CN109534315B - Amorphous carbon/nano-micron network film and preparation method thereof - Google Patents
Amorphous carbon/nano-micron network film and preparation method thereof Download PDFInfo
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Abstract
The invention provides an amorphous carbon/nano-micron network film and a preparation method thereof, belonging to the technical field of nano materials and comprising the following steps: amorphous carbon and a nano-micro network, wherein the amorphous carbon is filled in the pores of the nano-micro network to form a composite film without pores; the amorphous carbon is a two-dimensional amorphous carbon nano film composed of carbon atoms. According to the novel amorphous carbon/nano-micron network film provided by the invention, the amorphous carbon is filled in the nano-micron network to form the pore-free two-dimensional composite film, so that the oxidation erosion of substances such as external water, oxygen and the like to the surfaces of electronic devices, metal coatings and the like can be prevented, and the novel amorphous carbon/nano-micron network film has more excellent protective performance compared with the nano-micron network.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to an amorphous carbon/nano-micron network film and a preparation method thereof.
Background
Carbon is one of the first substances that humans have come into contact with since the discovery of C in r.e.smalley, h.w.kroto and r.f.curl60Then, studies on carbon nanomaterials have been kept in the spotlight. Thereafter, the carbon nanotube and graphene are successively found, and the carbon nanomaterial can be said to beThe revolution in material is led, and the development of other subject fields is greatly promoted.
Amorphous carbon, one of the allotropes of carbon, which has properties intermediate between those of diamond and graphite, is often considered to be a transition state. For nanoscale amorphous carbon films, there is also a large difference from the corresponding graphene with a two-dimensional monoatomic layer thickness. Specifically, the non-optical sp-passing between carbon and carbon atoms of the amorphous carbon film2Hybridized to form bonds, also sp1、sp3Hybridization, sp3The presence of (b) makes it of higher hardness. The nanometer amorphous carbon film has strong chemical inertia. The two properties make the amorphous carbon film expected to be applied to the fields of protection and the like.
Nano-micro networks refer to porous networks composed of pores on a nanometer to micrometer scale. Taking the carbon nanotube network film as an example, the carbon nanotube network film is a network structure formed by carbon nanotubes through the action of chemical bonds and physical bonds. The network has high transmittance to visible light due to the porous characteristic and the ultrathin structure of the network. Meanwhile, the carbon nano tube also has ultrahigh conductivity, mechanical strength and stability, and has wide application prospect in the fields of electronic devices, transparent conduction, flexible display and the like. However, the porous structure of the nano-micro network itself also brings problems, which affect its practical application, such as short lifetime, poor stability, etc.
Therefore, how to solve the problems has important scientific significance and application value.
Disclosure of Invention
It is an object of the present invention to overcome the above-mentioned shortcomings of the prior art by providing a novel amorphous carbon/nano-micron network thin film, which is a coplanar, non-porous two-dimensional composite thin film formed by filling amorphous carbon in a nano-micron network.
In particular, the present invention provides an amorphous carbon/nano-micro network film comprising: amorphous carbon and a nano-micro network, wherein the amorphous carbon is filled in the pores of the nano-micro network to form a non-porous coplanar composite film; the amorphous carbon is a two-dimensional amorphous carbon nano film composed of carbon atoms.
Optionally, the two-dimensional amorphous carbon nano-film is composed of pure carbon elements.
Optionally, the two-dimensional amorphous carbon nano-film has other element doping or modification, including any one or combination of nitrogen, boron, silicon, hydrogen, oxygen.
Optionally, the nano-micro network has a porous network structure with a size distribution from nano to micro scale.
Optionally, the nano-micro network comprises a conductive network and a non-conductive network; the conductive network comprises a metal network or a semiconductor network; the non-conductive network comprises one or more of a silicon oxide network and an aluminum oxide network.
Optionally, the amorphous carbon is bonded to the nano-micro network by means of physical and chemical bonds.
The invention also provides a preparation method of the amorphous carbon/nano-micron network film, which comprises the following steps:
preparing a nano-micron network on a substrate and placing the nano-micron network into a reaction cavity;
introducing a carbon source, and growing amorphous carbon in the pores to form the amorphous carbon/nano-micron network film.
Optionally, the substrate is a substrate that can support a nano-micro network.
Preferably, the substrate is a substrate having a catalytic carbon source decomposition reducing the amorphous carbon growth temperature.
Optionally, the carbon source may include not only carbon element but also other doping elements.
Optionally, other chemical substances containing other chemical elements can be introduced to modify or dope at the same time of introducing the carbon source.
Optionally, the carbon source comprises any one or combination of gaseous carbon source, liquid carbon source and solid carbon source.
The amorphous carbon/nano-micron network film provided by the invention has the characteristic that the amorphous carbon and the nano-micron network are coplanar, and the amorphous carbon film completely fills the nano-micron network pores and does not cover the surface of the nano-micron network.
The amorphous carbon/nano-micron network film and the preparation method thereof provided by the invention have the following characteristics:
the preparation method of the amorphous carbon/nano-micron network film provided by the invention is carried out at low temperature. At low temperature, the substrate has low solubility to carbon atoms, meanwhile, the surface of the substrate is in a solid state, and the decomposed carbon atoms do not vertically precipitate in the substrate, so that the amorphous carbon only grows on the surface of the substrate without covering the nano-micron network and is combined with the nano-micron network in a physical bond and chemical bond mode to form a structure that the amorphous carbon is coplanar with the nano-micron network and has no gap between the amorphous carbon and the nano-micron network. In addition, the thickness of the amorphous carbon grown by the growth mode is uniform and controllable, an amorphous carbon film with atomic-scale thickness can be formed, and the amorphous carbon film has the characteristics of being remarkably different from the amorphous carbon prepared by the conventional thermal evaporation mode in thickness and non-uniformity. The amorphous carbon/nano-micron network film provided by the invention has good transparent conductivity, can be used in the fields of transparent conductive electrodes, solar cells, photo-thermal conversion, photo-electric-thermal conversion, photocatalysis, transparent composite materials, water and oxygen isolating layers, transparent protective layers and the like, and is obviously different from the fields that amorphous carbon prepared by a conventional method is thick and opaque and cannot be used in the fields.
Compared with a single nano-micron network film, the amorphous carbon film is filled between pores of the nano-micron network, the seamless film can prevent external substances such as water, oxygen, acid, alkali, other metals, compounds and the like from oxidizing and corroding the surfaces of electronic devices, metal coatings and the like, and has more excellent protective performance compared with the nano-micron network. Because the amorphous carbon/nano-micron network film provided by the invention has the advantages that the thickness of the amorphous carbon film is uniform and can be regulated to an atomic level, and can be as low as one atomic layer or two atomic layers; the light transmittance can be kept to be certain or higher under the condition of maintaining the electrical performance of the original nano-micron network. This indicates that: if a conductive network is adopted, the prepared amorphous carbon/nano-micron network film has transparent conductivity; if a non-conductive network is adopted, the prepared amorphous carbon/nano-micron network film is non-conductive but transparent; and the prepared doped or modified amorphous carbon/nano-micron network film has unique performance, such as transparent conductivity, excellent electrochemical property, catalytic property, mechanical property and the like, has multiple excellent performances and can be widely used. At the same time, the amorphous carbon/nano-micron network film can be self-supporting under certain conditions.
Since the amorphous carbon film macroscopically shows insulation, the amorphous carbon film can be used as a barrier layer for carrier transmission, so that the amorphous carbon film can isolate the conduction of carriers in a plane and weaken the conduction of the carriers in a vertical plane, and is expected to be applied to the field of electric shielding as an insulation layer.
By adjusting the thickness of the amorphous carbon part, the optical path difference generated by reflection of the amorphous carbon part on the upper surface and the lower surface can be correspondingly adjusted, so that light with specific wavelength generates interference cancellation, the effect of reducing reflection is achieved, and the amorphous carbon part is expected to be applied to the field of solar cells.
The above and other objects, advantages and features of the present invention will become more apparent to those skilled in the art from the following detailed description of specific embodiments thereof, taken in conjunction with the accompanying drawings.
Drawings
Some specific embodiments of the invention will be described in detail hereinafter, by way of illustration and not limitation, with reference to the accompanying drawings. The same reference numbers in the drawings identify the same or similar elements or components. Those skilled in the art will appreciate that the drawings are not necessarily drawn to scale. In the drawings:
FIG. 1 is a schematic structural diagram of an apparatus for growing an amorphous carbon/nano-micron network film according to an in-situ method of preparing an amorphous carbon/nano-micron network film according to the present invention;
FIG. 2 is a schematic structural diagram of an apparatus for growing an amorphous carbon/nano-micron network film by a transfer method according to a method for preparing an amorphous carbon/nano-micron network film of the present invention;
FIG. 3 is a schematic structural diagram of an apparatus for growing an amorphous carbon/nano-micron network film by a transfer method according to a method for preparing an amorphous carbon/nano-micron network film of the present invention;
fig. 4 is a scanning electron microscope image of a carbon nanotube network thin film used in embodiment example 1 of the present invention.
Fig. 5 is a scanning electron microscope image of the amorphous carbon/carbon nanotube composite film prepared in example 1 of the present invention.
Fig. 6 shows raman characterization results of amorphous carbon regions in the amorphous carbon/carbon nanotube composite film prepared in example 1 of the present invention.
FIG. 7 shows the light transmittance characterization results of the amorphous carbon/carbon nanotube composite film prepared in example 1 of the present invention.
FIG. 8 is a graph showing the results of electrical property characterization of the amorphous carbon/carbon nanotube composite film prepared in example 1 of the present invention (sample size: 1X 1 cm)2)。
Fig. 9 is a schematic diagram of a gold gate periodic network prepared by micromachining in example 13 of the present invention.
The device comprises a substrate 1, a substrate 2, a nano-micro network 3, a carbon source 4, a container carrying the carbon source 11, a reaction cavity 21, a heating zone 22, a corresponding growth temperature zone 41, a second substrate 42, the carbon source 5 and a first substrate attached with a nano-micro network composite film.
Detailed Description
The invention is further illustrated by the following figures and embodiments. The claimed invention is not limited to the following examples, but is to be construed in breadth and scope in accordance with the appended claims.
The inventors of the present invention found that: the nano-micro network causes problems due to its own porous structure, and although the nano-micro network can be chemically stable, external molecules (such as water, oxygen, acid, metal) can penetrate through the nano-sized and micro-sized pores, so as to corrode metal, semiconductor or other materials in contact with the nano-sized and micro-sized pores and even cause short circuit. For example, when the nano-micron network is applied to a silicon-based photovoltaic device, external air and water molecules have continuous oxidation and corrosion effects on the silicon surface, which greatly reduces the stability of the photovoltaic device. Therefore, based on the above, the inventors creatively fill amorphous carbon in the porous network to form a composite film, so that the amorphous carbon/nano-micron network film can also maintain the corresponding light transmittance while maintaining the original nano-micron network electrical properties; has more excellent protection performance.
FIG. 1 is a schematic structural diagram of an apparatus for growing an amorphous carbon/nano-micron network film by an in-situ method according to a method for preparing an amorphous carbon/nano-micron network film of the present invention. FIG. 2 is a schematic structural diagram of an apparatus for growing an amorphous carbon/nano-micron network film by a transfer method according to a method for preparing an amorphous carbon/nano-micron network film of the present invention. FIG. 3 is a schematic structural diagram of an apparatus for growing an amorphous carbon/nano-micron network film by a transfer method according to a method for preparing an amorphous carbon/nano-micron network film of the present invention.
The invention provides an amorphous carbon/nano-micron network film, which comprises: amorphous carbon and a nano-micro network, the pores of the nano-micro network being completely filled with amorphous carbon, forming a coplanar, pore-free composite film; the amorphous carbon is a two-dimensional amorphous carbon nano film composed of carbon atoms. The two-dimensional amorphous carbon nano-film is composed of pure carbon elements. Optionally, the two-dimensional amorphous carbon nano-film has other element doping or modification, including any one or combination of nitrogen, boron, silicon, hydrogen, oxygen. The nano-micro network has a porous network structure with a size distribution from nano to micro scale.
The amorphous carbon/nano-micron network film provided by the invention is completely filled in nano-micron network pores without covering the surface of the nano-micron network, so that a coplanar structure is formed.
The amorphous carbon is a two-dimensional amorphous carbon nano film mainly composed of carbon atoms, can be composed of pure carbon elements, can also contain partial other elements, and the carbon atoms pass through sp1Hybridization, sp2Hybridisation or sp3The thickness of the amorphous carbon nano film is 0.1nm or more. Such as: the thickness of the amorphous carbon nano film is 0.1nm-1 nm; the thickness of the amorphous carbon nano film is 1nm-3 nm; the thickness of the amorphous carbon nano film is 3nm-5 nm; the thickness of the amorphous carbon nano film is more than 5 nm.
Amorphous carbon refers to a two-dimensional amorphous carbon nano-film composed mainly of carbon atoms, which also includes hydrogen atoms, oxygen atoms, nitrogen atoms, or other atoms. Such as: optionally, the atomic percentage of carbon element in the amorphous carbon film is 0.1-10%; the atomic percentage of carbon element in the amorphous carbon film is 10-30%; the atomic percentage of carbon element in the amorphous carbon film is 30-50%; the atomic percentage of carbon element in the amorphous carbon film is 50-80%; the atomic percentage of carbon element in the amorphous carbon film is 80-90%; the atomic percentage of carbon element in the amorphous carbon film is more than 90%.
The amorphous carbon/nano-micron network film provided by the invention has a nano-micron network which is a porous network, wherein the pore size is distributed from nano to micron scale. The nano-micro network may be a porous network consisting of nano-scale pores. Specifically, the pore size scale comprises 0.1nm-1nm, 1nm-100nm, 100nm-500nm, and 500nm-1000 nm; the nano-micro network may be a porous network consisting of micro-scale pores. Specifically, the size scale of the pores is above 1 μm. The nano-micro network may have both nano-scale and micro-scale pores. The porous network may be regular or irregular.
The thickness of the nano-micro network can also be adjusted according to the selected material, and is generally larger than 0.1 nm; preferably greater than 1 nm.
The nano-micro network includes a conductive network and a non-conductive network. Specifically, the conductive network is a metal network or a semiconductor network, and comprises one or more of a carbon nanotube network, a silver nanowire network, a gold nanowire network, an alloy nanowire network, a gold film with nano-micro pores and a carbon film with nano-micro pores. The non-conductive network is provided with an insulator network, and comprises one or more of a silicon oxide network and an aluminum oxide network;
amorphous carbon is bonded to the nano-micro network by means of physical and chemical bonds. Including covalent bonds, intermolecular forces, electrostatic forces, and the like.
The preparation method of the amorphous carbon/nano-micron network film provided by the invention is not limited. The present invention provides several methods for preparing amorphous carbon/nano-micron network films.
Specifically, the preparation method of the amorphous carbon/nano-micron network film comprises the following steps:
1) preparing a nano-micron network 2 on a substrate 1 and putting the nano-micron network into a reaction cavity 11;
2) a carbon source 3 is introduced and amorphous carbon is grown on the substrate 1 to form an amorphous carbon/nano-micron network film.
More specifically, the method for preparing the amorphous carbon/nano-micron network film by the transmission method comprises the following steps:
1) providing a first substrate, preparing a nano-micron network on the first substrate, and placing the nano-micron network into a cavity;
2) providing a container loaded with a carbon source, and placing the container on the upstream of the first substrate on which the nano-micron network film is prepared; completely exhausting the air in the reaction cavity, and heating the first substrate with the nano-micron network film under the protection of reducing gas;
3) introducing a carbon source, and growing the amorphous carbon/nano-micron network film on the first substrate.
In step 1, the first substrate is a substrate capable of supporting a nano-micron network, and can be rigid or flexible; including metal substrates such as copper foil, nickel foil, copper-nickel alloy foil; including non-metallic substrates such as silicon oxide substrates.
The method for preparing the nano-micro network in the step 1 can be from top to bottom, or from bottom to top, or a combination of the top to bottom and bottom to top methods. For example, typical top-down methods specifically include direct spreading of a nano-micron network on a substrate, spin coating, dip-coating, printing, roll coating, micro-nano processing, or an integration of two or more of the above methods. Common bottom-up methods include chemical, electrochemical, direct growth, or an integration of several methods. Or a combination of top-down and bottom-up approaches.
The container is a container which contains a carbon source and does not react with the carbon source in the step 2; preferably, the material is selected from one or more of stainless steel, quartz, glass, high temperature resistant metal, silicon oxide and aluminum oxide ceramic.
The method for removing the air in the step 2 comprises directly introducing cleaning gas for evacuation, including evacuation by using a vacuum pump. The used cleaning gas is inert gas; optionally, argon, helium, nitrogen or a mixture thereof is included.
The reducing gas in step 2 is a gas for protecting the substrate from oxidation, and preferably includes hydrogen and carbon monoxide.
In the step 2, the carbon source comprises a carbon-containing compound which is in a gas phase at room temperature and is selected from one or more of methane, ethane, ethylene and acetylene; comprises carbon-containing compound which is liquid at room temperature and is selected from one or more of ethanol, acetone, isopropanol and benzene; comprises a carbon-containing compound which is solid at room temperature and is selected from one or more of naphthalene, coronene, polymethyl methacrylate (PMMA) and Polyethylene (PS). Other substances can be introduced for modification or doping while introducing the carbon source; further, the pressure environment of the growth in step 3 is not limited, and may be a vacuum state, an atmospheric pressure state, a high pressure state, or a combination of these. According to the difference of carbon sources, the manner of introducing the carbon source in the step 3 comprises the following steps: the carbon-containing compound is introduced directly into the reaction vessel in a gas phase at room temperature, a carbon-containing compound in a liquid phase taken out by bubbling a carrier gas, a carbon-containing compound volatilized by heating, or a combination thereof.
Specifically, directly introducing the carbon-containing compound which is in a gas phase at room temperature means directly introducing the gas-phase carbon-containing compound into the cavity through the flow meter; the gas phase carbon-containing compound comprises one or more of methane, ethane and propane.
Specifically, the liquid-phase carbon-containing compound carried out by bubbling the carrier gas is carried out by introducing the carrier gas into the liquid carbon source and bubbling the carrier gas into the liquid carbon source. The liquid carbon source comprises one or more of ethanol, benzene and toluene.
Specifically, the volatilization of the carbon-containing compound by heating means that a carbon source is introduced into the chamber directly by means of heating. The carbon source may be liquid, such as ethanol, benzene; may be solid, such as one or more of Polymethylmethacrylate (PMMA), naphthalene, coronene, Polystyrene (PS).
The invention also provides a method for preparing the amorphous carbon/nano-micron network film by placing the carbon source in situ (namely an in-situ contact method). The method is suitable for the condition that the carbon source position is in situ, wherein the in situ means that the carbon source position is the same as the substrate placement area, and the contact means that the carbon source is in contact with the nano-micron network, and comprises the following steps:
1) providing a first substrate, and preparing a nano-micron network on the first substrate;
2) preparing a carbon source on a first substrate with a nano-micron network, and placing the first substrate in a non-growth temperature zone in a reaction cavity; completely exhausting the air in the reaction cavity, and then heating the growth temperature zone to the growth temperature (T1) under the protection of reducing gas;
3) after the temperature is stable, moving the nano-micron network/first substrate with the carbon source prepared to a growth temperature zone, and keeping for a certain time (t1), and growing on the first substrate to obtain an amorphous carbon/nano-micron network film;
further, the first substrate in step 1 above refers to a substrate capable of supporting a nano-micro network, and preferably, is a base capable of reducing a decomposition barrier of a carbon source. The first substrate may be rigid or flexible. Specifically, the method comprises the steps of preparing a substrate by using methods such as thermal evaporation, magnetron sputtering, electrochemistry, spin coating, chemical etching, titration and the like; optionally, the first substrate comprises copper, nickel, copper-nickel alloy, copper-iron alloy, polyimide/copper substrate, silicon oxide/nickel substrate, gallium/tungsten substrate. The method for preparing the nano-micro network can be from top to bottom or from bottom to top. For example, common top-down methods specifically include direct spreading, spin coating, dip-coating, printing, roll coating, micro-nano processing, or an integration of two or more of the foregoing methods on a substrate; common bottom-up methods include chemical, electrochemical, direct growth, or an integration of several methods; or a combination of top-down and bottom-up approaches.
Further, the manner of preparing the carbon source on the first substrate having the nano-micro network in the step 2 is not limited. Preferably, the method includes spin coating, titration, and evaporation. The carbon source comprises solid carbon source including one or more of naphthalene, coronene, polymethyl methacrylate (PMMA) and Polystyrene (PS); optionally, a liquid carbon source is provided, and comprises one or more of benzene and toluene; optionally, a mixture of a solid carbon source and a liquid carbon source is included. The carbon source can be introduced simultaneously with other substances for modification or doping. The method for removing the air comprises directly introducing cleaning gas for evacuation, including evacuation by using a vacuum pump. The cleaning gas is inert gas; optionally, argon, helium, nitrogen or a mixture thereof is included.
And 2, the non-growth temperature zone is a cavity zone which can not reach the temperature required by the growth of the amorphous carbon nano film/nano-micron network. The growth temperature zone is a cavity zone corresponding to the temperature of the growth of the amorphous carbon nano film/nano-micron network.
Further, the reducing gas in step 3 is a gas for protecting the substrate from oxidation, and preferably includes hydrogen and carbon monoxide. The pressure environment for the growth in step 3 is not limited, and may be a vacuum state, a normal pressure state, a high pressure state, or a combination of these. The holding time t1 can be set according to experimental requirements (such as film thickness).
The invention also provides a mode for growing the amorphous carbon/nano-micron network film at low temperature by using an in-situ non-contact method. The method is suitable for the condition that the carbon source position is in the original position, wherein the original position refers to the carbon source position is the same as the substrate placement area, and the non-contact refers to the carbon source not contacting with the nano-micron network, and comprises the following steps:
1) providing a first substrate, and preparing a nano-micron network on the first substrate;
2) providing a container loaded with a carbon source, and placing a first substrate with a nano-micron network prepared and the container in a non-growth temperature zone in a reaction cavity in an up-and-down opposite manner; completely exhausting the air of the reaction cavity, and then heating the growth temperature zone to the growth temperature (T1) under the protection of reducing gas;
3) after the temperature is stable, moving the carbon source and the first substrate with the nano-micron network to a growth temperature zone, and keeping for a certain time (t1), and growing an amorphous carbon/nano-micron network film on the first substrate;
further, the first substrate in step 1 above refers to a substrate capable of supporting a nano-micro network, and preferably, is a base capable of reducing a decomposition barrier of a carbon source. The first substrate may be rigid or flexible. Specifically, the method comprises the steps of preparing a substrate by using methods such as thermal evaporation, magnetron sputtering, electrochemistry, spin coating, chemical etching, titration and the like; optionally, the first substrate comprises copper, nickel, copper-nickel alloy, copper-iron alloy, polyimide/copper substrate, silicon oxide/nickel substrate, gallium/tungsten substrate. The method for preparing the nano-micron network can be from top to bottom or from bottom to top. For example, common top-down methods specifically include direct spreading, spin coating, dip-coating, printing, roll coating, micro-nano processing, or an integration of two or more of the foregoing methods on a substrate; common bottom-up methods include chemical, electrochemical, direct growth, or an integration of several methods; or a combination of top-down and bottom-up approaches.
Further, the container in the step 2 is a container which can contain a carbon source and does not react with the carbon source; preferably, the second substrate is one or more of stainless steel, quartz, glass, high temperature resistant metal, silicon oxide and aluminum oxide ceramic. The carbon source comprises solid carbon source including one or more of naphthalene, coronene, polymethyl methacrylate (PMMA) and Polystyrene (PS); optionally, a liquid carbon source is provided, and comprises one or more of benzene and toluene; optionally, a mixture of a solid carbon source and a liquid carbon source is included. Other substances can be introduced to modify or dope at the same time of introducing the carbon source.
The method for removing the air in the step 2 comprises directly introducing cleaning gas for evacuation, including evacuation by using a vacuum pump. The cleaning gas is inert gas; optionally, argon, helium, nitrogen or a mixture thereof is included. The non-growth temperature zone is a cavity area which can not reach the temperature required by the growth of the amorphous carbon/nano-micron network; the growth temperature zone is a cavity zone corresponding to the temperature of the growth of the amorphous carbon nano film/nano-micron network.
Further, the reducing gas in step 3 is a gas for protecting the substrate from oxidation, and preferably includes hydrogen and carbon monoxide. The pressure environment for the growth in step 3 is not limited, and may be a vacuum state, a normal pressure state, a high pressure state, or a combination of these. The holding time t1 can be set according to experimental requirements (such as film thickness).
The amorphous carbon/nano-micron network film provided by the invention is completely filled in nano-micron network pores without covering the surface of the nano-micron network, so that a coplanar seamless structure is formed.
The amorphous carbon/nano-micron network film and the preparation method thereof provided by the invention have the following characteristics:
compared with a single nano-micron network film, the amorphous carbon film is filled between the pores of the nano-micron network, the seamless film can prevent substances such as external water, oxygen and the like from oxidizing and eroding the surfaces of electronic devices, metal coatings and the like, and has more excellent protective performance compared with the nano-micron network.
The amorphous carbon/nano-micron network film provided by the invention can keep corresponding light transmittance under the condition of maintaining the original nano-micron network electrical property; the amorphous carbon/nano-micron network film can be transparent, semitransparent and opaque by controlling different thicknesses under the condition of maintaining the original nano-micron network electrical property. In addition, the amorphous carbon/nano-micron network film doped or modified by other elements or compounds can have unique properties including transparent conductivity, excellent electrochemical properties, catalytic properties, mechanical properties and the like, or has multiple excellent performances, and can be widely applied. At the same time, the amorphous carbon/nano-micron network film can be self-supporting under certain conditions.
Since the amorphous carbon film macroscopically shows insulation, the amorphous carbon film can be used as a barrier layer for carrier transmission, so that the amorphous carbon film can isolate the conduction of carriers in a plane and weaken the conduction of the carriers in a vertical plane, and is expected to be applied to the field of electric shielding as an insulation layer.
By adjusting the thickness of the amorphous part, the optical path difference generated by the reflection of the amorphous part on the upper surface and the lower surface can be correspondingly adjusted, so that the light with specific wavelength generates destructive interference, the effect of reducing reflection is achieved, and the method is expected to be applied to the field of solar cells.
The following is a detailed description with reference to specific examples.
Example 1
Step 1: and after the purchased high-purity copper foil is subjected to electrochemical polishing, washing the residual electrolyte on the high-purity copper foil with deionized water, washing the high-purity copper foil in acetone, alcohol and deionized water for 2 to 3 times, 10 minutes each time, and drying the copper foil with nitrogen.
Step 2: the self-supporting carbon nanotube network film 2 prepared by the CVD method is spread on the first substrate 1, the thickness of the carbon nanotube network film in the embodiment is about 10nm, and the pore size is between 20nm and 1000 nm.
And step 3: the first substrate 1 with the carbon nanotube film attached thereto was inverted on a container 4 containing a carbon source 3 as shown in fig. 1, and placed at one end of a quartz tube. In this embodiment, the carbon source is solid PMMA powder, the mass is preferably 20mg, and the container 4 is a quartz boat.
And 4, step 4: introducing cleaning gas into the reaction cavity until the air in the cavity is removed; in this embodiment, 500sccm of high purity argon gas is preferably used as the purge gas, and the purge time is 10 min.
And 5: after the cleaning, the flow meter is adjusted, and the temperature of the growth temperature zone is raised to T1 under the atmosphere of hydrogen and argon. After the temperature is stabilized, the substrate 1 with the amorphous carbon nano-film prepared and the container 4 are moved to the center of the tube furnace together, and the temperature is rapidly raised to T1 for growing for T1 time. In this example, the flow rate of hydrogen was 30sccm, the flow rate of argon was 300sccm, T1 was 400 ℃, and T1 was 40 min.
Step 6: and after the growth is finished, stopping heating, opening the tube furnace for rapidly cooling, closing the gas circuit after the temperature is reduced to the room temperature, and taking out the sample.
And 7: PMMA was spin coated on the sample and cured and the first substrate was removed in an etching solution followed by rinsing with deionized water 2-3 times for 10min each. And finally, transferring the composite film to a target substrate, and removing PMMA by using acetone after drying. The etching solution of this example was ferric chloride solution with a concentration of 0.1 mol/L.
This example finally yields an amorphous carbon/carbon nanotube composite film. As shown in FIG. 4, the carbon nanotube network film has a pore size of 20-1000nm and a thickness of about 10 nm. The scanning electron microscope image of the finally obtained amorphous carbon/carbon nanotube composite film is shown in fig. 5, and it can be seen that the amorphous carbon is completely filled between the carbon nanotubes without pores; the thickness of the amorphous carbon film is about 1nm, and the corresponding Raman characteristics are shown in FIG. 6. In addition, the amorphous carbon/carbon nanotube network composite film obtained integrally shows excellent transparent conductive property. Specifically, the light transmittance at 550nm was as high as 93%, as shown in fig. 7; the conductivity was good and there was little degradation in electrical properties, as shown in fig. 8. The prepared amorphous carbon/carbon nanotube network composite film with good transparent conductivity can be used in the fields of transparent conductive electrodes, solar cells, photo-thermal conversion, photo-electric-thermal conversion, photocatalysis, transparent composite materials, water and oxygen insulating layers, transparent protective layers and the like.
Example 2
Steps 1-2 were identical to 1-2 in example 1;
and step 3: the first substrate 1 with the carbon nanotube film attached thereto is placed in a temperature zone 22, and as shown in fig. 2, a carbon source is placed in a heating zone 21. In this embodiment, the carbon source is solid naphthalene powder, the mass is preferably 20mg, and the container for holding the carbon source is a quartz boat.
And 4, step 4: introducing cleaning gas into the reaction cavity until the air in the cavity is removed; in this embodiment, 500sccm of high purity argon gas is preferably used as the purge gas, and the purge time is 10 min.
And 5: after the cleaning was completed, the flow meter was adjusted and the temperature was raised to temperature range 22 to T1 under an atmosphere of hydrogen and argon. After the temperature is stabilized, the temperature of the temperature zone 21 is raised to T2, and the holding time is T1. In this example, the flow rate of hydrogen was 30sccm, the flow rate of argon was 300sccm, T1 was 400 ℃, T2 was 300 ℃, and T1 was 40 min.
Steps 6-7 remained the same as steps 6-7 in example 1;
this example finally yields an amorphous carbon/carbon nanotube composite film. The amorphous carbon/carbon nanotube composite film prepared was similar to the results of example 1.
Example 3:
the copper foil in example 2 was replaced with a copper-nickel alloy, which was prepared as follows: using the annealed high-purity copper foil as a cathode (25 μm in this example), using a high-purity nickel plate as an anode, and electroplating a 2-5 μm nickel film on the copper foil by an electrochemical method using a mixed solution of 250g/L nickel sulfate hexahydrate, 50g/L boric acid, 50g/L nickel chloride hexahydrate and 0.1g/L sodium dodecyl sulfate, with an electroplating current set at 0.01A/cm2The plating time is set to 5 to 30 minutes. After the electroplating, the copper/nickel foil plate was subjected to a heat treatment at 1000 ℃ for 2 hours in an argon and hydrogen atmosphere to form a copper-nickel alloy.
The subsequent steps were the same as in example 1.
Example results: finally obtaining the amorphous carbon/carbon nanotube composite film, and obtaining the amorphous carbon/carbon nanotube composite film with different thicknesses by adjusting the electroplating time and the growth time of nickel, wherein the thickness of the amorphous carbon/carbon nanotube composite film can reach 1nm or more.
Example 4:
step 1: the silica (300 nm)/silicon wafers were cleaned with acetone, alcohol and deionized water, respectively, and blown dry with nitrogen. Putting a high-purity copper target into a cavity, controlling the argon pressure to be 0.6Pa, sputtering the copper film at the sputtering power of 150W, and sputtering for 60 minutes;
step 2: and putting the sample after sputtering into a quartz tube, heating to 800 ℃ under the protection of argon and hydrogen, annealing for 30 minutes, and then naturally cooling to room temperature.
an amorphous carbon/carbon nanotube composite film having transparent conductive properties similar to example 1 was finally obtained.
Example 5:
step 1: the polyimide film with proper size is cut, washed by acetone, alcohol and deionized water respectively, and dried by nitrogen.
Step 2: putting a high-purity copper target into a cavity, controlling the argon pressure to be 0.6Pa, sputtering the copper film at the sputtering power of 150W, and sputtering for 5-60 minutes;
Step 6: after the cleaning was completed, the flow meter was adjusted and the temperature was raised to temperature range 22 to T1 under an atmosphere of hydrogen and argon. After the temperature is stabilized, the temperature of the temperature zone 21 is raised to T2, and the holding time is T1. In this example, the flow rate of hydrogen was 40sccm, the flow rate of argon was 300sccm, T1 was 400 ℃, T2 was 300 ℃, and T1 was 50 min.
And 7: and after the growth is finished, stopping heating, opening the tube furnace for rapidly cooling, closing the gas circuit after the temperature is reduced to the room temperature, and taking out the sample.
Finally obtaining the amorphous carbon/carbon nano tube composite film attached to the flexible polyimide substrate.
Example 6:
the melamine powder is added into 20mg of PMMA powder in example 1 and uniformly mixed, wherein the mass ratio of the PMMA powder to the melamine powder is between 1:1 and 10:1, and other steps are the same as example 1.
Example results: finally obtaining the nitrogen-doped amorphous carbon/carbon nano tube composite film.
Example 7:
the carbon nanotube film in example 1 was replaced with a silver nanowire film, and the silver nanowire film was spread on a copper substrate by a spin-coating method, which specifically comprises the following steps: and spin-coating the silver nanowire dispersion on the copper foil at the rotation speed of between 1000 and 5000rpm for 120s, and then placing the copper foil attached with the silver nanowires on a hot plate for heating and baking at 100 ℃ for 10 min. The other steps are the same as in example 1.
Example results: finally, the amorphous carbon/silver nanowire composite film is obtained, and the pore space and the thickness of the silver nanowire can be adjusted through different rotating speeds, so that the composite films with different transparent conductive performances are obtained.
Example 8:
step 1-2 is the same as step 1-2 in example 1;
and 3, placing the carbon nanotube film/copper foil in the cavity, and placing the liquid benzene in a stainless steel sealed container 41 shown in figure 3, wherein other parameters and conditions are kept consistent.
And 4, step 4: and introducing cleaning gas for emptying until the air is completely discharged. In this embodiment, the purge gas is high purity argon at a flow rate of 500 sccm.
And 5: the purge gas is turned off and the chamber is warmed to the target temperature T1 under the protection of hydrogen and argon. In this embodiment, the flow rate of hydrogen is preferably 30sccm, the flow rate of argon is 300sccm, and the target temperature is 150 ℃.
Step 6: the chamber region 32 is maintained at a temperature T1 and a carrier gas is introduced into the benzene containing vessel 41 to introduce the carbon source. Wherein, the carrier gas is high-purity argon with the flow rate of 10 sccm.
Example results: finally, the amorphous carbon/carbon nano tube composite film grown on the copper foil by adopting a transmission method is obtained.
Example 9:
step 1: after the purchased high-purity copper foil is subjected to electrochemical polishing, deionized water is used for washing away the electrolyte remained on the copper foil, the copper foil is washed in acetone, alcohol and deionized water for 2-3 times, 10 minutes each time, and the copper foil is dried by nitrogen.
Step 2: transferring the horizontally grown carbon nanotube array to a copper foil under the protection of PMMA, and removing the PMMA with acetone after drying; repeating the steps to obtain a cross type carbon nanotube net structure transferred to the copper foil;
example results: the amorphous carbon/carbon nanotube cross network composite film grown on the copper foil is obtained, and the transparent conductive property of the composite film can be adjusted by adjusting the thickness and the pores of the cross type carbon nanotube network.
Example 10
and 4, step 4: opening the mechanical pump to remove the air in the reaction cavity;
and 5: the vacuum pump was kept on, the flow meter was adjusted, and the temperature was raised to T1 under an atmosphere of hydrogen and argon. After the temperature is stable, the substrate with the amorphous carbon nano-film and the container with the carbon source are moved to the center of the tube furnace together, and then the substrate is moved to the center of the tube furnace, so that the temperature is rapidly increased to T1, and the substrate is grown for T1 time. In this example, the flow rate of hydrogen was 30sccm, the flow rate of argon was 300sccm, T1 was 400 ℃, and T1 was 40 min.
Step 6: and after the growth is finished, stopping heating, opening the tube furnace for rapidly cooling, closing the vacuum pump after the temperature is reduced to room temperature, closing the gas circuit after the normal pressure in the cavity is recovered, and taking out the sample.
And 7: the sample is floated in the etching solution, the first substrate is removed by reaction, and then rinsed 2-3 times with deionized water for 10min each. Finally, the composite film can be transferred to a target substrate. The etching solution of this example was ferric chloride solution with a concentration of 0.1 mol/L.
Example results: obtaining the amorphous carbon/carbon nano tube composite film.
Example 11
Step 1: and (3) carrying out electrochemical polishing on the purchased high-purity copper foil, cleaning the electrolyte remained on the copper foil, and drying.
Step 2: spreading the carbon nanotube film which grows continuously on the treated copper foil, and winding the carbon nanotube film at one end of a rotating wheel;
and step 3: the rolled carbon nanotube film/copper foil was placed in a cavity, the PMMA powder was placed in an open glass bottle, and the glass bottle was placed upstream of the cavity as shown in fig. 2.
And 4, step 4: and introducing cleaning gas for emptying until the air is completely discharged. In this embodiment, the purge gas is high purity argon at a flow rate of 500 sccm.
And 5: the purge gas is turned off and the chamber is warmed to the target temperature T1 under the protection of hydrogen and argon. In this embodiment, the flow rate of hydrogen is preferably 30sccm, the flow rate of argon is 300sccm, and the target temperature is 400 ℃.
Step 6: the temperature of the chamber region 32 was maintained at T1, the temperature of the region 31 was raised to T2, and the electric motor transmission wheel was operated at S1. In this embodiment, T1 is 500 deg.C, T2 is 60 deg.C, and the rotor speed S1 is preferably 1 rpm.
This example finally yields an amorphous carbon/carbon nanotube composite film that is continuously grown on copper foil.
Example 12
Step 1-2 is the same as step 1-2 of example 1;
and step 3: and spin-coating a layer of PMMA on the surface of the copper foil, photoetching according to a set mask, and then developing and fixing by using S1813 and water respectively. In this example, the thickness of PMMA was 200nm, and the developing and fixing time was 60 seconds.
And 4, step 4: the sample was blow dried with high purity nitrogen and placed in a thermal evaporation apparatus to evaporate the gold. In this example, the thickness of gold is 50nm.
And 5: the sample was taken out to obtain a copper foil (shown in fig. 9) prepared with a gold grid network pattern/PMMA, which was placed on one end of a quartz tube. In this example, the width of the gold grid network is 1 μm, and the pore size is 2 μm.
Step 6: introducing cleaning gas into the reaction cavity until the air in the cavity is removed; in this embodiment, 500sccm of high purity argon gas is preferably used as the purge gas, and the purge time is 10 min.
And 7: after the cleaning, the flow meter is adjusted, and the temperature of the growth temperature zone is raised to T1 under the atmosphere of hydrogen and argon. And after the temperature is stable, moving the copper foil with the gold grid network pattern/PMMA to the center of a tube furnace, rapidly heating the copper foil to T1, and growing for T1 time. In this example, the flow rate of hydrogen was 30sccm, the flow rate of argon was 300sccm, T1 was 400 ℃, and T1 was 40 min.
And 8: and after the growth is finished, stopping heating, cooling and taking out the sample.
This example finally yields an amorphous carbon/gold grid network composite film.
Example 13
Step 1-2 is the same as step 1-2 of example 1;
and step 3: spreading the carbon tube film on the surface of the copper foil, spin-coating a layer of PMMA, photoetching according to a set mask, and then developing and fixing by using S1813 and water respectively. In this example, the thickness of PMMA was 200nm, the thickness of the carbon tube film was 200nm, and the developing and fixing time was 60 seconds.
And 4, step 4: and taking out the sample, putting the sample into an RIE (reactive ion etching) chamber, and bombarding the carbon tube film which is not protected by PMMA (polymethyl methacrylate) by using high-energy ions. In this embodiment, the etching gas is oxygen, and the etching time is 100 s.
And 5: and taking out the sample to obtain the copper foil with the periodic carbon tube network pattern formed after photoetching and RIE etching. A copper foil prepared with carbon tube network pattern/PMMA was placed at one end of the quartz tube. In this example, the width of the carbon tube network is 10 μm, and the pore size is 50 μm.
Step 6: and introducing cleaning gas for emptying until the air is completely discharged. In this embodiment, the purge gas is high purity argon at a flow rate of 500 sccm.
And 7: the purge gas is turned off and the chamber is warmed to the target temperature T1 under the protection of hydrogen and argon. In this embodiment, the flow rate of hydrogen is preferably 30sccm, the flow rate of argon is 300sccm, and the target temperature is 500 ℃.
And 8: after the growth, the heating was stopped and the sample was taken out.
This example finally yields an amorphous carbon/carbon nanotube network composite film.
Example 14
Step 1: and after the purchased high-purity copper foil is subjected to electrochemical polishing, washing the residual electrolyte on the high-purity copper foil with deionized water, washing the high-purity copper foil in acetone, alcohol and deionized water for 2 to 3 times, 10 minutes each time, and drying the copper foil with nitrogen.
Step 2: the self-supporting carbon nanotube film 2 prepared by the CVD method is spread on a first substrate 1, the thickness of the carbon nanotube film in the embodiment is 20nm, and the pore size of the self-supporting amorphous carbon nanotube film is between 0.1nm and 20 nm.
And 7: preparing an etching solution, removing the first substrate by using the etching solution, and rinsing with deionized water for 10min for 2-3 times. Finally, the composite film can be transferred to a target substrate. The etching solution in this example was ferric chloride, and the concentration of the solution was 0.1 mol/L.
This example finally yields a self-supporting amorphous carbon/carbon nanotube composite film.
The low-temperature synthesis method provided by the invention selects the hydrocarbon with low bond energy as the low-temperature carbon source, the carbon source with low decomposition temperature (such as naphthalene and PMMA) has lower decomposition barrier compared with the conventional carbon source with high decomposition temperature (such as methane), the growth temperature of the amorphous carbon nano film is obviously reduced on the whole, and the reduction of the temperature has great significance for realizing the industrialization of the amorphous carbon/nano-micron network film, so that the energy consumption is greatly reduced, the production cost is reduced, and a foundation is laid for further large-scale growth.
The low-temperature synthesis method is beneficial to keeping the original appearance and excellent properties of the nano-micron network film, and especially ensures the original electrical properties. The nano-micron network has the characteristics of small size and high specific surface area, and compared with a block material, the nano-micron network has the advantages of high surface energy, more specific surface atoms and incomplete adjacent coordination, so the melting point is lower, and the nano-micron network is easy to melt or decompose at higher temperature; on the other hand, the substrate and the nano-micro network may be co-melted or reacted to destroy the original network structure, so that the original excellent properties of the nano-micro reticular film can be reduced even the original nano-micro reticular film structure is destroyed in the high-temperature process, and the realization of low-temperature growth is especially critical for improving the overall properties of the composite film.
The low-temperature synthesis method provided by the invention can grow the composite film at the temperature of below 200 ℃ by selecting the carbon source capable of being decomposed at low temperature, and the mode can expand the growth of the composite film on a flexible substrate which is not high in temperature resistance, thereby expanding the application prospect of the composite film.
The preparation method of the amorphous carbon/nano-micron network film provided by the invention is carried out at low temperature. At low temperature, the substrate has low solubility to carbon atoms, meanwhile, the surface of the substrate is in a solid state, and the decomposed carbon atoms do not precipitate vertically in the substrate, so that under the action of the substrate, the amorphous carbon grows only on the surface without covering the nano-micron network, and a structure that the amorphous carbon is coplanar with the nano-micron network and has no gap between the amorphous carbon and the nano-micron network is formed. In addition, the thickness of the amorphous carbon grown by the growth mode is uniform and controllable, an amorphous carbon film with atomic-scale thickness can be formed, and the amorphous carbon film has the characteristics of being remarkably different from the amorphous carbon prepared by the conventional thermal evaporation mode in thickness and non-uniformity.
Thus, it should be understood by those skilled in the art that while exemplary embodiments of the present invention have been illustrated and described in detail herein, many other variations or modifications which are consistent with the principles of the invention may be directly determined or derived from the disclosure of the present invention without departing from the spirit and scope of the invention. Accordingly, the scope of the invention should be understood and interpreted to cover all such other variations or modifications.
Claims (9)
1. An amorphous carbon/nano-micro network film, comprising: amorphous carbon and a nano-micro network, the nano-micro network having a porous network structure with a size distribution from nano-scale to micro-scale, the pores of the nano-micro network being completely filled with amorphous carbon to form a coplanar, pore-free composite film; the amorphous carbon is a two-dimensional amorphous carbon nano film consisting of carbon atoms;
the nano-micron network is prepared on a substrate, the substrate is a substrate with the functions of catalyzing the decomposition of a carbon source and reducing the growth temperature of the amorphous carbon, so that the amorphous carbon only grows on the surface of the substrate without the coverage of the nano-micron network at low temperature, and is combined with the nano-micron network by means of physical bonds and chemical bonds.
2. The amorphous carbon/nano-micro network film according to claim 1, wherein the two-dimensional amorphous carbon nano-film is composed of pure carbon element.
3. The amorphous carbon/nano-micro network film as recited in claim 1, wherein the two-dimensional amorphous carbon nano-film has other element doping or modification including any one or combination of nitrogen, boron, silicon, hydrogen, oxygen.
4. The amorphous carbon/nano-micro network film according to claim 1, wherein the nano-micro network comprises a conductive network and a non-conductive network; the conductive network comprises a metal network or a semiconductor network; the non-conductive network comprises an insulator network.
5. The amorphous carbon/nano-micro network film according to claim 1, wherein the amorphous carbon is bonded to the nano-micro network by means of physical and chemical bonds.
6. A method for preparing an amorphous carbon/nano-micro network thin film according to any one of claims 1 to 5, comprising the steps of:
preparing a nano-micron network on a substrate and placing the nano-micron network into a reaction cavity;
introducing a carbon source, and growing amorphous carbon in the pores to form an amorphous carbon/nano-micron network film;
the substrate is a substrate which can catalyze the decomposition of a carbon source and reduce the growth temperature of the amorphous carbon, so that the amorphous carbon can grow at a low temperature;
the amorphous carbon grows only on the surface of the substrate without covering the nano-micron network, and is combined with the nano-micron network by means of physical bonds and chemical bonds to form a structure that the amorphous carbon is coplanar with the nano-micron network and has no gap between the amorphous carbon and the nano-micron network.
7. The method of claim 6, wherein the substrate is a substrate that can support a nano-micro network.
8. The preparation method according to claim 6, wherein the carbon source is introduced simultaneously with other elements for modification or doping.
9. The method of claim 6, wherein the carbon source comprises any one or a combination of a gaseous carbon source, a liquid carbon source, and a solid carbon source.
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