treatment time is 2 to 10 hours, and the ultrasonic power is set between 5W and 100W. In particular, the mass ratio of the double acene small molecule dispersant to the single-walled carbon nanotubes mixed with metallic single-walled carbon nanotubes (m-SWCNTs) and semiconducting single-walled carbon nanotubes (s-SWCNTs) is 1: 0.5-2, and the concentration of the polyacene micromolecule dispersant in the organic solvent is 0.5-2 mg/ml.
S2, centrifuging the dispersion solution, and collecting the supernatant to obtain the semiconductor single-walled carbon nanotubes (S-SWCNTs) coated with the small molecular dispersant of the conjugated benzenes. The time of the centrifugal treatment is 2-10 hours, and the centrifugal rotating speed is set between 10000g-100000 g. The supernatant obtained after centrifugation contained a large amount of semiconducting single-walled carbon nanotubes (s-SWCNTs).
Referring to FIG. 2a, which is a graph showing the UV-visible absorption spectra of some of the small rylene molecules (4HP-C6, 4HP-C8) according to an exemplary embodiment of the present invention, it can be seen that the small rylene molecules have significant absorption in the yellow region, and thus exhibit a purple-red color.
Wherein the 4HP-C6 has the English name of 1,2,5,6-Tetra (5-hexylthiophen-2-yl) -Hexaazapentacene and the Chinese name of 1,2,5,6-Tetra (5-hexylthiophen-2-yl) -Hexaazapentacene, and the structural formula is as follows:
wherein the 4HP-C8 has the English name of 1,2,5,6-Tetra (5-octylthiopene-2-yl) -Hexaazapentacene and the Chinese name of 1,2,5,6-Tetra (5-octylthiophene-2-yl) -Hexaazapentacene, and the structural formula is as follows:
FIG. 2b is a diagram showing the UV/VIS absorption spectrum of the single-walled carbon nanotube after the selective dispersion of the small polyacene molecules (4HP-C6, 4-HP C8), wherein the peak of 600-.
Referring to fig. 2C, it is shown that the original single-walled carbon nanotube without separation and the single-walled carbon nanotube after selective dispersion by different polyacene small molecules (4-HP C6, 4-HP C8) have raman spectra (RBM peak) at 633nm excitation wavelength, and compared with the original single-walled carbon nanotube without separation, the single-walled carbon nanotube after selective separation by the multiple acencene small molecules has concentrated tube diameter distribution around 1.5 nm.
Referring to fig. 2d, it is shown that the raman spectra (G peak) of the original single-walled carbon nanotube and the single-walled carbon nanotube after selective dispersion of different complex rylene small molecules are obtained at 633nm excitation wavelength, and the presence of the metallic single-walled carbon nanotube results in a broad peak in the 1570-1590cm-1 region near the G peak when the original single-walled carbon nanotube is compared with the G peak of the single-walled carbon nanotube after separation, and it can be seen from the figure that the metallic broad peak at 1570-1590cm-1 of the single-walled carbon nanotube after selective separation of the complex rylene small molecules disappears, which indicates that the semiconductor single-walled carbon nanotube with high purity is obtained after selective separation and purification of the complex rylene small molecules.
S3, removing the polyacene micromolecule dispersant coated on the surface of the semiconductor single-walled carbon nanotubes (S-SWCNTs) to obtain the high-purity semiconductor single-walled carbon nanotubes (S-SWCNTs). The double-acene small molecule dispersant can be cracked by acid washing or gas etching or illumination, so that the semiconductor single-walled carbon nano-tube (s-SWCNTs) with clean surface can be obtained.
Referring to fig. 3a and 3b, in an embodiment of the present invention, the diameter of the single-walled carbon nanotube coated with small molecules of a compound benzene is about 2nm, and after the dispersant is cracked by an acid washing or gas etching or light irradiation method, the diameter of the obtained semiconductor single-walled carbon nanotube (s-SWCNTs) with a clean surface is about 1.5 to 1.6 nm.
Specifically, the supernatant obtained in step S2 contains a large number of semiconducting single-walled carbon nanotubes (S-SWCNTs) whose surfaces are coated with a small molecular dispersant of a conjugated benzene series. Wherein:
If the dispersing agent is removed by adopting an illumination method, a light source with the wavelength of 350-450 nm can be used for directly irradiating the supernatant, so that the compound acene micromolecule dispersing agent is cracked. Referring to fig. 4a-4c, in an embodiment of the present invention, before illumination, the diameter of the single-walled carbon nanotube coated with small molecules of the compound benzenes is about 2nm, and after illumination, the dispersant is cracked to obtain semiconductor single-walled carbon nanotubes (s-SWCNTs) with clean surfaces, the diameter of which is about 1.5 to 1.6 nm.
If the dispersant is removed by acid washing, the following two methods can be adopted:
Adding trifluoroacetic acid (or protonic acid such as hydrochloric acid or sulfuric acid or nitric acid) into the supernatant obtained in the step S2, stirring or shaking, and after the color changes, performing centrifugal treatment to obtain the semiconductor single-walled carbon nanotubes (S-SWCNTs) without the surface dispersant.
And a second method, filtering the supernatant obtained in the step S2 through a filter membrane with the aperture of about 100nm, collecting substances on the filter membrane, and performing acid washing treatment in the first method, wherein the two methods can crack the compound acene small-molecule dispersant.
Referring to fig. 5a-5b, in an embodiment of the present invention, before acid washing, the diameter of the single-walled carbon nanotube coated with small molecules of the compound benzenes is about 2nm, and after acid washing, the dispersant is cracked to obtain a semiconductor single-walled carbon nanotube (s-SWCNTs) with a clean surface, the diameter of which is about 1.5 to 1.6 nm.
If the dispersant is removed by adopting a gas etching method, the supernatant obtained in the step S2 needs to be centrifuged again or filtered by a filter membrane with the aperture of about 100nm, the centrifugal precipitate or the substances on the filter membrane are collected, the centrifugal precipitate or the substances on the filter membrane are etched for 3-5 min under hydrogen plasma, the etching power is 100-500W, the gas flow is 100-500 sccm, and the conjugated benzene micromolecule dispersant is cracked.
Referring to fig. 6 a-6 b, in an embodiment of the present invention, before gas etching, the diameter of the carbon nanotube coated with small molecules of the compound benzenes is about 2nm, and after gas etching, the dispersant is cracked to obtain semiconductor single-walled carbon nanotubes (s-SWCNTs) with clean surfaces, the diameter of which is about 1.5 to 1.6 nm.
the technical solution of the present invention will be described below with reference to some more specific embodiments.
Example 1 50mg of 4HP-C6 and 100mg of single-walled carbon nanotube powder were added to 100ml of toluene, sonicated at 5W for 2h, and then centrifuged at 10000g for 1h, after which the supernatant was collected, which contained a large amount of semiconducting carbon nanotubes. The dispersant is cracked by an acid washing or gas etching or illumination method, so that the semiconductor single-walled carbon nano-tube with a clean surface (the purity of s-SWCNTs is 99.9%) is obtained. The semiconducting single-walled carbon nanotubes (s-SWCNTs) obtained by the method can be directly used for preparing high-performance thin film transistors and used as hole transport layers in solar cells.
Example 2 200mg of 4HP-C8 and 100mg of single-walled carbon nanotube powder were added to 100ml of xylene, sonicated at 100W for 10h, then centrifuged at 20000g for 10h, and after centrifugation was completed, the supernatant was collected, which contained a large amount of semiconducting carbon nanotubes. The dispersant is cracked by an acid washing or gas etching or illumination method, so that the semiconductor single-walled carbon nano-tube with a clean surface (the purity of s-SWCNTs is 99.9%) is obtained. The semiconducting single-walled carbon nanotubes (s-SWCNTs) obtained by the method can be directly used for preparing high-performance thin film transistors and used as hole transport layers in solar cells.
Example 3 of a class a compound, 100mg of a compound R: C10H21 and 100mg of single-walled carbon nanotube powder were added to 100ml of p-xylene, sonicated at 50W for 10H, centrifuged at 10000g for 2H, and after centrifugation, the supernatant was collected, which contained a large amount of semiconducting carbon nanotubes. The dispersant is cracked by an acid washing or gas etching or illumination method, so that the semiconductor single-walled carbon nano-tube with a clean surface (the purity of s-SWCNTs is 99.9%) is obtained. The semiconducting single-walled carbon nanotubes (s-SWCNTs) obtained by the method can be directly used for preparing high-performance thin film transistors and used as hole transport layers in solar cells.
Example 4 of the group B compounds, 50mg of R: C12H23 compound and 25mg of single-walled carbon nanotube powder were added to 25ml of p-xylene, sonicated at 50W for 1H, centrifuged at 50000g for 2H, and after centrifugation, the supernatant was collected, which contained a large amount of semiconducting carbon nanotubes. The dispersant is cracked by an acid washing or gas etching or illumination method, so that the semiconductor single-walled carbon nano-tube with a clean surface (the purity of s-SWCNTs is 99.9%) is obtained. The semiconducting single-walled carbon nanotubes (s-SWCNTs) obtained by the method can be directly used for preparing high-performance thin film transistors and used as hole transport layers in solar cells.
It should be understood that the above-mentioned embodiments are merely illustrative of the technical concepts and features of the present invention, which are intended to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and therefore, the protection scope of the present invention is not limited thereby. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (9)
1. A method of obtaining high purity semiconducting single-walled carbon nanotubes, comprising:
Uniformly mixing a single-walled carbon nanotube and a polyacene small-molecule dispersant in a dispersion medium to form a dispersion solution, wherein the polyacene small-molecule dispersant has a structure represented by any one of the following formulas A, B, C, D:
Wherein R is selected from any one of a hydrogen atom or a straight chain, branched chain or cyclic alkyl chain with 1-20 carbon atoms, and the substitution position of R on the benzene ring in the formula B is para, meta or ortho;
separating the dispersion solution to form a solid phase portion and a liquid phase portion, the liquid phase portion comprising enriched semiconducting single-walled carbon nanotubes bound with the polyacene small-molecule dispersant;
Filtering or centrifuging the liquid phase part again to obtain the semiconductor single-walled carbon nano-tube of which the surface is combined with the polyacene small-molecule dispersant;
And cracking the conjugated benzene micromolecule dispersing agent by at least selecting any one of acid washing, gas etching or illumination modes, thereby removing the conjugated benzene micromolecule dispersing agent combined with the semiconductor single-walled carbon nanotube and obtaining the high-purity semiconductor single-walled carbon nanotube.
2. the method of obtaining high purity semiconducting single-walled carbon nanotubes of claim 1, wherein: the single-walled carbon nanotubes comprise intermixed metallic single-walled carbon nanotubes and semiconducting single-walled carbon nanotubes.
3. The method of obtaining high purity semiconducting single-walled carbon nanotubes of claim 1, wherein: the dispersion medium comprises an organic solvent, and the organic solvent comprises any one or the combination of more than two of toluene, xylene, chloroform, dichloromethane, cyclohexane, nitrogen methyl pyrrolidone and tetrahydrofuran.
4. The method of obtaining high purity semiconducting single-walled carbon nanotubes of claim 1, comprising: at least one of ultrasonic, vibration and stirring modes is selected to uniformly mix the single-walled carbon nanotube and the double-acene micromolecule dispersing agent in a dispersing medium to form the dispersing solution.
5. The method of obtaining high purity semiconducting single-walled carbon nanotubes of claim 4, comprising: and uniformly mixing the single-walled carbon nanotube and the double-acene micromolecule dispersant in a dispersion medium to form the dispersion solution through ultrasonic treatment, wherein the ultrasonic power is 5-100W, and the ultrasonic time is 2-10 h.
6. the method of obtaining high purity semiconducting single-walled carbon nanotubes of claim 1, wherein:
The acid substance adopted by the acid washing mode is selected from protonic acid, and the protonic acid comprises any one or the combination of more than two of trifluoroacetic acid, hydrochloric acid, sulfuric acid and nitric acid;
The gas etching mode adopts a hydrogen plasma etching mode, the etching power is 100-500W, the gas flow is 100-500 sccm, and the etching time is 3-5 min;
The illumination mode includes: the semiconducting single-walled carbon nanotube with the conjugated small-molecule dispersant is irradiated by a light source with the wavelength of 450nm or less, so that the conjugated small-molecule dispersant is cracked.
7. The method of claim 6, wherein the illumination comprises: the semiconductor single-walled carbon nanotube combined with the polyacene small-molecule dispersant is irradiated by a light source with the wavelength of 350-400 nm to crack the polyacene small-molecule dispersant.
8. The method of obtaining high purity semiconducting single-walled carbon nanotubes of claim 1, wherein: the mass ratio of the compound rylene micromolecule dispersant to the single-walled carbon nanotube is 1: 0.5 to 2.
9. The method of obtaining high purity semiconducting single-walled carbon nanotubes of claim 1, wherein: the concentration of the compound rylene micromolecule dispersant in the dispersion medium is 0.5-2 mg/ml.
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| CN109761223B (en) * | 2017-11-09 | 2020-10-30 | 北京华碳元芯电子科技有限责任公司 | Method for removing organic dispersant on surface of carbon nano tube film |
| CN109867273B (en) * | 2017-12-01 | 2021-04-02 | 北京华碳元芯电子科技有限责任公司 | Purification method of semiconductor single-walled carbon nanotube |
| CN109867274A (en) * | 2017-12-01 | 2019-06-11 | 北京华碳元芯电子科技有限责任公司 | The method of purification of semi-conductive single-walled carbon nanotubes and its preparation method of film |
| CN108163840B (en) * | 2017-12-27 | 2020-02-07 | 深圳市华星光电半导体显示技术有限公司 | Carbon nanotube purification method, thin film transistor and preparation method |
| CN110902670B (en) | 2018-09-14 | 2021-07-20 | 中国科学院苏州纳米技术与纳米仿生研究所 | Carbon nanotube oriented film, preparation method and application thereof |
| CN111092154B (en) * | 2019-12-06 | 2023-11-24 | 中国科学院空间应用工程与技术中心 | Method for preparing large-area and uniform carbon nano tube network film |
| CN111056526A (en) * | 2019-12-30 | 2020-04-24 | 中国科学院空间应用工程与技术中心 | Method for preparing semiconductor carbon nano tube array film |
| CN111573655B (en) * | 2020-06-18 | 2021-09-28 | 江南大学 | Method for enriching single chiral carbon nano tube with high yield |
| CN112552754A (en) * | 2020-12-10 | 2021-03-26 | 哈工大机器人(中山)无人装备与人工智能研究院 | Preparation method of graphene heat dissipation coating |
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