CN112680719A - Graphene film, preparation method thereof and thin film transistor array - Google Patents
Graphene film, preparation method thereof and thin film transistor array Download PDFInfo
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Abstract
The application discloses a graphene film, a preparation method thereof and a thin film transistor array. The preparation method of the graphene film comprises the following steps: preparing a graded porous silicon dioxide film filled with a metal catalyst; depositing graphene on the surface of the hierarchical porous silicon dioxide film by adopting an atomic layer deposition method; and removing the graded porous silicon dioxide film to obtain the graphene film. The graphene thin film prepared by the technical scheme has good conductivity, can replace the traditional ITO material to serve as a transparent electrode, and is widely applied to thin film transistors.
Description
Technical Field
The application relates to the technical field of graphene, in particular to a graphene film, a preparation method thereof and a thin film transistor array.
Background
With the rapid development of the electronic industry and the continuous demand for low energy consumption, multiple functions and environment-friendly electronic products, flexible electronic devices have become an important field for the development of the next generation of electronic industry due to their unique flexibility, ductility, high-efficiency, versatility and portability, and attract more and more attention. Among them, transistors are used as amplifiers and switches of driving parts of many electronic devices, and are applied to many electronic devices, so that flexible thin film transistors are also a research hotspot in recent years. For a flexible thin film transistor, an Indium Tin Oxide (ITO) material is conventionally used as a transparent electrode, but the ITO material has low conductivity, which results in poor conductivity of the thin film transistor.
Content of application
The graphene thin film has good conductivity, can replace a traditional ITO material, and can be widely applied to thin film transistors.
In order to achieve the above object, the method for preparing a graphene film provided by the present application includes the following steps:
preparing a graded porous silicon dioxide film filled with a metal catalyst;
depositing graphene on the surface of the hierarchical porous silicon dioxide film by adopting an atomic layer deposition method; and
and removing the graded porous silicon dioxide film to obtain the graphene film.
Alternatively, the step of preparing the graded porous silica film filled with the metal catalyst comprises:
preparing graded porous silicon dioxide by adopting a sol-gel method;
depositing a metal catalyst in the pore channels of the hierarchical porous silica by adopting an atomic layer deposition method; and
and dispersing the graded porous silicon dioxide deposited with the metal catalyst into an alcohol solution, and pressing to obtain the graded porous silicon dioxide film filled with the metal catalyst.
Optionally, the step of preparing the graded porous silica by a sol-gel method comprises:
mixing an organic solvent with water to obtain a mixed solvent;
and adding a silicon precursor source, a surfactant and a catalyst into the mixed solvent, stirring to disperse the mixture, and performing centrifugal separation to obtain the hierarchical porous silicon dioxide.
Optionally, the step of depositing a metal catalyst in the pores of the hierarchical porous silica by using an atomic layer deposition method comprises:
and alternately introducing a metal catalyst precursor and a first reducing gas into the pore channels of the hierarchical porous silica in an inert environment.
Optionally, the introducing time of the metal catalyst precursor is 0.01s-0.2s, the retention time is 2s-20s, and the purging time is 2s-30 s;
and/or the first reducing gas is introduced for 0.01s-0.5s, the residence time is 2s-20s, and the purging time is 2s-30 s.
Optionally, the metal catalyst is a copper catalyst, and the metal catalyst precursor is at least one of copper N, N-diisopropylacetate, copper 1, 5-cyclooctadiene (hexafluoro-2, 4-pentanedione), and copper acetylacetonate.
Optionally, the step of depositing graphene on the surface of the hierarchical porous silica thin film by using an atomic layer deposition method includes:
and putting the graded porous silicon dioxide film into a reaction cavity, introducing a carbon source precursor, performing primary purging by adopting protective gas, introducing second reducing gas, performing secondary purging by adopting the protective gas, and then performing heating annealing treatment.
Optionally, the introducing time of the carbon source precursor is 0.01s-0.1s, the retention time is 2s-10s, and the first purging time is 5s-20 s;
and/or the second reducing gas is introduced for 0.01s-0.2s, the residence time is 5s-20s, and the second purging time is 5s-20 s.
The application also provides a graphene film, and the graphene film is prepared by the preparation method of the graphene film.
The application also provides a thin film transistor array, the thin film transistor array includes the base plate and deposits in proper order and is in gate metal layer, gate insulation layer, amorphous silicon active layer, ohmic contact layer, source leakage metal level, passivation layer and graphite alkene thin layer on the base plate surface, just graphite alkene thin layer at least part runs through the passivation layer and with source leakage metal level is connected, graphite alkene thin layer be as before graphite alkene thin layer.
According to the technical scheme, the hierarchical porous silicon dioxide film filled with the metal catalyst is prepared, then the graphene is deposited on the surface of the hierarchical porous silicon dioxide film by adopting an atomic layer deposition method, and the graphene film can be obtained after the hierarchical porous silicon dioxide film is removed. Compared with a direct film forming process, the preparation process can effectively improve the porosity and the specific surface area of the film and improve more pore channels for the subsequent growth of graphene. Further, the graphene film is obtained by deposition through an atomic layer deposition method, and the graphene film obtained by deposition has good uniformity, compactness and step coverage rate due to the self-limiting adsorption property of the surface reaction of the atomic layer deposition method. Meanwhile, the atomic layer deposition method can realize the controllable growth of the single atomic layer graphene, is beneficial to the synthesis of high-quality graphene, can reduce the content of reducing gas during deposition, improves the conductivity of the product, and the high-activity atomic layer deposition precursor source and the reaction system can be prepared at a lower temperature, thereby saving energy and improving the quality of the product.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings used in the description of the embodiments or 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 application, 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 in an embodiment of a method for manufacturing a graphene film according to the present application;
FIG. 2 is a flowchart illustrating a detailed step of step S10 in FIG. 1;
FIG. 3 is a schematic illustration of the principle of the preparation of the hierarchical porous silica of the present application;
fig. 4 is a schematic cross-sectional structural diagram of a thin film transistor array according to the present application.
The reference numbers illustrate:
the implementation, functional features and advantages of the objectives of the present application will be further explained with reference to the accompanying drawings.
Detailed Description
The technical solutions in the embodiments of the present application will be described clearly and completely with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
In addition, technical solutions between the various embodiments of the present application may be combined with each other, but it must be based on the realization of the technical solutions by a person skilled in the art, and when the technical solutions are contradictory or cannot be realized, such a combination of technical solutions should be considered to be absent and not within the protection scope of the present application.
The application provides a preparation method of a graphene film.
Referring to fig. 1, in an embodiment of a method for preparing a graphene film, the method for preparing a graphene film includes the following steps:
step S10, preparing a hierarchical porous silica film filled with a metal catalyst;
step S20, depositing graphene on the surface of the hierarchical porous silicon dioxide film by adopting an atomic layer deposition method; and
and step S30, removing the hierarchical porous silicon dioxide film to obtain the graphene film.
The hierarchical porous silica is a material with a network structure formed by interconnected or closed pores, the boundaries or surfaces of the pores are formed by pillars or flat plates and comprise macropores, mesopores, micropores and the like, and the hierarchical porous silica has a large specific surface area and pore volume. The metal catalyst is filled in the pore channels of the graded porous silicon dioxide film, and can be a copper catalyst, a nickel catalyst or other reasonable and effective metal catalysts. And dispersing the graded porous silicon dioxide filled with the metal catalyst into a film forming solution, and pressing to obtain the graded porous silicon dioxide film filled with the metal catalyst. The graded porous silica film can be used as a template for subsequent graphene growth, wherein the metal catalyst is used as a catalyst for the graphene growth. And then depositing graphene on the surface of the hierarchical porous silicon dioxide film by adopting an atomic deposition method, and removing the hierarchical porous silicon dioxide film to obtain the graphene film. The atomic layer deposition method is a special chemical vapor deposition technology, and is a method for forming a thin film by alternately introducing vapor phase precursors into a reaction chamber and performing a chemical adsorption reaction on the surface of a deposition substrate. The present driver molecules reach the deposition matrix surface, they can be at surface chemical adsorption and take place surface reaction, atomic layer deposition's surface reaction has self-limitation nature, that is, chemical adsorption self-limitation nature and sequential reaction self-limitation nature, this kind of self-limitation characteristic is atomic layer deposition's basis, form nanoparticle or film through constantly repeating this kind of self-limitation reaction, produce splendid three-dimensional conformal nature stoichiometric film, because atomic layer deposition's surface chemical self-limitation adsorption performance, can obtain the application at high deep groove structure, its range of application is comparatively extensive, and the rete homogeneity that adopts the atomic layer deposition method to prepare, compactness, ladder coverage rate and thickness control all have obvious advantage in the aspect.
According to the technical scheme, the hierarchical porous silicon dioxide film filled with the metal catalyst is prepared, the graphene is deposited on the surface of the hierarchical porous silicon dioxide film by adopting an atomic layer deposition method, and the graphene film can be obtained after the hierarchical porous silicon dioxide film is removed. Compared with a direct film forming process, the preparation process can effectively improve the porosity and the specific surface area of the film and improve more pore channels for the subsequent growth of graphene. Further, the graphene film is obtained by deposition through an atomic layer deposition method, and the graphene film obtained by deposition has good uniformity, compactness and step coverage rate due to the self-limiting adsorption property of the surface reaction of the atomic layer deposition method. Meanwhile, the atomic layer deposition method can realize the controllable growth of the single atomic layer graphene, is beneficial to the synthesis of high-quality graphene, can reduce the content of reducing gas during deposition, improves the conductivity of the product, and the high-activity atomic layer deposition precursor source and the reaction system can be prepared at a lower temperature, thereby saving energy and improving the quality of the product.
Referring to fig. 2 and 3, in an embodiment of the present application, the step of preparing the graded porous silica thin film filled with the metal catalyst at step S10 includes:
step S11, preparing hierarchical porous silicon dioxide by adopting a sol-gel method;
step S12, depositing a metal catalyst in the pore channels of the hierarchical porous silicon dioxide by adopting an atomic layer deposition method; and
and step S13, dispersing the graded porous silicon dioxide deposited with the metal catalyst into an alcohol solution, and pressing to obtain the graded porous silicon dioxide film filled with the metal catalyst.
Specifically, the sol-gel method is a method that a compound containing high chemical activity components is used as a precursor, the raw materials are uniformly mixed in a liquid phase, hydrolysis and condensation chemical reactions are carried out, a stable transparent sol system is formed in a solution, the sol is slowly polymerized among aged colloidal particles to form gel with a three-dimensional network structure, and a solvent losing fluidity is filled among gel networks to form the gel. Because the hierarchical porous silica has a porous structure and has a large specific surface area and pore volume, the metal catalyst can be deposited in the pore channels of the hierarchical porous silica by adopting an atomic layer deposition method. Because the metal catalyst is obtained by deposition by adopting the atomic layer deposition method, and the surface reaction of the atomic layer deposition method has self-limiting adsorption performance, the deposited metal catalyst has good uniformity, compactness and step coverage rate, so that the graphene film obtained by subsequent deposition has good uniformity and high density. And then dispersing the graded porous silicon dioxide deposited with the metal catalyst into an alcohol solution to obtain a film forming solution, and pressing to obtain the graded porous silicon dioxide film filled with the metal catalyst. The preparation method is simple to operate, and is operated at normal temperature, so that the cost is low.
Further, the step S11 of preparing the graded porous silica by the sol-gel method includes:
mixing an organic solvent with water to obtain a mixed solvent;
and adding a silicon precursor source, a surfactant and a catalyst into the mixed solvent, stirring to disperse the mixture, and performing centrifugal separation to obtain the hierarchical porous silicon dioxide.
Specifically, mixing an organic solvent and water at a ratio of 0.3 to 0.5 to obtain a mixed solvent, wherein the organic solvent can be selected from alcohol solvents such as ethanol, isopropanol and butanol. And then adding a silicon precursor source, a surfactant and a catalyst into the mixed solvent, wherein the silicon precursor source can be Tetraethoxysilane (TEOS), and the surfactant can be hexadecyl trimethyl ammonium bromide or hexadecyl trimethyl ammonium chloride. The catalyst can be selected from ammonia water, the pH value of the system is controlled to be 8-10 after the ammonia water is added, the system is stirred at the rotating speed of 400rpm-800rpm at the temperature of 20-50 ℃ to rapidly disperse the catalyst for 4-10h, and then the hierarchical porous silicon dioxide powder can be obtained after centrifugal separation.
When the hierarchical porous silicon dioxide is prepared by adopting a sol-gel method, a silicon precursor is hydrolyzed to form a hydroxyl compound, the hydroxyl compound is subjected to polycondensation reaction to form sol, and the sol is aged to obtain gel. The surfactant has hydrophilic and lipophilic amphiphilic structures, different aggregation states can be easily formed in the solution, and the nanostructures with different morphologies can be effectively controlled to be formed in the sol solution, so that the hierarchical porous silicon dioxide structure can be obtained, has larger specific surface area and pore volume, can adsorb a large amount of gas and has an ultralow dielectric constant k value. The ultra-low dielectric constant value can reduce parasitic capacitance and leakage current; meanwhile, the display problems of signal crosstalk, RC circuit delay and the like caused by parasitic capacitance can be solved. And the preparation method adopts a sol-gel method to prepare the graded porous silicon dioxide, can be carried out at normal temperature, and has simple preparation process and low cost.
Further, in step S12, the step of depositing the metal catalyst in the pores of the hierarchical porous silica by using an atomic layer deposition method includes:
and alternately introducing a metal catalyst precursor and a first reducing gas into the pore channels of the hierarchical porous silica in an inert environment.
Wherein the introduction time of the metal catalyst precursor is 0.01s-0.2s, the retention time is 2s-20s, and the purging time is 2s-30 s; the introducing time of the first reducing gas is 0.01s-0.5s, the residence time is 2s-20s, and the purging time is 2s-30 s.
The growth thickness and uniformity of the metal catalyst can be accurately controlled by controlling the reaction time and the reaction period, so that a compact and uniform metal catalyst layer is obtained; and reaction impurities are not introduced in the reaction process of the pulse gas, so that the high purity of the metal catalyst is ensured.
In an alternative embodiment, the metal catalyst is a copper catalyst, and the precursor of the metal catalyst 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 the subsequent graphene growth, and when the copper catalyst is deposited by an atomic layer deposition method, the metal catalyst precursor is one or a mixture of organic copper compounds, such as copper N, N-diisopropyl acetate, copper 1, 5-cyclooctadiene (hexafluoro-2, 4-pentanedione) and copper acetylacetonate.
In an embodiment of the present application, in step S20, the depositing graphene on the surface of the graded porous silica thin film by using an atomic layer deposition method includes:
and putting the graded porous silicon dioxide film into a reaction cavity, introducing a carbon source precursor, performing primary purging by adopting protective gas, introducing second reducing gas, performing secondary purging by adopting the protective gas, and then performing heating annealing treatment.
The carbon source precursor can be selected from ethanol, n-propanol, isopropanol and 1-butanol; at least one of 2-butanol, 2-methyl-1-propanol and 2-methyl-2-propanol, wherein the protective gas is argon, and the second reducing gas is plasma hydrogen. Putting the graded silicon dioxide film filled with the metal catalyst into a reaction cavity, firstly introducing a carbon source precursor for 0.01-0.1 s, staying for 2-10 s, and performing first purging for 5-20 s by adopting argon protective gas; and then introducing second reducing gas plasma hydrogen into the reaction chamber for 0.01-0.2 s and keeping for 5-20 s, and performing secondary purging for 5-20 s under the protection of argon. And thus, completing one operation, then circulating the operation, wherein the total circulation time can be selected to be 50 times, heating and annealing for 30-120 min at the temperature of 200-250 ℃, at which the carbon source precursor decomposes carbon atoms under the catalysis of a metal catalyst, and the carbon atoms are connected to form a film on the surface of the template and in the pore channel, namely the graphene film.
It can be understood that when the graphene film is prepared by adopting the atomic layer deposition method, the graphene film with better uniformity and compactness can be obtained by strictly controlling the introduction time and the residence time of each component.
In an embodiment of the application, in step S30, the step of removing the graded porous silica film to obtain the graphene film includes:
and removing the graded porous silicon dioxide by adopting a hydrofluoric acid or sodium hydroxide solution, and removing the metal catalyst by adopting a metal salt solution to obtain the graphene film.
The hydrofluoric acid or sodium hydroxide solution can effectively remove the hierarchical porous silicon dioxide, when the metal catalyst is a copper catalyst, the metal salt is an iron trichloride solution, the iron trichloride solution can effectively remove metal copper, and optionally, the concentration of the iron trichloride solution is 0.5-2 mol/L.
The application also provides a graphene nanowire film, and the graphene nanowire film is prepared by the preparation method of the graphene nanowire film.
Referring to fig. 4, the present application further provides a thin film transistor array 100, where the thin film transistor array 100 includes a 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 nanowire thin film layer 80 sequentially deposited on a surface of the substrate 10, where at least a portion of the graphene nanowire thin film layer 80 penetrates through the passivation layer 70 and is connected to the source/drain metal layer 60, and the graphene nanowire thin film layer 80 is prepared by the method for preparing a graphene nanowire thin film as described above.
The graphene thin film and the method for preparing the same of the present application are described in detail below with reference to specific examples.
Example 1
In this embodiment, the graphene film may be prepared by the following steps:
(1) preparation of hierarchical porous silica: mixing ethanol and water to obtain a mixed solvent, wherein the ratio of the ethanol to the water is 0.3, adding tetraethoxysilane, hexadecyl trimethyl ammonium bromide and ammonia water into the mixed solvent, controlling the pH value of the system to be 8, stirring at the rotating speed of 450rpm at the temperature of 25 ℃ to rapidly disperse the mixture for 8 hours, and then carrying out centrifugal separation to obtain the hierarchical porous silicon dioxide powder.
(2) Depositing a copper catalyst in the pore channels of the graded porous silicon dioxide by adopting an atomic layer deposition method: and in an inert environment, alternately introducing N, N-diisopropyl copper acetate and first reducing gas hydrogen into the pore channels of the hierarchical porous silicon dioxide. Wherein the introduction time of the metal catalyst precursor is 0.01s, the retention time is 5s, and the purging time is 5 s; the first reducing gas was introduced for 0.05s, the residence time was 5s, and the purge time was 10 s.
(3) Preparing a graphene film: putting a hierarchical porous silicon dioxide filled with a copper catalyst into a reaction cavity by taking the hierarchical porous silicon dioxide as a template, introducing methanol for 0.02s, keeping the methanol for 5s, and performing first purging for 10s by adopting argon protective gas; and then introducing plasma hydrogen into the reaction chamber for 0.04s, keeping the plasma hydrogen for 10s, and performing secondary purging on the plasma hydrogen by adopting argon protection for 10 s. And finally, removing the graded porous silicon dioxide by adopting hydrofluoric acid or sodium hydroxide solution, and removing the copper catalyst by adopting ferric chloride solution to obtain the graphene film.
Example 2
In this embodiment, the graphene film may be prepared by the following steps:
(1) preparation of hierarchical porous silica: mixing isopropanol and water to obtain a mixed solvent, wherein the proportion of ethanol to water is 0.4, adding tetraethoxysilane, hexadecyl trimethyl ammonium bromide and ammonia water into the mixed solvent, controlling the pH value of the system to be 9, stirring at the rotating speed of 600rpm at the temperature of 40 ℃ to rapidly disperse the mixture for 5 hours, and then carrying out centrifugal separation to obtain the hierarchical porous silicon dioxide powder.
(2) Depositing a copper catalyst in the pore channels of the graded porous silicon dioxide by adopting an atomic layer deposition method: and alternately introducing 1, 5-cyclooctadiene (hexafluoro-2, 4-pentanedione) copper and a first reducing gas hydrogen into the pore channels of the graded porous silica in an inert environment. Wherein the introduction time of the metal catalyst precursor is 0.1s, the retention time is 10s, and the purging time is 10 s; the first reducing gas was introduced for 0.2s, the residence time was 15s, and the purge time was 10 s.
(3) Preparing a graphene film: taking the hierarchical porous silica filled with the copper catalyst as a template, putting the template into a reaction cavity, firstly introducing n-propanol for 0.1s, staying for 7s, and performing first purging on the template by adopting argon protective gas for 12 s; and then introducing plasma hydrogen into the reaction chamber for 0.05s, keeping the reaction chamber for 12s, and performing secondary purging on the reaction chamber by adopting argon protection for 12 s. And finally, removing the graded porous silicon dioxide by adopting hydrofluoric acid or sodium hydroxide solution, and removing the copper catalyst by adopting ferric chloride solution to obtain the graphene film.
Example 3
In this embodiment, the graphene film may be prepared by the following steps:
(1) preparation of hierarchical porous silica: mixing butanol and water to obtain a mixed solvent, wherein the ratio of ethanol to water is 0.5, adding tetraethoxysilane, hexadecyl trimethyl ammonium bromide and ammonia water into the mixed solvent, controlling the pH value of the system to be 10, stirring at the rotating speed of 600rpm at the temperature of 45 ℃ to rapidly disperse the mixture for 5 hours, and then carrying out centrifugal separation to obtain the hierarchical porous silicon dioxide powder.
(2) Depositing a copper catalyst in the pore channels of the graded porous silicon dioxide by adopting an atomic layer deposition method: and in an inert environment, alternately introducing copper acetylacetonate and first reducing gas hydrogen into the pore channels of the graded porous silicon dioxide. Wherein the introduction time of the metal catalyst precursor is 0.1s, the retention time is 15s, and the purging time is 15 s; the first reducing gas was introduced for 0.5s, the residence time was 15s, and the purge time was 20 s.
(3) Preparing a graphene film: taking the hierarchical porous silica filled with the copper catalyst as a template, putting the template into a reaction cavity, firstly introducing 1-butanol for 0.2s, keeping the time for 10s, and performing first purging on the template by adopting argon protective gas for 15 s; and then introducing plasma hydrogen into the reaction chamber for 0.06s, keeping the plasma hydrogen for 10s, and performing secondary purging on the plasma hydrogen by adopting argon protection, wherein the secondary purging time is 15 s. And finally, removing the graded porous silicon dioxide by adopting hydrofluoric acid or sodium hydroxide solution, and removing the copper catalyst by adopting ferric chloride solution to obtain the graphene film.
Conducting performance tests are carried out on the graphene thin film films prepared in examples 1 to 3, the graphene thin film films are prepared into 0.8mg/ml to 1.5mg/ml graphene liquid, conductivity measurement is carried out on the graphene liquid, and the test results show that the conductivity of the graphene thin film films is as high as 7.5 multiplied by 106S/m-8.2×106S/m, and therefore, the graphene film prepared by the method has higher conductivity, namely good conductivity. Meanwhile, the preparation of each example is carried outThe graphene carbon nanotube composite membrane has good performances in the aspects of transparency, uniformity, compactness, light transmittance, bendability, 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 application, and not intended to limit the scope of the present application, and all modifications and equivalents of the subject matter of the present application, which are made by the following claims and their equivalents, or which are directly or indirectly applicable to other related arts, are intended to be included within the scope of the present application.
Claims (10)
1. The preparation method of the graphene film is characterized by comprising the following steps:
preparing a graded porous silicon dioxide film filled with a metal catalyst;
depositing graphene on the surface of the hierarchical porous silicon dioxide film by adopting an atomic layer deposition method; and
and removing the graded porous silicon dioxide film to obtain the graphene film.
2. The method of preparing a graphene thin film according to claim 1, wherein the step of preparing a hierarchical porous silica thin film filled with a metal catalyst comprises:
preparing graded porous silicon dioxide by adopting a sol-gel method;
depositing a metal catalyst in the pore channels of the hierarchical porous silica by adopting an atomic layer deposition method; and
and dispersing the graded porous silicon dioxide deposited with the metal catalyst into an alcohol solution, and pressing to obtain the graded porous silicon dioxide film filled with the metal catalyst.
3. The method for preparing the graphene film according to claim 2, wherein the step of preparing the hierarchical porous silica by the sol-gel method comprises:
mixing an organic solvent with water to obtain a mixed solvent;
and adding a silicon precursor source, a surfactant and a catalyst into the mixed solvent, stirring to disperse the mixture, and performing centrifugal separation to obtain the hierarchical porous silicon dioxide.
4. The method for preparing the graphene film according to claim 2, wherein the step of depositing the metal catalyst in the pores of the hierarchical porous silica by using an atomic layer deposition method comprises:
and alternately introducing a metal catalyst precursor and a first reducing gas into the pore channels of the hierarchical porous silica in an inert environment.
5. The method for preparing the graphene film according to claim 4, wherein the introduction time of the metal catalyst precursor is 0.01s to 0.2s, the residence time is 2s to 20s, and the purging time is 2s to 30 s;
and/or the first reducing gas is introduced for 0.01s-0.5s, the residence time is 2s-20s, and the purging time is 2s-30 s.
6. The method according to claim 4, wherein the metal catalyst is a copper catalyst, and the metal catalyst precursor is at least one of copper N, N-diisopropylacetate, copper 1, 5-cyclooctadiene (hexafluoro-2, 4-pentanedionate), and copper acetylacetonate.
7. The method for preparing the graphene film according to any one of claims 1 to 6, wherein the step of depositing graphene on the surface of the hierarchical porous silica film by using an atomic layer deposition method comprises:
and putting the graded porous silicon dioxide film into a reaction cavity, introducing a carbon source precursor, performing primary purging by adopting protective gas, introducing second reducing gas, performing secondary purging by adopting the protective gas, and then performing heating annealing treatment.
8. The method for preparing the graphene film according to claim 7, wherein the carbon source precursor is introduced for 0.01s to 0.1s, the residence time is 2s to 10s, and the first purging time is 5s to 20 s;
and/or the second reducing gas is introduced for 0.01s-0.2s, the residence time is 5s-20s, and the second purging time is 5s-20 s.
9. A graphene thin film prepared by the method of any one of claims 1 to 8.
10. A thin film transistor array is characterized by comprising a 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 thin 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 thin film layer are sequentially deposited on the surface of the substrate, at least part of the graphene thin film layer penetrates through the passivation layer and is connected with the source drain metal layer, and the graphene thin film layer is the graphene thin film according.
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