CN101492151A - High-conductivity transparent metal single-wall nano-carbon tube film and method of producing the same - Google Patents
High-conductivity transparent metal single-wall nano-carbon tube film and method of producing the same Download PDFInfo
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- CN101492151A CN101492151A CNA2009100607761A CN200910060776A CN101492151A CN 101492151 A CN101492151 A CN 101492151A CN A2009100607761 A CNA2009100607761 A CN A2009100607761A CN 200910060776 A CN200910060776 A CN 200910060776A CN 101492151 A CN101492151 A CN 101492151A
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Abstract
The invention relates to a high-conductivity transparent metal single-wall carbon nanotube film, which mainly comprises a substrate and a metal single-wall carbon nanotube layer positioned on the substrate. Under the condition that the transmittance is 85 percent, the square resistance of the film is less than 100 ohms. The film is made by a wet processing through the steps of obtaining a raw material of a mixed single-wall carbon nanotube, separating the mixed single-wall carbon nanotube, and preparing the metal single-wall carbon nanotube layer. The invention uses the transparent metal single-wall carbon nanotube film to replace a common transparent conducting electrode ITO in the prior art, and can reduce manufacturing cost and improve the performance of photoelectric devices; and compared with the transparent conducting electrode ITO, the metal single-wall carbon nanotube film has the advantages of simple manufacture process, convenient large-scale production, and the like, and is particularly suitable for the field of manufacturing the photoelectric devices on a flexible substrate.
Description
Technical field
The present invention relates to thin-film material, particularly relate to a kind of high-conductivity transparent metal single-wall nano-carbon tube film and manufacture method thereof.
Background technology
Electrically conducting transparent indium tin oxide (ITO) has good electrical conductivity, and visible light and near infrared light are had very high transmitance.Therefore in field of optoelectronic devices certain application is arranged.Yet ITO has a lot of deficiencies, such as: (1) ito thin film is very crisp, is applied in poor effect on the flexible substrate; (2) ITO unstable chemcial property; (3) in manufacturing process, ITO needs 200 ℃ or higher temperature, and environment and equipment are all had specific (special) requirements, complex process; (4) since metal In at natural content seldom, the supply of ITO is limited by raw material, the market price can be more and more higher.
Compare with ITO, the transparent metal single-wall nano-carbon tube conductive film has following advantage at least: (1) manufacture craft simple and flexible, and pliability is good, and thin film deposition is not limited by substrate; (2) single-wall nano-carbon tube film manufacture craft maturation, cost is low; (3) very abundant in the occurring in nature carbon content, along with the maturation of SWNT the techniques of mass production, the cost of SWNT transparent conductive film can be more and more lower.
The transparency conductive electrode that satisfies application request is that square resistance is less than 100 Ω under 85% the condition at light transmittance.Electrical conductivity based on the single-wall nano-carbon tube film of prior art for preparing is difficult to satisfy this requirement.As everyone knows, can come the synthesizing single-wall CNT by comprising known methods such as arc discharge, thermal chemical vapor deposition, plasma activated chemical vapour deposition, laser deposition or electrolysis.SWNT has excellent mechanical performance, good electric property, good field emission characteristic and hydrogen memory property etc. efficiently.Specifically, because the high conductivity of single SWNT, so SWNT can be advantageously used in the formation conducting film.However, under the precondition of identical light transmission rate, compare gap in addition with ITO with the electrical conductivity of the single-wall nano-carbon tube film of process means preparation with existing technical scheme.SWNT based on existing material synthesis technology preparation comprises metal mold and semi-conductor type two classes.Principle from statistical distribution, have 1/3 to be that metal single-wall nano-carbon tube is (when n-m equals 3 integral multiple in the SWNT material that is synthesized, wherein n and m are called as the chirality factor of SWNT, the curl direction of graphite flake was relevant when the value of n and m curled into SWNT with graphite flake), have 2/3 to be semi-conductor type single-walled CNT (when n-m is not equal to 3 integral multiple).For mixed type SWNT (comprising metal single-wall nano-carbon tube and semi-conductor type single-walled CNT) film, the principal element that influences its electrical conductivity is the formation of Schottky barrier between metal single-wall nano-carbon tube and the semi-conductor type single-walled CNT.On the whole, this mixed type single-wall nano-carbon tube film has characteristic of semiconductor.Can improve the electrical conductivity of mixed type single-wall nano-carbon tube film by the method for chemical doping, but the stability of this single-wall nano-carbon tube film electrical conductivity that obtains by the method for chemical doping there is very big problem.Improving the most reliable method of single-wall nano-carbon tube film electrical conductivity is that the mixed type SWNT raw material that existing SWNT synthetic technology obtains are separated, the preparation metal single-wall nano-carbon tube film.
Therefore, find a kind of optimal design and preparation method of metal single-wall nano-carbon tube transparent conductive film, improve the electrical conductivity of single-wall nano-carbon tube film, this is very important.
Summary of the invention
Technical problem to be solved by this invention is: the problem at prior art exists provides a kind of design and manufacture method thereof that satisfies the high-conductivity transparent metal single-wall nano-carbon tube film electrode of application requirements.
The present invention solves its technical problem and adopts following technical scheme:
High-conductivity transparent metal single-wall nano-carbon tube film provided by the invention, it mainly is made up of substrate and the metal single-wall nano-carbon tube layer that is positioned at its top, is that the square resistance of this film is less than 100 Ω under 85% the condition at light transmittance.
High-conductivity transparent metal single-wall nano-carbon tube film provided by the invention is made by wet processing, and its step comprises the separation of the raw-material acquisition of mixed type SWNT, mixed type SWNT, the preparation of metal single-wall nano-carbon tube layer.
The present invention compared with prior art has following main advantage:
Have that manufacture craft is simple, cost is low and advantage such as suitable large-scale application.Replace ITO with transparent single-wall nano-carbon tube film, can reduce the manufacturing cost of photoelectric device, improve device performance, for example transparent conductive nano carbon pipe film is applied in that quantum efficiency can improve 1.4 times in the solar cell; Transparent single-wall nano-carbon tube film is particularly suitable for the manufacturing occasion of photoelectric device on the flexible substrate (referring to document: [Aurelien Du Pasquier, Husnu Emrah Unalan, AlokikKanwal, Steve Miller and Manish Chhowalla, Appl.Phys.Lett., 87,203511,2005.]).
Description of drawings
Fig. 1 to Fig. 4 is according to mixed type SWNT material separation process scheme figure of the present invention.
Fig. 5 is the AFM figure that adopts the non-directional metal single-wall nano-carbon tube film of vacuum filtration method preparation.
Fig. 6 to Figure 10 is the manufacture craft flow chart according to directed metal single-wall nano-carbon tube film of the present invention.
Among the figure: 1. hydrostatic column; 2. the first Iodixanol aqueous layer; 3. the second Iodixanol aqueous layer; 4. triiodo restrains husky alcohol solution layer; 5. density gradient layer; 6. mixed type SWNT layer; 7. the tetraiodo restrains husky alcohol solution layer; 8. pentaiodo restrains husky alcohol solution layer; 9. metal single-wall nano-carbon tube layer; 10.Si/SiO
2Substrate; 11. the metal single-wall nano-carbon tube layer of one dimension orientation; 12.Au film; 13. polyimide layer; 14. substrate; 15. the metal single-wall nano-carbon tube layer that two dimension is directed.
The specific embodiment
High-conductivity transparent metal single-wall nano-carbon tube film provided by the invention, it mainly is made up of substrate and the metal single-wall nano-carbon tube layer that is positioned at its top, is that the square resistance of this film is less than 100 Ω under 85% the condition at light transmittance.
Described substrate is made by transparent inorganic material or flexible clear materials, above it be the metal single-wall nano-carbon tube layer.The metal single-wall nano-carbon tube layer is the nondirectional metal single-wall nano-carbon tube layer (Fig. 5) by the vacuum filtration process preparation, or the metal single-wall nano-carbon tube layer 11 of the one dimension orientation by spraying process preparation (Fig. 6-Fig. 9), or the directed metal single-wall nano-carbon tube layer 15 (Figure 10) of two dimension by the preparation of trans-printing method.Note the metal single-wall nano-carbon tube layer 11 and the directed single-wall nano-carbon tube film layer 15 of two dimension of the one dimension orientation here, its kind comprises the film that directed single piece of metal type SWNT forms, or the film that directed metal single-wall nano-carbon tube is restrained or band forms.
Described transparent inorganic material is glass or quartz; Described flexible clear materials is a kind of in PETG, PEN, poly-ethylene sulfone, Merlon, polystyrene, polypropylene, polyester, polyimides, polyether-ether-ketone, PEI, acrylic resin, alkene-maleimide copolymer and the norbornene resin.
The thickness of described high-conductivity transparent metal single-wall nano-carbon tube film is 50～200nm.
The invention provides a kind of method by the low-cost manufacturing of wet processing (wet process) high-conductivity transparent metal single-wall nano-carbon tube film, its concrete steps comprise: (1) synthesizes mixed type (comprising metal mold and semi-conductor type) SWNT raw material by comprising known methods such as arc discharge, thermal chemical vapor deposition, plasma activated chemical vapour deposition, laser deposition or electrolysis; (2) adopt density gradient centrifugation method that mixed type SWNT raw material are separated, obtain the metal single-wall nano-carbon tube solution that diameter is evenly distributed and changes; (3) adopt the vacuum filtration method to prepare nondirectional metal single-wall nano-carbon tube film, perhaps adopt the directed metal single-wall nano-carbon tube film of spraying process and transfer method preparation.
1. the raw-material acquisition of mixed type SWNT:
Described raw material can synthesize by comprising known methods such as arc discharge, thermal chemical vapor deposition, plasma activated chemical vapour deposition, laser deposition or electrolysis.
For example adopt with the chemical vapor deposition method of alcohol as carbon source, specifically comprise three steps: at first be Preparation of catalysts, preparation prepares SiO successively successively on large-area Si sheet
2With Co film, SiO
2Thickness be 20～2000nm, the thickness of Co film is 0.5～5nm; Next is to be 550～800 ℃ in temperature, and the alcohol flow is 50～200Sccm, synthetic mixed type SWNT under the condition of reaction time 1～60min; Adopt hydrochloric acid solution and preparation gained metal single-wall nano-carbon tube head product fully to react then, again through filtration, the dry Co catalyst of removing, and, obtain mixed type SWNT raw material thus by removing after the carbon nano-particle oxidation of oxidant with graphite particulate, amorphous carbon and other form.
2. the separation of mixed type SWNT:
Referring to Fig. 1 to Fig. 4: adopt density gradient centrifugation (DGU) method that mixed type SWNT raw material are separated, obtain metal single-wall nano-carbon tube.So-called density gradient centrifugation method, refer to and in the hydrostatic column 1 of centrifuge special use, at first add a kind of material that can change in the short transverse generation linear gradient of this container, after treating that linear gradient produces, add dispersed mixed type SWNT to the interior appropriate location of container, guarantee in the density of this position mixed type SWNT solution identical with the density of surrounding environment.This container is put into the centrifugal back of centrifuge just can obtain metal single-wall nano-carbon tube solution.Hydrostatic column 1, its diameter are 10 millimeters, and be high 50 millimeters.Among Fig. 1, the first Iodixanol aqueous layer 2, the second Iodixanol aqueous layer 3 and triiodo restrain Iodixanol (Iodixanol) aqueous solution that husky alcohol solution layer 4 is variable concentrations of adding in hydrostatic column 1, after placing in air through 20 hours, these three layers of Iodixanol aqueous solution change the density gradient layer 5 (Fig. 2) in the linear variation of short transverse of this container into.Among Fig. 3 and Fig. 4, the mixed type SWNT layer of numbering 6 for injecting, numbering 7 and 8 is for being restrained husky alcohol solution layer by the SWNT layer 6 separated tetraiodo and pentaiodo restrains husky alcohol solution layer, the metal single-wall nano-carbon tube solution layer of numbering 9 for obtaining after centrifugal.
3. the preparation of metal single-wall nano-carbon tube film:
Dipping (dip coating), spraying (spraycoating), vacuum filtration (vacuum filtration), gel (aerogel) or the spin coating methods such as (spin-coating) of including but not limited to adopted in the preparation of described single-wall nano-carbon tube film.The thickness of single-wall nano-carbon tube film is preferably 50～200nm.Regulate single-wall nano-carbon tube film thickness and density by changing technological parameter, prepare metal single-wall nano-carbon tube film with above-mentioned optimization technological parameter.At the film that adopts the preparation of vacuum filtration method is nondirectional metal single-wall nano-carbon tube film, and its AFM figure sees Fig. 5.
Among Fig. 6 to Figure 10: numbering 10 is Si/SiO
2Substrate, the SiO of this substrate
2Thickness is 200 nanometers.Numbering 14 is any one backing material, this backing material includes but not limited to glass, quartz and other transparent inorganic substrates, perhaps can be the flexible and transparent substrate, described flexible transparent substrate can be the flexible and transparent substrate that the material selected in the group formed of PETG, PEN, poly-ethylene sulfone, Merlon, polystyrene, polypropylene, polyester, polyimides, polyether-ether-ketone, PEI, acrylic resin, alkene-maleimide copolymer and norbornene resin is made.Numbering 12 is the Au films with the vacuum evaporation method preparation.Numbering 13 is polyimides (PI) layers.
(1) preparation of non-directional metal single-wall nano-carbon tube layer: the metal single-wall nano-carbon tube solution that said method is obtained takes out, and is diluted to 5 * 10 with deionized water
-3Mg/ml gets 10 milliliters of solution after the dilution, filters the back SWNT and at first is deposited on the screen membrane, washes screen membrane to remove the SWNT surfactant with a large amount of water and methyl alcohol (each 50%) solution; The screen membrane that will have metal single-wall nano-carbon tube has SWNT one side on desired substrate, cover with filter paper, and placement one weight compresses on filter paper, after evaporating fully Deng moisture content, peel screen membrane gently, promptly finish metal single-wall nano-carbon tube film by the transfer of screen membrane to the requirement substrate.
(2) preparation of the metal single-wall nano-carbon tube layer 15 that two dimension is directed: comprise the preparation of metal single-wall nano-carbon tube solution, Si/SiO
2The functionalization of substrate surface, spin coating and transfer step.
The preparation of metal single-wall nano-carbon tube solution: metal single-wall nano-carbon tube is dissolved in the N-N-methyl-2-2-pyrrolidone N-, requires its concentration, obtain metal single-wall nano-carbon tube solution far below its solubility limit.
Si/SiO
2The functionalization of substrate surface: the method with thermal oxide prepares one deck SiO on described Si substrate
2, again with the Si/SiO that obtains
2Substrate is immersed in by H
2SO
4And H
2O
2Handled H 40～50 minutes in the solution that constitutes
2SO
4And H
2O
2Volume ratio be 3: 1, take out substrate then, and, use N with the flushing of a large amount of water
2Dry up; Substrate after drying up was immersed in the toluene solution that percentage by volume is 1% phenyl triethoxysilane 5～6 hours, took out substrate at last, cleaned for several times with toluene, obtained the Si/SiO of functionalization
2Substrate.
Spin coating: with the Si/SiO of described metal single-wall nano-carbon tube drips of solution in the functionalization of rotating at a high speed
2On the substrate, rotary speed surpasses per minute 6000 changes the Si/SiO of the SWNT that obtains aligning
2Substrate.
Shift: forming the Si/SiO of the metal single-wall nano-carbon tube that aligns
2Preparation layer of Au film 12 on the substrate, the thickness of film is 50～200 nanometers; At Si/SiO
2/ Au is last to be polyimide layer 13 with spin-coating method deposition one deck PI, and its thickness is 100～300 nanometers; Si/SiO
2/ SWCNT/Au/PI heated 2 minutes under 110 ℃ of conditions, removed the reagent that is adsorbed on the substrate surface, made PI that part flexural deformation takes place simultaneously, was easy to peel off; With PDMS (polysiloxanes) and Si/SiO
2After/SWCNT/Au/PI substrate PI side closely contacted, because the stronger effect of Van der Waals for, SWCNT/Au/PI was attached on the PDMS, mentions PDMS fast, makes SWCNT/Au/PI/PDMS from Si/SiO
2Break away from the substrate; SWCNT/Au/PI/PDMS is placed on the described substrate that will shift 14, and bonding wall carbon nanotube side is with after substrate fully contacts a period of time, and slowly pull-up PDMS makes PDMS break away from substrate; The PI of substrate/SWCNT/Au/PI eliminates with the method for common reactive ion etching, and the Au film is with Au-TFA or Transene solution removal; Just finish transfer process one time through after the above-mentioned steps; Repeat said process, on same substrate, realize shifting for the second time, and orientation direction and primary orientation direction that control is shifted for the second time are angled, when twice shift direction is orthogonal, obtain best electrical conductivity.
The present invention is described in further detail below in conjunction with instantiation, but do not limit the present invention.
1. the raw-material acquisition of mixed type SWNT:
From application point of view, chemical vapor deposition (CVD) is the synthetic most promising method of SWNT.Present embodiment adopts with the CVD technology of alcohol as carbon source, and at first the deposited by electron beam evaporation method prepares SiO successively on large-area Si sheet
2With Co film, SiO
2Thickness be 20～2000nm, preferable condition is 50～200nm, the thickness of Co film is 0.5～5nm, preferable condition is 0.5～2nm.The CVD temperature is 550～800 ℃, and preferable condition is 650～750 ℃, and the alcohol flow is preferably 50～200sccm, reaction time 1～60min.Owing in the preparation process of SWNT, all can generate the carbon nano-particle of fullerene, graphite particulate, amorphous carbon and other form usually simultaneously.Thereby generally all need to take various physico-chemical processes that the CNT head product of preparation gained is carried out purifying.At first to consider to remove the CATALYST Co particle, adopt hydrochloric acid solution and preparation gained SWNT head product fully to react, through filtration, drying and other steps, can remove catalyst then.The removal of the carbon nano-particle of graphite particulate, amorphous carbon and other form can adopt suitable oxidant with its oxidation.Its mechanism is to utilize oxidant inconsistent to the oxidation rate of SWNT and carbon nano-particle.The tube wall of SWNT is made up of the carbon atom (being hexatomic ring) of hexagonal array, and hexatomic ring is compared with five-membered ring, heptatomic ring, does not have dangling bonds, thereby more stable.Under the situation that oxidant exists, have the five-membered ring of more dangling bonds and heptatomic ring preferentially oxidized, and the hexatomic ring that does not have dangling bonds need the long period could be oxidized.Alternative oxidant is a lot, as potassium permanganate and nitric acid etc.Through above-mentioned steps, just can obtain mixed type SWNT raw material.
2. the separation of mixed type SWNT:
Referring to Fig. 1 to Fig. 4: at first 8～10mg mixed type SWNT is dispersed in mass volume ratio (grams per milliliter) and is in 8～10ml sodium taurocholate (SC) aqueous solution of 2%.In power density is 20W/cm
2Ultrasonic machine in just can obtain disperseing SWNT solution preferably after ultrasonic 18～22 hours; Next adopts density gradient centrifugation method that this solution is separated, and can obtain metal single-wall nano-carbon tube solution.So-called density gradient centrifugation method refers to and at first add a kind of material-Iodixanol that can change in the short transverse generation linear gradient of this container in the hydrostatic column 1 of centrifuge special use, produce linear gradient, wherein: the first Iodixanol aqueous layer 2 is 30% the Iodixanol aqueous solution for w/v; The second Iodixanol aqueous layer 3 is 20% the Iodixanol aqueous solution for w/v; It is 10% the Iodixanol aqueous solution for w/v that triiodo restrains husky alcohol solution layer 4.These three layers of Iodixanol aqueous solution distribute to the top from container bottom in container, and the content of every layer surfactant is identical with component, and described surfactant is meant and comprises that w/v is that 1.2% Triton-100 and w/v are the aqueous solution of 0.8% sodium taurocholate.Said vesse left standstill under normal temperature condition 20 hours, after treating that linear density gradient 5 produces, add mixed type SWNT solution to the interior appropriate location (numbering the position shown in 6 referring to Fig. 3 and Fig. 4) of container, the density of assurance mixed type SWNT solution is identical with the Iodixanol around this position.In the present embodiment, this container is put into centrifuge just can obtain metal single-wall nano-carbon tube solution in centrifugal 10 hours under the 15000rpm rotating speed, this solution takes out with buret, is kept at containers for future use.
3. vacuum filtration method prepares nondirectional metal single-wall nano-carbon tube film:
The advantage of vacuum filtration method is can control easily in this way the thickness of film.The concrete manufacture craft of metal single-wall nano-carbon tube film is as follows: the metal single-wall nano-carbon tube solution that will obtain as stated above takes out, and is diluted to 5 * 10 with deionized water
-3Mg/ml gets 10 milliliters of solution after the dilution, filter the back SWNT and at first be deposited on the screen membrane, with a large amount of be that the solution that 1: 1 water and methyl alcohol are formed washes screen membrane to remove surfactant by volume ratio.The screen membrane that will have metal single-wall nano-carbon tube has SWNT one side on desired substrate, cover with filter paper, and placement one weight compresses on filter paper, after evaporating fully Deng moisture content, peel screen membrane gently, can finish metal single-wall nano-carbon tube film by the transfer of screen membrane to the requirement substrate.
4. the printing transfer method prepares directed metal single-wall nano-carbon tube film:
Described film can be realized transfer between the different substrates with the trans-printing method.For example, at Si/SiO
2By the directed metal single-wall nano-carbon tube (Fig. 6) of method preparation of spin coating, concrete steps are on the substrate 10:
(1) preparation of metal single-wall nano-carbon tube solution:
Mixed type SWNT raw material are dissolved in N-N-methyl-2-2-pyrrolidone N-(NMP), require its concentration far below its solubility limit, what present embodiment adopted is 5 * 10
-3Mg/mL is single to guarantee SWNT fully, avoids the existence of SWNT tube bank, and described metal single-wall nano-carbon tube formulations prepared from solutions back is well preserved standby.
(2) Si/SiO
2The functionalization of substrate surface:
(100) the direction P type of employing mixes, the Si substrate of high conductivity, uses the method for thermal oxide to prepare one deck SiO on described substrate
2, thickness is probably in 200 nanometers.Si/SiO
2Substrate is immersed in H
2SO
4: H
2O
2Handled 45 minutes in (volume ratio is 3: 1), then described substrate is washed with a large amount of water, use N
2Dry up.This substrate was immersed in the toluene that w/v is 1% phenyl triethoxysilane (phenyltriethoxysilane) (Toluene) solution 6 hours, took out substrate and cleaned for several times standby again with toluene.
(3) spin coating: with the Si/SiO of SWNT drips of solution described in the step (1) in the functionalization of rotating at a high speed
2On the substrate 10, when the substrate rotary speed surpasses per minute 6000 commentaries on classics, on this substrate, just formed directed metal single-wall nano-carbon tube layer 11 (Fig. 6).
(4) shift: forming the Si/SiO of the SWNT that aligns
2Preparation layer of Au film 12 on the substrate 10, the thickness of film is (Fig. 7) in the 50-200 nanometer range; At Si/SiO
2/ Au is last with spin-coating method deposition one deck polyimide layer (PI) 13, and its thickness is 100-300 nanometer (Fig. 8); Si/SiO
2/ SWCNT/Au/PI heated 2 minutes under 110 ℃ of conditions, removed the reagent that is adsorbed on the substrate surface, made PI that part flexural deformation takes place simultaneously, was easy to peel off; With polysiloxanes (PDMS) and Si/SiO
2/ SWCNT/Au/PI substrate PI side contacts, compress and keep 1 hour after, mention PDMS fast, make SWCNT/Au/PI/PDMS from Si/SiO
2Break away from the substrate; SWCNT/Au/PI/PDMS is placed on the described substrate that will shift 14, and after guaranteeing the SWCNT side and the reception substrate fully contacting 1 hour, slowly pull-up PDMS makes PDMS break away from substrate 14.The PI of substrate/SWCNT/Au/PI can eliminate with the method (RIE) of common reactive ion etching, and the Au film can (Au-TFA Transene) removes with commercial solution.Just finish transfer process one time through after the above-mentioned steps, as Fig. 9.
By above-mentioned identical step, can realize on the substrate shifting for the second time same acceptance, and it be angled to control the orientation direction and the primary orientation direction that shift for the second time.The present invention has disclosed when twice shift direction is orthogonal, and as shown in figure 10, the directed metal single-wall nano-carbon tube layer 15 of gained two dimension can obtain best electrical conductivity along AC, BD direction.
Claims (8)
1. high-conductivity transparent metal single-wall nano-carbon tube film, comprise substrate, it is characterized in that: described film mainly is made up of substrate and the metal single-wall nano-carbon tube layer that is positioned at its top, is that the square resistance of this film is less than 100 Ω under 85% the condition at light transmittance.
2. high-conductivity transparent metal single-wall nano-carbon tube film according to claim 1 is characterized in that: substrate is made by transparent inorganic material or flexible clear materials, above it be the metal single-wall nano-carbon tube layer; The metal single-wall nano-carbon tube layer is the nondirectional metal single-wall nano-carbon tube layer by the vacuum filtration process preparation, or the metal single-wall nano-carbon tube layer (11) of the one dimension orientation by spraying process preparation, or the directed metal single-wall nano-carbon tube layer (15) of two dimension by the preparation of trans-printing method.
3. high-conductivity transparent metal single-wall nano-carbon tube film according to claim 2, it is characterized in that: the metal single-wall nano-carbon tube layer (11) of one dimension orientation comprises the film that directed single piece of metal type SWNT forms, or the film that directed metal single-wall nano-carbon tube is restrained or band forms.
4. high-conductivity transparent metal single-wall nano-carbon tube film according to claim 2 is characterized in that: described transparent inorganic material is glass or quartz; Described flexible clear materials is a kind of in PETG, PEN, poly-ethylene sulfone, Merlon, polystyrene, polypropylene, polyester, polyimides, polyether-ether-ketone, PEI, acrylic resin, alkene-maleimide copolymer and the norbornene resin.
5. high-conductivity transparent metal single-wall nano-carbon tube film according to claim 1 is characterized in that: the thickness of described film is 50～200nm.
6. the preparation method of the described high-conductivity transparent metal single-wall nano-carbon tube film of arbitrary claim in the claim 1 to 5 is characterized in that adopting the wet processing that may further comprise the steps:
A. the raw-material acquisition of mixed type SWNT:
Employing specifically comprises three steps with the chemical vapor deposition method of alcohol as carbon source: at first be Preparation of catalysts, preparation prepares SiO successively successively on large-area Si sheet
2With Co film, SiO
2Thickness be 20～2000nm, the thickness of Co film is 0.5～5nm; Next is to be 550～800 ℃ in temperature, and the alcohol flow is 50～200Sccm, synthetic mixed type SWNT under the condition of reaction time 1～60min; Adopt hydrochloric acid solution and preparation gained metal single-wall nano-carbon tube head product fully to react then, again through filtration, the dry Co catalyst of removing, and, obtain mixed type SWNT raw material thus by removing after the carbon nano-particle oxidation of oxidant with graphite particulate, amorphous carbon and other form;
B. the separation of mixed type SWNT:
Specifically: earlier 8～10mg mixed type SWNT raw material being dispersed in mass volume ratio and being in 8～10ml sodium taurocholate aqueous solution of 2%, is 20W/cm in power density
2The excusing from death machine in ultrasonic 18～22 hours, obtain finely dispersed SWNT solution; Adopt density gradient centrifugation method that this solution is separated again, obtain metal single-wall nano-carbon tube solution;
C. the preparation of metal single-wall nano-carbon tube layer:
The preparation of non-directional metal single-wall nano-carbon tube layer: the metal single-wall nano-carbon tube solution that said method is obtained takes out, and is diluted to 5 * 10 with deionized water
-3Mg/ml gets 10 milliliters of solution after the dilution, filter the back SWNT and at first be deposited on the screen membrane, with a large amount of be that the solution that 1: 1 water and methyl alcohol are formed washes screen membrane to remove the SWNT surfactant by volume ratio; The screen membrane that will have metal single-wall nano-carbon tube has SWNT one side on desired substrate, cover with filter paper, and placement one weight compresses on filter paper, after evaporating fully Deng moisture content, peel screen membrane gently, promptly finish metal single-wall nano-carbon tube film by the transfer of screen membrane to the requirement substrate
The preparation of the metal single-wall nano-carbon tube layer (15) that two dimension is directed: comprise the preparation of metal single-wall nano-carbon tube solution, Si/SiO
2The functionalization of substrate surface, spin coating and transfer step,
The preparation of metal single-wall nano-carbon tube solution: metal single-wall nano-carbon tube is dissolved in the N-N-methyl-2-2-pyrrolidone N-, requires its concentration, obtain metal single-wall nano-carbon tube solution far below solubility limit,
Si/SiO
2The functionalization of substrate surface: the method with thermal oxide prepares one deck SiO on described Si substrate
2, again with the Si/SiO that obtains
2Substrate is immersed in by H
2SO
4And H
2O
2Handled H 40～50 minutes in the solution that constitutes
2SO
4And H
2O
2Volume ratio be 3: 1, take out substrate then, and, use N with the flushing of a large amount of water
2Dry up; Substrate after drying up was immersed in the toluene solution that percentage by volume is 1% phenyl triethoxysilane 5～6 hours, took out substrate at last, cleaned for several times with toluene, obtained the Si/SiO of functionalization
2Substrate,
Spin coating: with the Si/SiO of described SWNT drips of solution in the functionalization of rotating at a high speed
2On the substrate, rotary speed surpasses per minute 6000 changes the Si/SiO of the SWNT that obtains aligning
2Substrate,
Shift: forming the Si/SiO of the metal single-wall nano-carbon tube that aligns
2Prepare layer of Au film (12) on the substrate, the thickness of film is 50～200 nanometers; At Si/SiO
2/ Au is last to be polyimide layer (13) with spin-coating method deposition one deck PI, and its thickness is 100～300 nanometers; Si/SiO
2/ SWCNT/Au/PI heated 2 minutes under 110 ℃ of conditions, removed the reagent that is adsorbed on the substrate surface, made PI that part flexural deformation takes place simultaneously, was easy to peel off; With PDMS is polysiloxanes and Si/SiO
2After/SWCNT/Au/PI substrate PI side closely contacted, because the stronger effect of Van der Waals for, SWCNT/Au/PI was attached on the PDMS, mentions PDMS fast, makes SWCNT/Au/PI/PDMS from Si/SiO
2Break away from the substrate; SWCNT/Au/PI/PDMS is placed on the described substrate that will shift (14), and bonding wall carbon nanotube side is with after substrate fully contacts a period of time, and slowly pull-up PDMS makes PDMS break away from substrate; The PI of substrate/SWCNT/Au/PI eliminates with the method for common reactive ion etching, and the Au film is with Au-TFA or Transene solution removal; Just finish transfer process one time through after the above-mentioned steps; Repeat said process, on same substrate, realize shifting for the second time, and orientation direction and primary orientation direction that control is shifted for the second time are angled, when twice shift direction is orthogonal, obtain best electrical conductivity.
7. preparation method according to claim 6, it is characterized in that: from the container bottom to the top, the initial density gradient layer of density gradient centrifugation is respectively that mass volume ratio is 30%, 20% and 10% Iodixanol aqueous layer, from the container bottom to the top, distribute, each layer all contains 2% surfactant, and described surfactant comprises that mass volume ratio is 1.2% the Triton-100 and the aqueous solution of 0.8% sodium taurocholate.
8. preparation method according to claim 7, it is characterized in that: described container left standstill under normal temperature condition 20 hours, after treating that the linear density gradient produces, add and to contain the metal single-wall nano-carbon tube mixed solution, guarantee that the density of this mixed solution is identical with surrounding environment density in this position to the interior appropriate location of container.
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| CNA2009100607761A CN101492151A (en) | 2009-02-17 | 2009-02-17 | High-conductivity transparent metal single-wall nano-carbon tube film and method of producing the same |
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| CNA2009100607761A CN101492151A (en) | 2009-02-17 | 2009-02-17 | High-conductivity transparent metal single-wall nano-carbon tube film and method of producing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102087920A (en) * | 2010-11-23 | 2011-06-08 | 奇瑞汽车股份有限公司 | Flexible light anode and preparation method thereof |
| CN102290506A (en) * | 2011-09-20 | 2011-12-21 | 苏州晶能科技有限公司 | Manufacturing technology of LED (Light Emitting Diode) module with graphical transparent thin-film electrode |
| CN103700430A (en) * | 2013-12-25 | 2014-04-02 | 中山大学 | Conductive film with ordered distribution and manufacturing method thereof |
| WO2014071669A1 (en) * | 2012-11-09 | 2014-05-15 | 深圳欧菲光科技股份有限公司 | Transparent conductor and manufacturing method thereof |
| CN103854723A (en) * | 2014-02-20 | 2014-06-11 | 中山大学 | Device with orderly-conductive film |
| CN104064504A (en) * | 2014-06-27 | 2014-09-24 | 华中科技大学 | Method using preservative film to transfer conductive film |
| US9510456B2 (en) | 2012-11-09 | 2016-11-29 | Shenzhen O-Film Tech Co., Ltd. | Transparent conductor and preparation method thereof |
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- 2009-02-17 CN CNA2009100607761A patent/CN101492151A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102087920A (en) * | 2010-11-23 | 2011-06-08 | 奇瑞汽车股份有限公司 | Flexible light anode and preparation method thereof |
| CN102290506A (en) * | 2011-09-20 | 2011-12-21 | 苏州晶能科技有限公司 | Manufacturing technology of LED (Light Emitting Diode) module with graphical transparent thin-film electrode |
| WO2014071669A1 (en) * | 2012-11-09 | 2014-05-15 | 深圳欧菲光科技股份有限公司 | Transparent conductor and manufacturing method thereof |
| US9510456B2 (en) | 2012-11-09 | 2016-11-29 | Shenzhen O-Film Tech Co., Ltd. | Transparent conductor and preparation method thereof |
| CN103700430A (en) * | 2013-12-25 | 2014-04-02 | 中山大学 | Conductive film with ordered distribution and manufacturing method thereof |
| CN103854723A (en) * | 2014-02-20 | 2014-06-11 | 中山大学 | Device with orderly-conductive film |
| CN104064504A (en) * | 2014-06-27 | 2014-09-24 | 华中科技大学 | Method using preservative film to transfer conductive film |
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