CN109761221B - Organic matter for separating and purifying semiconductor single-walled carbon nanotube, method and application - Google Patents
Organic matter for separating and purifying semiconductor single-walled carbon nanotube, method and application Download PDFInfo
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Abstract
The invention relates to an organic matter, a method and application for separating and purifying semiconductor single-walled carbon nanotubes, wherein the separation and purification method comprises the following steps: step (1): adding benzodithiophene substances and raw materials containing semiconductor single-walled carbon nanotubes into an organic solvent; and a step (2): and treating the organic solvent to separate the semiconductor single-walled carbon nanotubes in the organic solvent. The organic matter is benzodithiophene, and can be used in the fields of semiconductor devices, integrated circuits, display drivers, transparent conductive films, biological/chemical sensors, infrared detection, infrared thermotherapy and the like. The method can reduce the cost of separating the semiconductor single-walled carbon nanotube from the raw material, improve the yield and improve the purity of the semiconductor single-walled carbon nanotube.
Description
Technical Field
The invention belongs to the technical field of nano materials, and particularly relates to an organic matter, a method and application for separating and purifying a semiconductor single-walled carbon nanotube.
Background
Carbon nanotubes are a nanomaterial with great potential in semiconductor devices, integrated circuits, and biomedical applications. How to disperse and separate the carbon nanotubes from the raw material containing impurities is an important research content in the field.
At present, the carbon nanotubes are separated from impurities mainly by using a dispersant in a solvent, and the search for a suitable dispersant is a main research direction in the field at present.
Professor bauhinia of stanford university in usa proposed carbon nanotubes using polythiophene species separation. Michael s. arnold and IBM, university of wisconsin, usa, use copolymers of fluorene and pyridine to isolate carbon nanotubes.
The invention application with Chinese patent application publication No. CN106629670A discloses a method for dispersing carbon nanotubes by a Gemini type dispersing agent, which modifies the surface of the carbon nanotubes through a series of process flows to ensure that carbon nanotube aggregates are thoroughly opened to form a dispersion liquid. The method mainly comprises the following implementation steps: (1) preparing a solution of 4, 4-ditetradecyl diphenylmethane disulfonate serving as a carbon nano tube dispersant; (2) and (4) dispersing the carbon nanotubes.
At present, the types of substances capable of being used for dispersing and separating the carbon nano tubes are single, and the technical schemes have the defects of high price, low yield of the carbon nano tubes, low purity and the like, so that the schemes cannot be popularized and applied.
Based on the technical problems, the invention provides an organic matter for separating and purifying semiconductor single-walled carbon nanotubes, a separation and purification method and application.
Disclosure of Invention
The invention provides an organic matter for separating and purifying semiconductor single-walled carbon nanotubes, a separation and purification method and application, which are used for solving the technical defects that in the prior art, the molecular species of substances for separating the semiconductor single-walled carbon nanotubes are single, the price is high, and the separated semiconductor single-walled carbon nanotubes have low yield and low purity.
According to one aspect of the invention, a method for separating and purifying semiconductor single-walled carbon nanotubes is provided, which comprises the following steps:
step (1): adding benzodithiophene substances and raw materials containing semiconductor single-walled carbon nanotubes into an organic solvent; and
step (2): and treating the organic solvent to separate the semiconductor single-walled carbon nanotubes in the organic solvent.
According to another aspect of the invention, the benzodithiophene species comprises at least one of: benzodithiophene small molecules containing alkyl chains, benzodithiophene polymers, benzodithiophene copolymers, and benzodithiophene derivatives; the benzodithiophene derivative refers to a derivative of a benzodithiophene micromolecule containing an alkyl chain, a derivative of a benzodithiophene polymer and a derivative of a benzodithiophene copolymer, wherein the structural formula of the benzodithiophene micromolecule containing the alkyl chain is shown as the following formula (1):
in formula (1), R ═ is an alkyl chain of varying length, for example: -C8H17，-C9H19，-C26H53And the like. The yield of the semiconductor carbon nanotube can be adjusted by designing the length of the alkyl chain of the benzodithiophene micromolecule, and the longer the length of the alkyl chain is, the higher the yield is.
According to a further aspect of the invention, the benzodithiophene-based copolymer comprises: copolymers of benzodithiophene with carbazole, or fluorene, or pyridine or thiophene or benzo [2,1,3] thiadiazole-4, 8-diyl.
According to yet another aspect of the present invention, the mass ratio of the benzodithiophene species to the raw material comprising the carbon nanotubes ranges from 0.1:1 to 20: 1.
According to still another aspect of the present invention, the organic solvent is one of toluene, xylene, chloroform, tetrahydrofuran, cyclohexane, methylcyclohexane, ethylcyclohexane, nitrogen methyl pyrrolidone, and dimethyl sulfoxide.
According to yet another aspect of the present invention, treating the organic solvent to separate the semiconducting single-walled carbon nanotubes therein comprises: step (2-1): carrying out ultrasonic treatment on the organic solvent, and extracting a dispersion liquid formed after the ultrasonic treatment; step (2-2): and centrifuging the dispersion liquid, and extracting a supernatant liquid formed after the centrifugation, wherein the supernatant liquid contains the carbon nano tubes separated from the raw materials.
According to another aspect of the invention, the ultrasonic power range used for ultrasonic treatment of the organic solvent is 20W to 1500W, and the ultrasonic treatment time is 5 minutes to 300 minutes.
According to a further aspect of the invention, the dispersion is centrifuged at a centrifugation speed in the range of 3000rpm to 100000rpm for a period of time in the range of 0.5 hours to 300 hours.
The invention also provides an organic matter used in the separation and purification method, wherein the organic matter is benzodithiophene substances, and the benzodithiophene substances comprise at least one of the following substances: benzodithiophene small molecules containing alkyl chains, benzodithiophene polymers, benzodithiophene copolymers, and benzodithiophene derivatives; the benzodithiophene derivative refers to a derivative of a benzodithiophene micromolecule containing an alkyl chain, a derivative of a benzodithiophene polymer and a derivative of a benzodithiophene copolymer.
According to still another aspect of the present invention, the organic solvent is one of toluene, xylene, chloroform, tetrahydrofuran, cyclohexane, methylcyclohexane, ethylcyclohexane, nitrogen methyl pyrrolidone, and dimethyl sulfoxide.
Wherein, the structural formula of the benzodithiophene micromolecule containing the alkyl chain is shown as the following formula (1):
(R-is an alkyl chain of different length, e.g.: C8H17，-C9H19，-C26H53)
The invention also provides specific applications of the organic matter, and the organic matter is used for semiconductor devices, integrated circuits, display drivers, transparent conductive films, biological/chemical sensors, infrared detection and infrared thermotherapy.
Compared with the prior art that the semiconductor single-walled carbon nanotube is separated by adopting polythiophene substances or copolymer of fluorene and pyridine and the like, the method expands the types of substances which can be used for separating the semiconductor single-walled carbon nanotube, and has lower cost, higher yield and better separation purity.
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FIG. 1 is a schematic diagram of the effect test of the semiconductor single-walled carbon nanotube separation provided by the invention.
Detailed Description
The invention provides a method for separating a semiconductor single-walled carbon nanotube, which is used for providing a separation scheme of the semiconductor single-walled carbon nanotube with low cost, high yield and high purity.
The embodiments of the present invention will be described in detail below.
In a first embodiment of the invention, a method of separating semiconducting single-walled carbon nanotubes comprises:
step (1): adding benzodithiophene substances and raw materials containing semiconductor single-walled carbon nanotubes into an organic solvent;
step (2): and treating the organic solvent to separate the semiconductor single-walled carbon nanotubes in the organic solvent.
Preferably, the benzodithiophene species used in step (1) comprises at least one of: benzodithiophene small molecules containing alkyl chains of any length, benzodithiophene polymers, benzodithiophene copolymers, and benzodithiophene derivatives.
The structure of the benzodithiophene small molecule mentioned in this embodiment is:
wherein R represents an alkyl chain of optional length. Preferably, the alkyl chain length of the benzodithiophene micromolecule is C8-C26; for example: r ═ C8H17, -C9H19, -C26H 53.
Preferably, the benzodithiophene-based copolymer referred to in this embodiment includes: and carbazole, or fluorene, or pyridine, or thiophene, or benzo [2,1,3] thiadiazole-4, 8-diyl.
Preferably, in step (1), the mass ratio of the benzodithiophene species to the raw material comprising the semiconducting single-walled carbon nanotubes ranges from 0.1:1 to 20: 1. It should be noted that the above ratio ranges are only preferred embodiments of the present invention, and embodiments using other mass ratios than the above ratio range can also achieve the technical effect of separating the semiconductor single-walled carbon nanotubes.
Preferably, the organic solvents employed in this embodiment are: toluene, xylene, chloroform, tetrahydrofuran, cyclohexane, methylcyclohexane, ethylcyclohexane, N-methylpyrrolidone, and dimethyl sulfoxide.
Preferably, step (2) of the present embodiment specifically includes:
step (2-1): carrying out ultrasonic treatment on the organic solvent, and extracting a dispersion liquid formed after the ultrasonic treatment;
step (2-2): and centrifuging the dispersion liquid, and extracting supernatant liquid formed after the centrifugation, wherein the supernatant liquid contains the semiconductor single-walled carbon nanotubes separated from the raw material.
Preferably, the ultrasonic power range used for ultrasonic treatment of the organic solvent is 20-1500 watts.
Preferably, the centrifugation speed used for centrifuging the dispersion is in the range of 3000rpm to 100000 rpm.
The invention also provides an organic matter used in the separation and purification method, wherein the organic matter is benzodithiophene substances, and the benzodithiophene substances comprise at least one of the following substances: benzodithiophene small molecules containing alkyl chains, benzodithiophene polymers, benzodithiophene copolymers, and benzodithiophene derivatives; the benzodithiophene derivative refers to a derivative of a benzodithiophene micromolecule containing an alkyl chain, a derivative of a benzodithiophene polymer and a derivative of a benzodithiophene copolymer.
Preferably, the organic solvent is one of toluene, xylene, chloroform, tetrahydrofuran, cyclohexane, methylcyclohexane, ethylcyclohexane, azomethylpyrrolidone, and dimethyl sulfoxide.
Hereinafter, embodiments of the present invention will be described.
Example one
A method of separating semiconducting single-walled carbon nanotubes comprising the steps of: 1. putting 100mg of benzodithiophene micromolecules and a carbon nano tube raw material into 100ml of toluene according to the proportion of 1:1, and mixing, wherein the benzodithiophene micromolecules comprise alkyl chains with the length of 8; 2. performing ultrasonic treatment for 30 minutes at 150 watts (W) by using an ultrasonic cell crushing instrument; 3. taking out the dispersion liquid and centrifuging, wherein the centrifugation speed is 8000 revolutions per minute (rpm), and the centrifugation time is 2 hours (h); 4. after centrifugation, the supernatant was taken, and high-purity carbon nanotubes were suspended in the supernatant.
Example two
A method of separating semiconducting single-walled carbon nanotubes comprising the steps of: 1. 100mg of benzodithiophene polymer and carbon nanotube raw materials are put into 100ml of toluene according to the proportion of 0.5:1 and mixed; 2. performing ultrasonic treatment for 45 minutes at 500W by using an ultrasonic cell crushing instrument; 3. taking out the dispersion liquid and centrifuging at the speed of 12000rpm for 2 h; 4. after centrifugation, the supernatant was taken, and high-purity carbon nanotubes were suspended in the supernatant.
EXAMPLE III
A method of separating semiconducting single-walled carbon nanotubes comprising the steps of: 1. 100mg of carbazole-benzodithiophene copolymer and carbon nanotube raw materials are put into 100ml of toluene according to the proportion of 0.1:1 and mixed; 2. performing ultrasonic treatment for 300 minutes at 20W by using an ultrasonic cell crusher; 3. taking out the dispersion liquid and centrifuging at a speed of 100000rpm for 0.5 h; 4. after centrifugation, the supernatant was taken, and high-purity carbon nanotubes were suspended in the supernatant.
Example four
A method of separating semiconducting single-walled carbon nanotubes comprising the steps of: 1. 100mg of benzodithiophene and carbon nano tube raw materials are put into 100ml of toluene according to the proportion of 20:1 and mixed; 2. carrying out ultrasonic treatment for 5 minutes at 1500W by using an ultrasonic cell crushing instrument; 3. taking out the dispersion liquid and centrifuging at the speed of 3000rpm for 300 h; 4. after centrifugation, the supernatant was taken, and high-purity carbon nanotubes were suspended in the supernatant.
EXAMPLE five
A method of separating semiconducting single-walled carbon nanotubes comprising the steps of: 1. 100mg of the indenone-carbazole-benzodithiophene copolymer and the carbon nano tube raw material are put into 1000ml of toluene according to the proportion of 10:1 and mixed; 2. performing ultrasonic treatment for 45 minutes at 500W by using an ultrasonic cell crushing instrument; 3. taking out the dispersion liquid and centrifuging at the speed of 12000rpm for 2 h; 4. after centrifugation, the supernatant was taken, and high-purity carbon nanotubes were suspended in the supernatant.
EXAMPLE six
A method of separating semiconducting single-walled carbon nanotubes comprising the steps of: 1. putting 100mg of benzodithiophene micromolecules and a carbon nano tube raw material into 500ml of toluene according to the proportion of 1:1, and mixing, wherein the benzodithiophene micromolecules comprise an alkyl chain with the length of 26; 2. performing ultrasonic treatment for 30 minutes at 150 watts (W) by using an ultrasonic cell crushing instrument; 3. taking out the dispersion liquid and centrifuging, wherein the centrifugation speed is 8000 revolutions per minute (rpm), and the centrifugation time is 2 hours (h); 4. after centrifugation, the supernatant was taken, and high-purity carbon nanotubes were suspended in the supernatant.
The embodiment of the invention adopts benzodithiophene substances to separate the semiconductor single-walled carbon tube, and adopts the benzodithiophene substances to purify the high-purity semiconductor single-walled carbon nanotube, thereby having the characteristic of high yield.
FIG. 1 shows the results of testing the carbon nanotubes separated and purified according to the present invention. According to the relationship between the wavelength and the absorbance of the carbon nanotube as shown in fig. 1, the skilled person can find that the characteristic peak of the metallic carbon tube does not appear in the metallic carbon tube region, which indicates that the purity of the isolated and purified semiconductor single-walled carbon nanotube is high; and the highest absorption peak of the absorbance shown in the figure reaches 1.65, which indicates that the yield of the semiconductor single-walled carbon nanotube is high.
The comparison result of the technical effects of the embodiment of the invention and the prior art scheme is shown in table 1:
table 1 results of comparing the effects of the examples of the present invention with those of the prior art
In conclusion, the semiconductor single-walled carbon nanotube obtained by using benzodithiophene substances has high purity and low synthesis cost, and is suitable for industrial production; the method has wide application prospect in the fields of semiconductor devices, integrated circuits, display drivers, transparent conductive films, biological/chemical sensing, infrared detection, infrared thermotherapy and the like.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (6)
1. A method for separating and purifying semiconductor single-walled carbon nanotubes, which is characterized by comprising the following steps:
step (1): adding benzodithiophene substances and raw materials containing semiconductor single-walled carbon nanotubes into an organic solvent; and
step (2): treating the organic solvent to separate the semiconductor single-walled carbon nanotubes therein, wherein the benzodithiophene species comprises: a benzodithiophene small molecule comprising an alkyl chain,
the structural formula of the benzodithiophene micromolecule containing the alkyl chain is as follows:
r represents an alkyl chain of selectable length, and the yield of the semiconductor single-walled carbon nanotube is adjusted by designing the length of the alkyl chain, wherein the longer the length of the alkyl chain, the higher the yield of the semiconductor single-walled carbon nanotube.
2. The method of claim 1, wherein in step (1), the mass ratio of the benzodithiophene species to the feedstock comprising semiconducting single-walled carbon nanotubes is from 0.1:1 to 20: 1.
3. The method of claim 1 or 2, wherein the organic solvent is: at least one of toluene, xylene, chloroform, tetrahydrofuran, cyclohexane, methylcyclohexane, ethylcyclohexane, N-methylpyrrolidone, and dimethyl sulfoxide.
4. The method of claim 3, wherein in step (2), treating the organic solvent to separate the semiconducting single-walled carbon nanotubes therein comprises:
step (2-1): carrying out ultrasonic treatment on the organic solvent, and extracting a dispersion liquid formed after the ultrasonic treatment;
step (2-2): and centrifuging the dispersion liquid, and extracting supernatant liquid formed after the centrifugation, wherein the supernatant liquid contains the semiconductor single-walled carbon nanotubes separated from the raw material.
5. The method according to claim 4, wherein in the step (2-1), the organic solvent is sonicated at a sonication power in a range of 20W to 1500W for a sonication time period of 5 minutes to 300 minutes.
6. The method according to claim 5, wherein in the step (2-2), the dispersion is centrifuged at a centrifugation speed in the range of 3000rpm to 100000rpm for a period of 0.5 hours to 300 hours.
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