CN109913861B - Method for preparing carbon nano tube film - Google Patents
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- CN109913861B CN109913861B CN201711332304.8A CN201711332304A CN109913861B CN 109913861 B CN109913861 B CN 109913861B CN 201711332304 A CN201711332304 A CN 201711332304A CN 109913861 B CN109913861 B CN 109913861B
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Abstract
Provided is a method of preparing a carbon nanotube film, which includes: contacting the carbon nanotube solution with the surface of the substrate, and moving the carbon nanotube solution along a set direction relative to the surface of the substrate; and separating the surface of the substrate from the carbon nanotube solution, and drying the surface of the substrate to form a carbon nanotube film on the surface of the substrate.
Description
Technical Field
The present disclosure relates to carbon nanotubes, and more particularly, to a method of preparing a carbon nanotube film.
Background
Carbon nanotubes are considered to be excellent building materials for electronic devices in the post-molar times due to their excellent electrical properties and stability. In recent years, carbon nanotube network-like thin films have been increasingly emphasized. This is mainly based on the following two reasons: firstly, the semiconductor type carbon nanotube solution with the purity of more than 99 percent is commercialized due to the development of the separation and purification technology of the carbon nanotube solution; and on the basis of the seepage transport principle, the semiconductor type carbon nanotube film with the purity of not 100 percent is used as a channel material to prepare the transistor with high on-off ratio. These research advances have enabled devices based on carbon nanotube films to find applications in display driving, biosensing and sensing, among other fields.
The carbon nanotube orientation distribution in a typical carbon nanotube network-like thin film is disordered, so that the carbon nanotube network-like thin film contains a large number of cross nodes among the carbon nanotubes. The resistance of the junction is large, which results in a relatively small on-current and mobility of the device. However, it is also not favorable for device performance if the carbon nanotubes are aligned completely in parallel in a certain direction. This is because if they are completely parallel, there is no crossing junction between the carbon nanotubes, and the carbon nanotubes are in contact with each other to form a via. This in turn can lead to a reduction in the actual via count and thus detriment to device performance.
At present, there is no method for preparing a carbon nanotube film, in which a plurality of carbon nanotubes are arranged in parallel along a certain direction, and a small number of carbon nanotubes deviate from the direction to serve as connections between the parallel carbon nanotubes to assist in forming a conductive path, thereby reducing the number of nodes in the path to a certain extent, and ensuring the formation of a large number of paths, which is most beneficial to the device performance.
Disclosure of Invention
According to an aspect of the present disclosure, there is provided a method of preparing a carbon nanotube thin film, including: contacting the carbon nanotube solution with the surface of the substrate, and moving the carbon nanotube solution along a set direction relative to the surface of the substrate; and separating the surface of the substrate from the carbon nanotube solution, and drying the surface of the substrate to form a carbon nanotube film on the surface of the substrate.
According to at least one embodiment of the present disclosure, the step of moving the carbon nanotube solution in a set direction with respect to the surface of the substrate includes: the carbon nanotube solution is moved in a set direction at a set rate relative to the surface of the substrate.
According to at least one embodiment of the present disclosure, the substrate is a rigid substrate, and the step of moving the carbon nanotube solution in a set direction with respect to the surface of the substrate includes: the carbon nanotube solution is formed as a continuous stream flowing over the surface of the substrate.
According to at least one embodiment of the present disclosure, the step of forming the carbon nanotube solution into a continuous flow flowing on the surface of the substrate comprises: flowing a carbon nanotube solution into the container from a first end of the container and out of the container from a second end of the container, wherein the substrate is disposed in the container.
According to at least one embodiment of the present disclosure, the substrate is a flexible substrate, and the step of moving the carbon nanotube solution in a set direction with respect to the surface of the substrate includes: the substrate is moved in a set direction.
According to at least one embodiment of the present disclosure, the step of moving the substrate in the set direction includes: the substrate is fed into the container from a first end of the container and the substrate is removed from the container from a second end of the container, wherein the carbon nanotube solution is disposed in the container.
According to at least one embodiment of the present disclosure, the carbon nanotube solution is a single-walled carbon nanotube solution.
According to at least one embodiment of the present disclosure, the carbon nanotubes in the carbon nanotube film are preferentially oriented in a set direction.
According to at least one embodiment of the present disclosure, the density of the carbon nanotube film and the degree of orientation of the carbon nanotubes in the carbon nanotube film are related to a set rate and a concentration of the carbon nanotube solution.
According to at least one embodiment of the present disclosure, a rigid substrate includes: a silicon substrate, a glass substrate, a plastic, or a metal substrate.
According to another aspect of the present disclosure, there is provided a transistor including a source electrode, a drain electrode, and a channel between the source electrode and the drain electrode, the channel including a carbon nanotube film prepared by the method of preparing a carbon nanotube film described above.
Drawings
The accompanying drawings, which are included to provide a further understanding of the disclosure and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the disclosure and together with the description serve to explain the principles of the disclosure.
Fig. 1 schematically illustrates a flow diagram of a method of making a carbon nanotube film, according to some embodiments of the present disclosure;
fig. 2(a) shows a scanning electron microscope image of a carbon nanotube film prepared by a method of preparing a carbon nanotube film according to some embodiments of the present disclosure;
fig. 2(b) shows a scanning electron microscope image of a carbon nanotube thin film formed in the related art;
FIG. 3 illustrates a process for preparing a carbon nanotube film on a rigid substrate according to some embodiments of the present disclosure; and
fig. 4 illustrates a process of preparing a carbon nanotube film on a flexible substrate according to some embodiments of the present disclosure.
Detailed Description
The present disclosure is described in further detail below with reference to the accompanying drawings and examples. It is to be understood that the specific embodiments described herein are merely illustrative of the relevant disclosure and not restrictive of the disclosure. It should be further noted that, for the convenience of description, only the portions relevant to the present disclosure are shown in the drawings.
It should be noted that, in the present disclosure, the embodiments and features of the embodiments may be combined with each other without conflict. The present disclosure will be described in detail below with reference to the accompanying drawings in conjunction with embodiments.
The carbon nanotube solution referred to in the present disclosure refers to a solution formed by dispersing carbon nanotubes in water or an organic solvent.
The degree of orientation of carbon nanotubes in a carbon nanotube film referred to in this disclosure refers to the ratio of the number of carbon nanotubes in the carbon nanotube film aligned in a particular direction to the total number of carbon nanotubes in the carbon nanotube film.
Reference to preferred orientation in this disclosure refers to the direction having the highest degree of orientation, i.e., the direction having the highest ratio of the number of carbon nanotubes aligned along that direction to the total number of carbon nanotubes in the film.
Fig. 1 schematically illustrates a flow diagram of a method of preparing a carbon nanotube film, according to some embodiments of the present disclosure. Methods of preparing carbon nanotube films according to some embodiments of the present disclosure may include:
s1, making the carbon nanotube solution contact with the surface of the substrate and making the carbon nanotube solution move along the set direction relative to the surface of the substrate; and
and S2, separating the surface of the substrate from the carbon nano tube solution, and drying the surface of the substrate to form a carbon nano tube film on the surface of the substrate.
In step S1, the carbon nanotube solution may be prepared in advance, for example, by dispersing the carbon nanotube raw material in water or an organic solvent (e.g., toluene, xylene, chloroform, etc.) to form the carbon nanotube solution. In some embodiments, a previously prepared carbon nanotube solution is contained in a container, and then a substrate on which a carbon nanotube film is to be deposited is placed in the carbon nanotube solution such that the carbon nanotube solution is in contact with a surface of the substrate. In other embodiments, a substrate on which a carbon nanotube film is to be deposited is placed in a container, and a previously prepared carbon nanotube solution is then supplied into the container so that the carbon nanotube solution is in contact with a surface of the substrate. The carbon nanotube solution may be contacted with one or more surfaces of the substrate, as desired. In the case where only a carbon nanotube film needs to be deposited on the upper surface of the substrate, the lower surface of the substrate may be in contact with the bottom of the container, such that only the upper surface of the substrate is in contact with the carbon nanotube solution. In the case where it is desired to deposit carbon nanotube films on both the upper and lower surfaces of the substrate, the substrate may be suspended in a carbon nanotube solution such that both the upper and lower surfaces of the substrate are in contact with the carbon nanotube solution. For example, the substrate may be suspended in the carbon nanotube solution by providing a holder, a guide, or the like in the container, or the substrate may be suspended in the carbon nanotube solution by suspension or the like.
In step S1, the carbon nanotube solution may be moved in a set direction, or the substrate may be moved in a set direction, or the carbon nanotube solution and the substrate may be moved in opposite directions. In some embodiments, the carbon nanotube solution can be moved along a set method by a motive device while remaining in contact with a surface of a substrate on which the carbon nanotube film is to be deposited. The power means may be, for example, a pump, a paddle, etc. In other embodiments, the carbon nanotube solution may also move due to a liquid level difference. For example, a carbon nanotube solution entering a vessel may enter the vessel at a certain velocity due to the conversion of gravitational potential energy into kinetic energy; or the container may be tilted such that the inlet end of the carbon nanotube solution into the container is higher than the outlet end of the carbon nanotube solution out of the container, thereby allowing the carbon nanotube solution to flow from the inlet end to the outlet end. Furthermore, in some embodiments, a conveyor may be provided in the container, by which the substrate may be moved in the container. The conveyor may for example comprise a spindle and a conveyor belt driven by the spindle. In some embodiments, a container may have an inclined track disposed therein along which the substrate slides under the force of gravity. By moving the carbon nanotube solution, or moving the substrate, or moving the carbon nanotube solution and the substrate, a flowing continuous stream may be formed on the surface of the substrate.
In some embodiments, the moving speed of the carbon nanotube solution or the substrate may be constant to form a carbon nanotube thin film having a uniform thickness on the surface of the substrate. The density of the formed carbon nanotube film and the degree of orientation of the carbon nanotubes in the carbon nanotube film can be determined by controlling the moving speed of the carbon nanotube solution or the substrate. However, it will be understood by those skilled in the art that the speed of movement of the carbon nanotube solution or substrate may also be varied, for example, due to the shape of the container or the external temperature.
In step S2, the surface of the substrate on which the carbon nanotube film is to be deposited is separated from the carbon nanotube solution, and the surface is subjected to a drying process, thereby forming the carbon nanotube film on the surface. In some embodiments, the substrate may be removed from the container or the carbon nanotube solution in the container may be drained, thereby separating the surface of the substrate on which the carbon nanotube film is to be deposited from the carbon nanotube solution. In addition, in some embodiments, the surface of the substrate may be dried by blowing the substrate with nitrogen, drying the substrate, spin-drying the substrate, or the like, thereby forming a carbon nanotube thin film on the surface of the substrate. The density of the formed carbon nanotube film and the degree of orientation of the carbon nanotubes in the carbon nanotube film can be determined by controlling the concentration of the carbon nanotube solution. The carbon nanotube film formed on the surface of the substrate is preferentially oriented in the moving direction of the carbon nanotube solution or in the direction opposite to the moving direction of the substrate. For example, in the case where only the carbon nanotube solution moves and both the carbon nanotube solution and the substrate move, the carbon nanotube film formed on the surface of the substrate is preferentially oriented in the moving direction of the carbon nanotube solution; and in the case where only the substrate is moved, the carbon nanotube film formed on the surface of the substrate is preferentially oriented in a direction opposite to the moving direction of the substrate.
In some embodiments, the substrate on which the carbon nanotube film is to be deposited may be rigid, such as a silicon substrate or a glass substrate. In other embodiments, the substrate on which the carbon nanotube film is to be deposited may be flexible, such as a polyimide substrate, a polyethylene terephthalate substrate, or a polyether ether ketone substrate, among others.
In some embodiments, carbon nanotube films may be deposited on multiple substrates in the same vessel, wherein the surfaces of the multiple substrates on which the carbon nanotube films are to be deposited are spaced apart from each other. In other embodiments, carbon nanotube films may be deposited on multiple substrates in multiple containers, and the multiple containers may be in fluid communication, thereby increasing the utilization of the carbon nanotube solution.
In some embodiments, the carbon nanotube solution may be a single-walled carbon nanotube solution.
The carbon nanotubes in the carbon nanotube film obtained by the method of preparing a carbon nanotube film according to the embodiments of the present disclosure are preferentially oriented. In the carbon nanotube film, a plurality of carbon nanotubes are arranged in parallel, and a plurality of carbon nanotubes in a few carbon nanotubes deviate from the arrangement direction of the plurality of carbon nanotubes to form connection of the plurality of carbon nanotubes arranged in parallel, so that the electrical conductivity of the carbon nanotube film is ensured under the condition of reducing the cross nodes among the carbon nanotubes in the carbon nanotube film. In addition, according to the method of manufacturing a carbon nanotube film of an embodiment of the present disclosure, a carbon nanotube film having carbon nanotubes with a preferred orientation can be manufactured in a large area, and a carbon nanotube film having carbon nanotubes with a preferred orientation can be formed on a plurality of substrates at one time. Compared with other modes, the method for preparing the carbon nanotube film has the advantages of simple steps, high efficiency and accordance with the requirements of industrial application.
Fig. 2(a) shows a scanning electron microscope image of a carbon nanotube thin film prepared by a method of preparing a carbon nanotube thin film according to some embodiments of the present disclosure, and fig. 2(b) shows a scanning electron microscope image of a carbon nanotube thin film formed in the related art. It can be observed from fig. 2(a) and 2(b) that in the carbon nanotube film prepared by the method of preparing a carbon nanotube film according to some embodiments of the present disclosure, carbon nanotubes have a preferred orientation while a small amount of randomly oriented carbon nanotubes are present, whereas in the carbon nanotube film formed in the related art, carbon nanotubes are randomly distributed in various directions.
Fig. 3 illustrates a process for preparing a carbon nanotube film on a rigid substrate according to some embodiments of the present disclosure. In the embodiment shown in fig. 3, the rigid substrate 201 is fixed to the bottom surface of the container 202. The pre-prepared carbon nanotube solution enters the container from one end of the container and leaves the container from the other end of the container. The arrows in fig. 3 indicate the flow direction of the carbon nanotube solution. The carbon nanotube solution may flow in the container at a set speed. The upper surface of the rigid substrate 201 is in contact with a carbon nanotube solution. After a certain period of time, the rigid substrate 201 may be taken out of the container 202, and the upper surface of the rigid substrate 201 may be dried by nitrogen blow-drying or the like, so that a carbon nanotube film may be formed on the upper surface of the rigid substrate 201, and the carbon nanotubes in the carbon nanotube film are preferentially oriented in the direction indicated by the arrow in fig. 3. In some embodiments according to the present disclosure, after forming one carbon nanotube film, the rigid substrate 201 may be rotated by a certain angle (e.g., 90 °), and then the above process may be repeatedly performed, so that two carbon nanotube films with a preferred orientation direction at a certain angle may be obtained.
Although only one vessel 202 is shown in fig. 3, it will be understood by those skilled in the art that a plurality of vessels 202 may also be provided and that the plurality of vessels 202 may be in fluid communication, thereby improving the utilization of the carbon nanotube solution. For example, in the case where there are a plurality of containers 202 connected in series and a substrate on which a carbon nanotube film is to be deposited is provided in each container 202, a carbon nanotube solution flowing out of a former container may flow into a latter container. In some embodiments, the carbon nanotube solution may be recycled in a plurality of containers 202 in fluid communication.
In the embodiment shown in fig. 3, the density of the carbon nanotube film formed on the surface of the rigid substrate 201 and the degree of orientation of the carbon nanotubes in the carbon nanotube film may be controlled by controlling the flow rate of the carbon nanotube solution. In addition, the density of the carbon nanotube film formed on the surface of the rigid substrate 201 and the degree of orientation of the carbon nanotubes in the carbon nanotube film may also be controlled by controlling the concentration of the carbon nanotube solution.
Fig. 4 illustrates a process of preparing a carbon nanotube film on a flexible substrate according to some embodiments of the present disclosure. As shown in fig. 4, a plurality of rotating shafts 303 are provided in the container 302. The flexible substrate 301 is disposed on the plurality of rotation shafts 303 and is moved by the plurality of rotation shafts 303. The arrow in fig. 4 indicates the moving direction of the flexible substrate 301. In the embodiment shown in fig. 4, a container 302 contains a previously prepared carbon nanotube solution and the carbon nanotube solution is kept still. In the direction indicated by the arrow in fig. 4, the flexible substrate 301 enters the container 302 from one end of the container 302 and exits the container 302 from the other end of the container 302. In the embodiment shown in fig. 4, both the upper and lower surfaces of the flexible substrate 301 are in contact with the carbon nanotube solution contained in the container 302. After the flexible substrate 301 leaves the container 302, the surface of the flexible substrate 301 may be dried by nitrogen blow drying or the like, so that a carbon nanotube film is formed on the surface of the flexible substrate 301. In addition, according to actual needs, after the flexible substrate 301 leaves the container 302, it can enter the container 302 again along the direction shown in fig. 4, so that the carbon nanotube film can be obtained by multiple depositions. The carbon nanotubes in the carbon nanotube film formed on the surface of the substrate 301 may be preferentially oriented in a direction opposite to the direction indicated by the arrow in fig. 4.
Although only one vessel 302 is shown in fig. 4, one skilled in the art will appreciate that multiple vessels 302 may also be provided, and that the multiple vessels 302 may be in fluid communication and in series. For example, in the case where there are a plurality of containers 302 connected in series, the flexible substrate 301 exiting from the previous container may enter the subsequent container, so that a carbon nanotube film satisfying the need may be formed on the surface of the flexible substrate 301.
In the embodiment shown in fig. 4, the moving speed of the substrate 301 may be controlled by controlling the rotation speed of the rotation shaft 303, so that the density of the carbon nanotube film formed on the surface of the flexible substrate 301 and the degree of orientation of the carbon nanotubes in the carbon nanotube film may be controlled. In addition, the density of the carbon nanotube film formed on the surface of the flexible substrate 301 and the degree of orientation of the carbon nanotubes in the carbon nanotube film may also be controlled by controlling the concentration of the carbon nanotube solution.
Embodiments according to the present disclosure also provide a transistor. The transistor comprises a source electrode, a drain electrode and a channel, wherein the channel comprises the carbon nanotube film prepared by the method for preparing the carbon nanotube film. Most of the carbon nanotubes in the channel are arranged in parallel along the channel direction, and a small amount of carbon nanotubes deviate from the channel direction to be used as the connection between the parallel carbon nanotubes to assist in forming a conductive path. Therefore, the number of nodes in the path is reduced to a certain extent, and simultaneously, the formation of a large number of paths is ensured, so that the transistor has good performance.
It will be understood by those skilled in the art that the foregoing embodiments are merely for clarity of illustration of the disclosure and are not intended to limit the scope of the disclosure. Other variations or modifications may occur to those skilled in the art, based on the foregoing disclosure, and are still within the scope of the present disclosure.
Claims (7)
1. A method of making a carbon nanotube film, comprising:
contacting a carbon nanotube solution with a surface of a substrate and moving the carbon nanotube solution in a set direction relative to the surface of the substrate; and
separating the surface of the substrate from the carbon nanotube solution, and drying the surface of the substrate to form a carbon nanotube film on the surface of the substrate,
wherein the degree of orientation of carbon nanotubes in the carbon nanotube film formed is determined by controlling the moving speed of the carbon nanotube solution while the carbon nanotube solution is moving, the carbon nanotube film formed on the surface of the substrate is preferentially oriented in the moving direction of the carbon nanotube solution,
the substrate is disposed in a plurality of containers in fluid communication, a substrate on which a carbon nanotube film is to be deposited is disposed in each container, a carbon nanotube solution flowing out of a previous container can flow into a subsequent container in fluid communication therewith, thereby allowing the carbon nanotube solution to be recycled in the plurality of containers, and a carbon nanotube film can be formed on a surface of the substrate disposed in each container.
2. The method of claim 1, wherein the step of moving the carbon nanotube solution in a set direction relative to the surface of the substrate comprises: moving the carbon nanotube solution in a set direction at a set rate relative to the surface of the substrate.
3. The method of claim 1,
the substrate is a rigid substrate, an
The step of moving the carbon nanotube solution in a set direction relative to the surface of the substrate includes: forming the carbon nanotube solution into a continuous flow flowing over the surface of the substrate.
4. The method of claim 3, wherein forming the carbon nanotube solution as a continuous stream flowing over the surface of the substrate comprises: flowing the carbon nanotube solution into the container from a first end of the container and out of the container from a second end of the container,
wherein the base is disposed in the container.
5. The method of claim 1, wherein the carbon nanotube solution is a single-walled carbon nanotube solution.
6. The method of claim 1, wherein the density of the carbon nanotube film and the degree of orientation of carbon nanotubes in the carbon nanotube film are related to the concentration and relative movement speed of the carbon nanotube solution.
7. The method of claim 3, wherein the rigid substrate comprises: a silicon substrate, a glass substrate, a plastic substrate, or a metal substrate.
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| US8435374B2 (en) * | 2009-12-28 | 2013-05-07 | Beijing Funate Innovation Technology Co., Ltd. | Method for making carbon nanotube film |
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| CN106477548A (en) * | 2016-09-18 | 2017-03-08 | 北京华碳元芯电子科技有限责任公司 | A kind of preparation method of carbon nano-tube film |
| CN107337196A (en) * | 2016-04-28 | 2017-11-10 | 清华大学 | A kind of preparation method of carbon nano-tube film |
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| CN100355648C (en) * | 2005-11-30 | 2007-12-19 | 北京大学 | Method for preparing crossing array of Nano carbon tubes |
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| KR20100024879A (en) * | 2008-08-26 | 2010-03-08 | 서울대학교산학협력단 | Carbon nanotube structure |
| US8435374B2 (en) * | 2009-12-28 | 2013-05-07 | Beijing Funate Innovation Technology Co., Ltd. | Method for making carbon nanotube film |
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