Transparent conductive film and preparation method thereof, transparent conductive glass and preparation method and application thereof

Abstract

The invention belongs to the technical field of glass materials, and particularly relates to a transparent conductive film and a preparation method thereof, transparent conductive glass and a preparation method and application thereof. The transparent conductive film provided by the invention covers the transparent substrate glass, can endow the transparent substrate glass with high-temperature processing properties such as tempering, hot bending, interlayer or hollowness, and can still have high visible light permeability, low haze and low surface resistance, and the heating power density can be improved by reducing the resistance; therefore, the rapid heating requirement in the low-voltage driving scene in the fields of electric appliances and vehicles is met, and the industrial prospect is achieved. The transparent conductive glass provided by the invention still has high visible light permeability, low haze and low resistance after high-temperature heat treatment, and is particularly suitable for the fields of panel glass of a display refrigerator with low-voltage electric heating capacity or windshield, side window or sky screen glass of a vehicle.

Description

Technical Field

[0001] The present invention belongs to the technical field of glass materials, and in particular relates to a transparent conductive film and a preparation method thereof, and transparent conductive glass and a preparation method and application thereof. Background Art

[0002] Transparent conductive glass is a functional glass made by coating ordinary glass with a light-transmitting conductive film. It combines light transparency with electrical conductivity and is widely used in various fields. However, some fields have special functional requirements for transparent conductive glass.

[0003] For example, in display freezers, transparent conductive glass must have a light transmittance similar to that of ordinary glass and a very low electrical resistance. This ensures heating power under safe low-voltage conditions, while simultaneously achieving both light transmittance and defrosting. Another example is the transparent conductive glass used in vehicle windshields. On the one hand, it requires high light transmittance (minimum 70%) to meet vehicle safety requirements, while on the other hand, it requires extremely low electrical resistance to ensure sufficient heating power density for rapid ice melting, defrosting, and demisting under low vehicle voltage conditions.

[0004] Currently, there are two main types of industrialized transparent conductive glass that can balance performance and cost: one is to coat transparent oxide materials on glass, such as ITO or FTO, but the minimum resistance of this type of transparent conductive glass is 5-10Ω / m. 2 , cannot meet the low voltage heating requirements.

[0005] Another type of low-emissivity glass utilizes a silver-based film, embedding a single or multiple nanometer-thick silver film within a multilayer oxide or nitride material (less than 200 nanometers thick) to achieve high light transmittance and low electrical resistance. To protect the silver layer from damage, an absorbent barrier layer, such as NiCr or Ti, is typically added. By optimizing the film structure, such silver-based films can achieve a certain degree of light transmittance and low electrical resistance after tempering.

[0006] However, the light transmittance and resistance level of the above-mentioned transparent conductive glass are still insufficient for use in display refrigerators or transportation vehicles. Summary of the Invention

[0007] The purpose of the present invention is to provide a transparent conductive film and a preparation method thereof, transparent conductive glass and a preparation method and application thereof. The transparent conductive film provided by the present invention can give transparent substrate glass high-temperature processing resistance, high visible light transmittance, low haze and low surface resistance.

[0008] In order to achieve the above object, the present invention provides the following technical solutions:

[0009] The present invention provides a transparent conductive film, comprising a bottom layer, an intermediate layer, and a top layer arranged in sequence; the bottom layer comprises a first bottom layer, a second bottom layer, and a third bottom layer arranged in sequence from bottom to top; the first bottom layer comprises silicon dioxide doped with aluminum oxide (SiO2:Al); the second bottom layer comprises one or more of silicon aluminum nitride, silicon zirconium nitride, titanium zirconium oxide, and zinc tin oxide; the third bottom layer comprises zinc oxide doped with lanthanum oxide (ZnO:La); the intermediate layer comprises silver layers and dielectric layers arranged alternately, with silver layers at both ends; the thickness of the silver layer is less than 15 nanometers; the dielectric layer comprises a first dielectric layer, a second dielectric layer, and a third dielectric layer arranged in sequence from bottom to top; the first dielectric layer comprises slightly oxygen-deficient zinc oxide doped with aluminum oxide (ZnO 1-δ :Al); the second dielectric layer includes one or more of silicon aluminum nitride, silicon zirconium nitride, titanium zirconium oxide and zinc tin oxide; the third dielectric layer includes zinc oxide doped with lanthanum oxide; the top layer includes a first top layer, a second top layer and a third top layer arranged in sequence from bottom to top; the first top layer includes slightly oxygen-deficient zinc oxide doped with aluminum oxide; the second top layer includes one or more of silicon aluminum nitride, silicon zirconium nitride, titanium zirconium oxide and zinc tin oxide; the third top layer includes silicon dioxide doped with aluminum oxide.

[0010] Preferably, the thickness of the first bottom layer is 20 to 1000 nanometers; the doping amount of aluminum oxide in the first bottom layer is 2 to 40 wt%; the refractive index (n) of the first bottom layer is 1.45 to 1.65, and the extinction coefficient (k) is less than 0.01; the thickness of the second bottom layer is 5 to 40 nanometers; the refractive index of the second bottom layer is greater than 1.9, and the extinction coefficient is less than 0.01; the thickness of the third bottom layer is 6 to 30 nanometers; and the doping amount of lanthanum oxide in the third bottom layer is 0.1 to 10 wt%.

[0011] Preferably, the number of the silver layers is 2 to 4.

[0012] Preferably, the thickness of the first dielectric layer is 6 to 30 nanometers; the doping amount of aluminum oxide in the first dielectric layer is 2 to 10 wt%; the molecular formula of the slightly oxygen-deficient zinc oxide in the first dielectric layer is ZnO 1-δ , 0.001<δ<0.01; the thickness of the second dielectric layer is 40 to 100 nanometers; the refractive index of the second dielectric layer is greater than 1.9, and the extinction coefficient is less than 0.01; the thickness of the third dielectric layer is 6 to 30 nanometers; the doping amount of lanthanum oxide in the third dielectric layer is 0.1 to 10 wt%.

[0013] Preferably, the thickness of the first top layer is 6 to 30 nanometers; the doping amount of aluminum oxide in the first top layer is 2 to 10 wt%; the molecular formula of the slightly oxygen-deficient zinc oxide in the first top layer is ZnO 1-δ, 0.001<δ<0.01; the thickness of the second top layer is 20 to 200 nanometers; the refractive index of the second top layer is greater than 1.9, and the extinction coefficient is less than 0.01; the thickness of the third top layer is 20 to 1000 nanometers; the doping amount of aluminum oxide in the third top layer is 2 to 40 wt%; the refractive index of the third top layer is 1.45 to 1.65, and the extinction coefficient is less than 0.01.

[0014] Preferably, the thickness of the transparent conductive film is 100 to 2600 nanometers.

[0015] The present invention also provides a method for preparing the transparent conductive film described in the above scheme, comprising the following steps:

[0016] The transparent conductive film is obtained by sequentially depositing a bottom layer, a middle layer and a top layer from bottom to top by using physical vapor deposition or chemical vapor deposition.

[0017] The present invention also provides a transparent conductive glass, comprising a transparent substrate glass and a transparent conductive film covering the surface of the transparent substrate glass; the transparent conductive film is the transparent conductive film described in the above scheme or the transparent conductive film obtained by the preparation method described in the above scheme.

[0018] The present invention also provides a method for preparing the transparent conductive glass described in the above scheme, comprising the following steps:

[0019] The transparent conductive glass is obtained by sequentially depositing a bottom layer, an intermediate layer and a top layer on the surface of the transparent substrate glass from bottom to top by using physical vapor deposition or chemical vapor deposition.

[0020] The present invention also provides the use of the transparent conductive glass described in the above solution or the transparent conductive glass obtained by the preparation method described in the above solution in electrical products or the transportation field.

[0021] The present invention provides a transparent conductive film. The transparent conductive film provided by the present invention, except for the silver layer, is made of oxide or nitride materials that do not absorb visible light, thereby achieving high light transmittance. In addition, the film-forming surface of each silver layer (the direct contact layer when the silver layer is prepared) is zinc oxide doped with lanthanum oxide, and its lattice spacing is better matched with the lattice spacing of silver, thereby improving the crystallinity of the silver layer and achieving lower resistance at the same thickness. The present invention controls the thickness of the silver layer to be less than 15 nanometers, thereby avoiding the silver layer from undergoing a relaxation process to form aggregation during the preparation and subsequent high-temperature processing, thereby losing the original low resistance and high light transmittance. The present invention can further reduce the resistance by providing more silver layers. The present invention further improves the stability of the silver layer under subsequent high-temperature processing conditions by doping silicon dioxide with aluminum oxide, and by controlling its refractive index, it can fully control the damage to the silver layer from metal ions, oxygen or water vapor from the original sheet and the outside during high-temperature processing, and does not significantly affect the optical properties of the transparent conductive film, especially when used in an electrically heated glass interlayer.

[0022] The transparent conductive film provided by the present invention is coated on a transparent substrate glass and can give the transparent substrate glass high-temperature processing resistance, such as tempering, heat bending, interlayer or hollowing, while still having high visible light transmittance, low haze and low surface resistance. Reducing resistance can increase the heating power density to meet the rapid heating needs of electrical appliances and vehicles in low-voltage driving scenarios, and has industrial prospects.

[0023] The present invention also provides a method for preparing the transparent conductive film of the above-mentioned solution. The preparation method provided by the present invention has simple steps, convenient operation, good feasibility, high safety, and has the potential for large-scale production.

[0024] The present invention also provides a transparent conductive glass. The transparent conductive glass can maintain high visible light transmittance, low haze, and low electrical resistance even after heat treatment at 650°C for more than 400 seconds. It can be used in applications such as panel glass for display refrigerators with low-voltage electrical heating capabilities or windshields for vehicles.

[0025] The present invention also provides a method for preparing the transparent conductive glass described in the above solution. The preparation method provided by the present invention is low in cost, high in efficiency, and environmentally friendly.

[0026] The present invention also provides applications of the transparent conductive glass described above, or the transparent conductive glass obtained by the preparation method described above, in electrical appliances or transportation applications. The transparent conductive glass provided by the present invention maintains high visible light transmittance, low haze, and low electrical resistance even after high-temperature heat treatment. It is particularly suitable for use in display cabinet panels with low-voltage electrical heating capabilities, as well as in windshields, side windows, or skylights in vehicles. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0028] Figure 1 The transparent conductive glass provided by the present invention contains double-layer silver (a), triple-layer silver (b) and quadruple-layer silver (c) structures.

[0029] Figure 2 This is a structural diagram of the bottom layer (a), middle layer (b) and top layer (c) of the transparent conductive film in the transparent conductive glass provided by the present invention;

[0030] Figure 3 Microscope photos of the transparent conductive glass prepared in Example 2(a) and Comparative Example 2(b);

[0031] Reference numerals of the present invention are as follows: 1, 2, 3, and 4 are silver layers; 40 is a bottom layer; 41 is a first bottom layer; 42 is a second bottom layer; 43 is a third bottom layer; 50 is a dielectric layer A; 51 is a first dielectric layer of dielectric layer A; 52 is a second dielectric layer of dielectric layer A; 53 is a third dielectric layer of dielectric layer A; 60 is a dielectric layer B; 61 is a first dielectric layer of dielectric layer B; 62 is a second dielectric layer of dielectric layer B; 63 is a third dielectric layer of dielectric layer B; 70 is a dielectric layer C; 71 is a first dielectric layer of dielectric layer C; 72 is a second dielectric layer of dielectric layer C; 73 is a third dielectric layer of dielectric layer C; 80 is a top layer; 81 is a first top layer; 82 is a second top layer; 83 is a third top layer; 100 is float glass; and 200 is a transparent conductive film. DETAILED DESCRIPTION

[0032] The present invention provides a transparent conductive film, comprising a bottom layer, an intermediate layer, and a top layer arranged in sequence; the bottom layer comprises a first bottom layer, a second bottom layer, and a third bottom layer arranged in sequence from bottom to top; the first bottom layer comprises silicon dioxide doped with aluminum oxide; the second bottom layer comprises one or more of aluminum silicon nitride, zirconium silicon nitride, titanium zirconium oxide, and zinc tin oxide; and the third bottom layer comprises zinc oxide doped with lanthanum oxide;

[0033] The intermediate layer includes alternating silver layers and dielectric layers, with silver layers at both ends; the thickness of the silver layer is less than 15 nanometers; the dielectric layer includes a first dielectric layer, a second dielectric layer, and a third dielectric layer arranged in sequence from bottom to top; the first dielectric layer includes slightly oxygen-deficient zinc oxide doped with aluminum oxide; the second dielectric layer includes one or more of aluminum silicon nitride, zirconium silicon nitride, titanium zirconium oxide, and zinc tin oxide; the third dielectric layer includes zinc oxide doped with lanthanum oxide;

[0034] The top layer includes a first top layer, a second top layer and a third top layer arranged in sequence from bottom to top; the first top layer includes slightly oxygen-deficient zinc oxide doped with aluminum oxide; the second top layer includes one or more of silicon aluminum nitride, silicon zirconium nitride, titanium zirconium oxide layer and zinc tin oxide; the third top layer includes silicon dioxide doped with aluminum oxide.

[0035] The transparent conductive film provided by the present invention comprises a bottom layer (structured as Figure 2 The thickness of the first bottom layer may be 20 to 1000 nanometers, specifically 50 nanometers, 100 nanometers, 200 nanometers, 400 nanometers, 600 nanometers or 800 nanometers.

[0036] In the present invention, the doping amount of aluminum oxide in the first bottom layer may be 2-40 wt%, specifically 5 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt% or 35 wt%.

[0037] In the present invention, the refractive index of the first bottom layer can be 1.45 to 1.65, and the extinction coefficient can be less than 0.01. By providing the first bottom layer, the present invention blocks small-diameter metal ions and film surface defects from the glass from diffusing into the transparent conductive film during high-temperature tempering and thermal bending, thereby preventing the film layer function of the transparent conductive film from being destroyed.

[0038] In the present invention, the thickness of the second bottom layer may be 5 to 40 nanometers, specifically 10 nanometers, 15 nanometers, 20 nanometers, 25 nanometers, 30 nanometers or 35 nanometers.

[0039] In the present invention, the refractive index of the second bottom layer can be greater than 1.9, and the extinction coefficient can be less than 0.01. By providing the second bottom layer, the present invention adjusts the overall transmission and reflection of the film layer while being resistant to high temperatures.

[0040] In the present invention, the thickness of the third bottom layer may be 6 to 30 nanometers, specifically 10 nanometers, 15 nanometers, 20 nanometers or 25 nanometers.

[0041] In the present invention, the doping amount of lanthanum oxide in the third bottom layer can be 0.1-10 wt%, specifically 0.5 wt%, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 5 wt%, 7.5 wt% or 9 wt%. By providing the third bottom layer, the present invention ensures high temperature resistance while providing a better crystallization surface for the silver layer.

[0042] The transparent conductive film provided by the present invention includes an intermediate layer (structured as Figure 2The thickness of the silver layer is less than 15 nanometers, and can be specifically 13 nanometers, 10 nanometers, 8 nanometers, 6 nanometers or 3 nanometers.

[0043] In the present invention, the number of the silver layer can be 2 to 4 layers, specifically 3 layers.

[0044] In the present invention, the thickness of the first dielectric layer may be 6 to 30 nanometers, specifically 10 nanometers, 15 nanometers, 20 nanometers or 25 nanometers.

[0045] In the present invention, the doping amount of aluminum oxide in the first dielectric layer may be 2-10 wt%, specifically 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt% or 9 wt%.

[0046] In the present invention, the molecular formula of the slightly oxygen-deficient zinc oxide in the first dielectric layer can be ZnO 1-δ , 0.001<δ<0.01. The present invention improves the stability of the silver layer during subsequent coating and high-temperature processing and the weather resistance during use by providing the first dielectric layer.

[0047] In the present invention, the thickness of the second dielectric layer may be 40 to 100 nanometers, specifically 45 nanometers, 50 nanometers, 55 nanometers, 60 nanometers, 65 nanometers, 70 nanometers, 75 nanometers, 80 nanometers, 85 nanometers, 90 nanometers or 95 nanometers.

[0048] In the present invention, the refractive index of the second dielectric layer can be greater than 1.9, and the extinction coefficient can be less than 0.01. By providing the second dielectric layer, the present invention adjusts the optical properties of the transparent conductive film after high-temperature treatment to meet application requirements, such as light transmittance, reflectivity, transmission color, small-angle reflection color, and large-angle reflection color.

[0049] In the present invention, the thickness of the third dielectric layer may be 6 to 30 nanometers, specifically 8 nanometers, 10 nanometers, 12 nanometers, 15 nanometers, 18 nanometers, 21 nanometers, 24 nanometers or 27 nanometers.

[0050] In the present invention, the doping amount of lanthanum oxide in the third dielectric layer can be 0.1 to 10 wt%, specifically 0.5 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, or 9 wt%. By providing the third dielectric layer, the present invention can optimize the growth and crystallization properties of the silver layer, thereby achieving lower resistance for a silver layer of the same thickness.

[0051] The transparent conductive film provided by the present invention comprises a top layer (structured as Figure 2The thickness of the first top layer may be 6 to 30 nanometers, specifically 8 nanometers, 10 nanometers, 12 nanometers, 15 nanometers, 18 nanometers, 21 nanometers, 24 nanometers or 27 nanometers.

[0052] In the present invention, the doping amount of aluminum oxide in the first top layer may be 2-10 wt%, specifically 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt% or 9 wt%.

[0053] In the present invention, the molecular formula of the slightly oxygen-deficient zinc oxide in the first top layer can be ZnO 1-δ , 0.001<δ<0.01. The present invention protects the silver layer from being damaged by subsequent layer materials during the preparation process by providing the first top layer, and further improves the stability of the silver layer during subsequent high-temperature processing.

[0054] In the present invention, the thickness of the second top layer may be 20 to 200 nanometers, specifically 40 nanometers, 60 nanometers, 80 nanometers, 100 nanometers, 120 nanometers, 150 nanometers or 180 nanometers.

[0055] In the present invention, the refractive index of the second top layer can be greater than 1.9, and the extinction coefficient can be less than 0.01. By providing the second top layer, the present invention not only regulates the overall optical properties of the transparent conductive film, but also prevents external moisture, oxygen, etc. from diffusing into the film during subsequent high-temperature glass processing and room-temperature storage and use, thereby protecting the silver layer from damage.

[0056] In the present invention, the thickness of the third top layer may be 20 to 1000 nanometers, specifically 50 nanometers, 100 nanometers, 200 nanometers, 400 nanometers, 600 nanometers or 800 nanometers.

[0057] In the present invention, the doping amount of aluminum oxide in the third top layer may be 2-40 wt%, specifically 5 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt% or 35 wt%.

[0058] In the present invention, the refractive index of the third top layer can be 1.45 to 1.65, and the extinction coefficient can be less than 0.01. The present invention further improves the high temperature processing resistance and mechanical wear resistance of the overall transparent conductive film through the third top layer.

[0059] In the present invention, the thickness of the transparent conductive film may be 100 to 2600 nanometers, specifically 160 nanometers, 300 nanometers, 550 nanometers, 1000 nanometers, 1500 nanometers or 2100 nanometers.

[0060] The present invention also provides a method for preparing the transparent conductive film described in the above scheme, comprising the following steps:

[0061] The transparent conductive film is obtained by sequentially depositing a bottom layer, a middle layer and a top layer from bottom to top by using physical vapor deposition or chemical vapor deposition.

[0062] In the present invention, the physical vapor deposition (PVD) may be vacuum magnetron sputtering.

[0063] In the present invention, the chemical vapor deposition (CVD) may be atomic layer deposition.

[0064] In a specific embodiment of the present invention, the silver layer can be prepared by sputtering a silver target with a purity greater than 99.99% in a pure argon atmosphere, and the gas pressure can be controlled at 0.1-0.5 Pa, specifically 0.3 Pa.

[0065] In a specific embodiment of the present invention, the oxide film layer (the first bottom layer, the second bottom layer of oxide, the third bottom layer, the first dielectric layer, the second dielectric layer of oxide, the third dielectric layer, the first top layer, the second top layer of oxide and the third top layer) can be prepared by sputtering in an environment of oxygen and argon using an alloy target, and the mass ratio of oxygen to argon can be 1 to 5:1, specifically 3:1; or, the oxide film layer can be prepared using a metal oxide ceramic target, and the mass ratio of oxygen to argon can be 1:9 to 99, specifically 1:40 or 1:70.

[0066] In a specific embodiment of the present invention, the nitride film layer (the second bottom layer of nitride, the second dielectric layer of nitride and the second top layer of nitride) can be prepared by sputtering in a nitrogen and argon environment using an alloy target, and the mass ratio of nitrogen and argon can be 4:1 to 6, specifically 4:3.

[0067] The present invention also provides a transparent conductive glass, comprising a transparent substrate glass and a transparent conductive film covering the surface of the transparent substrate glass; the transparent conductive film is the transparent conductive film described in the above scheme or the transparent conductive film obtained by the preparation method described in the above scheme.

[0068] In the present invention, the transparent substrate glass may be transparent float glass; the thickness of the transparent substrate glass may be 0.5 to 8 mm, specifically 1 mm, 1.5 mm, 1.8 mm, 2.1 mm, 3 mm or 4 mm.

[0069] The structure of the transparent conductive glass provided by the present invention is as follows Figure 1As shown in Figure 2, a transparent conductive film containing two, three, or four layers of silver is deposited on a transparent glass substrate. In this transparent conductive film, the silver layer is sandwiched between two dielectric layers. In this transparent conductive film, the dielectric layer in direct contact with the transparent glass substrate is the bottom layer, while the dielectric layer farthest from the glass surface is the top layer.

[0070] The present invention also provides a method for preparing the transparent conductive glass described in the above scheme, comprising the following steps:

[0071] The transparent conductive glass is obtained by sequentially depositing a bottom layer, an intermediate layer and a top layer on the surface of the transparent substrate glass from bottom to top by using physical vapor deposition or chemical vapor deposition.

[0072] In the present invention, the physical vapor deposition or chemical vapor deposition method may be the same as the method for preparing the transparent conductive film described in the above solution, and will not be described in detail here.

[0073] The present invention also provides the use of the transparent conductive glass described in the above solution or the transparent conductive glass obtained by the preparation method described in the above solution in electrical products or the transportation field.

[0074] The transparent conductive glass provided by the present invention retains high visible light transmittance, low haze and low electrical resistance after high-temperature heat treatment, and is particularly suitable for use in fields such as panel glass of display refrigerators with low-voltage electric heating capabilities or windshields, side windows or skylight glass of vehicles.

[0075] In order to further illustrate the present invention, the scheme of the present invention is described in detail below with reference to the accompanying drawings and embodiments, but they should not be understood as limiting the scope of protection of the present invention.

[0076] Example 1 Double silver layer transparent conductive glass

[0077] In this embodiment, a 3mm thick float glass is used. The transparent conductive film prepared by vacuum magnetron sputtering has the following structures from bottom to top: 200nm thick SiO2:Al (Al 2wt%), 25nm thick Si3N4, 15nm thick ZnO:La (La 1wt%), 8nm thick Ag, 10nm thick ZnO:La. 1-δ :Al (Al 2wt%), ZnSnO with a thickness of 60nm x , ZnO:La (La 1wt%) with a thickness of 15nm, Ag with a thickness of 10nm, ZnO with a thickness of 10nm 1-δ:Al (Al 2wt%), Si3N4 with a thickness of 35nm and SiO2:Al (Al10wt%) with a thickness of 200nm, the silver layer is prepared by sputtering a silver target with a purity of >99.99%; the oxide film layer is prepared by sputtering an alloy target in an environment of oxygen and argon in a mass ratio of 3:1; the nitride film layer is prepared by sputtering an alloy target in an environment of nitrogen and argon in a mass ratio of 6:5 to obtain transparent conductive glass.

[0078] The transparent conductive glass of this embodiment was heat treated at 650°C for 400 seconds. The results showed that the visible light transmittance of the transparent conductive glass prepared in this embodiment was 89% and the surface resistance was 2.0Ω / m. 2 , the haze is 0.2%.

[0079] Example 2 Transparent conductive glass with three silver layers

[0080] This embodiment uses float glass with a thickness of 2.1 mm. The transparent conductive film prepared by vacuum magnetron sputtering has the following structures from bottom to top: SiO2:Al (Al 2 wt%) with a thickness of 180 nm, ZnSnO x , ZnO:La (La 0.5wt%) with a thickness of 15nm, Ag with a thickness of 14nm, ZnO with a thickness of 10nm 1-δ :Al (Al 2wt%), ZnSnO with a thickness of 55nm x , ZnO:La (La 0.5wt%) with a thickness of 15nm, Ag with a thickness of 12nm, ZnO with a thickness of 10nm 1-δ :Al (Al 2wt%), ZnSnO with a thickness of 47nm x , ZnO:La (La 0.5wt%) with a thickness of 15nm, Ag with a thickness of 10nm, ZnO with a thickness of 15nm 1-δ :Al (Al2wt%), Si3N4 with a thickness of 165nm and SiO2:Al (Al 10wt%) with a thickness of 40nm, the silver layer is prepared by sputtering a silver target with a purity of >99.99%; the oxide film layer is prepared by sputtering an alloy target in an environment of oxygen and argon in a mass ratio of 3:1; the nitride film layer is prepared by sputtering an alloy target in an environment of nitrogen and argon in a mass ratio of 6:5 to obtain transparent conductive glass.

[0081] The transparent conductive glass of this embodiment was heat treated at 650°C for 400 seconds. The results showed that the transparent conductive glass prepared in this embodiment had a visible light transmittance of 77% and a surface resistance of 0.8Ω / m. 2 , the haze is 0.25%.

[0082] Example 3 Transparent conductive glass with four silver layers

[0083] In this embodiment, a float glass with a thickness of 2.1 mm is used. The transparent conductive film prepared by vacuum magnetron sputtering has the following structures from bottom to top: SiO2:Al (Al 2 wt%) with a thickness of 200 nm, Si3N4 (20 nm), ZnO:La (La 5 wt%) with a thickness of 15 nm, Ag with a thickness of 12 nm, ZnO:La (10 nm), and ZnO:La (10 nm). 1-δ :Al (Al2wt%), ZnSnO with a thickness of 60nm x , ZnO:La (La 5wt%) with a thickness of 15nm, Ag with a thickness of 10nm, ZnO with a thickness of 10nm 1-δ :Al (Al 2wt%), ZnSnO with a thickness of 65nm x , ZnO:La (La5wt%) with a thickness of 15nm, Ag with a thickness of 10nm, ZnO with a thickness of 10nm 1-δ :Al (Al 2wt%), 40nm thick ZnSnO x , ZnO:La (La 5wt%) with a thickness of 15nm, Ag with a thickness of 8nm, ZnO with a thickness of 15nm 1-δ :Al (Al2wt%), Si3N4 with a thickness of 25nm and SiO2:Al (Al 30wt%) with a thickness of 250nm, the silver layer is prepared by sputtering a silver target with a purity of >99.99%; the oxide film layer is prepared by sputtering an alloy target in an environment of oxygen and argon in a mass ratio of 3:1; the nitride film layer is prepared by sputtering an alloy target in an environment of nitrogen and argon in a mass ratio of 6:5 to obtain transparent conductive glass.

[0084] The transparent conductive glass of this embodiment was heat treated at 650°C for 400 seconds. The results showed that the visible light transmittance of the transparent conductive glass prepared in this embodiment was 76% and the surface resistance was 0.7Ω / m. 2 , the haze is 0.3%.

[0085] Comparative Example 1: Double-silver-layer transparent conductive glass

[0086] The comparative example uses a float glass with a thickness of 3 mm, and the thin film structure prepared by vacuum magnetron sputtering is Si3N4 with a thickness of 25 nm, ZnO with a thickness of 15 nm, Ag with a thickness of 8 nm, NiCr with a thickness of 0.5 nm, ZnO with a thickness of 10 nm, ZnSnO with a thickness of 60 nm from bottom to top. x, ZnO with a thickness of 15 nm, Ag with a thickness of 10 nm, NiCr with a thickness of 0.5 nm, ZnO with a thickness of 10 nm and Si3N4 with a thickness of 35 nm. The silver layer is prepared by sputtering a silver target with a purity of >99.99%; the oxide film layer is prepared by sputtering an alloy target in an environment of oxygen and argon with a mass ratio of 3:1; the nitride film layer is prepared by sputtering an alloy target in an environment of nitrogen and argon with a mass ratio of 6:5 to obtain transparent conductive glass.

[0087] The transparent conductive glass of this comparative example was heat treated at 650°C for 400 seconds. The results showed that the visible light transmittance of the transparent conductive glass prepared in this comparative example was 81% and the surface resistance was 2.4Ω / m. 2 , the haze is 0.93%.

[0088] Comparative Example 2 Transparent conductive glass with three silver layers

[0089] This comparative example uses float glass with a thickness of 2.1 mm, and the thin film structure prepared by vacuum magnetron sputtering is ZnSnO with a thickness of 25 nm from bottom to top. x , ZnO with a thickness of 15nm, Ag with a thickness of 14nm, NiCr with a thickness of 0.5nm, ZnO with a thickness of 10nm, ZnSnO with a thickness of 55nm x , ZnO with a thickness of 15nm, Ag with a thickness of 12nm, NiCr with a thickness of 0.5nm, ZnO with a thickness of 10nm, ZnSnO with a thickness of 47nm x , ZnO with a thickness of 15 nm, Ag with a thickness of 10 nm, NiCr with a thickness of 0.5 nm, ZnO with a thickness of 15 nm, and Si3N4 with a thickness of 35 nm. The silver layer is prepared by sputtering a silver target with a purity of >99.99%; the oxide film layer is prepared by sputtering an alloy target in an environment of oxygen and argon with a mass ratio of 3:1; the nitride film layer is prepared by sputtering an alloy target in an environment of nitrogen and argon with a mass ratio of 6:5 to obtain transparent conductive glass.

[0090] The transparent conductive glass of this comparative example was heat treated at 650°C for 400 seconds. The results showed that the transparent conductive glass prepared in this comparative example had a visible light transmittance of 71% and a surface resistance of 0.9Ω / m. 2 , the haze is 1.1%.

[0091] It can be seen from the test results of the above embodiments and comparative examples that, compared with the comparative examples, embodiments 1 to 3 achieve higher visible light transmittance, lower resistance and haze.

[0092] Test Example 1

[0093] The surfaces of the transparent conductive glass films of Example 2(a) and Comparative Example 2(b) were observed under a microscope. Figure 3 shown.

[0094] according to Figure 3 It can be seen that Example 2 has almost no observable defects, while Comparative Example 2 has obvious micron-sized oxidation or agglomeration points due to the silver layer being partially destroyed by high temperature, which leads to an increase in the haze of the film layer and may even cause conductivity damage.

[0095] Test Example 2

[0096] The transparent conductive glass of Example 1 or Comparative Example 1 was simultaneously laminated into insulating glass with the same structure and used in a transparent cold chain display cabinet.

[0097] The results showed that the permeability of Example 1 was increased by 8% and the heating power density was increased by 20%.

[0098] Test Example 3

[0099] The transparent conductive glass of Example 2 or Example 3 is sandwiched with a float glass sheet with a thickness of 2.1 mm to be used for a heatable automobile windshield.

[0100] The results show that the visible light transmittance of Example 2 or Example 3 reaches above 72.5% and 71.5% respectively, and the standard 14V vehicle voltage can be used to achieve a heating power of more than 400W, thereby realizing rapid ice melting, defrosting and demisting in cold winter.

[0101] It can be seen from the above embodiments that the transparent conductive film provided by the present invention can provide the transparent substrate glass with high-temperature processing resistance, high visible light transmittance, low haze and low surface resistance.

[0102] Although the above embodiment provides a detailed description of the present invention, it is only a part of the embodiments of the present invention, not all of the embodiments. Other embodiments can be obtained based on this embodiment without creativity, and these embodiments all fall within the scope of protection of the present invention.

Claims

1. A transparent conductive film, characterized in that: including a bottom layer, a middle layer and a top layer arranged in sequence; The bottom layer includes a first bottom layer, a second bottom layer and a third bottom layer arranged in sequence from bottom to top; The first bottom layer comprises silicon dioxide doped with aluminum oxide; The second bottom layer comprises one or more of aluminum silicon nitride, zirconium silicon nitride, titanium zirconium oxide and zinc tin oxide; The third bottom layer includes zinc oxide doped with lanthanum oxide; The middle layer includes silver layers and dielectric layers arranged alternately, with silver layers at both ends; The thickness of the silver layer is less than 15 nanometers; The dielectric layer includes a first dielectric layer, a second dielectric layer and a third dielectric layer arranged in sequence from bottom to top; The first dielectric layer comprises slightly oxygen-deficient zinc oxide doped with aluminum oxide; The second dielectric layer comprises one or more of aluminum silicon nitride, zirconium silicon nitride, titanium zirconium oxide and zinc tin oxide; The third dielectric layer includes zinc oxide doped with lanthanum oxide; The top layer includes a first top layer, a second top layer and a third top layer arranged in sequence from bottom to top; The first top layer comprises slightly oxygen-deficient zinc oxide doped with aluminum oxide; The second top layer comprises one or more of aluminum silicon nitride, zirconium silicon nitride, titanium zirconium oxide layer and zinc tin oxide; The third top layer includes silicon dioxide doped with aluminum oxide.

2. The transparent conductive film according to claim 1, wherein: The thickness of the first bottom layer is 20 to 1000 nanometers; The doping amount of aluminum oxide in the first bottom layer is 2 to 40 wt%; The refractive index of the first bottom layer is 1.45 to 1.65, and the extinction coefficient is less than 0.01; The thickness of the second bottom layer is 5 to 40 nanometers; The refractive index of the second bottom layer is greater than 1.9, and the extinction coefficient is less than 0.01; The thickness of the third bottom layer is 6 to 30 nanometers; The doping amount of lanthanum oxide in the third bottom layer is 0.1-10 wt %.

3. The transparent conductive film according to claim 1, wherein: The number of the silver layers is 2 to 4.

4. The transparent conductive film according to claim 1, wherein The thickness of the first dielectric layer is 6 to 30 nanometers; The doping amount of aluminum oxide in the first dielectric layer is 2 to 10 wt%; The molecular formula of the slightly oxygen-deficient zinc oxide in the first dielectric layer is ZnO 1-δ , 0.001<δ<0.01; The thickness of the second dielectric layer is 40 to 100 nanometers; The refractive index of the second dielectric layer is greater than 1.9, and the extinction coefficient is less than 0.01; The thickness of the third dielectric layer is 6 to 30 nanometers; The doping amount of lanthanum oxide in the third dielectric layer is 0.1-10 wt %.

5. The transparent conductive film according to claim 1, wherein The thickness of the first top layer is 6 to 30 nanometers; The doping amount of aluminum oxide in the first top layer is 2 to 10 wt%; The molecular formula of the slightly oxygen-deficient zinc oxide in the first top layer is ZnO 1-δ , 0.001<δ<0.01; The thickness of the second top layer is 20 to 200 nanometers; The refractive index of the second top layer is greater than 1.9 and the extinction coefficient is less than 0.01; The thickness of the third top layer is 20 to 1000 nanometers; The doping amount of aluminum oxide in the third top layer is 2 to 40 wt %; The refractive index of the third top layer is 1.45-1.65, and the extinction coefficient is less than 0.

01.

6. The transparent conductive film according to claim 1, wherein: The thickness of the transparent conductive film is 100 to 2600 nanometers.

7. The method for preparing a transparent conductive film according to any one of claims 1 to 6, characterized in that: The following steps are involved: The transparent conductive film is obtained by sequentially depositing a bottom layer, a middle layer and a top layer from bottom to top by using physical vapor deposition or chemical vapor deposition.

8. A transparent conductive glass, characterized in that: It includes a transparent substrate glass and a transparent conductive film covering the surface of the transparent substrate glass; The transparent conductive film is the transparent conductive film according to any one of claims 1 to 6 or the transparent conductive film obtained by the preparation method according to claim 7.

9. The method for preparing the transparent conductive glass according to claim 8, characterized in that: The following steps are involved: The transparent conductive glass is obtained by sequentially depositing a bottom layer, an intermediate layer and a top layer on the surface of the transparent substrate glass from bottom to top by using physical vapor deposition or chemical vapor deposition.

10. Use of the transparent conductive glass according to claim 8 or the transparent conductive glass obtained by the preparation method according to claim 9 in electrical products or transportation fields.

Images