CN113046724A - Large-area graphite-phase carbon nitride film, preparation method and application - Google Patents
Large-area graphite-phase carbon nitride film, preparation method and application Download PDFInfo
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- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 55
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 55
- 239000010439 graphite Substances 0.000 claims abstract description 55
- 239000000758 substrate Substances 0.000 claims abstract description 47
- ROBVLQBZPQQRTQ-UHFFFAOYSA-N [N].C1=CN=NN=C1 Chemical compound [N].C1=CN=NN=C1 ROBVLQBZPQQRTQ-UHFFFAOYSA-N 0.000 claims abstract description 12
- -1 heterocyclic organic compound Chemical class 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 10
- 239000011261 inert gas Substances 0.000 claims abstract description 8
- 229920000877 Melamine resin Polymers 0.000 claims description 40
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 40
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000011521 glass Substances 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- 230000005693 optoelectronics Effects 0.000 claims 1
- 238000002203 pretreatment Methods 0.000 claims 1
- 230000005540 biological transmission Effects 0.000 abstract description 7
- 238000006068 polycondensation reaction Methods 0.000 abstract description 6
- 238000000151 deposition Methods 0.000 abstract description 4
- 239000007789 gas Substances 0.000 abstract description 3
- 239000003575 carbonaceous material Substances 0.000 abstract description 2
- 239000012071 phase Substances 0.000 description 82
- 239000010408 film Substances 0.000 description 60
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 54
- 229910052786 argon Inorganic materials 0.000 description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 239000010431 corundum Substances 0.000 description 18
- 229910052593 corundum Inorganic materials 0.000 description 18
- 239000010453 quartz Substances 0.000 description 15
- 239000010409 thin film Substances 0.000 description 11
- 238000000861 blow drying Methods 0.000 description 9
- 238000001816 cooling Methods 0.000 description 9
- 238000000227 grinding Methods 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 238000009210 therapy by ultrasound Methods 0.000 description 9
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- 238000010586 diagram Methods 0.000 description 5
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- 238000012986 modification Methods 0.000 description 3
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- 238000011160 research Methods 0.000 description 3
- 238000000089 atomic force micrograph Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
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- 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
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/34—Nitrides
- C23C16/347—Carbon nitride
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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
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Abstract
The invention discloses a preparation method of a large-area graphite-phase carbon nitride film with adjustable thickness, and relates to the technical field of carbon materials. The method comprises the following steps: respectively placing triazine nitrogen-containing heterocyclic organic compound powder and a substrate in a double-temperature-zone heating container, placing the triazine nitrogen-containing heterocyclic organic compound powder in the source zone, and placing the substrate in the growth zone; introducing inert gas into the dual-temperature-zone heating container, wherein the inert gas flows from the source zone to the growth zone; and controlling the temperature of the source region to be 250-300 ℃ and the temperature of the growth region to be 500-600 ℃, and keeping the temperature for 5-120 min to obtain the graphite phase carbon nitride film. The invention adopts a hot gas phase transmission assisted polycondensation deposition method to prepare a 4-inch large-area uniform graphite phase carbon nitride film, and the thickness of the obtained graphite phase carbon nitride can be easily and accurately controlled by the growth time.
Description
Technical Field
The invention belongs to the technical field of carbon materials, and particularly relates to a large-area graphite-phase carbon nitride film with adjustable thickness, a preparation method and application.
Background
Since the discovery of the photocatalytic hydrolysis capability of graphite-phase carbon nitride in the morning of 2008, the material attracts great research interest of researchers. Because of the excellent properties of graphite phase carbon nitride, including simple synthesis method, attractive electronic band structure, excellent physical and chemical stability, abundant earth reserves of constituent elements, easy modification and the like, a great deal of research work is used for researching the application of graphite phase carbon nitride in different fields, on one hand, graphite phase carbon nitride has attractive prospect in the field of photocatalysis, on the other hand, with the deep understanding of graphite phase carbon nitride, other excellent properties of graphite phase carbon nitride are gradually discovered as a high-efficiency and stable photocatalyst, however, the research of graphite phase carbon nitride in other fields has not made great progress, the most important reason is that the preparation method of graphite phase carbon nitride can only obtain powdered graphite phase carbon nitride, the crystal quality is very poor, and the preparation requirements of various devices can not be met, including crystallization, uniformity, conductivity, defects, and the like.
Disclosure of Invention
The invention aims to provide a large-area graphite-phase carbon nitride film with adjustable thickness and a preparation method thereof aiming at the defects and the defects of the method, the large-area graphite-phase carbon nitride film with 4 inches and large area is prepared by adopting a thermal vapor phase transmission assisted polycondensation deposition method, the thickness of the obtained graphite-phase carbon nitride can be easily and accurately controlled through the growth time, from dozens of nanometers to several micrometers, the patterning growth can also be realized by designing a mask, the film can be deposited on different substrates (quartz glass, FTO glass and silicon wafers), and simultaneously the obtained graphite-phase carbon nitride can be easily separated from the high-temperature resistant substrate through aqueous solution due to the unique property of the graphite-phase carbon nitride, so that the complete self-supporting large-area graphite-phase carbon nitride film is obtained.
The invention provides a preparation method of a large-area graphite-phase carbon nitride film with adjustable thickness, which comprises the following steps:
placing triazine nitrogen-containing heterocyclic organic compound powder and a high-temperature-resistant substrate in a dual-temperature-zone heating container, wherein two temperature control zones comprising a source zone and a growth zone are arranged in the dual-temperature-zone heating container; placing the triazine nitrogen-containing heterocyclic organic compound powder in the source region, placing the high-temperature resistant substrate in the growth region, and placing the triazine nitrogen-containing heterocyclic organic compound powder and the high-temperature resistant substrate on the same working surface;
introducing inert gas into the dual-temperature-zone heating container, wherein the inert gas flows from the source zone to the growth zone; and controlling the temperature of the source region to be 250-300 ℃ and the temperature of the growth region to be 500-600 ℃, and keeping the temperature for 5-120 min, so as to obtain the graphite phase carbon nitride film on the high-temperature resistant substrate.
Preferably, the triazine nitrogen-containing heterocyclic organic compound is melamine.
Preferably, the flow rate of the inert gas is 150-250 sccm.
Preferably, the thickness of the graphite phase carbon nitride film is 14-1000 nm.
Preferably, the temperature rise rate of the source region temperature is 8-12 ℃/min, and the temperature rise rate of the growth region temperature is 18-22 ℃/min
Preferably, the triazine nitrogen-containing heterocyclic organic compound powder is placed in the source region after being placed in a high-temperature-resistant vessel; the high-temperature resistant vessel is a crucible.
Preferably, the high temperature resistant substrate is quartz glass, FTO glass or a silicon wafer, and the pretreatment of the high temperature resistant substrate is to clean and blow-dry the surface of the high temperature resistant substrate by acetone, alcohol and deionized water respectively.
Preferably, the dual-temperature-zone heating container is a dual-temperature-zone tube furnace.
The second purpose of the invention is to provide a large-area graphite-phase carbon nitride film with adjustable thickness.
The third purpose of the invention is to provide the application of the large-area graphite phase carbon nitride film with adjustable thickness in photoelectric devices.
Compared with the prior art, the invention has the following beneficial effects:
the invention adopts a hot gas phase transmission assisted polycondensation deposition method to prepare a 4-inch large-area uniform graphite phase carbon nitride film, the thickness of the obtained graphite phase carbon nitride can be easily and accurately controlled through the growth time, from tens of nanometers to several micrometers, patterning growth can also be realized by designing a mask, the film can be deposited on different substrates (quartz glass, FTO glass and silicon wafers), and simultaneously the obtained graphite phase carbon nitride can be easily separated from the substrate through an aqueous solution due to the unique property of the graphite phase carbon nitride, so that the complete self-supporting large-area graphite phase carbon nitride film is obtained;
the prepared graphite phase carbon nitride film is immersed in water, so that the film and a substrate can completely fall off, and the continuous self-supporting large-area graphite phase carbon nitride film is obtained.
Drawings
Fig. 1 is a schematic diagram of a method for preparing a large-area graphite-phase carbon nitride film with adjustable thickness according to various embodiments.
FIG. 2 is an optical photograph of the graphite-phase carbon nitride thin films provided in examples 1 to 3.
FIG. 3 is a butterfly-shaped graphite-phase carbon nitride film as provided in example 4.
FIG. 4 is an atomic force micrograph of the graphite phase carbon nitride films provided in examples 1, 5, and 9.
Fig. 5 is a schematic diagram of water transfer of the graphite phase carbon nitride film provided in example 1.
Fig. 6 is a schematic diagram of an application of the large-area graphite-phase carbon nitride film with adjustable thickness in the photoelectric device provided in example 1.
Detailed Description
In order to make the technical solutions of the present invention better understood and implemented by those skilled in the art, the present invention is further described below with reference to the following specific embodiments and the accompanying drawings, but the embodiments are not meant to limit the present invention.
Example 1
A preparation method of a large-area graphite-phase carbon nitride film with adjustable thickness is shown in figure 1 and comprises the following steps:
step A, weighing 20g of melamine with the mass fraction of 99%, uniformly grinding the melamine, and placing the melamine in a corundum crucible, wherein the amount of the melamine is excessive;
b, respectively carrying out ultrasonic treatment on the cut quartz substrate with the size of 5 x 5cm for 10min by using acetone, alcohol and deionized water, and then carrying out blow-drying by using a nitrogen gun;
step C, respectively placing the corundum crucible containing the melamine and the quartz substrate in a source area and a growth area of the double-temperature-area tube furnace; the source region and the growth region are positioned on the same working surface, argon is introduced into the double-temperature-region tubular furnace, the argon flows from the source region to the growth region, and the flow rate of the argon is 200 sccm; controlling the temperature of the temperature growth area of the source area to be respectively set to be increased to 300 ℃ and 560 ℃ in 30min, then preserving the heat for 30min, and finally naturally cooling to room temperature to obtain a graphite phase carbon nitride film with the thickness of about 521 nm;
example 2
A preparation method of a large-area graphite-phase carbon nitride film with adjustable thickness is shown in figure 1 and comprises the following steps:
step A, weighing 20g of melamine with the mass fraction of 99%, uniformly grinding the melamine, and placing the melamine in a corundum crucible;
b, respectively carrying out ultrasonic treatment on the cut FTO glass substrate with the size of 5 x 5cm for 10min by using acetone, alcohol and deionized water, and then carrying out blow-drying by using a nitrogen gun;
step C, respectively placing the corundum crucible containing melamine and the FTO glass substrate in a source area and a growth area of the double-temperature-area tube furnace; the source region and the growth region are positioned on the same working surface, argon is introduced into the double-temperature-region tubular furnace, the argon flows from the source region to the growth region, and the flow rate of the argon is 150 sccm; controlling the temperature of the growth area of the source area to be respectively set to 300 ℃ and 560 ℃ after 30min, then preserving the heat for 2min, and finally naturally cooling to room temperature to obtain the graphite phase carbon nitride film with the thickness of about 14 nm.
Example 3
A preparation method of a large-area graphite-phase carbon nitride film with adjustable thickness is shown in figure 1 and comprises the following steps:
step A, weighing 20g of melamine with the mass fraction of 99%, uniformly grinding the melamine, and placing the melamine in a corundum crucible;
b, respectively carrying out ultrasonic treatment on the cut silicon wafer substrate with the size of 5 x 5cm for 10min by using acetone, alcohol and deionized water, and then carrying out blow-drying by using a nitrogen gun;
step C, respectively placing the corundum crucible containing melamine and the silicon wafer substrate in a source area and a growth area of the double-temperature-area tube furnace; the source region and the growth region are positioned on the same working surface, argon is introduced into the double-temperature-region tubular furnace, the argon flows from the source region to the growth region, and the flow rate of the argon is 250 sccm; controlling the temperature of the temperature growth area of the source area to be respectively set to be increased to 300 ℃ and 560 ℃ in 30min, then preserving the temperature for 60min, and finally naturally cooling to room temperature to obtain the graphite phase carbon nitride film with the thickness of about 942 nm.
Example 4
A preparation method of a large-area graphite-phase carbon nitride film with adjustable thickness is shown in figure 1 and comprises the following steps:
step A, weighing 20g of melamine with the mass fraction of 99%, uniformly grinding the melamine, and placing the melamine in a corundum crucible;
b, respectively carrying out ultrasonic treatment on the cut quartz substrate with the size of 5 x 5cm for 10min by using acetone, alcohol and deionized water, then blow-drying by using a nitrogen gun, and tightly attaching a butterfly-shaped metal mask plate to the surface of the quartz substrate;
step C, respectively placing the corundum crucible containing the melamine and the quartz substrate in a source area and a growth area of the double-temperature-area tube furnace; the source region and the growth region are positioned on the same working surface, argon is introduced into the double-temperature-region tubular furnace, the argon flows from the source region to the growth region, and the flow rate of the argon is 200 sccm; controlling the temperature of the growth area of the source area to be respectively set to 300 ℃ and 560 ℃ after 30min, then preserving the temperature for 30min, and finally naturally cooling to room temperature to obtain the butterfly-shaped graphite phase carbon nitride film with the thickness of about 521 nm.
Example 5
A preparation method of a large-area graphite-phase carbon nitride film with adjustable thickness is shown in figure 1 and comprises the following steps:
step A, weighing 20g of melamine with the mass fraction of 99%, uniformly grinding the melamine, and placing the melamine in a corundum crucible;
b, respectively carrying out ultrasonic treatment on the cut quartz substrate with the size of 5 x 5cm for 10min by using acetone, alcohol and deionized water, and then carrying out blow-drying by using a nitrogen gun;
step C, respectively placing the corundum crucible containing the melamine and the quartz substrate in a source area and a growth area of the double-temperature-area tube furnace; the source region and the growth region are positioned on the same working surface, argon is introduced into the double-temperature-region tubular furnace, the argon flows from the source region to the growth region, and the flow rate of the argon is 200 sccm; controlling the temperature of the growth area of the source area to be respectively set to 300 ℃ and 560 ℃ after 30min, then preserving the heat for 2min, and finally naturally cooling to room temperature to obtain the graphite phase carbon nitride film with the thickness of about 14 nm.
Example 6
A preparation method of a large-area graphite-phase carbon nitride film with adjustable thickness is shown in figure 1 and comprises the following steps:
step A, weighing 20g of melamine with the mass fraction of 99%, uniformly grinding the melamine, and placing the melamine in a corundum crucible;
b, respectively carrying out ultrasonic treatment on the cut quartz substrate with the size of 5 x 5cm for 10min by using acetone, alcohol and deionized water, and then carrying out blow-drying by using a nitrogen gun;
step C, respectively placing the corundum crucible containing the melamine and the quartz substrate in a source area and a growth area of the double-temperature-area tube furnace; the source region and the growth region are positioned on the same working surface, argon is introduced into the double-temperature-region tubular furnace, the argon flows from the source region to the growth region, and the flow rate of the argon is 200 sccm; controlling the temperature of the growth area of the source area to be respectively set to 300 ℃ and 560 ℃ after 30min, then preserving the temperature for 5min, and finally naturally cooling to room temperature to obtain the graphite phase carbon nitride film with the thickness of about 55 nm.
Example 7
A preparation method of a large-area graphite-phase carbon nitride film with adjustable thickness is shown in figure 1 and comprises the following steps:
step A, weighing 20g of melamine with the mass fraction of 99%, uniformly grinding the melamine, and placing the melamine in a corundum crucible;
b, respectively carrying out ultrasonic treatment on the cut quartz substrate with the size of 5 x 5cm for 10min by using acetone, alcohol and deionized water, and then carrying out blow-drying by using a nitrogen gun;
step C, respectively placing the corundum crucible containing the melamine and the quartz substrate in a source area and a growth area of the double-temperature-area tube furnace; the source region and the growth region are positioned on the same working surface, argon is introduced into the double-temperature-region tubular furnace, the argon flows from the source region to the growth region, and the flow rate of the argon is 200 sccm; controlling the temperature of the growth area of the source area to be respectively set to 300 ℃ and 560 ℃ after 30min, then preserving the temperature for 10min, and finally naturally cooling to room temperature to obtain the graphite phase carbon nitride film with the thickness of about 108 nm.
Example 8
A preparation method of a large-area graphite-phase carbon nitride film with adjustable thickness is shown in figure 1 and comprises the following steps:
step A, weighing 20g of melamine with the mass fraction of 99%, uniformly grinding the melamine, and placing the melamine in a corundum crucible;
b, respectively carrying out ultrasonic treatment on the cut quartz substrate with the size of 5 x 5cm for 10min by using acetone, alcohol and deionized water, and then carrying out blow-drying by using a nitrogen gun;
step C, respectively placing the corundum crucible containing the melamine and the quartz substrate in a source area and a growth area of the double-temperature-area tube furnace; the source region and the growth region are positioned on the same working surface, argon is introduced into the double-temperature-region tubular furnace, the argon flows from the source region to the growth region, and the flow rate of the argon is 200 sccm; controlling the temperature of the growth area of the source area to be respectively set to be increased to 300 ℃ and 560 ℃ in 30min, then preserving the heat for 20min, and finally naturally cooling to room temperature to obtain the graphite phase carbon nitride film with the thickness of about 237 nm.
Example 9
A preparation method of a large-area graphite-phase carbon nitride film with adjustable thickness is shown in figure 1 and comprises the following steps:
step A, weighing 20g of melamine with the mass fraction of 99%, uniformly grinding the melamine, and placing the melamine in a corundum crucible;
b, respectively carrying out ultrasonic treatment on the cut quartz substrate with the size of 5 x 5cm for 10min by using acetone, alcohol and deionized water, and then carrying out blow-drying by using a nitrogen gun;
step C, respectively placing the corundum crucible containing the melamine and the quartz substrate in a source area and a growth area of the double-temperature-area tube furnace; the source region and the growth region are positioned on the same working surface, argon is introduced into the double-temperature-region tubular furnace, the argon flows from the source region to the growth region, and the flow rate of the argon is 200 sccm; controlling the temperature of the temperature growth area of the source area to be respectively set to be increased to 300 ℃ and 560 ℃ in 30min, then preserving the temperature for 60min, and finally naturally cooling to room temperature to obtain the graphite phase carbon nitride film with the thickness of about 942 nm.
In order to illustrate the relevant performance of the large-area graphite-phase carbon nitride film with adjustable thickness, the film provided by the embodiment is subjected to relevant performance test and experiment, and the test is shown in fig. 2-6.
Fig. 1 is a schematic diagram of a method for preparing a large-area graphite-phase carbon nitride film with adjustable thickness according to various embodiments. The graphite phase carbon nitride is synthesized by the aid of thermal meteorological transmission assisted polycondensation, and as can be seen from figure 1, melamine can be uniformly and continuously provided by the aid of the thermal meteorological transmission assisted polycondensation in the double-temperature-zone, so that the uniform and controllable growth of a graphite phase carbon nitride film is realized, and the preparation method is simple and controllable, and is easy to realize large-scale production.
Fig. 2 is an optical photograph of the graphite phase carbon nitride thin films provided in examples 1 to 3, and examples 1 to 3 are graphite phase carbon nitride thin films prepared on different substrates, and it can be seen from fig. 2 that the graphite phase carbon nitride thin film with a large area and uniformity in 4 inches prepared in example 1 can realize the growth of the graphite phase carbon nitride thin film with a large area, and the thin films provided in examples 2 and 3 also have good light transmittance and can realize uniform growth of the thin film on different substrates.
Fig. 3 shows the butterfly-shaped graphite-phase carbon nitride film provided in example 4, which is grown by adding a butterfly-shaped metal mask. The patterned controlled growth facilitates the use of graphite phase carbon nitride films for patterning integrated electrical devices.
Fig. 4 is an atomic force micrograph of the graphite phase carbon nitride thin film provided in embodiments 1, 5 to 9, and fig. 4 is a graph in which the thickness of the graphite phase carbon nitride thin film can be accurately controlled by changing the growth time for 2,5,10,20,30, and 60 minutes from left to right, and is continuously adjustable from 14nm to 942nm, so that a thicker graphite phase carbon nitride thin film can be obtained by prolonging the growth time, the thickness of the thin film can be further reduced by shortening the growth time, but a thinner sample has certain difficulty in characterization and testing.
Fig. 5 is a schematic diagram of water transfer of the graphite phase carbon nitride film provided in embodiment 1, in which the graphite phase carbon nitride film is immersed in water to completely separate the graphite phase carbon nitride film from the substrate, so as to obtain a self-supporting continuous, uniform and transparent large-area graphite phase carbon nitride film, and the film transfer can be realized by directly taking the target substrate out of water, thereby avoiding pollution caused by a conventional transfer method.
Fig. 6 is a schematic view of an application of the thickness-adjustable large-area graphite-phase carbon nitride film in a photoelectric device according to example 1, in which a photodetector array is constructed on the surface of the grown large-area graphite-phase carbon nitride film, so that a clear imaging function is realized, and it is shown that the large-area graphite-phase carbon nitride film formed by thermal image transmission-assisted condensation polymerization has excellent photoelectric properties.
In conclusion, the invention adopts a hot gas phase transmission assisted polycondensation deposition method to prepare a 4-inch large-area uniform graphite phase carbon nitride film, the thickness of the obtained graphite phase carbon nitride can be easily and accurately controlled through the growth time, from tens of nanometers to several micrometers, patterning growth can also be realized by designing a mask, the film can be deposited on different substrates (quartz glass, FTO glass and silicon wafers), and simultaneously the obtained graphite phase carbon nitride can be easily separated from the substrate through an aqueous solution due to the unique property of the graphite phase carbon nitride, so that the complete self-supporting large-area graphite phase carbon nitride film is obtained;
the prepared graphite phase carbon nitride film is immersed in water, so that the film and a substrate can completely fall off, and the continuous self-supporting large-area graphite phase carbon nitride film is obtained.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, it is intended that such changes and modifications be included within the scope of the appended claims and their equivalents.
Claims (10)
1. A preparation method of a large-area graphite-phase carbon nitride film with adjustable thickness is characterized by comprising the following steps:
placing triazine nitrogen-containing heterocyclic organic compound powder and a high-temperature-resistant substrate in a dual-temperature-zone heating container, wherein two temperature control zones comprising a source zone and a growth zone are arranged in the dual-temperature-zone heating container; placing the triazine nitrogen-containing heterocyclic organic compound powder in the source region, placing the high-temperature resistant substrate in the growth region, and placing the triazine nitrogen-containing heterocyclic organic compound powder and the high-temperature resistant substrate on the same working surface;
introducing inert gas into the dual-temperature-zone heating container, wherein the inert gas flows from the source zone to the growth zone; and controlling the temperature of the source region to be 250-300 ℃ and the temperature of the growth region to be 500-600 ℃, and keeping the temperature for 5-120 min, so as to obtain the graphite phase carbon nitride film on the high-temperature resistant substrate.
2. The method for preparing large-area graphite-phase carbon nitride film with adjustable thickness according to claim 1, wherein the triazine nitrogen-containing heterocyclic organic compound is melamine.
3. The method for preparing a large-area graphite-phase carbon nitride film with adjustable thickness as claimed in claim 1, wherein the inert gas has a flow rate of 150-250 sccm.
4. The method for preparing a large-area graphite-phase carbon nitride film with adjustable thickness according to claim 1, wherein the thickness of the graphite-phase carbon nitride film is 14-1000 nm.
5. The method for preparing a large-area graphite-phase carbon nitride film with adjustable thickness according to claim 1, wherein the temperature rise rate of the source region temperature is 8-12 ℃/min, and the temperature rise rate of the growth region temperature is 18-22 ℃/min.
6. The method for preparing a large-area graphite-phase carbon nitride film with adjustable thickness according to claim 1, wherein the triazine nitrogen-containing heterocyclic organic compound powder is placed in the source region after being placed in a high-temperature-resistant vessel; the high-temperature resistant vessel is a crucible.
7. The method for preparing the large-area graphite-phase carbon nitride film with adjustable thickness according to claim 1, wherein the high-temperature-resistant substrate is quartz glass, FTO glass or a silicon wafer, and the pre-treatment of the high-temperature-resistant substrate is to clean and blow-dry the surface of the high-temperature-resistant substrate by acetone, alcohol and deionized water respectively.
8. The method of claim 1, wherein the dual-zone heating vessel is a dual-zone tube furnace.
9. A large-area graphite-phase carbon nitride film with adjustable thickness prepared by the preparation method of any one of claims 1 to 8.
10. Use of the thickness tunable large area graphite phase carbon nitride film of claim 9 in an optoelectronic device.
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