CN103310905A - Method for manufacturing nano-composite conductive thin film and nano-composite conductive thin film - Google Patents
Method for manufacturing nano-composite conductive thin film and nano-composite conductive thin film Download PDFInfo
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Abstract
The embodiment of the invention discloses a method for manufacturing a nano-composite conductive thin film. The method comprises the steps of forming a first organic nano material thin film layer on a substrate, and obtaining a first organic conductive thin film layer through reduction treatment; forming a conductive polymer thin film layer on the first organic conductive thin film layer; forming a second organic nano material thin film layer on the conductive polymer thin film layer, and obtaining a second organic conductive thin film layer through reduction treatment; and obtaining a composite conductive thin film by separating each layer from the substrate. According to the embodiment of the invention, the thickness of the nano-composite conductive thin film can be regulated and controlled through the layer number of organic nano thin films and/or conductive polymer thin films, high specific surface area, high mechanism strength, high conductivity and the like of the thin film can be realized, the manufacturing method is reasonable and simple, and the operation is easy.
Description
Technical field
The present invention relates to electronic material and components and parts field, particularly relate to a kind of method and composite conductive thin film thereof of making nano combined conductive film.
Background technology
Along with the exhaustion of traditional fossil energy and the aggravation of environmental problem, the development and use of clean energy resource and storage are just receiving increasing concern, and electric energy then is one of them important branch.When the storage of research electric energy, people not only can provide stable energy but also can satisfy the storage device of transient high power demand more and more interested for a long time to the sort of.Ultracapacitor, a kind of energy storage device between ordinary capacitor and battery is high because of its power density, energy density is high, have extended cycle life, maintenance cost low and the practical application in electric automobile, just is being subject to increasing attention.
At present, be one of main research aspect of ultracapacitor to the exploitation of electrode material for super capacitor, and conducting polymer, material with carbon element and metal oxide are the three class electrode materials of studying at most.Polyaniline, polypyrrole and polythiophene are the conducting polymers of commonly using.Under certain condition, by chemistry or electrochemical doping, the conductivity of conducting polymer can change in the broad range of insulator, semiconductor and metallic conductor, so no matter be the research to them is always a lot of in the academic research or in commercial Application.But, compare with traditional high molecular polymer.The aerial stability of conducting polymer, machinability and mechanical performance will differ from, and the conductivity of conducting polymer depends on their backbone structure, character and the doping level of dopant consumingly.Based on the characteristics of conducting polymer, for different application, add specific material and make it to form compound with conducting polymer, thereby reach the purpose of learning from other's strong points to offset one's weaknesses, improve material property.In the research of electrode material for super capacitor, activated carbon, carbon fiber, carbon nano-tube etc. often are used to conducting polymer compound, are exactly for comprehensive two materials advantage separately.
But in the method for the nano combined electric conducting material of existing manufacturing, thickness is difficult for regulating usually, and is difficult to take into account high-specific surface area, high mechanical properties and high conductivity, and pollution is larger, the method for operation more complicated.
Summary of the invention
One of purpose of the present invention provides a kind of nano combined conductive film thickness easily method and the nano combined conductive film thereof of the nano combined conductive film of manufacturing of adjusting.
One of purpose of the present invention provides a kind of method and the nano combined conductive film thereof that can realize the nano combined conductive film of manufacturing of high-specific surface area, high mechanical properties and high conductivity.
One of purpose of the present invention provides a kind of method and nano combined conductive film thereof that pollutes the little nano combined conductive film of manufacturing.
The disclosed technical scheme of the embodiment of the invention comprises:
A kind of method of making nano combined conductive film is characterized in that, comprising: form the first organic nano material thin layer at substrate; Described the first organic nano material thin layer is reduced processing, obtain the first electroconductive organic film layer; Form the conducting polymer thin film layer at described the first electroconductive organic film layer; Form the second organic nano material thin layer at described conducting polymer thin film layer; Described the second organic nano material thin layer is reduced processing, obtain the second electroconductive organic film layer; The film that described the first conductive membrane layer, described conducting polymer thin film layer and described the second electroconductive organic film layer form is peeled off from described substrate, obtained described composite conductive thin film.
Further, wherein saidly form the first organic nano material thin layer at substrate and comprise: the first organic nano material is dissolved in the first solvent, obtains the first organic nano material particle dispersing solution; Described the first organic nano material particle dispersing solution is added drop-wise to the first parfacies surface, so that described the first organic nano material particle disperses to spread in described the first parfacies surface; Compression spreads in the described first organic nano material particle on described the first parfacies surface, forms the first organic nano material particle membrane; Described the first organic nano material particle membrane is transferred on the described substrate, formed the first organic nano material thin layer at described substrate.
Further, described the first organic nano material is the graphene oxide that graphene oxide or nitrogen mix; Described the first solvent is the mixed solution of deionized water and methyl alcohol; Described the first parfacies is ultra-pure water.
Further, wherein saidly form the conducting polymer thin film layer at described the first electroconductive organic film layer and comprise: oxidant is dissolved in the organic solvent, obtains oxidizing agent solution; Described oxidizing agent solution is coated on described the first electroconductive organic film layer; After on described oxidizing agent solution being coated to described the first electroconductive organic film layer, described substrate is placed the conducting polymer monomer atmosphere scheduled time.
Further, described oxidant is toluene sulfonic acide iron or ferric trichloride; Described organic solvent is isopropyl alcohol or n-butanol; Described conducting polymer monomer is 3,4-ethylene dioxythiophene, aniline or pyrroles.
Further, wherein said at described conducting polymer thin film layer formation the second organic nano material thin layer: as the second organic nano material to be dissolved in the second solvent, to obtain the second organic nano material particle dispersing solution; Described the second organic nano material particle dispersing solution is added drop-wise to the second parfacies surface, so that described the second organic nano material particle disperses to spread in described the second parfacies surface; Compression spreads in the described second organic nano material particle on described the second parfacies surface, forms the second organic nano material particle membrane; Described the second organic nano material particle membrane is transferred on the described conducting polymer thin film layer, formed the second organic nano material thin layer at described conducting polymer thin film layer.
Further, described the second organic nano material is the graphene oxide that graphene oxide or nitrogen mix; Described the second solvent is the mixed solution of deionized water and methyl alcohol; Described the second parfacies is ultra-pure water.
Further, described described the first organic nano material thin layer is reduced to process comprise: the described substrate that will form described the first organic nano material thin layer places hydroiodic acid or glucose solution and heating water bath; Described described the second organic nano material thin layer is reduced to process comprise: the described substrate that will form described the second organic nano material thin layer places hydroiodic acid or glucose solution and heating water bath.
Embodiments of the invention also provide a kind of nano combined conductive film, and its special medical treatment is, comprising: the first electroconductive organic film layer; Conducting polymer thin film layer, described conducting polymer thin film layer are formed on described the first electroconductive organic film layer; The second electroconductive organic film layer, described the second electroconductive organic film layer is formed on the described conducting polymer thin film layer.
Further, described the first electroconductive organic film layer is the graphene oxide layer that the graphene oxide layer that has been reduced or the nitrogen that has been reduced mix; Described conducting polymer thin film layer is poly-3,4-ethylene dioxythiophene layer, polyaniline layer or polypyrrole layer; Described the second electroconductive organic film layer is the graphene oxide layer that the graphene oxide layer that has been reduced or the nitrogen that has been reduced mix.
In the embodiments of the invention, at first form organic nano film and reduce, then prepare conducting polymer thin film at the organic conductive nano thin-film, at last at conducting polymer thin film preparation organic nano film and reduce, thereby obtain the nano combined conducting membrane structure of organic conductive material-conducting polymer-organic conductive material, the thickness of this nano combined conductive film can be regulated and control by the number of plies of organic nano film and/or conducting polymer thin film.And the film forming on realization large tracts of land film forming and the flexible substrates.This organic conductive material-conducting polymer thin film-electroconductive organic film structure can be realized high-specific surface area, high mechanical properties and the high conductivity etc. of film.In addition, adopt hydroiodic acid or glucose as reducing agent, avoided the pollution because using hydrazine hydrate to produce as reducing agent, and improved reduction efficiency.This film can be peeled off from substrate and form independently film, satisfies different components to the requirement of material conductivity.The preparation method is rationally simple, easy operating.
Description of drawings
Fig. 1 is the schematic flow sheet of method of the nano combined conductive film of manufacturing of one embodiment of the invention.
Fig. 2 is the schematic top plan view of LB film-forming apparatus.
Fig. 3 is the structural representation of the nano combined conductive film of one embodiment of the invention.
Embodiment
As shown in Figure 1, in the one embodiment of the invention, a kind of method of making nano combined conductive film comprises step 10, step 12, step 14, step 16 and step 20.Below with reference to this embodiment these steps are conducted further description and illustrate.
Step 10: form the first organic nano material thin layer at substrate.
In the method for the nano combined conductive film of manufacturing of embodiments of the invention, can use substrate as auxiliary, form needed nano combined conductive film at substrate, then peel off film after the formation from substrate, can obtain needed nano combined conductive film.
Therefore, in the embodiments of the invention, at first can form the first organic nano material thin layer at substrate.In the embodiments of the invention, substrate can be the substrate of any suitable type, for example, among the embodiment, substrate can be the substrate of being made by quartz, silicon chip or tin indium oxide (ITO), perhaps also can be the substrate of the flexible substrates formation of other suitable type, can be according to the needs flexible choice of actual conditions.
In the embodiments of the invention, before substrate forms the first organic nano material thin layer, can also carry out various suitable processing to substrate, for example clean, hydrophilic treated or other help to form at substrate any suitable processing of the first organic nano material film.
In the embodiments of the invention, " the first organic nano material " here can be any suitable organic nano material, and for example, among the embodiment, the first organic nano material can be the graphene oxide that graphene oxide or nitrogen mix.Here, the first concrete organic nano material can be according to the needs of actual conditions and flexible choice is not limited in the graphene oxide that graphene oxide above-mentioned or nitrogen mix.
In the embodiments of the invention, can use any suitable method to form the first organic nano material thin layer at substrate, for example, among the embodiment, can use LB(Langmuir-Blodgett) film build method forms the first organic material film layer at substrate.
At this moment, among the embodiment, form the first organic nano material thin layer at substrate and comprise the following steps.
At first, the first organic nano material is dissolved in the first solvent, obtains the first organic nano material particle dispersing solution.At this moment, as mentioned before, the first organic nano material can be the graphene oxide that graphene oxide or nitrogen mix; The first solvent can be any volatile solution that is suitable for dissolving this first organic nano material, can be according to the kind of the first organic nano material and flexible choice, and for example, among the embodiment, the first solvent can be the mixed solution of deionized water and methyl alcohol.
Secondly, this first organic nano material particle dispersing solution is added drop-wise to the first parfacies surface, so that the first organic nano material particle disperses to spread in this first parfacies surface.Here, the first parfacies can be that any being suitable for disperses to sprawl thereon liquid for the first organic nano material particle, for example can be ultra-pure water.At this moment, after the first organic nano material particle dispersing solution was added drop-wise to the first parfacies surface, the first solvent can disperse drawout on the first parfacies surface with the first organic nano material particle.Through after the certain hour, the first solvent evaporates, like this, the first organic nano material particle that stays wherein disperses to spread on the surface of parfacies.
Again, compression spreads in the first organic nano material particle on the first parfacies surface, thereby forms the first organic nano material particle membrane on the first parfacies surface.Usually, the LB film build method can carry out in LB film-forming apparatus (described below), at this moment, after the first solvent evaporates, in the LB film-forming apparatus, use the first organic nano material particle on sliding barrier compression the first parfacies surface to the film forming mould, thereby form the first organic nano material particle membrane on the first parfacies surface.
At last, this first organic nano material particle membrane is transferred on the substrate, thereby formed the first organic nano material thin layer at substrate.The first organic nano material particle membrane is transferred to on-chip method can use any suitable film transfer method, such as vertical czochralski method, horizontal attachment method or parfacies reduction method etc.These methods are the common methods in the LB film build method, do not repeat them here.
One of ordinary skill in the art will readily recognize that the first organic nano material particle thin layer that forms at substrate can be one deck, also can be multilayer, can be according to the actual needs and set flexibly, such as 3 layers, 5 layers or 10 layers etc.The size of the first organic nano material particle also can arrange flexibly according to the needs of actual conditions.
As mentioned before, the LB film build method can carry out in the LB film-forming apparatus.Fig. 2 illustrates the schematic top plan view of a LB film-forming apparatus among the embodiment, wherein the first parfacies (for example, ultra-pure water) 2 is contained in the LB film groove 1, the first organic nano material particle membrane 3 is formed on the surface of the first parfacies 2, sliding barrier 5 compressions of LB film groove the first organic nano material particle membrane 3 is to the film forming mould, substrate 4 is connected to LB film groove rotation axis 6, and this LB film groove rotation axis 6 drives substrate 4 motions, thereby with horizontal attachment method the first organic nano material particle membrane 3 is transferred on the substrate 4.
Step 12: reduction is processed, and obtains the first electroconductive organic film layer.
After substrate has formed the first organic nano material thin layer, can reduce processing to on-chip this first organic nano material thin layer, thereby so that the first organic nano material in this first organic nano material thin layer is reduced, for example, graphene oxide is reduced into Graphene, etc., thereby so that the first organic nano material thin layer after the reduction forms the first electroconductive organic film layer.
In the embodiments of the invention, can use any suitable method of reducing that the first organic nano material thin layer is carried out.For example, among the embodiment, can this substrate that will form the first organic nano material thin layer place hydroiodic acid or glucose solution and heating water bath regular hour, thereby so that the first organic nano material (for example, graphene oxide) be reduced.Wherein the time of heating water bath can decide according to actual conditions, for example, can be 10 hours, can certainly be other any reasonable time.
Step 14: form the conducting polymer thin film layer at the first electroconductive organic film layer.
After having formed the first electroconductive organic film layer, can further form the conducting polymer thin film layer at this first electroconductive organic film layer.In the embodiments of the invention, the kind of the conducting polymer here can be any suitable wire polymer, can be according to the needs flexible choice of actual conditions, for example, among the embodiment, the conducting polymer here can be poly-3,4-ethylenedioxy thiophene, polyaniline or polypyrrole, namely the conducting polymer thin film layer here can be poly-3,4-ethylene dioxythiophene layer, polyaniline layer or polypyrrole layer, etc.
In the embodiments of the invention, forming the conducting polymer thin film layer at the first electroconductive organic film layer can comprise the following steps.
At first, oxidant is dissolved in the organic solvent, obtains oxidizing agent solution.In the embodiment of the invention, oxidant is as the synthetic reaction material of chemical oxidising polymerisation, its electron gain and cause conducting polymer monomer polymerization reaction take place from conducting polymer monomer (described below).Therefore, in the embodiment of the invention, this oxidant can be any material that can cause corresponding conducting polymer monomer polymerization reaction take place, for example can be ferric trichloride or toluene sulfonic acide iron etc.; Organic solvent can be to be suitable for aforementioned oxidant to be dissolved in wherein any suitable solvent, for example isopropyl alcohol or n-butanol etc.
Then, the oxidizing agent solution that obtains is coated on the first electroconductive organic film layer.Here, can use any suitable coating method that oxidizing agent solution is coated on the first electroconductive organic film layer, for example spin-coating method etc.
At last, on oxidizing agent solution being coated to the first electroconductive organic film layer after, this substrate (had coated on it the first electroconductive organic film layer of oxidizing agent solution) is placed the conducting polymer monomer atmosphere scheduled time.Here, the conducting polymer monomer can be the monomer of aforesaid poly-3,4-ethylene dioxythiophene, polyaniline or polypyrrole, namely can be 3,4-ethylene dioxythiophene, aniline layer or pyrroles.Conducting polymer monomer atmosphere can obtain by mode commonly used in this area, for example, the acquisition of conducting polymer monomer atmosphere can be by the conducting polymer monomer solution is added dropwise in the container, because the conducting polymer monomer solution has stronger volatility, thereby can in container, form conducting polymer monomer molecule atmosphere, etc.Here, the concrete value of being somebody's turn to do " scheduled time " can be set flexibly according to actual conditions, and for example, among the embodiment, this scheduled time can be 80 to 100 minutes.
The substrate of the first electroconductive organic film layer that will have oxidizing agent solution coated places after the conducting polymer monomer atmosphere, oxidant can and cause conducting polymer monomer molecule polymerization reaction take place from conducting polymer monomer molecule electron gain, thereby forms the conducting polymer thin film layer by the mode of chemical gaseous phase aggregation deposition at this first electroconductive organic film layer.
Step 16: form the second organic nano material thin layer at the conducting polymer thin film layer.
In the embodiments of the invention, formed after the conducting polymer thin film layer, can further form the second organic nano material thin layer at the conducting polymer thin film layer.
In the embodiments of the invention, with similar in the step 10, " the second organic nano material " here can be any suitable organic nano material, for example, among the embodiment, the second organic nano material can be the graphene oxide that graphene oxide or nitrogen mix.Here, the second concrete organic nano material can be according to the needs of actual conditions and flexible choice is not limited in the graphene oxide that graphene oxide above-mentioned or nitrogen mix.
In the embodiments of the invention, with similar in the step 10, can use any suitable method to form the second organic nano material thin layer at substrate, for example, among the embodiment, can use LB(Langmuir-Blodgett) film build method forms the second organic material film layer at substrate.
At this moment, among the embodiment, form the second organic nano material thin layer at the conducting polymer thin film layer and comprise the following steps.
At first, the second organic nano material is dissolved in the second solvent, obtains the second organic nano material particle dispersing solution.At this moment, as mentioned before, the second organic nano material can be the graphene oxide that graphene oxide or nitrogen mix; The second solvent can be any volatile solution that is suitable for dissolving this second organic nano material, can be according to the kind of the second organic nano material and flexible choice, and for example, among the embodiment, the second solvent can be the mixed solution of deionized water and methyl alcohol.
Secondly, this second organic nano material particle dispersing solution is added drop-wise to the second parfacies surface, so that the second organic nano material particle disperses to spread in this second parfacies surface.Here, the second parfacies can be that any being suitable for disperses to sprawl thereon liquid for the second organic nano material particle, for example can be ultra-pure water.At this moment, after the second organic nano material particle dispersing solution was added drop-wise to the second parfacies surface, the second solvent can disperse drawout on the second parfacies surface with the second organic nano material particle.Through after the certain hour, the second solvent evaporates, like this, the second organic nano material particle that stays wherein disperses to spread on the surface of parfacies.
Again, compression spreads in the second organic nano material particle on the second parfacies surface, thereby forms the second organic nano material particle membrane on the second parfacies surface.Usually, the LB film build method can carry out in LB film-forming apparatus (described below), at this moment, after the second solvent evaporates, in the LB film-forming apparatus, use the second organic nano material particle on sliding barrier compression the second parfacies surface to the film forming mould, thereby form the second organic nano material particle membrane on the second parfacies surface.
At last, this second organic nano material particle membrane is transferred on the substrate, thereby formed the second organic nano material thin layer at substrate.The second organic nano material particle membrane is transferred to on-chip method can use any suitable film transfer method, such as vertical czochralski method, horizontal attachment method or parfacies reduction method etc.These methods are the common methods in the LB film build method, do not repeat them here.
One of ordinary skill in the art will readily recognize that the second organic nano material particle thin layer that forms at substrate can be one deck, also can be multilayer, can be according to the actual needs and set flexibly, such as 3 layers, 5 layers or 10 layers etc.The size of the second organic nano material particle also can arrange flexibly according to the needs of actual conditions.
With similar in the step 10, the step of formation the second organic nano material thin layer in the step 16 also can be finished in LB film-forming apparatus shown in Figure 2, does not repeat them here.
Step 18: reduction is processed, and obtains the second electroconductive organic film layer.
After substrate has formed the second organic nano material thin layer, can reduce processing to on-chip this second organic nano material thin layer, thereby so that the second organic nano material in this second organic nano material thin layer is reduced, for example, graphene oxide is reduced into Graphene, etc., thereby so that the second organic nano material thin layer after the reduction forms the second electroconductive organic film layer.
In the embodiments of the invention, can use any suitable method of reducing that the second organic nano material thin layer is carried out.For example, among the embodiment, can this substrate that will form the second organic nano material thin layer place hydroiodic acid or glucose solution and heating water bath regular hour, thereby so that the second organic nano material (for example, graphene oxide) be reduced.Wherein the time of heating water bath can decide according to actual conditions, for example, can be 10 hours, can certainly be other any reasonable time.
Step 20: the film of peeling off each layer formation from substrate.
After abovementioned steps 10, step 12, step 14, step 16, step 18 are finished, formed the first conductive membrane layer, conducting polymer thin film layer and the second electroconductive organic film layer at substrate, this first conductive membrane layer, conducting polymer thin film layer and the second electroconductive organic film layer have formed jointly at on-chip film.This film can be peeled off it after forming from substrate, this film that strips down is the nano combined conductive film of embodiments of the invention manufacturing.This nano combined conductive film has the structure of " the first conductive membrane layer-conducting polymer thin film layer-second electroconductive organic film layer ".
In one embodiment of the present of invention, can place the sodium hydroxide solution regular hour to make the film separation of this " the first conductive membrane layer-conducting polymer thin film layer-second electroconductive organic film layer " by making through the substrate after step 10, step 12, step 14, step 16 and the step 18.Here, the concentration of sodium hydroxide solution can be selected according to actual conditions, for example can select 0.1 mol/L (mol/L), can certainly select other suitable concentration value.The time that substrate is put in sodium hydroxide solution can for example can be 15 minutes according to the actual conditions flexible choice also, etc.
For example, in one embodiment of the present of invention, a kind of method of making nano combined conductive film comprises the following steps: particularly
1. graphene oxide (GO) is dissolved in deionized water/methanol solution of mass ratio 1:5, the concentration of GO is the 0.5mg/ml(mg/ml), form finely disseminated GO solution;
2. toluene sulfonic acide iron is dissolved in aqueous isopropanol, the concentration of toluene sulfonic acide iron is 0.4～0.5g/ml(grams per milliliter);
3. adopt microsyringe to extract 150 μ l(microlitres) solution 1. drip ultra-pure water surface in LB film groove so that GO sprawls on the ultra-pure water surface;
4. control the GO on the sliding barrier compression of LB film groove ultra-pure water surface to the film forming mould, GO film forming mould is 25～30mN/m(milli ox/rice);
5. adopt the flat thin film-forming method of LB film water at the ITO of cleaning surfaces substrate deposition GO film;
6. with the oven dry under 95～100 ℃ of GO film, then the GO film is placed hydroiodic acid or glucose solution and heating water bath 10 hours, obtain redox graphene (rGO);
7. adopt spin coating instrument spin coating Fe (OT on the GO film
s)
3(toluene sulfonic acide iron) solution, revolution is the 1500-2000rps(revolution per second), then film is dried;
The film that 8. will 7. obtain places EDOT(3, the 4-ethylenedioxy thiophene) in the monomer atmosphere, be formed with the poly-3,4-ethylene dioxythiophene of organic polymer PEDOT(at film);
9. repeat 3. 4., adopt the flat thin film-forming method of LB film water at conducting polymer thin film deposition GO film;
10. repeat 6., then film is placed NaOH solution, film separation;
Thereby form the nano combined conducting membrane structure of a kind of independently rGO-PEDOT-rGO.
In the another embodiment of the present invention, similar among the preparation process of nano combined conductive film and the upper embodiment, difference is that conducting polymer is not the poly-3,4-ethylene dioxythiophene of PEDOT(), but polypyrrole.Because conducting polymer materials is polypyrrole, thereby obtains the composite Nano conducting membrane structure of redox graphene-polypyrrole-redox graphene.
In the another embodiment of the present invention, similar among the preparation process of nano combined conductive film and the upper embodiment, difference is that conducting polymer is not the poly-3,4-ethylene dioxythiophene of PEDOT(), but polyaniline.Because conducting polymer materials is polyaniline, thereby obtains the composite Nano conducting membrane structure of redox graphene-polyaniline-redox graphene.
In the embodiments of the invention, before step 20, aforesaid step 14 and/or step 16,18 can repeat repeatedly, namely so that in the film that substrate forms, comprise a plurality of conducting polymer thin film layers and/or the second electroconductive organic film layer, quantity and the position relationship between each layer of these layers can arrange as required flexibly, for example, can be arranged alternately between each layer, etc.
Fig. 3 is the structural representation according to the nano combined conductive film of the method manufacturing of an aforesaid embodiment of the present invention.Among this embodiment, nano combined conductive film comprises the first electroconductive organic film layer 7, conducting polymer thin film layer 8 and the second electroconductive organic film layer 9, wherein conducting polymer thin film layer 8 is formed on the first electroconductive organic film layer 7, and the second electroconductive organic film layer 9 is formed on the conducting polymer thin film layer 8.
Among the embodiment, this first electroconductive organic film layer is the graphene oxide layer that the graphene oxide layer that has been reduced or the nitrogen that has been reduced mix.This conducting polymer thin film layer is poly-3,4-ethylene dioxythiophene layer, polyaniline layer or polypyrrole layer.This second electroconductive organic film layer is the graphene oxide layer that the graphene oxide layer that has been reduced or the nitrogen that has been reduced mix.
In the embodiments of the invention, this first electroconductive organic film layer can be identical with this second electroconductive organic film layer, also can be different.
In the embodiments of the invention, at first form organic nano film and reduce, then prepare conducting polymer thin film at the organic conductive nano thin-film, at last at conducting polymer thin film preparation organic nano film and reduce, thereby obtain the nano combined conducting membrane structure of organic conductive material-conducting polymer-organic conductive material, the thickness of this nano combined conductive film can be regulated and control by the number of plies of organic nano film and/or conducting polymer thin film.And the film forming on realization large tracts of land film forming and the flexible substrates.This organic conductive material-conducting polymer thin film-electroconductive organic film structure can be realized high-specific surface area, high mechanical properties and the high conductivity etc. of film.In addition, adopt hydroiodic acid or glucose as reducing agent, avoided the pollution because using hydrazine hydrate to produce as reducing agent, and improved reduction efficiency.This film can be peeled off from substrate and form independently film, satisfies different components to the requirement of material conductivity.The preparation method is rationally simple, easy operating.
In the embodiments of the invention, in the preparation of nano thin-film, introduce the membrane structure that the LB membrane technology can obtain high density, ordered arrangement, so that effectively brought into play through the organic nano material conductivity of reduction processing.Organic nano material can form good dispersion soln in solvent, guarantee that LB film deposition rear film has good uniformity and compactness.
Abovely describe the present invention by specific embodiment, but the present invention is not limited to these specific embodiments.It will be understood by those skilled in the art that and can also make various modifications to the present invention, be equal to replacement, change etc., these conversion all should be within protection scope of the present invention as long as do not deviate from spirit of the present invention.In addition, the different embodiment of above many places described " embodiment " expression can certainly be with its all or part of combination in one embodiment.
Claims (10)
1. a method of making nano combined conductive film is characterized in that, comprising:
Form the first organic nano material thin layer at substrate;
Described the first organic nano material thin layer is reduced processing, obtain the first electroconductive organic film layer;
Form the conducting polymer thin film layer at described the first electroconductive organic film layer;
Form the second organic nano material thin layer at described conducting polymer thin film layer;
Described the second organic nano material thin layer is reduced processing, obtain the second electroconductive organic film layer;
The film that described the first conductive membrane layer, described conducting polymer thin film layer and described the second electroconductive organic film layer form is peeled off from described substrate, obtained described composite conductive thin film.
2. the method for claim 1 is characterized in that, wherein saidly forms the first organic nano material thin layer at substrate and comprises:
The first organic nano material is dissolved in the first solvent, obtains the first organic nano material particle dispersing solution;
Described the first organic nano material particle dispersing solution is added drop-wise to the first parfacies surface, so that described the first organic nano material particle disperses to spread in described the first parfacies surface;
Compression spreads in the described first organic nano material particle on described the first parfacies surface, forms the first organic nano material particle membrane;
Described the first organic nano material particle membrane is transferred on the described substrate, formed the first organic nano material thin layer at described substrate.
3. method as claimed in claim 2 is characterized in that: described the first organic nano material is the graphene oxide that graphene oxide or nitrogen mix; Described the first solvent is the mixed solution of deionized water and methyl alcohol; Described the first parfacies is ultra-pure water.
4. the method for claim 1, its special medical treatment be, wherein saidly forms the conducting polymer thin film layer at described the first electroconductive organic film layer and comprise:
Oxidant is dissolved in the organic solvent, obtains oxidizing agent solution;
Described oxidizing agent solution is coated on described the first electroconductive organic film layer;
After on described oxidizing agent solution being coated to described the first electroconductive organic film layer, described substrate is placed the conducting polymer monomer atmosphere scheduled time.
5. method as claimed in claim 4, its special medical treatment is: described oxidant is toluene sulfonic acide iron or ferric trichloride; Described organic solvent is isopropyl alcohol or n-butanol; Described conducting polymer monomer is 3,4-ethylene dioxythiophene, aniline or pyrroles.
6. the method for claim 1 is characterized in that, and is wherein said at described conducting polymer thin film layer formation the second organic nano material thin layer:
The second organic nano material is dissolved in the second solvent, obtains the second organic nano material particle dispersing solution;
Described the second organic nano material particle dispersing solution is added drop-wise to the second parfacies surface, so that described the second organic nano material particle disperses to spread in described the second parfacies surface;
Compression spreads in the described second organic nano material particle on described the second parfacies surface, forms the second organic nano material particle membrane;
Described the second organic nano material particle membrane is transferred on the described conducting polymer thin film layer, formed the second organic nano material thin layer at described conducting polymer thin film layer.
7. method as claimed in claim 6 is characterized in that: described the second organic nano material is the graphene oxide that graphene oxide or nitrogen mix; Described the second solvent is the mixed solution of deionized water and methyl alcohol; Described the second parfacies is ultra-pure water.
8. the method for claim 1 is characterized in that:
Described described the first organic nano material thin layer is reduced to process comprise:
The described substrate that has formed described the first organic nano material thin layer is placed hydroiodic acid or glucose solution and heating water bath;
Described described the second organic nano material thin layer is reduced to process comprise:
The described substrate that has formed described the second organic nano material thin layer is placed hydroiodic acid or glucose solution and heating water bath.
9. nano combined conductive film, its special medical treatment is, comprising:
The first electroconductive organic film layer;
Conducting polymer thin film layer, described conducting polymer thin film layer are formed on described the first electroconductive organic film layer;
The second electroconductive organic film layer, described the second electroconductive organic film layer is formed on the described conducting polymer thin film layer.
10. nano combined conductive film as claimed in claim 9 is characterized in that: described the first electroconductive organic film layer is the graphene oxide layer that the graphene oxide layer that has been reduced or the nitrogen that has been reduced mix; Described conducting polymer thin film layer is poly-3,4-ethylene dioxythiophene layer, polyaniline layer or polypyrrole layer; Described the second electroconductive organic film layer is the graphene oxide layer that the graphene oxide layer that has been reduced or the nitrogen that has been reduced mix.
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