CN107285298B - method for selectively separating single-walled carbon nanotubes with specific diameters and chiralities and application - Google Patents
method for selectively separating single-walled carbon nanotubes with specific diameters and chiralities and application Download PDFInfo
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Abstract
the invention discloses a method for selectively separating single-walled carbon nanotubes with specific diameters and chiralities and application thereof. The method comprises the following steps: uniformly mixing a single-walled carbon nanotube raw material and a conjugated polymer in a dispersion medium to form a dispersion solution; separating the dispersion solution to form a solid phase part and a liquid phase part, and enriching single-walled carbon nanotubes with specific diameters and chiralities in the liquid phase part; wherein the conjugated polymer is selected from alternating copolymers of meta-pyridine and dialkyl fluorene. The method is simple and efficient, has extremely high diameter and chiral selectivity, can realize low-cost and large-scale batch preparation of the specific-diameter and chiral single-walled carbon nanotubes, and the obtained specific-diameter and chiral single-walled carbon nanotubes are easy to prepare large-area uniform films and can show excellent performance in the aspect of application of micro-nano electronic devices.
Description
Technical Field
The invention particularly relates to a method for selectively separating single-walled carbon nanotubes with specific diameters and chiralities, and belongs to the technical field of carbon nanotubes.
Background
Single-walled carbon nanotubes (SWCNTs) have a unique one-dimensional nanostructure, and their excellent properties such as optics, electronics, mechanics, and thermodynamics make them have a good application prospect in many fields, especially in the fields of integrated circuits, field effect transistors, etc. The methods currently used for synthesizing single-walled carbon nanotubes are classified into chemical vapor deposition, arc catalysis, laser evaporation and the like, but the single-walled carbon nanotubes obtained by the methods are all mixtures of single-walled carbon nanotubes with different tube diameters, conductive properties and chirality. Of these, about 1/3 is metallic SWCNT and 2/3 is semiconducting SWCNT.
The semiconductor-type SWCNT is an excellent semiconductor nanomaterial, the intrinsic carrier mobility of which is as high as 70000cm2V-1s-1, and the semiconductor-type SWCNT of large diameter has higher mobility, so that the application thereof to field effect transistors is expected. The presence of metallic SWCNTs can greatly reduce the mobility and on-off ratio of electronic devices. The mixing of semiconducting SWCNTs of different chiralities also affects the uniformity and sensitivity of device performance, limiting their application in electronic devices. Therefore, it is necessary to effectively separate single-walled carbon nanotubes of different conductive properties and the narrower the diameter distribution and chiral distribution of the semiconductor-type SWCNTs is, the better. The separation of single-walled carbon nanotubes, particularly the separation of narrow-chirality large-diameter single-walled carbon nanotubes, is faced with great difficulty due to the very subtle differences between the compositions and chemical properties of the different types of single-walled carbon nanotubes.
SWCNT separation studies are mainly based on the weak physical and chemical property differences between carbon nanotubes of different chiralities due to differences in chemical and electronic structures. The existing method for separating and obtaining single chiral SWCNTs can be divided into a surfactant system, a biomolecule system and a conjugated molecule system according to different materials of dispersed carbon nanotubes, but the method has advantages and disadvantages in application. For example, the surfactant system is mainly to modify and disperse the surface of SWCNTs by a surfactant, and then combine a density gradient centrifugation method, a chromatography method and a two-aqueous phase extraction method to realize chiral separation. However, the density gradient centrifugation method and the chromatography method have a series of problems of complicated process, high cost, low yield and the like. In addition, the surfactant on the surface of the carbon nanotube is difficult to remove in the above method, which affects the electronic performance of the carbon nanotube. For another example, in a biomolecule system, since biomolecules have good biocompatibility, they are suitable for the field of biomedicine, but the cost of DNA and polypeptide of a specific sequence is too high, which limits the large-scale application and popularization. For example, Kim et al selectively isolated and enriched tubes (6,5) using double-stranded genomic DNA (salmon DNA), but the cost is extremely high and the purity of the isolated tubes (6,5) is low.
in contrast, the conjugated molecular system can realize the chiral selective separation of the single-walled carbon nanotube only by simple ultrasonic and centrifugal processes, has simple process, and can be used for mass production of the single chiral semiconductor SWCNTs. And because the conjugated polymer is a good semiconductor, the polymer adsorbed on the surface of the carbon nano tube can be applied to the fields of electronic devices, optical imaging and the like without removing.
At present, carbon nanotubes with smaller tube diameters such as (7,5), (7,6) and the like can be separated by using conjugated polymers, and a few transistor devices are reported. However, separation of the single-chiral carbon nanotubes having a diameter in the range of 1.1 to 1.3nm, which is most suitable for semiconductor devices, is rare, and separation satisfying the purity required for the devices is more difficult, and such reports have not been found so far.
Disclosure of Invention
The invention mainly aims to provide a method for selectively separating single-walled carbon nanotubes with specific diameters and chiralities and application thereof, 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 selectively separating the single-walled carbon nanotubes with specific diameters and chiralities, provided by the embodiment of the invention, comprises the following steps:
Uniformly mixing the raw material of the single-walled carbon nanotube and the conjugated polymer in a dispersion medium to form a dispersion solution,
And separating the dispersion solution to form a solid phase part and a liquid phase part, and enriching single-walled carbon nanotubes with specific diameters and chiralities in the liquid phase part.
Further, the conjugated polymer is selected from alternating copolymers of meta-pyridine and dialkyl fluorene.
More preferably, the conjugated polymer is selected from compounds having the structure shown in the following formula:
r is a linear alkyl group having 6 to 16 carbon atoms, and n is an integer of 5 to 60.
Furthermore, the content of the (10,8) -type single-walled carbon nanotubes in the single-walled carbon nanotubes with specific diameters and chiralities is more than 80%, and the diameter of the contained single-walled carbon nanotubes is 1.1-1.3 nm.
further, the single-walled carbon nanotubes with specific diameters and chiralities comprise no more than three chiral single-walled carbon nanotubes.
The single-walled carbon nanotube material provided by the embodiment of the invention comprises no more than three chiral single-walled carbon nanotubes, wherein the content of the (10,8) -type single-walled carbon nanotubes is more than 80%, and the diameter of the single-walled carbon nanotubes is 1.1-1.3 nm.
The embodiment of the invention also provides application of the single-walled carbon nanotube material.
Compared with the prior art, the method for selectively separating the single-walled carbon nanotubes with the specific diameters and chiralities is simple and efficient, has extremely high diameter and chirality selectivity, can realize low-cost and large-scale batch preparation of the single-walled carbon nanotubes with the specific diameters and chiralities, is easy to prepare large-area uniform films, and can show excellent performance in the aspect of application of micro-nano electronic devices.
Drawings
FIG. 1 is a graph of UV-Vis-NIR absorption spectra of supernatants obtained after centrifugation in one embodiment of the present invention;
FIG. 2 is a PLE plot of the supernatant obtained after centrifugation in one embodiment of the invention;
FIG. 3 is an AFM topography of single-walled carbon nanotubes obtained in accordance with an embodiment of the present invention;
Fig. 4 is a transfer graph of a transistor device in an embodiment of the invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention are described in detail below with reference to the accompanying drawings. Examples of these preferred embodiments are illustrated in the accompanying drawings. The embodiments of the invention shown in the drawings and described in accordance with the drawings are exemplary only, and the invention is not limited to these embodiments.
It should be noted that, in order to avoid obscuring the present invention with unnecessary details, only the structures and/or processing steps closely related to the scheme according to the present invention are shown in the drawings, and other details not so relevant to the present invention are omitted.
one aspect of the embodiments of the present invention provides a method for selectively separating single-walled carbon nanotubes of a specific diameter and chirality, comprising:
Uniformly mixing a single-walled carbon nanotube raw material and a conjugated polymer in a dispersion medium to form a dispersion solution, separating the dispersion solution to form a solid phase part and a liquid phase part, and enriching the single-walled carbon nanotube with specific diameter and chirality in the liquid phase part.
Wherein the conjugated polymer is an alternating copolymer of meta-pyridine and dialkyl fluorene, which is preferably selected from compounds having a structure represented by the following formula:
wherein two R on the bridging carbon atom on the fluorene group can be the same or different and are straight-chain alkyl with 6-16 carbon atoms, and n is any integer of 5-60.
Furthermore, the diameter of the carbon nanotube contained in the single-walled carbon nanotube raw material is 0.6-1.3 nm.
Further, the single-walled carbon nanotube material may be prepared by chemical vapor deposition, and may be, for example, a HiPco process or a CoMoCat process.
Further, the dispersion medium includes an organic solvent, such as any one or a combination of two or more selected from, but not limited to, toluene, xylene, chlorobenzene, tetrahydrofuran, chloroform, dichloromethane, hexane, and cyclohexane.
In some embodiments of the present invention, the single-walled carbon nanotube material and the conjugated polymer are uniformly mixed in the dispersion medium to form the dispersion solution, optionally at least one of ultrasound, vibration, stirring and grinding.
In some preferred embodiments of the present invention, the dispersion solution may be separated into a solid phase portion and a liquid phase portion by subjecting the dispersion solution to a centrifugation process at a centrifugation speed of preferably 10000g to 1000000g for a period of preferably 10min or more, and more preferably 10min to 4 hours, from which single-walled carbon nanotubes having a specific diameter and chirality can be obtained. Wherein, the higher the centrifugal speed and the longer the centrifugal time, the higher the chiral purity of the single-walled carbon nanotube obtained by separation.
In some preferred embodiments of the present invention, the liquid phase portion may be further filtered through a filter membrane with a pore size of 0.1 to 0.5 μm, so as to obtain a powder of the single-walled carbon nanotube with a specific diameter and chirality.
In some preferred embodiments of the present invention, the single-walled carbon nanotube with specific diameter and chirality can be further purified by subjecting the liquid phase portion to ultracentrifugation at 200000g to 1000000 g.
by the filtration treatment or the ultra-high speed centrifugation treatment, the surplus conjugated polymer can be basically washed away, and the single-wall carbon nanotube powder with the conjugated polymer basically removed can be obtained.
Furthermore, the content of the (10,8) -type single-walled carbon nanotubes in the single-walled carbon nanotubes with specific diameters and chiralities is more than 80%, and the diameter of the contained single-walled carbon nanotubes is 1.1-1.3 nm.
In a more typical embodiment of the present invention, a method for selectively separating single-walled carbon nanotubes of a specific diameter and chirality comprises the following steps: adding original single-walled carbon nanotubes and conjugated polymers into an organic solvent, mixing and dispersing; centrifuging the dispersion liquid, and collecting the supernatant to obtain solution of large-diameter narrow-chiral single-walled carbon nanotubes; filtering or ultra-high speed centrifuging the obtained carbon nano tube solution to obtain the single-walled carbon nano tube powder with the large tube diameter and the narrow chirality, from which the conjugated polymer is basically removed.
one aspect of the embodiments of the present invention provides a single-walled carbon nanotube material comprising a single-walled carbon nanotube with a specific diameter and chirality, wherein the content of a (10,8) -type single-walled carbon nanotube is greater than 80%, and the diameter of the single-walled carbon nanotube is 1.1-1.3 nm.
One aspect of embodiments of the present invention provides a use of the single-walled carbon nanotube material.
For example, embodiments of the present invention provide a class of electronic devices that use the single-walled carbon nanotube material as the semiconductor material.
The electronic device may be a transistor, a photovoltaic device, an electroluminescent diode, or the like, and is not limited thereto.
One aspect of the embodiments of the present invention provides a selective dispersant for carbon nanotubes with specific diameters and chiralities, which is selected from conjugated polymers having a structure shown in the following formula, and the polymers can be synthesized by Suzuki polymerization, and the process route is shown in the following formula:
Wherein R is a linear alkyl group having 6 to 16 carbon atoms, and n is any integer of 5 to 60.
The invention develops a simple and efficient selective separation method by utilizing a conjugated polymer with a unique spatial structure, can obtain single-walled carbon nanotubes with narrow diameter distribution, and can obtain (10,8) type large-diameter semiconductor single-walled carbon nanotubes with single chirality by an optimized separation process. The separation technology is simple and efficient, is easy to amplify, has low cost, can quickly obtain a large quantity of single-chiral single-walled carbon nanotubes, has extremely high application prospect, and can be widely applied to the fields of micro-nano electronic devices, circuits, biological medicines and the like.
the technical solution of the present invention is described in more detail with reference to several embodiments.
Example 1: 50mg of the conjugated polymer with the structure shown in the formula I and 25mg of HiPCO type single-walled carbon nanotubes are dissolved in 100mL of toluene solvent. The dispersion was carried out by sonication for 20 minutes, followed by centrifugation at 20000g for 30 minutes. Taking the supernatant to obtain the narrow chiral single-walled carbon nanotube solution. The near infrared-visible-ultraviolet absorption spectrum (UV-Vis-NIR) (refer to figure 1), the two-dimensional fluorescence spectrum and the three-dimensional fluorescence spectrum (PLE) (refer to figure 2) are used for testing, and the results of the three spectra are combined to prove that the separated supernatant mainly contains (10,8) single-walled carbon nanotubes. Filtering and drying to obtain the large-caliber narrow-chiral single-walled carbon nanotube powder, wherein the purity of the (10,8) -type single-walled carbon nanotube is more than 80%.
wherein the number average molecular weight was 13000 (average n value was 26).
Example 2: 100mg of the conjugated polymer having the structure represented by formula II and 25mg of a CoMoCat type single-walled carbon nanotube were dissolved in a mixed solvent of 96mL of toluene and 4mL of hexane. Dispersing for 3h by ultrasonic, and centrifuging at 100000g for 2 h. Taking the supernatant to obtain the narrow chiral single-walled carbon nanotube solution. Then, the carbon nano tube powder body with the conjugated polymer basically removed and the purity of the (10,8) type single-wall carbon nano tube is more than 90 percent can be obtained by ultra-high speed centrifugation, the centrifugation speed is 800000g and the centrifugation time is 2 hours, and the lower layer precipitated solid is collected and dried.
Wherein n is 10 and the number average molecular weight is 5500.
example 3: on a single crystal silicon wafer with a surface of 200 silicon oxide, the narrow chiral single-walled carbon nanotube solution obtained in example 1 can be prepared into a single chiral semiconductor carbon nanotube film by spin coating or drop coating (see fig. 3), and the density of carbon nanotubes in the film can be controlled by controlling the concentration of carbon nanotubes in the solution and the film-making conditions. And preparing a gold source and drain electrode with a micron-sized channel on the film by utilizing a photoetching technology and an electron beam coating technology, so that a micron-sized thin film transistor of the single chiral single-walled carbon nanotube can be obtained, wherein the channel L of the device is 20 microns, the channel W of the device is 400 microns, and the Vds of the device is-1V. Referring to fig. 4, a transfer graph of the transistor device is shown. It can be seen that the switching ratio of the transistor device exceeds 106.
Example 4: on a glass substrate, the narrow chiral single-walled carbon nanotube solution finally obtained in example 1 can be prepared into a semiconductor carbon nanotube film with single chirality by spin coating or drop coating. A palladium electrode is prepared on the film by utilizing a photoetching technology and an electron beam coating technology, and polymethyl methacrylate is spin-coated on the surface to serve as a passivation layer, so that an infrared photovoltaic device or an electroluminescent device of a single chiral single-walled carbon nanotube can be obtained.
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 (6)
1. A method for selectively separating single-walled carbon nanotubes of a specific diameter and chirality, comprising:
Uniformly mixing the raw material of the single-walled carbon nanotube and the conjugated polymer in a dispersion medium to form a dispersion solution,
Separating the dispersion solution to form a solid phase part and a liquid phase part, and enriching single-walled carbon nanotubes with specific diameters and chiralities in the liquid phase part, wherein the content of (10,8) -type single-walled carbon nanotubes in the single-walled carbon nanotubes with the specific diameters and the chiralities is more than 80%, and the diameter of the contained single-walled carbon nanotubes is 1.1-1.3 nm;
The conjugated polymer is selected from compounds having the structure shown in the following formula:
wherein R is a linear alkyl group having 6 to 16 carbon atoms, and n is any integer of 5 to 60;
The dispersion medium is selected from any one or combination of more than two of toluene, xylene, chlorobenzene, tetrahydrofuran, chloroform, dichloromethane, hexane and cyclohexane.
2. The method of claim 1, wherein the method comprises the steps of: the pipe diameter of the carbon nano tube contained in the single-walled carbon nano tube raw material is 0.6-1.3 nm.
3. The method of claim 1 for selectively separating single-walled carbon nanotubes of a particular diameter and chirality, comprising: at least one of the modes of ultrasound, oscillation, stirring and grinding is selected to uniformly mix the single-walled carbon nanotube raw material and the conjugated polymer in a dispersion medium to form the dispersion solution.
4. The method of claim 1 for selectively separating single-walled carbon nanotubes of a particular diameter and chirality, comprising: centrifuging the dispersion solution for a centrifugation time of 10min or more to separate the dispersion solution into a solid phase portion and a liquid phase portion,
and obtaining the single-walled carbon nanotube with the specific diameter and chirality from the liquid phase part.
5. The method of claim 4, comprising the steps of: and centrifuging the dispersion solution for 10min to 4h, so that the dispersion solution is separated into a solid phase part and a liquid phase part.
6. The method of claim 1 for selectively separating single-walled carbon nanotubes of a particular diameter and chirality, comprising: and filtering the liquid phase part by using a filter membrane with the aperture of the filter hole of 0.1-0.5 mu m to obtain the single-walled carbon nanotube powder with specific diameter and chirality.
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