CN112201408A - Preparation method of flexible transparent conductive film - Google Patents
Preparation method of flexible transparent conductive film Download PDFInfo
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- CN112201408A CN112201408A CN202011015699.0A CN202011015699A CN112201408A CN 112201408 A CN112201408 A CN 112201408A CN 202011015699 A CN202011015699 A CN 202011015699A CN 112201408 A CN112201408 A CN 112201408A
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Abstract
The invention belongs to the technical field of flexible electronic materials, and discloses a preparation method of a flexible transparent conductive film, which comprises the following steps: on a rigid substrate, a metal nanowire film coating step and a mask covering step are carried out in a variable order; bonding the metal nanowire film corresponding to the mask hollow-out region to the graphene oxide layer, and/or bonding the metal nanowire film corresponding to the mask coverage region to the graphene oxide layer; and adhering the metal nanowire film combined with the graphene oxide layer by using a flexible substrate with an adhesive surface, and peeling the metal nanowire film from the rigid substrate or the mask to obtain the flexible transparent conductive film with the mask hollow area pattern and/or the flexible transparent conductive film with the mask coverage area pattern. The method can selectively transfer the silver nanowire film pattern from the rigid substrate to the flexible substrate without damage, so that the preparation of the flexible transparent conductive film is realized, and the prepared flexible transparent conductive film has good pattern precision and photoelectric property.
Description
Technical Field
The invention belongs to the technical field of flexible electronic materials, and particularly relates to a preparation method of a flexible transparent conductive film.
Background
The transparent conductive film pattern is an important component of an electronic device, and is widely applied in the fields of touch display, organic electroluminescence, organic solar cells, electromagnetic shielding and the like. Currently, the most commonly used transparent conductive material is Indium Tin Oxide (ITO), but ITO is prepared by a vapor sputtering process, so that raw materials are seriously wasted, and in addition, the cost of high-conductivity ITO is high due to the scarcity of indium raw materials. In addition, the use of many transparent polymer substrates is limited by the high-temperature annealing process of ITO, and the ITO has poor bending resistance, so that the ITO cannot meet the requirements of flexible electronics. As a flexible alternative material of ITO, the flexible transparent conductive film with the silver nanowire film pattern formed on the flexible transparent substrate has excellent light transmittance, conductivity and bending resistance, and has a wide prospect in flexible electronics.
However, the preparation of thin film patterns of silver nanowires on flexible transparent substrates still faces a number of problems. The silver nanowire film pattern is prepared by adopting methods such as photoetching, plasma etching and the like, and the defects of complex process and equipment, serious consumption and pollution of chemical materials, high cost and the like exist. The method of ink-jet, silk-screen printing, gravure printing and the like for preparing the silver nanowire film pattern has the defects of complicated ink synthesis and equipment, limited pattern precision and scale production, requirement of subsequent treatment of the film and the like. More critically, for flexible substrates, the above methods suffer from limitations, such as damage to the flexible substrate caused by etching methods, high temperature treatment, poor film forming properties of silver nanowire inks on many flexible substrates, and the like. Part of flexible transparent substrate (such as PDMS) is difficult to directly deposit silver nanowire film on the substrate due to hydrophobicity, and the deposition of the silver nanowire film can be carried out after long-time plasma hydrophilic treatment, so that the process and equipment are complicated and energy is wasted; the same disadvantages exist with the method of preparing thin film patterns based on the hydrophilic-hydrophobic treatment of a substrate.
After preparing the silver nanowire thin film on the rigid substrate, transferring the patterned silver nanowire thin film to the flexible substrate is one of the alternative methods for preparing the flexible transparent conductive thin film. However, on one hand, how to realize the lossless transfer of the silver nanowire thin film pattern from the rigid substrate to the flexible substrate is a technical difficulty. The silver nanowire film is directly deposited on the glass substrate by methods of spin coating, spray coating, blade coating and the like, the silver nanowires are adhered to the glass substrate, although the conductivity is reduced after a 3M adhesive tape adhesion test, a considerable part of the silver nanowires still remains on the glass substrate, and the 3M adhesive tape adhesion and tearing transfer part cannot form a conductive network. Even if the flexible polymer precursor is coated on the surface of the film and peeled off after curing, a considerable part of the silver nanowires cannot be transferred to the flexible substrate, and the stress of the peeling process can cause network damage, so that the silver nanowire network on the flexible substrate is non-conductive or weakly conductive. In the prior art, a vacuum filtration method is usually adopted to prepare the silver nanowire film, the silver nanowire film is weakly adhered after being transferred to a glass substrate from a filter membrane, a flexible substrate material is coated on the surface of the film, and the silver nanowire film is peeled off after being cured and can be completely transferred to the flexible substrate. However, the vacuum filtration method involved in the process is complex in process in actual production and difficult to apply in large scale. On the other hand, there is no ideal method for realizing the selective transfer of specific patterns of thin films. The conventional patterning techniques, whether those in which a pattern is first prepared on a rigid substrate and then transferred to a flexible substrate or inks are printed on a flexible substrate by gravure printing or the like, present technical, equipment and material challenges.
Disclosure of Invention
The present invention is directed to overcoming the above-mentioned shortcomings of the prior art, and providing a method for preparing a flexible transparent conductive film, which can selectively transfer a silver nanowire film pattern from a rigid substrate to a flexible substrate without damage, thereby realizing the preparation of the flexible transparent conductive film.
In order to solve the above technical problems, an embodiment of the present invention provides a method for preparing a flexible transparent conductive film, including the following steps: performing a variable-order metal nanowire film coating step and a covering mask step on a rigid substrate, wherein the mask has a hollow area and a covering area; bonding the metal nanowire film corresponding to the mask hollow-out region to a graphene oxide layer, and/or bonding the metal nanowire film corresponding to the mask coverage region to a graphene oxide layer; and adhering the metal nanowire film combined with the graphene oxide layer by using a flexible substrate with an adhesive surface, and peeling the metal nanowire film from the rigid substrate or the mask to obtain the flexible transparent conductive film with the mask hollow area pattern and/or the flexible transparent conductive film with the mask coverage area pattern.
Compared with the prior art, the embodiment of the invention provides a preparation method of a flexible film for silver nanowire transfer by means of double-sided adhesion of graphene oxide layers. Based on this, the invention firstly provides two technical ideas: firstly, preparing a continuous silver nanowire film on a rigid substrate, and then selectively transferring the silver nanowire film with specific patterning to a flexible substrate; secondly, a patterned silver nanowire film is directly prepared on a rigid substrate, and then the patterned silver nanowire film is transferred to a flexible substrate. Corresponding to the two technical ideas, the invention provides two optional preparation processes:
one, optional first, preparation procedure comprises the following steps: s1: coating a metal nanowire film on a rigid substrate; s2: covering a mask on the metal nanowire film; s3: selectively combining the metal nanowire film of the mask hollow-out region or the mask covering region with the graphene oxide layer; s4: and adhering the metal nanowire film combined with the graphene oxide layer by using a flexible substrate with an adhesive surface, and peeling the metal nanowire film from the rigid substrate to obtain the flexible transparent conductive film with the mask hollow area pattern and/or the flexible transparent conductive film with the mask coverage area pattern.
Among them, the present application provides two more specific schemes for selectively bonding the metal nanowire thin film of the mask hollow area or the mask covered area to the graphene oxide layer in step S3.
As a first scheme, in order to selectively combine the metal nanowire thin film of the mask hollow-out region with the graphene oxide layer, the following steps are performed: s311: coating the graphene oxide dispersion liquid on the surface of the metal nanowire film covered with the mask, so that the metal nanowire film in the hollow area of the mask is combined with the graphene oxide layer; s312: the mask is removed.
As a second means, in order to selectively bond the metal nanowire thin film in the mask-covered region to the graphene oxide layer, the following steps are performed: s321: carrying out ultraviolet ozone treatment or plasma cleaning treatment on the metal nanowire film covered with the mask to enable the metal nanowire film in the mask hollow area to lose the adhesion force with the graphene oxide; s322: removing the mask; s323: and coating the graphene oxide dispersion liquid on the surface of the silver nanowire film, so that the metal nanowire film in the mask coverage area is combined with the graphene oxide layer.
The following is a detailed description of the first and second schemes:
the first scheme is as follows: preparing a metal nanowire film on a rigid substrate, covering a mask on the surface of the metal nanowire film, coating a graphene oxide dispersion liquid on the surface of the metal nanowire film covered with the mask, enabling the metal nanowire film in a mask hollow area to be combined with a graphene oxide layer, removing the mask, using a flexible substrate with a surface capable of being adhered, adhering the metal nanowire film combined with the graphene oxide layer and stripping the metal nanowire film from the rigid substrate, transferring the metal nanowires in the mask hollow area from the rigid substrate to the flexible substrate by virtue of double-sided adhesion of the graphene oxide layer, the metal nanowires and the flexible substrate, and obtaining the metal nanowire flexible transparent conductive film with patterns consistent with those in the mask hollow area.
As can be seen, the first scheme utilizes the adhesion between the graphene oxide layer and the metal nanowires, and the adhesion between the adhesive flexible substrate and the graphene oxide layer, and selectively transfers the metal nanowire film pattern of the mask hollow area from the rigid substrate to the flexible substrate by means of the graphene oxide, thereby manufacturing the flexible transparent conductive film having the mask hollow area pattern.
The second scheme is as follows: after preparing the metal nanowire film on the rigid substrate, covering a mask on the surface of the metal nanowire film, and carrying out ultraviolet ozone treatment or plasma cleaning treatment on the metal nanowire film covered with the mask; after the metal nanowires in the mask hollow area are subjected to ultraviolet ozone treatment or plasma cleaning treatment, the surface structure changes, the metal nanowires are weakly adhered to graphene oxide and cannot be combined with the graphene oxide layer on the surface, meanwhile, the adhesion performance of the rigid substrate and the graphene oxide is enhanced, and the transferability of the graphene oxide on the surface is weakened; the metal nanowires in the mask coverage area maintain the original surface structure characteristics and can be tightly combined with the graphene oxide layer. After removing the mask, coating the graphene oxide dispersion liquid on the surface of the silver nanowire film to combine the metal nanowire film in the mask covering area with the graphene oxide layer, then using a flexible substrate with an adhesive surface to adhere and strip the metal nanowire film combined with the graphene oxide layer from the rigid substrate, and transferring the silver nanowires in the mask covering area (without ultraviolet ozone treatment or plasma cleaning) from the rigid substrate to the flexible substrate by virtue of the double-sided adhesive effect of the graphene oxide layer, the metal nanowires and the flexible substrate to obtain the metal nanowire flexible transparent conductive film with the pattern consistent with that of the mask covering area.
As can be seen, the second scheme changes local surface characteristics of the metal nanowire film and the rigid substrate through ultraviolet ozone treatment or plasma cleaning treatment, and selectively transfers the metal nanowire film pattern of the mask coverage area from the rigid substrate to the flexible substrate by utilizing the selective adhesion of graphene oxide to metal nanowires with different surface characteristics and the adhesion between the adhesive flexible substrate and the graphene oxide layer, thereby manufacturing the flexible transparent conductive film with the mask coverage area pattern.
Further, with respect to the first aspect, after the flexible substrate having an adherable surface is used, the metal nanowire film having the graphene oxide layer bonded thereto is adhered and peeled off from the rigid substrate, and the flexible transparent conductive film having the mask hollow-out region pattern is obtained, the method further includes: s5: coating the graphene oxide dispersion liquid on the surface of the metal nanowire film left on the rigid substrate; s6: using a flexible substrate whose surface can be adhered, adhering the metal nanowire film combined with the graphene oxide layer and peeling the metal nanowire film from the rigid substrate to obtain the flexible transparent conductive film with the mask coverage area pattern. That is, for the metal nanowire pattern of the mask coverage area still remaining on the rigid substrate, the adhesion between the graphene oxide layer and the metal nanowires and the adhesion between the adhesive flexible substrate and the graphene oxide layer are reused, and the part of the metal nanowire pattern is transferred to the flexible substrate by means of the graphene oxide, so that the metal nanowire flexible transparent conductive film consistent with the mask coverage area pattern can be obtained. Two metal nanowire flexible film patterns are prepared through two times of transfer and respectively correspond to the mask hollow-out area pattern and the mask covering area pattern, and the metal nanowire film on the rigid substrate is completely utilized.
Second, an optional second preparation process comprises the following steps: SS 1: covering a mask on a rigid substrate; SS 2: coating a metal nanowire film on the surface of the rigid substrate covered with the mask; depositing the metal nanowire thin films on the mask surface of the mask covering area and the rigid substrate surface of the mask hollow area respectively; SS 3: coating graphene oxide dispersion liquid on the surface of the metal nanowire film, and enabling the metal nanowire film deposited on the mask surface of the mask covering area and the rigid substrate surface of the mask hollow area to be respectively combined with the graphene oxide layer; SS 4: separating the mask from the rigid substrate; SS 5: adhering the metal nanowire film combined with the graphene oxide layer on the rigid substrate by using a flexible substrate with an adhesive surface, and stripping the metal nanowire film from the rigid substrate to obtain a flexible transparent conductive film with a mask hollow area pattern; SS 6: and adhering the metal nanowire film with the graphene oxide layer combined on the surface of the mask by using the flexible substrate with the surface capable of being adhered, and stripping the metal nanowire film from the surface of the mask to obtain the flexible transparent conductive film with the mask coverage area pattern.
In the second preparation process, firstly, pattern structures of the silver nanowire film are respectively prepared on the surfaces of the rigid substrate and the mask, and then the metal nanowire film patterns on the rigid substrate or the mask are transferred to the flexible substrate without damage by means of graphene oxide by utilizing the adhesion effect between the graphene oxide layer and the metal nanowires and the adhesion effect between the flexible substrate with the surface capable of adhering and the graphene oxide layer, so that the flexible transparent conductive film with the mask hollow area patterns and the flexible transparent conductive film with the mask covering area patterns are prepared.
Preferably, in the method for preparing the flexible transparent conductive film provided by the present application, the rigid substrate is selected from a glass or a silicon wafer. The metal nanowire film can be coated on the rigid substrate by coating a metal nanowire dispersion liquid on the rigid substrate by bar coating, spin coating, spray coating, blade coating, and the like, wherein the metal nanowire dispersion liquid can be formed by dispersing metal nanowires in a solvent such as water, ethanol, isopropanol, and the like.
Preferably, in the preparation method of the flexible transparent conductive film provided by the present application, the metal nanowire film is a silver nanowire film; preferably, the diameter of the silver nanowire is 20-100 nm, and the length of the silver nanowire is 10-100 μm.
Preferably, in the method for preparing the flexible transparent conductive film provided by the application, the pattern structure or the hollow structure of the pattern mask should be consistent with the target pattern of the flexible transparent conductive film to be prepared, and the mask should have good bonding performance with rigid substrates such as glass, silicon wafers and the like.
Preferably, in the preparation method of the flexible transparent conductive film provided by the application, the concentration of the graphene oxide dispersion liquid is 0.5-5 mg/ml.
Preferably, in the preparation method of the flexible transparent conductive film provided by the present application, the graphene oxide dispersion is coated on the surface of the metal nanowire film by means of drop coating, dip coating, spray coating or spin coating.
Preferably, in the preparation method of the flexible transparent conductive film provided by the present application, the flexible substrate to which the surface can be adhered is a flexible substrate or a transparent adhesive tape, the surface of which is coated with glue. The glue can be selected from various commercial transparent glues and adhesives, and the transparent adhesive tape can be selected from various commercial transparent adhesive tapes with weak viscosity. In the step of adhering and peeling the metal nanowire film combined with the graphene oxide layer from the rigid substrate using the flexible substrate coated with the glue on the surface, the peeling should be completed before the glue on the flexible substrate is dried or cured.
Preferably, in the method for preparing the flexible transparent conductive film provided by the present application, the flexible substrate is preferably selected from polyethylene terephthalate (PET), polyethylene naphthalate (PEN), Polyethylene (PE), Polyimide (PI), Polydimethylsiloxane (PDMS), polyvinyl alcohol (PVA), Polyurethane (PU), Polymethylmethacrylate (PMMA), or the like.
In addition, in the preparation method of the flexible transparent conductive film, the time of the ultraviolet ozone treatment or the plasma cleaning treatment is adjusted according to the power of an instrument, for example, the power is 100W, and the effect that the surface characteristic of the metal nanowire film in the mask hollow area can be changed and the metal nanowire film cannot be tightly combined with the graphene oxide can be achieved within 1-2 min.
Compared with the traditional preparation method of the flexible metal nanowire film, the preparation method of the flexible transparent conductive film provided by the invention also has the following characteristics: the process is simple and environment-friendly, complex processes such as high temperature, high pressure, vacuum filtration and the like are avoided, expensive equipment and large material consumption are not needed, the complete transfer of the metal nanowire film patterns from the rigid substrate to various flexible substrates including hydrophobic substrates can be realized, and the prepared flexible transparent conductive film has good pattern precision and photoelectric property.
Drawings
Fig. 1 is a flow chart illustrating a process for preparing a flexible transparent conductive film according to a first embodiment of the present invention;
fig. 2 is an optical microscope magnified image of a silver nanowire-graphene oxide-PE flexible thin film gate pattern in example 1 of the present invention;
FIG. 3 is a flow chart illustrating the preparation of a flexible transparent conductive film according to a second embodiment of the present invention;
fig. 4 is an optical microscope magnified image of a silver nanowire-graphene oxide-PDMS flexible thin film gate pattern in example 2 of the present invention;
FIG. 5 is a flow chart illustrating the preparation of a flexible transparent conductive film according to a third embodiment of the present invention;
fig. 6 is an optical microscope magnified image of a silver nanowire-graphene oxide-PE flexible thin film gate pattern in example 3 of the present invention;
fig. 7 is a flowchart illustrating a process for manufacturing a flexible transparent conductive film according to a fourth embodiment of the present invention.
Detailed Description
In order that the objects, features and advantages of the present invention can be more clearly understood, embodiments of the present invention will be described in detail below with reference to the accompanying drawings. The materials used are not indicated by the manufacturer, and are all conventional products available by commercial purchase. The description of the exemplary embodiments is for exemplary purposes only and is not intended to limit the invention or its applications.
A flow chart of a method for preparing a flexible transparent conductive film according to a first embodiment of the present application is shown in fig. 1, and specifically includes the following steps: s1: coating a metal nanowire film on a rigid substrate; s2: covering a mask on the metal nanowire film; s311: coating the graphene oxide dispersion liquid on the surface of the metal nanowire film covered with the mask, so that the metal nanowire film in the hollow area of the mask is combined with the graphene oxide layer; s312: removing the mask; s411: adhering the metal nanowire film combined with the graphene oxide layer to a flexible substrate with an adhesive surface and peeling the metal nanowire film from the rigid substrate to obtain a flexible transparent conductive film with a mask hollow area pattern; s5: coating the graphene oxide dispersion liquid on the surface of the metal nanowire film left on the rigid substrate; s6: using a flexible substrate whose surface can be adhered, adhering the metal nanowire film combined with the graphene oxide layer and peeling the metal nanowire film from the rigid substrate to obtain the flexible transparent conductive film with the mask coverage area pattern.
Example 1 below is an example of the first embodiment of the present application, and comparative example 1 is a comparative example of example 1.
Example 1
(1) Diluting the aqueous dispersion of silver nanowires (diameter of 30nm and length of 20 μm) to 3mg/ml with ethanol, coating on a clean glass substrate by a coater, and naturally drying to form the silver nanowire network transparent conductive film.
(2) And covering a mask with a pattern structure on the surface of the silver nanowire film, and enabling the mask to be attached to the surface of the film. The mask pattern was a 500 μm by 20mm gate pattern with a stripe pitch of 500 μm.
(3) Preparing 2mg/ml graphene oxide dispersion liquid, dripping the graphene oxide dispersion liquid on the surface of the silver nanowire film in the hollow area of the mask, blowing away the redundant solution by using a nitrogen gun, and naturally drying.
(4) The mask is removed.
(5) The method comprises the steps of adopting a PE protective film (weak viscosity) purchased from Shanghai-Hai-Ri electronics company Limited as a flexible substrate, attaching the PE flexible substrate to the surface of a graphene oxide-silver nanowire-glass substrate (the PE flexible substrate is attached to a graphene oxide layer), removing bubbles and peeling. Through the steps, the silver nanowire film at the hollowed-out position of the mask is transferred to the PE substrate by the graphene oxide layer, so that a silver nanowire film grid pattern with the width and the distance of 500 micrometers is obtained, and an optical microscope magnified image of the silver nanowire film grid pattern is shown in FIG. 2.
(6) And (3) dripping the graphene oxide dispersion liquid on the surface of the silver nanowire pattern left on the glass substrate, blowing away the redundant solution by using a nitrogen gun, and naturally drying.
(7) And (3) attaching the PE flexible substrate in the step (5) to the surface of the graphene oxide-silver nanowire-rigid substrate (the PE flexible substrate is attached to the graphene oxide layer), removing bubbles and stripping. After the above steps, the silver nanowire thin film pattern left on the glass substrate is transferred to the PE substrate by the oxidized graphene, and a silver nanowire thin film gate pattern (having a width and a pitch of 500 μm) identical to the mask pattern described in the step (2) is obtained.
In the embodiment, two silver nanowire-graphene oxide-PE flexible thin film patterns are prepared through two times of transfer and respectively correspond to the mask pattern and the hollow pattern, the silver nanowire thin film is completely utilized, the pattern boundary is clear, the sheet resistance of the thin film region is about 25 omega/□, the conductivity is excellent, and the light transmittance is over 85%.
Comparative example 1
(1) Diluting the aqueous dispersion of silver nanowires (diameter of 30nm and length of 20 μm) to 3mg/ml with ethanol, coating on a clean glass substrate by a coater, and naturally drying to form the silver nanowire network transparent conductive film.
(2) And (3) attaching the PE protective film (weak adhesiveness) to the surface of the silver nanowire-glass substrate, removing bubbles and stripping.
Through the steps, the silver nanowire film is still completely positioned on the glass substrate, and the conductivity and the light transmittance are almost unchanged. No silver nanowire film was obtained on the PE protective film (weakly adhesive) substrate.
A flow chart of the method for preparing a flexible transparent conductive film according to the second embodiment of the present application is shown in fig. 3, and specifically includes the following steps: s1: coating a metal nanowire film on a rigid substrate; s2: covering a mask on the metal nanowire film; s311: coating the graphene oxide dispersion liquid on the surface of the metal nanowire film covered with the mask, so that the metal nanowire film in the hollow area of the mask is combined with the graphene oxide layer; s312: removing the mask; s411: and adhering the metal nanowire film combined with the graphene oxide layer by using a flexible substrate with an adhesive surface, and peeling the metal nanowire film from the rigid substrate to obtain the flexible transparent conductive film with the mask hollow area pattern.
Example 2 below is an example of a second embodiment of the present application, and comparative example 2 is a comparative example of example 2.
Example 2
(1) Diluting the aqueous dispersion of silver nanowires (diameter of 30nm and length of 20 μm) to 3mg/ml with ethanol, coating on a clean glass substrate by a coater, and naturally drying to form the silver nanowire network transparent conductive film.
(2) And covering a mask with a pattern structure on the surface of the silver nanowire film, and enabling the mask to be attached to the surface of the film. The mask pattern was a 150 μm by 20mm gate pattern with a stripe pitch of 300 μm.
(3) Preparing 2mg/ml graphene oxide dispersion liquid, dripping the graphene oxide dispersion liquid on the surface of the silver nanowire film in the hollow area of the mask, blowing away the redundant solution by using a nitrogen gun, and naturally drying.
(4) The PDMS film is prepared, and liquid glue (force No.7304) is spin-coated on the surface of the PDMS film, with the rotating speed of 3000rpm and the time of 1 min.
(5) And taking down the mask, attaching the PDMS substrate to the surface of the graphene oxide-silver nanowire-glass substrate, removing air bubbles, and stripping before the glue is cured.
Through the steps, the silver nanowire film at the hollowed-out position of the mask is transferred to the PDMS substrate by the graphene oxide layer, so that a silver nanowire-graphene oxide grid pattern with the width of 300 microns is obtained, and an optical microscope magnified image of the pattern is shown in FIG. 4.
The pattern of the silver nanowire-graphene oxide-PDMS flexible film prepared by the embodiment has clear pattern boundary, the sheet resistance of the film area is about 32 omega/□, the conductivity is excellent, and the light transmittance is more than 85%.
Comparative example 2
(1) Diluting the aqueous dispersion of silver nanowires (diameter of 30nm and length of 20 μm) to 3mg/ml with ethanol, coating on a clean glass substrate by a coater, and naturally drying to form the silver nanowire network transparent conductive film.
(2) The PDMS film is prepared, and liquid glue (force No.7304) is spin-coated on the surface of the PDMS film, with the rotating speed of 3000rpm and the time of 1 min.
(3) And attaching the PDMS substrate to the surface of the silver nanowire-glass substrate, removing air bubbles, and stripping before the glue is cured.
Through the steps, the silver nanowire film is still completely positioned on the glass substrate, and the conductivity and the light transmittance are almost unchanged. No silver nanowire film was obtained on the PDMS substrate.
A flow chart of the method for preparing a flexible transparent conductive film according to the third embodiment of the present application is shown in fig. 5, and specifically includes the following steps: s1: coating a metal nanowire film on a rigid substrate; s2: covering a mask on the metal nanowire film; s321: carrying out ultraviolet ozone treatment or plasma cleaning treatment on the metal nanowire film covered with the mask to enable the metal nanowire film in the mask hollow area to lose the adhesion force with the graphene oxide; s322: removing the mask; s323: and coating the graphene oxide dispersion liquid on the surface of the silver nanowire film, so that the metal nanowire film in the mask coverage area is combined with the graphene oxide layer. S421: adhering and peeling the metal nanowire film combined with the graphene oxide layer from the rigid substrate by using the flexible substrate with the adhesive surface to obtain the flexible transparent conductive film with the mask coverage area pattern
Examples 3 and 4 below are examples of the third embodiment of the present application, respectively, and comparative example 3 is a comparative example of examples 3 and 4.
Example 3
(1) Diluting the aqueous dispersion of silver nanowires (diameter of 30nm and length of 20 μm) to 3mg/ml with ethanol, coating on a clean glass substrate by a coater, and naturally drying to form the silver nanowire network transparent conductive film.
(2) Covering a mask with a pattern structure on the surface of the silver nanowire film, wherein the mask is tightly attached to the surface of the film, the mask is made of an Ecoflex silica gel material, the pattern is a grid pattern with the size of 5mm multiplied by 20mm, and the stripe interval is 5 mm.
(3) And carrying out ultraviolet ozone treatment on the silver nanowire film covering the mask (the silver nanowire film in the hollow area of the mask is subjected to ultraviolet ozone treatment), wherein the power of a lamp tube of the ultraviolet cleaning machine is 100W, the treatment time is 2min, and the wavelength of ultraviolet light is 185nm and 254 nm.
(4) Taking down the mask, dropping 2mg/ml of graphene oxide dispersion liquid on the surface of the silver nanowire film, blowing away excess solution with a nitrogen gun and drying.
(5) The method comprises the steps of adopting a PE protective film (micro adhesive tape) purchased from Shanghai-Nippon electronics company Limited as a flexible substrate, attaching the substrate to the surface of a graphene oxide-silver nanowire-glass substrate (the substrate is attached to a graphene oxide layer), removing bubbles and stripping.
After the above steps, the silver nanowire film covered by the mask pattern is transferred to the flexible substrate by the graphene oxide layer, and a silver nanowire-graphene oxide gate pattern having a width and a pitch of 5mm is obtained, and an optical microscope magnified image thereof is shown in fig. 6.
The gate pattern of the silver nanowire-graphene oxide-flexible substrate prepared by the embodiment has a clear pattern boundary which is consistent with the mask pattern, the sheet resistance of the thin film region is about 25 Ω/□, the conductivity is excellent, and the light transmittance is over 85%.
Example 4
The steps (1), (2), (4) and (5) of example 4 are all the same as example 3, except that step (3) is: and (3) carrying out plasma cleaning treatment on the silver nanowire film covering the mask (the silver nanowire film in the hollow area of the mask is subjected to plasma cleaning), wherein the power of the plasma cleaning machine is 100W, and the treatment time is 1 min.
Through the steps, the silver nanowire film covered by the mask pattern is transferred to the flexible substrate through the graphene oxide layer, the silver nanowire-graphene oxide flexible grid pattern with the width and the spacing of 5mm is obtained, the pattern boundary is clear and is consistent with the mask pattern, the sheet resistance of the film area is about 25 omega/□, the conductivity is excellent, and the light transmittance is over 85%.
Comparative example 3
For comparison, the steps (1), (2), (4) and (5) in example 3 were repeated, but the silver nanowire thin film covering the mask was not subjected to the ultraviolet ozone treatment of step (3). In the step (5), after the flexible substrate is torn off, the silver nanowire film is completely transferred to the flexible substrate by the oxidized graphene, and a complete silver nanowire-oxidized graphene flexible film, not a film pattern, is obtained.
A flow chart of the method for preparing a flexible transparent conductive film according to the fourth embodiment of the present application is shown in fig. 7, and specifically includes the following steps: SS 1: covering a mask on a rigid substrate; SS 2: coating a metal nanowire film on the surface of the rigid substrate covered with the mask; depositing the metal nanowire thin films on the mask surface of the mask covering area and the rigid substrate surface of the mask hollow area respectively; SS 3: coating graphene oxide dispersion liquid on the surface of the metal nanowire film, and enabling the metal nanowire film deposited on the mask surface of the mask covering area and the rigid substrate surface of the mask hollow area to be respectively combined with the graphene oxide layer; SS 4: separating the mask from the rigid substrate; SS 5: adhering the metal nanowire film combined with the graphene oxide layer on the rigid substrate by using a flexible substrate with an adhesive surface, and stripping the metal nanowire film from the rigid substrate to obtain a flexible transparent conductive film with a mask hollow area pattern; SS 6: and adhering the metal nanowire film with the graphene oxide layer combined on the surface of the mask by using the flexible substrate with the surface capable of being adhered, and stripping the metal nanowire film from the surface of the mask to obtain the flexible transparent conductive film with the mask coverage area pattern.
Example 5 below is an illustration of a fourth embodiment of the present application.
Example 5
(1) The clean glass substrate surface is covered with a glass mask with a pattern structure, and the mask is attached to the substrate surface. The mask pattern was a 500 μm by 20mm gate pattern with a stripe pitch of 500 μm.
(2) The method comprises the steps of spraying a dispersion of silver nanowires (diameter is 30nm, length is 20 mu m) in isopropanol on a substrate and a mask, drying at 100 ℃ for 5min, and forming a pattern structure of a silver nanowire network transparent conductive film on the mask and the substrate (hollow areas of the mask) respectively.
(3) Preparing 2mg/ml graphene oxide dispersion liquid, and spraying the graphene oxide dispersion liquid on the surfaces of the silver nanowire film of the mask and the substrate (the hollow area of the mask).
(4) The mask is removed.
(5) A PE tape (weak adhesion) purchased from shanghai-jiehai electronics ltd was used as a flexible substrate, attached to the surface of the graphene oxide-silver nanowire film pattern on the glass substrate, and bubbles were removed and peeled off. Through the steps, the silver nanowire film pattern on the glass substrate is transferred to the PE substrate through the graphene oxide layer, and the silver nanowire film grid pattern with the width and the distance of 500 micrometers is obtained.
(6) And (5) attaching the PE flexible substrate in the step (5) to the surface of the graphene oxide-silver nanowire film pattern on the pattern mask, removing bubbles and stripping. Through the steps, the silver nanowire film pattern on the glass mask is transferred to the PE substrate by the graphene oxide layer, and the silver nanowire film grid pattern with the width and the distance of 500 micrometers is obtained.
In conclusion, the silver nanowire film coated on the rigid substrate has a certain adhesion with the substrate, and the flexible substrate or the micro adhesive tape with the surface glue not dried can not transfer the silver nanowire conductive network from the glass substrate. In the embodiments 1 and 2, the silver nanowire film is completely transferred to the flexible substrate by virtue of the strong double-sided adhesion of the graphene oxide, the silver nanowires and the flexible substrate, and the silver nanowire film can be completely transferred even on the flexible substrate which is slightly adhered or the surface glue is not dried, so that the flexible film with excellent conductivity is formed.
Examples 1 and 2, the silver nanowire film covered with the mask is coated with the graphene oxide layer, and the silver nanowires in the hollowed-out region of the mask (i.e., covered with the graphene oxide layer) can be transferred to various flexible substrates. Further, in embodiment 1, the graphene oxide layer is covered on the surface of the silver nanowire film pattern left on the glass substrate again, and the part of the left silver nanowire film pattern is successfully transferred to the flexible substrate, so that the utilization efficiency of the silver nanowire film is effectively improved, and the preparation process of the silver nanowire flexible transparent conductive film is simplified. In comparative examples 1 and 2, the graphene oxide layer was not coated, and the silver nanowire thin film had weak adhesion to a slightly adhesive substrate and could not be transferred to a flexible substrate.
Examples 3 and 4 utilize the characteristics that after the silver nanowires are subjected to ultraviolet ozone treatment or plasma cleaning, the adhesion force between the silver nanowires and graphene oxide is obviously weakened due to the change of surface structure characteristics, and the silver nanowires cannot be transferred through the adhesion effect of the graphene oxide; meanwhile, the adhesion performance of the rigid substrate subjected to hydrophilic treatment and graphene oxide is enhanced, so that the transferability of the graphene oxide on the surface is reduced. The silver nanowire film is selectively subjected to ultraviolet ozone or plasma cleaning treatment through a mask, the mask is removed, a graphene oxide layer is coated, the silver nanowires in the area covered by the mask (shielded ultraviolet ozone or plasma cleaning treatment) can be transferred to various flexible substrates, and the effects can be achieved after the ultraviolet ozone or plasma cleaning treatment is carried out for 1-2 min. Obviously, compared with the treatment time of tens of minutes or even hours required by the methods of hydrophilic treatment of a hydrophobic substrate or ultraviolet ozone corrosion of a thin film, the method provided by the invention can obviously reduce energy consumption and pollution. In comparative example 3, no uv ozone or plasma cleaning treatment was performed, so that all the silver nanowire thin films had strong adhesion to graphene oxide, and the thin films were completely transferred to the flexible substrate.
In example 5, the pattern structures of the silver nanowire film are firstly prepared on the glass substrate and the glass mask, and then the patterns are transferred to the flexible substrate through the graphene oxide layer, so that two flexible film patterns are prepared, which correspond to the mask covering region pattern and the mask hollow region pattern, respectively, the silver nanowire film is completely utilized, the pattern boundary is clear, and the light transmittance and the electrical conductivity are excellent. If only a pattern of silver nanowires on a glass substrate is desired, the mask material may be replaced with other stronger materials that adhere strongly to the silver nanowires instead of glass.
In addition, in each embodiment, a nitrogen gun is used for blowing away redundant solution (recycling is realized), selective adhesion transfer can be realized only by using an extremely thin graphene oxide layer, the light transmittance of the film can be improved, and materials can be saved. Compared with the prior art, the preparation method of the flexible transparent conductive film provided by the invention has the advantages that the process is simple and environment-friendly, no complex procedures such as high temperature, high pressure, vacuum filtration and the like are required, expensive equipment and large material consumption are not required, the complete transfer of the metal nanowire film patterns from the rigid substrate to various flexible substrates including hydrophobic substrates can be realized, the pattern precision and the photoelectric property are good, and the complete utilization of the metal nanowire film can be realized.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and are intended to enable one skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (10)
1. A preparation method of a flexible transparent conductive film is characterized by comprising the following steps:
performing a variable-order metal nanowire film coating step and a covering mask step on a rigid substrate, wherein the mask has a hollow area and a covering area;
bonding the metal nanowire film corresponding to the mask hollow-out region to a graphene oxide layer, and/or bonding the metal nanowire film corresponding to the mask coverage region to a graphene oxide layer;
and adhering the metal nanowire film combined with the graphene oxide layer by using a flexible substrate with an adhesive surface, and peeling the metal nanowire film from the rigid substrate or the mask to obtain the flexible transparent conductive film with the mask hollow area pattern and/or the flexible transparent conductive film with the mask coverage area pattern.
2. The method for preparing a flexible transparent conductive film according to claim 1, comprising the steps of:
s1: coating a metal nanowire film on a rigid substrate;
s2: covering a mask on the metal nanowire film;
s3: selectively combining the metal nanowire film of the mask hollow-out region or the mask covering region with the graphene oxide layer;
s4: and adhering the metal nanowire film combined with the graphene oxide layer by using a flexible substrate with an adhesive surface, and peeling the metal nanowire film from the rigid substrate to obtain the flexible transparent conductive film with the mask hollow area pattern and/or the flexible transparent conductive film with the mask coverage area pattern.
3. The method of claim 2, wherein the step of selectively bonding the metal nanowire film of the mask hollow area to the graphene oxide layer in S3 comprises:
s311: coating the graphene oxide dispersion liquid on the surface of the metal nanowire film covered with the mask, so that the metal nanowire film in the hollow area of the mask is combined with the graphene oxide layer;
s312: the mask is removed.
4. The method of preparing a flexible transparent conductive film according to claim 2, wherein the step of selectively bonding the metal nanowire film of the mask-covered region to the graphene oxide layer in S3 comprises:
s321: carrying out ultraviolet ozone treatment or plasma cleaning treatment on the metal nanowire film covered with the mask to enable the metal nanowire film in the mask hollow area to lose the adhesion force with the graphene oxide;
s322: removing the mask;
s323: and coating the graphene oxide dispersion liquid on the surface of the silver nanowire film, so that the metal nanowire film in the mask coverage area is combined with the graphene oxide layer.
5. The method for preparing a flexible transparent conductive film according to claim 3, wherein the ratio of S4: after the metal nanowire film combined with the graphene oxide layer is adhered and peeled off from the rigid substrate by using the flexible substrate with the surface capable of being adhered, the method further comprises the following steps:
s5: coating the graphene oxide dispersion liquid on the surface of the metal nanowire film left on the rigid substrate;
s6: using a flexible substrate whose surface can be adhered, adhering the metal nanowire film combined with the graphene oxide layer and peeling the metal nanowire film from the rigid substrate to obtain the flexible transparent conductive film with the mask coverage area pattern.
6. The method for preparing a flexible transparent conductive film according to claim 1, comprising the steps of:
SS 1: covering a mask on a rigid substrate;
SS 2: coating a metal nanowire film on the surface of the rigid substrate covered with the mask; depositing the metal nanowire thin films on the mask surface of the mask covering area and the rigid substrate surface of the mask hollow area respectively;
SS 3: coating graphene oxide dispersion liquid on the surface of the metal nanowire film, and enabling the metal nanowire film deposited on the mask surface of the mask covering area and the rigid substrate surface of the mask hollow area to be respectively combined with the graphene oxide layer;
SS 4: separating the mask from the rigid substrate;
SS 5: adhering the metal nanowire film combined with the graphene oxide layer on the rigid substrate by using a flexible substrate with an adhesive surface, and stripping the metal nanowire film from the rigid substrate to obtain a flexible transparent conductive film with a mask hollow area pattern;
SS 6: and adhering the metal nanowire film with the graphene oxide layer combined on the surface of the mask by using the flexible substrate with the surface capable of being adhered, and stripping the metal nanowire film from the surface of the mask to obtain the flexible transparent conductive film with the mask coverage area pattern.
7. The method for preparing a flexible transparent conductive film according to any one of claims 1 to 6, wherein the rigid substrate is selected from a glass or silicon wafer.
8. The method for preparing a flexible transparent conductive film according to any one of claims 1 to 6, wherein the metal nanowire film is a silver nanowire film; preferably, the diameter of the silver nanowire is 20-100 nm, and the length of the silver nanowire is 10-100 μm.
9. The method for preparing a flexible transparent conductive film according to any one of claims 2 to 6, wherein the concentration of the graphene oxide dispersion liquid is 0.5-5 mg/ml; the graphene oxide dispersion liquid is coated on the surface of the metal nanowire film in a dropping, dip, spraying or spin coating mode.
10. The method for preparing a flexible transparent conductive film according to any one of claims 1 to 6, wherein the flexible substrate with the surface capable of being adhered is a flexible substrate with a surface coated with glue or a transparent adhesive tape; the flexible substrate is preferably selected from polyethylene terephthalate, polyethylene naphthalate, polyethylene, polyimide, polydimethylsiloxane, polyvinyl alcohol, polyurethane or polymethylmethacrylate.
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