CN112299401A - Nitrogen and boron co-doped graphene composite film and preparation method thereof - Google Patents
Nitrogen and boron co-doped graphene composite film and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a nitrogen and boron codoped graphene composite film and a preparation method thereof, and belongs to the field of transparent conductive film materials. The preparation method of the nitrogen and boron co-doped graphene composite film comprises the steps of doping a proper amount of nitrogen and boron for the first time when the graphene film is prepared by a CVD method and doping the nitrogen and boron co-doped graphene for the second time when the nitrogen and boron co-doped graphene is introduced into a target substrate, the two-time doping process is simple, and the doping of a dopant is stable, so that the prepared nitrogen and boron co-doped graphene composite film has smaller thickness and lower sheet resistance, and can be directly applied to the fields of high-performance composite materials, flexible display and flexible electronic devices, electrochemical energy storage, photoelectric detection and sensors and the like.
Description
Technical Field
The invention belongs to the field of transparent conductive film materials, and particularly relates to a nitrogen and boron codoped graphene composite film and a preparation method thereof.
Background
Graphene is used as a two-dimensional carbon material with a unique energy band structure, has high transmittance and good conductivity, can be used as a transparent conductive material, shows a wide prospect in various fields such as high-performance composite materials, flexible display and flexible electronic devices, electrochemical energy storage, photoelectric detection and sensors and the like, and is widely concerned internationally.
At present, there are many methods for preparing graphene films, and among them, Chemical Vapor Deposition (CVD) is one of the main methods for realizing mass production of transparent graphene films. The CVD method mainly takes transition metal and alloy as a catalyst and a carrier for graphene growth, and then grows the graphene with large area, high quality and controllable layer number. However, due to the multi-domain characteristic of the graphene prepared by the CVD method and the low intrinsic carrier concentration of the graphene, the sheet resistance of the graphene film is high, and the requirements of practical application cannot be met.
In the prior art, the sheet resistance of the graphene film is reduced by adopting adsorption doping, namely, charge transfer is generated between doping substances and graphene, and the dopant mainly obtains electrons from or loses electrons with the graphene or changes the position of the Fermi level of the graphene through dipole moment, so that the carrier density of the graphene film is increased, and the sheet resistance is reduced. For example, CN104409177A discloses a method for preparing a large-area stably doped graphene transparent conductive film in a large scale, in which a doping effect and stability of the graphene transparent conductive film are improved by using an interlayer structure, a dopant is first formed on a surface of graphene on an initial substrate or on a surface of a transparent substrate, then the graphene, the dopant and the transparent substrate are combined, and finally the graphene is separated from the initial substrate, so as to prepare the large-area stably doped graphene transparent conductive film. The graphene is used as an outer protective film of the dopant, so that the doping stability is improved; however, the sheet resistance of the sample is higher by about 500-1000 Ω/□ (Ω/□ represents the unit of sheet resistance), and the mentioned stability is not high temperature stability, and can not meet the process requirements of heating and electronic products in the manufacturing process of certain subsequent applications. CN108305705A discloses a graphene composite film, a method for preparing the same, and an application thereof, wherein the document adopts "two-step doping", the first doping is performed simultaneously with the peeling of the substrate, and the second doping can be performed directly by the dopant introduced into the second target substrate in advance after the prepared graphene/first target substrate structure printed with silver paste and doped with the dopant is heated. Because the method disclosed in the document does not have a high-temperature process after the second doping, the loss of the dopant doped into the graphene film for the second time due to a series of changes such as desorption and decomposition caused by subsequent treatment procedures such as water washing and high temperature is ensured, so that the sheet resistance of the graphene composite film prepared by using the single-layer graphene is reduced to about 200 Ω/□ and to about 175 Ω/□ at minimum, however, the method still cannot meet the application requirements of the graphene composite film under the condition of lower sheet resistance.
Disclosure of Invention
In view of one or more of the problems in the prior art, an aspect of the present invention provides a method for preparing a nitrogen and boron co-doped graphene composite film, including the following steps:
1) providing a dual-temperature-zone system, and respectively placing a carbon-nitrogen-boron source and a substrate in two temperature zones in the dual-temperature-zone system, wherein a carbon source, a nitrogen source and a boron source in the carbon-nitrogen-boron source are in a mass ratio of 1: 2-10: 0.5-1;
2) introducing reducing gas into the dual-temperature zone system, and respectively heating the dual-temperature zones to deposit and form nitrogen and boron co-doped graphene on the surface of the substrate;
3) attaching the nitrogen and boron co-doped graphene on the substrate to a transfer matrix to obtain the transfer matrix/nitrogen and boron co-doped graphene/substrate;
4) removing the substrate on the transfer matrix/nitrogen and boron co-doped graphene/substrate to obtain transfer matrix/nitrogen and boron co-doped graphene;
5) attaching the nitrogen and boron co-doped graphene on the transfer matrix/nitrogen and boron co-doped graphene to a first target matrix, and removing the transfer matrix to obtain the nitrogen and boron co-doped graphene/first target matrix;
6) silver paste is printed on the nitrogen and boron codoped graphene/first target substrate, and the obtained nitrogen and boron codoped graphene/first target substrate printed with the silver paste is subjected to high-temperature treatment;
7) nitrogen, boron codope graphite alkene one side laminating second target base member on the nitrogen of being printed with silver thick liquid, boron codope graphite alkene/first target base member the dopant is introduced in advance to the one side that second target base member and nitrogen, boron codope graphite alkene were laminated.
In the method, in the carbon, nitrogen and boron source in step 1), the carbon source is one or a mixture of sucrose, glucose, polyethylene glycol and cellulose, the nitrogen source is one or a mixture of urea, dicyandiamide, biuret, nitrilamine and melamine, and the boron source is one or a mixture of boric acid and boron oxide; the carbon source, the nitrogen source and the boron source in the carbon-nitrogen-boron source are 1: 4-10: 0.5-1, preferably 1: 4-8: 0.5-1 in mass ratio.
In the above method, the substrate in step 1) is selected from one or more alloy materials of Au, Pt, Pd, Ir, Ru, Co, Ni, and Cu.
In the method, the reducing gas in the step 2) is hydrogen, a mixed gas of hydrogen and nitrogen or a mixed gas of hydrogen and argon, and the flow rate of the reducing gas is 150-300 ml/min.
In the method, in the step 2), the heating temperature of the substrate is 600-1000 ℃ and the heating temperature of the carbon, nitrogen and boron source is 200-300 ℃ in the two heating temperature zones.
In the method, the deposition time in the step 2) is 10min to 20 min.
In the method, the transfer matrix in the step 3) is a PET silica gel protective film, a PET acrylic acid protective film, a PMMA silica gel protective film, a PMMA acrylic acid protective film, a PI silica gel protective film or a PI acrylic acid protective film.
In the above method, the method for removing the substrate on the transfer matrix/nitrogen and boron co-doped graphene/substrate in step 4) is a chemical etching method, wherein the specific operation method of the chemical etching method is as follows: and immersing the transfer matrix/nitrogen and boron co-doped graphene/substrate into etching liquid for etching, wherein an etchant in the etching liquid is at least one of ammonium persulfate, ferric chloride, copper chloride or hydrochloric acid hydrogen peroxide, and the concentration of the etchant in the etching liquid is 0.4-1.5 mol/L.
In the method, the first target substrate in the step 5) is a polyethylene film, a polyethylene terephthalate film, a polystyrene film or a polyvinyl chloride film, and the thickness of the first target substrate is 50-200 μm.
In the above method, the second target substrate in step 7) is an encapsulating material, and the encapsulating material includes: the thickness of the second target substrate is 10-150 mu m.
In the method, the high-temperature treatment in the step 6) is carried out at 125-145 ℃ for 0.5-2 hours.
The dopant is at least one of metal chloride, imidazole compounds and derivatives thereof or triazole compounds and derivatives thereof, and the concentration is 10 mmol/L-60 mmol/L; the method for introducing the dopant into the surface, attached to the nitrogen and boron co-doped graphene, of the second target substrate in the step 7) is soaking, spraying or spin coating.
The invention provides a nitrogen and boron co-doped graphene composite film, which comprises a nitrogen and boron co-doped graphene film, a first target substrate and a second target substrate, wherein the first target substrate and the second target substrate are arranged on two surfaces of the nitrogen and boron co-doped graphene film, silver paste is printed on one surface, attached to the first target substrate, of the nitrogen and boron co-doped graphene film, and a dopant is doped on one surface, attached to the second target substrate, of the nitrogen and boron co-doped graphene film.
The application of the nitrogen and boron codoped graphene composite film in electronic devices also belongs to the content of the invention.
According to the preparation method of the nitrogen and boron co-doped graphene composite film provided by the technical scheme, firstly, a nitrogen and boron co-doped graphene film growing on the surface of a metal substrate is prepared in a dual-temperature-zone system by adopting a carbon nitrogen boron source mixed in a proper proportion according to a CVD (chemical vapor deposition) method, so that the conductivity of graphene can be improved, the sheet resistance of the graphene is reduced, and the stable doping of nitrogen and boron in the graphene is realized; and then etching to remove the metal substrate, transferring to the first target base body, and silk-screening a silver paste lead on the surface of the nitrogen and boron co-doped graphene, wherein the silver paste needs to be baked at high temperature (about 135 ℃) after silk-screening, and the process can enable the sheet resistance of the nitrogen and boron co-doped graphene film to rise, so that the surface of the second target base body is attached to the nitrogen and boron co-doped graphene film after a dopant is introduced into the surface of the second target base body, and the nitrogen and boron co-doped graphene can be doped again to enable the sheet resistance of the nitrogen and boron co-doped graphene. Therefore, the application requirement of the graphene composite film on low sheet resistance can be met by adopting a two-step doping method, the first doping and the growth of the graphene film on the metal substrate are carried out simultaneously, and the process is simple and efficient; the second doping can be performed directly by introducing the dopant on the second target substrate in advance after the prepared nitrogen and boron co-doped graphene/first target substrate structure printed with the silver paste is subjected to high temperature, and a high-temperature process is not required after the second doping, so that the dopant doped to the graphene film for the second time is prevented from being lost due to a series of changes such as desorption and decomposition caused by subsequent treatment procedures such as washing, high temperature and the like, the sheet resistance of the nitrogen and boron co-doped graphene composite film provided by the invention is reduced, the process method is simple and efficient, and the prepared graphene composite film is thinner. The nitrogen and boron codoped graphene composite film prepared by the method can be directly applied to the preparation of electronic devices in the fields of high-performance composite materials, flexible display and flexible electronic devices, electrochemical energy storage, photoelectric detection and sensors and the like.
Drawings
FIG. 1 is a schematic diagram of a dual-temperature zone system;
fig. 2 is a schematic structural diagram of a nitrogen and boron co-doped graphene composite film.
Detailed Description
In the following, only certain exemplary embodiments are briefly described. As those skilled in the art will recognize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention. Accordingly, the drawings and description are to be regarded as illustrative in nature, and not as restrictive.
The various materials or reagents described in the examples are obtained solely for the purpose of providing a laboratory access to achieve the specific disclosure, and should not be construed as limiting the sources of the materials or reagents of the invention. In fact, the sources of the materials or reagents used are wide and any material or reagent that is accessible without violating laws and ethics may be substituted as indicated in the examples.
In one aspect of the invention, a preparation method of a nitrogen and boron co-doped graphene composite film is provided, which comprises the following steps:
1) providing a dual-temperature-zone system, and respectively placing a carbon-nitrogen-boron source and a substrate in two temperature zones in the dual-temperature-zone system, wherein a carbon source, a nitrogen source and a boron source in the carbon-nitrogen-boron source are in a mass ratio of 1: 2-10: 0.5-1;
2) introducing reducing gas into the dual-temperature zone system, and respectively heating the dual-temperature zones to deposit and form nitrogen and boron co-doped graphene on the surface of the substrate;
3) attaching the nitrogen and boron co-doped graphene on the substrate to a transfer matrix to obtain the transfer matrix/nitrogen and boron co-doped graphene/substrate;
4) removing the substrate on the transfer matrix/nitrogen and boron co-doped graphene/substrate to obtain transfer matrix/nitrogen and boron co-doped graphene;
5) attaching the nitrogen and boron co-doped graphene on the transfer matrix/nitrogen and boron co-doped graphene to a first target matrix, and removing the transfer matrix to obtain the nitrogen and boron co-doped graphene/first target matrix;
6) silver paste is printed on the nitrogen and boron codoped graphene/first target substrate, and the obtained nitrogen and boron codoped graphene/first target substrate printed with the silver paste is subjected to high-temperature treatment;
7) nitrogen, boron codope graphite alkene one side laminating second target base member on the nitrogen of being printed with silver thick liquid, boron codope graphite alkene/first target base member the dopant is introduced in advance to the one side that second target base member and nitrogen, boron codope graphite alkene were laminated.
According to some embodiments of the present invention, the dual-temperature zone system in step 1) above may be as shown in fig. 1, and includes a dual-temperature zone tube furnace 1, a quartz tube 2 penetrating through the interior of the dual-temperature zone tube furnace 1, and a resistance wire 7; the dual-temperature-zone tube furnace 1 is internally provided with two different temperature zones of a zone 3 for placing a carbon nitrogen boron source 5 and a zone 4 for placing a substrate 6, and the substrate 6 and the carbon nitrogen boron source 5 can be respectively heated. The resistance wire 7 is located near the two temperature zones and is suitable for heating the two temperature zones. The substrate 6 placed in the region 4 may be an alloy material selected from one or more of Au, Pt, Pd, Ir, Ru, Co, Ni, Cu; the carbon, nitrogen and boron source 5 placed in the area 3 is one or a mixture of sucrose, glucose, polyethylene glycol and cellulose as a carbon source, one or a mixture of urea, dicyandiamide, biuret, nitrilamine and melamine as a nitrogen source, and one or a mixture of boric acid and boron oxide as a boron source; wherein the mass ratio of the carbon source, the nitrogen source and the boron source is 1: 2-10: 0.5-1, such as 1: 2-4: 0.5-1, 1: 4-6: 0.5-1, 1: 6-8: 0.5-1, 1: 8-10: 0.5-1, 1:2:0.5, 1:2:1, 1:4:0.5, 1:4:0.8, 1:4:1, 1:6:0.5, 1:6:0.8, 1:6:1, 1:8:1, 1:10:0.5, 1:10:1, etc., preferably 1: 4-10: 0.5-1, more preferably 1: 4-8: 0.5-1.
According to some embodiments of the present invention, in the step 2), the reducing gas is hydrogen, a mixed gas of hydrogen and nitrogen, or a mixed gas of hydrogen and argon, and in the preparation process, as shown in fig. 1, the reducing gas is introduced into the quartz tube 2 from the gas inlet at a flow rate of 150 to 300ml/min, and is finally discharged from the gas outlet; after the reducing gas is introduced into the quartz tube 2, the two temperature zones (i.e. the boron carbon nitride source 5 in the zone 3 and the substrate 6 in the zone 4) are respectively heated, wherein the heating temperature of the substrate is 600-1000 ℃, such as 600 ℃, 700 ℃, 800 ℃, 900 ℃, 1000 ℃, etc., and the heating temperature of the boron carbon nitride source is 200-300 ℃, such as 200 ℃, 250 ℃, 300 ℃, etc., so that the boron carbon nitride is deposited on the surface of the substrate 6 to obtain the nitrogen and boron co-doped graphene film, and the deposition time is 10-20 min, such as 10min, 15min, 20min, etc.
According to some embodiments of the present invention, the transfer substrate of step 3) is a PET silicone protective film, a PET acrylic protective film, a PMMA silicone protective film, a PMMA acrylic protective film, a PI silicone protective film or a PI acrylic protective film, wherein the peel force of the transfer substrate is maintained at (1-20) g/25mm, such as: 1g/25mm, 2g/25mm, 5g/25mm, 7g/25mm, 10g/25mm, 12g/25mm, 14g/25mm, 16g/25mm, 18g/25mm, 20g/25mm, and the like.
According to some embodiments of the present invention, the method for removing the substrate on the transfer matrix/nitrogen and boron co-doped graphene/substrate in step 4) is a chemical etching method, wherein the specific operation method of the chemical etching method is as follows: and immersing the transfer matrix/nitrogen and boron co-doped graphene/substrate into etching liquid for etching, wherein an etchant in the etching liquid is at least one of ammonium persulfate, ferric chloride, copper chloride or hydrochloric acid hydrogen peroxide, and the concentration of the etchant in the etching liquid is 0.4-1.5 mol/L.
According to some embodiments of the present invention, the first target substrate in the above step 5) is a polyethylene film, a polyethylene terephthalate film, a polystyrene film, or a polyvinyl chloride film, and the first target substrate has a thickness of 50 to 200 μm, for example, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm, 110 μm, 120 μm, 130 μm, 140 μm, 160 μm, 180 μm, 200 μm, or the like.
According to some embodiments of the present invention, the temperature of the high temperature treatment in the above step 6) is 125-145 ℃, such as 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃ and the like, and the treatment time is 0.5-2 hours, such as 0.5 hour, 0.8 hour, 1 hour, 1.5 hours, 2 hours and the like.
According to some embodiments of the invention, the second target substrate in step 7) above is an encapsulating material comprising: TPU, tarpaulin, explosion-proof membrane or OCA optical cement, the thickness of the second target substrate is 10 to 150 μm, such as 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm, 110 μm, 120 μm, 130 μm, 140 μm, 150 μm, etc.; the dopant is at least one of metal chloride, imidazole compound and derivatives thereof or triazole compound and derivatives thereof, and the concentration is 10 mmol/L-60 mmol/L, such as 10mmol/L, 20mmol/L, 30mmol/L, 40mmol/L, 50mmol/L, 60mmol/L and the like; and the method for introducing the dopant into the surface, attached to the nitrogen and boron co-doped graphene, of the second target substrate in advance is soaking, spraying or spin coating.
In another aspect of the present invention, there is provided a nitrogen and boron co-doped graphene composite thin film prepared by the above method, as shown in fig. 2, which includes a nitrogen and boron co-doped graphene film 12, and a first target substrate 11 and a second target substrate 13 disposed on two surfaces of the nitrogen and boron co-doped graphene film 12, wherein a silver paste (not shown in the figure) is printed on a surface of the nitrogen and boron co-doped graphene film 12, which is attached to the first target substrate 11, and a dopant 14 is doped on a surface of the nitrogen and boron co-doped graphene film 12, which is attached to the second target substrate 13.
In another aspect of the invention, the application of the nitrogen and boron co-doped graphene composite film in an electronic device is also provided.
The following description of the preferred embodiments of the present invention is provided for the purpose of illustration and description, and is in no way intended to limit the invention.
Example 1: preparation of nitrogen and boron co-doped graphene composite film
As shown in fig. 1, a carbon nitrogen boron source is placed in a region 3 of a dual-temperature zone system, wherein a carbon source, a nitrogen source and a boron source are placed in a mass ratio of 1:2:0.5, a copper foil substrate is placed in a region 4, a reducing gas composed of a mixed gas of hydrogen and nitrogen (in a volume ratio of 1:1) is introduced into a quartz tube 2 from an air inlet, then the region 3 and the region 4 are heated, wherein the heating temperature of the region 3 is 250 ℃, the heating temperature of the region 4 is 900 ℃, so that carbon nitrogen boron is deposited on the copper foil substrate for 15min, and a nitrogen and boron co-doped graphene film growing on the copper foil substrate is obtained, which is named as copper foil/nitrogen and boron co-doped graphene, and the first doping is completed.
One surface of the nitrogen and boron co-doped graphene in the copper foil/nitrogen and boron co-doped graphene is bonded with one surface of the PET silica gel protective film, wherein the glue surface is bonded together by a rolling mode to form a structure of the PET silica gel protective film/nitrogen and boron co-doped graphene/copper foil; preparing hydrochloric acid/hydrogen peroxide etching liquid (the concentration is 1.0mol/L), placing the PET silica gel protective film/nitrogen and boron co-doped graphene/copper foil into the etching liquid for etching, and cleaning and air-drying the copper foil by using deionized water after the copper foil is completely removed to obtain the PET silica gel protective film/nitrogen and boron co-doped graphene; adhering one surface of the graphene and PET together by adopting a rapid rolling method to form a PET silica gel protective film/nitrogen and boron codoped graphene; tearing off the PET silica gel protective film to obtain a nitrogen and boron codoped graphene/PET composite structure, and detecting that the sheet resistance of the obtained nitrogen and boron codoped graphene/PET composite structure is 225 omega/□ by using a four-probe method (see table 1). Silver paste is printed on one side of the graphene with the nitrogen and boron co-doped graphene/PET composite structure in a silk screen mode and subjected to patterning treatment, the nitrogen and boron co-doped graphene/PET composite structure printed with the silver paste is placed in an oven after treatment, the composite structure is baked at 135 ℃ for 1 hour, and the sheet resistance of the obtained nitrogen and boron co-doped graphene/PET composite structure subjected to high-temperature treatment is increased to 260 omega/□ (see table 1). Placing OCA optical adhesive with the thickness of 30 mu m in benzotriazole doping liquid (the concentration is 20mmol/L) for soaking, washing and drying, and then attaching with the nitrogen and boron co-doped graphene/PET subjected to high-temperature treatment to obtain an OCA/secondary doped nitrogen and boron co-doped graphene/PET composite structure, wherein the secondary doping is completed, and the sheet resistance of the obtained OCA/secondary doped nitrogen and boron co-doped graphene/PET composite structure is 180 omega/□ (see table 1).
Example 2: preparation of nitrogen and boron co-doped graphene composite film
As shown in fig. 1, a carbon nitrogen boron source is placed in a region 3 of a dual-temperature zone system, wherein a carbon source, a nitrogen source and a boron source are placed in a mass ratio of 1:4:0.5, a copper foil substrate is placed in the region 4, a reducing gas composed of a mixed gas of hydrogen and argon (in a volume ratio of 1:1) is introduced into a quartz tube 2 from an air inlet, then the region 3 and the region 4 are heated, wherein the heating temperature of the region 3 is 200 ℃, the heating temperature of the region 4 is 1000 ℃, carbon nitrogen boron is deposited on the copper foil substrate for 20min, a nitrogen and boron co-doped graphene film growing on the copper foil substrate is obtained, and the film is named as copper foil/nitrogen and boron co-doped graphene, and the first doping is completed.
One surface of the nitrogen and boron co-doped graphene in the copper foil/nitrogen and boron co-doped graphene is bonded with one surface of the PET silica gel protective film, wherein the glue surface is bonded together by a rolling mode to form a structure of the PET silica gel protective film/nitrogen and boron co-doped graphene/copper foil; preparing hydrochloric acid/hydrogen peroxide etching liquid (the concentration is 1.0mol/L), placing the PET silica gel protective film/nitrogen and boron co-doped graphene/copper foil into the etching liquid for etching, and cleaning and air-drying the copper foil by using deionized water after the copper foil is completely removed to obtain the PET silica gel protective film/nitrogen and boron co-doped graphene; adhering one surface of the graphene and PET together by adopting a rapid rolling method to form a PET silica gel protective film/nitrogen and boron codoped graphene; the PET silica gel protective film is torn off to obtain a nitrogen and boron codoped graphene/PET composite structure, and the sheet resistance of the obtained nitrogen and boron codoped graphene/PET composite structure is 210 omega/□ (see Table 1). Silver paste is printed on one side of the graphene with the nitrogen and boron co-doped graphene/PET composite structure in a silk screen mode and subjected to patterning treatment, the nitrogen and boron co-doped graphene/PET composite structure printed with the silver paste is placed in an oven after treatment, the composite structure is baked at 135 ℃ for 1 hour, and the sheet resistance of the obtained nitrogen and boron co-doped graphene/PET composite structure subjected to high-temperature treatment is increased to 245 omega/□ (see table 1). Preparing benzotriazole doping liquid (the concentration is 30mmol/L), spraying the benzotriazole doping liquid on the surface of the OCA optical adhesive with the thickness of 20 mu m, air-drying the OCA optical adhesive, and attaching the OCA/secondary doped nitrogen and boron co-doped graphene/PET to obtain the OCA/secondary doped nitrogen and boron co-doped graphene/PET composite structure. At this time, the second doping is completed, and the sheet resistance of the obtained OCA/twice-doped nitrogen and boron co-doped graphene/PET composite structure is 155 Ω/□ (see table 1).
Example 3: preparation of nitrogen and boron co-doped graphene composite film
As shown in fig. 1, a carbon nitrogen boron source is placed in a region 3 in a dual-temperature zone system, wherein a carbon source, a nitrogen source and a boron source are placed in a mass ratio of 1:6:1, a copper foil substrate is placed in a region 4, a reducing gas consisting of a mixed gas of hydrogen and nitrogen (in a volume ratio of 1:1) is introduced into a quartz tube 2 from an air inlet, then the region 3 and the region 4 are heated, wherein the heating temperature of the region 3 is 300 ℃, the heating temperature of the region 4 is 600 ℃, so that carbon nitrogen boron is deposited on the copper foil substrate for 20min, and a nitrogen and boron co-doped graphene film growing on the copper foil substrate is obtained, named as copper foil/nitrogen and boron co-doped graphene, and the first doping is completed at this time.
One surface of the nitrogen and boron co-doped graphene in the copper foil/nitrogen and boron co-doped graphene is bonded with one surface of the PET acrylic acid protective film, wherein the glue surface is bonded together by a rolling mode to form a structure of the PET acrylic acid protective film/nitrogen and boron co-doped graphene/copper foil; preparing hydrochloric acid/hydrogen peroxide etching liquid (the concentration is 1.5mol/L), placing a PET acrylic acid protective film/nitrogen and boron co-doped graphene/copper foil into the etching liquid for etching, and cleaning and air-drying the copper foil with deionized water after the copper foil is completely removed to obtain a PET silica gel protective film/nitrogen and boron co-doped graphene; adhering one surface of the graphene and PET together by adopting a rapid rolling method to form a PET acrylic acid protective film/nitrogen and boron codoped graphene; the PET acrylic acid protective film is torn off to obtain a nitrogen and boron codoped graphene/PET composite structure, and the sheet resistance of the obtained nitrogen and boron codoped graphene/PET composite structure is 205 omega/□ (see Table 1). Silver paste is printed on one side of the graphene with the nitrogen and boron co-doped graphene/PET composite structure in a silk screen mode and subjected to patterning treatment, the nitrogen and boron co-doped graphene/PET composite structure printed with the silver paste is placed in an oven after treatment, the composite structure is baked at 135 ℃ for 1 hour, and the sheet resistance of the obtained nitrogen and boron co-doped graphene/PET composite structure subjected to high-temperature treatment is increased to 240 omega/□ (see table 1). Preparing a gold chloride doping solution (with the concentration of 40mmol/L), spin-coating the gold chloride doping solution on the surface of the explosion-proof film with the thickness of 50 microns, air-drying the gold chloride doping solution, and attaching the gold chloride doping solution to the nitrogen and boron co-doped graphene/PET subjected to high-temperature treatment to obtain an explosion-proof film/secondary doped nitrogen and boron co-doped graphene/PET composite structure, wherein the secondary doping is completed, and the sheet resistance of the obtained explosion-proof film/secondary doped nitrogen and boron co-doped graphene/PET composite structure is 150 omega/□ (see table 1).
Example 4: preparation of nitrogen and boron co-doped graphene composite film
As shown in fig. 1, a carbon nitrogen boron source is placed in a region 3 of a dual-temperature zone system, wherein a carbon source, a nitrogen source and a boron source are placed in a mass ratio of 1:8:0.5, a copper foil substrate is placed in a region 4, a reducing gas composed of a mixed gas of hydrogen and argon (in a volume ratio of 1:1) is introduced into a quartz tube 2 from an air inlet, then the region 3 and the region 4 are heated, wherein the heating temperature of the region 3 is 300 ℃ and the heating temperature of the region 4 is 900 ℃, so that carbon nitrogen boron is deposited on the copper foil substrate for 10min, and a nitrogen and boron co-doped graphene film growing on the copper foil substrate is obtained, which is named as copper foil/nitrogen and boron co-doped graphene, and the first doping is completed.
One surface of the nitrogen and boron co-doped graphene in the copper foil/nitrogen and boron co-doped graphene is bonded with one surface of the PI silica gel protective film, wherein the glue surface is a surface of the PI silica gel protective film, so that a PI silica gel protective film/nitrogen and boron co-doped graphene/copper foil structure is formed; preparing hydrochloric acid/hydrogen peroxide etching liquid (the concentration is 0.5mol/L), placing the PI silica gel protective film/nitrogen and boron co-doped graphene/copper foil into the etching liquid for etching, and cleaning and air-drying the copper foil with deionized water after the copper foil is completely removed to obtain the PI silica gel protective film/nitrogen and boron co-doped graphene; adhering one surface of the graphene to PVC by adopting a rapid rolling method, wherein the PI silica gel protective film/nitrogen and boron codoped graphene is adhered to the PVC; and tearing off the PI silica gel protective film to obtain a nitrogen and boron codoped graphene/PVC composite structure, wherein the sheet resistance of the obtained nitrogen and boron codoped graphene/PVC composite structure is 215 omega/□ (see table 1). Silver paste is printed on one side of the graphene with the nitrogen and boron co-doped graphene/PVC composite structure and is subjected to patterning treatment, the nitrogen and boron co-doped graphene/PVC composite structure printed with the silver paste is placed in an oven after treatment, the composite structure is baked at 135 ℃ for 1 hour, and the sheet resistance of the obtained nitrogen and boron co-doped graphene/PVC composite structure subjected to high-temperature treatment is increased to 250 omega/□ (see table 1). Placing the OCA optical adhesive with the thickness of 20 mu m into benzotriazole doping liquid (the concentration is 10mmol/L) for soaking, washing and drying, and then attaching the OCA optical adhesive with the nitrogen and boron co-doped graphene/PVC subjected to high-temperature treatment to obtain an OCA/secondary doped nitrogen and boron co-doped graphene/PVC composite structure, wherein the secondary doping is completed, and the sheet resistance of the obtained OCA/secondary doped nitrogen and boron co-doped graphene/PVC composite structure is 150 omega/□ (see table 1).
Example 5: preparation of nitrogen and boron co-doped graphene composite film
As shown in fig. 1, a carbon nitrogen boron source is placed in a region 3 in a dual-temperature zone system, wherein a carbon source, a nitrogen source and a boron source are placed in a mass ratio of 1:10:1, a copper foil substrate is placed in a region 4, a reducing gas composed of a mixed gas of hydrogen and argon (in a volume ratio of 1:1) is introduced into a quartz tube 2 from an air inlet, then the region 3 and the region 4 are heated, wherein the heating temperature of the region 3 is 300 ℃, the heating temperature of the region 4 is 1000 ℃, so that carbon nitrogen boron is deposited on the copper foil substrate for 15min, and a nitrogen and boron co-doped graphene film growing on the copper foil substrate is obtained, named as copper foil/nitrogen and boron co-doped graphene, and the first doping is completed at this time.
One surface of the nitrogen and boron co-doped graphene in the copper foil/nitrogen and boron co-doped graphene is bonded with one surface of the PI silica gel protective film, wherein the glue surface is a surface of the PI silica gel protective film, so that a PI silica gel protective film/nitrogen and boron co-doped graphene/copper foil structure is formed; preparing hydrochloric acid/hydrogen peroxide etching liquid (the concentration is 1.0mol/L), placing the PI silica gel protective film/nitrogen and boron co-doped graphene/copper foil into the etching liquid for etching, and cleaning and air-drying the copper foil with deionized water after the copper foil is completely removed to obtain the PI silica gel protective film/nitrogen and boron co-doped graphene; adopting a rapid rolling method to stick one surface of the PI silica gel protective film/nitrogen and boron codoped graphene together with PE; and tearing off the PI silica gel protective film to obtain a nitrogen and boron codoped graphene/PE composite structure, wherein the sheet resistance of the obtained nitrogen and boron codoped graphene/PE composite structure is 220 omega/□ (see table 1). Silver paste is printed on one side of the graphene with the nitrogen and boron co-doped graphene/PE composite structure in a silk screen mode and subjected to patterning treatment, the composite structure printed with the silver paste and doped with nitrogen and boron is placed in an oven and baked at 135 ℃ for 1 hour, and the sheet resistance of the obtained composite structure with the nitrogen and boron co-doped graphene/PE subjected to high-temperature treatment is increased to 260 omega/□ (see table 1). Placing OCA optical cement with the thickness of 30 mu m into gold chloride doping liquid (the concentration is 20mmol/L) for soaking, adhering the OCA optical cement with the nitrogen and boron co-doped graphene/PE subjected to high-temperature treatment after washing and drying, obtaining an OCA/secondary doped nitrogen and boron co-doped graphene/PE composite structure, finishing secondary doping at the moment, and obtaining an OCA/secondary doped nitrogen and boron co-doped graphene/PE composite structure with the square resistance of 165 omega/□ (see Table 1).
Example 6: preparation of nitrogen and boron co-doped graphene composite film
As shown in fig. 1, a carbon nitrogen boron source is placed in a region 3 of a dual-temperature zone system, wherein a carbon source, a nitrogen source and a boron source are placed in a mass ratio of 1:10:0.5, a copper foil substrate is placed in a region 4, a reducing gas composed of a mixed gas of hydrogen and nitrogen (in a volume ratio of 1:1) is introduced into a quartz tube 2 from an air inlet, then the region 3 and the region 4 are heated, wherein the heating temperature of the region 3 is 200 ℃, the heating temperature of the region 4 is 800 ℃, carbon nitrogen boron is deposited on the copper foil substrate for 20min, a nitrogen and boron co-doped graphene film growing on the copper foil substrate is obtained, and the film is named as copper foil/nitrogen and boron co-doped graphene, and the first doping is completed.
One surface of the nitrogen and boron co-doped graphene in the copper foil/nitrogen and boron co-doped graphene is bonded with one surface of the PET silica gel protective film, wherein the glue surface is bonded together by a rolling mode to form a structure of the PET silica gel protective film/nitrogen and boron co-doped graphene/copper foil; preparing hydrochloric acid/hydrogen peroxide etching liquid (the concentration is 1.0mol/L), placing the PET silica gel protective film/nitrogen and boron co-doped graphene/copper foil into the etching liquid for etching, and cleaning and air-drying the copper foil by using deionized water after the copper foil is completely removed to obtain the PET silica gel protective film/nitrogen and boron co-doped graphene; adhering one surface of the graphene and PET together by adopting a rapid rolling method to form a PET silica gel protective film/nitrogen and boron codoped graphene; the PET silica gel protective film is torn off to obtain a nitrogen and boron codoped graphene/PET composite structure, and the sheet resistance of the obtained nitrogen and boron codoped graphene/PET composite structure is 230 omega/□ (see Table 1). Silver paste is printed on one side of the graphene with the nitrogen and boron co-doped graphene/PET composite structure in a silk screen mode and subjected to patterning treatment, the nitrogen and boron co-doped graphene/PET composite structure printed with the silver paste is placed in an oven after treatment, the composite structure is baked at 135 ℃ for 1 hour, and the sheet resistance of the obtained nitrogen and boron co-doped graphene/PET composite structure subjected to high-temperature treatment is increased to 265 omega/□ (see table 1). Preparing imidazole doping liquid (the concentration is 20mmol/L), spraying the imidazole doping liquid on the surface of OCA optical cement with the thickness of 50 mu m, air-drying the OCA optical cement, and attaching the OCA optical cement and the boron-codoped graphene/PET with high-temperature treatment to obtain an OCA/secondary-doped nitrogen and boron-codoped graphene/PET composite structure, wherein the secondary doping is completed, and the sheet resistance of the obtained OCA/secondary-doped nitrogen and boron-codoped graphene/PET composite structure is 170 omega/□ (see table 1).
Comparative example 1:
as shown in fig. 1, a carbon nitrogen boron source is placed in a region 3 of a dual-temperature zone system, wherein a carbon source, a nitrogen source and a boron source are placed in a mass ratio of 1:1:0.1, a copper foil substrate is placed in a region 4, a reducing gas composed of a mixed gas of hydrogen and nitrogen (in a volume ratio of 1:1) is introduced into a quartz tube 2 from an air inlet, then the region 3 and the region 4 are heated, wherein the heating temperature of the region 3 is 200 ℃, the heating temperature of the region 4 is 800 ℃, carbon nitrogen boron is deposited on the copper foil substrate for 20min, a nitrogen and boron co-doped graphene film growing on the copper foil substrate is obtained, and the film is named as copper foil/nitrogen and boron co-doped graphene, and the first doping is completed.
One surface of the nitrogen and boron co-doped graphene in the copper foil/nitrogen and boron co-doped graphene is bonded with one surface of the PET silica gel protective film, wherein the glue surface is bonded together by a rolling mode to form a structure of the PET silica gel protective film/nitrogen and boron co-doped graphene/copper foil; preparing hydrochloric acid/hydrogen peroxide etching liquid (the concentration is 1.0mol/L), placing the PET silica gel protective film/nitrogen and boron co-doped graphene/copper foil into the etching liquid for etching, and cleaning and air-drying the copper foil by using deionized water after the copper foil is completely removed to obtain the PET silica gel protective film/nitrogen and boron co-doped graphene; adhering one surface of the graphene and PET together by adopting a rapid rolling method to form a PET silica gel protective film/nitrogen and boron codoped graphene; and tearing off the PET silica gel protective film to obtain a nitrogen and boron codoped graphene/PET composite structure, wherein the sheet resistance of the obtained nitrogen and boron codoped graphene/PET composite structure is 245 omega/□ (see table 1). Silver paste is printed on one side of the graphene with the nitrogen and boron co-doped graphene/PET composite structure in a silk screen mode and subjected to patterning treatment, the nitrogen and boron co-doped graphene/PET composite structure printed with the silver paste is placed in a baking oven after treatment, the composite structure is baked for 1 hour at 135 ℃, and the sheet resistance of the obtained nitrogen and boron co-doped graphene/PET composite structure subjected to high-temperature treatment is increased to 280 omega/□ (see table 1). Placing OCA optical adhesive with the thickness of 30 mu m in benzotriazole doping liquid (the concentration is 20mmol/L) for soaking, washing and drying, and then attaching with the nitrogen and boron co-doped graphene/PET subjected to high-temperature treatment to obtain an OCA/secondary doped nitrogen and boron co-doped graphene/PET composite structure, wherein the secondary doping is completed, and the sheet resistance of the obtained OCA/secondary doped nitrogen and boron co-doped graphene/PET composite structure is 205 omega/□ (see table 1).
Comparative example 2:
as shown in fig. 1, a carbon nitrogen boron source is placed in a region 3 in a dual-temperature zone system, wherein a carbon source, a nitrogen source and a boron source are placed in a mass ratio of 1:20:2, a copper foil substrate is placed in a region 4, a reducing gas consisting of a mixed gas of hydrogen and nitrogen (in a volume ratio of 1:1) is introduced into a quartz tube 2 from an air inlet, then the region 3 and the region 4 are heated, wherein the heating temperature of the region 3 is 300 ℃, the heating temperature of the region 4 is 900 ℃, so that carbon nitrogen boron is deposited on the copper foil substrate for 15min, and a nitrogen and boron co-doped graphene film growing on the copper foil substrate is obtained, named as copper foil/nitrogen and boron co-doped graphene, and the first doping is completed at this time.
One surface of the nitrogen and boron co-doped graphene in the copper foil/nitrogen and boron co-doped graphene is bonded with one surface of the PET silica gel protective film, wherein the glue surface is bonded together by a rolling mode to form a structure of the PET silica gel protective film/nitrogen and boron co-doped graphene/copper foil; preparing hydrochloric acid/hydrogen peroxide etching liquid (the concentration is 1.0mol/L), placing the PET silica gel protective film/nitrogen and boron co-doped graphene/copper foil into the etching liquid for etching, and cleaning and air-drying the copper foil by using deionized water after the copper foil is completely removed to obtain the PET silica gel protective film/nitrogen and boron co-doped graphene; adhering one surface of the graphene and PET together by adopting a rapid rolling method to form a PET silica gel protective film/nitrogen and boron codoped graphene; the PET silica gel protective film is torn off to obtain a nitrogen and boron codoped graphene/PET composite structure, and the sheet resistance of the obtained nitrogen and boron codoped graphene/PET composite structure is 240 omega/□ (see Table 1). Silver paste is printed on one side of the graphene with the nitrogen and boron co-doped graphene/PET composite structure in a silk screen mode and subjected to patterning treatment, the nitrogen and boron co-doped graphene/PET composite structure printed with the silver paste is placed in an oven after treatment, the composite structure is baked at 135 ℃ for 1 hour, and the sheet resistance of the obtained nitrogen and boron co-doped graphene/PET composite structure subjected to high-temperature treatment is increased to 275 omega/□ (see table 1). Placing OCA optical adhesive with the thickness of 30 mu m in benzotriazole doping liquid (the concentration is 20mmol/L) for soaking, washing and drying, and then attaching with the nitrogen and boron co-doped graphene/PET subjected to high-temperature treatment to obtain an OCA/secondary doped nitrogen and boron co-doped graphene/PET composite structure, wherein the secondary doping is completed, and the sheet resistance of the obtained OCA/secondary doped nitrogen and boron co-doped graphene/PET composite structure is 210 omega/□ (see table 1).
Comparative example 3:
as shown in fig. 1, a carbon nitrogen boron source is placed in a region 3 in a dual-temperature zone system, wherein a carbon source, a nitrogen source and a boron source are placed in a mass ratio of 1:2:1, a copper foil substrate is placed in a region 4, a reducing gas consisting of a mixed gas of hydrogen and nitrogen (in a volume ratio of 1:1) is introduced into a quartz tube 2 from an air inlet, then the region 3 and the region 4 are heated, wherein the heating temperature of the region 3 is 250 ℃, the heating temperature of the region 4 is 800 ℃, so that carbon nitrogen boron is deposited on the copper foil substrate for 15min, and a nitrogen and boron co-doped graphene film growing on the copper foil substrate is obtained, named as copper foil/nitrogen and boron co-doped graphene, and the first doping is completed at this time.
One surface of the nitrogen and boron co-doped graphene in the copper foil/nitrogen and boron co-doped graphene is bonded with one surface of the PET silica gel protective film, wherein the glue surface is bonded together by a rolling mode to form a structure of the PET silica gel protective film/nitrogen and boron co-doped graphene/copper foil; preparing benzotriazole/hydrochloric acid/hydrogen peroxide etching doping liquid (the concentration of benzotriazole is 20mmol/L, the concentration of hydrochloric acid/hydrogen peroxide is 1.0mol/L), placing a PET silica gel protective film/nitrogen and boron co-doped graphene/copper foil into the etching liquid for etching and secondary doping, cleaning and air-drying the copper foil by deionized water after the copper foil is completely removed to obtain the PET silica gel protective film/secondary doped nitrogen and boron co-doped graphene, and finishing the secondary doping; sticking a PET silica gel protective film/secondarily-doped nitrogen and boron co-doped graphene together with one surface of the graphene and PET by adopting a rapid rolling method; and tearing off the PET silica gel protective film to obtain a secondary doped nitrogen and boron codoped graphene/PET composite structure, wherein the sheet resistance of the secondary doped nitrogen and boron codoped graphene/PET composite structure is 215 omega/□ (see table 1). Silver paste is printed on one surface of the graphene of the secondary doped nitrogen and boron co-doped graphene/PET composite structure in a silk screen mode and subjected to patterning treatment, the composite structure printed with the silver paste and subjected to secondary doping of the nitrogen and boron co-doped graphene/PET is placed in an oven and baked at 135 ℃ for 1 hour, and the square resistance of the obtained secondary doped nitrogen and boron co-doped graphene/PET composite structure subjected to high-temperature treatment is increased to 235 omega/□ (see table 1). Placing the OCA optical adhesive with the thickness of 40 mu m into benzotriazole doping liquid (the concentration is 10mmol/L) for soaking, washing and drying, and then attaching the OCA optical adhesive with the nitrogen and boron co-doped graphene/PET printed with silver paste and subjected to secondary doping after high-temperature treatment to obtain an OCA/tertiary doped nitrogen and boron co-doped graphene/PET composite structure, wherein the third doping is completed, and the sheet resistance of the obtained OCA/tertiary doped nitrogen and boron co-doped graphene/PET composite structure is 185 omega/□ (see Table 1).
Table 1: comparison of sheet resistance of nitrogen and boron co-doped graphene/first target substrate, structure after high temperature treatment and second target substrate/nitrogen and boron co-doped graphene/first target substrate of each example and comparative example
As can be seen from table 1 above, the nitrogen and boron co-doped graphene/first target matrix structures obtained in the embodiments and the comparative examples of the present invention all have lower sheet resistance, and after the silver paste silk-screening and the high temperature treatment, the sheet resistance of the nitrogen and boron co-doped graphene/first target matrix structures in the embodiments and the comparative examples is significantly increased; however, after the dopant is introduced into the surface of the second target substrate and is bonded with the nitrogen and boron co-doped graphene/first target substrate, the sheet resistance of the second target substrate/nitrogen and boron co-doped graphene/first target substrate structure of each of the examples and the comparative examples is also significantly reduced. However, for examples 1 to 6 and comparative examples 1 to 2, due to the different proportional relationships between the carbon source, the nitrogen source and the boron source in the carbon-nitrogen-boron source, the second target matrix/nitrogen-boron-codoped graphene/first target matrix structure (i.e., the nitrogen-boron-codoped graphene composite film provided by the present invention) obtained in examples 1 to 6 has a lower sheet resistance than that of comparative examples 1 to 2, even lower than that of the graphene composite film disclosed in patent document CN108305705A, it can be seen that the co-doping of a certain amount of nitrogen and boron into graphene does not affect the conjugated structure of graphene itself, i.e., does not destroy the electron transfer between the large pi bonds, further retains the excellent conductivity of graphene itself, and further significantly reduces the sheet resistance of the nitrogen-boron-codoped graphene composite film. The composite thin film obtained in comparative example 3 further introduces a dopant between the first target substrate and the nitrogen and boron co-doped graphene, compared with the composite thin films obtained in examples 1 to 6, so that the nitrogen and boron co-doped graphene/first target substrate structure obtained in comparative example 3 has a lower sheet resistance, but the second target substrate/nitrogen and boron co-doped graphene/first target substrate structure obtained after the dopant is introduced again into the surface of the second target substrate does not have a lower sheet resistance, and is relatively higher than the nitrogen and boron co-doped graphene composite thin films obtained in examples 1 to 6, and it may be that the original electron transfer structure of graphene is damaged or influenced by introducing too much dopant, so that the conductivity of graphene is influenced, and further the sheet resistance of the prepared composite thin film is higher.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The preparation method of the nitrogen and boron co-doped graphene composite film is characterized by comprising the following steps:
1) providing a dual-temperature-zone system, and respectively placing a carbon-nitrogen-boron source and a substrate in two temperature zones in the dual-temperature-zone system, wherein a carbon source, a nitrogen source and a boron source in the carbon-nitrogen-boron source are in a mass ratio of 1: 2-10: 0.5-1;
2) introducing reducing gas into the dual-temperature zone system, and respectively heating the dual-temperature zones to deposit and form nitrogen and boron co-doped graphene on the surface of the substrate;
3) attaching the nitrogen and boron co-doped graphene on the substrate to a transfer matrix to obtain the transfer matrix/nitrogen and boron co-doped graphene/substrate;
4) removing the substrate on the transfer matrix/nitrogen and boron co-doped graphene/substrate to obtain transfer matrix/nitrogen and boron co-doped graphene;
5) attaching the nitrogen and boron co-doped graphene on the transfer matrix/nitrogen and boron co-doped graphene to a first target matrix, and removing the transfer matrix to obtain the nitrogen and boron co-doped graphene/first target matrix;
6) silver paste is printed on the nitrogen and boron codoped graphene/first target substrate, and the obtained nitrogen and boron codoped graphene/first target substrate printed with the silver paste is subjected to high-temperature treatment;
7) nitrogen, boron codope graphite alkene one side laminating second target base member on the nitrogen of being printed with silver thick liquid, boron codope graphite alkene/first target base member the dopant is introduced in advance to the one side that second target base member and nitrogen, boron codope graphite alkene were laminated.
2. The preparation method according to claim 1, wherein in the carbon, nitrogen and boron source in step 1), the carbon source is one of sucrose, glucose, polyethylene glycol and cellulose or a mixture thereof, the nitrogen source is one of urea, dicyandiamide, biuret, nitrilamine and melamine or a mixture thereof, and the boron source is one of boric acid and boron oxide or a mixture thereof; the carbon source, the nitrogen source and the boron source in the carbon-nitrogen-boron source are 1: 4-10: 0.5-1, preferably 1: 4-8: 0.5-1 in mass ratio.
3. The production method according to claim 1 or 2, wherein the substrate in step 1) is an alloy material selected from one or more of Au, Pt, Pd, Ir, Ru, Co, Ni, and Cu;
the reducing gas in the step 2) is hydrogen, a mixed gas of hydrogen and nitrogen or a mixed gas of hydrogen and argon, and the introducing flow rate of the reducing gas is 150-300 ml/min;
in the step 2), in the respective heating dual-temperature areas, the heating temperature of the substrate is 600-1000 ℃, and the heating temperature of the carbon-boron nitride source is 200-300 ℃;
the deposition time in the step 2) is 10 min-20 min.
4. The production method according to any one of claims 1 to 3, wherein the transfer substrate in step 3) is a PET silicone protective film, a PET acrylic protective film, a PMMA silicone protective film, a PMMA acrylic protective film, a PI silicone protective film, or a PI acrylic protective film.
5. The preparation method according to any one of claims 1 to 4, wherein the method for removing the substrate on the transfer matrix/nitrogen and boron co-doped graphene/substrate in the step 4) is a chemical etching method, wherein the specific operation method of the chemical etching method is as follows: and immersing the transfer matrix/nitrogen and boron co-doped graphene/substrate into etching liquid for etching, wherein an etchant in the etching liquid is at least one of ammonium persulfate, ferric chloride, copper chloride or hydrochloric acid hydrogen peroxide, and the concentration of the etchant in the etching liquid is 0.4-1.5 mol/L.
6. The production method according to any one of claims 1 to 5, wherein the first target substrate in step 5) is a polyethylene film, a polyethylene terephthalate film, a polystyrene film, or a polyvinyl chloride film, and the first target substrate has a thickness of 50 to 200 μm;
the second target substrate in step 7) is an encapsulating material, and the encapsulating material includes: the thickness of the second target substrate is 10-150 mu m.
7. The method according to any one of claims 1 to 6, wherein the high-temperature treatment in step 6) is carried out at a temperature of 125 to 145 ℃ for 0.5 to 2 hours.
8. The preparation method according to any one of claims 1 to 7, wherein the dopant is at least one of metal chloride, imidazole compound and its derivatives, or triazole compound and its derivatives, and the concentration is 10mmol/L to 60 mmol/L; the method for introducing the dopant into the surface, attached to the nitrogen and boron co-doped graphene, of the second target substrate in the step 7) is soaking, spraying or spin coating.
9. The nitrogen and boron co-doped graphene composite film obtained by the preparation method of any one of claims 1 to 8, which comprises a nitrogen and boron co-doped graphene film, and a first target substrate and a second target substrate that are disposed on two surfaces of the nitrogen and boron co-doped graphene film, wherein a silver paste is printed on a surface of the nitrogen and boron co-doped graphene film, which is attached to the first target substrate, and a dopant is doped on a surface of the nitrogen and boron co-doped graphene film, which is attached to the second target substrate.
10. The use of the nitrogen and boron co-doped graphene composite film of claim 9 in an electronic device.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115261819A (en) * | 2022-07-25 | 2022-11-01 | 天津师范大学 | Preparation and analysis evaluation method of modified graphene protective film deposited on surface of string |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110030991A1 (en) * | 2009-08-07 | 2011-02-10 | Guardian Industries Corp. | Large area deposition and doping of graphene, and products including the same |
| CN103779571A (en) * | 2012-10-25 | 2014-05-07 | 海洋王照明科技股份有限公司 | Boron-doped graphene thin film, and preparation method and application thereof |
| CN105714265A (en) * | 2016-05-05 | 2016-06-29 | 中国科学院上海高等研究院 | Preparation method of boron-doped graphene film |
| CN108305705A (en) * | 2017-12-15 | 2018-07-20 | 无锡格菲电子薄膜科技有限公司 | Graphene composite film and its preparation method and application |
-
2020
- 2020-11-10 CN CN202011247446.6A patent/CN112299401A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110030991A1 (en) * | 2009-08-07 | 2011-02-10 | Guardian Industries Corp. | Large area deposition and doping of graphene, and products including the same |
| CN103779571A (en) * | 2012-10-25 | 2014-05-07 | 海洋王照明科技股份有限公司 | Boron-doped graphene thin film, and preparation method and application thereof |
| CN105714265A (en) * | 2016-05-05 | 2016-06-29 | 中国科学院上海高等研究院 | Preparation method of boron-doped graphene film |
| CN108305705A (en) * | 2017-12-15 | 2018-07-20 | 无锡格菲电子薄膜科技有限公司 | Graphene composite film and its preparation method and application |
Non-Patent Citations (4)
| Title |
|---|
| SACHIN M. SHINDE等: "Grain structures of nitrogen-doped graphene synthesized by solid source-based chemical vapor deposition", 《CARBON》 * |
| SATORU SUZUKI等: "Chemical vapor deposition of boron- and nitrogen-containing graphene thin films", 《MATERIALS SCIENCE AND ENGINEERING B》 * |
| 付长璟编著: "《石墨烯的制备、结构及应用》", 30 June 2017 * |
| 瓦西里奥斯.格奥尔基拉斯: "《石墨烯表面功能化》" * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115261819A (en) * | 2022-07-25 | 2022-11-01 | 天津师范大学 | Preparation and analysis evaluation method of modified graphene protective film deposited on surface of string |
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