CN101298510A - Polythiofuran-carbon nanotube composite photosensitive film material and preparation thereof - Google Patents
Polythiofuran-carbon nanotube composite photosensitive film material and preparation thereof Download PDFInfo
- Publication number
- CN101298510A CN101298510A CNA2008100392040A CN200810039204A CN101298510A CN 101298510 A CN101298510 A CN 101298510A CN A2008100392040 A CNA2008100392040 A CN A2008100392040A CN 200810039204 A CN200810039204 A CN 200810039204A CN 101298510 A CN101298510 A CN 101298510A
- Authority
- CN
- China
- Prior art keywords
- carbon nanotube
- substituted thiophene
- thiophene
- preparation
- alcohol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Abstract
The invention pertains to the technical field of organic/inorganic nano-composite material, in particular to a polythiophene-carbon nano-tube composite light sensitive thin film material and a preparation method thereof. The composite thin film material consists of carbon nano-tube and the polythiophene, which has higher light sensitivity, compatibility and thermal stability as well as excellent solubility, film forming and electro-optical properties. The storage stability of the nano-composite light sensitive thin film material and the dispersion uniformity of the carbon nano-tube in the polythiophene, etc. are significantly superior to a traditional physical method. The preparation method of the invention has the advantages of simple technique, high quality of paint film, high input-output ratio and low cost etc. Products prepared by the invention are new generation green and environment protective chemical products which can be applied to fields such as conductive materials, solar cell materials, photoconductive materials and photoelectric conversion materials, etc.
Description
Technical field
The invention belongs to the Organic technical field, be specifically related to a kind of polythiofuran-carbon nanotube composite photosensitive film material and preparation method thereof.
Background technology
Along with exhausting day by day of development of modern industry and fossil energy, energy demand becomes the focus that countries in the world are paid close attention to.Develop various new forms of energy, development light weight, inexpensive, power supply that thing is beautiful become the target that scientist seek assiduously.As everyone knows, sun power is inexhaustible.But as industrial energy, sun power has the low shortcoming of energy density, and in order to make full use of this cheapness, environmental protection, reproducible new forms of energy, produce solar photocell cheap, efficient, the energy large-area preparation is the target that people pursued always.
At present, silica-based and other inorganic metal compound solar photocells main flow that is solar cells.Although yet production cost declines to a great extent in recent years, the cost problem remains its major obstacle that significantly replaces traditional energy.Because inorganic solar cell production process complexity, it is very difficult further significantly to reduce cost, and the problems such as the limit of cost height and effciency of energy transfer are restricted its large-scale promotion.
Utilizing the solar cell of photovoltaic effect carrying out to raise the efficiency and to reduce cost as the energy transformation device is the research of target, and the fast development of conjugation conducting polymer composite makes research and development low-cost solar battery become possibility.Polymer solar battery has become one of the research focus in this field because its cost is low, in light weight, easy to prepare and have molecule sanction property.
Early stage polymer thin-film solar cell material mainly concentrates on the organic dye such as phthalocyanine, perylene, and battery structure is based on individual layer Schottky-barrier formula.The photoelectric transformation efficiency of Schottky-barrier battery is not high always, and reason is that the metal electrode major part that incident light is positioned at battery sandwich has reflected away.
1986, (1986,48 (2): 183) employing had double-deck polymer thin-film solar cell (ITO/CuPc/PV/Ag) to Tang first, and photoelectric transformation efficiency reaches 1% first, and packing factor also reaches 0.65 for C.W.Tang, Appl.Phys.Lett..In this bilayer structure polymer thin-film solar cell, the photovoltaic performance of battery is by the interface of two kinds of polymkeric substance but not the interface of electrode/polymer materials decision.
Compare the Schottky-barrier battery, polymkeric substance p-n heterojunction bilayer structure battery has many advantages, can prepare the device of wide spectral response range to the choose reasonable of polymer materials, various polymeric donors, acceptor material make the high yield of photoproduction charged carriers become possibility.
1992, and Saricifici etc. (Saricifici N S, Heeger A J, Science, 1992,258:1474) find conjugated polymers and C
60Between photoinduction transfer transport phenomenon, when the energy of incident light greater than π-π
*The time, conjugated polymers deposits yields photoproduction exciton, from excited state to the charge transfer to C
60On occur as Pi Miaoji.C
60The photoluminescence that makes conjugated polymers is by cancellation, and this makes C
60Be applied to optical sensor and solar cell becomes possibility.Since then, the conjugated polymers electrooptical device has obtained the attention of academia.
Yu Gang (Yu G, Heeger A J, Appl Phys Lett, 1994,64 (25): 3422-3423) with C
60Mix with MEH-PPV, make MEH-PPV/C
60Blend film structure solar cell, effciency of energy transfer significantly improves than bi-layer devices.Because electron donor(ED) and electron acceptor(EA) be the network-like external phase of each self-forming mutually, the electronics that photoinduction produced and hole can be respectively separately mutually in carry and form network-like external phase, the electronics that photoinduction produced and hole can be respectively separately mutually in carry and on corresponding electrode, be collected, photo-generated carrier is greatly reduced by compound probability again before arriving corresponding electrode, so photo-quantum efficiency reaches 1000 to 10000 times of pure MEH-PPV.Yet because C
60Limited solubility and easy crystallinity, MEH-PPV/C
60The performance of blend film is difficult for optimizing.With the higher C of solubility
60Derivative PCBM replaces the C in the blending structure
60, photovoltaic energy conversion efficient can obviously improve.To the MEH-PPV/PCBM system, can obtain 3% effciency of energy transfer.
1998, (M.Granstrom such as Granstrom, K.Petritsch, A.C.Arias, at al., Nature, 1998,395:257) with regular n-octyl phenyl substituting polythiophene derivative (POPT) as electron donor material, replace polyphenylvinylenes (MEH-CN-PPV) replaced C with blue cyano group
60Prepared photocell as electron acceptor(EA).Find blend single layer device external quantum efficiency only 0.05%, only be equivalent to MEH-CN-PPV single layer device efficient.Estimation is because thermal treatment or the solvent treatment of POPT make individual layer blend MEH-CN-PPV/POPT device be separated the situation variation.
Calendar year 2001, and Saricifitci study group (S.E.Shaheen, C.J.Brabec, N.S.Saricifitci, et.al., Appl.Phys.Lett.2001 is 78:841) at effciency of energy transfer and conjugated polymers and C based on polymer thin-film solar cell
60There is the understanding of substantial connection in the pattern of derivative (mainly referring to PCBM) blend, has prepared conjugated polymers and C
60The derivative microfacies is mixed extraordinary device, has obtained 2.5% effciency of energy transfer (AM1.5).The reason that produces this good result is that the device two-phase is mixed fine.2002, the effciency of energy transfer of this solar cell reached 3% especially (C.J.Brabec, S.E.Shaheen, C.Winder, N.S.Sariciftci, et.al., Appl.Phys.Lett.2002,80:1288).
The group of Britain Camb (N.Tessler, N.T.Harrison, R, H.Friend, Advanced Materials, 1999,10 (1): 64-68) carry out blend and made carbon nano-tube film through chemical oxidation and thermal treatment again with carbon nanotube and PPV performed polymer.Because its work function is greater than ITO, so replace ITO to make the Al/PPV/NT/ITO device as the hole collector electrode with this film, photoelectric transformation efficiency has improved 3 times than the simple device efficiency of making negative electrode with ITO.
Conjugated polymers as electron donor(ED) and hole transport body, polyvinyl carbazole (PVK), poly-to vinylbenzene (PPV), polyaniline (PANI), polypyrrole (PPy), polyacetylene (PA), Polythiophene (PTh) etc. is arranged, wherein polythiophene class (PTh) is the comparatively popular class material of Recent study, and wherein that better performances is poly-3-alkylthrophene (P
3AT), generally contain the above alkylthrophene solubilized of 6 carbon atoms, but the following alkyl substituent of 10 carbon there is part to be gel.The stronger sulphur atom of electron-withdrawing power is arranged on the polythiophene class main chain, and maximum absorption band is near 600nm, with the solar spectrum comparison match.In addition, the polythiophene class derivative also has higher hole mobility, and this is very helpful for improving effciency of energy transfer.
Though thiofuran polymer has good charge transport properties,, make its effciency of energy transfer lower because its photoinduction charge separation is relatively poor.In order to improve this situation, just need mix electron acceptor (electric transmission body) and its formation heterojunction to promote effectively separating of electric charge.
As electron acceptor material, CdSe, TiO are arranged
2, C
60Derivative, carbon nanotube etc., C
60Can accept six electronics at most, higher electron affinity and ionizing potential be arranged with respect to conjugated polymers, and electron transport ability preferably, so it is higher as electron acceptor(EA) and the compound efficient of organic photovoltaic cell that can make of conjugated polymers.But C
60Solvent borne is poor in organic solvent, and easily crystallization is difficult to realize high doping content in the film process, has limited the raising of its processing characteristics and photoelectric transformation efficiency.So people have expected it is carried out graft modification, find 1-(3-methoxyl group carboxyl)-propyl group-1-phenyl-(6,6) C
61(PCBM) have solvability preferably, the doping content in polymkeric substance improves greatly and helps the formation that inierpeneirating network structure is a bulk heterojunction, has improved photoelectric transformation efficiency.
Certainly, improve the effciency of energy transfer of whole solar cell, the optimised devices structure also is vital.Four kinds of device architectures based on the conjugated polymer photovoltaic cell: (a) individual layer photovoltaic cell (photoactive layer only is made up of conjugated polymer, and often appearance is compound in carrier transport process, and efficient is lower); (b) double-deck photovoltaic cell (photoactive layer is made up of conjugated polymer and corresponding electron acceptor(EA), and is low to the utilising efficiency of conjugated polymer); (c) unordered bulk heterojunction (photoactive layer is formed by conjugated polymer and the unordered blend of electron acceptor(EA), exciton dissociation efficient height, but easily form isolated island, transmission range is also longer, power loss is bigger); (d) (photoactive layer is formed by conjugated polymer and the self-assembly of electron acceptor(EA) ordered nano orderly bulk heterojunction, heterojunction extensively is present in two-phase interface, exciton dissociation efficient height, carrier transport are the device architectures of present ideal polymer solar battery film of generally acknowledging apart from weak point).Wherein, individual layer and bilayer structure are because its born defective is eliminated, and then both belong to the bulk heterojunction photo-conductive film, have very big exciton separating interface, make most excitons can access effective separation, both make polymer solar battery after now the employing more.So-called bulk heterojunction photo-conductive film is accepted material (being generally the high inorganic semiconductor material of electric transmission rate) blend with electron donor material (being generally conjugated polymer) and electronics exactly, formation has the photo-conductive film material of two-phase continuous structure, and promptly the biphase phase interface is all heterojunction.Calculate as can be known through theory, the device architecture that most possibly reaches the commercialization utilization is exactly orderly bulk heterojunction, is expected to reach 10% effciency of energy transfer.
In recent years, there has been the people compound system of carbon nanotube and polymkeric substance to be used for the research of opto-electronic conversion.With C
60Compare, carbon nanotube (CNTs) has good electron-transporting equally, and its special one dimension length can reduce the loss that electronics jumps and caused between carbon nanotube, thereby increases the mobility of electronics.Musa etc. have prepared the matrix material of MWNTs and poly-3-octyl group thiophene composition, and specific conductivity has improved 5 orders of magnitude.(P3HT) report of composite photosensitive film material is also few and for CNTs and poly-(3-alkylthrophene).
Summary of the invention
The objective of the invention is to overcome the deficiency that prior art exists, nano combined photosensitive film material of a kind of polythiofuran-carbon nanotube and preparation method thereof is provided.
The present invention is the nano combined photosensitivity film of a kind of polythiofuran-carbon nanotube, it is made up of carbon nanotube and Polythiophene, the absorption of this film in visible region red shift along with the increase of content of carbon nanotubes, compare with simple Polythiophene, its absorption spectrum is taken into account the near infrared light zone more, mate more with the ground solar spectrum, thereby improved it solar energy utilization rate.In addition, the carbon nanotube of process surface modification treatment can have good consistency with Polythiophene solution, the film forming properties excellence, and this is that device is laid a good foundation in the future.
The present invention is the preparation method of the nano combined photosensitivity film of a kind of polythiofuran-carbon nanotube.This method is at first carried out chemically modified and organic amine modification to carbon nanotube, makes its surface be with a certain amount of organic group, improves the dispersiveness of carbon nanotube in organic solvent.Adopt the synthetic a kind of polythiofuran derivative of chemical oxidization method, use anhydrous FeCl
3As oxygenant.Then based on the preparation of the poly-polythiofuran derivative-carbon nanotube complex light sensitive film material of above-mentioned two kinds of materials.The package stability of this nano combined photo-conductive film material and the carbon nanotube dispersing uniformity in Polythiophene etc. will be better than traditional physical blending method far away.And advantage such as preparation method of the present invention has that simple process is convenient, film quality is high, input-output ratio is high, with low cost and application prospect is extensive, the product that utilizes the present invention to prepare has higher light sensitivity, consistency and thermostability, and have good solubility property, film forming properties and photoelectric properties, can be used for fields such as electro-conductive material, solar cell material, photoconductive material and photoelectric conversion material.
The preparation method of a kind of polythiofuran derivative-carbon nanotube composite photosensitive film that the present invention proposes is as follows:
(1) be 3:0.8-3 by volume with 100～1000mg multi-walled carbon nano-tubes adding 150ml vitriol oil and concentrated nitric acid: in the 1.2 mixed strong acids solution of forming, sonic oscillation was handled 3～12 hours, pour in the deionized water, and leave standstill more than 12 hours, filter and be washed to neutrality, oven dry obtains the carbon nanotube with carboxyl again;
(2) under nitrogen protection, the carbon nanotube of the above-mentioned band carboxylic acid of 80～800mg is placed the excessive thionyl chloride 12～72h that refluxes, reaction finishes, and excessive thionyl chloride is removed in underpressure distillation, and vacuum-drying obtains the carbon nanotube of chloride;
(3) carbon nanotube with the above-mentioned chloride of 50～500mg is dispersed in the anhydrous propanone, drip several fresh pyridines or triethylamine, under 58-65 ℃ of condition, dropwise Dropwise 5～20ml concentration is the organic amine of 0.005～0.025g/ml or the acetone soln of organic alcohol, the dropping time is not less than 30 minutes (as 30～80 minutes), dropwised successive reaction 4～72 hours, excessive organic amine or organic alcohol are removed with a large amount of acetone thorough washing, centrifuging, vacuum-drying obtains organic amine or organic pure modified carbon nanotube;
(4) under nitrogen protection; in the 250mL four-hole boiling flask, add the FERRIC CHLORIDE ANHYDROUS of 0.05～5g and the chloroform of 5～50ml; stir under the room temperature and obtained the muddy liquid of sap green in 5～90 minutes; the alkylated substituted thiazoline fen or the monomeric 5～50mL chloroformic solution of alkoxyl group substituted thiophene that dropwise add 0.5～5g then, stirring at room 4～72 hours.Slowly pour mixture in 50～1000mL methyl alcohol sedimentation, filter, remaining solid is soaked intrinsicization with strong aqua, be washed till neutrality with deionized water then, dry in the vacuum drying oven.With 10～100mL chloroform dissolving, remove by filter insoluble part then, filtrate is with the methyl alcohol sedimentation of 100～500mL, the solid of gained is washed till colourless with methyl alcohol, repeat chloroform dissolving-methyl alcohol settling process more than 3 times, removes impurity, promptly get the polythiofuran derivative of intrinsicization, productive rate is 35～85%.
(5) carbon nanotube with the above-mentioned organic amine of 50～500mg or organic pure modification processing is dispersed in the organic solvent, and the concentration of carbon nanotube is 0.5～10mg/mL; 50～500mg polythiofuran derivative is dissolved in the organic solvent, and the concentration of polythiofuran derivative is 0.5～10mg/mL; Under powerful agitation condition, polythiofuran derivative solution slowly is added dropwise in the carbon nano-tube solution, the weight ratio of carbon nanotube and polythiofuran derivative is 1: 1～20.Stirring at room 1～12 hour obtains a kind of polythiofuran derivative-carbon nano tube compound material solution.
(6) adopt coating method that above-mentioned polythiofuran derivative-carbon nano tube compound material solution is coated on the conductive matrices, its surface covered is 2.0～10.0mm/s, coating fluid viscosity is at 100～500cp, bake out temperature is 35～120 ℃, drying time is 0.5～6 hour, and the compound photosensitive coat thickness of exsiccant polythiofuran derivative-carbon nanotube is 15～45 μ m.
Among the present invention, described alkylated substituted thiazoline fen, can be the replacement of 3-alkyl and 3,4-dialkyl group substituted thiophene, for example 3-butyl substituted thiophene, 3-isopentyl substituted thiophene, 3-n-pentyl substituted thiophene, 3-hexyl substituted thiophene, 3-octyl group substituted thiophene, 3-iso-octyl substituted thiophene, 3-(2-ethyl) hexyl substituted thiophene, 3-dodecyl substituted thiophene, 3,4-two (isopentyl) substituted thiophene, 3,4-two (dodecyl) substituted thiophene etc.; Described alkoxyl group substituted thiophene, can be the replacement of 3-alkoxyl group and 3,4-dialkoxy substituted thiophene, for example 3-methoxyl group substituted thiophene, 3-pentyloxy substituted thiophene, 3-octyloxy substituted thiophene, 3-(dodecyl) thiophene-3-(pentyloxy) thiophene copolymers, 3-(dodecyl) thiophene-3-(octyloxy) thiophene copolymers etc.; Described organic amine can be ethamine, Tri N-Propyl Amine, Isopropylamine, n-Butyl Amine 99, isobutylamine, sec-butylamine, n-amylamine, n-octyl amine, octodrine, N, N-diisopropylethylamine, amino dodecane, stearylamine etc.; Described organic alcohol can be ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, Pentyl alcohol, neopentyl alcohol, octanol, decyl alcohol, lauryl alcohol, stearyl alcohol etc.; Described organic solvent can be chloroform, methylene dichloride, tetrachloroethane, tetrahydrofuran (THF), dioxane, acetonitrile, N, dinethylformamide, N,N-dimethylacetamide, N-Methyl pyrrolidone, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol phenyl ether, diethylene glycol dimethyl ether, dibutyl ethylene glycol ether, the two methyl ethers of glycol ether, diethyl carbitol, diethylene glycol ethyl ether butylcarbitol or its mixture.
Among the present invention, used conductive matrices, be conduction tinsel, ito glass or above scribble the polyester chips of conducting medium, or drum type, zonal conducting metal and electrical conductivity alloy.
A kind of polythiofuran derivative-carbon nanotube composite photosensitive film material of the present invention's preparation, the absorption of this film in visible region red shift along with the increase of content of carbon nanotubes, compare with simple polythiophene film, its absorption spectrum is taken into account the near infrared light zone more, mate more with the ground solar spectrum, thereby improved it solar energy utilization rate.In addition, surface treated carbon nanotube can have good consistency with polythiofuran derivative solution, the film forming properties excellence, and this is that device is laid a good foundation in the future.The package stability of this nano combined photo-conductive film material and the carbon nanotube dispersing uniformity in Polythiophene etc. will be better than traditional physical method far away.And advantage such as preparation method of the present invention has that simple process is convenient, film quality is high, input-output ratio is high, with low cost and application prospect is extensive, the product that utilizes the present invention to prepare has higher light sensitivity, consistency and thermostability, and have good solubility property, film forming properties and photoelectric properties, can be used for fields such as electro-conductive material, solar cell material, photoconductive material and photoelectric conversion material.
Advantage of the present invention is: 1. the present invention is the nano combined photosensitive film material of a kind of polythiofuran-carbon nanotube, it is made up of carbon nanotube and Polythiophene, the absorption of this film in visible region red shift along with the increase of content of carbon nanotubes, compare with simple Polythiophene, its absorption spectrum is taken into account the near infrared light zone more, mate more with the ground solar spectrum, thereby improved it solar energy utilization rate; 2. the product that utilizes the present invention to prepare has higher light sensitivity, consistency and thermostability, and having good solubility property, film forming properties and photoelectric properties, the package stability of this nano combined photo-conductive film material and the carbon nanotube dispersing uniformity in Polythiophene etc. will be better than traditional physical method far away; Advantage such as preparation method 3. of the present invention has that technology is easy, film quality is high, input-output ratio is high, with low cost and application prospect is extensive, the product that utilizes the present invention to prepare, be new generation of green environment-friendly and high-performance Chemicals, can be used for fields such as electro-conductive material, solar cell material, photoconductive material and photoelectric conversion material.
Description of drawings
Fig. 1 is the projection Electronic Speculum figure of polythiofuran-carbon nanotube laminated film, and left side figure is the polythiofuran-carbon nanotube matrix material, and right figure is a carbon nanotube.
Fig. 2 is the uv-visible absorption spectrum figure of polythiofuran-carbon nanotube laminated film, and a is a carbon nanotube; B is a Polythiophene; C is a Polythiophene: carbon nanotube=6: 1 (weight ratio); D is a Polythiophene: carbon nanotube=3: 1 (weight ratio).
Embodiment
Embodiment 1
With the 500mg multi-walled carbon nano-tubes adding 150mL vitriol oil and concentrated nitric acid is in the mixed strong acids solution of forming at 3: 1 by volume, and sonic oscillation was handled 4 hours, poured in the deionized water, and leave standstill more than 12 hours, filter and be washed to neutrality, dry again, obtain the carbon nanotube of chemical etching; Under nitrogen protection, the carbon nanotube of the above-mentioned band carboxylic acid of 400mg is placed the excessive thionyl chloride 36h that refluxes, reaction finishes, and excessive thionyl chloride is removed in underpressure distillation, and vacuum-drying obtains the carbon nanotube of chloride; Carbon nanotube with the above-mentioned chloride of 200mg is dispersed in the anhydrous propanone again, under 65 ℃ of conditions, dripping 10mL concentration is the acetone soln of the amino dodecane of 0.01g/mL, the dropping time was not less than 60～70 minutes, successive reaction 12 hours, centrifuging and be washed to neutrality, 40 ℃ of following vacuum-dryings of temperature obtained the amino dodecane modified carbon nanotube more than 12 hours; Under nitrogen protection; in the 250mL four-hole boiling flask, add the FERRIC CHLORIDE ANHYDROUS of 4.85g and the chloroform of 15mL; stir under the room temperature and obtained the muddy liquid of sap green in 15 minutes, dropwise add the monomeric 12mL chloroformic solution of 3-hexyl thiophene of 1.68g then, stirring at room 12 hours.Slowly pour mixture in 300mL methyl alcohol sedimentation, filter, remaining solid is soaked intrinsicization with strong aqua, be washed till neutrality with deionized water then, dry in the vacuum drying oven.With the dissolving of 50mL chloroform, remove by filter insoluble part then, filtrate is used the methyl alcohol sedimentation of 300mL, the solid of gained is washed till colourless with methyl alcohol, repeat chloroform dissolving-ethanol settling process more than 3 times, removes impurity, promptly get poly-(the 3-hexyl thiophene) of intrinsicization, productive rate is 60%.
Under powerful agitation condition, in the chloroformic solution of the carbon nanotube that the above-mentioned amino dodecane modification of 100mg is handled, slowly drip the chloroformic solution of 100mg poly-(3-hexyl thiophene), wherein, the concentration of carbon nanotube is 1.0mg/mL, the concentration of poly-(3-hexyl thiophene) is 6.0mg/mL, and carbon nanotube is 1: 6 with the weight ratio of poly-(3-hexyl thiophene).Stirring at room 3 hours obtains the chloroformic solution of a kind of carbon nano-tube/poly (3-hexyl thiophene) nano composite material.Adopt spin-coating method that the chloroformic solution of above-mentioned carbon nano-tube/poly (3-hexyl thiophene) nano composite material is coated on the ito glass sheet at last, its surface covered is 5.0mm/s, coating fluid viscosity is at 200cp, bake out temperature is 35 ℃, drying time is 2 hours, and the compound photosensitive coat thickness of exsiccant organic and inorganic is 35 μ m.
The projection Electronic Speculum figure of this poly-(3-hexyl thiophene)/carbon nanotube chloroformic solution sees Fig. 2 and be somebody's turn to do the photosensitive property that gathers (3-hexyl thiophene)/carbon nano-tube film as shown in Figure 1.
Embodiment 2
Identical with embodiment 1, but carbon nanotube became 1: 3 with the weight ratio of gathering (3-hexyl thiophene) by 1: 6.Should gather the photosensitive property of (3-hexyl thiophene)/carbon nano-tube film and see Fig. 4.
Embodiment 3
Identical with embodiment 1, but carbon nanotube became 1: 1 with the weight ratio of gathering (3-hexyl thiophene) by 1: 6.
Embodiment 4
Identical with embodiment 1, but the 3-hexyl thiophene becomes 3-octyl group substituted thiophene.
Embodiment 5
Identical with embodiment 1, but the 3-hexyl thiophene becomes 3,4-two (isopentyl) substituted thiophene.
Embodiment 6
Identical with embodiment 1, but amino dodecane becomes n-Butyl Amine 99, and consumption is constant.
Embodiment 7
Identical with embodiment 1, but amino dodecane becomes stearylamine, consumption becomes 6mL by 10mL, and concentration still is 0.01g/mL.
Embodiment 8
Identical with embodiment 1, but coating method changes dip coating into by spin-coating method, and conductive matrices changes metallic aluminium into by the ito glass sheet.
Embodiment 9
Identical with embodiment 1, but organic solvent becomes tetrahydrofuran (THF) by chloroform.
Embodiment 10
Identical with embodiment 1, but organic solvent becomes ethylene glycol monobutyl ether by chloroform, bake out temperature becomes 120 ℃, and drying time is 5 hours.
Embodiment 11
Identical with embodiment 1, but the compound photosensitive coat thickness of polythiofuran-carbon nanotube becomes 15 μ m by 35 μ m.
Embodiment 12
Identical with embodiment 1, but the compound photosensitive coat thickness of polythiofuran-carbon nanotube becomes 55 μ m by 35 μ m.
Polythiofuran-carbon nanotube complex light sensitive film that obtains among the embodiment 2-12 and the nano compound film of embodiment 1 have similar performance.
Claims (7)
1, the preparation method of the nano combined photosensitivity film of a kind of polythiofuran-carbon nanotube is characterized in that concrete steps are:
(1) be 3 by volume with 100～1000mg multi-walled carbon nano-tubes adding 150ml vitriol oil and concentrated nitric acid: 0.8-3: in the 1.2 mixed strong acids solution of forming, sonic oscillation was handled 3～12 hours, pour in the deionized water, and leave standstill more than 12 hours, filter and be washed to neutrality, oven dry obtains the carbon nanotube with carboxyl again;
(2) under nitrogen protection, the carbon nanotube of the above-mentioned band carboxylic acid of 80～800mg is placed the excessive thionyl chloride 12～72h that refluxes, reaction finishes, and excessive thionyl chloride is removed in underpressure distillation, and vacuum-drying obtains the carbon nanotube of chloride;
(3) carbon nanotube with the above-mentioned chloride of 50～500mg is dispersed in the anhydrous propanone, drip several fresh pyridines or triethylamine, under 58～65 ℃ of conditions, dropwise Dropwise 5～20ml concentration is the organic amine of 0.005～0.025g/ml or the acetone soln of organic alcohol, the dropping time was not less than 30 minutes, dropwised successive reaction 4～72 hours, excessive organic amine or organic alcohol are removed with a large amount of acetone thorough washing, centrifuging, vacuum-drying obtains organic amine or organic pure modified carbon nanotube;
(4) under nitrogen protection, in the 250mL four-hole boiling flask, add the FERRIC CHLORIDE ANHYDROUS of 0.05～5g and the chloroform of 5～50ml, stir under the room temperature and obtained the muddy liquid of sap green in 5～90 minutes, the alkylated substituted thiazoline fen or the monomeric 5～50mL chloroformic solution of alkoxyl group substituted thiophene that dropwise add 0.5～5g then, stirring at room 4～72 hours; Slowly pour mixture in 50～1000mL methyl alcohol sedimentation, filter, remaining solid is soaked intrinsicization with strong aqua, be washed till neutrality with deionized water then, dry in the vacuum drying oven; With 10～100mL chloroform dissolving, remove by filter insoluble part then, filtrate is with the methyl alcohol sedimentation of 100～500mL, the solid of gained is washed till colourless with methyl alcohol, repeat chloroform dissolving-methyl alcohol settling process more than 3 times, remove impurity, promptly get the polythiofuran derivative of intrinsicization;
(5) carbon nanotube with the above-mentioned organic amine of 50～500mg or organic pure modification processing is dispersed in the organic solvent, and the concentration of carbon nanotube is 0.5～10mg/mL; 50～500mg polythiofuran derivative is dissolved in the organic solvent, and the concentration of polythiofuran derivative is 0.5～10mg/mL; Under powerful agitation condition, slowly be added dropwise to polythiofuran derivative solution in the carbon nano-tube solution, the weight ratio of carbon nanotube and polythiofuran derivative is 1: 1～20, and stirring at room 1～12 hour obtains a kind of polythiofuran derivative-carbon nano tube compound material solution;
(6) adopt coating method that above-mentioned polythiofuran derivative-carbon nano tube compound material solution is coated on the conductive matrices, its surface covered is 2.0～10.0mm/s, coating fluid viscosity is at 100～500cp, oven dry then, bake out temperature is 35～120 ℃, drying time is 0.5～6 hour, and the compound photosensitive coat thickness of exsiccant polythiofuran derivative-carbon nanotube is 15～45 μ m.
2, preparation method according to claim 1, it is characterized in that described alkylated substituted thiazoline fen is 3-butyl substituted thiophene, 3-isopentyl substituted thiophene, 3-n-pentyl substituted thiophene, 3-hexyl substituted thiophene, 3-octyl group substituted thiophene, 3-iso-octyl substituted thiophene, 3-(2-ethyl) hexyl substituted thiophene, 3-dodecyl substituted thiophene, 3,4-two (isopentyl) substituted thiophene or 3,4-two (dodecyl) substituted thiophene; Described alkoxyl group substituted thiophene is 3-methoxyl group substituted thiophene, 3-pentyloxy substituted thiophene, 3-octyloxy substituted thiophene, 3-(dodecyl) thiophene-3-(pentyloxy) thiophene copolymers or 3-(dodecyl) thiophene-3-(octyloxy) thiophene copolymers.
3, preparation method according to claim 1 is characterized in that described organic amine is ethamine, Tri N-Propyl Amine, Isopropylamine, n-Butyl Amine 99, isobutylamine, sec-butylamine, n-amylamine, n-octyl amine, octodrine, N, N-diisopropylethylamine, amino dodecane or stearylamine; Described organic alcohol is ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, Pentyl alcohol, neopentyl alcohol, octanol, decyl alcohol, lauryl alcohol or stearyl alcohol.
4, preparation method according to claim 1, it is characterized in that described organic solvent is a chloroform, methylene dichloride, tetrachloroethane, tetrahydrofuran (THF), dioxane, acetonitrile, N, dinethylformamide, N, the N-N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol phenyl ether, diethylene glycol dimethyl ether, dibutyl ethylene glycol ether, the two methyl ethers of glycol ether, diethyl carbitol or diethylene glycol ethyl ether butylcarbitol, or wherein several mixtures.
5, preparation method according to claim 1, it is characterized in that used conductive matrices be conduction tinsel, ito glass or above scribble the polyester chips of conducting medium, or drum type, zonal conducting metal and electrical conductivity alloy.
6, preparation method according to claim 1 is characterized in that said coating method, can be spin-coating method, dip coating, draw together the method for being coated with or casting.
7, a kind of polythiofuran-carbon nanotube composite photosensitive film material of the acquisition of preparation method as claimed in claim 1 or 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100392040A CN101298510B (en) | 2008-06-19 | 2008-06-19 | Polythiofuran-carbon nanotube composite photosensitive film material and preparation thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100392040A CN101298510B (en) | 2008-06-19 | 2008-06-19 | Polythiofuran-carbon nanotube composite photosensitive film material and preparation thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101298510A true CN101298510A (en) | 2008-11-05 |
| CN101298510B CN101298510B (en) | 2010-06-02 |
Family
ID=40078472
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008100392040A Expired - Fee Related CN101298510B (en) | 2008-06-19 | 2008-06-19 | Polythiofuran-carbon nanotube composite photosensitive film material and preparation thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101298510B (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102102243A (en) * | 2010-12-13 | 2011-06-22 | 中国航空工业集团公司北京航空材料研究院 | Method for preparing polythiophene derivative-carbon nano tube nano composite fibers at low temperature |
| CN102142521A (en) * | 2010-01-29 | 2011-08-03 | 海洋王照明科技股份有限公司 | Organic solar battery and preparation method thereof |
| CN102161816A (en) * | 2011-01-10 | 2011-08-24 | 同济大学 | Method for preparing polythiophene-carbon nano tube composite photoconductive film material by click chemistry |
| CN102432982A (en) * | 2011-08-30 | 2012-05-02 | 同济大学 | Method for preparing phthalocyanine-carbon nanotube-polythiophene composite light-sensitive material by click chemical method |
| CN103033537A (en) * | 2012-12-20 | 2013-04-10 | 中国科学院微电子研究所 | Preparation method of gas sensor sensitive film based on flexible substrate |
| CN103755927A (en) * | 2013-12-30 | 2014-04-30 | 北京化工大学 | Preparation method of cadmium sulfide/poly 3-hexyl thiophene/carbon nanotube composite material |
| CN104592716B (en) * | 2015-01-13 | 2016-08-24 | 西安医学院 | A kind of preparation method of CNT-Conjugated Polymer Composites |
| CN109293934A (en) * | 2018-09-03 | 2019-02-01 | 重庆工业职业技术学院 | A kind of preparation method of polythiophene liquid crystal/multi-wall carbon nano-tube composite material |
| CN109467713A (en) * | 2018-11-12 | 2019-03-15 | 深圳烯湾科技有限公司 | Utilize the method and modified carbon nano-tube of poly- 3- hexyl thiophene modified carbon nano-tube |
| CN109517345A (en) * | 2018-11-12 | 2019-03-26 | 深圳烯湾科技有限公司 | Poly- 3- hexyl thiophene material of a kind of carbon nanotube bonding and preparation method thereof |
| CN110148532A (en) * | 2019-05-27 | 2019-08-20 | 南京林业大学 | A kind of hydrophily polythiophene grafting carbon nanotube electrode material for super capacitor |
| CN110272614A (en) * | 2019-07-18 | 2019-09-24 | 中国科学院合肥物质科学研究院 | A kind of composite heat-conducting high molecular material |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101020664B1 (en) * | 2004-05-28 | 2011-03-09 | 삼성에스디아이 주식회사 | A composition for preparing an emitter, an emitter and an electron emission device comprising the same |
| CN1300259C (en) * | 2005-04-20 | 2007-02-14 | 天津大学 | Method for preparing nonlinear optical material of linkage nano carbon tubes of polythiophene methylene |
| CN100491466C (en) * | 2006-09-27 | 2009-05-27 | 北京交通大学 | Method of preparing polythiophene or derivative thereof-multiwall carbon nano-tube composite material |
-
2008
- 2008-06-19 CN CN2008100392040A patent/CN101298510B/en not_active Expired - Fee Related
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102142521A (en) * | 2010-01-29 | 2011-08-03 | 海洋王照明科技股份有限公司 | Organic solar battery and preparation method thereof |
| CN102102243A (en) * | 2010-12-13 | 2011-06-22 | 中国航空工业集团公司北京航空材料研究院 | Method for preparing polythiophene derivative-carbon nano tube nano composite fibers at low temperature |
| CN102102243B (en) * | 2010-12-13 | 2012-07-25 | 中国航空工业集团公司北京航空材料研究院 | Method for preparing polythiophene derivative-carbon nano tube nano composite fibers at low temperature |
| CN102161816A (en) * | 2011-01-10 | 2011-08-24 | 同济大学 | Method for preparing polythiophene-carbon nano tube composite photoconductive film material by click chemistry |
| CN102161816B (en) * | 2011-01-10 | 2012-12-05 | 同济大学 | Method for preparing polythiophene-carbon nano tube composite photoconductive film material by click chemistry |
| CN102432982A (en) * | 2011-08-30 | 2012-05-02 | 同济大学 | Method for preparing phthalocyanine-carbon nanotube-polythiophene composite light-sensitive material by click chemical method |
| CN103033537A (en) * | 2012-12-20 | 2013-04-10 | 中国科学院微电子研究所 | Preparation method of gas sensor sensitive film based on flexible substrate |
| CN103755927A (en) * | 2013-12-30 | 2014-04-30 | 北京化工大学 | Preparation method of cadmium sulfide/poly 3-hexyl thiophene/carbon nanotube composite material |
| CN104592716B (en) * | 2015-01-13 | 2016-08-24 | 西安医学院 | A kind of preparation method of CNT-Conjugated Polymer Composites |
| CN109293934A (en) * | 2018-09-03 | 2019-02-01 | 重庆工业职业技术学院 | A kind of preparation method of polythiophene liquid crystal/multi-wall carbon nano-tube composite material |
| CN109293934B (en) * | 2018-09-03 | 2021-02-26 | 重庆工业职业技术学院 | Preparation method of polythiophene liquid crystal/multi-walled carbon nanotube composite material |
| CN109467713A (en) * | 2018-11-12 | 2019-03-15 | 深圳烯湾科技有限公司 | Utilize the method and modified carbon nano-tube of poly- 3- hexyl thiophene modified carbon nano-tube |
| CN109517345A (en) * | 2018-11-12 | 2019-03-26 | 深圳烯湾科技有限公司 | Poly- 3- hexyl thiophene material of a kind of carbon nanotube bonding and preparation method thereof |
| CN109517345B (en) * | 2018-11-12 | 2020-11-10 | 深圳烯湾科技有限公司 | Multi-walled carbon nanotube bonded poly (3-hexylthiophene) material and preparation method thereof |
| CN110148532A (en) * | 2019-05-27 | 2019-08-20 | 南京林业大学 | A kind of hydrophily polythiophene grafting carbon nanotube electrode material for super capacitor |
| CN110148532B (en) * | 2019-05-27 | 2021-03-12 | 南京林业大学 | Hydrophilic polythiophene grafted carbon nanotube supercapacitor electrode material |
| CN110272614A (en) * | 2019-07-18 | 2019-09-24 | 中国科学院合肥物质科学研究院 | A kind of composite heat-conducting high molecular material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101298510B (en) | 2010-06-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101298510B (en) | Polythiofuran-carbon nanotube composite photosensitive film material and preparation thereof | |
| Tang et al. | Recent development of conjugated oligomers for high-efficiency bulk-heterojunction solar cells | |
| JP6297891B2 (en) | Organic material and photoelectric conversion element | |
| Sharma et al. | Triazine-bridged porphyrin triad as electron donor for solution-processed bulk hetero-junction organic solar cells | |
| CN102725331A (en) | Cyclopentadienedithiophene-quinoxaline conjugated polymer and preparation method and uses thereof | |
| Yu et al. | Two-dimensional regioregular polythiophenes with conjugated side chains for use in organic solar cells | |
| Dyer-Smith et al. | Organic solar cells | |
| Dong et al. | Construction of a long range p/n heterojunction with a pair of nanometre-wide continuous D/A phases | |
| Lee et al. | Random copolymers based on 3‐hexylthiophene and benzothiadiazole with induced π‐conjugation length and enhanced open‐circuit voltage property for organic photovoltaics | |
| CN102161816B (en) | Method for preparing polythiophene-carbon nano tube composite photoconductive film material by click chemistry | |
| JP6200096B2 (en) | Copolymer and organic solar cell including the same | |
| JP5699524B2 (en) | Organic photoelectric conversion element and solar cell | |
| CN102070776B (en) | Preparation method and film forming method of segmented copolymers with fullerene at main chain | |
| CN102219773A (en) | X-type two-dimensional or three-dimensional conjugated molecules based on oligomerized thiophene as well as preparation method and application thereof | |
| Lee et al. | Synthesis of random copolymers based on 3-hexylthiophene and quinoxaline derivative: Influence between the intramolecular charge transfer (ICT) effect and π-conjugation length for their photovoltaic properties | |
| WO2012031403A1 (en) | Perylenetetracarboxylic acid diimide organic semiconductive material, preparation method and use thereof | |
| Choi et al. | Effect of side chains on solubility and morphology of poly (benzodithiohene-alt-alkylbithiophene) in organic photovoltaics | |
| CN102181179B (en) | Method for preparing soluble substituted phthalocyanine-carbon nano tube composite photosensitive material by click chemical method | |
| Nikitenko et al. | Thiazolothiazole-containing conjugated polymers for indoor organic photovoltaic cells | |
| JP2012109365A (en) | Organic photoelectric conversion element and solar cell | |
| CN102770476A (en) | Porphyrin copolymer containing quinoxaline unit, preparation method and uses thereof | |
| Sheibani et al. | Conjugated Polymer for Charge Transporting Applications in Solar Cells | |
| CN110003245B (en) | Alkyl/thioalkyl nitrogen heterocyclic aromatic ring end D (A-Ar)2Conjugated compound, preparation method and application thereof | |
| KR20130038548A (en) | The organic photovoltaic polymer containing phenazine derivative and manufacturing method thereof | |
| Dogan et al. | Photophysical and Photovoltaic Characterization of Flourene-Anthracene-Benzothiadiazole Based Donor–Acceptor Type Copolymers for Bulk Heterojunction Polymer Solar Cells |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20100602 Termination date: 20130619 |