CN109534315A - A kind of amorphous carbon/nano-micrometer network thin-film and preparation method thereof - Google Patents
A kind of amorphous carbon/nano-micrometer network thin-film and preparation method thereof Download PDFInfo
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- CN109534315A CN109534315A CN201811116233.2A CN201811116233A CN109534315A CN 109534315 A CN109534315 A CN 109534315A CN 201811116233 A CN201811116233 A CN 201811116233A CN 109534315 A CN109534315 A CN 109534315A
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Abstract
The present invention provides a kind of amorphous carbon/nano-micrometer network thin-films and preparation method thereof, belong to technical field of nano material, comprising: amorphous carbon and nano-micrometer network, the amorphous carbon is filled in the hole of the nano-micrometer network, to form imporous laminated film；The amorphous carbon is the two-dimentional amorphous carbon nano thin-film being made of carbon atom.The novel amorphous carbon of one kind provided by the invention/nano-micrometer network thin-film; its imporosity two dimension laminated film that amorphous carbon is filled in nano-micrometer network to be formed; it can prevent the oxidative attacks of the substances to surfaces such as electronic device, metal coatings such as external water, oxygen; compared to nano-micrometer network, there is more excellent protective value.
Description
Technical field
The present invention relates to technical field of nano material, more particularly to a kind of amorphous carbon/nano-micrometer network thin-film and its
Preparation method.
Background technique
Charcoal is earliest one of the substance of human contact, since R.E.Smalley, H.W.Kroto and R.F.Curl have found C60
Later, state in the ascendant is just always maintained to the research of carbon nanomaterial.Hereafter, carbon nanotube, graphene are successive
It was found that, it may be said that carbon nanomaterial has led the revolution in terms of material, and has greatly pushed the development in Other subjects field.
Amorphous carbon, one of the allotrope as carbon, property are often considered as between diamond and graphite
A kind of transition state.For the amorphous c film of nanoscale, with the graphene of corresponding two-dimentional monoatomic layer thickness
There is also larger differences.Specifically, it is not only between the carbon and carbon atom of amorphous c film and passes through sp2Hydridization bonding, also
There are sp1、sp3Hydridization, sp3Presence make it with higher hardness.The amorphous c film of nanoscale, while also having
There is very strong chemical inertness.The two properties, so that amorphous c film is expected to be applied to the fields such as protection.
Nano-micrometer network refers to the porous network being made of the hole of nanometer to micro-meter scale.It is thin with carbon nano tube network
For film, carbon nano tube network film is the network structure formed by carbon nanotube by the effect of chemical bond and secondary or physical bond.This
Kind network has very high transmitance to visible light due to the superthin structure of its porous feature and itself.Meanwhile carbon nanotube is same
Sample has electric conductivity, mechanical strength and the stability of superelevation, all has in fields such as electronic device, electrically conducting transparent, Flexible Displays
Have broad application prospects.However, the porous structure of nano-micrometer network itself also brings some problems, its reality is affected
Using, such as the service life is short, stability is poor.
Therefore, how to solve the above problems, there is important scientific meaning and application value.
Summary of the invention
It is a kind of novel amorphous it is an object of the invention in view of the above defects of the prior art, provide
Carbon/nano-micrometer network thin-film is that amorphous carbon is filled in nano-micrometer network is compound to form coplanar, imporous two dimension
Film.
Particularly, the present invention provides a kind of amorphous carbon/nano-micrometer network thin-films, comprising: amorphous carbon and receive-micro-
Rice network, the amorphous carbon is filled in the hole of the nano-micrometer network, to form imporosity, coplanar laminated film；
The amorphous carbon is the two-dimentional amorphous carbon nano thin-film being made of carbon atom.
Optionally, the two-dimentional amorphous carbon nano thin-film is made of pure carbon.
Optionally, the two-dimentional amorphous carbon nano thin-film has other element dopings or a modification, including nitrogen, boron, silicon,
Any one or more of combination of hydrogen, oxygen.
Optionally, the nano-micrometer network has porous network structure, and the size of the porous network structure is distributed
In nanometer to micro-meter scale.
Optionally, the nano-micrometer network includes conductive network and non-conductive network；The conductive network includes metal mesh
Network or semiconductor network；The non-conductive network includes one or more of silica network, aluminium oxide network.
Optionally, it is combined by way of secondary or physical bond and chemical bond between the amorphous carbon and the nano-micrometer network.
The present invention also provides a kind of amorphous carbon/nano-micrometer network thin-film preparation methods, comprising the following steps:
Nano-micrometer network is prepared on substrate, and is put into reaction cavity；
Carbon source is introduced, grows amorphous carbon in hole to form amorphous carbon/nano-micrometer network thin-film.
Optionally, the substrate is the substrate of sustainable nano-micrometer network.
Preferably, substrate is to decompose with catalysis carbon source, reduces the substrate of amorphous carbon growths temperature.
Optionally, the carbon source not only may include carbon, can also include other doped chemicals.
Optionally, can be introduced while introducing carbon source other chemical substances containing other chemical elements be modified or
Person's doping.
Optionally, the carbon source includes gaseous carbon source, liquid carbon source and any one or more of combination of solid-state carbon source.
Amorphous carbon provided by the invention/nano-micrometer network thin-film, amorphous carbon and nano-micrometer network have coplanar
Feature, amorphous c film are filled up completely nano-micrometer network pore, do not cover nano-micrometer network surface.
Amorphous carbon provided by the present invention/nano-micrometer network thin-film and preparation method thereof has a characteristic that
Amorphous carbon provided by the present invention/nano-micrometer network thin-film preparation method carries out at low temperature.In low temperature
Under, substrate is low to the solubility of carbon atom, meanwhile, substrate surface is solid-state, the vertical no precipitation in the substrate of the carbon atom of decomposition
Process, therefore, amorphous carbon only no nano-micrometer network coverage substrate surface grow, and with the nano-micrometer network it
Between combined by way of secondary or physical bond and chemical bond, it is coplanar and between the two with nano-micrometer network to form a kind of amorphous carbon
Seamless structure.In addition, the amorphous carbon thickness of this growth pattern growth uniformly, it is controllable, can be formed atomic-level thickness without
Shape C film, has the characteristics that be substantially distinguished from the amorphous carbon thickness thickness prepared by conventional thermal evaporation methods and non-uniform.
Amorphous carbon provided by the present invention/nano-micrometer network thin-film can have good transparent conductivity, can be used for electrically conducting transparent electricity
Pole, solar battery, photothermal conversion, photoelectricity hot-cast socket, photocatalysis, transparent composite, exclusion of water oxygen layer, transparent protective layer etc.
Field, with the amorphous carbon thickness that is prepared by usual manner it is thick, it is opaque, cannot be used for above-mentioned field and have apparent difference.
Compared to single nano-micrometer network thin-film, amorphous c film is filled between the hole of nano-micrometer network,
This seamless film can prevent the substances such as external water, oxygen, acid, alkali, other metals, compound to electronic device, metal
The oxidative attack on the surfaces such as coating has more excellent protective value compared to nano-micrometer network.Since the present invention is mentioned
The amorphous carbon of confession/nano-micrometer network thin-film, amorphous c film have thickness uniformly and can regulate and control to the thickness of atom level
Degree, can be down to an atomic layer or two atomic layers；In the case where maintaining original nano-micrometer network electric property, equally
It can keep certain or higher light transmittance.This shows: as used conductive network, the then amorphous carbon/nano-micrometer prepared
Network thin-film has transparent conductivity；Non-conductive network is such as used, then the amorphous carbon prepared/nano-micrometer network thin-film is not
It is conductive but transparent；And amorphous carbon/nano-micrometer the network thin-film for preparing doping or modification has unique performance, such as
Transparent conductivity or excellent electrochemical properties or catalytic property or mechanical property etc., and a variety of excellent properties are had both, it will
Open up wider purposes.Meanwhile the amorphous carbon/nano-micrometer network thin-film in certain circumstances can be with self-supporting.
Since amorphous c film is macroscopically presented as insulating properties, it is possible to as the barrier layer of carrier transport, every
Exhausted conduction of the carrier in face, while weakening the conduction in carrier direction in vertical plane, therefore be expected to answer as insulating layer
For electric shield field.
By the adjusting to amorphous carbon segment thickness, it can be accordingly adjusted in upper and lower surfaces and reflects generated light path
Difference, and then the light of specific wavelength is made to generate interference cancellation, play the role of anti-reflection, is expected to be applied to area of solar cell.
According to the following detailed description of specific embodiments of the present invention in conjunction with the accompanying drawings, those skilled in the art will be brighter
The above and other objects, advantages and features of the present invention.
Detailed description of the invention
Some specific embodiments of the present invention is described in detail by way of example and not limitation with reference to the accompanying drawings hereinafter.
Identical appended drawing reference denotes same or similar part or part in attached drawing.It should be appreciated by those skilled in the art that these
What attached drawing was not necessarily drawn to scale.In attached drawing:
Fig. 1 is that a kind of growth of amorphous carbon/nano-micrometer network thin-film preparation method in-situ method is amorphous according to the present invention
The structural schematic diagram of carbon/nano-micrometer network thin-film device；
Fig. 2 is that a kind of growth of amorphous carbon/nano-micrometer network thin-film preparation method transmission method is amorphous according to the present invention
The structural schematic diagram of carbon/nano-micrometer network thin-film device；
Fig. 3 is that a kind of growth of amorphous carbon/nano-micrometer network thin-film preparation method transmission method is amorphous according to the present invention
The structural schematic diagram of carbon/nano-micrometer network thin-film device；
Fig. 4 is the scanning electron microscope diagram of carbon nano tube network film used in embodiment 1 of the present invention.
Fig. 5 is the amorphous carbon/carbon nano-tube coextruded film scanning electron microscope (SEM) photograph prepared in the embodiment of the present invention 1.
Fig. 6 is the drawing in amorphous carbon region in the amorphous carbon/carbon nano-tube coextruded film prepared in the embodiment of the present invention 1
Graceful characterization result.
Fig. 7 is the amorphous carbon/carbon nano-tube coextruded film light transmission characterization knot prepared in the embodiment of the present invention 1
Fruit.
Fig. 8 is the amorphous carbon/carbon nano-tube coextruded film electric property characterization result prepared in the embodiment of the present invention 1
(sample size: 1 × 1cm2)。
Fig. 9 is the golden grid cycle network diagram prepared in the embodiment of the present invention 13 by micro Process.
Wherein, 1, substrate, 2, nano-micrometer network, 3, carbon source, 4, be loaded with the container of carbon source, 11, reaction cavity, 21, heating
Band, 22, corresponding growth warm area, the 41, second substrate, 42, carbon source, 5, with receiving-the first substrate of micronetwork laminated film.
Specific embodiment
The invention patent is described further below by drawings and embodiments.But protection orientation of the invention is not
It is confined to following instance, the full content in claims should be included.
The inventors found that: nano-micrometer network since the porous structure of its own can bring some problems, although
The chemical property of nano-micrometer network itself can be very stable, but extraneous molecule (such as water, oxygen, acid, metal) can be across these
The hole of nanometer, micron order size generates corrosiveness to the metal, semiconductor or other materials being in contact with it and even occurs
The situation of short circuit.For example, when nano-micrometer network application is in silicon-based photovoltaic device, external air and hydrone pair
Silicon face has the oxidation of duration, corrosiveness, this will substantially reduce the stability of photovoltaic device.Therefore, it is based on this, invention
Amorphous carbon is creatively filled in porous network and forms laminated film by people, so that amorphous carbon/nano-micrometer network is thin
Film can equally keep corresponding light transmittance in the case where maintaining original nano-micrometer network electric property；With superior
Protective value.
Fig. 1 is that a kind of growth of amorphous carbon/nano-micrometer network thin-film preparation method in-situ method is amorphous according to the present invention
The structural schematic diagram of carbon/nano-micrometer network thin-film device.Fig. 2 is a kind of amorphous carbon/nano-micrometer network according to the present invention
The structural schematic diagram of transmission method growth amorphous carbon/nano-micrometer network thin-film device of method for manufacturing thin film.Fig. 3 is basis
A kind of transmission method growth amorphous carbon/nano-micrometer network of amorphous carbon/nano-micrometer network thin-film preparation method of the present invention is thin
The structural schematic diagram of the device of film.
A kind of amorphous carbon/nano-micrometer network thin-film provided by the invention, comprising: amorphous carbon and nano-micrometer network,
The hole of the nano-micrometer network is filled up completely by amorphous carbon, forms coplanar, imporous laminated film；The nothing is fixed
Shape carbon is the two-dimentional amorphous carbon nano thin-film being made of carbon atom.Two-dimentional amorphous carbon nano thin-film is made of pure carbon.
Optionally, two-dimentional amorphous carbon nano thin-film has other element dopings or modification, including any in nitrogen, boron, silicon, hydrogen, oxygen
Kind or a variety of combinations.Nano-micrometer network has porous network structure, and the size of the porous network structure, which is distributed in, to be received
Rice is to micro-meter scale.
Amorphous carbon provided by the invention/nano-micrometer network thin-film, amorphous c film are filled up completely in nano-micrometer net
Network hole does not cover nano-micrometer network surface, forms a kind of coplanar structure.
Amorphous carbon refers to the two-dimentional amorphous carbon nano thin-film being mainly made of carbon atom, can be by pure carbon group
At can also contain the other elements in part, pass through sp between carbon atom1Hydridization, sp2Hydridization or sp3Hydridization bonding, amorphous carbon
Nano film thickness is 0.1nm or more.For example: amorphous carbon nano film thickness is 0.1nm-1nm；Amorphous carbon nano thin-film
With a thickness of 1nm-3nm；Amorphous carbon nano film thickness is 3nm-5nm；Amorphous carbon nano film thickness is in 5nm or more.
Amorphous carbon refers to the two-dimentional amorphous carbon nano thin-film by being mainly made of carbon atom, wherein also includes that hydrogen is former
Son, oxygen atom, nitrogen-atoms or other atoms.For example: optionally, the atomic percent of carbon is in amorphous c film
0.1%-10%；The atomic percent of carbon is 10%-30% in amorphous c film；Carbon in amorphous c film
Atomic percent is 30%-50%；The atomic percent of carbon is 50%-80% in amorphous c film；Amorphous carbon is thin
The atomic percent of carbon is 80%-90% in film；The atomic percent of carbon is 90% or more in amorphous c film.
Amorphous carbon provided by the invention/nano-micrometer network thin-film, the nano-micrometer network are a kind of porous networks,
In pore size distribution in nanometer to micro-meter scale.The nano-micrometer network can be to be made of the hole of nanoscale
Porous network.Specifically, the size scale of hole includes 0.1nm-1nm, 1nm-100nm, 100nm-500nm, 500nm-
1000nm；The nano-micrometer network can be the porous network being made of the hole of micro-meter scale.Specifically, hole is big
Small scale is at 1 μm or more.Nano-micrometer network can both have the hole of nanoscale, and there is also the holes of micro-meter scale.It is porous
Network can be rule, be also possible to irregular.
The thickness of nano-micrometer network is also adjustable according to selected material, generally higher than 0.1nm；It is preferably greater than
1nm。
Nano-micrometer network includes conductive network and non-conductive network.Specifically, conductive network has metalolic network or semiconductor
Network, including carbon nano tube network, silver nanowires network, nanowires of gold network, alloy nano-wire network, have nano-micrometer hole
One or more of the golden film of gap, carbon film with nano-micrometer hole.Non-conductive network has insulation volume grid, including oxidation
One or more of silicon network, aluminium oxide network；
It is combined by way of secondary or physical bond and chemical bond between amorphous carbon and nano-micrometer network.Including covalent bond, molecule
Between active force and electrostatic force etc..
For amorphous carbon provided by the invention/nano-micrometer network thin-film, preparation method is unlimited.The present invention provides
It is several to prepare amorphous carbon/nano-micrometer network thin-film method.
Specifically, a kind of amorphous carbon/nano-micrometer network thin-film preparation method, comprising the following steps:
1) nano-micrometer network 2 is prepared on substrate 1, and is put into reaction cavity 11；
2) carbon source 3 is introduced, grows amorphous carbon on substrate 1 to form amorphous carbon/nano-micrometer network thin-film.
More specifically, additionally providing a kind of " transmission method " prepares amorphous carbon/nano-micrometer network thin-film method, including
Following steps:
1) one first substrate is provided, prepares nano-micrometer network on the first substrate, and be put into cavity；
2) it provides one and is loaded with the container of carbon source, and be placed in the first substrate upstream for being prepared for nano-micrometer network thin-film；It is complete
The air of full discharge reaction cavity, to the first substrate liter for being prepared for nano-micrometer network thin-film under the protection of reducibility gas
Temperature；
3) carbon source is introduced, grows amorphous carbon/nano-micrometer network thin-film on the first substrate.
First substrate described in step 1 is the substrate of sustainable nano-micrometer network, can be rigid, be also possible to soft
Property；Including metal substrate, such as copper foil, nickel foil, corronil foil；Including nonmetallic substrate, such as silicon oxide substrate.
The method that nano-micrometer network is prepared described in the step 1 can be from top to bottom, be also possible to from bottom to top, or
It is from top to bottom and the combination of Self-absorption Correction Factor.For example, common top-to-bottom method specifically include will receive on substrate-
Micron network directly sprawls, spin coating, Best-Effort request, printing, roll coated, micro-nano technology or above two or a variety of methods
It is integrated.Common bottom-to-top method specifically includes chemical method, electrochemical process, direct growth method or several method
It is integrated.Or by from top to bottom and the combination of Self-absorption Correction Factor.
The container is the container for holding carbon source and not reacting with carbon source in step 2；Preferably, selected from stainless steel,
One of quartz, glass, refractory metal, silica, aluminium oxide ceramics are a variety of.
The method for excluding air includes being passed directly into purge gas emptying, including vacuum pump is used to arrange in step 2
It is empty.The purge gas used is inert gas；Optionally, including argon gas, helium, nitrogen or the mixed gas being made of them.
The reducibility gas is the not oxidized gas in protecting group bottom in step 2, it is preferable that including hydrogen, an oxygen
Change carbon.
The carbon source includes the carbon compound for being at room temperature gas phase in step 2, is selected from methane, ethane, ethylene, acetylene
One or more of；Including being at room temperature the carbon compound of liquid, selected from one of ethyl alcohol, acetone, isopropanol, benzene or
It is several；Including being at room temperature solid carbon compound, it is selected from naphthalene, coronene, polymethyl methacrylate (PMMA), poly- second
One or more of alkene (PS).Other materials can be introduced while introducing carbon source to be modified or adulterate；Further, on
The pressure atmosphere for stating the growth in step 3 is unlimited, can be vacuum state, can be normal pressure state, can be high pressure conditions, or
It is the combination of these types of mode.According to the difference of carbon source, the mode that step 3 introduces carbon source includes: to be introduced directly at room temperature as gas
The carbon compound of phase is bubbled the liquid phase carbon compound taken out of by carrier gas, contains carbon compound by what heating volatilized
The combination of object or these modes.
Specifically, it is introduced directly into and refers to gas phase carbon compound is passed through into flowmeter for the carbon compound of gas phase at room temperature
It is introduced directly into cavity；The gas phase carbon compound includes one of methane, ethane, propane or a variety of.
Specifically, referred to by the liquid phase carbon compound that carrier gas bubbling is taken out of and be passed through liquid carbon source using carrier gas, drum
It steeps and takes liquid carbon source out of.Liquid carbon source includes one of ethyl alcohol, benzene, toluene or a variety of.
Specifically, carbon compound is volatilized heating to refer to directly in the way of heating to cavity introducing carbon
Source.Carbon source can be liquid, such as ethyl alcohol, benzene；Can be it is solid, such as polymethyl methacrylate (PMMA), naphthalene, six benzos
One of benzene, polystyrene (PS) are a variety of.
The present invention also provides a kind of carbon sources to be in situ (i.e. former to prepare amorphous carbon/nano-micrometer network thin-film method
Position contact method).The case where this method is suitable for carbon source position in situ, the original position refers to carbon source position and substrate placement region
Identical, the contact refers to carbon source and nano-micrometer Internet contact, includes the following steps:
1) one first substrate is provided, and prepares nano-micrometer network on the first substrate；
2) carbon source is prepared on the first substrate of existing nano-micrometer network, and placed it in non-in reaction cavity
Grow warm area；The air of reaction cavity is completely exhausted out, then, temperature-raising region temperature raising will be grown under the protection of reducibility gas to life
Long temperature (T1)；
3) the nano-micrometer network for being prepared for carbon source/first substrate is moved into growth warm area after temperature is stablized, and keeps certain
Time (t1), growth obtains amorphous carbon/nano-micrometer network thin-film on the first substrate；
Further, the first substrate described in above-mentioned steps 1 is the substrate for referring to support nano-micrometer network, preferably
Ground, for the substrate that carbon source decomposes potential barrier can be reduced.First substrate can be rigid, and be also possible to flexible.Specifically, it wraps
Include the substrate prepared using the methods of thermal evaporation, magnetron sputtering, electrochemistry, spin coating, chemical etching, titration；Optionally, first
Substrate includes copper, nickel, corronil, copper-iron alloy, polyimides/copper substrate, silica/copper substrate, silica/nickel substrate,
Gallium/tungsten substrate.The method for preparing nano-micrometer network can be from top to bottom, be also possible to from bottom to top.For example, commonly certainly
Upper and lower method specifically include nano-micrometer network is directly sprawled on substrate, spin coating, Best-Effort request, printing, roll-in painting
Cover, micro-nano technology or above two or a variety of methods it is integrated；Common bottom-to-top method specifically include chemical method,
Electrochemical process, direct growth method or several method it is integrated；Either from top to bottom and the combination of Self-absorption Correction Factor.
Further, in above-mentioned steps 2 that carbon source preparation is unlimited in the mode of the first substrate of existing nano-micrometer network.
Preferably, including spin-coating method, titration, evaporation.Carbon source has solid-state carbon source, including naphthalene, coronene, poly-methyl methacrylate
One or more of ester (PMMA), polystyrene (PS)；Optionally, there are one of liquid carbon source, including benzene, toluene or several
Kind；Optionally, the mixture including solid-state carbon source and liquid carbon source.Other materials can be introduced while introducing carbon source to be modified
Or doping.The method for excluding air includes being passed directly into purge gas emptying, including vacuum pump is used to empty.Purge gas is
Inert gas；Optionally, including argon gas, helium, nitrogen or the mixed gas being made of them.
Non- growth warm area described in step 2, which refers to, is not achieved growth amorphous carbon nano thin-film/nano-micrometer network required temperature
Cavity area.Growth warm area refers to cavity area corresponding to growth amorphous carbon nano thin-film/nano-micrometer network temperature
Domain.
Further, reducibility gas described in above-mentioned steps 3 is the not oxidized gas in protecting group bottom, it is preferable that
Including hydrogen, carbon monoxide.The pressure atmosphere of growth in step 3 is unlimited, can be vacuum state, can be normal pressure state,
It can be high pressure conditions, or the combination of these types of mode.Keep a period of time t1 can be according to requirement of experiment (such as: film thickness)
To set.
The present invention also provides a kind of utilization " eyes with non-contact method in situ " low-temperature epitaxy amorphous carbon/nano-micrometer network thin-films
Mode.The case where this method is suitable for carbon source position in situ, the original position refers to that carbon source position is identical as substrate placement region,
It is described it is non-contact refer to that carbon source is not contacted with nano-micrometer network, include the following steps:
1) one first substrate is provided, and prepares nano-micrometer network on the first substrate；
2) container for being loaded with carbon source is provided, the first substrate and the container that are prepared for nano-micrometer network is opposite up and down
Ground is placed on non-growth warm area in reaction cavity；It is completely exhausted out the air of reaction cavity, then, under the protection of reducibility gas
Temperature-raising region temperature raising will be grown to growth temperature (T1)；
3) carbon source is moved into growth warm area with the first substrate for being prepared for nano-micrometer network after temperature is stablized, and keeps one
Fix time (t1), and growth obtains amorphous carbon/nano-micrometer network thin-film on the first substrate；
Further, the first substrate described in above-mentioned steps 1 is the substrate for referring to support nano-micrometer network, preferably
Ground, for the substrate that carbon source decomposes potential barrier can be reduced.First substrate can be rigid, and be also possible to flexible.Specifically, it wraps
Include the substrate prepared using the methods of thermal evaporation, magnetron sputtering, electrochemistry, spin coating, chemical etching, titration；Optionally, first
Substrate includes copper, nickel, corronil, copper-iron alloy, polyimides/copper substrate, silica/copper substrate, silica/nickel substrate,
Gallium/tungsten substrate.Its method for preparing nano-micrometer network can be from top to bottom, be also possible to from bottom to top.For example, common
Top-to-bottom method specifically include nano-micrometer network is directly sprawled on substrate, spin coating, Best-Effort request, printing, roll-in apply
Cover, micro-nano technology or above two or a variety of methods it is integrated；Common bottom-to-top method specifically include chemical method,
Electrochemical process, direct growth method or several method it is integrated；Either from top to bottom and the combination of Self-absorption Correction Factor.
Further, container described in above-mentioned steps 2 is the container that can be held carbon source and not react with carbon source；Preferably, institute
Stating substrate two is one of stainless steel, quartz, glass, refractory metal, silica, aluminium oxide ceramics or a variety of.Carbon source has
One or more of solid-state carbon source, including naphthalene, coronene, polymethyl methacrylate (PMMA), polystyrene (PS)；It can
Selection of land has one or more of liquid carbon source, including benzene, toluene；Optionally, the mixing including solid-state carbon source and liquid carbon source
Object.Other materials can be introduced while introducing carbon source to be modified or adulterate.
The method that air is excluded described in step 2 includes being passed directly into purge gas emptying, including vacuum pump is used to empty.
Purge gas is inert gas；Optionally, including argon gas, helium, nitrogen or the mixed gas being made of them.Non- growth warm area
Refer to and growth amorphous carbon/nano-micrometer network required temperature cavity area is not achieved；Growth warm area refers to growth amorphous carbon
Cavity area corresponding to nano thin-film/nano-micrometer network temperature.
Further, reducibility gas described in above-mentioned steps 3 is the not oxidized gas in protecting group bottom, it is preferable that
Including hydrogen, carbon monoxide.The pressure atmosphere of growth in step 3 is unlimited, can be vacuum state, can be normal pressure state,
It can be high pressure conditions, or the combination of these types of mode.Keep a period of time t1 can be according to requirement of experiment (such as: film thickness)
To set.
Amorphous carbon provided by the invention/nano-micrometer network thin-film, amorphous c film are being filled up completely in nano-micrometer
Network pore does not cover nano-micrometer network surface, forms a kind of coplanar seamless structure.
Amorphous carbon provided by the present invention/nano-micrometer network thin-film and preparation method thereof has a characteristic that
Compared to single nano-micrometer network thin-film, amorphous c film is filled between the hole of nano-micrometer network,
This seamless film can prevent the oxidative attacks of the substances to surfaces such as electronic device, metal coatings such as external water, oxygen, phase
Compared with nano-micrometer network, there is more excellent protective value.
Amorphous carbon provided by the present invention/nano-micrometer network thin-film is maintaining original nano-micrometer network electric property
In the case of, it can equally keep corresponding light transmittance；Provided amorphous carbon/nano-micrometer network thin-film maintain it is original receive-
, can be transparent, translucent through its different thickness is controlled in the case where micron network electric property, it can also be opaque.Separately
Outside, amorphous carbon/nano-micrometer network thin-film of provided doping or modification by other elements or compound can have
Unique property, including transparent conductivity, excellent electrochemical properties, catalytic property, mechanical property etc., or have both a variety of excellent
Anisotropic energy, will open up wider purposes.Meanwhile the amorphous carbon/nano-micrometer network thin-film in certain circumstances can be with
Self-supporting.
Since amorphous c film is macroscopically presented as insulating properties, it is possible to as the barrier layer of carrier transport, every
Exhausted conduction of the carrier in face, while weakening the conduction in carrier direction in vertical plane, therefore be expected to answer as insulating layer
For electric shield field.
By the adjusting to pars amorpha thickness, it can be accordingly adjusted in upper and lower surfaces and reflects generated optical path difference,
And then the light of specific wavelength is made to generate interference cancellation, play the role of anti-reflection, is expected to be applied to area of solar cell.
It is described in detail below with reference to specific embodiment.
Embodiment 1
Step 1: by high-purity copper foil of purchase after electrochemical polish, being washed with deionized water remaining on high-purity copper foil
Electrolyte, and clean 2-3 times in acetone, alcohol, deionized water, 10 minutes every time, with being dried with nitrogen copper foil.
Step 2: freestanding carbon nanotube network thin-film 2 prepared by CVD method being spread on the first substrate 1, the present embodiment
The thickness of middle carbon nano tube network film is about 10nm, and pore size is between 20nm-1000nm.
Step 3: by the first substrate 1 back-off with carbon nano-tube film on the container 4 for filling carbon source 3, such as Fig. 1 institute
Show, and places it in one end of quartz ampoule.The present embodiment carbon source is solid-state PMMA powder, and quality is preferably 20mg, and container 4 is stone
Ying Zhou.
Step 4: purge gas is passed through into reaction cavity until air is excluded completely in cavity；The present embodiment is preferred
500sccm high-purity argon gas is purge gas, scavenging period 10min.
Step 5: after the completion of cleaning, adjusting flowmeter, temperature-raising region temperature raising will be grown under the atmosphere of hydrogen and argon gas to T1.To
After temperature is stablized, the substrate 1 for being prepared for amorphous carbon nano thin-film and container 4 are moved to the center of tube furnace together, keeps it fast
Speed is warming up to T1, grows the t1 time.In the present embodiment, hydrogen flowing quantity 30sccm, argon flow 300sccm, T1 400
DEG C, t1 40min.
Step 6: after the completion of growth, stopping heating, open tube furnace fast cooling, be cooled to room temperature closing gas circuit, take out
Sample.
Step 7: spin coating PMMA and solidifying on sample, and remove the first substrate in etching solution, then use deionization
Water rinses 2-3 times, each 10min.Laminated film can be finally transferred to target substrate, remove PMMA with acetone after drying.This
Embodiment etching solution is ferric chloride solution, concentration 0.1mol/L.
The present embodiment finally obtains amorphous carbon/carbon nano-tube coextruded film.Wherein, as shown in figure 4, carbon nano tube network
For the hole of film in 20-1000nm, thickness is about 10nm.Amorphous carbon/carbon nano-tube coextruded film the scanning finally obtained
Electron microscope picture is as shown in Figure 5, it can be seen that amorphous carbon is filled up completely between carbon nanotube, without hole；Wherein, nothing
For the thickness of setting C film in 1nm or so, corresponding Raman characterization is as shown in Figure 6.In addition, obtained amorphous carbon/carbon nanometer
Excellent electrically conducting transparent property is integrally presented in managed network laminated film.Specifically, light transmittance is up to 93% at 550nm, such as Fig. 7
It is shown；Electric conductivity is fine, almost without decaying on electric property, as shown in Figure 8.It is prepared with good clear electric conductivity
Amorphous carbon/carbon nano tube network laminated film can be used for transparent conductive electrode, solar battery, photothermal conversion, photoelectric heat and turn
It changes, photocatalysis, transparent composite, exclusion of water oxygen layer, the fields such as transparent protective layer.
Embodiment 2
Step 1-2 is consistent with the 1-2 in embodiment 1；
Step 3: the first substrate 1 with carbon nano-tube film being placed in warm area 22, as shown in Fig. 2, carbon source is placed
In heating zone 21.The present embodiment carbon source is solid-state naphthalene powder, and quality is preferably 20mg, and the container for containing carbon source is quartz boat.
Step 4: purge gas is passed through into reaction cavity until air is excluded completely in cavity；The present embodiment is preferred
500sccm high-purity argon gas is purge gas, scavenging period 10min.
Step 5: after the completion of cleaning, adjusting flowmeter, warm area 22 is warming up under the atmosphere of hydrogen and argon gas to T1.To temperature
After degree is stablized, T2, retention time t1 are reached to the heating of warm area 21.In the present embodiment, hydrogen flowing quantity 30sccm, argon flow
It is 400 DEG C for 300sccm, T1, T2 is 300 DEG C, t1 40min.
Step 6-7 is consistent with step 6-7 in embodiment 1；
The present embodiment finally obtains amorphous carbon/carbon nano-tube coextruded film.Prepared amorphous carbon amorphous carbon/carbon
Nanotube composite film is similar to the result of embodiment 1.
Embodiment 3:
Change the copper foil in embodiment 2 into corronil, corronil preparation method is as follows: with the height after annealing
Pure copper foil does cathode (the present embodiment is 25 μm), and high-purity nickel is anode, and 2-5 μm of nickel is electroplated on copper foil using electrochemical method
Film, electroplate liquid used are the nickel sulfate hexahydrate of 250g/L, 50g/L boric acid, the dodecyl of 50g/L six water nickel chloride and 0.1g/L
The mixed solution of sodium sulphate, electroplating current are set as 0.01A/cm2, electroplating time is set as 5 minutes to 30 minutes.After plating
Copper/nickel foil plate passes through 1000 DEG C of heat treatment, 2 hours formation corronils in argon gas and atmosphere of hydrogen.
Subsequent step is same as Example 1.
Embodiment result: finally obtain amorphous carbon/carbon nano-tube coextruded film, by adjusting nickel electroplating time and
Growth time can obtain amorphous carbon/carbon nano-tube coextruded film of different-thickness, and specifically, thickness can achieve 1nm
Or more.
Embodiment 4:
Step 1: cleaning silica (300nm)/silicon wafer with acetone, alcohol and deionization respectively, and with being dried with nitrogen.It will be high
Fine copper target is put into cavity, and control ar pressure is 0.6Pa, sputtering power 150W, first sputters copper film, sputtering time is 60 points
Clock；
Step 2: the sample after being sputtered being put into quartz ampoule, 800 DEG C are warming up under the protection of argon gas and hydrogen
Annealing 30 minutes, is then naturally cooling to room temperature.
Step 3 is same as Example 2 to step 7；
Finally obtain amorphous carbon/carbon nano-tube coextruded film with electrically conducting transparent property similar to Example 1.
Embodiment 5:
Step 1: cutting appropriately sized Kapton, cleaned respectively with acetone, alcohol and deionization, and use nitrogen
Drying.
Step 2: high-purity copper target being put into cavity, control ar pressure is 0.6Pa, and sputtering power 150W first sputters copper
Film, sputtering time are 5-60 minutes；
Step 3- step 5 is same as Example 2.
Step 6: after the completion of cleaning, adjusting flowmeter, warm area 22 is warming up under the atmosphere of hydrogen and argon gas to T1.To temperature
After degree is stablized, T2, retention time t1 are reached to the heating of warm area 21.In the present embodiment, hydrogen flowing quantity 40sccm, argon flow
It is 400 DEG C for 300sccm, T1, T2 is 300 DEG C, t1 50min.
Step 7: after the completion of growth, stopping heating, open tube furnace fast cooling, be cooled to room temperature closing gas circuit, take out
Sample.
Final obtain is attached to flexible polyimide substrate amorphous carbon/carbon nano-tube coextruded film.
Embodiment 6:
To be added and melamine powder and be uniformly mixed in 20mg PMMA powder in embodiment 1, wherein PMMA powder with
The mass ratio of melamine powder is between 1:1 and 10:1, other steps are in the same manner as in Example 1.
Embodiment result: the final amorphous carbon/carbon nano-tube coextruded film for obtaining N doping.
Embodiment 7:
Change the carbon nano-tube film in embodiment 1 into silver nanowires film, silver nanowires film is sprawled by spin-coating method
In on copper-based bottom, the specific steps are as follows: silver nanowires dispersion liquid is spun on copper foil, revolving speed be set as 1000-5000rpm it
Between, the copper foil for being attached with silver nanowires is then placed in 100 DEG C of heated baking 10min on hot plate by revolving speed 120s.Other steps
With embodiment 1.
Embodiment result: finally obtaining amorphous carbon/silver nanowires laminated film, adjustable by different revolving speeds
The hole and thickness of silver nanowires obtain the laminated film of different electrically conducting transparent performances.
Embodiment 8:
Step 1-2 is identical as step 1-2 in embodiment 1；
Step 3: carbon nano-tube film/copper foil being placed in cavity, and liquid phenenyl is contained in as shown in Figure 3 stainless
Steel sealing container 41, other parameters, condition are consistent.
Step 4: it is passed through purge gas emptying, it is clean to air discharge.In the present embodiment, the purge gas is high-purity
Argon, flow 500sccm.
Step 5: closing purge gas, the cavity that heats up under the protection of hydrogen and argon gas is to target temperature T1.The present embodiment
Hydrogen flowing quantity is preferably 30sccm, and argon flow 300sccm, target temperature is 150 DEG C.
Step 6: holding 32 temperature of cavity area is T1, and the container 41 of Xiang Shengyou benzene is passed through carrier gas to introduce carbon source.Wherein,
Carrier gas is high-purity argon, flow 10sccm.
Embodiment result: final obtain is grown on amorphous carbon/carbon nano-tube coextruded film on copper foil using transmission method.
Embodiment 9:
Step 1: by high-purity copper foil of purchase after electrochemical polish, remaining electrolysis on copper foil is washed with deionized water
Liquid, and clean 2-3 times in acetone, alcohol, deionized water, 10 minutes every time, with being dried with nitrogen copper foil.
Step 2: the carbon nano pipe array of horizontal growth being protected with PMMA and is transferred to copper foil, is removed after dry with acetone
PMMA；This step is repeated, obtains being transferred to the chiasma type carbon nanotube mesh structures on copper foil；
Step 3- step 6 is same as Example 8；
Embodiment result: the amorphous carbon/carbon nanotube crossover network laminated film being grown on copper foil is obtained, tune is passed through
The thickness and hole of whole chiasma type carbon nano tube network, the electrically conducting transparent property of adjustable laminated film.
Embodiment 10
Step 1-3 is identical as step 1-3 in embodiment 1；
Step 4: opening mechanical pump, air in reaction cavity is excluded completely；
Step 5: keeping vacuum pump open state, adjust flowmeter, be warming up to T1 under the atmosphere of hydrogen and argon gas.To temperature
After degree is stablized, the center that the substrate for being prepared for amorphous carbon nano thin-film and the container for being loaded with carbon source move to tube furnace together is moved
To the center of tube furnace, so that it is rapidly heated to T1, grow the t1 time.In the present embodiment, hydrogen flowing quantity 30sccm, argon gas stream
Amount is 300sccm, and T1 is 400 DEG C, t1 40min.
Step 6: after the completion of growth, stopping heating, open tube furnace fast cooling, be cooled to room temperature closing vacuum pump, chamber
Gas circuit is closed after restoring normal pressure in vivo, takes out sample.
Step 7: sample being swum in etching solution, reaction the first substrate of removal then rinses 2-3 with deionized water
It is secondary, each 10min.Finally laminated film can be transferred to target substrate.The present embodiment etching solution is ferric chloride solution, concentration
For 0.1mol/L.
Embodiment result: amorphous carbon/carbon nano-tube coextruded film is obtained.
Embodiment 11
Step 1: by high-purity copper foil of purchase after electrochemical polish, and cleaning the electrolyte remained on copper foil, blow
It is dry.
Step 2: the carbon nano-tube film continuously grown being spread on processed copper foil, and winds and is wound on runner one
End；
Step 3: carbon nano-tube film/copper foil of winding being placed in cavity, PMMA powder is placed in the glass of opening
In glass bottle, and by vial as cavity upstream, as shown in Figure 2.
Step 4: it is passed through purge gas emptying, it is clean to air discharge.In the present embodiment, the purge gas is high-purity
Argon, flow 500sccm.
Step 5: closing purge gas, the cavity that heats up under the protection of hydrogen and argon gas is to target temperature T1.The present embodiment
Hydrogen flowing quantity is preferably 30sccm, and argon flow 300sccm, target temperature is 400 DEG C.
Step 6: holding 32 temperature of cavity area is T1, and region 31 is warming up to T2, and operation of electrically driven motor transmits runner, turns
Speed is set as S1.In the present embodiment, T1 is 500 DEG C, and T2 is 60 DEG C, and runner revolving speed S1 is preferably 1rpm.
The present embodiment finally obtains the amorphous carbon/carbon nano-tube coextruded film being continuously grown on copper foil.
Embodiment 12
Step 1-2 is identical as the step 1-2 of embodiment 1；
Step 3: in one layer of PMMA of copper foil surface spin coating, and according to the mask plate photoetching set, then respectively with
S1813 and water development, fixing.For PMMA with a thickness of 200nm, development, fixing time are 60s in the present embodiment.
Step 4: sample is dried up with High Purity Nitrogen, is placed in thermal evaporation apparatus, vapor deposition gold.In the present embodiment, golden thickness
For 50nm.
Step 5: sample being taken out, the copper foil (as shown in Figure 9) for being prepared with golden grid network pattern/PMMA is obtained, is put
In one end of quartz ampoule.In the present embodiment, the width of golden grid network is 1 μm, and pore size is 2 μm.
Step 6: purge gas is passed through into reaction cavity until air is excluded completely in cavity；The present embodiment is preferred
500sccm high-purity argon gas is purge gas, scavenging period 10min.
Step 7: after the completion of cleaning, adjusting flowmeter, temperature-raising region temperature raising will be grown under the atmosphere of hydrogen and argon gas to T1.To
After temperature is stablized, the copper foil for being prepared with golden grid network pattern/PMMA is moved into the center of tube furnace, it is made to be rapidly heated to T1,
Grow the t1 time.In the present embodiment, hydrogen flowing quantity 30sccm, argon flow 300sccm, T1 are 400 DEG C, t1 40min.
Step 8: after the completion of growth, stopping heating and cooling down, take out sample.
The present embodiment finally obtains amorphous carbon/gold grid network laminated film.
Embodiment 13
Step 1-2 is identical as the step 1-2 of embodiment 1；
Step 3: carbon periosteum is spread over into copper foil surface, and one layer of PMMA of spin coating, according to the mask plate photoetching set,
Then respectively with S1813 and water development, fixing.PMMA is in the present embodiment with a thickness of 200nm, carbon periosteum with a thickness of 200nm, show
Shadow, fixing time are 60s.
Step 4: sample is taken out, RIE chamber is put into, the carbon periosteum that do not protected by PMMA using high-energy ion bombardment.This
In embodiment, etching gas is oxygen, etch period 100s.
Step 5: sample being taken out, the copper foil for having periodical carbon managed network pattern formed after photoetching, RIE etching is obtained.
Carbon managed network pattern/PMMA copper foil will be prepared with and be placed on one end of quartz ampoule.In the present embodiment, the grid width of carbon managed network is 10
μm, pore size is 50 μm.
Step 6: it is passed through purge gas emptying, it is clean to air discharge.In the present embodiment, the purge gas is high-purity
Argon, flow 500sccm.
Step 7: closing purge gas, the cavity that heats up under the protection of hydrogen and argon gas is to target temperature T1.The present embodiment
Hydrogen flowing quantity is preferably 30sccm, and argon flow 300sccm, target temperature is 500 DEG C.
Step 8: stopping heating after the completion of growth, take out sample.
The present embodiment finally obtains amorphous carbon/carbon managed network laminated film.
Embodiment 14
Step 1: by high-purity copper foil of purchase after electrochemical polish, being washed with deionized water remaining on high-purity copper foil
Electrolyte, and clean 2-3 times in acetone, alcohol, deionized water, 10 minutes every time, with being dried with nitrogen copper foil.
Step 2: freestanding carbon nanotube film 2 prepared by CVD method being spread on the first substrate 1, carbon in the present embodiment
Nano-tube film with a thickness of 20nm, the self-supporting amorphous carbon nano thin-film pore size is between 0.1nm-20nm.
Step 3-6 is identical as 3-6 in embodiment 1.
Step 7: preparing in etching solution, and remove the first substrate using etching solution, then rinse 2-3 with deionized water
It is secondary, each 10min.Finally laminated film can be transferred to target substrate.The present embodiment etching solution is iron chloride, solution concentration
For 0.1mol/L.
The present embodiment finally obtains amorphous carbon/carbon nano-tube coextruded film of self-supporting.
Low-temperature synthetic method mentioned in the present invention selects the hydrocarbon with low bond energy as low temperature carbon source, low
The carbon source (such as naphthalene, PMMA) of decomposition temperature has lower decomposition gesture compared to conventional high decomposition temperature carbon source (such as methane)
It builds, reduces the growth temperature of amorphous carbon nano thin-film on the whole significantly, and the reduction of temperature is micro- to amorphous carbon/receive-
Industrialized realize of rice network thin-film has very great meaning, and energy consumption is greatly reduced in this, reduces production cost, is
Further large-scale growth is laid a good foundation.
Low-temperature synthetic method mentioned above is conducive to the pattern and excellent properties that keep nano-micrometer network thin-film script,
Especially guarantee original electrical properties.This is because nano-micrometer network has the characteristics that small size and high-specific surface area, compared with block
For body material, surface energy is high, specific surface atom number is more and near neighboring coordination is not complete, so fusing point is often lower, therefore temperature
It is easy to occur itself to melt or decompose when spending higher；On the other hand, it is also likely to be present between substrate and nano-micrometer network co-melting
Or it reacts and destroys original network structure, thus pyroprocess can reduce the excellent of nano-micrometer reticulated film script
Property even destroys original nano-micrometer reticulated film structure, so the realization of low-temperature epitaxy is for improving the whole of laminated film
Volume property also seems particularly critical.
Low-temperature synthetic method mentioned in the present invention, by selection can low-temperature decomposition carbon source, can down to 200 DEG C with
Growing mixed film under conditions of lower, this mode can expand laminated film and grow in the flexible substrate of non-refractory, in turn
The application prospect of laminated film is expanded.
Amorphous carbon provided by the present invention/nano-micrometer network thin-film preparation method carries out at low temperature.In low temperature
Under, substrate is low to the solubility of carbon atom, meanwhile, substrate surface is solid-state, the mistake of the carbon atom of decomposition vertical no precipitation in
Journey, therefore, under the action of substrate, amorphous carbon is only grown on the surface of no nano-micrometer network coverage, and it is fixed to form a kind of nothing
Shape carbon structure coplanar with nano-micrometer network and seamless therebetween.In addition, the amorphous carbon of this growth pattern growth is thick
Degree uniformly, it is controllable, atomic-level thickness amorphous c film can be formed, have to be substantially distinguished from and prepared by conventional thermal evaporation methods
Amorphous carbon thickness thickness and non-uniform feature.
So far, although those skilled in the art will appreciate that present invention has been shown and described in detail herein is exemplary
Embodiment still without departing from the spirit and scope of the present invention, can still directly determine according to the present disclosure
Or derive many other variations or modifications consistent with the principles of the invention.Therefore, the scope of the invention should be understood and defined as
Cover all such other variations or modifications.
Claims (10)
1. a kind of amorphous carbon/nano-micrometer network thin-film characterized by comprising amorphous carbon and nano-micrometer network, it is described
The hole of nano-micrometer network is filled up completely by amorphous carbon, to form a kind of coplanar, imporous laminated film；The nothing is fixed
Shape carbon is the two-dimentional amorphous carbon nano thin-film being made of carbon atom.
2. amorphous carbon according to claim 1/nano-micrometer network thin-film, which is characterized in that the two dimension amorphous carbon
Nano thin-film is made of pure carbon.
3. amorphous carbon according to claim 1/nano-micrometer network thin-film, which is characterized in that the two dimension amorphous carbon
Nano thin-film has other element dopings or modification, including any one or more of combination of nitrogen, boron, silicon, hydrogen, oxygen.
4. amorphous carbon according to claim 1/nano-micrometer network thin-film, which is characterized in that the nano-micrometer network
With porous network structure, the size of the porous network structure is distributed in nanometer to micro-meter scale.
5. amorphous carbon according to claim 1/nano-micrometer network thin-film, which is characterized in that the nano-micrometer network
Including conductive network and non-conductive network；The conductive network includes metalolic network or semiconductor network；The non-conductive network
Including the volume grid that insulate.
6. amorphous carbon according to claim 1/nano-micrometer network thin-film, which is characterized in that the amorphous carbon and institute
It states and is combined by way of secondary or physical bond and chemical bond between nano-micrometer network.
7. a kind of amorphous carbon/nano-micrometer network thin-film preparation method, which comprises the following steps:
Nano-micrometer network is prepared on substrate, and is put into reaction cavity；
Carbon source is introduced, grows amorphous carbon in hole to form amorphous carbon/nano-micrometer network thin-film.
8. preparation method according to claim 7, which is characterized in that the substrate is the lining of sustainable nano-micrometer network
Bottom.
9. preparation method according to claim 7, which is characterized in that other elements can be introduced while the introducing carbon source
It is modified or adulterates.
10. preparation method according to claim 7, which is characterized in that the carbon source include gaseous carbon source, liquid carbon source and
Any one or more of combination of solid-state carbon source.
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