Silver nanowire transparent conductive member, method for preparing the same, and use thereof

Abstract

The application relates to a silver nanowire transparent conductor and a preparation method and application thereof. The preparation method comprises the following steps: etching at least one groove on the surface of a transparent substrate and performing activation treatment to obtain a pretreated substrate, wherein the depth of the groove is 100-200 nm, and the width of the groove is 100-160 nm; placing the pretreated substrate in a silver nanowire dispersion liquid containing mercaptosiloxane, so that the groove bottom adsorbs and deposits a silver nanowire layer to obtain a composite conductor, wherein the thickness of the silver nanowire layer is 40-60 nm; placing the composite conductor in an inorganic oxide powder dispersion liquid, so that a protective layer is bonded to the surface of the silver nanowire layer, and residues attached outside the groove are removed to obtain a silver nanowire transparent conductor, wherein the sum of the thicknesses of the silver nanowire layer and the protective layer is less than or equal to the depth of the groove. The preparation method makes the silver nanowire transparent conductor have high conductivity while ensuring high transmittance, and the reliability is excellent.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of transparent conductive film, in particular to a silver nanowire transparent conductive piece and a preparation method and application thereof. BACKGROUND

[0002] The transparent conductive film is a basic optoelectronic material with high conductivity and high transmittance in the visible light band. For solid materials, transmittance and conductivity are a pair of contradictory properties. Generally, the increase of conductivity leads to the decrease of transmittance, so there are few commercialized transparent conductive films. Among them, the silver nanowire transparent conductive film has excellent photoelectric performance, simple process, easy realization of large-area film formation, bendable and low price, etc., showing considerable commercialization potential.

[0003] In the preparation process of the traditional silver nanowire transparent conductive film, additive manufacturing technology is usually used to prepare the silver nanowire transparent conductive film from bottom to top, so that the silver nanowire layer has good distribution and fixing effect, thereby improving the conductivity of the silver nanowire transparent conductive film. However, the silver nanowire transparent conductive film prepared based on additive manufacturing technology is difficult to maintain high transmittance.

[0004] In addition, when the silver nanowire transparent conductive film is applied in the heating field, it is also required to have high thermal stability and chemical stability. Therefore, in the traditional technology, a polymer material with good thermal stability and chemical stability is usually deposited on the surface of the silver nanowire layer as a protective film. However, the traditional polymer protective film cannot effectively isolate the moisture and oxygen in the air from eroding the silver nanowire layer, nor can it block the diffusion of silver atoms in the silver nanowire layer, thereby making the reliability of the silver nanowire transparent conductive film poor, greatly limiting the application of the silver nanowire transparent conductive film in the heating field. SUMMARY

[0005] Therefore, it is necessary to provide a silver nanowire transparent conductive piece and a preparation method and application thereof aiming at the above problems. The preparation method makes the silver nanowire transparent conductive piece have high conductivity while ensuring high transmittance, and has excellent reliability, which can be widely applied in the heating field.

[0006] A preparation method of a silver nanowire transparent conductive piece, comprising the following steps:

[0007] etching at least one groove on the surface of the transparent substrate and performing activation treatment to obtain a pretreated substrate, wherein the depth of the groove is 100-200 nm, and the width is 100-160 nm;

[0008] placing the pretreated substrate in a silver nanowire dispersion liquid containing mercaptosiloxane to make the groove bottom adsorb and deposit a silver nanowire layer, to obtain a composite conductor, wherein the thickness of the silver nanowire layer is 40-60 nm;

[0009] placing the composite conductor in an inorganic oxide powder dispersion liquid to make the surface of the silver nanowire layer bond a protective layer, and removing the silver nanowire residues and inorganic oxide powder residues attached outside the groove, to obtain a silver nanowire transparent conductor, wherein the sum of the thicknesses of the silver nanowire layer and the protective layer is less than or equal to the depth of the groove.

[0010] In one of the embodiments, the distance between two adjacent grooves is 500-1000 nm.

[0011] In one of the embodiments, the concentration of silver nanowires in the silver nanowire dispersion liquid containing mercaptosiloxane is 0.5-1 mg / mL, and the mass ratio of mercaptosiloxane to silver nanowires is 1:10-1:15.

[0012] In one of the embodiments, the concentration of inorganic oxide powder in the inorganic oxide powder dispersion liquid is 0.5-1 mg / mL.

[0013] In one of the embodiments, the inorganic oxide powder in the inorganic oxide powder dispersion liquid mainly includes at least one of silica powder, zinc oxide powder, and titanium dioxide powder.

[0014] In one of the embodiments, the particle size of the inorganic oxide powder in the inorganic oxide powder dispersion liquid is 10-20 nm.

[0015] In one of the embodiments, in the step of placing the pretreated substrate in the silver nanowire dispersion liquid containing mercaptosiloxane, the temperature of the silver nanowire dispersion liquid is 25-65℃, and the time is 5-10 min.

[0016] In one of the embodiments, in the step of placing the composite conductor in the inorganic oxide powder dispersion liquid, the temperature of the inorganic oxide powder dispersion liquid is 25-65℃, and the time is 5-10 min.

[0017] In one of the embodiments, before the step of performing the activation treatment, two baffles are placed on the surface of the transparent substrate having grooves, the two baffles are oppositely arranged on both sides of the grooves, and any of the baffles has intersection points with all the grooves, and then after the step of bonding the protective layer on the surface of the silver nanowire layer, the baffles are removed, and electrodes are arranged at the positions shielded by the baffles.

[0018] The silver nanowire transparent conductive piece prepared by the preparation method of the silver nanowire transparent conductive piece as described above comprises a transparent substrate with at least one groove, and a silver nanowire layer and a protective layer are sequentially stacked from the bottom of the groove to the opening direction, wherein the sum of the thicknesses of the silver nanowire layer and the protective layer is less than or equal to the depth of the groove.

[0019] The silver nanowire transparent conductive piece as described above is used for a camera window.

[0020] The preparation method of the present application introduces a groove structure of a specific size, and sequentially stacks a silver nanowire layer and a protective layer from the bottom of the groove to the opening direction, so that when light passes through the silver nanowire transparent conductive piece, Rayleigh scattering mainly occurs, and the scattering intensity is weak, so that the silver nanowire transparent conductive piece can maintain high transmittance, and can block silver nanowire electromigration, so that the silver nanowire transparent conductive piece has high conductivity. And because the silver nanowire single layer is adsorbed at the bottom of the groove, not only can the silver nanowire distribution be more uniform, which is conducive to improving the overall transmittance and conductivity, but also can ensure that the sum of the thicknesses of the silver nanowire layer and the protective layer is less than or equal to the depth of the groove, which is conducive to fully removing the residues attached outside the groove, thereby further improving the transmittance.

[0021] At the same time, the inorganic oxide powder as the protective layer has excellent thermal stability and chemical stability, and the groove structure of a specific size can also avoid the problem of densification such as voids in the protective layer, thereby effectively isolating water vapor and oxygen in the air, and because the inorganic oxide powder can realize single-layer chemical bonding with the silver nanowire layer, it is conducive to enhancing the bonding force between the silver nanowire layer and the protective layer, so as to greatly improve the reliability of the silver nanowire transparent conductive piece.

[0022] Therefore, the preparation method has a simple process and does not need to introduce additional material layers, so that the silver nanowire transparent conductive piece can have high conductivity while ensuring high transmittance, and has excellent reliability, thereby optimizing the application effect of the silver nanowire transparent conductive piece in the heating field such as the camera window. BRIEF DESCRIPTION OF DRAWINGS

[0023] Figure 1 is a side view structural diagram of the silver nanowire transparent conductive piece prepared in an embodiment of the present application;

[0024] Figure 2 is a schematic diagram of adding a baffle at both ends of the transparent substrate in the preparation process of an embodiment of the present application;

[0025] Figure 3 is a top view structural diagram of the silver nanowire transparent conductive piece prepared in an embodiment of the present application.

[0026] Wherein, 101, transparent substrate; 102, silver nanowire layer; 103, protective layer; 104, baffle; 105, electrode. DETAILED DESCRIPTION

[0027] For the purpose of promoting the understanding of the present application, the present application will be described in further detail below. It should be understood, however, that the present application can be carried out in many different forms and is not limited to the embodiments or examples described herein. Rather, these embodiments or examples are provided so that this disclosure will be thorough and complete, and fully convey the scope of the present application to those skilled in the art.

[0028] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the present application belongs. The terminology used in the description of the present application herein is for the purpose of describing particular embodiments or examples only and is not intended to be limiting of the present application.

[0029] In conjunction with Figure 1 As shown, the present application provides a preparation method of a silver nanowire transparent conductive member, comprising the following steps:

[0030] S1, etching at least one groove on the surface of a transparent substrate 101 and performing activation treatment to obtain a pretreated substrate, wherein the depth of the groove is 100-200 nm, and the width is 100-160 nm;

[0031] S2, placing the pretreated substrate in a silver nanowire dispersion liquid containing mercaptosiloxane, so that the groove bottom adsorbs and deposits a silver nanowire layer 102 to obtain a composite conductor, wherein the thickness of the silver nanowire layer is 40-60 nm;

[0032] S3, placing the composite conductor in an inorganic oxide powder dispersion liquid, so that the surface of the silver nanowire layer 102 is bonded with a protective layer 103, and removing the silver nanowire residues and inorganic oxide powder residues attached outside the groove to obtain a silver nanowire transparent conductive member, wherein the sum of the thicknesses of the silver nanowire layer 102 and the protective layer 103 is less than or equal to the depth of the groove.

[0033] Visible light passing through a traditional silver nanowire transparent conductive member will undergo multiple scattering phenomena including Mie scattering and Rayleigh scattering. Mie scattering will cause an increase in scattering index, which is not conducive to improving the transmittance.

[0034] In order to avoid Mie scattering of light through the silver nanowire transparent conductive part, in step S1, by introducing a groove structure of a specific size, and sequentially stacking the silver nanowire layer and the protective layer from the bottom of the groove to the opening direction in the subsequent preparation process, the light mainly undergoes Rayleigh scattering when passing through the silver nanowire transparent conductive part, and the scattering intensity is weak, so that the silver nanowire transparent conductive part can maintain high transmittance, and can block the silver nanowire electromigration, so that the silver nanowire transparent conductive part has high conductivity. Moreover, the groove structure of a specific size can also avoid the problem of compactness of the protective layer, such as the appearance of voids, so as to effectively isolate water vapor and oxygen in the air, and improve the reliability of the silver nanowire transparent conductive part.

[0035] Preferably, the pitch between any two adjacent grooves is 500-1000 nm, which is more conducive to making the silver nanowire transparent conductive part have excellent conductivity while ensuring high transmittance.

[0036] It should be noted that the pitch between any two grooves can be the same or different; any two grooves can be parallel or not parallel, and those skilled in the art can set it according to actual preparation needs.

[0037] More preferably, any two grooves are parallel to each other, and the pitch between any two grooves is the same, so that a regular groove structure can be obtained, and the transmittance and conductivity of the silver nanowire transparent conductive part are better.

[0038] Optionally, the transparent substrate includes but is not limited to a glass substrate, a polyarylether nitrile (PEN) substrate, or a polyethylene terephthalate (PET) substrate, and preferably is a glass substrate.

[0039] In an embodiment, the etching process is selected from laser etching.

[0040] In an embodiment, the activation treatment method is selected from plasma method, ultraviolet ozone method, and coupling agent method. The activation treatment can make the transparent substrate surface grafted with hydroxyl and carboxyl groups, which is more conducive to the effect of single-layer adsorption of silver nanowires in the groove.

[0041] In step S2, by placing the pretreated substrate after activation treatment in a silver nanowire dispersion liquid containing mercaptosilane, on the one hand, the silver nanowires can be single-layer adsorbed on the groove bottom, which not only can ensure that the silver nanowire layer 102 will not fill the groove, but also can make the silver nanowires more uniformly distributed, which is conducive to improving the overall transmittance and conductivity; on the other hand, it is conducive to the single-layer chemical bonding of the silver nanowire layer to the inorganic oxide powder, which enhances the bonding force between the silver nanowire layer 102 and the protective layer 103, and improves the reliability.

[0042] Preferably, the thickness of the silver nanowire layer 102 is 40-50 nm.

[0043] It should be noted that a small amount of silver nanowires may exist in a random wall-hanging phenomenon, and based on the action of gravity, the wall-hanging silver nanowires exist only on the side wall close to the groove bottom. Relative to the uniform and close distribution of the silver nanowire layer at the groove bottom, the sparse wall-hanging single silver nanowire cannot constitute a layered structure, and a small amount of wall-hanging silver nanowires affect the overall structure and performance of the silver nanowire transparent conductive member described in the present application. Therefore, in the macroscopic overall structure analysis, the silver nanowires with wall-hanging phenomenon are not considered too much.

[0044] In an embodiment, the concentration of silver nanowires in the mercapto-containing siloxane silver nanowire dispersion is preferably 0.5 mg / mL-1 mg / mL, which is more advantageous to make the deposition thickness of the silver nanowire layer 102 reach 40 nm-60 nm, and further make the silver nanowire transparent conductive member have high conductivity and high light transmittance.

[0045] In the mercapto-containing siloxane silver nanowire dispersion, the mass ratio of mercapto-containing siloxane to silver nanowire is preferably 1:10-1:15, and the single-layer adsorption effect of the silver nanowire layer 102 is better.

[0046] Specifically, the mercapto-containing siloxane is at least one of 3-mercaptopropyl triethoxysilane, 3-mercaptopropyl trimethoxysilane, and mercaptopropyl methyl dimethoxysilane.

[0047] In the step of placing the pretreated substrate in the mercapto-containing siloxane silver nanowire dispersion, the temperature of the silver nanowire dispersion is 25℃-65℃, and the time is 5 min-10 min, which is more advantageous to the single-layer adsorption of silver nanowires on the groove bottom.

[0048] In step S3, by placing the composite conductor in the inorganic oxide powder dispersion, single-layer chemical bonding of the silver nanowire layer and the inorganic oxide powder can be achieved, so that the protective layer 103 is deposited on the surface of the silver nanowire layer 102, and the sum of the thickness of the silver nanowire layer 102 and the protective layer 103 is less than or equal to the depth of the groove, which is advantageous to fully remove the silver nanowire residues and inorganic oxide powder residues attached outside the groove, further improve the transmittance, and not damage the silver nanowire layer 102, so that the silver nanowire transparent conductive member maintains high conductivity.

[0049] At the same time, the inorganic oxide powder has excellent thermal stability and chemical stability as a protective layer, and the inorganic oxide powder and the silver nanowire layer realize single-layer chemical bonding, which enhances the bonding force between the silver nanowire layer and the protective layer, thereby improving the reliability of the silver nanowire transparent conductive member.

[0050] In an embodiment, the concentration of the inorganic oxide powder in the inorganic oxide powder dispersion liquid is preferably 0.5 mg / mL to 1 mg / mL, which is more conducive to the single-layer chemical bonding of the silver nanowire layer and the inorganic oxide powder, and the silver nanowire transparent conductive member has more excellent reliability.

[0051] Specifically, the inorganic oxide powder in the inorganic oxide powder dispersion liquid mainly includes at least one of silica powder, zinc oxide powder, and titanium dioxide powder, which is more conducive to maintaining high transmittance of the silver nanowire transparent conductive member while protecting the silver nanowire layer 102.

[0052] Preferably, the particle size of the inorganic oxide powder in the inorganic oxide powder dispersion liquid is 10 nm to 20 nm, which can make the protective layer 103 more uniformly distributed, and is more conducive to making the silver nanowire transparent conductive member have high transmittance and high reliability.

[0053] It should be noted that, based on the single-layer chemical bonding of the silver nanowire layer and the inorganic oxide powder, the thickness of the protective layer is about the thickness of the single-layer paving of the inorganic oxide powder, and the present application does not limit this.

[0054] By removing the residues attached outside the grooves, the excess material deposited on the surface of the transparent substrate is removed, which is conducive to improving the transmittance of the silver nanowire transparent conductive member and will not affect the conductivity of the silver nanowire layer 102. The method for removing the residues attached outside the grooves is not limited, and polishing is preferably used.

[0055] In the step of placing the composite conductor in the inorganic oxide powder dispersion liquid, the temperature of the inorganic oxide powder dispersion liquid is 25°C to 65°C, and the time is 5 min to 10 min, which is more conducive to the single-layer chemical bonding of the inorganic oxide powder and the silver nanowire layer.

[0056] In an embodiment, in combination with the above-mentioned silver nanowire transparent conductive member and the preparation method thereof, Figure 2 and Figure 3 As shown in the above-mentioned silver nanowire transparent conductive member and the preparation method thereof, two baffles 104 are placed on the surface of the transparent substrate 101 having grooves before the step of performing the activation treatment, the two baffles 104 are oppositely arranged on both sides of the grooves, and any baffle 104 has an intersection with all the grooves, and then the baffles 104 are removed after the step of bonding the protective layer 103 on the surface of the silver nanowire layer 102, and the electrodes 105 are arranged on the positions shielded by the baffles 104, to ensure the contact and conduction of the silver nanowire layer 102 and the electrodes 105.

[0057] When any two grooves are parallel to each other and the spacing between any two grooves is the same, it is preferred that any baffle has a perpendicular intersection with all the grooves.

[0058] Therefore, the preparation method has a simple process, does not need to introduce an additional material layer, can make the silver nanowire transparent conductive member have high conductivity while ensuring high transmittance, and has excellent reliability.

[0059] The present application provides a silver nanowire transparent conductive member prepared by the above-mentioned preparation method of a silver nanowire transparent conductive member, the silver nanowire transparent conductive member comprising a transparent substrate 101 having at least one groove, and a silver nanowire layer 102 and a protective layer 103 being sequentially stacked from the bottom of the groove to the opening direction, wherein the sum of the thicknesses of the silver nanowire layer 102 and the protective layer 103 is less than or equal to the depth of the groove.

[0060] The present application also provides a silver nanowire transparent conductive member for a camera view window.

[0061] The silver nanowire transparent conductive member for a camera view window not only helps to reduce light scattering when natural light passes through the view window and improve imaging effect, but also can make the camera view window have excellent defrosting and defogging functions, solve the problem of unclear shooting image caused by view window fogging and frosting, and is especially suitable for high-humidity working environment.

[0062] In the following, the silver nanowire transparent conductive member, its preparation method and application will be further described through the following specific examples.

[0063] Example 1

[0064] The glass substrate was cleaned with acetone and ethanol under ultrasonic state for 10 min, and then dried naturally. Then, grooves with a depth of 100 nm, a width of 100 nm and a pitch of 500 nm were etched on the surface of the glass substrate by laser. Then, the surface of the glass substrate with grooves was placed between two baffles, the two baffles were oppositely arranged on both sides of the grooves, so that the baffles had perpendicular intersection points with all the grooves. Then, the surface of the glass substrate was subjected to plasma modification in a plasma cleaning machine, so that hydroxyl and carboxyl groups were grafted on the surface of the glass substrate, thereby obtaining a pretreated substrate.

[0065] Silver nanowires and 3-mercaptopropyl triethoxysilane were added to ethanol, and ultrasonic dispersion was performed for 15 min, followed by continuous stirring for 5 min. After three cycles, a silver nanowire dispersion liquid with 3-mercaptopropyl triethoxysilane adsorbed on the surface of the silver nanowires was obtained, wherein the mass ratio of 3-mercaptopropyl triethoxysilane to silver nanowires was 1:15, and the concentration of silver nanowires in the silver nanowire dispersion liquid was 0.5 mg / mL. The pretreated substrate was placed in the silver nanowire dispersion liquid at a temperature of 50°C, and after 5 min, the pretreated substrate was taken out, so that a silver nanowire layer with a thickness of 40 nm was adsorbed and deposited on the bottom of the groove of the pretreated substrate, thereby obtaining a composite conductor.

[0066] The silica powder with an average particle size of 10 nm was added to an ethanol solution and ultrasonically dispersed for 15 min to obtain a silica powder dispersion liquid with a silica powder concentration of 0.5 mg / mL. Then the silica powder dispersion liquid was heated to 45°C, and the composite conductor was placed in the silica powder dispersion liquid, and taken out after 5 min to bond a protective layer to the surface of the silver nanowire layer. The baffle was removed, and the electrode lines were etched at the position of the baffle, and an ion sputtering silver paste electrode was used. The remaining residues attached outside the grooves were removed by grinding and polishing to obtain a silver nanowire transparent conductive piece.

[0067] Example 2

[0068] The glass substrate was cleaned with acetone and ethanol under ultrasonic conditions for 10 min, and after natural drying, grooves with a depth of 200 nm, a width of 160 nm, and a pitch of 1000 nm were etched on the surface of the glass substrate by laser etching. Then the surface of the glass substrate with the grooves was placed with two baffles, and the two baffles were oppositely arranged on both sides of the grooves so that the baffles had perpendicular intersection points with all the grooves. Then the surface was subjected to plasma modification in a plasma cleaning machine to graft hydroxyl and carboxyl groups on the surface of the glass substrate to obtain a pretreated substrate.

[0069] The silver nanowires and mercaptopropylmethyldimethoxysilane were added to ethanol and ultrasonically dispersed for 15 min, and then continuously stirred for 5 min. After three cycles, a silver nanowire dispersion liquid of mercaptopropylmethyldimethoxysilane was obtained, wherein the mass ratio of mercaptopropylmethyldimethoxysilane to silver nanowires was 1:15, and the concentration of silver nanowires in the silver nanowire dispersion liquid was 1 mg / mL. The pretreated substrate was placed in the silver nanowire dispersion liquid at a temperature of 50°C, and taken out after 10 min to allow the grooves of the pretreated substrate to adsorb and deposit a silver nanowire layer with a thickness of 60 nm, thereby obtaining a composite conductor.

[0070] The silica powder with an average particle size of 20 nm was added to an ethanol solution and ultrasonically dispersed for 15 min to obtain a silica powder dispersion liquid with a silica powder concentration of 1 mg / mL. Then the silica powder dispersion liquid was heated to 45°C, and the composite conductor was placed in the silica powder dispersion liquid, and taken out after 10 min to bond a protective layer to the surface of the silver nanowire layer. The baffle was removed, and the electrode lines were etched at the position of the baffle, and an ion sputtering silver paste electrode was used. The remaining residues attached outside the grooves were removed by grinding and polishing to obtain a silver nanowire transparent conductive piece.

[0071] Example 3

[0072] The glass substrate is cleaned with acetone and ethanol under ultrasonic state for 10 minutes respectively, and then dried naturally. Grooves with a depth of 200 nm, a width of 140 nm and a pitch of 850 nm are etched on the surface of the glass substrate by laser. Then, the surface of the glass substrate with the grooves is placed with two baffles, the two baffles are oppositely arranged on both sides of the grooves, so that the baffles have perpendicular intersections with all the grooves. Then, the surface of the glass substrate is modified by plasma in a plasma cleaning machine, so that the glass substrate surface is grafted with hydroxyl and carboxyl groups, and a pretreated substrate is obtained.

[0073] The silver nanowires and mercaptopropylmethyldimethoxysilane are added into ethanol, ultrasonic dispersed for 15 minutes, and then continuously stirred for 5 minutes. After three cycles, a silver nanowire dispersion of mercaptopropylmethyldimethoxysilane is obtained, wherein the mass ratio of mercaptopropylmethyldimethoxysilane to silver nanowires is 1:10, and the concentration of silver nanowires in the silver nanowire dispersion is 0.5 mg / mL. The pretreated substrate is placed in the silver nanowire dispersion at a temperature of 65°C, and after 5 minutes, the pretreated substrate is taken out, so that the groove bottom of the pretreated substrate adsorbs and deposits a silver nanowire layer with a thickness of 40 nm, and a composite conductor is obtained.

[0074] The zinc oxide powder with an average particle size of 15 nm is added into an ethanol solution and ultrasonic dispersed for 15 minutes to obtain a zinc oxide powder dispersion with a concentration of 1 mg / mL. Then, the zinc oxide powder dispersion is heated to 25°C, and the composite conductor is placed in the zinc oxide powder dispersion, and after 10 minutes, the composite conductor is taken out, so that the silver nanowire layer is bonded with a protective layer. The baffles are removed, and electrode lines are etched at the positions of the baffles, and an ion sputtering silver paste electrode is used. By grinding and polishing, the residues attached outside the grooves are removed, and a silver nanowire transparent conductor is obtained.

[0075] Example 4

[0076] The glass substrate is cleaned with acetone and ethanol under ultrasonic state for 10 minutes respectively, and then dried naturally. Grooves with a depth of 150 nm, a width of 120 nm and a pitch of 650 nm are etched on the surface of the glass substrate by laser. Then, the surface of the glass substrate with the grooves is placed with two baffles, the two baffles are oppositely arranged on both sides of the grooves, so that the baffles have perpendicular intersections with all the grooves. Then, the surface of the glass substrate is modified by plasma in a plasma cleaning machine, so that the glass substrate surface is grafted with hydroxyl and carboxyl groups, and a pretreated substrate is obtained.

[0077] The silver nanowires and mercaptopropylmethyldimethoxysilane are added into ethanol, ultrasonic dispersion is carried out for 15 min, then continuous stirring is carried out for 5 min, and the silver nanowire dispersion liquid of mercaptopropylmethyldimethoxysilane is obtained after three cycles, wherein the mass ratio of mercaptopropylmethyldimethoxysilane to silver nanowires is 1:12, and the concentration of silver nanowires in the silver nanowire dispersion liquid is 0.8 mg / mL. The pretreated substrate is placed in the silver nanowire dispersion liquid with a temperature of 25℃, and is taken out after 10 min, so that the groove bottom of the pretreated substrate is adsorbed and deposited with a silver nanowire layer with a thickness of 50 nm, and a composite conductor is obtained.

[0078] The titanium dioxide powder with an average particle size of 10 nm is added into an ethanol solution, and ultrasonic dispersion is carried out for 15 min, so that a titanium dioxide powder dispersion liquid with a titanium dioxide powder concentration of 0.8 mg / mL is obtained. Then, the titanium dioxide powder dispersion liquid is heated to 65℃, and the composite conductor is placed in the titanium dioxide powder dispersion liquid, and is taken out after 5 min, so that the silver nanowire layer is bonded with a protective layer on the surface. The baffle is removed, and the electrode line is etched at the position of the baffle, and the silver paste electrode is adopted by ion sputtering. The remaining residues attached outside the groove are removed by grinding and polishing, and a silver nanowire transparent conductor is obtained.

[0079] Comparative Example 1

[0080] The glass substrate is cleaned with acetone and ethanol respectively under ultrasonic state for 10 min, and after natural drying, the left and right ends of the glass substrate surface are placed with baffles, and then the surface is subjected to plasma modification in a plasma cleaning machine, so that the glass substrate surface is grafted with hydroxyl and carboxyl groups, and a pretreated substrate is obtained.

[0081] The silver nanowires and 3-mercaptopropyltriethoxysilane are added into ethanol, ultrasonic dispersion is carried out for 15 min, then continuous stirring is carried out for 5 min, and the silver nanowire dispersion liquid of 3-mercaptopropyltriethoxysilane is obtained after three cycles, wherein the mass ratio of 3-mercaptopropyltriethoxysilane to silver nanowires is 1:15, and the concentration of silver nanowires in the silver nanowire dispersion liquid is 0.5 mg / mL. The pretreated substrate is placed in the silver nanowire dispersion liquid with a temperature of 50℃, and is taken out after 5 min, so that the pretreated substrate surface is adsorbed and deposited with a silver nanowire layer with a thickness of 30 nm, and a composite conductor is obtained.

[0082] The silica powder with an average particle size of 10 nm is added into an ethanol solution, and ultrasonic dispersion is carried out for 15 min, so that a silica powder dispersion liquid with a silica powder concentration of 0.5 mg / mL is obtained. Then, the silica powder dispersion liquid is heated to 45℃, and the composite conductor is placed in the silica powder dispersion liquid, and is taken out after 5 min, so that the silver nanowire layer is bonded with a protective layer on the surface. The baffle is removed, and the electrode line is etched at the position of the baffle, and the silver paste electrode is adopted by ion sputtering, and a silver nanowire transparent conductor is obtained.

[0083] Comparative Example 2

[0084] Comparative Example 2 differs from Example 1 in that the depth of the groove is 500 nm.

[0085] Comparative Example 3

[0086] Comparative Example 3 differs from Example 1 in that the width of the groove is 300 nm.

[0087] Comparative Example 4

[0088] The pretreatment substrate was prepared using the same method as in Example 1.

[0089] Silver nanowires and polydimethylsiloxane were added to ethanol and ultrasonically dispersed for 15 min, followed by continuous stirring for 5 min, and the surface of the silver nanowires was adsorbed with polydimethylsiloxane after three cycles. The mass ratio of polydimethylsiloxane to silver nanowires was 1:15, and the concentration of silver nanowires in the silver nanowire dispersion was 0.5 mg / mL. The pretreatment substrate was placed in the silver nanowire dispersion at a temperature of 50°C, and after 5 min, the silver nanowire dispersion completely filled the groove, and a composite conductor was obtained.

[0090] Silica powder with an average particle size of 10 nm was added to an ethanol solution and ultrasonically dispersed for 15 min to obtain a silica powder dispersion with a silica powder concentration of 0.5 mg / mL. The silica powder dispersion was then heated to 45°C, and the composite conductor was placed in the silica powder dispersion, and after 5 min, the silver nanowire layer was bonded with a protective layer. The shutter was removed, and the electrode line was etched at the position of the shutter, and a silver paste electrode was used. The remaining residues attached to the groove were removed by grinding and polishing to obtain a silver nanowire transparent conductor.

[0091] Comparative Example 5

[0092] Comparative Example 5 differs from Example 1 in that PET was coated on the groove surface of the composite conductor, and at this time, the groove was completely filled with PET.

[0093] The silver nanowire transparent conductors prepared in Examples 1-4 and Comparative Examples 1-5 were tested for performance, and the test results are shown in Table 1. Among them, the reliability test: under the conditions of an environmental setting temperature of 85°C, a humidity of 85%, and an input voltage of 12V, the working time of the silver nanowire transparent conductor maintaining the heating performance was determined.

[0094] Table 1

[0095]

[0096] According to Table 1, the silver nanowire transparent conductive member prepared by the preparation method provided by the application can have excellent conductivity and reliability while ensuring a high transmittance of more than 90%, and can maintain a heating effect of about 86h-93h under harsh environmental conditions of a temperature of 85℃ and a humidity of 85%.

[0097] Comparative Example 1 is a traditional layer structure, which has good conductivity but a transmittance of only 88% and poor reliability; Comparative Examples 2 and 3 have an increased scattering index due to Mie scattering of light through the silver nanowire transparent conductive member, so that the transmittance of the prepared silver nanowire transparent conductive member is reduced; Comparative Example 4 has a silver nanowire layer completely filling the grooves and silver nanowire residues existing outside the grooves, so that although the protective layer is further bonded, the protective layer mainly covers the upper surface of the silver nanowire in the grooves, but when the silver nanowire attached outside the grooves is removed by polishing, the protective layer is damaged, the protective effect is reduced, and thus the reliability is affected; Comparative Example 5 uses traditional PET as the protective layer, which has poor bonding effect with the silver nanowire layer, and the PET protective layer has poor compactness due to problems such as voids during preparation, so that water vapor is easily introduced under high humidity environmental conditions, and thus the silver nanowire transparent conductive member prepared has poor reliability.

[0098] The technical features of the above-described embodiments can be combined in any manner, and to make the description concise, not all possible combinations of the technical features in the above-described embodiments are described, however, as long as the combinations of the technical features do not exist contradictions, they should be considered as the scope of the present application.

[0099] The above-described embodiments only express several embodiments of the application, which are described in detail and specifically, but should not be understood as a limitation on the scope of the patent. It should be pointed out that for ordinary skilled persons in the art, several modifications and improvements can be made without departing from the concept of the application, which are all within the protection scope of the application. Therefore, the protection scope of the patent of the application should be subject to the appended claims.

Claims

1. A method for producing a silver nanowire transparent conductor, characterized by, The preparation method comprises the following steps: etching at least one groove on the surface of the transparent substrate and performing an activation treatment to obtain a pretreated substrate, wherein the depth of the groove is 100-200 nm, the width of the groove is 100-160 nm, any two grooves are parallel to each other, and the distance between any two grooves is the same; placing the pretreated substrate in a silver nanowire dispersion liquid containing mercaptosiloxane to enable the groove bottom to adsorb and deposit a silver nanowire layer, thereby obtaining a composite conductor, wherein the thickness of the silver nanowire layer is 40-60 nm; placing the composite conductor in an inorganic oxide powder dispersion liquid to enable the surface of the silver nanowire layer to bond a protective layer, removing the silver nanowire residues and inorganic oxide powder residues attached outside the groove, thereby obtaining a silver nanowire transparent conductive component, wherein the sum of the thicknesses of the silver nanowire layer and the protective layer is less than or equal to the depth of the groove.

2. The method for preparing a transparent conductive silver nanowire according to claim 1, characterized in that, The distance between two adjacent grooves is 500-1000 nm.

3. The method for preparing a transparent conductive silver nanowire according to claim 1, characterized in that, In the silver nanowire dispersion liquid containing mercaptosiloxane, the concentration of silver nanowires is 0.5-1 mg / mL, and the mass ratio of mercaptosiloxane to silver nanowires is 1:10-1:

15.

4. The method for preparing a transparent conductive silver nanowire according to claim 1, characterized in that, In the inorganic oxide powder dispersion liquid, the concentration of inorganic oxide powder is 0.5-1 mg / mL. The inorganic oxide powder in the inorganic oxide powder dispersion liquid mainly comprises at least one of silica powder, zinc oxide powder and titanium dioxide powder.

5. The method for preparing a transparent conductive silver nanowire according to claim 1, characterized in that, In the inorganic oxide powder dispersion liquid, the particle size of the inorganic oxide powder is 10-20 nm.

6. The method for preparing a transparent conductive silver nanowire according to claim 1, characterized in that, In the step of placing the pretreated substrate in the silver nanowire dispersion liquid containing mercaptosiloxane, the temperature of the silver nanowire dispersion liquid is 25-65°C, and the time is 5-10 min.

7. The method for preparing a transparent conductive silver nanowire according to claim 1, characterized in that, In the step of placing the composite conductor in the inorganic oxide powder dispersion liquid, the temperature of the inorganic oxide powder dispersion liquid is 25-65°C, and the time is 5-10 min.

8. The method for preparing a transparent conductive silver nanowire according to claim 1, characterized in that, Before the step of performing the activation treatment, two baffles are placed on the surface of the transparent substrate having the grooves, the two baffles are oppositely arranged on both sides of the grooves, and any baffle has intersection points with all the grooves, and then after the step of bonding the protective layer on the surface of the silver nanowire layer, the baffles are removed, and electrodes are arranged at the positions shielded by the baffles.

9. The silver nanowire transparent conductive film according to the production method of any one of claims 1 to 8, wherein The silver nanowire transparent conductive component comprises a transparent substrate having at least one groove, and a silver nanowire layer and a protective layer are sequentially arranged from the bottom of the groove to the opening direction, wherein the sum of the thicknesses of the silver nanowire layer and the protective layer is less than or equal to the depth of the groove.

10. A silver nanowire transparent conductive component according to claim 9 for use in a camera viewfinder.

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