CN111710475A - Shadow-eliminating patterned transparent conductive electrode preparation method - Google Patents
Shadow-eliminating patterned transparent conductive electrode preparation method Download PDFInfo
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Abstract
The invention relates to a preparation method of a shadow-eliminating patterned transparent conductive electrode, which specifically comprises the following steps: s1, depositing metal nanowires on the substrate to form a metal nanowire crosslinked network layer; s2, selectively modifying the metal nanowire crosslinked network by adopting a sulfhydryl compound, changing the thermal stability of part of the metal nanowire crosslinked network layer, and forming a thermal stability difference between a modified region and an unmodified region to obtain a structurally modified crosslinked network layer; s3, the cross-linked network layer which is structurally modified is heated, an insulating region is obtained at a position where the metal nanowire cross-linked network layer is poor in thermal stability, a conductive region is obtained at a position where the metal nanowire cross-linked network layer is good in thermal stability, and a shadow eliminating patterned transparent conductive electrode is formed. The patterned conductive electrode prepared by the method has small difference of optical properties between the pattern and the non-pattern area, has the characteristic of shadow elimination, and can meet the requirement of the invisible transparent electrode in practical application.
Description
Technical Field
The invention relates to the technical field of conductive electrode materials, in particular to a preparation method of a shadow-eliminating patterned transparent conductive electrode.
Background
The demands of new displays, sensors, biological human body detectors and the like are gradually increased at present, the requirements for wearable flexible panels are greatly improved, the development trend of the flexible panels is to improve the sensitivity, the flexibility and the stability, and the defects of high manufacturing cost, complex preparation process and poor flexibility of traditional transparent conductive electrodes which take ITO (indium tin oxide) as a main material are overcome, so that the flexible panels cannot meet the new demands. Therefore, new transparent conductive electrode materials are currently being studied.
Due to the characteristics of high transparency, small sheet resistance, good flexibility, high cost performance, large-area printing and compatibility with roll-to-roll processes, metal nanowire materials are one of the most possible materials to replace conventional electrodes. On the application level, the patterned metal nanowire network can be used as a high-performance flexible transparent electrode and used for manufacturing various flexible functional devices, such as a touch screen membrane in a display screen, a driving electrode of a liquid crystal membrane group and the like, the current common patterning technology comprises a laser etching method, a photoetching method, a transfer printing method, a template method and the like, and the methods have the problems of complex processes, or the need of using a large amount of chemical reagents, or low precision of flexible panel electrodes and are difficult to implement on a large scale; more importantly, the pattern has high visibility, and the difference between the optical performance of the pattern and the optical performance of the non-pattern area is large, so that the pattern is difficult to be applied as a transparent electrode in devices such as a touch panel screen, a light emitting diode and the like, and the development of the metal nanowire in the application field of the transparent panel is severely limited. In the method for realizing the pattern shadow eliminating property, the current technologies comprise ultraviolet/ozone treatment, sodium hypochlorite solution etching, selective gas introduction modification and the like, and disconnected nanowires in an insulating area are reserved on a patterned panel, so that the optical performance difference between a pattern area and a non-pattern area is greatly reduced. For example, patent CN105788760A, a reaction region is formed on the conductive layer, and one or more gases selected from ozone, hydrogen peroxide, organic amine, ammonia gas, halogen gas and its compound, carbon dioxide, organic acid, nitric acid, hydrochloric acid, sulfur vapor and sulfide vapor are introduced to react. In patent CN 106575552 a, an oxidizing agent such as hypochlorous acid or a salt thereof, dichromic acid or a salt thereof, permanganic acid or a salt thereof, hydrogen peroxide, or the like is used to insulate a non-protected region. These methods have the disadvantage of being liable to cause gas pollution and liquid pollution.
Disclosure of Invention
The invention aims to overcome at least one defect of the prior art and provides a shadow-eliminating preparation method of a patterned transparent conductive electrode, which is used for solving the problem that the optical performance difference of the traditional patterned transparent conductive electrode pattern and a non-pattern area is large.
The invention also aims to solve the problems that the traditional patterned conductive electrode has complex preparation process, needs a large amount of chemical reagents and is easy to cause gas pollution and liquid pollution.
The technical scheme adopted by the invention is as follows:
a preparation method of a shadow-eliminating patterned transparent conductive electrode comprises the following steps:
s1, depositing metal nanowires on the substrate to form a metal nanowire crosslinked network layer;
s2, selectively modifying the metal nanowire crosslinked network by adopting a sulfhydryl compound, changing the thermal stability of part of the metal nanowire crosslinked network layer, and forming a thermal stability difference between a modified region and an unmodified region to obtain a structurally modified crosslinked network layer;
s3, the cross-linked network layer with the structural modification is heated, an insulation area with fused metal nanowires is obtained at a position with poor thermal stability of the cross-linked network layer of the metal nanowires, and a complete conductive area with the metal nanowires is obtained at a position with good thermal stability of the cross-linked network layer of the metal nanowires, so that the shadow-eliminating patterned transparent conductive electrode is formed.
The modification of the sulfhydryl compound can effectively influence the Rayleigh instability of the metal nanowire, so that the Rayleigh instability of the metal nanowire can change the ratio of the diameter to the length of the metal nanowire in a heating state, the metal nanowire is split into nano silver particles, and an insulation effect is achieved. In the technical scheme, the Rayleigh instability principle is utilized, the heat resistance of the metal nanowire in the modified region is changed through the modification effect of the sulfhydryl compound, the sulfhydryl self-assembled monomolecular is attached to the surface of the metal nanowire in the modification process, the sulfhydryl compound is combined with the surface of the metal nanowire to change the heat resistance of the metal nanowire, the heat stability difference of the metal nanowire between the modified region and the unmodified region is utilized, heating is carried out through adjusting the heating temperature, the metal nanowire in the region with poor heat stability is fused, an insulating region is formed, the metal nanowire in the region with good heat stability is kept complete, a conductive electrode region is formed, and accordingly a shadow eliminating patterned transparent conductive electrode is formed. For example, a silver nanowire network having an average diameter of 30nm, has a thermal fusing temperature of about 260 ℃ when unmodified. When the silver nanowire is selectively modified by using a sulfhydryl compound for reducing the heat resistance of the silver nanowire, the fusing temperature of a modified region is lower than 260 ℃, and at the moment, a certain temperature value in a temperature range lower than 260 ℃ and higher than the fusing temperature of the modified region is selected to heat the selectively modified silver nanowire network, so that the unmodified region can keep the integrity and the conductivity of the silver nanowire network, the silver nanowire network in the modified region is fused, and the silver nanowire network in the unmodified region becomes an insulating region. When the silver nanowire is selectively modified by using a sulfhydryl compound for improving the heat resistance of the silver nanowire, the fusing temperature of the modified region is higher than 260 ℃, and at the moment, a certain temperature value in a temperature range higher than 260 ℃ and lower than the fusing temperature of the modified region is selected to heat the selectively modified silver nanowire network, so that the modified region can keep the integrity and the conductivity of the silver nanowire network, and the silver nanowire network in the unmodified region is fused to form an insulating region. If different metal nanowires are adopted, the original fusing temperatures of the metal nanowires are different, and the heating temperature is adjusted accordingly according to the type of the selected sulfhydryl compound to obtain the patterned conductive electrode. The minimum line width which can be processed by the preparation method of the patterned transparent conductive electrode in the technical scheme is about 10 microns.
The light transmittance and haze difference are important indexes influencing the shadow elimination of the patterned conductive electrode, the light transmittance and haze contrast test is respectively carried out on the conductive electrode area and the insulating area of the patterned conductive electrode prepared by the technical scheme, the data curve overlapping degree of the conductive electrode area and the insulating area is high, and good shadow elimination performance is embodied. The patterned conductive electrode prepared by the method has small difference of optical properties between the pattern and the non-pattern area, is simple in preparation method, does not need to use a large amount of chemical reagents, and is a novel efficient and environment-friendly patterned conductive electrode preparation method.
Preferably, the process of step S2 is: the method comprises the steps of using a sulfydryl compound as a raw material, using a patterned device to perform patterned selective modification on a metal nanowire crosslinked network layer, adding a sulfydryl self-assembled monolayer on the surface of the metal nanowire in a pattern area to change the thermal stability of the metal nanowire in the pattern area, cleaning and drying to form the structurally modified crosslinked network layer.
In the technical scheme, a pattern-carrying device is directly used to enable the sulfhydryl compound to form a modified region and a non-modified region on the surface of the metal nanowire crosslinking network layer, wherein the non-modified region is still a pure metal nanowire. When the thermal stability after modification is higher than that of the non-modified region, the modified region is not changed after heating, and the metal nanowires in the non-modified region are fused, so that the shadow-eliminating patterned transparent conductive electrode can be obtained. And when the thermal stability after modification is lower than that of the non-modified region, the metal nanowires in the modified region are fused after heating, and the non-modified region is not changed, so that the shadow-eliminating patterned transparent conductive electrode can be obtained.
The patterning selective modification process comprises the steps of forming a patterning covering layer on the surface of the metal nanowire crosslinking network layer through any one of processes of ink-jet printing, screen printing, offset printing, photoetching and soft stamp covering, and then selectively modifying uncovered metal nanowires by using a sulfhydryl compound by adopting a liquid phase or gas phase method; or the selective patterned modification is to selectively deposit the sulfhydryl compound on the metal nanowire crosslinking network layer directly by any process of ink-jet printing, silk-screen printing, offset printing and soft stamp transfer printing, so as to selectively modify the metal nanowire network.
In this scheme, the utensil of taking the pattern can be earlier through the preliminary treatment operation before using, and specific preliminary treatment operation can be including wasing and drying process, washs and uses cleaners such as ethanol solution, deionized water to wash in the supersound in proper order, can utilize equipment such as nitrogen gas rifle, oven to carry out drying process after the washing.
In the scheme, the patterning selective modification process comprises the steps of forming a pattern covering layer on the surface of a metal nanowire crosslinking network layer through any one process of ink-jet printing, screen printing, offset printing, photoetching and soft stamp covering, and then selectively modifying uncovered metal nanowires through a sulfhydryl compound by adopting a liquid phase or gas phase method, wherein when the liquid phase method is adopted, the sulfhydryl compound is generally dissolved in a solution of ethanol, isopropanol and the like, the solution is uniformly dispersed in the solution of ethanol, isopropanol and the like through treatment of magnetic stirring, ultrasonic treatment and the like to obtain a sulfhydryl compound dispersion liquid, an appliance is placed on the silver nanowire crosslinking network layer, the sulfhydryl compound dispersion liquid is dripped on the outer side of an appliance channel, the sulfhydryl compound dispersion liquid is selectively infiltrated and modified for a certain time by utilizing the capillary force in the channel, the appliance is peeled off, and the ethanol, the isopropanol, the soft stamp and the soft stamp are used for, And (4) sequentially and repeatedly cleaning by using cleaning agents such as deionized water and the like to remove the dispersion liquid remained on the surface, and drying by using a nitrogen gun to finish the selective modification.
Or the selective patterned modification is to selectively deposit the sulfhydryl compound on the metal nanowire crosslinking network layer directly by any process of ink-jet printing, silk-screen printing, offset printing and soft stamp transfer printing, so as to selectively modify the metal nanowires. One of the realizable modes is to change the surface of the device from hydrophobicity to hydrophilicity, soak the device in a sulfhydryl compound dispersion liquid for a certain time, take out and dry the device, deposit the sulfhydryl compound crystal on the surface of the device after drying, cover the surface of the device with the sulfhydryl compound crystal on the surface of a silver nanowire crosslinking network for a certain time for solid modification, contact the sulfhydryl compound crystal at the convex part of the device with the silver nanowire crosslinking network, and expose the silver nanowire crosslinking network corresponding to the concave part of the device in the air to realize selective modification. And then, stripping the tool, sequentially and repeatedly cleaning the partially modified silver nanowire crosslinked network layer by using cleaning agents such as ethanol, deionized water and the like to remove the solid crystals remained on the surface, and drying by using a nitrogen gun to finish selective modification. The sulfhydryl compound dispersion liquid is obtained by dissolving sulfhydryl compounds in solutions such as ethanol and isopropanol to form a liquid with a certain concentration, and uniformly dispersing the sulfhydryl compounds in the solutions such as ethanol and isopropanol by magnetic stirring and ultrasonic treatment.
As another preferable example, the process of step S2 is: the method comprises the steps of taking a sulfhydryl compound as a raw material, carrying out integral modification on a metal nanowire crosslinking network layer, adding a sulfhydryl self-assembly monomolecular layer on the surface of a metal nanowire to change the thermal stability of the metal nanowire, forming the integral structural modified crosslinking network layer, covering the integral structural modified crosslinking network layer by using a patterned protective layer, and removing the sulfhydryl self-assembly monomolecular layer on the surface of the metal nanowire in a pattern area to form the structural modified crosslinking network layer.
In the technical scheme, the metal nanowire crosslinking network layer is integrally modified, the sulfydryl self-assembled monolayer is added on the surface of the metal nanowire and combined with the metal nanowire, so that the thermal stability of the metal nanowire can be integrally changed, the integrally modified crosslinking network layer is covered by the patterned protective layer, the sulfydryl self-assembled monolayer in the pattern region is removed to obtain a non-modified region, and the sulfydryl self-assembled monolayer retention region is a modified region. And if the thermal stability of the modified region is different from that of the non-modified region, a metal nanowire retention region and a metal nanowire fusing region can be formed by a heating method, so that the shadow-eliminated patterned transparent conductive electrode is obtained.
The overall modification method can select any one of liquid phase modification, gas phase modification or solid state transfer modification. The liquid phase modification method comprises the steps of soaking the metal nanowire film in a sulfhydryl compound dispersion liquid, reacting for 5-30min, taking out a sample from the sulfhydryl compound dispersion liquid, sequentially cleaning the sample with an ethanol solution and deionized water, wherein the sulfhydryl compound dispersion liquid is obtained by dissolving a sulfhydryl compound in a solution of ethanol, isopropanol and the like, and uniformly dispersing the sulfhydryl compound in a solution of ethanol, isopropanol and the like through magnetic stirring, ultrasonic treatment and the like. The gas phase modification method is that the metal nanowire sample to be modified and the sulfhydryl compound are put in a closed box, and the modifying agent is gasified at a higher temperature (60-120 ℃) to perform modification reaction with the metal nanowire. The solid transfer printing modification method is that firstly the sulfhydryl compound is deposited on the surface of the soft stamp, and then the surface modification is realized by the soft stamp transfer printing on the metal nanowire film.
The protective layer with the pattern is any one of a metal mask, a film mask, a quartz mask and a polymer film.
The method for removing the sulfhydryl self-assembled monolayer in the pattern area adopts any one of plasma bombardment, ultraviolet/ozone treatment, intense pulsed light exposure, chemical corrosion and electric shock. In the uv/ozone treatment method, the process is usually accompanied by the generation of ozone upon irradiation with uv light.
The mercapto compound is any one or combination of more of phenethyl mercaptan, n-propyl mercaptan, isopropyl mercaptan, 3-mercaptopropionic acid, 1-propyl mercaptan, 1, 3-propanedithiol, 2, 3-dimercaptopropanol, n-butyl mercaptan, n-pentyl mercaptan, n-hexyl mercaptan, n-octyl mercaptan, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, dodecyl mercaptan, tetradecyl mercaptan, hexadecyl mercaptan, octadecyl mercaptan, 3-mercaptopropyltrimethoxysilane, 4-imidazoldithiocarboxylic acid, thiophenol and the like. Such as hexadecyl mercaptan, octadecyl mercaptan, 1-phenyl-5-mercapto tetrazole, 3-mercaptopropyl trimethoxysilane and the like, can reduce the thermal stability of the metal nanowire. And for example, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole and the like can improve the thermal stability of the metal nanowire.
The substrate is made of rigid materials, the rigid materials are any one of glass and silicon wafers, or the substrate is made of flexible materials, and the flexible materials are any one of polydimethylsiloxane, polyethylene terephthalate, polyether sulfone resin, polyethylene, polyimide, polycarbonate, polyurethane and polyethylene naphthalate.
The metal nano-wire is one or a mixture of copper nano-wire, silver nano-wire and gold nano-wire.
Compared with the prior art, the invention has the beneficial effects that:
(1) the patterned conductive electrode prepared by the method has small difference of optical properties between the pattern and the non-pattern area, has the characteristic of shadow elimination, and can meet the requirement of the invisible transparent electrode in practical application;
(2) the method can keep the electrical characteristics and high stability of the metal nanowire network layer through the selection of the sulfhydryl compound;
(3) the method does not need to use a large amount of chemical developing solution and a large exposure machine, and has simple manufacturing process and relatively low cost;
(4) the method can also be used for preparing metal nanowire network layers with various patterns by adjusting parameters such as the concentration, the modification time, the heating temperature, the heating time and the like of the sulfhydryl compound and designing different stamps and mask plate patterns, and provides method reference for the subsequent transparent electrode design with complex performance.
Drawings
Fig. 1 is a flowchart of a method for preparing a shadow-eliminating patterned transparent conductive electrode according to example 1.
Fig. 2 is a schematic view of a polydimethylsiloxane stamp of example 2.
Fig. 3 is a schematic diagram of a process for preparing a shadow-removed patterned transparent conductive electrode of example 2.
Fig. 4 is a schematic view of a metal mask in embodiment 4.
Fig. 5 is a schematic diagram of a process for preparing a shadow-removed patterned transparent conductive electrode of example 4.
Fig. 6 is a schematic diagram of a process for preparing a shadow-removed patterned transparent conductive electrode of example 6.
Fig. 7 is a schematic diagram of a process for preparing a shadow-removed patterned transparent conductive electrode of example 7.
Fig. 8 is a light transmittance test result of the conductive electrode region and the insulating region of example 2.
Fig. 9 is the haze test results for the conductive electrode region and the insulating region of example 2.
Fig. 10 is an SEM image of the conductive and insulating regions of the silver nanowire network.
The figure includes: example 2 silver nanowire crosslinked network layer 11; example 2 a substrate 12; embodiment 2 stamp body 13; example 2 channel 14; example 2 insulating region 15; example 2 conductive electrode area 16; example 4 a substrate 21; example 4 silver nanowire crosslinked network layer 22; example 4 exposed region 23; example 4 coverage area 24; example 42-mercaptobenzimidazole self-assembled monolayer 25; example 4 structurally modified cross-linked network layer 26; example 4 insulating region 27; example 4 conductive electrode region 28; example 6 a substrate 31; example 6 silver nanowire crosslinked network layer 32; embodiment 6 stamp bulge 33; example 6 stamp recess 34; example 6 insulating region 35; example 6 conductive electrode region 36; example 7 a substrate 41; example 7 silver nanowire crosslinked network layer 42; embodiment 7 stamp bulge 43; example 7 stamp recess 44; example 7 conductive electrode region 45; example 7 insulating region 46.
Detailed Description
The drawings are only for purposes of illustration and are not to be construed as limiting the invention. For a better understanding of the following embodiments, certain features of the drawings may be omitted, enlarged or reduced, and do not represent the size of an actual product; it will be understood by those skilled in the art that certain well-known structures in the drawings and descriptions thereof may be omitted.
Example 1
As shown in fig. 1, a flow chart of a method for preparing a shadow-eliminating patterned transparent conductive electrode comprises the following steps:
s1, depositing metal nanowires on the substrate to form a metal nanowire crosslinked network layer;
s2, selectively modifying the metal nanowire crosslinked network layer by adopting a sulfhydryl compound, changing the thermal stability of the partial region of the metal nanowire crosslinked network layer, and forming a thermal stability difference between the modified region and the unmodified region to obtain a structurally modified crosslinked network layer;
s3, the cross-linked network layer with the structural modification is heated, an insulation area with fused metal nanowires is obtained at a position with poor thermal stability of the cross-linked network layer of the metal nanowires, and a complete conductive area with the metal nanowires is obtained at a position with good thermal stability of the cross-linked network layer of the metal nanowires, so that the shadow-eliminating patterned transparent conductive electrode is formed.
The modification of the sulfhydryl compound can effectively influence the Rayleigh instability of the metal nanowire, so that the Rayleigh instability of the metal nanowire can change the ratio of the diameter to the length of the metal nanowire in a heating state, the metal nanowire is split into nano silver particles, and an insulation effect is achieved. In this embodiment 1, the rayleigh instability principle is utilized, the heat resistance of the metal nanowire in the modified region is changed through the modification effect of the thiol compound, the modification process is that a thiol self-assembled monomolecular is attached to the surface of the metal nanowire, the thiol compound is combined with the surface of the metal nanowire to change the heat resistance of the metal nanowire, then the thermal stability difference of the metal nanowire between the modified region and the unmodified region is utilized, and the heating temperature is adjusted to heat the metal nanowire, so that the metal nanowire in the region with poor thermal stability is fused, an insulating region is formed, the metal nanowire in the region with good thermal stability retains the integrity, and a conductive electrode region is formed, thereby forming a shadow-eliminating patterned transparent conductive electrode. For example, the heating fusing temperature of the silver nanowire is about 260 ℃ when the silver nanowire is not modified, after the silver nanowire is modified by using a sulfhydryl compound for reducing the heat resistance of the silver nanowire, the fusing temperature of a modified region is lower than 260 ℃, and at the moment, a certain temperature value in a temperature interval lower than 260 ℃ and higher than the fusing temperature of the modified region is selected to heat a part of modified silver nanowire, so that the integrity and the conductivity of the silver nanowire can be maintained in the non-modified region, the non-modified region becomes a conductive electrode region, and the silver nanowire in the modified region is broken, so that the silver nanowire becomes an insulating region. When the silver nanowire is modified by a mercapto compound for improving the heat resistance of the silver nanowire, the fusing temperature of the modified region is higher than 260 ℃, and at the moment, a certain temperature value in a temperature interval higher than 260 ℃ and lower than the fusing temperature of the modified region is selected to heat a part of modified silver nanowire, so that the modified region can keep the integrity and the conductivity of the silver nanowire, and the silver nanowire becomes a conductive electrode region, while the silver nanowire in an unmodified region breaks to become an insulating region. If different metal nanowires are adopted, the original fusing temperatures of the metal nanowires are different, and the heating temperature is adjusted accordingly according to the type of the selected sulfhydryl compound to obtain the patterned conductive electrode. The minimum line width which can be processed by the preparation method of the patterned transparent conductive electrode in the technical scheme is about 10 microns.
The patterned conductive electrode prepared by the method has small difference of optical properties between the pattern and the non-pattern area, is simple in preparation method, does not need to use a large amount of chemical reagents, and is a novel efficient and environment-friendly patterned conductive electrode preparation method.
The process of step S2 is: the method comprises the steps of using a sulfydryl compound as a raw material, using a patterned device to perform patterned selective modification on a metal nanowire crosslinked network layer, adding a sulfydryl self-assembled monolayer on the surface of the metal nanowire in a pattern area to change the thermal stability of the metal nanowire in the pattern area, cleaning and drying to form the structurally modified crosslinked network layer.
One of the schemes is that a pattern-carrying device is directly used to enable the sulfhydryl compound to form a modified region on the surface of the metal nanowire crosslinked network layer, and the non-modified region is still a pure metal nanowire. When the thermal stability after modification is higher than that of the non-modified region, the modified region is not changed after heating, and the metal nanowires in the non-modified region are fused, so that the shadow-eliminating patterned transparent conductive electrode can be obtained. And when the thermal stability after modification is lower than that of the non-modified region, the metal nanowires in the modified region are fused after heating, and the non-modified region is not changed, so that the shadow-eliminating patterned transparent conductive electrode can be obtained.
In this scheme, the utensil of taking the pattern can be earlier through the preliminary treatment operation before using, and specific preliminary treatment operation can be including wasing and drying process, washs and uses cleaners such as ethanol solution, deionized water in proper order to wash in the supersound, can utilize drying equipment such as nitrogen gun to carry out drying process after the washing.
In the scheme, the patterning selective modification process comprises the steps of forming a pattern covering layer on the surface of a metal nanowire crosslinking network layer through any one process of ink-jet printing, screen printing, offset printing, photoetching and soft stamp covering, and then selectively modifying uncovered metal nanowires through a sulfhydryl compound by adopting a liquid phase or gas phase method, wherein when the liquid phase method is adopted, the sulfhydryl compound is generally dissolved in a solution of ethanol, isopropanol and the like, the solution is uniformly dispersed in the solution of ethanol, isopropanol and the like through treatment of magnetic stirring, ultrasonic treatment and the like to obtain a sulfhydryl compound dispersion liquid, an appliance is placed on the silver nanowire crosslinking network layer, the sulfhydryl compound dispersion liquid is dripped on the outer side of an appliance channel, the sulfhydryl compound dispersion liquid is selectively infiltrated and modified for a certain time by utilizing capillary force in the channel, the appliance is peeled off, and the partially modified silver nanowire crosslinking network layer uses ethanol, And (4) sequentially and repeatedly cleaning by using cleaning agents such as deionized water and the like to remove the dispersion liquid remained on the surface, and drying by using a nitrogen gun to finish the selective modification.
Or the selective patterned modification is to selectively deposit the sulfhydryl compound on the metal nanowire crosslinking network layer directly by any process of ink-jet printing, silk-screen printing, offset printing and soft stamp transfer printing, so as to selectively modify the metal nanowires. The method comprises the following steps of firstly changing the surface of an appliance from hydrophobicity to hydrophilicity, soaking the appliance in a sulfhydryl compound dispersion liquid for a certain time, taking out and drying, depositing a sulfhydryl compound crystal on the surface of the appliance after drying, covering the surface of the appliance with the sulfhydryl compound crystal on the surface of a silver nanowire crosslinking network for a certain time for solid modification, contacting the sulfhydryl compound crystal at the convex part of the appliance with the silver nanowire crosslinking network, exposing the silver nanowire crosslinking network corresponding to the concave part of the appliance in the air to realize selective modification, then stripping the appliance, sequentially and repeatedly cleaning the partially modified silver nanowire crosslinking network layer by using cleaning agents such as ethanol, deionized water and the like to remove the solid crystal remained on the surface, and drying by using a nitrogen gun to finish the selective modification. The sulfhydryl compound dispersion liquid is obtained by dissolving sulfhydryl compounds in solutions such as ethanol and isopropanol to form a liquid with a certain concentration, and uniformly dispersing the sulfhydryl compounds in the solutions such as ethanol and isopropanol by magnetic stirring and ultrasonic treatment.
Alternatively, the process of step S2 is: the method comprises the steps of taking a sulfhydryl compound as a raw material, carrying out integral modification on a metal nanowire crosslinking network layer, adding a sulfhydryl self-assembly monomolecular layer on the surface of a metal nanowire to change the thermal stability of the metal nanowire, forming the integral structural modified crosslinking network layer, covering the integral structural modified crosslinking network layer by using a patterned protective layer, and removing the sulfhydryl self-assembly monomolecular layer on the surface of the metal nanowire in a pattern area to form the structural modified crosslinking network layer.
In this scheme, earlier to the whole modification of metal nano wire crosslinked network layer, increase sulfydryl self-assembly monolayer on metal nano wire surface, sulfydryl self-assembly monolayer combines with metal nano wire, can wholly change metal nano wire's thermal stability, and the crosslinked network layer after the reuse takes the protective layer of pattern to cover whole modification gets the non-modification zone, and the sulfydryl self-assembly monolayer that gets rid of the pattern region wherein remains the region and is the modification zone. And if the thermal stability of the modified region is different from that of the non-modified region, a metal nanowire retention region and a metal nanowire fusing region can be formed by a heating method, so that the shadow-eliminated patterned transparent conductive electrode is obtained.
The overall modification method can select any one of liquid phase modification, gas phase modification or solid state transfer modification. The liquid phase modification method comprises the steps of soaking the metal nanowire film in a sulfhydryl compound dispersion liquid, reacting for 5-30min, taking out a sample from the sulfhydryl compound dispersion liquid, sequentially cleaning the sample with an ethanol solution and deionized water, wherein the sulfhydryl compound dispersion liquid is obtained by dissolving a sulfhydryl compound in a solution of ethanol, isopropanol and the like, and uniformly dispersing the sulfhydryl compound in a solution of ethanol, isopropanol and the like through magnetic stirring, ultrasonic treatment and the like. The gas phase modification method is that the metal nanowire sample to be modified and the sulfhydryl compound are put in a closed box, and the modifying agent is gasified at a higher temperature (60-120 ℃) to perform modification reaction with the metal nanowire. The solid transfer printing modification method is that firstly the sulfhydryl compound is deposited on the surface of the soft stamp, and then the surface modification is realized by the soft stamp transfer printing on the metal nanowire film.
The protective layer with the pattern is any one of a metal mask, a film mask, a quartz mask and a polymer film.
The method for removing the sulfhydryl self-assembled monolayer in the pattern area adopts any one of plasma bombardment, ultraviolet/ozone treatment, intense pulsed light exposure, chemical corrosion and electric shock. In the uv/ozone treatment method, the process is usually accompanied by the generation of ozone upon irradiation with uv light.
The mercapto compound is any one or combination of more of phenethyl mercaptan, n-propyl mercaptan, isopropyl mercaptan, 3-mercaptopropionic acid, 1-propyl mercaptan, 1, 3-propanedithiol, 2, 3-dimercaptopropanol, n-butyl mercaptan, n-pentyl mercaptan, n-hexyl mercaptan, n-octyl mercaptan, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, dodecyl mercaptan, tetradecyl mercaptan, hexadecyl mercaptan, octadecyl mercaptan, 3-mercaptopropyltrimethoxysilane, 4-imidazoldithiocarboxylic acid, thiophenol and the like. Such as hexadecyl mercaptan, octadecyl mercaptan, 1-phenyl-5-mercapto tetrazole, 3-mercaptopropyl trimethoxysilane and the like, can reduce the thermal stability of the metal nanowire. And for example, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole and the like can improve the thermal stability of the metal nanowire.
The substrate is made of rigid materials, the rigid materials are any one of glass and silicon wafers, or the substrate is made of flexible materials, and the flexible materials are any one of polydimethylsiloxane, polyethylene terephthalate, polyether sulfone resin, polyethylene, polyimide, polycarbonate, polyurethane and polyethylene naphthalate.
The metal nano-wire is one or a mixture of copper nano-wire, silver nano-wire and gold nano-wire.
Example 2
This embodiment 2 is a specific example of the method for manufacturing a shadow-removed patterned transparent conductive electrode in the above embodiment 1. The patterned instrument in this embodiment employs a patterned stamp. Selectively modifying the metal silver nanowire crosslinked network layer by using a stamp with patterns, wherein the stamp material is Polydimethylsiloxane (PDMS), and before use, ultrasonic cleaning and nitrogen gun drying treatment are sequentially performed by using an ethanol solution and deionized water. As shown in fig. 2, which is a schematic view of a polydimethylsiloxane stamp, a stamp body 13 is provided with a pattern, channels 14 are formed in the pattern, and the channels 14 can be infiltrated with liquid. The mercapto compound used in this example 2 was Octadecylthiol (ODT), which was dissolved in an ethanol solution at a concentration of generally 0.1mol/L, and uniformly dispersed in the ethanol solution by magnetic stirring and ultrasonic treatment to obtain an octadecylthiol dispersion.
As shown in fig. 3, depositing silver nanowires on a substrate 12 to form a silver nanowire crosslinked network layer 11, placing a stamp on the silver nanowire crosslinked network layer 11, dropwise adding an octadecyl mercaptan dispersion liquid on the outer side of a channel 14, selectively permeating and modifying the octadecyl mercaptan dispersion liquid for 10 minutes by using capillary force in the channel 14, peeling off the stamp, sequentially and repeatedly cleaning the partially modified silver nanowire crosslinked network layer 11 by using ethanol and deionized water to remove the dispersion liquid remaining on the surface, drying by using a nitrogen gun, placing the dried silver nanowire crosslinked network layer on a constant temperature hot bench for heating at 200 ℃ for 10 minutes, fusing the silver nanowires in the modified region after heating to form an insulating region 15, keeping the integrity of the unmodified silver nanowires, forming a conductive electrode region 16, and obtaining the shadow-eliminating patterned transparent conductive electrode.
Example 3
This embodiment 3 is a specific example of the method for manufacturing a shadow-removed patterned transparent conductive electrode in the above embodiment 1. Selectively modifying the metal silver nanowire crosslinked network layer by using a stamp with patterns, wherein the stamp material is Polydimethylsiloxane (PDMS), and before use, the stamp material is sequentially washed by using an ethanol solution and deionized water, and then subjected to ultrasonic treatment and nitrogen gun drying treatment. The seal body of the used polydimethylsiloxane seal is provided with a pattern, the pattern is provided with a channel, and the channel can be infiltrated with liquid. In this embodiment 3, the mercapto compound is 1-phenyl-5-mercaptotetrazole (PMTA), the mercapto compound is dissolved in an ethanol solution, the general concentration is 0.1mol/L, and the solution is uniformly dispersed in the ethanol solution through magnetic stirring and ultrasonic treatment, so as to obtain a 1-phenyl-5-mercaptotetrazole dispersion solution.
The preparation process of this example 3 is: depositing silver nanowires on a substrate to form a silver nanowire crosslinked network layer, placing a stamp on the silver nanowire crosslinked network layer, dropwise adding 1-phenyl-5-mercaptotetrazole dispersion liquid on the outer side of a channel, selectively permeating and modifying the 1-phenyl-5-mercaptotetrazole dispersion liquid for 30 minutes by using capillary force in the channel, stripping the stamp, sequentially and repeatedly cleaning the partially modified silver nanowire crosslinked network layer by using ethanol and deionized water to remove residual dispersion liquid on the surface, drying by using a nitrogen gun, placing the silver nanowire crosslinked network layer on a constant-temperature heating table for heating at 230 ℃ for 10 minutes, fusing the silver nanowires in a modified region after heating to form an insulating region, keeping the integrity of unmodified silver nanowires, forming a conductive electrode region, and preparing the shadow-eliminating patterned transparent conductive electrode.
Example 4
This example 4 is a specific example of the method for preparing a shadow-eliminating patterned transparent conductive electrode of the above example 1, and the thiol compound used is 2-Mercaptobenzimidazole (MBI). Dissolving 2-mercaptobenzimidazole in ethanol solution, wherein the general concentration is 0.1mol/L, and uniformly dispersing the 2-mercaptobenzimidazole in the ethanol solution through magnetic stirring and ultrasonic treatment to obtain a 2-mercaptobenzimidazole dispersion liquid. As shown in fig. 4, in this embodiment 4, a metal mask is used as the patterned protection layer, and the metal mask includes an exposure region 23 and a coverage region 24.
As shown in fig. 5, silver nanowires are deposited on a substrate 21 to form a silver nanowire crosslinked network layer 22, and a 2-mercaptobenzimidazole dispersion liquid is used as a raw material, and a liquid phase modification method is adopted to perform integral modification on the surface of the silver nanowire crosslinked network layer 22, specifically, the silver nanowire crosslinked network layer 22 is immersed in the 2-mercaptobenzimidazole dispersion liquid, so that a 2-mercaptobenzimidazole self-assembled monolayer 25 is added on the surface of the silver nanowire crosslinked network layer to change the thermal stability of the silver nanowires, and thus an integrally structurally modified crosslinked network layer is formed. Covering a metal mask plate on the surface of the integrally modified silver nanowire crosslinked network layer, selecting a pattern area, placing the silver nanowire crosslinked network layer in a vacuum plasma surface treatment machine, carrying out 2min plasma bombardment treatment by using 80W power, removing the 2-mercaptobenzimidazole self-assembled monolayer 25 of the exposure area 23 to obtain a structurally modified crosslinked network layer 26, placing the crosslinked network layer on a constant temperature hot table for heating at 300 ℃ for 5min, fusing the silver nanowires of the unmodified area after heating to form an insulating area 27, keeping the integrity of the modified silver nanowires, and combining the structurally modified crosslinked network layer 26 with the conductive electrode area 28 to jointly form the vanishing patterned transparent conductive electrode.
Example 5
This example 5 is a specific example of the method for preparing a patterned transparent conductive electrode with a shadow-eliminating effect of example 1, and the thiol compound used is 2-Mercaptobenzoxazole (MBO). 2-mercaptobenzoxazole is dissolved in ethanol solution, the general concentration is 0.1mol/L, and the 2-mercaptobenzoxazole is uniformly dispersed in the ethanol solution by magnetic stirring and ultrasonic treatment to obtain 2-mercaptobenzoxazole dispersion liquid. In this embodiment 5, a metal mask is used as the patterned protection layer, and the metal mask includes an exposure region and a coverage region.
Depositing silver nanowires on a substrate to form a silver nanowire crosslinked network layer, taking a 2-mercaptobenzoxazole dispersion liquid as a raw material, and performing integral modification on the surface of the silver nanowire crosslinked network layer by adopting a liquid phase modification method, specifically, adding a 2-mercaptobenzoxazole self-assembled monolayer on the surface of the silver nanowire crosslinked network layer by adopting a soaking method of the silver nanowire crosslinked network layer in the 2-mercaptobenzoxazole dispersion liquid to change the thermal stability of the silver nanowires and form the integrally structurally modified crosslinked network layer. Covering a metal mask plate on the surface of the integrally modified silver nanowire crosslinked network layer, selecting a pattern area, placing the silver nanowire crosslinked network layer in a vacuum plasma surface treatment machine, carrying out 2min plasma bombardment treatment by using 80W power, removing a 2-mercaptobenzoxazole self-assembled monolayer in an exposure area to obtain a structurally modified crosslinked network layer, placing the crosslinked network layer on a constant temperature heating table for heating at 280 ℃ for 5min, fusing the silver nanowires in an unmodified area after heating to form an insulation area, wherein the modified silver nanowires retain the integrity, and combining the structurally modified crosslinked network layer with a conductive electrode area to jointly form a vanishing patterned transparent conductive electrode.
Example 6
This embodiment 6 is a specific example of the method for manufacturing a shadow-removed patterned transparent conductive electrode in the above embodiment 1. Selectively modifying the metal silver nanowire crosslinked network layer by using a stamp with patterns, wherein the stamp material is Polydimethylsiloxane (PDMS), and before use, the stamp material is sequentially washed by using an ethanol solution and deionized water, and then subjected to ultrasonic treatment and nitrogen gun drying treatment. The mercapto compound used in this example 6 was Octadecylthiol (ODT), which was dissolved in an ethanol solution at a concentration of generally 0.1mol/L, and uniformly dispersed in the ethanol solution by magnetic stirring and ultrasonic treatment to obtain an octadecylthiol dispersion.
As shown in fig. 6, silver nanowires are deposited on a substrate 31 to form a silver nanowire crosslinked network layer 32. The stamp is placed in a plasma surface treatment machine for 5min plasma bombardment treatment with 80w power, so that the stamp surface is changed from hydrophobicity to hydrophilicity. And soaking the seal in the octadecyl mercaptan dispersion liquid for 30min, taking out and drying, and depositing octadecyl mercaptan crystals on the surface of the seal after drying. Covering the surface of the stamp with the octadecyl mercaptan crystal on the surface of the silver nanowire crosslinking network for 60 minutes to perform solid modification, contacting the octadecyl mercaptan crystal at the convex part 33 of the stamp with the silver nanowire crosslinking network, exposing the silver nanowire crosslinking network corresponding to the concave part 34 of the stamp in the air to realize selective modification, then stripping the stamp, sequentially and repeatedly cleaning the partially modified silver nanowire crosslinking network layer by using ethanol and deionized water to remove the residual solid crystal on the surface, drying by using a nitrogen gun, heating on a constant temperature heating table, heating at 200 ℃ for 10 minutes, fusing the silver nanowires in the modified region to form an insulating region 35 after heating, keeping the integrity of the unmodified silver nanowires, forming a conductive electrode region 36, and preparing the shadow-eliminating patterned transparent conductive electrode.
Example 7
This embodiment 7 is a specific example of the method for manufacturing a shadow-removed patterned transparent conductive electrode in embodiment 1. Selectively modifying the metal silver nanowire crosslinked network layer by using a stamp with patterns, wherein the stamp material is Polydimethylsiloxane (PDMS), and before use, the stamp material is sequentially washed by using an ethanol solution and deionized water, and then subjected to ultrasonic treatment and nitrogen gun drying treatment. The mercapto compound used in this example 7 was 2-Mercaptobenzimidazole (MBI), which was dissolved in an ethanol solution at a concentration of generally 0.1mol/L and uniformly dispersed in the ethanol solution by magnetic stirring and ultrasonic treatment to obtain a 2-mercaptobenzimidazole dispersion.
As shown in fig. 7, silver nanowires are deposited on a substrate 41 to form a silver nanowire crosslinked network layer 42. The stamp is placed in a plasma surface treatment machine for 5min plasma bombardment treatment with 80w power, so that the stamp surface is changed from hydrophobicity to hydrophilicity. And soaking the seal in the 2-mercaptobenzimidazole dispersion liquid for 30min, taking out and drying, and depositing 2-mercaptobenzimidazole crystals on the surface of the seal after drying. Covering the surface of the stamp with the 2-mercaptobenzimidazole crystal on the surface of the silver nanowire crosslinking network for 60 minutes to perform solid modification, enabling the 2-mercaptobenzimidazole crystal at the convex part 43 of the stamp to be in contact with the silver nanowire crosslinking network, exposing the silver nanowire crosslinking network corresponding to the concave part 44 of the stamp to the air to realize selective modification, then peeling off the stamp, sequentially and repeatedly cleaning the partially modified silver nanowire crosslinking network layer by using ethanol and deionized water to remove the residual solid crystal on the surface, drying by using a nitrogen gun, heating on a constant temperature hot bench, heating at 300 ℃ for 5 minutes, keeping the integrity of the silver nanowire in the modified region after heating to form a conductive electrode region 45, fusing the unmodified silver nanowire to form an insulating region 46, and preparing the shadow-eliminating patterned transparent conductive electrode.
Example 8
This example 8 is a specific example of the method for preparing a shadow-eliminating patterned transparent conductive electrode of the above example 1, and the thiol compound used is 3-mercaptopropyltrimethoxysilane (MPTMS). In this embodiment 8, a metal mask is used as the patterned protection layer, and the metal mask includes an exposure region and a coverage region. The mercapto compound used is 3-mercaptopropyltrimethoxysilane solution. And depositing the silver nanowires on the substrate to form a silver nanowire crosslinked network layer. Putting the silver nanowire crosslinking network in a vacuum oven, dropwise adding a 3-mercaptopropyl trimethoxy silane solution in the vacuum oven to enable the surface of the solution to be opposite to the surface of the silver nanowire crosslinking network, fumigating for 60min at 90 ℃, transferring the 3-mercaptopropyl trimethoxy silane to the surface of the silver nanowire crosslinking network for integral modification, and adding a 3-mercaptopropyl trimethoxy silane self-assembly monomolecular layer on the surface of the silver nanowire crosslinking network to change the thermal stability of the silver nanowire to form an integrally structurally modified crosslinking network layer. Covering a metal mask plate on the surface of the integrally modified silver nanowire crosslinked network layer, selecting a pattern area, placing the silver nanowire crosslinked network layer in a vacuum plasma surface treatment machine, carrying out 2min plasma bombardment treatment by using 80W power, removing a 3-mercaptopropyltrimethoxysilane self-assembled monolayer in an exposure area to obtain a structurally modified crosslinked network layer, placing the crosslinked network layer on a constant temperature heating table for heating at 230 ℃ for 10min, wherein the integrity of the silver nanowires in an unmodified area is reserved after heating, the silver nanowires in the modified area form an insulation area, and the complete crosslinked network layer area is reserved as a conductive electrode area to form a vanishing patterned transparent conductive electrode.
The light transmittance and haze difference are important indicators affecting the shadow removal of the patterned conductive electrode. The patterned conductive electrode of example 2 was used to detect the differences in light transmittance and haze between the conductive electrode region and the insulating region, i.e., the shadow performance.
And detecting the light transmittance of the conductive electrode area and the insulating area. The illuminometer combining the micro collimator, the silicon photocell and the direct current complex emission type photoelectric galvanometer is selected, the manufactured patterned electrode is placed between the illuminometers, incident luminous flux To and transmitted luminous flux T of visible light (380 nm-780 nm) are measured in a conductive electrode area and an insulating area, the light transmittance difference of the two areas is obtained according To the formula of light transmittance T/To, and the test result is shown in fig. 8. From the results, it can be seen that the transmittance curves of the conductive electrode region and the insulating region almost overlap, indicating that the vanishing property is good.
And carrying out haze detection on the conductive electrode area and the insulating area. The total transmittance Tt of the sample light on the transparent glass is measured by a spectrophotometer, then the diffuse transmittances Td1 and Td2 of the conductive electrode region and the insulating region are measured by an integrating sphere accessory, the haze difference of the two regions in the visible light range is obtained according to the formula of Td/Tt, and the test result is shown in fig. 9. From the results, it can be seen that the haze curves of the conductive electrode region and the insulating region almost overlap, indicating good shadow-eliminating performance. The test results shown in fig. 8 and 9 are the test results of the combination of the silver nanowire crosslinked network layer and the glass substrate. Wherein the glass substrate has a light transmittance of 91% at 550nm and a haze of 0.9%.
As shown in fig. 10, an SEM image of the conductive electrode region and the insulating region of the silver nanowire network prepared in this example 2 shows that the conductive electrode region is located in the middle, and the insulating regions are located on the left and right sides, and as can be seen from the SEM image, the silver nanowires in the conductive electrode region are continuous, and the insulating regions are fused at multiple locations, so that discontinuous silver nanowires are formed. As can be seen, the line width of the patterned transparent conductive electrode prepared in this example 2 is about 10 μm.
Depositing silver nanowires on a substrate to form a silver nanowire crosslinked network layer, then integrally modifying the silver nanowire crosslinked network layer by respectively using 2-Mercaptobenzimidazole (MBI) and octadecyl mercaptan (ODT) by adopting a liquid phase modification method, and testing the change of the square resistance before modification and after treatment at different modification times.
TABLE 1 Effect of modification time on the sheet resistance of silver nanowire crosslinked networks
As can be seen from the data in Table 1, the change of the sheet resistance of the silver nanowire crosslinked network and the unmodified silver nanowire crosslinked network after being modified for 10-60min by using MBI and ODT is very small, which indicates that the modification of the mercapto compound has a negligible effect on the sheet resistance of the silver nanowire crosslinked network. In the embodiment 4, the cross-linked network layer 26 with the structural modification and the conductive electrode region 28 form the vanishing patterned transparent conductive electrode together, which still has good conductive performance.
Depositing silver nanowires on a substrate to form a silver nanowire crosslinked network layer, integrally modifying the silver nanowire crosslinked network layer by respectively using 2-Mercaptobenzimidazole (MBI) and octadecyl mercaptan (ODT) through a liquid phase modification method, heating the modified and unmodified silver nanowire crosslinked network layers for 5min at different temperatures by taking the unmodified silver nanowire crosslinked network as a blank example, and testing the square resistance value after heating.
TABLE 2 Effect of heat treatment at different temperatures on the sheet resistance of silver nanowire crosslinked networks before and after modification
As can be seen from the data in Table 2, the thermal instability of the silver nanowire can be effectively affected by the modification of the mercapto compound, and the resistance is increased when the silver nanowire is fused after the region with low thermal stability is heated. The square resistance of the unmodified silver nanowire after being heated at 300 ℃ for 5min is infinite, which indicates that the silver nanowire is completely fused. After the silver nanowire is modified by MBI, the thermal stability of the silver nanowire is improved, and the square resistance of the silver nanowire is not changed greatly before and after the silver nanowire is heated at 320 ℃ for 5min, which indicates that the silver nanowire is not obviously denatured. After ODT modification, the thermal stability of the silver nanowires is reduced, and the square resistance of the silver nanowires after being heated for 5min at 200 ℃ is increased to infinity, which indicates that the heating temperature reaches a melting point.
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the technical solutions of the present invention, and are not intended to limit the specific embodiments of the present invention. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention claims should be included in the protection scope of the present invention claims.
Claims (10)
1. A preparation method of a shadow-eliminating patterned transparent conductive electrode is characterized by comprising the following steps:
s1, depositing metal nanowires on the substrate to form a metal nanowire crosslinked network layer;
s2, selectively modifying the metal nanowire crosslinked network by adopting a sulfhydryl compound, changing the thermal stability of part of the metal nanowire crosslinked network layer, and forming a thermal stability difference between a modified region and an unmodified region to obtain a structurally modified crosslinked network layer;
s3, the cross-linked network layer with the structural modification is heated, an insulation area with fused metal nanowires is obtained at a position with poor thermal stability of the cross-linked network layer of the metal nanowires, and a complete conductive area with the metal nanowires is obtained at a position with good thermal stability of the cross-linked network layer of the metal nanowires, so that the shadow-eliminating patterned transparent conductive electrode is formed.
2. The method for preparing a shadow-eliminating patterned transparent conductive electrode as claimed in claim 1, wherein the process of step S2 is: the method comprises the steps of using a sulfydryl compound as a raw material, using a patterned device to perform patterned selective modification on a metal nanowire crosslinked network layer, adding a sulfydryl self-assembled monolayer on the surface of the metal nanowire in a pattern area to change the thermal stability of the metal nanowire in the pattern area, cleaning and drying to form the structurally modified crosslinked network layer.
3. The method for preparing a shadow-eliminating patterned transparent conductive electrode as claimed in claim 1, wherein the process of step S2 is: the method comprises the steps of taking a sulfhydryl compound as a raw material, carrying out integral modification on a metal nanowire crosslinking network layer, adding a sulfhydryl self-assembly monomolecular layer on the surface of a metal nanowire to change the thermal stability of the metal nanowire, forming the integral structural modified crosslinking network layer, covering the integral structural modified crosslinking network layer by using a patterned protective layer, and removing the sulfhydryl self-assembly monomolecular layer on the surface of the metal nanowire in a pattern area to form the structural modified crosslinking network layer.
4. The method for preparing the shadow-eliminating patterned transparent conductive electrode according to claim 2, wherein the patterned selective modification process comprises forming a patterned covering layer on the surface of the metal nanowire crosslinked network layer by any one of processes of ink-jet printing, screen printing, offset printing, photoetching and soft stamp covering, and then selectively modifying uncovered metal nanowires by a mercapto compound by a liquid phase or gas phase method; or the selective patterned modification is to selectively deposit the sulfhydryl compound on the metal nanowire crosslinking network layer directly by any process of ink-jet printing, silk-screen printing, offset printing and soft stamp transfer printing, so as to selectively modify the metal nanowire network.
5. The method for preparing a shadow-eliminating patterned transparent conductive electrode according to claim 3, wherein the overall modification method is any one of liquid phase modification, gas phase modification or solid state transfer modification.
6. The method for preparing a shadow-eliminating patterned transparent conductive electrode according to claim 3, wherein the patterned protective layer is any one of a metal mask, a film mask, a quartz mask and a polymer film.
7. The method for preparing the shadow-eliminating patterned transparent conductive electrode according to claim 3, wherein the method for removing the thiol self-assembled monolayer in the pattern region is any one of plasma bombardment, ultraviolet/ozone treatment, intense pulsed light exposure and chemical etching.
8. The method of claim 1, wherein the thiol compound is any one or more of phenethyl thiol, n-propyl thiol, isopropyl thiol, 3-mercaptopropionic acid, 1-propyl thiol, 1, 3-propanedithiol, 2, 3-dimercaptopropanol, n-butyl thiol, n-pentyl thiol, n-hexyl thiol, n-octyl thiol, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, dodecyl thiol, tetradecyl thiol, hexadecyl thiol, octadecyl thiol, 3-mercaptopropyltrimethoxysilane, 4-imidazoldithiocarboxylic acid, thiophenol, and the like.
9. The method for preparing the shadow-eliminating patterned transparent conductive electrode according to claim 1, wherein the substrate is made of a rigid material, the rigid material is made of any one of glass and a silicon wafer, or the substrate is made of a flexible material, and the flexible material is made of any one of polydimethylsiloxane, polyethylene terephthalate, polyether sulfone resin, polyethylene, polyimide, polycarbonate, polyurethane and polyethylene naphthalate.
10. The method for preparing the shadow-eliminating patterned transparent conductive electrode according to claim 1, wherein the metal nanowire is one or a mixture of copper nanowire, silver nanowire and gold nanowire.
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