CN116410627A - Preparation method of transparent conductive coating based on evaporation self-driving and transparent conductive coating - Google Patents
Preparation method of transparent conductive coating based on evaporation self-driving and transparent conductive coating Download PDFInfo
- Publication number
- CN116410627A CN116410627A CN202310348393.4A CN202310348393A CN116410627A CN 116410627 A CN116410627 A CN 116410627A CN 202310348393 A CN202310348393 A CN 202310348393A CN 116410627 A CN116410627 A CN 116410627A
- Authority
- CN
- China
- Prior art keywords
- transparent conductive
- conductive coating
- thickener
- preparation
- substrate
- 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.)
- Pending
Links
- 238000000576 coating method Methods 0.000 title claims abstract description 76
- 239000011248 coating agent Substances 0.000 title claims abstract description 66
- 238000001704 evaporation Methods 0.000 title claims abstract description 35
- 230000008020 evaporation Effects 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000002086 nanomaterial Substances 0.000 claims abstract description 39
- 239000000758 substrate Substances 0.000 claims abstract description 38
- 238000010438 heat treatment Methods 0.000 claims abstract description 37
- 239000006185 dispersion Substances 0.000 claims abstract description 35
- 239000002562 thickening agent Substances 0.000 claims abstract description 32
- 239000007788 liquid Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000007864 aqueous solution Substances 0.000 claims abstract description 15
- 239000007900 aqueous suspension Substances 0.000 claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims description 24
- 239000002184 metal Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 21
- 239000000919 ceramic Substances 0.000 claims description 20
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical group [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 19
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 19
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 19
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 19
- 239000002070 nanowire Substances 0.000 claims description 18
- 239000011521 glass Substances 0.000 claims description 9
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 8
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 7
- 229920000609 methyl cellulose Polymers 0.000 claims description 7
- 239000001923 methylcellulose Substances 0.000 claims description 7
- 235000010981 methylcellulose Nutrition 0.000 claims description 7
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 7
- 239000000661 sodium alginate Substances 0.000 claims description 7
- 235000010413 sodium alginate Nutrition 0.000 claims description 7
- 229940005550 sodium alginate Drugs 0.000 claims description 7
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000002041 carbon nanotube Substances 0.000 claims description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 4
- 230000003287 optical effect Effects 0.000 abstract description 9
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 48
- 239000002042 Silver nanowire Substances 0.000 description 48
- 230000000052 comparative effect Effects 0.000 description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 17
- 238000000879 optical micrograph Methods 0.000 description 9
- 239000000377 silicon dioxide Substances 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 230000008569 process Effects 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000004642 Polyimide Substances 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 238000001132 ultrasonic dispersion Methods 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 2
- 238000003618 dip coating Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000005693 optoelectronics Effects 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 238000011002 quantification Methods 0.000 description 2
- 230000000284 resting effect Effects 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 241000220225 Malus Species 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011195 cermet Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001918 dark-field optical micrograph Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 238000002073 fluorescence micrograph Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
Abstract
The invention provides a preparation method of a transparent conductive coating based on evaporation self-driving and the transparent conductive coating, and relates to the technical field of photoelectric functional coatings. The invention provides a preparation method of a transparent conductive coating based on evaporation self-driving, which comprises the following steps: mixing the linear nano material aqueous suspension and the thickener aqueous solution to obtain a dispersion; and vertically inserting a heatable substrate into the dispersion liquid, and heating the heatable substrate to evaporate water in the dispersion liquid to obtain the transparent conductive coating. The invention adopts the evaporation self-driven arrangement of the linear nano materials, and the finally formed linear nano materials in the transparent conductive coating have orderly arranged network structures, so that the coating has obvious optical and electrical anisotropism; the preparation method provided by the invention is simple to operate, can be directly molded at one time, and is suitable for large-scale production and manufacturing.
Description
Technical Field
The invention relates to the technical field of photoelectric functional coatings, in particular to a preparation method of a transparent conductive coating based on evaporation self-driving and the transparent conductive coating.
Background
In recent years, with the rapid development of the optoelectronic industry, a number of new generation optoelectronic products represented by touch screens, organic light emitting diodes, smart wearable devices, and solar cells are gradually affecting and improving people's lives. Among them, with the increasing demands for integration, flexibility and wearable of photovoltaic devices, a method for preparing a flexible photovoltaic thin film device in a large area has become an important research content in the photovoltaic field. The excellent performance of the transparent conductive electrode, which is one of the key components of the flexible photoelectric thin film device, has become a key factor affecting the performance of devices such as flexible solar cells, flexible display touch screens and the like.
Silver nanowires (AgNWs) are one-dimensional nanomaterials with a large aspect ratio (in space on the nanoscale in two dimensions and on the microscale in the third dimension), and have advantages including high electrical conductivity, high thermal conductivity, and stable chemical properties possessed by bulk silver, high specific surface area, high optical transparency, and high bending resistance possessed by nanowires, and attractive electrical and optical anisotropies. The unique physicochemical properties of silver nanowires make silver nanowires widely applied to industries such as flexible sensing, flexible solar cells, flexible display touch screens and the like in recent years. The large length-diameter ratio of the silver nanowires enables the coating to form a conductive network which is orderly arranged on the microcosmic scale, so that the connection resistance between the silver nanowires can be effectively reduced, the transparency is improved under the condition that the conductive performance is not influenced, and the photoelectric performance of the device is improved. Meanwhile, the ordered silver nanowire network structure with the microscopic anisotropic structure can endow the transparent electrode with unique electrical and optical anisotropism, so that the transparent electrode can be applied to the fields of antennas, polarization sensors, surface-enhanced Raman scattering and the like.
At present, the methods commonly used in the academic community for realizing the self-assembly of the one-dimensional nano materials include Langmuir-Blodgett technology, a dip-coating method, an external field assisted alignment method, a microfluidic technology, a photoetching technology and the like. Most of these methods require complex equipment and precise control of the nanowire self-assembled precursors, which makes them unusable for large-scale manufacturing.
Disclosure of Invention
The invention aims to provide a preparation method of a transparent conductive coating based on evaporation self-driving and the transparent conductive coating.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a transparent conductive coating based on evaporation self-driving, which comprises the following steps:
mixing the linear nano material aqueous suspension and the thickener aqueous solution to obtain a dispersion; the mass fraction of the thickener in the thickener aqueous solution is 0.01-0.2 wt%;
vertically inserting a heatable substrate into the dispersion liquid, heating the heatable substrate to evaporate water in the dispersion liquid, and obtaining a transparent conductive coating; the heating temperature is 60-90 ℃.
Preferably, the thickener is a water-soluble thickener.
Preferably, the thickener is sodium carboxymethyl cellulose, sodium alginate, sodium polyacrylate or methyl cellulose.
Preferably, the concentration of the linear nanomaterial in the dispersion is 0.005-0.05 mg/mL.
Preferably, the linear nanomaterial in the aqueous suspension of linear nanomaterial comprises metal nanowires, inorganic nonmetallic nanowires, or carbon nanotubes.
Preferably, the heatable substrate comprises a substrate sheet and a flat heater attached to the substrate sheet.
Preferably, the substrate sheet is a glass sheet; the flat heater is a metal ceramic heating plate.
Preferably, the heatable substrate is intermittently pulled during heating of the heatable substrate.
Preferably, the intermittent pulling comprises: the heatable substrate is pulled up a distance, allowed to rest for a period of time, and then the pulling-resting is repeated.
The invention provides the transparent conductive coating prepared by the preparation method of the technical scheme, and the transparent conductive coating has an ordered conductive network structure.
The invention provides a preparation method of a transparent conductive coating based on evaporation self-driving, which comprises the following steps: mixing the linear nano material aqueous suspension and the thickener aqueous solution to obtain a dispersion; and vertically inserting a heatable substrate into the dispersion liquid, and heating the heatable substrate to evaporate water in the dispersion liquid to obtain the transparent conductive coating. The invention adopts the evaporation self-driven arrangement of the linear nano material, and the finally formed linear nano material in the transparent conductive coating has a network structure which is orderly arranged, so that the coating has obvious optical and electrical anisotropism, has better transparency and certain conductivity, and solves the problems of poor conductivity and low transparency caused by disordered arrangement of the linear nano material in the coating in the prior art. The preparation method provided by the invention is simple, is simple and convenient to operate, has low cost, is easy to prepare in a large scale, and can be applied to the field of advanced photoelectric devices.
The invention uses the vertical dipping and evaporating process, so that the thickness of the finally prepared coating is uniform, the coating is suitable for any complex curved surface, and the actual requirements in the production and manufacturing process are met.
Drawings
FIG. 1 is a schematic illustration of a process for preparing a transparent conductive coating based on evaporation self-driving in accordance with the present invention;
FIG. 2 is an optical micrograph of a transparent conductive coating obtained after evaporating solutions of different sodium carboxymethyl cellulose concentrations in example 1, examples 2-4 and comparative examples 1-2;
FIG. 3 is a graph showing the quantification of the degree of alignment (Huffman orientation factor) of silver nanowires in transparent conductive coatings obtained by evaporating solutions of different sodium carboxymethyl cellulose concentrations in example 1, examples 2 to 4 and comparative examples 1 to 2;
FIG. 4 is an optical micrograph of the transparent conductive coating obtained at different evaporation temperatures for example 1, examples 5-6 and comparative examples 3-5;
fig. 5 is a graph showing the quantification of the degree of arrangement (hellman orientation factor) of silver nanowires in transparent conductive coatings obtained at different evaporation temperatures for example 1, examples 5 to 6 and comparative examples 3 to 5;
FIG. 6 is a macroscopic photograph of the transparent conductive coating obtained in example 1;
FIG. 7 is a graph showing the sheet resistance of the transparent conductive coating prepared in example 1 according to the measured azimuth angle α;
FIG. 8 is an optical micrograph of the transparent conductive coating obtained in example 1 in the path of polarized light;
FIG. 9 is a graph showing the variation of the transmitted light intensity of the transparent conductive coating obtained in example 1 according to the measured azimuth angle θ;
FIG. 10 is an optical micrograph of the silver nanowire coatings obtained in examples 7 to 9;
FIG. 11 is a fluorescence microscopy image of the silica nanowire coating obtained in example 10;
FIG. 12 is a schematic flow chart of example 11;
fig. 13 is a dark field optical micrograph of the silver nanowire alternating orthogonal arrangement coating obtained in example 11.
Detailed Description
The invention provides a preparation method of a transparent conductive coating based on evaporation self-driving, which comprises the following steps:
mixing the linear nano material aqueous suspension and the thickener aqueous solution to obtain a dispersion; the mass fraction of the thickener in the thickener aqueous solution is 0.01-0.2 wt%;
vertically inserting a heatable substrate into the dispersion liquid, heating the heatable substrate to evaporate water in the dispersion liquid, and obtaining a transparent conductive coating; the heating temperature is 60-90 ℃.
The invention mixes the linear nanometer material water suspension and thickener water solution to obtain dispersion liquid. In the present invention, the linear nanomaterial in the aqueous suspension of linear nanomaterial preferably includes a metal nanowire, an inorganic nonmetallic nanowire, or a carbon nanotube. In the present invention, the metal nanowire is preferably a silver nanowire; the length of the silver nanowire is preferably 40-60 mu m, and the diameter is preferably 20-40 nm. In the present invention, the inorganic nonmetallic nanowire is preferably a silica nanowire; the length of the silica nanowire is preferably 40-60 μm, and the diameter is preferably 20-40 nm. In the present invention, the carbon nanotubes preferably have a length of 30 to 50. Mu.m, and a diameter of 8 to 15nm. In the present invention, the mass fraction of the linear nanomaterial in the linear nanomaterial aqueous suspension is preferably 0.005 to 0.05mg/mL.
In the present invention, the thickener is preferably a water-soluble thickener, more preferably sodium carboxymethyl cellulose, sodium alginate, sodium polyacrylate, or methyl cellulose. In the present invention, the average molecular weight of the sodium carboxymethyl cellulose is mw=700000, and the polymerization degree ds=0.9. In the present invention, the viscosity of 1wt% sodium alginate aqueous solution is preferably 1.05 to 1.15 Pa.s; the average molecular weight MW of the sodium polyacrylate is preferably 400-500 ten thousand; the viscosity of the 1% by weight aqueous solution of methylcellulose is preferably 400 mPas.
In the present invention, the mass fraction of the thickener in the thickener aqueous solution is 0.01 to 0.2wt%, preferably 0.05 to 0.1wt%. The concentration of the thickener aqueous solution is controlled in the range, a flow field tends to be stable in the evaporation process, so that the linear nano materials are orderly arranged and deposited, and if the concentration is lower than 0.01wt percent, the linear nano materials cannot be orderly arranged, and if the concentration is higher than 0.2wt percent, the linear nano materials are bonded and the film of the thickener is uneven.
In the present invention, the method for preparing the thickener aqueous solution preferably includes: stirring the thickener and water at normal temperature to obtain a thickener aqueous solution. In the present invention, the water is preferably deionized water. In the present invention, the stirring is preferably magnetic stirring; the stirring speed is preferably 600r/min.
In the present invention, the mixing of the aqueous suspension of the linear nanomaterial and the aqueous solution of the thickener is preferably performed at room temperature. In the present invention, the mixing is preferably water bath ultrasonic dispersion. In the invention, the power of the water bath ultrasonic dispersion is preferably 150W; the time of the ultrasonic dispersion in the water bath is preferably 3 minutes.
In the present invention, the concentration of the linear nanomaterial in the dispersion is preferably 0.005 to 0.05mg/mL, more preferably 0.025mg/mL. In the present invention, the concentration of the linear nanomaterial in the dispersion liquid is in the above range, so that the density of the linear nanomaterial coating layer can be made uniform, and if the concentration is lower than 0.005mg/mL, the conductivity of the coating layer is lowered, and if the concentration is higher than 0.05mg/mL, the alignment effect is affected by excessive accumulation of the linear nanomaterial.
After the dispersion liquid is obtained, the heatable substrate is vertically inserted into the dispersion liquid, and the heatable substrate is heated to evaporate water in the dispersion liquid, so that the transparent conductive coating is obtained. In the present invention, the heatable substrate preferably includes a substrate sheet and a flat heater attached to the substrate sheet. In the present invention, the base sheet is preferably a glass sheet; the flat heater is preferably a cermet heater plate. In the invention, the metal ceramic heating plate is preferably a high-temperature co-fired metal ceramic heating plate, the voltage applied to the metal ceramic heating plate ranges from 10 to 30V, the corresponding heating power ranges from 2 to 20W, and the corresponding stable heating temperature ranges from 40 to 90 ℃. In the present invention, the method of attaching is preferably to attach using a polyimide tape.
In the present invention, the heating temperature is 60 to 90 ℃, preferably 65 to 90 ℃. In the present invention, the purpose of the heating is to enrich the thickener at the contact line, thereby changing the viscosity gradient of the dispersion so that the viscosity of the dispersion assumes a higher state as it approaches the contact line; and meanwhile, the dispersion liquid can generate a Marangoni flow in a counterclockwise direction, so that the flow field direction on the surface of the substrate sheet is ensured to be directed to a contact line from the inside of the liquid. Under the action of viscosity gradient of the dispersion liquid, the front end and the rear end of the linear nano material generate speed difference in the process of gradually moving to the contact line along with evaporation, so that a rotation moment is generated, the linear nano material deflects until the linear nano material is parallel to the contact line, and finally the linear nano material forms an orderly arrangement structure, so that the formed coating has better conductivity and light transmittance.
In the present invention, the heatable substrate preferably further comprises, before vertically inserting into the dispersion: the heatable substrate is preheated. In the present invention, it is preferable to preheat to the heating temperature. In a specific embodiment of the present invention, the preheating time is preferably 1min.
The invention preferably intermittently pulls the heatable substrate during heating of the heatable substrate. In the present invention, the intermittent pulling preferably includes: the heatable substrate is pulled up a distance, allowed to rest for a period of time, and then the pulling-resting is repeated. In the present invention, the distance per pull is preferably 100 to 1000 μm; the time for each resting is preferably 1 to 5 minutes, more preferably 2 minutes. In the present invention, the rate of the pulling is preferably 0.5 to 2mm/s, more preferably 1mm/s.
The invention can realize the preparation of transparent conductive coatings with orthogonal arrangement directions on the same substrate by combining the dipping and pulling method. In a specific embodiment of the invention, the nano motor is used to apply upward dragging motion to the heating plate, so that the arrangement direction of the silver nanowires is changed to be perpendicular to the contact line.
Preferably, the transparent conductive coating is obtained after the substrate sheet is taken down and cleaned after the water is completely evaporated. In the present invention, the washing is preferably performed with absolute ethanol.
The preparation method based on evaporation self-driving ensures that the linear nano materials are orderly arranged in the coating, so that the coating has better conductivity and light transmittance.
The invention provides the transparent conductive coating prepared by the preparation method of the technical scheme, and the transparent conductive coating has an ordered conductive network structure.
The invention realizes the large-area preparation of the transparent conductive coating with the ordered linear nano material network structure by evaporating the dispersion liquid containing the linear nano material and the thickener and adopting a vertical dipping evaporation mode. The preparation method provided by the invention has simple and convenient flow, is not limited by special equipment, can be popularized to different types of one-dimensional nano materials according to actual needs, and has strong universality and high feasibility. Therefore, the invention has a great application prospect in the field of photoelectric functional coatings.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The experimental methods used in the following examples are conventional methods unless otherwise specified.
Materials and reagents used in the examples described below, unless otherwise indicated, are all commercially available.
Example 1
The transparent conductive coating was prepared using the preparation process shown in fig. 1:
step 1: taking 0.1g of sodium carboxymethyl cellulose and 100mL of deionized water, and stirring at normal temperature until the sodium carboxymethyl cellulose is completely dissolved in the deionized water to obtain a first solution, wherein the mass fraction of the sodium carboxymethyl cellulose in the first solution is 0.1wt%;
step 2: adding 50 mu L of silver nanowire aqueous suspension into 20mL of the first solution, and performing ultrasonic treatment at room temperature of 150W for 3min until the silver nanowires are uniformly dispersed to obtain a dispersion, wherein the concentration of the silver nanowires in the dispersion is 0.025mg/mL;
step 3: adhering a glass sheet to a metal ceramic heating sheet through a polyimide tape, applying voltage of 30V to the metal ceramic heating sheet by using a constant-voltage direct-current power supply, preheating the metal ceramic heating sheet for 1min, and raising the temperature of the metal ceramic heating sheet to 90 ℃;
step 4: vertically inserting the metal ceramic heating plate attached with the glass plate into the dispersion liquid, and keeping the temperature of the metal ceramic heating plate stable to enable the solution to continuously evaporate;
step 5: and after the water is completely evaporated, stopping supplying power to the metal ceramic heating plate, taking down the glass plate, cleaning residual liquid and impurities on the surface of the glass plate by using absolute ethyl alcohol, and volatilizing the absolute ethyl alcohol to obtain the transparent conductive coating (silver nanowire coating) with the ordered silver nanowire network structure.
Examples 2 to 4 and comparative examples 1 to 2
Step 1: taking 0g (comparative example 1), 0.005g (comparative example 2), 0.01g (example 2), 0.2g (example 3), 0.05g (example 4) sodium carboxymethyl cellulose and 100mL deionized water respectively, stirring at normal temperature until the sodium carboxymethyl cellulose is completely dissolved in the deionized water to obtain a first solution, wherein the mass fraction of the sodium carboxymethyl cellulose in the first solution is 0wt% (comparative example 1), 0.005wt% (comparative example 2), 0.01wt% (example 2), 0.2wt% (example 3) and 0.05wt% (example 4) respectively;
examples 2 to 4 and comparative examples 1 to 2 were different from example 1 only in step 1, and the remaining steps 2 to 5 were identical to example 1.
Examples 5 to 6 and comparative examples 3 to 5
Step 3: a glass sheet was attached to a metal ceramic heating sheet by a polyimide tape, and a voltage of 0V (comparative example 3), 10V (comparative example 4), 15V (comparative example 5), 20V (example 5), 25V (example 6) was applied to the metal ceramic heating sheet using a constant voltage dc power supply, and the metal ceramic heating sheet was preheated for 1min to raise the temperature to 20 ℃ (room temperature, comparative example 3), 40 ℃ (comparative example 4), 50 ℃ (comparative example 5), 65 ℃ (example 5), 80 ℃ (example 6), respectively;
examples 5 to 6 and comparative examples 3 to 5 were different from example 1 only in step 3, and the remaining steps 1 to 2 and steps 4 to 5 were identical to example 1.
Examples 7 to 9
Step 1: dissolving 0.1g of sodium alginate (example 7), 0.1g of sodium polyacrylate (example 8) and 0.1g of methyl cellulose (example 9) into 100mL of deionized water respectively, and completely dissolving in the deionized water at normal temperature to obtain a first solution, wherein the mass fractions of sodium alginate, sodium polyacrylate and methyl cellulose in the first solution are all 0.1wt%;
examples 7 to 9 differ from example 1 only in step 1, and the remaining steps 2 to 5 remain identical to example 1.
Example 10
Step 2: adding 50 mu L of the aqueous suspension of the silicon dioxide nanowires into 20mL of the first solution, and performing ultrasonic treatment at room temperature of 150W for 3min until the silicon dioxide nanowires are uniformly dispersed to obtain a dispersion, wherein the concentration of the silicon dioxide nanowires in the dispersion is 0.025mg/mL;
example 10 differs from example 1 only in step 2, and the remaining steps 1 and steps 3 to 5 remain the same as example 1.
Example 11
Silver nanowire coatings with orthogonal alignment directions were prepared using the preparation process shown in fig. 12:
step 4: vertically inserting the metal ceramic heating plate attached with the glass plate into the dispersion liquid, keeping the temperature of the metal ceramic heating plate stable, and continuously evaporating the solution for 2min; the nano motor is used for lifting the metal ceramic heating plate to move upwards for 1mm at the speed of 1mm/s, then the metal ceramic heating plate is kept still for 2min, and the lifting operation of the metal ceramic heating plate and the resting operation are repeated for a plurality of times, so that the silver nanowire coating with the orthogonal arrangement direction is formed.
Example 11 differs from example 1 only in step 4, and the remaining steps 1 to 3 and step 5 remain the same as example 1.
Fig. 2 is an optical micrograph of a silver nanowire coating obtained after evaporating solutions of different sodium carboxymethyl cellulose concentrations in example 1, examples 2 to 4 and comparative examples 1 to 2, and it can be seen that the arrangement degree of silver nanowires gradually increases as the sodium carboxymethyl cellulose concentration increases. At a concentration of 0 (i.e., no sodium carboxymethylcellulose added) and 0.005wt% sodium carboxymethylcellulose, the silver nanowires were not aligned. It is stated that sodium carboxymethyl cellulose needs to be added and a certain concentration needs to be met before silver nanowires can be aligned. Meanwhile, as shown in fig. 3, the arrangement degree of silver nanowires can be quantified by a digital image processing method, and the arrangement degree of silver nanowires in a coating obtained by evaporating solutions with different concentrations of sodium carboxymethyl cellulose is quantified by a Hellman (HOF) orientation coefficient: in the following formula, phi represents an included angle between a calculated polar axis direction in k space and an arrangement direction of silver nanowires in real space after Fourier transformation of an image, and the range is 0-90 degrees; i represents the sum of each pixel value on the image calculation polar axis;
the trend obtained is consistent with the optical micrograph, i.e. the degree of alignment of silver nanowires (the hellman orientation factor) gradually increases with increasing concentration of sodium carboxymethylcellulose.
Fig. 4 is an optical micrograph of the silver nanowire coatings obtained at different evaporation temperatures of example 1, examples 5 to 6 and comparative examples 3 to 5, and it can be seen that the degree of arrangement of silver nanowires gradually increases as the evaporation temperature increases. The silver nanowires are not arranged at the evaporation temperature of 20 ℃ (room temperature) and at the evaporation temperature of 40 ℃ and at the evaporation temperature of 50 ℃. It is stated that a certain evaporation rate is required for the evaporation process to be able to align the silver nanowires. Meanwhile, as shown in fig. 5, the alignment degree of silver nanowires in the obtained coating was also quantified by the Hellman (HOF) orientation factor at different evaporation temperatures. The trend obtained is consistent with the optical micrograph, i.e. the degree of alignment of silver nanowires (hellman orientation coefficient) gradually increases with increasing evaporation temperature.
Fig. 6 is a macroscopic photograph of the coating obtained in example 1, showing that the silver nanowire coating obtained by the method has better transparency. As shown in fig. 7, the square resistance variation curve of the transparent conductive coating with the ordered silver nanowire network structure obtained in example 1 is obtained through measurement, when the azimuth angle α=0 or 180°, that is, the measurement direction is parallel to the ordered arrangement direction of the silver nanowires, the minimum square resistance is 250 Ω/sq, and the ratio of the maximum square resistance to the minimum square resistance in the measurement process is 22, which indicates that the silver nanowire coating obtained by the method has better electrical anisotropy. The coating obtained in example 1 was placed in an optical path where the polarization axes of the polarizer and the analyzer were perpendicular to each other, and a polarized light micrograph shown in fig. 8 was obtained. When the arrangement direction of the coated silver nanowires is 45 degrees with the included angle between the polarizer and the analyzer, most of the silver nanowires can be seen, and when the arrangement direction of the coated silver nanowires is parallel to the polar axis direction of the polarizer or the analyzer, only few silver nanowires can be seen, which means that most of the silver nanowires in the coating are arranged along the fixed direction. As shown in fig. 9, in the same optical path, the detected light intensity transmitted through the optical path changes with the detected azimuth angle, and accords with the law of malus, which indicates that the coating has high optical anisotropy and has practical value in the field of polarized optics.
Fig. 10 shows the silver nanowire coatings obtained in examples 7 to 9 after the thickener was replaced with sodium alginate, sodium polyacrylate and methylcellulose, respectively, and it can be seen that the silver nanowires are all in regular arrangement, which illustrates that the thickener used in the method can be flexibly selected according to actual production requirements.
Fig. 11 is a fluorescence microscopic image (the surface of the silica wire is connected with fluorescence, which is convenient for characterization) obtained after the silver nanowire is replaced by the silica nanowire in example 10, and it can be seen that the silica nanowire also shows a regular arrangement, which illustrates that the method is applicable to various one-dimensional nanomaterials with a certain length-diameter ratio.
Fig. 13 is an optical micrograph of the silver nanowire coating obtained in example 11, and it can be seen from fig. 13 that the present invention can realize the preparation of the silver nanowire coating with orthogonal arrangement directions on the same substrate in combination with the dip-coating method, so as to meet the requirements of personalized customization and patterning design of the regional anisotropy of the coating.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. The preparation method of the transparent conductive coating based on evaporation self-driving comprises the following steps:
mixing the linear nano material aqueous suspension and the thickener aqueous solution to obtain a dispersion; the mass fraction of the thickener in the thickener aqueous solution is 0.01-0.2 wt%;
vertically inserting a heatable substrate into the dispersion liquid, heating the heatable substrate to evaporate water in the dispersion liquid, and obtaining a transparent conductive coating; the heating temperature is 60-90 ℃.
2. The method of claim 1, wherein the thickener is a water-soluble thickener.
3. The preparation method according to claim 1 or 2, wherein the thickener is sodium carboxymethyl cellulose, sodium alginate, sodium polyacrylate or methyl cellulose.
4. The method according to claim 1, wherein the concentration of the linear nanomaterial in the dispersion is 0.005 to 0.05mg/mL.
5. The method of claim 1 or 4, wherein the linear nanomaterial in the aqueous suspension of linear nanomaterial comprises metal nanowires, inorganic nonmetallic nanowires, or carbon nanotubes.
6. The method of manufacturing according to claim 1, wherein the heatable substrate comprises a substrate sheet and a flat heater attached to the substrate sheet.
7. The method of manufacturing according to claim 6, wherein the substrate sheet is a glass sheet; the flat heater is a metal ceramic heating plate.
8. The method of claim 1, wherein the heatable substrate is intermittently pulled during heating of the heatable substrate.
9. The method of preparing according to claim 8, wherein the intermittent pulling comprises: the heatable substrate is pulled up a distance, allowed to rest for a period of time, and then the pulling-resting is repeated.
10. The transparent conductive coating prepared by the preparation method of any one of claims 1 to 9, wherein the transparent conductive coating has an ordered conductive network structure.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310348393.4A CN116410627A (en) | 2023-04-04 | 2023-04-04 | Preparation method of transparent conductive coating based on evaporation self-driving and transparent conductive coating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310348393.4A CN116410627A (en) | 2023-04-04 | 2023-04-04 | Preparation method of transparent conductive coating based on evaporation self-driving and transparent conductive coating |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116410627A true CN116410627A (en) | 2023-07-11 |
Family
ID=87050890
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310348393.4A Pending CN116410627A (en) | 2023-04-04 | 2023-04-04 | Preparation method of transparent conductive coating based on evaporation self-driving and transparent conductive coating |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116410627A (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101648183A (en) * | 2008-08-12 | 2010-02-17 | 索尼株式会社 | Method and apparatus for manufacturing thin film, and method for manufacturing electronic device |
| CN104226977A (en) * | 2013-06-19 | 2014-12-24 | 中国科学院化学研究所 | Method for directional ordered arrangement of metal nanowires |
| CN104616837A (en) * | 2015-02-02 | 2015-05-13 | 华南师范大学 | Plane ordered metal nanowire superposed transparent conducting thin film and preparation method thereof |
| WO2015124027A1 (en) * | 2014-02-20 | 2015-08-27 | 中山大学 | Orderly distributed conductive thin film, and device and nanometer conductor structure thereof |
| CN104876179A (en) * | 2015-04-16 | 2015-09-02 | 华中科技大学 | Large-area assembling method for non-contact type one-dimensional nano material |
| CN105139964A (en) * | 2015-07-17 | 2015-12-09 | 中国科学院合肥物质科学研究院 | Uniform-performance silver nanowire transparent conductive thin-film preparation method by means of dynamic infrared heating |
| CN111155324A (en) * | 2020-01-15 | 2020-05-15 | 东华大学 | Evaporation induction oriented self-assembly efficient conductive fabric coating and preparation method thereof |
| CN112093774A (en) * | 2019-06-17 | 2020-12-18 | 中国矿业大学(北京) | Method for large-scale directional arrangement of halloysite nanotubes |
| CN115340085A (en) * | 2022-05-12 | 2022-11-15 | 中山大学 | Carbon nanotube film with controllable surface density and preparation method and application thereof |
-
2023
- 2023-04-04 CN CN202310348393.4A patent/CN116410627A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101648183A (en) * | 2008-08-12 | 2010-02-17 | 索尼株式会社 | Method and apparatus for manufacturing thin film, and method for manufacturing electronic device |
| CN104226977A (en) * | 2013-06-19 | 2014-12-24 | 中国科学院化学研究所 | Method for directional ordered arrangement of metal nanowires |
| WO2015124027A1 (en) * | 2014-02-20 | 2015-08-27 | 中山大学 | Orderly distributed conductive thin film, and device and nanometer conductor structure thereof |
| CN104616837A (en) * | 2015-02-02 | 2015-05-13 | 华南师范大学 | Plane ordered metal nanowire superposed transparent conducting thin film and preparation method thereof |
| CN104876179A (en) * | 2015-04-16 | 2015-09-02 | 华中科技大学 | Large-area assembling method for non-contact type one-dimensional nano material |
| CN105139964A (en) * | 2015-07-17 | 2015-12-09 | 中国科学院合肥物质科学研究院 | Uniform-performance silver nanowire transparent conductive thin-film preparation method by means of dynamic infrared heating |
| CN112093774A (en) * | 2019-06-17 | 2020-12-18 | 中国矿业大学(北京) | Method for large-scale directional arrangement of halloysite nanotubes |
| CN111155324A (en) * | 2020-01-15 | 2020-05-15 | 东华大学 | Evaporation induction oriented self-assembly efficient conductive fabric coating and preparation method thereof |
| CN115340085A (en) * | 2022-05-12 | 2022-11-15 | 中山大学 | Carbon nanotube film with controllable surface density and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 濮丹凤: "《银纳米线柔性透明导电薄膜自组装制备与性能》", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》, no. 2, pages 35 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Lin et al. | Roll‐to‐Roll production of transparent silver‐nanofiber‐network electrodes for flexible electrochromic smart windows | |
| Jang et al. | Fabrication of metallic nanomesh: Pt nano-mesh as a proof of concept for stretchable and transparent electrodes | |
| JP6585152B2 (en) | Method for forming a conductive film | |
| Zhang et al. | Large-size graphene microsheets as a protective layer for transparent conductive silver nanowire film heaters | |
| Huang et al. | Large-scale synthesis of flowerlike ZnO nanostructure by a simple chemical solution route and its gas-sensing property | |
| US9655252B2 (en) | Low haze transparent conductive electrodes and method of making the same | |
| De et al. | Silver nanowire networks as flexible, transparent, conducting films: extremely high DC to optical conductivity ratios | |
| Zhang et al. | Wet chemical synthesis of silver nanowire thin films at ambient temperature | |
| Lin et al. | Effect of silver nitrate concentration of silver nanowires synthesized using a polyol method and their application as transparent conductive films | |
| Zhang et al. | Synthesis of nano/micro zinc oxide rods and arrays by thermal evaporation approach on cylindrical shape substrate | |
| Wang et al. | A facile method for preparing transparent, conductive, and paper-like silver nanowire films | |
| CN103700430B (en) | A kind of conductive film being distributed in order and its manufacture method | |
| Kim et al. | Industrially feasible approach to transparent, flexible, and conductive carbon nanotube films: cellulose-assisted film deposition followed by solution and photonic processing | |
| Wang et al. | Facile synthesis of ultralong and thin copper nanowires and its application to high-performance flexible transparent conductive electrodes | |
| He et al. | Aqueous graphene oxide-dispersed carbon nanotubes as inks for the scalable production of all-carbon transparent conductive films | |
| Tomašević-Ilić et al. | Transparent and conductive films from liquid phase exfoliated graphene | |
| JP5111324B2 (en) | Preparation method of carbon nanotube alignment film | |
| Woo et al. | Highly flexible and transparent film heater with electrospun copper conductive network via junction-free structure | |
| Zhao et al. | High-performance copper mesh transparent flexible conductors based on electroplating with vacuum-free processing | |
| Ko et al. | Meniscus-dragging deposition of single-walled carbon nanotubes for highly uniform, large-area, transparent conductors | |
| KR101359957B1 (en) | Carbon nano tube and silver nano wire dispersion liquid of one component type, Method for manufacturing conductive coating substrate using the same | |
| Cho et al. | Laser scribing of Ag-decorated graphene for high-performance and flexible heaters | |
| CN116410627A (en) | Preparation method of transparent conductive coating based on evaporation self-driving and transparent conductive coating | |
| Bobinger et al. | Comprehensive synthesis study of well-dispersed and solution-processed metal nanowires for transparent heaters | |
| Zhai et al. | One-step synthesis of ultra-high aspect ratio silver nanowires for high-performance flexible transparent conductive films |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |