CN112538611B - Graphene carbon nanotube composite film, preparation method thereof and thin film transistor array - Google Patents
Graphene carbon nanotube composite film, preparation method thereof and thin film transistor array Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
- C23C16/18—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material from metallo-organic compounds
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- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
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Abstract
The invention discloses a graphene carbon nanotube composite film, a preparation method thereof and a thin film transistor array applying the graphene carbon nanotube composite film, wherein the preparation method comprises the following steps: depositing a metal catalyst layer on the surface of the substrate by adopting an atomic layer deposition method; depositing a carbon nanotube nano-film on the surface of the metal catalyst layer by adopting an atomic layer deposition method, wherein the metal catalyst layer is partially exposed on the surface of the carbon nanotube nano-film; and depositing the graphene nano film on the surface of the carbon nano tube nano film by adopting an atomic layer deposition method, removing the metal catalyst layer by adopting a catalyst layer remover, and cleaning to obtain the graphene-carbon nano tube composite film. The technical scheme of the invention can enable the graphene carbon nanotube composite film to have good conductivity, can replace the traditional indium tin oxide material and can be widely applied to thin film transistors.
Description
Technical Field
The invention relates to the technical field of nanowire preparation, in particular to a graphene carbon nanotube composite film, a preparation method thereof and a thin film transistor array using the graphene carbon nanotube composite film.
Background
With the rapid development of the electronic industry and the continuous demand for low energy consumption, multi-function and environment-friendly electronic products, flexible electronic devices with unique flexibility, ductility, high-efficiency multi-functionality and portability and wearability have become an important trend in the development of the electronic industry. Among many electronic devices, flexible thin film transistors have also been a focus of research in recent years. For the thin film transistor, Indium Tin Oxide (ITO) material is conventionally used as the transparent electrode, but the ITO material has low conductivity, which results in poor conductivity of the thin film transistor.
The above is only for the purpose of assisting understanding of the technical aspects of the present invention, and does not represent an admission that the above is prior art.
Disclosure of Invention
The invention mainly aims to provide a graphene carbon nanotube composite film, a preparation method thereof and a thin film transistor array, aiming at enabling the graphene carbon nanotube composite film to have good conductivity, and the graphene carbon nanotube composite film can replace the traditional ITO material and be widely applied to thin film transistors.
In order to achieve the purpose, the preparation method of the graphene carbon nanotube composite film provided by the invention comprises the following steps:
depositing a metal catalyst layer on the surface of the substrate by adopting an atomic layer deposition method;
depositing a carbon nanotube nano-film on the surface of the metal catalyst layer by adopting an atomic layer deposition method, wherein the metal catalyst layer is partially exposed on the surface of the carbon nanotube nano-film; and
depositing a graphene nano film on the surface of the carbon nano tube nano film by adopting an atomic layer deposition method, removing the metal catalyst layer by adopting a catalyst layer remover, and cleaning to obtain the graphene carbon nano tube composite film.
In an embodiment of the present invention, the depositing a carbon nanotube nanofilm on the surface of the metal catalyst layer by using an atomic layer deposition method, where the step of the carbon nanotube nanofilm not covering the metal catalyst layer fully includes:
and putting the substrate deposited with the metal catalyst layer into a reaction cavity, keeping the vacuum degree of the reaction cavity at 0.01-0.05 torr, sequentially introducing a first carbon source precursor and a first reducing gas, heating to 400-600 ℃, purging by adopting a first protective gas, and depositing on the surface of the metal catalyst layer to obtain the carbon nano tube nano film.
In an embodiment of the invention, the first carbon source precursor is introduced for 0.01s-0.2s, the residence time is 2s-20s, the first reducing gas is introduced for 0.01s-0.3s, and the residence time is 2s-20 s.
In an embodiment of the invention, the first carbon source precursor is at least one selected from ethanol, propanol and butanol.
In an embodiment of the present invention, the step of depositing the graphene nanomembrane on the surface of the carbon nanotube nanomembrane by using an atomic layer deposition method includes:
and putting the substrate deposited with the carbon nano tube nano film into a reaction cavity, keeping the vacuum degree of the reaction cavity at 0.01-0.05 torr, sequentially introducing a second carbon source precursor and a second reducing gas, heating to 500-800 ℃, purging by adopting a second protective gas, and depositing on the surface of the carbon nano tube nano film to obtain the graphene nano film.
In an embodiment of the invention, the second carbon source precursor is introduced for 0.01s-0.2s, the residence time is 2s-20s, the second reducing gas is introduced for 0.01s-0.5s, and the residence time is 2s-25 s.
In an embodiment of the present invention, the step of depositing the metal catalyst layer on the surface of the substrate by using the atomic layer deposition method includes:
and placing the substrate into a reaction chamber, sequentially introducing a metal precursor and a third reducing gas, purging by adopting a third protective gas, and depositing on the surface of the substrate to obtain a metal catalyst layer.
In one embodiment of the invention, the introducing time of the metal precursor is 0.01s-0.2s, the residence time is 2s-20s, the introducing time of the third reducing gas is 0.01s-0.5s, and the residence time is 2s-20 s; and/or the metal catalyst layer is a copper catalyst layer, and the metal precursor is at least one of N, N-diisopropyl copper acetate, 1, 5-cyclooctadiene (hexafluoro-2, 4-pentanedione) copper and copper acetylacetonate.
The invention also provides a graphene carbon nanotube composite film, which is prepared by the preparation method of the graphene carbon nanotube composite film.
The invention also provides a thin film transistor array, which comprises an array substrate, and a gate metal layer, a gate insulating layer, an amorphous silicon active layer, an ohmic contact layer, a source drain metal layer, a passivation layer and a graphene carbon nanotube composite film layer which are sequentially deposited on the surface of the array substrate, wherein at least part of the graphene carbon nanotube composite film layer penetrates through the passivation layer and is connected with the source drain metal layer, and the graphene carbon nanotube composite film layer is the graphene carbon nanotube composite film.
According to the technical scheme, firstly, a metal catalyst layer is deposited on the surface of a substrate by adopting an atomic layer deposition method and used as a catalyst for subsequently growing carbon nano tubes and graphene; and then continuously depositing the carbon nanotube nano-film on the surface of the metal catalyst layer by adopting an atomic layer deposition method, wherein the metal catalyst layer is partially exposed on the surface of the carbon nanotube nano-film, and the exposed metal catalyst layer is used as a catalyst for subsequent graphene growth. And then continuously depositing the graphene nano film on the surface of the carbon nano tube nano film by adopting an atomic layer deposition method, removing the metal catalyst layer by adopting a catalyst layer remover, and cleaning to obtain the graphene carbon nano tube composite film. The graphene carbon nanotube composite film prepared by the invention is of a three-dimensional net structure, combines the advantages of the one-dimensional carbon nanotube and the two-dimensional graphene, improves the conductive path of a current carrier, reduces the electron scattering, and has high charge mobility and good conductivity. Meanwhile, the atomic layer deposition method can be used for realizing the controllable growth of the graphene carbon nanotube composite film with a single atomic layer, is beneficial to the synthesis of the graphene carbon nanotube composite film with high quality, can reduce the content of hydrogen during deposition, and improves the conductivity, namely the conductivity. And because the surface reaction of the atomic layer deposition method has self-limiting adsorption performance, the graphene carbon nanotube composite membrane obtained by deposition has good uniformity, compactness and step coverage rate, and the thickness is easy to control.
Drawings
In order to more clearly illustrate the embodiments or technical solutions of the present invention, the drawings used in the embodiments or technical solutions of the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the structures shown in the drawings without creative efforts.
FIG. 1 is a schematic flow chart illustrating steps of a method for preparing a graphene carbon nanotube composite film according to an embodiment of the present invention;
FIG. 2 is a schematic diagram of an embodiment of a method for preparing a graphene carbon nanotube composite film according to the present invention;
fig. 3 is a schematic cross-sectional structure diagram of the thin film transistor array according to the present invention.
The reference numbers illustrate:
| reference numerals | Name (R) | Reference numerals | Name (R) |
| 100 | Thin |
50 | |
| 10 | |
60 | Source |
| 20 | |
70 | |
| 30 | |
80 | Graphene carbon nanotube |
| 40 | Active layer of amorphous silicon |
The implementation, functional features and advantages of the objects of the present invention will be further explained with reference to the accompanying drawings.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive step based on the embodiments of the present invention, are within the scope of protection of the present invention.
In addition, technical solutions between various embodiments may be combined with each other, but must be realized by a person skilled in the art, and when the technical solutions are contradictory or cannot be realized, such a combination should not be considered to exist, and is not within the protection scope of the present invention.
The invention provides a preparation method of a graphene carbon nanotube composite film.
Referring to fig. 1 and 2, in an embodiment of the method for preparing the graphene-carbon nanotube composite film according to the present invention, the method includes the following steps:
step S10, depositing a metal catalyst layer on the surface of the substrate by adopting an atomic layer deposition method;
step S20, depositing a carbon nanotube nano-film on the surface of the metal catalyst layer by adopting an atomic layer deposition method, wherein the metal catalyst layer is partially exposed on the surface of the carbon nanotube nano-film;
and S30, depositing the graphene nano film on the surface of the carbon nano tube nano film by adopting an atomic layer deposition method, removing the metal catalyst layer by adopting a catalyst layer remover, and cleaning to obtain the graphene carbon nano tube composite film.
Specifically, the substrate may be a silicon substrate, a silicon oxide substrate, or a glass substrate, and a metal catalyst layer is first deposited on the surface of the substrate by an atomic layer deposition method to serve as a catalyst for subsequent growth of carbon nanotubes and graphene, where the metal catalyst layer is generally an inert metal catalyst layer, such as a copper catalyst layer or a nickel catalyst layer. In addition, the metal catalyst layer prepared by the atomic layer deposition method has small particle size, less impurities, high purity and strong activity, and is easy to form a single-layer graphene film by subsequent catalysis. And then depositing a carbon nano tube nano film on the surface of the metal catalyst layer by adopting an atomic layer deposition method, wherein the carbon nano tube is a one-dimensional nano material, and the deposited carbon nano tube nano film is in a connected grid structure, so that part of the metal catalyst layer is exposed on the surface of the carbon nano tube nano film, and part of the exposed metal catalyst layer can be used as a catalyst for subsequent graphene growth. And then depositing a graphene nano film on the surface of the carbon nano tube nano film, and then removing the metal catalyst layer by using a catalyst layer remover, wherein the catalyst layer remover generally adopts an active metal salt solution, so that the inert metal can be replaced by the active metal salt solution to be removed. And then, cleaning the graphene/carbon nanotube composite membrane by adopting water and an alcohol solution to obtain the clean graphene/carbon nanotube composite membrane. Because the carbon nano tube nano film is in a connected grid structure, the two-dimensional lamellar structure of the graphene fills the gaps of the grid structure to form a three-dimensional grid structure, namely the graphene carbon nano tube composite film.
Therefore, it can be understood that, in the technical scheme of the invention, firstly, the metal catalyst layer is deposited on the surface of the substrate by adopting an atomic layer deposition method to be used as a catalyst for the subsequent growth of the carbon nano tube and the graphene; and then depositing the carbon nanotube nano-film on the surface of the metal catalyst layer by adopting an atomic layer deposition method, wherein the metal catalyst layer is partially exposed on the surface of the carbon nanotube nano-film, and the exposed metal catalyst layer is used as a catalyst for subsequent graphene growth. And then depositing the graphene nano film on the surface of the carbon nano tube nano film by adopting an atomic layer deposition method, removing the metal catalyst layer by adopting a catalyst layer remover, and cleaning to obtain the graphene carbon nano tube composite film. The graphene carbon nanotube composite film prepared by the invention is of a three-dimensional net structure, combines the advantages of the one-dimensional carbon nanotube and the two-dimensional graphene, improves the conductive path of a current carrier, reduces the electron scattering, and has high charge mobility and good conductivity. Meanwhile, the atomic layer deposition method can be used for realizing the controllable growth of the graphene carbon nanotube composite film with a single atomic layer, is beneficial to the synthesis of the graphene carbon nanotube composite film with high quality, can reduce the content of hydrogen during deposition, and improves the conductivity, namely the conductivity. And because the surface reaction of the atomic layer deposition method has self-limiting adsorption performance, the graphene carbon nanotube composite membrane obtained by deposition has good uniformity, compactness and step coverage rate, and the thickness is easy to control.
Step S20, depositing a carbon nanotube nanomembrane on the surface of the metal catalyst layer by using an atomic layer deposition method, the carbon nanotube nanomembrane not covered with the metal catalyst layer comprising:
and putting the substrate deposited with the metal catalyst layer into a reaction cavity, keeping the vacuum degree of the reaction cavity at 0.01-0.05 torr, sequentially introducing a first carbon source precursor and a first reducing gas, heating to 400-600 ℃, purging by adopting a first protective gas, and depositing on the surface of the metal catalyst layer to obtain the carbon nano tube nano film.
When the atomic layer deposition method is adopted to prepare the carbon nano tube nano film, the reaction cavity is strictly kept under the vacuum condition, and the vacuum degree of the reaction cavity is kept within the range of 0.01torr to 0.05 torr. The first carbon source precursor is generally a hydrocarbon and mainly provides a carbon source, and the introduction of the first reducing gas mainly plays a role in protecting the metal catalyst layer so as to prevent the metal catalyst layer from being oxidized, so that the metal catalyst layer can be fully used as a catalyst for growing the carbon nanotubes and the graphene. The first reduction here is generally hydrogen or carbon monoxide. The first protective gas is typically an inert gas to prevent effects on the metal catalyst, such as argon. When the carbon nano tube nano film is prepared by adopting an atomic layer deposition method, a first carbon source precursor is firstly introduced and stays for a certain time, then a first reducing gas is introduced and stays for a certain time, a first protective gas is adopted for purging and heating after each gas introduction, when the temperature is heated to the range of 400-600 ℃, the first carbon source precursor can decompose carbon atoms under the catalysis of a metal catalysis layer, and the carbon atoms are connected to form a film on the surface of the metal catalysis layer, namely the carbon nano tube nano film.
When the carbon nano tube nano film is prepared by adopting an atomic layer deposition method, the introduction time and the retention time of each component are strictly controlled so as to ensure that the obtained carbon nano tube nano film has good performances such as uniformity, compactness and the like. For example, the first carbon source precursor is introduced for 0.01s, or 0.02s, or 0.05s, or 0.1s, or 0.2s, the residence time is 2s, or 10s, or 151s, or 20s, the first reducing gas is introduced for 0.01s, or 0.03s, or 0.05s, or 0.15s, or 0.3s, and the residence time is 2s, or 10s, or 15s, or 20 s.
In an embodiment of the present invention, the first carbon source precursor is at least one of ethanol, propanol and butanol. Ethanol, propanol and butanol are all alcohol substances which can be used as carbon sources, and the alcohol substances contain hydrogen bonds, can be easily combined with the substrate, and particularly can be easily attached to the surface of the silicon-containing substrate, so that the formation of the carbon nano tube nano film is facilitated. The decomposition temperature of the ethanol, the propanol and the butanol is in the range of 400 ℃ to 600 ℃, and compared with alkane substances, the decomposition temperature is low, and the operation is easy. The propanol may be isopropanol, and the butanol may be n-butanol or 2-butanol, and one or more of them may be used as a mixture.
In an embodiment of the invention, the depositing the graphene nano film on the surface of the carbon nanotube nano film by the atomic layer deposition method in step S30 includes:
and putting the substrate deposited with the carbon nano tube nano film into a reaction cavity, keeping the vacuum degree of the reaction cavity at 0.01-0.05 torr, sequentially introducing a second carbon source precursor and a second reducing gas, heating to 500-800 ℃, purging by adopting a second protective gas, and depositing on the surface of the carbon nano tube nano film to obtain the graphene nano film.
When the atomic layer deposition method is adopted to prepare the graphene nano film, the reaction cavity is strictly kept under a vacuum condition, and the vacuum degree of the reaction cavity is kept within the range of 0.01-0.05 torr. Here, the second carbon source precursor is also a hydrocarbon compound, and mainly provides a carbon source, and the second carbon source precursor may be the same as or different from the first carbon source precursor, and is not limited herein. The second reducing gas is introduced to protect the metal catalyst layer so as to prevent the metal catalyst layer from being oxidized, and thus the metal catalyst layer can be fully used as a catalyst for growing the carbon nanotubes and the graphene. The second reducing property here can also be hydrogen or carbon monoxide. The second shielding gas may also be an inert gas to prevent effects on the metal catalyst, such as argon, where the second shielding gas may be the same as or different from the first shielding gas. When the graphene nano-film is prepared by adopting an atomic layer deposition method, a second carbon source precursor is firstly introduced and stays for a certain time, then a second reducing gas is introduced and stays for a certain time, a second protective gas is adopted for purging and heating after each gas introduction, when the temperature is heated to the range of 500-800 ℃, the first carbon source precursor can decompose carbon atoms under the catalytic action of a metal catalyst layer, and the carbon atoms are connected to form a film on the surface of the metal catalyst layer, so that the graphene nano-film is obtained.
Certainly, when the graphene nano-film is prepared by a deposition method, the second carbon source precursor may also be an alkane, such as methane, and when methane is selected, the heating temperature is 800-.
In one embodiment of the invention, the second carbon source precursor is introduced for 0.01s-0.2s, the residence time is 2s-20s, the second reducing gas is introduced for 0.01s-0.5s, and the residence time is 2s-25 s.
Similarly, when the graphene nano-film is prepared by adopting an atomic layer deposition method, the introduction time and the residence time of each component are strictly controlled so as to ensure that the obtained graphene nano-film has good performances such as uniformity, compactness and the like. For example, the second carbon source precursor is introduced for 0.01s, or 0.02s, or 0.05s, or 0.1s, or 0.2s, the residence time is 2s, or 10s, or 151s, or 20s, the second reducing gas is introduced for 0.01s, or 0.05s, or 0.1s, or 0.3s, or 0.5s, and the residence time is 2s, or 10s, or 15s, or 25 s.
In an embodiment of the invention, in the step S10, depositing the metal catalyst layer on the substrate surface by using an atomic layer deposition method includes: and placing the substrate into a reaction chamber, sequentially introducing a metal precursor and a third reducing gas, purging by adopting a third protective gas, and depositing on the surface of the substrate to obtain the metal catalyst layer.
Specifically, the metal precursor is generally selected from an organic metal compound, which mainly provides a metal source, and since the organic metal compound contains a functional group, the organic metal compound can be bonded with the surface of the template so as to form the metal catalyst layer, and the organic metal compound has a low boiling point, and can be grown into a metal catalyst layer film at a low temperature. The third reducing gas can also adopt hydrogen or carbon monoxide to reduce metal ions in the organic metal compound into metal simple substances to obtain a metal catalyst layer as a catalyst for subsequent growth of the carbon nano tube and the graphene. The reducing gas may be a hydrogen plasma, which allows the reduction reaction to be carried out at low temperatures. The third protective gas can also be argon gas to prevent the metal catalyst layer from being oxidized. When the metal catalyst layer is prepared by adopting an atomic layer deposition method, firstly introducing a metal precursor, staying for a certain time, then introducing reducing gas, staying for a certain time, purging by adopting argon after each introduction of gas, and finally depositing on the surface of the substrate to obtain the metal catalyst layer.
The metal catalyst layer is obtained by deposition by an atomic deposition method, and the feeding time and the retention time are strictly controlled, so that the uniformity and the compactness of the metal catalyst layer are good. Generally, the metal precursor is introduced for a time of 0.01s to 0.2s, the residence time is 2s to 20s, and the third reducing gas is introduced for a time of 0.01s to 0.5s, the residence time is 2s to 20 s. Specifically, when the metal catalyst layer is prepared by adopting an atomic layer deposition method, firstly, a metal precursor is introduced for 0.01s, or 0.02s, or 0.1s, or 0.2s, and stays for 2s, or 10s, or 20s, argon is adopted for purging, then, a third reducing gas is introduced for 0.01s, or 0.03s, or 0.2s, or 0.5s, and stays for 2s, or 10s, or 20s, argon is adopted for purging, and finally, the metal catalyst layer can be deposited. The metal catalyst layer is obtained by deposition by an atomic layer deposition method, and due to the surface self-limiting adsorption performance of the atomic layer deposition method, the metal catalyst layer obtained by deposition has good uniformity, compactness and step coverage rate, and the thickness of the metal catalyst layer is easy to control.
In an embodiment of the invention, the metal catalyst layer is a copper catalyst layer, and the metal precursor is at least one of copper N, N-diisopropylacetate, copper 1, 5-cyclooctadiene (hexafluoro-2, 4-pentanedione) and copper acetylacetonate. Copper is selected as a catalyst for subsequent graphene growth, and when the atomic layer deposition method is adopted to prepare the copper catalyst layer, the metal precursor is one or a mixture of organic copper compounds, such as N, N-diisopropyl copper acetate, 1, 5-cyclooctadiene (hexafluoro-2, 4-pentanedione) copper and copper acetylacetonate.
It should be noted that, when the metal catalyst layer is a copper catalyst layer, the catalyst layer remover is an active metal salt solution, such as ferric chloride, and an iron chloride solution with a concentration of 0.5mol/L to 2mol/L, so that the copper catalyst layer can be effectively removed.
The invention also provides a graphene carbon nanotube composite film, which is prepared by the preparation method of the graphene carbon nanotube composite film.
Referring to fig. 3, the present invention further provides a thin film transistor array 100, where the thin film transistor array 100 includes an array substrate 10, and a gate metal layer 20, a gate insulating layer 30, an amorphous silicon active layer 40, an ohmic contact layer 50, a source/drain metal layer 60, a passivation layer 70, and a graphene carbon nanotube composite film layer 80 sequentially deposited on the surface of the array substrate 10, where at least a portion of the graphene carbon nanotube composite film layer 80 penetrates through the passivation layer 70 and is connected to the source/drain metal layer 60, and the graphene carbon nanotube composite film layer 80 is prepared by the method for preparing the graphene carbon nanotube composite film as described above.
The graphene carbon nanotube composite film and the method for preparing the same according to the present invention will be described in detail with reference to specific examples.
Example 1
In this embodiment, the graphene carbon nanotube composite film is prepared by the following steps:
(1) preparing a metal catalyst layer: putting a silicon oxide substrate into an atomic layer deposition reaction chamber, firstly introducing N, N-diisopropyl copper acetate for 0.02s and staying for 10s, purging for 5s by adopting argon, then introducing reducing gas hydrogen plasma for 0.03s and staying for 10s, purging for 10s by adopting argon, circulating for 50 times in this way, and finally depositing on the surface of the silicon oxide substrate to obtain a copper catalyst layer.
(2) Preparing a carbon nano tube nano film: placing the silicon oxide substrate deposited with the copper catalyst layer into an atomic layer deposition reaction chamber, keeping the vacuum degree at 0.01torr, heating to the temperature of 400 ℃, firstly introducing butanol for 0.02s and staying for 5s, purging with argon for 10s, then introducing hydrogen for 0.02s and staying for 5s, purging with argon for 10s, and repeating the steps for 50 times, and finally depositing on the surface of the copper catalyst layer opposite to the silicon oxide substrate to obtain the carbon nano tube nano film.
(3) Preparing a graphene carbon nanotube composite film: putting the silicon oxide substrate deposited with the carbon nano tube nano film into an atomic layer deposition reaction chamber, keeping the vacuum degree at 0.01torr, heating to the temperature of 500 ℃, firstly introducing isopropanol for 0.02s, staying for 5s, purging with argon for 10s, then introducing hydrogen for 0.04s, staying for 10s, purging with argon for 10s, and repeating the steps for 50 times to deposit on the surface of the carbon nano tube nano film back to the copper catalyst layer to obtain the graphene nano film. And then removing the copper catalyst layer by adopting an iron chloride solution with the concentration of 0.5mol/L, and cleaning by adopting a water and alcohol solution to obtain the transparent graphene carbon nano tube composite membrane.
Example 2
In this embodiment, the graphene carbon nanotube composite film is prepared by the following steps:
(1) preparing a metal catalyst layer: putting a silicon substrate into an atomic layer deposition reaction chamber, firstly introducing 1, 5-cyclooctadiene (hexafluoro-2, 4-pentanedione) copper for 0.04s, staying for 15s, purging for 10s by adopting argon gas, then introducing reductive gas hydrogen plasma for 0.05s, staying for 15s, purging for 15s by adopting argon gas, circulating for 100 times in this way, and finally depositing on the surface of the silicon substrate to obtain a copper catalyst layer.
(2) Preparing a carbon nano tube nano film: and (2) placing the silicon substrate deposited with the copper catalyst layer into an atomic layer deposition reaction chamber, keeping the vacuum degree at 0.03torr, heating to the temperature of 500 ℃, firstly introducing propanol for 0.1s, staying for 10s, purging for 15s by adopting argon, then introducing hydrogen for 0.15s, staying for 10s, purging for 15s by adopting argon, and repeating the steps for 50 times, and finally depositing on the surface of the copper catalyst layer back to the silicon substrate to obtain the carbon nano tube nano film.
(3) Preparing a graphene carbon nanotube composite film: placing the silicon substrate deposited with the carbon nano tube nano film into an atomic layer deposition reaction chamber, keeping the vacuum degree at 0.03torr, heating to the temperature of 600 ℃, firstly introducing ethanol for 0.12s, staying for 10s, purging with argon for 15s, then introducing hydrogen for 0.2s, staying for 20s, purging with argon for 20s, and repeating the steps for 50 times to obtain the graphene nano film by depositing on the surface of the carbon nano tube nano film, which is opposite to the copper catalyst layer. And then removing the copper catalyst layer by adopting a ferric chloride solution with the concentration of 2mol/L, and cleaning by adopting a water and alcohol solution to obtain the transparent graphene carbon nano tube composite membrane.
Example 3
In this embodiment, the graphene carbon nanotube composite film is prepared by the following steps:
(1) preparing a metal catalyst layer: putting a silicon oxide substrate into an atomic layer deposition reaction chamber, firstly introducing acetylacetone copper for 0.05s, staying for 20s, purging for 12s by adopting argon, then introducing reducing gas hydrogen plasma for 0.08s, staying for 20s, purging for 12s by adopting argon, circulating for 50 times, and finally depositing on the surface of the silicon oxide substrate to obtain a copper catalyst layer.
(2) Preparing a carbon nano tube nano film: and (2) placing the silicon oxide substrate deposited with the copper catalyst layer into an atomic layer deposition reaction chamber, keeping the vacuum degree at 0.05torr, heating to the temperature of 600 ℃, firstly introducing ethanol for 0.2s, staying for 20s, purging for 25s by adopting argon, then introducing hydrogen for 0.3s, staying for 20s, purging for 25s by adopting argon, circulating for 50 times in the way, and finally depositing on the surface of the copper catalyst layer back to the silicon oxide substrate to obtain the carbon nano tube nano film.
(3) Preparing a graphene carbon nanotube composite film: putting the silicon oxide substrate deposited with the carbon nano tube nano film into an atomic layer deposition reaction chamber, keeping the vacuum degree at 0.05torr, heating to the temperature of 600 ℃, firstly introducing isopropanol for 0.15s, staying for 15s, purging with argon for 20s, then introducing hydrogen for 0.5s, staying for 25s, purging with argon for 30s, and repeating the steps for 50 times to deposit the graphene nano film on the surface of the carbon nano tube nano film back to the copper catalyst layer. And then removing the copper catalyst layer by adopting a ferric chloride solution with the concentration of 2mol/L, and cleaning by adopting a water and alcohol solution to obtain the transparent graphene carbon nanotube composite membrane.
The conductivity tests of the graphene carbon nanotube composite films prepared in examples 1to 3 show that the graphene carbon nanotube composite films prepared in examples 1to 3 have an electron mobility of 1 × 104cm2V.s to 2X 104cm2Within the range of V.s, the graphene carbon nanotube composite membrane prepared by the invention has high electron mobility, namely good conductivity. Meanwhile, the graphene carbon nanotube composite films prepared in examples 1to 3 were hazed using a haze meterThe haze of the graphene carbon nanotube composite film prepared in each example is 0.7% to 1.8%, and the haze of the conventional ITO material is about 3%, that is, the haze of the graphene carbon nanotube composite film prepared in the present invention is small compared to the conventional ITO material. Meanwhile, the graphene carbon nanotube composite membrane prepared by each embodiment has good performances in the aspects of transparency, uniformity, compactness, light transmittance, flexibility, stability and the like, and has good prospects when being applied to thin film transistor arrays and display panels.
The above description is only an alternative embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications and equivalents of the present invention, which are made by the present specification and directly/indirectly applied to other related technical fields within the spirit of the present invention are included in the scope of the present invention.
Claims (7)
1. A preparation method of a graphene carbon nanotube composite film is characterized by comprising the following steps:
depositing a metal catalyst layer on the surface of the substrate by adopting an atomic layer deposition method;
depositing a carbon nanotube nano-film on the surface of the metal catalyst layer by adopting an atomic layer deposition method, wherein the metal catalyst layer is partially exposed on the surface of the carbon nanotube nano-film; and
depositing a graphene nano film on the surface of the carbon nano tube nano film by adopting an atomic layer deposition method, removing the metal catalyst layer by adopting a catalyst layer remover, and cleaning to obtain a graphene carbon nano tube composite film;
the step of depositing the carbon nanotube nanomembrane on the surface of the metal catalyst layer by adopting an atomic layer deposition method, wherein the metal catalyst layer is partially exposed on the surface of the carbon nanotube nanomembrane comprises the following steps:
putting the substrate deposited with the metal catalyst layer into a reaction cavity, keeping the vacuum degree of the reaction cavity at 0.01-0.05 torr, sequentially introducing a first carbon source precursor and a first reducing gas, heating to 400-600 ℃, purging by adopting a first protective gas, and depositing on the surface of the metal catalyst layer to obtain a carbon nano tube nano film; wherein the introducing time of the first carbon source precursor is 0.01s-0.2s, the retention time is 2s-20s, the introducing time of the first reducing gas is 0.01s-0.3s, and the retention time is 2s-20 s; the first carbon source precursor is at least one of ethanol, propanol and butanol.
2. The method for preparing the graphene-carbon nanotube composite film according to claim 1, wherein the step of depositing the graphene nanomembrane on the surface of the carbon nanotube nanomembrane by using an atomic layer deposition method comprises:
and putting the substrate deposited with the carbon nano tube nano film into a reaction cavity, keeping the vacuum degree of the reaction cavity at 0.01-0.05 torr, sequentially introducing a second carbon source precursor and a second reducing gas, heating to 500-800 ℃, purging by adopting a second protective gas, and depositing on the surface of the carbon nano tube nano film to obtain the graphene nano film.
3. The method for preparing the graphene-carbon nanotube composite film according to claim 2, wherein the second carbon source precursor is introduced for 0.01s to 0.2s and the residence time is 2s to 20s, and the second reducing gas is introduced for 0.01s to 0.5s and the residence time is 2s to 25 s.
4. The method for preparing the graphene-carbon nanotube composite film according to any one of claims 1to 3, wherein the step of depositing the metal catalyst layer on the surface of the substrate by using an atomic layer deposition method comprises:
and placing the substrate into a reaction chamber, sequentially introducing a metal precursor and a third reducing gas, purging by adopting a third protective gas, and depositing on the surface of the substrate to obtain a metal catalyst layer.
5. The method for preparing the graphene-carbon nanotube composite film according to claim 4, wherein the introducing time of the metal precursor is 0.01s-0.2s, the residence time is 2s-20s, the introducing time of the third reducing gas is 0.01s-0.5s, and the residence time is 2s-20 s;
and/or the metal catalyst layer is a copper catalyst layer, and the metal precursor is at least one of N, N-diisopropyl copper acetate, 1, 5-cyclooctadiene (hexafluoro-2, 4-pentanedione) copper and copper acetylacetonate.
6. A graphene-carbon nanotube composite film, which is prepared by the method for preparing the graphene-carbon nanotube composite film according to any one of claims 1to 5.
7. A thin film transistor array is characterized by comprising an array substrate, a gate metal layer, a gate insulating layer, an amorphous silicon active layer, an ohmic contact layer, a source drain metal layer, a passivation layer and a graphene carbon nanotube composite film layer, wherein the gate metal layer, the gate insulating layer, the amorphous silicon active layer, the ohmic contact layer, the source drain metal layer, the passivation layer and the graphene carbon nanotube composite film layer are sequentially deposited on the surface of the array substrate, at least part of the graphene carbon nanotube composite film layer penetrates through the passivation layer and is connected with the source drain metal layer, and the graphene carbon nanotube composite film layer is the graphene carbon nanotube composite film according to claim 6.
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