CN111908454A - Method for continuously preparing and transferring meter-scale single-walled carbon nanotube film and special device - Google Patents
Method for continuously preparing and transferring meter-scale single-walled carbon nanotube film and special device Download PDFInfo
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Abstract
The invention relates to a continuous preparation and transfer technology of a single-walled carbon nanotube film, in particular to a roll-to-roll continuous preparation and transfer method of a single-walled carbon nanotube film with a meter scale and a special device. Synthesizing single-walled carbon nanotubes by adopting a floating catalyst chemical vapor deposition method, and uniformly and continuously depositing a single-walled carbon nanotube film on the surface of a continuously-running microporous filter membrane by adopting a vapor suction filtration method; by adopting a roll-to-roll imprinting mode, the carbon nano tube film can be transferred to the flexible plastic substrate from the surface of the microporous filter membrane, so that a large-area uniform single-walled carbon nano tube film with meter-level width and unlimited long width can be obtained. The roll-to-roll continuous preparation and transfer technology of the single-walled carbon nanotube film provided by the invention realizes the macro preparation of the large-area and uniform single-walled carbon nanotube film under the conditions of normal pressure and room temperature, and has important significance for promoting the large-scale preparation and application of the single-walled carbon nanotube film in the field of transparent and flexible photoelectric devices in the future.
Description
Technical Field
The invention relates to a continuous preparation and transfer technology of a single-walled carbon nanotube film, in particular to a roll-to-roll continuous preparation and transfer method of a single-walled carbon nanotube film with a meter scale and a special device.
Background
The single-walled carbon nanotube film has excellent electrical, optical and mechanical properties, is used as a flexible and transparent electrical material with excellent performance, is widely applied to the field of electronic devices such as flexible thin film transistors, flexible circuits, flexible batteries and flexible transparent displays in recent years, and shows wide application prospects in future transparent and flexible electronic devices.
In the process of preparing the single-walled carbon nanotube film, the preparation method of the film is divided into dry preparation and wet preparation according to whether the film passes through the treatment processes of liquid phase dispersion and the like. The floating catalyst chemical vapor deposition method is a typical dry method for preparing single-walled carbon nanotube films, and in the process, a microporous filter membrane collecting device is arranged at the tail end of a reaction area, single-walled carbon nanotubes in vapor phase are directly deposited on a single microporous filter membrane, and the single-walled carbon nanotube films on the microporous filter membrane are transferred to substrates of plastics, glass, quartz and the like in transfer modes such as impressing and the like. [ document 1, Nasibulin AG, Kaskela A, Mustonen K, Anisimov AS, Ruiz V, Kivsto S, Rackauskasas S, Timmermans MY, Pudas, M, Aitchison B, Kauppinen M, Brown DP, Okhotnikov, OG, Kauppinen EI, ACS Nano,2011,5(4),3214-3221 ]. The liquid phase vacuum filtration film forming method and the spraying film forming method are two typical wet methods for preparing the single-walled carbon nanotube film. The liquid phase vacuum filtration membrane forming method is that a single-walled carbon nanotube film is formed on the surface of a microporous filter membrane by filtering a single-walled carbon nanotube solution, and then the microporous filter membrane is dissolved by an organic solvent to realize the transfer of the single-walled carbon nanotube film to a target substrate. [ document 2, Wu ZC, Chen ZH, Du X, Logan JM, Sippel J, Nikolou M, Kamaras K, Reynolds JR, Tanner DB, Hebard AF, Rinzler AG, Science,2004,305(5688), 1273-. The spraying film forming is that the single-wall carbon nanotube solution is directly formed into a single-wall carbon nanotube film on a target substrate in a spray nozzle spraying mode. [ document 3, Tenent RC, Barnes TM, Bergeson JD, Ferguson AJ, To B, Gedvilas LM, Heben MJ, Blackburn JL, Advanced materials,2009,21(31), 3210-.
The wet preparation process comprises a liquid phase dispersion process of the single-walled carbon nanotube, and inevitably causes the defects of structural damage, shortened length, interface pollution and the like of the carbon nanotube, so that the photoelectric property of the single-walled carbon nanotube film prepared by the wet method is far lower than an expected theoretical value. The single-walled carbon nanotube film prepared by the floating catalyst chemical vapor deposition method directly deposits the synthesized single-walled carbon nanotube on the microporous filter membrane, and the single-walled carbon nanotube in the film does not undergo any solution post-treatment process, so the single-walled carbon nanotube film has the advantages of high crystallinity, complete structure, no surface pollution and the like, and the prepared single-walled carbon nanotube film has excellent photoelectric performance. However, the single-walled carbon nanotube film prepared by the dry method can only realize the preparation of the small-area discontinuous single-walled carbon nanotube film, and the large-scale application of the single-walled carbon nanotube film in the field of large-area transparent flexible electronic devices is limited. In short, the current major bottleneck problem is how to realize continuous preparation and transfer of large-area and high-quality single-walled carbon nanotube films on the basis of dry preparation of the high-quality single-walled carbon nanotube films so as to meet the requirements of practical commercial application.
Disclosure of Invention
The invention aims to provide a continuous preparation and transfer method and a special device for a meter-scale single-walled carbon nanotube film, which overcome the discontinuity problem usually existing in the preparation of the single-walled carbon nanotube film by a floating catalyst chemical vapor deposition method.
The second purpose of the invention is to provide a roll-to-roll continuous preparation and transfer method and a special device for large-area (the width is meter-level, the length is not limited) single-walled carbon nanotube films at normal temperature and normal pressure, which overcome the problems of small size and discontinuous preparation process of the single-walled carbon nanotube films prepared by the existing method.
The technical scheme of the invention is as follows:
a method for continuously preparing and transferring a meter-scale single-walled carbon nanotube film is characterized in that the single-walled carbon nanotube film on the surface of a microporous filter membrane is transferred to a flexible plastic substrate in an impressing manner by a roll-to-roll impressing and transferring manner under the conditions of normal pressure and room temperature, so that large-area and continuous transfer to the flexible plastic substrate is realized, and the single-walled carbon nanotube film with meter-scale width, unlimited long width and uniformity is obtained.
The continuous preparation and transfer method of the meter-scale single-walled carbon nanotube film adopts a floating catalyst chemical vapor deposition method to synthesize single-walled carbon nanotubes, and the single-walled carbon nanotube film is uniformly and continuously deposited on the surface of a continuously-running microporous filter membrane by a vapor suction filtration method.
The continuous preparation and transfer method of the meter-scale single-walled carbon nanotube film comprises the steps that in the roll-to-roll imprinting transfer process, a pair of parallel rollers which run in opposite directions are used, a microporous filter membrane and a flexible plastic substrate are tightly clamped between the rollers, pressure is applied to the rollers, the microporous filter membrane and the flexible plastic substrate are tightly attached to the positions, the flexible plastic substrate is continuously pulled out from a roll of the flexible plastic substrate, the single-walled carbon nanotube film is continuously transferred onto the flexible plastic substrate from the microporous filter membrane under the continuous roller pressure of the rollers, and the transferred microporous filter membrane is used for deposition and transfer of the single-walled carbon nanotube film again, so that roll-to-roll continuous preparation and transfer of the meter-scale single-walled carbon nanotube film are realized.
A continuous preparation and transfer device for a meter-scale single-walled carbon nanotube film comprises: the floating catalyst chemical vapor deposition tube furnace comprises a floating catalyst chemical vapor deposition tube furnace, a roll type microporous filter membrane, a gas phase suction filtration chamber, a roll type flexible plastic substrate and a roller, and the specific structure is as follows:
the tail end of the floating catalyst chemical vapor deposition tube furnace is communicated with a gas phase suction filtration device through a pipeline, the gas phase suction filtration device mainly comprises a gas phase suction filtration chamber, an air exhaust port, a microporous filter membrane and rollers, two groups of rollers are symmetrically arranged, the microporous filter membrane surrounds the outer sides of the rollers which are oppositely arranged, each group of rollers comprises an upper roller, a middle roller and a lower roller, the rollers positioned in the middle outwards protrude out of other rollers, and the gas phase suction filtration chamber is arranged between the two groups of rollers in the annular microporous filter membrane; the upper part of the top opening of the gas-phase suction filtration chamber corresponds to an outlet of the single-walled carbon nanotube along the flowing direction of the carrier gas, the bottom of the gas-phase suction filtration chamber is provided with an air exhaust port, the upper part of the microporous filter membrane corresponds to the outlet of the single-walled carbon nanotube along the flowing direction of the carrier gas, and the single-walled carbon nanotube is deposited on the surface of the microporous filter membrane along the flowing direction of the single-walled carbon nanotube along the flowing direction of the carrier gas under the driving of the carrier gas.
The continuous preparation and transfer device for the meter-scale single-walled carbon nanotube film is characterized in that a microporous filter membrane surrounds a roller and a gas-phase suction filtration chamber for a circle, the roller is connected with a stepping motor, the microporous filter membrane continuously operates around the gas-phase suction filtration chamber under the transmission of the roller and the stepping motor, and air flow entering the gas-phase suction filtration chamber is discharged from an air exhaust port.
The continuous preparation and transfer device for the meter-scale single-walled carbon nanotube film comprises a flexible plastic substrate, wherein a coiled flexible plastic substrate is wound on the flexible plastic substrate, one end of the flexible plastic substrate is output along the upper horizontal direction and bypasses a group of rollers, each roller comprises an upper roller, a middle roller and a lower roller, the rollers positioned in the middle protrude outwards from other rollers, the rollers wound with the flexible plastic substrate and the rollers wound with microporous filter membranes are oppositely arranged, so that the corresponding flexible plastic substrate and the microporous filter membranes are oppositely arranged, the single-walled carbon nanotube film is rolled by the middle rollers of the two groups of opposite rollers along the operation of the microporous filter membranes, the single-walled carbon nanotube film is continuously transferred to the outer surface of the flexible plastic substrate, and one end of the flexible plastic substrate is output along the lower horizontal direction; the flexible plastic substrate is continuously pulled out from the flexible plastic substrate roll under the transmission of the roller and the stepping motor, the protective film of the flexible plastic substrate is torn off, and the protective film of the flexible plastic substrate separated from the flexible plastic substrate is wound on another roller which is independently arranged.
The continuous preparation and transfer device for the meter-scale single-walled carbon nanotube film adopts a smooth, flat and uniformly breathable flexible microporous membrane, including but not limited to a mixed cellulose membrane, a polypropylene membrane or a polyvinylidene fluoride membrane, with the thickness of 100-200 μm, the average pore diameter of 0.45-2 μm and the porosity of 75-95%; the flexible plastic substrate used is a smooth, flat, flexible transparent substrate, including but not limited to a polyethylene terephthalate substrate or a polyethylene naphthalate substrate.
The continuous preparation and transfer device for the meter-scale single-walled carbon nanotube film is characterized in that the size of the microporous filter membrane is the same as that of the flexible plastic substrate in the width direction; in the length direction, the length of the microporous filter membrane is fixed and surrounds the gas-phase suction filtration device for a circle, the length of the flexible plastic substrate is not limited, and the single-walled carbon nanotube film transferred to the flexible plastic substrate can continuously move outwards under the transmission of the roller and the stepping motor.
The design idea of the invention is as follows:
the single-walled carbon nanotube is synthesized by a floating catalyst chemical vapor deposition method, and a single-walled carbon nanotube film is uniformly and continuously deposited on the surface of the continuously moving microporous filter membrane by a vapor suction filtration film-forming method. Under the action of continuous rolling of the roller, the single-walled carbon nanotube film on the microporous filter membrane is completely and continuously transferred to the flexible plastic substrate in a roll-to-roll imprinting mode, so that a large-area uniform single-walled carbon nanotube film with meter-level width and unlimited long width is obtained; the transferred microporous filter membrane is used for the deposition and the roll-to-roll transfer of the single-walled carbon nanotube film again under the transmission of the roller and the stepping motor, and the continuous preparation and the transfer of the single-walled carbon nanotube film with large area and uniformity are realized.
The advantages and the outstanding effects of the invention are embodied in the following aspects:
1. compared with the existing single-walled carbon nanotube film forming and transferring method, the continuous preparation and transfer technology of the single-walled carbon nanotube film can realize the uniform and continuous preparation and transfer of the large-area single-walled carbon nanotube film under the conditions of normal pressure and room temperature. The existing single-walled carbon nanotube film preparation and transfer method is characterized in that: the preparation and transfer of the single-walled carbon nanotube film are discontinuous, the film forming area is small, the yield is low, and the large-scale application is difficult. The preparation and transfer technology of the single-walled carbon nanotube film, which is related by the invention, is characterized in that: based on a gas-phase suction filtration film-forming technology, the single-walled carbon nanotubes synthesized by the floating catalyst chemical vapor deposition method are uniformly and continuously deposited on the microporous filter membrane, and the film-forming area of the single-walled carbon nanotube film is large; the single-walled carbon nanotube film on the microporous filter membrane is completely and continuously transferred to the flexible plastic substrate by a pair of rollers which are arranged in parallel and run oppositely, and the transferred microporous filter membrane can be used for the secondary deposition and transfer of the single-walled carbon nanotube film.
2. The invention designs a roll-to-roll continuous transfer device of the single-walled carbon nanotube film under the conditions of normal pressure and room temperature, and realizes the complete, uniform and continuous transfer of the single-walled carbon nanotube film from the microporous filter membrane to the flexible plastic substrate by controlling the pressure and the running speed of the roller, thereby obtaining the large-area, uniform and continuous single-walled carbon nanotube film which can be widely applied to the field of flexible and transparent photoelectric devices.
Drawings
FIG. 1 is a schematic diagram of the continuous preparation and transfer of single-walled carbon nanotube films. In the figure, 1, a floating catalyst chemical vapor deposition tube furnace; 2. the single-walled carbon nanotube flows along with the carrier gas; 3. a microporous filtration membrane; 4. a single-walled carbon nanotube film; 5. pumping and filtering the chamber; 6. an air exhaust port; 7. a roll of flexible plastic substrate; 8. a flexible plastic substrate; 9. and (3) a roller.
FIG. 2 is a schematic diagram of a roll-to-roll transfer process of single-walled carbon nanotube film. In the figure, 3, a microporous filter membrane; 4. a single-walled carbon nanotube film; 8. a flexible plastic substrate; 9. a roller; 10. and (5) extruding the roller.
FIG. 3 is a schematic diagram of an axial structure of a single-walled carbon nanotube film continuous preparation and transfer device. Wherein fig. 3(a) is an isometric view of the entire device; fig. 3(b) is a partially enlarged isometric view of the roll-to-roll transfer position. In the figure, 3, a microporous filter membrane; 5. pumping and filtering the chamber; 6. an air exhaust port; 7. a roll of flexible plastic substrate; 8. a flexible plastic substrate; 9. a roller; 11. a flexible plastic substrate protective film; 12. a stepper motor.
FIG. 4 is an optical photograph and a scanning electron microscope photograph of the surface of the microporous filter membrane after 3 times of deposition and transfer.
Fig. 5 is an optical photograph of a single-walled carbon nanotube film about 2 meters long.
FIG. 6 is a TEM image of a single-walled carbon nanotube film.
FIG. 7 is a Raman spectrum of a single-walled carbon nanotube film.
Fig. 8 is a statistical distribution graph of the light transmittance (a) and the surface resistance (b) of the single-walled carbon nanotube film.
Fig. 9 is an optical photograph of a large area, transparent, flexible thin film transistor device constructed using a single-walled carbon nanotube film.
Fig. 10 is a transfer characteristic curve for a 265 carbon nanotube thin film transistor device.
Detailed Description
In the specific implementation process of the invention, the continuous preparation and transfer method of the large-area and uniform single-walled carbon nanotube film comprises the following steps:
under the conditions of normal pressure and room temperature, the microporous filter membrane continuously runs around the gas-phase suction filtration device under the transmission of a roller and a stepping motor, and the single-walled carbon nanotubes synthesized by the floating catalyst chemical vapor deposition method are uniformly and continuously deposited on the surface of the microporous filter membrane through the gas-phase suction filtration membrane forming device. In the imprinting transfer process, the microporous filter membrane and the flexible plastic substrate are tightly clamped between the rollers through the pair of rollers which run in parallel in opposite directions, pressure is applied to the rollers, the microporous filter membrane and the flexible plastic substrate are tightly attached at the position, the single-walled carbon nanotube film is continuously transferred to the flexible plastic substrate from the microporous filter membrane under the continuous roller pressure of the rollers, and the transferred microporous filter membrane can be used for deposition and transfer of the single-walled carbon nanotube film again. Meanwhile, the flexible plastic substrate is driven by the roller and the stepping motor to realize the continuous preparation and the roll-to-roll transfer of the single-walled carbon nanotube film through three processes of pulling out, roll transferring and pulling out from the flexible plastic substrate roll.
The method provides a technology for continuously depositing and transferring the single-walled carbon nanotube film under the conditions of normal pressure and room temperature. The technology integrates the growth, film forming and transfer processes of the single-walled carbon nanotube, simplifies the preparation steps of the single-walled carbon nanotube film, does not destroy the intrinsic structure of the single-walled carbon nanotube, realizes the continuous preparation and transfer of the single-walled carbon nanotube film with high quality, meter-sized width and unlimited length, and meets the large-scale preparation requirements of the film in large-area, transparent and flexible electronic devices.
As shown in fig. 1-3, the continuous preparation and transfer device for single-walled carbon nanotube film of the present invention mainly comprises: the device comprises a floating catalyst chemical vapor deposition tube furnace 1, a microporous filter membrane 3, a suction filtration chamber 5, a flexible plastic substrate 8, a roller 9 and the like, and has the following specific structure:
the tail end of the floating catalyst chemical vapor deposition tube furnace 1 is communicated with a gas phase suction filtration device through a pipeline, the gas phase suction filtration device mainly comprises a suction filtration chamber 5, an air exhaust port 6, a microporous filter membrane 3, rollers 9 and the like, two groups of rollers 9 are symmetrically arranged, the microporous filter membrane 3 surrounds the outer sides of the rollers 9 which are oppositely arranged, each group of rollers 9 comprises an upper roller, a middle roller and a lower roller, the rollers positioned in the middle outwards protrude out of other rollers, and the suction filtration chamber 5 is arranged between the two groups of rollers 9 in the annular microporous filter membrane 3; the upper part of the top opening of the suction filtration chamber 5 corresponds to the outlet of the single-walled carbon nanotube along the flow direction 2 of the carrier gas, the bottom of the suction filtration chamber 5 is provided with an air exhaust port 6, the upper part of the microporous filter membrane 3 corresponds to the outlet of the single-walled carbon nanotube along the flow direction 2 of the carrier gas, and the single-walled carbon nanotube is deposited on the surface of the microporous filter membrane 3 along the flow direction 2 of the single-walled carbon nanotube along the carrier gas under the driving of the carrier gas to form a single-walled carbon nanotube film; the microporous filter membrane 3 surrounds the gas-phase suction filtration chamber 5 for a circle, the microporous filter membrane 3 can continuously run around the suction filtration chamber 5 under the transmission of the roller 9 and the stepping motor 12, and the air flow entering the suction filtration chamber 5 is discharged from the air suction port 6.
A flexible plastic substrate roll 7 is provided with a rolled flexible plastic substrate 8, one end of the flexible plastic substrate 8 is output along the upper horizontal direction and bypasses a group of rollers 9, each roller 9 comprises an upper roller, a middle roller and a lower roller, the roller positioned in the middle protrudes outwards from other rollers, the rollers 9 wound with the flexible plastic substrate 8 are arranged opposite to the rollers 9 wound with the microporous filter membrane 3, so that the corresponding flexible plastic substrate 8 and the microporous filter membrane 3 are arranged oppositely, the single-walled carbon nanotube film 4 runs along the microporous filter membrane 3 and is rolled by the middle rollers of the two groups of opposite rollers 9, the single-walled carbon nanotube film 4 is continuously transferred to the outer surface of the flexible plastic substrate 8, and one end of the flexible plastic substrate 8 is output along the lower horizontal direction; the flexible plastic substrate 8 is continuously pulled out from the flexible plastic substrate roll 7 under the transmission of the roller 9 and the stepping motor 12, the flexible plastic substrate protective film 11 is torn off, and the flexible plastic substrate protective film 11 separated from the flexible plastic substrate 8 is wound on another roller which is independently arranged.
As shown in figure 1, the single-walled carbon nanotube is synthesized in a floating catalyst chemical vapor deposition tube furnace 1, and is deposited on a microporous filter membrane 3 along with the single-walled carbon nanotube along with a carrier gas flowing direction 2, the carrier gas enters a suction filtration chamber 5, and is finally discharged from an air exhaust port 6. The flexible plastic substrate 8 is continuously pulled out from the flexible plastic substrate roll 7, the single-walled carbon nanotube film 4 deposited on the microporous filter membrane 3 is continuously transferred onto the flexible plastic substrate 8 under the continuous rolling of the roller 9, and the transferred microporous filter membrane 3 is used for deposition and transfer of the single-walled carbon nanotube film again, so that continuous preparation and transfer of the single-walled carbon nanotube film with meter-scale width and unlimited length are realized.
As shown in fig. 2, the single-walled carbon nanotube film 4 is rolled by the rollers 9 to realize roll-to-roll continuous transfer of the single-walled carbon nanotube film 4. Under the continuous extrusion action of a pair of rollers 9 which run in opposite directions and are arranged in parallel, the single-walled carbon nanotube film 4 on the microporous filter membrane 3 is closely attached to the flexible plastic substrate 8, a roller extrusion force 10 perpendicular to the plane of the attachment position is applied to the rollers 9, and the single-walled carbon nanotube film 4 is completely imprinted on the microporous filter membrane 3 and transferred to the flexible plastic substrate 8.
As shown in fig. 3(a) -3 (b), the single-walled carbon nanotube film continuous preparation and transfer device comprises a single-walled carbon nanotube film continuous deposition device and a roll-to-roll transfer device. Before the single-walled carbon nanotube film 4 is rolled and transferred, the flexible plastic substrate 8 needs to be torn off the protective film 11 of the flexible plastic substrate covering the flexible plastic substrate to expose a smooth and flat surface of the flexible plastic substrate. In addition, the microporous filter membrane 3 and the flexible plastic substrate 8 are continuously operated under the cooperative transmission of a plurality of rollers 9 and stepping motors 12.
The adopted microporous filter membrane is a smooth, flat and uniformly breathable flexible microporous membrane, and comprises but is not limited to a mixed cellulose membrane, a polypropylene membrane and a polyvinylidene fluoride membrane, the thickness of the microporous filter membrane is 100-200 mu m, the average pore diameter is 0.45-2 mu m, and the porosity is 75% -95%; the adopted flexible plastic substrate is a smooth, flat and flexible transparent substrate, and includes but is not limited to a polyethylene terephthalate (PET) substrate and a polyethylene naphthalate (PEN) substrate.
In the width direction, the sizes of the microporous filter membrane and the flexible plastic substrate are the same; in the length direction, the length of the microporous filter membrane is fixed and surrounds the gas-phase suction filtration device for a circle, the length of the flexible plastic substrate is not limited, and the single-walled carbon nanotube film transferred to the flexible plastic substrate can continuously move outwards under the transmission of the roller and the stepping motor.
The feasibility of the present invention is further demonstrated by the following examples.
Examples
In this example, the continuous preparation and transfer process of the single-walled carbon nanotube film is shown in FIG. 1. The single-walled carbon nanotube is prepared by a floating catalyst chemical vapor deposition method, the reaction temperature of the chemical vapor deposition is 1100 ℃, and ferrocene, thiophene and toluene are mixed according to the mass ratio of 6.7: 1: 222, injecting the catalyst solution into the tubular furnace at a rate of 4 mu L/min, simultaneously introducing 8000sccm hydrogen and 11sccm ethylene into the tubular furnace, and allowing the hydrogen and the ethylene to carry the catalyst to enter a constant-temperature reaction region of the tubular furnace to synthesize the single-walled carbon nanotube. The synthesized single-walled carbon nanotube flows into the gas-phase suction filtration device from the tail end of the tube furnace along with the carrier gas, the gas flow rate at the gas extraction port is adjusted, the gas flow of about 8011sccm flowing into the gas-phase suction filtration device is completely extracted from the gas extraction port, the single-walled carbon nanotube is uniformly deposited on a microporous filter membrane (such as a polypropylene membrane, the thickness of which is 150 μm, the average pore diameter is 1 μm, and the porosity is 85%) at the outlet position in the flow direction of the carrier gas, and a single-walled carbon nanotube film with the width of 0.5m is formed; the microporous filter membrane continuously runs around the gas-phase suction filtration chamber at a moving speed of about 1mm/s under the transmission of the roller and the stepping motor, and the continuous deposition of the single-walled carbon nanotube film with the width of 0.5m is realized. The single-walled carbon nanotube film was transferred to the surface of a flexible PET substrate having a width of 0.6m at a transfer rate of about 1mm/s under a roll pressure of about 10 kPa. The transferred microporous filter membrane can be used for the deposition and transfer of the single-walled carbon nanotube film again.
As shown in fig. 4, after 3 times of deposition and transfer, the surface of the microporous filter membrane still remained clean and flat, and the scanning electron microscope shows that no single-walled carbon nanotube remained on the surface of the microporous filter membrane after transfer. As shown in fig. 5, by the continuous preparation and transfer method, a single-walled carbon nanotube film having a length of about 2m was obtained on a flexible PET substrate. As shown in fig. 6, the tem image of the single-walled carbon nanotube film is mainly composed of single-walled carbon nanotubes overlapped with each other, and the diameter of the single-walled carbon nanotubes is about 2.0 nm. As shown in FIG. 7, the high G/D peak intensity ratio of the Raman spectrum curve of the film shows that the film has few defects of single-walled carbon nanotubes and high quality. As shown in fig. 8, the average light transmittance and the surface resistance of the single-walled carbon nanotube film and the corresponding standard deviation are 90% ± 0.35% and 65 Ω/□ ± 4.9 Ω/□ respectively, and the single-walled carbon nanotube film exhibits excellent photoelectric properties and uniformity. As shown in fig. 9, a large-area, transparent, flexible carbon nanotube thin film transistor electronic device is fabricated using the currently fabricated large-area single-walled carbon nanotube thin film as a transparent, flexible electrode material. As shown in fig. 10, the transfer characteristic curve of the source-drain current of 265 thin film transistors varying with the gate-source voltage shows excellent performance uniformity for all devices; the result shows that the single-walled carbon nanotube film has good application prospect in large-area, low-cost and large-scale preparation of transparent and flexible carbon nanotube film transistor devices.
The embodiment result shows that the continuous preparation and transfer technology of the single-walled carbon nanotube film provided by the invention realizes continuous macro preparation and transfer of a large-area and uniform single-walled carbon nanotube film under the conditions of normal pressure and room temperature to obtain a meter-scale and uniform single-walled carbon nanotube film, and has important significance for promoting large-scale preparation and application of the single-walled carbon nanotube film in the field of transparent and flexible photoelectric devices in the future.
Claims (8)
1. A continuous preparation and transfer method of a meter-scale single-walled carbon nanotube film is characterized in that the single-walled carbon nanotube film on the surface of a microporous filter membrane is subjected to roll-to-roll imprinting transfer under the conditions of normal pressure and room temperature, and the single-walled carbon nanotube film is imprinted and transferred to a flexible plastic substrate from the surface of the microporous filter membrane, so that large-area continuous transfer to the flexible plastic substrate is realized, and the single-walled carbon nanotube film with meter-scale width, unlimited long width and uniformity is obtained.
2. The method for continuously preparing and transferring a meter-scale single-walled carbon nanotube film according to claim 1, wherein single-walled carbon nanotubes are synthesized by a floating catalyst chemical vapor deposition method, and the single-walled carbon nanotube film is uniformly and continuously deposited on the surface of a continuously operable microporous filter membrane by a vapor suction filtration method.
3. The method for continuously preparing and transferring the meter-scale single-walled carbon nanotube film according to claim 1, wherein in the roll-to-roll imprinting transfer process, a pair of parallel rollers operating in opposite directions are used, the microfiltration membrane and the flexible plastic substrate are tightly clamped between the rollers, pressure is applied to the rollers, the microfiltration membrane and the flexible plastic substrate are tightly attached to each other at the position, the flexible plastic substrate is continuously pulled out from the roll of the flexible plastic substrate, the single-walled carbon nanotube film is continuously transferred onto the flexible plastic substrate from the microfiltration membrane under the continuous roller pressure of the rollers, and the transferred microfiltration membrane is used for deposition and transfer of the single-walled carbon nanotube film again, so that roll-to-roll continuous preparation and transfer of the meter-scale single-walled carbon nanotube film are realized.
4. A continuous preparation and transfer device for the meter-scale single-walled carbon nanotube film used in the method of any one of claims 1 to 3, the device comprising: the floating catalyst chemical vapor deposition tube furnace comprises a floating catalyst chemical vapor deposition tube furnace, a roll type microporous filter membrane, a gas phase suction filtration chamber, a roll type flexible plastic substrate and a roller, and the specific structure is as follows:
the tail end of the floating catalyst chemical vapor deposition tube furnace is communicated with a gas phase suction filtration device through a pipeline, the gas phase suction filtration device mainly comprises a gas phase suction filtration chamber, an air exhaust port, a microporous filter membrane and rollers, two groups of rollers are symmetrically arranged, the microporous filter membrane surrounds the outer sides of the rollers which are oppositely arranged, each group of rollers comprises an upper roller, a middle roller and a lower roller, the rollers positioned in the middle outwards protrude out of other rollers, and the gas phase suction filtration chamber is arranged between the two groups of rollers in the annular microporous filter membrane; the upper part of the top opening of the gas-phase suction filtration chamber corresponds to an outlet of the single-walled carbon nanotube along the flowing direction of the carrier gas, the bottom of the gas-phase suction filtration chamber is provided with an air exhaust port, the upper part of the microporous filter membrane corresponds to the outlet of the single-walled carbon nanotube along the flowing direction of the carrier gas, and the single-walled carbon nanotube is deposited on the surface of the microporous filter membrane along the flowing direction of the single-walled carbon nanotube along the flowing direction of the carrier gas under the driving of the carrier gas.
5. The continuous preparation and transfer device for the meter-scale single-walled carbon nanotube film according to claim 4, wherein the microporous filter membrane surrounds the roller and the gas-phase suction filtration chamber for a circle, the roller is connected with the stepping motor, the microporous filter membrane continuously operates around the gas-phase suction filtration chamber under the transmission of the roller and the stepping motor, and the gas flow entering the gas-phase suction filtration chamber is discharged from the gas exhaust port.
6. The continuous preparation and transfer device of meter-scale single-walled carbon nanotube film according to claim 4, wherein the flexible plastic substrate is wound up and mounted with a roll of flexible plastic substrate, one end of the flexible plastic substrate is output along the upper horizontal direction and bypasses a set of rollers, the rollers comprise an upper roller, a middle roller and a lower roller, the rollers located in the middle protrude outwards from other rollers, the rollers wound with the flexible plastic substrate are arranged opposite to a set of rollers wound with the microporous filter membrane, so that the corresponding flexible plastic substrate and the microporous filter membrane are arranged opposite to each other, the single-walled carbon nanotube film is rolled by the middle rollers of the two sets of opposite rollers along the microporous filter membrane, the single-walled carbon nanotube film is continuously transferred to the outer surface of the flexible plastic substrate, and one end of the flexible plastic substrate is output along the lower horizontal direction; the flexible plastic substrate is continuously pulled out from the flexible plastic substrate roll under the transmission of the roller and the stepping motor, the protective film of the flexible plastic substrate is torn off, and the protective film of the flexible plastic substrate separated from the flexible plastic substrate is wound on another roller which is independently arranged.
7. The continuous preparation and transfer device for the meter-scale single-walled carbon nanotube film according to claim 4, wherein the microporous membrane is a smooth, flat, air-permeable and uniform flexible microporous membrane, including but not limited to a mixed cellulose membrane, a polypropylene membrane or a polyvinylidene fluoride membrane, with a thickness of 100-200 μm, an average pore diameter of 0.45-2 μm, and a porosity of 75-95%; the flexible plastic substrate used is a smooth, flat, flexible transparent substrate, including but not limited to a polyethylene terephthalate substrate or a polyethylene naphthalate substrate.
8. The continuous preparation and transfer device for the meter-scale single-walled carbon nanotube film according to claim 4, wherein the microporous filter membrane and the flexible plastic substrate have the same size in the width direction; in the length direction, the length of the microporous filter membrane is fixed and surrounds the gas-phase suction filtration device for a circle, the length of the flexible plastic substrate is not limited, and the single-walled carbon nanotube film transferred to the flexible plastic substrate can continuously move outwards under the transmission of the roller and the stepping motor.
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