CN111293035B - Preparation method of carbon nanotube film - Google Patents
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Abstract
The invention provides a preparation method of a carbon nanotube film, which comprises the following steps: 1) Preparing a carbon nano tube dispersion liquid, and adjusting the pH value to be more than 7; 2) Self-assembling a polylysine molecular layer or a 3-aminopropyltriethoxysilane molecular layer on the surface of the substrate; 3) Dripping the carbon nano tube dispersion liquid obtained in the step 1) on the substrate obtained in the step 2), uniformly covering the whole substrate with the carbon nano tube dispersion liquid, standing for deposition, and recovering the carbon nano tube dispersion liquid which is not deposited; 4) Cleaning the substrate obtained in the step 3) to remove the surfactant, and drying the substrate by using inert gas or nitrogen to obtain the silicon nitride substrate. Based on the above, the carbon nanotube film prepared by the method provided by the invention has good application prospects in large-scale integrated circuits and large-area transparent conductive films.
Description
Technical Field
The invention belongs to the field of nano material preparation, and particularly relates to a method for preparing a carbon nano tube film.
Background
Single-Wall Carbon Nanotubes (SWCNTs) are one-dimensional tubular molecules formed by curling graphene, and not only have the characteristics of excellent mechanical properties, thermal properties, high carrier mobility and the like of graphene, but also show excellent chemical stability and energy gap with adjustable structure due to the one-dimensional helical structure of SWCNTs. The semiconductor SWCNTs have a symmetrically split energy band structure, so that the semiconductor SWCNTs have extremely high electron and hole mobility and excellent grid regulation and control characteristics, high-performance n-type and p-type transistors can be prepared without chemical doping, and the semiconductor SWCNTs are ideal materials for preparing high-speed, low-power-consumption and high-integration digital circuits. The energy efficiency of carbon nanotube electronic devices can be improved by more than one order of magnitude over conventional Si-based semiconductor devices. And the short channel effect of the Si-based semiconductor material can be effectively overcome, and the theoretical and technical limits of the silicon-based CMOS technology are expected to be broken through. The best carbon nanotube devices currently have roughly 5-6 times faster speed than silicon devices, while the power consumption is only 1/100 that of silicon devices. In particular, three-dimensional carbon nanotube integrated circuits, the Stanford university research group predicts that the speed will be 1000 times more advantageous than silicon-based integrated circuits. These breakthrough results highlight the huge application prospects of the carbon nanotube semiconductor industry in the future.
At present, there are two major technical bottlenecks in the application of carbon nanotubes in electronic devices and integrated circuits. One is the problem of preparing high-purity semiconductor carbon nanotubes, and the other is the problem of preparing carbon nanotube films with uniform wafer areas through deposition. The properties of carbon nanotubes derive from their structure. Small differences in structure will result in large differences in properties. SWCNTs of different chiral structure can exhibit metallic or semiconducting properties. And the energy gap and the diameter of the semiconductor carbon nano-tubes with different diameters are approximately in inverse proportion. The preparation of the carbon nanotube field effect transistor only needs a semiconductor carbon nanotube, and the existence of the metal SWCNTs can easily cause the conduction of a source electrode and a drain electrode of a device, so that the turn-off of the field effect transistor cannot be realized. Especially, in the application of carbon nanotubes in highly integrated micro-nano electronic devices, it is usually necessary to integrate thousands of devices on a wafer-level substrate, and if one of the devices is degraded in performance due to the presence of the metal carbon nanotubes, the failure of the whole integrated circuit will be caused. This requires the macroscopic preparation of pure semiconducting carbon nanotubes. In recent years, the research of solution separation technology on the separation of SWCNTs structure has made a breakthrough. Separation techniques such as density gradient centrifugation, ion exchange chromatography, two-phase separation, and gel chromatography have been reported in succession. The gel chromatography separation technology in the separation technologies has the characteristics of simplicity, high efficiency, low cost and easiness in automatic separation, and can realize the macro preparation of the high-purity semiconductor carbon nano tube. By utilizing the technology, not only are metal/semiconductor SWCNTs with higher purity separated, but also thirteen near-single chiral semiconductor SWCNTs, even near-single chiral SWCNT mirror images are separated, and a material guarantee is provided for the application of the carbon nano tube in the aspect of integrated circuits.
However, the high purity semiconductor carbon nanotubes separated and prepared by the liquid phase separation technology usually exist in the form of solution, and how to deposit the carbon nanotube dispersion on the substrate with the wafer area is still a great problem in preparing the carbon nanotube film with uniform thickness and controllable density. The controllable preparation of the carbon nanotube film with uniform wafer area is the key for ensuring the performance stability and controllability of the carbon nanotube integrated circuit. At present, methods for preparing carbon nanotube films by depositing carbon nanotube dispersion liquid mainly comprise a spin coating method, a suction filtration method, a printing method, a dip coating method and the like, but the methods have some defects respectively, and the carbon nanotube films with uniform wafer area and thickness and controllable density cannot be prepared. The carbon nanotube film obtained by the spin-coating method is sparse, if a denser film needs to be obtained, a carbon nanotube solution with higher concentration needs to be used, and multiple spin-coating is needed, so that the carbon nanotube dispersion liquid is wasted, and the uniformity of the prepared film is poor; the suction filtration method needs a large amount of carbon nano tube dispersion liquid, the thickness of the prepared carbon nano tube film is usually several nanometers to dozens of nanometers, and a single-layer uniform carbon nano tube film is difficult to obtain, so that the grid regulation and control capability of the prepared carbon nano tube device is poor; the printing method depends on an expensive printer, and the continuity and the uniformity of the film are poor; the traditional dip coating method is generally suitable for carbon nanotube dispersion liquid dispersed by organic solvent and polymer, and is not suitable for carbon nanotube dispersion liquid dispersed by common surfactant.
In order to make carbon nanotubes have better applications in large-scale integrated circuits, there is a need for a carbon nanotube film with uniform wafer area and thickness and controllable density.
Disclosure of Invention
Therefore, the present invention is directed to a method for preparing a carbon nanotube film, which solves the problems and disadvantages of the prior art. The method provided by the invention can be used for industrially preparing the carbon nanotube film with uniform wafer area and thickness and controllable density aiming at the carbon nanotube dispersion liquid. The method provided by the invention is simple, rapid and low in cost, and lays a material guarantee foundation for the application of the carbon nano tube in the aspect of integrated circuits.
The purpose of the invention is realized by the following technical scheme.
The invention provides a preparation method of a carbon nano tube film, which comprises the following steps:
1) Preparing carbon nano tube dispersion liquid, and adjusting the pH value to be more than 7;
2) Self-assembling a polylysine (PLL, poly-L-Lysine) molecular layer or a 3-aminopropyltriethoxysilane molecular layer on the surface of the substrate;
3) Dripping the carbon nano tube dispersion liquid obtained in the step 1) on the substrate obtained in the step 2), uniformly covering the whole substrate with the carbon nano tube dispersion liquid, standing for deposition, and recovering the carbon nano tube dispersion liquid which is not deposited;
4) Cleaning the substrate obtained in the step 3) to remove the surfactant, and drying the substrate to obtain the finished product.
According to the preparation method provided by the invention, the carbon nanotube dispersion liquid can be single-wall carbon nanotube dispersion liquid, double-wall carbon nanotube dispersion liquid or multi-wall carbon nanotube dispersion liquid with different structures and different diameters; the carbon nano tubes can also be used as raw materials to prepare metallic, semiconducting, single chiral or even single helical structure carbon nano tube dispersion liquid in a separating way.
According to the preparation method provided by the invention, in the step 1), the carbon nano tube dispersion liquid is prepared by the method comprising the following steps:
mixing the carbon nano tube powder with a water solution of a surfactant, and obtaining a dispersion liquid of the carbon nano tube through ultrasonic dispersion and centrifugal purification.
Preferably, the surfactant is selected from one or more of Sodium Dodecyl Sulfate (SDS), sodium Dodecyl Benzene Sulfonate (SDBS), sodium Deoxycholate (DOC), sodium Cholate (SC), and Deoxyribonucleotide (DNA).
Preferably, the concentration of the surfactant in the carbon nanotube dispersion liquid is 0.05-1wt%; more preferably 0.1-0.5wt%.
Preferably, the concentration of the carbon nanotubes in the carbon nanotube dispersion liquid is 0.01 mu g/mL-4mg/mL; more preferably 1. Mu.g/mL to 100. Mu.g/mL.
According to the preparation method provided by the invention, in the step 1), the solution for adjusting the pH value of the carbon nanotube dispersion is selected from one or more of the following solutions:
NaHCO 3 solution, na 2 CO 3 Solution, naOH solution, KOH solution and mixed solution of the solution and NaCl.
According to the preparation method provided by the invention, in the step 1), the pH of the carbon nano tube dispersion liquid is 8-12, preferably 9-10.
According to the preparation method provided by the invention, in the step 2), the substrate can be selected from a rigid substrate or a flexible substrate;
preferably, the rigid substrate is selected from silicon wafers (SiO) 2 Si), quartz (Quartz), gallium arsenide (GaAs) or Sapphire (Sapphire) substrates, silicon carbide (SiC);
preferably, the flexible substrate is selected from polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polydimethylsiloxane (PDMS), or Polyimide (PI).
According to the preparation method provided by the invention, in the step 2), the substrate can be planar, curved, concave-convex or even three-dimensional in appearance;
preferably, the substrate may be square, circular or irregularly shaped.
According to the preparation method provided by the invention, in the step 2), the size of the substrate is larger than 4 inches, and the wafer level is reached.
According to the preparation method provided by the invention, in the step 2), the self-assembly is completed by the method comprising the following steps:
(1) preparing a polylysine aqueous solution with a concentration of 0.01-1wt% or an isopropanol solution of 3-aminopropyltriethoxysilane with a concentration of 0.01-1 wt%;
preferably, the concentration of the polylysine aqueous solution is 0.1 to 0.5wt%;
preferably, the concentration of the isopropanol solution of 3-aminopropyltriethoxysilane is 0.1-0.5wt%;
(2) cleaning and drying the substrate;
preferably, the substrate is sequentially cleaned by deionized water, alcohol and acetone for 20-40 minutes in an ultrasonic way, and N is used 2 Drying;
(3) and (3) immersing the substrate obtained in the step (2) into polylysine aqueous solution or isopropanol solution of 3-aminopropyltriethoxysilane, and standing for 5-60 minutes to obtain the nano-crystalline silicon substrate.
Preferably, in the step (3), the substrate is immersed in polylysine aqueous solution or isopropanol solution containing 3-aminopropyltriethoxysilane, and kept stand for 10-30 minutes to obtain the substrate;
optionally comprises a step (4), the substrate obtained in the step (3) is cleaned and dried, preferably deionized water is used for cleaning, preferably N is used for cleaning 2 And (5) drying.
According to the preparation method provided by the invention, in the step 3), the temperature of the standing deposition is in the range of 15-70 ℃, preferably 20-50 ℃, and more preferably 22-28 ℃.
According to the preparation method provided by the invention, in the step 3), the standing and depositing time is 1 minute to 20 hours, preferably 10 minutes to 5 hours; the density of the carbon nanotube film is determined by the concentration of the used carbon nanotube dispersion liquid and the standing time, wherein the concentration of the used carbon nanotube dispersion liquid is 0.01 mu g/mL-4mg/mL, and the higher the concentration is, the higher the density of the deposited carbon nanotube film is; the standing time is in the range of 1 minute to 20 hours, and the longer the standing time is, the higher the density of the deposited carbon nanotube film is, and a person skilled in the art can adjust the appropriate deposition time according to application requirements.
According to the preparation method provided by the invention, in the step 4), one or more of deionized water, methanol, ethanol, acetone and toluene are used for cleaning;
preferably, the blow-drying uses an inert gas or N 2 (ii) a More preferably, the inert gas is argon. Compared with the prior art, the method provided by the invention has the following advantages:
1. the method provided by the invention can realize the controllable deposition of the large-area uniform carbon nanotube film on the PLL functionalized substrate by adjusting the pH value of the carbon nanotube dispersion liquid to be alkaline and realizing the synergistic effect between the carbon nanotube dispersion liquid and a polylysine (PLL, poly-L-Lysine) molecular layer or a 3-Aminopropyltriethoxysilane (APTES) molecular layer which is self-assembled on the surface of the substrate;
2. the invention can prepare the wafer-level uniform carbon nanotube film, has no limitation on the carbon nanotube raw material, the dispersant type and the target substrate, namely the large-area uniform carbon nanotube film can be prepared on any substrate by using any carbon nanotube dispersion liquid dispersed by the dispersant;
3. the method is simple to operate, the carbon nanotube films with different densities can be obtained by controlling the time and the concentration of the carbon nanotube dispersion liquid, various different use requirements are met, and the automatic and large-scale continuous preparation of the wafer-level carbon nanotube film can be realized;
4. the invention does not need a large amount of dispersion liquid of the carbon nano tube to soak the substrate, and the prepared solution can be recycled, thereby greatly saving raw materials and reducing the cost.
Based on the above, the carbon nanotube film prepared by the method provided by the invention has a good application prospect in large-scale integrated circuits and large-area transparent conductive films.
Drawings
Embodiments of the invention are described in detail below with reference to the attached drawing figures, wherein:
FIG. 1 shows a substrate and selected spot locations in accordance with one embodiment of the present invention, where FIGS. a and b show 4 inches of SiO in FIG. 1, respectively 2 Selecting 9 point test Atomic Force Microscope (AFM) pictures at different positions on a Si wafer and a 2x2cm quartz substrate to check the morphology and the density of the carbon tube film;
FIG. 2 is a photograph of a wafer-scale semiconducting carbon nanotube film obtained according to example 1 of the present invention, showing an Atomic Force Microscope (AFM) topography of a representative carbon nanotube film on a substrate;
FIG. 3 is an Atomic Force Microscope (AFM) photograph of a wafer-shaped semiconductor carbon nanotube film obtained in example 1 according to the present invention, wherein the Atomic Force Microscope (AFM) photograph shows micro-regions of the semiconductor carbon nanotube film having diameters in the range of 1. + -. 0.3 nm, wherein 1 to 9 respectively show the morphologies of the carbon nanotube film corresponding to the corresponding regions in FIG. 1 (a);
FIG. 4 shows an embodiment 2 according to the invention at 2X2cm 2 Semiconductor carbon nano-particles with diameter range of 1.4 +/-0.3 nm deposited on ST-cut quartz substrateThe tube thin film micro-area Atomic Force Microscope (AFM) photographs, 1-9, respectively show the morphologies of the carbon nanotube thin films corresponding to the corresponding areas in FIG. 1 (b).
FIG. 5 shows an embodiment 3 according to the invention at 2X2cm 2 Atomic Force Microscope (AFM) photographs of micro-regions of the semiconductor carbon nanotube film with a diameter range of 1.4 + -0.3 nm deposited on an ST-cut quartz substrate, 1-9 respectively show the morphologies of the carbon nanotube film corresponding to the corresponding regions in FIG. 1 (b).
Detailed Description
The present invention is described in further detail below with reference to specific embodiments, which are provided to illustrate the present invention in detail, but not to limit the scope of the present invention.
Example 1
Using the method of the present invention, at 4 inches of SiO 2 Semiconductor carbon nanotube film deposited on Si wafer with diameter range of 1 + -0.3 nm:
1) The carbon nanotube is semiconductor carbon nanotube dispersion with purity higher than 95% obtained by separating HiPco carbon nanotube (Nanoinegris, diameter 1 + -0.3 nm) by gel chromatography, the concentration is 1 μ g/mL, the surfactant in the solution is sodium deoxycholate with concentration of 0.05-0.5wt%, and NaCl/NaHCO is added 3 And (4) adjusting the pH to be 8 for depositing the carbon nano tube film.
2) Take a 4 inch piece of SiO 2 silicon/Si wafer, siO 2 Is 500nm, is cleaned by ultrasonic cleaning with deionized water, alcohol and acetone for 30 minutes in sequence, and is treated with N 2 Blow-drying, namely cleaning the SiO 2 Putting the silicon wafer/Si into Polylysine (PLL) water solution with the mass concentration of 0.5wt%, standing for 15 minutes, taking out, washing with deionized water, and using N 2 And drying by blowing, and obtaining the self-assembled polylysine molecular layer on the surface of the substrate.
3) Taking 10mL of the carbon nano tube dispersion liquid obtained in the step 1) to be dripped on the surface of the silicon wafer, uniformly coating the whole silicon wafer, standing for 5 hours at room temperature, and recovering the non-deposited SiO 2 A carbon nanotube dispersion on a Si silicon wafer;
4) Cleaning SiO with deionized water 2 N used together with Si substrate 2 Blow-drying over 4 inches of SiO 2 the/Si silicon wafer was deposited to obtain a uniform carbon nanotube film as shown in fig. 2.
Referring to the position of fig. 1 (a), the carbon nanotube film obtained according to the present embodiment at different positions on a 4-inch silicon wafer has a profile as shown in fig. 3; as can be seen from the figure, the method of the invention deposits the continuous and uniform semiconductor carbon nanotube film on the whole surface of the substrate, and is suitable for preparing the carbon nanotube large-scale integrated circuit.
Example 2
Using the method of the invention, at 2x2cm 2 Depositing a carbon nanotube film on a quartz substrate (ST-cut quartz):
1) The carbon nano tube is semiconductor carbon nano tube dispersion liquid with the purity higher than 95 percent, which is obtained by separating Arc-discharge carbon nano tubes (Nanointegris, the diameter is 1.4 +/-0.3 nanometers) by adopting gel chromatography, the concentration is 100 mu g/mL, the surfactant in the dispersion liquid is sodium deoxycholate, the concentration is 0.1wt percent, naCl/NaOH solution is added, the pH is adjusted to be 10, and the dispersion liquid is used for depositing the carbon nano tube film.
2) Taking a piece of 2x2cm 2 Ultrasonic cleaning quartz substrate (ST-cut quartz) with deionized water, alcohol, and acetone sequentially for 30 min, and treating with N 2 Blow drying, placing the cleaned quartz substrate in 0.01 wt% Polylysine (PLL) aqueous solution, standing for 15 min, taking out, cleaning with deionized water and washing with N 2 And drying by blowing, and obtaining the self-assembled polylysine molecular layer on the surface of the substrate.
3) Taking 400 mu L of the carbon nano tube dispersion liquid obtained in the step 1) to be dripped on the surface of the quartz substrate, uniformly coating the whole quartz substrate, standing for 10 minutes at 50 ℃, and recovering the carbon nano tube dispersion liquid which is not deposited on the quartz substrate;
4) Cleaning the quartz substrate with deionized water and using N 2 Blow-drying to obtain the area of 2x2cm 2 Continuous and uniform semiconductor carbon nanotube film with large diameter.
Referring to the position of FIG. 1 (b), the morphology of the carbon nanotube film obtained according to this embodiment is shown in FIG. 4; as can be seen from the figure, the method of the invention deposits a continuous and uniform semiconductor carbon nanotube film on the whole surface of the substrate, and is suitable for preparing a carbon nanotube large-scale integrated circuit.
Example 3
Using the method of the invention, at 2x2cm 2 Depositing a carbon nanotube film on a quartz substrate (ST-cut quartz):
1) The carbon nanotube is semiconductor carbon nanotube dispersion liquid with purity higher than 95% obtained by separating Arc-discharge carbon nanotube (diameter of 1.4 + -0.3 nm) by gel chromatography, the concentration is 50 μ g/mL, the surfactant in the solution is sodium deoxycholate with concentration of 0.1wt%, and NaCl/NaHCO is added 3 And (4) adjusting the pH to be 8, and depositing the carbon nanotube film.
2) Taking a piece of 2x2cm 2 A quartz substrate (ST-cut quartz), ultrasonic cleaning with deionized water, alcohol and acetone for 30 minutes in sequence, and treating with N 2 Blow-drying, placing the cleaned quartz substrate into 1wt% isopropanol solution of 3-aminopropyltriethoxysilane, standing for 15 min, taking out, cleaning with deionized water, and washing with N 2 And drying by blowing, and obtaining the self-assembled 3-aminopropyltriethoxysilane molecular layer on the surface of the substrate.
3) Taking 400 mu L of the carbon nano tube dispersion liquid obtained in the step 1) to be dripped on the surface of the quartz substrate, uniformly coating the whole quartz substrate, standing for 60 minutes at room temperature, and recovering the carbon nano tube dispersion liquid which is not deposited on the quartz substrate;
4) Cleaning the quartz substrate with deionized water and using N 2 Blow-drying to obtain the area of 2x2cm 2 A continuous uniform film of semiconducting carbon nanotubes of large diameter.
Referring to the position of fig. 1 (b), the morphology of the carbon nanotube film obtained according to the present embodiment is shown in fig. 5; as can be seen from the figure, the method of the invention deposits the continuous and uniform semiconductor carbon nanotube film on the whole surface of the substrate, and is suitable for preparing the carbon nanotube large-scale integrated circuit.
Comparative example 1
Comparative example 1 a carbon nanotube film was prepared with reference to the prior art scheme:
1) The carbon nanotube is semiconductor carbon nanotube dispersion liquid with purity higher than 95% obtained by separating HiPco carbon nanotube (Nanoinegris, diameter of 1 +/-0.3 nm) by gel chromatography, the concentration is 100 mug/mL, and the surfactant in the solution is sodium deoxycholate, and the concentration is 0.5wt%.
2) Take a 2 inch piece of SiO 2 silicon/Si wafer, siO 2 The thickness of the glass is 500nm, ultrasonic cleaning is carried out for 30 minutes by using deionized water, alcohol and acetone in sequence, and blow-drying is carried out by using N2 for standby.
3) And (2) dripping 1mL of the carbon nanotube solution obtained in the step 1) on the surface of the silicon wafer, manually, stably, continuously and moderately inclining the substrate at room temperature to ensure that the carbon nanotube dispersion liquid continuously, uniformly and stably flows through the position of the surface of the substrate but does not overflow the substrate, in the flowing process, the solvent water is continuously evaporated, and the rest carbon tubes are remained on the surface of the substrate.
4) Cleaning SiO with deionized water 2 N combined with Si substrate 2 Blow-drying over 2 inches of SiO 2 And depositing the/Si silicon wafer to obtain the carbon nano tube film.
The scheme adopts manual continuous operation, is difficult to control, wastes time and labor, requires high concentration of the carbon nanotube dispersion liquid, is difficult to realize on a large-area (such as 2 inches) substrate, and when the area of the substrate is larger, the solution is difficult to uniformly flow in each place of the substrate through manual operation, so that the carbon nanotube film on the whole substrate is possibly locally uniform but is not uniform on the whole.
Comparative example 2
Comparative example 2 is different from example 1 in that in comparative example 2, in order to achieve uniform deposition of the carbon nanotube film, a volatile organic solvent is generally used to disperse the carbon nanotubes. In the embodiment, a pH regulation method is adopted, and the carbon nanotube film is uniformly deposited on the substrate by utilizing the pH regulation and the cooperative regulation of self-assembly molecules on the substrate. The pH of the carbon nanotube dispersion is usually in the range of 13>pH>7-13 when the pH value is less than or equal to 7, dissolvingThe interaction between the carbon nano tube in the liquid and the self-assembled monolayer on the substrate is very weak, and only a few carbon nano tubes exist on the substrate, so that a continuous carbon nano tube film cannot be formed; when the pH is 13 or more, the amino structure of polylysine may be destroyed or even the substrate (e.g., siO) may be corroded due to the strong alkalinity of the solution 2 Si silicon wafer or glass) resulting in failure to successfully prepare carbon nanotube films.
The above-mentioned embodiments are further illustrative of the purpose, process, embodiments and effective results of the present invention, it should be understood that the above-mentioned embodiments are only illustrative of the present invention and are not intended to limit the present invention, and any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (27)
1. A method for preparing a carbon nanotube film, the method comprising the steps of:
1) Preparing a carbon nano tube dispersion liquid and adjusting the pH value to be more than 7;
2) Self-assembling a polylysine molecular layer or a 3-aminopropyltriethoxysilane molecular layer on the surface of the substrate;
3) Dripping the carbon nano tube dispersion liquid obtained in the step 1) on the substrate obtained in the step 2), uniformly covering the whole substrate with the carbon nano tube dispersion liquid, standing for deposition, and recovering the carbon nano tube dispersion liquid which is not deposited;
4) Cleaning the substrate obtained in the step 3), and drying by blowing to obtain the substrate;
in step 1), the carbon nanotube dispersion is prepared by a method comprising:
mixing carbon nanotube powder with a surfactant aqueous solution, performing ultrasonic dispersion, and performing centrifugal purification to obtain a carbon nanotube dispersion solution;
the surfactant is selected from one or more of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, sodium deoxycholate, sodium cholate and deoxyribonucleotide.
2. The production method according to claim 1, wherein the concentration of the surfactant in the carbon nanotube dispersion liquid is 0.05 to 1wt%.
3. The production method according to claim 2, wherein the concentration of the surfactant in the carbon nanotube dispersion liquid is 0.1 to 0.5wt%.
4. The production method according to claim 1, wherein the concentration of carbon nanotubes in the carbon nanotube dispersion liquid is 0.01 μ g/mL to 4mg/mL.
5. The production method according to claim 4, wherein the concentration of the carbon nanotubes in the carbon nanotube dispersion is 1 μ g/mL-100 μ g/mL.
6. The method of claim 1, wherein, in step 1), the solution for adjusting the pH of the carbon nanotube dispersion is selected from one or more of:
NaHCO 3 solution, na 2 CO 3 Solution, naOH solution, KOH solution and mixed solution of the solution and NaCl.
7. The production method according to claim 1, wherein, in step 1), the pH of the carbon nanotube dispersion liquid is 8 to 12.
8. The production method according to claim 7, wherein, in step 1), the pH of the carbon nanotube dispersion liquid is 9 to 10.
9. The production method according to claim 1, wherein, in step 2), the substrate is selected from a rigid substrate or a flexible substrate.
10. The method of claim 9, wherein the rigid substrate is selected from a silicon wafer, a quartz wafer, a gallium arsenide wafer, or a sapphire substrate.
11. The method of claim 9, wherein the flexible substrate is selected from the group consisting of polyethylene terephthalate, polyethylene naphthalate, polydimethylsiloxane, or polyimide.
12. The production method according to claim 1, wherein, in step 2), the self-assembly is accomplished by a method comprising the steps of:
(1) preparing 0.01-1wt% polylysine aqueous solution or 0.01-1wt% 3-aminopropyltriethoxysilane isopropanol solution;
(2) cleaning and blow-drying the substrate;
(3) and (3) immersing the substrate obtained in the step (2) into polylysine aqueous solution or isopropanol solution of 3-aminopropyltriethoxysilane, and standing for 5-60 minutes to obtain the nano-crystalline silicon substrate.
13. The method according to claim 12, wherein the concentration of the aqueous solution of polylysine is 0.1 to 0.5wt%.
14. The method of claim 12, wherein the 3-aminopropyltriethoxysilane solution in isopropanol has a concentration of 0.1-0.5wt%.
15. The production method according to claim 12, wherein in the step (2), the substrate is cleaned and blown dry by ultrasonic cleaning of the substrate with deionized water, alcohol, acetone for 20 to 40 minutes in this order, and with N 2 And (4) drying.
16. The production method according to claim 12, wherein in step (3), the substrate is immersed in an aqueous polylysine solution or an isopropyl alcohol solution of 3-aminopropyltriethoxysilane, and allowed to stand for 10 to 30 minutes.
17. The production method according to claim 12, further comprising a step (4) of cleaning and blow-drying the substrate obtained in the step (3).
18. The production method according to claim 17, wherein, in step (4), the substrate cleaning is performed using deionized water.
19. The production method according to claim 17, wherein, in the step (4), the blow-drying uses N 2 The process is carried out.
20. The production method according to claim 1, wherein, in step 3), the temperature of the standing sedimentation ranges from 15 ℃ to 70 ℃.
21. The production method according to claim 20, wherein, in step 3), the temperature of the standing sedimentation is in the range of 20 to 50 ℃.
22. The production method according to claim 21, wherein, in step 3), the temperature of the standing sedimentation is in the range of 22 to 28 ℃.
23. The production method according to claim 1, wherein, in the step 3), the time of the standing deposition is 1 minute to 20 hours.
24. The production method according to claim 23, wherein, in the step 3), the time of the standing deposition is 10 minutes to 5 hours.
25. The method of claim 1, wherein, in the step 4), the washing uses one or more of deionized water, methanol, ethanol, acetone, and toluene.
26. The method for preparing a glass composition as defined in claim 1, wherein, in the step 4), the blow-drying uses an inert gas or N 2 。
27. The production method according to claim 26, wherein, in step 4), the inert gas is argon.
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